JPH11119364A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive material high in sensitivity and small in fog and superior in storage stability by incorporating a specified compound. SOLUTION: The photosensitive material contains at least one of the compounds represented by formulae I and II and at least one of the compounds represented by formula III, and in the formulae I-III, Z is a group adsorbable to silver halide or a light-absorbing group; L is a bonding group containing at least one C, N, S, or O atom; k1 is 0-4; k2 is 1-4; k3 is 0 or 1; XY is a partial structure composing an electron donative group and it has an oxidation potential of 0-1.4 V and X is an electron donor and Y is a releasable group except H atom; each of k4 and k5 is 1-4; k6 is 0 or 1; and each of A1 and A2 is H atom or a univalent substituent and each may combine with each other to form a ring.

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) 259-265 (1966) has proposed supersensitization by hole capture.

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) At least one compound represented by the following general formula (I) or (II) is combined with the following general formula (L)
A silver halide photographic material comprising at least one compound represented by the formula: General formula (I)

[0008]

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In the formula, Z represents an adsorbing group to silver halide 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 represents 0, ₁ , 2, 3, 4. k ₂ is 1, 2, 3,
4 is represented. k ₃ is 0 or 1. XY has a partial structure constituting an electron donating group. General formula (II)

[0010]

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In the formula, Z, L, X, and Y have the same meanings as in formula (I). k ₄ and k ₅ represent 1, 2, 3, and 4, respectively. k ₆ is 0
Or 1. YX is composed of a partial structure constituting an electron donating group. However, 1) XY (or YX) is 0 to 1.4v
Has an oxidation potential between 2) X is an electron donating group.
3) Y represents a leaving group other than a hydrogen atom, and XY (or Y
In the oxidized form of X), the bond is cleaved to give a radical X. and a leaving group Y. General formula (L)

[0012]

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In the formula (L), A ₁ and A ₂ each represent a hydrogen atom or a monovalent substituent. Further, they may combine with each other to form a ring. (2) The silver halide photographic material as described in (1), which is spectrally sensitized with a sensitizing dye other than the general formula (I) or (II) described in (1).

[0014]

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
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.

Of the light absorbing groups represented by Z, preferably
More preferably, it is a compound selected from the following formulas (III), (IV), (V), (VI) and (VII). General formula (III)

[0017]

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In the formula (III), L₁, L_Two, L_Three, L_Four, L
_Five, L₆, And L₇Represents a methine group. p₁, And p_Two
Represents 0 or 1. n₁Represents 0, 1, 2, or 3.
Z₁And Z_TwoForms a 5- or 6-membered nitrogen-containing heterocyclic ring
Group of atoms necessary for M ₁Represents the charge-balancing counterion
Then m₁Is 0 or more and 4 or more necessary to neutralize the molecular charge
Represents the number below. R₁And R_TwoIs an alkyl group, aryl
Represents a group or a heterocyclic group. Where R₁, R_Two, Z₁, Z
_Two, L₁, L_Two, L_Three, L_Four, L_Five, L₆, And L₇of
At least one of them is (L) k_Three-XY or (L) k₆
-YX has been substituted.

Formula (IV)

[0020]

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In the formula (IV), L ₈ , L ₉ , L ₁₀ and L ₁₁
Represents a methine group. p ₃ is 0 or 1. n ₂ is 0,
Represents 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 ₁ is represented by:

[0022]

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Z ₄ represents an atomic 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. G ₂ and G ₃ each independently represent a cyano group, an ester group, an acyl group, a carbamoyl group, or an alkylsulfonyl group. However,
R ₃ , R ₄ , Z ₃ , Z ₄ , L ₈ , L ₉ , L ₁₀ , L ₁₁ , G
₂ , and at least one of G ₃ is (L) k ₃ -X
Y or (L) k ₆ -YX. General formula (V)

[0024]

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In the formula (V), L ₁₂ , L ₁₃ , L ₁₄ and L ₁₅
Represents a methine group. p ₄ is 0 or 1. n ₃ is 0,
Represents 1, 2, or 3. Z ₅ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. R ₅ represents an alkyl group, an aryl group, or a heterocyclic group. 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. G ₄ represents a substituted or unsubstituted amino group or a substituted or unsubstituted aryl group. However, at least one of R ₅ , Z ₅ , L ₁₂ , L ₁₃ , L ₁₄ , L ₁₅ and G4 is (L) k ₃ -XY or (L) k ₆
-YX has been substituted. General formula (VI)

[0026]

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In the formula (VI), L ₁₆ , L ₁₇ , L ₁₈ , L ₁₉ , L
_{20, L 21, L 22,} L 23, and L ₂₄ each represents a methine group. p
₅ and p ₆ represent 0 or 1. n ₄ and n ₅ 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 , R ₇ ,
And R ₈ represents an alkyl group, an aryl group, or a heterocyclic group. However, R ₆ , R ₇ , R ₈ , Z ₆ , Z ₇ , Z ₈ ,
At least one of L ₁₆ , L ₁₇ , L ₁₈ , L ₁₉ , L ₂₀ , L ₂₁ , L ₂₂ , L ₂₃ , and L ₂₄ is (L) k ₃ -XY or (L) k ₆ -YX Has been replaced by

Formula (VII)

[0029]

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In the formula (VII), L_{twenty five}, L₂₆, L₂₇, L₂₈, L
₂₉, And L₃₀Represents a methine group. p ₇Represents 0 or 1
You. n₆And n₇Represents 0, 1, 2, or 3. Z₉,
And Z _TenIs to form a 5- or 6-membered nitrogen-containing heterocycle
Represents the required atomic group. M_FiveRepresents a charge-balancing counter ion,
m_FiveIs from 0 to 4 required to neutralize the molecular charge
Represents a number. R₉, And R_TenIs an alkyl group, an aryl group,
Or a heterocyclic group. G ₁’Is G₁Is synonymous with However
Then R₉, R_Ten, Z₉, Z_Ten, L_{twenty five}, L₂₆, L₂₇,
L₂₈, L₂₉, L₃₀, And G₁’At least one
Is (L) k_Three-XY or (L) k₆Replaced with -YX
I have.

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

Formulas (III), (IV), (V), (VI) and
And (VII), Z₁, Z_Two, Z _Three, Z_Five, Z₆, Z
₈, And Z₉A 5- or 6-membered nitrogen-containing heterocyclic ring represented by
The

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 A quinoxaline nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, and a 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.

Assuming that the substituent on Z ₁ , Z ₂ , Z ₃ , Z ₅ , Z ₆ , Z ₈ and Z ₉ is V, the substituent represented by V is not particularly limited. Atoms (eg, chlorine, bromine, iodine, fluorine), mercapto groups, cyano groups, carboxyl groups, phosphoric acid groups, sulfo groups, hydroxy groups, carbon numbers 1 to 10, preferably carbon numbers 2 to 8, more preferably carbon numbers 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, preferably 6 to 12, 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); 0 to 15, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms (for example, trimethylammonium group, triethylammonium group), 0 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably Is a hydrazino group having 1 to 6 carbon atoms (eg, trimethylhydrazino group), a ureido group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (eg, ureido group, N, N -Dimethylureido group), having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably Ku imido group having 1 to 6 carbon atoms (e.g., succinimido group), from 20 1 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms
Alkyl or arylthio groups such as methylthio,
Ethylthio, carboxyethylthio, sulfobutylthio, phenylthio, etc.), 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), an aryloxycarbonyl group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms (eg, 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.

Preferred substituents on Z ₁ , Z ₂ , Z ₃ , Z ₅ , Z ₆ , Z ₈ , and Z ₉ are the above-mentioned alkyl, aryl, alkoxy, halogen, acyl, and cyano. Group, sulfonyl group, and benzene ring condensation, more preferably alkyl group, aryl group, halogen atom, acyl group, sulfonyl group, and benzene ring condensation, particularly preferably methyl group, phenyl group, methoxy group, chlorine Atom, bromine atom, iodine atom and benzene ring condensation. Most preferably, a phenyl group, a chlorine atom,
Bromine atom and iodine atom.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R
₇ , R ₈ , R ₉ , and R ₁₀ each represent an alkyl group, an aryl group, or a heterocyclic group;
8, preferably 1 to 7, particularly preferably 1 to 4, unsubstituted alkyl groups (for example methyl, ethyl, propyl,
Isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), carbon atoms 1 to 18,
Preferably, it is a substituted alkyl group of 1 to 7, particularly preferably 1 to 4, for example, a heterocyclic group substituted by V mentioned as a substituent such as Z1 described above. 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), alkoxycarbonylalkyl group (for example, ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl), aryloxycarbonylalkyl group (for example, 3
-Phenoxycarbonylpropyl), an acyloxyalkyl group (for example, 2-acetyloxyethyl), an acylalkyl group (for example, 2-acetylethyl), a carbamoylalkyl group (for example, 2-morpholinocarbonylethyl), a sulfamoylalkyl group (for example, N, N- Dimethylcarbamoylmethyl), a sulfoalkyl group (for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-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, methanesulfonylcarbamoylmethyl group), unsubstituted aryl having 6 to 20, preferably 6 to 10, and more preferably 6 to 8 carbon atoms. Group (eg, phenyl group, 1-naphthyl group), a substituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms (for example, a substituent such as Z ₁ described above) And an aryl group substituted by V. Specific examples include a p-methoxyphenyl group, a p-methylphenyl group and a p-chlorophenyl group.), Having 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. 10, more preferably an unsubstituted heterocyclic group having 4 to 8 carbon atoms (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), 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
_As the alkyl group of ₇ , R ₈ , R ₉ , and R ₁₀ , the above-mentioned unsubstituted alkyl group, carboxyalkyl group, sulfoalkyl group, sulfoalkenyl group, unsubstituted alkyl group, unsubstituted aryl group, unsubstituted hetero group A ring group,
More preferably, methyl, ethyl, 2-sulfoethyl,
3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, carboxymethyl, phenyl, 2-pyridyl, 2
-Thiazolyl.

Z ₄ represents the group of atoms required to form an acidic nucleus, but can take the form of an acidic nucleus of any common merocyanine dye. The term "acid nucleus" used herein refers to, for example, "The Theory of the Photographic Process" edited by James.
otographic Process) 4th edition, Macmillan Publishing Co., 19
Defined in 1982 by 198 Tribute. Specifically, U.S. Patent Nos. 3,567,719 and 3,575,869.
No. 3,804,634, 3,837,862
No. 4,002,480, 4,925,777
And JP-A-3-167546. The acidic nucleus is preferred when it forms a 5- or 6-membered nitrogen-containing heterocycle consisting of carbon, nitrogen and chalcogen (typically oxygen, sulfur, selenium and tellurium) atoms, and includes the following nuclei. 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazoline-5
-One, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidin-4-one, 2-oxazoline-5-one, 2-thiooxazoline-2,4-dione, isoxazolin-5-one, 2-thiazoline −
4-one, thiazolidine-4-one, thiazolidine-
2,4-dione, rhodanine, thiazolidine-2,4-
Dithione, isorhodanine, indan-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-dihydroisoquinoline-4-
On, 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-
Core of dihydrobenzo [d] thiophen-1,1-dioxide, 3-dicyanomethine-2,3-dihydrobenzo [d] thiophen-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 ₇ and Z _{10 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.

G ₂ and G ₃ include a cyano group, an ester group (eg, ethoxycarbonyl, methoxycarbonyl), an acyl group, a carbamoyl group, or an alkylsulfonyl group (eg, ethylsulfonyl, methylsulfonyl).

Examples of G ₄ include a substituted or unsubstituted amino group or aryl group. Examples of the substituent include V described above.

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}, L_{twenty two}, L
_{twenty three}, L_{twenty four}, L_{twenty five}, L₂₆, L₂₇, L₂₈, L₂₉And L₃₀Haso
Each independently represents a methine group. L ₁~ L₃₀The method represented by
The tin group may have a substituent, and examples of the substituent include
For example, a substituted or unsubstituted carbon number of 1 to 15, preferably
Is 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms
(E.g., methyl, ethyl, 2-carboxy)
Ethyl), substituted or unsubstituted carbon atoms having 6 to 20, preferably
Preferably it has 6 to 15 carbon atoms, more preferably 6 carbon atoms.
To 10 aryl groups (eg, phenyl, o-carboxy)
(Ciphenyl), 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 R₁, R_Two, R_Three,
R_Four, R_Five, R ₆, R₇, R₈, R₉, R_Ten, Z₁, Z
_Two, Z_Three, Z_Four, Z_Five, Z₆, Z₇, Z ₈, Z₉, Z_Ten
And the like can form a ring.

N ₁ , n ₂ , n ₃ , n ₄ , and n ₆ are preferably 0, 1, 2, more preferably 0, 1, and particularly preferably 1. n ₅ and n ₇ are preferably 0 and 1, and more preferably 0. n ₁ ,
_{When 2} , ₃ , ₄ , ₅ , ₆ , ₇ is 2 or more, the methine group is repeated but need not be the same.

When M ₁ , M ₂ , M ₃ , M ₄ , and M ₅ are needed to neutralize the ionic charge of the dye, they can be used in the formula to indicate the presence of a cation or anion. Is included. 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 (for example, a fluorine ion, a chloride ion, an iodine ion), a substituted arylsulfonate ion (for example, p-toluenesulfonic acid ion, p-toluene ion). Chlorobenzenesulfonate ion),
Aryl disulfonic acid ions (eg, 1,3-benzenesulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ions (eg, methyl sulfate ion), sulfate ions, thiocyanate Ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion and trifluoromethanesulfonate 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 represented by S
O ₃ ^- but is indicated as, when having a proton as a counter ion can be expressed as SO ₃ H.
m ₁ , m ₂ , m ₃ , m ₄ , and m ₅ represent the numbers required to balance the charges, and are 0 when forming a salt in the molecule.
It is. p ₁ , p ₂ , p ₃ , p ₄ , p ₅ , p ₆ , and p
₇ independently represents 0 or 1. Preferably it is 0.

The adsorptive group to silver halide represented by Z may be any, but preferably contains at least one of a nitrogen, sulfur, phosphorus, selenium, or 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 nitrogen acid, a thioester, or an analog of selenium or tellurium, phosphorus, thioamide, selenamide, telluramide, carbon acid, or the like. The acid compound preferably has an acid dissociation constant pKa of 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 PhotographicPr"
ocess) pp. 32-34 (1977). R ''-
Substituted or unsubstituted alkyl and aryl thiols having the SH, R ′ ″-SH structure, and analogs of selenium and tellurium are used. R ″ is an aliphatic, aromatic, or heterocyclic group, and may be substituted with the aforementioned V, and may be substituted with a group containing a halogen, oxygen, sulfur, or a nitrogen atom. R ″ ′ is an aliphatic, aromatic, or heterocyclic group, and is substituted with a sulfonyl group. This represents a thiosulfonic acid group.

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

[0053]

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In the formula, Z ₁₁ is one or more hetero atoms (for example, a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom,
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. The presence of a nitrogen atom conjugated to a thiol group is determined by mercaptan (-N = C-SH) and thioamide (-NH-C =
There is a mutual isomerism between 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, 4,5-diphenyl-1,2,4-triazolium-3-thiolate.

The deprotonating nitric acid serves as the 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)

[0056]

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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. General formula (XIII)

[0058]

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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. R ₁₁ is an aliphatic, aromatic, or heterocyclic group. These may be substituted by the above-mentioned V, and preferably by a group containing a halogen, oxygen, sulfur or nitrogen atom. General formula (XIV)

[0060]

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In the formula, Z ₁₄ is one or more hetero atoms (for example, nitrogen atom, oxygen atom, sulfur atom, selenium atom,
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.

Preferred among the heterocyclic nitric 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:

[0064]

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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 ₁₂ )
It is represented by _3- P. R ₁₂ is an aliphatic group, an aromatic group, or a heterocyclic group, and may be substituted with V described above, 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.

Further, thioamides, thiosemicarbazides, telluroreas, and selenoureas having the general formula shown below are preferably used.

[0068]

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U ₁ is a substituted or unsubstituted amino group, a substituted or unsubstituted hydrazino group, a substituted or unsubstituted alkylthio group, an arylthio group, a substituted or unsubstituted alkoxy group, or an aryloxy group. As the substituent, the aforementioned V
Is mentioned. B and D are a substituted or unsubstituted aliphatic group, aromatic group, heterocyclic group, or together 5 or 6
A member ring may be formed. R ₁₂ represents a substituted or unsubstituted aliphatic group, aromatic group, or heterocyclic group. As the substituent, the aforementioned V can be mentioned.

Many of the thioamide silver ligands are described in US Pat. No. 3,598,598. Preferred thioamides are N, N'-tetraalkylthiourea, N-hydroxyethylbenzothiazolin-2-one, phenyldimethyldithiocarbamate, and N-substituted thiazolin-2-one.

A carbon acid derived from active methylene having an acid dissociation constant of 5 or more and 14 or less is also preferably used. For example, bromomalonitrile, 1-methyl-3-methyl-1,3,5-trithiane bromide, acetylene and the like. Canadian Patent No. 1,080,532 and U.S. Pat. No. 4,374,279 describe that a carbon acid becomes a silver ligand. As the carbon acid, the following are preferably used.

[0072]

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R ₁₃ is an aliphatic group, an aromatic group, or a heterocyclic group, and may be substituted with the above-mentioned V, and may be substituted with a halogen, oxygen, sulfur, or nitrogen atom. F ″ and G ″ each independently increase the pKa of CH from 5 to 1.
4, CO ₂ R ₁₃ , COR ₁₃ , CHO,
It is selected from CN, SO ₂ R ₁₃ , SOR ₁₃ , NO _{2 and the} like.

[0074] Cationic surfactants also act as adsorbing groups for silver halide. These have a hydrocarbon group having 4 or more carbon atoms which may be substituted with a halogen, oxygen, sulfur, or nitrogen atom, and examples of the cation portion include an ammonium group, a sulfonium group, and a phosphonium group. Such cationic surfactants are available from Journal Colloid Interface Science (J.Col.
loid interface Sci.), vol. 22, p. 391 (196
6 years). Preferred are dimethyldodecylsulfonium, tetradecyltrimethylammonium, betaine N-dodecylnicotinate, and decamethylenepyridinium ion.

Preferred examples of the adsorptive group to silver halide include alkyl mercaptan, cyclic or acyclic thioether group, benzothiazole, tetraazaindene, benzotriazole, tetraalkylthiourea, mercapto-substituted heterocyclic compound (particularly, Mercaptotetrazole,
Mercaptotriazole, mercaptothiadiazole,
Mercaptoimidazole, mercaptooxadiazole, mercaptothiazole, mercaptobenzimidazole, mercaptobendithiazole, mercaptobenzoxazole, mercaptopyrimidine, mercaptotriazine, phenylmercaptotetrazole, 1,2,4
-Triazolium thiolate).

Preferred examples of Z are shown below, but are not limited thereto.

[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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Hereinafter, L-YX and L-XY will be described in detail. The oxidation potential of X is preferably -0.7 v
This is the case when they are more basic.

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.

[0086]

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[0087]

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X is preferably the following general formula (XXI):
(XXII), (XIII) and (XXIV). General formula (XXI)

[0089]

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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 ₂₁
Represents a monovalent substituent. R ₂₂ and R ₂₃ are a hydrogen atom,
Represents an alkyl group, an aryl group, or a heterocyclic group. Also,
R ₂₂ and R ₂₃ , R ₂₂ and Ar ₁₁ , and R ₂₃ and Ar ₁₁ may together form a 5- to 8-membered ring. General formula (XXII)

[0091]

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In the formula (XXII), Ar ₁₂ represents an aryl group or a heterocyclic group. R ₂₄ has a Hammett σ value of −1 to +1
Represents a monovalent substituent having R ₂₅ , R ₂₆ , and R ₂₇ represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ₂₅ and Ar ₁₂ , R ₂₆ and Ar ₁₂ , R ₂₅ and R ₂₆ ,
R ₂₆ and R ₂₇ may together form a 5- to 8-membered ring. General formula (XXIII)

[0093]

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In the formula (XXIII), W is an oxygen atom, a sulfur atom,
Or a selenium atom. Ar ₁₃ represents an aryl group or a heterocyclic group. R ₂₈ represents an alkyl group, a carboxyl group, NR
₂ , (OR) _n , or (SR) _n . n is 1, 2,
3. R ₂₉ and R ₃₀ represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ₂₉ and Ar ₁₃ may together form a 5- to 8-membered ring. General formula (XXIV)

[0095]

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

Formulas (XXI), (XXII), (XXIII) and (XXIV)
Will be described in more detail. Ar ₁₁ , Ar ₁₂ , Ar
_The aryl group represented by ₁₃ is preferably phenyl, naphthyl, phenanthryl, anthryl, and preferably a heterocyclic group such as pyridine, indole, benzimidazole, thiazole, benzothiazole, thiadiazole and the like. These may be substituted by V described above. _{R 22, R 23, R 25} , R 26, R 27, R 29,
R ₃₀ is a hydrogen atom, an alkyl group (for example, methyl or ethyl), an aryl group (for example, phenyl), or a heterocyclic group (for example, pyridine or benzothiazole), which may be substituted with V described above. good.

R ₂₄ has a Hammett σ value of −1 to +1,
More preferably, it represents a monovalent substituent having -0.7 to +0.7. For example, R, OR, SR, halogen, CH
O, C (O) R, COOR, CONR ₂ , SO ₃ R, S
O 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) R ₂₈ represents an alkyl group, a carboxyl group, an NR
₂ , (OR) n or (SR) n. n is 1, 2,
3. These may be further substituted by V described above. Preferred as R ₂₁ is the aforementioned V. In the formula (XXIV), ring represents a substituted or unsubstituted 5-, 6-, or 7-membered unsaturated group, and is preferably a heterocyclic group. Preferred are those mentioned above as the heterocyclic group for V. Preferred examples of X are shown below, but are not limited thereto. The portion indicated by the dotted line is a portion substituted by the leaving group Y. The linking group L may be substituted at any other position.

[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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Y is preferably represented by the general formula (XXXI) or (XX
XII) and (XXXIII). Note that the dotted line indicates the position of connection with X. General formula (XXXI)

[0106]

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General formula (XXXII)

[0108]

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

[0110]

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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) or (II) of the present invention can generate two electrons by the following mechanism, which contributes to high sensitivity.

[0113]

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Next, specific examples of the general formulas (I) and (II) are shown, but the present invention is not limited thereto.

[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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The light-absorbing group of Z represented by the general formula (I) of the present invention is a heterocyclic compound-cyanine soybean and related compound (FM Hemorer) by FM Harmer.
Sounds-Cyanine Dyes and Related Compounds), John Wiley & Sons, New York, London, 1964, DMSturmer, Heterocyclic
Heterocyclic Compounds- Special Topics in Heterocyclic Compounds
Special topics in heterocyclic chemistry)
Chapter 8, Section 14, pp. 482-515, John Wiley & Sons, New York, London, 1977, "Rodd's Chemistr."
y of Carbon Compounds) '' 2nd.Ed.vol.IV, partB, 197
Seventh Edition, Chapter 15, Chapters 369-422, Elsevier
Science Public Company, Inc. (Elsevie
r Science Publishing Company Inc.), New York, etc.
Regarding the adsorptive group to silver halide, US Pat.
No. 538,843, line 16, page 37 to page 17, line 29, can be synthesized based on a method described in a patent or the like.

For the linking reaction of the linking group L of ZL-YX, the bond forming reaction including the amide bond forming reaction and the 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, Volume IV, Maruzen, Tokyo (1977), Yoshiro Ogata, Organic Reactions, Maruzen, Tokyo (1962), LFFieser, M. Fieser, Advanced Or
Many books on organic chemistry, such as ganic Chemistry, Maruzen, and Tokyo (1962), can be referred to.

The compounds represented by formulas (I) and (II) represented by the present invention include those described in European Patent No. 786,690 A1.
No. 786, 691A1, and 786, 692A1.

The compounds represented by formulas (I) and (II) of the present invention may be used alone, but are more preferably used in combination with other spectral sensitizing dyes.

Next, the compound represented by formula (L) of the present invention will be described in detail. A ₁ and A ₂ represent a hydrogen atom or a monovalent substituent. Further, they may combine with each other to form a ring. The monovalent substituent may be any, but preferably includes the aforementioned V. Preferred are compounds selected from the following formulas (AI), (A-II), (A-III), (A-IV) and (AV).

[0152]

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In the general formula (AI), R _a1 represents an alkyl group, an alkenyl group, an aryl group, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryl group. R _a2 represents a hydrogen atom or a group represented by R _a1 . However, when R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group,
A carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. R _a1
And R _a2 may combine with each other to form a 5- to 7-membered ring. In the general formula (A-II), X represents a heterocyclic group, and R _b1 represents an alkyl group, an alkenyl group or an aryl group. X and R _b1 may combine with each other to form a 5- to 7-membered ring. In the general formula (A-III), Y is -N =
Represents a group of nonmetallic atoms necessary for forming a 5-membered ring together with C-. Y further represents a nonmetallic atom group necessary for forming a 6-membered ring together with the -N = C- group, and -N = C
The terminal of Y bonded to the carbon atom of the group is -N (R _c1 )-, -C
Groups selected from (R _c2 ) (R _c3 )-, -C (R _C4 ) =, -O- and -S- (bonded to the carbon atom -N = C- on the left side of each group) Represents R _{c1 to} R _c4 represent a hydrogen atom or a substituent. In formula (A-IV), R _d1 and R _d2 may be the same or different and each represents an alkyl group or an aryl group. However, when R _d1 and R _d2 are simultaneously an unsubstituted alkyl group and R _d1 and R _d2 are the same group, R _d1 and R _d2 are an alkyl group having 8 or more carbon atoms. In the general formula ( _AV ), R _e1 and R _e2 may be the same or different, and are respectively a hydroxylamino group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, and an alkylthio group. Group, arylthio group, alkyl group or aryl group. However, R _e1 and R _e2 are not simultaneously —NHR _e3 (R _e3 is an alkyl group or an aryl group). R _a1 and R _a2 , or X and R _b1 may be bonded to each other to form a 5- to 7-membered ring. The present inventors have found that oxygen is involved in one of the causes of fluctuations in photographic properties due to storage of the photosensitive material and fluctuations in photographic properties after photographing and until development processing. Some compounds in the light-sensitive material react with oxygen, which affects the photographic properties. However, the compounds represented by the above general formulas (AI) to (AV) may capture these compounds. It is estimated that there is not. Increasing the amount of gelatin applied may increase photographic properties. It is presumed that trace impurities in gelatin react with oxygen, which affects photographic properties. In addition, the general formulas (AI) to (A-
It was found that the compound represented by V) can improve pressure resistance. Hereinafter, the present invention will be described in more detail.

The compounds represented by formulas (AI) to (AV) will be described in more detail. The alkyl group referred to in the present invention is a linear, branched, or cyclic alkyl group, and may have a substituent. In the general formula (AI), R
_a1 is an alkyl group (preferably an alkyl group having 1 to 36 carbon atoms such as methyl, ethyl, i-propyl, cyclopropyl, butyl, isobutyl, cyclohexyl, t-octyl, decyl, dodecyl, hexadecyl, benzyl),
An alkenyl group (preferably an alkenyl group having 2 to 36 carbon atoms, for example, allyl, 2-butenyl, isopropenyl,
Oleyl, vinyl), aryl group (preferably having 6 carbon atoms)
Aryl groups such as phenyl and naphthyl, and acyl groups (preferably acyl groups having 2 to 36 carbon atoms such as acetyl, benzoyl, pivaloyl, α- (2,4-di-tert-amylphenoxy) butyryl, myristoyl) ,
Stearoyl, naphthoyl, m-pentadecylbenzoyl, isonicotinoyl), alkyl or arylsulfonyl group (preferably alkyl or arylsulfonyl group having 1 to 36 carbon atoms such as methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkyl or aryl A sulfinyl group (preferably an alkyl or arylsulfinyl group having 1 to 40 carbon atoms such as methanesulfinyl and benzenesulfinyl), a carbamoyl group (including an N-substituted carbamoyl group, and preferably a carbamoyl group having 0 to 40 carbon atoms; N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N-butyl-N-
Phenylcarbamoyl), a sulfamoyl group (including an N-substituted sulfamoyl group, preferably having 1 to 40 carbon atoms)
For example, N-methylsulfamoyl, N, N-diethylsulfamoyl, N-phenylsulfamoyl, N-cyclohexyl-N-phenylsulfamoyl, N-ethyl-N-dodecylsulfamoyl) , An alkoxycarbonyl group (preferably having 2 to 2 carbon atoms)
36 alkoxycarbonyl groups such as methoxycarbonyl, cyclohexyloxycarbonyl, benzyloxycarbonyl, isoamyloxycarbonyl, hexadecyloxycarbonyl) or aryloxycarbonyl groups (preferably aryloxycarbonyl groups having 7 to 40 carbon atoms, such as phenoxycarbonyl , Naphthoxycarbonyl). R _a2 represents a hydrogen atom or a group represented by R _a1 .

In the formula (A-II), a heterocyclic group (a group forming a 5- to 7-membered heterocyclic ring having at least one of a nitrogen atom, a sulfur atom, an oxygen atom and a phosphorus atom as a ring-constituting atom) The bonding position of the hetero ring (position of the monovalent group) is preferably a carbon atom, for example, 1,
3,5-triazin-2-yl, 1,2,4-triazin-3-yl, pyridin-2-yl, pyrazinyl, pyrimidinyl, prenyl, quinolyl, imidazolyl, 1,
2,4-triazol-3-yl, benzimidazol-2-yl, thienyl, furyl, imidazolidinyl, pyrrolinyl, tetrahydrofuryl, morpholinyl, phosphinolin-2-yl). R _b1 has the general formula (A-
It represents an alkyl group, alkenyl group or aryl group having the same meaning as R _{a1 in} I).

In the general formula (A-III), Y is -N = C
-Non-metallic atoms necessary to form a 5-membered ring with
(For example, when the formed ring group is imidazolyl, benzimida
Zolyl, 1,3-thiazol-2-yl, 2-imidazo
Phosphorus-2-yl, purinyl, 3H-indole-2-i
). Y is a 6-membered ring together with a -N = C- group
Are non-metallic atoms necessary to form
= C-group bonded to the carbon atom at the end of Y is -N (R_c1)-, -C
(R_c2) (R_c3)-, -C (R_c4) =, -O-, -S-
Groups (bonded to the carbon atom of -N = C- on the left side of each group)
). R _c1~ R_c4May be the same or different,
Hydrogen atom or substituent (eg, alkyl group, alkenyl
Group, aryl group, alkoxy group, aryloxy group,
Alkylthio group, arylthio group, alkylamino group,
Represents a reel amino group or a halogen atom). By Y
Examples of the formed 6-membered ring group include quinolyl and isoquino
Ryl, phthalazinyl, quinoxalinyl, 1,3,5-to
Liazin-5-yl, 6H-1,2,5-thiadiazine
-6-yl.

In the general formula (A-IV), R _d1 and R
_d2 is an alkyl group (preferably an alkyl group having 1 to 36 carbon atoms, for example, methyl, ethyl, i-propyl, cyclopropyl, n-butyl, isobutyl, hexyl, cyclohexyl, t-octyl, decyl, dodecyl, hexadecyl, benzyl ) Or an aryl group (preferably having 6 carbon atoms)
-40 aryl groups, for example, phenyl, naphthyl). However, when R _d1 and R _d2 are simultaneously an unsubstituted alkyl group and R _d1 and R _d2 are the same group, R _d1 and R _d2 are an alkyl group having 8 or more carbon atoms.

In the general formula (AV), R _e1 and R _e1
e2 is a hydroxylamino group, a hydroxyl group, an amino group, an alkylamino group (preferably an alkylamino group having 1 to 50 carbon atoms, such as methylamino, ethylamino, diethylamino, methylethylamino, propylamino, dibutylamino, cyclohexyl Amino, t-octylamino, dodecylamino, hexadecylamino,
Benzylamino, benzylbutylamino), an arylamino group (preferably an arylamino group having 6 to 50 carbon atoms such as phenylamino, phenylmethylamino, diphenylamino, naphthylamino), and an alkoxy group (preferably having 1 to 36 carbon atoms) For example, methoxy, ethoxy, butoxy, t-butoxy, cyclohexyloxy, benzyloxy, octyloxy, tridecyloxy, hexadecyloxy), an aryloxy group (preferably an aryloxy group having 6 to 40 carbon atoms) For example, phenoxy, naphthoxy), an alkylthio group (preferably an alkylthio group having 1 to 36 carbon atoms, for example, methylthio, ethylthio, i-propylthio, butylthio,
Cyclohexylthio, benzylthio, t-octylthio, dodecylthio), an arylthio group (preferably an arylthio group having 6 to 40 carbon atoms, for example, phenylthio,
Naphthylthio), an alkyl group (preferably having 1 to 3 carbon atoms)
6 alkyl groups such as methyl, ethyl, propyl,
Butyl, cyclohexyl, i-amyl, sec-hexyl, t-octyl, dodecyl, hexadecyl), and an aryl group (preferably an aryl group having 6 to 40 carbon atoms, such as phenyl and naphthyl). Where _Re1 and _Re2
Are not simultaneously -NHR (R is an alkyl group or an aryl group).

R _a1 and R _a2 , X and R _b1 are bonded to each other to form 5
A 7-membered ring, for example, a succinimide ring,
Examples include a phthalimide ring, a triazole ring, a urazole ring, a hydantoin ring, and a 2-oxo-4-oxazolidinone ring. Each group of the compounds represented by the general formulas (AI) to (AV) may be further substituted with a substituent.
Examples of these substituents include an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, an acylamino group, a sulfonamide group,
Alkylamino group, arylamino group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, halogen atom, cyano group, nitro group, sulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, hydroxyamino group And the like.

In formula (AI), R _a2 represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, and R _a1 represents an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, or an alkoxycarbonyl group. And R _a2 is an alkyl group or an alkenyl group, and R _a1 is an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. The compound is a group.
Most preferably, R _a2 is an alkyl group and R _a1 is an acyl group.

In formula (A-II), R _b1 is preferably an alkyl group or an alkenyl group, more preferably an alkyl group. On the other hand, the general formula (A-II) is preferably represented by the following general formula (A-II-1), more preferably X is 1,3,5-triazin-2-yl; The compound represented by A-II-2) is most preferred.

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In the general formula (A-II-1), R_b1Haichi
R of general formula (A-II)_b1And X ₁Forms a 5- to 6-membered ring
Represents the group of non-metallic atoms required to form. The general formula (A-
Of the compounds represented by II-1), X₁Is 5-6 members
It is more preferable to form a teloaromatic ring.

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In the general formula (A-II-2), R_b1Haichi
R of the general formula (A-II)_b1Represents R _b2And R_b3Are the same
And may be different from each other.
Express. Compound represented by the general formula (A-II-2)
Chi, R_b2And R_b3Is a hydroxyamino group, hydroxy
Group, amino group, alkylamino group, arylamino
Group, alkoxy group, aryloxy group, alkylthio
Group, arylthio group, alkyl group or aryl group
Is particularly preferred.

Among the compounds represented by the general formula (A-III), it is preferable that Y is a group of non-metallic atoms necessary for forming a 5-membered ring, and is bonded to a carbon atom of a -N = C- group. More preferably, the terminal atom of Y is a nitrogen atom. Y
Most preferably forms an imidazoline ring. This imidazoline ring may be condensed with a benzene ring.

Of the compounds represented by formula (A-IV), those in which R _d1 and R _d2 are alkyl groups are preferred. On the other hand, in the general formula ( _AV ), a group in which _Re1 and _Re2 are selected from a hydroxyamino group, an alkylamino group, and an alkoxy group is preferable. Particularly preferably, R _e1 is a hydroxylamino group and R _e2 is an alkylamino group.

Of the compounds represented by the general formulas (AI) to (AV), those having a total carbon number of 15 or less are preferable in that they act on layers other than the addition layer. Compounds having a total carbon number of 16 or more are preferred for the purpose of acting only on the additive layer. General formulas (AI) to (A-
V) Among the compounds represented by the general formula (AI),
Those represented by (A-II), (A-IV) and (A-V) are preferred, and more preferably those represented by the general formulas (AI) and (A-
(IV) and (AV), and more preferably those represented by the general formulas (AI) and (AV). The general formulas (AI) to (AV) of the present invention are described below.
Specific examples of the compound represented by are given below, but the invention is not limited thereto.

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[0171]

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[0173]

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These compounds are represented by the general formula (AI)
Correspondence with (A-V) is as follows. General formula (AI): A-33 to A-55. General formula (A-II): A-5 to A-7, A-10, A-2
0, A-30. General formula (A-III): A-21 to A-29, A-31, A
-32. General formula (A-IV): A-8, A-11, A-19. General formula (AV): A-1 to A-4, A-9, A-12
~ A-18. These compounds of the present invention are described in J. Org. Chem., 27, 4054 ('
62), J. Amer. Chem. Soc., 73, 2981 ('51),
The compound can be easily synthesized by the method described in No. 10692 or the like or a method analogous thereto. In the present invention,
Compounds represented by the general formulas (AI) to (AV)
It may be added by dissolving in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof, or may be added by emulsification and dispersion. Further, it may be added in advance during the preparation of the emulsion. In the case of dissolving in water, if the solubility is increased by increasing or decreasing the pH, the pH may be increased or decreased and dissolved, and then added. In the present invention, two or more of the compounds represented by formulas (AI) to (AV) may be used in combination. For example, using water-soluble and oil-soluble materials together
This is advantageous in photographic performance. Compounds (AI) to (AV)
The amount of coating is preferably from ^{10 -4 mmol / m 2 ~10mmol /} m 2, more preferably ^{10 -3 mmol / m 2 ~1mmol /} m 2.

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 per mol of silver halide, and 7.5 × 10 ^{−6 to} 1.5 × 10 ³ mol. 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 between 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 light-sensitive material of the present invention, the aspect ratio of the silver halide grains forming the emulsion layer is 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 group VIII metal 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, mercaptotetrazole (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, a 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 promoting 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 dye diffusion. 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 types of interfaces for various purposes such as coating aids, antistatic properties, improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties (eg, acceleration of development, 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.

A silver halide photographic light-sensitive material carrying magnetic recording which may be used in the present invention (hereinafter also referred to as a "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. HEI 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.

[0195]

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.

Next, the emulsion was adjusted to pH 7 with HNO ₃ (3N), and 1.0 g of KBr was added. After that, 366.5 ml of a 1.9 MAg NO ₃ aqueous solution and an aqueous KBr solution were added, followed by 1.9 MAg.
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 the usual flocculation method, and then sensitizing dyes SD-1 and SD-
2 or SD-3 was added at 4 × 10 ⁻⁴ mol / l, and gold / sulfur / selenium sensitization was optimally performed in the presence thereof.

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(2) Preparation of Coated Samples Emulsion layers and protective layers as shown in Table 1 were coated on a triacetyl cellulose film support provided with an undercoat layer to prepare Samples 101 to 324.

[0202]

[Table 1]

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

Processing method Step Processing time Processing temperature Replenishment capacity 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 4 minutes 20 seconds 38 ° C 25ml 30 liters Rinse with water (1) 1 minute 05 seconds 24 ° C Counterflow piping system of 10 liters from (2) to (1) Rinse with water (2) 1 minute 00 seconds 24 ° C 1200ml 10 liters Constant 1 minute 05 seconds 38 ° C 25 ml 10 liter Drying 4 minutes 20 seconds 55 ° C Replenishment amount is 35 mm width per 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 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) NaEthylenediaminetetraacetate 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 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, 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 10 for the values of samples 101, 201 and 301.
It was represented by a relative value of 0. In addition, the prepared sample is kept at 50 ° C.
The sensitivity and the fogging when aged for 3 days under the condition of 80% RH are also shown. The emulsions and compound species used for each sample and the results of the sensitivity of each sample are shown in Tables 2, 3, and 4 below.

[0206]

[Table 2]

[0207]

[Table 3]

[0208]

[Table 4]

From Tables 2, 3, and 4, it can be seen that the compounds of the present invention have higher fresh sensitivity than the comparative compounds.
In addition, there is little desensitization and increase in fogging after thermo.

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-3) (5.0 × 10 ⁻⁴ )
mol / molAg) and (Inv-18) (5.0 × 10 ⁻⁵ mol / molAg), (L
A-3) (5 × 10 ⁻³ mol / mol Ag)
A sample in which (SD-3) and (Inv-18) were added in the same amounts as 01 and 201 was designated as 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.
It was indicated by a relative value of 2. As a result, while the sensitivity of the comparative sample 202 was 100 (reference), the sample 201 of the present invention was 11
The sensitivity was as high as 0, and the increase in fogging during the aging was small.

Example 3 Emulsion 1 of Example 1 of JP-A-7-92601 was compared with spectral sensitizing color
Sensitizing dye (SD-1) (8.0 × 10^-Fourmol / molAg),
(PMT-1) (8.0 × 10^-Fivemol / molAg) or sensitizing dye (SD-
1) (8 × 10^-Fourmol / molAg), (PMT-1) (8 × 10^-Fivemo
l / molAg), (A-50) (8 × 10^-3mol / molAg)
Only a different tetrahedral silver iodobromide emulsion was prepared.
Emulsions 301 and 302 were used. Also, JP-A-7-92601
No. 1 in Emulsion 1 in the second double jet
That the silver potential of + was changed from +65 mV to +115 mV
And sensitizing dye (SD-1) (8 × 10^-Fourmo
l / molAg), (Inv-13) (8.0 × 10^-Five(mol / molAg) or sensitization
Dye (SD-1) (8 × 10 ^-Fourmol / molAg), (Inv-13) (8
× 10^-Fivemol / molAg), (A-50) (8 × 10^-3mol / molAg)
Prepare a cubic silver iodobromide emulsion that differs only by changing
This was used as emulsions 303 and 304. Multi-layer color exposure
The material is in accordance with sample 401 of Example 4 of JP-A-7-92601.
It was produced similarly. Sample 4 of Example 4 of JP-A-7-92601
01 emulsion 15 or emulsion 30 or emulsion 30
The samples changed to 2 are referred to as sample 311 and sample 312.
Was. Similarly, the emulsion J of the fifteenth layer of the same Example was replaced with the emulsion 303
Alternatively, the sample changed to the emulsion 304 is
Sample 314 was obtained. The sensitivity of the sample thus obtained was evaluated.
Was. 1/50 second as in Example 4 of JP-A-7-92601
Exposure and color reversal processing to measure yellow density.
became. Sensitivity is the lowest density obtained by giving sufficient exposure +
Find the reciprocal of the exposure required to give a density of 0.2,
It is shown as a relative value with the sensitivity of the comparative sample 311 being 100.
Was. As a result, the sensitivity of the sample 312 of the present invention was as high as 111.
Sensitivity. In addition, 50% RH 80% RH for 3 days
The increase was small. Similarly, the sensitivity of the comparative sample 313
Is 100, the sensitivity of the sample 314 of the present invention is 11
3 and high sensitivity. In addition, at 50 ℃, 80% for 3 days
The increase in the number of heads was also small.

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) in the eleventh layer of sample 101 of Example 1 of JP-A-5-313297 were prepared by using emulsion 401 and sensitizing dye (SD-2) (9 × 10 ^-4 mol / mol Ag). , (I
nv-48) (9 × 10 ⁻⁵ mol / mol Ag) or sensitizing dye (SD-2) (9
× 10 ⁻⁴ mol / molAg), (Inv-48) (9 × 10 ⁻⁵ mol / molAg)
g) and (A-3) (9 × 10 ⁻³ mol / molAg),
1 and sample 412. Similarly, sample 10 of the same example
Emulsion 402 comprising Emulsion-2 of the eleventh layer and sensitizing dye (2)
And sensitizing dye (SD-2) (8 × 10 ⁻⁴ mol / molAg), (Inv-1) (8
× 10 ^-5 mol / molAg) or sensitizing dye (SD-2) (8 × 10
^-4 mol / molAg), (Inv-1) (8 × 10 ^-5 mol / molAg), (A-
3) The sample was replaced with (8 × 10 ⁻³ mol / mol Ag) to obtain a sample 413 and a sample 414. 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. Assuming that the sensitivity of the comparative sample 411 is 100, the sensitivity of the sample 412 of the present invention is 111, which is high.
There was little increase in fog at 0 ° C. and 80% RH for 2 days. Further, when the sensitivity of the comparative sample 413 is assumed to be 100, the sensitivity of the sample 414 of the present invention is 115, which is high.
The increase in fogging in two days at 80% RH was also small.

Example 5 Emulsion F of Example 2 of 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-1) (2 × 10 ^-Fourmol / molAg), (9) (2 × 10^-3mol / molA
g) or sensitizing dye (SD-1) (2 × 10^-Fourmol / molAg),
(9) (2 × 10^-3mol / molAg), (A-50) (2 × 10^-3mol /
molAg) was prepared.
This was used as emulsions 501 and 502. Multi-layer color
The printing paper is in accordance with Sample 20 of Example 1 of JP-A-6-347944.
It was produced similarly. Sample 2 of Example 1 of JP-A-6-347944
0, the emulsion of the first layer is emulsion 501 or emulsion 50.
The samples changed to 2 are referred to as sample 511 and sample 512.
Was. To check the sensitivity of the sample thus obtained, Fuji FW
Optical optics to the light of a
Exposure for 1/10 second through the filter and blue filter,
The same processing steps and processing solutions as in Example 1 of JP-A-6-347944 were used.
For color development. As a result, Comparative Sample 5
The sensitivity of Sample 512 of the present invention when the sensitivity of Sample No. 11 was set to 100
The temperature is 115, which is high sensitivity.
There was also little increase in cover over days.

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) (S-16) (2 × 10 ^-5 mol / molAg) or sensitizing dye
(SD-3) (2 × 10 ⁻⁴ mol / molAg), (S-16) (2 × 10 ⁻⁵
mol / molAg) and (A-3) (2 × 10 ⁻³ mol / molAg).
01 and Emulsion 602. Coating sample is Japanese Patent Application Hei 7-2320
Emulsion 601 or Emulsion 602 was prepared by using the emulsion of Example 1 of No. 36
The emulsion layer and the surface protective layer were combined on the support and coated on both sides by the simultaneous extrusion method in the same manner as in the same example, and these were used as Samples 611 and 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, exposure was performed for 0.05 seconds from both sides using an X-ray orthoscreen HGM manufactured by Fuji Photo Film Co., Ltd. 1
In the same manner as in the above, processing was performed using an automatic developing machine and a processing solution. The sensitivity was represented by the logarithm of the reciprocal of the exposure required to give a density of fog +0.1, and the sensitivity of sample 611 was set to 100, and the other values were represented by relative values. As a result, the sensitivity of the sample 612 of the present invention was 11
The sensitivity was as high as 8, and there was little increase in fog at 40 ° C. and 80% RH for 4 days. 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 in 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 prepared by combining emulsion 701 with sensitizing dye (SD-2) (5
× 10 ⁻⁴ mol / molAg), (Ins-4) (5 × 10 ⁻⁵ mol / molAg)
Alternatively, sensitizing dye (SD-2) (5 × 10 ⁻⁴ mol / mol Ag), (Ins
-4) (5 × 10 ⁻⁵ mol / mol Ag), (A-3) (5 × 10 ⁻³ mol / mol Ag)
Sample 711 and Sample 712 in place of IAg). To check the sensitivity of the sample thus obtained, Fuji FW
A 1/100 second exposure was given to light from a sensitometer (Fuji Photo Film Co., Ltd.) through an optical wedge and a green filter, and processed by Fuji Photo Film CN16 to compare the photographic properties. 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 111, which was high, and the increase in fog at 60 ° C. and 50% RH for 3 days was small.

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. 74-168991, 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), (Inv-36) (5 × 10 ⁻⁵ mo
l / molAg) or sensitizing dye (SD-1) (5 × 10 ⁻⁴ mol / molA
g), (Inv-36) (5 × 10 ⁻⁵ mol / mol Ag), (A-3) (5 × 1
0 ^-3 mol / molAg), and replace Sample 811 and Sample 8
It was set to 12. 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 processed for Fuji Photo Film CN16 to compare the photographic properties. The sensitivity is represented by the logarithm of the reciprocal of the exposure required to give a density of fog + 0.2, and the sensitivity of sample 811 is 1
00. The sensitivity of Sample 812 of the present invention was 115, which was high, and there was little increase in fog at 40 ° C. and 80% RH for 3 days.

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 prepare 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
Sensitizing dye (SD-2) (9 × 10 ^-4 mol / molAg), (Inv-1)
(9 × 10 ⁻⁵ mol / molAg) or (SD-2) (9 × 10 ⁻⁴ mo
l / molAg), (Inv-1) (9 × 10 ⁻⁵ mol / molAg), (A-50)
(9 × 10 ⁻³ mol / molAg) to obtain Sample 901 and Sample 902. 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 passed through an optical wedge and a green filter to be 1/100.
Second exposure was performed, color development was performed using the same processing steps and processing solution as in Example 1 of JP-A-7-159950, and 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 115, which was as high as 115, compared to the sensitivity of the comparative sample 901 of 100 (reference), and the increase in fog at 50 ° C. and 60% RH for 3 days was small.

[0219]

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

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[Procedure amendment]

[Submission date] December 11, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

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Claims (2)

[Claims] 1. A composition comprising at least one compound represented by the following formula (I) or (II) and at least one compound represented by the following formula (L): Silver halide photographic material. General formula (I) In the formula, Z represents an adsorbing group to silver halide 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 is 0,
1, 2, 3, and 4. k ₂ represents 1, ₂ , 3, 4. k ₃
Is 0 or 1. XY has a partial structure constituting an electron donating group. General formula (II) In the formula, Z, L, X, and Y have the same meanings as in formula (I).
k ₄ and k ₅ represent 1, 2, 3, and 4, respectively. k ₆ is 0 or 1. YX has a partial structure constituting an electron donating group. However, 1) XY (or 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 XY (or YX) cleaves a bond to give a radical X and a leaving group Y. General formula (L) In the formula (L), A ₁ and A ₂ each represent a hydrogen atom or 1
Represents a valent substituent. Further, they may combine with each other to form a ring. 2. The general formula (I) or (II) according to claim 1.
2. The silver halide photographic material according to claim 1, which is spectrally sensitized with a sensitizing dye other than the above.