JP2532849B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, it has a rapid bleach-fixing ability and is capable of storing a dye image obtained with time. The present invention relates to a method for processing an excellent silver halide color photographic light-sensitive material which does not increase yellow stain.

BACKGROUND OF THE INVENTION A recent trend is to shift from a centralized processing type in which the demand in the market is processed by a few large labs to a distributed processing type in which processing is performed by a large number of small labs. In such a small laboratory, there is an increasing demand for a compact processing machine and at the same time, a rapid processing capable of supporting a short-time service. In particular, high-sensitivity silver halide color photographic light-sensitive materials for photography have a long processing time, and in order to reduce the time from receiving the photographed color negative film at the counter to delivering the print to the customer, the color negative film It is absolutely necessary to reduce the processing time. Above all, the desilvering step occupies nearly half of the total processing time, and speeding up the desilvering step is an important issue.

As a means for accelerating the desilvering process, for example, German Patent No. 866,605 proposes a bleach-fixing solution containing a ferric aminopolycarboxylic acid complex salt and thiosulfate in one bath. When an aminopolycarboxylic acid ferric iron complex salt having a weak bleaching power (oxidizing power) is made to coexist with a thiosulfate having a reducing power, the bleaching power is remarkably weakened and a high-sensitivity and high-silver color light-sensitive material is sufficiently desilvered. Is extremely difficult and cannot be put to practical use.

On the other hand, there has been proposed a method of adding various bleaching accelerators to a bleaching solution, a bleach-fixing solution or their pre-bath in order to enhance the bleaching power of the ferric aminopolycarboxylic acid complex salt.

Examples of these bleaching accelerators include U.S. Pat.
3,858, British Patent 1,138,842, JP-A-53-141623
No. 54-52534, various mercapto compounds described in JP-A-53-95631, etc., compounds having a disulfide bond described in JP-A-53-95630, and thiazolidine described in JP-B-53-9854. Derivatives, isothiourea derivatives described in JP-A-53-94927, thiourea derivatives described in JP-B-45-8506 and 49-26586, thioamide compounds described in JP-A-49-42349, JP The dithiocarbamate salts described in JP-A-55-26506 are known.

On the other hand, on the other hand, a technique of using, as a bleaching agent, an aminopolycarboxylic acid ferric iron complex salt having a high bleaching power such as diethylenetriaminepentaacetic acid ferric iron complex salt and cyclohexanediaminetetraacetic acid ferric iron complex salt (for example, JP-A-59- 149358
No. 61-47959), an attempt to increase the bleaching power of the bleach-fixing solution, a short bleaching process before the bleach-fixing process, and in this case the bleaching solution overflow solution was bleached. Method of pouring into fixing solution (JP-A-61-75352)
No. 61-75353), and a method of carrying out a fixing process for a short time before the bleach-fixing process (Japanese Patent Laid-Open No. 61-51143).

With these techniques, the bleaching speed by the bleach-fixing solution is improved to some extent. However, since the bleach-fixing solution contains a large amount of a bleaching agent, the swelling of gelatin is suppressed, the permeation of the fixing agent into the light-sensitive material is suppressed, and the fixing speed is delayed. Also, the use of bleach accelerators increases the bleaching rate, but often slows the fixing rate. Therefore, traces of silver halide often remain in the light-sensitive material without being desilvered, and in such a case, traces of silver halide remain almost unaffected immediately after processing, It has been found that the storage with time has a great relation to the increase in yellow stain of the dye image.

Such an increase in yellow stain occurs when a large amount of light-sensitive material samples are continuously bleach-fixed and the amount of components accumulated in the bleach-fixing solution, particularly the amount of iodide ions released from the light-sensitive material, exceeds a certain limit. It turned out to be extremely remarkable.

Further, the amount of iodide ions accumulated in the bleach-fixing solution strongly depends on the limit composition amount calculated from the halogen composition in the silver halide emulsion used for the light-sensitive material and the replenishing amount of the processing solution, It has been found that the increase in yellow stain is affected by the amount of 1.0 × 10 ^-3 g / ion or more per 1 bleach-fixing solution. Further, the present inventors have found that the silver bleaching rate is rather increased when 1.0 × 10 ⁻³ gram ion or more of iodide ion is present in the bleach-fixing solution 1.

As a result of various studies based on the above findings, the present inventors have set the iodide ion concentration in the solution to a specific level or higher and use a specific coupler in the silver halide color photographic light-sensitive material to rapidly bleach-fix. The present invention has been completed by discovering that it is an excellent method that has a high speed and that the increase in yellow stain is suppressed to a low level even when the resulting dye image is stored with time.

OBJECT OF THE INVENTION Accordingly, an object of the present invention is to provide a method for processing an excellent silver halide color photographic light-sensitive material which has a rapid bleach-fixing speed and does not cause an increase in yellow stain even when the dye image obtained is stored with time. To provide.

[Construction of the Invention] The above object of the present invention is to subject a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support to imagewise exposure and then to treat it with at least a color developing solution and a bleach-fixing solution. In the method for processing a silver halide color photographic light-sensitive material, the silver halide emulsion layer comprises 2 mol%
To 20 mol% of silver iodide grains and at least one of the silver halide emulsion layers has the following general formulas (Ma-1) to (Mc
-14) each containing at least one coupler selected from the couplers and / or a polymer coupler derived from the coupler, and 1.0 × 10 ⁻³ per liter of the bleach-fixing solution in the bleach-fixing solution. It has been achieved by a processing method of a silver halide color photographic light-sensitive material characterized by containing iodide ions of gram ion or more.

(In the formula, Xa _{1 to} Xa ₁₁ , Xb _{1 to} Xb ₈ , and Xc _{1 to} Xc ₁₄ each represent a hydrogen atom or a group capable of splitting off upon reaction with an oxidant of a color developing agent. R _{11 to} R ₄₂ , R _{51 to} R ₉₀ each represent a hydrogen atom or a substituent.) According to a preferred embodiment of the present invention, at least one selected from the couplers represented by the general formulas (Ma-1) to (Mc-14). A silver halide color photographic light-sensitive material characterized by containing a sensitizing dye represented by the following general formula [I] in a silver halide emulsion layer containing a certain type of coupler and / or a polymer coupler derived from the coupler. It is in the processing method of the material.

General formula [I](In the formula, Z₁And Z₂Are benzes fused to heterocycles
Group of atoms necessary to form a ring or naphthalene ring
I forgot. R₁And R₂Are alkyl and alkenyl groups, respectively
Or represents an aryl group, R₃Is hydrogen atom or carbon number
Represents an alkyl group of 1 to 3, X₁ Represents anion
, P represents 0 or 1. Y₁And Y₂Is an acid
Elemental atom, sulfur atom, selenium atom, tellurium atom or --NH
Represents-. ) [Specific Structure of the Invention] Silver halide color copying used in the processing method of the present invention.
The following couplers are used for the true light-sensitive material.

The general formulas (Ma-1) to (Ma-11) according to the present invention,
(Mb-1) to (Mb-8), (Mc-1) to (Mc-14) In the coupler represented by, Xa ₁ to Xa ₁₁ , Xb _{1 to} Xb
₈ , Xc _{1 to} Xc ₁₄ each represent a hydrogen atom or a group capable of splitting off upon reaction with an oxidant of a color developing agent.

R _{11 to} R ₄₂ and R _{51 to} R ₉₀ each represent a hydrogen atom or a substituent.

Note that general formulas (Ma-1) to (Ma-11), (Mb-1) to
The couplers represented by (Mb-8) and (Mc-1) to (Mc-14) are represented by Xa _{1 to} Xa ₁₁ , Xb _{1 to} Xb ₈ and Xc _{1 to} Xc _{14, respectively.}
Only at the position where is bonded to the oxidant of the color developing agent.

The substituents represented by R _{11 to} R ₄₂ and R _{51 to} R ₉₀ are not particularly limited, but typically include alkyl, aryl, anilino,
Examples include groups such as acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl. In addition to these, a halogen atom and cycloalkenyl,
Alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy,
Siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups, and spiro compound residues, Examples include bridged hydrocarbon compound residues.

The alkyl group represented by R _{11 to} R ₄₂ and R _{51 to} R ₉₀ preferably has 1 to 32 carbon atoms and may be linear or branched.

The aryl group represented by R _{11 to} R ₄₂ and R _{51 to} R ₉₀ is preferably a phenyl group.

Examples of the acylamino group represented by R _{11 to} R ₄₂ and R _{51 to} R ₉₀ include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R _{11 to} R ₄₂ and R _{51 to} R ₉₀ include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkylthio group represented by R _{11 to} R ₄₂ and R _{51 to} R ₉₀ , the alkyl component in the arylthio group, and the aryl component include the alkyl groups and aryl groups represented by the above R _{11 to} R ₄₂ and R _{51 to} R ₉₀ .

The alkenyl group represented by R _{11 to} R ₄₂ and R _{51 to} R ₉₀ has 2 to 32 carbon atoms, and the cycloalkyl group includes
Those having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms are preferable, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R _{11 to} R ₄₂ and R _{51 to} R ₉₀ is preferably a cycloalkenyl group having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms.

Examples of the sulfonyl group represented by R _{11 to} R ₄₂ and R _{51 to} R ₉₀ include an alkylsulfonyl group and an arylsulfonyl group; a sulfinyl group includes an alkylsulfinyl group and an arylsulfinyl group; and a phosphonyl group includes an alkylphosphonyl group. , An alkoxyphosphonyl group, an aryloxyphosphonyl group, an arylphosphonyl group, etc .; an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc .; a carbamoyl group, an alkylcarbamoyl group,
Arylcarbamoyl group, etc .; As a sulfamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, etc .; As an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc .; As a carbamoyloxy group, an alkylcarbamoyloxy group, Arylcarbamoyloxy group, etc .; Ureido group, alkylureido group, arylureido group, etc .; Sulfamoylamino group, alkylsulfamoylamino group, arylsulfamoylamino group, etc .; Heterocyclic group, 5 A 7-membered one is preferable, and specifically, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group, etc .; As the heterocyclic oxy group, one having a 5- to 7-membered heterocycle is preferable. Preferably, for example 3,4,5,6-tetrahydr Lopyranyl-2-oxy group, 1-phenyltetrazole-5
-Oxy group and the like; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5- Triazole-6-thio group, etc .; siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; imide group, succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutar Imido group, etc .; spiro [3.3] heptane-as the spiro compound residue
1-yl and the like; examples of the bridged carbonized compound residue include bicyclo [2.2.1] heptan-1-yl, tricyclo [ ^3.3.1.13'7 ] decan-1-yl, 7,7-dimethyl-bicyclo [ 2.2.1] Heptan-1-yl and the like can be mentioned.

Xa _{1 to} Xa ₁₁ , Xb _{1 to} Xb ₈ , and Xc _{1 to} Xc ₁₄ can be split off by a reaction with an oxidant of a color developing agent, for example, a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.).
And alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfone Examples thereof include amides, nitrogen-containing heterocycles bonded by N atoms, alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl groups, with halogen atoms being preferred, and chlorine atoms being particularly preferred.

The compounds represented by the formulas and the exemplified compounds described below also include tautomers. Formulas (Ma-1) to (Ma-1
1), (Mb-1) to (Mb-8), (Mc-1) to (Mc-1)
Among those represented by 4), preferred is the formula (Ma-
2), (Ma-3), (Ma-4), (Mb-1), (Mb-
3), (Mb-4), (Mc-2), (Mc-3), (Mc-
4), (Mc-9), (Mc-10) and (Mc-12), particularly (Ma-3), (Mb-1) and (Mc-).
3), (Mc-9) and (Mc-10).

Preferred examples of the substituents on the heterocycle (for example, R _{11 to} R ₄₂ , R _{51 to} R ₉₀ ) in the compound represented by each formula are described below.

At least one of the substituents (for example, R _{11 to} R ₄₂ , R _{51 to} R ₉₀ ) on the heterocycle is preferably represented by the following general formula.

In the general formula —R ¹ —SO ₂ —R ² formula, R ¹ represents an alkylene group, and R ² represents an alkyl group, a cycloalkyl group or an aryl group.

The alkylene group represented by R ¹ preferably has a straight chain portion having 2 or more carbon atoms, more preferably 3 to 6, and may be straight chain or branched. The cycloalkyl group represented by R _2, preferably from 5 to 6 membered.

When the coupler according to the present invention is used for positive image formation,
The most preferable substituent of the carbon atom adjacent to the carbon atom to which Xa _{1 to} Xa ₁₁ , Xb _{1 to} Xb ₈ and Xc _{1 to} Xc ₁₄ are bonded is represented by the following general formula.

General formula In the formula, R ₁₀₁ , R ₁₀₂ and R ₁₀₃ are the same as R ₁₁ , R ₁₃ and R, respectively.
_The same as ₁₄ and R ₁₆ can be mentioned.

Also, two of R ₁₀₁ , R ₁₀₂ and R ₁₀₃ , for example R ₁₀₁
And R ₁₀₂ may combine with each other to form a saturated or unsaturated ring (eg, cycloalkane, cycloalkene, heterocycle), and R ₁₀₃ further bonds to the ring to form a bridged hydrocarbon compound residue. You may.

Among the above general formulas, preferred is (i) when at least two of R _{101 to} R ₁₀₃ are alkyl groups, (ii) one of R _{101 to} R ₁₀₃ , for example, R ₁₀₃ is a hydrogen atom. And when the other two, R ₁₀₁ and R ₁₀₂ , combine to form a cycloalkyl with the root carbon atom.

Further preferred among (i) is a case where two of R _{101 to} R ₁₀₃ are alkyl groups and the other one is a hydrogen atom or an alkyl group.

When the coupler according to the present invention is used for forming a negative image, Xa _{1 to} Xa ₁₁ , Xb _{1 to} Xb ₈ , and Xc _{1 to} Xc ₁₄ are preferably used as a substituent of a carbon atom adjacent to the carbon atom to which they are bonded. Is represented by the following general formula.

General formula R ₁₀₄ —CH ₂ — In the formula, as R _{104, the same} as the above R ₁₁ , R ₁₃ , R ₁₄ and R ₁₆ can be mentioned. Preferred as R ₁₀₄ is a hydrogen atom or an alkyl group.

 Specific examples of the coupler used in the present invention are shown below.

In addition to the typical examples of the coupler according to the present invention,
Specific examples of the coupler according to the present invention include Japanese Patent Application No. 61-134.
Exemplified compounds No. 1, 4 to 6, 8 to 10, 12 to 14, 16 to described in No. 287 (purification) on pages 58 to 62
31, 33, 35, 38, 40, 41, 43, 45, 47, 49 to 52, 55 to 6
2, 64-69, 71-75, 77, 78, 80-83, 85, 88, 91, 9
2, 99, 100, 102, 104, 108, 110-112, 114-116, 118
~ 120, 122, 124, 127, 128, 130, 132-137, 139-14
5, 147-152, 154-159, 161-166, 168-174, 176-18
1, 183-190, 192, 195, 196 can be mentioned.

The color tone of the color-forming dye produced by the coupler of the present invention can be changed depending on the conditions such as the arrangement of ring-constituting atoms of the coupler, the type of substituents, the type of color-developing agent, etc., but it is mainly magenta and is a multicolor photograph. Although it can be used for applications, the reddish tone also has good light absorption characteristics,
It can be used for single color photographs and the like.

The coupler of the present invention usually contains 1 mol per mol of silver halide.
× 10 ^-3 mol to 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10
It can be used in the range of ^-1 mol.

The coupler of the present invention can also be used in combination with other types of magenta couplers.

Silver halide emulsions usable in the light-sensitive material applicable to the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide and silver chloroiodobromide. Any of these silver halides may be used. However, the processing method of the present invention is particularly suitable for processing a silver halide color photographic light-sensitive material containing at least 0.5 mol% or more, particularly 2 mol% to 20 mol% of silver iodide grains.

The crystal of the silver halide grain used in the present invention may be a normal crystal, a twin crystal or any other crystal, and any ratio of {100} plane to {111} plane can be used.

In the present invention, the silver halide emulsion layer containing the coupler of the present invention preferably contains a sensitizing dye represented by the following general formula [I].

General formula [I] (In the formula, Z₁And Z₂Are each a benzene fused to a heterocycle
The atomic groups necessary to form a zen ring or naphthalene ring
Represent. R₁And R₂Are alkyl group and alkenyl, respectively
Represents a group or an aryl group, R₃Is a hydrogen atom or carbon
Represents an alkyl group of the number 1 to 3, X₁ Represents anion
, P represents 0 or 1. Y₁And Y₂Is an acid
Elemental atom, sulfur atom, selenium atom, tellurium atom or --NH
-Represents an atom. ) In the general formula [I], Z₁And Z₂Are heterocycles
To form a benzene ring or naphthalene ring fused to
Represents a group of atoms necessary for the benzene ring and naphtha
The len ring also includes those having a substituent, and as the substituent,
Halogen atom, aryl group, alkenyl group, alkyl group
Alternatively, it is an alkoxy group. More preferred substituents are halo
Gen atom, phenyl group and methoxy group, most preferred
A preferred substituent is a phenyl group.

 Preferably Z₁And Z₂Are both oxazole ring or thia
Benzene ring fused to the sol ring
At least one of the benzene rings is phenyl
Or substituted at the 5-position of one benzene ring.
Phenyl group, 5-position of other benzene ring is replaced by halogen atom
It has been done. R₁And R₂Are each alkyl
A group, an alkenyl group or an aryl group, preferably
A, respectively substituted with a carboxyl group or a sulfo group
A sulfonyl group, most preferably a sulfo group having 1 to 4 carbon atoms.
Alkyl group, most preferably sulfoethyl group
Is. R₃Is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
And preferably a hydrogen atom or an ethyl group.
X₁ Represents an anion, and p represents 0 or 1. Y₁
And Y₂Are oxygen atom, sulfur atom, selenium atom,
Represents a tellurium atom or -NH-.

The sensitizing dye represented by the general formula [I] preferably used in the present invention can be used in combination with other sensitizing dyes as a so-called supersensitizing combination. In this case,
Each sensitizing dye is dissolved in the same or different solvent and these solutions are mixed prior to addition to the emulsion,
Alternatively, they may be separately added to the emulsion. When they are added separately, their order and time interval can be arbitrarily determined according to the purpose.

Specific compounds of the sensitizing dye represented by the general formula [I] are shown below, but the sensitizing dye used in the present invention is not limited to these compounds.

The addition amount of the sensitizing dye represented by the general formula [I], which is preferably used in the present invention, to the emulsion is preferably 1 × 10 ^{−6 to} 5 × 10 ⁻³ mol, and more preferably 5 mol, per mol of silver halide. It is x10 ^-5 to 1 x 10 ^-3 mol.

The silver halide emulsion layer according to the present invention contains the above-mentioned coupler of the present invention, and the silver halide emulsion layer and other silver halide emulsion layers can contain a coupler other than the present invention. .

As the couplers other than the present invention which can be used in the present invention, various yellow couplers, magenta couplers and cyan couplers can be used without particular limitation. These couplers may be so-called 2-equivalent type or 4-equivalent type couplers, and diffusible dye-releasing couplers and the like can be used in combination with these couplers.

Hereinafter, couplers other than the present invention which can be used in combination with the present invention will be described.

Useful cyan couplers used in the present invention include:
For example, phenol-based and naphthol-based couplers can be used. Specific examples of cyan couplers include U.S. Pat.Nos. 2,369,929, 2,434,272, 2,474,293 and 2,5.
21,908, 2,895, 826, 3,034,892, 3,311,4
No. 76, No. 3,458,315, No. 3,476,563, No. 3,583,971
No., No. 3,591,383, No. 3,767,411, No. 3,772,002,
No. 3,933,494, No. 4,004,929, West German patent application (OLS)
2,414,830, 2,454,329, JP-A-48-59838, 51
-26034, 48-5055, 51-146827, 52-69624
No. 52-90932, No. 58-95346, and Japanese Patent Publication No. 49-11572.

As the magenta coupler, a pyrazolone-based compound, a pyrazolotriazole-based compound, a pyrazolinobenzimidazole-based compound, an indazolone-based compound or the like is used. As a pyrazolone-based magenta coupler, U.S. Pat.Nos. 2,600,788 and 3,0
62,653, 3,127,269, 3,311,476, 3,419,39
No. 1, 3,519,429, 3,558,318, 3,684,514,
3,888,680, JP-A-49-29639, 49-111631,
49-129538, 50-13041, JP-B-53-47167, 54-
No. 10491, the compound described in the same 55-30615, as the pyrazolotriazole-based magenta couplers, the couplers described in U.S. Pat.No. 1,247,493, Belgian Patent 792,525, and the diffusion-resistant colored magenta couplers. , Generally, a compound in which an arylazo substitution is used at the coupling position of a colorless magenta coupler is used,
For example, U.S. Pat.Nos. 2,801,171, 2,983,608, and 3,005,
712, 3,684,514, British Patent 937,621, JP-A-49-
The compounds described in Nos. 123625 and 49-31448 can be mentioned.

Further, a colored magenta coupler of the type described in U.S. Pat. No. 3,419,391, in which a dye flows out into a processing solution upon reaction with an oxidized product of a developing agent, can also be used.

As the yellow coupler, an open chain ketomethylene compound has been conventionally used, and a benzoylacetanilide type yellow coupler and a pivaloylacetanilide type yellow coupler which are generally widely used can be used. Further, a 2-equivalent type yellow coupler in which the carbon atom at the coupling position is substituted with a substituent capable of leaving during the coupling reaction is also advantageously used. Examples of these are U.S. Patents 2,875,057, 3,265,506, and
3,664,841, 3,408,194, 3,277,155, 3,44
7,928, 3,415,652, JP-B-49-13576, JP-A-48
-29432, 48-68834, 49-10736, 49-122335
No. 50, No. 50-28834, No. 50-132926, etc., together with the synthetic method.

The amount of the diffusion-resistant coupler used in the present invention is generally 0.05 to 0.05 mol per mol of silver in the photosensitive silver halide emulsion layer.
~ 2.0 moles.

In the present invention, a DIR compound is preferably used in addition to the above-mentioned diffusion-resistant coupler.

Further, in addition to the DIR compound, compounds that release a development inhibitor upon development are also included in the present invention.
3,297,445, 3,379,529, West German patent application (OLS) 2,4
17,914, JP-A Nos. 52-15271, 53-9116, and 59-1238
38, 59-127038 and the like.

The silver halide color photographic light-sensitive material used in the present invention may further contain various photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants described in Research Disclosure No. 17643 , A plasticizer, a wetting agent and the like can be used.

In the silver halide color photographic light-sensitive material used in the present invention, an aqueous silver colloid used for preparing an emulsion includes gelatin, a derivative gelatin, a graft polymer of gelatin and another polymer, a protein such as albumin and casein. , Hydroxyethyl cellulose derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinyl imidazole,
Any one such as a single or copolymer synthetic hydrophilic polymer such as polyacrylamide is included.

Examples of the support of the silver halide color photographic light-sensitive material used in the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support having a reflective layer, or a reflective plate, such as a glass plate, Examples include a polyester film such as cellulose acetate, cellulose nitrate or polyethylene terephthalate, a polyamide film, a polycarbonate film, a polystyrene film, and the like, and may be other ordinary transparent supports. These supports are appropriately selected according to the purpose of use of the light-sensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the silver halide emulsion layer and other photographic constituent layers used in the present invention. U.S. Patent 2,761,79
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 1 and No. 2,941,898.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined.

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness according to the purpose, and various layers such as a filter layer, an anti-curl layer, a protective layer and an antihalation layer are appropriately used as constituent layers. It can be used in combination. A hydrophilic colloid which can be used in the emulsion layer as described above can be similarly used as a binder in these constituent layers, and various hydrophilic colloids can be contained in the emulsion layer as described above. The above photographic additives can be incorporated.

In the method of processing a silver halide color photographic light-sensitive material of the present invention, as a silver halide color photographic light-sensitive material,
If the photosensitive material contains a coupler and is processed by a so-called internal development method, color paper, color negative film, color positive film, slide color reversal film, movie color reversal film, TV color reversal film. It can be applied to any silver halide color photographic light-sensitive material such as reverse color paper.

In the present invention, the silver halide color photographic light-sensitive material containing the above-mentioned coupler of the present invention is exposed and then color-developed, and then bleaching containing 1.0 × 10 ⁻³ g ion or more of iodide ion per bleach-fixing solution. It is characterized by processing with a fixer.

The iodide ion may be present in an amount of 1.0 × 10 ⁻³ gram ion or more per bleach-fixing solution, but when the iodide ion concentration exceeds 0.2 gram ion per bleach-fixing solution,
Since the bleaching speed will be delayed due to a large delay in fixing, it is preferable to use at 0.2 g ion / l or less.

That is, in the present invention, the iodide ion supplied from the light-sensitive material and / or the replenisher in the bleach-fixing solution is
Even when accumulated over 1.0 × 10 ^-3 g ions,
It has been found that the increase in yellow stain can be suppressed to a low level during storage of a dye image obtained by processing using the solution.

The iodide ion in the bleach-fixing solution used in the present invention may be potassium iodide, sodium iodide or the like as a bleach-fixing solution or its replenishing solution even if it is eluted and accumulated in the bleach-fixing solution when the light-sensitive material is processed. In addition to the other components, the iodide ion in the bleach-fixing solution can be kept above a certain level.

In the processing method of the present invention, the bleach-fixing solution containing a light-sensitive material containing the coupler of the present invention is a treatment containing 1.0 × 10 ⁻³ g ion / l or more iodide ion,
Any processing method such as color development, bleach-fixing, and subsequent washing with water or a stabilizing treatment in place of washing with water can be applied.

The color developing agent used in the color developing solution of the present invention includes various ones widely used in various color photographic processes. These developers include aminophenol-based and p-phenylenediamine-based derivatives. These compounds are generally used in the form of a salt, for example in the form of the hydrochloride or sulfate, for stability in the free state. It is generally preferred that these compounds are used in a concentration of about 0.1 g to about 50 g per color developing solution 1,
More preferably, a concentration of about 1 g to about 30 g per 1 is used.

Examples of aminophenol developers include o-aminophenol, p-aminophenol, and 5-amino-2.
-Hydroxytoluene, 2-amino-3-hydroxytoluene, 2-hydroxy-3-amino-1,4-dimethylbenzene and the like.

Particularly useful color developing agents are N, N-dialkyl-p-phenylenediamine compounds, in which the alkyl and phenyl groups may or may not be substituted. Among them, particularly useful compounds are N, N-diethyl-p-phenylenediamine hydrochloride, N-methyl-
p-phenylenediamine hydrochloride, N, N-dimethyl-p-
Phenylenediamine hydrochloride, 2-amino-5- (N-ethyl-N-dodecylamino) -toluene, N-ethyl-
N-β-methanesulfonamidoethyl-3-methyl-4
-Aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline sulfate, 4-amino-3-methyl-N, N-diethylaniline sulfate, 4-amino-N
Examples thereof include-(methoxyethyl) -N-ethyl-3-methylaniline-p-toluenesulfonate.

Further, instead of using the color developing agent as a color developing solution, a color developing agent can be added to the light-sensitive material, and the color developing agent used in that case includes a dye precursor. A typical dye precursor is JP-A-SHO
58-65429, those described in paragraphs 58-24137 etc. are used,
Specifically, for example, 2 ', 4'-bismethanesulfonamido-4-diethylaminodiphenylamine, 2'-methanesulfonamido-4'-(2,4,6-triisopropyl) benzenesulfonamido-2-methyl- 4-N-
(2-Methanesulfonamidoethyl) ethylaminodiphenylamine, 2'-methanesulfonamido-4'-
(2,4,6-Triisopropyl) benzenesulfonamide-4- (hydroxytrisethoxy) diphenylamine, 4-N- (2-methanesulfonamidoethyl) ethylamino-2-methyl-2 ', 4'-bis ( 2,4,6-Triisopropyl) benzenesulfonamide diphenylamine, 2,4'-bismethanesulfonamide-4-N, N-diethylaminodiphenylamine, 4-n-hexyloxy-2'-methanesulfonamide-4'- (2,4,6-Triisopropyl) benzenesulfonamide diphenylamine, 4-methoxy-2'-methanesulfonamide-4 '
-(2,4,6-triisopropyl) benzenesulfonamidodiphenylamine, 4-dihexylamino-4'-
(2,4,6-triisopropylbenzenesulfonamide)
Diphenylamine, 4-n-hexyloxy-3'-methyl-4 '-(2,4,6-triisopropylbenzenesulfonamide) diphenylamine, 4-N, N-diethylamino-4'-(2,4,6- Triisopropylbenzenesulfonamide) diphenylamine, 4-N, N-dimethylamino-2-phenylsulfonyl-4 ′-(2,4,6-triisopropylbenzenesulfonamide) diphenylamine and the like can be mentioned.

The amount of the dye precursor added to the light-sensitive material is preferably 0.5 to 22 mg, more preferably ^{4 to 12} mg, per 100 cm ² of the light-sensitive material.

The color developing solution further contains sodium sulfite, ammonium sulfite, potassium bisulfite, and other sulfites, bisulfite adducts of aldehydes and ketones, and hydroxylamine, diethylhydroxylamine, dimethoxyethylhydroxylamine, and other hydroxylamines. A stabilizer, a halide such as sodium bromide, and a development inhibitor such as an organic inhibitor may be contained.

The color developer of the invention may contain the following developer components in addition to the above components.

As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, silicate, sodium carbonate, potassium carbonate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc., alone or in combination And can be used. Further, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate and borate are used for the necessity of preparation or for the purpose of increasing ionic strength. be able to.

Inorganic and organic antifoggants can be added if necessary.

Further, a development accelerator can be used if necessary. U.S. Pat.Nos. 2,648,604 and
3,671,247, various pyridinium compounds represented by JP-B-44-9503, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Pat.No. 2,533,990, Second 2,531,832
No. 2,950,970, No. 2,577,127, and Shokoku Sho
Polyethylene glycol and its derivatives described in 44-9504 publication, nonionic compounds such as polythioethers, organic solvents and organic amines described in JP-B-44-9509, ethanolamine, ethylenediamine, diethanolamine, triethanolamine, etc. included. Also, US Patent No. 2,
Examples thereof include benzyl alcohol, phenethyl alcohol described in No. 304,925, acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine and amines.

Further, the color developing solution of the present invention, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, other JP-B-47-33378, 44-9509 described each publication The compound can be used as an organic solvent for increasing the solubility of the developing agent.

Further, the color developer used in the present invention, as a chelating agent, ethylenediaminetetraacetic acid, aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, citric acid, oxycarboxylic acids such as gluconic acid, 1-hydroxyethylidene-1,1- An organic phosphonic acid such as diphosphonic acid,
It may contain aminopolyphosphonic acid such as aminotri (methylenephosphonic acid), polyhydroxy compound such as 1,2-dihydroxybenzene-3,5-disulfonic acid, and the like.

Other compounds that can be added to the color developing solution of the present invention include fluorescent whitening agents, especially triazylstilbene-based fluorescent whitening agents, and alkanolamines such as polyethyleneimine.

Further, an auxiliary developing agent can be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol hexalphate (methol), phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetrahydrochloride. Methyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably 0.01 g to 1.0 g / l. Besides this,
If necessary, a competitive coupler, a fogging agent, a colored coupler, a development inhibitor releasing type coupler (a so-called DIR coupler), a development inhibitor releasing compound, or the like can be added.

Furthermore, other various additives such as stain inhibitors, sludge inhibitors, and multi-layer effect accelerators can be used.

Each component of the color developing solution can be prepared by sequentially adding to a certain amount of water and stirring. In this case, the component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. More generally, a concentrated aqueous solution containing a plurality of components each of which can stably coexist, or a solution prepared in advance in a small container in a solid state is added to water and stirred to prepare a color developer of the present invention. Obtainable.

In the present invention, the above-mentioned color developing solution can be used in an arbitrary pH range, but is preferably from pH 9.5 to 13.0, more preferably from pH 9.8 to 13.0, from the viewpoint of rapid processing.

In the present invention, the processing temperature for color development is 30 ° C.
As described above, the higher the temperature is 50 ° C. or lower, the faster the processing can be performed in a shorter time, which is preferable. However, it is preferable that the temperature is not so high from the viewpoint of image storage stability.

The bleaching agent that can be preferably used in the bleach-fixing solution used in the present invention is a metal complex salt of an organic acid. The complex salt is obtained by coordinating a metal ion such as iron, cobalt or copper with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes a polycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these are as follows.

(1) diethylenetriaminepentaacetic acid (2) diethylenetriaminepentamethylenephosphonic acid (3) cyclohexanediaminetetraacetic acid (4) ethylenediaminetetraacetic acid (5) methyliminodiacetic acid (6) propyliminodiacetic acid (7) butyliminodiacetic acid (8) cyclohexane Diamine tetramethylene phosphonic acid (9) Triethylene tetramine hexamethylene acetate (10) Triethylene tetramine hexamethylene phosphonic acid (11) Glycol ether diamine tetra methylene phosphonic acid (12) Glycol ether diamine tetra methylene phosphonic acid (13) 1,2-Diaminopropane Tetraacetic acid (14) 1,2-diaminopropanetetramethylenephosphonic acid (15) 1,3-diaminopropan-2-oltetraacetic acid (16) 1,3-diaminopropan-2-oltetramethylenephosphonic acid (17) Ethylenediamine diorthohydroxyphenyl Acetic acid (18) Ethylenediaminedioltohydroxyphenylmethylenephosphonic acid (19) Ethylenediaminetetramethylenephosphonic acid (20) N-hydroxyethyliminodiacetic acid (21) 1,3-Diaminopropane tetraacetic acid (22) 1,3-Diaminopropane Tetramethylenephosphonic acid These bleaching agents are 5-450 g / l, more preferably 20-25
It is used at 0 g / l, more preferably at 25-100 g / l. As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a preservative is applied. Further, a bleach-fixing solution having a composition in which a small amount of an ethylenediaminetetraacetic acid iron (III) complex bleaching agent and a halide such as ammonium bromide other than the above silver halide fixing agent are added in a small amount, or conversely, a halogenating agent such as ammonium bromide is used. Bleach-fixing solution having a composition containing a large amount of a halide, and a special bleach-fixing solution having a composition comprising a combination of an ethylenediaminetetraacetic acid iron (III) complex bleaching agent and a large amount of a halide such as ammonium bromide. be able to. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

The silver halide fixing agent contained in the bleach-fixing solution is a compound which forms a water-soluble complex salt by reacting with silver halide as used in ordinary fixing processing, for example, potassium thiosulfate, sodium thiosulfate, thiol. Typical examples thereof include thiosulfates such as ammonium sulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount in the range of 5 g / l or more so that they can be dissolved, but generally 20 g to 120 g / l are used.

The bleach-fixing solution contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Various pH buffering agents such as sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be contained alone or in combination of two or more kinds.
Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants may be contained. In addition, preservatives such as bisulfite adducts of hydroxylamine, hydrazine, and aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohol and nitrates, organic agents such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. A solvent and the like can be contained as appropriate.

The bleach-fixing solution used in the present invention includes JP-B-46-280, JP-B-45-8506, JP-B-46-556, and Belgian Patent No. 770,910.
Various bleaching accelerators described in JP-B Nos. 45-8836, 53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The processing temperature is 80 ° C. or lower and the temperature is 3 ° C. or higher, preferably 5 ° C. or lower than the temperature of the processing solution in the color developing tank, but it is preferably 55 ° C. or lower to suppress evaporation and the like.

In the present invention, at least color development and bleach-fixing treatment may be carried out. However, as shown in JP-A-61-75353, bleaching treatment may be carried out after color development, and then bleach-fixing treatment may be carried out. In this case, an overflow of the bleaching bath may be introduced into the bleach-fixing bath as disclosed in JP-A-61-75352. Further, as shown in JP-A-61-51148, the bleach-fixing process may be performed after the pre-fixing process. In this case, the overflow of the pre-fixing bath may be introduced into the bleach-fixing bath as shown in JP-A-61-51143.

In the present invention, washing with water or an alternative stabilizing treatment with washing instead of water is performed.

Hereinafter, the washing stabilizing solution applicable to the present invention will be described.

The pH of the washing alternative stabilizer applicable to the present invention is preferably in the range of 5.5 to 10.0, and more preferably pH 6.3 to 9.5.
And particularly preferably in the range of pH 7.0 to 9.0. As the pH adjusting agent which can be contained in the stabilizing solution for washing with water applicable to the present invention, any of generally known alkali agents or acid agents can be used.

The treatment temperature of the stabilizing treatment is 15 ° C to 60 ° C, preferably 20 ° C.
The range of ℃ ~ 45 ℃ is good. The processing time is also preferably shorter from the viewpoint of rapid processing, but usually 20 seconds to 10 minutes,
The time is most preferably 1 minute to 3 minutes. In the case of the multiple tank stabilization treatment, it is preferable that the treatment is performed in a shorter time in the former tank and the treatment time is longer in the latter tank. In particular, it is desirable to sequentially perform the treatments with a treatment time that is 20% to 50% longer than that in the previous tank. No water washing treatment is required after the stabilization treatment applicable to the present invention, but rinsing by small amount of water washing and surface washing in an extremely short time can be arbitrarily performed as necessary.

In the case of using a multi-tank countercurrent method, it is preferable to supply a post-bath bath and overflow from a pre-bath, when a stabilizing treatment step applicable to the present invention is supplied in a stabilizing treatment step using a multi-tank countercurrent method. Of course, it can also be processed in a single tank. As a method of adding the above compound, the compound and other additives are added to a stabilization tank as a concentrated solution, or the above-mentioned compound and other additives are added to a stabilization tank to be replaced with a water washing alternative stabilizing solution. Although there are various methods such as a method of supplying the liquid, the liquid may be added by any method.

As described above, in the present invention, the treatment with the water-washing alternative stabilizing solution refers to the treatment for the stabilizing treatment which does not substantially perform the water-washing treatment, and the treatment liquid used for the stabilizing treatment is called the water-washing alternative stabilizing solution. The tank is called a stabilizing bath or stabilizing tank.

The stabilization tank in the stabilization treatment applicable to the present invention is 1 to
When the number of tanks is five, the effect of the present invention is large, particularly preferably one to three tanks, and preferably at most nine tanks or less.

[Specific effects of the invention] As described above, according to the processing method of the present invention, an excellent method for processing a silver halide color photographic light-sensitive material which does not increase in yellow stain during storage of a dye image obtained is provided. I was able to provide it.

[Specific Examples of the Invention] Hereinafter, the present invention will be specifically described with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 A negative image-forming silver iodobromide emulsion was coated on a cellulose triacetate film. Silver amount 30 mg / dm ² , gelatin 30 mg / dm ² ,
And a coupler shown in Table 1 below is dissolved and dispersed in 1/2 weight of tricresyl phosphate (hereinafter referred to as TCP) to form a silver halide emulsion layer containing 2.0 × 10 ^-5 mol / dm ^2. , 4 gelatin per 100 ml as a protective layer on it
An aqueous gelatin solution containing g, 1,2-bisvinylsulfonylethane (0.35 g) and a surfactant was applied at a gelatin concentration of 13 mg / dm ² to prepare a light-sensitive material sample.

A 20 CMC wedge exposure was applied to the above sample using a tungsten light source and adjusting the color temperature to 4800 ° K with a filter.

 The exposed photosensitive material was subjected to the following processing.

The processing steps were as follows: color development 3 minutes 15 seconds, bleach-fixing 2 minutes 00 seconds, water washing 2 minutes, stable 30 seconds.

Each treatment was performed at 37.8 ° C., and each treatment liquid used was a treatment liquid prepared according to the following formulation.

[Color developer] Potassium carbonate 30g Sodium hydrogen carbonate 2.5g Potassium sulfite 5g Sodium bromide 1.3g Potassium iodide 2mg Hydroxylamine sulfate 2.5g Sodium chloride 0.6g Sodium diethylenetriaminepentaacetate 2.5g N-ethyl-N-β-hydroxy Ethyl-3-methyl-4-aminoaniline sulphate 4.8 g Potassium hydroxide 1.2 g Water is added to make 1 and the pH is adjusted to 10.06 with potassium hydroxide or 20% sulfuric acid.

[Bleach fixer] Diethylenetriamine iron (III) pentaacetate 150g Ammonium thiosulfate 180g Ammonium sulphite (50%) 20ml Bleach accelerator AC-1 (Note 1) 1g Potassium iodide Add water to make 1 and ammonia. Adjust to pH 7.5 with water (Note 1) AC-1 [Stabilizer] Formalin (37% solution) 7.0 ml Finish by adding water.

The residual silver in the exposed and unexposed areas of each of the samples treated above was determined by the fluorescent X-ray method.

Further, an optical densitometer PDA-65 (manufactured by Konishi Rokusha Kogyo Co., Ltd.) was used to measure the yellow densities of the unexposed portion of the sample immediately after the treatment and the sample which was stored at 75 ° C. and 60% RH for 2 weeks, and the density difference Δ
The increase in yellow stain was evaluated by determining D.

 The results are shown together in Table 1.

The couplers for comparison are as follows.

As is clear from Table 1, when the iodine ion concentration in the bleach-fixing solution was 1.0 × 10 ⁻³ gram ion / l or more, the amount of residual silver in the unexposed area increased, and in the couplers other than the present invention, It can be seen that the increase in yellow stain due to storage is remarkable, but the increase in stain is almost eliminated by using the coupler of the present invention.

When a similar experiment was conducted using other couplers of the present invention, exemplified by Nos. 6, 16, 19, 40, 47 and 49, almost the same results as above were obtained.

Example 2 According to the layer structure adopted for a high-sensitivity silver halide color photographic light-sensitive material in the industry, an antihalation layer and a red-light-sensitive halogenation layer were prepared from the support while interposing various auxiliary layers. A silver emulsion layer, a green light-sensitive silver halide emulsion layer and a blue light-sensitive silver halide emulsion layer were formed, and a monodisperse high-sensitivity silver halide emulsion layer was arranged on the outermost side of the blue light-sensitive silver halide emulsion layer. The coated silver amount was approximately 13 mg / dm ² for the blue-sensitive silver halide emulsion layer and approximately 18 mg for the green-sensitive silver halide emulsion layer.
/ dm ² , and the concentration of the red-sensitive silver halide emulsion layer was adjusted to approximately 13 mg / dm ² . Further, in the layers 3 and 4, the exemplified compound [I-
16] sensitizing dye respectively 6.0 mg / m ² of, 4.0 mg / m to be ^2, the layer 6, Exemplified Compound to layer 7 [I-11] sensitizing dye each 7.0 mg / m ^2, It was adjusted to 4.0 mg / m ² .

Layer 1: Silver nitrate was reduced using hydroquinone as a reducing agent to prepare 0.8 g of black colloidal silver having high absorptivity for light in the wavelength range of 400 to 700 nm with 3 g of gelatin to form an antihalation layer.

Layer 2 ... Intermediate layer consisting of gelatin (dry film thickness 0.8 μm) Layer 3 ... 1.5 g of low-sensitivity red-sensitive silver iodobromide emulsion (Ag I; 6 mol%), 1.9 g of gelatin and 0.96 g of 1- Hydroxy-
4- (β-methoxyethylaminocarbonylmethoxy)
-N- [δ- (2,4-di-t-amylphenoxy) butyl] -2-naphthamide (hereinafter, cyan coupler (C-
1)), 0.028 g of 1-hydroxy-4- [4-
(1-Hydroxy-8-acetamido-3,6-disulfo-2-naphthylazo) phenoxy] -N- [δ- (2,4
-Di-amylphenoxy) butyl] -2-naphthamide disodium (hereinafter referred to as colored cyan coupler (CC-
A low-sensitivity red-sensitive silver halide emulsion layer containing 0.4 g of tricresyl phosphate (hereinafter referred to as TCP) in which 1) is dissolved.

Layer 4 ... 1.1 g of high-sensitivity red-sensitive silver iodobromide emulsion. (Ag I; 8 mol%), 1.2 g of gelatin and 0.41 g of cyan coupler (C-1), 0.026 g of colored cyan coupler (CC-
A high-sensitivity red-sensitive silver halide emulsion layer containing 0.15 g of TCP dissolved in 1).

Layer 5: 0.04 g in which 0.08 g of 2,5-di-t-octylhydroquinone (hereinafter referred to as a stain inhibitor (HQ-1)) was dissolved.
An intermediate layer containing g of dibutyl phthalate (hereinafter referred to as DBP) and 1.2 g of gelatin.

Layer 6 ... Low-sensitivity green-sensitive silver iodobromide emulsion (Ag I; 15 mol%), 1.7 g of gelatin, and 0.6 g of magenta coupler shown in Table 2 and 0.066 g of 1- (2,4,6-tri). Chlorophenyl) -4- (1-naphthylazo) -3- (2-chloro-
5-octadecenylsuccinimidoanilino) -5-pyrazolone (hereinafter, colored magenta coupler (CM-1)
A low-sensitivity green light-sensitive silver halide emulsion layer containing 0.3 g of TCP dissolved therein.

Layer 7 ... High-sensitivity green light-sensitive silver iodobromide emulsion (Ag I; 11 mol%), 1.9 g of gelatin, and 0.19 g of magenta couplers shown in Table 2 and 0.049 g of colored magenta couplers (CM-
A high speed green light sensitive silver halide emulsion layer containing 1.2 g of TCP in which 1) is dissolved.

Layer 8: 0.2 g of yellow colloidal silver, 0.2 g of stain inhibitor (HQ-
Yellow filter layer containing 0.11 g of DBP dissolved in 1) and 2.1 g of gelatin.

Layer 9: 0.95 g of low-sensitivity blue-sensitive silver iodobromide emulsion (Ag I; 6 mol%), 1.9 g of gelatin and 1.84 g of α- [4- (1
-Benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidinyl)]-α-pivaloyl-2-chloro-5
-[Γ- (2,4-di-t-amylphenoxy) butanamide] acetanilide (hereinafter yellow coupler Y-
1) A low-sensitivity blue-sensitive silver halide emulsion layer containing 0.93 g of DBP in which the so-called) is dissolved.

Layer 10: 1.2 g of high-sensitivity monodisperse blue-sensitive silver iodobromide emulsion Ag I; 7
Mol%), 2.0 g of gelatin, and 0.23 g of DBP in which 0.46 g of yellow coupler (Y-1) was dissolved, a high-sensitivity blue-sensitive silver halide emulsion layer.

Layer 11: Second protective layer made of gelatin.

Layer 12: First protective layer containing 2.3 g of gelatin.

The types of magenta couplers used in Layers 6 and 7 of the above photographic constituent layers were changed as shown in Table 2 below to prepare Sample No. 2-
1-22-72 was created.

The multilayer sample obtained above was exposed under the same conditions as in Example-1. Then, the bleach-fixing time was changed from 2 minutes 00 seconds to 3 minutes 15 seconds, the bleaching agents shown in Table 2 below were used in the amounts shown in Table 2 and the pH of the bleach-fixing solution was adjusted to 7.0. −
It processed on the same conditions as 1.

The sample after the treatment was evaluated in the same manner as in Example-1. The results are also shown in Table-2.

As is clear from Table 2, when the iodine ion concentration in the bleach-fixing solution was 1.0 × 10 ⁻³ gram ion / l or more, the amount of silver remaining in the unexposed area was large, and the coupler of the invention other than the present invention was stored. It can be seen that the increase in yellow stain due to the above is remarkable, but the increase in stain is almost eliminated by using the coupler of the present invention.

Other couplers of the present invention, Ex. No. 167, 175, 7, 32, 5
When a similar experiment was performed using 4 and 79, almost the same result as the above was obtained.

Example-3 Using the same light-sensitive material as used in Example-2, Example-
Processed as in 2. However, here, the sensitizing dye in the sensitive material was changed as shown in Table 3. As the bleach-fixing solution, the bleach-fixing solution containing the EDTAFe salt used in Example-2 as a bleaching agent was used.

The sample after the treatment was evaluated in the same manner as in Example-2.

 The results are shown in Table-3.

As is clear from Table 3, by using the coupler of the present invention and using the sensitizing dye preferably used in the present invention, the amount of silver remaining in the unexposed area and the exposed area is small, and the yellow stain is extremely increased. You can see that it can be kept low.

Front page continuation (72) Inventor Masao Ishikawa 1 Sakura-cho, Hino City Konishi Roku Photo Industry Co., Ltd. (56) References JP-A-61-90155 (JP, A) JP-A-61-90156 (JP, A) ) JP-A-60-230140 (JP, A) JP-A-59-162548 (JP, A) JP-A-58-16235 (JP, A) JP-A-61-112145 (JP, A) JP-A-61- 183944 (JP, A) British patent 926569 (GB, A)

Claims (2)

(57) [Claims] 1. A silver halide color photograph in which a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support is imagewise exposed and then treated with at least a color developing solution and a bleach-fixing solution. In the method for processing a light-sensitive material, the silver halide emulsion layer comprises 2 mol% to 20 mol%.
At least one coupler selected from the couplers represented by the following general formulas (Ma-1) to (Mc-14), and / or at least one of the silver halide emulsion layers. Alternatively, a silver halide containing a polymer coupler derived from the coupler and containing 1.0 × 10 ⁻³ g ion or more of iodide ion per liter of the bleach-fixing solution in the bleach-fixing solution. Color photographic light-sensitive material processing method. (In the formula, Xa _{1 to} Xa ₁₁ , Xb _{1 to} Xb ₈ , and Xc _{1 to} Xc ₁₄ each represent a hydrogen atom or a group capable of splitting off upon reaction with an oxidant of a color developing agent. R _{11 to} R ₄₂ , R _{51 to} R ₉₀ each represent a hydrogen atom or a substituent.) 2. The formulas (Ma-1) to (Mc-14)
At least one type of coupler selected from the respective couplers shown.
Polymers derived from pullers and / or couplers
In the silver halide emulsion layer containing a coupler, the following general
Characterized by containing a sensitizing dye represented by the formula [I]
A silver halide color according to claim (1)
Processing method of photographic light-sensitive material. General formula [I](In the formula, Z₁And Z₂Are benzes fused to heterocycles
Group of atoms necessary to form a ring or naphthalene ring
I forgot. R₁And R₂Are alkyl and alkenyl groups, respectively
Or represents an aryl group, R₃Is hydrogen atom or carbon number
Represents an alkyl group of 1 to 3, X₁ Represents anion
, P represents 0 or 1. Y₁And Y₂Is an acid
Elemental atom, sulfur atom, selenium atom, tellurium atom or --NH
Represents-. )