JP2814144B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly to a method for suppressing the generation of sludge and scum in a stabilizing solution and storing a color negative film. The present invention relates to a method for processing a silver halide color photographic light-sensitive material in which occurrence of yellow stain and fading of a magenta dye are prevented, and dark fading of a cyan dye due to storage of color paper is suppressed.

[Conventional technology]

Silver halide color photographic light-sensitive materials are subjected to development processing at color photographic development laboratories and small shops called minilabs. In general, a color negative film for photography is developed to form a negative image, and the negative image is printed on a color negative photosensitive material for printing using a printing machine, and the photosensitive material is developed in a developing device different from the developing device. And a positive image is obtained on the photosensitive material. In the process of obtaining a color photographic image as described above, it was necessary to install an automatic developing machine for a color negative film, and an automatic developing machine for a color negative paper and equipment for an automatic photographic printing apparatus.
Usually, a predetermined space is required as a work space around these devices.

In particular, of these equipment, around the automatic processor, space for replacing the tank solution and installing a tank for replenisher according to the processing amount, space for adjusting the replenisher solution, The space required for replenishment, such as the space for transferring the refill to the replenishment tank and the space required for adjusting the replenishment cock, occupies a considerable amount of weight in the development facility. In addition, the development process of the photosensitive material is composed of two or more processing steps as described above, and a replenisher is prepared for each replenishment, so that a lot of space is required as described above. In these replenishing operations, the frequency of dissolution adjustment of the replenisher is high and a great amount of time is required.

When an automatic developing machine for a color negative film and an automatic developing machine for a color negative paper are used separately, a temperature control device, a processing solution circulation device, a filter device, a replenishing tank, A replenishing device or the like is required, which leads to a result that goes against downsizing and cost reduction of the automatic developing machine. As one means for solving such a problem, an automatic developing machine which can process a negative photosensitive material and a positive photosensitive material with the same processing bath or the same replenisher is also known. Various problems occur in such an automatic developing machine.

In particular, when the stabilizing solution is treated with a common tank or a common replenishing solution, sludge and scum are remarkably generated in the stabilizing solution, causing clogging of a filter of an automatic developing machine or the like, which causes a failure. Further, it was found that magenta stain was generated after the processing, the stability of the dye image was high, and the discoloration of the cyan dye was large in the color paper.

According to the study by the present inventors, the former problem is that the stability of the stabilizer itself decreases when a photosensitive material having a different silver content or silver halide composition is processed, and the latter problem is the stabilizer solution. It has been clarified in many years of research that it is due to formaldehyde in the water. However, formaldehyde is effective in preventing the stability of dye images, especially yellow stain, and it is extremely difficult to remove it from the stabilizing bath due to the situation that it has been conventionally used in processing color negative films. It was a difficult problem.

[Object of the invention]

Accordingly, an object of the present invention is, firstly, to provide a method for processing a silver halide color photographic light-sensitive material which enables processing of at least two kinds of light-sensitive materials having different amounts of coated silver with a common stabilizing solution. A second object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material in which generation of sludge and scum in a stabilizing tank is improved. A third object is to provide a method for processing a silver halide color photographic light-sensitive material in which the generation of yellow stain due to storage of a processed color negative film is suppressed and the discoloration of magenta dye is also prevented. An object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material capable of suppressing dark fading of a cyan dye by storing color negative paper after color processing.

 Other objectives will become apparent in the description below.

[Means for solving the problem]

The method for processing a silver halide color photographic light-sensitive material of the present invention to achieve the above object, to the total silver coating amount of silver halide contained in the silver halide color photographic material is 2 g / m ² no 1
0 g / m ² a is a silver halide color photographic light-sensitive material (A)
And silver halide color photographic light-sensitive material (B) having a total coated silver halide amount of 1 g / m ² or less contained in the silver halide color photographic light-sensitive material. It is characterized by being treated with a stabilizing solution containing at least one compound selected from the group consisting of a methylenetetramine-based compound and compounds represented by the following general formulas [F-1] to [F-10].

[Wherein, R _{1 to} R ₆ each represent a hydrogen atom or a monovalent organic group. ] [Wherein, R _{71 to} R ₇₅ each represent a hydrogen atom or a methylol group. X represents an oxygen atom or a sulfur atom. ] [Represents wherein, V ₁ and W ₁ each represent a hydrogen atom, a lower alkyl group or an electron withdrawing group, also attached at V ₁ and W ₁ 5
A 6-membered or 6-membered nitrogen-containing heterocyclic ring may be formed. Y ₁ represents a hydrogen atom or a group which is eliminated by hydrolysis.

Z represents a group of nonmetallic atoms necessary for forming a monocyclic or condensed nitrogen-containing heterocyclic ring together with a nitrogen atom and a C ＝ O group. ] [Wherein, R ₈ represents a hydrogen atom or an aliphatic group, and R ₉ and R ₁₀
Represents an aliphatic group or an aryl group, and R ₉ and R ₁₀ may combine with each other to form a ring. Z ₁ and Z ₂ each represent an oxygen atom, a sulfur atom or —N (R ₁₁ ) —. Where Z ₁ and Z ₂
Are not simultaneously oxygen atoms. R ₁₁ is a hydrogen atom,
Represents a hydroxy group, an aliphatic group or an aryl group. ] Wherein R ₁₂ represents a hydrogen atom or an aliphatic hydrocarbon group;
₂ represents a group which leaves by hydrolysis, M represents a cation, W ₂ and Y ₂ each represent a hydrogen atom or a group which leaves by hydrolysis, n represents an integer of 1 to 10, and Z ₃ represents And R
_{And 13} represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a group which is eliminated by hydrolysis. Z ₃ may combine with R ₁₃ to form a ring. In a preferred embodiment of the present invention, at least 50 mol% of the silver halide grains contained in the silver halide emulsion layer of the silver halide color photographic light-sensitive material (B) is silver chloride.

(Operation)

Color negative film and color negative paper are currently processed on separate processors. However, considering space saving, it is preferable to perform treatment in the same treatment bath, and liquid management can be reduced to half. However, processing color negative film and color negative paper in the same bath causes various problems.

In particular, when the stabilizer bath is used in common, the photosensitive material having a high Ag content and the photosensitive material having a low Ag content are processed unevenly, so that the processing becomes unstable, and sludge caused by silver is easily generated in the stabilizer bath. In addition, magenta stain after processing is likely to occur. In particular, this is likely to occur when formaldehyde is present.

On the other hand, in the processing of color negative films, if formaldehyde is not used, yellow stain and magenta dye fading due to storage will be caused, but in the case of color negative paper, the dark fading of cyan dye will worsen due to the presence of formaldehyde. I understood.

By adding the compound of the present invention to the stabilizer bath, the generation of sludge and scum is improved, and furthermore, the yellow discoloration of the color negative film, the magenta dye fading due to the storage of the color negative film, and the dark fading of the cyan dye of the color negative paper are eliminated.

The hexamethylenetetramine-based compound used for the stabilizer in the present invention is preferably a compound represented by the following general formula [A-1]
Or a salt thereof.

In the general formula [A-1], each group represented by A _{1 to} A ₄ includes those having a substituent. As the substituent, for example,
Examples include a carbamoyl group, a halogen atom such as a chlorine atom, an aryl group such as a phenyl group, an oxycarbonyl group such as a hydroxyl group, a carboxyl group, and a methoxycarbonyl group.

The alkyl group represented by A _{1 to} A ₄ has 1 to 5 carbon atoms.
Those having a carbon chain of are preferred.

Examples of the salt of the compound represented by the general formula [A-1] include inorganic acid salts such as hydrochloride, sulfate and nitrate, organic acid salts such as phenol salt, double or complex salts with metal salts, hydrated salts, and molecules. Inner salts and the like.

The compound represented by the general formula [A-1] is specifically,
Beilsteins Handbuch der Organishen
Chemie), the second supplement, Vol. 26, pp. 200-212. Among them, those soluble in water are preferred in the present invention.

Hereinafter, typical examples of the compound represented by the general formula [A-1] or a salt thereof will be given.

The compound of the general formula [A-1] can be easily obtained as a commercial product, but can also be easily synthesized using the method described in the above-mentioned literature.

The compounds of the general formula [A-1] may be used alone or in combination of two or more. The addition amount is 0.01 g per processing solution.
A range of 2020 g is preferred.

Next, the compounds represented by formulas [F-1] to [F-10] used in the present invention will be described.

In the general formula [F-1], R _{1 to} R ₆ each represent a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an aralkyl group, an amino group, an alkoxy group, a hydroxy group, an acyl group, a sulfonyl group, an alkylthio group,
Examples thereof include an arylthio group, a heterocyclic residue, a carbamoyl group, a sulfamoyl group, and an alkylamino group.

These monovalent organic groups can have a substituent (for example, a hydroxy group, an acyl group, a sulfonyl group, a halogen atom, an amino group, a carboxy group, etc., and preferably have a hydroxy group, a halogen atom). .
Further, the total number of carbon atoms of the substituents represented by R _{1 to} R ₆ is preferably 10 or less.

The group of R ₁ , R ₃ , and R _{5 and} the group of R ₂ , R ₄ , and R ₆ may be the same or different, but it is preferred that one of the groups is a hydrogen atom.

Specific examples of the compound represented by the formula [F-1] are shown below, but it should not be construed that the invention is limited thereto.

The triazine-based compound represented by the general formula [F-1] is preferably used in a range of 0.05 g to 50 g, more preferably 0.1 g to 20 g, per one stabilizing solution.

Specific examples of the methylol-based compound represented by the general formula [F-2], [F-3] or [F-4] include the following compounds.

(F-2-1) Dimethylol urea (F-2-2) Trimethylol urea (F-2-3) Monomethylol urea (F-2-4) Tetramethylol urea (F-2-5) Dimethylol thiourea (F-2-6) Monomethylolthiourea (F-3-1) Trimethylolmelamine (F-3-2) Tetramethylolmelamine (F-3-3) Pentamethylolmelamine (F-3-4) Hexamethylol Melamine (F-3-5) Monomethylolmelamine (F-4-1) Dimethylolguanidine (F-4-2) Monomethylolguanidine (F-4-3) Trimethylolguanidine The amount of addition is 0.05 to 1 per stabilizing solution. It is preferably 20 g, more preferably 0.1 to 10 g /, and within this range, the effects of the present invention can be exhibited effectively.

In the general formulas [F-5] and [F-6], the electron withdrawing groups represented by V ₁ and W ₁ include Hammett's σ
p-value (Lange'a Handbook of Chemistry 12th ed.Vol.3,
C.Hansch & A.Leo, Substituent Constants for Correl
ation Analysis in Chemistry and Biology (Jone Wile
y & Sons, New York 1979)), and specifically, an acyl group (eg, acetyl,
Benzoyl, monochloroacetyl, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl, methoxyethoxycarbonyl, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl, p-chlorophenoxycarbonyl, etc.), carbamoyl group (eg, N-methylcarbamoyl, N, N-tetramethylenecarbamoyl, N-
Phenylcarbamoyl, etc.), cyano group, alkylsulfonyl group (eg, methanesulfonyl, ethanesulfonyl, etc.), arylsulfonyl group (eg, benzenesulfonyl, p-toluenesulfonyl, etc.), sulfamoyl group (eg, sulfamoyl, N-methylsulfa Moyl, N, N-pentamethylenesulfamoyl, etc.). Examples of the lower alkyl group include methyl, ethyl, propyl, butyl and the like.

Examples of the group that is released by hydrolysis represented by Y ₁ include:
For example, a trialkyl-substituted silyl group (eg, trimethylsilyl etc.), an acyl group (eg, acetyl, benzoyl, monochloroacetyl, trifluoroacetyl etc.), a sulfate group, an aminocarbonyl group (eg, N, N-dimethylcarbonyl, N-methyl) Carbonyl, N-phenylcarbonyl, etc.) and sulfonate groups (for example, methanesulfonate, benzenesulfonate, p-toluenesulfonate, etc.).

Examples of the 5- or 6-membered nitrogen-containing heterocyclic ring formed together with the nitrogen atom represented by Z and the C ＝ O group include [C ₁ N ₄ ],
[C ₂ N ₃ ], [C ₃ N ₂ ], [C ₄ N], [C ₂ N ₄ ], [C ₃ N ₃ ],
[C ₄ N ₂ ], [C ₅ N], [C ₂ N ₂ O], [C ₃ NO], [C ₃ N
₂ O], [C ₄ NO], [C ₂ N ₂ S], [C ₃ NS], [C ₃ N ₂ S],
[C ₂ N ₂ Se], [C ₃ NSe], [C ₄ NSe], [C ₃ NTe], etc., monocycles composed of elemental constitutions, [C ₃ N ₂ -C ₆ ], [C ₄ N −
_{C 6], [C 4 N} -C 3 N 2], [C 3 N 2 -C 3 N 2], [C 3 NS-
_{C 6], [C 5 N} -C 5 N], [C 5 N-C 6], [C 4 N 2 -C 6] fused ring compound consisting of elements constituting the and the like, on these rings Is, for example, an alkyl group (eg, methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, sulfopropyl, etc.), an aryl group (eg, phenyl, p-methoxyphenyl, etc.), a hydroxy group, an alkoxy group (eg,
Methoxy, ethoxy, methoxyethoxy, etc.), aryloxy group (eg, phenoxy, p-carboxyphenyl, etc.), carboxy group, sulfo group, alkoxylcarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl etc.), aryloxycarbonyl group (eg, Phenoxycarbonyl), an amino group (eg, N, N-dimethylamino, N-ethylamino, N-phenylamino, etc.), an acylamide group (eg, acetamido, benzamide, etc.), a carbamoyl group (eg, carbamoyl,
N-methylcarbamoyl, N, N-tetramethylenecarbamoyl, etc.), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, etc.), sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dimethylsulfur) Famoyl, etc.), alkylsulfonyl groups (eg, methanesulfonyl, ethanesulfonyl, etc.), arylsulfonyl groups (eg, benzenesulfonyl, p-
Groups such as toluenesulfonyl) and acyl groups (eg, acetyl, benzoyl, etc.) can be substituted.

In the general formula [F-5], a 5-membered or 6-membered compound which can be formed via V ₁ and W ₁ which are divalent electron-withdrawing groups, respectively.
As the membered nitrogen-containing heterocycle, the following general formula [F-5-a]
Are shown.

In the general formula [F-5-a], V ₁ and W ₁ are each —CO
-, --CO--O--, --SO--, --SO ₂ or --CS--
₁ represents a nonmetallic atomic group necessary to form a monocyclic or condensed 5-membered or 6-membered combined with V ₁ and W _1.

The 5-membered or 6-membered monocyclic or condensed ring formed by Z ₁ may have an optional substituent, such as an alkyl group (eg, methyl, ethyl,
Methoxyethyl, benzyl, carboxymethyl, sulfopropyl, etc.), aryl group (eg, phenyl, p-methoxyphenyl, etc.), hydroxy group, alkoxy group (eg, methoxy, ethoxy, methoxyethoxy, etc.), aryloxy group (eg, Phenoxy, p-carboxyphenyl and the like), carboxy group, sulfo group, alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl and the like), aryloxycarbonyl group (for example,
Phenoxycarbonyl, etc.), amino group (for example, N, N-
Dimethylamino, N-ethylamino, N-phenylamino, etc.), acylamide group (eg, acetamido, benzamide, etc.), carbamoyl group (eg, carbamoyl, N-methylcarbamoyl, N, N-tetramethylenecarbamoyl, etc.), sulfonamide Groups (eg, methanesulfonamide, benzenesulfonamide, etc.), sulfamoyl groups (eg, N-ethylsulfamoyl, N, N-
Dimethylsulfamoyl, etc.), alkylsulfonyl groups (eg, methanesulfonyl, ethanesulfonyl, etc.),
Arylsulfonyl group (for example, benzenesulfonyl,
groups such as p-toluenesulfonyl) and an acyl group (eg, acetyl, benzoyl, etc.).

General formulas [F-5] and [F-6] used in the present invention
Specific examples of the compound represented by are shown below, but it should not be construed that the invention is limited thereto.

The amount of the compound represented by the formula [F-5] or [F-6] to be added is preferably 0.01 to 20 g, more preferably 0.03 to 15 g, particularly preferably 0.05 to 10 g per stabilizing solution.

In the general formula [F-7], as the aliphatic group represented by R ₈ , R ₉ and R ₁₀ , a saturated alkyl group (for example,
Unsubstituted alkyl groups such as methyl, ethyl and butyl and substituted alkyl groups such as benzyl, carboxymethyl, hydroxymethyl and methoxyethyl), unsaturated alkyl groups (e.g. allyl, 2-butenyl etc.), cyclic And an alkyl group (eg, cyclopentyl, cyclohexyl, etc.).

The aryl groups represented by R ₉ , R ₁₀ and R ₁₁ include substituted and unsubstituted ones. Examples of the substituent include an alkyl group (eg, methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, sulfopropyl, etc.). ), An aryl group (eg, phenyl, p-methoxyphenyl, etc.), a hydroxy group, an alkoxy group (eg, methoxy, ethoxy, methoxyethoxy, etc.), an aryloxy group (eg, phenoxy, p-carboxyphenyl, etc.), a carboxy group , A sulfo group, an alkoxycarbonyl group (for example,
Methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl, etc.), amino group (eg, N, N-dimethylamino, N-
Ethylamino, N-phenylamino, etc.), acylamide group (eg, acetamido, benzamide, etc.), carbamoyl group (eg, carbamoyl, N-methylcarbamoyl, N, N-tetramethylenecarbamoyl, etc.), sulfonamide group (eg, methane Sulfonamide, benzenesulfonamide, etc.), sulfamoyl group (for example, N-
Ethylsulfamoyl, N, N-dimethylsulfamoyl, etc.), alkylsulfonyl group (eg, methanesulfonyl, ethanesulfonyl, etc.), arylsulfonyl group (eg, benzenesulfonyl, p-toluenesulfonyl, etc.), acyl group (eg, Acetyl, benzoyl, etc.).

Ring R ₉ and R ₁₀ form attached is a heterocyclic 5-8 membered, including those portions of the bonded carbon is substituted with other heteroatoms.

R ₈ is preferably a hydrogen atom.

Hereinafter, specific examples of the compound represented by Formula [F-7] used in the present invention are shown, but the invention is not limited to these compounds.

The addition amount of the compound represented by the general formula [F-7] is preferably 0.01 to 20 g, more preferably 0.03 to 1 g per stabilizing solution.
It is 5 g, particularly preferably 0.05 to 10 g.

In the general formulas [F-8] to [F-10], R ₁₂ and R
Examples of the aliphatic hydrocarbon group represented by ₁₃ and Z ₃ include a saturated alkyl group (for example, an unsubstituted alkyl group such as methyl, ethyl, and butyl and carboxymethyl, methoxymethyl,
Substituted alkyl groups such as methoxyethyl, hydroxyethyl and benzyl), unsaturated alkyl groups (for example, allyl,
2-butenyl), a cyclic alkyl group (eg, cyclopentyl, cyclohexyl, etc.) and the like. The aryl group represented by R ₁₃ and Z ₃ may be substituted, and examples of the substituent include an alkyl group (eg, methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, sulfopropyl) and an aryl group (eg, phenyl, p -Methoxyphenyl and the like), hydroxy group, alkoxy group (for example, methoxy, ethoxy, methoxyethoxy and the like), aryloxy group (for example, phenoxy, p-carboxyphenyl and the like), carboxy group, sulfo group, alkoxycarbonyl group (for example, A methoxycarbonyl group, an ethoxycarbonyl group), an aryloxycarbonyl group (eg, phenoxycarbonyl etc.), an amino group (eg, N, N-dimethylamino, N-ethylamino, N-phenylamino etc.),
Acylamide group (eg, acetamido, benzamide, etc.), carbamoyl group (eg, carbamoyl, N-methylcarbamoyl, N, N-tetramethylenecarbamoyl, etc.), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, etc.), sulfamoyl Groups (eg, N-ethylsulfamoyl, N, N-diethylsulfamoyl, etc.), alkylsulfonyl groups (eg,
Any group selected from groups such as methanesulfonyl, ethanesulfonyl group), arylsulfonyl group (eg, benzenesulfonyl, p-toluenesulfonyl, etc.), and acyl group (eg, acetyl, benzoyl, etc.) can be mentioned.

Examples of the group eliminated by hydrolysis represented by V ₂ , W ₂ , Y ₂ and Z ₃ include, for example, an acyl group (eg, acetyl, benzoyl, trifluoroacetyl, monochloroacetyl, etc.), a trialkylsilyl group ( For example, trimethylsilyl and the like).

The ring formed by R ₁₃ bonding to Z ₃ is a 5- to 8-membered saturated ring or a condensed ring, and includes a ring in which part of the bonding carbon chain is substituted with another hetero atom. Specifically, 1,2-dioxacyclopentane, m-dioxane, trioxane,
And rings such as tetraoxane and benzodioxolan.

Examples of the cation represented by M include a hydrogen ion,
Alkali metal ions (eg, lithium, sodium,
Ions such as potassium), alkaline earth metal ions (eg, ions such as magnesium and calcium), ammonium ions, organic ammonium ions (eg, ammonium ions such as triethylammonium, tripropylammonium, tetramethylammonium), and pyridinium ions Is mentioned.

In general formulas [F-8] to [F-10], the aliphatic hydrocarbon group represented by R ₁₂ is preferably a lower alkyl group having 1 or 2 carbon atoms, and more preferably, R ₁₂ is a hydrogen atom. More preferably, there is.

Hereinafter, specific examples of the compounds represented by formulas [F-8] to [F-10] are shown, but the invention is not limited thereto.

The amount of the compound represented by the general formula [F-8], [F-9] or [F-10] is preferably 0.01 to 20 g, more preferably 0.03 to 15 g, and particularly preferably 0.05 to 20 g per treatment solution.
~ 10g.

In the present invention, the stabilizer preferably contains a chelating agent having a chelate stability constant for iron ions of 8 or more. Here, the chelate stability constant is LGSillen
・ Stability Constants of Metal-i by AEMartell
on Complexes ", The Chemical Society, London (196
Four). "Organic Sequeste" by S. Chaberek / AEMartell
ring Agents ", a constant generally known by Wiley (1959) and the like.

Examples of the chelating agent having a chelating stability constant for iron ions of 8 or more include an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent, an inorganic phosphoric acid chelating agent, a polyhydroxy compound, and the like. In addition, the said iron ion is
It means ferric ion (Fe ³⁺ ).

Specific examples of the chelating agent having a chelate stability constant with ferric ion of 8 or more include the following compounds, but are not limited thereto. That is,
Ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine,
Ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid , 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2 , 3-tricarboxylic acid,
Catechol-3,5-diphosphonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, sodium hexametaphosphate, and particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1- Diphosphonic acid and the like, among which 1-hydroxyethylidene-1,1
Diphosphonic acid is most preferably used.

The amount of the chelating agent used is 0.01 to 50 g per stabilizing solution.
And more preferably in the range of 0.05 to 20 g to obtain good results.

Preferred compounds to be added to the stabilizing solution include ammonium compounds. These are supplied by ammonium salts of various inorganic compounds. Specifically, ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, fluoride Ammonium, ammonium acid fluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate,
Ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, ammonium laurate tricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, Ammonium hydrogen oxalate, ammonium phthalate, ammonium bitartrate, ammonium thiosulfate, ammonium sulfite, ammonium ethylenediaminetetraacetate, ferric ammonium ethylenediaminetetraacetate, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate, ammonium phthalate , Ammonium picrate, pyrrolidine dithiocarbamate Chloride, ammonium salicylate, ammonium succinate, ammonium sulfanilic acid, ammonium tartrate, ammonium thioglycolic acid, 2,4,6-nitrophenol and ammonium. These may be used alone or in combination of two or more. The amount of the ammonium compound added is preferably in the range of 0.001 mol to 1.0 mol, more preferably in the range of 0.002 to 2.0 mol, per 1 stabilizing solution.

Further, it is preferable that the stabilizing solution contains a sulfite. The sulfite may be any organic or inorganic substance, as long as it releases sulfite ions, but is preferably an inorganic salt. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite,
Examples include ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite. The sulfite is preferably added to the stabilizing solution in an amount of at least 1 × 10 ⁻³ mol /, more preferably 5 × 10 ⁻³ mol / 〜10 ⁻¹ mol /. Is added, which has an effect of preventing stains in particular. As an addition method, it may be added directly to the stabilizing solution, but it is preferably added to the stabilizing replenishing solution.

The stabilizer preferably contains a metal salt in combination with the chelating agent. Such metal salts include Ba, Ca, Ce, Co,
In, La, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Zr, Mg, Al or Sr metal salts, halides, hydroxides, sulfates, carbonates, phosphates, acetates Etc. or a water-soluble chelating agent. Use amount of 1 × 10 ^-4 per stable liquid
The range is preferably 1 × 10 ^-1 mol, more preferably 4 × 10 ^-1 mol.
^{-4 to} 2 × 10 ^-2 mol.

Stabilizers include organic acid salts (citric acid, acetic acid, succinic acid,
Oxalic acid, benzoic acid, etc.), pH adjusters (phosphate, off-acid, hydrochloric acid, sulfate, etc.) can be added. These compounds may be used in any combination in amounts that are necessary to maintain the pH of the stabilizing bath, and that do not adversely affect the stability during storage of color photographic images and the occurrence of precipitation. Absent.

In the present invention, known fungicides such as 5-chloro-2-methylisothiazoline 3-one and benzisothiazoline can be used in combination as long as the effects of the present invention are not impaired.

The stabilizing solution may contain a surfactant. Examples of the surfactant include compounds represented by formulas [I] to [II] and water-soluble organic siloxane compounds described in JP-A-62-250449.

In the treatment of the present invention, silver may be recovered from the stabilizing solution. Further, the stabilizer is subjected to an ion exchange treatment, an electrodialysis treatment (see JP-A-59-96352) and a reverse osmosis treatment (JP-A-60-24105).
No. 3, No. 62-254151, and JP-A-2-132440) are also preferable embodiments for carrying out the present invention. It is also preferable to use water which has been previously deionized from water used for the stabilizing solution. That is, the antifungal property of the stabilizing solution, the stability of the stabilizing solution, and the pores for storing the image are removed.
As a means of deionization treatment, Ca, Mg
Any type may be used as long as the ion content is 5 ppm or less, but for example, treatment with an ion exchange resin or a reverse osmosis membrane is preferably used alone or in combination. Ion exchange resins and reverse osmosis membranes are described in detail in Published Technical Report No. 87-1984.

The salt concentration in the stabilizing solution is preferably 1,000 ppm or less, more preferably 800 ppm or less, for achieving the effects of the present invention.

The presence of a soluble iron salt in the stabilizing solution is preferred for achieving the effects of the present invention. The soluble iron salt is preferably used in the stabilizing solution at a concentration of at least 5 × 10 ⁻³ mol /,
It is more preferably in the range of 8 × 10 ^{−3 to} 150 × 10 ⁻³ mol /, and even more preferably in the range of 12 × 10 ^{−3 to} 100 × 10 ⁻³ mol /.
Range.

In the present invention, the pH of the stabilizer is in the range of 5.5 to 12.0,
Preferably, the pH is in the range of 7.0 to 10.0 for achieving the effects of the present invention. The pH adjusting agent that can be contained in the stabilizing solution may be any of commonly known alkali agents and acid agents.

The processing temperature at the time of the stabilization treatment is preferably from 15 ° C to 70 ° C, and more preferably from 20 ° C to 55 ° C. The processing time is preferably 150 seconds or less, more preferably 3 seconds to 120 seconds, and most preferably 6 seconds to 90 seconds.

The replenishing amount of the stabilizing solution is preferably 1000 ml or less, more preferably 150 ml or more and 500 ml or less per 1 m ^{2 of the} light-sensitive material, from the viewpoint of rapid processing and preservation of the dye image.

The stabilization tank is preferably composed of a plurality of tanks,
It is preferably from 2 to 6 tanks, particularly preferably 2 to 3 tanks, more preferably 2 tanks and a counter current method (a method of supplying to a post-bath and overflowing from a pre-bath). .

No water washing is required after stabilization,
Rinsing, washing of the surface, etc. by washing with a small amount of water within an extremely short time can be arbitrarily performed as necessary.

In the present invention, the object of the present invention can be more effectively obtained when a photosensitive material having a high silver chloride concentration is processed particularly when chloride is contained at least 3 × 10 ^-2 mol per color developing solution. Especially 3.5 × 10 ^{-2 to} 20 per color developing solution
× 10 ^-2 mol, especially 4.0 × 1 per color developing solution
Good results can be obtained with 0 ^{-2 to} 12 × 10 ^-2 mol.

The above-mentioned chloride may be any compound that releases chloride ions in a color developing solution, and specific compounds include potassium chloride, sodium chloride, lithium chloride, magnesium chloride and the like.

Usually, sulfite is used as a preservative in the color developer, but the sulfite concentration in the color developer is less than 1%.
When it is used in an amount of 1.6 × 10 ^-2 mol or less per unit, it is possible to suppress a decrease in color density considered to be caused by dissolution physical development of a photosensitive material mainly containing silver chloride, and a decrease in preservation ability is extremely small. Therefore, it is possible to provide a color developing solution that enables rapid processing using a silver chloride-based photosensitive material or a method for processing a silver halide color photograph using the color developing solution. A sulfite concentration of 1.6 × 10 ^-2 mol / or less is preferably used. Further, it is 1 × 10 ⁻² mol / or less, more preferably 4 × 10 ⁻³ mol /, to exhibit this effect more favorably.

Examples of the sulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the like.

However, when the silver halide composition of the silver halide color photographic light-sensitive material is different, for example, when the light-sensitive material (A) is a silver iodobromide emulsion and the light-sensitive material (B) is silver chlorobromide or silver chloride, The color developing solutions are preferably processed in separate baths. In this case, the concentration of sulfurous acid in the color developing solution of the light-sensitive material (A) is 5 × 10 ⁻³ mol / or more, preferably 1 × 10 ⁻² mol /. The amount is particularly preferably 2 × 10 ^-2 mol / or more.

As the color developing agent used in the color developing solution of the present invention, a p-phenylenediamine compound having a water-soluble group is preferably used because it exhibits the desired effects of the present invention and generates little fog.

The p-phenylenediamine-based compound having a water-soluble group has less contamination of the photosensitive material and has less skin damage than the para-phenylenediamine-based compound having no water-soluble group such as N, N-diethyl-p-phenylenediamine. Not only has the advantage of being less susceptible to fogging, but in particular, the object of the present invention can be more efficiently achieved by combining it with the color developing solution of the present invention.

The water-soluble group are those having at least one is listed on the amino group or benzene nucleus of p- phenylenediamine compound, as a specific water-soluble group _{- (CH 2) n '-CH} 2 OH, - _{(CH 2) m '-NHSO 2} - (CH 2) n' -CH3, - (CH 2) m '-O- (CH 2) n' -CH 3, - (CH 2 CH 2 O) n 'C _{m 'H 2m' +1 (m} ' and n' represents an integer of 0 or more, respectively.), - COOH group, and as -SO ₃ H group and the like.

Specific examples of the color developing agent preferably used in the invention are shown below.

Among the color developing agents exemplified above, fog is less likely to be used in the present invention because of little occurrence of fog.
1), (C-2), (C-3), (C-4), (C-
6), (C-7) and (C-15), particularly preferably Nos. (C-1) and (C-3).

The above color developing agents are usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate and the like.

The color developing agent having a water-soluble group preferably used in the present invention may be used in an amount of usually 0.5 × 10 ^-3 mol or more, particularly 1 × 10 ^-2 to 2 × 10 ^-1 mol per 1 color developing solution. Color developing solution 1 is preferable from the viewpoint of rapid processing.
More preferably, the range is from 1.5 × 10 ^{-2 to} 2 × 10 ^-1 mol.

The color developing agents may be used alone or in combination of two or more, and if desired, used in combination with a black and white developing agent such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone or methol. You may.

Further, instead of using the above color developing agent in a color developing solution, a color developing agent can be added to a photographic material, and a color precursor is used as a color developing agent used in that case. A typical dye precursor is disclosed in
Nos. 58-65429 and 58-24137 are used, and specifically, for example, 2 ', 4'-bismethanesulfonamido-4-diethylaminodiphenylamine, 2'-
Methanesulfonamide-4 '-(2,4,6-triisopropyl) benzenesulfonamido-2-methyl-4-N-
(2-methanesulfonamidoethyl) ethylaminodiphenylamine, 2'-methanesulfonamido-4'-
(2,4,6-triisopropyl) benzenesulfonamido-4- (hydroxytrisethoxy) diphenylamine, 4-N- (2-methanesulfonamidoethyl) ethylamino-2-methyl-2 ', 4'-bis ( (2,4,6-triisopropyl) benzenesulfonamidediphenylamine, 2,4'-bismethanesulfonamide-4-N, N-diethylaminodiphenylamine, 4-n-hexyloxy-2'-methanesulfonamide-4'- (2,4,6-triisopropyl) benzenesulfonamidodiphenylamine, 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-triisopropylbenzenesulfonamido) diphenylamine, 4-N, N-diethylamino-4'-(2,4,6- Triisopropylbenzenesulfonamido) diphenylamine, 4-N, N-dimethylamino-2-phenylsulfonyl-4 '-(2,4,6-triisopropylbenzenesulfonamido) diphenylamine and the like.

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

In the present invention, the processing time of the color development step may be any time, but in the case of the photosensitive material having a total coated silver amount of 2 g / m ² or more, 10 seconds to 4 minutes is usually used, and preferably 20 seconds to 200 seconds, more preferably 30 seconds to 200 seconds
It is in the range of seconds, most preferably in the range of 45 seconds to 200 seconds.
Further, for the light-sensitive material having a total coated silver amount of 1 g / m ² or less according to the present invention, usually 3 seconds to 4 minutes is used, preferably 5 seconds to 2 minutes, more preferably 7 seconds to 60 minutes. It is in the range of seconds, most preferably in the range of 8 seconds to 50 seconds. These two
The processing time of the color developing step of the photosensitive materials having different total coated silver amounts of the species may be the same or different, but usually, the processing time of the light-sensitive material having a small coated silver amount is shortened. It is processed.

The replenishment rate of the color developing solution according to the present invention, when the total coating amount of silver of the present invention is a light-sensitive material of 2g / m ² ~10g / m ^2, the photosensitive material 1
provide an advantage of the present invention when m ² per 10ml~900ml better, especially the range of 20Ml～700ml, especially when the range of 30Ml～500ml, the effect of the present invention can be obtained satisfactorily. Further, in the case of a light-sensitive material having a total coated silver amount of 1 g / m ² or less according to the present invention, the effect of the present invention is more favorably exhibited when the light-sensitive material is 10 ml to 400 ml per 1 m ² of the light-sensitive material, and in particular, 20 ml to 200 ml. In case of range, especially 30m
When the amount is in the range of 1 to 100 ml, the effects of the present invention can be obtained well.

In the present invention, usually, after color development processing, processing is performed with a processing solution having bleaching ability.

As a bleaching agent used in the bleaching solution or bleach-fixing solution used as the processing solution having the bleaching ability, a metal complex salt of an organic acid is used, and the metal complex salt oxidizes a metal salt formed by development to produce a silver halide. The compound is formed by complexing with a metal ion such as iron, cobalt, or copper with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid. Most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these organic acids include the following.

(1) ethylenediaminetetraacetic acid (2) diethylenetriaminepentaacetic acid (3) ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid (4) 1,3-propylenediaminetetraacetic acid (5) nitrilotriacetic acid (6) cyclohexanediaminetetraacetic acid (7) iminodiacetic acid (8) dihydroxyethylglycine citric acid (9) Ethyl ether diamine tetraacetic acid (10) Glycol ether diamine tetraacetic acid (11) Ethylene diamine tetrapropionic acid (12) Phenylenediamine tetraacetic acid Among the ferric salts of the above aminopolycarboxylic acids, preferred organic acids are (1) , (2), (4),
(10), especially (1), (2) and (4).

The bleaching solution or the bleach-fixing solution used contains not only the metal complex salt of an organic acid as described above as a bleaching agent but also various additives. Examples of the additives include alkali halides or ammonium halides, for example, rehalogenating agents such as potassium bromide, sodium bromide, sodium chloride and ammonium bromide, metal salts, chelating agents, nitrates and commonly known bleaching accelerators. It is desirable to make it. Further, pH buffers such as borates, oxalates, acetates, carbonates, and phosphates, and alkylamines, polyethylene oxides, and the like which are known to be added to normal bleaching solutions can be appropriately added. .

As a fixing agent used in a fixing solution or a bleach-fixing solution,
All types of fixing agents can be used. For example, thiosulfate or a combination of thiocyanate or a combination of thiosulfate and thiocyanate is mentioned, but is not particularly limited. When using thiosulfate, add at least
0.4 mol / is preferable, and when a thiocyanate is used, its addition amount is preferably at least 0.5 mol /.

Further, the fixing solution and the bleach-fixing solution include sulfites such as ammonium sulfite, potassium sulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, and the like, boric acid, borax, sodium hydroxide, potassium hydroxide. , Sodium carbonate, potassium carbonate,
A pH buffer consisting of various salts such as sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be used alone or in combination of two or more.

In the present invention, air or oxygen is optionally blown in the bleach bath or bleach-fix bath and in the bleach replenisher or bleach-fix replenisher storage tank to increase the activity of the bleach solution or bleach-fix solution. Or an appropriate oxidizing agent, for example, hydrogen peroxide, bromate, persulfate, etc., may be added as appropriate, or a member having good oxygen permeability, for example, a silicon tube may be disposed in the circulation path to achieve an aeration effect. There are ways to increase

The pH of the bleaching solution used in the present invention is usually from 2.5 to 6.5, and is preferably from 3.0 to 5.5 in the present invention.

The pH of the fixing solution or the bleach-fixing solution used in the present invention is usually from 5.0 to 9.0, preferably from 5.5 to 8.5.

In the processing method of the present invention, after bleaching and fixing (or bleach-fixing) processing after color development processing, stable processing can be carried out without washing with water, or washing processing can be performed, followed by stabilizing processing. Immediately stabilizing significantly demonstrates the effect of the present invention. In addition to the above steps, known auxiliary steps such as hardening, neutralization, black and white development, reversal, and a small amount of water washing step may be added as necessary. The following steps are included as typical specific examples of a preferable treatment method.

In the above, the solid line indicates that the total coated silver amount of the present invention is 2 g / m ² or more 1
The broken line indicates the processing flow of the photosensitive material (A) of 0 g / m ² or less, and the broken line indicates the processing flow of the photosensitive material (B) of the present invention having a total coated silver amount of 1 g / m ² or less. Among these steps, the steps (1), (2) and (3) are particularly preferably used.

As another preferred embodiment of the processing method of the present invention, there is a method in which part or all of the overflow of a color developing solution flows into a bleaching solution or a bleach-fixing solution which is a subsequent step. This is because when a certain amount of the color developing solution flows into the bleaching solution or bleach-fixing solution, the generation of sludge in the bleaching solution or bleach-fixing solution is suppressed, and more surprisingly, the effect of recovering silver from the bleach-fixing solution is improved. Is also improved.

In addition to the above-mentioned method, when the part or all of the overflow of the stabilizer according to the present invention is poured into the bleach-fixing solution or the fixing solution, the above-mentioned effect is particularly excellent.

Further, it is also a preferable embodiment for carrying out the present invention that a part or all of the bleaching solution or the fixing solution is poured from a processing tank for a high silver content photosensitive material into a processing tank for a low silver content photosensitive material,
The effects of the present invention are more favorably exhibited.

Examples of the processing solution relating to the processing of the present invention include a color developing solution, a bleaching solution, a bleach-fixing solution, a fixing solution, a stabilizing solution, a black-and-white developing solution, a stopping solution, a rinsing solution, and a hardening solution. The bleaching solution is described in JP-A-2-44347, pages (3) to (4).
And JP-A-2-43546, pages (37) to (38)
The conventional additives such as bleaching agent, pH, acid and addition amount of the acid and bleaching accelerator described in JP-A-2-44347, page (4) are used for the fixing solution. Conventional additives such as a fixing agent, a fixing accelerator, a preservative, and a chelating agent are used. A bleach-fixing solution is disclosed in JP-A-2-43546.
No., pages (37) to (38) are used. Further, the stabilizer according to the present invention includes a bactericide, an antibacterial agent, a chelating agent, a surfactant, a fluorescent brightener and the like described in JP-A-2-43546, pages (38) to (39). Is used.

Bleaching solution, the bleach-fixing solution, replenishing amount of the fixing solution, when the total amount of coated silver of 2 g / m ² or more light-sensitive material, the photosensitive material 1 m ² per 50ml
900900 ml is usually used, preferably in the range of 100 ml to 500 ml, and in the case of a photosensitive material having a total coated silver amount of 1 g / m ² or less, 10 ml to 400 ml is usually used per 1 m ² of the photosensitive material, preferably 20 ml. It is in the range of ~ 100ml.

Next, a preferred photosensitive material to which the present invention is applied will be described.

The silver halide grains used in the light-sensitive material include silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide.
The preferably to 10 g / m ² of the photosensitive material (A), preferably contains at least 1 mol% silver iodide, particularly preferably silver iodobromide containing 30 mol% or less than 2 mol% of silver iodide Silver emulsions are preferable, and examples thereof include high iodine content photosensitive materials disclosed in JP-A-2-190854 and JP-A-2-190855.

The light-sensitive material (B) having a silver content of 1 g / m ² or less is preferably silver chloride or silver chlorobromide, but preferably contains a high concentration of silver chloride, for example, 50 mol% or more of silver chloride. .

 Hereinafter, the high concentration silver chloride emulsion will be described.

Silver halide grains preferably used in the light-sensitive material are silver chloride-based silver halide grains containing at least 50 mol% or more of silver chloride, more preferably 80 mol% or more,
The content is more preferably 90 mol% or more, particularly preferably 95 mol% or more, and most preferably 98 mol% or more.

The silver halide emulsion mainly composed of silver chloride may contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride. In this case, silver bromide is preferably 20 mol% or less, More preferably 10 mol% or less, further preferably 3 mol% or less.
Mol% or less, and 1 mol% when silver iodide is present.
The following is preferred, more preferably 0.5 mol% or less, and most preferably zero. Such silver halide grains mainly composed of silver chloride comprising 50 mol% or more of silver chloride may be applied to at least one silver halide emulsion layer, but are preferably used for all photosensitive silver halide emulsion layers. Is to be applied.

The crystal of the silver halide grains may be a normal crystal, a twin crystal or any other crystal, and any ratio of [1.0.0] plane to [1.1.1] plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be a layer (phase) -like structure (core-shell type) in which the inside and the outside are different. Good. Further, these silver halides are of a type in which a latent image is mainly formed on the surface,
It may be of a type formed inside the particles. Further, tabular silver halide grains (JP-A-58-113934, Japanese Patent Application No. 59-1700)
No. 70) can also be used. JP-A-64-2683
No. 7, No. 64-26838, No. 64-77047 and the like can be used.

The silver halide grains may be obtained by any preparation method such as an acidic method, a neutral method, and an ammonia method.

Further, for example, a method may be used in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size. When growing silver halide grains, controlling the pH, pAg, etc. in the reaction vessel, for example, an amount of silver ion corresponding to the growth rate of the silver halide grains as described in JP-A-54-48521. And halide ions are preferably sequentially and simultaneously injected and mixed.

The silver halide emulsion layer of the light-sensitive material processed according to the present invention has a color coupler. These color couplers react with the color developer oxidation products to form non-diffusible dyes. The color coupler is advantageously incorporated in or in close proximity to the photosensitive layer in non-diffusible form.

Thus, the red-sensitive layer can contain, for example, a non-diffusible color coupler which produces a cyan partial color image, generally a phenol or α-naphthol coupler. The green light-sensitive layer comprises, for example, at least one non-diffusible color coupler which produces a magenta partial color image.
-It can include pyrazolone-based color couplers and pyrazolotriazole. The blue-sensitive layer can include, for example, at least one non-diffusing color coupler that produces a yellow partial color image, generally a color coupler having an open chain ketomethylene group. For example, the color coupler is 6,
It can be a four or two equivalent coupler.

In the present invention, a 2-equivalent coupler is particularly preferred.

Suitable couplers are disclosed, for example, in the following publications: Agfa's research report (Mitteilunglnausden Forschu
ngslaboratorien der Agfa), Leverkusen / Munchen, Vol.III.p.111 (196
1) “Color coupler” (Farbkuppler) by W.Pelz; K. Venkataraman, “The Chemirsry of Synthetic D”
yes), Vol. 4, 341-387, Academic Press (Acad
emic Press), "The Theory of the Photograph Process"
ic Process), 4th edition, pages 353-362; and Research Disclosure No. 17643, section VII.

In the present invention, in particular, magenta couplers represented by the general formula [M-1] as described on page 26 of JP-A-63-106655 (specific examples of these magenta couplers are described in JP-A-63-106655). No. 1 to No. 77 described in JP-A-106655, pages 29 to 34) and cyan represented by the general formula [CI] or [C-II] also described on page 34. Couplers (Specific examples of cyan couplers include (C'-1) to (C'-8) described in the same specification, pages 37 to 42).
2), (C "-1) to (C" -36)), and high-speed yellow couplers also described on page 20 (specific examples of cyan couplers described on pages 21 to 26 in the same specification). (Y'-1) to (Y'-39) are preferred from the viewpoint of the effects of the present invention.

In the present invention, in particular, when the magenta coupler represented by the general formula [MI] is used, the effects of the object of the present invention are more favorably exhibited.

In the magenta coupler represented by, Z represents a group of nonmetal atoms necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent.

 R represents a hydrogen atom or a substituent.

R is not particularly limited as a substituent, but typically, alkyl, aryl, anilino, acylamino,
Examples of each group include sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl.In addition, halogen atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, Aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups And spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R is preferably a phenyl group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkyl component and the aryl component in the alkylthio group and the arylthio group represented by R include the alkyl group and the aryl group represented by R.

R represents an alkenyl group having 2 to 32 carbon atoms, and a cycloalkyl group having 3 to 12 carbon atoms, particularly 5 carbon atoms.
To 7 are preferable, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R has 3 carbon atoms.
~ 12, especially 5-7 are preferred.

As the sulfonyl group represented by R, an alkylsulfonyl group, an arylsulfonyl group, or the like; As the sulfinyl group, an alkylsulfinyl group, an arylsulfinyl group, or the like; As the phosphonyl group, an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group An acylcarbonyl group such as an alkylcarbonyl group or an arylcarbonyl group; a carbamoyl group such as an alkylcarbamoyl group or an arylcarbamoyl group; a sulfamoyl group such as an alkylsulfamoyl group or an arylsulfamoyl group; As an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc .; As a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc .; a ureido group Such as alkyl ureido groups and aryl ureido groups; sulfamoylamino groups such as alkylsulfamoylamino groups and arylsulfamoylamino groups; and heterocyclic groups having 5 to 7 members are preferred. Is a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group or the like; As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable, and for example, 3,4,5,6 -Tetrahydropyranyl-2-oxy group, 1-phenyltetrazol-5-oxy group, etc .; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, a 2-pyridylthio group, a 2-benzothiathio group. Zolylthio group, 2,4-diphenoxy-1,3,5-triazole-6-thio group, etc .; siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutyl Proxy group or the like; succinimide imide group as a group, 3-heptadecyl succinic acid imide group, a phthalimide group, a glutarimide group and the like; spiro [3.3] As a spiro compound residue heptane -
1-yl and the like; bicyclo [2.2.1] as a bridged hydrocarbon compound residue
Heptan-1-yl, tricyclo [3.3.1.1 ^3,7 ] decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptane-1-yl and the like.

Examples of the group capable of leaving by reaction with an oxidized form of the color developing agent represented by X include a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, etc.), alkoxy, aryloxy,
Heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl,
Alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring linked by N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl , (R ₁ ′ has the same meaning as R, Z ′ has the same meaning as Z, and R ₂ ′ and R ₃ ′ each represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group.) And preferably a halogen atom, particularly a chlorine atom.

Examples of the nitrogen-containing heterocyclic ring formed by Z or Z ′ include a pyrazole ring, an imidazole ring, a triazole ring, and a tetrazole ring. Examples of the substituent that the ring may have include those described above for R. Is mentioned.

The compound represented by the general formula [MI] is more specifically represented by the following general formulas [M-II] to [M-VII].

In the general formulas [M-II] to [M-VII], R _{1 to} R ₈
And X have the same meanings as R and X described above.

Among the general formulas [MI], preferred are those represented by the following general formula [M-VIII].

In the formula, R ₁ , X and Z ₁ have the same meanings as R, X and Z in the general formula [MI].

Among the magenta couplers represented by the general formulas [M-II] to [M-VII], those particularly preferred are those represented by the general formula [MI]
I] is a magenta coupler represented by

Formula (M-I) formed by Z in the ring and Formula [M-VIII] ring has optionally substituents also formed by Z ₁ in, and Formula [M-II] - [ M
-VI], R _{2 to} R ₈ are preferably those represented by the following general formula [M-IX].

In the formula [M-IX] -R ¹ -SO ₂ -R ² , 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 2 or more carbon atoms in the straight-chain portion, more preferably 3 to 6, and may be linear or branched.

The cycloalkyl group represented by R ² preferably have 5-6 membered.

Further, when used in positive image forming, most preferably as substituents R and R ₁ on the heterocyclic ring represented by the following general formula [M-
X].

In the formula, R ₉ , R ₁₀ and R ₁₁ have the same meanings as R described above.

Further, two of R ₉ , R ₁₀ and R ₁₁ , for example, R ₉ and R ₁₀ may be bonded to each other to form a saturated or unsaturated ring (for example, cycloalkane,
Cycloalkene, heterocyclic ring) may be formed, it may constitute the bridged hydrocarbon compound residue bound R ₁₁ further ring.

Preferred among Formula [M-X] is, (i) R ₉ ~
When at least two of R ₁₁ are alkyl groups, (ii) R 11
One example R ₁₁ in the ₉ to R ₁₁ is a hydrogen atom, a, if the other two R ₉ and R ₁₀ form a cycloalkyl together with the root carbon atom bonded.

Further, among (i), preferred are two of R _{9 to} R _11.
One is an alkyl group and the other is a hydrogen atom or an alkyl group.

When used for forming a negative image, the substituents R and R ₁ on the heterocyclic ring are most preferably represented by the following general formula [MX
I].

Formula [M-XI] R ₁₂ —CH ₂ — wherein R ₁₂ has the same meaning as R described above.

Preferred as R ₁₂ is a hydrogen atom or an alkyl group.

 Hereinafter, typical specific examples of the compound according to the present invention will be shown.

In addition to the above typical examples of the compound according to the present invention, specific examples of the compound according to the present invention are described in JP-A-62-166339, pages (18) to (32). Among the compounds, Nos. 1-4, 6, 8, 17-17, 19-24, 26-43, 45-59, 61-10
Compounds represented by 4,106 to 121,123 to 162,164 to 223 can be exemplified.

In addition, the coupler is used in the Journal of the Chemical Societe
y), Perkin I (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437, and JP-A-58-42045.
Nos. 59-162548, 59-171956, 60-33552
No. 60-43659, No. 60-172,982, No. 60-190779
, 62-209457 and 63-307453.

The coupler of the present invention is generally used in an amount of 1 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 ^-1 molar range.

Further, the coupler of the present invention can be used in combination with another type of magenta coupler.

The photosensitive material total coating amount of silver of 2g / m ² ~10g / m ² of the present invention are preferably in the range of 3 to 10 g / m ^2, more preferably from 4~9g / m ² . Further, the total amount of coated silver 1 g / m ² or less of the photographic material of the present invention is preferably 0.2 to 0.9 g / m
² , more preferably in the range of 0.3 to 0.7 g / m ² .

When a nitrogen-containing heterocyclic mercapto compound is used in a light-sensitive material using a silver chloride-based emulsion, the effects of the present invention are not only excellent, but also when a bleach-fix solution is mixed in a color developing solution. Since another effect of making the effect on the photographic performance extremely small is exhibited, it can be cited as a more preferable embodiment in the present invention.

Specific examples of these nitrogen-containing heterocyclic mercapto compounds include (I ') described in JP-A-63-106655, pages 42 to 45.
-1) to (I'-87).

The silver halide emulsions can be prepared by conventional methods (eg, single or double inflow with constant or rapid acceleration of the material). Particularly preferred is the method of adjustment by the double inflow method while adjusting the pAg; Research Disclosure No. 1764
3, see sections I and II.

Silver halide emulsions can be chemically sensitized.
Sulfur-containing compounds such as allyl isothiocyanate, allyl thiourea or thiosulfate are particularly preferred.
Reducing agents can also be used as chemical sensitizers, such as silver compounds as described in Belgian Patents 493,464 and 568,687, and polyamines or aminomethylsulfinic acid derivatives such as, for example, diethylenetriamine according to Belgian Patent 547,323. is there. Noble metals and noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable sensitizers. This chemical sensitization method is based on Zeitschrift Fair Bissenshaftrich Photography (Z.Wiss.Phot.) 46 ,
65-72 (1951) R. Kosiovsk
y); see also Research Disclosure No. 17643, supra, section III.

Silver halide emulsions can be prepared by optically known methods, for example, neuthocyanin, basic or acidic carbocyanine,
It can be sensitized using common polymethine dyes such as rhodocyanine and hemicyanine, styryl dyes, oxonol and the like: FM Hammer (FM
Hamer) 's The Cyanine Dyes and related Com
pounds) (1964) Ullmanns Enzyk
lpadie der technischen Chemie) 4th edition, volume 18, page 431 and following, and the above-mentioned Research Disclosure No. 1
See 7643, section IV.

Conventional antifoggants and stabilizers can be used in the silver halide emulsion. Azaindene is a particularly suitable stabilizer, with tetra- and pentazaindene being preferred, especially those substituted with hydroxyl or amino groups. Compounds of this type are, for example, Bir
r), Zeitschrift Fuer Bissenshaftriche Photography (Z.Wiss.Photo) 47, 19
52, pp. 2-58, and Research Disclosure N above
o.17643, section IV.

The components of the light-sensitive material can be contained by a usual known method; for example, US Pat. Nos. 2,322,027 and 2,533,5
No. 14, 3,689,271, 3,764,336 and 3,765,897
No. The components of the light-sensitive material, such as couplers and UV absorbers, can also be included in the form of a charged latex; DE-A 2,541,274 and EP-A 1
See No. 4,921. The components can also be fixed in the light-sensitive material as polymers; see, for example, DE 2,044,
No. 992, U.S. Pat. Nos. 3,370,952 and 4,080,211.

Usual supports can be used as supports for the light-sensitive material, for example, supports of cellulose esters such as cellulose acetate and supports of polyester. In the present invention, reflective supports such as paper supports can also be used, and these can be coated, for example, with polyolefins, especially polyethylene or polypropylene; in this regard, the above-mentioned Research Disclosure No. 17643, See Section V VI.

In the present invention, when a vinyl sulfone-based hardener is used in a light-sensitive material, the effects of the present invention are more favorably exhibited.

The vinyl sulfone hardener is a compound having a vinyl group bonded to a sulfonyl group or a group capable of forming a vinyl group, and preferably has at least a vinyl group bonded to a sulfonyl group or a group capable of forming a vinyl group. It has two. For example, a compound represented by the following general formula [VS-I] is preferably used in the present invention.

In the general formula [VS-I] L- (SO 2 -X) m the above general formula [VS-I], L is an m-valent linking group, X is -CH = CH ₂ or -CH ₂ CH ₂ Y And Y represents a group capable of leaving in the form of HY by a base, for example, a halogen atom, a sulfonyloxy group, a sulfoxy group, a residue of a tertiary amine (including a salt) and the like.

m represents an integer of 2 to 10, and when m is 2 or more, -SO ₂
-X may be the same or different.

The m-valent linking group L is, for example, an aliphatic hydrocarbon group (for example, alkylene, alkylidene, alkylidine, or the like, or a group formed by bonding them), an aromatic hydrocarbon group (for example, arylene, or the like) -O-, -NR'- (R 'represents a hydrogen atom or an alkyl group having preferably 1 to 15 carbon atoms), -SO ₂ - or SO ₃ - is the m-valent group formed by causing one or more combined bond represented by, -N
When two or more R'- are contained, those R 'may combine with each other to form a ring. The linking group L further includes those having a substituent such as a hydroxy group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an alkyl group or an aryl group.

Examples of X, -CH = CH ₂ or -CH ₂ CH ₂ Cl and the like are preferable.

Hereinafter, typical specific examples of the vinyl sulfone hardener will be described.

Vinyl sulfone hardeners used in the present invention include, for example, German Patent No. 1,100,942 and U.S. Pat.
And aromatic compounds, such as those described in
Nos. 29622, 47-25373 and 47-24259, alkyl compounds linked by a hetero atom, sulfonamides described in JP-B-47-8736, etc.
Ester compounds, 1,3,5-tris [β- (vinylsulfonyl)-, as described in JP-A-49-24435, etc.
Propionyl] -hexahydro-S-triazine or an alkyl compound described in JP-B-50-35807, JP-A-51-44164, and the like, and a compound described in JP-A-59-18944 and the like. Include.

These vinyl sulfone hardeners are dissolved in water or an organic solvent, and are dissolved in a binder (for example, gelatin) in an amount of 0.1%.
005 to 20% by weight, preferably 0.02 to 10% by weight.

For the addition to the photographic layer, a batch method or an in-line addition method is employed.

The layer in which these hardeners are added to the photographic layer is not particularly limited, and may be added to, for example, the uppermost layer, the lowermost layer, or all layers.

Further, in the present invention, the silver halide color photographic light-sensitive material preferably contains at least one of the compounds represented by the following formulas [B-1] to [B-3].

[In the formula, R ¹ represents an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxycarbonyl group, an amino group, a carboxylic acid group (including its salt) or a sulfonic acid group (including its salt). R ² and R ³ each represent a hydrogen atom, a halogen atom, an amino group, a nitro group, a hydroxyl group, an alkoxycarbonyl group, a carboxylic acid group (including its salt) or a sulfonic acid group (including its salt). M represents a hydrogen atom, an alkali metal or an ammonium group. ] [Wherein, R ⁴ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a halogenated alkyl group, -R ¹² -OR ¹³ , -CON
HR ¹⁴ (where R ¹² represents an alkylene group, R ¹³ and R ¹⁴ each represent a hydrogen atom, an alkyl group, or an arylalkyl group), an arylalkyl group, R ⁵ and R ⁶ each represent a hydrogen atom, R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a halogenated alkyl group, an arylalkyl group, —R ¹⁵ —OR ¹⁶ , or —CONHR ¹⁷ ; Here, R ¹⁵ is an alkylene group, R ¹⁶ and R ¹⁷ each represent a hydrogen atom or an alkyl group.), R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an amino Represents a group or a nitro group. Specific examples of the compound represented by the general formula [B-1] include the following exemplified compounds.

Some of the compounds represented by the general formula [B-1] are known as preservatives such as mandarin orange and some are commercially available, and can be easily obtained by those skilled in the art.

Preferred examples of the above-mentioned compounds include [B-
1-1], [B-1-2], [B-1-3], [B-1
-4] and [B-1-5].

The compound of the general formula [B-1] used in the present invention is preferably used in an amount of 0.03 to 50 g, more preferably 0.12 g to 10 g, particularly preferably 0.15 to 5 g, per 1 stabilizing solution of the present invention. is there.

Specific examples of the compound represented by Formulas [B-2] and [B-3] are described below, but are not limited thereto.

[B-2-1] 2-methyl-4-isothiazoline-3-
On [B-2-2] 5-chloro-2-methyl-4-isothiazolin-3-one [B-2-3] 2-Methyl-5-phenyl-4-isothiazolin-3-one [B-2- 4] 4-bromo-5-chloro-2-methyl-
4-isothiazolin-3-one [B-2-5] 2-hydroxymethyl-4-isothiazolin-3-one [B-2-6] 2- (2-ethoxyethyl) -4-isothiazolin-3-one [ B-2-7] 2- (N-methyl-carbamoyl) -4
-Isothiazolin-3-one [B-2-8] 5-bromomethyl-2- (N-dichlorophenyl-carbamoyl) -4-isothiazoline-3-
ON [B-2-9] 5-chloro-2- (2-phenylethyl) -4-isothiazolin-3-one [B-2-10] 4-methyl-2- (3,4-dichlorophenyl) -4 -Isothiazolin-3-one [B-3-1] 1,2-benzisothiazolin-3-one [B-3-2] 2- (2-bromoethyl) -1,2-benzisothiazolin-3-one [B -3-3] 2-Methyl-1,2-benzisothiazolin-3-one [B-3-4] 2-Ethyl-5-nitro-1,2-benzisothiazolin-3-one [B-3-5] 2-benzyl-1,2-benzisothiazolin-3-one [B-3-6] 5-chloro-1,2-benzisothiazolin-3-one These exemplified compounds are described in US Pat. No. 2,767,172, US Pat. Patent No. 2,767,173, U.S. Patent No. 2,767,1
No. 74, U.S. Pat. No. 2,870,015, British Patent No. 848,130, French Patent No. 1,555,416 describe synthesis methods and examples of application to other fields. Some are commercially available, top side 300
(Permachem Asia KK), Topside 600 (Permachem Asia KK), Fineside J-700 (Tokyo Fine Chemical KK), Proxel GXL (ICI
(Co., Ltd.).

The compounds represented by the general formulas [B-1] to [B-3] are used in an amount of 0.1 mg to 500 mg, preferably 0.5 mg to 100 mg, per 1 m ² of the light-sensitive material. . These compounds represented by [B-1] to [B-3] may be used in combination of two or more.

In the present invention, as a photosensitive material, a color paper, a color negative film, a color positive film, a color reversal film for a slide, a color for a movie, as long as the photosensitive material is processed by a so-called internal developing method containing a coupler in the photosensitive material. It can be applied to any two kinds of photosensitive materials such as a reversal film, a color reversal film for TV, and a reversal color paper. Most preferably, a color paper is used as the photosensitive material (B) and a color negative film is used as the photosensitive material (A). That is.

[Effects of the Invention] According to the present invention, it is possible to process light-sensitive materials having different silver amounts in a common tank or a common replenisher, thereby suppressing generation of sludge and scum in a stabilizing tank, and furthermore, after color processing. Provided is a method for processing a silver halide color photographic light-sensitive material which prevents generation of yellow stain and magenta dye due to storage of a color negative film and can suppress dark fading of a cyan dye by storing color paper after color processing. can do.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited to these examples.

Example 1 <Preparation of Color Paper Sample> Each layer having the following constitution was applied on a support in which polyethylene was laminated on one side of a paper support and polyethylene containing titanium oxide was laminated on the first layer side of the other side. Then, the following multilayer silver halide color photographic light-sensitive material was prepared. The coating solution was prepared as follows.

First layer coating solution 26.7 g of yellow coupler (Y-1), 10.0 g of dye image stabilizer (ST-1), 6.67 g of (ST-2), additive (HQ-
1) Add 0.67 g to 6.5 g of high boiling organic solvent (DNP) in 60 g of ethyl acetate.
Add and dissolve the solution, and add this solution to a 20% surfactant (SU-1).
The emulsion was emulsified and dispersed in 220 ml of a 10% aqueous gelatin solution containing 7 ml using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

In addition, (H-1) was added to the second and fourth layers as a hardener.
(H-2) was added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

[Preparation Method of Blue-Sensitive Silver Halide Emulsion] The following (solution A) and (solution B) were adjusted to pAg = 6.5 and pH = 3.0 in 1000 ml of a 2% aqueous gelatin solution kept at 40 ° C.
Simultaneous addition over 30 minutes, and the following (Solution C) and (Solution D)
Was added simultaneously over 180 minutes while controlling pAg = 7.3 and pH = 5.5.

At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Add water 200 ml (Solution B) Add 10 g of silver nitrate water and 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Add water and 600 ml (Solution D) After adding 300 g of silver nitrate and adding 600 ml of water, desalting was performed using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd., and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.85 μm. Thus, a monodisperse cubic emulsion EMP-1 having a coefficient of variation (σ / r) = 0.07 and a silver chloride content of 99.5 mol% was obtained.

To the above emulsion EMP-1, 9
After 0-minute chemical ripening, the blue-sensitive silver halide emulsion (Em-
B) was obtained.

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-5 6 × 10 ^-4 mol / mol AgX Sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX BS-2 1 × 10 ^-4 mol / mol AgX [Preparation method of green-sensitive silver halide emulsion] Addition time of (solution A) and (solution B) and (C solution) and (D
EMP-2), except that the addition time of the liquid was changed, a monodisperse cubic emulsion EMP-2 having an average particle size of 0.43 μm, a coefficient of variation (σ / r) = 0.08, and a silver chloride content of 99.5 mol% was prepared. Obtained.

EMP-2 was chemically ripened at 55 ° C. for 120 minutes using the following compound to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ^-4 mol / mol AgX Sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX [Red-sensitive halogenation Preparation method of silver emulsion] (solution A) and (solution B) addition time and (solution C) and (D
EMP-3 in the same manner as in EMP-1 except that the addition time of the solution was changed. A monodispersed cubic emulsion EMP-3 having an average particle size of 0.50 μm, a coefficient of variation (σ / r) = 0.08, and a silver chloride content of 99.5 mol% was obtained. Obtained.

EMP-3 was chemically ripened at 69 ° C. for 90 minutes using the following compounds to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ^-4 mol / mol AgX Sensitizing dye RS-1 1 × 10 ^-4 mol / mol AgX The total coated silver amount of the color paper sample thus prepared was 0.58 g / m ² . The total amount of silver applied was changed as shown in Table 1 below to prepare and use color paper samples for experiments.

In all examples the following <Preparation of color negative film sample>, the addition amount of silver halide photographic light-sensitive material is particularly shows the number of grams per 1 m ² unless otherwise noted. Further, silver halide and colloidal silver are shown in terms of silver. The sensitizing dye was represented by the number of moles per mole of silver.

On a triacetyl cellulose film support, each layer having the composition shown below was sequentially formed from the support side to prepare a multilayer color photographic light-sensitive material sample 1.

Sample-1 First layer; Antihalation layer (HC) Black colloidal silver 0.11 UV absorber (UV-1) 0.18 Colored cyan coupler (CC-1) 0.02 High boiling solvent (Oil-1) 0.18 High boiling solvent (Oil- 2) 0.20 gelatin 1.5 second layer; intermediate layer (IL-1) gelatin 1.2 third layer; low red-sensitive emulsion layer (RL) Silver iodobromide emulsion (3 mol% of silver iodide) 0.75 sensitizing dye (S-1) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.2 × 10 ^-4 (Mol / silver 1 mol) Cyan coupler (C-1) 0.45 Cyan coupler (C-2) 0.15 Colored cyan coupler (CC-1) 0.07 DIR compound (D-1) 0.001 DIR compound (D-2) 0.01 High Boiling point solvent (Oil-1) 0.5 Gelatin 1.0 Fourth layer; High-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (7 mol% of silver iodide) 0.75 Sensitizing dye (S 1) 1.5 × 10 ^-4 (mol / mole of silver) Sensitizing dye (S-2) 1.6 × 10 -4 ( mol / mole of silver) Sensitizing dye (S-3) 0.1 × 10 -4 ( mol / Silver 1 mol) Cyan coupler (C-2) 0.22 Colored cyan coupler (CC-1) 0.03 DIR compound (D-2) 0.02 High boiling solvent (Oil-1) 0.24 Gelatin 1.0 Fifth layer; Intermediate layer (IL-2) ) Gelatin 1.0 sixth layer; low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (4 mol% of silver iodide) 0.9 Sensitizing dye (S-4) 7.0 × 10 ^-4 (mol / silver 1) Mol) Sensitizing dye (S-5) 0.8 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.17 Magenta coupler (M-2) 0.43 Colored magenta coupler (CM-1) 0.10 DIR compound (D-3) 0.02 High boiling point solvent (Oil-1) 0.58 Gelatin 1.1 7th layer; high sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (silver iodide 8 mol%) 0.8 Sensitized color Element (S-6) 1.1 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-7) 2.0 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-8) 0.3 × 10 ^{− 4} (mol / silver 1 mol) Magenta coupler (M-1) 0.03 Magenta coupler (M-2) 0.13 Colored magenta coupler (CM-1) 0.04 DIR compound (D-3) 0.006 High boiling solvent (Oil-2) 0.35 Gelatin 0.9 8th layer; Yellow filter layer (YC) Yellow colloidal silver 0.1 Additive (HS-1) 0.07 Additive (HS-2) 0.07 Additive (SC-1) 0.12 High boiling solvent (Oil-2) 0.15 Gelatin 1.0 Ninth layer; low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (6 mol% of silver iodide) 0.5 Sensitizing dye (S-9) 5.8 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.58 Yellow coupler (Y-2) 0.34 DIR compound (D-1) 0.003 DIR compound (D-2) 0.006 High boiling solvent (Oil-2) 0.18 Gelatin 1.2 10th layer: high sensitivity blue-sensitive emulsion layer (B-H) (12 mol% silver iodide) iodobromide emulsion 0.5 Sensitizing dye (S-10) 3.0 × 10 -4 ( mol / silver Mol) Sensitizing dye (S-11) 1.2 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.18 Yellow coupler (Y-2) 0.10 High boiling solvent (Oil-2) 0.05 Gelatin 1.0 11th layer; first protective layer (PRO-1) Silver iodobromide emulsion (fine particles) 0.3 UV absorber (UV-1) 0.07 UV absorber (UV-2) 0.1 Additive (HS-1) 0.2 Additive ( HS-2) 0.1 High boiling solvent (Oil-1) 0.07 High boiling solvent (Oil-3) 0.07 Gelatin 0.8 12th layer; 2nd protective layer (PRO-2) Alkali-soluble matting agent (average particle size 2 μm) 0)
13 Polymethyl methacrylate (average particle size: 3 μm) 0.02 Gelatin 0.5 In addition to the above composition, each layer has a coating aid SU-2, a dispersion aid SU-1, a hardener H-1, H-2, Dye AI-1, AI-2
Was added as appropriate.

The emulsions used in the above samples are those shown in Table 1 below. Both are monodisperse emulsions.

The color negative film sample thus prepared had a total coated silver amount (total of each emulsion layer) of 4.5 g / m ² .

As shown in Table 1 below, the total coated silver amount was changed. At this time, the total coated silver amount of each emulsion layer was 4.
Experimental samples were prepared by changing the total amount of silver applied to each layer of the color negative film sample of 50 g / m ^{2 so} that the ratio was the same as the amount of silver applied to each layer.

After the obtained color paper was exposed according to a conventional method, a running process was performed according to the following processing steps.

The obtained color negative film sample was exposed according to a conventional method, and then processed using the following processing conditions and processing solutions. However, the bleaching solution, the fixing solution, and the stabilizing solution used the same tank as the color paper.

(Color negative film processing) However, the stabilization treatment was performed in a three-tank countercurrent, in which the stabilizing solution was replenished to the last tank, and the overflow flowed into the preceding tank.

Color developing tank solution (for color paper) Triethanolamine 10 g Diethylene glycol 5 g N, N-diethylhydroxyamine 3.0 g Potassium bromide 20 mg Potassium chloride 2.2 g Diethylenetriaminepentaacetic acid 5 g Potassium sulfite 0.2 g Color developing agent (3-methyl -4-Amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate) 8.0 g Potassium carbonate 25 g Potassium hydrogen carbonate 5 g Add water to make the total amount 1 and add potassium hydroxide or sulfuric acid. Adjust to pH10.10.

Replenisher for color development (for color paper) Triethanolamine 14.0 g Diethylene glycol 8.0 g N, N-diethylhydroxylamine 4.0 g Potassium bromide 8 mg Diethylenetriaminepentaacetic acid 7.5 g Potassium sulfite 0.3 g Color developing agent (3-methyl-4-amino) -N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate) 12 g Potassium carbonate 30 g Potassium bicarbonate 1 g Add water to make the total volume 1 and adjust to pH 10.80 with potassium hydroxide or sulfuric acid. adjust.

Color developing tank liquid (for color negative film) Diethylenetriaminepentaacetic acid 1.0 g Potassium sulfite 4.0 g Potassium bromide 1.3 g Hydroxylamine sulfate 2.4 g Color developing agent 4- (N-ethyl-N-β-hydroxyethylamino) -2-methyl Aniline sulfate 4.2 g Potassium iodide 2.3 mg Potassium carbonate 30 g Add water to make the total amount 1 and adjust to pH10.01 with potassium hydroxide or sulfuric acid.

Replenisher for color development (for color negative film) Diethylenetriaminepentaacetic acid 1.2 g Potassium sulfite 4.8 g Hydroxylamine sulfate 3.0 g Color developing agent 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 6.1 g Potassium carbonate 30 g Potassium bromide 0.5 g Add water to make the total amount 1 and adjust to pH 10.07 with potassium hydroxide or sulfuric acid.

 The composition of the bleaching solution used is as follows.

Ferric ammonium 1,3-diaminopropanetetraacetate 0.3
5 mol Disodium ethylenediaminetetraacetate 2 g Ammonium bromide 150 g Glacial acetic acid 40 ml Ammonium sulfate 40 g Add water to make 1 and adjust the pH to 4.5 using aqueous ammonia or glacial acetic acid.

 The composition of the bleaching replenisher used was as follows.

Ferric ammonium 1,3-diaminopropanetetraacetate 0.4
0 mol Disodium ethylenediaminetetraacetate 2 g Ammonium bromide 170 g Ammonium nitrate 50 g Glacial acetic acid 61 ml Add water to 1 and adjust to pH 3.5 using aqueous ammonia or glacial acetic acid.

The compositions of the fixing solution and the fixing replenisher used are as follows.

Sodium thiosulfate 50 g Potassium thiocyanate 2.0 mol Anhydrous potassium bisulfite 20 g Sodium metabisulfite 4.0 g Disodium ethylenediaminetetraacetate 1 g Add water to 1 and adjust to pH 6.5 using aqueous ammonia or glacial acetic acid. .

The compositions of the stabilizer and the replenisher used are as follows.

Adjust pH to 8.5 and add water to 1

The automatic developing machine used had the processing steps shown in FIG. 1 and had a processing step A for a color negative film and a processing step B for a color paper. What was used was used.

In FIG. 1, 1a is a color developing tank for a color negative film, 1b
Denotes a color developing tank for color paper, 2 denotes a bleaching tank, 3 denotes a fixing tank, 4 denotes a first stabilizing tank, 5 denotes a second stabilizing tank, and 6 denotes a third stabilizing tank. In the same figure, reference numerals 7 to 11 denote replenishing metering pumps.

Of the compositions of the above stabilizing solution and stabilizing replenishing solution, formaldehyde was changed to the compounds shown in Table 1, and a running process was performed using the prepared color paper and color negative film.

In the running process, the automatic developing machine is filled with the color developing tank solution for the color paper and the color negative film described above, and while the bleaching tank solution, the fixing tank solution and the stabilizing tank solution are filled, the color paper and the color negative film sample are processed. The above-mentioned color developing replenisher, bleach-fix replenisher and stable replenisher were replenished through a metering pump.

Further, the running process was discontinuously performed until the total amount of the replenished stable replenisher became three times the tank capacity of the color developing tank.

As for the processing ratio between the color paper and the color negative film, the color paper 1 was subjected to the running process at the area ratio of the color negative film 7. After the completion of the running process, the occurrence of scum in the first tank of the stability tank was observed. Further, the magenta density of the unexposed portion of the color paper sample processed after the running process was measured.

 The results are summarized in Table 1.

In the above table, ○ indicates that no scum was generated, Δ indicates that some occurrence was observed, X indicates that occurrence was clearly observed, and that the more the number of ×, the more scum was generated. Means

From Table 1 above, when two types of light-sensitive materials satisfying the conditions of the present invention are combined and processed, scum is generated in the formalin-containing stabilizer and in the non-added stabilizer, and stain is generated in the unexposed portion of the paper. Although large, by using a stabilizer to which the compound of the present invention is added, no scum is generated,
It can be seen that there is no increase in the density of the unexposed portion of the color paper.

Example 2 Compound A-1- of the present invention in the stabilizer used in Example 1
The running process was performed in the same manner as in Example 1 except that the concentration of No. 1 was changed as shown in Table 2 below. At that time, the transmission green density of the color negative film near the density of 1.0 and the transmission blue density of the unexposed area were measured.
It was stored in RH for 3 weeks, and the difference in concentration before and after storage was determined. Further, the occurrence of scum in the first tank of the stability tank was also observed.

 Table 2 summarizes the results.

Color paper of Example 3 Example 1, 1 m ² per each 0.58g each coating amount of silver in the color negative samples, using a sample of 4.5 g, changing the formaldehyde stabilizing solution in the compounds of Table 2, similarly to Example 1 Was performed. After the treatment, the same evaluation as in Example 1 was performed, and the color negative film sample and the color paper sample were stored at 60 ° C. and 80% RH for 3 weeks.
Before and after storage, the density of the transmission green (G) of the color negative film near the density of 1.0 and the density of the highest density reflection red (R) of the color paper were measured.

 The results are shown in Table 2 above.

From the results shown in Table 2, when a color paper or a color negative film was treated using the stabilizer to which the compound of the present invention was added, no scum was generated in the stabilizer and there was no magenta stain of the color paper. It can be seen that the concentration fluctuation after storage is small.

F-1-10, F-3-1, F-3-4, F-4-
1, F-6-1, F-7-1, F-7-15, F-10-13
And F-10-17 were also examined, but almost the same effects as those of the exemplified compound of the present invention could be obtained.

Example 4 The same experiment as in Example 1 was carried out, except that the silver halide composition of the color paper used in Example 3 was changed as shown in Table 3, and the scum was generated in the stable liquid. The magenta stain was examined.

As shown in Table 3 above, when a sample having a silver chloride molar ratio of 50 mol% or more was used, no scum was generated and there was no magenta stain in the unexposed portion of the color paper.

Example 5 Using the color paper and the color negative film sample used in Example 2, using Exemplified Compound A-1-1 instead of formaldehyde in the stabilizing solution, and changing the addition amount as shown in Table 4, A similar experiment was performed. The processed color paper and color negative film were stored under the conditions of Example 2, and the density fluctuation before and after storage was examined.

As shown in Table 4 above, the amount of the compound of the present invention is preferably 0.05 to 10 g per stabilizing solution.

Example 6 Cyan couplers (C'-2), (C'-) described in JP-A-63-106655, pp. 34 to 42 were used as the cyan couplers in the color paper samples using the experiment of Example 1. 27),
(C'-32), (C'-33), (C'-34), (C'-
36), (C'-37), (C'-38), (C'-39),
(C'-53), (C "-2), (C" -8) and (C "
When the same experiment was carried out by changing each to -9), the reduction in red density was further improved by about 10 to 20%.

Example 7 The magenta coupler (M-2) in the color negative film sample prepared in Example 1 was replaced with a magenta coupler represented by the aforementioned general formula [MI], specifically, an exemplary magenta coupler, 1,2,4 , 10, 20, 21, 31, 40, 60, 63, 64, 74, 76, and 81, and the same experiment as in Example 1 was performed except for the above.
As a result, the decrease in green density after storage of the color negative film was improved by 5 to 10%. The scum was also slightly improved overall.

Example 8 The same experiment as in Example 1 was changed to the following processing steps, and the same processing as in Example 1 was performed. As a result, the same result as in Example 1 was obtained. However, the same color developing solution and stabilizing solution as in Example 1 were used.

Color paper processing conditions Color negative film processing conditions Stabilization was carried out in a countercurrent system from stabilization tank 3 to 1, and part of the stabilizing solution was allowed to flow into the bleach-fixing solution (50 ml / m ² ).

 The composition of each processing solution is as follows.

Bleach-fix solution (same as tank solution and replenisher) Ammonium thiosulfate (70%) 250 ml Ammonium thiocyanate 100 g Sodium sulfite 20 g Ammonium ferric (III) diethylenetriaminepentaacetate 150 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Add water And pH 7.0 with acetic acid or aqueous ammonia.
Was adjusted.

Example 9 The same evaluation as in Example 1 was performed except that the stabilizer for color paper was changed to the composition shown below and the treatment process was changed as shown in FIG. Almost the same effect was obtained, but the G density in the unexposed area of the color paper was improved by 0.01 to 0.02,
The occurrence of scum in the tank also tended to improve.

In FIG. 2, A is a color negative film processing step, B is a color paper processing step, and 10-a,
11-a, 12-a, 13-a, 14-a and 15-a are color developing tanks, bleaching tanks, fixing tanks, first stabilizing tanks, second stabilizing tanks, and stabilizing tanks for processing color negative films, respectively. The third tank,
10-b, 11-b, 12-b, 13-b, 14-b, 15-b are color developing tanks for processing color paper, bleaching tanks, fixing tanks, the first stabilizing tank, and the second stabilizing tank. This is the third stabilization tank.

The compositions of the stabilizer and the replenisher for color paper are as follows.

The pH was adjusted to 8.5 and water was added to 1.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing processing steps of an automatic developing machine used in an embodiment of the present invention, and FIG. 2 is an explanatory view showing other processing steps of the automatic developing machine same as the above.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 11/00 501

Claims (2)

(57) [Claims] 1. A silver halide color photographic light-sensitive material (A) wherein the total amount of silver halide contained in the silver halide color photographic light-sensitive material is 2 g / m ² to 10 g / m ^2; A silver halide color photographic light-sensitive material (B) having a total silver halide coating amount of 1 g / m ² or less contained in a color photographic light-sensitive material is prepared by mixing at least two different light-sensitive materials with a hexamethylenetetramine compound and The following general formula [F-1]
A method for processing a silver halide color photographic light-sensitive material, characterized by processing with a stabilizing solution containing at least one compound selected from the group consisting of compounds represented by formula [F-10]. [Wherein, R _{1 to} R ₆ each represent a hydrogen atom or a monovalent organic group. ] [Wherein, R _{71 to} R ₇₅ each represent a hydrogen atom or a methylol group. X represents an oxygen atom or a sulfur atom. ] [Represents wherein, V ₁ and W ₁ each represent a hydrogen atom, a lower alkyl group or an electron withdrawing group, also attached at V ₁ and W ₁ 5
A 6-membered or 6-membered nitrogen-containing heterocyclic ring may be formed. Y ₁ represents a hydrogen atom or a group which is eliminated by hydrolysis. Z represents a group of nonmetallic atoms necessary for forming a monocyclic or condensed nitrogen-containing heterocyclic ring together with a nitrogen atom and a C ＝ O group. ] [Wherein, R ₈ represents a hydrogen atom or an aliphatic group, and R ₉ and R ₁₀
Represents an aliphatic group or an aryl group, and R ₉ and R ₁₀ may combine with each other to form a ring. Z ₁ and Z ₂ each represent an oxygen atom, a sulfur atom or —N (R ₁₁ ) —. Where Z ₁ and Z ₂
Are not simultaneously oxygen atoms. R ₁₁ is a hydrogen atom,
Represents a hydroxy group, an aliphatic group or an aryl group. ] Wherein R ₁₂ represents a hydrogen atom or an aliphatic hydrocarbon group;
₂ represents a group which leaves by hydrolysis, M represents a cation, W ₂ and Y ₂ each represent a hydrogen atom or a group which leaves by hydrolysis, n represents an integer of 1 to 10, and Z ₃ represents And R
_{And 13} represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a group which is eliminated by hydrolysis. Z ₃ may combine with R ₁₃ to form a ring. ] 2. The silver halide color photographic light-sensitive material (B) according to claim 1, wherein at least 50 mol% of the silver halide grains contained in the silver halide emulsion layer is silver chloride. A method for processing silver halide color photographic light-sensitive materials.