JPH1172862A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material having high sensitivity, less liable to fog and excellent in shelf stability by incorporating a specified compd. SOLUTION: The silver halide photographic sensitive material contains at least one compd. represented by the formula, wherein Z is a silver halide adsorbing group or a light absorbing group, L is a combining group contg. at least one C, N, S or O atom, k1 and k2 are 1, 2, 3 or 4, YX comprises partial structure of electron donative group and has 0-1.4 V oxidation potential, X is an electron donative group, Y is a releasable group other than H and the oxidized body of YX gives a radical X. and a released group Y by the cleavage of the bond. The compd. is preferably used in combination with other spectral sensitizing 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 photographic material, and more particularly, to a silver halide photographic material having high sensitivity, less fogging and excellent storage stability.

[0002]

2. Description of the Related Art Hitherto, great efforts have been made to increase the sensitivity of silver halide photographic materials. Also,
In particular, high sensitivity of spectrally sensitized silver halide photographic materials has been strongly desired. Spectral sensitization technology is a very important and essential technology for producing a photosensitive material having high sensitivity and excellent color reproducibility. The spectral sensitizer has a function of absorbing light in a long wavelength range, which is essentially not absorbed by the silver halide photographic emulsion, and transmitting the light to the silver halide. Therefore, an increase in the amount of light supplemented by the spectral sensitizer is advantageous for increasing photographic sensitivity. For this reason, attempts have been made to increase the amount of light captured by increasing the amount of addition to the silver halide emulsion. However, attempts have been made to increase the amount of light trapped by increasing the amount added to silver halide. However, if the addition amount of the spectral sensitizer to the silver halide emulsion exceeds the optimum amount, a large desensitization is brought about. This is generally referred to as dye desensitization, and is a reduction that causes desensitization in a photosensitive region unique to silver halide, which has substantially no light absorption by a sensitizing dye. If the dye desensitization is large, the overall sensitivity will be low although there is a spectral sensitizing effect. In other words,
As the dye desensitization decreases, the spectral sensitivity increases accordingly. Therefore, in spectral sensitization technology, improvement of dye desensitization is a major problem.

[0003] In addition, T. Tani et al.
Journal of Physica
As described in Chemistry, Vol. 94, p. 1298 (1990), it is known that a sensitizing dye having a reduction potential nobler than -1.25 v has a low relative quantum yield of spectral sensitization. I have. In order to increase the relative quantum yield of the spectral sensitization of such dyes, the “Theory of the Photogragh process”
Phonic Process) pp. 259-265 (1966), super sensitization by hole capture has been proposed.

A compound having a lower oxidation potential than a sensitizing dye may be used in combination as a supersensitizer for eliminating the above desensitization. For example, U.S. Pat. No. 2,313,922
No. 2,075,046 and 2,448,858
No. 2,680,686; British Patent No. 1,230,
No. 449, Belgian Patent No. 771,168 and the like are known. However, the effect of increasing the sensitivity by these methods is insufficient, and there has been a demand for further increasing the sensitivity.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide light-sensitive material having high sensitivity, less fogging and excellent storage stability.

[0006]

The object of the present invention has been achieved by the following means as a result of intensive studies. That is,

(1) A silver halide photographic material comprising at least one compound represented by the following general formula (I): General formula (I)

[0008]

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In the formula (I), Z represents a silver halide adsorbing group or a light absorbing group. L represents a linking group containing at least one carbon atom, nitrogen atom, sulfur atom, or oxygen atom. k ₁ and k ₂ represent ₁ , ₂ , 3, and 4, respectively. YX is composed of a partial structure constituting an electron donating group. However, 1) YX has an oxidation potential between 0 and 1.4v. 2) X is an electron donating group. 3) Y represents a leaving group other than a hydrogen atom, and the oxidized form of YX is cleaved to give a radical X and a leaving group Y. (2) The silver halide photographic material as described in (1), which has been spectrally sensitized with a sensitizing dye other than the compound represented by the following formula (I).

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds used in the present invention will be described below in detail.

Hereinafter, the compounds used in the present invention will be described in detail. The light absorbing group represented by Z may be any methine dye, but preferably includes 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
e Dyes and Related Compounds), John Wiley & Sons, New York, London, 1964, D.M.
(DMSturmer), Heterocyclic Compounds-Special Topics in Heterocyclic Compounds-Special topi
cs in heterocyclic chemistry) ”, Chapters 18, 14
, 482-515, etc. The general formulas of the cyanine dye, merocyanine dye and rhodacyanine dye are preferably those shown in (XI), (XII) and (XIII) of U.S. Pat. No. 5,340,694, Nos. 21 and 22.

[0012] Among the light absorbing groups represented by Z, a compound selected from the following formulas (II), (III), (IV) and (V) is more preferable. . General formula (II)

[0013]

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In the formula (II), L₁, L_Two, L_Three, L_Four,
L_Five, L₆, And L₇Represents a methine group. p₁, And p
_TwoRepresents 0 or 1. n₁Represents 0, 1, 2, or 3
You. Z ₁And Z_TwoForms a 5- or 6-membered nitrogen-containing heterocyclic ring
Represents the group of atoms necessary for M₁Is the charge-balancing counterion
And m₁Is zero or more necessary to neutralize the molecular charge
Represents a number of 4 or less. R₁And R_TwoIs an alkyl group, aryl
A heterocyclic group or a heterocyclic group. Where R₁, R_Two, Z₁,
Z_Two, L₁, L_Two, L_Three, L_Four, L_Five, L₆, And L₇
At least one of which is substituted with L-YX. General formula (III)

[0015]

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In the formula (III), L ₈ , L ₉ , L ₁₀ and L ₁₁ represent a methine group. p3 represents 0 or 1. n2 represents 0, 1, 2, or 3. Z ₃ represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. R ₃ represents an alkyl group, an aryl group, or a heterocyclic group. 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. G is represented below.

[0017]

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Z ₄ represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. R ₄ represents an alkyl group, an aryl group, or a heterocyclic group. F and F ′ each independently represent a cyano group, an ester group, an acyl group, a carbamoyl group, or an alkylsulfonyl group. Where R ₃ ,
At least one of _{R 4, Z 3, Z 4} , L 8, L 9, L 10, L 11, F, and F 'is replaced by L-YX. General formula (IV)

[0019]

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In the formula (IV), L ₁₂ , L ₁₃ , L ₁₄ , L ₁₅ ,
L ₁₆ , L ₁₇ , L ₁₈ , L ₁₉ and L ₂₀ represent a methine group.
p ₄ and p ₅ represents 0 or 1. n ₃ and n4 are 0,
Represents 1, 2, or 3. Z ₅ , Z ₆ and Z ₇ are 5 or 6
Represents an atom group necessary for forming a 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 ,
R ₆ and R ₇ represent an alkyl group, an aryl group, or a heterocyclic group. However, R ₅ , R ₆ , R ₇ , Z ₅ , Z ₆ ,
_{Z 7, L 12, L 13} , L 14, L 15, L 16, L 17, L 18, L
_19, and at least one of L ₂₀ is substituted with L-YX. General formula (V)

[0021]

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In the formula (V), L_{twenty one}, L_{twenty two}, L_{twenty three}, L_{twenty four}, L
_{twenty five}, And L₂₆Represents a methine group. p ₆Represents 0 or 1
You. n_FiveAnd n₆Represents 0, 1, 2, or 3. Z₈,
And Z ₉Is to form a 5- or 6-membered nitrogen-containing heterocycle
Represents the required atomic group. M_FourRepresents a charge-balancing counter ion,
m_FourIs from 0 to 4 required to neutralize the molecular charge
Represents a number. R₈, And R₉Is an alkyl group, an aryl group,
Or a heterocyclic group. G ₁Is synonymous with G. Where R
₈, R₉, Z₈, Z₉, L_{twenty one}, L_{twenty two}, L_{twenty three}, L_{twenty four},
L_{twenty five}, L₂₆, And G₁At least one of them is L-YX
Has been replaced by

Formulas (II), (III), (IV),
And (V), preferably (II).

Formulas (II), (III), (IV),
And (V), Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ ,
As the 5- or 6-membered nitrogen-containing heterocyclic ring represented by Z ₇ and Z ₈ ,

Thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindone) Renin), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4,5-b Quinoxalin nucleus, oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus and pyrimidine nucleus.

Preferred are a benzoxazole nucleus, a benzothiazole nucleus, a benzimidazole nucleus and a quinoline nucleus, and more preferred are a benzoxazole nucleus and a benzothiazole nucleus. Particularly preferred is a benzoxazole nucleus.

When the substituent on Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₇ , and Z ₈ is V, the substituent represented by V is not particularly limited. Atoms (eg, chlorine, bromine, iodine, fluorine), mercapto group, cyano group, carboxyl group, phosphoric acid group, sulfo group, hydroxy group, carbon number 1 to 10, preferably carbon number 2 to 8, more preferably carbon number A carbamoyl group having 2 to 5 (eg, methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl), a sulfamoyl group having 0 to 10, preferably 2 to 8, and more preferably 2 to 5 carbon atoms (eg, methylsulfamoyl, Ethylsulfamoyl, piperidinosulfonyl), a nitro group, having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms, and more preferably having 1 carbon atom. 8 alkoxy groups (eg, methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy), and aryloxy groups having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 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 (for example, methanesulfonyl, ethanesulfonyl, benzenesulfonyl and the like), 1 to 20 carbon atoms, preferably 1 carbon atom To 10, more preferably a sulfinyl group having 1 to 8 carbon atoms (eg, methanesulfinyl, benzenesulfinyl), a sulfonylamino group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms (eg, Methanesulfonylamino, ethanesulfonylamino, ben Such emission sulfonylamino)

An amino group, a substituted amino group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, 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 alkyl or arylthio group having 1 to 20, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (eg, methylthio, ethylthio, carboxyethylthio, sulfobutylthio, phenylthio, etc.), 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms
An alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl) having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms;
More preferably, an aryloxycarbonyl group having 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, preferably, an unsaturated hydrocarbon group having 2 to 18 carbon atoms, more preferably 3 to 10 carbon atoms, and particularly 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. ), A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg, phenyl, naphthyl, p-carboxyphenyl, p-nitrophenyl,
3,5-dichlorophenyl, p-cyanophenyl, m-
Fluorophenyl, p-tolyl),

An optionally substituted heterocyclic group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 6 carbon atoms (eg, pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino, tetrahydro Furfuryl). Further, a structure in which a benzene ring, a naphthalene ring, or an anthracene ring is condensed can be employed. Further, V may further substitute on these substituents.

Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ and Z ₇
Preferred as the above substituents are the above-described alkyl groups, aryl groups, alkoxy groups, halogen atoms, acyl groups, cyano groups, sulfonyl groups, and benzene ring condensation, more preferably alkyl groups, aryl groups, halogen atoms, An acyl group, a sulfonyl group and a benzene ring condensation are preferred, and a methyl group, a phenyl group, a methoxy group, a chlorine atom, a bromine atom, an iodine atom and a benzene ring condensation are particularly preferred. Most preferred are a phenyl group, a chlorine atom, a bromine atom and an iodine atom.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R
₇ , R ₈ and R ₉ each represent an alkyl group, an aryl group, or a heterocyclic group, for example, an unsubstituted alkyl group having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms (eg, Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms, such as Z ₁ described above. And the heterocyclic group substituted by V mentioned as the substituent. Preferably, an aralkyl group (eg, benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (eg, an allyl group), a hydroxyalkyl group (eg, 2-hydroxyethyl, 3-hydroxypropyl), a carboxyalkyl group (eg, 2- Carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl group (for example, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), aryloxyalkyl group (for example, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl), an alkoxycarbonylalkyl group (eg, ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl),
Aryloxycarbonylalkyl group (eg, 3-phenoxycarbonylpropyl), acyloxyalkyl group (eg, 2-acetyloxyethyl), acylalkyl group (eg, 2-acetylethyl), carbamoylalkyl group (eg, 2-morpholinocarbonylethyl), sulfo Famoylalkyl groups (eg, N, N-dimethylcarbamoylmethyl), sulfoalkyl groups (eg, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl,
-Sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfoalkenyl group (for example, sulfopropenyl group), sulfatoalkyl group (for example, 2- Sulfatoethyl group, 3-sulfatopropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl group (for example, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl), alkylsulfonylcarbamoylmethyl group (For example, a methanesulfonylcarbamoylmethyl group)}, an unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms (for example, phenyl group or naphthyl group), and 6 carbon atoms. To 20, preferably 6 to 1 carbon atoms
0, more preferably an aryl group V is substituted cited as substituents, such as Z ₁ of the substituted aryl group (e.g., above 8 to 6 carbon atoms. Specifically p- methoxyphenyl group, p- methyl Phenyl group, p-chlorophenyl group, etc.), unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms (for example, 2-furyl group, 2 -Thienyl group, 2-pyridyl group, 3-pyrazolyl, 3-isoxazolyl, 3-isothiazolyl, 2-imidazolyl,
-Oxazolyl, 2-thiazolyl, 2-pyridazyl, 2
-Pyrimidyl, 3-pyrazyl, 2- (1,3,5-triazolyl), 3- (1,2,4-triazolyl), 5-tetrazolyl), having 1 to 20 carbon atoms, preferably 3 to 1 carbon atoms
0, more preferably include heterocyclic group V mentioned as substituents is substituted, such as Z ₁ substituted Hajime Tamaki (e.g., the aforementioned 8 from 4 carbon atoms. Specifically 5-methyl-2
-Thienyl group, 4-methoxy-2-pyridyl group and the like. ).

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R
Preferably, the alkyl group of ₇ , R ₈ and R ₉ is
The above-mentioned unsubstituted alkyl group, carboxyalkyl group, sulfoalkyl group, sulfoalkenyl group, unsubstituted alkyl group, unsubstituted aryl group, unsubstituted heterocyclic group, more preferably methyl, ethyl, 2-sulfoethyl, 3- Sulfopropyl, 3-sulfobutyl, 4-sulfobutyl,
Carboxymethyl, phenyl, 2-pyridyl and 2-thiazolyl.

Z ₄ represents the group of atoms necessary to form an acidic nucleus, but can take the form of an acidic nucleus of any common merocyanine dye. The acidic nucleus referred to here is, for example, “The Theory of Japan” edited by James.
The Photographic Process "(The The
ory of the Photographic Pr
ocess) 4th edition, Macmillan Publishing Co., 1977,
198 pages. Specifically, U.S. Patent Nos. 3,567,719, 3,575,869, 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,
Thiazolidine-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] thiophene-
The core of 1,1-dioxide.

Z ₄ is 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, 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 ₆ and Z _{9 is obtained} by removing an oxo group or a thioxo group from the heterocyclic ring represented by Z ₄ . 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 with the oxo or thioxo group removed, more preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline -5-one, rhodanine, barbituric acid, 2
-Thiobarbituric acid obtained by removing an oxo group or a thioxo group, particularly preferably 2 or 4-thiohydantoin, 2-oxazoline-5-one or rhodanine obtained by removing an oxo group or a thioxo group. is there.

Examples of F and F ′ include a cyano group, an ester group (eg, ethoxycarbonyl, methoxycarbonyl), an acyl group, a carbamoyl group, and an alkylsulfonyl group (eg, ethylsulfonyl, methylsulfonyl).

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L
_{7, L 8, L 9,} L 10, L 11, L 12, L 13, L 14,
_{L 15, L 16, L 17} , L 18, L 19, L 20, L 21, L 22, L
₂₃ , L ₂₄ , L ₂₅ and L ₂₆ each independently represent a methine group. The methine group represented by L _{1 to} L ₂₆ may have a substituent, for example, a substituted or unsubstituted C ₁ to C 15, preferably C ₁ to C 10, more preferably C ₁ to C An alkyl group of the formulas 1 to 5 (eg, methyl, ethyl, 2-carboxyethyl), substituted or unsubstituted C 6 to C 20, preferably C 6 to C 1
5, more preferably an aryl group having 6 to 10 carbon atoms (eg, phenyl, o-carboxyphenyl), substituted or unsubstituted 3 to 20 carbon atoms, preferably 4 carbon atoms
To 15, more preferably a C6 to C10 heterocyclic group (e.g., N, N-, diethylbarbituric acid group), a halogen atom (e.g., chlorine, bromine, fluorine, iodine), and a C1 to C15, preferably C1 to C10, more preferably C1 to C5 alkoxy group (for example, methoxy, ethoxy), C1 to C15, preferably C1 to C10, more preferably C1 to C5 alkylthio group ( For example, methylthio, ethylthio), carbon number 6
To 20, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms, for example, phenylthio, 0 to 15 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 10 carbon atoms. Amino groups (eg, N, N-diphenylamino, N-methyl-N
-Phenylamino, N-methylpiperazino) and the like. It may also form a ring with other methine groups, or R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ ,
R ₈ , R ₉ , Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z
_A ring can be formed together with ₇ , Z ₈ , Z _{9 and the} like.

N ₁ , n ₂ , n ₃ and n ₅ are preferably 0, 1, and 2, more preferably 0 and 1, and particularly preferably 1. n ₄ and n ₆ are preferably 0 and 1, and more preferably 0. n ₁ , ₂ ,
_{When 3} , ₄ , ₅ , ₆ is 2 or more, the methine group is repeated but need not be identical.

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, such as a halogen anion (for example, a fluorine ion, a chloride ion, an iodine ion), a substituted arylsulfonate ion (for example, p-toluenesulfonic acid ion,
-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. For example, in the present invention, the sulfo group is described as SO ₃ —, but when it has a hydrogen ion as a counter ion,
It can be written as ₃ H. m ₁ , m ₂ , m ₃ ,
And m ₄ represent the number required to balance the charges and is 0 when forming a salt in the molecule. p ₁ , p ₂ ,
p ₃ , p ₄ , p ₅ and p ₆ are each independently 0 or 1
Represents Preferably it is 0.

The silver halide adsorption group represented by Z may be any, but preferably contains at least one of a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom and a tellurium atom. These may be silver ligands or cationic surfactants. The silver ligand comprises a sulfur acid or an analog of selenium or tellurium, a nitric acid, a thioester, or an analog of selenium or tellurium, phosphorus, thioamide, selenamide, telluramide, carbon acid, or the like. The acid compound is
Preferably, the acid dissociation constant pKa is 5 or more and 14 or less. More preferably, the silver ligand promotes adsorption to silver halide. As the sulfuric acid, silver ion and silver mercaptan, or mercaptan or thiol which forms a double salt is preferable. Thiols with stable C—S bonds are used as adsorbent groups for silver, rather than sulfide ion precursors. "The Theory of the PhotographicProces"
s) Pages 32-34 (1977) Substituted or unsubstituted alkyl and aryl thiols having the R "-SH, R""-SH structure, and analogs of selenium and tellurium are used. R ″ is an aliphatic, aromatic, or heterocyclic group, which may be substituted with a group containing a halogen, oxygen, sulfur, or nitrogen atom. R '''is aliphatic,
An aromatic or heterocyclic group, which is substituted with a sulfonyl group. This represents a thiosulfonic acid group.

Heterocyclic thiols containing an oxygen, sulfur, tellurium or nitrogen atom are more preferred. It is represented by the following general formula (XI).

[0044]

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Wherein Z ₁₀ is one or more heteroatoms (eg, nitrogen, oxygen, sulfur, selenium,
It preferably represents a 5- or 6-membered heterocyclic ring containing a tellurium atom, and may be a benzo-fused ring or a naphtho-fused ring. V ₁ represents a hydrogen atom or a monovalent substituent. The presence of a nitrogen atom conjugated to a thiol group is determined by mercaptan (-N =
C-SH) and thioamide (-NH-C = S). The triazolium thiolates of the U.S. patent are related to mesoionic compounds, which cannot be tautomerized, but are active silver ligands. Preferred heterocyclic thiol silver ligands used in the present invention are mercaptotetrazole, mercaptoimidazole, mercaptothiadiazole, mercaptoimidazole, mercaprobenzothiazole, mercaptobenzoxazole, mercaptopyrimidine, mercaptotriazine, phenylmercaptotetrazole, 1,4,4 5-trimethyl-1,2,4-triazolium-3-thiolate and 1-methyl,
5-diphenyl-1,2,4-triazolium-3-thiolate.

The deprotonating nitric acid serves as a silver ion ligand. Many nitric acids are 5- or 6-membered heterocycles consisting of one or two nitrogen atoms, or a sulfur atom, or a selenium, or tellurium atom. For example, it is represented by the following general formulas (XII), (XIII), and (XIV). General formula (XII)

[0047]

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Wherein Z ₁₂ is one or more heteroatoms (eg, nitrogen, oxygen, sulfur, selenium,
It preferably represents a 5- or 6-membered heterocyclic ring containing a tellurium atom, and may be a benzo-fused ring or a naphtho-fused ring. V ₂ represents a hydrogen atom or a monovalent substituent. General formula (XIII)

[0049]

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Wherein Z ₁₃ is one or more heteroatoms (eg, nitrogen, oxygen, sulfur, selenium,
It preferably represents a 5- or 6-membered heterocyclic ring containing a tellurium atom, and may be a benzo-fused ring or a naphtho-fused ring. V ₃ represents a hydrogen atom or a monovalent substituent. R ″ is an aliphatic, aromatic, or heterocyclic group, and may be substituted with a group containing a halogen, oxygen, sulfur, or nitrogen atom. General formula (XIV)

[0051]

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Wherein Z ₁₄ is one or more heteroatoms (eg, nitrogen, oxygen, sulfur, selenium,
It preferably represents a 5- or 6-membered heterocyclic ring containing a tellurium atom, and may be a benzo-fused ring or a naphtho-fused ring. V ₄ represents a hydrogen atom or a monovalent substituent.

Preferred among the heterocyclic nitrogen acids are azoles, purines, hydroxyazaindenes, imides and the like, which are described in US Pat. No. 2,857,274. Most preferred are uracil, tetrazole, benzotriazole, benzothiazole, benzoxazole, adenine, rhodanine, and 1,3,3a, 7-tetrazaindene (e.g., 5-bromo-4-hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene)

Cyclic and acyclic thioesters and their preferred selenium and tellurium analogs are described in US Pat. No. 5,246,827. The preferred structure is given by:

[0055]

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Where a = 1 to 30, b = 1 to 30,
c = 1 to 30. However, a + b + c is 30 or less.
Z_Fifteen, Z₁₆, And Z₁₇Is a 5- to 18-membered ring, preferably 5
To form an 8-membered ring. These are one or more sulfur sources
Including selenium, selenium, or tellurium atoms
good. Of these, particularly preferred is -CH_TwoC
H_TwoSCH_TwoCH_Three, 1,10-Dithia-4,7,1
3,16-tetraoxacyclooctadecane, -CH_Two
CH_TwoSeCH_TwoCH_Three, -CH_TwoCH_TwoTeCH _TwoC
H_Three, -CH_TwoCH_TwoSCH_TwoCH_TwoSCH_TwoCH_Three,
Thiomorpholine.

Phosphorus, which is an active ligand for silver halide, is often used. Preferred phosphorus compounds are (R ′)
It is represented by _3- P. R is an aliphatic group, an aromatic group, or a heterocyclic group, and may be substituted with a halogen, oxygen, sulfur, or nitrogen atom. Particularly preferably, P (CH ₂ CH ₂ C
N) ₃ , and m-sulfophenyl-dimethylphosphine. R ″ ′ is an aliphatic, aromatic, or heterocyclic group, and is substituted with a sulfonyl group. This represents a thiosulfonic acid group. Hereinafter, L-YX will be described in detail. The oxidation potential of X is preferably lower than -0.7v.

L represents a divalent linking group or a single bond. The linking group preferably comprises an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. Preferably, an alkylene group (eg, methylene, ethylene, propylene, butylene, pentylene), an arylene group (eg, phenylene, naphthylene), an alkenylene group (eg, ethenylene, propenylene), an alkynylene group (eg, ethinylene, propynylene), amide Group, ester group, sulfamide group,
Sulfonic acid ester group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -N (Ra)-(Ra is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group Represents a heterocyclic divalent group (for example, 6-chloro-1,3,3).
5-triazine-2,4-diyl group, pyrimidine-2,
4-diyl group, quinoxaline-2,3-diyl group)
One or more carbon atoms composed of two or more
Represents a divalent linking group of 0 or less. More preferably, an alkylene group having 1 to 4 carbon atoms (eg, methylene, ethylene, propylene, butylene), an arylene group having 6 to 10 carbon atoms (eg, phenylene, naphthylene), alkenylene having 1 to 4 carbon atoms Group (for example,
Ethenylene, propenylene), alkynylene group having 1 to 4 carbon atoms (eg, ethinylene, propynylene)
Is a divalent linking group having 1 to 10 carbon atoms formed by combining one or more of Specifically, the following linking groups are preferably used.

[0059]

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X is preferably represented by the following general formula (XX)
I), (XXII), (XIII), and (XXIV)
It is represented by General formula (XXI)

[0061]

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In the formula (XXI), m ₁₁ represents 0 or 1.
Z ₂₁ represents an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom. Ar ₁₁ represents an aryl group or a heterocyclic group.
R ₁₁ represents a monovalent substituent. R ₁₂ and R ₁₃ represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ₁₂ and R ₁₃ , R ₁₂ and Ar ₁₁ , R ₁₃ and Ar ₁₁ are each 5
May form an 8-membered ring. General formula (XXII)

[0063]

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In the formula (XXII), Ar ₁₂ represents an aryl group or a heterocyclic group. R ₁₄ represents a monovalent substituent having a Hammett σ value of -1 to +1. R ₁₅ , R ₁₆ , and R
₁₇ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ₁₅ and Ar ₁₂ , R ₁₆ and Ar ₁₂ , R ₁₅ and R _12
16 , R ₁₆ and R ₁₇ may together form a 5- to 8-membered ring. General formula (XXIII)

[0065]

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In the formula (XXIII), W is an oxygen atom, a sulfur
Represents an atom or a selenium atom. Ar ₁₃Is an aryl group,
Represents a heterocyclic group. R₁₈Is an alkyl group, carboxyl
Group, NR_Two, (OR)_nOr (SR)_nRepresents n is
1, 2, and 3. R₁₉And R ₂₀Is hydrogen atom, alkyl
Represents a group, an aryl group, or a heterocyclic group. Also, R₁₉And A
r₁₃May together form a 5- to 8-membered ring. General formula (XXIV)

[0067]

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In the formula (XXIV), ring represents a substituted or unsubstituted 5-, 6-, or 7-membered unsaturated group.

Formulas (XXI), (XXII) and (XX)
III) and (XXIV) will be described in more detail. The aryl group represented by Ar ₁₁ , Ar ₁₂ , and Ar ₁₃ is preferably phenyl, naphthyl, phenanthryl, anthryl, and the heterocyclic group is preferably pyridine, indole, benzimidazole, thiazole, benzothiazole, thiadiazole and the like. Can be R
₁₂ , R ₁₃ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₉ , and R ₂₀ are a hydrogen atom,
An alkyl group (eg, methyl, ethyl), an aryl group (eg, phenyl), or a heterocyclic group (eg, pyridine, benzothiazole), which may be substituted by V described above. R ₁₄ is 1 having a Hammett σ value of from −1 to +1 and more preferably from −0.7 to +0.7.
Represents a valent substituent. For example, R, OR, SR, halogen, CHO, C (O) R, COOR, CONR ₂ , SO
₃ R, SO ₂ NR ₂ , SO ₂ R, SOR, C (S) R,
And the like. (Where R represents an aliphatic group, an aromatic group, or a heterocyclic group). In the formula (XXIV), ring represents a substituted or unsubstituted 5-, 6-, or 7-membered unsaturated group, and is preferably a heterocyclic group. Y is preferably a group represented by the general formula (XXXI), (XXXII), or (XXXIII)
It is represented by General formula (XXXI)

[0070]

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Formula (XXXII)

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In the formula (XXXII), M represents Si, Sn, or Ge. R ₂₁ represents an alkyl group. General formula (XXXIII)

[0073]

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In the formula (XXXIII), Ar ₁₄ represents an aryl group. M represents Si, Sn, or Ge. R ₂₁ represents an alkyl group.

The compound represented by the general formula (I) of the present invention can absorb one photon and generate two photons by the mechanism shown below, which contributes to high sensitivity.

[0076]

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Next, specific examples of X will be shown, but the present invention is not limited thereto.

[0078]

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[0079]

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[0080]

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[0081]

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Specific examples of the compound represented by formula (I) of the present invention are shown below, but the present invention is not limited thereto.

[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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Z represented by the general formula (I) of the present invention is a compound represented by "Heterocyclic Compounds-Cyanine" by FM Harmer.
Dyes and Related Compounds), John Willie
John Wiley & Sons, New York, London, 1964
(DMSturmer), Heterocyclic Compounds-Special topi
cs in heterocyclic chemistry) ", Chapter 18, Chapter 14
Verses 482-515, John Wiley & Sons, New York, London, 1977, "Rod's Chemistry of
Carbon Compounds (Rodd's Chemistry of Carbon)
Vol.IV, partB, 1977, 15th.
Chapters, 369-422, Elsevier Science
Public Company, Inc. (Elsevier Science Pu
blishing Company Inc.), New York or US Patent No. 3,266,897, Belgian Patent No. 67
No. 1,402, JP-A-60-138548, JP-A-5
9-68732, JP-A-59-123838, JP-B-58-9939, JP-A-59-137951, JP-A-57-202531, and JP-A-57-164732.
JP-A-57-14836, JP-A-57-1163
No. 40, U.S. Pat. No. 4,418,140;
-95728, JP-A-55-79436, OLS
2,205,029, OLS1,962,605,
JP-A-55-59463, JP-B-48-18257.
No., JP-B-53-28084, JP-A-53-4872.
3, JP-B-59-52414, JP-A-58-217
No. 928, JP-B-49-8334, U.S. Pat.
98,602; U.S. Patent No. 887,009; British Patent No. 965,047; Belgian Patent No. 737809.
No. 3,622,340, JP-A-60-8
No. 7322, JP-A-57-211142 and JP-A-58
-158631, JP-A-59-15240, U.S. Pat. No. 3,671,255, JP-B-48-34166,
JP-B-48-322112, JP-A-58-22183
9, JP-B-48-32367, JP-A-60-130
731, JP-A-60-122936, JP-A-60-122
No. 117240, U.S. Pat. No. 3,228,770, JP-B-43-13496, JP-B-43-10256, JP-B-47-8725, JP-B-47-30206, JP-B-47-4417, and JP-B-51 -25340, UK Patent 1,165,075, US Patent 3,512,9
No. 82, U.S. Pat. No. 1,472,845, JP-B-39-
No. 22067, JP-B-39-22068, U.S. Pat. No. 3,148,067, U.S. Pat. No. 3,759,901
No. 3,909,268, Japanese Patent Publication No. 50-40
No. 665, JP-B-39-2829, U.S. Pat.
8,066, JP-B-45-22190, U.S. Pat. No. 1,399,449, British Patent 1,287,284
No. 3,900,321, U.S. Pat.
5,391, U.S. Patent 3,910,792, British Patent 1,064,805, U.S. Patent 3,544,336
No. 4,003,746; British Patent 1,34
No. 4,525, British Patent No. 972,211, Japanese Patent Publication No. 43
-4136, U.S. Patent 3,140,178, French Patent 2,015,456, U.S. Patent 3,114,637
No., Belgian Patent No. 681,359, U.S. Pat. No. 3,22
0,839, British Patent 1,290,868, US Patent 3,137,578, US Patent 3,420,670
No. 2,759,908; U.S. Pat.
2,340, OLS2,501,261, DAS
No. 1,772,424, U.S. Pat. No. 3,157,509
No. 1, French Patent 1,351,234, US Patent 3,63
0,745, French Patent 2,005,204, German Patent 1,447,796, US Patent 3,915,710
No. JP-B-49-8334, British Patent 1,021,1
No. 99, UK Patent 919,061, Japanese Patent Publication No. 46-17
No. 513, U.S. Pat. No. 3,202,512, OLS2.
553,127, JP-A-50-104927, French Patent 1,467,510, U.S. Pat.
No. 6, US Pat. No. 3,503,936, US Pat.
No. 76,638, French patent 2,093,209, British patent 1,246,311, U.S. Pat.
No. 8, US Pat. No. 3,535,115, British Patent 1,1
No. 61,264, U.S. Pat. No. 3,841,878, U.S. Pat. No. 3,615,616, JP-A-48-39039.
No., UK Patent 1,249,077, JP-B-48-34
No. 166, US Pat. No. 3,671,255, British Patent 1
No. 459160, JP-A-50-6323, British Patent 1,402,819, OLS 2,031,314,
Research Disclosure 13651, U.S. Pat. No. 3,910,791, U.S. Pat. No. 3,954,478
No. 3,813,249; British Patent 1,38
7,654, JP-A-57-135945, JP-A-5-135
7-96331, JP-A-57-22234, JP-A-59-26731, OLS 2,217,153, British Patent 1,394,371, British Patent 1,308,7
77, British Patent 1,389,089, British Patent 1,
No. 347,544, German Patent 1,107,508, U.S. Pat. No. 3,386,831, British Patent 1,129,6
No. 23, JP-A-49-14120, JP-B-46-34
675, JP-A-50-43923, U.S. Pat.
42,481; British Patent 1,269,268; U.S. Patent 3,128,185; U.S. Patent 3,295,98.
No. 1, US Pat. No. 3,396,023, US Pat.
No. 95,827, JP-B-48-38418, JP-A-Showa 4
8-47335, JP-A-50-87028, U.S. Pat. No. 3,236,652, U.S. Pat. No. 3,443,951
No., UK Patent 1,065,669, US Patent 3,31
2,552, U.S. Patent 3,310,405, U.S. Patent 3,300,312, British Patent 952,162,
UK Patent 952,162, UK Patent 948,442
No., JP-A-49-120628, JP-B-48-353
No. 72, JP-B-47-5315, JP-B-39-187
06, JP-B-43-4941, JP-A-59-345
The compound can be synthesized based on the method described in No. 30 or the like.

For the linking reaction of the linking group L of ZL-YX, a bond forming reaction including an amide bond forming reaction and an ester bond forming reaction may use a method known in organic chemistry. Can be. About these synthetic reactions, for example, the Chemical Society of Japan
4. Synthesis and Reaction of Organic Compounds, Vol. IV, Maruzen, Tokyo (1977), Yoshiro Ogata, Organic Reactions, Maruzen, Tokyo (1962), L. F. Fieser, M.S. Fies
er, Advanced Organic Chemi
Many books on organic chemistry, such as Stry, Maruzen, and Tokyo (1962), can be referred to.

The compound represented by the general formula (I) of the present invention may be used alone, but is more preferably used in combination with another spectral sensitizing dye.

Next, the silver halide photographic light-sensitive material of the present invention will be described in detail. The compound represented by formula (I) of the present invention can be used alone or in combination with other sensitizing dyes in a silver halide photographic material.

The time at which the compound of the present invention (and the same applies to other sensitizing dyes) is added to the silver halide emulsion of the present invention can be determined at any stage in the emulsion preparation which has been recognized to be useful. It may be inside. For example, U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666, JP-A-58-184142, and JP-A-60-196749. As disclosed, the timing before silver halide grain forming step and / or before desalting, the timing during and / or after desalting and before the start of chemical ripening, JP-A-58-113.
As disclosed in Japanese Patent No. 920 or the like, the compound may be added at any time before the chemical ripening or during the process, or at any time before the application of the emulsion after the chemical ripening until coating. Further, as disclosed in U.S. Pat. No. 4,225,666, JP-A-58-7629 and the like, the same compound may be used alone or in combination with a compound having a different structure.
For example, it may be divided and added during the particle formation step and during the chemical ripening step or after the completion of the chemical ripening, or may be divided and added before or during the chemical ripening and after the completion of the chemical ripening. The type of the compound to be added and the combination of the compounds may be changed and added.

The addition amount of the compound of the present invention varies depending on the shape and size of silver halide grains, but it can be used in an amount of 1 × 10 ^-6 to 8 × 10 ^-3 mol per mol of silver halide. For example, when the silver halide grain size is 0.
In the case of 2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−6 to} 3.5 × 10 ⁻³ mol, and 7.5 × 10 ^{−6 to} 1.5 × 10 per mol of silver halide. An addition amount of ^-3 mol is more preferred.

The compounds of the present invention can be dispersed directly in an emulsion. These can be first dissolved in an appropriate solvent, for example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. At this time, additives such as a base, an acid, and a surfactant can be made to coexist. Also, ultrasonic waves can be used for dissolution. As a method for adding the methine compound, as described in US Pat. No. 3,469,987, the compound is dissolved in a volatile organic solvent, and the solution is dispersed in a hydrophilic colloid. A method of adding a dispersion to a water-soluble solvent, as described in JP-B-46-24185, and adding this dispersion to an emulsion, as described in U.S. Pat. No. 3,822,135. A method in which a methine compound is dissolved in a surfactant and the solution is added to an emulsion as described in JP-A-51-74624. Method of adding the compound into the medium, JP-A-50-80
No. 826, a method of dissolving a methine compound in an acid substantially free of water and adding the solution to an emulsion is used. In addition, the method described in U.S. Pat. Nos. 2,912,343, 3,342,605, 2,996,287, and 3,429,835 may be used for addition to the emulsion. .

The supersensitizers useful in the spectral sensitization of the present invention include, for example, US Pat. Nos. 3,511,664, 3,615,613, 3,615,632, and 3,615. Nos. 641, 4,596,767, 4,945,038, 4,965,182, 4,965,182, etc., pyrimidylamino compounds, triazinylamino compounds, azolium compounds, etc. The method described in the above-mentioned patent is also preferable as to its use.

The silver halide which can be used in the silver halide light-sensitive material of the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. Preferred silver halides are silver bromide, silver chlorobromide, silver iodochlorobromide, or high silver chloride described in JP-A-2-42. The composition and processing of the light-sensitive material will be described below. The composition and processing described in JP-A-2-42 are preferably used particularly in high silver chloride. Also, JP-A-63-2
The constitution and processing described in No. 64743 are particularly preferably used for silver chlorobromide.

The silver halide grains may have different phases in the inside and the surface layer, or may consist of a uniform phase. Also, particles whose latent image is mainly formed on the surface (for example, a negative photosensitive material), particles that are mainly formed inside the particle (for example, an internal latent image photosensitive material), or particles that have been previously fogged (For example, a direct positive photosensitive material). Silver halide grains having the various halogen compositions, crystal habits, intragrain structures, shapes and distributions described above,
Used in photosensitive photographic materials (elements) for various uses.

The silver halide grains in the photographic light-sensitive material are regular, such as cubic, tetradecahedral, and rhombodecahedral.
It may have an irregular crystal form, may have an irregular crystal form such as a sphere or a plate, or may have a complex form of these crystal forms. It may consist of a mixture of particles of different crystal forms.

In the photographic material of the present invention, the silver halide grains forming the emulsion layer have an aspect ratio of 3 or more and 1 or more.
The case where it is 00 or less is preferable. Here, the aspect ratio of 3 or more and 100 or less means that the silver halide grains having an aspect ratio (equivalent circle diameter of silver halide grains / grain thickness) of 3 or more and 100 or less correspond to all the silver halide grains in the emulsion. It means that there is at least 50% of the projected area. The aspect ratio is preferably 3 or more and 20 or less, and most preferably 4 or more.
It is 12 or less. Tabular grains are described in Gatoff, Photographic Science and Engineering,
14, 248-257 (1970); US Pat.No. 4,434,226, 4,41
4,310, 4,433,048, 4,439,520 and GB 2,112,157
Can be easily adjusted by the method described in (1). In the photographic light-sensitive material of the present invention, its abundance is at least 70%, particularly preferably at least 85%.

The compounds of the present invention are used for the following applications for sensitizers, sensitizing dyes, filters, antihalation or irradiation prevention. These dyes can be added to desired layers such as an intermediate layer, a protective layer and a back layer in addition to the photosensitive emulsion layer. The compound of the present invention is used in various color and black-and-white silver halide photographic materials. More specifically, a light-sensitive material for color positive, a light-sensitive material for color paper, a light-sensitive material for color negative, a light-sensitive material for color reversal (with or without a coupler), a silver halide photographic light-sensitive material for direct positive, Photosensitive materials for plate making (for example, squirrel film,
Lith dupe film, etc., photosensitive materials for cathode ray tube displays, photosensitive materials for X-ray recording (especially materials for direct and indirect photography using a screen), photosensitive materials used in a silver salt diffusion transfer process, Photo-sensitive material used in color diffusion transfer process, die transfer process (imhibition pro
cess), a photosensitive material used in a silver dye bleaching method, a photosensitive material for thermal development, and the like.

The silver halide photographic emulsion used in the present invention is described in Chimie et Physiqu by P. Glafkides.
e Photograhique "(Paul Montel, 1967), GF Deffein (GFDuff
in) "Photographic Emulsion Chemistry" (The FocalPress, 1966); Making and Coating by VLZelikman et al.・ Photographic ・
Emulsion (Making and Coating Photographic Emul
sion) "(The Focal Press)
Ed., 1964) and the like.

In forming silver halide grains, in order to control the growth of the grains, a silver halide solvent such as ammonia, rodankari, rodanammon, thioether compound (for example, US Pat. No. 3,271,157)
Nos. 3,574,628 and 3,704,130
Nos. 4,297,439 and 4,276,374) and thione compounds (for example, JP-A-53-14431).
9, No. 53-82408 and No. 55-77737), amine compounds (for example, JP-A-54-100717).
Number etc.) can be used. In the course of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be coexisted. As the internal latent image type silver halide emulsion used in the present invention, for example, US Pat. No. 2,592,250,
Conversion-type silver halide emulsions described in 3,206,313, 3,447,927, 3,761,276, and 3,935,014, etc., core / shell type halides Silver emulsions and silver halide emulsions containing different types of metals are included.

The silver halide emulsion is usually chemically sensitized. For chemical sensitization, for example, H. Frieser, “Die Grundlagen der Photographische”, edited by D. Grundlagen der Photographische.
n Prozesse mit Silberhalogeniden) ", Akademische Verlagsgesellsch
aft), (1968) pp. 675-734 can be used. That is, sulfur sensitization using a compound containing sulfur (e.g., thiosulfate, thioureas, mercapto compounds, rhodanines) that can react with active gelatin or silver; selenium sensitization; ,
Reduction sensitization method using stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds); noble metal compounds (for example, gold complex salts, Pt, I
A noble metal sensitization method using a complex of a metal of Group VIII of the periodic table such as r or Pd) can be used alone or in combination.

The photographic light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. it can. That is, thiazoles such as benzothiazolium salts described in U.S. Pat. Nos. 3,954,478 and 4,942,721, JP-A-59-191332, and JP-B-59-26731. Ring-opened products thereof, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazole , Mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketonization Compounds such as oxazolinethione; azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; and JP-A-62-87957. Many compounds known as antifoggants or stabilizers can be added, such as the acetylene compounds described, and the like.

The silver halide photographic light-sensitive material of the present invention can contain a color coupler such as a cyan coupler, a magenta coupler and a yellow coupler, and a compound dispersing the coupler. That is, in the color development processing, aromatic 1
It may contain a compound capable of developing color by oxidative coupling with a secondary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative). For example,
Examples of magenta couplers include 5-pyrazolone couplers, pyrazorobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (eg, benzoylacetoanilides, pivaloylacetoanilides). Some cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible couplers having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ion. Further, a colored coupler having a color correcting effect or a coupler that releases a development inhibitor during development (a so-called DIR coupler) may be used. Also DI
In addition to the R coupler, a colorless DIR coupling compound which is colorless and releases a development inhibitor may be contained.

The photographic light-sensitive material of the present invention may be, for example, polyalkylene oxide or a derivative thereof such as an ether, ester or amine, a thioether compound, a thiomorpholine or a quaternary ammonium, for the purpose of increasing sensitivity, increasing contrast, or accelerating development. It may contain salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. The silver halide light-sensitive material of the present invention may contain various dyes other than the methine compound of the present invention as a filter dye or for various purposes such as prevention of irradiation. Such dyes include, for example, British Patent Nos. 506,385 and 1,17.
7,429, 1,311,884, 1,33
8,799, 1,385,371, 1,46
7,214, 1,433,102, 1,55
3,516, JP-A-48-85130, and JP-A-49-1
No. 14420, No. 52-117123, No. 55-16
No. 1233, No. 59-111640, Japanese Patent Publication No. 39-2
No. 2069, No. 43-13168, No. 62-2735
No. 27, U.S. Pat. Nos. 3,247,127 and 3,46.
Oxonol dyes having a pyrazolone nucleus or a barbituric acid nucleus described in US Pat. Nos. 9,985 and 4,078,933; U.S. Pat. Nos. 2,533,472 and 3,37;
Other oxonol dyes described in JP-A No. 9,533, British Patent No. 1,278,621, JP-A Nos. 1-134447 and 1-183652, and British Patent No. 575,6
Nos. 91, 680, 631, 599, 623, 786, 907, 907, 125, and 1,04
No. 5,609, U.S. Pat. No. 4,255,326, Japanese Patent Publication No. Sho 59-211043, azo dyes described in JP-A Nos. 50-100116 and 54-118247, and British Patent No. 2,014, Azomethine dyes described in US Pat. No. 2,865,598 and US Pat.
No. 752, anthraquinone dyes described in U.S. Pat. Nos. 2,533,009, 2,688,541 and 2,538,008, British Patent 584,609,
No. 1,210,252, JP-A-50-40625,
No. 51-3623, No. 51-10927, No. 54-
118247, JP-B-48-3286, and 59-3
Arylidene dyes described in No. 7303, etc.
Nos. 8-3082, 44-16594, 59-28
No. 898 and the like, British Patent No. 44
Nos. 6,583 and 1,335,422;
Triarylmethane dyes described in U.S. Pat. No. 2,228,250 and the like, British Patent Nos. 1,075,653 and 1,153,
No. 341, No. 1, 284, 730, No. 1, 475, 2
No. 28, No. 1,542,807, etc .; merocyanine dyes described in U.S. Pat.
294, 539 and JP-A-1-291247.

The following method can be used to prevent such diffusion of the dye. For example, a method of coexisting a hydrophilic polymer having a charge opposite to that of a dissociated anionic dye in a layer as a mordant and localizing the dye in a specific layer by interaction with dye molecules is disclosed in U.S. Pat.
8,564, 4,124,386, 3,62
No. 5,694 and the like. Further, a method of dyeing a specific layer using a dye solid insoluble in water is disclosed in
-12639, 55-155350, 55-1
No. 55351, No. 63-27838, No. 63-197
943, European Patent No. 15,601 and the like. Further, a method of dyeing a specific layer by using metal salt fine particles to which a dye is adsorbed is disclosed in U.S. Pat. Nos. 2,719,088, 2,496,841, and 2,496,843; No. 45237 and the like.

The photographic light-sensitive material of the present invention has various interfaces for various purposes such as coating aid, antistatic, improvement of slipperiness, emulsification / dispersion, prevention of adhesion, and improvement of photographic properties (eg, development acceleration, high contrast, sensitization). An active agent may be included. In practicing the present invention, other additives are used together with the silver halide emulsion or other hydrophilic colloid, for example, an anti-fading agent, an inorganic or organic hardening agent, an anti-fog agent,
UV absorbers, mordants, plasticizers, latex polymers,
Matting agents and the like can be mentioned. Specifically, Research Disclosure Vol.
176 (1978, XI), D-17643, and the like. In the photographic light-sensitive material used in the present invention, a hydrophilic polymer such as gelatin is used as a protective colloid. Finished silver halide emulsions, etc.
Coated on a suitable support such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, other plastic bases or glass plates.

Exposure for obtaining a photographic image may be performed using a usual method. That is, any of various known light sources such as natural light (daylight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, and cathode ray tube flying spot can be used. Exposure time is 1/1 which is usually used in cameras
Exposure time from 000 seconds to 1 second, of course, 1/1000
Exposure shorter than one second, for example, exposure of 1/10 ⁴ to 1/10 ⁶ seconds using a xenon flashlight or a cathode ray tube, or exposure longer than 1 second can be used. 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. Photographic processing of photosensitive materials made using the present invention includes, for example, Research Disclosure (Research Disclosure).
Disclosure) 176, pp. 28-30 (RD-1764)
As described in 3), any of a known method and a known processing solution can be applied. This photographic processing may be either photographic processing for forming a silver image (black-and-white photographic processing) or photographic processing for forming a dye image (color photographic processing), depending on the purpose. Processing temperature is usually 1
The temperature is selected between 8 ° C and 50 ° C, but may be lower than 18 ° C or higher than 50 ° C.

The silver halide photographic light-sensitive material carrying magnetic recording which may be used in the present invention (hereinafter also referred to as "light-sensitive material")
Are disclosed in JP-A-6-35118 and JP-A-6-17528.
No., a thin layer support of a pre-heat treated polyester described in detail in Hatsumei Kyokai Disclosure No. 94-6023, for example,
Polyethylene aromatic dicarboxylate polyester support, 50 μm to 300 μm, preferably 50 μm
Heat treatment (annealing) at a temperature of 40 ° C. or more and a glass transition temperature or less at a temperature of 40 to 200 μm, more preferably 80 to 115 μm, and particularly preferably 85 to 105 μm.
No. 43-2603, No. 43-2604
U.S. Pat. No. 5,326,689 by ultraviolet irradiation described in JP-B-45-3828, surface treatment such as corona described in JP-B-48-5043 and JP-A-51-131576.
No. described in US Pat. No. 2,761, if necessary
No. 791 described in JP-A-59-23.
No. 505, JP-A-4-195726, JP-A-6-59
357 may be applied. In addition,
The magnetic layer described above is disclosed in JP-A-4-124462,
It may be in the form of a stripe described in JP-A-124645.
Further, if necessary, an antistatic treatment described in JP-A-4-62543 is used, and finally a product coated with a silver halide emulsion is used. The silver halide emulsion used here is described in JP-A-4-166.
No. 932, JP-A-3-41436, JP-A-3-414
No. 37 is used. Sensitive materials made in this way are Tokuho 4-868
No. 17 manufactured by the manufacturing control method described in
Preferably, the production data is recorded by the method described in No. 46. Thereafter or before that, Japanese Patent Application Laid-Open No. 4-125560.
According to the method described in No. 5, the film is cut into a narrower film than the conventional 135 size, and the perforations are perforated with two holes per side per the small format screen to match the smaller format screen. The film thus formed is a cartridge package of Japanese Patent Application Laid-Open No. 4-157559, a cartridge shown in FIG. 9 of Japanese Patent Application Laid-Open No. 5-210202, or US Pat. No. 4,221,479.
Film Patrone and USP 4,834,306, U
S4,834,366, USP 5,226,613
No. 4,846,418. The film cartridge or film cartridge used here is USP 4,848,693.
No. 5, US Pat. No. 5,317,355 are preferred from the viewpoint of light shielding properties. Furthermore, US
It is preferable to use a cartridge having a lock mechanism as described in P5,296,886, a cartridge in which a use state described in US Pat. No. 5,347,334 is displayed, or a cartridge having a double exposure prevention function. Further, Japanese Patent Laid-Open No. 6-85
As described in No. 128, a cartridge to which a film can be easily mounted by simply inserting the film into the cartridge may be used. The film cartridge thus produced can be used for various purposes such as photographing, developing, and enjoying various photographs by using a camera, a developing machine, and laboratory equipment described below. For example, JP-A-6-8886, JP-A-6-999
08-No. 08-573, No. 08
No. 98, JP-A-6-101135 and JP-A-6-205690, which are capable of taking out and changing the type of film during photographing, JP-A-5-293138 and JP-A-5-283382. , For example, a camera capable of magnetically recording on a film the panoramic photography, the high-vision photography, and the normal photography (magnetic recording capable of selecting the print aspect ratio), and the dual recording described in JP-A-6-101194. The function of a film cartridge (patrone) can be sufficiently exhibited by using a camera having an exposure preventing function or a camera having a use state display function such as a film described in JP-A-5-150577. The film photographed in this way is disclosed in
Magnetic recording on a film described in JP-A-6-95265 and JP-A-4-123054, by processing with an automatic processing machine described in JP-A-222514 and JP-A-6-222545, or before, during or after the processing. Or the aspect ratio selection function described in JP-A-5-19364 may be used. In the case of cine-type development, the film is spliced and processed according to the method described in JP-A-5-119461. Further, when or after the development processing,
Attachment described in No. 48805, detach processing is performed. After processing in this manner, the film information is converted into a print through back printing and front printing on color paper by the method described in JP-A-2-184835, JP-A-4-186335, and JP-A-6-79968. Is also good. Further, JP-A-5-11353, JP-A-5-23
The index print and return cartridge described in No. 2594 may be returned to the customer.

[0113]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 (1) Preparation of Emulsion An aqueous solution containing gelatin having an average molecular weight of 15,000 (water 12
100 ml, gelatin 7.0 g, while stirring keeping the containing KBr4.5G) to 30 ° C., tabular added by 1.9MAgNO ₃ solution and 1.9MKBr aqueous double jet of 70 seconds at 25 ml / min Particle nuclei were obtained.
400 ml of this emulsion was used as a seed crystal, and 650 ml of an inert gelatin aqueous solution (containing 20 g of gelatin and 1.2 g of KBr) was added thereto, and the temperature was raised to 75 ° C., followed by ripening for 40 minutes.
Then, an AgNO ₃ aqueous solution (including 1.7 g of AgNO ₃ ) was added over 1 minute and 30 seconds, and subsequently, NH ₄ NO ₃ (50 w
t%) aqueous solution 7.0 ml and NH ₃ (25 wt%) 7.0 ml
And aged for an additional 40 minutes.

[0115] Then after adding KBr1.0g and to pH7 with HNO ₃ (3N) emulsion, the 1.9MAgNO ₃ solution 366.5ml of KBr aqueous solution, followed by 1.9MA
gNO ₃ aqueous solution (53.6 ml) and KBr (KI: 33.3 mol)
% Aqueous solution, and 1.9 MAgNO ₃ aqueous solution 1
Emulsion 1 was obtained by adding 60.5 ml of an aqueous KBr solution while maintaining the pAg at 7.9.

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 Emulsion layers and protective layers as shown in Table 1 were applied to a triacetyl cellulose film support provided with an undercoat layer to prepare Samples 101 to 115.

[0119]

[Table 1]

These samples were exposed to sensitometry exposure (1/100 second) and subjected to the following color development processing.

Processing method Step Processing time Processing temperature Compensation 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 Rinse 2 minutes 10 seconds 24 ° C 1200 ml 20 liter Fixing 4 minutes 20 seconds 38 ° C 25ml 30 liters Rinse with water (1) 1 minute 05 seconds 24 ° C 10 liter countercurrent piping from (2) to (1) Rinse with water (2) 1 minute 00 seconds 24 ° C 1200ml 10 liters Constant 1 minute 05 seconds 38 ° C 25ml 10 liter Drying 4 minutes 20 seconds 55 ° C Replenishment amount is 35mm width per 1m 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 Add water 1.0 liter 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 Ammonia water (27%) 6.5ml 4.0ml Add water and 1.0L 1.0 liter pH 6.0 5.7 (Fixer) Mother liquor (g) Replenisher (g) Nato ethylenediaminetetraacetate Salt 0.5 0.7 Sodium sulfite 7.0 8.0 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 (stable solution) Mother liquor (g) Replenisher (g) Formalin ( 37%) 2.0ml 3.0ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 0.45 Ethylenediaminetetraacetic acid disodium salt 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, and the fresh sensitivity and fogging were evaluated. Sensitivity is defined as the reciprocal of the exposure that gives a density 0.2 higher than the fog density,
The sensitivity of each sample was expressed as a relative value with the value of sample 101 taken as 100. The emulsion and methine compound species used for each sample and the sensitivity results for each sample are shown in Table 2 below.

[0123]

[Table 2]

[0124]

Embedded image

Table 2 shows that the compounds of the present invention have higher fresh sensitivity than the comparative compounds.

Example 2 A tabular silver iodobromide emulsion was prepared in the same manner as in Emulsion D of Example 5 of JP-A-8-29904 to prepare Emulsion 2. The multilayer color photosensitive material was prepared in the same manner as in Sample 5 of Example 5 of JP-A-8-29904. Sample 1 of Example 5 of JP-A-8-29904
01 was replaced with Emulsion 2,
S-1, 2, 3 were converted to sensitizing dye (SD-2) (5.0 × 10 ⁻⁴ ).
mol / molAg) and (SD-2) (5.0 × 10 ⁻⁴ mol / molAg), (12)
(0.4 × 10 ^-4 mol / molAg)
01 and Sample 202. In order to examine the sensitivity of the sample thus obtained, light of a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.) was exposed to light for 1/100 second through an optical wedge and a red filter, and Example 1 of JP-A-8-29904 was used. Color development was performed using the same processing steps and processing solution as described above, and cyan density was measured. Sensitivity is fog density + 0.2
The relative value of was displayed. As a result, the sensitivity of the comparative sample 201 was 100 (reference), whereas the sample 202 of the present invention was 195.
And high sensitivity.

Example 3 Emulsion 1 of Example 1 of JP-A-7-92601 was prepared by changing the spectral sensitizing dye to sensitizing dye (SD-1) (8.0 × 10 ⁻⁴ mol / mol Ag) or sensitizing dye. Dye (SD-1) (8 × 10 ⁻⁴ mol / molAg) + (5
1) A tetradecahedral silver iodobromide emulsion was prepared, which was different only in that the emulsion was replaced with (0.8 × 10 ⁻⁴ mol / mol Ag).
01 and 302. The emulsion 1 of Example 1 of JP-A-7-92601 was different from the emulsion 1 of Example 1 in that the silver potential in the second double jet was changed from +65 mV to +115 mV, and the spectral sensitizing dye was a sensitizing dye (SD-1). (8 × 10 ^-4 mol / molA
g) or sensitizing dye (SD-1) (8 × 10 ⁻⁴ mol / molAg)
+ (1) (0.8 × 10 ⁻⁴ mol / molAg) was prepared to prepare a cubic silver iodobromide emulsion, which was different from that of emulsion 30.
3 and 304. Multilayer color photosensitive material is disclosed in
It was prepared in the same manner according to Sample 401 of Example 4 of No. 92601. Fifteenth sample 401 of Example 4 of JP-A-7-92601
Samples in which Emulsion J of the layer was changed to Emulsion 301 or Emulsion 302 were designated as Samples 311 and 312. Similarly, the emulsion J of the fifteenth layer in the same Example was replaced with the emulsion 303 or the emulsion 3
Samples changed to 04 were designated as Sample 313 and Sample 314. The sample thus obtained was evaluated for sensitivity. JP-A-7-
In the same manner as in Example 4 of No. 92601, 1/50 second exposure and color reversal development were performed to measure yellow density. The sensitivity was determined by calculating the reciprocal of the amount of exposure necessary to give a density of +0.2 of the minimum density obtained by giving sufficient exposure.
Are shown as relative values with the sensitivity of 100 as 100. as a result,
The sensitivity of Sample 312 of the present invention was 185, which was high.
Similarly, when the sensitivity of Comparative Sample 313 was set to 100, the sensitivity of Sample 314 of the present invention was 193, which was high.

Example 4 An octahedral silver bromide internal latent image type direct positive emulsion and a hexagonal tabular silver bromide internal latent image type direct positive were prepared in the same manner as in Emulsions 1 and 5 of Example 1 of JP-A-5-313297. Emulsions were prepared and used as Emulsion 401 and Emulsion 402. The color diffusion transfer photographic film is a sample 101 of Example 1 of JP-A-5-313297.
In the same manner. Emulsion-2 and sensitizing dye (2) of the eleventh layer of sample 101 of Example 1 of JP-A-5-313297 were prepared by using emulsion 401 and sensitizing dye (SD-3) (9 × 10 ^-4 mol / mol Ag). Or sensitizing dye (SD-3) (9 × 10 ^-4 mol / molAg) + (13)
(0.9 × 10 ⁻⁴ mol / molAg),
And Sample 412. Similarly, sample 101 of the same embodiment
In the eleventh layer, emulsion-2 and sensitizing dye (2) were added to emulsion 402 and sensitizing dye (SD-3) (8 × 10 ⁻⁴ mol / mol Ag) or sensitizing dye (SD-3) (8 × 10 ^-4 mol / molAg) + (63) (0.8 × 10
Replaced with ^-4 mol / ^molAg), Sample 413 and Sample 41
And 4. In order to examine the sensitivity of the sample thus obtained, the same exposure and processing steps as in Example 1 of JP-A-5-313297 were performed, and the processing was performed using the processing solution, and the transfer density was measured with a color densitometer. The sensitivity was expressed as a relative value at a density of 1.0. When the sensitivity of the comparative sample 411 is 100, the sensitivity of the sample 412 of the present invention is 195, which is a high sensitivity. When the sensitivity of the comparative sample 413 is 100, the sensitivity of the sample 414 of the present invention is 2
05 and high sensitivity.

Example 5 Emulsion F of Example 2 in JP-A-4-42536 was compared with red-sensitive sensitization.
Do not add dye (S-1) before sulfur sensitization,
In addition to sulfur sensitization of tilthiourea, chloroauric acid is also used
Optimal gold sulfur sensitization, after gold sulfur sensitization, sensitizing dye (S
D-2) (2 × 10 ^-Fourmol / molAg) (Comparative dye of the present invention)
Or sensitizing dye (SD-2) (2 × 10^-Fourmol / molAg) +12 (0.
2 × 10^-Fourmol / molAg)
A silver emulsion was prepared and used as emulsions 501 and 502.
Was. The multi-layer color printing paper is the same as that of Example 1 of
It was prepared in the same manner according to Sample 20. JP-A-6-347944
The emulsion of the first layer in Sample 20 of Example 1 was
Or the sample changed to emulsion 502
Charge 512. To check the sensitivity of the sample thus obtained
The Fuji FW type photometer (Fuji Photo Film Co., Ltd.)
Light passes through optical wedge and red filter for 1/10 second
Exposure was given, and the same processing steps as in Example 1 of
A color development process was performed using the above process and processing solution. The result
As a result, when the sensitivity of the comparative sample 511 is set to 100,
The sensitivity of Sample 512 was 205, which was high.

Example 6 A tabular silver chloride emulsion was prepared in the same manner as in Emulsion A of Example 1 of JP-A-8-122954.
Sensitizing dye-1 and sensitizing dye (SD-3) (2 × 10 ^-4 mol /
molAg) or sensitizing dye (SD-3) (2 × 10 ^-4 mol / molA
g) + (14) (0.2 × 10 ⁻⁴ mol / mol Ag), and chemical sensitization was performed only by the addition, and these were designated as Emulsion 601 and Emulsion 612. The coated sample was prepared by replacing the emulsion of Example 1 of Japanese Patent Application No. 7-232036 with Emulsion 601 or Emulsion 602, and combining an emulsion layer and a surface protective layer on a support in the same manner as in Example 1 by simultaneous extrusion. This was used as Sample 611 and Sample 612. The amount of silver applied per side was 1.75 g / m ² . In order to examine the sensitivity of the sample thus obtained, 0.05 g from both sides was measured using an X-ray orthoscreen HGM manufactured by Fuji Photo Film Co., Ltd.
After exposure for 2 seconds, the film was processed using an automatic developing machine and a processing solution in the same manner as in Example 1 of Japanese Patent Application No. 7-232036. Sensitivity +
The logarithm of the reciprocal of the exposure required to give a density of 0.1 was expressed as the logarithm of the sensitivity of Sample 611, and the others were expressed as relative values. As a result, the sensitivity of Sample 612 of the present invention was 201, which was high. The same effect was obtained by exposing with HR-4 or HGH instead of the X-ray orthoscreen HGM used at the time of exposure.

Example 7 Emulsion D of Example 2 of Japanese Patent Application No. 7-146891 was a sensitizing dye-
A tabular silver chloride emulsion was prepared, the only difference being that no 2 and 3 were added. The coated sample was prepared in the same manner as in the coated sample F of Example 3 of Japanese Patent Application No. 74-168991. Emulsion F and sensitizing dye-1 of coating sample F of Example 3 of Japanese Patent Application No. 74-168991 were added to emulsion 701 and sensitizing dye (SD-3) (5
× 10 ^-4 mol / molAg) or sensitizing dye (SD-3) (5 × 10
⁻⁴ mol / molAg) + (15) (0.5 × 10 ⁻⁴ mol / molAg) to obtain Sample 711 and Sample 712. In order to examine the sensitivity of the sample thus obtained, the light of a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.) was exposed to light for 1/100 second through an optical wedge and a green filter, and subjected to Fuji Photo Film CN16 processing to improve the photographic properties. Compared. The sensitivity is represented by the logarithm of the reciprocal of the exposure amount required to give a density of fog + 0.2, and the sensitivity of sample 711 was set to 100. The sensitivity of Sample 712 of the present invention was 199, which was high.

Example 8 An octahedral silver chloride emulsion was prepared in the same manner as in Emulsion F of Example 3 of Japanese Patent Application No. 7-146891, and this was used as an emulsion layer 801. The coated sample was prepared in the same manner as in the coated sample F of Example 3 of Japanese Patent Application No. 74-168991. Emulsion F and sensitizing dye-1 of Coating Sample F of Example 3 of Japanese Patent Application No. 74-168991 were added to Emulsion 801 and sensitizing dye (S
D-1) (5 × 10 ^-4 mol / mol Ag) or sensitizing dye (SD-1)
(5 × 10 ⁻⁴ mol / molAg) + (1) (0.5 × 10 ⁻⁴ mol / molAg)
Sample 811 and Sample 812 were used instead of g).
In order to examine the sensitivity of the sample thus obtained, the light of a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.) was exposed to light for 1/100 second through an optical wedge and a blue filter, and was processed by Fuji Photo Film CN16. Compared.
The sensitivity is represented by the logarithm of the reciprocal of the exposure amount required to give a density of fog + 0.2, and the sensitivity of sample 811 was set to 100.
The sensitivity of Sample 812 of the present invention was 201, which was high.

Example 9 A silver iodobromide emulsion was prepared in the same manner as in Emulsion E of Example 1 of JP-A-7-159950 to obtain Emulsion 9. The multilayer color photographic material was prepared in the same manner as in Sample 1 of Example 1 of JP-A-7-159950. The emulsion E of the tenth layer in the sample 101 of Example 1 of JP-A-7-159950 was replaced with Emulsion 9 and ExS-3
With sensitizing dye (SD-3) (9.8 × 10 ^-4 mol / molAg) or
(SD-3) (9.8 × 10 ⁻⁴ mol / molAg) + (63) (0.1 × 1
0 ^-4 mol / molAg) to replace the sample 901 and sample 902
And To examine the sensitivity of the sample thus obtained, the light of a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.) was exposed to light for 1/100 second through an optical wedge and a green filter. Color development was performed using the same processing steps and processing solution as described above, and the magenta density was measured.

The sensitivity was indicated by a relative value of fog + 0.2. As a result, the sensitivity of the sample 902 of the present invention was 183, which was high, with the sensitivity of the comparative sample 901 being 100 (reference).

[0135]

According to the present invention, a silver halide photographic material having high image quality and high sensitivity can be obtained.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 10, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0076

[Correction method] Change

[Correction contents]

[0076]

Embedded image

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material containing at least one compound represented by the following general formula (I). General formula (I) In the formula (I), Z represents a silver halide adsorbing group or a light absorbing group. L represents a linking group containing at least one carbon atom, nitrogen atom, sulfur atom, or oxygen atom. k ₁ and k ₂ represent ₁ , ₂ , 3, and 4, respectively. YX is composed of a partial structure constituting an electron donating group. However, 1) YX is from 0 to 1.4.
It has an oxidation potential between v. 2) X is an electron donating group.
3) Y represents a leaving group other than a hydrogen atom, and the oxidized form of YX is cleaved to give a radical X and a leaving group Y. 2. The silver halide photographic light-sensitive material according to claim 1, which has been spectrally sensitized with a sensitizing dye other than the compound represented by the following general formula (I).