JPH06148831A - Photographic processing composition and processing method - Google Patents

Abstract

PURPOSE:To provide a photographic processing compsn. having biodegrada-bility and improving desilverability, bleaching fog and aging stain. CONSTITUTION:An Fe (III) chelate compd. of a compd. represented by the formula is incorporated. In the formula, each of R<1> and R<4> is H, an aliphatic group, etc., each of L1-L4 is alkylene, W is alkylene, arylene and/or a combining group contg. a heterocyclic group, (n) is 0 or 1 and each of A1-A4 is carboxy, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing composition for a silver halide photographic light-sensitive material and a processing method using the same.

[0002]

2. Description of the Related Art Generally, a silver halide black-and-white photographic light-sensitive material is processed by a processing step such as black-and-white development, fixing and washing after exposure to give a silver halide color photographic light-sensitive material (hereinafter
It is called a color photosensitive material. ) Is subjected to processing steps such as color development, desilvering, washing with water and stabilization after exposure.
After exposing the silver halide color reversal light-sensitive material, black and white development,
After the reversal processing, processing is performed by processing steps such as color development, desilvering, washing with water and stabilization. In the color development step in color development, the exposed silver halide grains are reduced to silver by the color developing agent, and the produced oxidation product of the color developing agent reacts with the coupler to form an image dye.
In the subsequent desilvering process, the developed silver produced in the developing process is oxidized to a silver salt by a bleaching agent (oxidizing agent) having an oxidizing action (bleaching), and then unused halogenation is performed by a fixing agent which forms soluble silver. Together with silver, it is removed from the photosensitive layer (fixing). Bleaching and fixing may be performed as independent bleaching and fixing steps, or may be performed simultaneously as a bleach-fixing step. For details of these processing steps and their compositions, see "The Theory of Photographic Process" by James (4th Edition) (James,
"The Theory of Photographic Process"4'th editio
n) (1977), Research Disclosure No. 1
7643, pages 28-29, ibid. No. 18716, 651, left column to right column, ibid., No. 307105, pages 880-881.

In addition to the above basic processing steps, various auxiliary steps are added for the purpose of maintaining the photographic and physical quality of the dye image, or maintaining the stability of processing. For example, washing step, stabilization step, hardening step,
Stopping process etc. are included. Further, in order to adjust the gradation and the like of the developed silver halide black and white light-sensitive material, it is treated with a reducing solution containing an oxidant. The oxidizing agent of the treatment liquid used in the above bleaching treatment or reducing treatment is generally ethylenediaminetetraacetic acid ferric iron complex salt or 1,3-diaminopropanetetraacetic acid ferric iron complex salt, but these are biodegradable. Hateful.
In recent years, from the viewpoint of environmental protection, it has been desired to detoxify the photographic processing waste liquid generated from these photographic processings, and particularly, a processing composition that is easily biodegradable is desired. Is being studied.

As a bleaching agent having biodegradability, N-
Ferric iron complex salts of (2-carboxymethoxyphenyl) iminodiacetic acid are disclosed in West German Patent Publication No. 3912551, and ferric iron complex salts of β-alanine diacetic acid and glycine dipropionic acid are disclosed in European Patent Publication No. 430000A. . However, a processing solution having a bleaching ability composed of these bleaching agents cannot be said to have sufficient desilvering property, and continuous processing using these causes a problem that the desilvering property is lower than that in the initial stage of continuous processing and bleaching. It was found that there were problems such as deterioration of fog and insufficient stain prevention. For these color processing, in recent years, a small automatic developing machine called a minilab has been provided with a rapid processing service to customers.In addition to quick bleaching, the stability of the basic performance of these bleaching agents in continuous processing is also high. Is an essential issue. Furthermore, from the viewpoint of environmental protection as well, it is desired to reduce the concentration of the metal chelate compound used as a bleaching agent. However, the above-mentioned bleaching agent could not obtain sufficient desilvering property from the initial stage of continuous processing at a dilute concentration.

[0005]

SUMMARY OF THE INVENTION It is, therefore, a first object of the present invention to provide a treatment composition which is easy to handle and has no environmental problem of waste liquid, and a treatment method using the same. A second object of the present invention is to provide a processing composition having a bleaching ability which is excellent in desilvering property even in a particularly dilute concentration, and a processing method using the same. A third object of the present invention is to provide a processing composition having a bleaching ability with less bleaching fog and a processing method using the same. A fourth object of the present invention is to provide a processing composition having a bleaching ability with little stain over time and a processing method using the same. A fifth object of the present invention is to provide a treatment composition capable of stably maintaining the above performance even after continuous treatment, and a treatment method using the same. A sixth object of the present invention is to provide a treatment composition preferable from the viewpoint of biodegradability and environmental protection, and a treatment method using the same.

[0006]

The above object was achieved by the following method. That is, Fe (III), Mn (III), or a compound represented by the following general formula (I) or a salt thereof,
Co (III), Rh (II), Rh (III), Au (II), A
A processing composition for a silver halide photographic light-sensitive material containing a u (III) or Ce (IV) chelate compound and a processing method using the same. General formula (I)

[0007]

[Chemical 2]

(In the formula, R ¹ and R ² represent a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group. L ₁ , L ₂ ,
L ₃ and L ₄ each represent an alkylene group. W represents a linking group containing an alkylene group, an arylene group and / or a divalent heterocyclic group. n represents 0 or 1. A ₁ , A ₂ ,
A ₃ and A ₄ each represent a carboxy group, a phosphono group, a sulfo group or a hydroxy group. )

First, the compound represented by formula (I) will be described in detail below. The aliphatic group represented by R ¹ and R ² may be linear, branched or cyclic,
It is preferably linear or branched. Examples of the aliphatic group include an alkyl group, an alkenyl group and an alkynyl group, preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms. The aliphatic group may be substituted, and examples of the substituent include an alkyl group (eg, methyl, ethyl, iso-propyl), an aralkyl group (eg, phenylmethyl), an alkenyl group (eg, allyl), an alkoxy group (eg, methoxy). , Ethoxy), aryl groups (eg phenyl, p-methylphenyl), acylamino groups (eg acetylamino), sulfonylamino groups (eg methanesulfonylamino), ureido groups (eg methylureido), alkoxycarbonylamino groups, aryloxycarbonyl. Amino group, aryloxy group (eg phenyloxy), sulfamoyl group (eg methylsulfamoyl), carbamoyl group (eg carbamoyl, methylcarbamoyl), mercapto group, alkylthio group (eg methylthio, carboxy) Rumechiruchio), an arylthio group (e.g., phenylthio), a sulfonyl group (e.g. methanesulfonyl),
Sulfinyl group (eg methanesulfinyl), hydroxy group, halogen atom (eg chlorine atom, bromine atom, fluorine atom), cyano group, sulfo group, carboxyl group, phosphono group, aryloxycarbonyl group (eg phenyloxycarbonyl), acyl group (Eg acetyl, benzoyl), alkoxycarbonyl group (eg methoxycarbonyl), acyloxy group (eg acetoxy),
Examples thereof include an acylamino group (eg, acetylamino), a sulfonamide group (eg, methanesulfonamide), a nitro group, a hydroxamic acid group and the like.

When the above substituent has a carbon atom, it preferably has 1 to 10 carbon atoms, and more preferably 1
~ 4. The aryl group represented by R ¹ and R ² is a monocyclic or bicyclic aromatic hydrocarbon group which may have a substituent. It is preferably a phenyl group which may have a substituent or a naphthyl group, and more preferably a phenyl group which may have a substituent. As the substituent of the aryl group represented by R ¹ and R ² , those exemplified as the substituent which the aliphatic group represented by R ¹ and R ² may have can be applied.

The heterocyclic group represented by R ¹ and R ² is a 3- to 10-membered heterocyclic group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom and is saturated or unsaturated. May be a single ring, or may form a condensed ring with another aromatic ring or a hetero ring. The heterocycle is preferably a 5- or 6-membered unsaturated heterocycle. Examples of the heterocycle include pyridine, pyrazine, pyrimidine, pyridazine, triazine, tetrazine, thiophene, furan, pyran, pyrrole, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, oxadiazole, thiadiazole, thianthrene, isobenzofuran. , Chromene, xanthene, phenoxathine, indolizine,
Isoindole, indole, triazole, triazolium, tetrazole, quinolidine, isoquinoline, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pterindine, carbazole,
Carboline, phenanthridine, acridine, pteridine, phenanthroline, phenazine, phenothiazine,
Examples include phenoxazine, chroman, pyrroline, pyrazoline, indoline, isoindoline and the like. Preferred are pyridine, pyrazine, pyrimidine, pyridazine, thiophene, furan, pyrrole, imidazole, pyrazole, thiazole, isothiazole, oxazole and isoxazole.

The heterocyclic group represented by R ¹ and R ² may have a substituent, and examples of the substituent include R ¹ and R 2.
What was mentioned as a substituent which the aliphatic group represented by ² may have is applicable. R ¹ and R ² may be linked to form a ring.

The alkylene group represented by L ₁ , L ₂ , L ₃ and L ₄ may be linear, branched or cyclic, and is preferably a linear alkylene group. The alkylene group preferably has 1 to 6 carbon atoms. The alkylene group may be substituted, and as the substituent, those exemplified as the substituents which the aliphatic group represented by R ¹ and R ² may have can be applied. The substituent is preferably an alkoxy group, a sulfo group, a hydroxy group, a carboxy group or a phosphono group, and more preferably a carboxy group. L ₁ ~
Specific examples of preferred L ₄ include the following.

[0014]

[Chemical 3]

A methylene group or an ethylene group is particularly preferable. The divalent linking group represented by W can be preferably represented by the following general formula (W).

[0016] Formula ^{(W) - (W 1 -D} ) t -W 2 - wherein, W ¹ and W ² may be different even in the same, an alkylene group (preferably having 1 to 10 carbon atoms , Straight chain,
It represents a branched or cyclic alkylene group), an arylene group (preferably having 6 to 10 carbon atoms), an aralkylene group (preferably having 7 to 10 carbon atoms), or a divalent heterocyclic group. D
Represents -O-, -S-, -N (Rw)-, or a divalent heterocyclic group. Rw is a hydrogen atom or -COOM ₁ , -PO ₃
M ₂ M _3, -OH or -SO ₃ M ₄ alkyl group or a carbon number of carbon atoms which may be 1-8 substituted with 6-10
Represents an aryl group of. M ₁ , M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation, and examples of the cation include alkali metals (lithium, sodium, potassium etc.), ammonium (ammonium, tetraethylammonium etc.) and pyridinium. it can. The linking group represented by W may have a substituent, and as the substituent, those exemplified as the substituents which the aliphatic group represented by R ¹ and R ² may have are applicable. .

The divalent heterocyclic group is preferably a 5- or 6-membered ring in which the hetero atom is nitrogen, and more preferably a divalent heterocyclic group such as an imidazolyl group having adjacent carbon atoms. As W ¹ and W ² , an alkylene group having 1 to 4 carbon atoms is preferable. t represents an integer of 0 to 3, and when t is 2 or 3, W ¹ -D may be the same or different. t is preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0. Specific examples of W include the following.

[0018]

[Chemical 4]

[0019]

[Chemical 5]

N represents 0 or 1, and is preferably 0. A ₁ , A ₂ , A ₃ and A ₄ each represent a carboxy group, a phosphono group, a sulfo group or a hydroxy group. It is preferably a carboxy group or a phosphono group, more preferably a carboxy group. The compound represented by the general formula (I) may form a salt, and examples of the salt include sodium salt, potassium salt, ammonium salt and the like. Specific examples of the compound represented by formula (I) and salts thereof are shown below, but the invention is not limited thereto.

[0021]

[Chemical 6]

[0022]

[Chemical 7]

[0023]

[Chemical 8]

[0024]

[Chemical 9]

[0025]

[Chemical 10]

The compound represented by the general formula (I) can be synthesized, for example, by reacting a hydrazine derivative with a diketone derivative as shown below.

[0027]

[Chemical 11]

(Wherein R ¹ , R ² , L ₁ , L ₂ , L ₃ ,
L ₄ , W, n, A ₁ , A ₂ , A ₃ and A ₄ have the same meanings as those in formula (I). The hydrazine derivative as a raw material can be synthesized by reacting a halogen-substituted carboxylic acid derivative, phosphonic acid derivative, sulfonic acid derivative or alcohol derivative or an α, β-unsaturated compound with hydrazine. In this case, a solvent may be used, and the solvent is not limited as long as it does not participate in the reaction, and examples thereof include water, alcohol (eg, methanol, ethanol, isopropanol, etc.), acetonitrile, dimethylformamide and the like.

When the compound is synthesized from a halogen-substituted carboxylic acid derivative, phosphonic acid derivative, sulfonic acid derivative or alcohol derivative, it is preferably carried out in the presence of a base, and the base is an alkali (sodium hydroxide, potassium hydroxide). , Sodium carbonate, potassium carbonate, etc.) or a tertiary amine (triethylamine, etc.). This reaction is usually carried out at 0 to 100 ° C, preferably 10 to 80 ° C.

The reaction between the hydrazine derivative and the diketone derivative is usually carried out at 0 to 100 ° C., preferably 10 to 5
It is 0 ° C. A solvent may be used in this reaction, and the solvent is not limited as long as it does not participate in the reaction, for example, water, alcohol (for example, methanol, ethanol,
Isopropanol etc.), acetonitrile, dimethylformamide and the like. Synthesis example, synthesis of compound 1

[0031]

[Chemical 12]

Synthesis of Compound 1a 506 g (3.89 mol) of hydrazine sulfate was dissolved in 1 liter of water, and 934 g of sodium chloroacetate was added at room temperature.
(8.02 mol) was added. Add a small amount of phenolphthalene and, with stirring, 622 g (15.6 g) of sodium hydroxide.
1 liter aqueous solution of (mol) was slowly added dropwise so that the solution remained a pale red color.

After completion of dropping, the mixture was reacted at room temperature for 3 hours, and then about 670 ml (7.81 mol) of concentrated hydrochloric acid was added. After standing overnight, the precipitated crystals were collected by filtration, washed with 4 liters of water, and then dried under reduced pressure to obtain 415 g of white crystals 1a.
(2.80 mol) was obtained. 72% yield

Synthesis of Compound 1 29.6 g (0.20 mol) of Compound 1a synthesized above and 14.5 g (0.1% of 40% aqueous glyoxal solution)
(0 mol) was suspended in 60 ml of water and reacted at room temperature under a nitrogen atmosphere for 6 hours, and then the solid was collected by filtration. After washing with water and drying under reduced pressure, 29.0 g of pale yellow crystal 1 is obtained.
(0.0911 mol) was obtained. Yield 91%, melting point 176 ~
177 ° C (decomposition). Other compounds can be similarly synthesized.

The compound represented by the general formula (I) is Fe (II
I), Mn (III), Co (III), Rh (II), Rh (II
I), Au (II), Au (III) or Ce (IV) chelate compounds (hereinafter sometimes simply referred to as the metal chelate compounds of the present invention) are oxidizing agents for silver halide photographic light-sensitive materials (color light-sensitive materials). As a bleaching agent for papers and a reducing agent for black-and-white light-sensitive materials for plate making). Particularly, it is excellent as a bleaching agent for color light-sensitive materials. To use the metal chelate compound of the present invention as a bleaching agent, the imagewise exposed silver halide color photographic light-sensitive material is subjected to color development and then treated with a processing solution containing the metal chelate compound of the present invention as a bleaching agent. Bleaching of developed silver is extremely rapid, and there is no remarkable bleaching fog found in conventional bleaching agents capable of rapid bleaching. The metal salt constituting the metal chelate compound of the present invention includes Fe (III), Mn (III), Co (II
I), Rh (II), Rh (III), Au (II), Au (III)
And a salt of Ce (IV). More preferably Fe
(III), Mn (III), Co (IV)) salts, especially Fe
The salt of (III) is preferred.

The metal chelate compound of the present invention is a compound represented by the general formula (I) and a salt of the metal (for example, ferric sulfate, ferric chloride, ferric nitrate, phosphoric acid). Examples of the respective salts such as iron salts include sodium salts, ammonium salts, potassium salts and lithium salts.)
And may be formed by reaction in solution. Similarly, an ammonium salt or an alkali metal salt of the compound represented by the general formula (I) (for example, lithium salt, sodium salt,
A potassium salt) and a salt of the metal may be formed by a reaction in a solution. Of course, an isolated metal chelate compound may be used. Specific examples of the metal chelate compound of the present invention are shown below. The metal chelate compound of the present invention may be a complex formed from the compound represented by the general formula (I) and the metal salt, and It is not limited to the thing.

[0037]

[Chemical 13]

The present invention is characterized by a novel oxidizing agent in a photographic processing composition, particularly a bleaching agent in a processing composition having a bleaching ability for a color light-sensitive material, and other materials are required. The material or the like that can be generally applied can be appropriately selected. The metal chelate compound of the present invention may be contained in any processing liquid (for example, a fixing liquid or an intermediate bath between the color development and the desilvering process).
It is particularly effective as a bleaching agent of a processing solution (bleaching solution or bleach-fixing solution) having a bleaching ability for a color light-sensitive material by containing 0.005 to 1 mol per liter of processing solution. Hereinafter, the processing liquid having a bleaching ability of a preferred embodiment will be described. The metal chelate compound of the present invention is added to the processing solution having a bleaching ability in an amount of 0.
It is effective as a bleaching agent to contain 005 to 1 mol, more preferably 0.01 to 0.5 mol, and 0.05 to 0.
5 mol is particularly preferred. The metal chelate compound of the present invention is 0.005-0.2 mol, preferably 0.01-0.2 mol, and more preferably 0.05 mol per liter of the treatment liquid.
Even when used in a dilute concentration of 5 to 0.18 mol, excellent performance can be exhibited. When the metal chelate compound of the present invention is used as a bleaching agent in a processing solution having a bleaching ability, it is in a range where the effect of the present invention is exhibited (preferably, processing solution 1).
It may be used in combination with other bleaching agents in an amount of 0.01 mol or less per liter, preferably 0.005 mol or less per liter of the processing liquid. Examples of such bleaching agents include the compounds Fe (III), Co (III) or Mn (I
II) Chelating bleach, persulfate (for example, peroxodisulfate), hydrogen peroxide, bromate and the like.

Examples of the compound forming the chelate bleaching agent include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N, N ', N'-triacetic acid, and 1,2-diaminopropane. Tetraacetic acid, 1,3-diaminopropanetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid,
Ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1,3-diaminopropanol-N, N,
N ', N'-tetramethylenephosphonic acid, ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid, 1,3
-Propylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, nitrilodiacetic acid monopropionic acid, nitrilomonoacetic acid dipropionic acid, 2-hydroxy-3-aminopropionic acid-N, N-diacetic acid, serine -N, N-
Diacetic acid, 2-methyl-serine-N, N-diacetic acid, 2-hydroxymethyl-serine-N, N-diacetic acid, hydroxyethyliminodiacetic acid, methyliminodiacetic acid, N- (2-
(Acetamido) -iminodiacetic acid, nitrilotripropionic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,4-diaminobutanetetraacetic acid, 2-methyl-1,3-diaminopropanetetraacetic acid, 2-dimethyl-
In addition to 1,3-diaminopropanetetraacetic acid, citric acid and alkali metal salts (for example, lithium salt, sodium salt, potassium salt) and ammonium salt thereof, JP-A-63-80256 and 63-97952.
No. 63-97953, No. 63-97954, JP-A No. 1-393740, No. 3-216650, and No. 3-.
180842, JP-A-4-73645 and JP-A-4-73.
No. 647, No. 4-127145, No. 4-134450.
No. 4-174432, European Patent Publication No. 43000.
The bleaching agents described in 0A1 and West German Laid-Open Patent No. 3912551 can also be mentioned, but the bleaching agents are not limited thereto.

The processing solution having a bleaching ability containing the metal chelate compound according to the present invention contains the metal chelate compound as a bleaching agent, and also contains chloride, bromide, a rehalogenating agent for promoting the oxidation of silver, It is preferred to add a halide such as iodide. Further, an organic ligand that forms a sparingly soluble silver salt may be added instead of the halide. The halide is added as an alkali metal salt or ammonium salt, or a salt such as guanidine or amine. Specific examples include sodium bromide, ammonium bromide, potassium chloride, guanidine hydrochloride, potassium bromide, potassium chloride and the like. In the processing solution having bleaching ability of the present invention, the amount of the rehalogenating agent is appropriately 2 mol / liter or less, and in the case of the bleaching solution, it is preferably 0.01 to 2.0 mol / liter, and more preferably 0. 0.1 to 1.7 mol / liter, particularly preferably 0.1 to 0.6 mol / liter. In the bleach-fixing solution, 0.001-2.
0 mol / liter is preferable, 0.001 to 1.0 mol / liter is more preferable, and 0.001 to 0.5 mol / liter.
L is particularly preferred.

The processing solution having bleaching ability according to the present invention may contain a compound represented by the general formula (I) which is formed separately from the metal chelate compound of the present invention,
The less stable the metal chelate compound is, the more it is preferable to add it, and it is usually used in the range of 30 times the molar amount.

The bleaching solution or bleach-fixing solution according to the present invention further contains a bleaching accelerator, a corrosion inhibitor for preventing corrosion of the processing bath, a buffer for maintaining the pH of the solution, a fluorescent whitening agent, a defoaming agent and the like. It is added as needed. Examples of bleaching accelerators include US Pat. No. 3,893,858, German Patent No. 1,290,812, and British Patent No. 1,138,8.
42, JP-A-53-95630, Research Disclosure No. 17129 (1978), a compound having a mercapto group or a disulfide group, a thiazolidine derivative described in JP-A-50-140129, U.S. Pat. , 706,561, thiourea derivatives, iodides described in JP-A-58-16235, polyethylene oxides described in German Patent 2,748,430, and polyamines described in JP-B-45-8836. As the compound, the imidazole compound described in JP-A-49-40493 can be used. Among them, the mercapto compounds described in British Patent 1,138,842 are preferable. As the corrosion inhibitor, nitrate is preferably used, and ammonium nitrate, sodium nitrate, potassium nitrate or the like is used. The addition amount is 0.01
~ 2.0 mol / liter, preferably 0.05-0.5
Mol / liter.

The bleaching solution or bleach-fixing solution of the present invention has a pH of 2.0 to 8.0, preferably 3.0 to 7.5. When bleaching or bleach-fixing is carried out immediately after color development in a photographic light-sensitive material, the pH of the solution should be 7.0 or less, preferably 6.4 or less in order to suppress bleaching fog.
Particularly in the case of a bleaching solution, 3.0 to 5.0 is preferable. pH
When it is 2.0 or less, the metal chelate of the present invention tends to be unstable, and the pH is preferably 2.0 to 6.4. For color print materials, a pH range of 3-7 is preferred. As the pH buffer for this purpose, any one can be used as long as it is difficult to be oxidized by the bleaching agent and has a buffering action in the above pH range. For example, acetic acid, glycolic acid, lactic acid, propionic acid, butyric acid, malic acid, chloroacetic acid, levulinic acid, ureidopropionic acid, formic acid, monobromoacetic acid, monochloropropionic acid, pyrivic acid, acrylic acid, isobutyric acid, pivalic acid, aminobutyric acid. , Valeric acid, isovaleric acid, asparagine, alanine, arginine, ethionine, glucine, glutamine, cysteine, serine,
Methionine, leucine, histidine, benzoic acid, chlorobenzoic acid, hydroxybenzoic acid, nicotinic acid, oxalic acid, malonic acid, succinic acid, tartaric acid, maleic acid, fumaric acid, oxaloic acid, glutaric acid, abipic acid, aspartic acid, glutamic acid , Cystine, ascorbic acid, phthalic acid, terephthalic acid, and other organic acids; pyridine, dimethylpyrazole, 2-methyl-o-oxazoline, aminoacetonitrile, imidazole, and other organic bases. A plurality of these buffers may be used in combination. In the present invention, an organic acid having a pKa of 2.0 to 5.5 is preferable, and acetic acid, glycolic acid or a combination of acetic acid and glycolic acid is particularly preferable. These organic acids can also be used as alkali metal salts (for example, lithium salt, sodium salt, potassium salt) and ammonium salt. The amount of these buffers used is appropriately 3.0 mol or less, preferably 0.1 to 2.0 mol, per liter of the processing solution having a bleaching ability.
It is more preferably 0.2 to 1.8 mol, and particularly preferably 0.4 to 1.5 mol. In order to adjust the pH of the processing solution having a bleaching ability to the above range, the above and an acid and an alkali agent (for example, aqueous ammonia, KOH, NaOH, potassium carbonate, sodium carbonate, imidazole, monoethanolamine, diethanolamine) are used in combination. May be. Of these, aqueous ammonia, KOH, NaOH, potassium carbonate and sodium carbonate are preferred.

With the recent growing awareness of global environmental protection, efforts are being made to reduce the nitrogen atoms emitted into the environment. From such a viewpoint, it is desired that the treatment liquid of the present invention does not substantially contain ammonium ions. In addition, in the present invention, the concentration of ammonium ion is 0.
1 mol / liter or less, preferably 0.0
8 mol / liter or less, more preferably 0.01 mol / liter
Less than or equal to 1 liter, particularly preferably represents a state of not containing at all. In order to reduce the ammonium ion concentration in the range of the present invention, an alkali metal ion or an alkaline earth metal ion is preferable as an alternative cation species, an alkali metal ion is particularly preferable, and a lithium ion, a sodium ion, or a potassium ion is particularly preferable. However, specifically, sodium salts and potassium salts of an organic acid ferric iron complex as a bleaching agent, potassium bromide as a rehalogenating agent in a treatment liquid having a bleaching ability, sodium bromide, potassium nitrate, Examples thereof include sodium nitrate. Further, as the alkaline agent used for pH adjustment, potassium hydroxide,
Sodium hydroxide, potassium carbonate, sodium carbonate and the like are preferable.

The processing solution having a bleaching ability of the present invention is particularly preferably subjected to aeration during processing because the photographic performance is kept extremely stable. Means known in the art can be used for the aeration, and blowing of air into the processing liquid having a bleaching ability or absorption of air using an ejector can be performed. At the time of blowing air, it is preferable to discharge the air into the liquid through an air diffusing tube having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Z-121, Eusing Process C-41, No. 3, issued by Eastman Kodak Company.
The matters described in the edition (1982), pages BL-1 to BL-2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is strengthened, and the implementation thereof is described in JP-A-3-33847, No. 8
The contents of the page, upper right column, line 6 to lower left column, line 2
It can be used as is. The bleaching or bleach-fixing process is 3
It can be performed in a temperature range of 0 ° C to 60 ° C, preferably 35 ° C.
~ 50 ° C. The time of the bleaching and / or bleach-fixing treatment step is used in the range of 10 seconds to 7 minutes in the light-sensitive material for photography, but is preferably 10 seconds to 4 minutes. In the case of print sensitive materials, it is 5 seconds to 70 seconds, preferably 5 seconds to 70 seconds.
It is 60 seconds, more preferably 10 seconds to 45 seconds. Under these preferable processing conditions, good results were obtained quickly and without an increase in stain.

The light-sensitive material processed with a processing solution having a bleaching ability is subjected to fixing or bleach-fixing processing. As such fixing solution or bleach-fixing solution, those described in JP-A-3-33847, page 6, lower right column, line 16 to page 8, upper left column, line 15 are also preferable. Incidentally, ammonium thiosulfate has been generally used as the fixing agent in the desilvering process, but other known fixing agents such as mesoionic compounds,
It may be replaced with a thioether compound, thioureas, a large amount of iodide, hypo, or the like. Regarding these, JP-A-60-61749, JP-A-60-147735, and JP-A-60-147735.
No. 21444, JP-A Nos. 1-2201659 and 1-2.
10951, 2-44355, U.S. Pat.
78,424 and the like. For example, ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, guanidine thiosulfate, ammonium thiocyanate,
Sodium thiocyanate, potassium thiocyanate, dihydroxyethyl-thioether, 3,6-dithia-1,
8-octanediol, imidazole and the like can be mentioned.
Of these, thiosulfates and mesoions are preferable. Ammonium thiosulfate is preferable from the viewpoint of quick fixability, but sodium thiosulfate and mesoions are more preferable from the viewpoint of preventing the treatment liquid from substantially containing ammonium ions due to environmental problems as described above. Further, by using two or more fixing agents in combination, more rapid fixing can be performed. For example, in addition to ammonium thiosulfate or sodium thiosulfate, it is also preferable to use the above-mentioned ammonium thiocyanate, imidazole, thiourea, thioether, etc. in this case. 01-10
It is preferably added in the range of 0 mol%. The amount of the fixing agent is 0.1 to 3 per liter of the bleach-fixing solution or the fixing solution.
It is 0 mol, preferably 0.5 to 2.0 mol. The pH of the fixing solution depends on the type of the fixing agent, but is generally 3.0 to
9.0, especially when thiosulfate is used.
8 to 8.0 is preferable for obtaining stable fixing performance.

A preservative is added to the bleach-fixing solution or the fixing solution,
It is also possible to enhance the stability of the liquid over time. In the case of a bleach-fixing solution or a fixing solution containing thiosulfate, sulfite as a preservative, and / or bisulfite adduct of hydroxylamine, hydrazine and aldehyde (for example, bisulfite adduct of acetaldehyde, particularly preferred) The bisulfite adduct of aromatic actide described in JP-A-1-298935) is effective. Also, JP-A-62-14304
It is also preferable to use the sulfinic acid compound described in No. 8.
It is also preferable to add a buffer to the bleach-fixing solution and the fixing solution in order to keep the pH of the solution constant. For example, phosphates, imidazoles such as imidazole, 1-methyl-imidazole, 2-methyl-imidazole, 1-ethyl-imidazole, triethanolamine,
Examples thereof include N-allylmorpholine and N-benzoylpiperazine.

Further, by adding various chelating agents to the fixing solution, it is possible to conceal the iron ions brought in from the bleaching solution and improve the stability of the solution. Such a preferable chelating agent is 1-hydroxyethylidene-
1,1-diphosphonic acid, nitrilotrimethylenephosphonic acid, 2-hydroxy-1,3-diaminopropanetetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid Acetic acid, glycol ether diamine tetraacetic acid, ethylenediamine tetrapropionic acid, phenylenediamine tetraacetic acid, 1,3-diaminopropanol-NN, N ',
N'-tetramethylenephosphonic acid, ethylenediamine-N,
N, N ', N'-tetramethylenephosphonic acid, 1,3-propanediamine, N, N, N', N'-tetramethylenephosphonic acid, serine-N, N-diacetic acid, 2-methyl-serine-
N, N-diacetic acid, 2-hydroxymethyl-serine-N,
N-diacetic acid, hydroxyethyliminodiacetic acid, methyliminodiacetic acid, N- (2-acetamido) -iminodiacetic acid, nitrilotripropionic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,4-diaminobutanetetraacetic acid, 2 -Methyl-1,3-diaminopropanetetraacetic acid, 2-dimethyl-1,3-diaminopropanetetraacetic acid, alanine, tartaric acid, hydrazidediacetic acid, N-hydroxy-iminodipropionic acid and alkali metal salts thereof (for example, Examples thereof include lithium salt, sodium salt, potassium salt) and ammonium salt.

The fixing step can be carried out in the range of 30 to 60 ° C., preferably 35 to 50 ° C. The time of the fixing treatment step is 15 seconds to 2 minutes, preferably 25 seconds to 1 minute 40 seconds for the photosensitive material for photographing, and 8 seconds to 80 seconds, preferably 10 seconds for the photosensitive material for printing. 45 seconds. The desilvering process is generally performed by combining a bleaching process, a bleach-fixing process and a fixing process. Specific examples include the following. Bleaching-fixing Bleaching-bleaching fixing Bleaching-bleaching fixing-fixing Bleaching-washing-fixing Bleaching fixing Fixing-bleaching fixing In the photographic light-sensitive material ,,, or is preferable. Is preferable for a photosensitive material for printing. The present invention is, for example, a conditioning bath after color development processing,
It can also be applied to desilvering treatment via a stop bath, a washing bath or the like.

The processing method of the present invention is preferably carried out using an automatic processor. Regarding the conveying method in such an automatic developing machine, see JP-A-60-191257, 60.
No. 191258 and No. 60-191259. Further, in order to perform rapid processing, it is preferable to shorten the crossover between processing tanks in an automatic processor. An automatic processor having a crossover time of 5 seconds or less is described in JP-A 1-319038.
When performing continuous processing using an automatic processor by the processing method of the present invention, the consumption of processing liquid components accompanying the processing of the light-sensitive material is supplemented, and undesired components eluted from the light-sensitive material are added to the processing liquid. In order to suppress the accumulation, it is preferable to add a replenisher according to the amount of the processed light-sensitive material. Further, two or more processing baths may be provided in each processing step, and in that case, it is preferable to adopt a countercurrent system in which the replenisher is poured from the rear bath to the front bath. In particular, it is preferable to use a cascade of 2 to 4 stages in the washing process and the stabilizing process. The amount of the replenisher is preferably reduced as long as the compositional change in each processing solution does not cause photographic performance or other inconveniences of stains on the solution.

The amount of the color developing replenisher is 50 ml to 3000 ml, preferably 50 ml to 2200 ml per 1 m ² of the light-sensitive material in the case of the color photographic material, and 15 ml to 500 ml per 1 m ² of the light-sensitive material in the case of the color print material. , Preferably 20 ml to 350 ml. The amount of the bleach replenisher is 10 ml to ¹⁰ per 1 m ^{2 of} the light-sensitive material in the case of color photographic materials.
It is 00 ml, preferably 50 to 550 ml. In the case of printing materials, 15 ml-500 ml per 1 m ^{2 of} light-sensitive material,
It is preferably 20 ml to 300 ml. The amount of bleach-fixing replenisher is 20 for 1 m ^{2 of} light-sensitive material in the case of color photographic material.
It is 0 ml to 3000 ml, preferably 250 ml to 1300 ml, and in the case of printing materials, it is 20 per 1 m ^{2 of} light-sensitive material.
The volume is from 300 to 300 ml, preferably from 50 to 200 ml. The bleach-fixing solution may be replenished as a single solution, or the bleaching composition and the fixing composition may be separately supplemented, or the bleaching bath and / or the overflow solution from the fixing bath may be mixed. It may be used as a bleach-fix replenisher. The amount of fixing replenisher is 30 for 1 m ^{2 of} light-sensitive material in the case of color photographic materials.
It is 0 ml to 3000 ml, preferably 300 ml to 1200 ml, and in the case of a printing material, it is 20 per 1 m ² of the light-sensitive material.
The volume is from 300 to 300 ml, preferably from 50 to 200 ml. The replenishing amount of washing water or stabilizing solution is 1 to 50 times, preferably 2 to 30 times, the amount carried in from the previous bath per unit area,
It is more preferably 2 to 15 times.

The processing solution having bleaching ability of the present invention is
The overflow solution after use in the treatment can be recovered, the components can be added to modify the composition, and then the overflow solution can be reused. Such usage is usually called regeneration, but the present invention can also favor such regeneration. For details of the reproduction, see Fuji Photo Film Co., Ltd., Fuji Film Processing Manual, Fuji Color Negative Film, CN-16 processing (revised August 1990), pp. 39-.
The matters described on page 40 can be applied. The kit for adjusting the processing solution having the bleaching ability of the present invention may be a liquid or a powder, but when the ammonium salt is excluded, most of the raw materials are supplied as a powder, and since the hygroscopicity is low,
Makes powder easier. From the viewpoint of reducing the amount of waste liquid, the regenerating kit is preferably a powder because it can be added directly without using excess water.

Regarding the regeneration of the processing solution having a bleaching ability,
In addition to the aeration mentioned above, "Basics of photographic engineering-silver salt photography-" (edited by the Photographic Society of Japan, published by Corona Publishing Co., 1979)
Year)) etc. can be used. Specifically, in addition to electric field regeneration, there is a method of regenerating bleaching solution with bromic acid, zincic acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using catalyst, bromic acid, ozone, etc. Can be mentioned.
In the electrolytic regeneration, the cathode and the anode are put in the same bleaching bath, or the anode bath and the cathode bath are regenerated in separate baths by using a diaphragm. The fixing solution can be reprocessed at the same time. The fixing solution and the bleach-fixing solution are regenerated by electrolytically reducing accumulated silver ions. Other,
It is also preferable to remove accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance. Ion exchange or ultrafiltration is used to reduce the amount of washing water used, and it is particularly preferable to use ultrafiltration.

In the present invention, the color light-sensitive material is subjected to color development processing after imagewise exposure and before desilvering processing. As the color developing solution usable in the present invention, those described in JP-A-3-33847, page 9, line 6 in the upper left column to line 6 in the lower right column on page 11 and Japanese Patent Application No. And those described in No. 29075. As the color developing agent in the color developing step, a known aromatic primary amine color developing agent can be applied, a preferable example is a p-phenylenediamine derivative, and a typical example is 4-amino-N-ethyl. -N-
(Β-hydroxyethyl) -3-methylaniline, 4-
Amino-N-ethyl-N- (3-hydroxypropyl)
-3-Methylaniline, 4-amino-N-ethyl-N-
(4-Hydroxybutyl) -3-methylaniline, 4-
Amino-N-ethyl-N- (β-methanesulfonamidoethyl) -3-methylaniline, 4-amino-N- (3
-Carbamoylpropyl-Nn-propyl-3-methylaniline, 4-amino-N-ethyl-N-([beta] -hydroxyethyl) -3-methoxyaniline, etc., as well as European Patent Publication No. 410450 and Japanese Patent Laid-Open No. Hei. Those described in No. -11255 and the like can also be preferably used. Also,
These p-phenylenediamine derivatives and salts such as sulfates, hydrochlorides, sulfites, naphthalenedisulfonic acid and p-toluenesulfonic acid may be used. The amount of the aromatic primary amine developing agent used is preferably 0.0002 mol to 0.2 mol, and more preferably 0.001 mol to 0.1 mol, per liter of the color developing solution. The processing temperature of the color developing solution in the present invention is 20 to 55 ° C., preferably 3
It is 0 to 55 ° C. The processing time is 2 for the photosensitive material for photography.
It is 0 second to 5 minutes, preferably 30 seconds to 3 minutes and 20 seconds. More preferably, it is 1 minute to 2 minutes and 30 seconds, and for printing materials, it is 10 seconds to 1 minute and 20 seconds, preferably 10 seconds to 6 seconds.
It is 0 second, and more preferably 10 to 40 seconds.

The processing method of the present invention can also be used for color reversal processing. The black-and-white developing solution used at this time is a so-called black-and-white first developing solution used in the reversal process of a commonly known color photosensitive material. Various well-known additives that have been used in addition to the black-and-white developing solution used in the processing solution for the black-and-white silver halide light-sensitive material can be contained in the black-and-white first developing solution of the color reversal sensitizing material. Typical additives include a developing agent such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, a preservative such as sulfite, and an accelerator composed of an alkali such as sodium hydroxide, sodium carbonate or potassium carbonate. , Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole and methylbenzthiazole, hard water softeners such as polyphosphates, development inhibitors consisting of trace amounts of iodides and mercapto compounds. You can

In the present invention, the desilvered photosensitive material is washed and / or stabilized with water. Regarding the washing and stabilizing steps to be carried out, the stabilizing solution described in US Pat. No. 4,786,583 and the like can be mentioned. Formaldehyde is used as a stabilizer in the stabilizer, but from the viewpoint of work environment safety, N-methylolazole, hexamethylenetetramine, formaldehyde bisulfite adduct, dimethylolurea, azolylmethylamine derivative Are preferred. Regarding these, JP-A-2-153348,
It is described in Japanese Patent Application Nos. 2-400906, 2-401513 and 3-48679. Especially 1,2,4-
Azoles such as triazole and 1,4-bis (1,
A combination of azolylmethylamine and its derivatives (such as 2,4-triazol-1-ylmethyl) piperazine (described in Japanese Patent Application No. 3-159918) has high image stability,
In addition, formaldehyde vapor pressure is low, which is preferable.

Examples of the light-sensitive material applicable to the processing of the present invention include a color negative film, a color reversal film, a color paper, a color reversal paper, a direct positive color light-sensitive material, a motion picture color negative film and a motion picture color positive film. Japanese Patent Laid-Open No. 3-33847
No. 3-293662, No. 4-130432 and the like. Further, the type of silver halide used in the support of the light-sensitive material of the present invention; coating method; silver halide emulsion layer, surface protective layer (eg, silver iodobromide, silver iodochlorobromide, silver bromide). , Silver chlorobromide, silver chloride), its grain shape (eg, cubic, tabular, spherical), its grain size, its volatility, its crystalline structure (eg, core / shell structure,
Multi-phase structure, homogeneous phase structure), its manufacturing method (eg, single jet method, double jet method), binder (eg, gelatin), hardener, antifoggant, metal doping agent, silver halide solvent, thickener , Emulsion precipitation agents, dimensional stabilizers, anti-adhesion agents, stabilizers, stain inhibitors, dye image stabilizers, stain inhibitors, chemical sensitizers, spectral sensitizers, sensitivity enhancers, supersensitizers, Nucleating agent, coupler (for example, yellow coupler of piparoylacetanilide type or benzoylacetanilide type, magenta coupler of 5-pyrazolone type or pyrazoloazole type, cyan coupler of phenol type or naphthol type, DIR coupler, bleach accelerator releasing type Couplers, competitive couplers, colored couplers), coupler dispersion methods (for example, oil-in-water dispersion method using a high boiling point solvent), plasticizers, electrification Stop, lubricants, coating aids, surface active agents, brighteners, formalin Kas Ben jar, light scattering agents,
Matting agent, light absorber, ultraviolet absorber, filter dye,
Irradiation dyes, development improvers, matting agents, preservatives (for example, 2-phenoxyethanol), anti-violent agents, etc. are not particularly limited. For example, Product Licensing Magazine, Vol. December) and Research Disclosure (hereinafter referred to as RD) No. 17
643 (December 1978), RD magazine No. 18716.
(November 1976), RD magazine No. 307105 (19)
(November 1989) etc. can be referred to.

The processing composition of the present invention can be used in any color light-sensitive material, but in the present invention, the dry film thickness of the support of the color light-sensitive material and all the constituent layers except the undercoat layer and back layer of the support are used. 2 when the color photosensitive material for photography is
It is preferably 0.0 μm or less in order to achieve the object of the present invention, more preferably 18.0 μm or less, and in the case of a print material, 16.0 μm or less, more preferably 13.0 μm or less. . Outside the preferred thickness range described above, bleach fog and stain after processing due to the developing agent remaining after color development increase. The generation of these bleached fog and stains is due to the green-sensitive photosensitive layer,
As a result, magenta color increase is likely to be larger than other cyan or yellow color increase. Incidentally, it is desirable that the lower limit value in the film thickness regulation is reduced within the range not significantly impairing the performance of the light-sensitive material from the above regulation. The lower limit of the total dry film thickness of the support of the light-sensitive material and the constituent layers of the support except the undercoat layer of the support is 12.0 μm in the case of a color light-sensitive material for photographing.
And 7.0 μ in the case of a print material. In the case of a photographic material, a layer is usually provided between the light-sensitive layer closest to the support and the undercoat layer of the support. The lower limit of the total dry film thickness of this layer (or a plurality of layers) is 1 0.0 μ.
Further, the film thickness may be reduced in either the photosensitive layer or the non-photosensitive layer. Swelling rate in the color light-sensitive material of the present invention [(25 ° C., equilibrium swollen film thickness in H ₂ O −25 ° C., 55
% Of dry total film thickness at RH / 25 ° C., total dry film thickness at 55% RH) × 100] is preferably 50 to 200%, and 70 to
150% is more preferable. If the swelling ratio deviates from the above value, the amount of the color developing agent remaining becomes large, and the film properties such as photographic performance, desilvering property, and film strength are adversely affected. Further, the swelling speed of the color light-sensitive material of the present invention is 90% of the maximum swelling film thickness in the color developing solution (30 ° C., 3 minutes 15 seconds), which is taken as the saturated swelling film thickness until it reaches 1/2 of this. When the time is defined as the swelling speed T1 / 2, T1 / 2 is preferably 15 seconds or less.
More preferably, T1 / 2 is 9 seconds or less.

The silver halide contained in the photographic emulsion layer of the color light-sensitive material used in the present invention may have any silver halide composition. For example, silver chloride, silver bromide, silver chlorobromide,
Examples thereof include silver iodobromide, silver iodochloride and silver iodochlorobromide. In the case of a color light-sensitive material for photography or a color reversal light-sensitive material (for example, color negative film, reversal film, color reversal paper), silver iodobromide, silver iodochloride, containing 0.1 to 30 mol% of silver iodide, Alternatively, silver iodochlorobromide is preferable. Particularly, silver iodobromide containing 1 to 25 mol% of silver iodide is preferable. In the case of a direct positive color light-sensitive material, silver bromide or silver chlorobromide is preferred, and silver chloride is also preferred for rapid processing. In the case of a light-sensitive material for paper, silver chloride or silver chlorobromide is preferable, and particularly silver chloride is 80 mol%.
Above, more preferably 95 mol% or more, most preferably 98 mol% or more silver chlorobromide is preferable.

Various color couplers can be used in the color light-sensitive material applied to the processing according to the present invention. Specific examples thereof are RD No. 17643, VII-C.
To G, the same No. 307105, VII-C to G, JP-A-62-215272, JP-A-3-338.
No. 47, No. 2-333144, European Patent Publication No. 4479.
69A, 482552A and the like. Yellow couplers include, for example, US Pat.
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401,752, No. 4,
No. 248,961, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020 and 1,476,760.
U.S. Pat. Nos. 3,973,968 and 4,31
No. 4,023, No. 4,511,649, No. 5,1
18,599, European Patents 249,473A, 0,447,969, JP-A-63-23145, JP-A-63-123047, JP-A-1-250944, 1-213648 and the like. They can be used in combination as long as they do not impair the effects of the present invention. Particularly preferable yellow couplers are yellow couplers represented by the general formula (Y) described in JP-A-2-139544, page 18, upper left column to page 22, lower left column, Japanese Patent Application No. 3-179042, and European Patent Publication No. 0447969. Acyl couplers characterized by an acyl group described in Japanese Patent No.
The yellow couplers of the general formula (Cp-2) described in No. 203545 and European Patent Publication No. 0446863A2 are mentioned.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure Magazine No. 24220 (6 June 1984)
JP, 60-33552, Research Disclosure No. 24230 (June 1984), JP, 60-43659, 61-72238, 60.
-35730, 55-118034, 60-1
More preferred are those described in US Pat. No. 8,5951, US Pat. No. 4,500,630, US Pat. Particularly preferred magenta couplers are pyrazoloazole-based magenta couplers of the general formula (I) on page 3, lower right column to page 10, lower right column of JP-A-2-139544 and JP-A-2-135944. Examples include 5-pyrazolone magenta couplers represented by the general formula (M-1) from page 17, lower left column to page 21, upper left column. Most preferable are the above-mentioned pyrazoloazole-based magenta couplers. Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat. Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200. No. 2,369,929,
No. 2,801,171, No. 2,772,162
No. 2, No. 2,895,826, No. 3,772,00
No. 2, No. 3,758,308, No. 4,334,0
No. 11, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 0,121,365.
A, 0,249,453A, U.S. Pat.
No. 46,622, No. 4,333, 999, No. 4,
775,616, 4,451,559, 4,427,767, 4,690,889, 4,254,212, 4,296,199,
Those described in JP-A-61-42658 and the like are preferable.
Further, pyrazoloazole couplers described in JP-A-64-553, 64-554, 64-555 and 64-556, and European Patent Publication Nos. 0,488,24.
No. 8 and No. 0,491,197, pyrrolotriazole couplers, European Patent Publication No. 0,456,226A.
Pyrroylimidazole couplers described in JP-A-64-
Pyrazolopyrimidine couplers described in US Pat. No. 4,675,531, US Pat. No. 4,818,672, and JP-A-2-33144.
Imidazole couplers described in JP-A-64-32
260, a cyclic active methylene-based cyan coupler,
The couplers described in JP-A-1-183658, JP-A-2-262655, JP-A-2-85851, and JP-A-3-48243 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A.
No. etc. Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237.
No., British Patent No. 2,125,570, European Patent No. 9
No. 6,570, West German Patent (Publication) No. 3,234,533
Those described in No. 10 are preferable. Couplers that release a photographically useful residue upon coupling can also be used in the present invention. DIR couplers releasing a development inhibitor are disclosed in the above-mentioned RD magazine No. 17643, VII to F, JP-A Nos. 57-151944 and 57-15423.
No. 4, No. 60-184248, No. 63-37346.
U.S. Pat. Nos. 4,248,962 and 4,782.
Those described in No. 012 are preferable. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patents 2,097,140 and 2,131,
188, JP-A-59-157638 and JP-A-59-17.
Those described in No. 0840 are preferable.

Other couplers which can be used in the color photographic element of the present invention include US Pat. No. 4,130,427.
Competitive couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,61
No. 8, etc., multi-equivalent couplers, JP-A-60-1859.
No. 50, No. 62-24252, etc., DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DI.
R redox-releasing redox compounds, EP 17
No. 11449 and No. 2424 of RD magazine, couplers that release dyes that undergo color restoration after separation described in No. 3,302A.
No. 1, JP-A-61-201247 and the like, bleach accelerator releasing couplers, US Pat. No. 4,553,477 and the like, ligand-releasing couplers, JP-A-63-75747.
And the couplers which release the leuco dye described in U.S. Pat. No. 4,774,181 and which release the fluorescent dye described in U.S. Pat. No. 4,774,181. Suitable supports that can be used in the present invention are, for example, Research Disclosure (R) mentioned above.
D) No. 17643, page 28, and No. 18716, page 647, right column to page 648, left column. still,
The present invention can also be applied as a reducing liquid for correcting a silver image composed of halftone dots and / or line images obtained by developing a silver halide light-sensitive material for plate-making after exposure.

[0064]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 On a subbed cellulose triacetate film support,
A multilayer color light-sensitive material sample 101 composed of each layer having the following composition was prepared. (Composition of photosensitive layer) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin hardening agent ExS: Sensitizing dye The coating amount is g / g for silver halide and colloidal silver.
The amount of silver in m ² units, the amount in g / m ² for couplers, additives and gelatin, and the number of moles per mole of silver halide in the same layer for sensitizing dyes. Indicated by.

First layer: antihalation layer Black colloidal silver Silver coverage 0.20 Gelatin 2.20 UV-1 0.11 UV-2 0.20 Cpd-1 4.0 × 10 ^-2 Cpd-2 1. 9 x 10 ^-2 HBS-1 0.30 HBS-2 1.2 x 10 ^-2

Second layer: intermediate layer Fine grain silver iodobromide (AgI 1.0 mol% sphere equivalent diameter 0.07 μm) Silver coating amount 0.15 Gelatin 1.00 ExC-4 6.0 × 10 ⁻² Cpd− 3 2.0 x 10 ^-2

Third layer: low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion A Silver coating amount 0.42 Silver iodobromide emulsion B Silver coating amount 0.40 Gelatin 1.90 ExS-1 6.8 × 10 ^{− 4} mol ExS-2 2.2x10 ^-4 mol ExS-3 6.0x10 ^-5 mol ExC-1 0.65 ExC-3 1.0x10 ^-2 ExC-4 2.3x10 ^-2 HBS-1 0.32

Fourth Layer: Medium Sensitivity Red Sensitive Emulsion Layer Silver Iodobromide Emulsion C Silver Coating Weight 0.85 Gelatin 0.91 ExS-1 4.5 × 10 ^-4 Mol ExS-2 1.5 × 10 ^-4 Mol ExS-3 4.5x10 ^-5 mol ExC-1 0.13 ExC- ² 6.2x10 ^-2 ExC-4 4.0x10 ^-2 ExC-6 3.0x10 ^-2 HBS- 1 0.10

Fifth layer: High-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion D Silver coating amount 1.50 Gelatin 1.20 ExS-1 3.0 × 10 ⁻⁴ mol ExS-2 9.0 × 10 ⁻⁵ Mol ExS-3 3.0 × 10 ⁻⁵ mol ExC-2 8.5 × 10 ⁻² ExC-5 3.6 × 10 ⁻² ExC-6 1.0 × 10 ⁻² ExC-7 3.7 × 10 ^-2 HBS-1 0.12 HBS-2 0.12

Sixth layer: Intermediate layer Gelatin 1.00 Cpd-4 8.0 × 10 ^-2 HBS-1 8.0 × 10 ^-2

Seventh layer: low-sensitivity green emulsion layer Silver iodobromide emulsion E Silver coating amount 0.28 Silver iodobromide emulsion F Silver coating amount 0.16 Gelatin 1.20 ExS-4 7.5 × 10 ^{− 4} mol ExS-5 3.0x10 ^-4 mol ExS-6 1.5x10 ^-4 mol ExM-1 0.50 ExM-2 0.10 ExM-5 3.5x10 ^-2 HBS-10 .20 HBS-3 3.0 × 10 ^-2

Eighth layer: Medium-speed green emulsion layer Silver iodobromide emulsion G Silver coating amount 0.57 Gelatin 0.45 ExS-4 5.2 × 10 ⁻⁴ mol ExS-5 2.1 × 10 ⁻⁴ Mol ExS-6 1.1x10 ^-4 mol ExM-1 0.12 ExM-2 7.1x10 ^-3 ExM-3 3.5x10 ^-2 HBS-1 0.15 HBS-3 1.0 × 10 ^-2

Ninth layer: intermediate layer gelatin 0.50 HBS-1 2.0 × 10 ^-2

10th layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion H Silver coating amount 1.30 Gelatin 1.20 ExS-4 3.0 × 10 ⁻⁴ mol ExS-5 1.2 × 10 ⁻⁴ Mol ExS-6 1.2x10 ^-4 mol ExM-4 5.8x10 ^-2 ExM-6 5.0x10 ^-3 ExC- ² 4.5x10 ^-3 Cpd-5 1.0x10 ^-2 HBS-1 0.25

Eleventh layer: Yellow filter layer Gelatin 0.50 Cpd-6 5.2 × 10 ^-2 HBS-1 0.12

Twelfth layer: intermediate layer Gelatin 0.45 Cpd-3 0.10.

Thirteenth layer: Low-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion I Silver coating amount 0.20 Gelatin 1.00 ExS-7 3.0 × 10 ⁻⁴ mol ExY-1 0.60 ExY-22 .3 × 10 ^-2 HBS-1 0.15

14th layer: Medium sensitivity blue emulsion layer Silver iodobromide emulsion J Silver coating amount 0.19 Gelatin 0.35 ExS-7 3.0 × 10 ^-4 mol ExY-1 0.22 HBS-17 0.0 × 10 ^-2

Fifteenth layer: intermediate layer Fine grain silver iodobromide (AgI 2 mol%, uniform AgI type, spherical equivalent diameter 0.13 μm) Silver coating amount 0.20 Gelatin 0.36

16th layer: High-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion K Silver coating amount 1.55 Gelatin 1.00 ExS-8 2.2 × 10 ⁻⁴ mol ExY-1 0.21 HBS-17 0.0 × 10 ^-2

17th layer: 1st protective layer Gelatin 1.80 UV-1 0.13 UV-2 0.21 HBS-1 1.0 × 10 ^-2 HBS-2 1.0 × 10 ^-2

Eighteenth layer: Second protective layer Fine particle silver chloride (sphere equivalent diameter 0.07 μm) Silver coating amount 0.36 Gelatin 0.70 B-1 (diameter 1.5 μm) 2.0 × 10 ^-2 B- 2 (diameter 1.5 μm) 0.15 B-3 3.0 × 10 ^-2 W-1 2.0 × 10 ^-2 H-1 0.35 Cpd-7 1.00

In addition to the above, the samples thus prepared were
1,2-Benzisothiazolin-3-one (200 ppm average for gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm) and 2-phenoxyethanol (about 10,000 ppm) were added. Furthermore, B-
4 to B-6, W-2, W-3, F-1 to F-1
5, iron salt, lead salt, gold salt, platinum salt, iridium salt, rhodium salt and palladium salt are contained.

[0084]

[Table 1]

In Table 1, (1) Each emulsion was reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Each emulsion was subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the example of JP-A-3-237450. There is. (3) Low molecular weight gelatin was used for the preparation of tabular grains according to the example of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure using a high voltage electron microscope.

[0086]

[Chemical 14]

[0087]

[Chemical 15]

[0088]

[Chemical 16]

[0089]

[Chemical 17]

[0090]

[Chemical 18]

[0091]

[Chemical 19]

[0092]

[Chemical 20]

[0093]

[Chemical 21]

[0094]

[Chemical formula 22]

[0095]

[Chemical formula 23]

[0096]

[Chemical formula 24]

[0097]

[Chemical 25]

[0098]

[Chemical formula 26]

[0099]

[Chemical 27]

The multi-layer color light-sensitive material 101 produced had a thickness of 35.
mm width, cut and processed, white light (light source color temperature 4800 °
The wedge exposure of K) was applied, and processing was performed using a cine type automatic processor in the processing steps shown below. However, the samples for which the performance was evaluated were processed after the samples which had been subjected to imagewise exposure until the cumulative replenishment amount of the color developing solution became three times the volume of the mother liquor tank. The conditions for aeration of the bleaching solution at this time were such that 200 ml / min was foamed from the piping part having a large number of 0.2 mmφ pores provided at the bottom of the bleaching solution tank.

Treatment Process Process Treatment time Treatment time Replenishment amount ^* Tank capacity Color development 3 minutes 15 seconds 37.8 ℃ 23ml 10 liters Bleach 3 minutes 38.0 ℃ 5ml 5 liters Water wash 30 seconds 38.0 ℃ 30ml 5 liters Fixed 1 minute 40 seconds 38.0 ℃ 30ml 10 liters Washed with water (1) 30 seconds 38.0 ℃ -5 liters Washed with water (2) 20 seconds 38.0 ℃ 30ml 5 liters Stabilized 20 seconds 38.0 ℃ 20ml 5 liters Dry 1 minute 55 ℃ * Replenishment amount is 35ml width Amount of permeation Washing method from (2) to (1) Countercurrent method The amount of developer brought into the bleaching process and the amount of fixer brought into the washing process are per 1 m length of 35 mm wide photosensitive material. It was 2.5 ml and 2.0 ml. The crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.9 Potassium carbonate 30.0 30.0 Potassium bromide 1.4 0.4 Potassium iodide 1.5 mg -Hydroxylamine sulfate 2.4 3.6 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 6.4 Add water to 1000 ml 1000 ml pH 10.05 10.10

(Bleaching solution) Mother liquor Replenishing solution Iron nitrate nonahydrate 0.15 mol 0.23 mol Chelating compound (described in Table 2) 0.16 mol 0.24 mol Sodium bromide 0.3 mol 0.45 mol Sodium nitrate 0.2 mol 0.30 mol Acetic acid 0.50 mol Add 0.75 mol water 1000ml 1000ml pH 4.5 4.0 (The chelate compound here constitutes ferric sodium salt of organic acid which becomes bleaching agent)

(Fixer) Common mother liquor and replenisher (g) Ethylenediaminetetraacetic acid diammonium salt 1.7 Ammonium sulfite 14.0 Ammonium thiosulfate aqueous solution (700 g / liter) 260.0 ml Water was added 1000 ml pH 7.0

(Washing water during bleaching and fixing and washing water after fixing) Mother liquor and replenisher common tap water is H type strong acid cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type. Strongly basic anion exchange resin (the same Amberlite IRA-4
00) packed in a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then 20 mg of sodium diisocyanurate dichloride /
L and 150 mg / L of sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizer) Mother liquor and replenisher (g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0 .05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1000 ml pH 8.5

With respect to the multilayer color light-sensitive material sample 101 subjected to the above processing, the amount of residual silver in the highest color density portion was measured by fluorescent X-ray analysis. The results are shown in Table 2. Further, Dmin values measured with green light (G light) were read for these photosensitive material samples 101 obtained by processing.
Next, as the standard bleaching solution without bleaching fog, the following processing solution formulation was changed, the bleaching processing time was 390 seconds, the processing temperature was 38 ° C, the replenisher solution amount was 25 ml / 35 mm width photosensitive material length 1 m, and others were changed. Processing was carried out without doing.

(Standard bleaching solution) Mother liquor (g) Replenishing solution (g) Diethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 11.0 Ammonium bromide 100 120 Ammonium nitrate 30.0 35.0 Ammonia water (27 wt) %) 6.5ml 4.0ml Add water 1000ml 1000ml pH 6.0 5.7

The Dmin value of the processed light-sensitive material obtained by using the above standard bleaching solution was also read. These obtained Dmin values were determined based on the Dmin value of the standard bleaching solution and the difference ΔDmin between the photosensitive materials. The Dmin value obtained using the standard bleaching solution was 0.60. Bleach fog (ΔDmin) = (Dmin of each sample)-(Dmin of standard bleach) The results are shown in Table 2. Next, using the above multilayer color light-sensitive material sample 101, the increase in stain during storage of the processed light-sensitive material was stored under the following conditions, and the Dm of the uncolored portion was stored.
It was calculated from the change in the in concentration before and after storage. Dark / humid heat conditions: 60 ° C., 70% RH, 4-hour stain increase (ΔD) = (Dmin after storage) − (Dmin before storage) The results are also shown in Table 2.

[0110]

[Table 2]

[0111]

[Chemical 28]

From the results shown in Table 2, the metal chelate compound of the present invention can reduce the amount of residual silver as compared with the metal chelate compound of the comparative chelate compound, and at the same time, has an excellent effect on bleaching fog and stain on storing a color image after processing. You can see that.

Example 2 Sample 103 described in JP-A-4-145433 was processed as follows. (Color developer) Water 600 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 2.0 g Potassium bromide 0.015 g Potassium chloride 3.1 g Triethanolamine 10.0 g Potassium carbonate 27 g Optical brightener (WHITEX 4B, manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g Diethylhydroxylamine 4.2 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g Water was added. 1000 ml pH (25 ° C) 10.05

(Bleach-fixing solution) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Iron chloride 0.50 mol Chelate compound (described in Table 3) 0.55 mol Ammonium bromide 40 g Water 1000 ml pH ( 25 ° C.) 6.8 (Here, the chelate compound constitutes a ferric ammonium salt of an organic acid that serves as a bleaching agent.)

(Rinse solution) Ion-exchanged water (calcium,
Magnesium is 3ppm or less.) Further, the samples that are uniformly exposed so that the gray concentration becomes 1.5 are processed in the same manner as above, and the amount of silver remaining in the highest concentration part of these samples is measured by the fluorescent X-ray method. It was quantified. The results are shown in Table 3.

[0116]

[Table 3]

From the above results, it was found that when the metal chelate compound of the present invention was used, the amount of residual silver was smaller than that of the metal chelate compound of Comparative Compound A. Example 3 302 as defined in the OECD Chemicals Testing Guidelines
The results of the biodegradability test based on the B modified Zahn-Wellens method are shown in Table 4.

[0118]

[Table 4]

From the above results, it was confirmed that the metal chelate compound of the present invention is excellent in biodegradability.

[0120]

INDUSTRIAL APPLICABILITY The metal chelate compound of the present invention in the practice of the present invention is a compound having biodegradability and contributes to environmental protection. The occurrence of stains is small, rapid processing with excellent desilvering property is possible, and there is little fluctuation in processing performance before and after running.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 12, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

[0014]

[Chemical 3]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

[0018]

[Chemical 5]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

Examples of the compound forming the chelate bleaching agent include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-hydroxyethyl) -N, N ', N'-triacetic acid, and 1,2-diamino. Propane tetraacetic acid, 1,3-diaminopropane tetraacetic acid, nitrilotriacetic acid, cyclohexanediamine tetraacetic acid, iminodiacetic acid, dihydroxyethylglycine, ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine tetrapropionic acid, phenylenediamine tetra Acetic acid, 1,3-diaminopropanol-N, N,
N ', N'-tetramethylenephosphonic acid, ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid, 1,3
-Propylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, nitrilodiacetic acid monopropionic acid, nitrilomonoacetic acid dipropionic acid, 2-hydroxy-3-aminopropionic acid-N, N-diacetic acid, serine -N, N-
Diacetic acid, 2-methyl-serine-N, N-diacetic acid, 2-hydroxymethyl-serine-N, N-diacetic acid, hydroxyethyliminodiacetic acid, methyliminodiacetic acid, N- (2-
(Acetamido) -iminodiacetic acid, nitrilotripropionic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,4-diaminobutanetetraacetic acid, 2-methyl-1,3-diaminopropanetetraacetic acid, 2-dimethyl-
In addition to 1,3-diaminopropanetetraacetic acid, citric acid and alkali metal salts (for example, lithium salt, sodium salt, potassium salt) and ammonium salt thereof, JP-A-63-80256 and 63-97952.
No. 63-97953, No. 63-97954, JP-A No. 1-393740, No. 3-216650, and No. 3-.
180842, JP-A-4-73645 and JP-A-4-73.
No. 647, No. 4-127145, No. 4-134450.
No. 4-174432, European Patent Publication No. 43000.
The bleaching agents described in 0A1 and West German Laid-Open Patent No. 3912551 can also be mentioned, but the bleaching agents are not limited thereto.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

The bleaching solution or bleach-fixing solution of the present invention has a pH of 2.0 to 8.0, preferably 3.0 to 7.5. When bleaching or bleach-fixing is carried out immediately after color development in a photographic light-sensitive material, the pH of the solution should be 7.0 or less, preferably 6.4 or less in order to suppress bleaching fog.
Particularly in the case of a bleaching solution, 3.0 to 5.0 is preferable. pH
When it is 2.0 or less, the metal chelate of the present invention tends to be unstable, and the pH is preferably 2.0 to 6.4. For color print materials, a pH range of 3-7 is preferred. As the pH buffer for this purpose, any one can be used as long as it is difficult to be oxidized by the bleaching agent and has a buffering action in the above pH range. For example, acetic acid, glycolic acid, lactic acid, propionic acid, butyric acid, malic acid, chloroacetic acid, levulinic acid, ureidopropionic acid, formic acid, monobromoacetic acid, monochloropropionic acid, pyrivic acid, acrylic acid, isobutyric acid, pivalic acid, aminobutyric acid. , Valeric acid, isovaleric acid, asparagine, alanine, arginine, ethionine, glucine, glutamine, cysteine, serine,
Methionine, leucine, histidine, benzoic acid, chlorobenzoic acid, hydroxybenzoic acid, nicotinic acid, oxalic acid, malonic acid, succinic acid, tartaric acid, maleic acid, fumaric acid, oxaloic acid, glutaric acid, adipic acid, aspartic acid, glutamic acid , Cystine, ascorbic acid, phthalic acid, terephthalic acid, and other organic acids; pyridine, dimethylpyrazole, 2-methyl-o-oxazoline, aminoacetonitrile, imidazole, and other organic bases. A plurality of these buffers may be used in combination. In the present invention, an organic acid having a pKa of 2.0 to 5.5 is preferable, and acetic acid, glycolic acid or a combination of acetic acid and glycolic acid is particularly preferable. These organic acids can also be used as alkali metal salts (for example, lithium salt, sodium salt, potassium salt) and ammonium salt. The amount of these buffers used is appropriately 3.0 mol or less, preferably 0.1 to 2.0 mol, per liter of the processing solution having a bleaching ability.
It is more preferably 0.2 to 1.8 mol, and particularly preferably 0.4 to 1.5 mol. In order to adjust the pH of the processing solution having a bleaching ability to the above range, the above and an acid and an alkali agent (for example, aqueous ammonia, KOH, NaOH, potassium carbonate, sodium carbonate, imidazole, monoethanolamine, diethanolamine) are used in combination. May be. Of these, aqueous ammonia, KOH, NaOH, potassium carbonate and sodium carbonate are preferred.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

[Correction content]

A preservative is added to the bleach-fixing solution or the fixing solution,
It is also possible to enhance the stability of the liquid over time. In the case of a bleach-fixing solution or a fixing solution containing thiosulfate, sulfite as a preservative, and / or bisulfite adduct of hydroxylamine, hydrazine, aldehyde (for example, bisulfite adduct of acetaldehyde, particularly preferred) The bisulfite adduct of aromatic aldehyde described in JP-A 1-298935) is effective. Also, JP-A-62-14304
It is also preferable to use the sulfinic acid compound described in No. 8.
It is also preferable to add a buffer to the bleach-fixing solution and the fixing solution in order to keep the pH of the solution constant. For example, phosphates, imidazoles such as imidazole, 1-methyl-imidazole, 2-methyl-imidazole, 1-ethyl-imidazole, triethanolamine,
Examples thereof include N-allylmorpholine and N-benzoylpiperazine.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

Further, by adding various chelating agents to the fixing solution, it is possible to conceal the iron ions brought in from the bleaching solution and improve the stability of the solution. Such a preferable chelating agent is 1-hydroxyethylidene-
1,1-diphosphonic acid, nitrilotrimethylenephosphonic acid, 2-hydroxy-1,3-diaminopropanetetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-hydroxyethyl) -N, N ′, N ′ -Triacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid Acetic acid,
Ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1,3-diaminopropanol-NN,
N ', N'-tetramethylenephosphonic acid, ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid, 1,3
-Propanediamine, N, N, N ', N'-tetramethylenephosphonic acid, serine-N, N-diacetic acid, 2-methyl-serine-N, N-diacetic acid, 2-hydroxymethyl-serine-N, N-diacetic acid, hydroxyethyliminodiacetic acid, methyliminodiacetic acid, N- (2-acetamido) -iminodiacetic acid, nitrilotripropionic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,4-diaminobutanetetraacetic acid, 2 -Methyl-1,3-diaminopropanetetraacetic acid, 2-dimethyl-1,3-diaminopropanetetraacetic acid, alanine, tartaric acid, hydrazidediacetic acid, N-
Examples thereof include hydroxy-imino dipropionic acid and alkali metal salts (for example, lithium salt, sodium salt, potassium salt) and ammonium salt thereof.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0057

[Correction method] Change

[Correction content]

Examples of the light-sensitive material applicable to the processing of the present invention include a color negative film, a color reversal film, a color paper, a color reversal paper, a direct positive color light-sensitive material, a motion picture color negative film and a motion picture color positive film. Japanese Patent Laid-Open No. 3-33847
No. 3-293662, No. 4-130432 and the like. Further, the type of silver halide used in the support of the light-sensitive material of the present invention; coating method; silver halide emulsion layer, surface protective layer (eg, silver iodobromide, silver iodochlorobromide, silver bromide). , Silver chlorobromide, silver chloride), its grain shape (eg, cubic, tabular, spherical), its grain size, its volatility, its crystalline structure (eg, core / shell structure,
Multi-phase structure, homogeneous phase structure), its manufacturing method (eg, single jet method, double jet method), binder (eg, gelatin), hardener, antifoggant, metal doping agent, silver halide solvent, thickener , Emulsion precipitation agents, dimensional stabilizers, anti-adhesion agents, stabilizers, stain inhibitors, dye image stabilizers, stain inhibitors, chemical sensitizers, spectral sensitizers, sensitivity enhancers, supersensitizers, Nucleating agent, coupler (for example, yellow coupler of piparoylacetanilide type or benzoylacetanilide type, magenta coupler of 5-pyrazolone type or pyrazoloazole type, cyan coupler of phenol type or naphthol type, DIR coupler, bleach accelerator releasing type Couplers, competitive couplers, colored couplers), coupler dispersion methods (for example, oil-in-water dispersion method using a high boiling point solvent), plasticizers, electrification Stop, lubricants, coating aids, surface active agents, brighteners, formalin scavengers, light scattering agents,
Matting agent, light absorber, ultraviolet absorber, filter dye,
Irradiation dyes, development improvers, matting agents, preservatives (for example, 2-phenoxyethanol), anti-violent agents, etc. are not particularly limited. For example, Product Licensing Magazine, Vol. December) and Research Disclosure (hereinafter referred to as RD) No. 17
643 (December 1978), RD magazine No. 18716.
(November 1976), RD magazine No. 307105 (19)
(November 1989) etc. can be referred to.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0112

[Correction method] Change

[Correction content]

From the results shown in Table 2, the metal chelate compound of the present invention can reduce the amount of residual silver as compared with the metal chelate compound of the comparative chelate compound, and at the same time, exhibits an excellent effect on bleaching fog and stain on storing a color image after processing. You can see that. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] February 3, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0101

[Correction method] Change

[Correction content]

Treatment Process Process Treatment time Treatment time Replenishment amount ^* Tank capacity Color development 3 minutes 15 seconds 37.8 ℃ 23ml 10 liters Bleach 3 minutes 38.0 ℃ 5ml 5 liters Water wash 30 seconds 38.0 ℃ 30ml 5 liters Fixed 1 minute 40 seconds 38.0 ℃ 30ml 10 liters Water wash (1) 30 seconds 38.0 ℃ -5 liters Water wash (2) 20 seconds 38.0 ℃ 30ml 5 liters Stabilized 20 seconds 38.0 ℃ 20ml 5 liters Dry 1 minute 55 ℃ * Replenishment amount is 35mm width 1m length Washing in countercurrent method from (2) to (1) The amount of developing solution brought into the bleaching process and the amount of fixing solution brought into the washing process are per 1m length of 35mm wide photosensitive material. They were 2.5 ml and 2.0 ml, respectively. The crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0103

[Correction method] Change

[Correction content]

(Bleaching solution) Mother liquor Replenishing solution Iron nitrate nonahydrate 0.15 mol 0.23 mol Chelating compound (described in Table 2) 0.16 mol 0.24 mol Sodium bromide 0.3 mol 0.45 mol Sodium nitrate 0.2 mol 0.30 mol Acetic acid 0.50 mol 0.75 mol Water added 1000 ml 1000 ml pH (adjusted by adding NaOH) 4.5 4.0 (where the chelate compound constitutes the ferric acid sodium salt of the organic acid that acts as a bleaching agent)

Claims (4)

[Claims] 1. A compound represented by the following general formula (I) or a salt thereof: Fe (III), Mn (III), Co (III), R
h (II), Rh (III), Au (II), Au (III) or C
A processing composition for a silver halide photographic light-sensitive material, comprising at least one e (IV) chelate compound. General formula (I) (In the formula, R ¹ and R ² represent a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group. L ₁ , L ₂ , L ₃ and L ₄
Each represents an alkylene group. W represents a linking group containing an alkylene group, an arylene group and / or a divalent heterocyclic group. n represents 0 or 1. A ₁ , A ₂ , A ₃ and A ₄
Each represents a carboxy group, a phosphono group, a sulfo group or a hydroxy group. ) 2. An imagewise exposed silver halide photographic light-sensitive material comprising a compound represented by the general formula (I) according to claim 1 or a salt thereof of Fe (III), Mn (III) and Co (III). , R
h (II), Rh (III), Au (II), Au (III) or C
A processing method for a silver halide photographic light-sensitive material, which comprises processing with a processing solution containing at least one e (IV) chelate compound. 3. Fe (III), Mn (III), Co of the compound represented by the general formula (I) according to claim 1 or a salt thereof.
(III), Rh (II), Rh (III), Au (II), Au
A processing composition having a bleaching ability for a silver halide color photographic light-sensitive material, comprising at least one of (III) or Ce (IV) chelate compounds as a bleaching agent. 4. A method of treating an imagewise exposed silver halide color photographic light-sensitive material with a processing solution having a bleaching ability containing a bleaching agent after color development, wherein the bleaching agent is represented by the general formula of claim 1. Fe (III), Mn (III), Co (III), Rh (II) of the compound represented by (I) or a salt thereof,
A method for processing a silver halide color photographic light-sensitive material, which is at least one of Rh (III), Au (II), Au (III) and Ce (IV) chelate compounds.