JP2000080297A - New compound and silver halide photosensitive material containing the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound capable of providing a silver halide photosensitive material having high sensitivity and small remaining color. SOLUTION: This new compound is a compound of formula I [Z1 is an atomic group required for forming a 5- or 6-membered nitrogen-containing heterocycle; R1 is an alkyl, an aryl or a heterocycle; L1 and L2 are each methine; (p1) is 0 or 1; M1 is a valence-balanced paired ion; (m1) is a number required for neutralizing the electric charge of the molecule; A is an atomic group required for forming a nitrogen-containing heterocycle, with the proviso that a thiazoline nuclear is omitted], e.g. a compound of formula II. The compound of formula I is synthesized by starting from the reaction of a compound of formula III with a compound of formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel compound and a silver halide photographic material containing the novel compound. More specifically, the present invention relates to a silver halide photographic material having high sensitivity and little residual color.

[0002]

2. Description of the Related Art Hitherto, great efforts have been made to increase the sensitivity of silver halide photographic light-sensitive materials and to reduce residual coloring (residual color) after processing. It is known that sensitizing dyes used for spectral sensitization greatly affect the performance of silver halide photographic materials. In sensitizing dyes, slight differences in structure greatly affect photographic performance such as sensitivity, fogging, storage stability, and residual color.However, it is difficult to predict the effects in advance. Many researchers have tried to synthesize a number of sensitizing dyes and examine their photographic performance.

Also, high aspect ratio tabular silver halide grains (hereinafter referred to as tabular grains) disclosed in US Pat. No. 5,494,789 have a large surface area to volume ratio as photographic characteristics. A large amount of sensitizing dye can be adsorbed on the surface. As a result, higher color sensitization sensitivity can be obtained.

The term “aspect ratio” as used herein indicates the ratio of the diameter to the thickness of tabular grains. The diameter of a tabular grain refers to the diameter of a circle having an area equal to the projected area of the grain when the emulsion is observed with a microscope or an electron microscope. The thickness is indicated by the distance between two parallel planes constituting a tabular grain.

[0005] As described above, tabular grains are advantageous for obtaining high color sensitization sensitivity. However, on the other hand, there is a problem that a large amount of the sensitizing dye is adsorbed, so that the residual color after the treatment is increased.

For the above reasons, sensitizing dyes having high sensitivity and little residual color have been demanded.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel compound and to provide a silver halide light-sensitive material containing the novel compound with high sensitivity and little residual color.

[0008]

Means for Solving the Problems The object of the present invention has been achieved by the following (1) to (5) as a result of intensive studies. (1) A silver halide photographic material comprising at least one compound represented by the following general formula (I). General formula (I)

[0009]

Embedded image

In the formula (I), Z ₁ represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. However, these may be fused with an aromatic ring. R ₁ represents an alkyl group, an aryl group, or a heterocyclic group. L ₁ and L ₂ represent a methine group. p ₁ represents 0 or 1. M ₁ represents a charge balancing counter ion, and m ₁ represents a number required to neutralize the charge of the molecule. Q represents a group necessary for forming a methine dye. A ₁ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. However, thiazoline nuclei are excluded. (2) (1)
A silver halide photographic light-sensitive material, wherein the compound represented by the general formula (I) is selected from the compounds represented by the following general formula (II). General formula (II)

[0011]

Embedded image

In the formula (II), Z ₂ represents an oxygen atom, a sulfur atom,
Represents a selenium atom, tellurium atom, carbon atom or nitrogen atom. R ₁ , Q, M ₁ , m ₁ and A ₁ have the same meanings as in formula (I). (3) A silver halide photographic material, wherein the compound of the general formula (I) described in (1) is selected from the compounds represented by the following general formula (III). General formula (III)

[0013]

Embedded image

In the formula (III), A ₂ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. Z ₁ , R ₁ , Q, L ₁ , L
₂ , M ₁ , m ₁ and A ₁ have the same meanings as in formula (I). (4) The general formula (I) described in (1), (2), (3),
At least one of the compounds represented by (II) and (III)
And the silver halide grains forming the emulsion layer containing the compound have an average aspect ratio of 3 or more and 1000 or more.
A silver halide photographic material characterized by the following. (5) A compound represented by the general formula (I) described in (1).

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds of the general formulas (I), (II) and (III) used in the present invention will be described below in detail. Although any methine dye can be formed by Q, preferred examples include a cyanine dye, a merocyanine dye, a rhodocyanine dye, a trinuclear merocyanine dye, an allopolar dye, a hemicyanine dye, and a styryl dye. For more information on these dyes, see FM Harmer, Heterocyclic Compounds-Cyanine Dyes and Reynolded Compounds.
Related Compounds), John Willie and
John Wiley & Sons, New York, London, 1964, DMSturm
er), Heterocyclic Compounds-Special topics in hetecyclic chemistry.
rocyclic chemistry) ", Chapter 18, Section 14, Chapter 48
It is described on pages 2 to 515 and the like. Cyanine dye,
The general formulas of merocyanine dyes and rhodocyanine dyes are described in U.S. Pat. No. 5,340,694, p.
Those shown in (XII) and (XIII) are preferred. In the general formula (I) and the like, when a cyanine dye is formed by Q, it can be represented by the following resonance formula.

[0016]

Embedded image

In the general formulas (I) and (III), as the 5- or 6-membered nitrogen-containing heterocyclic ring formed by Z ₁ , an aromatic ring may be condensed. The aromatic ring may be a benzene ring, a naphthalene ring or the like, or a heteroaromatic ring such as a pyrazine ring or a thiophene ring.

The nitrogen-containing heterocycle is preferably a 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-dimethylindolenine), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, -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.

More preferably, a benzoxazole nucleus,
A benzothiazole nucleus, a benzimidazole nucleus and a quinoline nucleus, more preferably a benzoxazole nucleus and a benzothiazole nucleus. Particularly preferred is a benzothiazole nucleus.

The substituent on Z ₁ may have a substituent in addition to the cyclic amide group characteristic of the present invention.
There are no particular restrictions on the substituent represented by V. For example, a halogen atom (eg, chlorine, bromine, iodine,
Fluorine), mercapto group, cyano group, carboxyl group,
Phosphoric acid group, sulfo group, hydroxy group, carbon number 1 to 1
0, preferably a carbamoyl group having 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms (eg, methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl), 0 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably A sulfamoyl group having 2 to 5 carbon atoms (eg, methylsulfamoyl, ethylsulfamoyl, piperidinosulfonyl), a nitro group, 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms 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), an ammonium group having 0 to 15 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms (for example, trimethylammonium group, triethylammonium group);
A hydrazino group having 0 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (for example, trimethylhydrazino group), 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms
(E.g., ureido group, N, N-dimethylureido group), an imide group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (e.g., succinimide group), An alkyl or arylthio group having 1 to 20, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (eg, methylthio, ethylthio, carboxyethylthio, sulfobutylthio, phenylthio, etc.), 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms
An alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl) having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms;
More preferably, an aryloxycarbonyl group having 6 to 8 carbon atoms (for example, phenoxycarbonyl),

An unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methyl, ethyl, propyl, butyl), and 1 to 18 carbon atoms, preferably 1 to 1 carbon atoms
0, more preferably a substituted alkyl group having 1 to 5 carbon atoms (hydroxymethyl, trifluoromethyl, benzyl,
Carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl, and here, preferably, an unsaturated hydrocarbon group having 2 to 18 carbon atoms, more preferably 3 to 10 carbon atoms, and particularly preferably 3 to 5 carbon atoms (for example, vinyl group Ethynyl group, 1-cyclohexenyl group, benzylidine group, benzylidene group) are also included in the substituted alkyl group. ), A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg, phenyl, naphthyl, p-carboxyphenyl, p-nitrophenyl,
3,5-dichlorophenyl, p-cyanophenyl, m-
Fluorophenyl, p-tolyl),

An optionally substituted heterocyclic group having 1 to 20, 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, 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 are the above-mentioned alkyl group, aryl group, alkoxy group, halogen atom, acyl group, cyano group, sulfonyl group and benzene ring condensation, more preferably alkyl group, aryl group. Groups, a halogen atom, an acyl group, a sulfonyl group, and a benzene ring condensation, and particularly preferably a methyl group, a phenyl group, a methoxy group, a chlorine atom, a bromine atom, an iodine atom, and a benzene ring condensation. Most preferably, a phenyl group,
They are chlorine atom, bromine atom and iodine atom.

The methine groups represented by L ₁ and L ₂ may have a substituent, and examples of the substituent include the substituents represented by V described above. Preferably it is an unsubstituted methine group.
p ₁ is 0 or 1, preferably 0.

In the general formulas (I), (II) and (III),
R ₁ represents an alkyl group, an aryl group, or a heterocyclic group, for example, an unsubstituted alkyl group having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms (eg, methyl, ethyl, propyl) Isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms, such as the alkyl groups substituted by V described above. Can be 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), an alkoxyalkyl group (eg, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), an aryloxyalkyl group (eg, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl), Alkoxycarbonylalkyl group (for example, ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl), aryloxycarbonylalkyl group (for example, 3-phenoxycarbonylpropyl), acyloxyalkyl group (for example, 2-acetyloxyethyl), acylalkyl group (for example, 2 -Acetylethyl), a carbamoylalkyl group (eg, 2-morpholinocarbonylethyl), a sulfamoylalkyl group (eg, N, N-dimethylcarbamoylmethyl), a sulfoalkyl group (eg, 2-sulfoethyl) , 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-
Sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl),
Sulfoalkenyl group, sulfatoalkyl group (for example,
2-sulfatoethyl group, 3-sulfatopropyl, 4
-Sulfatobutyl), a heterocyclic-substituted alkyl group (eg, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl), an alkylsulfonylcarbamoylalkyl group (eg, methanesulfonylcarbamoylmethyl group), an acylcarbamoylalkyl A group (eg, acetylcarbamoylmethyl group), an acylsulfamoylalkyl group (eg, acetylsulfamoylmethyl group),
Alkylsulfonylsulfamoylalkyl group (eg, methanesulfonylsulfamoylmethyl group)}, an unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and more preferably 6 to 8 carbon atoms (eg, a phenyl group) , 1-naphthyl group), having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and more preferably 6 carbon atoms.
To 8 substituted aryl groups (for example, the aforementioned aryl groups substituted with V. Specific examples include a p-methoxyphenyl group, a p-methylphenyl group, and a p-chlorophenyl group), and a carbon number of 1 To 20, preferably 3 to 10, more preferably 4 to 8 unsubstituted heterocyclic groups (eg, 2-furyl, 2-thienyl,
2-pyridyl group, 3-pyrazolyl, 3-isoxazolyl, 3-isothiazolyl, 2-imidazolyl, 2-oxazolyl, 2-thiazolyl, 2-pyridazyl, 2-pyrimidyl, 3-pyrazyl, 2- (1,3,5- Triazolyl),
3- (1,2,4-triazolyl), 5-tetrazolyl), a substituted heterocyclic group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms (for example, when the aforementioned V is Specific examples include a substituted heterocyclic group.
Examples thereof include a methyl-2-thienyl group and a 4-methoxy-2-pyridyl group. ).

R ₁ is preferably an alkyl group,
More preferred are the above-mentioned carboxyalkyl groups, sulfoalkyl groups, and alkylsulfonylcarbamoylalkyl groups, and particularly preferred are the alkylsulfonylcarbamoylalkyl groups.

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 dye. Typical cations include hydrogen ions (H ⁺ ), inorganic cations such as alkali metal ions (eg, sodium ion, potassium ion, lithium ion), alkaline earth metal ions (eg, calcium ion), and ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, pyridinium ion, and ethylpyridinium ion. The anion may be either an inorganic anion or an organic anion,
Halogen anions (for example, fluorine ions, chlorine ions,
Iodine ion), substituted arylsulfonate ion (eg, p-toluenesulfonic acid ion, p-chlorobenzenesulfonic acid ion), aryldisulfonic acid ion (eg, 1,3-benzenesulfonic acid ion, 1,5-naphthalenedisulfonic acid) Acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethane Sulfonate ions. Further, another dye having a charge opposite to that of the ionic polymer or the dye may be used. CO ₂
^-, SO ₃ ^-, when having a hydrogen ion as a counter ion can be indicated CO ₂ H, and SO ₃ H. m
₁ represents the number required to balance the charges and is 0 when a salt is formed in the molecule.

In the general formula (II), Z ₂ is an oxygen atom,
Represents a sulfur atom, a selenium atom, a tellurium atom, a carbon atom, or a nitrogen atom. In the case of a carbon atom or a nitrogen atom, the same alkyl group, aryl group or heterocyclic group as R ₁ may be substituted. Z ₂ is preferably an oxygen atom or a sulfur atom, and more preferably a sulfur atom.

A ₁ and A ₂ form a nitrogen-containing heterocyclic ring, preferably a 5-, 6-, 7- or 8-membered ring, and more preferably a 5- or 6-membered ring. And particularly preferably a case where a 5-membered ring is formed. However, A ₁ does not form a thiazoline ring as described below. These compounds having a thiazoline ring are not preferred because residual color deteriorates.

[0032]

Embedded image

The divalent linking group represented by A ₁ and A ₂ will be described. 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), arylene group (eg, phenylene, naphthylene), alkenylene group (eg, ethenylene, propenylene), alkynylene group (eg, ethinylene, propynylene), amide group, ester group,
Sulfoamide group, sulfonic ester group, ureido group,
Sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -N (Ra)-(Ra represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group.), Heterocycle 2 One or more valence groups (eg, 6-chloro-1,3,5-triazine-2,4-diyl group, pyrimidine-2,4-diyl group, quinoxaline-2,3-diyl group) It represents a divalent linking group having 1 to 20 carbon atoms. The divalent linking group may further have a substituent represented by V described above. Among the above divalent linking groups, the case where no arylene group is contained is preferred. Further, it is preferable that the aryl group is not contained as a substituent. These arylene groups,
When an aryl substituent is contained, it is not preferable because the residual color deteriorates.

More preferably, an alkylene group having 1 to 6 carbon atoms which may be substituted by a substituent V (for example, methylene, ethylene, trimethylene, tetramethylene);
Alkenylene groups having 1 to 6 carbon atoms (eg, propenylene, butynyleneylene), alkynylene groups having 1 to 6 carbon atoms (eg, propynylene, butynylene), or 1 carbon atom in which one carbon atom is replaced by an oxygen atom It is a divalent linking group of 6 or more and 6 or less. Particularly preferably, it is an alkylene group having 1 to 6 carbon atoms which may be substituted by the substituent V or a divalent linking group in which one carbon atom is replaced by an oxygen atom.

The most preferred examples of the heterocyclic ring formed by A ₁ and A ₂ are shown below.

[0036]

Embedded image

A ₂₁ , A ₂₂ , A ₂₃ and A ₂₄ are preferred, and A ₂₁ is most preferred. In the general formula (II), the following are preferred.

[0038]

Embedded image

The case where the compound represented by the general formula (I) is a compound selected from the following general formulas (IV), (V) and (VI). General formula (IV)

[0040]

Embedded image

In the formula (IV), L ₁₁ , L ₁₂ , L ₁₃ , L ₁₄ , L
₁₅ , L ₁₆ and L ₁₇ represent a methine group. p ₁₁ and p ₁₂ represent 0 or 1. n ₁₁ represents 0, 1, 2, or 3. Z
₁₁ and Z ₁₂ represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. However, these may be fused with an aromatic ring. M ₁₁ represents a charge balancing counter ion;
₁₁ represents a number of 0 or more and 4 or less necessary for neutralizing the electric charge of the molecule. R ₁₁ and R ₁₂ represent an alkyl group, an aryl group, or a heterocyclic group. However, it is represented by a nitrogen-containing heterocyclic moiety (* 1) formed by Z ₁₁ or the like substituted with R ₁₁ or a nitrogen-containing heterocyclic moiety (* 2) formed by Z ₁₂ or the like substituted by R _12. And one of them is the same as the heterocyclic ring (* 3) represented by the portion of the general formula (I) except for = Q.

[0042]

Embedded image

General formula (V)

[0044]

Embedded image

In the formula (V), Z ₁ , R ₁ , L ₁ , L ₂ , P
₁ and A ₁ have the same meanings as in formula (I). L ₂₀ and L ₂₁
Represents a methine group. n ₁₂ represents 0, 1, 2, or 3.
M ₁₂ represents a charge-balancing counter ion, and m ₁₂ represents a number from 0 to 4 required to neutralize the charge of the molecule. R ₁₄ represents an alkyl group, an aryl group, or a heterocyclic group. General formula (VI)

[0046]

Embedded image

In the formula (VI), L ₂₂ , L ₂₃ , L ₂₄ , L ₂₅ , L
₂₆ , L ₂₇ , L ₂₈ , L ₂₉ and L ₃₀ represent a methine group. p ₁₄
And p ₁₅ represents 0 or 1. n ₁₃ and n ₁₄ are 0, 1,
Represents 2 or 3. Z ₁₅ , Z ₁₆ and Z ₁₇ each represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. However, an aromatic ring may be condensed on Z ₁₅ and Z ₁₇ .
M ₁₃ represents a charge-balancing counter ion, and m ₁₃ represents a number from 0 to 4 required to neutralize the charge of the molecule. R ₁₅ ,
R ₁₆ and R ₁₇ represent an alkyl group, an aryl group, or a heterocyclic group. However, among the nitrogen-containing heterocyclic moiety (* 4) formed by Z ₁₅ or the like substituted with R ₁₅ or the nitrogen-containing heterocyclic moiety (* 5) formed by Z ₁₇ or the like substituted by R ₁₇ Either one is the same as the heterocycle (* 3) represented by the portion of the general formula (I) except for = Q.

[0048]

Embedded image

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

In the general formulas (IV), (V), and (VI)), the 5- or 6-membered nitrogen-containing heterocyclic ring represented by Z ₁₁ , Z ₁₂ , Z ₁₅ , and Z ₁₇ is aromatic. The ring may be condensed.
Examples of the aromatic ring include a benzene ring and a naphthalene ring,
It may be a heteroaromatic ring such as a pyrazine ring or a thiophene ring. Specifically, the heterocyclic ring mentioned as an example of Z ₁ is preferable.

R ₁₁ , R ₁₂ , R ₁₄ , R ₁₅ , R ₁₆ , and R
₁₇ represents an alkyl group, an aryl group, and a heterocyclic group, respectively, and the groups exemplified as R ₁ are preferable.

Z ₁₄ represents a group of atoms necessary for forming an acidic nucleus, and can take the form of an acidic nucleus of any general merocyanine dye. The acidic nucleus referred to here is, for example, “The Theory of Japan” edited by James.
The Photographic Process "(The The
ory of the Photographic Pr
ocess) 4th edition, Macmillan Publishing Co., 1977,
198 pages. Specifically, U.S. Patent Nos. 3,567,719, 3,575,869, 3,804,634, 3,837,862, 4,002,480, 4, 925,777 and JP-A-3-167546. Preferred when the acidic nucleus forms a 5- or 6-membered nitrogen-containing heterocycle consisting of carbon, nitrogen and chalcogen (typically oxygen, sulfur, selenium and tellurium) atoms,
The following nuclei include: 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazolin-5-one,
Hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidin-4-one, 2-oxazoline-5
-One, 2-thiooxazoline-2,4-dione, isoxazolin-5-one, 2-thiazolin-4-one,
Thiazolidine-4-one, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indane-1,3-dione, thiophen-3-one, thiophen-3-one-1,1- Dioxide, indoline-2-one, indoline-3-one, 2
-Oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo-6,7-dihydrothiazolo [3,
2-a] pyrimidine, cyclohexane-1,3-dione,
3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, chroman-2,4-dione, indazolin-2-one, pyrido [ 1,2-a] pyrimidine-
1,3-dione, pyrazolo [1,5-b] quinazolone,
Pyrazolo [1,5-a] benzimidazole, pyrazolopyridone, 1,2,3,4-tetrahydroquinoline-
2,4-dione, 3-oxo-2,3-dihydrobenzo [d] thiophene-1,1-dioxide, 3-dicyanomethine-2,3-dihydrobenzo [d] thiophene-
The core of 1,1-dioxide.

[0053] Preferably hydantoin as Z _14, 2 or 4-thiohydantoin, 2-oxazolin-5-one, 2-thio-oxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine -
2,4-dithione, barbituric acid and 2-thiobarbituric acid, more preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, rhodanine, barbituric acid, 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 _{16 is obtained} by removing an oxo group or a thioxo group from the heterocyclic ring represented by Z ₁₄ . Preferably, hydantoin, 2 or 4-thiohydantoin, 2-oxazolin-5-one, 2-thiooxazoline-2,4-
Dione, thiazolidine-2,4-dione, rhodanine,
Thiazolidine-2,4-dithione, barbituric acid, 2
-Thiobarbituric acid is obtained by removing an oxo group or a thioxo group, more preferably hydantoin,
2 or 4-thiohydantoin, 2-oxazoline-5
-One, rhodanine, barbituric acid, 2-thiobarbituric acid from which an oxo group or a thioxo group has been removed, particularly preferably 2 or 4-thiohydantoin;
It is obtained by removing an oxo group or a thioxo group from 2-oxazolin-5-one or rhodanine.

L₁₁, L₁₂, L₁₃, L₁₄, L_Fifteen, L₁₆, L
₁₇, L₂₀, L_{twenty one}, L_{twenty two}, L_{twenty three}, L_{twenty four}, L_{twenty five}, L₂₆,
L₂₇, L₂₈, L₂₉And L₃₀Each independently represents a methine group
Represent. L ₁₁~ L₃₀The methine group represented by has a substituent
May be substituted, for example, substituted or unsubstituted
Having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms.
More preferably, an alkyl group having 1 to 5 carbon atoms (for example,
Tyl, ethyl, 2-carboxyethyl), substituted or
Unsubstituted C6 to C20, preferably C6 to C1
5, more preferably an aryl group having 6 to 10 carbon atoms
(Eg phenyl, o-carboxyphenyl), also substituted
Or unsubstituted C3 to C20, preferably C4
To 15, more preferably a heterocyclic ring having 6 to 10 carbon atoms
Groups (eg, N, N-, diethylbarbituric acid groups), c
Rogen atoms (eg chlorine, bromine, fluorine, iodine), carbon
1 to 15, preferably 1 to 10 carbon atoms, more preferably
Preferably, it is an alkoxy group having 1 to 5 carbon atoms (for example, methoxy
Ethoxy), having 1 to 15 carbon atoms, preferably having 1 to 15 carbon atoms
Alkyl having 1 to 10, more preferably 1 to 5 carbon atoms
Luthio group (eg, methylthio, ethylthio), carbon number 6
To 20, preferably 6 to 15 carbon atoms, more preferably
Or an arylthio group having 6 to 10 carbon atoms (for example, phenyl
Ruthio), having from 0 to 15 carbon atoms, preferably from 2 carbon atoms
10, more preferably an amino group having 4 to 10 carbon atoms
(For example, N, N-diphenylamino, N-methyl-N
-Phenylamino, N-methylpiperazino) and the like
Can be It may also form a ring with other methine groups,
I'm Z₁₁, Z₁₂, Z_Fifteen, Z₁₆Can form a ring with
it can.

N ₁₁ , n ₁₂ and n ₁₃ are preferably 0,
1, 2, more preferably 0, 1 and particularly preferably 1. n ₁₄ is preferably 0 or 1, and more preferably 0. n ₁₁ , ₁₂ , ₁₃ , ₁₄ are 2
At this point, the methine group is repeated but need not be the same.

M ₁₁ , M ₁₂ , M ₁₃ , m ₁₁ , m ₁₂ , and m ₁₃ have the same meanings as M ₁ , m ₁ and are preferably the same.

P ₁₁ , p ₁₂ , p ₁₄ and p ₁₅ each independently represent 0 or 1. Preferably it is 0.

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

[0060]

Embedded image

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

The general formula (I) of the present invention (general formula (I)
The general concepts (II), (III), (IV), (V),
(VI) (including Heterocyclic Compounds-Cyanine Dyes and Relat Compounds) by FM Harmer.
ed Compounds) ", John Willie and Sons
(John Wiley & Sons)-New York, London, 1
964, DMSturmer, Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry (H
eterocyclic Compounds-Special topics inheterocycli
c chemistry), Chapter 18, Section 14, 482 to 5
Page 15, John Wile and Sons
y & Sons)-New York, London, 1977, `` Rodd's Chemistry of Carbon Compounds '' 2nd.
Ed.vol.IV, partB, 1977, Chapter 15, Chapters 369-422, Elsevier Science Publishing Company, Inc.
Inc.), New York, and the like.

The compounds represented by formulas (I) to (VI) (hereinafter referred to as the compounds of the present invention) of the present invention may be used alone or in combination with other spectral sensitizing dyes. .

Next, the silver halide photographic material of the present invention will be described in detail.

The timing 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 at any stage of 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, 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 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 and the combination of the compounds may be changed and added.

The 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 the 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 this 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. As described in JP-B-46-24185, and a method of dispersing in a water-soluble solvent and adding this dispersion to the emulsion, described in U.S. Pat. No. 3,822,135. A method of dissolving the compound in a surfactant and adding the solution to the emulsion, and dissolving using a compound that causes a red shift as described in JP-A-51-74624, and then adding the solution to the emulsion. For example, as described in JP-A-50-80826, a method of dissolving a compound in an acid substantially free of water and adding the solution to an emulsion is used. In addition, US Pat.
No. 2,343, No. 3,342,605, No. 2,99
Nos. 6,287, 3,429,835 and the like can also be used.

The compounds of the present invention can be used as various filter dyes, irradiation prevention dyes or antihalation dyes for the purpose of improving sharpness and color resolution. This compound is prepared by a conventional method using a silver halide photographic light-sensitive material layer, a filter layer and / or
Alternatively, it can be contained in a coating solution such as an antihalation layer. 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 appropriately 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 the interaction with the dye molecule. Examples of the polymer mordant include U.S. Pat. Nos. 2,548,564, 4,124,386, 3,625,694, 3,958,995, 4,168,976, and 3,445. , No. 231 and the like.

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 the method of 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 structure 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, 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, a plate, or the like, or may have a complex form of these crystal forms. It may consist of a mixture of particles of different crystal forms.

Preferred silver halide emulsions usable in the silver halide light-sensitive material of the present invention are tabular silver halide grains having a higher surface area / volume ratio to which a sensitizing dye disclosed in the present invention has been adsorbed. And the aspect ratio (equivalent circle diameter / grain thickness of silver halide grains) is 3 or more and 1000 or more.
In the following, the order is preferably from 8 to 1,000, from 8 to 100, from 15 to 80, and from 20 to 80. Here, the aspect ratio of 3 or more and 1000 or less means that the aspect ratio (equivalent circle diameter / grain thickness of silver halide grains).
Means that at least 50% of the projected area of all silver halide grains in the emulsion is present. Preferably, the emulsion is at least 70%, particularly preferably at least 85%. The thickness of the tabular grains is
It is less than 0.2 μm, preferably less than 0.1 μm, more preferably less than 0.07 μm. Tabular grains are written by Gaft, Photographic Science and Engineering (Gutoff, Photographic Science and Engine)
ering), Vol. 14, pp. 248-257 (1970); US 4,434,226
No. 4,414,310, 4,433,048, 4,439,520 and GB
It can be easily adjusted by the method described in 2,112,157.

The compounds of the present invention are used in photographic materials for the following applications 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 compounds of the present invention are 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, lith 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 for color diffusion transfer process, die transfer process (imhibition pro
cess), a photosensitive material for silver dye bleaching, 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, for example, ammonia, rodankari, rodanammon, thioether compounds (for example, 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).
Nos. 9, 53-82408 and 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 and the like may coexist. 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, see, for example, H. Frieser, “Die Grundlagen der Photographische”, edited by D. Grundlagen der Photographischen.
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, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketonization Azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; see 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 forming a 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 which releases a development inhibitor during development (a so-called DIR coupler) may be used. Also DI
In addition to the R coupler, the product of the coupling reaction may contain a colorless DIR coupling compound which is colorless and releases a development inhibitor.

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, and the like, US Pat. Nos. 2,533,472 and 3,37.
Other oxonol dyes described in JP-A No. 9,533, UK Patent No. 1,278,621, JP-A Nos. 1-134447 and 1-183652, and UK 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, and the like. Azomethine dyes described in US Pat. No. 2,865,598 and US Pat.
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. 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 using metal salt fine particles having a dye adsorbed thereon 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, improvement of slipperiness, emulsification / dispersion, prevention of adhesion, and improvement of photographic properties (eg, development acceleration, high contrast, sensitization). An active agent may be included. In practicing the present invention, other additives are used together with the silver halide emulsion or other hydrophilic colloid, for example, an anti-fading agent, an inorganic or organic hardening agent, an anti-fog agent,
UV absorbers, mordants, plasticizers, latex polymers,
Matting agents and the like can be mentioned. Specifically, Research Disclosure Vol.
176 (1978, XI), D-17643, and the like. In the photographic light-sensitive material used in the present invention, a hydrophilic polymer such as gelatin is used as a protective colloid. Finished silver halide emulsions, etc.
Coated on a suitable support such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, other plastic bases or glass plates.

Exposure for obtaining a photographic image may be performed by a usual method. That is, any of a variety of known light sources such as natural light (daylight), a tungsten lamp, a fluorescent lamp, a mercury lamp, a xenon arc lamp, a carbon arc lamp, a xenon flash lamp, and a 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 for 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. Alternatively, 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)
Any of the known methods and known processing solutions as described in 3) 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 "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 Publication 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 the camera described in JP-A-6-205690, which are capable of taking out and changing the type of film in the middle of photographing, JP-A-5-293138, 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-4-123504, either by processing with a self-developing 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 at the time of development processing, splicing is performed by 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.

[0092]

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 Emulsions 1, 2, and 3 were prepared by the following method. (1) Preparation of Emulsion 1 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 seed crystals, and 650 ml of an inert gelatin aqueous solution (containing 20 g of gelatin and 1.2 g of KBr) was added to the emulsion, and the temperature was raised to 75 ° C., followed by ripening for 40 minutes.
And AgNO ₃ aqueous solution (including 1.7 g of AgNO ₃ )
Is added over 1 minute and 30 seconds, followed by NH ₄ NO ₃ (5
(0 wt%) aqueous solution (7.0 ml) and NH ₃ (25 wt%).
0 ml was added and aged for an additional 40 minutes.

[0093] Then after adding KBr1.0g and to pH7 with HNO ₃ (3N) emulsion, the 1.9MAgNO ₃ solution 366.5ml of KBr aqueous solution, followed by 1.9MA
gNO ₃ aqueous solution (53.6 ml) and KBr (KI 33.3 mol)
An aqueous solution of 1.9 MAgNO ₃ and an aqueous solution of KBr were added while maintaining the pAg at 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 4.1 × 10 ⁻⁴ mol of sensitizing dye was added to 1 mol of silver, and sensitization of gold, sulfur and selenium was carried out in the presence of silver. Performed optimally.

(2) Preparation of Emulsion 2 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.
350 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 to the emulsion.
And AgNO ₃ aqueous solution (including 1.7 g of AgNO ₃ )
Is added over 1 minute and 30 seconds, followed by NH ₄ NO ₃ (5
(0 wt%) aqueous solution (6.2 ml) and NH ₃ (25 wt%).
2 ml was added and aged for an additional 40 minutes.

[0097] Then after adding KBr1.0g and to pH7 with HNO ₃ (3N) emulsion, the 1.9MAgNO ₃ solution 366.5ml of KBr aqueous solution, followed by 1.9MA
gNO ₃ aqueous solution (53.6 ml) and KBr (KI 33.3 mol)
An aqueous solution of 1.9 MAgNO ₃ and an aqueous solution of KBr were added while maintaining the pAg at 8.3 to obtain Emulsion 2.

Emulsion 2 obtained was a triple structure grain having a region having the highest silver iodide content in the intermediate shell, an average aspect ratio of 6.7, and a tabular grain having an aspect ratio of 6 or more. The ratio of the tabular grains having an aspect ratio of 3 or more and 100 or less to the total projected area was 80%, and the ratio of the tabular grains to the total projected area was 95%. 11% variation coefficient of particle size
The average particle size was 1.00 μm in sphere equivalent diameter.

Emulsion 2 was desalted by the usual flocculation method, and 5.4 × 10 ^-4 mol of a sensitizing dye was added to 1 mol of silver, and sensitization of gold, sulfur and selenium was carried out in the presence of silver. Performed optimally.

(3) Preparation of Emulsion 3 0.5 M silver nitrate of 0.5 M was stirred by double jet method with stirring into 1.5 liter of 0.8% low molecular weight (molecular weight 10,000) gelatin solution having 0.05 mol of potassium bromide. The solution and a 0.5 M potassium bromide solution are added in 15 cc for 15 seconds. During this time, the gelatin solution was kept at 40 ° C. At this time, the pH of the gelatin solution was 5.0. After addition, 75
The temperature was raised to ° C. After the addition of 220 cc of a 10% solution of trimellitated gelatin (95% trimellitization), the emulsion was ripened for 20 minutes. Thereafter, 80 cc of a 0.47 M silver nitrate solution was added. Further, after aging for 10 minutes, 150 g of silver nitrate for 60 minutes and a potassium bromide solution containing 5 mol% of potassium iodide to maintain pBr at 2.55 were accelerated (the flow at the end was (19 times the flow rate at the time) was added at 0 mV by the control double jet method. After completion of the addition, 30 cc of a 10% KI solution was added. Then, the pH of the emulsion was adjusted to 7.2 by adding 1N NaOH, and then 327 cc of a 0.5 M silver nitrate solution and 10 ⁻² M of yellow blood salt were added.
16.4 cc of the solution was added, and 327 cc of a 0.5 M potassium bromide solution was added by a control double jet method at a potential of 0 mV for 20 minutes. (Formation of shell) Thereafter, the emulsion was cooled to 35 ° C., washed with water by a usual flocculation method, and 80 g of deionized alkali-treated bone gelatin and 40 cc of 2% Zn (NO ₃ ) ₂ were added at 40 ° C. Dissolved, pH
Was adjusted to 6.5 and pAg to 8.6, and stored in a cool dark place.

The tabular grains have a projected area equivalent circle diameter (hereinafter referred to as circle equivalent diameter) variation coefficient of 15%, an equivalent circle diameter of 2.5 μm, and an average thickness of 0.10 μm (aspect ratio). Ratio 25), which was silver iodobromide containing 5.7 mol% of silver iodide.

Emulsion 3 was desalted by the usual flocculation method, and 9.3 × 10 ^-4 mol of sensitizing dye was added to 1 mol of silver, and sodium thiosulfate and potassium chloroaurate were added in the presence of silver. And potassium thiocyanate at 60 ° C. for optimal chemical sensitization.

(4) Preparation of Coated Sample An emulsion layer and a protective layer as shown in Table 1 were coated on a triacetyl cellulose film support provided with an undercoat layer to prepare a sample.

[0104]

[Table 1]

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

Processing method Step Processing time Processing temperature Compensation tank capacity Color development 2 minutes 45 seconds 38 ° C 33 ml 20 liter Bleaching 6 minutes 30 seconds 38 ° C 25 ml 40 liter Rinse 2 minutes 10 seconds 24 ° C 1200 ml 20 liter 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 per 35 mm width 1 m length Next, the composition of the processing solution is described. (Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg -Hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 5.5 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) Ethylenediaminetetraacetic acid sodium 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 salt of ethylenediaminetetraacetic acid 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 processed sample was measured with a green filter, and the fresh sensitivity and the residual color after the processing were evaluated. The sensitivity was defined as the reciprocal of the exposure amount giving a density 0.2 higher than the fog density. Further, the residual coloring (residual color) after the treatment was visually observed, and the evaluation was performed in the order of 、, △, Δ, and × in the order of least residual color. The emulsion and sensitizing dye used for each sample and the results of sensitivity and residual color of each sample are shown in Table 2 below.

[0108]

[Table 2]

[0109]

Embedded image

Table 2 shows that the compound of the present invention has higher sensitivity and less residual color than the comparative compound. Also,
It can be seen that the sensitivity is significantly improved when the aspect ratio of the emulsion is increased.

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 3. The multi-layer color photographic material was prepared in the same manner as in Sample 101 of Example 5 of JP-A-8-29904. Sample 1 of Example 5 of JP-A-8-29904
01 was replaced with Emulsion 3,
S-1, 2, and 3 are sensitizing dyes (SS-3) (5.0 × 10 ⁻⁴ )
mol / Agmol) or sensitizing dye (7) (5.0 × 10 ⁻⁴ mo
1 / Agmol), and these were designated as Sample 201 and Sample 202. To check the sensitivity of the sample thus obtained, Fuji FW
Exposure to 1/100 second exposure to light from a type sensitometer (Fuji Photo Film Co., Ltd.) through an optical wedge and a red filter. To measure the cyan density. The sensitivity was indicated by a relative value of fog density + 0.2. As a result, the sample 202 of the present invention had a high sensitivity of 115, compared to the sensitivity of the comparative sample 201 of 100 (reference). Also, the residual color after the treatment was small.

Example 3 Emulsion 1 of Example 1 of JP-A-7-92601 was prepared by changing the spectral sensitizing dye to sensitizing dye (SS-2) (8 × 10 ^-4 mol / Agmol) or sensitizing dye ( 13) A tetrahedral silver iodobromide emulsion was prepared, which was different only in that the emulsion was replaced with (8 × 10 ⁻⁴ mol / Agmol).
This was used as emulsions 301 and 302. Also, JP-A-7-
Emulsion 1 of Example 1 of No. 92601 differs from emulsion 1 of Example 1 in that the silver potential in the second double jet was changed from +65 mV to +115 mV and the spectral sensitizing dye was sensitizing dye (SS-2) (8 × 1
0 ^-4 mol / Agmol) or sensitizing dye (13) (8 × 10 ^-4
mol / Agmol), and these emulsions were designated as emulsions 303 and 304. The multilayer color photosensitive material is described in Example 4 of JP-A-7-92601.
Was prepared in the same manner according to Sample 401. Emulsion 1 of the ninth layer of Sample 401 of Example 4 of JP-A-7-92601
Alternatively, samples 311 and 312 were changed to the emulsion 302. Similarly, the ninth layer emulsion 1
Were changed to Emulsion 303 or Emulsion 304, respectively, as Samples 313 and 314. The sample thus obtained was evaluated for sensitivity. In the same manner as in Example 4 of JP-A-7-92601, 1/50 second exposure and color reversal development were performed to measure yellow density. The sensitivity was calculated as the reciprocal of the amount of exposure necessary to give a density of +0.2 of the minimum density obtained by giving sufficient exposure, and was shown as a relative value with the sensitivity of Comparative Sample 311 being 100. As a result, the sensitivity of Sample 312 of the present invention was 138, which was high. Also, the residual color after the treatment was small. Further, similarly, the sensitivity of the comparative sample 313 is set to 100
The sensitivity of Sample 314 of the present invention was 131, which was high. Also, the residual color after the treatment was 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 the sample 101 of Example 1 of JP-A-5-313297.
In the same manner. Emulsion-2 and sensitizing dye (2) in the 16th layer of sample 101 of Example 1 of JP-A-5-313297 were prepared by using emulsion 401 and sensitizing dye (SS-1) (9 × 10 ^-4 mol / Agmol).
Alternatively, Sample 411 and Sample 412 were used instead of the sensitizing dye (1) (9 × 10 ⁻⁴ mol / Agmol). 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 carried out and the processing was carried out using a processing solution, and the transfer density was measured with a color densitometer. The sensitivity was expressed as a relative value at a density of 1.0. When the sensitivity of the comparative sample 411 was set to 100, the sensitivity of the sample 412 of the present invention was 125, which was high, and the residual color after the treatment was small.

Example 5 Emulsion F of Example 2 in JP-A-4-42536 was different from Example 1 in that no red-sensitive sensitizing dye (S-1) was added before sulfur sensitization, In addition, gold sulfur sensitization was optimally performed by using chloroauric acid together. After gold sulfur sensitization, sensitizing dye (SS-3) (2 × 10 ^-4 mol / Agmol) or sensitizing dye (7) (2 × 10 ⁻⁴ mol / Agmol) were prepared except that emulsions 501 and 5 were added.
02. The multi-layer color printing paper was prepared in the same manner as in Sample 1 of Example 1 of JP-A-6-347944. JP 6-3479A
Sample 511 was prepared by changing the emulsion of the fifth layer in Sample 20 of Example 1 of No. 44 to Emulsion 501 or Emulsion 502.
And Sample 512. In order to examine the sensitivity of the sample thus obtained, the light from a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.) was passed through an optical wedge and a red filter.
/ 10 seconds of exposure, and color development was carried out using the same processing steps and processing solution as in Example 1 of JP-A-6-347944.
As a result, when the sensitivity of Comparative Sample 511 was set to 100, the sensitivity of Sample 512 of the present invention was 137, which was high. Also, the residual color after the treatment was small.

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 (SS-2) (2 × 10 ⁻⁴ mo
l / Agmol) or sensitizing dye (13) (2 × 10 ⁻⁴ mol / Ag
(mol), emulsion 601 and emulsion 602 were obtained. The coated sample was prepared by replacing the emulsion of Example 1 in JP-A-8-122954 with Emulsion 601 or Emulsion 602, and combining both an emulsion layer and a surface protective layer on a support in the same manner as in Example 1 by simultaneous extrusion. This was applied and used as Sample 611 and Sample 612.
The amount of silver applied per side was 1.75 g / m ² . 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., and Example 1 of JP-A-8-122954 was used. 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 taken as 100, and the other values were represented by relative values. As a result, the sensitivity of Sample 612 of the present invention was 128, which was high. Also, the residual color after the treatment was small. The same effect was obtained by exposing with HR-4 or HGH instead of the X-ray orthoscreen HGM used at the time of exposure.

Example 7 Emulsion D of Example 2 of JP-A-8-227117 was a sensitizing dye-
A tabular silver chloride emulsion which was different only in that no 2 and 3 were added was prepared and this was designated as emulsion 701. The coated sample was prepared in the same manner as in the coated sample F of Example 3 of JP-A-8-227117. Emulsion F and sensitizing dye-1 of coating sample F in Example 3 of JP-A-8-227117 were prepared by combining emulsion 701 with sensitizing dye (SS-1).
(5 × 10 ⁻⁴ mol / Agmol) or sensitizing dye (1) (5 ×
10 ^-4 mol / Agmol) to obtain Sample 711 and Sample 712. In order to examine the sensitivity of the sample thus obtained, the light of a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.) was passed through an optical wedge and a blue filter to be 1/100.
Second exposure was performed, and Fuji Photo Film CN16 processing was performed to compare 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 126, which was high. Also, the residual color after the treatment was small.

Example 8 An octahedral silver chloride emulsion was prepared in the same manner as in Emulsion F of Example 3 of JP-A-8-227117, 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 JP-A-8-227117. Emulsion F and sensitizing dye-1 of coating sample F of Example 3 of JP-A-8-227117 were prepared by combining emulsion 801 with sensitizing dye (SS-3) (5 × 10 ^-4 mol / Agmol) or sensitizing dye ( 7) Replaced with (5 × 10 ⁻⁴ mol / Agmol), sample 81
1 and sample 812. 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 red filter. Compared. The sensitivity is represented by the logarithm of the reciprocal of the amount of exposure required to give a density of fog + 0.2.
The sensitivity of 11 was set to 100. The sensitivity of Sample 812 of the present invention was 128, which was high. Also, the residual color after the treatment was small.

Example 9 A tabular grain emulsion was prepared in the same manner as in emulsion CC of EP 0699950, and a sensitizing dye (SS-2) was used in place of Dye 1 and Dye 8 at the time of chemical sensitization. After adding 10 ^-4 mol / Agmol and chemically sensitizing, (SS-2) was added to 3 × 10 ^-4 mol / Agmol.
Then, (SS-2) was added to 3 × 10 ⁻⁴ mol / Agmol
The added emulsion was 901 and (13) was 5 × 10 ⁻⁴ mol / Agmo
After addition and chemical sensitization, (13) was added to 3 × 10 ⁻⁴ mol / Ag
mol, and then (13) was added to 3 × 10 ⁻⁴ mol / Agmo
The added emulsion was designated as 902. The coated sample was prepared in the same manner as the coated sample of the example of EP 0699950,
A sample using the emulsion 901 was referred to as a sample 911, and a sample using the emulsion 902 was referred to as a sample 912. Exposure and development were performed in the same manner as in the patent, and the photographic properties were compared. Sensitivity is +0.2
Expressed as the logarithm of the reciprocal of the exposure required to give a density of
The sensitivity was expressed as a relative value with the sensitivity of Sample 911 taken as 100. The sensitivity of Sample 912 of the present invention was 128, which was high. Also, the residual color after the treatment was small.

Example 10, Synthesis of Compound (7) The compound was synthesized by the following scheme 1. Scheme 1

[0120]

Embedded image

(A) 5 g (0.0304 mol),
(B) 3.9 g (0.049 mol), acetic acid 20 ml
Was heated at an external temperature of 145 ° C. for 10 hours. After completion of the reaction, acetic acid was distilled off, and the pH was adjusted to 7 with 100 ml of water and 1N sodium hydroxide. The obtained crystals were separated by suction filtration, and further dissolved by heating under reflux in a mixed solvent of methanol / methylene chloride, and methylene chloride was distilled off. The precipitated crystals are separated by suction filtration and dried (c) 4.
34 g (58% yield) were obtained. (C) 4 g (0.016
2 mol) and 4 g (0.032 mol) of (d) were heated at an external temperature of 150 ° C. for 2 hours. After completion of the reaction, acetone 10
0 ml was added, and the obtained crystals were separated by suction filtration.
After drying, (e) 5.72 g (96% yield) was obtained. (E)
5.72 g (0.0155 mol), (f) 13.3 m
l (0.066 mol), 4.5 ml of acetic acid, pyridine 1
7 ml and triethylamine 8.8 ml were added, and the
Heat at 0 ° C. for 4 hours. After allowing the reaction solution to cool, 300 ml of ethyl acetate was added, and the oily substance was purified by a Sephadex column (eluent methanol).
g was added, and the precipitated crystals were separated by suction filtration. After drying the obtained crystals, 0.39 g (yield 6%, λmax = 553 nm, ε = 87,000 (in methanol)) of purple powder (7) was obtained.

Example 11, Synthesis of Compound (8) The compound was synthesized by the following scheme 2. Scheme 2

[0123]

Embedded image

(A) 5 g (0.0304 mol), 4.94 g of sodium hydroxide, 23 m of dimethylformamide
Under stirring and cooling with ice, 6 g (0.043 mol) of (g) was added dropwise, and the mixture was heated at an external temperature of 100 ° C. for 1 hour. After completion of the reaction, 100 ml of chloroform and 100 ml of water were added, the chloroform layer was extracted by extraction, dried over magnesium sulfate, purified by silica gel chromatography (eluent methanol / chloroform = 1/8), and dried (h).
93 g (yield 27%) were obtained. (H) 1.92 g (0.
0083 mol), (d) 2 g (0.016 mol)
Was heated at an external temperature of 150 ° C. for 2 hours. After the reaction was completed, 100 ml of acetone was added, and the obtained crystals were separated by suction filtration and dried to obtain (i) 2.85 g (yield 97%). (I) 2.8 g (0.008 mol), (f) 6.
8 ml (0.034 mol), acetic acid 2.3 ml, pyridine 13 ml and triethylamine 1.1 ml were added, and the mixture was heated at an external temperature of 120 ° C. for 4 hours. After allowing the reaction solution to cool, 300 ml of ethyl acetate was added, and the oily substance was purified by a Sephadex column (eluent: methanol).
8 g was added, and the precipitated crystals were separated by suction filtration. After drying the obtained crystals, 0.2 g of purple powder (8) (7% yield, λmax = 563 nm, ε = 99200 (in methanol)) was obtained.

[0125]

According to the present invention, a silver halide photographic material having high sensitivity and little residual color can be obtained.

Claims (5)

[Claims] 1. A silver halide photographic material comprising at least one compound represented by the following general formula (I). General formula (I) In the formula (I), Z ₁ represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. However, these may be fused with an aromatic ring. R ₁ represents an alkyl group, an aryl group, or a heterocyclic group. L ₁ and L ₂ represent a methine group. p ₁ represents 0 or 1. M ₁ represents a charge balancing counter ion, and m ₁ represents a number required to neutralize the charge of the molecule.
Q represents a group necessary for forming a methine dye. A ₁ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. However, thiazoline nuclei are excluded. 2. A silver halide photographic light-sensitive material, wherein the compound of the general formula (I) according to claim 1 is selected from the compounds represented by the following general formula (II). General formula (II) In the formula (II), Z ₂ represents an oxygen atom, a sulfur atom, a selenium atom,
Represents a tellurium atom, a carbon atom, or a nitrogen atom. R ₁ ,
Q, M ₁ , m ₁ and A ₁ have the same meanings as in formula (I). 3. A silver halide photographic material, wherein the compound of the formula (I) according to claim 1 is selected from the compounds represented by the following formula (II). General formula (III) In the formula (III), A ₂ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. Z ₁ , R ₁ , Q, L ₁ , L ₂ , M ₁ ,
m ₁ and A ₁ have the same meanings as in formula (I). 4. The general formula (I) according to claim 1, 2, or 3,
At least one of the compounds represented by (II) and (III)
And the silver halide grains forming the emulsion layer containing the compound have an average aspect ratio of 3 or more and 1000 or more.
A silver halide photographic material characterized by the following. 5. A compound represented by the general formula (I) according to claim 1.