JPH07114162A - Photographic processing composition and processing method - Google Patents

Abstract

PURPOSE:To improve desilverability, bleaching fog, aging stain and fog due to contaminants. CONSTITUTION:This photographic processing compsn. contains an iron (III) chelate compd. of a compd. represented by the formula, wherein R1 is H or a substituent each of X1-X3 is H or -L1-A, each of L1-L7 is, e.g. alkylene, each of A and A1-A3 is, e.g. -COOM and M is H or a cation.

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 which is excellent in environmental protection and a processing method using the same. In particular, the present invention relates to a processing composition having a bleaching ability for a silver halide color photographic light-sensitive material containing a bleaching agent which is excellent in biodegradability and excellent in bleaching ability even at a dilute concentration, 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 exposed and then processed by processing steps such as black-and-white development, fixing and washing with water to obtain 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 edi
tion) (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 solution 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 not biodegradable. . In recent years, from the viewpoint of environmental protection, there has been a demand for detoxifying photographic processing waste liquid generated from these photographic processings, and particularly for a processing composition that is easily biodegradable. Is being studied.

As a bleaching agent having biodegradability, N-
The ferric iron complex salt of (2-carboxymethoxyphenyl) iminodiacetic acid is described in West German Patent Publication No. 3912551, and the ferric iron complex salt of β-alanine diacetic acid or glycine dipropionic acid is disclosed in European Patent Publication No. 430000A and ethylenediamine disuccinic acid. Ferric acid complex salts of acids are disclosed in JP-A-5-72695. 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, compared to the initial stage of continuous processing,
It was found that there are problems that the desilvering property is lowered, deterioration of bleaching fog is caused, fog is generated in an unexposed area due to mixing of a bleaching solution into a color developing solution, and stain prevention is insufficient. For these color processing, a small automatic developing machine called a minilab has recently been provided with a rapid processing service to customers, and in addition to quick bleaching, stability of these performances in continuous processing 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 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. A seventh object of the present invention is to provide a processing composition and a processing method using the same which can stably maintain the performance with little influence on photographic properties even when a bleaching solution is mixed in the developing solution.

[0006]

The above object was achieved by the following method. That is, (1) Fe (III), Mn (III), Co (III), Rh (II), R of a compound represented by the following general formula (I) or a salt thereof:
A processing composition for a silver halide photographic light-sensitive material containing an h (III), Au (II), Au (III) or Ce (IV) chelate compound, and a processing method using the same. General formula (I)

[0007]

[Chemical 2]

(Where R₁Represents a hydrogen atom or a substituent
You X₁, X₂And X₃Is a hydrogen atom or -L₁
Represents -A. L₁, L₂, L₃, L_Four, L_Five, L₆Over
And L ₇Are divalent aliphatic groups, divalent aromatic groups or
It represents a divalent linking group of those combinations. A,
A₁, A₂And A₃Are -COOM, -OM,-, respectively.
SO₃M or -PO (OM)₂Represents, and M is a hydrogen atom
Or represents a cation. )

First, the compound represented by formula (I) will be described in detail below. In the formula, the substituent represented by R ₁ is an alkyl group (preferably having 1 to 20 carbon atoms,
More preferably 1-4. For example, methyl, ethyl, iso
-Propyl), aralkyl group, (preferably having 7 to 7 carbon atoms)
23, more preferably 7 to 13. For example, phenylmethyl), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 4 carbon atoms, for example, allyl), an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 4 carbon atoms, such as methoxy and ethoxy). , An aryl group (preferably having 6 to 20 carbon atoms, more preferably 6 to 13 carbon atoms, such as phenyl and p-methylphenyl), an acylamino group (preferably having 1 to 20 carbon atoms, more preferably 2 to 5 carbon atoms, such as acetylamino). , A sulfonylamino group (preferably having 1 to 20 carbon atoms, for example, methanesulfonylamino), a ureido group (preferably having 2 to 20 carbon atoms, such as methylureido), an alkoxycarbonylamino group, (preferably having 2 to 20 carbon atoms, for example. Methoxycarbonylamino), an aryloxy group (preferably having 6 to 20 carbon atoms. Luoxy), a sulfamoyl group (preferably having 0 to 20 carbon atoms, for example, methylsulfamoyl), a carbamoyl group (preferably having 1 to 20 carbon atoms, for example, carbamoyl and methylcarbamoyl), a mercapto group, an alkylthio group (preferably having 1 carbon atom). To 20, for example, methylthio, carboxylmethylthio), arylthio group (preferably having 6 to 20 carbon atoms, for example, phenylthio), sulfonyl group (preferably having 1 to 20 carbon atoms, for example, methanesulfonyl), sulfinyl group (preferably having 1 to carbon atoms). 20.
For example, methanesulfinyl), aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, for example, phenoxycarbonylamino), hydroxy group, cyano group, sulfo group, carboxyl group, phosphono group, aryloxycarbonyl group (preferably having 7 carbon atoms). -20. For example, phenyloxycarbonyl), an acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 7, for example, acetyl, benzoyl), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 2 carbon atoms). 5. For example, methoxycarbonyl, an acyloxy group (preferably having 1 to 2 carbon atoms)
0. Examples thereof include acetoxy), nitro group, hydroxamic acid group, amino group, and heterocyclic group. Preferred as the substituent are an alkyl group, an alkoxy group, a sulfinyl group, a hydroxy group, a cyano group, a sulfo group, a carboxyl group, a phosphono group, an acyl group and a nitro group,
An alkyl group, an alkoxy group and a hydroxy group are particularly preferable. Moreover, these substituents may be further substituted.

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L
_The divalent linking group represented by ₇ is a divalent aliphatic group, a divalent aromatic group, or a divalent linking group of a combination thereof. As the divalent aliphatic group, a linear, branched or cyclic alkylene group (preferably having 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), an alkynylene group (preferably having 2 to 6 carbon atoms) ) Is mentioned. Also,
These divalent aliphatic groups may have a substituent,
For example, those mentioned as the substituents represented by R ₁ can be applied. ) The substituent is preferably a hydroxy group or a carboxyl group.

The divalent aliphatic group is preferably an alkylene group, more preferably a linear alkylene group. The linear alkylene group is particularly preferably a methylene group or an ethylene group.

Examples of the divalent aromatic group include a divalent aromatic hydrocarbon group (arylene group) and a divalent aromatic heterocyclic group. Divalent aromatic hydrocarbon group (arylene group)
May be monocyclic or bicyclic, and preferably has 6 to 20 carbon atoms.
And examples thereof include a phenylene group and a naphthylene group. The divalent aromatic heterocyclic group is a 3- to 10-membered group containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom, and even if it is a single ring, it is further combined with another aromatic ring or heterocycle. You may form a condensed ring. The divalent aromatic heterocyclic group is preferably a 5- or 6-membered one containing at least one nitrogen atom as a hetero atom, and examples thereof include the following.

[0013]

[Chemical 3]

The divalent aromatic group is preferably an arylene group (preferably having 6 to 20 carbon atoms), more preferably a phenylene group or a naphthylene group, and particularly preferably a phenylene group. The divalent aromatic group may have a substituent, and for example, those exemplified as the substituent represented by R ₁ can be applied.

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L
₇ may be a combination of a divalent aliphatic group and a divalent aromatic group, and examples thereof include the following.

[0016]

[Chemical 4]

The divalent linking group represented by L ₂ , L ₃ and L ₄ is preferably a divalent aliphatic group, and L ₁ ,
L ₅ , L ₆ and L ₇ are preferably a divalent aliphatic group or a divalent aromatic. More preferably L ₁ , L ₂ , L ₃ ,
The divalent linking group represented by L ₄ , L ₅ , L ₆ and L ₇ is a divalent aliphatic group.

A, A ₁ , A ₂ and A ₃ are each -C
OOM, -OM, represents a -SO ₃ M or -PO (OM) _2. A, A ₁ , A ₂ and A ₃ may be the same or different. A, A ₁ , A ₂ and A ₃
Of the groups represented by, preferably —COOM, —OM
And more preferably -COOM.

M represents a hydrogen atom or a cation, and as the cation, ammonium (for example, ammonium,
Tetraethylammonium), alkali metals (eg lithium, potassium, sodium), pyridinium and the like can be mentioned. The compound represented by the general formula (I) is an ammonium salt (for example, ammonium salt, tetraethylammonium salt), an alkali metal salt (for example, lithium salt, sodium salt, potassium salt) or an acidic salt (for example, hydrochloride, sulfate, oxalate). Acid salt).

When the compound is isolated, the number of ammonium, alkali metal or acid contained in the compound is preferably 0 to 6 (eg monosodium salt, disodium salt, trisodium salt).

Of the compounds represented by the general formula (I), compounds in which X ₁ , X ₂ and X ₃ are hydrogen atoms are preferable. Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0022]

[Chemical 5]

[0023]

[Chemical 6]

[0024]

[Chemical 7]

[0025]

[Chemical 8]

[0026]

[Chemical 9]

The compound represented by the above general formula (I) is
For example, it can be synthesized according to the scheme shown below.

[0028]

[Chemical 10]

Triamine derivative (1) and halogen-substituted alkylenecarboxylic acid (other than --OM, --SO ₃ M, --P)
A secondary amine-substituted triamine derivative (2) can be synthesized by reacting with O (OM) ₂ ), and by treatment with an acid (for example, hydrochloric acid, sulfuric acid, etc.),
The H-form (3) of the desired compound (carboxylic acid, alcohol, sulfonic acid, phosphonic acid) can be obtained. Further, when further substitution is desired, the target product (4) can be obtained by adding a halogen-substituted alkylenecarboxylic acid or the like in an excess amount as compared with the above case. However, it is generally desirable to set the reaction temperature higher than that during the synthesis of the secondary amine (2), and to extend the reaction time.

The reaction was monitored by NMR, and if the raw material (halogen-substituted alkylenecarboxylic acid, etc.) disappeared before the completion of the reaction, additional reaction was carried out at any time. Another synthetic method is known as a method of introducing methylenecarboxylic acid. The Strecker method can also be used (synthesis method of (5)).

Next, representative synthetic examples of the compounds of the present invention are shown below. The compound of the present invention is described in “Bretan of the Chemical Society of Japan”, Vol. 50, 34.
Pages 13-3414 (1977) (BULLETIN OF THECHE
MICAL SOCIETY OF JAPAN VOL.50 3413-341
4 (1977)) 2- (aminomethyl) -2-methyl-1,3-propanediamine-N, N ′, N ″ -triacetic acid (2- (aminomethyl) -2-methyl
-1,3-propanediamine-N, N ', N "-triaceti
acid), "Buretan of the Chemical Society of Japan," Vol. 41, 838-843 (1968) (BULLETIN OF THE CHEMICAL SOCIETY O
F JAPAN VOL.41 838-843 (1968)) 1,2,3-triaminopropane-N, N, N ',
N ', N ", N" -hexaacetic acid (1,2,3-Triaminopropane-N, N, N',
N ′, N ″, N ″ -hexaacetic acid) can be synthesized by a synthetic method and a method similar thereto.

Synthesis Example 1 Synthesis of Compound 2 1,1,1-tris (hydroxymethyl) ethane 126
g (1.05 mol) and 550 ml of pyridine were placed in a 2-liter three-necked flask, and the internal temperature was cooled to 10 ° C. with an ice bath while stirring well. Benzenesulfonyl chloride 664 g (3.76 mol) was added dropwise thereto over 2 hours and a half. After stirring at room temperature for 24 hours, this reaction solution was slowly added dropwise to a mixed solution of 1 liter of water, 2 liters of methanol and 800 ml of concentrated hydrochloric acid. The white precipitate thus deposited was washed 4 times with water, then with 300 ml of methanol and dried. 556 g (yield 98%) of 1,1,1-tris (benzenesulfonyloxymethyl) ethane was obtained. Next, 500 g (0.925 mol) of the obtained 1,1,1-tris (benzenesulfonyloxymethyl) ethane, 513 g (2.75 mol) of potassium phthalimide and 610 ml of xylene were placed in a three-necked flask and heated in an oil bath at 170 ° C. Heated and stirred. After 3 hours, the solvent was distilled off under reduced pressure and the residue was recrystallized from acetic acid. 261 g of 1,1,1-tris (phthalimidomethyl) ethane (yield 51%) was obtained.

An aqueous solution prepared by dissolving 261 g of the obtained 1,1,1-tris (phthalimidomethyl) ethane and 344 g of potassium hydroxide in 1 liter of water was placed in a three-necked flask and heated under reflux in an oil bath for 2 hours.

By distilling the reaction solution under atmospheric pressure while continuing to add water, 1,1,1-tris (aminomethyl) ethane azeotroped with water was obtained. Concentrated hydrochloric acid is added to the distillate to make pH 1
Adjusted to ~ 2 and concentrated under reduced pressure. Concentration was stopped before drying, and methanol was added to precipitate crystals. After filtration, washing with methanol and drying, 56 g of 1,1,1-tris (aminomethyl) ethane trihydrochloride (yield 48
%) Was obtained.

10.1 g (4.47 × 10 ^-2 mo) of 1,1,1-tris (aminomethyl) ethane trihydrochloride obtained.
l), 16.4 g of sodium chloroacetate (1.41 × 1)
(0 ⁻¹ mol) and 30 ml of water were placed in a three-necked flask, and the mixture was heated and stirred at 50 ° C. in a water bath. The pH was maintained at 9 to 10 while 54 mol (0.27 mol) of a 5N sodium hydroxide aqueous solution was added dropwise to this solution. After reacting for 5 hours, the solution was adjusted to pH 2 by adding concentrated hydrochloric acid, and the volume was about 30 ml.
It was concentrated under reduced pressure until. To this, 100 ml of ethanol was added and left overnight in the refrigerator.

The precipitated crystals were collected by filtration and recrystallized with concentrated hydrochloric acid. 4.7 g (yield 26%) of the target compound 2 was obtained. Melting point 125-130 ° C (decomposition)

Synthesis Example 2 Synthesis of Compound 8 17.8 g (0.20) of 1,2,3-triaminopropane
mol), 94.2 g (1.0 mol) of chloroacetic acid and 70 ml of water were placed in a three-necked flask, and the mixture was heated and stirred at 40 ° C. in a hot water bath for 20 hours while adding a sodium hydroxide aqueous solution and keeping the pH at 9-11. Then, 5 ml of 10N sodium hydroxide aqueous solution was further added, and the mixture was stirred at 50 ° C. for 1 hour. After cooling, 6.8 g (0.1
7 mol) and 43.6 g (0.89 mo) of sodium cyanide
l) was added, and 70 ml of an aqueous solution containing 0.10 mol of formaldehyde was added dropwise over 5 hours while maintaining the temperature at 25 ° C.

Thereafter, about 70 ml of the solvent was distilled off under reduced pressure at 60 ° C., 100 ml of water was added, and 100 ml of water was again distilled off under reduced pressure under the same conditions. After cooling the residue to 25 ° C., 70 ml of an aqueous solution containing 0.10 mol of formaldehyde was slowly added dropwise with stirring. Then, the solvent was distilled off again under reduced pressure at 60 ° C. in an amount of about 70 ml. This operation was repeated 8 times. The total amount of formaldehyde added was 0.80 mol. The reaction solution was adjusted to pH 1 with 6N hydrochloric acid and left in a refrigerator overnight to obtain a white precipitate. This precipitate was collected by filtration and the filtrate was concentrated to obtain a further precipitate. Both precipitates were combined, washed with water and dried under reduced pressure overnight. Target compound 8 71
g (yield 78%) was obtained. Melting point 230 ° C to 233 ° C (decomposition) Other compounds can be similarly synthesized.

The compound represented by the general formula (I) is Fe
(III), Mn (III), Co (III), Rh (II), Rh (II
I), a metal chelate compound formed from a salt of a metal selected from Au (II), A (III) and Ce (IV) (hereinafter sometimes referred to simply as the metal chelate compound of the present invention). By doing so, it has an effect as an oxidizing agent for a silver halide photographic light-sensitive material (in particular, a bleaching agent for a color light-sensitive material). According to a preferred embodiment of the processing composition containing the metal chelate compound of the present invention, a processing solution containing at least the metal chelate compound of the present invention after color development of the imagewise exposed silver halide color photographic light-sensitive material. The developed bleaching of the developed silver is extremely rapid, and there is no remarkable bleaching fog observed in the conventional bleaching agent capable of rapid bleaching. The metal salt constituting the metal chelate compound of the present invention includes Fe (III), Mn (III), Co (III) and Rh (I
I), Rh (III), Au (II), Au (III) and Ce (IV). More preferably Fe (III), Mn (III),
A salt of Ce (IV), particularly a salt of Fe (III) is preferable.

The metal chelate compound of the present invention is a compound represented by the general formula (I) (free acid) and a salt of the metal (for example, ferric sulfate, ferric chloride, ferric nitrate). Salt, ferric ammonium sulfate, ferric phosphate, etc.) may be used by reacting in a solution. Similarly, an ammonium salt or alkali metal salt (for example, a lithium salt, a sodium salt, a potassium salt) of the compound represented by the general formula (I) (free acid) is reacted with a salt of the metal in a solution. You may use it. Further, the metal chelate compound of the present invention may be isolated as a metal chelate compound. The compound (free acid) represented by the general formula (I) is used at a molar ratio of 1.0 or more with respect to the metal ion. This ratio is preferably as large as possible when the stability of the metal chelate compound is low, and is usually used in the range of 1 to 30. Hereinafter, specific examples and synthetic examples of the metal chelate compound of the present invention will be shown. 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. , But is not limited to the following.

[0041]

[Chemical 11]

[0042]

[Chemical 12]

Synthesis Example 3 Synthesis of K-2 Compound 2 (1.0 g, 2.5 × 10 ^-3 mol), 1N sodium hydroxide (7.5 ml, 7.5 × 10 ^-3 mol) and water (10 ml) were placed in a beaker. The mixture was put and stirred well. A solution prepared by dissolving 1.0 g (2.5 × 10 ⁻³ mol) of iron nitrate in 10 ml of water was added dropwise to this solution little by little. The precipitated yellow crystals were collected by filtration and washed with water and acetone. 8. Target compound K-2
1 g (yield 95%) was obtained. Elemental analysis value C ₁₁ H ₁₈ N ₃ FeO ₆ · 1 / 2H ₂ OH% C% N% Calculated value 5.42 37.41 11.90 Measured value 5.21 37.43 12.03

The present invention is characterized by being a bleaching agent in a processing composition having a bleaching ability for a color light-sensitive material, as an oxidizing agent in a photographic processing composition. Regarding other requirements such as materials, A generally applicable material or the like 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 bleach 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, nitritotripropionic acid, ethylenediaminediacetic acid, ethylenediaminedippionic acid, 1,4-diaminobutanetetraacetic acid, 2-methyl-1,3-diaminopropanetetraacetic acid, 2-dimethyl-
In addition to 1,3-diaminopropanetetraacetic acid, citric acid and their alkali metal salts (for example, lithium salt, sodium salt, potassium salt) and ammonium salt, JP-A-63-80256 and 63-97952. No. 63-97953,
63-97954, JP-A-1-93740, 3-216650, 3-
180842, JP-A-4-73645, and JP-A-4-73647
No. 4-127145, No. 4-134450, No. 4-174432, European Patent Publication No. 430000A1.
Examples thereof include, but are not limited to, the bleaching agents described in U.S. Pat. No. 3,912,551.

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 a chloride, a bromide, a rehalogenating agent for accelerating 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 bleaching solution or bleach-fixing solution according to the present invention may further contain a bleaching accelerator, a corrosion inhibitor for preventing the corrosion of the processing bath, a buffering agent 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, pyruvic acid, acrylic acid, isobutyric acid, pivalic acid, aminobutyric acid. , Valeric acid, isovaleric acid, asparagine, alanine, arginine, ethionine, glycine, 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, picolinic acid, organic acids such as salicylic acid, pyridine, dimethylpyrazole, 2-methyl-o
Examples include organic bases such as oxazoline, aminoacetonitrile, and imidazole. A plurality of these buffers may be used in combination. In the present invention, pKa is 2.0 to
5.5 organic acids are preferred, especially acetic acid, glycolic acid,
Malonic acid, succinic acid, maleic acid, fumaric acid, picolinic acid, glutaric acid, adipic acid and combinations of two or more thereof are preferred. These organic acids can also be used as alkali metal salts (for example, lithium salt, sodium salt, potassium salt) and ammonium salt. The total amount of these buffers used is 0.1 per liter of processing solution having bleaching ability.
~ 3.0 mol is suitable, preferably 0.1-2.0.
Mol, 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 bleaching ability to the above range, the above-mentioned acid and alkaline agent (for example, aqueous ammonia, KOH, NaOH,
Potassium carbonate, sodium carbonate, imidazole, monoethanolamine, diethanolamine) may be used in combination. 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 not contained at all. In order to reduce the ammonium ion concentration to 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 treated with a processing solution having a bleaching ability is fixed or bleach-fixed. As the fixing solution or the 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. Although ammonium thiosulfate has been generally used as a fixing agent in the desilvering process,
It may be replaced with other known fixing agents such as mesoionic compounds, thioether compounds, thioureas, large amounts of iodides and hypo. Regarding these, JP-A-60-6
No. 1749, No. 60-147735, No. 64-21444, JP-A-1-2016
59, 1-210951, 2-44355, U.S. Pat.No. 4,378,
No. 424, etc. 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, etc. 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. It is preferably added in the range of 01 to 100 mol%. The amount of the fixing agent is 0.1 to 3.0 mol, preferably 0.5 to 2.0 mol, per liter of the bleach-fixing solution or the fixing solution. The pH of the fixing solution depends on the type of the fixing agent, but is generally 3.0 to 9.0,
Particularly when thiosulfate is used, 5.8 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, 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.

Further, by adding various chelating agents to the fixing solution, it is possible to conceal the iron ions carried 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-N, N,
N ', N'-tetramethylenephosphonic acid, ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid, 1,3
-Propylenediamine-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, nitritotripropionic 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-imino dipropionic acid and alkali metal salts thereof (for example, lithium salt, sodium salt, potassium salt), ammonium salt and the like can be mentioned. The amount of the above chelating agent added is preferably 0.01 to 0.5 mol / liter, more preferably 0.03 to 0.2 mol / liter.

The fixing step can be carried out in the range of 30 ° C to 60 ° C, preferably 35 ° C to 50 ° C. The time of the fixing process is 15 seconds to 2 minutes, preferably 25 seconds to 1 minute 40 seconds for the photographic light-sensitive material, and 8 seconds to 80 seconds, preferably 10 seconds-for the printing light-sensitive material. 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 light-sensitive material for photographing, is preferable, and further preferable. Is preferable in the light-sensitive 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 according to 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.

In the present invention, it is preferable that the agitation of each treatment liquid is strengthened as much as possible so that the effects of the present invention can be more effectively exhibited. As a concrete method for strengthening stirring, JP-A-62-183460, JP-A-62-183461,
The method described in JP-A-3-33847, page 8,
That is, a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material as used in a color negative film processor FP-560B manufactured by Fuji Photo Film Co., Ltd., or a rotating means described in JP-A-62-183461 is used. A method of increasing the stirring effect, and further moving the light-sensitive material (film) while contacting the emulsion surface with the wiper blade provided in the liquid,
Examples include a method of improving the stirring effect by making the emulsion surface turbulent, and a method of increasing the circulation flow rate of the entire processing solution. Of these, the method of colliding the jet stream of the processing liquid is the most preferable, and it is preferable to adopt this method for all the processing tanks.

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 a color photographic material, and 15 ml per m ² of the light-sensitive material in the case of a color print material. 500 m
1, preferably 20 ml to 350 ml. The amount of the bleach replenisher is, in the case of a color photographic material, 10 ml to 1000 ml, preferably 50 ml to 550 ml, per 1 m ^{2 of} the light-sensitive material. In the case of printing materials, it is 15 per 1 m ^{2 of} light-sensitive material.
It is from ml to 500 ml, preferably from 20 ml to 300 ml. The amount of bleach-fix replenisher is 1
200 ml to 3000 ml, preferably 250 ml per m ^2.
˜1300 ml, and in the case of printing materials, ²⁰ ml to 300 ml, preferably 50 ml to ² per 1 m ^{2 of} light-sensitive material.
It is 00 ml. The bleach-fixing solution may be replenished as a single solution, or the bleaching composition and the fixing composition may be separately replenished, 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. In the case of a color photographic material, the amount of the fixing replenisher is 300 ml to 3000 ml, preferably 30 ml per 1 m ^{2 of} the photographic material.
0 ml to 1200 ml, and in the case of printing materials, ²⁰ ml to 300 ml, preferably 50 ml per 1 m ^{2 of} light-sensitive material
~ 200 ml. The replenishing amount of the washing water or the stabilizing solution is 1 to 50 times, preferably 2 to 30 times, and more preferably 2 to 15 times the amount brought in from the previous bath per unit area.

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 Film Processing Manual issued by Fuji Photo Film Co., Ltd., 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 the 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 electrolytic 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 diaphragm and the anode tank and the cathode bath are separated into different baths, and the bleaching solution and the developer and / or the diaphragm are also used. Alternatively, the fixing solution can be regenerated 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- (β-hydroxyethyl) -3-methoxyaniline, etc., as well as European Patent Publication No. 410450 and JP-A No. 4450/1998. Those described in -11255 and the like can also be preferably used. Further, salts of these p-phenylenediamine derivatives with sulfates, hydrochlorides, sulfites, naphthalenedisulfonic acid, p-toluenesulfonic acid, etc. 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 of the black-and-white silver halide light-sensitive material can be contained in the black-and-white first developing solution of the color reversal photographic 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, 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 with water and / or stabilized. 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,
4-270344, 4-313753, 5-
No. 34889 and 5-165178. In particular, azoles such as 1,2,4-triazole and azolylmethylamine and its derivatives such as 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine are used in combination (JP-A-4-359249). No.)
However, the image stability is high and the 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 color negative film for movies, a color positive film for movies, and the like. No. 33847, No. 3-293662
No. 4-130432 and the like. Also,
Support of the light-sensitive material according to the present invention; coating method; types of silver halide used in silver halide emulsion layers, surface protective layers, etc. (eg, silver iodobromide, silver iodochlorobromide, silver bromide, salts) Silver bromide, silver chloride), its grain form (eg cubic, tabular,
Spherical), its particle size, its variation rate, its crystal structure (eg, core / shell structure, multiphase structure, homogeneous phase structure), its manufacturing method (eg, single jet method, double jet method), binder (eg, gelatin) ), Hardening agents, antifoggants, metal doping agents, silver halide solvents, thickeners, emulsion precipitation agents, size stabilizers, anti-adhesion agents, stabilizers, stain inhibitors, dye image stabilizers, stain prevention Agent,
Chemical sensitizers, spectral sensitizers, sensitivity enhancers, supersensitizers, nucleating agents, couplers (for example, pivaloyl acetanilide type or benzoyl acetanilide type yellow couplers, 5
-Pyrazolone type or pyrazoloazole type magenta coupler, phenol type or naphthol type cyan coupler, D
IR couplers, bleach accelerator releasing couplers, competitive couplers, colored couplers), coupler dispersion methods (for example, oil-in-water dispersion method using a high boiling point solvent), plasticizers, antistatic agents, lubricants, coating aids, Surface active agent, whitening agent, formalin scavenger, light scattering agent, matting agent, light absorbing agent,
There are no particular restrictions on UV absorbers, filter dyes, irradiation dyes, development improvers, matting agents, preservatives (eg 2-phenoxyethanol), anti-vibration agents, etc. For example, Product Licensing Magazine (Product Lice
nsing) 92, 107-110 (December 1971)
And Research Disclosure Magazine
losure, RD) No. 17643 (December 1978), RD Magazine No. 18716 (1979 11)
Month), RD magazine No. 307105 (November 1989), etc. can be referred to.

The processing composition of the present invention can be used in any color light-sensitive material. 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 2 in case of color photographic material for photography
In order to achieve the object of the present invention, it is preferably 0.0 μm or less, more preferably 18.0 μm or less, and in the case of a printing material, 16.0 μm or less, more preferably 13.0 μm or less. . Outside the preferred thickness range, 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 the 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., 5
The total dry film thickness at 5% RH / 25 ° C., the total dry film thickness at 55% RH) × 100] is preferably 50 to 200%, and 70
~ 150% is more preferred. If the swelling ratio is out of the above range, the residual amount of the color developing agent will increase, and the photographic performance, the image quality such as desilvering property, and the film physical properties such as film strength will be adversely affected. Furthermore, the swelling speed of the color photographic 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, and reaches a half of this value. 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, and specific examples thereof are RD No. 17643, VII-C to RD.
G, the same No. 307105, the patents described in VII-C to G, JP-A-62-215272, JP-A-3-33847, and JP-A-2-3144.
It is described in European Patent Publication Nos. 447969A and 482552A. Examples of yellow couplers include US Pat.
3,933,501, 4,022,620, 4,326,024,
No. 4,401,752, No. 4,248,961, Japanese Patent Publication No. 58-1073
9, British Patents 1,425,020, 1,476,760, U.S. Patents 3,973,968, 4,314,023, 4,511,
No. 649, No. 5,118,599, European Patent No. 249,473A,
No. 0,447,969, JP-A-63-23145, and 63-123047.
And those described in JP-A Nos. 1-250944 and 1-213648 can be used in combination unless the effects of the present invention are impaired. Particularly preferred 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, JP-A-5-2248, and European Patent Publication No. 0447969. An acylacetamide-based yellow coupler characterized by the acyl group described and JP-A-5-27389.
General formula (Cp-2) described in European Patent Publication No. 0446863A2
The yellow coupler of.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,6 are preferred.
36, U.S. Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (6 June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61
-72238, 60-35730, 55-118034, 60-18595
Those described in US Pat. No. 4,500,630, US Pat. No. 4,540,654, US Pat. No. 4,556,630, and WO88 / 04795 are more preferable. 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-2-139544. 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-based and naphthol-based couplers, and U.S. Pat.Nos. 4,052,212, 4,146,396, and
4,228,233, 4,296,200, 2,369,929,
No. 2,801,171, No. 2,772,162, No. 2,895,826
No. 3, No. 3,772,002, No. 3,758,308, No. 4,33
4,011, 4,327,173, West German Patent Publication 3,329,729
U.S. Pat.Nos. 0,121,365A, 0,249,453A, U.S. Patents 3,446,622, 4,333,999, 4,77.
No. 5,616, No. 4,451,559, No. 4,427,767, No.
4,690,889, 4,254, 212, 4,296,199,
Those described in JP-A-61-42658 and the like are preferable. Further, JP-A 64-553, 64-554, 64-555, 64-5
Pyrazoloazole couplers described in 56, European Patent Publication No. 0,488,248, pyrrolotriazole couplers described in 0,491,197, pyrroloimidazole couplers described in European Patent Publication 0,456,226A, JP-A-64-46753. Pyrazolopyrimidine couplers described, U.S. Pat.
672, imidazole couplers described in JP-A-2-33144, cyclic active methylene type cyan couplers described in JP-A-64-32260, JP-A-1-83658, JP-A-2-262655 and JP-A-2-262655.
The couplers described in 85851 and 3-48243 can also be used.

Typical examples of polymerized dye-forming couplers are US Pat. Nos. 3,451,820, 4,080,211, 4,367,282, 4,409,320 and 4,576,910.
, British Patent 2,102,137, European Patent 341,188A and the like. Examples of couplers in which the color forming dye has an appropriate diffusibility include U.S. Pat.No. 4,366,237 and British Patent No.
Those described in 2,125,570, European Patent 96,570 and West German Patent (Publication) 3,234,533 are preferable. Couplers that release a photographically useful residue upon coupling can also be used in the present invention. DIR releasing a development inhibitor
The couplers include the patents described in RD magazine No. 17643, VII to F, JP-A-57-151944, JP-A-57-154234, and JP-A-57-154234.
60-184248, 63-37346, U.S. Patent 4,248,962,
Those described in JP-A-4,782,012 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,
Those described in JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers which can be used in the color photographic element of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,33.
Multi-equivalent couplers described in No. 8,393 and No. 4,310,618,
DIR described in JP-A-60-185950 and JP-A-62-24252
Redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 17
No. 11449, No. 24241, RD magazine, JP-A-61-2.
Bleach accelerator releasing couplers described in 01247 etc., ligand releasing couplers described in U.S. Pat.
Examples thereof include couplers releasing a fluorescent dye described in US Pat. No. 4,774,181. Suitable supports usable in the present invention are, for example, Research Disclosure (RD) No. 17643, page 28, and No. 1871.
No. 6, page 647, right column to page 648, left column.
The present invention can also be applied as a reducing liquid for correcting a silver image consisting of halftone dots and / or line images obtained by developing a silver halide light-sensitive material for plate making after exposure.

[0070]

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,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition) 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 Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

[0073]

Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A Silver 0.25 Silver iodobromide emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion E Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

6th layer (intermediate layer) Cpd-1 0.10 HBS-1 0.50 gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion C Silver 0.35 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.72

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion D Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExM-2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.89

Ninth layer (high-sensitivity green emulsion layer) Silver iodobromide emulsion E Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.40

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60

11th layer (low-sensitivity blue emulsion layer) Silver iodobromide emulsion C Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 HBS-1 0.28 Gelatin 1.08

Twelfth layer (medium-speed blue-sensitive emulsion layer) Silver iodobromide emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78

Thirteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion F Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86

Fourteenth layer (first protective layer) Silver iodobromide emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt and rhodium salt.

[0088]

[Table 1]

In Table 1, (1) Emulsions A to F were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to F were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope.

[0090]

[Chemical 13]

[0091]

[Chemical 14]

[0092]

[Chemical 15]

[0093]

[Chemical 16]

[0094]

[Chemical 17]

[0095]

[Chemical 18]

[0096]

[Chemical 19]

[0097]

[Chemical 20]

[0098]

[Chemical 21]

[0099]

[Chemical formula 22]

[0100]

[Chemical formula 23]

[0101]

[Chemical formula 24]

[0102]

[Chemical 25]

[0103]

[Chemical formula 26]

[0104]

[Chemical 27]

As described above, the multilayer color light-sensitive material sample 101
Was exposed to light and then processed by the following method using an automatic processor (until the cumulative replenishment amount of the developing solution became three times the tank capacity). (Processing method) Processing temperature Processing temperature Replenishment amount Tank capacity Color development 3 minutes 10 seconds 38 ℃ 20 ml 20 liters Bleaching 3 minutes 00 seconds 38 ℃ 25 ml 40 liters Water washing (1) 15 seconds 24 ℃ (2) (1) 10 liter counter-current piping system Washing with water (2) 15 seconds 24 ℃ 15 ml 10 liters fixed 3 minutes 00 seconds 38 ℃ 15 ml 30 liters Water washing (3) 30 seconds 24 ℃ From (4) ( 3) To 10 liter countercurrent piping system Washing with water (4) 30 seconds 24 ℃ 1200 ml 10 liter Stabilization 30 seconds 38 ℃ 20 ml 10 liter Dry 4 minutes 20 seconds 55 ℃ * Replenishment amount is 35 mm width 1 m length Hit

Next, the composition of the processing liquid will be described. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.3 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.3 Sodium sulfite 4.0 4.9 Potassium carbonate 30.0 39.3 Potassium bromide 1.4 0.25 Potassium iodide 1.5 mg-hydroxyamine sulfate 2.4 3.2 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 6.2 Water was added to 1.0 liter 1.0 liter pH (to potassium hydroxide and sulfuric acid 10.05 10.15

(Bleaching Solution) Tank Solution Replenishing Solution Compounds shown in Table 0.28 mol 0.34 mol Ferric nitrate nonahydrate 0.25 mol 0.30 mol 3-mercapto-1,2,4-triazole 0.03 g 0.08 g bromide Ammonium 140.0 g 160.0 g Ammonium nitrate 30.0 g 35.0 g Ammonia water (27%) 6.5 ml 4.0 ml Water added 1.0 liter 1.0 liter pH (adjusted with ammonia water and nitric acid) 6.0 5.7

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ethylenediaminetetraacetic acid disodium salt 0.5 0.7 Ammonium sulfite 20.0 22.0 Ammonium thiosulfate aqueous solution (700 g / l) 295.0 ml 320.0 ml acetic acid (90%) 3.3 4.0 In addition 1.0 liter 1.0 liter pH (adjusted with aqueous ammonia and acetic acid) 6.7 6.8

(Stabilizing Solution) Tank Solution / Replenishing Solution Common (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 1.0 liter 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 a standard bleaching solution free from bleaching fog, the following processing solution formulation was changed to bleaching processing time of 390 seconds and the processing was performed without changing the other.

(Standard bleaching solution) Mother liquor (g) Replenishing solution (g) Ethylenediaminetetraacetic acid ferric sodium trihydrate 1000.0 120.0 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 processed light-sensitive material obtained by using the above standard bleaching solution was also read with the Dmin value. These obtained Dmin values were determined based on the Dmin value of the standard bleaching solution, and the difference ΔDmin between the light-sensitive materials. The Dmin value obtained using the standard bleaching solution at this time was 0.
It was 60. Bleach fog (ΔDmin) = (Dmin of each sample) −
(Dmin of standard bleaching solution) 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 undeveloped portion D
It was calculated from the change in concentration before and after storage for min. Dark / humid heat conditions: 60 ° C., 70% RH, 4 week increase in stain (ΔD) = (Dmin after storage) − (Dmi before storage
n) The results are also shown in Table 2.

Then, 1 ml of the mother liquor of the bleaching solution was added to 1 liter of the color developing solution to prepare a color developing solution, and the same processing as above was carried out. Concentration of Dmin part at this time and Dmin when processed with a color developing solution which does not mix bleaching solution
The change in the density of each part was determined. Dmin (G) change due to mixing of bleaching solution = (Dmin in sample containing bleaching solution)-(Dmin in sample containing no bleaching solution) The results are also shown in Table 2.

[0114]

[Table 2]

[0115]

[Chemical 28]

From the results of Table 2, the metal chelate compound of the compound represented by the general formula (I) 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 bleach fog and a color image after processing. It can be seen that the stain on storage also shows an excellent effect. Furthermore, it can be seen that the increase in the density of the Dmin portion due to the incorporation of the bleaching solution into the color developing solution is small, which is excellent.

Example 2 Sample 103 described in JP-A-4-145433 was processed as follows. [Processing step] [Temperature] [Time] Color development 38 ° C 45 seconds Bleach fixing 35 ° C 25 seconds Rinse 35 ° C 20 seconds Rinse 35 ° C 20 seconds Rinse 35 ° C 20 seconds Dry 80 ° C 60 seconds (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. 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 to 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 (shown in Table 3) 0.55 mol Ammonium bromide 40 g Water 1000 ml pH ( 25 ° C) 6.8

(Rinse Solution) Ion-exchanged water (3 pp for each of calcium and magnesium)
m or less) Furthermore, the samples that were uniformly exposed to give a gray density of 1.5 were processed in the same manner as above, and the amount of silver remaining in the highest density portions of these samples was quantified by the fluorescent X-ray method. . The results are shown in Table 3.

[0120]

[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 JP-A-5-216191 In the bleaching solution of Example 4, 1,3-diaminopropanetetraferric ammonium ammonium monohydrate was added in an equimolar amount to the ferric complex of compound 25 of the present invention. Example 4 of Japanese Unexamined Patent Publication No. 5-126191, except that
It was confirmed that the effect of the present invention was excellent when the same processing as that of processing J (photosensitive material sample 405) was performed.

Example 4 The amounts of Exemplified Compound 25 and ferric nitrate nonahydrate in No. 118 of Example 1 were halved, and the pH was 4.2 in the tank solution and 4.0 in the replenisher. Succinic acid was added to the tank solution at 0.2 mol / liter, the replenisher was 0.3 mol / liter, glutaric acid was added to the tank solution 0.45 mol / liter, the replenisher was added to 0.67 mol / liter, and malonic acid was used. 0.05 mol / l for tank liquid and 0.075 mol / l for replenisher
It was confirmed that the effect of the present invention was excellent when the same treatment was carried out except that each liter was added.

Example 5 302 as specified in the OECD Chemicals Testing Guideline
Table 4 shows the results of the biodegradability test based on the B modified Zahn-Wellens method.

[0125]

[Table 4]

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

[0127]

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 treatment composition of the present invention using the same has no bleaching fog, Stain generation is small, rapid processing with excellent desilvering property is possible, and there is little fluctuation in processing performance due to mixing of a bleaching solution into a color developing solution.

Claims (4)

[Claims] 1. A compound represented by the following general formula (I):
Fe or its salt Fe (III), Mn (III), Co (III), R
h (II), Rh (III), Au (II), Au (III) or Ce (I
V) It contains at least one chelating compound.
A processing composition for a silver halide photographic light-sensitive material. General formula (I)(R in the formula₁Represents a hydrogen atom or a substituent. X₁, X
₂And X₃Is a hydrogen atom or -L₁Represents -A
You L₁, L₂, L₃, L_Four, L_Five, L₆And L ₇Haso
Divalent aliphatic group, divalent aromatic group or a combination thereof
Represents a mixed divalent linking group. A, A₁, A₂as well as
A₃Are -COOM, -OM, -SO respectively₃M or-
PO (OM)₂Represents a hydrogen atom or a cation
Represent. ) 2. An imagewise exposed silver halide photographic light-sensitive material comprising the 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 Ce (I
V) A method for processing a silver halide photographic light-sensitive material, which comprises processing with a processing solution containing at least one chelate compound. 3. A compound represented by the general formula (I) as defined in claim 1 or a salt thereof of Fe (III), Mn (III) and Co.
(III), Rh (II), Rh (III), Au (II), Au (III)
Alternatively, a processing composition having a bleaching ability for a silver halide color photographic light-sensitive material, which contains at least one Ce (IV) chelate compound 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), R 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 h (III), Au (II), Au (III) and Ce (IV) chelate compounds.