JP2003131351A - Treatment method for diminishing sensitizing dye stain of silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a treatment method for diminishing stains of a silver halide photographic sensitive material due to a residual sensitizing dye. SOLUTION: In the treatment method for diminishing sensitizing dye stains of a silver halide photographic sensitive material, a developed silver halide photographic sensitive material is brought into contact with a reducer.

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, preferably a silver halide photographic light-sensitive material, and more particularly to a method for reducing stains resulting from residual sensitizing dye in the light-sensitive material after processing. is there.

[0002]

2. Description of the Related Art With the remarkable progress of digital cameras and color printers, in the processing of silver halide color photographic light-sensitive materials, it is desired to promptly provide customers with high quality images. However, if the conventional processing method is simply shortened, the processing is completed before the sensitizing dye in the light-sensitive material is sufficiently washed out, so the image is colored by the large amount of the sensitizing dye remaining on the white background of the color print. It became hard to appreciate it. 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, improves the sensitivity and the sensitivity-granular ratio because the amount of sensitizing dye used per unit volume can be increased. On the other hand, the amount of sensitizing dye remaining in the processed 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.
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. Also, in US Pat. No. 6,153,364, 2,
A stain reduction method using a 6-diarylaminotriazine compound has been proposed.

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 contains N-
It has been proposed to irradiate a light-sensitive material with light in the presence of an oxyazinium compound to reduce stain. 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. See also Research Disclosure 2
No. 0733 discloses a method of destroying the sensitizing dye by immersing the photographic element after development and bleach-fixing by adding a perchlorate or a persulfate to a washing bath, but the stability of the oxidizing agent is sufficient. is not.

[0008]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a processing method which provides a silver halide photographic light-sensitive material having a reduced stain after processing due to a residual sensitizing dye.

[0009]

The above-mentioned problems have been solved by the following inventions. That is, (1) a processing method for reducing the sensitizing dye stain of a silver halide photographic light-sensitive material, which comprises bringing the developed silver halide photographic light-sensitive material into contact with a reducing agent. (2) The processing method for reducing the sensitizing dye stain of a silver halide photographic light-sensitive material according to (1), wherein the reducing agent is brought into contact with the silver halide photographic light-sensitive material as an aqueous solution. (3) The processing method for reducing the sensitizing dye stain of the silver halide photographic light-sensitive material according to (1) or (2), wherein at least one compound selected from hydrazines is used as a reducing agent.

Next, the reducing agent used in the present invention will be described in detail. The contact between the silver halide photographic light-sensitive material and the reducing agent is preferably performed after the development step, more preferably after the fixing step in which the silver halide is substantially removed from the silver halide photographic light-sensitive material. Any reducing agent may be used in this reducing treatment, for example,
Those described in the following documents can be preferably used. Specific examples thereof include metals and metal salts (for example, alkali metal (for example, sodium), alkaline earth metal (for example, calcium)) described in the literature,
Zinc, aluminum, CrCl ₂ , TiCl ₃ , SmI
₂ ), metal hydrides and metal hydrogen complex compounds (for example, L
iAlH ₄ , (C ₆ H ₅ ) ₃ SnH, NaBH ₄ , (C
₂ H ₅ ) ₃ SiH, NaBH ₃ CN), boranes (eg B
H ₃ , dimethylamine borane), hydrazines (eg N ₂ H ₄ ), diimides, phosphorus compounds (eg (CH
₃ O) ₃ P), (CH ₃ ) SiI, etc., and other sulfur compounds (eg, NaSH, Na ₂ S, Na ₂
S ₂ O ₄ ), hydroquinones (eg hydroquinone), phenylenediamine (eg amidole), Sn
Cl ₂ , ascorbic acid and its derivatives (eg L
-Ascorbic acid, L-sodium ascorbate, D
L-ascorbic acid, sodium D-ascorbate,
L-ascorbic acid-6-acetate, L-ascorbic acid-5,6-diacetate, L-ascorbic acid-
5,6-O-isopropylidene), amines and polyamines, formamidinesulfinic acid, silane compounds,
Examples thereof include thiourea dioxide. Also, electrode (cathode) reduction can be used. Among these, hydrazines are particularly preferable. References: Jerry March, Advanced Organic Chemistry (Advan)
ced Organic Chemistry, John Wiley and Sons (John Wiley)
& Sons), New York
Chapter 19, Oxidati (1992)
ons And Reductions, p. 1158
~ 1238, edited by The Chemical Society of Japan, 4th Edition Experimental Chemistry Lecture, Volume 26, Organic Synthesis VIII, Chapter 2, General Reduction, p. 159-266, Maruzen (1992).

These reducing agents decolorize the sensitizing dye by reacting with the sensitizing dye, or hydrophilize the sensitizing dye to accelerate the elution of the sensitizing dye from the sensitizing material. The residual color due to the sensitizing dye is reduced.

When the silver halide photographic light-sensitive material is brought into contact with the reducing agent of the present invention, the reducing agent may be supplied in any form, and it is particularly preferable to supply it as a solution (preferably an aqueous solution). The reducing agent solution is applied to silver halide photographic light-sensitive materials by spraying or line jetting, coating with rollers or sheets, adhesion with sheets,
They may be contacted by any method such as dipping similar to the ordinary photoprocessing step. Here, the sheet refers to a polymer fiber cloth capable of holding a reducing agent solution. The concentration of the reducing agent solution is preferably 0.005 to 3.0 mol / L, more preferably 0.01 to 1.5 mol / L, and further preferably 0.02 to 0.5 mol / L. When the treating composition containing the reducing agent is used after being diluted with water or another treating composition, the concentration in the treating 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 a reducing agent in order to bring the silver halide photographic light-sensitive material into contact with the reducing agent in the processing step. This bath is called a reduction bath. The reducing bath or the composition thereof may be an aqueous solution of a reducing 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 increases the solubility of the reducing agent in the reducing bath. As the organic reducing agent, it is useful to add, for example, ethylene glycols, alkanolamines, aryl sulfonic acids, alkyl sulfonic acids or urea compounds described in JP-A No. 11-174643. 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 reducing bath in order to adjust the reducing power and solubility of the reducing agent.
Examples of the inorganic buffering agents include carbonates, bicarbonates, phosphates, borates, tetraborates and the like, and potassium salts, sodium salts or ammonium salts are preferable. As the organic buffer, succinic acid, maleic acid, glycolic acid, malonic acid, fumaric acid, succinic acid, sulfosuccinic acid,
Organic acids such as acetic acid or organic bases such as imidazole and dimethylimidazole can be preferably used.

The reduction bath treatment of the silver halide photographic light-sensitive material is preferably carried out after the fixing step in which the silver halide is substantially removed from the light-sensitive material. Preferred specific examples of processing steps including a reduction bath treatment (hereinafter simply referred to as “reduction”) of the silver halide photographic light-sensitive material will be given, but the present invention is not limited thereto. Color development-bleach-fix-wash-stable-reduction-dry Color development-bleach-fix-wash-reduction-stable-dry color development-bleach-fix-stable-reduce-bleach-fix-reduce-stable -Dry color development-bleach-fix-washing-reduction-dry color development-bleach-fixing-reduction-water washing-dry color development-bleach-fixing-water washing-reduction-water washing-drying and the desilvering step consisting of bleaching and fixing , Bleach-fix, bleach-
Either bleach-fixing or bleach-fixing-fixing may be used. Further, black and white development and reversal may be performed as a pre-process of color development.

The reducing agent of the present invention may be added in any form of a tank solution for a reducing bath, a replenishing solution, a concentrated replenishing solution and a kit. Further, the reducing agent of the present invention may be contained in the reducing bath additive composition. The additive composition has a function of adding photographic performance to a tank solution or a replenisher solution required for processing for forming an image of a silver halide color photographic light-sensitive material before or during processing. It is a composition.

The silver halide photographic light-sensitive material used in the present invention can be any of ordinary silver halides such as silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide and mixtures thereof. Can also be included. In one embodiment, the light-sensitive material is a high silver chloride light-sensitive material containing at least 50 mol% or more chloride, more preferably at least 90 mol% or more silver chloride, and is used as 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 individual silver halide photographic light-sensitive materials are described in, for example, Research Disclosure (hereinafter abbreviated as RD), and RD17643 23 to 27.
Pages, RD18716 647-650 pages, RD
307105 Pages 866-868, 873-879
RD 36544 501-541 pages. 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. , Filters, binders, hardeners, plasticizers, lubricants, coating aids, surface-active agents,
Antistatic agent, matting agent, paper and film support,
Alternatively, it relates to various image forming methods for negative image and positive image forming color elements.

Any of spectral sensitizing dyes and supersensitizers 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-Cyanin
e Dyes and Related Compounds ", John Wiley & Sons-New York, London, 1964, Day M Starmer
(DMSturmer) `` Heterocyclic Compounds-Special topi
cs inheterocyclic chemistry) ", Chapter 18, 14
S., pp. 482-515, John Wiley & Sons, Inc.-New York, London, 1977, "Rods Chemistry of the."
Carbon Compounds (Rodd's Chemistry of Carbon
Compounds) ”2nd.Ed.vol.IV, partB, 1977, 15th
Chapter, pages 369-422, Elsevier Science
Public Company, Inc. (Elsevier Science Pu
blishing Company Inc.), published in New York, etc.

To further explain, pages 23 to 24 of RD17643, page 648 of RD18716, right column to 649.
Page right column, RD308119 page 996 right column to page 998 right column, European Patent No. 0565096A1, page 65, pages 7-1.
Those described in line 0 can be preferably used. Also, US Pat. No. 5,747,236 (particularly pages 30 to 39), US Pat. No. 5,340,694 (particularly pages 21 to 60, provided that (XI), (XII), (XII
In the sensitizing dye shown in I), n ₁₂ , n ₁₅ , n ₁₇ , n
The number of ₁₈ is not limited and is an integer of 0 or more (preferably 4 or less)
And The sensitizing dyes represented by the general formulas and specific examples described in 1) can also be preferably used.

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. General formula (X)

[0024]

[Chemical 1]

In the formula (X), L ₁₁ , L ₁₂ , L ₁₃ , L ₁₄ and 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 represent an alkyl group, an aryl group, or a heterocyclic group. General formula (XI)

[0026]

[Chemical 2]

In the formula (XI), L ₁₈ , L ₁₉ , L ₂₀ , and L
₂₁ represents a methine group. p ₁₃ represents 0 or 1. q ₁₁ is 0
Or represents 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 ^'represents a (N-R _{1 4)} heterocyclic ring together with q _11, or acyclic atomic group necessary for forming an acidic end groups. However, the ring may be condensed to Z ₁₃ , and Z ₁₄ and Z ₁₄ ′. M ₁₂ represents a charge balancing counterion,
m ₁₂ represents a number of 0 or more necessary for neutralizing 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. General formula (XII)

[0028]

[Chemical 3]

In the formula (XII), L_{twenty two}, L_{twenty three}, L_{twenty four},
L_{twenty five}, L₂₆, L₂₇, L₂₈, L₂₉And L₃₀Represents the methine group
You p₁₄And p₁₅Represents 0 or 1. q₁₂Is 0 or 1
Represent. n₁₃And n₁₄Represents 0, 1, 2, 3 or 4.
Z₁₅, And Z₁₇Is necessary to form a nitrogen-containing heterocycle
Represents a group of atoms. Z₁₆And Z₁₆ ^'Is (N-R₁₆) Q₁₂With
Represents an atomic group necessary for forming a heterocycle.
However, Z₁₅, Z₁₆And Z₁₆ ^', And Z₁₇The ring is condensed
You may stay. M_{1 3}Represents a charge-balancing counterion, m₁₃Is a minute
Represents a number of 0 or greater required to neutralize the charge of the offspring.
R₁₅, And R₁₇Is an alkyl group, aryl group, or heterocycle
Represents a group. R ₁₆Is a hydrogen atom, an alkyl group, an aryl group,
Or represents a heterocyclic group.

Hereinafter, general formulas (X), (XI), and (X
The methine dye represented by II) will be described in detail.

Regarding a group and the like in the following description, when a specific part is referred to as a "group", the part may be one or more (up to the maximum possible) substitutions, even if the part is not itself substituted. It means that it may be substituted with a group.
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.

When such a substituent is represented by W, the substituent represented by W may be any one, and is not particularly limited. For example, a halogen atom, an alkyl group [(cycloalkyl group, bicycloalkyl group, (Including a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), and an alkynyl group. ], Aryl group, heterocyclic group (may be referred to as heterocyclic group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyl Oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group , Alkyl and aryl sulfonylamino groups, mercapto groups, alkylthio groups, arylthio groups, heterocyclic thio groups, sulfamoyl groups, sulfo groups, alkyl and aryl sulfinyl groups, alkyl and aryl sulfonyl groups, acyl groups, aryl groups Xycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imido group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group , A boronic acid group (-B (OH) ₂ ), a phosphato group (-OPO (O
H) ₂ ), a sulfato group (—OSO ₃ H), and other known substituents can be given 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 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), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, ie, having 5 to 3 carbon atoms
It is a monovalent group obtained by removing one hydrogen atom from a bicycloalkane of 0. For example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-
And a tricyclo structure having many ring structures. The alkyl group in the substituents described below (for example, an alkyl group of an alkylthio group) represents an alkyl group having such a concept, and further includes an alkenyl group and an alkynyl group. ], An alkenyl group [represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group.
They are alkenyl groups (preferably having 2 to 30 carbon atoms).
A substituted or unsubstituted alkenyl group, 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 in which one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms is removed. A group of, for example, 2-cyclopenten-1-yl,
2-cyclohexen-1-yl), a bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a bicycloalkene having one double bond. It is a monovalent group with one hydrogen atom removed.
For example, bicyclo [2,2,1] hept-2-ene-1
-Yl, bicyclo [2,2,2] oct-2-ene-4
-Yl). ], 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), heterocyclic groups (preferably 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocycles) A monovalent group obtained by removing one hydrogen atom from a compound, and 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, 1-methyl-2-
It may be a cationic heterocyclic group such as 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-octyl. Oxy, 2-methoxyethoxy), aryloxy group (preferably having 6 carbon atoms)
To 30 substituted or unsubstituted aryloxy groups, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy groups (preferably having a carbon number 3 to 20 silyloxy groups, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), heterocyclic oxy groups (preferably having 2 to 3 carbon atoms).
0-substituted or unsubstituted heterocyclic oxy group, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkyl group having 2 to 30 carbon atoms) Carbonyloxy group, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy group (preferably A substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy,
Morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, Methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxy. Carbonyloxy, p-
Methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), an amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon atom having 6 to 30 carbon atoms) A substituted anilino group, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), an ammonio group (preferably an ammonio group, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, aryl, Heterocyclic-substituted ammonio groups, such as trimethylammonio, triethylammonio, diphenylmethylammonio), acylamino groups (preferably formylamino groups, substituted or unsubstituted alkylcarbonylamino groups having 1 to 30 carbon atoms, Having 6 to 30 carbon atoms A substituted or unsubstituted arylcarbonylamino group, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably A substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, for example, carbamoylamino,
N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), an 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), an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m-n- Octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, N −
n-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, for example, methyl Sulfonylamino,
Butylsulfonylamino, phenylsulfonylamino,
2,3,5-trichlorophenylsulfonylamino, p
-Methylphenylsulfonylamino), a mercapto group,
An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio,
Ethylthio, n-hexadecylthio), arylthio group (preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), heterocyclic thio group (preferably having carbon number) 2 to 30 substituted or unsubstituted heterocyclic thio groups, for example 2-benzothiazolylthio,
1-phenyltetrazol-5-ylthio), a 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, N-acetylsulfamoyl, N-benzoylsulfamoyl,
N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms) Groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p
-Methylphenylsulfinyl), an alkyl and arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, for example, methylsulfonyl, ethylsulfonyl) , Phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, carbon Number 4 to 3
A heterocyclic carbonyl group linked to a carbonyl group at 0 substituted or unsubstituted 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-nitrophenoxy). Carbonyl, p
-T-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), carbamoyl. A group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N,
N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted carbon atom having 3 to 30 carbon atoms) Substituted heterocyclic azo group such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (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, A substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, phosphinyl,
Dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms,
For example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy, a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino). , Dimethylaminophosphinylamino), a phospho group, a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl), a hydrazino group ( Preferably, a substituted or unsubstituted hydrazino group having 0 to 30 carbon atoms, for example, trimethylhydrazino, a ureido group (preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms, for example, N, N).
-Dimethylureido).

Further, two Ws jointly form a ring (an aromatic or non-aromatic hydrocarbon ring or a heterocycle. These can be further combined to form a polycyclic condensed ring.
For example, benzene ring, naphthalene ring, anthracene 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. Ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring Ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiine ring, phenothiazine ring, phenazine 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 the hydrogen atom. Examples of such substituents include -CONHS
O ₂ - group (sulfonylcarbamoyl group, a carbonyl sulfamoyl group), - CONHCO- group (carbonylation carbamoyl group), - SO ₂ NHSO ₂ - group (sulfonylsulfamoyl group), and the like. More specifically, an alkylcarbonylaminosulfonyl group (for example, acetylaminosulfonyl), an arylcarbonylaminosulfonyl group (for example, benzoylaminosulfonyl group),
Examples thereof include an alkylsulfonylaminocarbonyl group (for example, methylsulfonylaminocarbonyl) and an arylsulfonylaminocarbonyl group (for example, p-methylphenylsulfonylaminocarbonyl).

General formulas (X), (XI), and (XII)
In the formula, Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₅ and Z ₁₇ each represent a group of atoms necessary for forming a nitrogen-containing heterocycle, preferably a 5- or 6-membered nitrogen-containing heterocycle. However, the ring may be condensed to these. The ring may be either an aromatic ring or a non-aromatic ring. An aromatic ring is preferable, and examples thereof include a hydrocarbon aromatic ring such as a benzene ring and a naphthalene ring, and a heteroaromatic ring such as a pyrazine ring and a thiophene ring.

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 nucleus, 3,3-
Dialkyl indolenine nucleus (eg 3,3-dimethylindolenine), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus,
2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4,5-b] quinoxaline nucleus, oxadiazole nucleus, thiadiazole nucleus,
Examples thereof include a tetrazole nucleus and a pyrimidine nucleus, but preferably a benzothiazole nucleus, a benzoxazole nucleus, a 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenin), a benzimidazole nucleus, a 2-pyridine nucleus. , 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, more preferably benzothiazole nucleus, benzoxazole nucleus, 3,3-dialkylindolenine nucleus (for example, 3 , 3-Dimethylindolenine) and benzimidazole nuclei, particularly preferably benzoxazole nuclei, benzothiazole nuclei, and benzimidazole nuclei, and most preferably benzoxazole nuclei and benzothiazole nuclei.

These include the substituent 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 together represent an atomic group 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" (The The) edited by James.
Theory of the Photograph
ic Process) 4th edition, Macmillan Publishing Company, 1
977, pp. 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- or 6-membered nitrogen-containing heterocycle) consisting of carbon, nitrogen, and / or chalcogen (typically oxygen, sulfur, selenium, and tellurium) atoms. Is more preferable, and more preferably, a 5- or 6-membered nitrogen-containing heterocycle consisting of carbon, nitrogen, and / or chalcogen (typically oxygen, sulfur, selenium, and tellurium) atoms is formed. 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-dihydrothiazolo [3,2-a] pyrimidine, cyclohexane-1,3-dione, 3,4 -Dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, chroman-2,4-dione, 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 group 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 and Z ₁₄ ^' and (N-R ₁₄ ) q ₁₁ are preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, 2-thiooxazoline-2,4-dione and thiazolidine-2,4. Zeon,
Rhodanine, thiazolidine-2,4-dithione, barbituric acid, and 2-thiobarbituric acid, and more preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, rhodanine, barbituric acid, and 2-thiobarbituric acid. It is an acid. Particularly preferred are 2- or 4-thiohydantoin, 2-oxazoline-5-one, and rhodanine.

The heterocyclic ring formed by Z ₁₆ and 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, Z ₁₄ and Z ₁₄ ^' and (NR
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 oxo group or the thioxo group is removed from the acidic nuclei specifically mentioned above for Z ₁₄ and Z ₁₄ 'and (N-R ₁₄ ) q ₁₁ , and 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 oxo group or thioxo group is removed And particularly preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, rhodanine, barbituric acid, 2-thiobarbituric acid from which an oxo group or a thioxo group has been removed, and most preferably It is 2- or 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 a heterocyclic group. It is a cyclic group, preferably an alkyl group, an aryl group, and a heterocyclic group. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ ,
Examples of the alkyl group, aryl group, and heterocyclic group represented by R ₁₇ include, for example, an unsubstituted alkyl group having 1 to 18, preferably 1 to 7 and particularly preferably 1 to 4 carbon atoms ( For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), carbon atoms 1 to 1
8, preferably 1 to 7, and particularly preferably 1 to 4 substituted alkyl groups {for example, the above-mentioned alkyl groups substituted with W can be mentioned. In particular, the above-mentioned alkyl group having an acid group is preferable. Preferably, an aralkyl group (eg, benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (eg, an allyl group, a vinyl group, that is, a substituted alkyl group includes an alkenyl group and an alkynyl group) and hydroxy. Alkyl group (for example, 2-hydroxyethyl, 3-hydroxypropyl), carboxyalkyl group (for example, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl group (for example, 2-methoxy) Ethyl, 2- (2-methoxyethoxy) ethyl), aryloxyalkyl group (for example, 2-phenoxyethyl,
2- (1naphthoxy) ethyl), alkoxycarbonylalkyl group (eg ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl), aryloxycarbonylalkyl group (eg 3-phenoxycarbonylpropyl), acyloxyalkyl group (eg 2-acetyloxy) Ethyl), an acylalkyl group (eg 2-acetylethyl), a carbamoylalkyl group (eg 2-morpholinocarbonylethyl), a sulfamoylalkyl group (eg N, N-dimethylsulfamoylmethyl),
Sulfoalkyl group (for example, 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), an alkylsulfonylcarbamoylalkyl group (for example, methanesulfonylcarbamoylmethyl group), an acyl group. Lucarbamoylalkyl group (eg acetylcarbamoylmethyl group), acylsulfamoylalkyl group (eg acetylsulfamoylmethyl group), alkylsulfonylsulfamoylalkyl group (eg methanesulfonylsulfamoylmethyl group)}, carbon number 6 Etc., preferably an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms (examples of the substituent include the above-mentioned W. For example, phenyl group, 1 naphthyl group, p- A methoxyphenyl group, a p-methylphenyl group, a p-chlorophenyl group, etc.), an unsubstituted or substituted heterocycle having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms. Group (Examples of the substituent include the aforementioned W. For example, 2-furyl group, 2-thienyl group, 2-pyridyl group, 3-pyrazolyl group, 3-isoxazolyl group, 3-isothiazolyl group, 2-imidazolyl group,
2-oxazolyl, 2-thiazolyl, 2-pyridazyl,
2-pyrimidyl, 3-pyrazyl, 2- (1,3,5-triazolyl), 3- (1,2,4-triazolyl), 5-tetrazolyl, 5-methyl-2-thienyl group, 4-methoxy-2-pyridyl group and the like can be mentioned. ) 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 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 examples of the substituent include W described above. 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 aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg phenyl, o-
Carboxyphenyl), a substituted or unsubstituted C3 to C20, preferably C4 to C15, more preferably C6 to C10 heterocyclic group (for example, N, N-dimethylbarbituric acid group), a halogen atom. (For example, chlorine, bromine, iodine, fluorine), C1 to C15, preferably C1 to C10, more preferably C1 to C5 alkoxy group (eg methoxy, ethoxy), C0 to C15, preferably Is an amino group having 2 to 10 carbon atoms, more preferably 4 to 10 carbon atoms (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 1 carbon atoms
2, more preferably an arylthio group having 6 to 10 carbon atoms (eg, phenylthio, p-methylphenylthio) and the like. 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, 2, 3 and more preferably 0, 1, 2;
It is particularly preferably 0 or 1. When n ₁₁ , n ₁₂ , n ₁₃ and n ₁₄ are 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 cations or anions 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 they have a hydrogen ion as a counter ion.

M ₁₁ , m ₁₂ , and m ₁₃ represent a number of 0 or more necessary for balancing charges, 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.

[0062]

[Chemical 4]

[0063]

[Chemical 5]

[0064]

[Chemical 6]

[0065]

[Chemical 7]

The dye of the present invention is F.M.Harmer
(FM Harmer) "Heterocyclic Compounds-
Cyanine soybean and related compounds
(Heterocyclic Compounds-Cyanine Dyes and Related C
ompounds) ", John Willie & Sons (Joh
n Wiley & Sons) -New York, London, 196
4 Years, DMSturmer, "Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry (Heter
ocyclic Compounds-Special topics in heterocyclic c
hemistry) ", Chapter 18, Section 14, 482-51
Page 5, John Wiley and Sons
& Sons) -New York, London, 1977,
"Rodd's Chemistry of Carbon Compounds" 2nd.Ed.v
ol.IV, partB, 1977, Chapter 15, 369-42
Page 2, Elsevier Science Publishing Company In
c.) It can be synthesized based on the method described in the publisher, New York, etc.

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.

Along with 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.

A supersensitizer useful in the spectral sensitization of the present invention (eg, pyrimidylamino compound, triazinylamino compound, azolium compound, aminostyryl compound, aromatic organic acid formaldehyde condensate, azaindene compound, cadmium salt). , And a combination of a supersensitizer and a sensitizing dye are described in, for example, US Pat.
No. 4, No. 3,615, 613, No. 3, 615, 632
Issue No. 3,615,641 Issue 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 timing of adding a sensitizing dye (also for a supersensitizer) to the silver halide emulsion of the present invention has been recognized to be useful until now. 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 formation step of silver halide and / or before desalting, during the desalting step and / or after the desalting and before the start of chemical ripening, JP 58
As disclosed in JP-A-113920, it may be added at any time or step immediately before the chemical ripening or during the step, or after the chemical ripening and before the coating until the emulsion is coated. Also, US Pat. No. 4,225,666
As disclosed in JP-A No. 58-7629 and the like, the same compound alone or in combination with a compound having a different structure can be used, for example, during the grain forming step and during the chemical ripening step or after the completion of the chemical ripening step. Or may be added in divided portions such as before chemical ripening or before and after chemical ripening, or may be added by changing the kind of compound and combination of compounds to be added in divided portions. .

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
It can be used at × 10 ^-3 mol. For example, when the size of silver halide grains is 0.2 to 1.3 μm, the addition amount of 2 × 10 ^{−6 to} 3.5 × 10 ⁻³ mol is preferable per mol of silver halide, and 7.5 mol is preferable. × 10 ^{-6 to} 1.5 × 10
^A more preferred amount is ^-3 mol.

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 in each processing bath for color development, bleaching, fixing, washing with water, stabilization, adjustment, black and white development, reversal, pre-bleaching and the like. 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.

[0074]

EXAMPLES Hereinafter, it will be described in more detail with reference to Examples that the sensitizing dye stain can be reduced by bringing the silver halide photographic light-sensitive material into contact with a reducing agent in the presence of the compound of the present invention. It is not limited to these.

Example 1 [Preparation of Photosensitive Material Sample] After corona discharge treatment was applied to the surface of a support whose both surfaces were coated with polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and Apply the first to seventh layers in order,
Silver halide color photographic light-sensitive material P having the following layer structure
-1 was created. The coating liquid for each photographic constituent layer was prepared as follows.

Preparation of fifth layer coating solution 250 g of cyan coupler (ExC), 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, silver chlorobromide emulsion C
(Cube, 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 mole ratio). Coefficients of variation of grain size distribution are 0.09 and 0.11, respectively. For each size emulsion, 0.5 mol% of silver bromide was localized on a part of the grain surface based on the silver chloride emulsion). In this emulsion, the red sensitizing dyes G and H described later are added to the large-sized emulsion C per mol of silver in an amount of 9.0 × 10 ^-5 mol and the small-sized emulsion C respectively.
12.0 × 10 ⁻⁵ mol, respectively. 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 following composition. 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. A for each layer
b-1, Ab-2, Ab-3, and Ab-4, respectively, in a total amount of 15.0 mg / m ² , 60.0 mg / m ² , 5.0.
It was added as a mg / m ² and 10.0 mg / m ^2.

[0078]

[Chemical 8]

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

[0080]

[Chemical 9]

(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

[0083]

[Chemical 10]

(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

[0086]

[Chemical 11]

(Sensitizing dyes G and H were used in an amount of 9.0 × 10 ^-5 mol per mol of silver halide for a large-sized emulsion,
12.0 × 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. )

[0088]

[Chemical 12]

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 / m² Becomes
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. Second layer, fourth layer
And catechol-3,5-disulfonic acid dina
Thorium 6mg / m², 6 mg / m², 18m
g / m²Was added. Irradiation prevention
In order to add the following dyes (the amount in parentheses indicates the coating amount):
Added

[0090]

[Chemical 13]

(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: [white pigment polyethylene resin of the first layer side (TiO _2: content of 16 wt%, ZnO: content of 4 wt% polyethylene resin-laminated paper and optical brightener (4,4'-bis (5 -Methylbenzoxazolyl)
Stilbene content 0.03% by mass, containing bluish dye (ulterior blue)] First layer (blue sensitive emulsion layer) Silver chlorobromide emulsion A (cubic, large size emulsion A with an average grain size of 0.74 μm and 0) 5: 5 mixture with 0.65 μm small size emulsion A (molar ratio of silver) .Coefficients of variation of grain size distribution are 0.08 and 0.10, respectively. 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

[0092] 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

[0093] 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. Chloride 0.4 mol% silver bromide with size The silver was locally contained on a part of the surface of the grain having the substrate. )                                                   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

[0094] 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

[0095] Fifth layer (red sensitive emulsion layer)   Silver chlorobromide emulsion C (cubic, large size emulsion C having an average grain size of 0.40 μm and 0 ． 5: 5 mixture with 30 μm small size emulsion C (silver molar ratio). Particle size distribution Coefficients of variation are 0.09 and 0.11. Chloride 0.5 mol% silver bromide with size The silver was locally contained on a part of the surface of the grain having the substrate. )                                                   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

[0096] 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

[0097] 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

[0098]

[Chemical 14]

[0099]

[Chemical 15]

[0100]

[Chemical 16]

[0101]

[Chemical 17]

[0102]

[Chemical 18]

[0103]

[Chemical 19]

[0104]

[Chemical 20]

[0105]

[Chemical 21]

[0106]

[Chemical formula 22]

The following development processing was carried out on Photosensitive Material Sample P-1.

[Processing Step] Treatment process temperature time Color development 38.5 ℃ 45 seconds Bleach-fixing 38.0 ° C 45 seconds Washing with water 38.0 ° C for 10 seconds Reduction 38.0 ° C 40 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

[0110] [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

[0111] [Reducing liquid]       Reducing agent (Table 1) Table 1       Add water to a total volume of 1000 mL       pH (25 ℃, adjusted with sulfuric acid and sodium hydroxide) 7.0

[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 with respect to the photosensitive material sample which was imagewise exposed and developed. 515
the nm absorbance was D _G. Next, each sample was washed with water at 40 ° C. in a 1: 1 mixture of methanol and water for 3 minutes, dried and then subjected to the same measurement, and the absorbance at 515 nm at this time was defined as _DGw . ΔD _GW was calculated based on the following formula, and the degree of stain due to the residual sensitizing dye was evaluated. [Delta] D _G is the smaller the value less retained sensitizing dye, meaning that stain reduction effect is large. ΔD _G = D _G - D _GW

[0113]

[Table 1]

In Samples 12 to 16 prepared by adding the reducing agent of the present invention to Sample 11 prepared without adding the reducing agent in the reducing bath, the magenta concentration was lowered and the sensitizing dye stain was reduced. It was shown that

Example 2 Samples 21 and 22 were prepared by subjecting Fuji Color Superior Zoom Master 800 manufactured by Fuji Photo Film Co., Ltd., which was imagewise exposed, to Process CN-16L manufactured by the same company. Sample 21,
For No. 22, the transmission absorption measurement of the minimum concentration part was performed using a U-3500 type spectrophotometer manufactured by Hitachi Ltd.
nm, it was determined absorbance D ₅₀₀ ^0, D ₅₅₅ ⁰ at 555 nm. Next, the samples 21 and 22 were subjected to the following post-treatment. [Post-treatment step] Reduction 38.0 ° C. 30 seconds Drying 80 ° C. [Reducing liquid] Reducing agent (Table 2) Table 2 Water was added to the total amount 1000 mL pH (25 ° C., adjusted with sulfuric acid and sodium hydroxide) 7.0 again The same transmission absorption measurement was performed to obtain the absorbances D ₅₀₀ and D ₅₅₅ at ₅₀₀ nm and 555 nm. Differences in stain before and after the treatment, ΔD ₅₀₀ and ΔD _555, were calculated by the following equation. ΔD ₅₀₀ , ΔD _5
55 means 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

[0116]

[Table 2]

From this, it was confirmed that sample 21 containing no reducing agent was used.
On the other hand, it was shown that the stain was reduced in the sample 22 treated with the reducing agent.

Example 3 Samples 31 and 32 were prepared by subjecting Fujichrome Provia 100 manufactured by Fuji Photo Film Co., Ltd., which was imagewise exposed, to Process CR-56P manufactured by the same company. Hitachi U
Performs transmission absorption measurement of the minimum density portion with -3500 spectrophotometer to determine the absorbance D ₅₄₀ ⁰ at 540nm of two processed color reversal films. Samples 31, 32
After the same post-treatment as in Example 2, the transmission absorption measurement of the minimum concentration part was performed again to obtain the absorbance D ₅₄₀ at ₅₄₀ nm. The difference ΔD ₅₄₀ in stain before and after the post-treatment was calculated by the following formula. ΔD540 means that the larger the value is, the larger the stain reducing effect is. ΔD ₅₄₀ = D ₅₄₀ ⁰ −D _{540 The} results are shown in Table 3.

[0119]

[Table 3]

From the above, in the case of the sample 32 which was subjected to the reducing bath treatment containing the reducing agent of the present invention after the treatment, the blank sample 3 was used.
It was shown that the stain was reduced from 1.

[0121]

From Examples 1 to 3, it can be seen that according to the present invention, the stain caused by the residual sensitizing dye of the light-sensitive material can be reduced after the processing of the silver halide photographic light-sensitive material.

Claims (3)

[Claims] 1. A processing method for reducing the sensitizing dye stain of a silver halide photographic light-sensitive material, which comprises contacting a developed silver halide photographic light-sensitive material with a reducing agent. 2. The processing method for reducing the sensitizing dye stain of a silver halide photographic light-sensitive material according to claim 1, wherein the reducing agent is brought into contact with the silver halide photographic light-sensitive material as an aqueous solution. 3. The processing method for reducing the sensitizing dye stain of a silver halide photographic light-sensitive material according to claim 1, wherein at least one compound selected from hydrazines is used as a reducing agent.