JP2003121974A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method 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, the silver halide photographic sensitive material containing a sensitizing dye is brought into contact with an oxidizer other than hypochlorites, persulfates and aminopolycarboxylates after a fixing step in which silver halide is substantially removed by desilvering after exposure and development.

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

[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 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 was difficult for me to appreciate it. Also in the color negative film, the density in the minimum density portion is increased, causing a situation in which the color balance is lost 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 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 minimum density portion of the color negative film or a highlight portion of the color reversal film is colored.

Research Disclosure Magazine 20733
As an example of a method for removing stains caused by a sensitizing dye, a method using a bistriazinylaminostilbenedisulfonic acid compound is disclosed in JP-A No. 1994-96, and this method has been widely used in the processing of color photographic light-sensitive materials. . Japanese Patent Application Laid-Open No. 6-329936 discloses a bistriazinylaminostilbenedisulfonic acid compound which is excellent in solubility and can reduce stain even by a treatment which 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 that has flowed out of the silver halide photographic light-sensitive material is accumulated in the processing solution, and 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 dye from being washed out. 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. Also, Research Disclosure Magazine 20733 discloses a method of destroying the sensitizing dye by dipping the photographic element after development bleach-fixing by adding perchlorate or persulfate to a washing bath. Is not enough.

[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 present invention described below. That is, the present invention provides a silver halide photographic light-sensitive material containing <1> sensitizing dye,
After the fixing step in which the silver halide is substantially removed by exposure, development and desilvering, contact with an oxidizing agent other than hypochlorite, persulfate and aminopolycarboxylic acid iron salt is performed. It is a characteristic method of processing a silver halide photographic light-sensitive material.

<2> The method for processing a silver halide photographic light-sensitive material according to <1>, wherein the oxidizing agent is an aqueous solution. <3> The halogen according to <1> or <2>, wherein the oxidizing agent is at least one compound selected from organic peracids, organic peroxides or hydrogen peroxide and adducts thereof. It is a method of processing a silver halide photographic light-sensitive material.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The oxidizing agent used in the present invention will be described in detail. The contact between the silver halide photographic light-sensitive material and the oxidizing agent is performed after the fixing step in which the silver halide is substantially removed from the silver halide photographic light-sensitive material. The oxidant used in the present invention is an oxidant excluding hypochlorite, persulfate and aminopolycarboxylic acid iron salt, and desensitizes the sensitizing dye by attacking the sensitizing dye. Alternatively, any material may be used as long as it reduces the residual color due to the sensitizing dye in the silver halide light-sensitive material by making the sensitizing dye hydrophilic and promoting the elution of the sensitizing dye from the silver halide light-sensitive material. Absent.

Examples of the oxidizing agent used in the present invention include organic peracids, organic peroxides, other oxidizing organic compounds, hydrogen peroxide and its adducts, metal oxides or metal salts, and the like. Of these, organic peracids, organic peroxides, other oxidizable organic compounds, hydrogen peroxide and its adducts are preferable, and organic peracids, organic peroxides, hydrogen peroxide and their adducts are more preferable.

As the oxidizing agent used in the present invention, for example, those described in the following documents can be preferably used. 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 23, Organic Synthesis V, Oxidation Reaction, Maruzen (1991)

Specific examples of the oxidizing agent used in the present invention are shown below, but the present invention is not limited thereto. Examples of the organic peracid and organic peroxide used in the present invention include m-chloroperbenzoic acid (MCPBA), perbenzoic acid, peracetic acid, t-
Butyl hydroperoxide and the like can be mentioned.

Examples of the oxidizing organic compound used in the present invention include dimethyl sulfoxide / oxalyl chloride, dimethyl sulfoxide / trifluoroacetic anhydride, dimethyl sulfoxide / dicyclohexylcarbodiimide, and quinones (2,3-dichloro-5,6-dicyano). -1,4-benzoquinone, etc.), nitrobenzene, p-nitrosodimethylaniline, dimethylaminopyridine N-oxide, triphenylmethyl cation, diethyl azodicarboxylate, diphenyl nitroxide, 2-sulfonyloxaziridine, iodosobenzene diacetate. , N-bromosuccinimide, chloramine T, chloramine B thiosulfonate and the like.

Further, the hydrogen peroxide used in the present invention
As an adduct, NaBO₂・ H₂O ₂・ 3H₂O, 2Na
CO₃・ 3H₂O₂, Na_FourP₂O₇・ 2H₂O₂2Na₂S
O_Four・ H₂O₂・ 2H₂O etc. are mentioned. Also peroxy
Acid salts (eg K₂S₂O₈, K ₂C₂O₆, K₂P₂O₈),
Peroxy complex compounds (eg K₂[Ti (O₂) C₂
O_Four] ・ 3H₂O, 4K₂SO_Four・ Ti (O₂) OH / SO_Four
・ 2H₂O, Na₃[VO (O₂) (C₂H_Four)₂] ・ 6H₂
O) and the like.

The metal oxides and salts used in the present invention include chromic acid compounds (eg, CrO ₃ ), osmium tetroxide, ruthenium tetroxide, lead oxide, lead acetate, mercury oxide, mercury acetate, silver carbonate, Silver oxide, silver nitrate, thallium acetate, thallium nitrate, copper chloride, copper acetate, palladium chloride, iron chloride, potassium ferricyanide, VOCl ₃ , V ₂
O ₅ , K ₂ Cr ₂ O ₇ , cerium acetate, cerium ammonium nitrate (CAN), sodium bismuthate, nickel peroxide and the like can be mentioned, and metal complexes such as potassium hexacyanoferrate are also included.

Examples of the oxidizing agent used in the present invention include oxygen, ozone, selenium dioxide, chlorine, bromine, iodine, bromine-hexamethylphosphoramide, orthoperiodic acid, nitric acid, and nitrous acid, in addition to the above-mentioned oxidizing agents. , Nitrogen dioxide, potassium nitrosodisulfonate, tetrabutylammonium periodate, potassium periodate, microorganisms and enzymes, etc., and electrode (anodic) oxidation can be used.

When the silver halide photographic light-sensitive material is brought into contact with the oxidizing agent in the present invention, the oxidizing agent may be supplied in any form, preferably as a solution, and more preferably as an aqueous solution. preferable. The solution (oxidizing agent) 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 normal photographic processing step. Good. Here, the sheet means a polymer fiber cloth capable of holding an oxidant solution.

The concentration of the solution (oxidizing agent) is 0.005
3.0 mol / L is preferable, more preferably 0.01
~ 1.5 mol / L, more preferably 0.02 to 0.
It is 5 mol / L. When the treating composition containing the oxidizing 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.

In the processing method of the present invention, in order to bring the silver halide photographic light-sensitive material into contact with the oxidizing agent of the present invention described above, the silver halide photographic light-sensitive material is treated in a processing bath (hereinafter referred to as an oxidant). This bath is called an "oxidation bath".)
Soaking is the preferred embodiment. The oxidizing agent or the composition thereof in the oxidizing bath may simply be an aqueous solution of the oxidizing agent in the present invention, or may be a composition according to the washing composition and the stable composition.

It is also a preferred embodiment to add to the oxidizing bath a compound which increases the solubility of the oxidizing agent in the oxidizing bath.
As the organic oxidizing agent, it is useful to add, for example, ethylene glycols, alkanolamines, arylsulfonic acids, alkylsulfonic 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, alkyl ethoxylate, or alkylnaphthalene sulfonic acid can be added.

Further, in the treatment method of the present invention, an arbitrary buffer can be added to the oxidizing bath in order to adjust the oxidizing power and the solubility of the oxidizing agent. The buffer may be either an inorganic buffer or an organic buffer, and examples of the inorganic buffer include carbonates, bicarbonates, phosphates, borates, tetraborates, and other inorganic salts, among which potassium is used. Salts, sodium salts or ammonium salts are preferred. On the other hand, as the organic buffer, succinic acid, maleic acid, glycolic acid, malonic acid,
Organic acids such as 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 in the present invention is carried out after the fixing step in which the silver halide is substantially removed from the silver halide photographic light-sensitive material by exposure, development and desilvering. . 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-oxidation-dry Color development-bleach-fix-wash-oxidation-stable-dry color development-bleach-fix-oxidation-bleach-fix-oxidation-stable -Dry color development-bleaching-fixing-water washing-oxidation-dry color development-bleaching-fixing-oxidation-water washing-dry color development-bleaching-fixing-water washing-oxidation-water washing-drying and a desilvering step comprising bleaching and fixing May be any of bleach-fix, bleach-bleach-fix and bleach-fix-fix. Further, black and white development and reversal may be performed as a pre-process of color development.

The oxidizing agent in the present invention may be added in any form of tank solution, replenishing solution, concentrated replenishing solution and kit of the oxidizing bath. The oxidizing agent used in the present invention may be contained in the oxidizing 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 may 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 silver halide photographic light-sensitive material comprises at least 50 mol%
The above chlorides, more preferably at least 90 mol%
It is a high silver chloride light-sensitive material containing the above silver chloride, and is used, for example, as a color print light-sensitive material.

In another embodiment, the at least one emulsion is predominantly silver bromide, preferably at least 50 mol% silver bromide. Most preferably the silver halide photographic silver light-sensitive 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 referred to as "RD"), and RD17643 23-2.
7 pages, RD18716 pages 647 to 650, R
D307105 Pages 866-868, 873-87
9 pages, RD 36544 501-541 pages. These are useful silver halide emulsions (negative or positive type) and their preparation methods, various sensitizers,
Dye-forming coupler, spectral sensitizing dye, supersensitizer, image dye stabilizer, dye, ultraviolet absorber, filter, binder, hardener, plasticizer, lubricant, coating aid, surface active agent, static It relates to inhibitors, matting agents, paper and film supports, or various methods of imaging negative and positive image forming color elements.

The silver halide photographic light-sensitive material in the present invention contains a sensitizing dye. Any sensitizing dye may be used, and examples thereof include those described in RD described above. Preferable examples of the sensitizing dyes used include 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 the details of the sensitizing dyes, see FM Harmer, "Heterocyclic Compounds, Cyanine and Relative Compounds (Heterocyclic).
Compounds-Cyanine Dyes a
nd Related Compounds ", John Wiley and Sons (John Wiley)
& Sons) -New York, London, 1964
Annual), DM Sturmer (DM Sturm)
er) "Heterocyclic Compound Special Topics in Heterocyclic Compound (Heterocyclic Compound)
s-Special topics in heater
Oclic Chemistry ", Chapter 18, Section 14, pp. 482-515), John Willie
And Sons (John Wiley & Son)
s) -New York, London, 1977, "Rod's Chemistry of Carbon Compounds".
on Compounds "2nd. Ed. vol. I
V, part B, 1977, Chapter 15, pages 369-422), Elsevier Science Public Company, Inc.
Publishing Company Inc. (Published in New York), etc.

For 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.

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

[0033]

[Chemical 1]

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 represent 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, a ring may be condensed with 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.

[0035]

[Chemical 2]

In the general formula (XI), L ₁₈ , L ₁₉ , L ₂₀ and L ₂₁ 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 ′} represent an atomic group necessary for forming a heterocyclic ring or an acyclic acidic terminal group together with (N—R ₁₄ ) q 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 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.

[0037]

[Chemical 3]

In the general 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.
Z₁₅And Z₁₇Is the source needed to form a nitrogen-containing heterocycle
Represents a group of children. Z₁₆And Z₁₆'Is (N-R₁₆) Q₁₂along with
Represents an atomic group necessary for forming a heterocycle. Was
But Z₁₅, Z₁₆And Z ₁₆’And Z₁₇The ring is condensed
May be. M₁₃Represents a charge-balancing counterion, m ₁₃Is the molecule
Represents a number of 0 or more necessary to neutralize the electric charge of. R₁₅,
And R₁₇Represents an alkyl group, an aryl group, or a heterocyclic group.
You R₁₆Is a hydrogen atom, an alkyl group, an aryl group, or
Represents a cyclic group. Hereinafter, general formulas (X), (XI), and
The methine dye represented by (XII) is described in detail.
It

Regarding the groups 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 Xycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide 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 (OH) ₂ ), a sulfato group (-OSO).
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 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)},

Aryl group (preferably having 6 to 30 carbon atoms)
A substituted or unsubstituted aryl group of, for example, 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, one hydrogen atom) A monovalent group in which an atom is removed, more preferably 3 to 30 carbon atoms.
Is a 5- or 6-membered aromatic heterocyclic group. For example,
2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, 1-methyl-2-pyridinio,
It may be a cationic heterocyclic group such as 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 group, 6 to 30
A substituted or unsubstituted arylsulfinyl group, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl),
Alkyl and aryl sulfonyl groups (preferably a substituted or unsubstituted alkyl sulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl sulfonyl group having 6 to 30 carbon atoms, for example, methyl sulfonyl, ethyl sulfonyl,
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 A heterocyclic carbonyl group bonded to a carbonyl group with 4 to 30 substituted or unsubstituted carbon atoms, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2- Pyridylcarbonyl, 2-
Furyl carbonyl),

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 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 removed and further substituted with the above-mentioned group. Examples of such substituents include -CONHS
O ₂ - group (sulfonylcarbamoyl group, a carbonyl sulfamoyl group), - CONHCO- group (carbonylation carbamoyl group), - SO2NHSO ₂ - group (sulfonylsulfamoyl group), and the like. More specifically,
Alkylcarbonylaminosulfonyl group (for example, acetylaminosulfonyl), arylcarbonylaminosulfonyl group (for example, benzoylaminosulfonyl group), alkylsulfonylaminocarbonyl group (for example, methylsulfonylaminocarbonyl), 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, a ring may be condensed with 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-dimethylindolenine), a benzimidazole nucleus,
2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4
A quinoline nucleus, a 1-isoquinoline nucleus, a 3-isoquinoline nucleus, more preferably a benzothiazole nucleus, a benzoxazole nucleus, a 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), a benzimidazole nucleus. Of these, a benzoxazole nucleus, a benzothiazole nucleus and a benzimidazole nucleus are particularly preferable, and a benzoxazole nucleus and a benzothiazole nucleus are most preferable.

General formulas (X), (XI), and (XII)
Wherein the nitrogen-containing heterocycle represented by Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₅ and Z ₁₇ is condensed even if the substituent represented by W and the ring are substituted. Good. Preferred are alkyl groups, aryl groups, alkoxy groups, halogen atoms,
Aromatic ring condensation.

General formulas (X), (XI), and (XII)
Among them, specific examples of the heterocyclic ring formed by Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₅ and Z ₁₇ include US Pat. No. 5,340,
Nos. 694, columns 23 to 24 include the same as those listed as examples of Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ and Z ₁₆ .

Z ₁₄ , Z _{14 '} and (N-R ₁₄ ) q ₁₁ each 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, and a sulfonyl group are more preferable, and a thiocarbonyl group and a carbonyl group are more preferable. 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- 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-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 exo-methylene 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 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 preferably 2- or 4-thiohydantoin,
2-oxazoline-5-one, Rhodanine.

The heterocyclic ring formed by Z ₁₆ and Z _{16 '} and (N-R ₁₆ ) q ₁₂ is as described above for the heterocyclic ring of Z ₁₄ and Z _14' and (N-R ₁₄ ) q _11. The same ones mentioned are mentioned. Preferably, Z ₁₄ and Z _{14 ′} and (N
It is obtained by removing an oxo group or a thioxo group from the acidic nucleus described in the explanation of the heterocycle of —R ₁₄ ) q ₁₁ .

[0061] More preferably, which except for the above-mentioned Z ₁₄ and Z _{14 'and} (N-R ₁₄₎ Specific examples include oxo group from the acidic nucleus of q _11, or a thioxo group, 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 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),

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-
A chlorophenyl group etc. are mentioned. ), Carbon number 1 to 2
0, preferably an unsubstituted heterocyclic group having 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms (for example, a 2-furyl group,
2-thienyl group, 2-pyridyl group, 3-pyrazolyl, 3
-Isoxazolyl, 3-isothiazolyl, 2-imidazolyl, 2-oxazolyl, 2-thiazolyl, 2-pyridazyl, 2-pyrimidyl, 3-pyrazyl, 2- (1,
3,5-triazolyl), 3- (1,2,4-triazolyl), 5-tetrazolyl), a substituted heterocyclic group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms. (For example, the above-mentioned heterocyclic group substituted with W mentioned as an example of the substituent can be mentioned. Specifically, 5
-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, a carbonyl sulfamoyl group), - CONHCO- group (carbonylation carbamoyl group), - SO ₂ NHSO ₂ - group (sulfonylsulfamoyl group), a sulfonamido group, a sulfamoyl group, a phosphato group , A phosphono group, a boronic acid group, a phenolic hydroxyl group, and the like, and a group capable of dissociating a proton depending on the pka of these and the surrounding pH. 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, -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), a carbon number of 1 to 15, preferably a carbon number of 1 to 10, and more preferably a carbon number of 1 to 5 (eg methoxy, ethoxy), a carbon number of 0 to 15, Preferably 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 also form a ring with another methine group,
Alternatively, a ring can be formed 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-
Examples thereof include organic ions such as diazabicyclo [5.4.0] -7-undecenium ion). The anion may be either an inorganic anion or an organic anion,
Halogen anion (eg, fluorine ion, chlorine ion,
(Iodine ion), substituted aryl sulfonate ion (eg p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulfonate ion (eg 1,3-benzene sulfonate ion, 1,5-naphthalenedisulfone) Acid ion, 2,6-naphthalenedisulfonate ion), alkylsulfate ion (for example, methylsulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethane A sulfonate ion is mentioned. In addition, ionic polymers or other dyes having an opposite charge to the dye may be used. In addition, CO ₂
-, SO ₃ -, when having a hydrogen ion as a counter ion can be indicated CO ₂ H, and SO ₃ H.

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

[0071]

[Chemical 4]

[0072]

[Chemical 5]

[0073]

[Chemical 6]

[0074]

[Chemical 7]

The sensitizing dye in the present invention is FM
FM Harmer, "Heterocyclic Compounds-Cyanine Soybean and Related Compounds (Heterocyclic C)
Ompounds-Cyanine Dyes and
Related Compounds ", John Wiley & Sons (John Wiley & Sons)
Sons, Inc.-New York, London, 1964), DM Sturme.
r) "Heterocyclic Compounds-Special Topics in Heterocyclic Compounds"
-Special topics in hetero
Cyclic Chemistry ", Chapter 18, Chapter 1
Verse 4, pages 482-515), John Wiley & Sons
Company-New York, London, 1977, "Rods Chemistry of Carbon Compounds (Ro
dd's Chemistry of CarbonC
omounds "2nd. Ed. vol. IV, pa
rtB, 1977, Chapter 15, 369-422.
Page), Elsevier Science Public Company, Inc. (Elsevier Science Pu)
blushing Company Inc. (Published by the company),
It can be synthesized based on the method described in 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, No. 52-109925, and the like.

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.

Any supersensitizer useful in the spectral sensitization of the present invention may be used, and examples thereof include pyrimidylamino compounds, triazinylamino compounds, azolium compounds, aminostyryl compounds and aromatic organic acids. A formaldehyde condensate, an azaindene compound, and a cadmium salt are listed, and examples of combinations of a supersensitizer and a sensitizing dye include US Pat. No. 3,511,664,
3,615,613, 3,615,632, 3,615,641, 4,596,767, 4,945,038, 4,965,182, 4 , 965,182, 2,933,390, 3,635,721, 3,743,510, 3,617,295, 3,635,721, etc. However, the method described in the above-mentioned patent is also preferable for its usage.

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 chemical ripening or during the step, or before the emulsion is coated after the chemical ripening and before coating. 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 aging or before and after chemical ripening, or may be added by dividing the compound and the combination of compounds. .

In the present invention, the addition amount of the sensitizing dye (and the same applies to the supersensitizer) varies depending 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 dispersed directly 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, an additive such as a base, an acid or a surfactant can be coexistent. Ultrasonic waves can also be used for dissolution. As a method for adding this compound, as described in US Pat. No. 3,469,987, the compound is dissolved in a volatile organic solvent, and the solution is dispersed in a hydrophilic colloid to prepare a dispersion of this compound. No. 3,822,135, a method of adding the compound to an emulsion, a method of dispersing it in a water-soluble solvent and adding the dispersion to the emulsion, as described in JP-B-46-24185, etc., described in US Pat. No. 3,822,135. , A method of dissolving the compound in a surfactant and adding the solution into the emulsion,
As described in JP-A-51-74624, a method of dissolving using a compound for red-shifting and adding the solution into an emulsion, as described in JP-A-50-80826,
A method in which the compound is dissolved in an acid substantially free of water and the solution is added to the emulsion is used. In addition, U.S. Pat. Nos. 2,912,343 and 3,3,3 are added to the emulsion.
42,605, 2,996,287, 3,42
The method described in No. 9,835 can also be used.

In the present invention, any known processing composition can be used for each processing bath such as color development, bleaching, fixing, washing, stabilizing, adjusting, black and white developing, 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 3
4 lines to page 33, right column, line 37.

[0083]

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 of the present invention containing a sensitizing dye into contact with an oxidizing agent. 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 sides were coated with polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. , Further coating the first to seventh layers in order,
Silver halide color photographic light-sensitive material P having the following layer structure
-1 was produced. The coating liquid for each photographic constituent layer was prepared as follows.

Fifth layer coating solution preparation 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, 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. 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.

[0088]

[Chemical 8]

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

[0090]

[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

[0093]

[Chemical 10]

(Sensitizing dye D was added 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, per mol of silver halide. 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

[0096]

[Chemical 11]

(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. )

[0098]

[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 / 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.

[0101]

[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 Polyethylene resin laminated paper [White pigment (TiO ₂ :
Content 16% by mass, ZnO: content 4% by mass] and fluorescent whitening agent (4,4′-bis (5-methylbenzoxazolyl) stilbene content 0.03% by mass), bluish dye (ultra-blue) )including]

[0103] 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

[0104] 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

[0105] 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

[0106] 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

[0107] 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

[0108] 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

[0109] 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

[0110]

[Chemical 14]

[0111]

[Chemical 15]

[0112]

[Chemical 16]

[0113]

[Chemical 17]

[0114]

[Chemical 18]

[0115]

[Chemical 19]

[0116]

[Chemical 20]

[0117]

[Chemical 21]

[0118]

[Chemical formula 22]

The following development processing was carried out on the photosensitive material sample P-1. [Treatment Process] Treatment Process Temperature Time Color development 38.5 ° C. 45 seconds Bleach-fixing 38.0 ° C. 45 seconds Wash 38.0 ° C. 10 seconds Oxidation 38.0 ° C. 40 seconds Dry 80 ° C.

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

[0121] [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

[0122] [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) 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 _G 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

[0124]

[Table 1]

Table 1 shows that the samples 11 to 16 prepared by adding the oxidizing agent of the present invention to the sample 11 prepared by not adding the oxidizing agent to the oxidizing bath had a lower magenta density and thus sensitized. It shows that the dye stain was reduced.

(Example 2) Sample 2 was obtained by applying the process CN-16L of Fuji Color Superior Zoom Master 800 manufactured by Fuji Photo Film Co., Ltd., which was imagewise exposed, to Fuji Photo Film Co., Ltd.
1, 22 were produced. Performs transmission absorption measurement of the minimum density portion with the specimen 21 by Hitachi Ltd. U-3500 spectrophotometer, was determined 500 nm, the absorbance D _{50 ⁰ 0,} D _{555 0} at 555 nm. Next, the samples 21 and 22 were subjected to the following post-treatment.

[Post-Processing Step] Oxidation 38.0 ° C 30 seconds Dry 80 ℃

[Oxidizing liquid] Oxidizing agent (described in Table 2) Water described in Table 2 was added to obtain a total amount of 1000 mL pH (25 ° C., adjusted with sulfuric acid and sodium hydroxide) 7.0 The same permeation absorption measurement was performed again to 500 nm. 555 nm
Absorbances D ₅₀₀ and D _{5 55} were determined. Differences in stain before and after the treatment, ΔD ₅₀₀ and ΔD _555, were calculated by the following equation. ΔD ₅₀₀ ,
ΔD ₅₅₅ means that the larger the value, the greater the stain reduction effect. The results are shown in Table 2. ΔD ₅₀₀ = D ₅₀₀ ⁰ -D ₅₀₀ ΔD ₅₅₅ = D ₅₅₅ ⁰ -D ₅₅₅

[0129]

[Table 2]

Table 2 shows sample 21 made without oxidant.
On the other hand, it is shown that the stain is reduced in the sample 22 treated with the oxidizing agent in the present invention.

Example 3 Image-wise exposed Fuji Photo Film Provia 100 manufactured by Fuji Photo Film Co., Ltd. was subjected to Process CR-56P manufactured by the same company to prepare samples 31 and 32. Using a U-3500 type spectrophotometer manufactured by Hitachi, Ltd., the transmission absorption measurement of the minimum density part was performed, and the absorbance D of the two processed color reversal films at 540 nm was measured.
I asked for ₅₄₀ ⁰ . 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.
The absorbance D ₅₄₀ at 40 nm was calculated, and the difference ΔD ₅₄₀ in stain before and after the post-treatment was calculated by the following formula.
The results are shown in Table 3. ΔD ₅₄₀ means that the larger the value, the greater the stain reduction effect. ΔD ₅₄₀ = D ₅₄₀ ⁰ −D ₅₄₀

[0132]

[Table 3]

Table 3 shows that the stain is reduced in the sample 32 which was subjected to the oxidation bath treatment containing the oxidizing agent in the present invention after the treatment, as compared with the blank sample 31.

[0134]

INDUSTRIAL APPLICABILITY The present invention can provide a processing method for providing a silver halide photographic light-sensitive material having a reduced stain resulting from a residual sensitizing dye after processing.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material containing a sensitizing dye is exposed, developed, and desilvered to remove silver halide. A method of processing a silver halide photographic light-sensitive material, which comprises contacting with an oxidizing agent except for a sulfate and an aminopolycarboxylic acid iron salt. 2. The method of processing a silver halide photographic light-sensitive material according to claim 1, wherein the oxidizing agent is an aqueous solution. 3. The oxidant is at least one compound selected from organic peracids, organic peroxides, or hydrogen peroxide and its adducts.
The method for processing a silver halide photographic light-sensitive material described in 1.