JP2000256573A - Methine compound and silver halide photosensitive material containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel methine compound that has high sensitivity, reduced color retaining, additionally shows high performance in coloring agents, a light- absorbing agent, colorants for optical disks, electrophotography, spectral sensitization pigments for photoelectric transducers and the like, and is useful in silver halide photosensitive material. SOLUTION: This novel compound is represented by formula I [Z1 is the atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring; Z2 is the atomic group necessary for forming a 5- or 6-membered heterocyclic ring that is ring-condensed with a benzene ring; L' is H, a halogen, mercapto, alkyl(thio), alkenyl(thio), aryl(thio); L1, L2 are each methine; p is 0 or 1; V1 is a substituent; n is 0-2], typically the compound of formula II. The compound of formula I is prepared, for example, by starting with a compound of formula III to prepare a compound of formula IV and adding triethyl orthoacetate and ethanol to the resultant compound of formula IV and allowing them to react with each other under heating.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colorant, a light absorber, a dye for an optical disc, a silver halide photograph, an electrophotograph,
The present invention relates to a spectral sensitizing dye for a photoelectric conversion element, a methine compound useful as a medicament, and a nitrogen-containing heterocyclic compound and a quaternary salt compound as raw materials thereof.

[0002]

2. Description of the Related Art A compound that absorbs light in the visible region exhibits various colors depending on the wavelength of the absorbed light. These compounds are called dyes or dyes. They are used for coloring various materials, and as more advanced uses, dyes for optical discs, which are high-density information recording materials, and silver halide photographs and electrophotographics, which are image information recording materials. Are used as spectral sensitizing dyes and filter dyes. Dyes used in these applications are often processed into the desired state after they are first made into a solution, but the actual state used is a solid state such as amorphous or solid dispersion or an adsorbed state. Physical properties greatly affect performance. The formation of molecular aggregates is often affected by slight structural changes in the molecule.

On the other hand, the spectral sensitization technique is an extremely important and indispensable subject for producing a high-density silver halide photosensitive material. Heretofore, various spectral sensitizing dyes and spectral sensitizers have been developed, and techniques for their supersensitization, addition methods, and the like have been developed. As a spectral sensitizing dye used for spectral sensitization, it is known that a spectral sensitizer of, for example, a cyanine dye, a merocyanine dye or a rhodocyanine dye is used alone or in combination (for example, supersensitization). The conditions that must be satisfied as sensitizing dyes used in photographic materials are that not only high spectral sensitivity can be obtained but also that fog is low, and exposure characteristics (e.g., latent image stability, reciprocity characteristics, Temperature, humidity preservation, etc.), sensitivity of sample storage before exposure,
There are many things such as little change in gradation and fog and no remaining in the photosensitive material after development processing. Among these,
Particularly high sensitivity is an essential condition, and many efforts have been made in the past. For example, JP-A-60-202
No. 436, No. 60-220339, No. 60-2514
No. 7, No. 61-123834, No. 62-87953
No. 63-264743, JP-A-1-15534
No. 1-177533, No. 1-187743, No. 1-216342, No. 2-42, JP-B-60-57
No. 583, U.S. Pat. No. 6,418,570, and the like. However, the conventional compounds sometimes have insufficient spectral sensitivity in a specific emulsion or a specific wavelength range, and have not yet been at a satisfactory level.

Further, with the recent rapid development of silver halide photographic materials and the addition of large amounts of sensitizing dyes, sensitizing dyes contained in silver halide photographic materials do not end up being eluted during processing. The problem of leaving coloring in the photosensitive material (so-called residual color) is increasing. Heretofore, as a sensitizing dye having a small residual color, a sensitizing dye having a hydrophilic substituent such as a sulfamoyl group or a carbamoyl group in a nucleus (for example, JP-A No.
Nos. 147451, JP-A-61-294429, JP-B-45-3249 and JP-A-61-77843) have been studied, but they are still not at a satisfactory level.
The sensitizing dyes described in U.S. Pat. No. 3,282,933 and European Patent No. 451,816 A1 also have an effect of improving the residual color, but a sufficient effect is obtained in terms of compatibility between residual color and sensitivity. Not.

Further, few methine compounds having a heterocyclic fused benzene ring fused basic nucleus have been known so far, and Zu Nauchn Prikl Fotogr. 1997, 42
(6), 27. The indole [2,3-f] benzthiazole-containing cyanine dye having a nucleus, and benzothieno [2.
3-f] cyanine dye having benzothiazole, cyanine dye having methylenedioxy-substituted benzothiazole described in JP-A-2-272443, or EP 334
No. 289, an oxindole-fused oxazole derivative, Chem. Pharm. Bull. 1986, 34 (3), 1384. A tetrahydrodioxoquinazoline-fused thiazole derivative described in
A coumarin-fused thiazole derivative described in Curr. Sci. 1984, 53 (8), 424., a cyanine dye having a dihydrooxobenzo-fused thiazole as a nucleus, and the like are known. British Patent No. 1,168,495 describes a cyanine dye derived from benzofuro [2,3-f] benzoxazole, but the indole [3,2- f] benzoxazole, benzothieno [3,2-f] benzoxazole, benzofuro [3,
2-f] benzoxazole and the like are not known.

[0006]

The silver halide photographic light-sensitive material has a high sensitivity and a small residual color, a colorant, a light absorber,
Novel methine compounds expected to have good performance in other uses such as dyes for optical discs, electrophotography, and spectral sensitizing dyes for photoelectric conversion elements, and nitrogen-containing heterocyclic compounds and quaternary salts as raw materials It is to provide a compound. Also,
An object of the present invention is to provide a silver halide photographic material having high sensitivity and little residual color.

[0007]

Means for Solving the Problems The above object of the present invention has been intensively studied, and as a result, the following items (1) to (9) have been achieved. That is,

(1) A compound represented by the following general formula (I). General formula (I)

[0009]

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In the general formula (I), Z ₁ represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. Z ₂
Represents an atom group necessary for condensing with a benzene ring to form a 5- or 6-membered heterocyclic ring. The heterocyclic ring formed by Z ₂ may be condensed at any position on the benzene ring. Z ₂ may be further substituted or a heterocyclic ring or a benzene ring may be condensed. R ₁ represents a hydrogen atom, a halogen atom, a mercapto group, an alkyl group, an alkenyl group, an aryl group, an alkylthio group, an alkenylthio group, or an arylthio group. L ₁ and L ₂ each represent a methine group. p ₁ represents 0 or 1. V ₁ represents a substituent, and n represents 0, 1, or 2.

(2) A compound represented by the following general formula (II). General formula (II)

[0012]

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In the general formula (II), Z ₁ , Z ₂ , R ₁ ,
L ₁ , L ₂ , p ₁ , V ₁ , and n have the same meanings as those described in the description of the general formula (I). R ₂ represents an alkyl group or an aryl group. M ₁ represents a charge balancing counter ion, and m ₁ represents a number from 0 to 10 required to neutralize the charge of the molecule.

(3) A compound represented by the following general formula (III). General formula (III)

[0015]

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In the general formula (III), Z ₁ , Z ₂ , L ₁ ,
L ₂ , p ₁ , R ₂ , M ₁ and m ₁ are represented by the general formulas (I) and (I)
This is the same as that described in the explanation of I). Q ₁ represents a methine group or a polymethine group necessary for forming a methine dye.

(4) Z ₂ in the general formula (I) is a furan ring,
The compound according to (1), which represents a thiophene ring or a pyrrole ring.

(5) Z ₂ in the general formula (II) is a furan ring,
The compound according to (2), which represents a thiophene ring or a pyrrole ring.

(6) Z ₂ in the general formula (III) is a furan ring,
The compound according to (3), which represents a thiophene ring or a pyrrole ring.

(7) The compound according to (1) or (4), wherein the compound represented by the general formula (I) is represented by the following general formula (IV) or (V). General formula (IV)

[0021]

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In the general formula (IV), Z_FourIs an oxygen atom, or
Any of sulfur atoms, and Z _ThreeIs 5 or 6
Lists the atoms required to form a 10-membered nitrogen-containing heterocycle.
You. V _Two, And V_ThreeRepresents a substituent, or
V such as benzene ring or hetero ring_Two, V_ThreeShrink including
A ring may be formed. R₁, L₁, L_Two, P₁,
V₁, N has the same meaning as described in the description of the general formula (I).
You. General formula (V)

[0023]

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In the general formula (V), Z ₆ represents NR ₃ ,
Z ₅ is an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring, and represents an atomic group containing no sulfur atom. Here, R ₃ represents a hydrogen atom or a substituent.
R ₁ , L ₁ , L ₂ , p ₁ , V ₁ , and n have the same meanings as those described in the description of the general formula (I). V ₂ and V ₃ have the same meanings as those described in the description of formula (IV).

(8) The compound according to (2) or (5), wherein the compound represented by the general formula (II) is represented by the following general formula (VI) or (VII). General formula (VI)

[0026]

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In the general formula (VI), Z ₄ and Z ₃ represent the general formula (I
R ₁ , L ₁ , and L ₁ are the same as those described in the description of V).
₂ , p ₁ , R ₂ , M ₁ and m ₁ , V ₁ and n have the same meanings as those described in the description of the general formulas (I) and (II). V ₂ and V ₃ have the same meanings as those described in the description of formula (IV). General formula (VII)

[0028]

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In the general formula (VII), Z ₆ and Z ₅ have the same meanings as those described in the description of the general formula (V), and R ₁ , L ₁ ,
L ₂ , p ₁ , R ₂ , M ₁ , V ₁ , n and m ₁ have the same meanings as those described in the description of the general formulas (I) and (II). V ₂ and V ₃ have the same meanings as those described in the description of formula (IV).

(9) The compound according to (3) or (6), wherein the compound represented by the general formula (III) is represented by the following general formula (VIII) or (IX). General formula (VIII)

[0031]

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In the general formula (VIII), Z ₄ and Z ₃ have the same meanings as those described in the description of the general formula (IV), and L ₁ , L ₂ ,
p ₁ , R ₂ , M ₁ , V ₁ , n and m ₁ have the same meanings as those described in the description of the general formulas (I) and (II). V ₂ ,
And V ₃ have the same meaning as described in the description of the general formula (IV), and Q ₁ has the same meaning as described in the description of the general formula (III). General formula (IX)

[0033]

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In the general formula (IX), Z ₆ and Z ₅ have the same meanings as those described in the description of the general formula (V), and L ₁ , L ₂ ,
p ₁ , R ₂ , M ₁ , V ₁ , n and m ₁ have the same meanings as those described in the description of the general formulas (I) and (II). V ₂ ,
And V ₃ have the same meaning as described in the description of the general formula (IV), and Q ₁ has the same meaning as described in the description of the general formula (III).

(10) A silver halide photographic material containing at least one compound represented by formulas (I) to (IX) described in (1) to (9).

Of the formulas (I), (IV) and (V), (IV) or (V) is preferred, and (IV) is more preferred. Of the general formulas (II), (VI) and (VII), it is preferably (VI) or (VII), more preferably (VI). General formulas (III), (VIII) and (IX)
Among them, (VIII) or (IX) is preferable, and (VIII) is more preferable. Each of the general formulas (IV) to (IX) is a novel compound. Formulas (I), (IV) and (V)
Is a heterocyclic compound represented by FM Hammer (FMH
armer), Heterocyclic Compounds-Cyanine Soybeans and Relatable Compounds (He
rerocyclic Compounds-Cyanine Dyes and Related Compo
unds) ", the nitrogen atom can be easily quaternized, leading to quaternary salt compounds represented by the general formulas (II), (VI) and (VII). These can be used to lead to methine compounds represented by the general formulas (III), (VIII) and (IX).

Z ₂ in the general formula (I) represents an atomic group necessary for forming a 5- or 6-membered heterocyclic ring by condensing with a benzene ring, and the heterocyclic ring formed by Z ₂ is a benzene ring. The ring may be fused at any of the above positions. Therefore, the general formula (I) can be represented by any of the following general formulas (X), (XI) and (XII). General formula (X)

[0038]

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In the general formula (X), Z ₁ , Z ₂ , R ₁ ,
L ₁ , L ₂ , p ₁ , V ₁ , and n have the same meanings as those described in the description of the general formula (I). General formula (XI)

[0040]

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In the general formula (XI), Z ₁ , Z ₂ , Q ₁ ,
R ₁ , L ₁ , L ₂ , p ₁ , M ₁ , m ₁ , V ₁ , and n have the same meanings as those described in the description of the general formula (I). General formula (XII)

[0042]

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In the general formula (XII), Z ₁ , Z ₂ , Q ₁ ,
R ₁ , L ₁ , L ₂ , p ₁ , M ₁ , m ₁ , V ₁ , and n have the same meanings as those described in the description of the general formula (I). Of the general formulas (X), (XI) and (XII), preferred is (XI). The same applies to general formulas (II) and (III).

[0044]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention will be described below in detail. Formula (I), Formula (II), Formula (I
In II), Z ₁ represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. The nitrogen-containing heterocyclic ring formed by Z ₁ may be any, but is preferably a thiazole nucleus, an oxazoline nucleus, a thiazoline nucleus, an oxazole nucleus, a selenazole nucleus, a tellurazole nucleus, an isoxazole nucleus, an isothiazole nucleus, a pyrazole nucleus, , 3
-Dialkyl-3H-pyrrole nucleus (for example, 3,3-dimethyl-3H-pyrrole), imidazole nucleus, imidazoline nucleus, 2-pyridine nucleus, 4-pyridine nucleus, pyridazine nucleus, pyrazine nucleus, pyrimidine nucleus and the like. Is more preferably a thiazole nucleus, an oxazole nucleus,
A selenazole nucleus, a 3,3-dialkyl-3H-pyrrole nucleus (for example, 3,3-dimethyl-3H-pyrrole), an imidazole nucleus, a 2-pyridine nucleus, and a 4-pyridine nucleus;
Particularly preferred are a thiazole nucleus, an oxazole nucleus, an imidazole nucleus, a 2-pyridine nucleus and a 4-pyridine nucleus.

Assuming that the substituent on Z ₁ is V, the substituent represented by V is not particularly limited. For example, a halogen atom (eg, chlorine, bromine, iodine, fluorine), a mercapto group, a cyano group, Carboxyl group, phosphate group, sulfo group, hydroxy group, carbamoyl group having 1 to 10, preferably 2 to 8, more preferably 2 to 5 carbon atoms (eg, methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl) Having 0 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 5 carbon atoms.
(E.g., methylsulfamoyl, ethylsulfamoyl, piperidinosulfonyl), a nitro group, having 1 to 20 carbon atoms, preferably 1 to 1 carbon atoms
0, more preferably an alkoxy group having 1 to 8 carbon atoms (for example, methoxy, ethoxy, 2-methoxyethoxy,
Phenylethoxy), an aryloxy group having 6 to 20, preferably 6 to 12, and 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 12, more preferably a sialoxy group having 2 to 8 carbon atoms (eg, acetyloxy, benzoyloxy);
It preferably has 2 to 12 carbon atoms, and more preferably 2 carbon atoms.
To 8 acylamino groups (eg, acetylamino), 1 to 20, preferably 1 to 10, more preferably 1 to 8 carbon atoms, sulfonyl groups (eg, methanesulfonyl, ethanesulfonyl, benzenesulfonyl), 1 to 20, preferably 1 to 1 carbon atoms
0, more preferably a sulfinyl group having 1 to 8 carbon atoms (for example, methanesulfinyl, ethanesulfinyl, benzenesulfinyl), a sulfonylamino group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms. Groups (eg, methanesulfonylamino, ethanesulfonylamino, benzenesulfonylamino),

An amino group, a substituted amino group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (eg, methylamino, dimethylamino, benzylamino, anilino, diphenylamino); An ammonium salt having a number of 0 to 15, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms (eg, trimethylammonium, triethylammonium);
To 15, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, such as a trimethylhydrazino group, 1 to 15 carbon atoms, preferably 1 carbon atoms.
To 10, more preferably a ureido group having 1 to 6 carbon atoms (e.g., a ureido group, an N, N-dimethylureido group);
C1 to C15, preferably C1 to C10, more preferably C1 to C6 imide group (for example, succinimide group), C1 to C20, preferably C1 to C12, more preferably C1 to C12 1 to 8 alkylthio groups (eg methylthio, ethylthio, propylthio),
An arylthio group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms (eg, phenylthio, p-methylphenylthio, p-chlorophenylthio, 2-pyridylthio, naphthylthio), 2 carbon atoms To 20, preferably 2 to 12, more preferably 2 to 8 alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl, 2-benzyloxycarbonyl), 6 to 20 carbon atoms, preferably 6 to 20 carbon atoms 12, more preferably 6 to 10 carbon atoms
Aryloxycarbonyl group (for example, phenoxycarbonyl),

An unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methyl, ethyl, propyl, butyl), and 1 to 18 carbon atoms, preferably A substituted alkyl group having 1 to 10, more preferably 1 to 5 carbon atoms {eg, hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl, and here having 2 to 18 carbon atoms, preferably C3 to C10, more preferably C3 to C5 unsaturated hydrocarbon group (for example, vinyl group, ethynyl group, 1-cyclohexenyl group, benzylidine group, benzylidene 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),

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

Z ₂ is a group of atoms necessary for condensing with a benzene ring to form a 5- or 6-membered heterocyclic ring. The heterocyclic ring formed by Z ₂ may be condensed at any position on the benzene ring.

As Z ₂ , a furan ring, a thiophene ring,
Examples include a pyrrole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring. Any of these heterocycles may be a dihydro or tetrahydro form which is a reduced form, and may be oxo-substituted. Further, it may be further substituted or condensed with an aromatic ring. Z ₂ is preferably a furan ring, a thiophene ring, a pyrrole ring or a benzofuran, a benzothiophene or an indole, more preferably a furan ring, a pyrrole ring, or a benzofuran or an indole, particularly preferably a furan ring or a benzofuran. It is.

The heterocyclic ring formed by Z ₃ includes thiazole, imidazole, oxazole, pyridine and the like, and is preferably oxazole.

The heterocyclic ring formed by Z ₅ includes imidazole, oxazole, pyridine and the like, and is preferably oxazole.

Z ₄ represents either an oxygen atom or a sulfur atom, preferably an oxygen atom, and Z ₆ represents NR ₃ .

V ₁ represents a substituent, and examples thereof include those described in the description of V. n represents 0, 1, or 2, and when n = 2, a plurality of V ₁ may be the same or different.

V ₂ and V ₃ represent a hydrogen atom or a substituent, and examples of the substituent include those described in the description of V. A condensed ring containing V ₂ and V ₃ may be formed. In this case, the condensed ring containing V ₂ and V ₃ includes an aromatic ring or a heterocyclic ring, and the aromatic ring includes, for example, benzene, naphthalene, and anthracene. Examples of the heterocyclic ring include those described in the description of Z ₂ and Z ₁ . V ₂ and V ₃ are preferably a hydrogen atom or V
_1, an aromatic ring or a heterocyclic ring is a condensed ring containing V _2.

R ₃ represents a hydrogen atom or a substituent, and examples of the substituent include those described for the substituent V. R ₃ is preferably a hydrogen atom, an unsubstituted alkyl group having 18 or less carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl) and a substituted alkyl group (eg, a halogen atom, an alkoxy group, a cyano group, A sulfo group, a hydroxy group, an acyl group, an acylamino group, an aryloxy group, an alkyl group substituted with an arylamino group), an unsubstituted aryl group having 20 or less carbon atoms (eg, phenyl, naphthyl) and a substituted aryl group (eg, , A halogen atom, an alkoxy group, a cyano group,
Sulfo group, hydroxy group, acyl group, acylamino group,
An aryloxy group, an aryl group substituted with an arylamino group, an unsubstituted heterocyclic group having 18 or less carbon atoms (eg, furan, thiophene, pyrrole group) or a substituted heterocyclic group (eg, a halogen atom, an alkoxy group as a substituent) , A cyano group, a sulfo group, a hydroxy group, an acyl group, an acylamino group, a heterocyclic group substituted with an arylamino group), an alkoxy group, a cyano group, a sulfo group, a hydroxy group, an acyl group, an acylamino group, an aryloxy group, or An arylamino group. More preferably, a hydrogen atom, an unsubstituted alkyl group having 18 or less carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl) and a substituted alkyl group (eg, a halogen atom, an alkoxy group,
A cyano group, a sulfo group, a hydroxy group, an acyl group, an acylamino group, an aryloxy group, an alkyl group substituted with an arylamino group), particularly preferably methyl, ethyl, propyl, butyl, an alkoxyalkyl group, a cyanoalkyl group, A sulfoalkyl group, a hydroxyalkyl group, a carboxyalkyl group, and an aminoalkyl group.

R ₁ is preferably a hydrogen atom, a mercapto group, a halogen atom (eg, fluorine, chlorine, bromine, iodine), an unsubstituted alkyl group having 18 or less carbon atoms (eg, methyl, ethyl, propyl), a substituted alkyl group (As a substituent, for example, a halogen atom, an alkoxy group, a cyano group,
Sulfo group, hydroxy group, acylamino group, aryloxy group, alkyl group substituted with arylamino group), unsubstituted alkenyl group having 18 or less carbon atoms (eg, vinyl, propenyl, butenyl, isopropenyl, isobutenyl)
And a substituted alkenyl group (for example, a halogen atom, an alkoxy group, a cyano group, a sulfo group, a hydroxy group, an acylamino group, an aryloxy group, an alkenyl group substituted with an arylamino group), an unsubstituted aryl having 18 or less carbon atoms Group (eg, phenyl, naphthyl) and substituted aryl group (eg, halogen atom, alkoxy group, cyano group, sulfo group, hydroxy group, acylamino group, aryloxy group, aryl group substituted with arylamino group), carbon An unsubstituted alkylthio group of the number 18 or less (for example, methylthio, ethylthio, propylthio,
Butylthio, pentylthio) and substituted alkylthio groups (for example, a halogen atom, an alkoxy group,
Cyano group, sulfo group, hydroxy group, acylamino group,
An aryloxy group, an alkylthio group substituted by an arylamino group, an alkenylthio group having 18 or less carbon atoms (for example, vinylthio, propenylthio, butenylthio) and a substituted alkenylthio group (for example, a halogen atom, an alkoxy group, a cyano group) Group, sulfo group, hydroxy group, acylamino group, aryloxy group, alkenylthio group substituted with arylamino group), unsubstituted arylthio group having 18 or less carbon atoms (eg, phenylthio, naphthylthio) and substituted arylthio group (as a substituent) Examples thereof include a halogen atom, an alkoxy group, a cyano group, a sulfo group, a hydroxy group, an acylamino group, an aryloxy group, and an arylthio group substituted with an arylamino group. More preferably, a hydrogen atom, a mercapto group, a halogen atom, an unsubstituted alkyl group having 8 or less carbon atoms (eg, methyl, ethyl, propyl), an unsubstituted aryl group having 8 or less carbon atoms (eg, phenyl, naphthyl), An unsubstituted alkylthio group having 8 or less (eg, methylthio, ethylthio, propylthio, butylthio, pentylthio) and an unsubstituted arylthio group having 10 or less carbon atoms (eg, phenylthio, naphthylthio). Particularly preferably, a hydrogen atom, a mercapto group, a halogen atom, an unsubstituted alkyl group having 3 or less carbon atoms (eg, methyl, ethyl, propyl),
An unsubstituted alkylthio group having 3 or less carbon atoms (eg, methylthio, ethylthio, propylthio).

L ₁ and L ₂ each independently represent a methine group. The methine group represented by L ₁ and L ₂ may have a substituent. Examples of the substituent include a substituted or unsubstituted C ₁ to C 15, preferably C ₁ to C 10,
Particularly preferably, an alkyl group having 1 to 5 carbon atoms (for example,
Methyl, ethyl, 2-carboxyethyl), substituted or unsubstituted, having 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms.
5, more preferably an aryl group having 6 to 10 carbon atoms (eg, phenyl, o-carboxyphenyl), substituted or unsubstituted 3 to 20 carbon atoms, preferably 4 to 1 carbon atoms.
5, more preferably a heterocyclic group having 6 to 10 carbon atoms (for example, N, N-dimethylbarbituric acid group), a halogen atom (for example, chlorine, bromine, iodine, fluorine), and a carbon atom having 1 to 1
5, preferably an alkoxy group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methoxy, ethoxy), 0 to 15 carbon atoms, preferably 2 to 1 carbon atoms
0, more preferably an amino group having 4 to 10 carbon atoms (eg, methylamino, N, N-dimethylamino, N-methyl-N-phenylamino, N-methylpiperazino), 1 to 15 carbon atoms, preferably 1 carbon atom To 10, more preferably an alkylthio group having 1 to 5 carbon atoms (eg, methylthio, ethylthio), an arylthio group having 6 to 20, preferably 6 to 12, and more preferably 6 to 10 carbon atoms (eg, phenylthio, p-methylphenylthio) and the like. Further, a ring may be formed with another methine group, or an auxochrome ring may be formed.

P ₁ each independently represents 0 or 1.
Preferably it is 0.

R ₂ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and examples of the substituent include those described in the description of the substituent V and the like.
Examples of the alkyl group include an unsubstituted alkyl group having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, Octadecyl), aralkyl groups (eg, benzyl, 2-phenylethyl, naphthylmethyl, 2- (4-
Biphenyl) ethyl), unsaturated hydrocarbon groups (eg, allyl, crotyl), hydroxyalkyl groups (eg,
-Hydroxyethyl, 3-hydroxypropyl), an alkoxyalkyl group (for example, 2-methoxyethyl, 2-
(2-methoxyethoxy) ethyl), an aryloxyalkyl group (for example, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl, 2- (4-biphenyloxy) ethyl, 2- (o, m, p-halophenoxy) ) Ethyl, 2-
(O, m, p-methoxyphenoxy) ethyl), an alkoxycarbonylalkyl group (for example, ethoxycarbonylethyl, 2-benzyloxycarbonylethyl), an aryloxycarbonylalkyl group (3-phenoxycarbonylpropyl, 2- (1-naphtho) (Oxycarbonyl) ethyl), acyloxyalkyl group (eg, 2-acetyloxyethyl), acylalkyl group (2-acetylethyl), carbamoylalkyl group (eg, 2-morpholinocarbonylethyl), sulfamoylalkyl group (eg, N, N-dimethylsulfamoylmethyl), a heterocyclic-substituted alkyl group (for example, 2-pyrrolidin-2-one-1-yl) ethyl) and the like.

M ₁ is included in the formula to indicate the presence of a cation or an anion when necessary to neutralize the ionic charge of the molecule. Typical cations include inorganic ions such as hydrogen ions (H ⁺ ), alkali metal ions (sodium ions, potassium ions, lithium ions), alkaline earth metal ions (eg, calcium ions), and ammonium ions (eg, ammonium ions). , Tetraalkylammonium ions, pyridinium ions, and ethylpyridinium ions). The anion may be either an inorganic anion or an organic anion, and may be a halogen anion (eg, a fluorine ion, a chloride ion, a bromine ion, an iodine ion), a substituted arylsulfonate ion (eg, a p-toluenesulfonic acid ion, -Chlorobenzenesulfonate ion), aryldisulfonate ion (for example, 1,3
-Benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate Acid ion, picrate ion,
An acetate ion and a trifluoromethanesulfonic acid ion are mentioned. Further, an ionic polymer or a molecule having a charge opposite to that of the molecule may be used. m ₁ represents the number necessary to balance the charges, and is 0 when a salt is formed in the molecule.

Although any methine dye can be formed by Q, preferred examples include a cyanine dye, a merocyanine dye, a rhodocyanine dye, a trinuclear merocyanine dye, an allopolar dye, a hemicyanine dye, and a styryl dye. For more information on these dyes, see
Heterocyclic Compounds-Cyanin, by FM Harmer, Heterocyclic Compounds-Related Compounds.
e Dyes and Related Compounds), John Wiley & Sons, New York, London, 1964, D.M.
(DMSturmer), Heterocyclic Compounds-Special Topics in Heterocyclic Compounds-Special Top
ics in Heterocyclic Chemistry) ", Chapter 18, Chapter 14
Verses 482-515, John Willie and
John Wiley & Sons, Inc.-New York, London, 1977, and the like. The general formula of a cyanine dye, a merocyanine dye, and rhodacyanine dye is
U.S. Pat. No. 5,340,694, pages 21 and 22, (X
Those shown in (I), (XII) and (XIII) are preferred.

In the general formula (III), when a cyanine dye is formed by Q, it can be represented by the following resonance formula.

[0065]

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The number of methine groups in Q is preferably 0
To 7, more preferably 0 to 5, particularly preferably 3. Here, Q is as described above (cyanine dye, merocyanine dye, rhodacyanine dye, trinuclear merocyanine dye, allopolar dye, hemicyanine dye, styryl dye, etc.)
It is assumed that the number of methine groups may be 0 as long as it forms the dye of the formula (for example, simple merocyanine). The methine group is preferably substituted by a substituent (heterocyclic group, aliphatic group, or aromatic group) necessary for forming a methine dye, and a preferable substituent is a heterocyclic group or an aromatic group. And particularly preferably a heterocyclic group. As the heterocyclic group, those described above as examples of Z ₄ and Z ₆ are preferable. Examples of the aromatic group include a substituted or unsubstituted aromatic group (for example, a 4-dimethylaminophenyl group, a 4-methoxyphenyl group, a phenyl group, and a 4-dimethylaminonaphthyl group). As the aliphatic group, an alkoxycarbonyl group (for example, an ethoxycarbonyl group) and an acyl group (for example, an acetyl group) are preferable. Other examples include the substituents represented by the aforementioned V. For example, a substituted or unsubstituted amino group (eg, amino group, dimethylamino group), cyano group, alkoxycarbonyl group (eg, ethoxycarbonyl), substituted or unsubstituted An unsubstituted alkylsulfonyl group (eg, methylsulfonyl group) and a substituted or unsubstituted acyl group (eg, acetyl group) are preferred.

Specific examples of the compounds represented by the general formula (I) (including the general formulas (IV) and (V) as subordinate concepts) of the present invention are shown below. is not.

[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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Specific examples of the compounds represented by the general formula (II) (including the subordinate general formulas (VI) and (VII)) of the present invention are shown below. is not.

[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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The specific examples of the compounds represented by the general formula (III) (including the general formulas (VIII) and (IX) as subordinate concepts) of the present invention are shown below. is not.

[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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The general formulas (I), (II) and (II) of the present invention
Compounds represented by I) (including the general formulas (IV) to (IX) as subordinate concepts) are described in "Heterocyclic Compounds-Cyanine Soybeans and Related Compounds" by FM Harmer (FM Harmer). Heterocyclic Com
pounds-Cyanine Dyes and Related Compounds) ", John Wiley & Sons
Co.-New York, London, 1964, DMSturmer, "Heterocyclic Compounds-Special Topics in Heterocyclic Compoud."
s-Special Topics in Heterocyclic Chemistry) "
Chapter 18, Section 14, pages 482-515, John Wiley & Sons, Inc.-New York, London, 1977, "Rodd's Chemi.
stry of Carbon Compounds) "Second Edition, Volume IV,
Part B, Chapter 15, pages 369-422 Elsevier
Science Public Company, Inc. (Elsevi)
er Science Publishing Company Inc.)-New York, published in 1977, for example.

The methine compound represented by the general formula (I) of the present invention (hereinafter referred to as the methine compound of the present invention)
The heterocyclic compound represented by I) or (III) (hereinafter, heterocyclic compound)) can be used alone or in combination with other sensitizing dyes in a silver halide photographic material.

The timing of adding the methine compound of the present invention (also the heterocyclic compound) to the silver halide emulsion of the present invention may be determined during any process of emulsion preparation which has been recognized to be useful. It may be. For example, U.S. Pat. Nos. 2,735,766 and 3,628,960,
As disclosed in JP-A-4,183,756, JP-A-4,225,666, JP-A-58-184142, JP-A-60-196,749, etc., a step of forming silver halide grains and / or desalting. Before, during and / or after desalination and before the start of chemical ripening.
As disclosed in No. 3920, etc., it 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 and before coating. Further, as disclosed in U.S. Pat. No. 4,225,666, JP-A-58-7629, etc., the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle forming step. It may be divided and added during the ripening step or after the completion of chemical ripening, or may be divided and added before or after the completion of the chemical ripening or during the step,
Compounds to be divided and added may be added by changing the kind of the combination of the compounds.

The addition amount of the methine compound and / or the heterocyclic compound of the present invention varies depending on the shape and size of the silver halide grains.
It can be used at 0 ^-6 to 8 × 10 ^-3 mol. For example,
When the silver halide grain size is 0.2 to 1.3 μm, 2 × 10 ^{−6 to} 3.5 × per mol of silver halide.
The addition amount of 10 ⁻³ mol is preferable, and 7.5 × 10 ⁻⁶ to 1.
An addition amount of 5 × 10 ⁻³ mol is more preferred.

The methine compound of the present invention (the same applies to the heterocyclic compound of the present invention) can be directly dispersed 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 methine compound of the present invention has sharpness,
It can be used as various filter dyes, irradiation prevention dyes or antihalation dyes for the purpose of improving color resolution and the like. This methine compound can be contained in a coating solution such as a silver halide photographic light-sensitive material layer, a filter layer and / or an antihalation layer by a conventional method. The amount of the dye used may be an amount sufficient to color the photographic layer, and those skilled in the art can easily select this amount according to the purpose of use. In general, it is preferable to use such that the optical density is in the range of 0.05 to 3.0. The timing of addition may be any step before coating. Alternatively, a polymer having a charge opposite to that of the dye ion may coexist in the layer as a mordant, and the dye may be localized in the characteristic layer by interaction with the dye molecule. As the polymer mordant, for example, US Pat.
8,564, 4,124,386, 3,62
5,694, 3,958,995, 4,16
Nos. 8,976 and 3,445,231.

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 silver iodide content is preferably at most 10 mol%, more preferably at most 1 mol%. More preferably, 0.
5 mol% or less. 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.
The constitution and processing described in JP-A-63-264743 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, Vol. 14, pp. 248-257 (1970); US Pat.
Nos. 34,226, 4,414,310, 4,43
3,048, 4,439,520 and GB 2,1
It can be easily adjusted by the method described in 12,157. In the photographic light-sensitive material of the present invention, its abundance is at least 70%, particularly preferably at least 85%.

The methine compound of the present invention is used in the following photographic materials for the purpose of sensitizing agents, 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 methine compound of the present invention is used for 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, Photographic materials for plate making (eg, lith film, lith dupe film, etc.), cathode ray tube display materials, X-ray recording materials (especially materials for direct and indirect photography using a screen), silver salt diffusion transfer process (Silver Salt) diffusion transfer proces
s), the photosensitive material used in the color diffusion transfer process, the die transfer process (im
It is used as a light-sensitive material used in the inhibition process, a light-sensitive material used in the silver dye bleaching method, a light-sensitive material for heat development, and the like. The compound represented by formula (II) or (III) of the present invention can be contained in a silver halide photographic material in the same manner as the methine compound.

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, for example, ammonia, rodankari, rodanammon, thioether compounds (eg, US Pat. No. 3,271,157) may be used as a silver halide solvent.
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 may contain a color coupler such as a cyan coupler, a magenta coupler and a yellow coupler, and a compound dispersing the coupler. That is, in the color development processing, aromatic 1
It may contain a compound capable of developing color by oxidative coupling with a secondary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative). For example,
Examples of magenta couplers include 5-pyrazolone couplers, pyrazorobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (eg, benzoylacetoanilides, pivaloylacetoanilides). Some cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible couplers having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ion. Further, a colored coupler having a color correcting effect or a coupler that releases a development inhibitor during development (a so-called DIR coupler) may be used. Also DI
In addition to the R coupler, a colorless DIR coupling compound which is colorless and releases a development inhibitor may be contained.

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

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

The photographic light-sensitive material of the present invention has various interfaces for various purposes such as a coating aid, antistatic, improvement of slipperiness, emulsification / dispersion, prevention of adhesion and improvement of photographic properties (for example, 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.

The silver halide photographic light-sensitive material carrying magnetic recording which may be used in the present invention (hereinafter also referred to as "light-sensitive material")
Are disclosed in JP-A-6-35118 and JP-A-6-17528.
No., a thin layer support of a pre-heat treated polyester described in detail in Hatsumei Kyokai Disclosure No. 94-6023, for example,
Polyethylene aromatic dicarboxylate polyester support, 50 μm to 300 μm, preferably 50 μm
Heat treatment (annealing) at a temperature of 40 ° C. or more and a glass transition temperature or less at a temperature of 40 to 200 μm, more preferably 80 to 115 μm, and particularly preferably 85 to 105 μm.
No. 43-2603, No. 43-2604
U.S. Pat. No. 5,326,689 by ultraviolet irradiation described in JP-B-45-3828, surface treatment such as corona described in JP-B-48-5043 and JP-A-51-131576.
No. described in US Pat. No. 2,761, if necessary
No. 791 described in JP-A-59-23.
No. 505, JP-A-4-195726, JP-A-6-59
357 may be applied. In addition,
The magnetic layer described above is disclosed in JP-A-4-124462,
It may be in the form of a stripe described in JP-A-124645.
Further, if necessary, an antistatic treatment described in JP-A-4-62543 is used, and finally a product coated with a silver halide emulsion is used. The silver halide emulsion used here is described in JP-A-4-166.
No. 932, JP-A-3-41436, JP-A-3-414
No. 37 is used. Sensitive materials made in this way are Tokuho 4-868
No. 17 manufactured by the manufacturing control method described in
Preferably, the production data is recorded by the method described in No. 46. Thereafter or before that, Japanese Patent Application Laid-Open No. 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 photography, development processing, and various ways of enjoying 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 panoramic photography, high-vision photography, and normal photography (magnetic recording capable of selecting a print aspect ratio), and a dual recording method 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 to 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.

[0114]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1: Synthesis of compound (I-1) The entire process of the synthesis of compound (I-1) is shown in the following scheme 1. Scheme 1

[0115]

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Synthesis of Compound (I-1-e) 10 g of 5-fluoro-2-nitrophenol was placed in a 300 ml three-necked flask, and dissolved in 70 ml of DMF. Next, 10 g of potassium carbonate and 10.8 g of benzyl bromide were added to the reaction solution, and the mixture was stirred at room temperature for 3 hours. Water 500
Then, the mixture was extracted with 500 ml of ethyl acetate. The organic phase was separated, washed twice with 200 ml of water and then saturated saline 10
Washed with 0 ml, dried over magnesium sulfate, filtered and evaporated under reduced pressure. By recrystallizing the obtained crude crystals of the compound (I-1-e) from methanol, 7.0 g (yield: 64%) of the compound (I-1-e) was obtained.

Synthesis of Compound (I-1-d) In a nitrogen stream, 6.4 g of sodium hydride was placed in a 300 ml three-necked flask, washed twice with 10 ml of toluene, and 300 ml of DMSO was added.
3.1 g was added and the mixture was stirred at an external temperature of 80 degrees for 20 minutes. After cooling to room temperature, 33.0 g of compound (I-1-e) was added, and the mixture was stirred at room temperature for 25 hours. 100 ml of a saturated ammonium chloride aqueous solution and 500 ml of distilled water were added to the reaction solution, and the mixture was extracted with 600 ml of dichloromethane. Organic phase is distilled water 500m
and 200 ml of saturated saline. After the organic phase was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was washed with methanol, cooled, and filtered to obtain the compound (I).
-3-d) 34.5 g (yield 65%, melting point 72 ° C) was obtained.

Synthesis of Compound (I-1-c) In a nitrogen stream, 10.0 g of Compound (I-1-d) was placed in a 300 ml eggplant flask containing a magnetic stirrer, and 150 ml of dimethylacetamide and 50 ml of acetonitrile were added and stirred. After that, sodium carbonate 5.0 g and palladium acetate 2.
5 g and 11.6 g of triphenylphosphine were sequentially added, heated to an external temperature of 170 ° C., and stirred at this temperature for 4 hours. Thereafter, 500 ml of distilled water was added, and 500 ml of ethyl acetate was added.
The extract was washed with 300 ml of distilled water and 100 ml of saturated saline in this order, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. Next, acetonitrile was added to this to dissolve it, dust was filtered off, and 30 ml of a 1N aqueous sodium hydroxide solution was added to precipitate crystals. This is collected by filtration, and this operation is repeated once again after dissolving in acetonitrile. The resulting crystals were dried under reduced pressure to give compound (I-1).
-C) 1.9 g (24% yield) were obtained.

Synthesis of Compound (I-1-b) Under a nitrogen stream, 1.9 g of Compound (I-1-c) was placed in a 300 ml eggplant flask containing a magnetic stirrer, 150 ml of acetonitrile was added, and the mixture was stirred. After adding 2.5 ml of trimethylsilyl iodide and stirring at an external temperature of 50 ° C. for 1 hour, 2.0 ml of trimethylsilyl iodide was added and the mixture was further stirred at this temperature for 2 hours. After cooling, sulfuric acid was added to make it acidic, extracted with dichloromethane, washed successively with saturated saline, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. Silica gel column chromatography (SiO _2: 100 g, solvent: hexane / ethyl acetate = 100 to 20) to give the compound (I-1-b) 0.95g (70% yield, mp 159
° C).

Synthesis of Compound (I-1) Compound (I-1) was placed in a 200 ml eggplant flask containing a magnetic stirrer.
-1-b) 0.9 g was added, and 1.5 g of sodium dithionite, 10 ml of water, 6 ml of ethanol and 12 ml of a 1N aqueous sodium hydroxide solution were sequentially added thereto.
After heating for 0 minutes, the mixture was cooled, garbage was filtered off, and sulfuric acid was added to adjust the pH to ６6. The precipitated crystals were collected by filtration and dried under reduced pressure to obtain compound (I-1-a). The obtained compound (I-1-a) was placed in a 200-ml eggplant flask containing a magnetic stirrer, 5 ml of triethyl orthoacetate and 40 ml of ethanol were added, and the mixture was heated at an external temperature of 110 ° C.
After stirring for 5 hours, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (SiO ₂ : 100 g, solvent: hexane / ethyl acetate = 7) to give 400 mg of compound (I-1) (compound (I- Yield 4 from 1-b)
6%). Mp ^{124 ℃, 1 H-NMRδ (} DMSO-d 6, 300M
Hz) 2.69 (3H, s, Me), 7.43 (1H, t, J8.2Hz), 7.53 (1H,
dt, J1.4Hz, 8.2Hz), 7.71 (1H, d, J8.2Hz), 8.05 (1H,
s), 8.22 (1H, d, J8.2Hz), 8.41 (1H, s).

Example 2: Synthesis of compound (II-1) The synthesis of compound (II-1) is shown in the following scheme 2. Scheme 2

[0122]

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Synthesis of Compound (II-1) 0.3 g of Compound (I-1) and 0.5 g of propane sultone
And stirred at 150 ° C. for 3 hours. After cooling, 100 ml of ethyl acetate was added, the mixture was stirred at room temperature for 2 hours, and the crystals were collected by filtration and dried to obtain 0.44 g of compound (II-1) (yield 95).
%; Melting point: 283 ° C.).

Example 3: Synthesis of compound (II-1) The synthesis of compound (III-41) is shown in the following scheme 3. Scheme 3

[0125]

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Synthesis of compound (III-41) 0.44 g of compound (II-1), 1.5 ml of triethylorthopropionic acid, 1.5 ml of pyridine, 0.6 ml of acetic acid and 0.7 ml of triethylamine were mixed, and the mixture was added at 150 ° C. 20
Stirred for minutes. After cooling, 50 ml of ethyl acetate was added, the mixture was stirred at room temperature for 30 minutes, the crystals were filtered, the resulting crystals were added with acetone, boiled for 30 minutes, cooled, filtered, and the crystals were dried under reduced pressure to give the compound ( III-41) 0.33 g (yield 63%) was obtained. (Λ _max 520 nm, ε 1.34 × 1
0 ⁵ , melting point 269 ° C)

Example 4 Preparation of emulsion 30 g of gelatin and 6 g of potassium bromide were added to 1 liter of water,
While stirring, a silver nitrate aqueous solution (5 g as silver nitrate) and a potassium bromide aqueous solution containing 0.15 g of potassium iodide were added to the vessel kept at 0 ° C. over 1 minute by the double jet method. Further, an aqueous silver nitrate solution (145 g as silver nitrate) and potassium iodide4.
An aqueous potassium bromide solution containing 2 g was added by the double jet method. At this time, the flow rate was accelerated so that the flow rate after the addition was 5 times that at the start of the addition. After completion of the addition, soluble salts were removed at 35 ° C. by a sedimentation method, and the temperature was raised to 40 ° C., and 75 g of gelatin was added to adjust the pH to 6.7. The resulting emulsion has a projected area diameter of 0.
Tabular grains having a thickness of 98 μm and an average thickness of 0.138 μm had a silver iodide content of 3 mol%. This emulsion was subjected to chemical sensitization in combination with gold and sulfur sensitization. Preparation of Photographic Material 101 In addition to gelatin, an average molecular weight of 8000 was used as a surface protective layer.
Aqueous gelatin solution containing polyacrylamide, sodium polystyrene sulfonate, polymethyl methacrylate fine particles (average particle size: 3.0 μm), polyethylene oxide, hardener and the like was used. Sample 10 was prepared by adding S-1 as a sensitizing dye to the above emulsion at a ratio of 500 mg / 1 mol Ag and potassium iodide at a ratio of 200 mg / 1 mol Ag.
It was set to 1. Emulsions having the same composition as Sample 101 except that the dye of the present invention and S-2 and S-3 as shown in Table 1 were added instead of the sensitizing dye S-1 were Samples 102 to 108, respectively.

[0128]

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[0129]

[Table 1]

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

[0131]

[Table 2]

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

[0133]

[Table 3]

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

Example 5 (1) Preparation of Emulsion An aqueous solution containing gelatin having an average molecular weight of 15,000 (water 12
00 ml, gelatin 7.0 g, KBr 4.5 g)
While maintaining the temperature at 0 ° C. and stirring, 1.9 MAgNO ₃ aqueous solution and 1.
A 9M KBr aqueous solution was added by a double jet method at 25 ml / min for 70 seconds to obtain nuclei of tabular grains. 400 ml of this emulsion was used as a seed crystal, and an inert gelatin aqueous solution 6
50 ml (containing 20 g of gelatin and 1.2 g of KBr) was added, the temperature was raised to 75 ° C., and the mixture was aged for 40 minutes. And AgNO ₃
An aqueous solution (containing 1.7 g of AgNO ₃ ) was added over 1 minute and 30 seconds, followed by 7.0 ml of an aqueous solution of NH ₄ NO ₃ (50 wt%) and NH
₃ (25 wt%) was added, and the mixture was aged for 40 minutes.

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

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

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

(2) Preparation of Coated Samples Emulsion layers and protective layers as shown in Table 4 were applied to a triacetyl cellulose film support provided with an undercoat layer to prepare Samples 201 to 212.

[0140]

[Table 4]

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

Processing method Step Processing time Processing temperature Supplementary capacity Tank capacity Color development 2 minutes 45 seconds 38 ° C 33ml 20 liter Bleaching 6 minutes 30 seconds 38 ° C 25ml 40 liter Rinse 2 minutes 10 seconds 24 ° C 1200ml 20 liters 4 minutes 20 seconds 38 ° C 25ml 30 liters Rinse with water (1) 1 minute 05 seconds 24 ° C 10 liters of counter-current piping from (2) to (1) Rinse with water (2) 1 minute 00 seconds 24 ° C 1200ml 10 liters Stable 1 Minutes 05 seconds 38 ° C 25ml 10 liters Drying 4 minutes 20 seconds 55 ° C Replenishment amount per 35mm width 1m length Next, the composition of the processing solution is described. (Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg -Hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 5.5 Add water 1.0 liter 1.0 liter pH 10.05 10.05 (bleach solution) Mother liquor (g) ) Replenisher (g) Sodium ferric ethylenediaminetetraacetate trihydrate 100.0 120.0 Disodium ethylenediaminetetraacetate 10.0 11.0 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5 ml 4.0 ml Add water and 1.0 liter 1.0 liter pH 6.0 5.7 (Fixer) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetate Calcium salt 0.5 0.7 Sodium sulfite 7.0 8.8 Sodium bisulfite 5.0 5.5 Ammonium thiosulfate aqueous solution (70%) 170.0 ml 200.0 ml Add water 1.0 liter 1.0 liter pH 6.7 6.6 (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 concentration of the treated sample was measured with a green filter. The sensitivity was defined as the reciprocal of the exposure amount giving a density 0.2 higher than the fog density, and the sensitivity of each sample was represented by a relative value with the value of sample 201 being 100. The emulsion and methine compound species used for each sample and the results of the sensitivity of each sample are shown in Table 5 below.
Shown in

[0144]

[Table 5]

Table 5 shows that the sample of the present invention has higher sensitivity than the comparative sample.

[0146]

According to the present invention, there is provided a novel compound effective for improving the residual color of a silver halide light-sensitive material and increasing the sensitivity.

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

[Procedure amendment]

[Submission date] April 27, 1999 (1999.4.2
7)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0063

[Correction method] Change

[Correction contents]

Although any methine dye can be formed by Q ₁ , preferred examples include a cyanine dye, a merocyanine dye, a rhodocyanine dye, a trinuclear merocyanine dye, an allopolar dye, a hemicyanine dye, and a styryl dye. For more information on these dyes, see
Heterocyclic Compounds-Cyanin, by FM Harmer, Heterocyclic Compounds-Related Compounds.
e Dyes and Related Compounds), John Wiley & Sons, New York, London, 1964, D.M.
(DMSturmer), Heterocyclic Compounds-Special Topics in Heterocyclic Compounds-Special Top
ics in Heterocyclic Chemistry) ", Chapter 18, Chapter 14
Verses 482-515, John Willie and
John Wiley & Sons, Inc.-New York, London, 1977, and the like. The general formula of a cyanine dye, a merocyanine dye, and rhodacyanine dye is
U.S. Pat. No. 5,340,694, pages 21 and 22, (X
Those shown in (I), (XII) and (XIII) are preferred.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0064

[Correction method] Change

[Correction contents]

In the general formula (III), when a cyanine dye is formed by Q ₁ , it can be represented by the following resonance formula.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0066

[Correction method] Change

[Correction contents]

The number of methine groups in Q ₁ is preferably 0 to 7, more preferably 0 to 5, and particularly preferably 3
It is. Here, the number of methine groups is 0 if Q ₁ forms the above-mentioned dye (cyanine dye, merocyanine dye, rhodacyanine dye, trinuclear merocyanine dye, allopolar dye, hemicyanine dye, styryl dye, etc.). (For example, simple merocyanine). The methine group is preferably substituted by a substituent (heterocyclic group, aliphatic group, or aromatic group) necessary for forming a methine dye, and a preferable substituent is a heterocyclic group or an aromatic group. And particularly preferably a heterocyclic group. Those as the heterocyclic groups listed as examples of Z ₁ described above is preferred. Examples of the aromatic group include a substituted or unsubstituted aromatic group (for example, a 4-dimethylaminophenyl group, a 4-methoxyphenyl group, a phenyl group, and a 4-dimethylaminonaphthyl group). As the aliphatic group, an alkoxycarbonyl group (for example, an ethoxycarbonyl group) and an acyl group (for example, an acetyl group) are preferable.
Other examples include the substituents represented by V described above.
For example, a substituted or unsubstituted amino group (eg, amino group, dimethylamino group), cyano group, alkoxycarbonyl group (eg, ethoxycarbonyl), substituted or unsubstituted alkylsulfonyl group (eg, methylsulfonyl group), substituted or unsubstituted Substituted acyl group (eg acetyl group)
Is preferred.

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Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C07D 487/04 139 C07D 487/04 139 144 144 487/14 487/14 491/048 491/048 491/052 491/052 491/056 491/056 495/04 103 495/04 103 498/04 101 498/04 101 103 103 103 513/04 301 513/04 301 325 325 351 351 519 519 519/00 519/00 311 311 G03C 1/12 G03C 1 / 12

Claims (10)

[Claims] 1. A compound represented by the following general formula (I). General formula (I) In the general formula (I), Z ₁ represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. Z ₂ represents an atom group necessary for forming a 5- or 6-membered heterocyclic ring by condensing with a benzene ring. The heterocyclic ring formed by Z ₂ may be condensed at any position on the benzene ring. Z ₂ may be further substituted or a heterocyclic ring or a benzene ring may be condensed. R ₁ represents a hydrogen atom, a halogen atom, a mercapto group, an alkyl group, an alkenyl group, an aryl group, an alkylthio group, an alkenylthio group, or an arylthio group. L ₁ and L ₂ each represent a methine group. p ₁
Represents 0 or 1. V ₁ represents a substituent, n is 0,
Represents 1 or 2. 2. A compound represented by the following general formula (II). General formula (II) In the general formula (II), Z ₁ , Z ₂ , R ₁ , L ₁ , L ₂ ,
p ₁ , V ₁ , and n have the same meanings as those described in the description of the general formula (I). R ₂ represents an alkyl group or an aryl group. M
₁ represents a charge balancing counter ion, and m ₁ represents a number from 0 to 10 required to neutralize the charge of the molecule. 3. A compound represented by the following general formula (III). General formula (III) In the general formula (III), Z ₁ , Z ₂ , L ₁ , L ₂ , p ₁ ,
R ₂ , M ₁ , and m ₁ have the same meanings as those described in the description of formulas (I) and (II). Q ₁ represents a methine group or a polymethine group necessary for forming a methine dye. 4. The method according to claim 1, wherein Z ₂ in the general formula (I) represents a furan ring, a thiophene ring or a pyrrole ring.
A compound as described. 5. The method according to claim ₂ , wherein Z ₂ in the general formula (II) represents a furan ring, a thiophene ring or a pyrrole ring.
A compound as described. 6. The compound according to claim 3, wherein Z ₂ in the general formula (III) represents a furan ring, a thiophene ring or a pyrrole ring.
A compound as described. 7. The compound represented by the general formula (I) is
Represented by the general formula (IV) or (V)
The compound according to claim 1. General formula (IV)In the general formula (IV), Z_FourIs an oxygen or sulfur atom
And Z _ThreeIs a 5- or 6-membered nitrogen-containing compound
Represents the group of atoms necessary to form a ring. V _Two,as well as
V_ThreeEach represents a substituent or a benzene ring
V such as heterocycle_Two, V_ThreeTo form a fused ring containing
May be. R₁, L₁, L_Two, P₁, V₁, N is general
It has the same meaning as described in the description of formula (I). General formula (V)In the general formula (V), Z₆Is NR_ThreeAnd Z_FiveIs
Necessary to form a 5- or 6-membered nitrogen-containing heterocycle
It is an atomic group, and represents an atomic group that does not contain a sulfur atom. However
Then R_ThreeRepresents a hydrogen atom or a substituent. R₁, L₁, L
_Two, P₁, V₁, N are those described in the description of the general formula (I)
Is synonymous with V_Two, And V_ThreeIs the description of general formula (IV)
It is synonymous with what was stated. 8. The compound according to claim 2, wherein the compound represented by the general formula (II) is represented by the following general formula (VI) or (VII). General formula (VI) In the general formula (VI), Z ₄ and Z ₃ have the same meanings as those described in the description of the general formula (IV), and R ₁ , L ₁ , L ₂ , p ₁ ,
R ₂ , M ₁ and m ₁ , V ₁ and n are represented by the general formulas (I) and (I
This is the same as that described in the explanation of I). V ₂ and V ₃ have the same meanings as those described in the description of formula (IV). General formula (VII) In the general formula (VII), Z ₆ and Z ₅ have the same meanings as those described in the description of the general formula (V), and R ₁ , L ₁ , L ₂ , p ₁ ,
R ₂ , M ₁ , V ₁ , n and m ₁ are represented by the general formulas (I) and (I
This is the same as that described in the explanation of I). V ₂ and V ₃ have the same meanings as those described in the description of formula (IV). 9. The compound according to claim 3, wherein the compound represented by the general formula (III) is represented by the following general formula (VIII) or (IX). General formula (VIII) In the general formula (VIII), Z ₄ and Z ₃ have the same meanings as those described in the description of the general formula (IV), and L ₁ , L ₂ , p ₁ , R ₂ , M
₁ , V ₁ , n and m ₁ have the same meanings as those described in the description of the general formulas (I) and (II). V ₂ and V ₃ have the same meanings as described in the description of the general formula (IV), and Q ₁ has the same meaning as described in the description of the general formula (III). General formula (IX) In the general formula (IX), Z ₆ and Z ₅ have the same meanings as those described in the description of the general formula (V), and L ₁ , L ₂ , p ₁ , R ₂ ,
M ₁ , V ₁ , n and m ₁ have the same meanings as those described in the description of the general formulas (I) and (II). V ₂ and V ₃ have the same meanings as described in the description of the general formula (IV), and Q ₁ has the same meaning as described in the description of the general formula (III). 10. The general formula (I) according to claims 1 to 9
A silver halide photographic material containing at least one compound represented by (IX).