JPH06180483A - Photographic processing composition and processing method - Google Patents

Abstract

PURPOSE:To impart biodefradability and to improve desilverability and bleach fog ad stains caused by the lapse of time. CONSTITUTION:The Fe(III) chelete compound of a compound to be used is represented by formula I, R1 is H or nonsubstituted alkyl or-L2-A2; R2 is H or L3-A3; each of L1-L3 is alkylene; each of A1-A3 is carboxy, phosphono, sulfo, or hydroxy; W is >=2 alkylene; and (n) is an integer between 2 and 6.

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 step, the developed silver produced in the developing step is oxidized (bleaching) into a silver salt by a bleaching agent (oxidizing agent) having an oxidizing action, and further unused by a fixing agent which forms soluble silver. Is removed from the photosensitive layer together with the silver halide of (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 the composition thereof, see "The Theory of Photographic Process" by James (Part 4).
Edition) (James, "The Theory of Photographic Process"
4'th edition) (1977), Research Disclosure No. 17643, pages 28-29, Id. 1871.
No. 651, left column to right column, No. 307105, 880 to 880
881 page.

In addition to the above basic processing steps, various auxiliary steps are added for the purpose of maintaining the photographic and physical qualities 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.

[0006]

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.

[0007]

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 (hereinafter sometimes simply referred to as the metal chelate compound of the present invention) and a processing method using the same. General formula (I)

[0008]

[Chemical 2]

(Where R is₁Is a hydrogen atom,
Kill group or -L₂-A₂Represents R ₂Is a hydrogen atom or
Is -L₃-A₃Represents L₁, L₂And L₃Is that
Represents an alkylene group. A₁, A₂And A₃Is it
Carboxy group, phosphono group, sulfo group or hydro group
Represents a xy group. W is an alkylene group having 2 or more carbon atoms
Represent. n represents an integer of 2 to 6. )

First, the compound represented by the general formula (I) or a salt thereof will be described in detail below. The unsubstituted alkyl group represented by R ₁ may be linear, branched or cyclic, and is preferably linear or branched. 1 as the number of carbons
Nos. 1 to 6 are preferable, and Nos. 1 to 3 are more preferable.

The alkylene group for L ₁ , L ₂ and L ₃ may be linear, branched or cyclic, and is preferably a linear alkylene group. The alkylene group of L ₁ , L ₂ and L ₃ may have a substituent, and as the substituent, an alkenyl group (eg allyl), an alkynyl group, an alkoxy group (eg methoxy, ethoxy), an aryl group ( For example, phenyl, p-methylphenyl), acylamino group (eg acetylamino), sulfonylamino group (eg methanesulfonylamino), ureido group, alkoxycarbonylamino group (eg methoxycarbonylamino), aryloxycarbonylamino group (eg phenoxycarbonyl). Amino), aryloxy groups (eg phenyloxy), sulfamoyl groups (eg methylsulfamoyl), carbamoyl groups (eg carbamoyl, methylcarbamoyl), alkylthio groups (eg methylthio, carboxymethylthio), arylthio groups. O group (eg phenylthio), sulfonyl group (eg methanesulfonyl), sulfinyl group (eg methanesulfinyl), hydroxy group, halogen atom (eg chlorine atom, bromine atom, fluorine), cyano group, sulfo group, carboxy group, phosphono group , Aryloxycarbonyl groups (eg phenyloxycarbonyl), acyl groups (eg acetyl, benzoyl), alkoxycarbonyl groups (eg methoxycarbonyl), acyloxy groups (eg acetoxy), nitro groups, hydroxamic acid groups and the like. Among them, alkoxy group, sulfo group, carboxy group,
A hydroxy group and a phosphono group are preferable, and a carboxy group is particularly preferable. The alkylene group of L ₁ , L ₂ and L ₃ preferably has 1 to 6 carbon atoms, and a particularly preferred group is a methylene group or an ethylene group. L ₁ , L
Specific examples of the alkylene groups of ₂ and L ₃ include the following.

[0012]

[Chemical 3]

A ₁ , A ₂ and A ₃ are preferably carboxy groups or phosphono groups, with carboxy groups being particularly preferred. R ₁ is preferably a hydrogen atom. R ₂ is -L ₃
-A ₃ is preferable. The alkylene group having 2 or more carbon atoms for W may be linear, branched or cyclic, and preferably,
It is a linear alkylene group. The alkylene group of W may have a substituent, and as the substituent, those mentioned as the substituents which the alkylene group represented by L ₁ , L ₂ and L ₃ may have are applied. it can. Of these, an alkoxy group, a carboxy group and a hydroxy group are preferable, and a carboxy group and a hydroxy group are more preferable. The alkylene group of W has preferably 2 to 6 carbon atoms, more preferably 2 or 3 carbon atoms, and particularly preferably an ethylene group. n represents an integer of 2 to 6, in which case W may be the same or different. When R ₂ is a hydrogen atom, n is preferably an integer of 4 to 6, R ₂
But in the case of -L ₃ -A _3, n is preferably 2 or 3
And more preferably 2. The following is represented by the general formula (I)
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0014]

[Chemical 4]

[0015]

[Chemical 5]

The compound represented by the general formula (I) is an ammonium salt (eg ammonium salt, tetraethylammonium salt), an alkali metal salt (eg lithium salt, sodium salt, potassium salt) or an acid salt (eg hydrochloride salt, sulfuric acid). Salt, oxalate). The compounds represented by formula (I) are disclosed in JP-A-59-70652 and JP-A-63-70652.
It can be synthesized by the synthetic method described in 146998 or the like and a method similar thereto.

Next, typical synthetic examples of the compound represented by the general formula (I) of the present invention are shown below. Synthesis example 1. Synthesis of Compound 1 28.0 g (0.240 mol) of sodium chloroacetate
Is dissolved in 50 ml of water, and while stirring at room temperature, 2
-(2-aminoethoxy) ethanol 10.5 g (0.
10 mol) was slowly added dropwise. Then, 24.0 g (0.240 mol) of 40% sodium hydroxide aqueous solution was added to p
The solution was slowly added dropwise so as to maintain H9 to 10. After completion of dropping, the mixture was stirred at 50 ° C. for 2 hours. After cooling to room temperature, concentrated hydrochloric acid (24.3 g, 0.24 mol) was added, and the mixture was concentrated under reduced pressure until the reaction liquid became about 50 ml. After desalting by gel filtration column chromatography, the eluent was concentrated and acetone was added to precipitate a white solid. The target product 1 is obtained by filtering the solid and drying it under reduced pressure.
7.9 g (0.0357 mol) was obtained. Yield 36% Other compounds can be similarly synthesized.

The metal salt constituting the metal chelate compound of the present invention includes Fe (III), Mn (III), Co (III) and Rh.
(II), Rh (III), Au (II), Au (III) and Ce
It is selected from the salts of (IV). More preferably Fe (III),
The salts are Mn (III) and Co (IV), and Fe (III) salts are particularly preferable. 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, ferric phosphate, etc.). , Examples of the respective salts include, for example, sodium salt, ammonium salt, potassium salt, and lithium salt.)
And may be formed by reaction in solution. Similarly, the salt of the compound represented by the general formula (I) and the salt of the metal may be formed by reaction in a solution. Of course, an isolated metal chelate compound may be used. 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.

The metal chelate compound of the present invention has an effect as an oxidizing agent for a silver halide photographic light-sensitive material (a bleaching agent for a color light-sensitive material and a reducing agent for a black-and-white light-sensitive material 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 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 and the like 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.

The processing solution having a bleaching ability of a preferred embodiment will be described below. The metal chelate compound of the present invention is effective as a bleaching agent when it is contained in a processing solution having a bleaching ability in an amount of 0.005 to 1 mol per liter of the processing solution as described above, and 0.01 to 0.5 mol is more preferable. Preferably 0.0
5 to 0.5 mol is particularly preferred. The metal chelate compound of the present invention is 0.005 to 0.2 per 1 liter of the processing liquid.
Even when used at a dilute concentration of mol, preferably 0.01 to 0.2 mol, more preferably 0.05 to 0.18 mol,
It can exhibit excellent performance. 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 0.01 mol or less per 1 liter of the processing solution, preferably 1 liter of the processing solution). (0.005 mol or less) may be used in combination with other bleaching agents. Examples of such bleaching agents include Fe (III), Co (III) or Mn (III) chelate bleaching agents, persulfates (for example, peroxodisulfate), hydrogen peroxide and bromate of the following compounds. And so on.

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.

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, as 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 a 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 buffering agent for keeping 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 pH of the bleaching solution or bleach-fixing solution of the present invention is 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, glycine, glutamine, cysteine, serine, methionine, leucine, histidine, benzoic acid, chlorobenzoic acid, hydroxybenzoic acid, nicotinic acid, oxalic acid, malon Acid, succinic acid, tartaric acid, maleic acid, fumaric acid, oxaloic acid, glutaric acid,
Organic acids such as abipic acid, aspartic acid, glutamic acid, cystine, ascorbic acid, phthalic acid and terephthalic 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
The organic acid of 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, and more preferably 0.2 to 1.8 mol, per liter of the processing solution having a bleaching ability. , 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, an acid and an alkaline agent (for example, ammonia water, KOH, NaOH, potassium carbonate, sodium carbonate, imidazole, monoethanolamine, diethanolamine) are used. You may use together. Of these, aqueous ammonia, KOH, NaOH, potassium carbonate and sodium carbonate are preferred.

With the recent growing awareness of global environment conservation, 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 to the range of the present invention, alkali metal ions and alkaline earth metal ions are preferable as alternative cation species, particularly alkali metal ions are preferable, and lithium ion, sodium ion, and potassium ion are 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 liquid 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 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 improve the stability of the solution by concealing iron ions carried in from the bleaching 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.

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 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. ,
It is preferably 20 ml to 350 ml. The amount of bleach replenisher is 10 m per 1 m ^{2 of} light-sensitive material for color photographic materials.
1 to 1000 ml, preferably 50 to 550 ml.
For print materials, photosensitive materials 1 m ² per 15ml~
It is 500 ml, preferably 20 to 300 ml. The amount of bleach-fixing replenisher is 1 m for light-sensitive materials in the case of color photographic materials.
²⁰⁰ ml to 3000 ml, preferably 250 ml per ²
1300 ml, and in the case of printing materials, photosensitive material 1
²⁰ ml to 300 ml, preferably 50 ml to ²⁰ per m ^2.
It is 0 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. In the case of a color photographic material, the amount of the fixing replenisher is 300 to 3000 ml, preferably 3 to 1 m ² of the light-sensitive material.
00 ml to 1200 ml, and in the case of a printing material, ²⁰ ml to 300 ml, preferably 50 m per 1 m ² of the light-sensitive material.
1 to 200 ml. Replenishment amount of washing water or stabilizing solution is 1 to 50 times the amount brought in from the previous bath per unit area,
It is preferably 2 to 30 times, more preferably 2 to 15 times.

The processing solution having a 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 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 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.

Further, salts of these p-phenylenediamine derivatives with sulfates, hydrochlorides, sulfites, naphthalenedisulfonic acid, p-toluenesulfonic acid and the like may be used.
The amount of the aromatic primary amine developing agent used is Color Developer 1
It is preferably 0.0002 mol to 0.2 mol, and more preferably 0.001 mol to 0.1 mol per liter. The processing temperature of the color developer in the present invention is 20 to 5
The temperature is 5 ° C, preferably 30 to 55 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 for the light-sensitive material for photography.
It's 20 minutes. It is more preferably 1 minute to 2 minutes 30 seconds, and for printing materials, 10 seconds to 1 minute 20 seconds, preferably 10 seconds to 60 seconds, and more preferably 10 seconds 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 light-sensitive 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,
No. 4-270344, European Patent Publication No. 504609A.
No. 2 is described. In particular, the combined use of azoles such as 1,2,4-triazole and azolylmethylamine and its derivatives such as 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine results in improved image stability. It is preferable because of its high vapor pressure and low formaldehyde vapor pressure.

Examples of the light-sensitive material applicable to the processing of the present invention include color negative films, color reversal films, color papers, color reversal papers, direct positive color light-sensitive materials, motion picture color negative films, motion picture color positive films, and the like. 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.

It is desirable that the lower limit of the film thickness regulation is reduced within the range not deteriorating 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 excluding the undercoat layer of the support is 12.0 μ in the case of a color light-sensitive material for photographing and 7.0 μ in the case of a print material. is there. 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, and 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 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, Japanese Patent Application No. 3-179042, European Patent. Published 044796
No. 9, an acylacetamide-based yellow coupler characterized by an acyl group, and a general formula (Cp-) described in Japanese Patent Application No. 3-203545 and European Patent Publication No. 0446863A2.
2) Yellow coupler.

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.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 0,121,365A and 0,249,453A.
U.S. Pat. Nos. 3,446,622 and 4,33.
No. 3,999, No. 4,775,616, No. 4,4
No. 51,559, No. 4,427,767, No. 4,
Those described in 690,889, 4,254,212, 4,296,199, JP-A-61-42658 and the like are preferable. Furthermore, JP-A-64-553
No. 64, No. 554, No. 64-555, No. 64-5
No. 56, pyrazoloazole couplers, and European Patent Publication Nos. 0,488,248 and 0,491,197.
No. 4,456,226A, pyrrolo imidazole couplers described in European Patent Publication No. 0,456,226A, pyrazolopyrimidine couplers described in JP-A-64-46753, and U.S. Pat. No. 4,818,672.
No. 2, JP-A-2-33144, imidazole couplers, JP-A-64-32260, cyclic active methylene cyan couplers, JP-A-1-183658,
No. 2-262655, No. 2-85851, No. 3-4
The coupler described in No. 8243 can also be used.

Typical examples of polymerized dye-forming couplers are 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.

[0054]

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 of} 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 2.2 × 10 ⁻⁴ mol ExS-3 6.0 × 10 ⁻⁵ mol ExC-1 0.65 ExC-3 1.0 × 10 ⁻² ExC-4 2.3 × 10 ⁻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 3.0x10 ^-5 mol ExC-2 8.5x10 ^-2 ExC-5 3.6x10 ^-2 ExC-6 1.0x10 ^-2 ExC-7 3.7x10 ^-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 sensitivity 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 speed blue sensitive 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 grain 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 include
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.

[0074]

[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.

[0076]

[Chemical 6]

[0077]

[Chemical 7]

[0078]

[Chemical 8]

[0079]

[Chemical 9]

[0080]

[Chemical 10]

[0081]

[Chemical 11]

[0082]

[Chemical 12]

[0083]

[Chemical 13]

[0084]

[Chemical 14]

[0085]

[Chemical 15]

[0086]

[Chemical 16]

[0087]

[Chemical 17]

[0088]

[Chemical 18]

[0089]

[Chemical 19]

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.

Processing process Processing time Processing 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 35ml width Amount of perfume Washing in countercurrent from (2) to (1) The amount of developer brought into the bleaching process and the amount of fixer brought into the washing process are per 1m 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 treatment 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 reacts with iron nitrate in the liquid to form ferric sodium salt of organic acid which becomes a 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 / l) 260.0 ml Water added 1000 ml pH 7.0

(Washing water between 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 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 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 similarly 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.

[0100]

[Table 2]

[0101]

[Chemical 20]

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.

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 (here, the chelate compound reacts with iron nitrate in the liquid to form a ferric ammonium salt of an organic acid that becomes a bleaching agent)

(Rinse solution) Ion-exchanged water (3 ppm each for calcium and magnesium)
Hereinafter, the samples to which uniform exposure was performed so that the gray density became 1.5 were processed in the same manner as above, and the amount of silver remaining in the highest density portion of these samples was quantified by the fluorescent X-ray method. The results are shown in Table 3.

[0106]

[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.

[0108]

[Table 4]

From the above results, it was confirmed that the compound represented by the general formula (I) which forms the metal chelate compound of the present invention is excellent in biodegradability.

[0110]

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 13, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

The alkylene group for L ₁ , L ₂ and L ₃ may be linear, branched or cyclic, and is preferably a linear alkylene group. The alkylene group of L ₁ , L ₂ and L ₃ may have a substituent, and as the substituent, an alkenyl group (eg allyl), an alkynyl group, an alkoxy group (eg methoxy, ethoxy), an aryl group ( For example, phenyl, p-methylphenyl), acylamino group (eg acetylamino), sulfonylamino group (eg methanesulfonylamino), ureido group, alkoxycarbonylamino group (eg methoxycarbonylamino), aryloxycarbonylamino group (eg phenoxycarbonyl). Amino), aryloxy groups (eg phenyloxy), sulfamoyl groups (eg methylsulfamoyl), carbamoyl groups (eg carbamoyl, methylcarbamoyl), alkylthio groups (eg methylthio, carboxymethylthio), arylthio groups. O group (eg phenylthio), sulfonyl group (eg methanesulfonyl), sulfinyl group (eg methanesulfinyl), hydroxy group, halogen atom (eg chlorine atom, bromine atom, fluorine), cyano group, sulfo group, carboxy group, phosphono group , Aryloxycarbonyl groups (eg phenyloxycarbonyl), acyl groups (eg acetyl, benzoyl), alkoxycarbonyl groups (eg methoxycarbonyl), acyloxy groups (eg acetoxy), nitro groups, hydroxamic acid groups and the like. Among them, alkoxy group, sulfo group, carboxy group,
A hydroxy group and a phosphono group are preferable, and a carboxy group is particularly preferable. The alkylene group of L ₁ , L ₂ and L ₃ is
The carbon number is preferably 1 to 6, and particularly preferably a methylene group or an ethylene group. L ₁ ,
Specific examples of the alkylene group of L ₂ and L ₃ include the following.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[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, ethylenediamine diacetic acid, ethylenediamine dipropionic acid, 1,4-diaminobutanetetraacetic acid, 2-methyl-1,3-diaminopropanetetraacetic acid, 2,2-dimethyl-1, 3-diaminopropanetetraacetic acid, citric acid and their alkali metal salts (for example, lithium salt, sodium salt, potassium salt), ammonium salts and the like can be mentioned, as well as 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 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

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, glycine, glutamine, cysteine, serine, methionine, leucine, histidine, benzoic acid, chlorobenzoic acid, hydroxybenzoic acid, nicotinic acid, oxalic acid, malon Acid, succinic acid, tartaric acid, maleic acid, fumaric acid, oxaloic acid, glutaric acid,
Organic acids such as adipic acid, aspartic acid, glutamic acid, cystine, ascorbic acid, phthalic acid, terephthalic 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
The organic acid of 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, and more preferably 0.2 to 1.8 mol, per liter of the processing solution having a bleaching ability. , Particularly preferably 0.4 to 1.5 mol.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction content]

Further, by adding various chelating agents to the fixing solution, it is possible to improve the stability of the solution by concealing iron ions carried in from the bleaching 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
-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 5]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction content]

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
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.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

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. 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.

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 C
at least one e (IV) chelate compound
Processing composition for silver halide photographic light-sensitive material characterized by
object. General formula (I)(In the formula, R₁Is a hydrogen atom, an unsubstituted alkyl group or-
L₂-A₂Represents R ₂Is a hydrogen atom or -L₃-A
₃Represents L₁, L₂And L₃Each is an arche
Represents a group. A₁, A₂And A₃Are each
Represents an oxy group, a phosphono group, a sulfo group or a hydroxy group
You W represents an alkylene group having 2 or more carbon atoms. n is
It represents an integer of 2 to 6. ) 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.