JPH10104774A - Silver halide emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a spectrally sensitized silver halide photographic sensitive material less liable to residual coloring. SOLUTION: This silver halide photographic sensitive material contains at least one kind of compd. represented by the formula, wherein R1 is pyridinium salt substd. alkyl, Z1 is a group of atoms required to form a 5- or 6-membered N-contg. hetero ring, each of L1 and L2 is methine, p. is 0 or l, M. is a counter ion equilibrating an electric charge, m. is a number of 0-10 required to neutralize electric charges in each molecule and Q is heterocyclic or arom. group substd. (poly)methine required to form the methine dye.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion having improved residual color and sensitivity during development processing, and a silver halide photographic material containing the emulsion.

[0002]

2. Description of the Related Art With the recent rapid development processing and the addition of a large amount of a sensitizing dye, the sensitizing dye contained in a silver halide photographic material does not elute during the processing, but the sensitizing dye is colored. The problem of leaving (so-called residual color) is increasing. Heretofore, sensitizing dyes having a small residual color, such as those having a hydrophilic substituent such as a sulfamoyl group or a carbamoyl group in the nucleus (for example, JP-A-1-147451, JP-A-61-294429, and JP-B-45) -3249,
Japanese Patent Application Laid-Open No. 61-77843) has been studied, but is still not at a satisfactory level. See also U.S. Pat.
The sensitizing dyes described in No. 2933 and European Patent No. 451816 A1 also have the effect of improving the residual color, but they have not obtained a sufficient effect in terms of achieving both the residual color and the sensitivity.

A great deal of effort has conventionally been made to increase the sensitivity of silver halide photographic light-sensitive materials. It is considered that, in the sensitizing dye, the efficiency of transmitting light energy to silver halide is improved by increasing the light absorptivity, thereby achieving higher spectral sensitivity. However, the amount of sensitizing dye adsorbed on the surface of the silver halide grains is limited, and it is difficult to adsorb a sensitizing dye having a monolayer saturation adsorption or more. Therefore, at present, the absorptance of the incident light quantum of each silver halide grain in the spectral sensitization region is extremely low.

[0004] A method proposed to solve these points will be described below. PBGilman, Jr. and colleagues are working on Photographic Science and Engineering (Photographic Sc).
ience and Engineering) Volume 20, Issue 3, Page 97 (19
In 1976), the cationic dye was adsorbed on the first layer,
Further, an anionic dye was adsorbed to the second layer using electrostatic force. GBBird et al. In U.S. Pat.
No. 622,316, multiple dyes were adsorbed in multiple layers on silver halide and sensitized by the contribution of Forster-type excitation energy transfer. Sugimoto et al. Conducted spectral sensitization by energy transfer from a luminescent dye in JP-A-63-138,341 and JP-A-64-84,244. Earl Steiger (R. Steiger) and others
Photographic Science and Engineering 27
In Vol. 2, p. 59 (1983), spectral sensitization by energy transfer from a gelatin-substituted cyanine dye was attempted. Conducted spectral sensitization by energy transfer from a cyclodextrin-substituted dye in JP-A-61-251842.

A so-called linked dye having two chromophores which are not separately conjugated but linked by a covalent bond is described, for example, in US Pat. Nos. 2,393,351 and 2,4.
Nos. 25,772, 2,518,732, 2,52
Nos. 1,944 and 2,592,196, European Patent No. 5
No. 65,083. However, these were not aimed at improving the light absorption rate. BB Bird has been actively pursuing the improvement of light absorption.
(GBBird), AL Borror et al., U.S. Pat. Nos. 3,622,317 and 3,976,491.
In No. 3, the light absorption rate was increased by adsorbing a linked sensitizing dye molecule having a plurality of cyanine chromophores, and sensitization was achieved by the contribution of energy transfer. Ukai, Okazaki and Sugimoto disclosed in JP-A-64-91134 a spectral sensitizer capable of adsorbing at least one substantially non-adsorbable dye containing at least two sulfo groups and / or carboxyl groups onto silver halide. It was proposed to bind to the dye. Also,
Proposed spectral sensitization with a cyanine dye polymer in U.S. Pat. No. 4,950,587. As described above, many studies have been made to improve the light absorptivity, but none of them has a sufficient effect of increasing the sensitivity.
Development suppression was also a problem. For the above reasons, there has been a demand for a spectral sensitization technique for improving the light absorptance of a silver halide photosensitive material and increasing the sensitivity.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide emulsion having less residual color during development processing and having higher sensitivity, and a photographic material containing the emulsion.

[0007]

The above object of the present invention has been attained by the following (1) and (2). (1) A silver halide emulsion containing at least one compound represented by the following general formula (I). General formula (I)

[0008]

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In the formula (I), R ₁ represents an alkyl group substituted with a pyridinium salt. The alkyl group substituted with a pyridinium salt means an alkyl group substituted with a pyridinio group. Z ₁ represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. L ₁ and L ₂ represent a methine group. p ₁ represents 0 or 1. M ₁ represents a charge balancing counter ion, and m ₁ represents a number from 0 to 10 required to neutralize the charge of the molecule. Q represents a methine group or a polymethine group necessary for forming a methine dye. (2) The silver halide emulsion according to (1), wherein the compound represented by the general formula (I) is a compound represented by the following general formula (II). General formula (II)

[0010]

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In the formula (II), L represents a divalent linking group. V
₁ , V ₂ , V ₃ , V ₄ and V ₅ represent a hydrogen atom or a substituent. Z ₁ , L ₁ , L ₂ , p ₁ , Q, M ₁ , and m
₁ has the same meaning as that of formula (I) in (1). The compound represented by the general formula (I) is preferably a compound represented by the above general formula (II) or the following general formula (III), and more preferably a compound represented by the general formula (II) . General formula (III)

[0012]

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In the formula (III), L represents a divalent linking group. V
_{6, V 7, V 8,} V 9, V 10, and V ₁₁ represents a hydrogen atom or a substituent. However, any one of V ₆ , V ₇ , V ₉ , V ₁₀ , and V ₁₁ represents a direct bond to the alkylene chain L. Z ₁ , L ₁ , L ₂ , p ₁ , Q, M ₁ , and m ₁ have the same meanings as those in the general formula (I) of (1). Further, it is more preferable that the compound represented by the general formula (I) is a compound selected from the following general formulas (IV), (V) and (VI). General formula (IV)

[0014]

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In the formula (IV), L ₃ , L ₄ , L ₅ , L ₆ , L
₇ , L ₈ and L ₉ represent a methine group. p ₂ and p ₃
Represents 0 or 1. n ₁ represents 0, 1, 2, or 3. Z ₂ and Z ₃ represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M ₂ represents a charge-balancing counter ion, and m ₂ represents a number from 0 to 4 required to neutralize the charge of the molecule. R ₂ and R ₃ represent an alkyl group. However, at least one of R ₂ and R ₃ represents an alkyl group substituted with a pyridinium salt represented by R ₁ in the general formula (I). General formula (V)

[0016]

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In the formula (V), L ₁₀ , L ₁₁ , L ₁₂ and L ₁₃
Represents a methine group. p ₄ is 0 or 1. n ₂ is 0,
Represents 1, 2, or 3. Z ₄ and Z ₅ each represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M
₃ represents a charge-balancing counter ion, and m ₃ represents a number from 0 to 4 required to neutralize the charge of the molecule. R ₅ represents an alkyl group, an aryl group, or a heterocyclic group. R ₄ represents an alkyl group substituted with a pyridinium salt represented by R ₁ in the general formula (I). General formula (VI)

[0018]

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In the formula (VI), L ₁₄ , L ₁₅ , L ₁₆ , L ₁₇ , L
₁₈ , L ₁₉ , L ₂₀ , L ₂₁ and L ₂₂ represent a methine group. p ₅
And p ₆ represents 0 or 1. n ₃ and n ₄ are 0, 1,
Represents 2 or 3. Z ₆ , Z ₇ and Z ₈ represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring.
M ₄ represents a charge-balancing counter ion, and m ₄ represents a number from 0 to 4 required to neutralize the charge of the molecule. R ₆ and R
₈ represents an alkyl group. R ₇ represents an alkyl group, an aryl group, or a heterocyclic group. However, at least one of R ₆ and R ₈ represents an alkyl group substituted with a pyridinium salt represented by R ₁ in the general formula (I).

Hereinafter, the compounds used in the present invention will be described in detail. Although any methine dye can be formed by Q, preferred examples include a cyanine dye, a merocyanine dye, a rhodocyanine dye, a trinuclear merocyanine dye, an allopolar dye, a hemicyanine dye, and a styryl dye. For more information on these dyes, see
Heterocyclic Compounds-Cyanin by FM Harmer, Heterocyclic Compounds-Cyanin Soybeans and Related Compounds
e Dyes and Related Compounds), John Wiley & Sons, New York, London, 1964, D.M.
(DMSturmer), Heterocyclic Compounds-Special topi in Heterocyclic Compounds
cs in heterocyclic chemistry) ", Chapter 18, Chapter 14
, Pp. 482-515. The general formulas of cyanine dyes, merocyanine dyes, and rhodacyanine dyes are described in U.S. Patent Nos. 5,340,694, 21,22.
Those shown on pages (XI), (XII) and (XIII) are preferred. Further, in the general formula (I), when a cyanine dye is formed by Q, it can be represented by the following resonance formula.

[0021]

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Formulas (I), (II), (III), (IV) and (V)
And (VI), Z₁, Z_Two, Z _Three, Z_Four, Z₆as well as
Z₈As the 5- or 6-membered nitrogen-containing heterocyclic ring represented by
Azoline nucleus, thiazole nucleus, benzothiazole nucleus, oxo
Sazoline nucleus, oxazole nucleus, benzoxazole nucleus,
Selenazoline nucleus, selenazole nucleus, benzoselenazole
Nucleus, 3,3-dialkylindolenine nucleus (eg, 3,
3-dimethylindolenine), imidazoline nucleus, imida
Sol nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4
A pyridine nucleus, a 2-quinoline nucleus, a 4-quinoline nucleus, 1-
Isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4,
5-b] quinoxaline nucleus, oxadiazole nucleus, thiazi
Azole nucleus, tetrazole nucleus, pyrimidine nucleus
Can be.

Preferred are benzoxazole nucleus, benzothiazole nucleus, benzimidazole nucleus and quinoline nucleus, more preferably benzoxazole nucleus and benzothiazole nucleus, particularly preferably benzothiazole nucleus.

Assuming that the substituent on Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₆ and Z ₈ is V, the substituent represented by V is not particularly limited. ,
Bromide, iodine, fluorine), mercapto group, cyano group, carboxyl group, phosphate group, sulfo group, hydroxy group, carbamoyl having 1 to 10, preferably 2 to 8, more preferably 2 to 5 carbon atoms Groups (eg, methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl), sulfamoyl groups having 0 to 10, preferably 2 to 8, more preferably 2 to 5 carbon atoms (eg, methylsulfamoyl, ethylsulfamoyl, Piperidinosulfonyl), nitro group, alkoxy group having 1 to 20, preferably 1 to 10, more preferably 1 to 8 carbon atoms (eg, methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy) , Having 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms
2, more preferably an aryloxy group having 6 to 10 carbon atoms (eg, phenoxy, p-methylphenoxy, p-
Chlorophenoxy, naphthoxy),

An acyl group having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (eg, acetyl, benzoyl, trichloroacetyl), 1 to 20 carbon atoms, preferably 2 to 20 carbon atoms 1
2, more preferably an acyloxy group having 2 to 8 carbon atoms (eg, acetyloxy, benzoyloxy), an acylamino group having 1 to 20, preferably 2 to 12, and more preferably 2 to 8 carbon atoms (eg, acetyl Amino), a sulfonyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms (eg, methanesulfonyl, ethanesulfonyl, benzenesulfonyl, etc.); A sulfinyl group having 1 to 10, more preferably 1 to 8 carbon atoms (eg, methanesulfinyl, benzenesulfinyl), a sulfonylamino having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms Groups (eg, methanesulfonylamino, ethanesulfonylamino Benzene sulfonylamino),

An amino group, a substituted amino group having 1 to 20, preferably 1 to 12, more preferably 1 to 8 carbon atoms (eg, methylamino, dimethylamino,
Benzylamino, anilino, diphenylamino), an ammonium group having 0 to 15 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms (for example, trimethylammonium group, triethylammonium group);
A hydrazino group having 0 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (for example, trimethylhydrazino group), 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms
(E.g., ureido group, N, N-dimethylureido group), an imide group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (e.g., succinimide group), An alkylthio group having 1 to 20, preferably 1 to 12, more preferably 1 to 8 carbon atoms, or an arylthio group (for example,
-Pyridylthio), an alkoxycarbonyl group having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl), and 6 to 20 carbon atoms, preferably Is an aryloxycarbonyl group having 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms (for example, phenoxycarbonyl);

An unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methyl, ethyl, propyl, butyl), and 1 to 18 carbon atoms, preferably 1 to 1 carbon atoms
0, more preferably a substituted alkyl group having 1 to 5 carbon atoms (hydroxymethyl, trifluoromethyl, benzyl,
Carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl, and here an unsaturated hydrocarbon group having 2 to 18 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms (for example, vinyl group, ethynyl group, 1-cyclohexenyl group, benzylidine group, benzylidene group) are also included in the substituted alkyl group. ), Having 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms.
5, more preferably a substituted or unsubstituted aryl group having 6 to 10 carbon atoms (for example, phenyl, naphthyl, p-carboxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-cyanophenyl, m-fluorophenyl, p-tolyl),

An optionally substituted heterocyclic group having 1 to 20, preferably 2 to 10, more preferably 4 to 6 carbon atoms (eg, pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino, tetrahydro Furfuryl). Further, a structure in which a benzene ring or a naphthalene ring is condensed can be employed. Further, V may further substitute on these substituents. Preferred substituents are the aforementioned alkyl groups, aryl groups, alkoxy groups, halogen atoms and benzene ring condensation, and more preferably methyl group, phenyl group, methoxy group, chlorine atom, bromine atom, iodine atom, and benzene ring. Condensation.

R ₁ in the general formula (I) represents an alkyl group substituted with a pyridinium salt. The alkyl group substituted with a pyridinium salt means an alkyl group substituted with a pyridinio group. R ₁ may be any alkyl group substituted with a pyridinium salt, but the alkyl group described herein includes an alkenyl group and an alkynyl group, and is, for example, a carbon atom of 1 to 18, preferably 1 to 7, particularly preferably 1 to 4 unsubstituted alkyl groups (for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), having 1 to 18, preferably 1 carbon atoms
To 7, particularly preferably 1 to 4 substituted alkyl groups (substituents include those described in the description of V. C 1 to 18, preferably 1 to 7, particularly preferably 1 to 4 carbon atoms) Alkenyl groups (eg ethenyl, 1
-Methyl-ethenyl, 1,2-dimethylethenyl, (1
-Propenyl), (2-butenyl) and the like, which may be substituted. Examples of the substituent include those described in the description of V. ), An alkynyl group having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms (eg, ethynyl, propynyl, etc., which may be substituted. The substituent is described in the description of V. And the like.). The binding position of the pyridinio group on the pyridine ring may be on a nitrogen atom or a carbon atom, but is more preferably on a nitrogen atom. However, if a pyridinio group is further substituted on the pyridinio group to form a viologen, it is not preferable because desensitization occurs.

L represents a divalent linking group. As the divalent linking group, for example, an alkylene group having 1 to 20 carbon atoms (eg, ethylene, propylene, butylene, 1-methylethylene, 2-methylpropylene, etc., which may be substituted. And a hetero atom (e.g., an oxygen atom, a sulfur atom, a nitrogen atom) or an aryl group (e.g., 1,2-phenylene, 1,3-phenylene,
4-phenylene, 1,2-naphthylene), a heterocyclic ring (eg, 2,3-pyridylene) and the like may be present. ), An alkenylene group having 1 to 20 carbon atoms (for example,
1,2-ethenylene, 1-methyl-1,2-ethenylene, 1,2-dimethyl-1,2-ethenylene, 1,3-
(1-propenylene), 1,4- (2-butenylene) and the like, which may be substituted. Examples of the substituent include those described in the description of V. ), Having 1 to 1 carbon atoms
And 20 alkynylene groups (for example, ethynylene, propynylene, etc., which may be substituted. Examples of the substituent include those described in the description of V). L is preferably an alkylene group, and particularly preferably an ethylene group or a propylene group.

V ₁ , V ₂ , V ₃ , V ₄ , and V ₅ each represent a hydrogen atom or a substituent, and examples of the substituent include those described in the description of V. Preferably a hydrogen atom,
A halogen atom (particularly preferably a chloro or bromo group), an alkyl group, a cyano group, an acyl group or an amino group;
Particularly preferred are a hydrogen atom, a halogen atom, a methyl group and an ethyl group.

V ₆ , V ₇ , V ₈ , V ₉ , V ₁₀ and V ₁₁ each represent a hydrogen atom or a substituent.
And the like described in the description. Preferred are a hydrogen atom, a halogen atom (particularly preferably a chloro or bromo group), an alkyl group, a cyano group, an acyl group, an amino group and the like, and particularly preferred are a hydrogen atom, a halogen atom, a methyl group and an ethyl group. _{However, V 6, V 7, V} 8, V
_9, one of V ₁₀ and V ₁₁ represents a direct bond between the linking group L.

R in the general formulas (IV), (V) and (VI)
₂ , R ₃ , R ₄ , R ₆ and R ₈ each represent an alkyl group. However, one of R ₂ and R ₃ , R ₄ ,
One of R ₆ and R ₈ is an alkyl group substituted with a pyridinium salt represented by R ₁ . R ₂ , R ₃ ,
Examples of the alkyl group other than the alkyl group substituted by the pyridinium salt represented by R ₁ among R ₄ , R ₆ , and R ₈ include, for example, carbon atoms 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms. (E.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms. The base {for example, the aforementioned Z
Examples of the substituent include a heterocyclic group substituted with V as the substituent such as ₁ . Preferably an aralkyl group (eg benzyl,
2-phenylethyl), unsaturated hydrocarbon group (for example, allyl group), hydroxyalkyl group (for example, 2-hydroxyethyl, 3-hydroxypropyl), carboxyalkyl group (for example, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl groups (for example, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), aryloxyalkyl groups (for example, 2-phenoxyethyl, 2-
(1-naphthoxy) ethyl), an alkoxycarbonylalkyl group (eg, ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl), an aryloxycarbonylalkyl group (eg, 3-phenoxycarbonylpropyl), an acyloxyalkyl group (eg, 2-acetyloxyethyl) ), Acylalkyl groups (eg, 2-acetylethyl), carbamoylalkyl groups (eg, 2-morpholinocarbonylethyl), sulfamoylalkyl groups (eg, N, N-dimethylcarbamoylmethyl), sulfoalkyl groups (eg, 2-sulfoethyl) , 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2-
[3-Sulfopropoxy] ethyl, 2-hydroxy-3
-Sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfoalkenyl group (eg, sulfoallyl group), sulfatoalkyl group (eg, 2-sulfatoethyl group, 2-fluphatopropyl, 4-sulfatobutyl), complex A ring-substituted alkyl group (eg, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl), an alkylsulfonylcarbamoylmethyl group (eg, a methanesulfonylcarbamoylmethyl group)}.

The alkyl groups of R ₂ , R ₃ , R ₄ , R ₆ and R ₈ are preferably the above-mentioned unsubstituted alkyl groups, carboxyalkyl groups and sulfoalkyl groups, more preferably unsubstituted alkyl groups, And a sulfoalkyl group.

Z ₅ represents a group of atoms necessary to form an acidic nucleus, but can take the form of an acidic nucleus of any general merocyanine dye. The acidic nucleus here refers to, for example, the Theory of the Photographic Process, edited by James.
tographic Process) 4th edition, Macmillan Publishing Company, 197
7 years, defined by 198 pages. Specifically, U.S. Patent Nos. 3,567,719, 3,575,869,
Nos. 3,804,634, 3,837,862, 4,002,480, 4,925,777, and JP-A-3-167546. Preferred when the acidic nucleus forms a 5- or 6-membered nitrogen-containing heterocycle consisting of carbon, nitrogen and chalcogen (typically oxygen, sulfur, selenium and tellurium) atoms,
The following nuclei include: 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazolin-5-one,
Hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidin-4-one, 2-oxazoline-5
-One, 2-thiooxazoline-2,4-dione, isoxazolin-5-one, 2-thiazolin-4-one,
Thiaziridin-4-one, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indane-1,3-dione, thiophen-3-one, thiophen-3-one-1,1- Dioxide, indoline-2-one, indoline-3-one, 2
-Oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, cyclohexane-1,3-
Dione, 3,4-dihydroisoquinolin-4-one,
1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, chroman-2,4-dione, indazolin-2-one, pyrido [1,2-a] pyrimidine-1,3 -Dione, pyrazolo [1,5-b] quinazolone, pyrazolo [1,5-a] benzimidazole, pyrazolopyridone, 1,2,3,4-tetrahydroquinoline-2,4-dione, 3-oxo-2,3 -Dihydrobenzo [d] thiophene-1,1-dioxide,
3-dicyanomethine-2,3-dihydrobenzo [d] thiophen-1,1-dioxide nucleus.

Z ₅ is preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, 2-thiooxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-.
2,4-dithione, barbituric acid, and 2-thiobarbituric acid, and more preferably, hydantoin, 2 or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine, barbituric acid, and 2-thiobarbitic acid. Tool acid. Particularly preferred are 2 or 4-thiohydantoin, 2-oxazolin-5-one and rhodanine.

The 5- or 6-membered nitrogen-containing heterocyclic ring formed by Z _{7 is obtained} by removing an oxo group or a thioxo group from the heterocyclic ring represented by Z ₅ . Preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazolin-5-one, 2-thiooxazoline-2,4-
Dione, thiazolidine-2,4-dione, rhodanine,
Thiazolidine-2,4-dithione, barbituric acid, 2
-Thiobarbituric acid is obtained by removing an oxo group or a thioxo group, more preferably hydantoin,
2 or 4-thiohydantoin, 2-oxazoline-5
-One, rhodanine, barbituric acid, 2-thiobarbituric acid from which an oxo group or a thioxo group has been removed, particularly preferably 2 or 4-thiohydantoin;
It is obtained by removing an oxo group or a thioxo group from 2-oxazolin-5-one or rhodanine.

Examples of the alkyl group represented by R ₅ and R ₇ include the unsubstituted alkyl group and the substituted alkyl group mentioned above as examples of R ₂ and R _3, and the same is preferable. An unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms (eg, phenyl group, 1-naphthyl group);
A substituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and more preferably 6 to 8 carbon atoms (for example, an aryl group substituted by V mentioned as a substituent such as Z ₂ described above. Specific examples include a p-methoxyphenyl group, a p-methylphenyl group, and a p-chlorophenyl group.), A C 1 to C 20, preferably a C 3 to C 10, and more preferably a C 4 to C 8 free radical. Substituted heterocyclic groups (eg, 2-furyl, 2-thienyl, 2
-Pyridyl group, 3-pyrazolyl, 3-isoxazolyl, 3-isothiazolyl, 2-imidazolyl, 2-oxazolyl, 2-thiazolyl, 2-pyridazyl, 2-pyrimidyl, 3-pyrazyl, 2- (1,3,5-triazolyl ), 3- (1,2,4-triazolyl), 5-tetrazolyl), a substituted heterocyclic group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms (for example, as described above). V mentioned as substituents such as Z ₂ are mentioned heterocyclic groups substituted. Specifically 5-methyl-2
-Thienyl group, 4-methoxy-2-pyridyl group and the like. ). Preferred as R ₅ and R ₇ are methyl, ethyl, 2-sulfoethyl, 2-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, carboxymethyl, phenyl, 2-pyridyl, 2-thiazolyl, more preferably ethyl, 2-sulfoethyl, carboxymethyl, phenyl and 2-pyridyl.

L₁, L_Two, L_Three, L_Four, L_Five, L₆, L
₇, L₈, L₉, L_Ten, L₁₁, L₁₂, L₁₃, L₁₄,
L_Fifteen, L₁₆, L₁₇, L₁₈, L₁₉, L₂₀, L_{twenty one}And L_{twenty two}Is
Each independently represents a methine group. L₁~ L_{twenty two}Represented by
The methine group may have a substituent.
For example, substituted or unsubstituted carbon atoms having 1 to 15, preferably
Or 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms
5 alkyl groups (eg, methyl, ethyl, 2-carboxy)
Silethyl), substituted or unsubstituted carbon atoms having 6 to 20,
Preferably 6 to 15 carbon atoms, more preferably carbon
6 to 10 aryl groups (eg phenyl, o-carbo)
Xyphenyl), substituted or unsubstituted 3 to 2 carbon atoms
0, preferably 4 to 15 carbon atoms, more preferably charcoal
Heterocyclic group having a prime number of 6 to 10 (for example, N, N-, diethyl
Barbituric acid groups), halogen atoms (eg chlorine, odor
, Fluorine, iodine), having 1 to 15 carbon atoms, preferably charcoal
A compound having a prime number of 1 to 10, more preferably a carbon number of 1 to 5
Lucoxy group (for example, methoxy, ethoxy), having 1 carbon atom
15, preferably 1 to 10 carbon atoms, more preferably
Is an alkylthio group having 1 to 5 carbon atoms (eg, methylthio
E, ethylthio), having 6 to 20 carbon atoms, preferably carbon
A number of 6 to 15, more preferably 6 to 10 carbon atoms
Reelthio group (for example, phenylthio), carbon number 0 to 1
5, preferably 2 to 10 carbon atoms, more preferably charcoal
An amino group having a prime number of 4 to 10 (for example, N, N-diphenyl);
Ruamino, N-methyl-N-phenylamino, N-methyl
Rupiperazino) and the like. With other methine groups
May form a ring, or Z_Two, Z _Three, Z_Four,
Z₆, Z₈And a ring can also be formed.

N ₁ , n ₂ and n ₃ are preferably 0,
1, 2, and 3. n ₁ is more preferably 0, 1
And particularly preferably 1. n ₄ is preferably 0 or 1, and more preferably 0. n ₁ , n
_{When 2} , n ₃ and n ₄ are 2 or more, the methine group is repeated but need not be the same.

M ₁ , M ₂ , M ₃ and M ₄ are included in the formula to indicate the presence of a cation or an anion when necessary to neutralize the ionic charge of the dye. Typical cations include hydrogen ions (H ⁺ ), inorganic cations such as alkali metal ions (eg, sodium ion, potassium ion, lithium ion), alkaline earth metal ions (eg, calcium ion), and ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, pyridinium ion, and ethylpyridinium ion. The anion may be either an inorganic anion or an organic anion, and may be a halogen anion (eg, a fluorine ion, a chloride ion, an iodine ion), a substituted arylsulfonate ion (eg, p-toluenesulfonate,
-Chlorobenzenesulfonic acid ion), aryldisulfonic acid ion (for example, 1,3-benzenesulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-
Naphthalenedisulfonic acid ion), alkyl sulfate ion (eg, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, and trifluoromethanesulfonic acid ion. Further, another dye having a charge opposite to that of the ionic polymer or the dye may be used. m ₁ , m ₂ , m ₃ and m ₄ represent the numbers required to balance the charges and are 0 when forming a salt in the molecule. p ₁ , p ₂ , p ₃ , p ₄ , p ₅ and p ₆ each independently represent 0 or 1. Preferably it is 0.

The number of methine groups in Q is preferably 0
To 7, more preferably 0 to 5, particularly preferably 3. The methine group is preferably substituted by a substituent (heterocyclic group, aliphatic group, or aromatic group) necessary for forming a methine dye, and a preferable substituent is a heterocyclic group or an aromatic group. And particularly preferably a heterocyclic group. As the heterocyclic group, those described above as examples of Z1 and Z5 are preferable. As the aromatic group, a substituted or unsubstituted aromatic group (for example, a 4-dimethylaminophenyl group,
4-methoxyphenyl group, phenyl group, 4-dimethylaminonaphthyl group) and the like. As the aliphatic group, an alkoxycarbonyl group (for example, an ethoxycarbonyl group) and an acyl group (for example, an acetyl group) are preferable.
Other examples include the substituents represented by V described above.
For example, a substituted or unsubstituted amino group (eg, amino group, dimethylamino group), cyano group, alkoxycarbonyl group (eg, ethoxycarbonyl), substituted or unsubstituted alkylsulfonyl group (eg, methylsulfonyl group), substituted or unsubstituted Substituted acyl group (eg acetyl group)
Is preferred.

Of the general formulas (IV), (V) and (VI), the most preferred is (IV).

Specific examples of the general formula (I) of the present invention (including the general formulas (II), (III), (IV), (V), and (VI) as subordinate concepts) are shown below. Does not limit the invention.

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[0046]

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[0048]

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[0051]

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[0052]

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[0053]

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The compound of the present invention represented by the general formula (I) (including the general formulas (II), (III), (IV), (V), and (VI) as subordinate concepts) is a compound represented by FM・ Hammer (FMHarmer)
By Heterocycling Compounds-Cyanine Soybeans and Related Compounds (Heterocycl
ic Compounds-Cyanine Dyes and Related Compound
s) ", John Wiley and Sons
& Sons)-New York, London, 1964,
Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry by DMSturmer
Compouds-Special Topics in Heterocyclic Chemist
ry), Chapter 18, Section 14, pages 482-515, John Wiley & Sons
-New York, London, 1977, "Rods Chemistry of Carbon Compounds (Rod
d's Chemistry of Carbon Compouds), Second Edition, Volume IV, Part B, Chapter 15, Chapters 369-422-Elsevier Science Publishing Company Inc.-
The compound can be synthesized with reference to the method described in New York, 1977, and the like.

The following shows a synthesis example. Synthesis of Synthesis Example 1- (6) N- (3-bromopropyl) pyridinium bromide (5.6 g) and 5-chloro-2-methylbenzothiazole (3.8 g) were mixed and stirred at an external temperature of 150 ° C. for about 8 hours. Thereafter, 100 ml of ethyl acetate and 50 ml of acetone were added, and the mixture was stirred at room temperature for 1 to 2 hours, decanted, and dried under reduced pressure to obtain a highly viscous oil. To this, 8.8 ml of ethyl orthopropionate and 16 m of pyridine were added.
After adding 1 ml of acetic acid and 6 ml of acetic acid and stirring at an external temperature of 140 ° C. for 1 hour, 150 ml of ethyl acetate was added and the mixture was stirred at room temperature for 1 hour. The precipitated crystals are collected by filtration, washed with ethyl acetate, and then dissolved by heating in methanol. The crystals do not completely dissolve, and are separated by filtration into crystals and filtrate. The crystals are recrystallized from acetone-ethyl acetate to obtain crystals A. The filtrate is concentrated and purified by column chromatography (carrier: Sephadex LH20, eluent: methanol) to obtain crystal B. Crystals A and B
Is mixed and dissolved in methanol-chloroform under heating, concentrated under normal pressure, and left for several hours to precipitate crystals. This was collected by filtration and washed with methanol to give purple crystals (6).
16 g (13% yield from benzothiazole) were obtained. Absorption maximum (methanol): 563.9 nm (ε = 1.11 × 1
0 ⁵ ), melting point 274-278 ° C

Synthesis Example 2-Synthesis of (11) N- (3-bromopropyl) pyridinium bromide (2.8 g) and 5-phenyl-2-methylbenzoxazole (2.1 g) were mixed and stirred at an external temperature of 150 ° C. for 10.5 hours. did. Thereafter, 100 ml of ethyl acetate and 50 ml of acetone were added, and the mixture was stirred at room temperature for 1 to 2 hours, decanted, and dried under reduced pressure to obtain a highly viscous oil. To this were added 5 ml of ethyl orthopropionate, 6 ml of pyridine, 2 ml of acetic acid and 1.5 ml of triethylamine, and the mixture was stirred at an external temperature of 140 ° C. for 0.5 hour.
0 ml was added and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were collected by filtration, washed with ethyl acetate, and recrystallized from methanol to obtain 280 mg of orange crystals (11) (yield 6% from benzoxazole). Absorption maximum (methanol):
504.0 nm (ε = 1.54 × 10 ⁵ ), melting point 275
285 ° C

The photographic emulsion used in the present invention may be spectrally sensitized with other methine dyes and the like together with the compound of the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Styryl dyes and hemioxonol dyes are included. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes.
Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of, i.e., indolenine nucleus, benzoindolenine nucleus, indole nucleus,
A benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like can be applied. These nuclei may be substituted on carbon atoms. In a merocyanine dye or a complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
A 5- to 6-membered heterocyclic nucleus such as a rhodanine nucleus and a thiobarbituric acid nucleus can be applied. The compounds of the present invention may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for supersensitization. A representative example is U.S. Pat. No. 2,688,545.
No. 2,977,229 and 3,397,060
No. 3,522,052, No. 3,527,641
No. 3,617,293 and 3,628,964
No. 3,666,480, 3,672,898
No. 3,679,428 and 3,769,301
No. 3,814,609 and 3,837,862
No. 4,026,707 and British Patent No. 1,344.
No. 281, No. 1, 507, 803, JP-B-43-49
Nos. 3,236 and 53-12,375,
Nos. 110,618 and 52-109,925. Along with the compound of the present invention, a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. The compound of the present invention may be added to the emulsion at any stage in the preparation of the emulsion which has been known to be useful. Most commonly, it is performed after completion of chemical sensitization but before coating, but US Pat.
As described in JP-A Nos. 8,969 and 4,225,666, spectral sensitization can be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can be carried out prior to chemical sensitization as described in US Pat. No. 3,928, or can be added prior to completion of silver halide grain precipitation to start spectral sensitization. Furthermore, these compounds may be added separately as taught in U.S. Pat. No. 4,225,666, i.e., some of these compounds may be added prior to chemical sensitization and the remainder may be chemically sensitized. It is also possible to add the silver halide grains at any time during silver halide grain formation, including the method taught in U.S. Pat. No. 4,183,756. The addition amount is from 4 × 10 ^-6 to 1 mol per mol of silver halide.
Although it can be used in an amount of 8 × 10 ^-3 mol, about 5 × 10 ^-5 to 2 × 10 ^-3 mol is more effective for a more preferable silver halide grain size of 0.2 to 1.2 μm. The compound represented by the general formula (II) or (III) is used in an amount of 0.01 to 30 wt.
%, Most preferably 0.1 to 0.1%.
It is in the range of 10 wt%. The use ratio of the general formulas (II) / (III) is preferably from 100/1 to 1/100 (weight ratio), more preferably from 10/1 to 1/10. In the photographic light-sensitive material containing the silver halide emulsion of the present invention, the silver halide emulsion used, silver halide grains, additives for the light-sensitive material such as couplers, antifoggants, etc. Regarding the treatment of liquids and the like, and the processing agents, etc., from the right column on page (88) of JP-A-5-197062 (Japanese Patent Application No. 4-25875), the present invention from the right column on page 7 to the right on page 94 of the same publication The description up to “applicable to image-sensitive material” in column 24, line 24 can be adopted.

Exposure for obtaining a photographic image may be performed by a usual method. That is, natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, laser, LED,
Any of various known light sources such as a CRT can be used. The exposure time is usually from 1/1000 second to 1 second, which is usually used in a camera, or is shorter than 1/1000 second, for example, 1/10 ⁴ to 1/1 using a xenon flashlight.
It can be used exposure of 0 ⁶ seconds, it can be used longer exposure than 1 second. If necessary, the spectral composition of light used for exposure can be adjusted by a color filter. Laser light can also be used for exposure. Further, exposure may be performed by light emitted from a phosphor excited by an electron beam, X-ray, γ-ray, α-ray, or the like.

[0059]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 Preparation of emulsion 30 g of gelatin and 6 g of potassium bromide in 1 liter of water were added to a container kept at 60 ° C while stirring, and an aqueous solution of silver nitrate (5 g as silver nitrate) and potassium bromide containing 0.15 g of potassium iodide were stirred. The aqueous solution was added by the double jet method over 1 minute. Further, an aqueous solution of silver nitrate (145 g as silver nitrate) and an aqueous solution of potassium bromide containing 4.2 g of potassium iodide were added by a double jet method. At this time, the flow rate was accelerated so that the flow rate after the addition was 5 times that at the start of the addition. After completion of the addition, the soluble salts were removed at 35 ° C. by sedimentation, and the temperature was raised to 40 ° C., and 75 g of gelatin was added.
Was adjusted to 6.7. The resulting emulsion was tabular grains having a projected area diameter of 0.98 μm and an average thickness of 0.138 μm, and the silver iodide content was 3 mol%. This emulsion contains gold,
Chemical sensitization was performed in combination with sulfur sensitization. Preparation of Photographic Material 101 In addition to gelatin, an average molecular weight of 8000 was used as a surface protective layer.
Aqueous gelatin solution containing polyacrylamide, sodium polystyrene sulfonate, polymethyl methacrylate fine particles (average particle size: 3.0 μm), polyethylene oxide, hardener and the like was used. Sample 101 was prepared by adding S-1 as a sensitizing dye to the above emulsion at a ratio of 500 mg / 1 mol Ag and potassium iodide at a ratio of 200 mg / 1 mol Ag. Emulsions having the same composition as Sample 101 except that the dye of the present invention and S-2 and S-3 as shown in Table 1 were added instead of the sensitizing dye S-1 were prepared as Samples 102 to 1 respectively.
08.

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[0061]

[Table 1]

Further, 4-hydroxy-6- as a stabilizer
Methyl-1,3,3a, 7-tetrazaindene and 2,6
-Bis (hydroxyamino) -4-diethylamino-
1,3,5-Triazine and nitrone, trimethylolpropane as a dry antifoggant, a coating aid, and a hardening agent are added to form a coating solution, which is coated on both sides of a polyethylene terephthalate support and dried simultaneously with a protective layer. As a result, a photographic material was prepared. The coated silver amount of this photographic material is 2 g / m ² per one side. Preparation of Developed Kit A developing kit (concentrated solution) comprising the following parts (A), (B) and (C) was prepared. Part (A) 10 liters of developer (used solution) Potassium hydroxide 291 g Potassium sulfite 442 g Sodium hydrogen carbonate 75 g Boric acid 10 g Diethylene glycol 120 g Ethylenediaminetetraacetic acid 17 g 5-Methylbenzotriazole 0.6 g Hydroquinone 300 g 1-phenyl-4,4 -Dimethyl-3-pyrazolidone 20 g Water was added to adjust 2.5 L pH to 11.0. Part (B) Developing solution (used solution) 10 liters Triethylene glycol 20 g 5-Nitroindazole 2.5 g Glacial acetic acid 3 g 1-Phenyl-3-pyrazolidone 15 g Add water 250 ml Part (C) Developing solution (used solution) Glutaraldehyde for 10 liters 99 g 126 g of sodium metabisulfite Water was added to 250 ml to prepare a starter having the following composition. Starter 720 g of glacial acetic acid 300 g of potassium bromide 1.5 g of water was added 1.5 liter of developer was prepared 2.5 g of part (A), 250 ml of part (B) and 250 ml of part (C) were successively stirred in about 6 liters of water. While adding and dissolving, the total amount was finally adjusted to 10 liters with water.
Next, a starter was added at a rate of 20 ml per liter of the working solution. For fixing, Fuji F (manufactured by Fuji Photo Film Co., Ltd.) was used. For washing with water, water containing 0.5 g / liter of ethylenediaminetetraacetic acid / disodium salt / dihydrate (antifungal agent) was used. Next, the developing process was performed as follows using a roller transport type automatic developing machine system.

[0063]

[Table 2]

The remaining color after processing (the value obtained by measuring the transmission optical density of the non-image area with green light) is shown. The results are shown in Table 3.

[0065]

[Table 3]

As shown in the table, it can be seen that all of the emulsions containing the compound of the present invention have little residual color.

Example 2 (1) Preparation of Emulsion An aqueous solution containing gelatin having an average molecular weight of 15,000 (water 12
00 ml, gelatin 7.0 g, KBr 4.5 g)
While maintaining the temperature at 0 ° C. and stirring, 1.9 MAgNO ₃ aqueous solution and 1.
A 9M KBr aqueous solution was added by a double jet method at 25 ml / min for 70 seconds to obtain nuclei of tabular grains. 400 ml of this emulsion was used as a seed crystal, and an inert gelatin aqueous solution 6
50 ml (containing 20 g of gelatin and KBr 1.2) was added, the temperature was raised to 75 ° C., and the mixture was aged for 40 minutes. Then, an AgNO ₃ aqueous solution (containing 1.7 g of AgNO ₃ ) was added over 1 minute and 30 seconds, and then 7.0 mL of an NH ₄ NO ₃ (50 wt%) aqueous solution and NH ₄ NO ₃ were added.
₃ (25% by weight) was added, and the mixture was aged for 40 minutes.

Next, the emulsion was adjusted to pH 7 with HNO ₃ (3N) and KBr
After adding 1.0 g, 366.5 aqueous 1.9 MAgNO ₃ solution.
ml and KBr aqueous solution, followed by 1.9 MAgNO ₃ aqueous solution 53.6
ml and an aqueous solution of KBr (containing 33.3 mol% of KI), and 160.5 ml of an aqueous 1.9 MAgNO ₃ solution and an aqueous KBr solution are pAg.
Was added while maintaining 7.9 to obtain Emulsion 1.

Emulsion 1 obtained was a triple structure grain having a region having the highest silver iodide content in the intermediate shell, an average aspect ratio of 2.8, and a tabular grain having an aspect ratio of 3 or more. The ratio to the total projected area was 26%. The coefficient of variation of the particle size was 7%, and the average of the particle size was 0.98 μm in sphere equivalent diameter.

Emulsion 1 was desalted by a usual flocculation method, and a sensitizing dye was added to 1 mol of silver, and gold, sulfur and selenium sensitization was optimally performed in the presence of the sensitizing dye.

(2) Preparation of Coated Samples Samples 201 to 212 were prepared by coating an emulsion layer and a protective layer as shown in Table 4 on a triacetyl cellulose film support provided with an undercoat layer.

[0072]

[Table 4]

The absorption spectrum of the prepared coated sample was measured using a spectrophotometer U-3410 manufactured by Hitachi, Ltd. with an integrating sphere. The value S obtained by integrating the absorption intensity on the longer wavelength side than 350 nm with respect to the horizontal axis (eV) was determined. Table 5 shows the results. These samples were exposed for sensitometry (1/10
0 seconds), and the following color development processing was performed.

Processing method Step Processing time Processing temperature Replenishment amount Tank capacity Color development 2 minutes 45 seconds 38 ° C 33 ml 20 liter Bleaching 6 minutes 30 seconds 38 ° C 25 ml 40 liter Washing water 2 minutes 10 seconds 24 ° C 1200 ml 20 liters Fixed 4 Minutes 20 seconds 38 ℃ 25ml 30 liters Rinse with water (1) 1 minute 05 seconds 24 ℃ From (2) to (1) 10 liter countercurrent piping Rinse with water (2) 1 minute 00 seconds 24 ℃ 1200ml 10 liters Stabilization 1 minute 05 seconds 38 ° C 25 ml 10 liters Drying 4 minutes 20 seconds 55 ° C Replenishment amount is 35 mm width 1 m length Next, the composition of the processing solution is described. (Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg -Hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 5.5 1.0 liter with addition of water 1.0 liter pH 10.05 10.05 (bleach solution) Mother liquor (g) Replenisher (g) Sodium ferric ethylenediaminetetraacetate trihydrate 100.0 120.0 Disodium ethylenediaminetetraacetate 10.0 11.0 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Aqueous ammonia (27%) 6.5 ml 4.0 ml Add water 1.0 liter 1.0 Liters pH 6.0 5.7 (Fixing solution) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid Lithium salt 0.5 0.7 Sodium sulfite 7.0 8.8 Sodium bisulfite 5.0 5.5 Ammonium thiosulfate aqueous solution (70%) 170.0 ml 200.0 ml Add water 1.0 liter 1.0 liter pH 6.7 6.6 (stabilizer) Mother liquor (g) Replenisher (g) Formalin ( 37%) 2.0 ml 3.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 0.45 Disodium ethylenediaminetetraacetate 0.05 0.08 Add water 1.0 liter 1.0 liter pH 5.8-8.0 5.8-8.0

The density of the treated sample was measured with a green filter. The sensitivity was defined as the reciprocal of the exposure amount giving a density 0.2 higher than the fog density, and the sensitivity of each sample was represented by a relative value with the value of sample 201 being 100. The emulsion and methine compound species used for each sample and the results of the sensitivity of each sample are shown in Table 5 below.
Shown in

[0076]

[Table 5]

As shown in Table 5, the sensitivity of the sample of the present invention was higher than that of the comparative sample.
Further, it can be seen that the light absorption in the silver halide emulsion is large.

[0078]

By using the sensitizing dye represented by the formula (I), a silver halide photographic light-sensitive material having less residual color and high sensitivity can be obtained.

Claims (2)

[Claims] 1. A silver halide emulsion containing at least one compound represented by the following general formula (I). General formula (I) In the formula (I), R ₁ represents an alkyl group substituted with a pyridinium salt. Z ₁ represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. L ₁ and L ₂ represent a methine group. p ₁ represents 0 or 1. M ₁ represents a charge balancing counter ion, and m ₁ represents a number from 0 to 10 required to neutralize the charge of the molecule. Q represents a methine group or a polymethine group necessary for forming a methine dye. 2. The silver halide emulsion according to claim 1, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (II). General formula (II) In the formula (II), L represents a divalent linking group. V _1, V _2, V
₃ , V ₄ and V ₅ represent a hydrogen atom or a substituent. Z
₁ , L ₁ , L ₂ , p ₁ , Q, M ₁ , and m ₁ are claims 1
Has the same meaning as that of the general formula (I).