EP0649057A2 - Composition de traitement photographique et méthode de traitement l'utilisant - Google Patents

Composition de traitement photographique et méthode de traitement l'utilisant Download PDF

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Publication number
EP0649057A2
EP0649057A2 EP94116246A EP94116246A EP0649057A2 EP 0649057 A2 EP0649057 A2 EP 0649057A2 EP 94116246 A EP94116246 A EP 94116246A EP 94116246 A EP94116246 A EP 94116246A EP 0649057 A2 EP0649057 A2 EP 0649057A2
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EP
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Prior art keywords
group
processing
iii
acid
silver halide
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EP94116246A
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German (de)
English (en)
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EP0649057A3 (fr
EP0649057B1 (fr
Inventor
Hisashi C/O Fuji Photo Film Co. Ltd. Okada
Tadashi C/O Fuji Photo Film Co. Ltd. Inaba
Yoshihiro C/O Fuji Photo Film Co. Ltd. Fujita
Yasuhiro C/O Fuji Photo Film Co. Ltd. Katsuoka
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Publication of EP0649057A3 publication Critical patent/EP0649057A3/fr
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Publication of EP0649057B1 publication Critical patent/EP0649057B1/fr
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes

Definitions

  • the present invention relates to a processing composition used for a silver halide photographic material and a processing process therewith.
  • a silver halide black and white photographic material is processed in the processing processes such as black and white developing, fixing and rinsing after exposing
  • a silver halide color photographic material (hereinafter referred to as a color light-sensitive material) is processed in the processing processes such as color developing, desilvering, rinsing and stabilizing after exposing
  • a silver halide color reversal material is processed in a processing process such as black and white developing after exposing and in the processing processes such as color developing, desilvering, rinsing and stabilizing after a reversal processing.
  • an exposed silver halide grain is reduced to silver by a color developing agent and at the same time a generated oxidation product of the color developing agent reacts with a coupler to form a dye image.
  • auxiliary processes are supplemen- tarily carried out for a purpose of maintaining a photographic and physical quality of a dye image or a processing stability. They include, for example, a rinsing process, a stabilizing process, a hardening process and a stopping process.
  • Processing is carried out in a reducer containing an oxidant in order to adjust a gradation of a silver halide black and white light-sensitive material which is subjected to a development processing.
  • a ferric ethylenediaminetetraacetate complex salt and a ferric 1,3-dia- minopropanetetraacetate complex salt are used as an oxidant for a processing solution used for the bleaching processing described above and a reducing processing.
  • they are less susceptible to biodegradation.
  • it is desired from a viewpoint of an environmental protection to convert a photographic processing waste solution generated from these photographic processings to harmlessness.
  • a processing composition which is easily susceptible to biodegradation is desired and an alternative for the above-mentioned bleaching agents which are not biodegraded has been investigated.
  • a bleaching agent having a biodegradability a ferric complex salt of N-(2-carboxymethoxyphenyl)iminodiacetic acid in German Patent Publication 3912551 and a ferric complex salt of ,8-alaninediacetic acid and a ferric complex salt of glycinedipropionic acid in European Patent Publication 430000A.
  • the processing solutions having a bleaching ability comprising these bleaching agents do not necessarily have a sufficient desilver property and it has been found that there are involved the problems that a continuous processing with them leads to degradation of the desilver property as compared with that at the beginning of the continuous processing and that magenta stain is generated.
  • An object of the present invention is to provide a processing composition which has a good handling property and is free from an environmental problem in a waste solution and a processing process therewith.
  • Another object of the present invention is to provide a processing composition which is stable as well particularly in a diluted concentration and which has a bleaching ability with an excellent desilver property and a processing process therewith.
  • Further object of the present invention is to provide a processing composition which has a bleaching ability with small aging stain and a processing process therewith.
  • Still further object of the present invention is to provide a processing composition which can stably maintain the above performances even after a continuous processing and a processing process therewith.
  • Yet further object of the present invention is to provide a processing composition which is preferred particularly from the viewpoints of a biodegradability and an environmental protection and a processing process therewith.
  • a processing composition for a silver halide photographic material which contains at least one member of chelate compounds of a compound represented by formula (I) or a salt thereof with a Fe (III), Mn (III), Co (III), Rh (II), Rh (III), Au (II), Au (III), or Ce (IV) (hereinafter referred to simply as the metal chelate compound of the present invention) and a processing process therewith: wherein R 1 represents a hydrogen atom, an aliphatic group or an aromatic group; R 2 represents an aromatic group; L 3 represents a divalent aliphatic group; n represents 0 or 1; X 1 represents a hydrogen atom or -L 4- A 2 ; L L 2 and L 4 each represents a divalent aliphatic group, a divalent aromatic group, or a divalent linkage group comprising a combination thereof; A 1 and A 2 each represents a carboxy group, a phosphono group, a s
  • the aliphatic group represented by R 1 may be linear, branched or cyclic and is preferably linear or branched.
  • the aliphatic group includes an alkyl group, an alkenyl group and an alkynyl group and is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms.
  • the aliphatic group may be substituted and the substituent includes, for example, an alkyl group (for example, methyl, ethyl and isopropyl), an aralkyl group (for example, phenylmethyl), an alkenyl group (for example, allyl), an alkoxy group (for example, methoxy and ethoxy), an aryl group (for example, phenyl and p-methylphenyl), an acylamino group (for example, acetylamino), a sulfonylamino group (for example, methanesulfonylamino), a ureido group (for example, methylureido), an alkoxycarbonylamino group, an aryloxycarbonylamino group, an aryloxy group (for example, phenyloxy), a sulfamoyl group (for example, methylsulfamoyl), a carbamoyl group (for
  • substituents for the aliphatic group have carbon atoms, they have preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
  • a hydroxy group or the carboxyl group is preferred as the substituent.
  • the aromatic group represented by R 1 and R 2 is a monocyclic or dicyclic aromatic hydrocarbon group which may have a substituent. It is preferably a phenyl or naphthyl group which may have a substituent, more preferably a phenyl group which may have a substituent. A hydroxy group or a carboxyl group is preferred as the substituent of the aromatic group represented by R 1 and R 2 .
  • the divalent aliphatic group represented by L 3 may have a substituent. It is preferably an alkylene group. It has preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 1 to 2 carbon atoms. A methylene group is particularly preferred.
  • R 1 is preferably a hydrogen atom. n is preferably 0.
  • the divalent aliphatic group represented by L 1 , L 2 and L 4 is preferably an alkylene group or an alkenylene group.
  • the alkylene group represented by L 1 , L 2 and L 4 may be linear, branched or cyclic and is preferably a linear alkylene group.
  • the alkylene group may be substituted and the substituent includes, for example, an alkyl group (for example, methyl, ethyl and isopropyl), an aralkyl group (for example, phenylmethyl), an alkenyl group (for example, allyl), an alkoxy group (for example, methoxy and ethoxy), an aryl group (for example, phenyl and p-methylphenyl), an acylamino group (for example, acetylamino), a sulfonylamino group (for example, methanesulfonylamino), a ureido group (for example, methylureido), an alkoxycarbonylamino group, an aryloxycarbonyl group, an aryloxy group (for example, pheny
  • the substituents of the alkylene group represented by L L 2 and L 4 are preferably a hydroxy group, a sulfo group, a carboxy group, a phosphono group, and an alkyl group having 1 to 3 carbon atoms which may be substituted (the substituents are, for example, a hydroxy group and a carboxy group) and more preferably a hydroxy group, a carboxy group, a hydroxy-substituted alkyl group, and a carboxy-substituted alkyl group.
  • L 1 , L 2 and L 4 are alkylene groups, they have preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. They are further preferably methylene and ethylene, particularly preferably methylene.
  • the alkenylene group represented by L 1 , L 2 and L 4 may be linear, branched or cyclic and is preferably a linear alkenylene group.
  • the alkenylene group may be substituted and those enumerated in the case where L 1 , L 2 and L 4 are the alkylene groups can be applied as the substituent therefor.
  • the alkenyl group has preferably 2 to 10 carbon atoms and is more preferably a vinylene group.
  • the divalent aromatic group represented by L 1 , L 2 and L 4 is a monocyclic or dicyclic aromatic hydrocarbon and may have a substituent.
  • L 1 , L 2 and L 4 are the alkylene groups can be applied as the substituent therefor, and it includes preferably an alkyl group, an acylamino group, an alkylsulfonamide group, an alkoxy group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfo group, a phosphono group, an acyl group, an alkoxycarbonyl group, a nitro group, a carboxy group, a hydroxy group, a halogen atom, and a hydroxamic acid group.
  • L 1 , L 2 and L 4 are arylene groups, they are preferably phenylene and naphthylene, more preferably phenylene, and particularly preferably 1,2-phen
  • the divalent linkage group consisting of a combination of the aliphatic group and the aromatic group each represented by L 1 , L 2 and L 4 is a group consisting of a combination of the aliphatic group and the aromatic group each described above and is preferably an aralkylene group having 7 to 10 carbon atoms.
  • the aralkylene group may be substituted and those enumerated in the case where L L 2 and L 4 are the alkylene groups can be applied as the substituent therefor.
  • alkylene group having 1 to 6 carbon atoms or 1,2-phenylene is preferred as L 1 , L 2 and L 4 , methylene or ethylene is further preferred, and methylene is particularly preferred.
  • a 1 and A 2 each represent a carboxy group, a phosphono group, a sulfo group or a hydroxy group and are preferably the carboxy group or the phosphono group, more preferably the carboxy group.
  • the compound represented by Formula (I) may be an ammonium salt (for example, an ammonium salt and a tetraethylammonium salt) and an alkaline metal salt (for example, a lithium salt, a potassium salt and a sodium salt).
  • an ammonium salt for example, an ammonium salt and a tetraethylammonium salt
  • an alkaline metal salt for example, a lithium salt, a potassium salt and a sodium salt
  • the compound of the present invention can be synthesized by the process described in Australian Journal of Chemistry, 1982, 35, 2371 and the following process: wherein X 1 , R 1 , R 2 , L 3 and n are synonymous with those in formula (I); and M 1 , M 2 and M 3 each represent a hydrogen atom or a cation.
  • L a and L b each represents a splitting-off group (e.g., a halogen atom).
  • the acid anhydride (1B) is synthesized from the iminodiacetic acid derivative (1A) and then it reacts with the amine compound (1C) to thereby synthesize the specified product (1 D).
  • the synthetic process for the acid anhydride (1 B) is not specifically limited, and a process described in, for example, "New Experimental Chemistry Course 14 (II)", pp. 1120 to 1130 (Maruzen) can be applied. Among them, a process using an acid anhydride (e.g., acetic anhydride) is preferred.
  • a solvent may be used in this reaction and the solvent is not limited as long as it does not take part in the reaction. It includes, for example, acetonitrile, dimethylformamide, pyridine, ether, tetrahydrofuran, acetone, and benzene.
  • a base may be used and those which are not reacted with the acid anhydride are preferred as the base. Tertiary amines (e.g., triethylamine) and pyridine are more preferred. This reaction is usually carried out at 0 to 100 ° C, preferably 10 to 80 ° C.
  • the synthetic process for the specified product (1 D) from the acid anhydride (1 B) and the amine compound (1 C) is not specifically limited and a synthetic process for an amide derivative from an acid anhydride and amine can widely be utilized.
  • a process described in "New Experimental Chemistry Course 14 (II)", pp. 1145 to 1147 (Maruzen) can be applied.
  • a solvent may be used in this reaction and the solvent includes, for example, the amine compound (1 C) which is a raw material, water, alcohols, acetonitrile, dimethylformamide, pyridine, ether, tetrahydrofuran, acetone, and benzene.
  • This reaction is usually carried out at -20 to 150°C, preferably 0 to 70 °C, and more preferably 0 to 40 °C.
  • the amide or thioamide compound (2C) is synthesized from the amine compound (2A) and the compound (2B) and then it can be reacted with the amine compound (2E) to thereby synthesize the specified product (2D).
  • the synthetic process for the amide or thioamide compound (2C) is not specifically limited and there can be applied, for example, a process described in "New Experimental Chemistry Course 14 (II)", pp. 1142 to 1151 and 14 (III) pp. 1827 to 1832 (Maruzen).
  • a solvent may be used in this reaction and the solvent includes, for example, the amine compound (2A) which is a raw material, tertiary amine, water, alcohols, acetonitrile, dimethylformamide, pyridine, ether, tetrahydrofuran, acetone, and benzene.
  • the amine compound (2A) which is a raw material, tertiary amine, water, alcohols, acetonitrile, dimethylformamide, pyridine, ether, tetrahydrofuran, acetone, and benzene.
  • tertiary amine e.g., triethylamine
  • This reaction is usually carried out at -20 to 150°C, preferably 0 to 70°C, and more preferably 0 to 40 ° C.
  • the synthetic process for the specified product (2D) from the compound (2C) and the amine compound (2E) is not specifically limited and there can be applied, for example, a process described in "New Experimental Chemistry Course 14 (III)", pp. 1342 to 1347 (Maruzen).
  • a solvent may be used in this reaction.
  • the solvent is not specifically limited as long as it does not take part in the reaction and includes, for example, water, alcohols (e.g., methanol, ethanol), acetonitrile, dimethylformamide, dimethylacetamide, and pyridine.
  • a base is preferably allowed to coexist in order to remove an acid generated.
  • Preferred as the base are tertiary amines (e.g., triethylamine), alkoxide (e.g., methoxide), OH-, and C0 3 2-. This reaction is usually carried out at 0 to 150°C, preferably 0 to 100°C, and more preferably 20 to 80 °C.
  • the other compounds can be synthesized in the same manner.
  • a metal salt constituting the metal chelate compound of the present invention is selected from Fe (III), Mn (III), Co (III), Rh (II), Rh (III), Au (II), Au (III), and Ce (IV). More preferred are salts of Fe (III), Mn (III) and Ce (IV), and particularly preferred is a salt of Fe (III).
  • the metal chelate compounds of the present invention may be prepared for use by reacting the compounds represented by formula (I) with the salts of the above metals (for example, a ferric sulfate salt, a ferric chloride salt, a ferric nitrate salt, a ferric ammonium sulfate salt, and a ferric phosphate salt) in a solution.
  • the salts of the above metals for example, a ferric sulfate salt, a ferric chloride salt, a ferric nitrate salt, a ferric ammonium sulfate salt, and a ferric phosphate salt
  • the ammonium salts and alkaline metal salts for example, a lithium salt, a sodium salt and a potassium salt
  • the metal chelate compound of the present invention which is isolated as a metal chelate compound, may be used.
  • the compound represented by formula (I) is used in a mole ratio of 1.0 or more based on a metal ion constituting the chelate compound. This ratio is preferably large in the case where a stability of the metal chelate compound is low, and it is usually used in the range of 1 to 30.
  • the metal chelate compound of the present invention has an effect as an oxidant for a silver halide photographic light-sensitive material (a bleaching agent for a color material and a reducing agent for a plate- making black and white light-sensitive material). In particular, it is excellent as the bleaching agent for the color light-sensitive material.
  • the metal chelate compound of the present invention is used as the bleaching agent by processing an imagewise exposed silver halide color photographic material with a processing solution containing the metal chelate compound of the present invention as the bleaching agent after it is subjected to a color development, so that developed silver is very rapidly bleached and a marked bleaching fog observed in a conventional bleaching agent which can carry out a rapid bleaching is not found.
  • the present invention is characterized by a novel oxidant in a photographic processing composition, particularly a bleaching agent in a processing composition having a bleaching ability for a color light-sensitive material, and with respect to the requisites for the other base materials, the base materials which can generally be applied can suitably be selected.
  • the metal chelate compound of the present invention may be contained in any processing solution (for example, a fixing solution and an intermediate bath provided between a color developing process and a desilver process). It is particularly effective as the bleaching agent for a processing solution having a bleaching ability (a bleaching solution or a bleach-fixing solution) for a color light-sensitive material in a content of 0.005 to 1 mole per liter of the processing solution.
  • the processing solution having a bleaching ability of a preferred embodiment will be explained below.
  • the metal chelate compound of the present invention is effectively contained as a bleaching agent in a processing solution having a bleaching ability in an amount of 0.005 to 1 mole per liter of the processing solution, more preferably 0.01 to 0.5 mole, and particularly preferably 0.05 to 0.5 mole per liter of the processing solution.
  • Use of the metal chelate compound of the present invention even in a diluted concentration of 0.005 to 0.2 mole, preferably 0.01 to 0.2 mole and more preferably 0.05 to 0.18 mole per liter of the processing solution can demonstrate an excellent performance.
  • the metal chelate compound of the present invention in a processing solution having a bleaching ability, it may be used in combination with the other bleaching agents in the range in which the effects of the present invention can be demonstrated (preferably, 0.01 mole or less, more preferably 0.005 mole or less per liter of the processing solution).
  • bleaching agents include Fe (III), Co (III) and Mn (III) chelate series bleaching agents of the compounds shown below, persulfates (for example, peroxodisulfate), hydrogen peroxide, and bromates.
  • the compounds forming the above chelate series bleaching agents include ethylenediaminetetracetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(Q-hydroxyethyl)-N,N',N'-triacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetracetic acid, nitrilotriacetic acid, cyclohex- anediaminetetracetic acid, iminodiacetic acid, dihydroxyethyl glycine, ethyl ether diaminetetracetic acid, glycol ether diaminetetracetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetracetic acid, 1,3-diaminopropanol-N,N,N',N'-tetramethylenephosphonic acid, ethylenediamine-N,N,N',N'- tetramethylenephosphonic acid,
  • JP-A-63-80256 there can be enumerated as well the bleaching agents described in JP-A-63-80256 (the term JP-A as used herein means an unexamined published Japanese patent application), JP-A-63-97952, JP-A-63-97953, JP-A-63-97954, JP-A-1-93740, JP-A-3-216650, JP-A-3-180842, JP-A-4-73645, JP-A-4-73647, JP-A-4-127145, JP-A-4-134450, JP-A-4-174432, European Patent Publication 430000A1, and West German Patent Publication 3912551. However, they will not be limited thereto.
  • the processing solution containing the metal chelate compound according to the present invention and having a bleaching ability contains the metal chelate compound and in addition thereto, preferably added thereto are halides such as chloride, bromide and iodide as a rehalogenizing agent. Further, an organic ligand forming a scarcely soluble silver salt may be added in place of the halides.
  • the halides are added in the forms of an alkaline metal salt, an ammonium salt, a guanidine salt, and an amine salt. To be concrete, there are included sodium bromide, ammonium bromide, potassium chloride, guanidine hydrochlorate, potassium bromide, and potassium chloride.
  • an amount of the rehalogenizing agent is suitably 2 mole/liter or less, and in case of a bleaching solution, it is preferably 0.01 to 2.0 mole/liter, further preferably 0.1 to 1.7 mole/liter, and particularly preferably 0.1 to 0.6 mole/liter.
  • a bleach-fixing solution it is preferably 0.001 to 2.0 mole/liter, further preferably 0.001 to 1.0 mole/liter, and particularly preferably 0.001 to 0.5 mole/liter.
  • the processing solution having the bleaching ability according to the present invention can contain the compound (free acid) represented by formula (I) which is formed separately from the metal chelate compound of the present invention, and the lower the stability of the metal chelate compound is, the more the compound (free acid) represented by formula (I) is preferably added.
  • the compound (free acid) represented by formula (I) is used in a mole ratio of 0 to 30 based on the metal chelate compound of the present invention.
  • a bleaching accelerator for preventing corrosion of a processing bath
  • a corrosion inhibitor for preventing corrosion of a processing bath
  • a buffer agent for keeping pH of a processing solution
  • a fluorescent whitening agent for whitening a processing solution
  • a deforming agent for forming a deforming agent according to necessity.
  • the bleaching accelerator for example, the compounds having a mercapto group or a disulfide group, described in U.S. Patent 3,893,858, German Patent 1,290,812, British Patent 1,138,842, JP-A-53-95630, and Research Disclosure No. 17129 (1978); the thiazolidine derivatives described in JP-A-50-140129; the thiourea derivatives described in U.S.
  • the bleaching accelerator may be used in an amount of 0.01 mmole/liter to 0.1 mole/liter, preferably 0.1 mmole/liter to 0.05 mole/liter, more preferably 0.5 mmole/liter to 0.015 mole/liter.
  • Nitrates such as ammonium nitrate, sodium nitrate and potassium nitrate are preferably used as the corrosion inhibitor.
  • the addition amount thereof is 0.01 to 2.0 mole/liter, preferably 0.05 to 0.5 mole/liter.
  • a pH value of the bleaching solution or bleach-fixing solution of the present invention is 2.0 to 8.0, preferably 3.0 to 7.5.
  • the processing solution is used at pH of 7.0 or lower, preferably 6.4 or lower in order to suppress a bleaching fog.
  • a pH of 3.0 to 5.0 is preferred.
  • the pH value of 2.0 or lower is liable to make the metal chelate compound according to the present invention instable and accordingly, a pH of 2.0 to 6.4 is preferred.
  • a pH of 3 to 7 is preferred for a color printing material.
  • Any compounds can be used as a pH buffer agent used for the above purpose as long as they are less liable to be susceptible to oxidation by a bleaching agent and have a buffer action in the above pH range.
  • organic acids such as acetic acid, glycolic acid, lactic acid, propionic acid, butyric acid, malic acid, chloroacetic acid, levulinic acid, ureidopropionic acid, formic acid, mon- obromoacetic 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, mal
  • buffer agents may be used in combination of plural ones.
  • the organic acids having a pKa of 2.0 to 5.5 are preferred. Particularly preferred are acetic acid, glycolic acid, malonic acid, succinic acid, maleic acid, fumaric acid, picolinic acid, and the combined use thereof.
  • These organic acids can be used as well in the forms of an alkaline metal salt (for example, a lithium salt, a sodium salt and a potassium salt) and an ammonium salt.
  • These buffer agents may be used in an amount of suitably 3.0 mole or less, preferably 0.1 to 2.0 mole, more preferably 0.2 to 1.8 mole, and particularly preferably 0.4 to 1.5 mole per liter of a processing solution having a bleaching ability.
  • the above acids and the alkali agents for example, aqueous ammonia, KOH, NaOH, potassium carbonate, sodium carbonate, imidazole, monoethanolamine, and diethanolamine
  • aqueous ammonia, KOH, NaOH, potassium carbonate, and sodium carbonate are preferred.
  • substantially containing no ammonium ion means a status that a concentration of the ammonium ion is 0.1 mole/liter or less, preferably 0.08 mole/liter or less, more preferably 0.01 mole/liter or less and it is particularly preferably not contained at all.
  • An alkaline metal ion and an alkaline earth metal ion are preferred as an alternative cation specimen for reducing an ammonium ion concentration to the range of the present invention, and the alkaline metal ion is particularly preferred. Of them, a lithium ion, a sodium ion and a potassium ion are particularly preferred.
  • potassium nitrate and sodium nitrate are included.
  • Potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate are preferred as an alkali agent used for controlling pH.
  • the processing solution having the bleaching ability according to the present invention is particularly preferably subjected to an aeration since the photographic performances can be very stably maintained.
  • a conventional means publicly known in the art can be applied to the aeration, and the blowing of air into the processing solution having the bleaching ability and the absorption of air utilizing an ejector can be carried out.
  • air is preferably discharged in a solution through a diffusion tube having fine pores.
  • a diffusion tube is widely used for an aeration tank and the others in an active sludge treatment.
  • the aeration there can be utilized the items described in Z-121, Using Process published by Eastman Kodack Co., Ltd., C-41 the 3rd edition (1982), pp. BL-1 to BL-2.
  • stirring is preferably strengthened and in carrying out it, the content described at page 8, a right upper column, the sixth line to a left lower column, the second line of JP-A-3-33847 can be utilized as it is.
  • the bleaching or bleach-fixing process can be carried out at a temperature range of 30 to 60 °C, preferably 35 to 50 ° C.
  • a processing time at the bleaching or bleach-fixing process is in a range of 10 seconds to 7 minutes, preferably 10 seconds to 4 minutes in case of a light-sensitive material for photographing. Also, it is 5 to 70 seconds, preferably 5 to 60 seconds, and more preferably 10 to 45 seconds in case of a light-sensitive material for printing. A rapid processing and the excellent results without increase in a stain have been achieved in these preferred processing conditions.
  • a light-sensitive material which was processed in the processing solution having the bleaching ability is subjected to a fixing or bleach-fixing processing.
  • Those described at page 6, a right lower column, the sixteenth line to page 8, a left upper column, the fifteenth line of JP-A-3-33847 are preferred for such fixing solution or bleach-fixing solution.
  • ammonium thiosulfate has been used as a fixing agent in a desilver process but it may be substituted with the other conventional fixing agents, for example, a mesoion series compound, a thioether series compound, thioureas, a lot of iodides, and hypo.
  • a mesoion series compound for example, a mesoion series compound, a thioether series compound, thioureas, a lot of iodides, and hypo.
  • ammonium thiosulfate sodium thiosulfate, potassium thiosulfate, guanidine thiosulfate, ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, dihydroxyethyl-thioether, 3,6-dithia-1,8-octanediol, and imidazole.
  • thiosulfates and mesoions are preferred.
  • Ammonium thiosulfate is preferred from a viewpoint of a rapid fixability.
  • sodium thiosulfate and mesoions are further preferred from a viewpoint that an ammonium ion is not substantially contained in a processing solution.
  • combined use of two or more kinds of the bleaching agents enables a further rapid fixing to be carried out.
  • ammonium thiosulfate and sodium thiosulfate preferred as well is combined use of ammonium thiocyanate, imidazole, thiourea, and thioether each described above.
  • the second fixing agent is added preferably in a range of 0.01 to 100 mole % based on ammonium thiosulfate and sodium thiosulfate.
  • An addition amount of the fixing agent is 0.1 to 3.0 mole, preferably 0.5 to 2.0 mole per liter of a bleach-fixing solution or a bleaching solution.
  • a pH value of a fixing solution depends on the kind of a fixing agent, and it is generally 3.0 to 9.0. Particularly in the case where thiosulfates are used, it is preferably 5.8 to 8.0 in terms of obtaining a stable bleaching performance.
  • a preservative can be added to a bleach-fixing solution and a fixing solution to increase an aging stability of the solution.
  • effective as the preservative are sulfite and/or hydroxylamine, hydrazine, and a bisulfite adduct of aldehyde (for example, a bisulfite adduct of acetaldehyde, particularly preferably the bisulfite adducts of aromatic aldehydes described in JP-A-1-298935).
  • the sulfinic acid compounds described in JP-A-62-143048 also are preferably used as well.
  • a buffer agent is preferably added to the bleach-fixing solution and the fixing solution in order to keep a pH uniform.
  • phosphate for example, phosphate, imidazole, imidazoles such as 1-methyl-imidazole, 2-methyl-imidazole and 1-ethyl-imidazole, triethanolamine, N-allylmorpholine, and N-benzoylpiperazine.
  • various chelate compounds can be added to mask the iron ions carried over from a bleaching solution to achieve the improvement in a stability of the solution.
  • Such preferred chelate compound includes 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilomethylenephosphonic acid, 2-hydroxy-1,3-diaminopropanetetracetic acid, ethylenediaminetetracetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(Q-oxyethyl)-N,N',N'-triacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethyl glycine, ethyl ether diaminetetraacetic acid, glycol ether diaminetetraacetic acid
  • a preferred addition amount of the chelate compounds described above is 0.3 to 10 times, more preferably 0.5 to 3 times in terms of a mole ratio based on an iron ion carried over.
  • An amount of the above chelate compounds which are incorporated into a fixing solution of 1 liter is preferably 0.01 to 0.5 mole, particularly preferably 0.03 to 0.2 mole.
  • the fixing process can be carried out in a range of 30 to 60 ° C, preferably 35 to 50 ° C.
  • Time in a fixing processing process is 15 seconds to 2 minutes, preferably 25 seconds to 1 minute and 40 seconds in case of a light-sensitive material for photographing, and 8 to 80 seconds, preferably 10 to 45 seconds in case of a light-sensitive material for printing.
  • a desilvering process is carried out in a combination of a bleaching process, a bleach-fixing (blixing) process and a fixing process, and to be concrete, the following ones are included:
  • Preferred for a light-sensitive material for photographing is (1), (2), (3) or (4), more preferably (1), (2) or (3).
  • Preferred for a light-sensitive material for printing is (5).
  • the present invention can be applied as well to a desilvering processing in which, for example, a controlling bath, a terminating bath and a rinsing bath are put after a color development processing.
  • the processing process according to the present invention is preferably carried out with an automatic developing machine.
  • a transporting method in such automatic developing machine is described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259.
  • a crossover is preferably shortened in the automatic developing machine in order to carry out a rapid processing.
  • the automatic developing machine in which the crossover time is shortened to 5 seconds or shorter is described in JP-A-1-319038.
  • a replenishing solution is preferably added according to an amount of a processed light-sensitive material in order to replenish the components in a processing solution consumed in the processing of a light-sensitive material and control the accumulation of undesirable components eluted from a light-sensitive material in a processing solution.
  • Two or more processing baths may be provided at the respective processing processes.
  • a countercurrent system is preferably applied in which a replenishing solution is flowed from a following bath to a preceding bath.
  • a cascade of 2 to 4 stages is preferably applied.
  • An amount of a replenishing solution is preferably reduced as long as a composition change in the respective processing solutions does not cause inconvenience in the photographic properties and a stain of the solutions.
  • An amount of a replenishing solution for a developing solution is 50 to 3000 ml, preferably 50 to 2200 ml per m 2 of a light-sensitive material in case of a color photographing material, and 15 to 500 ml, preferably 20 to 350 ml m 2 of the light-sensitive material in case of a color printing material.
  • An amount of a replenishing solution for a bleaching solution is 10 to 1000 ml, preferably 50 to 550 ml per m 2 of the light-sensitive material in case of the color photographing material, and 15 to 500 ml, preferably 20 to 300 ml m 2 of the light-sensitive material in case of the printing material.
  • An amount of a replenishing solution for a bleach-fixing solution is 200 to 3000 ml, preferably 250 to 1300 ml per m 2 of the light-sensitive material in case of the color photographic material, and 20 to 300 ml, preferably 50 to 200 ml m 2 of the light-sensitive material in case of the printing material.
  • the bleach-fixing solution may be replenished as a single solution or may be replenished dividing into a bleaching composition and a fixing composition or as a bleach-fixing replenishing solution prepared by mixing the overflowing solutions from a bleaching bath and/or a fixing bath.
  • An amount of a replenishing solution for a fixing solution is 300 to 3000 ml, preferably 300 to 1200 ml per m 2 of the light-sensitive material in case of the color photographing material, and 20 to 300 ml, preferably 50 to 200 ml m 2 of the light-sensitive material in case of the printing material.
  • a replenishing amount of a rinsing solution or a stabilizing solution is 1 to 50 times, preferably 2 to 30 times and more preferably 2 to 15 times as much as an amount carried over from a preceding bath per a unit area.
  • the processing solution having the bleaching ability in the present invention can be reused after recovering an overflowed solution used for the processing and adding the components to adjust the components.
  • regeneration used for the processing and adding the components to adjust the components.
  • generation can be preferably carried out.
  • the details of the regeneration there can be applied the matters described in Processing Manual, Fuji Color Negative Film, CN-16 Processing (revised in August 1990), pp. 39 to 40, published by Fuji Photo Film Co., Ltd.
  • a kit used for preparing the processing solution having the bleaching ability according to the present invention may be either of a liquid form or of a powder form.
  • the powder form is easy to prepare since almost all raw materials are supplied in a powder form and less hygroscopic in the case where an ammonium salt is removed.
  • the above kit for regeneration is preferably of the powder form from a viewpoint of reduction in an amount of a waste solution since it can be directly added without using extra water.
  • an anode and a cathode are put in the same bleaching bath or the regeneration is carried out with an anode bath and a cathode bath each separated to different baths with a diaphragm.
  • a bleaching solution and a developing solution and/or a fixing solution can be simultaneously subjected to a regeneration processing with a diaphragm.
  • a bleaching solution and a bleach-fixing solution are regenerated by subjecting the accumulated silver ions to an electrolytic reduction.
  • the accumulated halogen ions are preferably removed with an anionic ion exchange resin in terms of maintaining a fixing performance.
  • An ion exchange or a ultrafiltration is used in order to reduce an amount of rinsing water, and the ultrafiltration is particularly preferably used.
  • a color light-sensitive material is subjected to a color development processing before a desilver processing after an imagewise exposure.
  • a color developing solution which can be used in the present invention includes those described at page 9, a left upper column, the sixth line to page 11, a right lower column, the sixth line of JP-A-3-33847 and those described in JP-A-5-197107.
  • a publicly known aromatic primary amine color developing agent can be applied as a color developing agent used in a color developing process.
  • a preferred example is a p-phenylenediamine derivative, and the representative examples thereof include 4-amino-N-ethyl-N-(Q-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-( ⁇ -methanesulfonamidoethyl)-3-methylaniline, 4-amino-N-(3-carbamoylpropyl-N-n-propyl)-3-methylaniline, and 4-amino-N-ethyl-N-(Q-hydroxyethyl)-3-methoxyaniline.
  • those described in European Patent Publication No. 410
  • a use amount of the aromatic primary amine developing agent is preferably 0.0002 to 0.2 mole, more preferably 0.001 to 0.1 mole per liter of a color developing solution.
  • a processing temperature in the color developing solution in the present invention is 20 to 55 °C, preferably 30 to 55 ° C.
  • a processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes and 20 seconds, and further preferably 1 minute to 2 minutes and 30 seconds in a light-sensitive material for photographing. In a material for printing, it is 10 seconds to 1 minute and 20 seconds, preferably 10 seconds to 60 seconds, and further preferably 10 seconds to 40 seconds.
  • a black/white developing solution used for the above processing is a socalled first black/white developing solution used for the reversal processing of a conventional color light-sensitive material.
  • Various well known compounds which are added to a black/white developing solution used for a processing solution for a black/white silver halide light-sensitive material can be incorporated into the first black/white developing solution used for the color reversal light-sensitive material.
  • a developing agent such as 1-phenyl-3-pyrazolidone, metol and hydroquinone
  • a preservative such as sulfite
  • an accelerator consisting of an alkali such as sodium hydroxide, sodium carbonate and potassium carbonate
  • an inorganic or organic inhibitor such as potassium bromide, 2-methylbenzimidazole and methylbenzothiazole
  • a water softening agent such as polyphosphate
  • a development inhibitor consisting of a trace amount of iodide and a mercapto compound.
  • a light-sensitive material which is subjected to a desilver processing is subjected to a washing or stabilizing process.
  • a stabilizing solution described in U.S. Patent 4,786,583 can be enumerated.
  • formaldehyde is used as a stabilizing agent, and preferred from a viewpoint of a working environmental safety are N-methylolazole, hexamethlenetetramine, a formaldehyde bisulfite adduct, dimethylolurea, and an azolylmethylamine derivative.
  • azoles such as 1,2,4-triazole described in European Patent Publication 519190A2, and azolylmethylamine and the derivatives thereof, such as 1,4-bis(1,2,4-triazole-1-ylmethyl) piperazine since an image stability is high and a vapor pressure of formaldehyde is low.
  • stirring is preferably strengthened as much as possible in terms of more effectively demonstrating the effects of the present invention.
  • the concrete method for strengthening stirring includes the methods described in JP-A-62-183460, JP-A-62-183461, and JP-A-3-33847 (page 8), that is, a method employed for a color negative film processor FP-560B manufactured by Fuji Photo Film Co., Ltd., in which a jet stream of a processing solution is struck against an emulsion side of a light-sensitive material, a method described in JP-A-62-183461, in which a stirring effect is increased with a rotating means, a method in which a stirring effect is improved by moving a light-sensitive material (film) while contacting an emulsion layer side thereof to a wiper blade to cause a turbulent flow on an emulsion layer surface, and a method in which a circulating flow amount of a whole processing solution is increased.
  • the method in which a jet stream of a processing solution is struck is most preferred, and this method is preferably employed in the whole processing baths.
  • a light-sensitive material which can be applied to the processing of the present invention includes a color negative film, a color reversal film, a color paper, a color reversal paper, a direct positive color light-sensitive material, a color negative film for a movie, and a color positive film for a movie. They are described in, for example, JP-A-3-33847, JP-A-3-293662, and JP-A-4-130432.
  • a support for the light-sensitive material there are no specific limitations to a support for the light-sensitive material according to the present invention; a coating method; the kind of silver halides used for a silver halide emulsion layer and a surface protective layer (for example, silver iodobromide, silver iodochlorobromide, silver bromide, silver chlorobromide, and silver chloride), the grain forms thereof (for example, cube, plate and sphere), the grain sizes thereof, the fluctuations thereof, the crystal structures thereof (for example, a core/sell structure, a multi-layer structure, and a uniform layer structure), the manufacturing processes thereof (for example, a single jet process and a double jet process), a binder (for example, gelatin), a hardener, an anti-foggant, a metal doping agent, a silver halide solvent, a thickener, an emulsion breaker, a dimension stabilizer, an anti-adhesion agent, a stabilizer, an anti-
  • a dry film thickness of the whole constitutional layers of a color light-sensitive material excluding a support and a subbing layer and a back layer each provided on the support is preferably 20.0 /1.m or less more preferably 18.0 /1.m or less in case of a color light-sensitive material for photographing, and preferably 16.0 /1.m or less, more preferably 13.0 ⁇ m or less in case of a printing material in terms of achieving the objects of the present invention.
  • a bleaching fog and a stain after processing are increased, which are attributable to a developing agent remaining in a light-sensitive material after a color development processing.
  • the generation of these bleaching fog and stain is attributable to a green-sensitive layer, and a magenta color is resultingly liable to increase as compared with the other cyan and yellow colors.
  • a lower limit in a layer thickness regulation is desirably reduced from the above regulation within the range in which the properties of a light-sensitive material are not damaged to a large extent.
  • the lower limit of the whole dry layer thickness of the constitutional layers excluding those of a support and a subbing layer provided on the support is 12.0 ⁇ m in case of a color light-sensitive material for photographing and 7.0 ⁇ m in case of a printing material.
  • a layer is usually provided between a light-sensitive layer closest to a support and a subbing layer, and the lower limit of the whole dry layer thickness of this layer (may be plural layers) is 1.0 ⁇ m.
  • the layer thickness may be reduced either in a light-sensitive layer or a non-light-sensitive layer.
  • a swelling rate of the color light-sensitive material according to the present invention is preferably 50 to 200 %, more preferably 70 to 150 %, wherein the swelling rate is defined by the following equation:
  • the swelling rate deviated from the above values will increase a residual amount of a color developing agent and exert an adverse influence to a photographic performance, an image quality such as a desilver performance and a film property such as a film strength.
  • a swelling speed T i12 of the color light-sensitive material according to the present invention is preferably 15 seconds or less, more preferably 9 seconds or less, wherein the swelling speed is defined by the time in which the layer thickness is swollen to 1/2 of a saturated swollen layer thickness defined by 90 % of the maximum swollen layer thickness in a color developing solution (30 °C, 3 minutes and 15 seconds).
  • Silver halide contained in a photographic emulsion layer of the color light-sensitive material used in the present invention may be of any silver halide composition.
  • it is silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride, or silver iodochlorobromide.
  • silver bromide or silver chlorobromide is preferred. Silver chloride is preferred as well for carrying out a rapid processing.
  • silver chloride or silver chlorobromide is preferred. Particularly preferred is silver chlorobromide containing silver chloride of 80 mole % or more, more preferably 95 mole % or more, most preferably 98 mole % or more.
  • color couplers can be used for the color light-sensitive material applied to the processing according to the present invention.
  • The-concrete examples thereof are described in the patents described in above RD No. 17643, VII-C to G and No. 307105, VII-C to G, and JP-A-62-215272, JP-A-3-33847, JP-A-2-33144, and European Patent Publications 447969A and 482552A.
  • a yellow coupler includes those described in, for example, U.S. Patents 3,933,501, 4,022,620, 4,326,024, 4,401,752, and 4,248,961, JP-B-58-10739, British Patents 1,425,020 and 1,476,760, U.S. Patents 3,973,968, 4,314,023, 4,511,649, and 5,118,599, European Patents 249,473A and 0,477,969, JP-A-63-23145, JP-A-63-123047, JP-A-1-250944, and JP-A-1-213648.
  • the particularly preferred yellow coupler includes the yellow couplers represented by formula (Y) described in a left upper column at page 18 to a left lower column at page 22 of JP-A-2-139544, the acyl acetamide series yellow couplers characterized by an acyl group, described in JP-A-5-2248 and European Patent Publication 0447969, and the yellow couplers represented by Formula (Cp-2) described in JP-A-5-27389 and European Patent Publication 0446863A2.
  • the 5-pyrazolone series and pyrazoloazole series compounds are preferred as a magenta coupler. More preferred are the compounds described in U.S. Patents 4,310,619 and 4,351,897, European Patent 73,636, U.S. Patents 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, and JP-A-60-185951, U.S. Patents 4,500,630, 4,540,654, and 4,556,630, and International Publication W088/04795.
  • the particularly preferred magenta coupler includes the pyrazoloazole series magenta couplers described in a right lower column at page 3 to a right lower column at page 10 of JP-A-2-139544 and the 5-pyrazolone magenta couplers represented by Formula (M-I) described at a left lower column at page 17 to a left upper column at page 21 of JP-A-2-139544.
  • M-I 5-pyrazolone magenta couplers represented by Formula (M-I) described at a left lower column at page 17 to a left upper column at page 21 of JP-A-2-139544.
  • Most preferred are the pyrazoloazole series magenta couplers described above.
  • a cyan coupler includes the phenol series and naphthol series couplers.
  • Preferred are the compounds described in U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011, and 4,327,173, West German Patent Publication 3,329,729, European Patents 0,121,365A and 0,249,453A, U.S. Patents 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4,690,889, 4,254,212, and 4,296,199, and JP-A-61-42658.
  • Patent 4,818,672 and JP-A-2-33144 the cyclic active methylene series cyan couplers described in JP-A-64-32260, and the couplers described in JP-A-1-183658, JP-A-2-262655, JP-A-2-85851, and JP-A-3-48243.
  • Preferred as a coupler capable of forming a dye having an appropriate dispersing property are the compounds described in U.S. Patent 4,366,237, British Patent 2,125,570, European Patent 96,570, and West German Patent (published) 3,234,533.
  • a DIR coupler releasing a development inhibitor are the compounds described in the patents described in above RD No. 17643, Item VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, and U.S. Patents 4,248,962 and 4,782,012.
  • Preferred as a coupler releasing imagewise a nucleus-forming agent or a development accelerator in developing are the compounds described in British Patents 2,097,140 and 2,131,188, JP-A-59-157638, and JP-A-59-170840.
  • the compounds capable of being used for the color photographic element of the present invention include the competitive couplers described in U.S. Patent 4,130,427; the polyequivalent couplers described in U.S. Patents 4,283,472, 4,338,393 and 4,310,618; the DIR redox compound-releasing couplers, DIR coupler-releasing couplers, DIR coupler-releasing redox compounds, or DIR redox-releasing redox compounds described in JP-A-60-185950 and JP-A-62-24252; the couplers releasing a dye the color of which is recovered after splitting off, described in European Patent 173,302A; the bleaching accelerator- releasing couplers described in RD No. 11449 and No.
  • the support in case of using it for a color negative film are those having a layer which has a conductivity and a transparent magnetic substance layer on one face as described in JP-A-4-62543, those having a magnetic recording layer, described in International Patent Publication W090/04205, FIG. 1A, and those having a stripe magnetic recording layer and a transparent magnetic recording layer which is adjacent to the stripe magnetic recording layer, described in JP-A-4-124628.
  • the protective layer described in JP-A-4-73737 is preferably provided on these magnetic recording layers.
  • a thickness of the support is preferably 70 /1.m to 120 /1.m.
  • a package (patrone) in which the color negative film of the present invention is storred may be any one of existing or publicly known ones.
  • preferred are those having the forms described in U.S. Patent 4,834,306, Fig. 1 to Fig. 3 and those described in U.S. Patent 4,846,418, Fig. 1 to Fig. 3.
  • color negative film preferred as the color negative film are those having the contents described at page 14, left upper column, the first line to page 18, left lower column, the eleventh line of JP-A-4-125558.
  • the present invention can also be applied as a reducing solution which corrects a silver image consisting of a halftone dot and/or a line drawing which is obtained by subjecting a silver halide light-sensitive material for plate making to a development processing after exposing.
  • the base materials used for the respective layers are classified as follows:
  • the numerals corresponding to the respective components show the coated amounts in terms of a g/m 2 unit and the coated amounts converted to silver in case of silver halide. Provided that in case of the sensitizing dyes, the coated amount per mole of silver halide contained in the same layer is shown in terms of a mole unit.
  • W-1 to W-3, B-4 to B-6, and F-1 to F-17, an iron salt, a lead salt, a gold salt, a platinum salt, an iridium salt, a palladium salt, and a rhodium salt were appropriately incorporated into the respective layers in order to improve a preservation performance, a processing performance, an anti-pressure performance, anti-mold and fungicidal performances, an anti-static performance, and a coating performance.
  • Cpd-4 was dispersed in a form of a solid matter according to the process described in International Patent 88-4794.
  • the couplers and the additives each contained in the respective layers were dispersed in a gelatin solution by the methods shown in Table 2.
  • the addition methods in the respective layers are shown in Table 3.
  • the multi-layer color light-sensitive material 101 prepared was cut to a 35 mm width and subjected to wedge exposing to a white light (a color temperature of a light source: 4800 ° K and an exposure: 5CMS). Then, it was processed in the processing processes shown below with a cine type automatic developing machine. Provided that the samples to be evaluated for the performances thereof were processed after the imagewise exposed samples were processed until an accumulated replenishing amount of a color developing solution reached a three times as much amount as a tank capacity of the base solution thereof.
  • the processing was carried out while bubbles were discharged at 200 ml/minute from the pores of 0.2 mm ⁇ provided at a bottom of a bleaching solution tank.
  • the rinsing is of a counter current system from (2) to (1).
  • An amount of the color developing solution carried over to the bleaching process and an amount of the fixing solution to the rinsing process were 2.5 ml and 2.0 ml per meter of the light-sensitive material having a 35 mm width, respectively.
  • a time for a crossover is 5 seconds at any process and this time is included in a processing time of a preceding process.
  • compositions of the processing solutions are shown below: wherein the chelate compound is reacted with ferric nitrate in the solution to form an organic acid ferric sodium salt which becomes a bleaching agent.
  • Rinsing water between bleaching and fixing and rinsing water after fixing (common to both of the base solution and replenishing solution)
  • City water was introduced into a mixed bed type column filled with an H type strong acidic cation exchange resin (Amberlite IR-120B) and an OH type strong base anion exchange resin (Amberlite IRA-400) each manufactured by Rohm & Haas Co., Ltd. to reduce the ion concentrations of calcium and magnesium to 3 mg/liter or less, respectively, and subsequently sodium dichloroisocyanurate 20 mg/liter and sodium sulfate 150 mg/liter were added.
  • the pH of this solution resided in the range of 6.5 to 7.5.
  • the multi-layer color light-sensitive material 101 which was subjected to the above processings was measured for a residual silver amount at a maximum color developing part by an X-ray fluorescence analysis.
  • Sample 103 described in JP-A-4-145433 was processed in the following manner. wherein the chelate compound is reacted with iron chloride in the solution to form an organic acid ferric ammonium salt which becomes a bleaching agent.
  • Example 1 0.15 mole of malonic acid was added to the bleaching solution, whereby magenta stain after aging was improved as compared with a case where malonic acid was not added.
  • Sample 301 was prepared in the same manner as that in Example 1 described in JP-A-5-165176, except that polyethylene naphthalate having a thickness of 100 ⁇ m was used for a support in place of a subbed cellulose triacetate film support which was used for the multi-layer color light-sensitive material A prepared in Example 1 of JP-A-5-165176 and there was used that prepared by coating a stripe magnetic recording layer described in Example 1 of JP-A-4-124628 on the back face of the above support.
  • This Sample 301 was used to carry out the same test as that in Samples No. 101 and 105 in Example 1 of the present invention to find that the effects of the present invention were obtained similarly to Example 1 in the present invention.
  • Sample 302 was prepared in the same manner as that in Example 1 of the present invention, except that the support which was used for the multi-layer color light-sensitive material 101 prepared in Example 1 of the present invention was replaced with the same support and back layer as those of Sample No. 1-3 in Example 1 of JP-A-4-62543 and that C 8 F l7 SO 2 N(C 3 H 7 )CH 2 COOK was coated on the second protective layer so that the coated amount thereof became 15 mg/m 2.
  • This Sample 302 was processed to the format shown in Fig. 5 of JP-A-4-62543, and it was subjected to the same test as those in Samples No. 101 and 105 in Example 1 of the present invention to find that the effects of the present invention were obtained similarly to Example 1 of the present invention.
  • Sample 101 was cut to a 35 mm width and subjected to photographing with a camera. Then, it was subjected to the following processing by every 1 m 2 per day over a period of 15 days (running processing).
  • a stabilizing solution and a fixing solution are of a countercurrent system from (2) to (1), and all of the overflowed solution from the rinsing bath was introduced into the fixing bath (2).
  • the amounts of the developing solution carried over to the bleaching process, the bleaching solution carried over to the bleach-fixing process, the bleach-fixing solution carried over to the fixing process, and the fixing solution carried over to the rinsing process were 2.5 ml, 2.0 ml, 2.0 ml, and 2.0 ml per 1.1 meter of the light-sensitive material with a 35 mm width, respectively.
  • a crossover time is 6 seconds at either processes, and this time is included in a processing time of the preceding process.
  • the aperture areas in the processing machine described above were 120 cm 2 in the color developing solution, 120 cm 2 in the bleaching solution, and 100 cm 2 in the other processing solutions.
  • compositions of the processing solutions are shown below:
  • the residual silver amount at the maximum density part was measured in the same manner as that in Example 1 to find that it was 4.0 mg/cm 2 and a desilvering performance was good.
  • the metal chelate compound of the present invention in the embodiment of the present invention is a compound having a biodegradability and contributes to an environmental protection.
  • the processing composition of the present invention using it enables a rapid processing providing an excellent desilvering performance and has less fluctuation in a processing performance before and after running.

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US6756372B2 (en) 1999-09-13 2004-06-29 Boehringer Ingelheim Pharmaceuticals, Inc. Compounds useful as reversible inhibitors of cysteine proteases

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US8012909B2 (en) 2007-03-27 2011-09-06 Fujifilm Corporation Heat-sensitive transfer image-forming method
JP2008238736A (ja) 2007-03-28 2008-10-09 Fujifilm Corp 感熱転写受像シート
JP2008238737A (ja) 2007-03-28 2008-10-09 Fujifilm Corp 感熱転写受像シート及びその製造方法
JP4878327B2 (ja) 2007-03-30 2012-02-15 富士フイルム株式会社 感熱転写受像シートおよびその製造方法
JP5279942B1 (ja) * 2011-11-09 2013-09-04 国立大学法人九州大学 コバルト抽出方法

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US6395897B1 (en) 1999-03-02 2002-05-28 Boehringer Ingelheim Pharmaceuticals, Inc. Nitrile compounds useful as reversible inhibitors of #9 cathepsin 5
US6608057B2 (en) 1999-03-02 2003-08-19 Boehringer Ingelheim Pharmaceuticals, Inc. Compounds useful as reversible inhibitors of cathepsin S
US6730671B2 (en) 1999-03-02 2004-05-04 Boehringer Ingelheim Pharmaceuticals, Inc. Compounds useful as reversible inhibitors of cathespin S
US6756372B2 (en) 1999-09-13 2004-06-29 Boehringer Ingelheim Pharmaceuticals, Inc. Compounds useful as reversible inhibitors of cysteine proteases
US6982272B2 (en) 1999-09-13 2006-01-03 Boehringer Ingelheim Pharmaceuticals, Inc. Compounds useful as reversible inhibitors of cysteine proteases
US7056915B2 (en) 1999-09-13 2006-06-06 Boehringer Ingelheim Pharmaceuticals, Inc. Compounds useful as reversible inhibitors of cysteine proteases
US7265132B2 (en) 1999-09-13 2007-09-04 Boehringer Ingelheim Pharmaceuticals Inc. Compounds useful as reversible inhibitors of cysteine proteases
US7279472B2 (en) 1999-09-13 2007-10-09 Boehringer Ingelheim Pharmaceuticals Inc. Compounds useful as reversible inhibitors of cysteine proteases
US6858623B2 (en) 2000-09-08 2005-02-22 Boehringer Ingelheim Pharmaceuticals, Inc. Compounds useful as reversible inhibitors of cysteine proteases

Also Published As

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JP3075657B2 (ja) 2000-08-14
EP0649057A3 (fr) 1995-09-20
DE69422578T2 (de) 2000-06-15
DE69422578D1 (de) 2000-02-17
EP0649057B1 (fr) 2000-01-12
JPH07114161A (ja) 1995-05-02

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