JP2003121958A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method for a silver halide photographic sensitive material giving a silver halide photographic sensitive material with reduced stains due to a residual sensitizing dye after processing. SOLUTION: In the processing method for a silver halide photographic sensitive material, an exposed silver halide photographic sensitive material is brought into contact with an oxidizer in the presence of a compound selected from organoboron compounds, organosilicon compounds, organotin compounds, organogermanium compounds and organoaluminum compounds.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly to a silver halide for reducing stains caused by residual sensitizing dye in a processed silver halide photographic light-sensitive material. The present invention relates to a method for processing a photographic light-sensitive material.

[0002]

2. Description of the Related Art With the remarkable progress of digital cameras and color printers, in processing silver halide color photographic light-sensitive materials, it is desired to promptly provide high quality images to customers. However, simply shortening the processing time of the conventional processing means that the processing is completed before the sensitizing dye in the silver halide color photographic light-sensitive material is sufficiently washed out, so that the large amount of residual dye remaining on the white background of the color print increases. Due to the dye, the image was colored and became unbearable for viewing. Also in the color negative film, the density in the minimum density portion is increased, so that the color balance is disturbed and proper printing cannot be provided.

Further, in recent years, the use of tabular silver halide grains, which is an important basic technique in high-sensitivity photographic light-sensitive materials, makes it possible to increase the amount of sensitizing dye used per unit volume. While providing the effect of improvement, the amount of the sensitizing dye remaining in the processed silver halide light-sensitive material is increased. Depending on the processing conditions, an increase in the amount of residual sensitizing dye cannot be ignored, and a phenomenon such as an increase in the density of the minimum density portion of the color negative film or a coloring of the highlight portion of the color reversal film occurs.

Research Disclosure Magazine 20733
The publication discloses a method using a bistriazinylaminostilbenedisulfonic acid compound as an example of a method for removing stains caused by a sensitizing dye, and this method has been widely used in the processing of color photographic light-sensitive materials. It was Japanese Unexamined Patent Publication No. 6-329936 discloses a bistriazinylaminostilbenedisulfonic acid compound which has excellent solubility and can reduce stain even by a treatment that shortens the time. US Pat. No. 6,153,364 proposes a stain reduction method using a 2,6-diarylaminotriazine compound.

The compound contained in the photographic processing solution in order to reduce the stain caused by the sensitizing dye is called a stain reducing agent and promotes the outflow of the sensitizing dye from the silver halide light-sensitive material. The effect of the stain-reducing agent decreases as the rinse liquid becomes fatigued after continuous processing of the silver halide photographic light-sensitive material, as compared with the case where the rinse liquid is new. This is because the sensitizing dye flowing out from the silver halide photographic light-sensitive material is accumulated in the processing solution, and a part of the sensitizing dye that is stable in a normal processing bath is incorporated into the silver halide light-sensitive material, resulting in sensitization. This is to prevent the washout of the dye. This inhibitory effect is remarkable in recent photographic processing liquids in which the amount of waste liquid has been reduced.

Further, as the amount of the coating sensitizing dye of the silver halide photographic light-sensitive material increases, the stain reducing agent in the photographic processing solution also needs to have a high concentration, which causes a problem of solubility in the kit and reduces the stain. In the high concentration range of the agent, the stain reducing effect depending on the concentration added may not always be exhibited. Therefore, in order to reduce the stain caused by the sensitizing dye, the fundamental solution is to decompose the sensitizing dye itself remaining in the silver halide photographic light-sensitive material to make it colorless.

US Pat. No. 6,207,359 B1 proposes a method of reducing stain by irradiating a light-sensitive material with light in the presence of an N-oxyazinium compound. However, since this compound produces pyridines by the reaction, the silver halide light-sensitive material is in a basic atmosphere, which is not preferable for image storability.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material which gives a silver halide photographic light-sensitive material in which stains due to residual sensitizing dye after processing are reduced. Is to provide.

[0009]

The above-mentioned problems have been solved by the present invention described below. That is, the present invention is

<1> An exposed silver halide photographic light-sensitive material is treated with an oxidizing agent in the presence of a compound selected from organic boron compounds, organic silicon compounds, organic tin compounds, organic germanium compounds and organic aluminum compounds. It is a method of processing a silver halide photographic light-sensitive material, which is characterized by bringing them into contact with each other.

<2> The compound selected from the organoboron compound, the organosilicon compound, the organotin compound, the organogermanium compound and the organoaluminum compound is a compound represented by the general formula (A). <1> The method for processing a silver halide photographic light-sensitive material described in <1>.

[0012]

[Chemical 2]

(Wherein Ra ¹ , Ra ² , Ra ³ and Ra
⁴ are each independently an aliphatic group, an aromatic group, a heterocyclic group,
Or Si (Ra ⁵ ) (Ra ⁶ ) -Ra ^7, which represents Ra ⁵ , R
a ⁶ and Ra ⁷ each independently represent an aliphatic group or an aromatic group. M is, boron ions (B ^-), silicon (Si),
It represents tin (Sn), germanium (Ge) or aluminum ion (Al ⁻ ). (G ⁺ ) _n represents a cation or a cationic compound necessary for neutralizing the charge as a whole molecule, and n is 0 or 1. )

<3> The method for processing a silver halide photographic light-sensitive material according to <2>, wherein the compound represented by the general formula (A) is an aqueous solution. <4> The method of processing a silver halide photographic light-sensitive material according to <2> or <3>, wherein M in the general formula (A) is boron.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, an organoboron compound, an organosilicon compound, an organotin compound, an organogermanium compound and an organoaluminum compound which coexist when a silver halide photographic light-sensitive material and an oxidizing agent are brought into contact with each other,
The oxidant produces active radical species that attack the sensitizing dye and reduce stain. Therefore,
Such a compound that coexists is referred to as a stain reducing agent precursor. The stain reducing agent precursor is preferably an organic boron compound, an organic silicon compound, an organic tin compound or an organic germanium compound, and particularly preferably an organic boron compound.

In the present invention, the stain-reducing agent precursor, which is coexisted when the silver halide photographic light-sensitive material and the oxidizing agent are brought into contact with each other, is preferably an electron-donating compound, particularly preferably represented by the following general formula (A). Is a compound. Next, the compound represented by formula (A), which is particularly preferably used in the invention, will be described.

[0017]

[Chemical 3]

In the formula, Ra ¹ , Ra ² , Ra ³ and Ra ⁴ are
Each independently an aliphatic group, aromatic group, heterocyclic group, or S
i (Ra ⁵⁾ represent ^{(Ra 6) -Ra 7, Ra} 5, Ra 6,
Ra ^7's each independently represent an aliphatic group or an aromatic group. M represents boron ion (B ⁻ ), silicon (Si), tin (Sn), germanium (Ge) or aluminum ion (Al ⁻ ). (G ⁺ ) _n represents a cation or a cationic compound necessary for neutralizing the charge as a whole molecule, and n is 0 or 1.

First, the groups used in the present invention will be described in detail. In the present invention, when a specific part of the general formula is referred to as a “group”, the part may have no further substituent, and one or more (up to the maximum possible number). ) Means that it may have a substituent. For example, an “alkyl group” means a substituted or unsubstituted alkyl group. Further, the substituents applicable to the compound used in the present invention, as long as it does not adversely affect the photograph,
Any substituent may be used.

When such a substituent is represented by W, the substituent represented by W is not particularly limited, and examples thereof include a halogen atom, an aliphatic group {alkyl group (cycloalkyl group,
Bicycloalkyl group, including tricycloalkyl group),
It includes an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group) and an alkynyl group. }, An aryl group,
Heterocyclic group (also called heterocyclic group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group,
Acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfur Famoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl Group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, Suhono group, a silyl group, a hydrazino group, a ureido group, a boronic acid group (-B (OH) _2), phosphato group (-OPO (OH) _2), a sulfato group (-O
SO ₃ H) and other known substituents are mentioned as examples.

More specifically, W is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom),
Alkyl group {Represents a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-
Butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl,
Cyclopentyl, 4-n-dodecylcyclohexyl),
Bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. For example, bicyclo [ 1,
2,2] heptan-2-yl, bicyclo [2,2,2]
Octan-3-yl), and further includes a tricyclo structure having many ring structures. Alkyl group in the substituents described below (for example, alkyl group of alkylthio group)
Represents an alkyl group having such a concept. }

Alkenyl group {Represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl,
Geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms). For example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably 5 carbon atoms
To 30 substituted or unsubstituted bicycloalkenyl groups, that is, monovalent groups obtained by removing one hydrogen atom from a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl and bicyclo [2,2,2] oct-2-en-4-yl) are included. }, An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl group), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms). Groups such as phenyl, p-
Tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and one hydrogen atom is The removed monovalent group is more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl. Incidentally, it may be a cationic heterocyclic group such as 1-methyl-2-pyridinio or 1-methyl-2-quinolinio).

A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example,
Methoxy, ethoxy, isopropoxy, t-butoxy,
n-octyloxy, 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy,
2-methylphenoxy, 4-t-butylphenoxy, 3
-Nitrophenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably carbon) A substituted or unsubstituted heterocyclic oxy group having a number of 2 to 30, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), an acyloxy group (preferably a formyloxy group, a substituted or unsubstituted group having a carbon number of 2 to 30) A substituted alkylcarbonyloxy group, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy,
Benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy group (preferably having 1 carbon atom)
To 30 substituted or unsubstituted carbamoyloxy groups, for example N, N-dimethylcarbamoyloxy,
N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy),
Alkoxycarbonyloxy group (preferably having 2 carbon atoms
To 30 substituted or unsubstituted alkoxycarbonyloxy groups such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-
Octylcarbonyloxy),

An aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxy). Carbonyloxy), an amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms,
A substituted or unsubstituted anilino group having 6 to 30 carbon atoms,
For example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), ammonio group (preferably ammonio group, having 1 to 3 carbon atoms).
A substituted or unsubstituted 0-substituted or unsubstituted alkyl, aryl, or heterocyclic-substituted ammonio group, for example, trimethylammonio, triethylammonio, diphenylmethylammonio), an acylamino group (preferably formylamino group, having 1 to 30 carbon atoms) A substituted or unsubstituted alkylcarbonylamino group, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-triamino -N
-Octyloxyphenylcarbonylamino), an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylamino) Carbonylamino, morpholinocarbonylamino),

Alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino,
N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably having 7 to 3 carbon atoms)
0 substituted or unsubstituted aryloxycarbonylamino group, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m-n-octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably having a carbon number of 0 to 30 substituted or unsubstituted sulfamoylamino groups, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, N-n-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably having carbon atoms). 1 to 30 substituted or unsubstituted alkylsulfonylamino, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5- Li chlorophenyl sulfonylamino, p- methylphenyl sulfonylamino), a mercapto group, an alkylthio group (preferably having 1 to 30 carbon atoms
A substituted or unsubstituted alkylthio group such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio having 6 to 30 carbon atoms, for example, phenylthio, p-chlorophenylthio, m-methoxyphenyl Thio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio),

Sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl group. , N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl groups (preferably substituted or unsubstituted with 1 to 30 carbon atoms). Alkylsulfinyl groups, 6 to 30 substituted or unsubstituted arylsulfinyl groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably having 1 to 30 carbon atoms). Replaced or nothing Substituted alkylsulfonyl group, 6 to 30 substituted or unsubstituted arylsulfonyl group, for example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, having 2 to 30 carbon atoms). Substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, heterocyclic carbonyl group bonded to the carbonyl group at a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms , For example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl,
Benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl),

An aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl,
o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably having 2 carbon atoms).
To 30 substituted or unsubstituted alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), carbamoyl groups (preferably having 1 carbon atom).
To 30 substituted or unsubstituted carbamoyl, such as carbamoyl, N-methylcarbamoyl, N, N-
Dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl),
Aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, 3 carbon atoms)
To 30 substituted or unsubstituted heterocyclic azo groups such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo, imide groups (preferably N-succinimide, N
-Phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably having 2 to 30 carbon atoms). 30 substituted or unsubstituted phosphinyl groups, for example, phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyloxy groups (preferably substituted or unsubstituted phosphinyl having 2 to 30 carbon atoms) Oxy group, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino group (preferably having 2 carbon atoms)
To 30 substituted or unsubstituted phosphinylamino groups such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), phospho groups, silyl groups (preferably substituted or unsubstituted with 3 to 30 carbon atoms). Silyl group, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl), hydrazino group (preferably substituted or unsubstituted hydrazino group having 0 to 30 carbon atoms, for example, trimethylhydrazino), ureido group (preferably carbon) It represents a substituted or unsubstituted ureido group of the numbers 0 to 30, such as N, N-dimethylureido).

Further, two W's may be combined to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocycle. These can be further combined to form a polycyclic condensed ring. For example, benzene. Ring, naphthalene ring, anthracene ring, quinoline ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, Pyrimidine ring, pyridazine ring, indolizine ring, indole ring,
Benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, phthalazine ring, naphthyridine ring,
Quinoxaline ring, quinoxazoline ring, isoquinoline ring,
Carbazole ring, phenanthridine ring, acridine ring,
Phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiine ring, phenothiazine ring,
Examples thereof include a phenazine ring, a triazine ring, a triazole ring, a cyclopentanediene ring and a pyrene ring. ) Can also be formed.

Among the above-mentioned substituents W, those having a hydrogen atom may be substituted with the above-mentioned group after removing at least one of them. Examples of such a substituent include a -CONHSO ₂ -group (sulfonylcarbamoyl group, carbonylsulfamoyl group), -CONHCO-
Group (carbonylation carbamoyl group), - SO ₂ NHSO ₂ -
And a group (a sulfonylsulfamoyl group).
More specifically, an alkylcarbonylaminosulfonyl group (for example, acetylaminosulfonyl), an arylcarbonylaminosulfonyl group (for example, benzoylaminosulfonyl group), an alkylsulfonylaminocarbonyl group (for example, methylsulfonylaminocarbonyl),
An arylsulfonylaminocarbonyl group (eg, p-
Methylphenylsulfonylaminocarbonyl).

Next, the compound represented by formula (A) in the present invention will be described in detail.

[Chemical 4]

In the general formula (A), R _a ¹ , R _a ² , R _a ³ and R a
_a ⁴ is each independently an aliphatic group, an aromatic group, a heterocyclic group,
Alternatively, it represents Si (R _a ⁵ ) (R _a ⁶ ) -R _a ⁷ . M represents boron ion (B ⁻ ), silicon (Si), tin (Sn), germanium (Ge) or aluminum ion (Al ⁻ ). n is 0 or 1, and when M is a boron ion (B ⁻ ) or an aluminum ion (Al ⁻ ), n is 1,
When M is silicon (Si), tin (Sn) or germanium (Ge), n is 0. M is preferably boron (B ⁻ ), silicon (Si), tin (Sn) or germanium (Ge), and more preferably boron ion (B ⁻ ).

In the general formula (A), when R _a ^{1 to} R _a ⁴ represent an aliphatic group, examples of the aliphatic group include an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group and an alkynyl group. , A substituted alkynyl group, an aralkyl group,
Or a substituted aralkyl group and the like, and among them, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group, or a substituted aralkyl group is preferable,
An alkyl group and a substituted alkyl group are particularly preferable. Further, the aliphatic group may be a cyclic aliphatic group or a chain aliphatic group. The chain aliphatic group may have a branch.

Examples of the alkyl group include linear, branched, and cyclic alkyl groups, and the number of carbon atoms in the alkyl group is preferably 1-30, more preferably 1-20. The alkyl group may be a substituted alkyl group having a substituent or an unsubstituted alkyl group, and the preferred range of the number of carbon atoms in the alkyl portion of the substituted alkyl group is the same as in the case of the alkyl group. . As the alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, a neopentyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, Examples thereof include dodecyl group and octadecyl group.

Examples of the substituent of the substituted alkyl group include a carboxyl group, a sulfo group, a cyano group, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), a hydroxy group, and an alkoxycarbonyl group having 30 or less carbon atoms (eg, , Methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group), alkylsulfonylaminocarbonyl group having 30 or less carbon atoms, arylsulfonylaminocarbonyl group, alkylsulfonyl group, arylsulfonyl group, acylaminosulfonyl group having 30 or less carbon atoms, Alkoxy group having 30 or less carbon atoms (eg, methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.), alkylthio group having 30 or less carbon atoms (eg,
A methylthio group, an ethylthio group, a dodecylthio group, etc.), an aryloxy group having 30 or less carbon atoms (for example, a phenoxy group, a p-tolyloxy group, a 1-naphthoxy group, a 2-naphthoxy group, etc.), a nitro group, a carbon number of 30 or less. Alkyl group, alkoxycarbonyloxy group, aryloxycarbonyloxy group,

An acyloxy group having 30 or less carbon atoms (eg, acetyloxy group, propionyloxy group, etc.), an acyl group having 30 or less carbon atoms (eg, acetyl group, propionyl group, benzoyl group, etc.), carbamoyl group (eg, carbamoyl group) Group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (for example, sulfamoyl group,
N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), aryl groups having 30 or less carbon atoms (for example, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group) Etc.), substituted amino groups (for example, amino groups, alkylamino groups, dialkylamino groups, arylamino groups, diarylamino groups, acylamino groups, etc.), substituted ureido groups, substituted phosphono groups, heterocyclic groups and the like. Here, the carboxyl group, sulfo group, hydroxy group, and phosphono group may be in a salt state. In that case, examples of the cation that forms a salt include G ⁺ described below.

Examples of the alkenyl group include linear, branched, and cyclic alkenyl groups, and the number of carbon atoms of the alkenyl group is preferably 2 to 30, and more preferably 2 to 20. Further, the alkenyl group may be a substituted alkenyl group having a substituent or an unsubstituted alkenyl group, and the preferable range of the number of carbon atoms in the alkenyl portion of the substituted alkenyl group is the same as in the case of the alkenyl group. . Examples of the substituent of the substituted alkenyl group include the same substituents as in the case of the substituted alkyl group.

Examples of the alkynyl group include linear, branched and cyclic alkynyl groups, and the number of carbon atoms of the alkynyl group is preferably 2-30, more preferably 2-20. The alkynyl group may be a substituted alkynyl group or an unsubstituted alkynyl group, and the preferred range of the number of carbon atoms in the alkynyl portion of the substituted alkynyl group is the same as in the case of the alkynyl group. Examples of the substituent of the substituted alkynyl group include the same substituents as in the case of the substituted alkyl group.

Examples of the aralkyl group include linear, branched and cyclic aralkyl groups. The number of carbon atoms in the aralkyl group is preferably 7 to 35, more preferably 7 to 25. Further, the aralkyl group may be either an aralkyl group having a substituent or an unsubstituted aralkyl group, and the preferred range of the number of carbon atoms in the aralkyl portion of the substituted aralkyl group is the same as in the case of the aralkyl group. Examples of the substituent of the substituted aralkyl group include the same substituents as in the case of the substituted alkyl group.

When R _a ^{1 to} R _a ⁴ represent an aromatic group, examples of the aromatic group include an aryl group and a substituted aryl group. The number of carbon atoms in the aryl group is 6
-30 are preferable and 6-20 are more preferable. The preferred range of the number of carbon atoms in the aryl portion of the substituted aryl group is the same as that of the aryl group. Examples of the aryl group include a phenyl group, an α-naphthyl group, a β-naphthyl group, and the like. Examples of the substituent of the substituted aryl group include the same substituents as in the case of the substituted alkyl group.

When R _a ^{1 to} R _a ⁴ represent a heterocyclic group, examples of the heterocyclic group include a heterocyclic group having a substituent and an unsubstituted heterocyclic group. Examples of the substituent of the heterocyclic group having a substituent include the same substituents as those exemplified when R _a ^{1 to} R _a ⁴ represent a substituted aryl group. Among them, R _a ¹
The heterocyclic group to R _a ⁴ each represents a furan ring, a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring,
A heterocyclic group containing a nitrogen atom, a sulfur atom, or an oxygen atom such as a pyridine ring is preferable.

R_a ¹~ R_a ^FourIs -Si (R_a ^Five) (R_a ⁶) -R_a ⁷To
When represented, R_a ^Five, R_a ⁶And R_a ⁷Is fat independently
It represents a group or an aromatic group. The aliphatic group and aromatic group are R_a ¹
~ R _a ^FourAre the same as the above-mentioned aliphatic group and aromatic group respectively represented by
The same applies to the preferred examples.

In the general formula (A), R _a ¹ , R _a ² , R _a ³ ,
And two or more of R _a ⁴ may be linked directly or via a substituent to form a ring. When forming a ring,
As the ring, any ring selected from the following rings (C1) to (C3) is preferable, and among them, the ring (C2) is preferable. The following is exemplified by the boron ion (B ⁻ ) which is preferable as a representative of M.

[0043]

[Chemical 5]

In the ring in (C1) above, R
_b represents a divalent group shown below.

[Chemical 6]

Among the organoboron compounds represented by the general formula (A), those in which at least one of R _a ^{1 to} R _a ⁴ is an alkyl group are preferable, from the viewpoint of improving decoloring property and storability. A triarylalkyl type organic boron compound in which one is an alkyl group and the other three are aryl groups is more preferable. In particular, a triarylalkyl type organic boron compound in which an aryl group is substituted with an electron-withdrawing group is preferable, and among them, the sum of Hammet (σ) values of the substituents (electron-withdrawing groups) on the three aryl groups is +0. 36 ~
A value of +2.58 is more preferable. The electron withdrawing group is preferably a halogen atom or a trifluoromethyl group, more preferably a fluorine atom or a chlorine atom.

The aryl group substituted with an electron-withdrawing group includes 3-fluorophenyl group, 4-fluorophenyl group, 2-fluorophenyl group, 3-chlorophenyl group,
4-chlorophenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-difluorophenyl group, 4-bromophenyl group, 3,4-
A difluorophenyl group, a 5-fluoro-2-methylphenyl group, a 5-fluoro-4-methylphenyl group, a 5-chloro-2-methylphenyl group, a 5-chloro-4-methylphenyl group and the like can be mentioned.

As the anion part of the general formula (A),
For example, tetramethylborate, tetraethylborate, tetrabutylborate, triisobutylmethylborate, di-n-butyl-di-t-butylborate, tri-m-chlorophenyl-n-hexylborate, triphenylmethylborate, triphenylethyl Borate,
Triphenylpropyl borate, triphenyl-n-butyl borate, trimesityl butyl borate, tritolyl isopropyl borate, triphenylbenzyl borate, tetra-m-fluorobenzyl borate, triphenylphenethyl borate, triphenyl-p-chlorobenzyl borate, Triphenylethenyl butylborate, di (α-naphthyl) -dipropylborate, triphenylsilyltriphenylborate, tritoluylsilyltriphenylborate, tri-n-butyl (dimethylphenylsilyl) borate, diphenyldihexylborate, tri- m-fluorophenylhexyl borate,
Tri (5-chloro-4-methylphenyl) hexyl borate, tri-m-fluorophenyl cyclohexyl borate, tri- (5-fluoro-2-methylphenyl) hexyl borate and the like can be mentioned.

In the general formula (A), G ⁺ represents a group capable of forming a cation. Among them, organic cationic compounds, transition metal coordination complex cations (such as the compounds described in Japanese Patent No. 2791143) or metal cations (for example, Na ⁺ ,
K ⁺ , Li ⁺ , Ag ⁺ , Fe ²⁺ , Fe ³⁺ , Cu ⁺ , Cu ²⁺ ,
Zn ²⁺ , Al ³⁺ , 1 / 2Ca ^2+, etc.) are preferable. Examples of the organic cationic compound include quaternary ammonium cation, quaternary pyridinium cation, quaternary quinolinium cation, phosphonium cation, iodonium cation, sulfonium cation, and dye cation.

As the quaternary ammonium cation,
Examples thereof include tetraalkylammonium cations (eg, tetramethylammonium cation, tetrabutylammonium cation), tetraarylammonium cations (eg, tetraphenylammonium cation), and the like. As the quaternary pyridinium cation,
N-alkylpyridinium cation (for example, N-methylpyridinium cation), N-arylpyridinium cation (for example, N-phenylpyridinium cation), N-alkoxypyridinium cation (for example,
4-phenyl-N-methoxy-pyridinium cation), N-benzoylpyridinium cation and the like. Examples of the quaternary quinolinium cation include N-alkylquinolinium cations (for example, N-methylquinolinium cation), N-arylquinolinium cations (for example, N-phenylquinolinium cation), and the like. To be Examples of the phosphonium cation include a tetraarylphosphonium cation (eg, tetraphenylphosphonium cation). Examples of the iodonium cation include a diaryliodonium cation (eg, diphenyliodonium cation). Examples of the sulfonium cation include a triarylsulfonium cation (eg, triphenylsulfonium cation).

Further, as a concrete example of G ⁺ , paragraphs [0020] to [00] of JP-A-9-188686 can be cited.
38] and the like.

In each of the above-exemplified cationic compounds (exemplary compounds), the alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group,
An unsubstituted alkyl group such as an ethyl group, a propyl group, an isopropyl group, a butyl group, and a hexyl group, and the substituted alkyl group represented by R _a ^{1 to} R _a ⁴ are preferable. Especially, the number of carbon atoms is 1 to
12 alkyl groups are preferred. In each of the above-exemplified cationic compounds, the aryl group is
For example, a phenyl group, a halogen atom (eg, chlorine atom) -substituted phenyl group, an alkyl (eg, methyl group) -substituted phenyl group, and an alkoxy (eg, methoxy group) -substituted phenyl group are preferable.

In the general formula (A), G ⁺ is shown in order to neutralize the electric charge of M, but the counter ion necessary for neutralizing the molecule as a whole may be optionally present. ,
It does not have to exist. For example, M is boron (B ^-)
Even in the case of, since there is an inner salt when there is a substituent having a positive charge, G ⁺ need not be present. Further, when there is a substituent having a plurality of positive charges, it may have an anion as a counter ion.

Specific examples of the organic boron compound represented by the above general formula (A) include US Pat. No. 3,567,453.
No. 4,343,891 and JP-A-62.
-143044, JP 62-150242 A, JP 9-188684 A, JP 9-188 A.
685, JP-A-9-188686, JP-A-9-188710, and JP-B-8-9643.
The compounds described in JP-A No. 11-269210 and the compounds exemplified below may be mentioned.

As the organic boron compound, "chemistry of functional dyes" (1981, CMC Publishing Co., p.393-).
p.416) and "coloring materials" (60 [4] 212-224 (1
And a spectral sensitizing dye-based organoboron compound having the cationic dye described in 987)) as a cation moiety in its structure. Examples of the spectral sensitizing dye-based organic boron compound include JP-A-62-143044 and JP-A-1-1382.
No. 04, Tokuyohei 6-505287, Japanese Patent Laid-Open No. 4-261.
Compounds described in No. 406 and the like can be mentioned.

As the dye constituting the cation part of the spectral sensitizing dye-based organic boron compound, a cationic dye having a maximum absorption wavelength in a wavelength region of 300 nm or more, preferably 400 to 1100 nm is used. You can Among them, cationic cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, rhodacyanine dyes, complex cyanine dyes, complex merocyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarylium Methine dyes such as dyes, crocorium dyes, azamethine dyes, triarylmethane dyes; and coumarin dyes, arylidene dyes, anthraquinone dyes, azo dyes, azomethine dyes,
Spiro compound, metallocene dye, fluorenone dye, fulgide dye, perylene dye, phenazine dye, phenothiazine dye, quinone dye, indico dye, diphenylmethane dye, polyene dye, acridine dye, acridinone dye, diphenylamine dye, quinacridone dye, quinophthalone dye, phenoxazine Examples thereof include dyes, phthaloperylene dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, metal complex dyes, indoline dyes, azine dyes, xanthene dyes, rhodamine dyes, and oxazine dyes. Among these, the above-mentioned methine dyes are preferable, and cyanine dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, oxonol dyes,
A rhodacyanine dye is more preferable, a cyanine dye, a merocyanine dye and a rhodacyanine dye are further preferable, a cyanine dye and a merocyanine dye are particularly preferable, and a cyanine dye is most preferable.

The details of these dyes will be described later. Further, a spectral sensitizing dye type organic boron compound is preferable, but silicon, tin, germanium, or aluminum can be used instead of boron in the boron compound. Further, the compound represented by the general formula (A) in the present invention may be used in combination with another radical generator.

Next, specific examples of the compound represented by the general formula (A) are shown, but the present invention is not limited to these.

[0058]

[Chemical 7]

[0059]

[Chemical 8]

[0060]

[Chemical 9]

[0061]

[Chemical 10]

[0062]

[Chemical 11]

[0063]

[Chemical 12]

The stain-reducing agent precursor used in the present invention produces an active radical species by an oxidation treatment, which attacks the sensitizing dye to make it colorless, so that the silver halide sensitizing dye in which the amount of the applied sensitizing dye is increased. Even if the material is processed or continuously processed, the stain caused by the sensitizing dye can be suppressed to a low level. Further, even if the reaction product of the stain reducing agent precursor used in the present invention remains in the light-sensitive material, the influence on the image stability is small. This is a preferable feature in performing development processing with a shortened processing time.

The amount of the stain reducing agent precursor used in the present invention is 1 × 10 ^-6 per 1 m ² of the light-sensitive material.
mol to 2 × 10 ⁻³ mol is preferable and 2 × 10 ⁻⁶ mo
1 to 1 × 10 ⁻³ mol is more preferable, 5 × 10 ⁻⁶ mo
1 to 5 × 10 ⁻⁴ mol is more preferable.

The stain reducing agent precursor used in the present invention may be contained in the unexposed silver halide photographic light-sensitive material in advance, or may be contained in the processing solution and imagewise exposed to the silver halide photographic light-sensitive material. May be incorporated by immersion, or both may be combined. Of these, it is particularly preferable to use the stain-reducing agent precursor used in the present invention in a treatment liquid prepared as an aqueous solution. The stain reducing agent precursor used in the present invention may be used alone or in combination of a plurality of compounds.

Any method may be used for incorporating the stain reducing agent precursor used in the present invention into the silver halide photographic light-sensitive material. For example, the method of adding a sensitizing dye described below can be used. In addition, other known dispersion methods can be used. That is, a method for producing a solid particle colloid of a photographically useful compound having a submicron size described in British Patent No. 1,570,362, or oil-in-water dispersion described in US Pat. No. 2,322,027. There is a law. A latex dispersion method can also be used, and specific examples of the steps, effects and latex for impregnation are described in US Pat. No. 4,199,633 and West German Patent Application (OLS) Nos. 2,541,274 and 2 , 541,230 and EP 294,104A.
No. etc.

When the stain reducing agent precursor used in the present invention is contained in the processing liquid, it is contained in any processing bath such as color development, bleaching, fixing, washing with water, stabilization, adjustment, black and white development, reversal and pre-bleaching. be able to. Further, the stain reducing agent precursor used in the present invention may be contained in any of the tank solution, the replenishing solution, the concentrated replenishing solution and the kit of the treatment bath. A stain reducing agent precursor may also be included in the processing additive composition. The processing additive composition is added to a tank solution or a replenishing solution required for processing for forming an image of a silver halide color photographic light-sensitive material before or during processing to control photographic performance. It is a composition having a function.

The silver halide photographic light-sensitive material used in the present invention is a conventional silver halide such as silver chloride or silver bromide.
Any of silver bromoiodide, silver chlorobromide, silver chloroiodide and a mixture thereof can be contained. In one aspect,
This photosensitive material contains at least 50 mol% of chloride,
More preferably, it is a high silver chloride light-sensitive material containing at least 90 mol% or more of silver chloride, and is used as, for example, a color print light-sensitive material.

In another embodiment, the at least one emulsion is predominantly silver bromide (at least 50 mol% silver bromide). Most preferably the photographic silver halide photographic material has one or more color records, each color record having one or more predominantly silver bromide emulsions such as those used in color negative and color reversal films. The silver halide photographic light-sensitive material processed according to the present invention can be a single color element or a multicolor element. The photosensitive material can also have a magnetic recording layer known in the art.

Details of the individual silver halide photographic light-sensitive materials are described, for example, in Research Disclosure (hereinafter "RD").
Abbreviated. ), RD17643 23
~ 27 pages, RD18716 pages 647-650, RD307105 pages 866-868, 873
To 879 pages and RD 36544 pages 501 to 541. These are useful silver halide emulsions (negative or positive type) and their preparation methods, various sensitizers, dye-forming couplers, spectral sensitizing dyes, supersensitizers, image dye stabilizers, dyes, ultraviolet absorbers. , Imaging of filters, binders, hardeners, plasticizers, lubricants, coating aids, surfactants, antistatic agents, matting agents, paper and film supports, or negative and positive image forming color elements. It is related to the law.

Any spectral sensitizing dye or supersensitizer may be used, and examples thereof include those described in RD above.

The spectral sensitizing dyes used are preferably cyanine dyes, merocyanine dyes, rhodacyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, allopolar dyes, hemicyanine dyes and styryl dyes. Cyanine dyes, merocyanine dyes and rhodacyanine dyes are more preferred, and cyanine dyes are particularly preferred. For more information on these dyes,
FM Harmer, "Heterocyclic Compounds, Cyanine and Related Compounds (Heterocy)
CLICK COMPOUNDS-Cyanine Dy
es and Related Compound
s) ”, John Willie and Sons (John
Wiley & Sons, Inc.-New York, London, 1964, D.M. Starmer (D.M.
Stermer) “Heterocyclic Compounds Special Topics in Heterocyclic Chemistry (Heterocyclic Com)
pounds-Special topics inh
“Etherocyclic chemistry” ”,
Chapter 18, Section 14, 482-515 Tribute, John
Willie & Sons (John Wiley &
Sons, Inc.-New York, London, 1977, "Rod's Chemistry of Carbon Compounds (Rod's Chemistry of C.
arbon Compounds) "2nd. Ed. v
ol. IV, part B, 1977, Chapter 15, Chapter 3.
69-422, Elsevier Science Public Company, Inc.
nce Publishing Company In
c. ) Published in the company, New York, etc.

To add further explanation, the RD17643
23 to 24, RD18716, page 648, right column to 649
Page right column, RD308119 page 996 right column to page 998 right
Column, EP 0 565 096 A1, page 65 7-1
The ones described in line 0 can be preferably used.
Wear. Also, US Pat. No. 5,747,236 (especially
30-39), US Pat. No. 5,340,694 (special
21 to 60 pages, provided that (XI), (XII), (X
In the sensitizing dyes shown in III), n ₁₂,
n₁₅, N₁₇, N₁₈There is no limit to the number of
4 or less). ), The general formula and
And the sensitizing dyes shown in the specific examples can also be preferably used.
Wear.

Next, cyanine dyes, merocyanine dyes (including trinuclear or tetranuclear merocyanine dyes, etc.) and rhodacyanine dyes preferably used in the present invention are shown below by general formulas.

[0076]

[Chemical 13]

In the general formula (X), L ₁₁ , L ₁₂ , L ₁₃ ,
L ₁₄ , L ₁₅ , L ₁₆ and L ₁₇ represent a methine group. p ₁₁ ,
And p ₁₂ represents 0 or 1. n ₁₁ represents 0, 1, 2, 3 or 4. Z ₁₁ and Z ₁₂ represent an atomic group necessary for forming a nitrogen-containing heterocycle. However, the ring may be condensed to these. M ₁₁ represents a charge-balancing counterion, and m ₁₁ represents a number of 0 or more necessary for neutralizing the charge of the molecule. R ₁₁
And R ₁₂ represents an alkyl group, an aryl group, or a heterocyclic group.

[0078]

[Chemical 14]

In the general formula (XI), L ₁₈ , L ₁₉ , L ₂₀ and L ₂₁ each represent a methine group. p ₁₃ represents 0 or 1.
q ₁₁ represents 0 or 1. n ₁₂ represents 0, 1, 2, 3 or 4. Z ₁₃ represents an atomic group necessary for forming a nitrogen-containing heterocycle. Z ₁₄ and Z _{14 ′} are (N—R ₁₄ ) q
Represents a group of atoms necessary for forming a heterocyclic ring or an acyclic acidic end group together with ₁₁ . However, the ring may be condensed to Z ₁₃ , and Z ₁₄ and Z _{14 ′} . M ₁₂ represents a charge-balancing counterion, and m ₁₂ represents a number of 0 or more necessary to neutralize the charge of the molecule. R ₁₃ represents an alkyl group, an aryl group, or a heterocyclic group. R ₁₄ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

[0080]

[Chemical 15]

In the formula (XII), 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 represent 0 or 1. q ₁₂ represents 0 or 1. n ₁₃ and n ₁₄ are 0, 1, 2, 3 or 4
Represents Z ₁₅ and Z ₁₇ represent an atomic group necessary for forming a nitrogen-containing heterocycle. Z ₁₆ and Z _{16 '} are (N-R ₁₆ )
Represents an atomic group necessary for forming a heterocycle together with q _{1 2} . However, the ring may be condensed to Z ₁₅ , Z ₁₆ and Z _{16 ′} , and Z ₁₇ . M ₁₃ represents a charge balancing counter ion, and m ₁₃ represents a number of 0 or more necessary for neutralizing the charge of the molecule. R ₁₅ and R ₁₇ represent an alkyl group, an aryl group, or a heterocyclic group. R ₁₆ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

Hereinafter, general formulas (X), (XI), and (X
The methine dye represented by II) will be described in detail. Regarding the groups and the like in the following description, when a specific part is referred to as a “group” as described above, the part may be one or more (up to the maximum possible number) even if the part itself is not substituted. ) It means that it may be substituted with a substituent. For example, "alkyl group" means a substituted or unsubstituted alkyl group. Further, the substituent that can be used in the compound of the present invention may be any substituent regardless of the presence or absence of substitution. Examples of such a substituent include those mentioned above for W.

General formulas (X), (XI) and (XII)
Medium, Z₁₁, Z₁₂, Z₁₃, Z₁₅, And Z ₁₇Is a nitrogen-containing complex
Forming a ring, preferably a 5- or 6-membered nitrogen-containing heterocycle
Represents the atomic group necessary for. However, the ring is condensed to these
You may stay. The ring may be an aromatic ring or a non-aromatic ring.
It may be offset. Preferably it is an aromatic ring, for example benzene.
Aromatic hydrocarbon rings such as zen ring and naphthalene ring,
Heteroaromatic rings such as gin ring and thiophene ring
It

Examples of the nitrogen-containing heterocycle include thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, tellrazoline nucleus, tellurazole nucleus, benzoterrazole. Nuclear, 3,
3-dialkylindolenine nuclei (eg 3,3-dimethylindolenine), imidazoline nuclei, imidazole nuclei,
Benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4,5-b] quinoxaline nucleus, oxadiazole nucleus, Thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus and the like can be mentioned, but preferably benzothiazole nucleus, benzoxazole nucleus, 3,3-dialkylindolenine nucleus (eg 3,3-dimethylindolenine), benzimidazole nucleus, 2 -Pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, and more preferably benzothiazole nucleus, benzoxazole nucleus, 3,3-dialkylindolenine nucleus. (Eg 3,3-dimethylindolenine), with a benzimidazole nucleus Ri, particularly preferably a benzoxazole nucleus, benzothiazole nucleus, benzimidazole nucleus, and most preferably a benzoxazole nucleus, a benzothiazole nucleus.

These include the above-mentioned substituents represented by W,
And the ring may be substituted or condensed. Preferred are alkyl groups, aryl groups, alkoxy groups, halogen atoms, and aromatic ring condensation.

Specific examples of the heterocycle formed by Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₅ and Z ₁₇ include US Pat.
340, 694 Nos. 23 to 24, Z ₁₁ , Z ₁₂ , Z ₁₃ ,
Z _14, and include those similar to those listed as examples of Z _16.

Z ₁₄ and Z _{14 ′} and (N—R ₁₄ ) q ₁₁ represent, together with each other, a group of atoms necessary for forming a heterocyclic ring or an acyclic acidic terminal group. The heterocycle (preferably a 5- or 6-membered heterocycle) may be any, but an acidic nucleus is preferred. Next, the acidic nucleus and the acyclic acidic terminal group will be described. The acidic nuclei and acyclic acidic end groups can take the form of the acidic nuclei and acyclic acidic end groups of any common merocyanine dye. In a preferred form, Z ¹⁴ is a thiocarbonyl group, a carbonyl group, an ester group, an acyl group, a carbamoyl group, a cyano group or a sulfonyl group, more preferably a thiocarbonyl group or a carbonyl group. Z _{14 ′} represents the remaining atomic group necessary for forming an acidic nucleus and an acyclic acidic end group. When forming an acyclic acidic terminal group, a thiocarbonyl group, a carbonyl group, an ester group, an acyl group, a carbamoyl group, a cyano group, a sulfonyl group and the like are preferable. q ₁₁ is 0 or 1, but is preferably 1.

The acidic nucleus and the acyclic acidic terminal group referred to here are, for example, "The Theory of the Photographic Process" (edited by James), edited by James.
Theory of the Photograph
ic Process) 4th edition, Macmillan Publishing Company, 1
977, 197-200. Here, the acyclic acidic terminal group means an acidic or electron-accepting terminal group that does not form a ring. The acidic nucleus and the acyclic acidic terminal group are specifically,
U.S. Pat. Nos. 3,567,719, 3,575,86
No. 9, No. 3, 804, 634, No. 3, 837, 862
No. 4, 002, 480, 4, 925, 777
No. 3,167,546, US Pat. No. 5,99.
4,051 and US Pat. No. 5,747,236.

The acidic nucleus forms a heterocycle (preferably a 5-membered or 6-membered nitrogen-containing heterocycle) composed of carbon, nitrogen, and / or chalcogen (typically oxygen, sulfur, selenium, and tellurium) atoms. And more preferably when forming a 5- or 6-membered nitrogen-containing heterocycle consisting of carbon, nitrogen, and / or chalcogen (typically oxygen, sulfur, selenium, and tellurium) atoms. Specifically, for example, the following cores can be mentioned.

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
-Thiooxazolidine-2,5-dione, 2-thiooxazoline-2,4-dione, isoxazoline-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-dihydro Thiazolo [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, indazoline-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-1,1-dioxide nucleus.

Further, the carbonyl or thiocarbonyl group forming these nuclei is used as a raw material for a nucleus having an exomethylene structure in which the active methylene position of the acidic nucleus is substituted, and an acyclic acidic terminal group. A nucleus having an exomethylene structure substituted at the active methylene position of an active methylene compound having a structure such as ketomethylene or cyanomethylene, and a nucleus in which this nucleus is repeated.

The acidic nucleus and the acyclic acidic terminal group may be substituted or condensed with the substituent or ring represented by the above-mentioned substituent W. Z ₁₄ , Z _{14 '} , (N-
R ₁₄ ) q ₁₁ is preferably hydantoin, 2 or 4
-Thiohydantoin, 2-oxazoline-5-one, 2
-Thiooxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, barbituric acid, 2-thiobarbituric acid, more preferably hydantoin, 2 or 4-thiohydantoin, 2 -Oxazoline-5-one, rhodanine, barbituric acid, and 2-thiobarbituric acid. Particularly preferred are 2- or 4-thiohydantoin, 2-oxazoline-5-one, and rhodanine.

The heterocyclic ring formed by Z ₁₆ , Z _{16 '} and (N-R ₁₆ ) q ₁₂ includes Z ₁₄ and Z _14' and (N
The same as those mentioned in the description of the heterocycle of —R ₁₄ ) q ₁₁ can be mentioned. Preferably, the aforementioned Z ₁₄ , Z _{14 ′} and (N—R
₁₄ ) an oxo group from the acidic nucleus described in the description of the heterocycle of q ₁₁ ,
Alternatively, it does not include a thioxo group.

More preferably, the aforementioned Z ₁₄ , Z _{14 '} ,
(N—R ₁₄ ) q _{11 is} a specific example of the acidic nucleus from which an oxo group or a thioxo group has been removed, more preferably hydantoin, 2 or 4-thiohydantoin, 2
-Oxazoline-5-one, 2-thiooxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, barbituric acid, 2-thiobarbituric acid from which an oxo group or a thioxo group has been removed It is particularly preferable that hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, rhodanine, barbituric acid, 2-thiobarbituric acid from which an oxo group or a thioxo group is removed, most preferably 2 Alternatively, it is 4-thiohydantoin, 2-oxazoline-5-one, or rhodanine from which an oxo group or a thioxo group has been removed. q ₁₂ is 0 or 1, but is preferably 1.

R ₁₁ , R ₁₂ , R ₁₃ , R ₁₅ , and R ₁₇ are an alkyl group, an aryl group, and a heterocyclic group, and R ₁₄ and R ₁₆ are a hydrogen atom, an alkyl group, an aryl group, and It is a heterocyclic group, preferably an alkyl group, an aryl group, and a heterocyclic group. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ ,
Specific examples of the alkyl group, aryl group and heterocyclic group represented by R ₁₆ and R ₁₇ include, for example, 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and particularly preferably 1
To 4 unsubstituted alkyl groups (eg, methyl, ethyl,
Propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), carbon atom 1
To 18, preferably 1 to 7, and particularly preferably 1 to 4 substituted alkyl groups {for example, an alkyl group substituted with the aforementioned W as a substituent can be mentioned. In particular, the above-mentioned alkyl group having an acid group is preferable. Preferably, an aralkyl group (for example, benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (for example, an allyl group, a vinyl group, that is, a substituted alkyl group includes an alkenyl group and an alkynyl group) and hydroxy. Alkyl groups (eg,
2-hydroxyethyl, 3-hydroxypropyl), carboxyalkyl group (for example, 2-carboxyethyl,
3-carboxypropyl, 4-carboxybutyl, carboxymethyl), an alkoxyalkyl group (for example, 2-
Methoxyethyl, 2- (2-methoxyethoxy) ethyl), aryloxyalkyl group (eg 2-phenoxyethyl, 2- (1naphthoxy) ethyl), alkoxycarbonylalkyl group (eg ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl) ), An aryloxycarbonylalkyl group (eg, 3-phenoxycarbonylpropyl), an acyloxyalkyl group (eg, 2
-Acetyloxyethyl), an acylalkyl group (for example, 2-acetylethyl), a carbamoylalkyl group (for example, 2-morpholinocarbonylethyl),

A sulfamoylalkyl group (for example, N, N
-Dimethylsulfamoylmethyl), sulfoalkyl groups (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 (for example, 2-
(Pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl), alkylsulfonylcarbamoylalkyl group (for example, methanesulfonylcarbamoylmethyl group), acylcarbamoylalkyl group (for example, acetylcarbamoylmethyl group), acylsulfamoylalkyl group (For example, acetylsulfamoylmethyl group), alkylsulfonylsulfamoylalkyl group (for example, methanesulfonylsulfamoylmethyl group)}, and has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and more preferably 6 carbon atoms. 8 unsubstituted aryl group (eg phenyl group, 1 naphthyl group), substituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and more preferably 6 to 8 carbon atoms (for example, examples of the substituents are mentioned. The above W replaced Reel group. Specifically p- methoxyphenyl group, p- methylphenyl group, p-
Examples thereof include a chlorophenyl group. ), An unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms (for example, 2-furyl group, 2-thienyl group, 2-pyridyl group, 3-pyrazolyl, 3-iso). Oxazolyl, 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), carbon number 1 to 2
A substituted heterocyclic group having 0, preferably 3 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms (for example, the above-mentioned W-substituted heterocyclic group mentioned as an example of the substituent can be mentioned. -Methyl-2-thienyl group, 4-methoxy-2
-Pyridyl group and the like. ) Is mentioned.

The substituent represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ is preferably an unsubstituted alkyl group or a substituted alkyl group, and preferably a substituted alkyl group. It is an alkyl group having the above-mentioned acid group. As the acid group, preferably a sulfo group, a carboxyl group, -CONH
SO ₂ - group, -CONHCO- group, -SO ₂ NHSO ₂ -
A group, particularly preferably a sulfo group or a carboxyl group, and most preferably a sulfo group.

Here, the acid group will be described. The acid group is a group having a dissociative proton. Specifically, for example, a sulfo group, a carboxyl group, a sulfato group, -CO
NHSO ₂ — group (sulfonylcarbamoyl group, carbonylsulfamoyl group), —CONHCO— group (carbonylcarbamoyl group), —SO ₂ NHSO ₂ — group (sulfonylsulfamoyl group), sulfonamide group, sulfamoyl group, phosphato group , Phosphono group, boronic acid group, phenolic hydroxyl group, etc., and their pka and surrounding pH
In some cases, a group capable of dissociating a proton may be mentioned. For example, a proton-dissociable acidic group capable of dissociating 90% or more between pH 5 and 11 is preferable.

More preferably, a sulfo group, a carboxyl group, a -CONHSO ₂ -group, a -CONHCO- group, and -S.
O ₂ NHSO ₂ — group, particularly preferably sulfo group,
It is a carboxyl group, most preferably a sulfo group.

L ₁₁ , L ₁₂ , L ₁₃ , L ₁₄ , L ₁₅ , L ₁₆ , L
₁₇ , L ₁₈ , L ₁₉ , L ₂₀ , L ₂₁ , L ₂₂ , L ₂₃ , L ₂₄ ,
L ₂₅ , L ₂₆ , L ₂₇ , L ₂₈ , L ₂₉ , and L ₃₀ each independently represent a methine group. The methine group represented by L _{1 to} L ₃₀ may have a substituent, and the substituent may be the above-mentioned W.
Is mentioned. For example, a substituted or unsubstituted C1 to C1
An alkyl group having 5, preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms (eg, methyl, ethyl, 2
-Carboxyethyl), a substituted or unsubstituted C6 to C20, preferably C6 to C15, more preferably C6 to C10 aryl group (eg phenyl, o-carboxyphenyl), substituted or unsubstituted 3 to 2 carbon atoms
0, preferably 4 to 15, more preferably 6 to 10 carbon heterocyclic groups (eg N, N-dimethylbarbituric acid group), halogen atoms, (eg chlorine, bromine,
(Iodine, fluorine), an alkoxy group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methoxy, ethoxy), 0 to 1 carbon atoms.
5, preferably 2 to 10 carbon atoms, more preferably 4 to 10 carbon amino groups (eg methylamino, N, N
-Dimethylamino, N-methyl-N-phenylamino,
N-methylpiperazino), an alkylthio group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg methylthio, ethylthio), 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms. More preferably, an arylthio group having 6 to 10 carbon atoms (eg phenylthio, p-methylphenylthio) and the like can be mentioned. It may form a ring with another methine group, or may form a ring together with Z _{11 to} Z ₁₇ and R _{11 to} R ₁₇ .

L ₁₁ , L ₁₂ , L ₁₆ , L ₁₇ , L ₁₈ , L ₁₉ , L
₂₂ , L ₂₃ , L ₂₉ , and L ₃₀ are preferably unsubstituted methine groups.

N ₁₁ , n ₁₂ , n ₁₃ and n ₁₄ each independently represent 0, 1, 2, 3 or 4. Preferably 0, 1,
It is 2 or 3, more preferably 0, 1 or 2, and particularly preferably 0 or 1. n ₁₁ , n ₁₂ , n ₁₃ , and n ₁₄
When is 2 or more, the methine groups are repeated but need not be the same.

P ₁₁ , p ₁₂ , p ₁₃ , p ₁₄ and p ₁₅ each independently represent 0 or 1. It is preferably 0.

M ₁₁ , M ₁₂ and M ₁₃ are included in the formula to indicate the presence of a cation or anion when required to neutralize the ionic charge of the dye. Typical cations include hydrogen ions (H +), alkali metal ions (eg sodium ion, potassium ion,
Inorganic cations such as lithium ion) and alkaline earth metal ions (eg calcium ion), ammonium ions (eg ammonium ion, tetraalkylammonium ion, triethylammonium ion, pyridinium ion, ethylpyridinium ion, 1,8
-Diazabicyclo [5.4.0] -7-undecenium ion) and the like. The anion may be an inorganic anion or an organic anion, a halogen anion (eg, fluorine ion, chlorine ion, iodine ion), a substituted aryl sulfonate ion (eg, p-toluene sulfonate ion, p-ion). Chlorbenzenesulfonate ion), aryldisulfonate ion (for example, 1,3-benzenesulfonate ion, 1, 5
-Naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkylsulfate ion (for example, methylsulfate ion), sulfate ion, thiocyanate ion,
Examples include perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, and trifluoromethanesulfonate ion. Furthermore, an ionic polymer or another dye having a charge opposite to that of the dye may be used. Also,
CO ₂ − and SO ₃ − can also be expressed as CO ₂ H and SO ₃ H when having hydrogen ions as counter ions.

M ₁₁ , m ₁₂ , and m ₁₃ represent a number of 0 or more necessary for balancing the charge, preferably a number of 0 to 4, more preferably a number of 0 to 1, and a molecule It is 0 when a salt is formed therein.

Next, specific examples of the sensitizing dye of the present invention are shown below, but of course, the sensitizing dye of the present invention is not limited to these.

[0107]

[Chemical 16]

[0108]

[Chemical 17]

[0109]

[Chemical 18]

[0110]

[Chemical 19]

The sensitizing dye used in the present invention is,
FM Harmer, "Heterocyclic Compounds-Cyanine Soybean and Related Compounds (Heterocyclic C)
Ompounds-Cyanine Dyes and
Related Compounds ", John Wiley and Sons (John Wiley)
& Sons) -New York, London, 1964
Annually, DM Sturme
r) “Heterocyclic Compounds-Special Topics in Heterocyclic Compounds”
s-Special topics in heater
ocracy chemistry) ", 18th
Chapter, Section 14, 482-515, John Wiley & Sos
ns) -New York, London, 1977,
"Rods Chemistry of Carbon Compounds (Rodd's Chemistry of Car
bon Compounds) "2nd. Ed. vo
l. IV, part B, 1977, Chapter 15, Chapter 36
9-422, Elsevier Science Public Company, Inc.
ce Publishing Company In
c. ) It can be synthesized based on the method described in, for example, the publisher, New York.

In the present invention, one kind of sensitizing dye may be used, but two or more kinds may be used, and a combination of sensitizing dyes is often used particularly for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,977,
No. 229, No. 3,397,060, No. 3,522,0
No. 52, No. 3,527, 641, No. 3, 617, 29
No. 3, No. 3,628,964, No. 3,666,480
Issue 3, Issue 3,672,898, Issue 3,679,428
No. 3,303,377, No. 3,769,301
Nos. 3,814,609 and 3,837,862
No. 4,026,707, British Patent 1,344,2
No. 81, No. 1,507, 803, Japanese Patent Publication No. 43-493
No. 36, No. 53-12375, JP-A No. 52-1106.
18 and 52-109925.

In addition to the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

In the spectral sensitization of the present invention, useful supersensitizers (eg, pyrimidylamino compounds, triazinylamino compounds, azolium compounds, aminostyryl compounds, aromatic organic acid formaldehyde condensates, azaindene compounds, cadmium salts). ), And a combination of a supersensitizer and a sensitizing dye are described in, for example, US Pat.
No. 64, No. 3,615, 613, No. 3, 615, 63
No. 2, No. 3,615, 641, No. 4,596, 767
No. 4,945,038, 4,965,182
No. 4,965,182, 2,933,390
Issue No. 3,635,721 Issue 3,743,510
No. 3,617,295, No. 3,635,721, etc., and the method described in the above-mentioned patent is also preferable for the usage thereof.

In the present invention, the time for adding a sensitizing dye (also for a supersensitizer) to the silver halide emulsion of the present invention has been found to be useful so far. Any of the steps may be performed. For example,
US Pat. Nos. 2,735,766 and 3,628,960
Nos. 4,183,756, 4,225,666
No. 58-184142 and 60-19674.
No. 9, etc., the time before the grain forming step of silver halide and / or before desalting, the time during the desalting step and / or after the desalting until the start of chemical ripening, 58-1
As disclosed in Japanese Patent No. 13920, it may be added at any time or step immediately before the chemical ripening or during the step or before the emulsion is coated after the chemical ripening and before the coating. Further, as disclosed in U.S. Pat. No. 4,225,666 and JP-A-58-7629, the same compound may be used alone or in combination with a compound having a different structure.
For example, it may be added dividedly during the grain formation step and during the chemical ripening step or after the chemical ripening, or before the chemical aging or during the step and after the chemical ripening. The compound and the kind of combination of the compound may be changed and added.

In the present invention, the addition amount of the sensitizing dye (and the same applies to the supersensitizer) depends on the shape and size of the silver halide grains and may be any addition amount. Per mol, preferably 1 x 1
^0-8 to 8 × 10 ^-1 mol, more preferably 1 × 10
^-6 to 8 x 10 ^-3 . For example, when the silver halide grain size is 0.2 to 1.3 μm, the addition amount of 2 × 10 ^{−6 to} 3.5 × 10 ⁻³ mol is preferable, and 7.5 mol per 1 mol of silver halide. The addition amount of × 10 ^{-6 to} 1.5 × 10 ^-3 mol is more preferable.

In the present invention, the sensitizing dye (also for the supersensitizer) can be directly dispersed in the emulsion. Further, these may be first dissolved in a suitable solvent such as 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 coexistent. Ultrasonic waves can also be used for dissolution. As a method of 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 to prepare a dispersion of this compound. The method of adding to the emulsion,
As described in JP-B-46-24185, a method of dispersing in a water-soluble solvent and adding this dispersion into an emulsion, as described in US Pat. No. 3,822,135,
A method in which a compound is dissolved in a surfactant and the solution is added to the emulsion, a method in which a compound for red-shifting is used to dissolve the compound and the solution is added to the emulsion as described in JP-A-51-74624. As described in JP-A-50-80826, a method in which a compound is dissolved in an acid containing substantially no water and the solution is added to the emulsion is used. In addition, U.S. Pat. No. 2,912,343 is used for addition to the emulsion.
Issue 3, Issue 3,342,605, Issue 2,996,287
No. 3,429,835 and the like.

In the present invention, any known processing composition can be used for each processing bath such as color development, bleaching, fixing, washing with water, stability, adjustment, black and white development, reversal and pre-bleaching. Details thereof are described in, for example, JP 2001-92090 A.
No., page 32, right column, line 9 to page 38, right column, line 30,
JP-A-2001-109117, page 30, right column 34
Lines to page 37, right column, line 37.

In addition to the above treatment bath, a treatment bath containing the stain reducing agent precursor used in the present invention may be separately provided. This bath will be referred to as an absorption bath. The absorption bath or the composition thereof may simply be an aqueous solution of the stain reducing agent precursor in the present invention, or may be a composition according to the washing composition and the stable composition. It is a preferred embodiment to add a compound that increases the solubility of the stain reducing agent precursor in the present invention to the absorption bath or its composition. For example, ethylene glycols, alkanolamines, aryl sulfonic acids, alkyl sulfonic acids or urea compounds described in JP-A No. 11-174643 can be added. Further, a surface active agent such as polyethylene glycol, a block polymer of polyethylene glycol and polypropylene glycol, an alkyl ethoxylate or an alkylnaphthalene sulfonic acid can be added. Among them, average molecular weight 300 to 2000
Particularly preferred are polyethylene glycols, block polymers of polyethylene glycol and polypropylene glycol, and ethylene urea. When a compound that increases the solubility is added, its concentration is 0.1 to 100 g / L, preferably 0.5 g to 50 g / L, more preferably 1 to
It is 20 g / L.

The concentration of the stain reducing agent precursor used in the present invention in the solution is 0.05 to 2 in the working solution.
0 mmol / L, preferably 0.15 to 15 mm
ol / L, more preferably 0.2 to 10 mmol / L. When the treatment composition containing the stain reducing agent precursor used in the present invention is used after diluted with water or another treatment composition, the concentration in the treatment composition is the concentration ratio to the concentration in the working solution. It is the value multiplied by.

The contact between the silver halide photographic light-sensitive material and the oxidizing agent is carried out after the silver halide photographic light-sensitive material incorporates the stain reducing agent precursor used in the present invention. The oxidizing agent used for this oxidative treatment may be any one as long as it generates an active radical species, and for example, those described in the following documents are preferably used. Specific examples include manganese compounds (for example, potassium permanganate and manganese dioxide) and chromic acid compounds (for example, Cr) described in the literature.
O ₃ ), osmium tetroxide, ruthenium tetroxide, and other metal oxidants (for example, lead oxide, lead acetate, mercury oxide, mercury acetate, silver carbonate, silver oxide, silver nitrate, thallium acetate, thallium nitrate, copper chloride, acetic acid) Copper, palladium chloride, iron chloride,
Potassium ferricyanide, VOCl ₃ , V ₂ O ₅ , cerium acetate, cerium ammonium nitrate (CAN), sodium bismuthate, nickel peroxide, organic peracids and organic peroxides (for example, metachloroperbenzoic acid (MCPBA), Perbenzoic acid, peracetic acid, t-butyl hydroperoxide), oxidation by organic compounds (for example, dimethyl sulfoxide / oxalyl chloride, dimethyl sulfoxide / trifluoroacetic anhydride, dimethyl sulfoxide / dicyclohexylcarbodiimide, quinones (2,3-dichloro) -5,6-dicyano-1,4-benzoquinone, etc.), nitrobenzene, p-nitrosodimethylaniline, dimethylaminopyridine N-oxide, triphenylmethyl cation, diethyl azodicarboxylate,
Diphenyl nitroxide, tetrabutylammonium periodate, 2-sulfonyloxaziridine, iodosobenzene diacetate), oxygen, ozone, selenium dioxide,
Chlorine, bromine, iodine, bromine-hexamethylphosphoramide, sodium hypochlorite, sodium chlorite, sodium chlorate, sodium hypobromite, orthoperiodic acid, nitric acid, nitrous acid, nitrogen dioxide, nitrosodisulfone potassium acid, ammonium persulfate, microbes and enzymes, the electrode (anode) oxide, and the like, Besides, for example, hydrogen peroxide and its adducts (e.g., NaBO ₂ · H ₂ O
_{2 · 3H 2 O, 2NaCO 3} · 3H 2 O 2, Na 4 P 2 O 7 · 2
_{H 2 O 2, 2Na 2 SO} 4 · H 2 O 2 · 2H 2 O), peroxy acid salt _{(e.g., K 2 S 2 O 8,} K 2 C 2 O 6, K 2 P
₂ O ₈ ), a peroxy complex compound (for example, K ₂ [Ti
(O ₂ ) C ₂ O ₄ ] ・ 3H ₂ O, 4K ₂ SO ₄・ Ti (O ₂ )
OH ・ SO ₄・ 2H ₂ O, Na ₃ [VO (O ₂ ) (C ₂ H ₄ )
₂ ] · 6H ₂ O), K ₂ Cr ₂ O ₇ , potassium periodate, potassium hexacyanoferrate, thiosulfonate, peracetic acid, N-bromosuccinimide, chloramine T, chloramine B, Fe (III ) 1,3-PDTA, Fe (III)
EDTA etc. are mentioned. Among these, organic peracids and peroxides, sodium hypochlorite, sodium chlorite, sodium chlorate, ammonium persulfate, hydrogen peroxide and its adducts, potassium hexacyanoferric acid is preferred, hypochlorous acid Sodium, ammonium persulfate,
Hydrogen peroxide water and potassium hexacyanoferric acid are particularly preferable. Among the stain-reducing agent precursors according to the present invention, the electron-donor type radical generator, in particular, produces an active radical species by the reaction with these oxidizing agents, and the radical species attack the sensitizing dye to cause desensitization. The residual color due to the sensitizing dye in the material is reduced.

Jerry Mar
ch), Advanced Organic Chemistry (Advanced Organic Chemistry)
ry), John Willie and Sons (John)
Wiley & Sons, New York (New)
York) (1992) Chapter 19, O
xations And Reductions,
p. 1158-1238, edited by The Chemical Society of Japan, 4th Edition Experimental Chemistry Lecture, Volume 23, Organic Synthesis V, Oxidation Reaction, Maruzen (1991).

Containing a stain reducing agent precursor,
Alternatively, when the incorporated silver halide photographic light-sensitive material is brought into contact with an oxidizing agent, the oxidizing agent may be supplied in any form, and it is particularly preferable to supply it as a solution. The oxidizing agent solution may be brought into contact with the silver halide photographic light-sensitive material by any method such as spraying or spraying with a line jet, coating with a roller or a sheet, adhesion with a sheet, and dipping similar to a usual photographic processing step. Here, the sheet means a polymer fiber cloth capable of holding an oxidant solution. The concentration of the oxidant solution is 0.005-3.0
mol / L is preferable, and more preferably 0.01 to
1.5 mol / L, more preferably 0.02-0.5 m
ol / L. When the treatment composition containing the oxidizing agent is used after being diluted with water or another treatment composition, the concentration in the treatment composition is the concentration in the working solution multiplied by the concentration factor.

It is a preferred embodiment that the silver halide photographic light-sensitive material is immersed in a processing bath containing the oxidant in order to bring the silver halide photographic light-sensitive material into contact with the oxidizing agent in the developing step. This bath will be called an oxidation bath. The oxidizing bath or the composition thereof may be simply an aqueous solution of the oxidizing agent, or may be a composition according to the washing composition and the stable composition. It is a preferred embodiment to add a compound that enhances the solubility of the stain reducing agent precursor to the oxidizing bath or its composition. Examples of organic oxidizing agents include ethylene glycols, alkanolamines, aryl sulfonic acids, alkyl sulfonic acids, and JP-A-1.
It is useful to add a urea compound or the like described in 1-174743. Further, a surface active agent such as polyethylene glycol, a block polymer of polyethylene glycol and polypropylene glycol, an alkyl ethoxylate or an alkylnaphthalene sulfonic acid can be added.

Further, an optional buffer may be added to the oxidizing bath in order to adjust the oxidizing power and solubility of the oxidizing agent.
As the inorganic buffering agent, there are inorganic salts such as carbonate, bicarbonate, phosphate, borate, tetraborate, etc., and potassium salt, sodium salt or ammonium salt is preferable. As the organic buffer, succinic acid, maleic acid, glycolic acid,
Organic acids such as malonic acid, fumaric acid, succinic acid, sulfosuccinic acid and acetic acid, or organic bases such as imidazole and dimethylimidazole can be preferably used.

The oxidation bath treatment of the silver halide photographic light-sensitive material is carried out after the absorption step of incorporating the stain reducing agent precursor in the present invention into the silver halide photographic light-sensitive material. Preferred specific examples of the treatment process will be given below, but the treatment process is not limited thereto. Color development-bleach-fix-wash-stable-absorption-oxidation-dry Color development-bleach-fix-wash-absorption-oxidation-stable-dry color development-bleach-fix-stable-absorption-oxidation-dry color development-bleach -Fixing-Absorption-Oxidation-Stable-Dry color development-Bleach-Fixing-Washing-Absorption-Oxidation-Dry color development-Bleach-Fixing-Absorption-Oxidation-Water washing-Dry color development-Bleach-Fixing-Water washing-Absorption-Oxidation The desilvering process including washing with water, drying, and bleaching and fixing may be any of bleach-fixing, bleach-bleach-fixing and bleach-fixing-fixing. Further, black and white development and reversal may be performed as a pre-process of color development. Furthermore, it is possible to combine both oxidation and bleaching as follows. Color development-washing-absorption-bleaching (oxidation) -fixing-washing-drying Color development-washing-absorption-bleaching (oxidation) -fixing-stable-drying

[0127]

[Examples] The following specifically describes that the stains caused by the sensitizing dyes can be reduced by bringing an oxidizing agent into contact with the silver halide photographic light-sensitive material in the presence of the stain reducing agent precursor in the present invention. I will explain
The present invention is not limited to these. (Example 1) [Preparation of photosensitive material sample] After performing corona discharge treatment on the surface of a support having both sides of paper coated with polyethylene resin,
A gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and then the first layer to the seventh layer were sequentially coated to prepare a silver halide color photographic light-sensitive material P-1 having the following layer structure. The coating liquid for each photographic constituent layer was prepared as follows.

Preparation of Fifth Layer Coating Solution Cyan coupler (ExC) 300 g, color image stabilizer (Cp
d-1) 250 g, color image stabilizer (Cpd-14) 30
g, color image stabilizer (Cpd-15) 100 g, color image stabilizer (Cpd-16) 80 g, color image stabilizer (Cpd-17)
50 g and 10 g of color image stabilizer (Cpd-18) are dissolved in 230 g of solvent (Solv-5) and 350 ml of ethyl acetate, and this liquid is emulsified and dispersed in 6500 g of 10% gelatin aqueous solution containing 25 g of sodium dodecylbenzenesulfonate. Dispersion C was prepared.

On the other hand, a silver chlorobromide emulsion C (cubic, 5: 5 mixture of large size emulsion C having an average grain size of 0.40 μm and small size emulsion C having a grain size of 0.30 μm (silver molar ratio). Coefficients of variation were 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was localized on a part of the grain surface based on the silver chloride emulsion). This emulsion contains the red sensitizing dyes G and H shown below.
However, it is 9.0 × 10 ⁻⁵ mol for each large-sized emulsion C and 1 for each small-sized emulsion C per mol of silver.
2.0 × 10 ⁻⁵ mol of each is added. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion C and the silver chlorobromide emulsion C were mixed and dissolved to prepare a coating solution for the fifth layer having the composition described below. The emulsion coating amount indicates a coating amount equivalent to silver.

The coating solutions for the first to fourth layers, the sixth layer and the seventh layer were prepared in the same manner as the coating solution for the fifth layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Further, Ab-1, Ab-2, Ab-3 and Ab are used as antiseptics in each layer.
-4 each has a total amount of 15.0 mg / m ² , 60.0 m
g / m ² , 5.0 mg / m ² and 10.0 mg / m ² were added.

[0131]

[Chemical 20]

The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer.・ Blue sensitive emulsion layer

[0133]

[Chemical 21]

(Sensitizing dyes A and C were added per mol of silver halide in an amount of 0.42 × 10 ^-4 mol for a large size emulsion and 0.50 × 10 ^-4 mol for a small size emulsion. Sensitizing dye B was added in an amount of 3.4 × 10 ⁻⁴ mol for a large-sized emulsion and 4.1 × 10 ⁻⁴ mol for a small-sized emulsion, per mol of silver halide.)

Green sensitive emulsion layer

[0136]

[Chemical formula 22]

(Sensitizing dye D was added per mol of silver halide in an amount of 3.0 × 10 ^-4 mol for a large-sized emulsion and 3.6 × 10 ^-4 mol for a small-sized emulsion. Sensitizing dye E was added per mol of silver halide in an amount of 4.0 × 10 ⁻⁴ mol for a large-sized emulsion and 7.0 × 10 ⁻⁵ mol for a small-sized emulsion. F is 2.0 × per mol of silver halide for large-sized emulsions.
10 ⁻⁴ mol, and 2.8 × 10 ⁻⁴ mol was added to the small size emulsion. )

Red sensitive emulsion layer

[0139]

[Chemical formula 23]

(Sensitizing dyes G and H were added per mol of silver halide of 8.0 × 10 ^-5 mol for a large-sized emulsion,
10.7 × 10 ^-5 mol was added to the small size emulsion. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 3.0 × 10 ^-3 mol per mol of silver halide. )

[0141]

[Chemical formula 24]

Blue-sensitive emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer
1- (3-methylureidophenyl) -5 for the emulsion layer
-Mercaptotetrazole was added to each silver halide.
3.3 x 10 per le^-FourMole, 1.0 × 10^-3Mole and
And 5.9 x 10^-FourMol added. Second layer, fourth layer, sixth layer
0.2mg / m for each layer and 7th layer², 0.2
mg / m², 0.6 mg / m², 0.1 mg / m²Becomes
So added. For blue-sensitive emulsion layer and green-sensitive emulsion layer
4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene per mol of silver halide
1 x 10 ^-FourMole, 2 × 10^-FourMol added. Red sensitive emulsion
Copolymer latex of methacrylic acid and butyl acrylate
Cousin (mass ratio 1: 1, average molecular weight 200,000-400)
000) is 0.05 g / m²Was added.

6 mg each of disodium catechol-3,5-disulfonate was added to the second, fourth and sixth layers.
/ M ² , 6 mg / m ² , and 18 mg / m ² were added. The following dyes (the amount in parentheses indicates the coating amount) were added to prevent irradiation.

[0144]

[Chemical 25]

(Layer Structure) Each layer structure is shown below. Numbers indicate coating materials (g / m ² ). The silver halide emulsion shows the equivalent amount of silver coating. Support Polyethylene resin laminated paper [White pigment (TiO ₂ :
Content 16% by mass, ZnO: content 4% by mass, fluorescent whitening agent (4,4′-bis (5-methylbenzoxazolyl) stilbene content 0.03% by mass), bluish dye (ultra-blue) )including]

[0146] First layer (blue sensitive emulsion layer)   Silver chlorobromide emulsion A (cubic, large size emulsion A having an average grain size of 0.74 μm and 0 ． 5: 5 mixture with 65 μm small size emulsion A (silver molar ratio). Particle size distribution Coefficients of variation are 0.08 and 0.10. 0.3 mol silver bromide for each size emulsion % Was locally contained in a part of the surface of the grain based on silver chloride. )                                                       0.24 Gelatin 1.25 Yellow coupler (ExY) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.07 Solvent (Solv-1) 0.21

[0147] Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-4) 0.09 Color mixing prevention aid (Cpd-5) 0.018 Stabilizer (Cpd-6) 0.13 Color mixing inhibitor (Cpd-7) 0.01 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

[0148] Third layer (green sensitive emulsion layer)   Silver chlorobromide emulsion B (cubic, large size emulsion B having an average grain size of 0.45 μm and 0 ． 1: 3 mixture with 35 μm small size emulsion B (silver molar ratio). Particle size distribution Coefficients of variation are 0.10 and 0.08, respectively. 0.4 mol silver bromide for each size emulsion % Was locally contained in a part of the surface of the grain based on silver chloride. )                                                     0.14 Gelatin 1.36 Magenta coupler (ExM) 0.15 UV absorber (UV-1) 0.05 Ultraviolet absorber (UV-2) 0.03 Ultraviolet absorber (UV-3) 0.02 Ultraviolet absorber (UV-4) 0.04 Color image stabilizer (Cpd-2) 0.02 Color mixing inhibitor (Cpd-4) 0.002 Stabilizer (Cpd-6) 0.09 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0.10 Solvent (Solv-4) 0.20 Solvent (Solv-5) 0.20 Solvent (Solv-8) 0.05

[0149] Fourth layer (color mixing prevention layer) Gelatin 0.71 Color mixing inhibitor (Cpd-4) 0.06 Color mixing prevention aid (Cpd-5) 0.013 Stabilizer (Cpd-6) 0.10 Stabilizer (Cpd-12) 0.01 Color mixing inhibitor (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

[0150] Fifth layer (red sensitive emulsion layer)   Silver chlorobromide emulsion C (cubic, large size emulsion A with an average grain size of 0.40 μm and 0 ． 5: 5 mixture with 30 μm small size emulsion A (silver molar ratio). Particle size distribution Coefficients of variation are 0.09 and 0.11. 0.5 mol silver bromide for each size emulsion % Was locally contained in a part of the surface of the grain based on silver chloride. )                                                     0.20 Gelatin 1.11. Cyan coupler (ExC) 0.25 Color image stabilizer (Cpd-1) 0.25 Color image stabilizer (Cpd-14) 0.03 Color image stabilizer (Cpd-15) 0.10 Color image stabilizer (Cpd-16) 0.08 Color image stabilizer (Cpd-17) 0.05 Color image stabilizer (Cpd-18) 0.01 Solvent (Solv-5) 0.23

[0151] Sixth layer (UV absorption layer) Gelatin 0.46 Ultraviolet absorber (UV-1) 0.14 UV absorber (UV-2) 0.05 Ultraviolet absorber (UV-3) 0.04 UV absorber (UV-4) 0.05 Ultraviolet absorber (UV-5) 0.02 Solvent (Solv-7) 0.25

[0152] Seventh layer (protective layer) Gelatin 1.00 Acrylic modified copolymer of polyvinyl alcohol (Modification degree 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

[0153]

[Chemical formula 26]

[0154]

[Chemical 27]

[0155]

[Chemical 28]

[0156]

[Chemical 29]

[0157]

[Chemical 30]

[0158]

[Chemical 31]

[0159]

[Chemical 32]

[0160]

[Chemical 33]

[0161]

[Chemical 34]

The following development processing was carried out on the unexposed photosensitive material sample P-1. [Treatment Process] Treatment Time Temperature Color development 38.5 ° C. 45 seconds Bleach-fixing 38.0 ° C. 45 seconds Washed with water 38.0 ° C. 10 seconds Absorption room temperature 20 seconds Oxidation room temperature 20 seconds Washed room temperature 10 seconds Dry 80 °

The composition of each processing liquid is as follows. [Color developer] 800 mL of water Triisopropanolamine 8.8g Ethylenediaminetetraacetic acid 4.0 g Sodium sulfite 0.10g Potassium chloride 10.0g 4,5-dihydroxybenzene- Sodium 1,3-disulfonate 0.50 g Disodium-N, N-bis (sulfonate Ethyl) hydroxylamine 8.5 g 4-amino-3-methyl-N-ethyl-N- (Β-methanesulfonamidoethyl) aniline ・ 3/2 Sulfate ・ Monohydrate 4.8g 26.3 g potassium carbonate Add water to a total volume of 1000 mL pH (25 ° C, adjusted with sulfuric acid and KOH) 10.15

[0164] [Bleaching fixer] 400 mL of water Ammonium thiosulfate (750 g / mL) 110 mL Ethylenediaminetetrairon (III) acetate ammonium 42g Ethylenediamine tetraacetic acid 5g Ammonium sulfate 12g Imidazole 10g Ethylenediaminetetraacetic acid 9.0g Ammonium sulfite 45g m-carboxybenzenesulfinic acid 8g Add water to a total volume of 1000 mL pH (25 ° C, adjusted with nitric acid and ammonia water) 6.50

[0165] [Absorbing liquid] Stain reducing agent precursor in the present invention (Table 1)                                     1 mmol Polyethylene glycol molecular weight 300 50g Add water to a total volume of 1000 mL pH (25 ° C, adjusted with sulfuric acid and sodium hydroxide) 7.0

[0166] [Oxidizing liquid] Oxidizing agent (listed in Table 1) Listed in Table 1 Add water to a total volume of 1000 mL pH (25 ° C, adjusted with sulfuric acid and sodium hydroxide) 8.5

[Evaluation] The reflection spectrum of the minimum density portion was measured using a U-3500 type spectrophotometer manufactured by Hitachi Ltd. equipped with a 150 mmΦ integrating sphere for the photosensitive material sample which was imagewise exposed and developed. Measured, 45
The absorbance at 0 nm was designated as D _B. Next, each sample was washed with distilled water at 40 ° C. for 5 minutes, dried and then subjected to the same measurement, and the absorbance at 450 nm at this time was _defined as D _Bw . ΔD _B was calculated based on the following formula, and the degree of stain due to the residual sensitizing dye was evaluated. A smaller ΔD _B means that the residual sensitizing dye is smaller and the stain reducing effect is larger. ΔD _B = D _B −D _BW

[0168]

[Table 1]

From Table 1, in Sample 11 in which the stain reducing agent precursor of the present invention was not added to the absorbing bath, and in Samples 12 and 15 in which the stain reducing agent precursor of the present invention was added to the absorbing bath but no oxidizing agent was added to the oxidizing bath In contrast,
Samples 13 and 14 prepared by adding the stain reducing agent precursor of the present invention and adding the oxidizing agent to the oxidizing bath,
In 16 to 19, it was shown that the yellow density was lowered and the sensitizing dye stain was reduced.

(Example 2) Fuji exposed imagewise
Photo Fujifilm superior zoom mass made by film
Sample 21 by applying the same process CN-16L
Was produced. Next, the process CN-16L stabilization bath
Add stain reducer precursor b-1 in Ming
Then, the photosensitive material was subjected to Process CN-16L to obtain Sample 2
2 was produced. About samples 21 and 22 Hitachi
U-3500 type spectrophotometer manufactured by KK
The transmission absorption measurement is performed and the absorption at 500 nm and 555 nm is measured.
Luminosity D ₅₀₀ ⁰  , D₅₅₅ ⁰I asked. Next, for samples 21 and 22
The following post-treatment was performed.

[Post-Processing Step] Oxidation room temperature 30 seconds Rinse at room temperature for 20 seconds Dry 80 ℃

[0172] [Oxidizing liquid] Sodium hypochlorite 10 mmol Add water to a total volume of 1000 mL pH (25 ° C, adjusted with sulfuric acid and sodium hydroxide) 8.5

The same transmission / absorption measurement was performed again to 500 n.
m, was determined absorbance D _500, D _{5 55} at 555 nm. The differences ΔD ₅₀₀ and ΔD ₅₅₅ in the stain before and after the post-treatment were calculated by the following formula. ΔD ₅₀₀ and ΔD ₅₅₅ mean that the larger the value, the greater the stain reduction effect. ΔD ₅₀₀ = D ₅₀₀ ⁰ -D ₅₀₀ ΔD ₅₅₅ = D ₅₅₅ ⁰ -D ₅₅₅

[0174]

[Table 2]

From Table 2, it can be seen that the sample 21 after the post-oxidation treatment using the normal stabilizer was compared with the sample 21 after the post-oxidation treatment using the stabilizer containing the stain reducing agent precursor of the present invention. It was shown that the stain was reduced.

Example 3 A sample 31 was prepared by subjecting Fujichrome Provia 100 manufactured by Fuji Photo Film Co., Ltd. exposed imagewise to the process CR-56P manufactured by the same company. Next, the stain reducing agent precursor b-32 of the present invention was added to the stabilizing bath of Process CR-56P, and the photosensitive material was subjected to Process CR-56P to prepare Sample 32.
Using a U-3500 type spectrophotometer manufactured by Hitachi, Ltd., the transmission absorption measurement at the minimum density part was performed to determine the absorbance D ₅₄₀ ⁰ at ₅₄₀ nm of the two treated color reversal films. After performing the same post-treatment as in Example 2 on Samples 31 and 32, the transmission absorption measurement of the minimum concentration part was performed again to obtain 540n.
The absorbance D ₅₄₀ at m was determined, and the difference in stain ΔD ₅₄₀ before and after the post-treatment was determined by the following formula. ΔD ₅₄₀ means that the larger the value, the greater the stain reduction effect. ΔD ₅₄₀ = D ₅₄₀ ⁰ −D ₅₄₀

[0177]

[Table 3]

From Table 3, in the case of the sample 31 which was subjected to the post-oxidation treatment using the usual stabilizing solution, the sample 32 which was subjected to the post-oxidation treatment using the stabilizing solution containing the stain reducing agent precursor of the present invention was used. It was shown that the stain was reduced.

[0179]

INDUSTRIAL APPLICABILITY The present invention can provide a method for processing a silver halide photographic light-sensitive material, which provides a silver halide photographic light-sensitive material in which stain caused by residual sensitizing dye after processing is reduced.

Claims (4)

[Claims] 1. An exposed silver halide photographic light-sensitive material is contacted with an oxidizing agent in the presence of a compound selected from organic boron compounds, organic silicon compounds, organic tin compounds, organic germanium compounds and organic aluminum compounds. A method of processing a silver halide photographic light-sensitive material, comprising: 2. The compound selected from the organic boron compound, the organic silicon compound, the organic tin compound, the organic germanium compound and the organic aluminum compound is a compound represented by the general formula (A). The method of processing a silver halide photographic light-sensitive material according to claim 1. [Chemical 1] (In the formula, Ra ¹ , Ra ² , Ra ³ and Ra ⁴ are each independently an aliphatic group, an aromatic group, a heterocyclic group, or Si (R
a ⁵⁾ represent ^{(Ra 6) -Ra 7, Ra} 5, Ra 6, Ra
Each ⁷ independently represents an aliphatic group or an aromatic group. M
Is boron ion (B ⁻ ), silicon (Si), tin (S
n), germanium (Ge) or aluminum ion (Al ⁻ ). (G ⁺ ) _n represents a cation or a cationic compound necessary for neutralizing the charge as a whole molecule, and n is 0 or 1. ) 3. The method for processing a silver halide photographic light-sensitive material according to claim 2, wherein the compound represented by the general formula (A) is an aqueous solution. 4. The method for processing a silver halide photographic light-sensitive material according to claim 2 or 3, wherein M in the general formula (A) is boron.