EP1241522A1 - Processing method for silver halide color photographic material - Google Patents

Processing method for silver halide color photographic material Download PDF

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Publication number
EP1241522A1
EP1241522A1 EP02005892A EP02005892A EP1241522A1 EP 1241522 A1 EP1241522 A1 EP 1241522A1 EP 02005892 A EP02005892 A EP 02005892A EP 02005892 A EP02005892 A EP 02005892A EP 1241522 A1 EP1241522 A1 EP 1241522A1
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EP
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Prior art keywords
group
acid
formula
compound
processing
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP02005892A
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German (de)
French (fr)
Inventor
Hiroyuki Seki
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Fujifilm Corp
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Fuji Photo Film Co Ltd
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Publication of EP1241522A1 publication Critical patent/EP1241522A1/en
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    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/50—Reversal development; Contact processes
    • 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
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers
    • 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
    • G03C7/421—Additives other than bleaching or fixing agents
    • 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
    • G03C2200/00—Details
    • G03C2200/15—Buffer
    • 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
    • G03C2200/00—Details
    • G03C2200/21—Developer or developing
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/305—Additives other than developers
    • 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
    • G03C7/407—Development processes or agents therefor
    • 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 (development) processing method for a silver halide color photographic material (hereinafter described as simply photographic material), and in particular a processing method using a bleaching solution.
  • the present invention specifically relates to a photographic processing method with which desilvering, color restoration and stain prevention are improved to achieve an excellent development quality.
  • Silver halide color photographic materials give rise to images by processing after imagewise exposure.
  • the material is subjected to development, and then processed with a bleaching solution and a fixing solution.
  • the bleaching agent contained in the bleaching solution the iron (III) complex salt of ethylenediaminetetraacetic acid (EDTA) has been widely used.
  • EDTA ethylenediaminetetraacetic acid
  • a more active bleaching agent showing a higher bleaching speed with a smaller use amount than that of the EDTA iron (III) complex salt is earnestly demanded, and a variety of bleaching agents have been proposed.
  • a highly active bleaching agent such as 1,3-PDTA iron (III) complex salt, which works rapidly at a low amount, is used in combination with a color-forming developer containing phosphate ion, it has been confirmed that the bleaching solution is liable to turn turbid or form a precipitate along with a prolonged usage for processing.
  • a bleaching agent has a serious disadvantage when the processing is conducted in a continuous mode.
  • the processing with a highly active bleaching agent has another drawback that photographic materials processed such as color print papers and films processed with the highly active bleaching agent tends to get stained when stored under a high temperature and high humid condition. Still another drawback accompanied by the highly active bleaching agent exists that, when such a highly active bleaching agent is used for a rapid bleaching treatment in the color-forming development (i.e., the color development) using the above-described developer, failure of color restoration, which indicates the fact that the degree of dye formation is incomplete, often takes place.
  • An object of the present invention to solve is the drawbacks mentioned above associated with the processing using a phosphate ion-containing color-forming developer, and in particular the processing of reversal color photographic materials.
  • the object is to provide a method of processing a silver halide color photographic material wherein the bleaching solution neither becomes turbid nor generates any precipitate.
  • Another object of the present invention is to provide a method of processing a silver halide color photographic material which gives sufficient color-formation and little failure of color restoration in the processing, and shows little stain formation even when the processed material is stored under high temperature and highly humid conditions.
  • One processing method that achieves the purpose of the present invention characteristically uses a bleaching solution containing at least one of the ion (III) complex salts of a compound represented by formula (I) , and at least one of compounds represented by one of formulae (II) to (V).
  • This type of bleaching solution will not become turbid when used for a long time with a color-forming developer containing of 0.05 to 0.25 mol/L of phosphate ion. Moreover, failure of color restoration as well as stain formation is suppressed.
  • the diaminopolycarboxylic acid compound represented by formula (I) is characterized by the number of atoms in the linking group for the two amino nitrogen atoms, the compound represented by formula (II) is characterized by being a carboxymethyliminosuccinic acid derivative, the compound represented by formula (III) is characterized by being a hydroxyalkyliminodiacetic acid derivative, the compound represented by formula (IV) is characterized by being an alkylenediaminedicarboxylic acid derivative, and the compound represented by formula (V) is characterized by being a nitrogen-containing heterocyclic carboxylic acid derivative.
  • processing method of the present invention can be applied to any type of color photographic materials, it is particularly preferable and effective to apply to color reversal processing since phosphate ion-containing color-forming developers are extensively used for the processing of color reversal photographic materials.
  • the method of the present invention can be applied to the ordinary color processing comprising development with a phosphate ion-containing color-forming developer followed by desilvering with use of a processing solution having a bleaching capability.
  • color-forming development i.e., color development
  • other steps such as pre-bleaching, etc.
  • the method of the present invention can be effectively applied to such processing.
  • a 1 to A 4 which may be the same or different, each represents -CH 2 OH, -PO 3 (M 2 ) 2 or -COOM 1 ;
  • M 1 and M 2 each represents a hydrogen atom, an alkali metal atom (e.g., Na or K), an ammonium group or an organic ammonium group (e.g., methylammonium or trimethylammonium).
  • X 1 represents a straight-chain or branched-chain alkylene group containing 3 to 6 carbon atoms, a ring-forming, saturated or unsaturated divalent organic group, or -(B 1 O)n 5 -B 2 -.
  • B 1 and B 2 may be the same or different, each represents an alkylene group having 1 to 5 carbon atoms (containing those of the substituent).
  • Symbols n 1 to n 4 which may be the same or different, each represents an integer of from 1 to 10, and at least one of them is not less than 2.
  • the alkylene group represented by X 1 includes ethylene, trimethylene or tetramethylene.
  • the alkylene group represented by B 1 or B 2 includes methylene, ethylene or trimethylene.
  • Suitable substituents for X 1 or the alkylene group represented by B 1 or B 2 include hydroxyl and an alkyl group having 1 to 3 carbon atoms (e.g., methyl or ethyl) .
  • n 5 represents an integer of 1 to 8, preferably 1 to 4, and more preferably 1 to 2.
  • preferable examples of the compound represented by formula (I) are shown not for the purpose of restricting the scope of the present invention thereto.
  • each of compounds (I-11), (I-12), (I-13), (I-14) and (I-15) includes both of the cis- and trans-forms.
  • particularly preferable compounds are (I-3), (I-4), (I-8), (I-11) and (I-16).
  • iron (III) complex salt of the compound represented by formula (I) those having the stoichiometric ratio of ferric ion (i.e., iron (III) ion) to the compound of formula (I) of 1:1 are preferred.
  • the complex salt may have an amine, a thiocyanate group or a cyanate group as a ligand.
  • the negative or positive excessive atomic valence is neutralized with a water-soluble cation or anion.
  • the complex salt may be hydrated, too.
  • some examples for the ion (III) complex of the compound represented by formula (I) are exemplified not for the purpose of restricting the scope of the present invention thereto.
  • R 1 represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, a carboxyalkyl group or an alkoxyalkyl group
  • R 2 and R 3 each represents a hydrogen atom, an alkyl group, a carboxyalkyl group or an alkoxyalkyl group
  • M 6 , M 7 and M 8 each represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an onium group.
  • R 1 represent an alkyl group, a hydroxyalkyl group, a carboxyalkyl group or an alkoxyalkyl group
  • the number of the carbon atoms contained in each alkyl group is 1 to 8, preferably 1 to 4, and the alkyl group may be straight or branched.
  • the carbon atom number of the alkoxyalkyl group is 1 to 3, preferably 1 or 2.
  • R 1 include a hydrogen atom, methyl, ethyl, carboxymethyl, and carboxyethyl groups, among these, hydrogen, carboxymethyl and methyl groups are preferred.
  • R 2 and R 3 each represents an alkyl group, a craboxylalkyl group or an alkoxyalkyl gruop
  • the carbon atom number of each alkyl group is 1 to 8, and more preferably 1 to 4.
  • the alkyl group may be of straight chain or branched chain.
  • the carbon atom number of the alkoxy group in the alkoxylalkyl group is 1 to 3, preferably 1 or 2.
  • R 2 or R 3 includes a hydrogen atom, methyl, ethyl, carboxymethyl and carboxyethyl groups, among these, a hydrogen atom, carboxymethyl and methyl groups are preferred.
  • the alkali metal atom represented by M 6 , M 7 or M 8 includes metal atoms such as Li, Na and K, alkaline earth metal atoms such as Ca, Mg and Ba, and onium groups such as ammonium (e.g., ammonium or tetraethylammonium) and pyridinium. More preferable M 6 , M 7 or M 8 is a hydrogen atom, an ammonium group or an alkali metal atom.
  • each exemplary compound represented by each formula is shown in the acid form (i.e., COOH) .
  • other forms such as the metal or ammonium salt are not excluded.
  • the compounds represented by formula (II) can be prepared with reference to the synthetic methods described in Kireto Kagaku (Chelate Chemistry) (5), edited by Kagehira Ueno and published by Nankodo Co., Ltd., Inorganic Chemistry, 7, 2405 (1968), Chm. Zvesti ., 20, 414 (1966) , and Zhurnal Obshchei Khinii , 49, 659 (1978). Many of the compounds are commercially available, too.
  • L 0 represents a divalent alkylene group having 2 to 8 carbon atoms, and may be straight or branched with preferably 2 to 4 carbon atoms, more preferably with 2 to 3 carbon atoms.
  • the alkylene group may be substituted by a hydroxy group or an alkoxy group.
  • the carbon atom number is 1 to 4, preferably 1 to 3.
  • M 9 and M 10 have the same meaning as M 6 , M 7 and M 8 , and preferable groups for M 9 and M 10 are common to those for M 6 , M 7 and M 8 .
  • the compounds represented by formula (III) can also be synthesized with reference to the methods described in KiretoKagaku (Chelate Chemistry) (5), edited by Kagehira Ueno and published by Nankodo Co., Ltd., Inorganic Chemistry, 7, 2405 (1968), Chm. Zvesti., 20, 414 (1966), and Zhurnal Obshchei Khinii , 49, 659 (1978). Many of the compounds are commercially available, too.
  • X 2 , X 3 and X 4 each represents a methylene group, an ethylene group, n- and i-propylene groups, each of which may be substituted with a hydroxy group, a methoxy group or an ethoxy group.
  • M 11 and M 12 have the same meaning as M 6 , M 7 and M 8 , and preferable groups for M 11 and M 12 are common to those for M 6 , M 7 and M 8 .
  • Z represents a nitrogen-containing heterocyclic group, which is preferably a nitrogen-containing 5- or 6-membered ring group, and more preferably an aromatic heterocyclic group.
  • Particularly preferred groups are azoles, azines and pyridines.
  • Preferable azole rings are pyrrole, pyrroline, pyrazole, pyrazoline, imidazole, imidazoline, triazole, thiazole, oxazole, isoxazole and tetrazole.
  • Preferable azine rings are pyrimidine, pyridazine, oxazine and thiazine.
  • the nitrogen-containing heterocyclic group may be substituted with an alkyl or alkoxyl group each containing 1 to 4 carbon atoms, a hydroxy group or a carboxymethyl group.
  • each of those groups comprises the same ones as the corresponding group represented by R 1 .
  • Preferable examples thereof are also common to those of R 1 .
  • M 13 has the same meaning as M 6 , M 7 and M 8 , and its preferable examples are also common to those for M 6 , M 7 and M 8 .
  • the compounds represented by formula (V) can be not only synthesized by ordinary processes, but are commercially available.
  • G 1 and G 2 each represents a carboxyl group, a phosphono group, a sulfo group, a hydroxy group, a mercapto group, an aryl group, a heterocyclic group, an alkylthio group, an amidino group, a guanidino group or a carbamoyl group;
  • L 1 , L 2 and L 3 each represents a divalent aliphatic or aromatic group or a divalent linking group comprising a combination thereof;
  • m and n each represents 0 or 1;
  • X represents a hydrogen atom, an aliphatic or aromatic group; and M represents a hydrogen atom or a cation.
  • the aryl (aromatic hydrocarbon) group represented by G1 or G2 may comprise single or bicyclic rings, preferably containing 5 to 20 carbon atoms. Examples thereof include phenyl and naphthyl.
  • the substituent which this aryl group may have includes an alkyl group (e.g., methyl or ethyl), an aralkyl group (e.g., phenylmethyl), an alkenyl group (e.g., allyl), an alkynyl group an alkoxy group (e.g., methoxy or ethoxy), an aryl group (e.g., phenyl or p-methylphenyl), an acylamino group (e.g., acetylamino), a sulfonylamino group (e.g., methanesulfonylamino), an ureido group, an alkoxycarbonylamino group (e.g., methoxycarbony
  • the heterocyclic group represented by G 1 or G 2 is a 3-to 10-membered heterocyclic group containing at least one oxygen or sulfur atom therein, and may be saturated or unsaturated. It may further contain a single ring or form a condensed ring with another aromatic ring or heterocyclic ring.
  • heterocyclic rings which are 5- or 6-membered unsaturated heterocyclic group, include, for example, pyridine, pyrazine, pyrimidine, pyridazine, triazine, tetrazine, thiophene, furan, pyran, pyrrole, imidazole, pyrazole, thiazole, isothiazole oxazole, isoxazole, oxadiazole, thiadiazole, thianthrene, isobenzofuran, chromene, xanthene, phenoxazine, indolizine, isoindole, indole, triazole, triazolium, tetrazole, quinolizine, isoquinoline, quinoline, phthalazine, naphthylidine, quinoxaline, quinazoline, cinnoline, pterin, carbazole, carboline, phenanthridine,
  • pyridine, pyrazine, pyrimidine, pyridazine, thiophene, furan, pyrrole, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole and indole are preferred. More preferable heterocyclic rings are imidazole and indole.
  • the alkylthio group represented by G 1 or G 2 is represented by -SR 1 (R 1 represents an alkyl group.).
  • the alkyl group for R 1 may be straight-chained, branched or cyclic, preferably containing 1 to 10 carbon atoms.
  • the alkyl group more preferably comprises a straight-chain containing 1 to 4 carbon.
  • the alkyl group represented by R 1 may have a substituent group, which includes the same substituents as those for the aryl group represented by G 1 or G 2 .
  • Specific examples of the alkylthio group represented by G 1 or G 2 include, for example, methylthio, ethylthio, hydroxyethylthio and carboxymethylthio. Preferable ones are methylthio and ethylthio.
  • the carbamoyl group represented by G 1 or G 2 may be substituted, thus being shown as -CONR 1 R 2 wherein R 1 and R 2 each represents a hydrogen atom, a substituted or unsubstituted alkyl or aryl group.
  • the alkyl group represented by R 1 and R 2 may be straight-chained, branched or cyclic, and preferably have 1 to 10 carbon atoms.
  • the aryl group represented by R 1 and R 2 preferably has 6 to 10 carbon atoms, phenyl being more preferred.
  • R 1 and R 2 may be connected together to form a ring such as, for example, morpholine, piperidine, pyrrolidine and piperadine.
  • Particularly preferred groups as R 1 and R 2 are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms and a phenyl group which may be substituted.
  • Substitutents for the alkyl or aryl group represented by R 1 and R 2 include those which the aryl group represented by G 1 or G 2 may have.
  • Specific examples of the carbamoyl group represented by G 1 or G 2 include, for example, carbamoyl, N-methyl carbamoyl, N-phenylcarbamoyl and morpholinocarbonyl.
  • the divalent aliphatic group represented by L 1 , L 2 and L 3 includes a straight-chained, branched or cyclic alkylene group (preferably of 1 to 6 carbon atoms) , an alkenylene group (preferably of 2 to 6 carbon atoms), and an alkynylene group (preferably of 2 to 6 carbon atoms) .
  • These divalent aliphatic groups may be substituted with, for example, those which the aryl group represented by G 1 or G 2 may have.
  • Preferable substituents include carboxyl and hydroxy, carboxyl being more preferred.
  • divalent aliphatic group for L 1 , L 2 and L 3 include methylene, ethylene, 1-carboxy-methylene, 1-carboxy-ethylene, 2-hydroxy-ethylene, 2-hydroxy-propylene, 1-phosphono-methylene, 1-phneyl-methylene and 1-carboxy-butylene.
  • divalent aromatic hydrocarbon (arylene) groups and divaltent aromatic heterocyclic groups are exemplified.
  • the divalent aromatic hydrocarbon (arylene) group may comprise a single ring or bicyclic rings, and preferably contains 6 to 20 carbon atoms, exemplified by phenylene and naphthylene groups.
  • the divalent aromatic heterocyclic group is 3- to 10-membered, containing at least one of a nitrogen, oxygen or sulfur atom, andmay comprise a single ring or be condensed with another aromatic or heterocyclic ring. 5- to 6-membered aromatic heterocyclic groups containing nitrogen as the heteroatom are preferred. Specific examples of the divalent aromatic heterocyclic group include the following.
  • the divalent aromatic group is preferably arylene (preferably having 6 to 20 carbon atoms), more preferably phenylene or naphthylene, particularly preferably being phenylene.
  • the divalent aromatic group for L 1 , L 2 and L 3 may have a substituent that is common to those which the aryl group represented by G 1 or G 2 may have. Among such groups, carboxyl, hydroxy and aryl are preferred, carboxyl being more preferred.
  • L 1 , L 2 and L 3 each may be a group comprising a divalent aliphatic group and a divalent aromatic group such as, for example, those to follow.
  • Preferable groups for L 1 , L 2 and L 3 include an alkylene or o-phenylene group preferably with 1 to 3 carbon atoms, and particularly preferable ones are methylene and ethylene.
  • n each represents 0 or 1.
  • m is 1, and n is 0.
  • the aliphatic group represented by X includes a straight-chained, branched or cyclic alkyl group (preferably having 1 to 6 carbon atoms) , an alkenyl group (preferably having 2 to 6 carbon atoms), and an alkynyl group (preferably having 2 to 6 carbon atoms) .
  • an alkyl and alkenyl groups are preferred. Specific examples are methyl, ethyl, cyclohexyl, benzyl and allyl.
  • the aromatic group for X includes an aromatic hydrocarbon (aryl) group or an aromatic heterocyclic group such as, for example, phenyl, naphthyl, 2-pyridyl and 2-pyrrole. Among these, an aryl group is preferred, and phenyl is more preferred.
  • X is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, hydrogen being more preferred.
  • the cation represented by M includes ammonium (e.g., ammonium and tetraethylammonium) and an alkali metal (e.g., Li, K and Na) and pyridinium.
  • the compound represented by formula (I) may be an ammonium salt (e.g., ammonium salt and tetraethylammonium salt) , an alkali metal (e.g., Li, K and Na) salt or an acid salt such as hydrochloric, sulfuric or oxalic acid salt.
  • the number of the ammonium, alkali metal or acid contained in the compound is preferably be from 0 to 6 for the isolated compound (e.g., mono-sodium salt, di-sodium salt, or tri-sodium salt).
  • L 2 ' in formula (VII) has the same meaning as L 2 in formula (VI).
  • G 2 ' has the same meaning as G 2 in formula (VI).
  • M' and M'' each has the same meaning as M in formula (VI).
  • the compound represented by formula (VI) can be prepared based on the synthetic process described in Japanese Patent application (Laid-Open) No. 95319/1994, in particular paragraphs [0036] to [0042] thereof.
  • iron (III) complex salt of the compound represented by formula (VI) those having the stoichiometric ratio of ferric ion (i.e., iron (III) ion)to the compound of formula (I) of 1:1 is preferred. Further the complex salt may be coordinated with an amine, a thiocyanate group or a cyanate group as a ligand. Further, the negative or positive excessive atomic valence is neutralized with a water-soluble cation or anion. The complex salt may be hydrated, too. In the following, some examples for the ion (III) complex of the compound represented by formula (VI) are exemplified not for the purpose of restricting the scope of the present invention thereto.
  • the ion (III) complex salt of the compound represented by formulae (I) to (VI) may be in the form of isolated solid (e.g., powdery, granular or bulky solid), or non-isolated solution (e.g., aqueous solution).
  • the ion (III) complex salt of the compound represented by formulae (I) and (VI) can be synthesized by reacting the compound represented by formulae (I) and (VI) with an iron salt in a solution.
  • the ammonium or alkali metal salt e.g., Li, Na or K salt
  • the ammonium or alkali metal salt may be used.
  • the iron chelate compound is used in the form of solution without compound isolation, unnecessary extra salts formed in the solution by the reaction are preferably eliminated.
  • such salts can be eliminated by ultrafiltration, electro-osmosis, salt filtration via solvent condensation or salt separation by the addition of a poor solvent. Among these methods, electro-osmosis is most preferred.
  • the pH range for the solution of the iron (III) complex salt of the compound represented by formulae (I) and (VI) is preferably from 4 to 9, more preferably from 5 to 8, and specially preferably from 6 to 8.
  • the concentration of the iron complex salt is preferably from 1 to 80% by weight (i.e., by mass), more preferably from 1 to 50% by weight, and specially preferably from 3 to 35% by weight.
  • the solvent for the solution of an non-isolated iron chelate compound is preferably water.
  • the ratio of the compound represented by formulae (I) and (VI) to the iron ion is preferably not less than 1.0, more preferably 1.05 to 2, and particularly preferably 1.1 to 1.2 in terms of molar ratio.
  • any salt or any metal form of iron can be used as the iron (III) source, including inorganic salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, ferrous sulfate, ferrous chloride, ferrous nitrate, ferrous ammonium sulfate, ferrous phosphate, iron tritetraoxide, iron sesquioxide and iron hydroxide, organic salts such as iron acetate.
  • metallic iron iron powder or steel wool can also be used.
  • These ferric ion source materials may be used individually or in combination of two or more of them in arbitrary mixing ratios. Any kind of solvent that is not involved in the reaction may be used as the reaction solvent, but water is the best.
  • the compound represented by formulae (I) and (VI) is supplied in the form of the iron (III) complex salt having been prepared in advance wherein a foreign compound other than the iron (III) complex salt is contained in such complex salt at a content preferably of from 0 to 10% by weight, more preferably from 0 to 7% by weight, and particularly preferably from 0 to 5% by weight of the iron (III) complex.
  • an iron complex salt-containing material resulting from the reaction between the compound represented by formula (I) and iron sesquioxide, or another iron complex salt-containing material that is obtained by reacting the compound represented by formulae (I) and (VI) with ferric chloride followed by desalting to a pre-determined level can be preferably used.
  • “foreign compound” indicates any by-product formed by the reaction between the compound represented by formulae (I) and (VI) and an iron salt.
  • the bleaching solution of the present invention may be prepared by adding and dissolving the iron (III) complex salt that has been prepared in advance by reacting the compound represented by formulae (I) and (VI) with an iron (III) compound (e.g., ferric oxide, ferric sulfate, ferric chloride, ferric bromide or ferric nitrate) .
  • an iron (III) compound e.g., ferric oxide, ferric sulfate, ferric chloride, ferric bromide or ferric nitrate
  • a complex-forming reaction may be conducted in the bleaching solution by adding a complex-forming compound and an iron (III) compound (e.g., ferric sulfate, ferric chloride, ferric bromide or ferric nitrate) to form an iron (III) complex salt-containing aqueous solution.
  • the complex-forming compound may be used in a quantity slightly larger than the stoichiometric amount for the ion (III) complex salt formation. In general
  • the compound capable of forming a complex salt with ferric ion used in the present invention may contain an iron (III) complex-forming compound other than those represented by formulae (I) and (VI), but its content is preferably below 50 mol%, more preferable below 20 mol%, the remaining being those represented by formulae (I) and (VI). Further in the present invention, the compound represented by formula (I) occupies 30 to 95%, preferably 60 to 90% of the total amount of the complex-forming compound capable of forming an iron (III) complex salt in the bleaching solution, while those represented by formulae (II) to (V) is used in 5 to 70%, preferably 10 to 40%. Such compounds represented by formulae (II) to (V) may be used individually or in combination of two or more.
  • iron (III) complex-forming compounds other than those represented by formulae (I) to (V) may be jointly used.
  • Such other compounds include EDTA, diethylentriaminepentaacetic acid, iminodiacetic acid, methyliminodiacetic acid, N-(2-acetoamido)iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraquismethylenephosphonic acid, nitrilotrismethylenephosphonic acid and diethylenetriaminepentaquismethylenephosphonic acid; still other compounds can be used.
  • an inorganic oxidizing agent may further be used as the bleaching agent of the bleaching solution.
  • Such inorganic oxidizing agents include hydrogen peroxide, hypochlorite salts, persulfate salts and bromate salts (with alkali metals or alkaline earth metals). Self-evidently, still other oxidizing compounds can be used.
  • the concentration of the iron (III) complex salt of the compound represented by formulae (I) and (VI) in the bleaching solution is appropriately from 0.003 to 3.0 mol/L, preferably from 0.02 to 1.50 mol/L, and more preferably from 0.05 to 0.50 mol/L. However, with a still more diluted range of from 0.05 to 0.20, the iron (III) complex salt exhibits a superior effect. In cases where an inorganic oxidizing agent is jointly used, an iron (III) concentration of from 0.005 to 0.03 mol/L is preferred.
  • a halogen compound such as chloride, bromide or iodide may be added as a rehalogenating agent which promotes the oxidation of silver.
  • a halogen compound such as chloride, bromide or iodide may be added as a rehalogenating agent which promotes the oxidation of silver.
  • an organic legand capable of forming a silver salt sparingly soluble in water.
  • Such halogen compounds are preferably incorporated in the form-of an alkali metal salt or ammonium salt while such organic legands are preferably incorporated in the form of the salt of guanidine or amines.
  • Specific compounds include sodium bromide, potassium bromide, ammonium bromide, potassium bromide and guanidine hydrochloride. Among these, ammonium bromide is specially preferred.
  • the bromide ion concentration in the bleaching solution is preferably from 0.05 to 2.0 mol/L, more preferably from 0.5 to 1.5 mol/L. In cases where an inorganic oxidizing agent is jointly used, the bromide ion concentration is preferably from 0.05 to 0.1 mol/L.
  • the compound represented by the following formula [A] is preferably contained to enhance the advantages of the present invention.
  • a 5 represents an n 51 -valent organic group
  • n 51 represents an integer of 1 to 6
  • M 5 represents an ammonium group, an organic ammonium group, an alkali metal (Na, K or Li), or a hydrogen atom.
  • a 5 never represents an unsubstituted methyl, ethyl or ethylene group.
  • the n 51 -valent organic group represented by A 5 includes an alkylene group (e.g., methylene, trimethylene or tetramethylene), an alkenylene group (e.g., ethenylene), an alkynylene group (e.g., ethynylene) , a cycloalkylene group (e.g., 1,4-cyclohexanediyl), an arylene group (e.g., o-phenylene or p-phenylene), an alkanetolyl group (e.g., 1,2,3-propanetolyl), an arenetolyl group (e.g., 1,2,4-benzentolyl) and an alkyl group (e.g., propyl, butyl, octyl or cyclohexyl).
  • an alkylene group e.g., methylene, trimethylene or tetramethylene
  • an alkenylene group e
  • the n 51 -valent group represented by A 5 includes those having a substituent (e.g., hydroxy, alkyl or a halogen atom) .
  • a substituent e.g., hydroxy, alkyl or a halogen atom
  • Examples include 1,2-dihydroxyethylene, hydroxyethylene, 2-hydroxy-1,2,3-propanetolyl, methyl-p-phenylene, 1-hydroxy-2-chloroethylene, chloromethylene, and chloroethenylene.
  • the preferred concrete compounds represented by formula [A] are shown below.
  • the organic acid described above may be used in the form of the metal salt (e.g., Na or K salt) or ammonium salts.
  • the metal salt e.g., Na or K salt
  • ammonium salts e.g., ammonium salts.
  • the compounds represented by formula [A] is contained in an amount of preferably 0.01 to 0.25 mol, more preferably 0.02 to 0.15 mol per 1 liter of the processing tank solution.
  • a preferable pH range for the bleaching solution of the present invention is from 4.0 to 7.0, in particular from 4.2 to 6.0.
  • the pH of the bleaching solution can be adjusted to such ranges by using an inorganic or organic acid well known in the art individually or in combination.
  • the bleaching solution may contain an organic acid having pKa of 2.0 to 5.5 at a concentration of from 0.1 to 2 mol/L.
  • the pKa value means the absolute value of the reciprocal of acid dissociation constant determined under the condition of 0.1 mol/L ionic strength at 25°C.
  • the organic acid having a pKa of 2.0 to 5.5 may not be necessarily the compound represented by formula [A] above, but other mono-basic or poly-basic acids may be used, too.
  • the organic acid may be used in the form of the metal salt (e.g., Na or K salt) or the ammonium salt thereof.
  • the organic acid include, in addition to those represented by formula [A], aliphatic mono-basic acids such as formic acid, acetic acid, monochloroacetic acid, monobromoacetic acid, glycolic acid, propionic acid, monochloropropionic acid, lactic acid, pyruvic acid, acrylic acid, butyric acid, isobutyric acid, pivalic acid, aminobutyric acid, valeric acid or isovaleric acid; aminoacid compounds such as asparagine, alanine, arginine, ethionine, glycine, glutamine, cysteine, serine, methionine or leucine; aromatic monobasic acids such as benzoic acid or mono-substituted benzoic acid including chloro- or hydroxy-benzoic acid and nicotinic acid; aliphatic dibasic acids such
  • the bleaching solution of the present invention is preferably incorporated with a compound selected from imidazoles at a concentration of from 1 to 50 g/L.
  • a compound selected from imidazoles may have a substituent selected from alkyl groups having 1 to 6 carbon atoms, alkenyl groups having 2 to 6 carbon atoms, hydroxyalkyl or carboxyalkyl groups having 1 to 6 carbon atoms, and carboxyl groups at the 1-, 2-, 4- or 5-position.
  • imidazole compounds include imidazole, 2-methylimidazole, 4-methylimidazole, 4-methyl-5-(hydroxymethyl)imidazole and imidazole-4,5-dicarboxylic acid.
  • imidazole, 2-methylimidazole and imidazole-4,5-dicarboxylic acid are particularly preferred.
  • the concentration of the imidazole compound is preferably from 1.0 to 30.0 g/L, more preferably from 1.5 to 5.0 g/L in the bleaching solution.
  • the bleaching solution of the present invention is reusable when the overflow solution after processing is collected and appropriately replenished to recover the original composition.
  • Such reusing methods are usually called regeneration, to which reference can be made to paragraphs [0033] to [0034] of Japanese Patent Application (Laid-Open) No. 303186/1993.
  • the bleaching solution is used at a temperature between 20 and 50°C, preferably between 25 and 45°C.
  • the solution may contain various types of fluorescent brightening agents, anti-foaming agents and surfactants.
  • a preferable replenishing amount for the bleaching solution of the present invention is up to 500 ml, more preferably up to 300 ml, most preferably up to 200 ml, per 1 m 2 of silver halide color photographic material. It is noted that, for the lower replenishing amounts, the advantageous features of the present invention become the more prominent.
  • the air or oxygen may be blown in the solution during processing or in a stock tank of the bleaching solution or a replenisher, if desired.
  • a suitable oxidizing agent such as hydrogen peroxide, bromate salts or persulfate salts may be incorporated.
  • the conventionally known developing agents can be used, such as dihydroxybenzenes (e.g., hydroquinone or hydroquinone monosulfonate), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone or 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone), aminophenols (e.g., N-methyl-p-aminophenol, N-methyl-3-methyl-p-aminophenol and its derivatives), ascorbic acid and its isomers and derivatives.
  • These developing agents may be used individually or in combination.
  • Preferable developing agents are potassium or sodium hydroquinone monosulfonate.
  • the developing agent is used at a concentration of 1 x 10 -5 to 2 mol/L in the developer.
  • the black-and-white developer used in the present invention can contain a preservative if needed.
  • a sulfite salt or bisulfite salt is usually used at a content of 0.01 to 1 mol/L, preferably 0.1 to 0.5 mol/L.
  • Ascorbic acid which also acts as a very efficient preservative, is used at a content of 0.01 to 0.5 mol/L.
  • the hydroxylamines represented by formula (I) in Japanese Patent Application (Laid-Open) No. 144446/1991, saccharides, o-hydroxyketones and hydrazines can also be used. The content of these compounds is 0.1 mol/L or less.
  • the pH of the black-and-white developer of the present invention is preferably in the range of 8 to 12, most preferably 9 to 11.
  • buffering agents can be adopted to maintain a preferable pH value.
  • Preferable buffering agents include carbonates, phosphates, borates, 5-sulfosalicylic acid salts, hydroxybenzoic acid salts, glycine salts, N,N-dimethylglycine salts, leucine salts, norleucine salts, guanine salts, 3,4-dihydroxyphenylalanine salts, alanine salts, aminobutyric acid salts, valine salts and lysine salts.
  • carbonates, borates and 5-sulfosalicylic acid salts are specially preferred.
  • These buffering agents may be used individually or in combination of two or more thereof.
  • an acid and/or alkali may be used together to secure the targeted pH value.
  • inorganic or organic water-soluble acids can be preferably used, such as sulfuric, nitric, hydrochloric, acetic, propionic or ascorbic acid.
  • alkali agent various hydroxides or ammonium salts can be incorporated preferably including potassium hydroxide, sodium hydroxide, aqueous ammonia, triethanolamine and diethanolamine.
  • the black-and-white developer for use in the present invention preferably contains a silver halide solvent that acts as development accelerator.
  • a silver halide solvent that acts as development accelerator.
  • Preferable examples include thiocyan salt, sulfite salts, thiosulfate, 2-methylimidazole and the thioethers described in Japanese Patent Application (Laid-Open) No. 63580/1982.
  • a preferable addition amount of the silver halide solvent is from 0.005 to 0.5 mol/L.
  • development accelerators are quaternary amines, poly(ethylene oxide)s, 1-phenyl-3-pyrrazolidone and its derivatives, primary amines and N,N,N',N'-tetramethyl-p-phenylenediamine.
  • the black-and-white developer for use in the present invention can further contain not only a dissolution aid such as diethylene glycol, propylene glycol and other poly (ethylene glycol)s and various amines including diethanolamine and triethanolamine, but also a quaternary ammonium salts as a sensitizing agent. Moreover, a surfactant and a gelatin hardener may be incorporated.
  • a dissolution aid such as diethylene glycol, propylene glycol and other poly (ethylene glycol)s and various amines including diethanolamine and triethanolamine, but also a quaternary ammonium salts as a sensitizing agent.
  • a surfactant and a gelatin hardener may be incorporated.
  • anti-foggants may be used for the purpose of preventing development fog.
  • Suitable anti-foggants include alkali metal halides such as sodium chloride, potassium chloride, potassium bromide, sodium bromide and potassium iodide, and organic anti-foggants.
  • Preferable organic anti-foggants include nitrogen-containing heterocyclic compounds such as, for example, benzotriazole, 6-nitrobenzoimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole and hydroxyazaindolizine, mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole and 2-mercaptobenzothiazole, and mercapto-substituted aromatic compounds such as thiosalicylic acid.
  • the anti-foggant includes the components eluted from the color reversal photographic materials during development to accumulate in the bath.
  • the iodide is incorporated at a concentration between 5 x 10 -6 and 5 x 10 -4 mol/L.
  • the bromide which also preferably acts as an anti-foggant, is incorporated at a concentration of 0.001 to 0.1 mol/L, and more preferably 0.01 to 0.05 mol/L.
  • a swelling-suppressing agent e.g., inorganic salts such as sodium sulfate and potassium sulfate
  • a hard water-softener may be incorporated.
  • Preferable hard water-softeners usable in the present invention include amino-polycarboxylic acids, amino-polyphosphonic acids, phosphonocarboxylic acids, organic and inorganic phosphonic acids and the above-described compounds represented by formula (I) that are associated with the present invention. Some specific examples are shown below, but the scope of the present invention is not restricted to those examples at all.
  • These hard water-softening agents may be used individually or in combination of two or more thereof.
  • a preferable range for the added amount of such a hard water-softening agent is from 0.1 to 20 g/L, more preferably from 0.5 to 10 g/L.
  • the standard processing time of the black-and-white development is, in most cases, from 4 to 8 min, and mostly 6 min. However, by extending or cutting short the development time appropriately, the photographic speed of an improperly exposed photographic material can be shifted to a higher or lower value. Such process manipultion is called push/shallow processing altogether.
  • the photographic speed can be regulated by changing the processing time between 2 and 18 min.
  • the processing temperature is usually 20 to 50°C, preferably 33 to 45°C.
  • the replenishing amount of the black-and-white developer is from 100 to 5000 ml per 1 m 2 of the processed photographic material, preferably from 200 to 2500 ml per 1 m 2 of the processed photographic material.
  • the black-and-white development is followed by rinsing with water and/or a rinsing solution, if needed. Thereafter, reversal processing and then color-forming development are carried out.
  • rinsing with water or a rinsing solution may be carried out with a single bath, it is more preferable to adopt a multi-stage counter current system using two or more tanks in order to reduce the replenishing amount.
  • a relatively large amount of water is replenished.
  • the rinsing with a rinsing solution is conducted with a reduced replenishing amount comparable to the replenishing amount for other processing baths.
  • the replenishing amount for the rinsing with water is preferably from 3 to 20 L per 1m 2 of the photographic material.
  • the replenishing amount for the rinsing with a rinsing solution is preferably from 50 ml to 2 L, more preferably from 100 ml to 500 ml per 1 m 2 of the processed photographic material, thus achieving a marked reduction of water usage compared with the rinsing with water.
  • the rinsing bath of the present invention may contain an oxidizing agent, a chelating agent, a buffering agent, an antiseptic, and a fluorescent brightening agent depending on need.
  • an image-reversing step or light-fogging is conducted.
  • chemical fogging agents well known in the art are contained.
  • Useful fogging agents include stannous ion-containing complex salts such as stannous ion-organic phosphoric acid complex salts (U.S. Patent 3,617,282), stannous ion-organic phosphonocarboxylic acid complex salts (Japanese Patent Publication No. 32616/1981) and stannous ion-amino-polycarboxylic acid complex salts (U.S.
  • Patent 1,209,050 the stannous ion complex salts represented by formulae (II) and (III) of Japanese Patent Application (Laid-Open) No. 109573/1999; boron-containing compounds such as borohydrides (U.S. Patent 2,984,567) and heterocyclic amine borane salts (British Patent 1,011,000).
  • the pH of the reversal bath ranges from an acid to alkaline side depending on the type of fogging agent used, namely from 2 to 12. More frequently it ranges from 2.5 to 10, and more preferably from 3 to 9.
  • the stannic ion in the reversal bath has a concentration between 1 x 10 -3 and 5 x 10 -2 mol/L, preferably between 2 x 10 -3 and 1.5 x 10 -2 mol/L.
  • concentration is from 1 x 10 -3 and 5 x 10 -2 mol/L, preferably from 2 x 10 -3 and 1.5 x 10 -2 mol/L.
  • the reversal bath preferably contains propionic acid, acetic acid or the alkylenedicarboxylic acid compounds represented by formula (I) of Japanese Patent Application (Laid-Open) No. 109572/1999.
  • acetic acid is particularly preferred.
  • the reversal bath preferably contains a sorbic acid salt or the quaternary ammonium compound described in U.S. Patent 5,811,225 as bactricide.
  • the image reversal processing lasts usually for 10 sec to 3 min, preferably for 20 sec to 2 min, and more preferably for 30 to 90 sec.
  • the temperature of the reversal bath which preferably is in the temperature range for either of the first development, the subsequent rinsing or the rinsing with water, and the color-forming development, is usually set at 20 to 50°C, preferably 33 to 45°C.
  • the replenishing amount for the reversal bath is 10 to 2000 ml, preferably 200 to 1500 ml per 1 m 2 of the processed photographic material.
  • tin (II) chelates and boron-containing fogging agents are effecttive over a wide range of pH, the addition of a pH-buffer is not required. However, it nonetheless causes no harm to add a compound that provides pH-buffering capability.
  • Such compounds include acids, alkalis or salts exemplified by organic acids such as citric or malic, inorganic acids such as boric, sulfuric or hydrochloric, alkali carbonates, caustic alkalis, borax or potassium metaborate.
  • a hard water-softening agent such as aminopolycarboxylic acid, a swelling-suppressing agent such as sodium sulfate or an anti-oxidant such as p-aminophenol may be added.
  • the photographic material that has been processed with a reversal bath then proceeds to a color-forming development step.
  • the color-forming developer for use in the color-forming development of the present invention is an aqueous alkaline solution mainly containing a color-forming developing agent of an aromatic primary amine.
  • a color-forming developing agent p-phenylenediamines are preferably used.
  • Typical examples of such p-phenylenediamine compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamideethyl-aniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline, and their salts such as sulfate, hydrochlorate, phosphate, p-toluenesulfonate, tetraphenylborate, p- (t-octyl)benzenesulfonate.
  • Two or more compounds may be used as the developing agent, if needed.
  • a preferable concentration of the color-forming developing agent is from 0.005 to 0.1 mol/L, a more preferable one being from 0.01 to 0.05 mol/L.
  • the pH of the color-forming developer for use in the present invention is preferably 8 to 13, more preferably 10.0 to 12.5.
  • a phosphate salt is used as an essential alkali agent in the present invention.
  • the counter ion can be an alkali metal such as sodium, potassium or lithium, ammonium and an organic onium.
  • the sodium or potassium salts are preferred.
  • the concentration of the phosphate salt is preferably 0.05 to 0.25 mol/L, more preferably 0.05 to 0.15 mol/l in terms of phosphate ion concentration.
  • An alkali agent and a buffering agent other than phosphates may be jointly used.
  • Alkali agents and buffering agents which may be used in combination with a phosphate salt and have a buffering region of pH 8.0 or more include carbonates, borates, 5-sulfosalicylates, tetraborates, hydroxybenzoates, glycine salts, N,N-dimethylglycine salts, leucine salts, norleucine salts, guanine salts, 3,4-dihydroxyphenylalanine salts, alanine salts, aminobutyrates, 2-amino-2-methyl-1,3-propanediol salts, valine salts, proline salts, trishydroxyaminomethane salts and lysine salts.
  • carbonates and 5-sulfosalicylates are preferred due to their high solubility and an excellent buffering ability at a high pH region of 10.0 or more, thus effectively suppressing the variation of pH by expanding the buffering region secured by phosphate ion.
  • alkali agent and the buffering agent include phosphates such as trisodium phosphate, tripotassium phosphate, disodium phosphate and dipotassium phosphate.
  • Alkali agents which may be used in combination with these include sodium and potassium carbonates, sodium and potassium bicarbonates, dipotassium 5-sulfosalicylate, sodium and potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, potassium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).
  • Preferable compounds are trisodium or tripotassium phosphate, disodium or dipotassium phosphate, dipotassium or disodium 5-sulfosalicylate.
  • the added amount of the buffering agent in the developer is preferably not less than 0.05 mol/L, more preferably 0.05 to 0.4 mol/L. In cases where two or more buffering agents are jointly used, these values hold for the total amount thereof.
  • Useful development accelerators include various pyridinium compounds typically disclosed in U.S. Patent 2648604, and Japanese Patent Publication No. 9503/1969 and U.S. Patent 3171247 and other cationic compounds; cationic dyes such as phenosafranine; neutral salts such as thallium nitrate and potassium nitrate; the poly(ethylene glycol)s and their derivatives described in Japanese Patent Publication No. 9304/1969, U.S. Patents 2533990, 2531832, 2950970 and 2577127; nonionic compounds such as polyethylene glycols and polythioethers; and the thioether compounds described in U.S. Patent 3201242.
  • benzyl alcohol diethylene glycol that acts as solvent for benzyl alcohol, triethanolamine and diethanolamine can be used.
  • these compounds is used as scarcely as possible, since they tend to cause various problems including the increase of environmental load, solution stability and the formation of tarry substance.
  • a silver halide solvent may be incorporated such as, for example, the alkali metal salt of thiocyanic acid, 2-methylimidazole, the thioether compounds disclosed in Japanese Patent Application (Laid-Open) No. 63580/1982 and the like.
  • a particularly preferable compound is 3,6-dithiaoctane-1,8-diol.
  • the preferable content of the silver halide solvent is common to that for the black-and-white developer used for the first development.
  • anti-foggants may be incorporated in the color-forming developer for the purpose of maintaining the developer composition and performance when the development is conducted along with a constant feeding of color film rolls, i.e., in the so-called running mode.
  • Preferable anti-foggants used in development include alkali metal halides such as potassium and sodium chlorides, potassium and sodium bromide and potassium iodide, and organic anti-foggants.
  • Organic anti-foggants include, for example, nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole and hydroxyazaindolizine; mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzoimidazole and 2-mercaptobenzothiazole; and mercapto-substituted aromatic compounds such as thiosalicylic acid.
  • nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole,
  • the anti-foggant in the developer includes the component that is eluted from the processed color reversal photographic material to accumulate in the developer. Since the concentration of such anti-foggant in the developer has little effect on the photographic characteristics in the case of color reversal development, any control thereof is not necessary.
  • Typical preservatives are hydroxylamines and sulfite salts, the latter being more preferred. They are used at a concentration of from 0 to 0.1 mol/L.
  • the color-forming developer used in the present invention may contain an organic preservative instead of hydroxyamine or sulfite ion.
  • the organic preservative means any organic compound capable of retarding the deterioration of the primary aromatic amine as the color-forming developing agent; more concretely, it designates organic compounds having a function of preventing the oxidation (e.g., by the air) of the color-forming developing agent.
  • Particularly effective organic preservatives include hydroxylamine derivatives except hydroxylamine, hydroxamic acids, hydrazines, hydrazides, phenols, ⁇ -hydroxyketones, ⁇ -aminoketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds and condensed ring-type amines.
  • Still other types of preservatives may be used including the various metals disclosed in Japanese Patent Application (Laid-Open) Nos. 44148/1982 and 53749/1982, the salicylic acids disclosed in Japanese Patent Application (Laid-Open) No. 180588/1984, the amines disclosed in Japanese Patent Application (Laid-Open) Nos. 239447/1988, 128340/1988, 186939/1989 and 187557/1989, the alkanolamines described in Japanese Patent Application (Laid-Open) No. 3532/1979, the polyethyleneimines described in Japanese Patent Application (Laid-Open) No. 94349/1981 and the aromatic polyhydroxy compounds described in U.S. Patent 3,746,544 depending on need.
  • alkanolamines such as triethanolamine, dialkylhydroxylamines such as N,N-diethylhydroxylamine and N,N-di(sulfoethyl)hydroxylamine, hydrazine derivatives except hydrazine such as N,N-bis(carboxymethyl)hydrazine, or aromatic polyhydroxy compounds such as sodium catechol-3,5-disulfonate are preferably added.
  • the addition amount of such an organic preservative is preferably 0.02 to 0.5 mol/L, more preferably 0.05 to 0.2 mol/L. If necessary, two or more compounds may be jointly used.
  • the color-forming developer of the present invention may contain an organic solvent such as diethylene glycol and triethylene glycol; a dye-forming coupler; a competing coupler such as citrazinic acid, J-acid or H-acid; a nucleating agent such as sodium boron hydride; an auxiliary developing agent such as 1-phenyl-3-pyrrazolidone; a tackifier; a chelating agent such as an aminopolycarboxylic acid (e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriamine pentaacetic acid, triethylenetetraminehexaacetic acid and the compounds described in Japanese Patent Application (Laid-Open) No.
  • an organic solvent such as diethylene glycol and triethylene glycol
  • an organic phosphonic acid e.g., 1-hydroxyethylidene-1,1'-diphosphonic acid and those described in Research Disclosure No. 18170 (1979 May)
  • an aminophosphonic acid e.g., aminotris(methylenephosphonic acid), and ethylenediamine-N,N,N',N'-tetramethylenphosphonic acid
  • a phosphonocarboxylic acid e.g., those described in Japanese Patent Application (Laid-Open) Nos. 102726/1978, 42730/1978, 121127/1979, 4024/1980, 4025/1980, 126241/1980, 65955/1980 and 65956/1980, and Research Disclosure No. 18170 (1979 May)
  • These chelating agents two or more of which may be used together depending on need, may be contained at an amount of 0.05 to 20 g/L, preferably 0.1 to 5 g/L.
  • a surfactant may be incorporated.
  • Suitable compounds include alkylsulfonic acids, arylsulfonic acids, aliphatic and aromatic carboxylic acids and polyalkyleneimines.
  • the processing temperature of the color-forming development applied to the present invention is 20 to 50°C, preferably 33 to 45°C.
  • the processing time is from 20 sec to 5 min, preferably from 20 sec to 4 min.
  • the replenishing amount which is as small as possible within the range of maintaining developer activity, is appropriately from 100 to 2500 ml, preferably from 400 to 1200 ml per 1 m 2 of the processed photographic material.
  • the color reversal photographic material that has been subjected to color-forming development is then subjected to a desilvering treatment.
  • the desilvering treatment is carried out in one of the following procedures.
  • No. 1 and No. 3 are particularly preferred.
  • Replenishment in each procedure may be carried out individually on each processing bath in the conventional manner.
  • the solution overflowing from the bleaching solution may be introduced to the blix bath, whereby the blix bath is replenished only with the fixing solution.
  • the overflowing solution of the bleaching solution is introduced to the blix bath, the overflowing solution of the fixing solution is introduced to the blix bath by means of counterflow system, whereby the two introduced solutions are overflown from the blix bath.
  • blix accelerators can be incorporated in the bleaching or blix bath, or the adjustment bath preceding the bleaching or blix treatment.
  • Such blix accelerators include the various mercapto compounds disclosed in U.S. Patent 3,893,858, British 1,138,842 and Japanese Patent Application (Laid-Open) No. 141623/1978 ; the disulfide bond-containing compounds described in Japanese Patent Application (Laid-Open) No. 95630/1978; the thiazolidine derivatives described in Japanese Patent Publication No. 9854/1978; the isothiourea derivatives described in Japanese Patent Application (Laid-Open) No. 94927/1978; the thiourea derivatives described in Japanese Patent Publication Nos. 8506/1970 and 26586/1974; the thioamide compounds described in Japanese Patent Application (Laid-Open) No.
  • blix accelerators include alkylmercapto compounds unsubstituted or substituted with a hydroxy group, a carboxyl group, a sulfonic acid group or an amino group.
  • the amino group may have a substituent such as alkyl or acetoxyalkyl.
  • Specific compounds are, for example, trithioglycerin, ⁇ , ⁇ '-thiodipropionic acid and ⁇ -mercaptobutyric acid.
  • the compounds described in U.S. Patent 4,552,834 can also be used.
  • the content thereof which depends on the type of the photographic material to be processed, the processing temperature and the processing time needed for the processing in concern, is appropriately 1 x 10 -5 to 10 -1 mol, preferably 1 x 10 -4 to 5 x 10 -2 mol per 1 liter of the processing solution.
  • an image-stabilizing agent is preferably incorporated.
  • the formaldehyde-bisulfide adduct described in U.S. Patent 5,037,725 is preferably contained.
  • the secondary amine described in U.S. Patent 5,523,195 may be incorporated.
  • the pH of the adjustment solution is usually 3 to 11, preferably 4 to 9, and more preferably 4.5 to 7.
  • the processing time with the adjustment solution is preferably for 20 sec to 3 min, more preferably 20 sec to 2 min, and most preferably 30 to 60 sec.
  • the replenishing amount for the adjustment solution is preferably from 30 to 2000 ml, particularly preferably from 50 to 1500 ml per 1 m 2 of the processed photographic material.
  • the temperature for the adjustment processing is preferably from 20 to 50°C, particularly preferably from 30 to 40°C.
  • the blix (bleach-fix) solution contains as a fixing agent a water-soluble silver halide solvent including thiosulfate salts such as sodium or ammonium thiosulfate, thiocyanate salts such as sodium, ammonium or potassium thiocyanate, thioether compounds such as ethylenebisthioglycolic acid or 3,6-dithia-1,8-octanediol, and thiourea. These compounds may be used individually or in combination of two or more thereof.
  • a special blix formulation comprising a fixing agent and a large amount of a halide such as potassium iodide as described in Japanese Patent Application (Laid-Open) No. 155354/1980 can be adopted, too.
  • the amount of such a fixing agent is from 0.1 to 3 mol, preferably from 0.2 to 2 mol per 1 liter of the blix solution.
  • the advantageous effects of the present invention i.e., prevention color restoration failure, stain reduction and smudge prevention for the processed material are fully achieved when the bleaching solution having a specific pH value contains an iron (III) complex salt represented by formula (I) or (II) together with a carboxylic acid represented by formula [A], and when the fixing or blix solution contains a compound selected from imidazoles at a content of 1 to 50 g/L.
  • Preferable imidazoles include unsubstituted imidazole, those having at the 1-, 2-, 4- or 5-position a substituent selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a hydroxyalkyl or carboxyalkyl group having 1 to 6 carbon atoms or an imidazol derivatives substituted with a carboxyl group.
  • Specially preferable imidazole derivatives are imidazole, 2-methylimidazole, 4-methylimidazole, 4-methyl-5-(hydroxymethyl)imidazole and imidazole-4,5-dicarboxylic acid.
  • imidazole, 2-methylimidazole and imidazole-4,5-dicarboxylic acid are still more preferred, imidazole being the most preferred.
  • the content range for such an imidazole derivative is preferably 1 to 25 g/L, more preferably 1.5 to 10 g/L.
  • the fixing agent thereof is a water-soluble silver halide solvent well known in the art, including thiosulfates such as sodium or ammonium thiosulfate, thiocyanate salts such as sodium, ammonium or potassium thiocyanate, thioether compounds such as ethylenebisthioglicolic acid or 3,6-dithia-1,8-octanediol, and thiourea. These compounds may be individually or in combination of two or more thereof.
  • the concentration of such a fixing agent is from 0.1 to 3 mol, preferably 0.2 to 2 mol per 1 L of the fixing solution.
  • the solution having a fixing function can contain, as a preservative, a sulfite salt (e.g., sodium, potassium or ammonium sulfite), a bisulfite salt, hydroxylamine, hydrazine or an aldehyde-bisulfite adduct (e.g., acetaldehyde-sodium bisulfite).
  • a sulfite salt e.g., sodium, potassium or ammonium sulfite
  • a bisulfite salt e.g., sodium, potassium or ammonium sulfite
  • bisulfite salt e.g., sodium, potassium or ammonium sulfite
  • hydroxylamine hydrazine
  • aldehyde-bisulfite adduct e.g., acetaldehyde-sodium bisulfite
  • Other effective preservatives include sulfinic acids (e.g., benzenes
  • bistriazinylarylenediamine may be used depending on need.
  • fluorescent brightening agents bis(triazinylamino)stylbenesulfonic acid compounds can also be used, including conventionally known or commercially available diaminostylbene compounds. Particularly, those described in Japanese Patent Application (Laid-Open) Nos. 329936/1994, 140625/1995 and 140849/1998 are preferably used.
  • descriptions are found in, for example, Senshoku Nouto (Book on Dyeing) 9th Edition (published by Irozomesha) , pp. 165 to 168.
  • Blankophor BSU liq. and Hakkol BRK are specially preferred.
  • these triazine group-containing compounds may be incorporated in any processing bath, they are preferably incorporated in the color-forming developer or the fixing solution.
  • the replenishing amount for the bleaching, fixing or blix bath which can be set arbitrary so as to maintain the function of each bath, is preferably 30 to 2,000 ml, more preferably 50 to 1,000 ml per 1 m 2 of the processed photographic material.
  • the processing temperature is preferably 20 to 50°C, more preferably 33 to 45°C, while the processing time is 10 sec to 10 min, preferably 20 sec to 6 min.
  • the photographic material is usually subjected to rinsing and/or stabilizing treatment.
  • the stabilizing bath usually but not always contains an image stabilizer.
  • Stabilizing baths not containing stabilizer are called wash-replacing stabilizing bath to differentiate from stabilizer-containing ones.
  • the function of such a wash-replacing stabilizing bath is regarded as substantially the same as that of the rinse bath (washing bath). Accordingly, in the following, a common explanation will be given for all the related processing steps except image stabilizing step.
  • the amount of washing water in the water-washing step is set in the wide range according to various conditions such as the characteristics of the photographic material, the use, the water-washing temperature and the number of washing tank (the number of stages).
  • the relation between the number of washing tanks and the quantity of water for a multi-stage counter-current system can be obtained by the method described in Journal of the Society of Motion Picture and Television Engineers, 64, pp. 248 to 253 (May, 1955).
  • the number of steps in the multi-stage counter-current system is preferably between 2 and 15, particularly preferably between 2 and 10.
  • Bokin Bokin- Bokabi-zai Jiten (Encyclopedia of Antibacterial and Antifungal Agents) edited by the Society for Antibacterial and Antifungal Agents, Japan (1986).
  • aldehydes such as formaldehyde, acetaldehyde or pyruvinaldehyde, which inactivate remaining magenta couplers thus preventing dye fading as well as stain formation, the methylol compounds and hexamethylenetetramine described in U.S. Patent 4786583, the hexahydrotriazines described in Japanese Patent Application (Laid-Open) No. 153348/1990, the formaldehyde-bisulfite adduct described in U.S. Patent . 4921779, and the azolylmethylamines described in European Patent Application (Laid-Open) Nos. 504609 and 519190 may be incorporated.
  • aldehydes such as formaldehyde, acetaldehyde or pyruvinaldehyde, which inactivate remaining magenta couplers thus preventing dye fading as well as stain formation
  • a surfactant as a water-draining agent, EDTA or a chelating agent such as those represented by formula (II) as a hard water-softener may be incorporated.
  • Suitable surfactants include nonionic ones of poly (ethylene glycol) type or polyhydric alcohol type, anionic ones such as alkylbenzenesulfonic acid salts, sulfuric acid esters of higher alcohols or alkylnaphthalenesulfonic acid salts, cationic ones such as quaternary ammonium salts or amine salts, or amphoteric ones such as amino acid salts or betaines. Two or more of these surfactants may be used together.
  • the fluorine-containing surfactants as disclosed in U.S. Patent 5,716,765 or siloxane-type ones may be also used.
  • alkyl poly (ethylene oxide)s, alkyl phenoxypoly(ethylene oxide)s or alkyl phenoxypoly(hydroxypropylene oxide)s are preferred.
  • particularly preferable anionic surfactants are those comprising an alkyl-poly(oxyethylene) of 8 to 15 carbon atoms and an alcohol of 10 to 30 carbon atoms, the most preferable ones being those comprising an alkyl-poly(oxyethylene) of 8 to 11 carbon atoms and an alcohol of 15 to 25 carbon atoms.
  • a solubilizing agent such as amines (e.g., diethanolamine or triethanolamine) or glycols (e.g., diethylene glycol or propylene glycol) are preferably incorporated.
  • a chelating agent is preferably incorporated in order to capture heavy metals, thus improving the solution stability and reducing contamination.
  • the stabilizing or rinse bath preferably contains a bactericide and a fungicide with the purpose of preventing the propagation of bacteria and fungi. Commercially available bactericides and fungicides can be used for such a purpose.
  • the baths may contain a surfactant, a fluorescent brightening agent and a hardener.
  • the pH of the stabilizing or rinse bath, and that of the washing water for use in the present invention is usually between 4 and 9, and preferably between 5 and 8.
  • Ordinary ranges of the processing temperature and time for these baths are from 15 to 45°C and from 20 sec to 10 min, preferably from 25 to 40°C and from 30 sec to 2 min, though they vary widely depending on the nature and the application of the photographic material to be processed.
  • the stabilizing or rinse bath of the present invention exhibits a marked advantageous effect of contamination prevention in the case where the photographic material is processed by a desilvering treatment immediately followed by a treatment with the stabilizing or rinse bath of the present invention, i.e., without intervening washing with water after desilvering.
  • the replenishing amount of the stabilizing or rinse bath of the present invention is preferably 200 to 2,000 ml per 1 m 2 of the processed photographic material.
  • the overflowing liquid yielded along with the replenishment of the washing water and/or the stabilizing solution can be again used in other processing steps including desilvering.
  • the stabilization treatment is conducted without washing with water in the processing of photographic materials according to the present invention
  • the methods well known in the art and described in Japanese Patent Application (Laid-Open) Nos. 8543/1982, 14834/1983 and 220345/1985 can be adopted.
  • chelating agents such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound can be used.
  • the photographic material having been subjected to washing with water and/or stabilization treatment is then dried.
  • the material just after leaving the washing bath may be squeezed with a squeezing roller or a piece of water-absorbing cloth to decrease the water content in the image-forming layers and accelerate drying.
  • adoption of higher temperatures or modifying the nozzle shape to intensify the drying air stream is self-evidently effective.
  • Film drying can also be accelerated by the adjustment of the angle at which the drying air is directed toward the material surface as described in Japanese Patent Application (Laid-Open) No. 157650/1991.
  • the amount of developed silver in the present invention indicates the total of the silver amounts developed by black-and-white and color-forming developments. Thus, the total amount of developed silver reaches to 3.0 to 7.0 g/m 2 when the processed photographic material is a reversal-type color material such as a reversal color film. While commercially available color negative photographic materials and reflection-type color photographic materials such as color photographic paper are developed only at exposed areas thereof thus giving the amount of developed silver below 2 g/m 2 , the reversal color photographic material undergoes development at exposed areas in the first development, and then color-forming development of the unexposed, remaining silver halide.
  • the present invention exhibits its advantageous features particularly in the processing of color reversal films.
  • silver halide color reversal films comprise a red-sensitive unit, a green-sensitive unit and a blue-sensitive unit arranged on a support in this order described from the support side. Between the red-sensitive unit and the green-sensitive unit, and/or between the green-sensitive unit and the blue-sensitive unit, one or more interlayers that do not form color are provided.
  • each photosensitive unit comprises three layers
  • a low-speed emulsion layer, a medium-speed emulsion layer and a high-speed emulsion layer are preferably arranged in this order from the support side.
  • a photo-insensitive interlayer that may contain a photo-insensitive silver halide emulsion may be provided.
  • all of the blue-, green- and red-sensitive units preferably comprise three layers, it is also possible to have the blue-sensitive unit comprising two layers or less, and the green- and red-sensitive units comprising three layers.
  • the blue-sensitive layers contain a yellow coupler
  • the green-sensitive ones contain a magenta coupler
  • the red-sensitive ones contain a cyan coupler.
  • the other couplers may be mixed in the above combinations.
  • the silver/coupler ratio in each photosensitive layer is preferably regulated so as to be the largest in the low-speed layer.
  • An interlayer that does not develop color is preferably provided between the units each being different in spectral sensitivity.
  • Such a non-color-forming interlayer may contain a photo sensitive emulsion, a photo-insensitive one or one fogged in advance.
  • the interlayer may be of monolayer structure or comprise two to five sub-layers. In the latter case, it is preferred that a sub-layer placed far from the support contains colloidal silver particles or a silver halide emulsion that has been superficially or internally fogged beforehand. In the case where a silver halide emulsion is incorporated in an interlayer, the interlayer or the layer adjacent to the interlayer is preferably contain a color mixing-preventing agent.
  • a red-sensitive unit On a support are provided a red-sensitive unit, a green-sensitive unit and a blue-sensitive unit in this order from the support side wherein at least the red- and green-sensitive units comprise three photosensitive emulsion layers. And the three emulsion layers are arranged in the order of low-speed, medium-speed and high-speed layers from the support side.
  • the silver/coupler ratio in these photosensitive layers is preferably from 25 to 150 whereby the medium-speed layer has a silver/coupler ratio of 5 to 30, and the high-speed layer has a silver/coupler ratio of 2 to 20.
  • an interlayer comprising two to five sub-layers is provided between the red-sensitive unit and the green-sensitive unit, and between the green-sensitive unit and the blue-sensitive unit.
  • the sub-layer adjacent to the green-sensitive layer may contain colloidal silver particles or a fogged silver halide emulsion.
  • the sub-layer adjacent to the blue-sensitive layer may contain colloidal silver particles or a fogged silver halide emulsion.
  • the thickness of the interlayer (total of all the sub-layer thickness) is usually 0.5 to 5 ⁇ m, preferably 1.0 to 3.0 ⁇ m. The thickness can be readily obtained from the specific gravity of each ingredient, or alternatively by examining the cross-section of the coated product with an electron microscope.
  • an anti-halation layer in the support side of the red-sensitive unit, and at least one protective layer located farther than the blue-sensitive unit from the support.
  • At least one of protective layer preferably contains a silver halide emulsion.
  • the layers of the following compositions were provided to prepare a multi-layer color photographic material.
  • the resulting material was designated as Sample 101.
  • the numerals indicate the added amount per m 2 .
  • Second layer inter-layer Gelatin 0.40 g Compound Cpd-A 0.2 mg Compound Cpd-J 1.0 mg Compound Cpd-K 3.0 mg Compound Cpd-M 0.030 g UV absorber U-6 6.0 mg High boiling point organic solvent Oil-3 0.010 g High boiling point organic solvent Oil-4 0.010 g High boiling point organic solvent Oil-7 2.0 mg High boiling point organic solvent Oil-8 4.0 mg Dye D-7 4.0 mg
  • every emulsion layer was added with additives F-1 to F-8. Further, each layer was incorporated with gelatin hardener H-1, surfactants W-3, W-4, W-5 and W-6 as a coating aid or an emulsifier.
  • Emulsions used in Sample 101 Emulsions
  • B Monodisperse (111) internal latent image type tabular grains with mean aspect ratio of 2.0 0.25 10 4.8
  • C Monodisperse (111) tabular grains with mean aspect ratio of 2.0 0.30 10 4.0
  • D Monodisperse (111) tabular grains with mean aspect ratio of 3.0 0.35 12 4.8
  • E Monodisperse (111) tabular grains with mean aspect ratio of 3.0 0.40 10 2.5
  • Monodisperse, cubic grains 0.15 9 3.5 H Monodisperse, cubic, internal latent image type grains 0.24 12 4.9
  • Dye E-1 was dispersed by the following process. To 1430 g of a wet cake of dye E-1 containing 30% of methanol, 200 g of Pluronic F88, (an ethylene oxide-propylene oxide block copolymer) made by BASF Corp. were added together with water to give a slurry with a dye content of 6%. Then, an Ultra-viscomill (UVM-2, a product of Imex Corp.) was charged with 1700 ml of zirconia beads having a mean diameter of 0.5 mm. The slurry was passed through the mill, and subjected to grinding for 8 hours at a peripheral speed of about 10 m/sec and a discharge rate of 0.5 L/min.
  • Pluronic F88 an ethylene oxide-propylene oxide block copolymer made by BASF Corp.
  • the resulting dispersion was diluted with water to give a dye concentration of 3%.
  • the diluted dispersion was then heated at 90°C for 10 hours for stabilization.
  • the average size of the obtained dye particles was 0.60 ⁇ m with a distribution width of 18% in terms of standard deviation of (particle size x 100/average particle size).
  • the photographic material prepared above (Sample No. 101) was exposed to a CIE D50 light source through an optical wedge designed for live scene shooting photographic materials (neutral color, density gradient of 0.4/cm and density range of 4.8) ; thereafter the material was processed by the following processing procedures (development treatment A) Process step Duration (min) Temp. (°C) Tank volume (L) Replenished amount (ml/m 2 ) First development 6 38 165 2,200 First washing 2 38 50 7,500 Image reversal 2 38 86 1,100 Color-forming development 6 38 165 2,200 Pre-bleaching 2 38 65 1,100 Bleaching 4 38 150 220 Fixing 4 38 108 1,100 Second washing 4 38 55 7,500 Final rinsing 1 25 44 1,100
  • each processing bath was as follows. [First developer] Tank solution Replenisher Nitrilo-N,N,N-trimethylenephosphoric acid pentasodium salt 1.5 g 1.5 g Diethylenetriaminepentaacetic acid pentasodium salt 2.0 g 2.0 g Sodium sulfite 28 g 30 g Hydroquinone potassium monosulfonate 18 g 20 g Potassium carbonate 20 g 20 g Potassium bicarbonate 15 g 15 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrrazolidone 1.5 g 2.0 g Potassium bromide 2.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 g Potassium iodide 4.0 mg 1.5 mg Diethylene glycol 15 g 15 g Water to make 1000 ml 1000 ml PH 9.65 9.70 The pH was adjusted with sulfuric acid or potassium hydroxide.
  • Tank solution Replenisher Nitrilo-N,N,N-trimethylenephosphoric acid pentasodium salt 3.0 g The same as tank sol.
  • Stannous chloride dihydrate 2.0 g p-Aminophenol 0.001 g
  • Sodium hydroxide 8 g
  • Acetic acid 15 ml Water to make 1000 ml PH 6.00 The pH was adjusted with acetic acid or sodium hydroxide.
  • Tank solution Replenisher Bleaching agent (shown in Table 4) 0.15 mol 0.30 mol Added compound (shown in Table 4) 0.02 mol 0.04 mol Compound VI Iron (III) complex (shown in Table 4) 0.03 mol 0.06 mol Potassium bromide 100 g 200 g Ammonium nitrate 10 g 20 g Water to make 1000 ml 1000 ml PH 5.0 4.8 The pH was adjusted with nitric acid or ammonium hydroxide.
  • the amount of residual silver, the deposition of ferric compound (i.e., iron (III) compound, stain formation and failure of color restoration were evaluated by the following methods.
  • Amount of residual silver the silver amount remaining in the processed photosensitive material was quantitatively measured by fluorescent X-ray analysis. By measuring the silver amount of the sample for which the treatment with a bleaching solution was omitted and subtracting the weight of the colloidal silver from the measured value, the amount of developed silver was determined to be 4.5 g/m 2 .
  • Failure of color destoration the photographic characteristic (HD) curve was obtained for each photosensitive material that had been processed in the above-described manner with a transmission densitometer having a measuring optical system in conformity with International Standard ISO 5.
  • the D max (R) which indicates the maximum density measured with red light was read.
  • a reference sample for comparison was prepared by repeating the same processing as above except that the bleaching solution was replaced to the following reference bleaching solution having a sufficiently high bleaching activity and that the bleaching time was changed to 6 min.
  • the corresponding D max (R) was similarly obtained and designated Ref.
  • D max (R) was similarly obtained and designated Ref.
  • Precipitation formation of ferric compound each bleaching tank solution after 2 round treatments (One round treatment corresponds to the processing amount for the replenishing volume integral equal to the tank volume.) was poured in a beaker, and the turbidity of the solution was visually inspected. At the same time, the existence of precipitate on the bottom of the beaker was checked. The following evaluation criteria were adopted.
  • Table 4 shows the evaluation results obtained by the methods described above.
  • the term "turbidity" has the same meaning as "precipitate formation”.
  • Test No. (I) Added compound (VI) Amount of residual Ag (mg/m 2 ) Color restoration failure (%) Stain Turbidity Note 1 I-8 - - 7.0 92 0.28 xx Compar. example 2 I-8 Compar. comp. (1) - 6.5 90 0.21 xx Compar. example 3 I-8 Compar. comp. (2) - 15.6 85 0.09 O Compar.
  • Table 4 indicates the following facts.
  • the conventional iron (III) PDTA Compounds (1) to (3)
  • Comparative Compound (1) is effective to suppress stain formation, precipitate deposition still takes place ⁇ Test No. 2>.
  • Comparative Compound (2) was added, both precipitate and stain formations were suppressed, but the amount of residual silver further increased ⁇ Test No. 3>.
  • color development was also incomplete.
  • a bleaching solution containing at least one iron (III) complex salt represented by formula (I) and at least one compound represented by formulae (II) to (V) is used for the processing of color photographic materials
  • precipitate deposition in the time-elapsed bleaching solution, stain formation and incomplete color development are difficult to occur even when a color-forming developer containing phosphate ion at a concentration of from 0.05 to 0.25 mol/L is used and the photographic material to be processed is a color reversal material that develops a large quantity of silver.
  • a bleaching solution can achieve a photographic processing of desirable developing quality.
  • the iron (III) complex salt of the iminocarboxylic acid represented by formula (VI) to the bleaching solution described above, the advantageous features of the present invention are enhanced.

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Abstract

A method of processing a silver halide color photographic Material, wherein the color-forming developer used for the color development step comprises phosphate ion at a concentration of from 0.05 to 0.25 mol/L, and the bleaching solution used for the bleaching step comprises at least one iron (III) complex salt of the compound represented by the following formula (I), and at least one of compounds represented by the following formulae (II), (III), (IV) and (V).

Description

    FIELD OF THE INVENTION
  • The present invention relates to a (development) processing method for a silver halide color photographic material (hereinafter described as simply photographic material), and in particular a processing method using a bleaching solution. The present invention specifically relates to a photographic processing method with which desilvering, color restoration and stain prevention are improved to achieve an excellent development quality.
    • BACKGROUND OF THE INVENTION
  • Silver halide color photographic materials give rise to images by processing after imagewise exposure. In such processing, the material is subjected to development, and then processed with a bleaching solution and a fixing solution. As the bleaching agent contained in the bleaching solution, the iron (III) complex salt of ethylenediaminetetraacetic acid (EDTA) has been widely used. However, from the viewpoints of rapid development processing and reduction of processing waste, a more active bleaching agent showing a higher bleaching speed with a smaller use amount than that of the EDTA iron (III) complex salt is earnestly demanded, and a variety of bleaching agents have been proposed. The iron (III) complex salt of 1,3-propylenediaminetetraacetic acid (1,3-PDTA), which is a specially desirable bleaching agent from the above viewpoints, is increasingly used in replace of the EDTA iron (III) complex salt. However, when a highly active bleaching agent such as 1,3-PDTA iron (III) complex salt, which works rapidly at a low amount, is used in combination with a color-forming developer containing phosphate ion, it has been confirmed that the bleaching solution is liable to turn turbid or form a precipitate along with a prolonged usage for processing. Thus, such a bleaching agent has a serious disadvantage when the processing is conducted in a continuous mode.
  • Further, the processing with a highly active bleaching agent has another drawback that photographic materials processed such as color print papers and films processed with the highly active bleaching agent tends to get stained when stored under a high temperature and high humid condition. Still another drawback accompanied by the highly active bleaching agent exists that, when such a highly active bleaching agent is used for a rapid bleaching treatment in the color-forming development (i.e., the color development) using the above-described developer, failure of color restoration, which indicates the fact that the degree of dye formation is incomplete, often takes place.
  • It has been confirmed that these drawbacks are particularly noticeable for photographic materials such as color reversal photographic materials that form a large quantity of developed silver in the development step. In such cases, an unfavorable image quality deterioration results.
    • SUMMARY OF THE INVENTION
  • Accordingly, An object of the present invention to solve is the drawbacks mentioned above associated with the processing using a phosphate ion-containing color-forming developer, and in particular the processing of reversal color photographic materials. Specifically, the object is to provide a method of processing a silver halide color photographic material wherein the bleaching solution neither becomes turbid nor generates any precipitate.
  • Another object of the present invention is to provide a method of processing a silver halide color photographic material which gives sufficient color-formation and little failure of color restoration in the processing, and shows little stain formation even when the processed material is stored under high temperature and highly humid conditions.
  • As a result of the extensive study carried out by the present inventors on the above-mentioned problems, they have found that the use of the iron (III) complex salt of a specific aminopolycarboxyacetic acid instead of EDTA iron (III) complex salt together with a specific complex-forming agent can prevent the above-described bleaching solution using a phosphate ion-containing color-forming developer from becoming turbid or precipitation formation. Based on this founding followed by a further thorough investigation, the present invention has been made. That is, the present invention is achieved by the following processing methods.
  • 1. A method of processing a silver halide color photographic material, wherein the color-forming developer used for the color development step comprises phosphate ion at a concentration of from 0.05 to 0.25 mol/L, and in which the bleaching solution used for the bleaching step comprises at least one iron (III) complex salt of the compound represented by the following formula (I), and at least one compound represented by the following formulae (II), (III), (IV) and (V):
    Figure 00040001
    wherein A1, A2, A3 and A4 may be the same or different, each represents -CH2OH, -PO3(M2)2 or -COOM1, and may be the same or different; M1 and M2 each represents a hydrogen atom, an alkali metal atom, an ammonium group or an organic ammonium group; X1 represents a straight-chain or branched-chain alkylene group having 3 to 6 carbon atoms, a ring-forming, saturated or unsaturated divalent organic group or - (B1O) n5-B2-; n5 represents an integer of 1 to 8; B1 and B2 may be the same or different, each representing an alkylene group having 1 to 5 carbon atoms; and n1, n2, n3 and n4 may be the same or different, each represents an integer not exceeding 10;
    Figure 00050001
    wherein R1 represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, a carboxyalkyl group or an alkoxyalkyl group; R2 and R3 each represents a hydrogen atom, an alkyl group or an alkoxyalkyl group; and M6, M7 and M8 each represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an onium group;
    Figure 00050002
    wherein L0 represents a divalent alkylene group having 2 to 8 carbon atoms, and M9 and M10 each represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an onium group; M11OOC―X2―NH―X3―NH―X4―COOM12 wherein in the formula, X2, X3 and X4 each represents a substituted or unsubstituted alkylene group having 1 to 3 carbon atoms, and M11 and M12 each represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an onium group;
    Figure 00060001
    wherein Z represents a nitrogen-containing heterocyclic ring; R4 represents a hydrogen atom, an alkyl group or an alkoxyalkyl group; M13 represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an onium group; and m represents an integer of 1 to 3.
  • 2. A method of processing a silver halide color photographic material according to the above item 1, wherein the bleaching solution further contains at least one iron (III) complex salt of the compound represented by formula (VI):
    Figure 00060002
    wherein G1 and G2 each represents a carboxyl group, a phosphono group, a sulfo group, a hydroxy group, a mercapto group, an aryl group, a heterocyclic group, an alkylthio group, an amidino group, a guanidino group or a carbamoyl group; L1, L2 and L3 each represents a divalent aliphatic or aromatic group or a divalent linking group comprising a combination thereof; m and n each represents 0 or 1; X represents a hydrogen atom, an aliphatic or aromatic group; and M represents a hydrogen atom or a cation.
  • 3. The method of processing a silver halide color photographic material according to the above item 2, wherein the content ratio of the iron (III) complex salt of the compound represented by formula (I) to the iron (III) complex salt of the compound represented by formula (VI) is in the range of from 0.1 to 0.8.
  • 4. The method of processing a silver halide color photographic material according to any one of the above items 1 to 3, wherein the compound represented by formula (I) is 1,3-propylenediaminetetraacetic acid.
  • 5. The method of processing a silver halide color photographic material according to any one of the above items 1 to 4, wherein the compound represented by formula (II) is selected from the group consisting of iminodisuccinic acid, N-carboxymethylaspartic acid and N,N'-dicarboxymethylaspartic acid.
  • 6. The method of processing a silver halide color photographic material according to any one of the above items 1 to 5, wherein the compound represented by formula (III) is N-(2-hydroxyethyl)aminodiacetic acid.
  • 7. The method of processing a silver halide color photographic material according to any one of the above items 1 to 6, wherein the compound represented by formula (IV) is ethylenediamine-N,N'-diacetic acid.
  • 8. The method of processing a silver halide color photographic material according to any one of the above items 1 to 6, wherein the compound represented by formula (V) is pyridine-2-carboxylic acid.
  • 9. The method of processing a silver halide color photographic material according to any one of the above items 1 to 8, wherein the compound represented by formula (VI) is N-carboxymethylaspartic acid.
  • One processing method that achieves the purpose of the present invention characteristically uses a bleaching solution containing at least one of the ion (III) complex salts of a compound represented by formula (I) , and at least one of compounds represented by one of formulae (II) to (V). This type of bleaching solution will not become turbid when used for a long time with a color-forming developer containing of 0.05 to 0.25 mol/L of phosphate ion. Moreover, failure of color restoration as well as stain formation is suppressed. The diaminopolycarboxylic acid compound represented by formula (I) is characterized by the number of atoms in the linking group for the two amino nitrogen atoms, the compound represented by formula (II) is characterized by being a carboxymethyliminosuccinic acid derivative, the compound represented by formula (III) is characterized by being a hydroxyalkyliminodiacetic acid derivative, the compound represented by formula (IV) is characterized by being an alkylenediaminedicarboxylic acid derivative, and the compound represented by formula (V) is characterized by being a nitrogen-containing heterocyclic carboxylic acid derivative.
  • It has been further found that the advantageous features of the bleaching solution according to the present invention are enhanced by incorporating the ion (III) complex salt of the compound represented by formula (VI).
  • Though the processing method of the present invention can be applied to any type of color photographic materials, it is particularly preferable and effective to apply to color reversal processing since phosphate ion-containing color-forming developers are extensively used for the processing of color reversal photographic materials.
  • The method of the present invention can be applied to the ordinary color processing comprising development with a phosphate ion-containing color-forming developer followed by desilvering with use of a processing solution having a bleaching capability. However, since a color processing method in which color-forming development (i.e., color development) is not directly followed by bleaching but by other steps such as pre-bleaching, etc., also suffers from the same problems mentioned previously such as deposition or precipitation of insoluble matters, the method of the present invention can be effectively applied to such processing.
    • DETAILED DESCRIPTION OF THE INVENTION
  • The present invention is described more in detail below. First of all, the compounds represented by formula (I) are explained.
  • In formula (I) , A1 to A4, which may be the same or different, each represents -CH2OH, -PO3(M2)2 or -COOM1; M1 and M2 each represents a hydrogen atom, an alkali metal atom (e.g., Na or K), an ammonium group or an organic ammonium group (e.g., methylammonium or trimethylammonium).
  • X1 represents a straight-chain or branched-chain alkylene group containing 3 to 6 carbon atoms, a ring-forming, saturated or unsaturated divalent organic group, or -(B1O)n5-B2-. B1 and B2 may be the same or different, each represents an alkylene group having 1 to 5 carbon atoms (containing those of the substituent). Symbols n1 to n4, which may be the same or different, each represents an integer of from 1 to 10, and at least one of them is not less than 2. The alkylene group represented by X1 includes ethylene, trimethylene or tetramethylene. The alkylene group represented by B1 or B2 includes methylene, ethylene or trimethylene. Suitable substituents for X1 or the alkylene group represented by B1 or B2 include hydroxyl and an alkyl group having 1 to 3 carbon atoms (e.g., methyl or ethyl) . n5 represents an integer of 1 to 8, preferably 1 to 4, and more preferably 1 to 2. In the following, preferable examples of the compound represented by formula (I) are shown not for the purpose of restricting the scope of the present invention thereto.
    Figure 00120001
    Figure 00120002
    Figure 00120003
    Figure 00120004
    Figure 00120005
    Figure 00120006
    Figure 00120007
    Figure 00120008
    Figure 00130001
    Figure 00130002
    Figure 00130003
    Figure 00130004
    Figure 00130005
    Figure 00130006
    Figure 00140001
    Figure 00140002
    Figure 00140003
    Figure 00140004
    Figure 00140005
    Figure 00140006
    Figure 00150001
    Figure 00150002
    Figure 00150003
    Figure 00150004
    Figure 00150005
    Figure 00150006
    Figure 00150007
  • Among the above-exemplified compounds, each of compounds (I-11), (I-12), (I-13), (I-14) and (I-15) includes both of the cis- and trans-forms.
  • The compounds represented by formula (I) exemplified above can be synthesized in the generally known processes.
  • Among the specific examples, particularly preferable compounds are (I-3), (I-4), (I-8), (I-11) and (I-16).
  • In the iron (III) complex salt of the compound represented by formula (I), those having the stoichiometric ratio of ferric ion (i.e., iron (III) ion) to the compound of formula (I) of 1:1 are preferred. Further the complex salt may have an amine, a thiocyanate group or a cyanate group as a ligand. Further, the negative or positive excessive atomic valence is neutralized with a water-soluble cation or anion. The complex salt may be hydrated, too. In the following, some examples for the ion (III) complex of the compound represented by formula (I) are exemplified not for the purpose of restricting the scope of the present invention thereto.
    Figure 00170001
    Figure 00170002
    Figure 00170003
    Figure 00170004
    Figure 00170005
    Figure 00170006
    Figure 00180001
    Figure 00180002
    Figure 00180003
    Figure 00180004
    Figure 00190001
    Figure 00190002
  • Now, the compound represented by formula (II) is explained. In formula (II) , R1 represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, a carboxyalkyl group or an alkoxyalkyl group; R2 and R3 each represents a hydrogen atom, an alkyl group, a carboxyalkyl group or an alkoxyalkyl group; and M6, M7 and M8 each represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an onium group.
  • In cases where R1 represent an alkyl group, a hydroxyalkyl group, a carboxyalkyl group or an alkoxyalkyl group, the number of the carbon atoms contained in each alkyl group is 1 to 8, preferably 1 to 4, and the alkyl group may be straight or branched. The carbon atom number of the alkoxyalkyl group is 1 to 3, preferably 1 or 2. Preferable R1 include a hydrogen atom, methyl, ethyl, carboxymethyl, and carboxyethyl groups, among these, hydrogen, carboxymethyl and methyl groups are preferred.
  • In cases where R2 and R3 each represents an alkyl group, a craboxylalkyl group or an alkoxyalkyl gruop, the carbon atom number of each alkyl group is 1 to 8, and more preferably 1 to 4. The alkyl group may be of straight chain or branched chain. The carbon atom number of the alkoxy group in the alkoxylalkyl group is 1 to 3, preferably 1 or 2. Preferable R2 or R3 includes a hydrogen atom, methyl, ethyl, carboxymethyl and carboxyethyl groups, among these, a hydrogen atom, carboxymethyl and methyl groups are preferred.
  • The alkali metal atom represented by M6, M7 or M8 includes metal atoms such as Li, Na and K, alkaline earth metal atoms such as Ca, Mg and Ba, and onium groups such as ammonium (e.g., ammonium or tetraethylammonium) and pyridinium. More preferable M6, M7 or M8 is a hydrogen atom, an ammonium group or an alkali metal atom.
  • Some specific examples of the compound represented by formula (II) of the present invention are listed not for the purpose of restricting the scope of the present invention thereto. In the present specification, each exemplary compound represented by each formula is shown in the acid form (i.e., COOH) . However, other forms such as the metal or ammonium salt are not excluded.
    Figure 00220001
    Figure 00220002
    Figure 00220003
    Figure 00220004
    Figure 00220005
    Figure 00230001
    Figure 00230002
  • The compounds represented by formula (II) can be prepared with reference to the synthetic methods described in Kireto Kagaku (Chelate Chemistry) (5), edited by Kagehira Ueno and published by Nankodo Co., Ltd., Inorganic Chemistry, 7, 2405 (1968), Chm. Zvesti., 20, 414 (1966) , and Zhurnal Obshchei Khinii, 49, 659 (1978). Many of the compounds are commercially available, too.
  • Now, the compound represented by formula (III) is explained. In formula (III), L0 represents a divalent alkylene group having 2 to 8 carbon atoms, and may be straight or branched with preferably 2 to 4 carbon atoms, more preferably with 2 to 3 carbon atoms. The alkylene group may be substituted by a hydroxy group or an alkoxy group. In the case where the substituent is alkoxy, the carbon atom number is 1 to 4, preferably 1 to 3.
  • M9 and M10 have the same meaning as M6, M7 and M8, and preferable groups for M9 and M10 are common to those for M6, M7 and M8.
  • In the following, some examples for the compound represented by formula (III) are exemplified not for the purpose of restricting the scope of the present invention thereto.
    Figure 00250001
    Figure 00250002
    Figure 00250003
    Figure 00250004
    Figure 00250005
  • Similarly to those represented by formula (II), the compounds represented by formula (III) can also be synthesized with reference to the methods described in KiretoKagaku (Chelate Chemistry) (5), edited by Kagehira Ueno and published by Nankodo Co., Ltd., Inorganic Chemistry, 7, 2405 (1968), Chm. Zvesti., 20, 414 (1966), and Zhurnal Obshchei Khinii, 49, 659 (1978). Many of the compounds are commercially available, too.
  • Now, the compound represented by formula (IV) is explained. In formula (IV), X2, X3 and X4 each represents a methylene group, an ethylene group, n- and i-propylene groups, each of which may be substituted with a hydroxy group, a methoxy group or an ethoxy group. M11 and M12 have the same meaning as M6, M7 and M8, and preferable groups for M11 and M12 are common to those for M6, M7 and M8.
  • Some specific examples of the compound represented by formula (IV) are listed below not for the purpose of restricting the scope of the present invention thereto.
    • IV-1
    Ethylenediamine-N,N'-diacetic acid
    IV-2
    Propylenediamine-N,N'-diacetic acid
    IV-3
    1-Methyl-ethylenediamine-N,N'-diacetic acid
    IV-4
    Ethylenediamine-N,N'-dipropionic acid
    IV-5
    Ethylenediamine-N,N'-dilactic acid
    IV-6
    Propylenediamine-N,N'-dilactic acid
    IV-7
    2-Hydroxy-propylenediamine-N,N'-diacetic acid
    IV-8
    2-Methoxy-propylenediamine-N,N'-diacetic acid
  • The compounds represented by formula (IV) are commercially available.
  • Now, the compound represented by formula (V) is described. In formula (V) , Z represents a nitrogen-containing heterocyclic group, which is preferably a nitrogen-containing 5- or 6-membered ring group, and more preferably an aromatic heterocyclic group. Particularly preferred groups are azoles, azines and pyridines.
  • Preferable azole rings are pyrrole, pyrroline, pyrazole, pyrazoline, imidazole, imidazoline, triazole, thiazole, oxazole, isoxazole and tetrazole.
  • Preferable azine rings are pyrimidine, pyridazine, oxazine and thiazine.
  • The nitrogen-containing heterocyclic group may be substituted with an alkyl or alkoxyl group each containing 1 to 4 carbon atoms, a hydroxy group or a carboxymethyl group.
  • In cases where R4 represents an alkyl group, an alkoxyalkyl group or a carboxyalkyl group, each of those groups comprises the same ones as the corresponding group represented by R1. Preferable examples thereof are also common to those of R1.
  • M13 has the same meaning as M6, M7 and M8, and its preferable examples are also common to those for M6, M7 and M8.
  • Some specific examples of the compound represented by formula (V) are listed below not for the purpose of restricting the scope of the present invention thereto.
    • V-1
    Pyridine-2-carboxylic acid
    V-2
    Pyrimidine-2-carboxylic acid
    V-3
    Pyrimidine-5-carboxylic acid
    V-4
    4-Carboxy-2-imidazole
    V-5
    4-Carboxy-2-methylimidazole
    V-6
    N-methylpyridine-2-carboxylic acid
    V-7
    Pyridine-2,4-dicarboxylic acid
    V-8
    Pyridine-2,6-dicarboxylic acid
  • The compounds represented by formula (V) can be not only synthesized by ordinary processes, but are commercially available.
  • Next, the compound represented by formula (VI) is described. In formula (VI) , G1 and G2 each represents a carboxyl group, a phosphono group, a sulfo group, a hydroxy group, a mercapto group, an aryl group, a heterocyclic group, an alkylthio group, an amidino group, a guanidino group or a carbamoyl group; L1, L2 and L3 each represents a divalent aliphatic or aromatic group or a divalent linking group comprising a combination thereof; m and n each represents 0 or 1; X represents a hydrogen atom, an aliphatic or aromatic group; and M represents a hydrogen atom or a cation.
  • The aryl (aromatic hydrocarbon) group represented by G1 or G2 may comprise single or bicyclic rings, preferably containing 5 to 20 carbon atoms. Examples thereof include phenyl and naphthyl. The substituent which this aryl group may have includes an alkyl group (e.g., methyl or ethyl), an aralkyl group (e.g., phenylmethyl), an alkenyl group (e.g., allyl), an alkynyl group an alkoxy group (e.g., methoxy or ethoxy), an aryl group (e.g., phenyl or p-methylphenyl), an acylamino group (e.g., acetylamino), a sulfonylamino group (e.g., methanesulfonylamino), an ureido group, an alkoxycarbonylamino group (e.g., methoxycarbonylamino), an aryloxycarbonylamino group (e.g., phenoxycarbonylamino), an aryloxy group (e.g., phenyloxy), a sulfamoyl group (e.g., methylsulfamoyl), a carbamoyl group (e.g., carbamoyl or methylcarbamoyl), an alkylthio group (e.g., methythio or carboxymethylthio), an arylthio group (e.g., phenylthio), a sulfonyl group (e.g., methanesulfonyl) , a sulfinyl group (e.g., methanesulfinyl), a hydroxy group, a halogen atom (e.g., Cl, Br or F), a cyano group, a sulfo group, a carboxy group, a phosphono group, an aryloxycarbonyl group (e.g., phenyloxy carbonyl), an acyl group (e.g., acetyl or benzoyl) , an alkoxycarbonyl group (e.g., methoxycarbonyl), an acyloxy group (e.g., acetoxy), a nitro group and a hydroxamic acid group.
  • The heterocyclic group represented by G1 or G2 is a 3-to 10-membered heterocyclic group containing at least one oxygen or sulfur atom therein, and may be saturated or unsaturated. It may further contain a single ring or form a condensed ring with another aromatic ring or heterocyclic ring. Such heterocyclic rings, which are 5- or 6-membered unsaturated heterocyclic group, include, for example, pyridine, pyrazine, pyrimidine, pyridazine, triazine, tetrazine, thiophene, furan, pyran, pyrrole, imidazole, pyrazole, thiazole, isothiazole oxazole, isoxazole, oxadiazole, thiadiazole, thianthrene, isobenzofuran, chromene, xanthene, phenoxazine, indolizine, isoindole, indole, triazole, triazolium, tetrazole, quinolizine, isoquinoline, quinoline, phthalazine, naphthylidine, quinoxaline, quinazoline, cinnoline, pterin, carbazole, carboline, phenanthridine, acrylidine, pteridine, phenanthroline, phenazine, phenothiazine, phenoxazine, coumarone, pyrroline, pyrrazoline, indoline, and isoindoline. Among them, pyridine, pyrazine, pyrimidine, pyridazine, thiophene, furan, pyrrole, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole and indole are preferred. More preferable heterocyclic rings are imidazole and indole.
  • The alkylthio group represented by G1 or G2 is represented by -SR1 (R1 represents an alkyl group.). The alkyl group for R1 may be straight-chained, branched or cyclic, preferably containing 1 to 10 carbon atoms. The alkyl group more preferably comprises a straight-chain containing 1 to 4 carbon. The alkyl group represented by R1 may have a substituent group, which includes the same substituents as those for the aryl group represented by G1 or G2. Specific examples of the alkylthio group represented by G1 or G2 include, for example, methylthio, ethylthio, hydroxyethylthio and carboxymethylthio. Preferable ones are methylthio and ethylthio.
  • The carbamoyl group represented by G1 or G2 may be substituted, thus being shown as -CONR1R2 wherein R1 and R2 each represents a hydrogen atom, a substituted or unsubstituted alkyl or aryl group. The alkyl group represented by R1 and R2 may be straight-chained, branched or cyclic, and preferably have 1 to 10 carbon atoms. The aryl group represented by R1 and R2 preferably has 6 to 10 carbon atoms, phenyl being more preferred. R1 and R2 may be connected together to form a ring such as, for example, morpholine, piperidine, pyrrolidine and piperadine. Particularly preferred groups as R1 and R2 are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms and a phenyl group which may be substituted.
  • Substitutents for the alkyl or aryl group represented by R1 and R2 include those which the aryl group represented by G1 or G2 may have. Specific examples of the carbamoyl group represented by G1 or G2 include, for example, carbamoyl, N-methyl carbamoyl, N-phenylcarbamoyl and morpholinocarbonyl.
  • The divalent aliphatic group represented by L1, L2 and L3 includes a straight-chained, branched or cyclic alkylene group (preferably of 1 to 6 carbon atoms) , an alkenylene group (preferably of 2 to 6 carbon atoms), and an alkynylene group (preferably of 2 to 6 carbon atoms) . These divalent aliphatic groups may be substituted with, for example, those which the aryl group represented by G1 or G2 may have. Preferable substituents include carboxyl and hydroxy, carboxyl being more preferred.
  • Specific examples of the divalent aliphatic group for L1, L2 and L3 include methylene, ethylene, 1-carboxy-methylene, 1-carboxy-ethylene, 2-hydroxy-ethylene, 2-hydroxy-propylene, 1-phosphono-methylene, 1-phneyl-methylene and 1-carboxy-butylene.
  • As the divalent aromatic group for L1, L2 and L3, divalent aromatic hydrocarbon (arylene) groups and divaltent aromatic heterocyclic groups are exemplified. The divalent aromatic hydrocarbon (arylene) group may comprise a single ring or bicyclic rings, and preferably contains 6 to 20 carbon atoms, exemplified by phenylene and naphthylene groups. The divalent aromatic heterocyclic group is 3- to 10-membered, containing at least one of a nitrogen, oxygen or sulfur atom, andmay comprise a single ring or be condensed with another aromatic or heterocyclic ring. 5- to 6-membered aromatic heterocyclic groups containing nitrogen as the heteroatom are preferred. Specific examples of the divalent aromatic heterocyclic group include the following.
    Figure 00320001
    Figure 00320002
  • The divalent aromatic group is preferably arylene (preferably having 6 to 20 carbon atoms), more preferably phenylene or naphthylene, particularly preferably being phenylene. The divalent aromatic group for L1, L2 and L3 may have a substituent that is common to those which the aryl group represented by G1 or G2 may have. Among such groups, carboxyl, hydroxy and aryl are preferred, carboxyl being more preferred. L1, L2 and L3 each may be a group comprising a divalent aliphatic group and a divalent aromatic group such as, for example, those to follow.
    Figure 00330001
    Figure 00330002
  • Preferable groups for L1, L2 and L3 include an alkylene or o-phenylene group preferably with 1 to 3 carbon atoms, and particularly preferable ones are methylene and ethylene.
  • Symbols m and n each represents 0 or 1. Preferably, m is 1, and n is 0.
  • The aliphatic group represented by X includes a straight-chained, branched or cyclic alkyl group (preferably having 1 to 6 carbon atoms) , an alkenyl group (preferably having 2 to 6 carbon atoms), and an alkynyl group (preferably having 2 to 6 carbon atoms) . Among these, an alkyl and alkenyl groups are preferred. Specific examples are methyl, ethyl, cyclohexyl, benzyl and allyl. The aromatic group for X includes an aromatic hydrocarbon (aryl) group or an aromatic heterocyclic group such as, for example, phenyl, naphthyl, 2-pyridyl and 2-pyrrole. Among these, an aryl group is preferred, and phenyl is more preferred. Preferably X is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, hydrogen being more preferred.
  • The cation represented by M includes ammonium (e.g., ammonium and tetraethylammonium) and an alkali metal (e.g., Li, K and Na) and pyridinium. The compound represented by formula (I) may be an ammonium salt (e.g., ammonium salt and tetraethylammonium salt) , an alkali metal (e.g., Li, K and Na) salt or an acid salt such as hydrochloric, sulfuric or oxalic acid salt.
  • The number of the ammonium, alkali metal or acid contained in the compound is preferably be from 0 to 6 for the isolated compound (e.g., mono-sodium salt, di-sodium salt, or tri-sodium salt).
  • Among the compounds represented by formula (VI), preferable ones are those represented by the following formula (VII).
    Figure 00350001
  • L2' in formula (VII) has the same meaning as L2 in formula (VI). And, G2' has the same meaning as G2 in formula (VI). M' and M'' each has the same meaning as M in formula (VI).
  • Some specific examples of the compound represented by formula (VI) are exemplified below not for the purpose of restricting the scope of the present invention thereto.
    Figure 00350002
    Figure 00350003
    Figure 00350004
    Figure 00360001
    Figure 00360002
    Figure 00360003
    Figure 00370001
    Figure 00370002
    Figure 00370003
    Figure 00380001
    Figure 00380002
    Figure 00390001
    Figure 00390002
    Figure 00390003
    Figure 00400001
    Figure 00400002
    Figure 00400003
  • The compound represented by formula (VI) can be prepared based on the synthetic process described in Japanese Patent application (Laid-Open) No. 95319/1994, in particular paragraphs [0036] to [0042] thereof.
  • As the iron (III) complex salt of the compound represented by formula (VI), those having the stoichiometric ratio of ferric ion (i.e., iron (III) ion)to the compound of formula (I) of 1:1 is preferred. Further the complex salt may be coordinated with an amine, a thiocyanate group or a cyanate group as a ligand. Further, the negative or positive excessive atomic valence is neutralized with a water-soluble cation or anion. The complex salt may be hydrated, too. In the following, some examples for the ion (III) complex of the compound represented by formula (VI) are exemplified not for the purpose of restricting the scope of the present invention thereto.
    Figure 00420001
    Figure 00420002
    Figure 00420003
    Figure 00420004
    Figure 00430001
    Figure 00430002
    Figure 00430003
  • The ion (III) complex salt of the compound represented by formulae (I) to (VI) may be in the form of isolated solid (e.g., powdery, granular or bulky solid), or non-isolated solution (e.g., aqueous solution).
  • The ion (III) complex salt of the compound represented by formulae (I) and (VI) can be synthesized by reacting the compound represented by formulae (I) and (VI) with an iron salt in a solution. As the compound represented by formulae (I) and (VI), the ammonium or alkali metal salt (e.g., Li, Na or K salt) may be used.
  • In cases where the iron chelate compound is used in the form of solution without compound isolation, unnecessary extra salts formed in the solution by the reaction are preferably eliminated. In the present invention, such salts can be eliminated by ultrafiltration, electro-osmosis, salt filtration via solvent condensation or salt separation by the addition of a poor solvent. Among these methods, electro-osmosis is most preferred. In cases where the solvent is water, the pH range for the solution of the iron (III) complex salt of the compound represented by formulae (I) and (VI) is preferably from 4 to 9, more preferably from 5 to 8, and specially preferably from 6 to 8. The concentration of the iron complex salt is preferably from 1 to 80% by weight (i.e., by mass), more preferably from 1 to 50% by weight, and specially preferably from 3 to 35% by weight. The solvent for the solution of an non-isolated iron chelate compound is preferably water. The ratio of the compound represented by formulae (I) and (VI) to the iron ion is preferably not less than 1.0, more preferably 1.05 to 2, and particularly preferably 1.1 to 1.2 in terms of molar ratio.
  • In the synthesis of the iron chelate of the compound represented by formulae (I) and (VI) associated with the present invention, any salt or any metal form of iron can be used as the iron (III) source, including inorganic salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, ferrous sulfate, ferrous chloride, ferrous nitrate, ferrous ammonium sulfate, ferrous phosphate, iron tritetraoxide, iron sesquioxide and iron hydroxide, organic salts such as iron acetate. As metallic iron, iron powder or steel wool can also be used. These ferric ion source materials may be used individually or in combination of two or more of them in arbitrary mixing ratios. Any kind of solvent that is not involved in the reaction may be used as the reaction solvent, but water is the best.
  • As a preferable embodiment of the present invention, the compound represented by formulae (I) and (VI) is supplied in the form of the iron (III) complex salt having been prepared in advance wherein a foreign compound other than the iron (III) complex salt is contained in such complex salt at a content preferably of from 0 to 10% by weight, more preferably from 0 to 7% by weight, and particularly preferably from 0 to 5% by weight of the iron (III) complex. More specifically, an iron complex salt-containing material resulting from the reaction between the compound represented by formula (I) and iron sesquioxide, or another iron complex salt-containing material that is obtained by reacting the compound represented by formulae (I) and (VI) with ferric chloride followed by desalting to a pre-determined level can be preferably used. Here, "foreign compound" indicates any by-product formed by the reaction between the compound represented by formulae (I) and (VI) and an iron salt.
  • The bleaching solution of the present invention may be prepared by adding and dissolving the iron (III) complex salt that has been prepared in advance by reacting the compound represented by formulae (I) and (VI) with an iron (III) compound (e.g., ferric oxide, ferric sulfate, ferric chloride, ferric bromide or ferric nitrate) . Alternatively, a complex-forming reaction may be conducted in the bleaching solution by adding a complex-forming compound and an iron (III) compound (e.g., ferric sulfate, ferric chloride, ferric bromide or ferric nitrate) to form an iron (III) complex salt-containing aqueous solution. In the latter case, the complex-forming compound may be used in a quantity slightly larger than the stoichiometric amount for the ion (III) complex salt formation. In general, use in excess of 0.01 to 20 mol% is preferred.
  • The compound capable of forming a complex salt with ferric ion used in the present invention may contain an iron (III) complex-forming compound other than those represented by formulae (I) and (VI), but its content is preferably below 50 mol%, more preferable below 20 mol%, the remaining being those represented by formulae (I) and (VI). Further in the present invention, the compound represented by formula (I) occupies 30 to 95%, preferably 60 to 90% of the total amount of the complex-forming compound capable of forming an iron (III) complex salt in the bleaching solution, while those represented by formulae (II) to (V) is used in 5 to 70%, preferably 10 to 40%. Such compounds represented by formulae (II) to (V) may be used individually or in combination of two or more. When two or more compounds are jointly used, the mixing ratio is arbitrary. Furthermore, within the scope of the present invention, iron (III) complex-forming compounds other than those represented by formulae (I) to (V) may be jointly used. Such other compounds include EDTA, diethylentriaminepentaacetic acid, iminodiacetic acid, methyliminodiacetic acid, N-(2-acetoamido)iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraquismethylenephosphonic acid, nitrilotrismethylenephosphonic acid and diethylenetriaminepentaquismethylenephosphonic acid; still other compounds can be used.
  • In the present invention, in addition to the complex-forming compound represented by formulae (I) and (VI) and, in some cases, the iron (III) complex salt of another chelating agent described above, an inorganic oxidizing agent may further be used as the bleaching agent of the bleaching solution. Such inorganic oxidizing agents include hydrogen peroxide, hypochlorite salts, persulfate salts and bromate salts (with alkali metals or alkaline earth metals). Self-evidently, still other oxidizing compounds can be used.
  • The concentration of the iron (III) complex salt of the compound represented by formulae (I) and (VI) in the bleaching solution is appropriately from 0.003 to 3.0 mol/L, preferably from 0.02 to 1.50 mol/L, and more preferably from 0.05 to 0.50 mol/L. However, with a still more diluted range of from 0.05 to 0.20, the iron (III) complex salt exhibits a superior effect. In cases where an inorganic oxidizing agent is jointly used, an iron (III) concentration of from 0.005 to 0.03 mol/L is preferred.
  • In the bleaching solution of the present invention, a halogen compound such as chloride, bromide or iodide may be added as a rehalogenating agent which promotes the oxidation of silver. Further, instead of the halogen compound, one may employ an organic legand capable of forming a silver salt sparingly soluble in water. Such halogen compounds are preferably incorporated in the form-of an alkali metal salt or ammonium salt while such organic legands are preferably incorporated in the form of the salt of guanidine or amines. Specific compounds include sodium bromide, potassium bromide, ammonium bromide, potassium bromide and guanidine hydrochloride. Among these, ammonium bromide is specially preferred. The bromide ion concentration in the bleaching solution is preferably from 0.05 to 2.0 mol/L, more preferably from 0.5 to 1.5 mol/L. In cases where an inorganic oxidizing agent is jointly used, the bromide ion concentration is preferably from 0.05 to 0.1 mol/L.
  • In the bleaching solution associated with the present invention, the compound represented by the following formula [A] is preferably contained to enhance the advantages of the present invention. A5(-COOM5)n51
  • In formula [A], A5 represents an n51-valent organic group, n51 represents an integer of 1 to 6, and M5 represents an ammonium group, an organic ammonium group, an alkali metal (Na, K or Li), or a hydrogen atom. However, A5 never represents an unsubstituted methyl, ethyl or ethylene group.
  • In formula [A] , the n51-valent organic group represented by A5 includes an alkylene group (e.g., methylene, trimethylene or tetramethylene), an alkenylene group (e.g., ethenylene), an alkynylene group (e.g., ethynylene) , a cycloalkylene group (e.g., 1,4-cyclohexanediyl), an arylene group (e.g., o-phenylene or p-phenylene), an alkanetolyl group (e.g., 1,2,3-propanetolyl), an arenetolyl group (e.g., 1,2,4-benzentolyl) and an alkyl group (e.g., propyl, butyl, octyl or cyclohexyl).
  • The n51-valent group represented by A5 includes those having a substituent (e.g., hydroxy, alkyl or a halogen atom) . Examples include 1,2-dihydroxyethylene, hydroxyethylene, 2-hydroxy-1,2,3-propanetolyl, methyl-p-phenylene, 1-hydroxy-2-chloroethylene, chloromethylene, and chloroethenylene. The preferred concrete compounds represented by formula [A] are shown below.
    • (A-1)
    HOOCCH2C(OH) (COOH)CH2COOH
    (A-2)
    HOOC(CHOH)2COOH
    (A-3)
    HOOCCH(OH)CH2COOH
    (A-4)
    HOOCCH=CHCOOH
    (A-5)
    Propylene glycolic acid
    (A-6)
    Butylene glycolic acid
    (A-7)
    Phthalic acid
    (A-8)
    Terephthalic acid
    (A-9)
    Cyclohexane-1,4-dicarboxylic acid
    (A-10)
    Acetyl-1,2-dicarboxylic acid
    (A-11)
    2-Methylterephthalic acid
    (A-12)
    1,1,2,2-tetracarboxyethylene
    (A-13)
    1,1,2,2-tetracarboxyethane
    (A-14)
    Aspartic acid
    (A-15)
    Glutaric acid
    (A-16)
    HOOCCH2COOH
  • Among these exemplary compounds, particularly preferable ones are (A-3), (A-4), (A-15) and (A-16), (A-3) and (A-16) being most preferred. Addition of the organic acid represented by formula [A] improves the stability of the bleaching solution by suppressing the precipitation or deposition of the ferric compound. Although the mechanism is not clear, it is probable that the acid contributes to the improved stability by weakly coordinating with the iron (III) complex. Besides, the interference effect to be described later seems to be operating. Accordingly, with a bleaching solution containing the compound represented by formula [A], the bath can be kept stable at a lower pH than the conventional bleaching solution, thus effectively suppressing stain formation.
  • The organic acid described above may be used in the form of the metal salt (e.g., Na or K salt) or ammonium salts.
  • The compounds represented by formula [A] is contained in an amount of preferably 0.01 to 0.25 mol, more preferably 0.02 to 0.15 mol per 1 liter of the processing tank solution.
  • A preferable pH range for the bleaching solution of the present invention is from 4.0 to 7.0, in particular from 4.2 to 6.0. The pH of the bleaching solution can be adjusted to such ranges by using an inorganic or organic acid well known in the art individually or in combination. Particularly, the bleaching solution may contain an organic acid having pKa of 2.0 to 5.5 at a concentration of from 0.1 to 2 mol/L. The pKa value means the absolute value of the reciprocal of acid dissociation constant determined under the condition of 0.1 mol/L ionic strength at 25°C. The organic acid having a pKa of 2.0 to 5.5 may not be necessarily the compound represented by formula [A] above, but other mono-basic or poly-basic acids may be used, too. The organic acid may be used in the form of the metal salt (e.g., Na or K salt) or the ammonium salt thereof. Preferable examples of the organic acid include, in addition to those represented by formula [A], aliphatic mono-basic acids such as formic acid, acetic acid, monochloroacetic acid, monobromoacetic acid, glycolic acid, propionic acid, monochloropropionic acid, lactic acid, pyruvic acid, acrylic acid, butyric acid, isobutyric acid, pivalic acid, aminobutyric acid, valeric acid or isovaleric acid; aminoacid compounds such as asparagine, alanine, arginine, ethionine, glycine, glutamine, cysteine, serine, methionine or leucine; aromatic monobasic acids such as benzoic acid or mono-substituted benzoic acid including chloro- or hydroxy-benzoic acid and nicotinic acid; aliphatic dibasic acid such as tartaric acid, malonic acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, glutaric acid or adipic acid; aminoacid-based dibasic acids such as aspartic acid, glutamic acid, cystine and ascorbic acid; aromatic dibasic acids such as phthlic acid and terephthalic acid; other basic acids such as citric acid and still other organic acid. In the present invention, acetic acid and glycolic acid are particularly preferred for use.
  • In addition to the organic acid having a pKa of 2.0 to 5.5, the bleaching solution of the present invention is preferably incorporated with a compound selected from imidazoles at a concentration of from 1 to 50 g/L. Preferable imidazole compounds may have a substituent selected from alkyl groups having 1 to 6 carbon atoms, alkenyl groups having 2 to 6 carbon atoms, hydroxyalkyl or carboxyalkyl groups having 1 to 6 carbon atoms, and carboxyl groups at the 1-, 2-, 4- or 5-position. Preferable examples of such imidazole compounds include imidazole, 2-methylimidazole, 4-methylimidazole, 4-methyl-5-(hydroxymethyl)imidazole and imidazole-4,5-dicarboxylic acid. Among these compounds, imidazole, 2-methylimidazole and imidazole-4,5-dicarboxylic acid are particularly preferred. The concentration of the imidazole compound is preferably from 1.0 to 30.0 g/L, more preferably from 1.5 to 5.0 g/L in the bleaching solution.
  • The bleaching solution of the present invention is reusable when the overflow solution after processing is collected and appropriately replenished to recover the original composition. Such reusing methods are usually called regeneration, to which reference can be made to paragraphs [0033] to [0034] of Japanese Patent Application (Laid-Open) No. 303186/1993.
  • The bleaching solution is used at a temperature between 20 and 50°C, preferably between 25 and 45°C. The solution may contain various types of fluorescent brightening agents, anti-foaming agents and surfactants.
  • A preferable replenishing amount for the bleaching solution of the present invention is up to 500 ml, more preferably up to 300 ml, most preferably up to 200 ml, per 1 m2 of silver halide color photographic material. It is noted that, for the lower replenishing amounts, the advantageous features of the present invention become the more prominent.
  • In order to activate the bleaching solution of the present invention, the air or oxygen may be blown in the solution during processing or in a stock tank of the bleaching solution or a replenisher, if desired. Alternatively, a suitable oxidizing agent such as hydrogen peroxide, bromate salts or persulfate salts may be incorporated.
  • Following the description on the bleaching solution used in the present invention, the entire procedure of the color reversal processing according to the present invention will now be described. In the first place, the black-and-white (first) development as the first step is explained.
  • In the black-and-white development, the conventionally known developing agents can be used, such as dihydroxybenzenes (e.g., hydroquinone or hydroquinone monosulfonate), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone or 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone), aminophenols (e.g., N-methyl-p-aminophenol, N-methyl-3-methyl-p-aminophenol and its derivatives), ascorbic acid and its isomers and derivatives. These developing agents may be used individually or in combination. Preferable developing agents are potassium or sodium hydroquinone monosulfonate. The developing agent is used at a concentration of 1 x 10-5 to 2 mol/L in the developer.
  • The black-and-white developer used in the present invention can contain a preservative if needed. As the preservative, a sulfite salt or bisulfite salt is usually used at a content of 0.01 to 1 mol/L, preferably 0.1 to 0.5 mol/L. Ascorbic acid, which also acts as a very efficient preservative, is used at a content of 0.01 to 0.5 mol/L. The hydroxylamines represented by formula (I) in Japanese Patent Application (Laid-Open) No. 144446/1991, saccharides, o-hydroxyketones and hydrazines can also be used. The content of these compounds is 0.1 mol/L or less.
  • The pH of the black-and-white developer of the present invention is preferably in the range of 8 to 12, most preferably 9 to 11. A variety of buffering agents can be adopted to maintain a preferable pH value. Preferable buffering agents include carbonates, phosphates, borates, 5-sulfosalicylic acid salts, hydroxybenzoic acid salts, glycine salts, N,N-dimethylglycine salts, leucine salts, norleucine salts, guanine salts, 3,4-dihydroxyphenylalanine salts, alanine salts, aminobutyric acid salts, valine salts and lysine salts. From viewpoint of keeping the above pH range and low cost, carbonates, borates and 5-sulfosalicylic acid salts are specially preferred. These buffering agents may be used individually or in combination of two or more thereof. Furthermore, an acid and/or alkali may be used together to secure the targeted pH value.
  • As the acid compound, inorganic or organic water-soluble acids can be preferably used, such as sulfuric, nitric, hydrochloric, acetic, propionic or ascorbic acid. As the alkali agent, various hydroxides or ammonium salts can be incorporated preferably including potassium hydroxide, sodium hydroxide, aqueous ammonia, triethanolamine and diethanolamine.
  • The black-and-white developer for use in the present invention preferably contains a silver halide solvent that acts as development accelerator. Preferable examples include thiocyan salt, sulfite salts, thiosulfate, 2-methylimidazole and the thioethers described in Japanese Patent Application (Laid-Open) No. 63580/1982. A preferable addition amount of the silver halide solvent is from 0.005 to 0.5 mol/L.
  • Other development accelerators are quaternary amines, poly(ethylene oxide)s, 1-phenyl-3-pyrrazolidone and its derivatives, primary amines and N,N,N',N'-tetramethyl-p-phenylenediamine.
  • The black-and-white developer for use in the present invention can further contain not only a dissolution aid such as diethylene glycol, propylene glycol and other poly (ethylene glycol)s and various amines including diethanolamine and triethanolamine, but also a quaternary ammonium salts as a sensitizing agent. Moreover, a surfactant and a gelatin hardener may be incorporated.
  • During the black-and-white development, a variety of anti-foggants may be used for the purpose of preventing development fog. Suitable anti-foggants include alkali metal halides such as sodium chloride, potassium chloride, potassium bromide, sodium bromide and potassium iodide, and organic anti-foggants. Preferable organic anti-foggants include nitrogen-containing heterocyclic compounds such as, for example, benzotriazole, 6-nitrobenzoimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole and hydroxyazaindolizine, mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole and 2-mercaptobenzothiazole, and mercapto-substituted aromatic compounds such as thiosalicylic acid. The anti-foggant includes the components eluted from the color reversal photographic materials during development to accumulate in the bath.
  • As an anti-foggant, the iodide is incorporated at a concentration between 5 x 10-6 and 5 x 10-4 mol/L. The bromide, which also preferably acts as an anti-foggant, is incorporated at a concentration of 0.001 to 0.1 mol/L, and more preferably 0.01 to 0.05 mol/L.
  • To the black-and-white developer for use in the present invention, a swelling-suppressing agent (e.g., inorganic salts such as sodium sulfate and potassium sulfate) and/or a hard water-softener may be incorporated.
  • Preferable hard water-softeners usable in the present invention include amino-polycarboxylic acids, amino-polyphosphonic acids, phosphonocarboxylic acids, organic and inorganic phosphonic acids and the above-described compounds represented by formula (I) that are associated with the present invention. Some specific examples are shown below, but the scope of the present invention is not restricted to those examples at all.
  • Ethylenediaminetetracetic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid, propylenediaminetetraacetic acid, diethylentriaminepentaacetic acid, triethylenetetraminehexaacetic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid and 1-hydroxyethylidene-1,1-diphosphonic acid. These hard water-softening agents may be used individually or in combination of two or more thereof. A preferable range for the added amount of such a hard water-softening agent is from 0.1 to 20 g/L, more preferably from 0.5 to 10 g/L.
  • The standard processing time of the black-and-white development is, in most cases, from 4 to 8 min, and mostly 6 min. However, by extending or cutting short the development time appropriately, the photographic speed of an improperly exposed photographic material can be shifted to a higher or lower value. Such process manipultion is called push/shallow processing altogether. Usually, the photographic speed can be regulated by changing the processing time between 2 and 18 min. The processing temperature is usually 20 to 50°C, preferably 33 to 45°C. The replenishing amount of the black-and-white developer is from 100 to 5000 ml per 1 m2 of the processed photographic material, preferably from 200 to 2500 ml per 1 m2 of the processed photographic material.
  • In the photographic processing of the present invention, the black-and-white development is followed by rinsing with water and/or a rinsing solution, if needed. Thereafter, reversal processing and then color-forming development are carried out.
  • Though rinsing with water or a rinsing solution may be carried out with a single bath, it is more preferable to adopt a multi-stage counter current system using two or more tanks in order to reduce the replenishing amount. In the rinsing with water, a relatively large amount of water is replenished. On the other hand, the rinsing with a rinsing solution is conducted with a reduced replenishing amount comparable to the replenishing amount for other processing baths. The replenishing amount for the rinsing with water is preferably from 3 to 20 L per 1m2 of the photographic material. The replenishing amount for the rinsing with a rinsing solution is preferably from 50 ml to 2 L, more preferably from 100 ml to 500 ml per 1 m2 of the processed photographic material, thus achieving a marked reduction of water usage compared with the rinsing with water.
  • The rinsing bath of the present invention may contain an oxidizing agent, a chelating agent, a buffering agent, an antiseptic, and a fluorescent brightening agent depending on need.
  • Then, an image-reversing step or light-fogging is conducted. In the reversal bath, chemical fogging agents well known in the art are contained. Useful fogging agents include stannous ion-containing complex salts such as stannous ion-organic phosphoric acid complex salts (U.S. Patent 3,617,282), stannous ion-organic phosphonocarboxylic acid complex salts (Japanese Patent Publication No. 32616/1981) and stannous ion-amino-polycarboxylic acid complex salts (U.S. Patent 1,209,050); the stannous ion complex salts represented by formulae (II) and (III) of Japanese Patent Application (Laid-Open) No. 109573/1999; boron-containing compounds such as borohydrides (U.S. Patent 2,984,567) and heterocyclic amine borane salts (British Patent 1,011,000). The pH of the reversal bath ranges from an acid to alkaline side depending on the type of fogging agent used, namely from 2 to 12. More frequently it ranges from 2.5 to 10, and more preferably from 3 to 9.
  • The stannic ion in the reversal bath has a concentration between 1 x 10-3 and 5 x 10-2 mol/L, preferably between 2 x 10-3 and 1.5 x 10-2 mol/L. In the case where a boron-containing fogging agent is used in the reversal bath, its concentration is from 1 x 10-3 and 5 x 10-2 mol/L, preferably from 2 x 10-3 and 1.5 x 10-2 mol/L.
  • For the purpose of enhancing the solubility of the tin (II) chelate, the reversal bath preferably contains propionic acid, acetic acid or the alkylenedicarboxylic acid compounds represented by formula (I) of Japanese Patent Application (Laid-Open) No. 109572/1999. Among these, acetic acid is particularly preferred. Further, the reversal bath preferably contains a sorbic acid salt or the quaternary ammonium compound described in U.S. Patent 5,811,225 as bactricide.
  • The image reversal processing lasts usually for 10 sec to 3 min, preferably for 20 sec to 2 min, and more preferably for 30 to 90 sec. The temperature of the reversal bath, which preferably is in the temperature range for either of the first development, the subsequent rinsing or the rinsing with water, and the color-forming development, is usually set at 20 to 50°C, preferably 33 to 45°C.
  • The replenishing amount for the reversal bath is 10 to 2000 ml, preferably 200 to 1500 ml per 1 m2 of the processed photographic material.
  • Since tin (II) chelates and boron-containing fogging agents are effecttive over a wide range of pH, the addition of a pH-buffer is not required. However, it nonetheless causes no harm to add a compound that provides pH-buffering capability. Such compounds include acids, alkalis or salts exemplified by organic acids such as citric or malic, inorganic acids such as boric, sulfuric or hydrochloric, alkali carbonates, caustic alkalis, borax or potassium metaborate. If necessary, a hard water-softening agent such as aminopolycarboxylic acid, a swelling-suppressing agent such as sodium sulfate or an anti-oxidant such as p-aminophenol may be added.
  • The photographic material that has been processed with a reversal bath then proceeds to a color-forming development step. The color-forming developer for use in the color-forming development of the present invention is an aqueous alkaline solution mainly containing a color-forming developing agent of an aromatic primary amine. As the color-forming developing agent, p-phenylenediamines are preferably used. Typical examples of such p-phenylenediamine compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamideethyl-aniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and their salts such as sulfate, hydrochlorate, phosphate, p-toluenesulfonate, tetraphenylborate, p- (t-octyl)benzenesulfonate. Two or more compounds may be used as the developing agent, if needed. A preferable concentration of the color-forming developing agent is from 0.005 to 0.1 mol/L, a more preferable one being from 0.01 to 0.05 mol/L.
  • The pH of the color-forming developer for use in the present invention is preferably 8 to 13, more preferably 10.0 to 12.5. To keep the pH in the above range, a phosphate salt is used as an essential alkali agent in the present invention. Any of tertiary, secondary or primary phosphates can be used wherein the counter ion can be an alkali metal such as sodium, potassium or lithium, ammonium and an organic onium. Among them, the sodium or potassium salts are preferred. The concentration of the phosphate salt is preferably 0.05 to 0.25 mol/L, more preferably 0.05 to 0.15 mol/l in terms of phosphate ion concentration. An alkali agent and a buffering agent other than phosphates may be jointly used.
  • Alkali agents and buffering agents which may be used in combination with a phosphate salt and have a buffering region of pH 8.0 or more include carbonates, borates, 5-sulfosalicylates, tetraborates, hydroxybenzoates, glycine salts, N,N-dimethylglycine salts, leucine salts, norleucine salts, guanine salts, 3,4-dihydroxyphenylalanine salts, alanine salts, aminobutyrates, 2-amino-2-methyl-1,3-propanediol salts, valine salts, proline salts, trishydroxyaminomethane salts and lysine salts. Among these, carbonates and 5-sulfosalicylates are preferred due to their high solubility and an excellent buffering ability at a high pH region of 10.0 or more, thus effectively suppressing the variation of pH by expanding the buffering region secured by phosphate ion.
  • Specific examples of the alkali agent and the buffering agent include phosphates such as trisodium phosphate, tripotassium phosphate, disodium phosphate and dipotassium phosphate. Alkali agents which may be used in combination with these include sodium and potassium carbonates, sodium and potassium bicarbonates, dipotassium 5-sulfosalicylate, sodium and potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, potassium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). Preferable compounds are trisodium or tripotassium phosphate, disodium or dipotassium phosphate, dipotassium or disodium 5-sulfosalicylate.
  • In using these buffering agents, one may add a single phosphate (salt) or two or more in the developer, and can achieve a targeted pH value by using an acid or an alkali agent.
  • The added amount of the buffering agent in the developer is preferably not less than 0.05 mol/L, more preferably 0.05 to 0.4 mol/L. In cases where two or more buffering agents are jointly used, these values hold for the total amount thereof.
  • In practicing the present invention, a various types of development accelerators may be used according to need.
  • Useful development accelerators include various pyridinium compounds typically disclosed in U.S. Patent 2648604, and Japanese Patent Publication No. 9503/1969 and U.S. Patent 3171247 and other cationic compounds; cationic dyes such as phenosafranine; neutral salts such as thallium nitrate and potassium nitrate; the poly(ethylene glycol)s and their derivatives described in Japanese Patent Publication No. 9304/1969, U.S. Patents 2533990, 2531832, 2950970 and 2577127; nonionic compounds such as polyethylene glycols and polythioethers; and the thioether compounds described in U.S. Patent 3201242.
  • Further, depending on need, benzyl alcohol, diethylene glycol that acts as solvent for benzyl alcohol, triethanolamine and diethanolamine can be used. However, these compounds is used as scarcely as possible, since they tend to cause various problems including the increase of environmental load, solution stability and the formation of tarry substance.
  • Similarly to the black-and-white developer, a silver halide solvent may be incorporated such as, for example, the alkali metal salt of thiocyanic acid, 2-methylimidazole, the thioether compounds disclosed in Japanese Patent Application (Laid-Open) No. 63580/1982 and the like. A particularly preferable compound is 3,6-dithiaoctane-1,8-diol. The preferable content of the silver halide solvent is common to that for the black-and-white developer used for the first development.
  • Although fog prevention is not necessary for color-forming development for the present invention, various anti-foggants may be incorporated in the color-forming developer for the purpose of maintaining the developer composition and performance when the development is conducted along with a constant feeding of color film rolls, i.e., in the so-called running mode. Preferable anti-foggants used in development include alkali metal halides such as potassium and sodium chlorides, potassium and sodium bromide and potassium iodide, and organic anti-foggants. Organic anti-foggants include, for example, nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole and hydroxyazaindolizine; mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzoimidazole and 2-mercaptobenzothiazole; and mercapto-substituted aromatic compounds such as thiosalicylic acid. The anti-foggant in the developer includes the component that is eluted from the processed color reversal photographic material to accumulate in the developer. Since the concentration of such anti-foggant in the developer has little effect on the photographic characteristics in the case of color reversal development, any control thereof is not necessary.
  • Various preservatives can be used in the color-forming developer for use in the present invention.
  • Typical preservatives are hydroxylamines and sulfite salts, the latter being more preferred. They are used at a concentration of from 0 to 0.1 mol/L.
  • The color-forming developer used in the present invention may contain an organic preservative instead of hydroxyamine or sulfite ion.
  • The organic preservative means any organic compound capable of retarding the deterioration of the primary aromatic amine as the color-forming developing agent; more concretely, it designates organic compounds having a function of preventing the oxidation (e.g., by the air) of the color-forming developing agent. Particularly effective organic preservatives include hydroxylamine derivatives except hydroxylamine, hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds and condensed ring-type amines. These compounds are described in Japanese Patent Publication No. 30496/1973, Japanese Patent Application (Laid-Open) Nos. 143020/1977, 4235/1988, 30845/1988, 21647/1988, 44655/1988, 53551/1988, 43140/1988, 56654/1988, 58346/1988, 43138/1988, 146041/1988, 44657/1988 and 44656/1988, U.S. Patents 3,615,503 and 2,494,903, Japanese Patent Application (Laid-Open) Nos. 97953/1989, 186939/1989, 186940/1989, 187557/1989 and 306244/1990. Still other types of preservatives may be used including the various metals disclosed in Japanese Patent Application (Laid-Open) Nos. 44148/1982 and 53749/1982, the salicylic acids disclosed in Japanese Patent Application (Laid-Open) No. 180588/1984, the amines disclosed in Japanese Patent Application (Laid-Open) Nos. 239447/1988, 128340/1988, 186939/1989 and 187557/1989, the alkanolamines described in Japanese Patent Application (Laid-Open) No. 3532/1979, the polyethyleneimines described in Japanese Patent Application (Laid-Open) No. 94349/1981 and the aromatic polyhydroxy compounds described in U.S. Patent 3,746,544 depending on need. In particular, alkanolamines such as triethanolamine, dialkylhydroxylamines such as N,N-diethylhydroxylamine and N,N-di(sulfoethyl)hydroxylamine, hydrazine derivatives except hydrazine such as N,N-bis(carboxymethyl)hydrazine, or aromatic polyhydroxy compounds such as sodium catechol-3,5-disulfonate are preferably added.
  • The addition amount of such an organic preservative is preferably 0.02 to 0.5 mol/L, more preferably 0.05 to 0.2 mol/L. If necessary, two or more compounds may be jointly used.
  • The color-forming developer of the present invention may contain an organic solvent such as diethylene glycol and triethylene glycol; a dye-forming coupler; a competing coupler such as citrazinic acid, J-acid or H-acid; a nucleating agent such as sodium boron hydride; an auxiliary developing agent such as 1-phenyl-3-pyrrazolidone; a tackifier; a chelating agent such as an aminopolycarboxylic acid (e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriamine pentaacetic acid, triethylenetetraminehexaacetic acid and the compounds described in Japanese Patent Application (Laid-Open) No. 195845/1983), an organic phosphonic acid (e.g., 1-hydroxyethylidene-1,1'-diphosphonic acid and those described in Research Disclosure No. 18170 (1979 May)), an aminophosphonic acid (e.g., aminotris(methylenephosphonic acid), and ethylenediamine-N,N,N',N'-tetramethylenphosphonic acid), and a phosphonocarboxylic acid (e.g., those described in Japanese Patent Application (Laid-Open) Nos. 102726/1978, 42730/1978, 121127/1979, 4024/1980, 4025/1980, 126241/1980, 65955/1980 and 65956/1980, and Research Disclosure No. 18170 (1979 May)). These chelating agents, two or more of which may be used together depending on need, may be contained at an amount of 0.05 to 20 g/L, preferably 0.1 to 5 g/L.
  • If necessary, a surfactant may be incorporated. Suitable compounds include alkylsulfonic acids, arylsulfonic acids, aliphatic and aromatic carboxylic acids and polyalkyleneimines.
  • The processing temperature of the color-forming development applied to the present invention is 20 to 50°C, preferably 33 to 45°C. The processing time is from 20 sec to 5 min, preferably from 20 sec to 4 min. The replenishing amount, which is as small as possible within the range of maintaining developer activity, is appropriately from 100 to 2500 ml, preferably from 400 to 1200 ml per 1 m2 of the processed photographic material.
  • The color reversal photographic material that has been subjected to color-forming development is then subjected to a desilvering treatment. The desilvering treatment is carried out in one of the following procedures.
  • 1. (Color-forming development) - Adjustment - Bleach - Fix
  • 2. (Color-forming development) - Rinse with water - Bleach - Fix
  • 3. (Color-forming development) - Bleach - Fix
  • 4. (Color-forming development) - Rinse with water - Bleach - Rinse with water -Fix
  • 5. (Color-forming development) - Bleach - Rinse with water -Fix
  • 6. (Color-forming development) - Rinse with water - Blix
  • 7. (Color-forming development) - Adjustment - Blix
  • 8. (Color-forming development) - Blix
  • 9. (Color-forming development) - Rinse with water - Bleach - Blix
  • 10. (Color-forming development) - Bleach - Blix
  • 11. (Color-forming development) - Rinse with water - Bleach - Blix - Fix
  • The "Adjustment" described above is sometimes called "pre-bleaching".
  • Among the exemplified procedures, No. 1 and No. 3 are particularly preferred.
  • Replenishment in each procedure may be carried out individually on each processing bath in the conventional manner. Alternatively, in Nos. 9 and 10, the solution overflowing from the bleaching solution may be introduced to the blix bath, whereby the blix bath is replenished only with the fixing solution. In No. 11 the overflowing solution of the bleaching solution is introduced to the blix bath, the overflowing solution of the fixing solution is introduced to the blix bath by means of counterflow system, whereby the two introduced solutions are overflown from the blix bath.
  • In practicing the present invention, a variety of blix accelerators can be incorporated in the bleaching or blix bath, or the adjustment bath preceding the bleaching or blix treatment.
  • Examples of such blix accelerators include the various mercapto compounds disclosed in U.S. Patent 3,893,858, British 1,138,842 and Japanese Patent Application (Laid-Open) No. 141623/1978 ; the disulfide bond-containing compounds described in Japanese Patent Application (Laid-Open) No. 95630/1978; the thiazolidine derivatives described in Japanese Patent Publication No. 9854/1978; the isothiourea derivatives described in Japanese Patent Application (Laid-Open) No. 94927/1978; the thiourea derivatives described in Japanese Patent Publication Nos. 8506/1970 and 26586/1974; the thioamide compounds described in Japanese Patent Application (Laid-Open) No. 42349/1974; and the dithiocarbamic acid salts described in Japanese Patent Application (Laid-Open) No. 26506/1970. Still other examples of blix accelerators include alkylmercapto compounds unsubstituted or substituted with a hydroxy group, a carboxyl group, a sulfonic acid group or an amino group. The amino group may have a substituent such as alkyl or acetoxyalkyl. Specific compounds are, for example, trithioglycerin, α,α'-thiodipropionic acid and δ-mercaptobutyric acid. The compounds described in U.S. Patent 4,552,834 can also be used.
  • In cases where a compound containing a mercapto group or a disulfide bond in the molecule or a thiazoline derivative or an isothiourea derivative is contained in the adjustment or bleaching solution, the content thereof, which depends on the type of the photographic material to be processed, the processing temperature and the processing time needed for the processing in concern, is appropriately 1 x 10-5 to 10-1 mol, preferably 1 x 10-4 to 5 x 10-2 mol per 1 liter of the processing solution.
  • In the adjustment solution, an image-stabilizing agent is preferably incorporated. In particular, the formaldehyde-bisulfide adduct described in U.S. Patent 5,037,725 is preferably contained. The secondary amine described in U.S. Patent 5,523,195 may be incorporated. The pH of the adjustment solution is usually 3 to 11, preferably 4 to 9, and more preferably 4.5 to 7. The processing time with the adjustment solution is preferably for 20 sec to 3 min, more preferably 20 sec to 2 min, and most preferably 30 to 60 sec. The replenishing amount for the adjustment solution is preferably from 30 to 2000 ml, particularly preferably from 50 to 1500 ml per 1 m2 of the processed photographic material. The temperature for the adjustment processing is preferably from 20 to 50°C, particularly preferably from 30 to 40°C.
  • The blix (bleach-fix) solution contains as a fixing agent a water-soluble silver halide solvent including thiosulfate salts such as sodium or ammonium thiosulfate, thiocyanate salts such as sodium, ammonium or potassium thiocyanate, thioether compounds such as ethylenebisthioglycolic acid or 3,6-dithia-1,8-octanediol, and thiourea. These compounds may be used individually or in combination of two or more thereof. In some cases, a special blix formulation comprising a fixing agent and a large amount of a halide such as potassium iodide as described in Japanese Patent Application (Laid-Open) No. 155354/1980 can be adopted, too. The amount of such a fixing agent is from 0.1 to 3 mol, preferably from 0.2 to 2 mol per 1 liter of the blix solution.
  • The advantageous effects of the present invention, i.e., prevention color restoration failure, stain reduction and smudge prevention for the processed material are fully achieved when the bleaching solution having a specific pH value contains an iron (III) complex salt represented by formula (I) or (II) together with a carboxylic acid represented by formula [A], and when the fixing or blix solution contains a compound selected from imidazoles at a content of 1 to 50 g/L.
  • Preferable imidazoles include unsubstituted imidazole, those having at the 1-, 2-, 4- or 5-position a substituent selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a hydroxyalkyl or carboxyalkyl group having 1 to 6 carbon atoms or an imidazol derivatives substituted with a carboxyl group. Specially preferable imidazole derivatives are imidazole, 2-methylimidazole, 4-methylimidazole, 4-methyl-5-(hydroxymethyl)imidazole and imidazole-4,5-dicarboxylic acid. Among these, imidazole, 2-methylimidazole and imidazole-4,5-dicarboxylic acid are still more preferred, imidazole being the most preferred. The content range for such an imidazole derivative is preferably 1 to 25 g/L, more preferably 1.5 to 10 g/L.
  • In the case where a fixing solution is used in the present invention, the fixing agent thereof is a water-soluble silver halide solvent well known in the art, including thiosulfates such as sodium or ammonium thiosulfate, thiocyanate salts such as sodium, ammonium or potassium thiocyanate, thioether compounds such as ethylenebisthioglicolic acid or 3,6-dithia-1,8-octanediol, and thiourea. These compounds may be individually or in combination of two or more thereof. The concentration of such a fixing agent is from 0.1 to 3 mol, preferably 0.2 to 2 mol per 1 L of the fixing solution. In addition to the various additive described previously, the solution having a fixing function can contain, as a preservative, a sulfite salt (e.g., sodium, potassium or ammonium sulfite), a bisulfite salt, hydroxylamine, hydrazine or an aldehyde-bisulfite adduct (e.g., acetaldehyde-sodium bisulfite). Other effective preservatives include sulfinic acids (e.g., benzenesulfinic acid) and ascorbic acid. The solution may further contain a fluorescent brightening agent of various types, an anti-foaming agent, a surfactant, polyvinylpyrrolidone, a bactericide, a fungicide or an organic solvent such as methanol.
  • In the present invention, well-known compounds such as bistriazinylarylenediamine may be used depending on need. As other fluorescent brightening agents, bis(triazinylamino)stylbenesulfonic acid compounds can also be used, including conventionally known or commercially available diaminostylbene compounds. Particularly, those described in Japanese Patent Application (Laid-Open) Nos. 329936/1994, 140625/1995 and 140849/1998 are preferably used. As for commercially available compounds, descriptions are found in, for example, Senshoku Nouto (Book on Dyeing) 9th Edition (published by Irozomesha) , pp. 165 to 168. Among the compounds described therein, Blankophor BSU liq. and Hakkol BRK are specially preferred.
  • Though these triazine group-containing compounds may be incorporated in any processing bath, they are preferably incorporated in the color-forming developer or the fixing solution.
  • The replenishing amount for the bleaching, fixing or blix bath, which can be set arbitrary so as to maintain the function of each bath, is preferably 30 to 2,000 ml, more preferably 50 to 1,000 ml per 1 m2 of the processed photographic material.
  • The processing temperature is preferably 20 to 50°C, more preferably 33 to 45°C, while the processing time is 10 sec to 10 min, preferably 20 sec to 6 min.
  • After desilvered by fixing or blix treatment, the photographic material is usually subjected to rinsing and/or stabilizing treatment. The stabilizing bath usually but not always contains an image stabilizer. Stabilizing baths not containing stabilizer are called wash-replacing stabilizing bath to differentiate from stabilizer-containing ones. The function of such a wash-replacing stabilizing bath is regarded as substantially the same as that of the rinse bath (washing bath). Accordingly, in the following, a common explanation will be given for all the related processing steps except image stabilizing step.
  • The amount of washing water in the water-washing step is set in the wide range according to various conditions such as the characteristics of the photographic material, the use, the water-washing temperature and the number of washing tank (the number of stages).
  • The relation between the number of washing tanks and the quantity of water for a multi-stage counter-current system can be obtained by the method described in Journal of the Society of Motion Picture and Television Engineers, 64, pp. 248 to 253 (May, 1955). The number of steps in the multi-stage counter-current system is preferably between 2 and 15, particularly preferably between 2 and 10.
  • Although adoption of a multi-stage counter-current system achieves a remarkable reduction of the amount of washing water, bacteria propagates in the tanks due to an increased retention time of water whereby floating matters are formed and tend to deposit on the photographic material. To solve this problem, the method of reducing the amount of calcium and magnesium as described in Japanese Patent Application (Laid-Open) No. 288838/1987 is quite effective. It is also effective to use the isothiazolones or cyabendazoles described in Japanese Patent Application (Laid-Open) No. 8542/1983, chlorine-based bactericides such as chlorinated sodium isocyanurate disclosed in Japanese Patent Application (Laid-Open) No. 120145/1986, benzotriazoles described in Japanese Patent Application (Laid-Open) No. 267761/1986, cupper ion, and the bactericides described in Bokin, Bobai no Kagaku (Bactericidal and Fungicidal Chemistry) authored by Hiroshi Horiguchi (1986, Sankyo Shuppan), Biseibutsu no Mekkin, Sakkin, Bobai Gijutsu (Sterilizing, Bactericidal and Antifungal Technologies for Microorganism) edited by Eisei Gijutsu Kai (Society for Hygiene Technology) (1982, Kogyo Gijutsu Kai) and Bokin- Bokabi-zai Jiten (Encyclopedia of Antibacterial and Antifungal Agents) edited by the Society for Antibacterial and Antifungal Agents, Japan (1986).
  • Further, aldehydes such as formaldehyde, acetaldehyde or pyruvinaldehyde, which inactivate remaining magenta couplers thus preventing dye fading as well as stain formation, the methylol compounds and hexamethylenetetramine described in U.S. Patent 4786583, the hexahydrotriazines described in Japanese Patent Application (Laid-Open) No. 153348/1990, the formaldehyde-bisulfite adduct described in U.S. Patent . 4921779, and the azolylmethylamines described in European Patent Application (Laid-Open) Nos. 504609 and 519190 may be incorporated.
  • As is described in U.S. Patents 4960687, 4975356 and 5037725, it is preferred to incorporate an image stabilizer or a precursor thereof in the adjusting bath, and not to incorporate any image stabilizer in the stabilizing bath from the viewpoint of preventing film surface contamination after processing and uneven development.
  • In washing water, the stabilizing bath or the rinse solution, a surfactant as a water-draining agent, EDTA or a chelating agent such as those represented by formula (II) as a hard water-softener may be incorporated.
  • Suitable surfactants include nonionic ones of poly (ethylene glycol) type or polyhydric alcohol type, anionic ones such as alkylbenzenesulfonic acid salts, sulfuric acid esters of higher alcohols or alkylnaphthalenesulfonic acid salts, cationic ones such as quaternary ammonium salts or amine salts, or amphoteric ones such as amino acid salts or betaines. Two or more of these surfactants may be used together. The fluorine-containing surfactants as disclosed in U.S. Patent 5,716,765 or siloxane-type ones may be also used.
  • Among various nonionic surfactants, alkyl poly (ethylene oxide)s, alkyl phenoxypoly(ethylene oxide)s or alkyl phenoxypoly(hydroxypropylene oxide)s are preferred. And particularly preferable anionic surfactants are those comprising an alkyl-poly(oxyethylene) of 8 to 15 carbon atoms and an alcohol of 10 to 30 carbon atoms, the most preferable ones being those comprising an alkyl-poly(oxyethylene) of 8 to 11 carbon atoms and an alcohol of 15 to 25 carbon atoms.
  • In order to enhance the solubility of surfactants, a solubilizing agent such as amines (e.g., diethanolamine or triethanolamine) or glycols (e.g., diethylene glycol or propylene glycol) are preferably incorporated.
  • In the stabilizing or rinse bath, a chelating agent is preferably incorporated in order to capture heavy metals, thus improving the solution stability and reducing contamination. As the chelating agent, one can utilize the same compounds that are incorporated in the developer and the bleaching solution as described hereinabove. The stabilizing or rinse bath preferably contains a bactericide and a fungicide with the purpose of preventing the propagation of bacteria and fungi. Commercially available bactericides and fungicides can be used for such a purpose. Furthermore, the baths may contain a surfactant, a fluorescent brightening agent and a hardener.
  • The pH of the stabilizing or rinse bath, and that of the washing water for use in the present invention is usually between 4 and 9, and preferably between 5 and 8. Ordinary ranges of the processing temperature and time for these baths are from 15 to 45°C and from 20 sec to 10 min, preferably from 25 to 40°C and from 30 sec to 2 min, though they vary widely depending on the nature and the application of the photographic material to be processed. It is noted that the stabilizing or rinse bath of the present invention exhibits a marked advantageous effect of contamination prevention in the case where the photographic material is processed by a desilvering treatment immediately followed by a treatment with the stabilizing or rinse bath of the present invention, i.e., without intervening washing with water after desilvering.
  • The replenishing amount of the stabilizing or rinse bath of the present invention is preferably 200 to 2,000 ml per 1 m2 of the processed photographic material. The overflowing liquid yielded along with the replenishment of the washing water and/or the stabilizing solution can be again used in other processing steps including desilvering.
  • To reduce the use amount of washing water, ion exchange, reverse osmosis or ultra-filtration is effectively adopted. Among these methods, ultra-filtration is particularly preferred. All the processing solutions used to practice the present invention work at a temperature between 10 and 50°C. Although the temperature usually is in the range of from 33 to 38°C, one can adopt higher temperatures exceeding the upper limit to accelerate processing thus curtailing the processing time, or lower ones below the lower limit to improve image quality as well as the solution stability.
  • In the case where the stabilization treatment is conducted without washing with water in the processing of photographic materials according to the present invention, the methods well known in the art and described in Japanese Patent Application (Laid-Open) Nos. 8543/1982, 14834/1983 and 220345/1985 can be adopted. Alternatively, as preferable embodiments of the present invention, chelating agents such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound can be used.
  • The photographic material having been subjected to washing with water and/or stabilization treatment is then dried. The material just after leaving the washing bath may be squeezed with a squeezing roller or a piece of water-absorbing cloth to decrease the water content in the image-forming layers and accelerate drying. To improve the drying efficiency of the dryer, adoption of higher temperatures or modifying the nozzle shape to intensify the drying air stream is self-evidently effective. Film drying can also be accelerated by the adjustment of the angle at which the drying air is directed toward the material surface as described in Japanese Patent Application (Laid-Open) No. 157650/1991.
  • Color photographic materials for use in practicing the present invention are described hereinbelow. The amount of developed silver in the present invention indicates the total of the silver amounts developed by black-and-white and color-forming developments. Thus, the total amount of developed silver reaches to 3.0 to 7.0 g/m2 when the processed photographic material is a reversal-type color material such as a reversal color film. While commercially available color negative photographic materials and reflection-type color photographic materials such as color photographic paper are developed only at exposed areas thereof thus giving the amount of developed silver below 2 g/m2, the reversal color photographic material undergoes development at exposed areas in the first development, and then color-forming development of the unexposed, remaining silver halide. This means that more than 90%, substantially 100% of the silver halide contained in the photographic material is developed. Hence, the bleaching load for the reversal material is much higher than those for color negative films or color papers, thus sometimes resulting in incomplete bleaching. The present invention exhibits its advantageous features particularly in the processing of color reversal films.
  • Usually, silver halide color reversal films comprise a red-sensitive unit, a green-sensitive unit and a blue-sensitive unit arranged on a support in this order described from the support side. Between the red-sensitive unit and the green-sensitive unit, and/or between the green-sensitive unit and the blue-sensitive unit, one or more interlayers that do not form color are provided.
  • In the case where each photosensitive unit comprises three layers, a low-speed emulsion layer, a medium-speed emulsion layer and a high-speed emulsion layer are preferably arranged in this order from the support side. Between these emulsion layers, a photo-insensitive interlayer that may contain a photo-insensitive silver halide emulsion may be provided.
  • Although all of the blue-, green- and red-sensitive units preferably comprise three layers, it is also possible to have the blue-sensitive unit comprising two layers or less, and the green- and red-sensitive units comprising three layers.
  • The blue-sensitive layers contain a yellow coupler, the green-sensitive ones contain a magenta coupler, and the red-sensitive ones contain a cyan coupler. However, for the purpose of controlling color reproduction capability, the other couplers may be mixed in the above combinations.
  • It is preferred to divide the total amount of silver halide emulsion within the unit to the high-speed layer in 10 to 60% by weight, to the medium-speed layer in 10 to 50% by weight and to the low-speed layer in 30 to 70% by weight. The silver/coupler ratio in each photosensitive layer is preferably regulated so as to be the largest in the low-speed layer.
  • An interlayer that does not develop color is preferably provided between the units each being different in spectral sensitivity. Such a non-color-forming interlayer may contain a photo sensitive emulsion, a photo-insensitive one or one fogged in advance.
  • The interlayer may be of monolayer structure or comprise two to five sub-layers. In the latter case, it is preferred that a sub-layer placed far from the support contains colloidal silver particles or a silver halide emulsion that has been superficially or internally fogged beforehand. In the case where a silver halide emulsion is incorporated in an interlayer, the interlayer or the layer adjacent to the interlayer is preferably contain a color mixing-preventing agent.
  • A more preferable embodiment of the color reversal film associated with the present invention is described below.
  • On a support are provided a red-sensitive unit, a green-sensitive unit and a blue-sensitive unit in this order from the support side wherein at least the red- and green-sensitive units comprise three photosensitive emulsion layers. And the three emulsion layers are arranged in the order of low-speed, medium-speed and high-speed layers from the support side. The silver/coupler ratio in these photosensitive layers is preferably from 25 to 150 whereby the medium-speed layer has a silver/coupler ratio of 5 to 30, and the high-speed layer has a silver/coupler ratio of 2 to 20.
  • Further, between the red-sensitive unit and the green-sensitive unit, and between the green-sensitive unit and the blue-sensitive unit, an interlayer comprising two to five sub-layers is provided. In the interlayer provided between the red- and green-sensitive units, the sub-layer adjacent to the green-sensitive layer may contain colloidal silver particles or a fogged silver halide emulsion. In the interlayer provided between the green- and blue-sensitive units, the sub-layer adjacent to the blue-sensitive layer may contain colloidal silver particles or a fogged silver halide emulsion. The thickness of the interlayer (total of all the sub-layer thickness) is usually 0.5 to 5 µm, preferably 1.0 to 3.0 µm. The thickness can be readily obtained from the specific gravity of each ingredient, or alternatively by examining the cross-section of the coated product with an electron microscope.
  • It is further preferable to arrange an anti-halation layer in the support side of the red-sensitive unit, and at least one protective layer located farther than the blue-sensitive unit from the support. At least one of protective layer preferably contains a silver halide emulsion.
  • Various techniques as well as inorganic or organic materials applicable to the silver halide emulsion and the silver halide photographic material using the emulsion for use in the present invention are described in the following parts of European Patent No. 436938A2 and in the other European Patents described below.
    No. Item Reference site
    1 Layer structure From p. 146, line 34 to p. 147, line 25.
    2 Silver halide emulsion From p. 147, line 26 to p. 148, line 12.
    3 Yellow coupler From p. 137, line 35 to p. 146, line 33, and p. 149, lines 21 to 23.
    4 Magenta coupler From p. 149, lines 24 to 12; Eu. P. No. 421,453A1, from p. 3, line 5 to p. 25, line 55.
    5 Cyan coupler From p. 149, lines 29 to 33; Eu. P. No. 432,804A2, from p. 3, line 28 to p. 40, line 2.
    6 Polymer coupler From p. 149, lines 34 to 38; Eu. P. No. 435,334A1, from p. 113, line 39 top. 123, line 37.
    7 Colored coupler From p. 53, line 42 to p. 137, line 34, and from p. 149, lines 39 to 45.
    8 Other functional coupler From p. 7, line 1 to p. 53, line 41, and from p. 149, line 46 to p. 150, line 3; Eu. P. No. 435,334A2, from p. 3, line 1 to p. 29, line 50.
    9 Antiseptic, preservative From p. 150, lines 25 to 28.
    10 Formalin scavenger From p. 149, lines 15 to 17.
    11 Other additives From p. 153, lines 38 to 47; Eu. P. No. 421,453A1, from p. 75, line 21 to p. 84, line 56.
    12 Dispersing method From p. 150, lines 4 to 24.
    13 Support From p. 150, lines 32 to 34.
    14 Layer thickness, physical property of film From p. 150, lines 35 to 49.
    15 Color-forming development, black-and-white development From p. 150, line 50 to p. 151, line 47; fogging process of Eu. P. No. 442,323A2, from p. 34, lines 11 to 54, and from p. 27, line 40 to p. 37, line 40.
    16 Desilvering From p. 151, line 48 to p. 152, line 53.
    17 Automatic processor From p. 152, line 54 to p.153, line 2.
    18 Washing and stabilizing processes From p. 153, lines 3 to 37.
    • EXAMPLE (Example 1)
  • The present invention is explained more in detail with reference to examples, which, however, are not construed to restrict the scope of the present invention.
    • (1) Preparation of photographic material Preparation of Sample 101:
  • On a support comprising a 127 µm-thick cellulose triacetate film that had been coated with a subbing layer, the layers of the following compositions were provided to prepare a multi-layer color photographic material. The resulting material was designated as Sample 101. In the following compositions, the numerals indicate the added amount per m2.
    First layer: anti-halation layer
    Black colloidal silver 0.25 g
    Gelatin 2.40 g
    UV absorber U-1 0.10 g
    UV absorber U-3 0.10 g
    UV absorber U-4 0.10 g
    High boiling point organic solvent Oil-1 0.050 g
    High boiling point organic solvent Oil-2 0.050 g
    High boiling point organic solvent Oil-5 0.010 g
    Dye D-4 1.0 mg
    Dye D-8 2.5 mg
    Fine-crystalline solid dispersion of Dye E-1 0.05 g
    Second layer: inter-layer
    Gelatin 0.40 g
    Compound Cpd-A 0.2 mg
    Compound Cpd-J 1.0 mg
    Compound Cpd-K 3.0 mg
    Compound Cpd-M 0.030 g
    UV absorber U-6 6.0 mg
    High boiling point organic solvent Oil-3 0.010 g
    High boiling point organic solvent Oil-4 0.010 g
    High boiling point organic solvent Oil-7 2.0 mg
    High boiling point organic solvent Oil-8 4.0 mg
    Dye D-7 4.0 mg
    Third layer: inter-layer
    Yellow colloidal silver 0.010 g
    Gelatin 0.50 g
    Compound Cpd-M 0.010 g
    High boiling point organic solvent Oil-3 0.010 g
    Fourth layer: low-speed red-sensitive emulsion layer
    Emulsion A Silver amount 0.20 g
    Emulsion B Silver amount 0.20 g
    Emulsion C Silver amount 0.15 g
    Gelatin 0.70 g
    Coupler C-1 0.050 g
    Coupler C-2 0.080 g
    Coupler C-3 0.010 g
    Coupler C-6 6.0 mg
    Coupler C-9 5.0 mg
    Coupler C-11 0.030 g
    UV absorber U-1 0.010 g
    UV absorber U-2 0.010 g
    Compound Cpd-A 1.0 mg
    Compound Cpd-I 0.020 g
    Compound Cpd-J 2.0 mg
    High boiling point organic solvent Oil-2 0.10 g
    High boiling point organic solvent Oil-5 0.010 g
    Additive P-1 0.020 g
    Fifth layer: medium-speed red-sensitive emulsion layer
    Emulsion C Silver amount 0.25 g
    Emulsion D Silver amount 0.25 g
    Gelatin 0.60 g
    Coupler C-1 0.040 g
    Coupler C-2 0.10 g
    Coupler C-3 0.020 g
    Coupler C-6 7.0 mg
    Coupler C-11 0.050 g
    UV absorber U-1 0.010 g
    UV absorber U-2 0.010 g
    High boiling point organic solvent Oil-2 0.10 g
    Additive P-1 0.020 g
    Fifth layer: high-speed red-sensitive emulsion layer
    Emulsion E Silver amount 0.25 g
    Emulsion F Silver amount 0.35 g
    Gelatin 1.50 g
    Coupler C-1 0.10 g
    Coupler C-3 0.060 g
    Coupler C-6 0.010 g
    Coupler C-11 0.020 g
    UV absorber U-1 0.010 g
    UV absorber U-2 0.010 g
    High boiling point organic solvent Oil-2 0. 10 g
    High boiling point organic solvent Oil-9 0.010 g
    Compound Cpd-K 1.0 mg
    Compound Cpd-L 1.0 mg
    Compound Cpd-F 0.050 g
    Additive P-1 0.10 g
    Seventh layer: inter-layer
    Gelatin 0.70 g
    Additive P-2 0.10 g
    Compound Cpd-I 0.010 g
    Dye D-5 0.020 g
    Dye D-9 6.0 mg
    Compound Cpd-M 0.040 g
    Compound Cpd-O 3.0 mg
    Compound Cpd-P 5.0 mg
    High boiling point organic solvent Oil-6 0.050 g
    Eighth layer: inter-layer
    Yellow colloidal silver Silver amount 0.010 g
    Gelatin 1.00 g
    Additive P-2 0.05 g
    UV absorber U-1 0.010 g
    UV absorber U-3 0.010 g
    Compound Cpd-A 0.050 g
    Compound Cpd-M 0.050 g
    High boiling point organic solvent Oil-3 0.010 g
    High boiling point organic solvent Oil-6 0.050 g
    Ninth layer: low-speed green-sensitive emulsion layer
    Emulsion G Silver amount 0.20 g
    Emulsion H Silver amount 0.35 g
    Emulsion I Silver amount 0.30 g
    Gelatin 1.50 g
    Coupler C-4 0.020 g
    Coupler C-7 0.070 g
    Coupler C-8 0.070 g
    Coupler C-12 0.020 g
    Coupler C-13 0.010 g
    Compound Cpd-B 0.030 g
    Compound Cpd-D 5.0 mg
    Compound Cpd-E 5.0 mg
    Compound Cpd-G 2.5 mg
    Compound Cpd-F 0.010 g
    Compound Cpd-K 2.0 mg
    UV absorber U-6 5.0 mg
    High boiling point organic solvent Oil-2 0.15 g
    High boiling point organic solvent Oil-6 0.030 g
    High boiling point organic solvent Oil-4 8.0 mg
    Additive P-1 5.0 mg
    Tenth layer: medium-speed green-sensitive emulsion layer
    Emulsion I Silver amount 0.30 g
    Emulsion J Silver amount 0.30 g
    (An internally fogged silver bromide emulsion (cubic grains with an average equivalent sphere grain diameter of 0.11 µm) Silver amount 5. 0 mg
    Gelatin 0.70 g
    Coupler C-4 0.030 g
    Coupler C-8 0.020 g
    Coupler C-12 0.020 g
    Coupler C-13 0.010 g
    Compound Cpd-B 0.030 g
    Compound Cpd-F 0.010 g
    Compound Cpd-G 2.0 mg
    High boiling point organic solvent Oil-2 0.050 g
    High boiling point organic solvent Oil-5 6. 0 mg
    Eleventh layer: high-speed green-sensitive emulsion layer
    Emulsion K Silver amount 0.55 g
    Gelatin 0.70 g
    Coupler C-3 5.0 mg
    Coupler C-4 0.35 g
    Coupler C-8 0.010 g
    Coupler C-12 0.020 g
    Compound Cpd-B 0.050 g
    Compound Cpd-F 0.010 g
    Compound Cpd-K 2.0 mg
    High boiling point organic solvent Oil-2 0. 050 g
    Twelfth layer: inter-layer
    Gelatin 0.30 g
    Compound Cpd-M 0.05 g
    High boiling point organic solvent Oil-3 0.025 g
    High boiling point organic solvent Oil-6 0.025 g
    Dye D-6 5.0 mg
    Thirteenth layer: yellow filter layer
    Yellow colloidal silver Silver amount 0.050 g
    Gelatin 0.70 g
    Compound Cpd-C 0.010 g
    Compound Cpd-M 0.030 g
    High boiling point organic solvent Oil-1 0.020 g
    High boiling point organic solvent Oil-6 0.030 g
    Fine-crystalline solid dispersion of Dye E-2 0.030 g
    Fourteenth: inter-layer
    Gelatin 0.30 g
    Compound Cpd-Q 0.20 g
    Fifteenth layer: low-speed blue-sensitive emulsion layer
    Emulsion L Silver amount 0.20 g
    Emulsion M Silver amount 0.20 g
    Gelatin 0.80 g
    Coupler C-5 0.30 g
    Coupler C-6 0.010 g
    Coupler C-10 0.030 g
    Compound Cpd-I 8.0 mg
    Compound Cpd-K 1.0 mg
    Compound Cpd-M 5.0 mg
    UV absorber U-6 0.010 g
    High boiling point organic solvent Oil-2 0.010 g
    High boiling point organic solvent Oil-3 0.010 g
    Sixteenth layer: medium-speed blue-sensitive emulsion layer
    Emulsion N Silver amount 0.20 g
    Emulsion O Silver amount 0.20 g
    (An internally fogged silver bromide emulsion: cubic grains
    with an average equivalent sphere grain diameter of 0.11 µm) Silver amount 0.010 mg
    Gelatin 0.90 g
    Coupler C-5 0.50 g
    Coupler C-6 0.020 g
    Coupler C-10 0.060 g
    Compound Cpd-N 2.0 mg
    High boiling point organic solvent Oil-2 0.080 g
    Seventeenth layer: high-speed blue-sensitive emulsion layer
    Emulsion O Silver amount 0.20 g
    Emulsion P Silver amount 0.25 g
    Gelatin 2.00 g
    Coupler C-3 5.0 mg
    Coupler C-5 0.20 g
    Coupler C-6 0.020 g
    Coupler C-10 1.00 g
    High boiling point organic solvent Oil-2 0.10 g
    High boiling point organic solvent Oil-6 0.020 g
    UV absorber U-6 0.10 g
    Compound Cpd-B 0.020 g
    Compound Cpd-N 5.0 mg
    Eighteenth layer: first protective layer
    Gelatin 0.80 g
    UV absorber U-1 0.10 g
    UV absorber U-2 0.050 g
    UV absorber U-5 0.20 g
    Compound Cpd-O 5.0 mg
    Compound Cpd-A 0.030 g
    Compound Cpd-H 0.20 g
    Dye D-1 8.0 mg
    Dye D-2 0.010 g
    Dye D-3 0.010 g
    High boiling point organic solvent Oil-3 0.10 g
    Nineteenth layer: second protective layer
    Colloidal silver Silver amount 0.11 mg
    Fine grain silver iodobromide emulsion with an average grain size of 0.06 µm and AgI content of 1 mol% Silver amount 0.10 g
    Gelatin 0.70 g
    UV absorber U-1 0.010 g
    UV absorber U-6 0.010 g
    High boiling point organic solvent Oil-3 0.010 g
    Twentieth layer: third protective layer
    Gelatin 1.00 g
    Poly(methyl methacrylate) (average particle size: 1.5 µm) 0.10 g
    Methyl methacrylate/methacrylic acid copolymer (6:4) (average particle size: 1.5 µm) 0.10 g
    Silicone oil SO-1 0.10 g
    Surfactant W-1 3.0 mg
    Surfactant W-2 8.0 mg
    Surfactant W-3 0.040 g
    Surfactant W-7 0.015 g
  • In addition to the above-described ingredients, every emulsion layer was added with additives F-1 to F-8. Further, each layer was incorporated with gelatin hardener H-1, surfactants W-3, W-4, W-5 and W-6 as a coating aid or an emulsifier.
  • Moreover, phenol, 1,2-benzoisothiazoline-3-one, 2-phenoxyethanol, phenethylalcohol or p-butyl benzoate was added as antiseptic or fungicide.
    Emulsions used in Sample 101
    Emulsion Features Equivalent sphere grain diameter (µm) Coefficient of variation (%) AgI content (%)
    A Monodisperse, tetradecahedral grains 0.13 10 4.5
    B Monodisperse (111) internal latent image type tabular grains with mean aspect ratio of 2.0 0.25 10 4.8
    C Monodisperse (111) tabular grains with mean aspect ratio of 2.0 0.30 10 4.0
    D Monodisperse (111) tabular grains with mean aspect ratio of 3.0 0.35 12 4.8
    E Monodisperse (111) tabular grains with mean aspect ratio of 3.0 0.40 10 2.5
    F Monodisperse (111) tabular grains with mean aspect ratio of 4.5 0.55 12 2.5
    G Monodisperse, cubic grains 0.15 9 3.5
    H Monodisperse, cubic, internal latent image type grains 0.24 12 4.9
    I Monodisperse (111) tabular grains with mean aspect ratio of 4.0 0.30 12 3.5
    J Monodisperse (111) tabular grains with mean aspect ratio of 5.0 0.45 10 3.0
    K Monodisperse (111) tabular grains with mean aspect ratio of 5.5 0.60 13 3.5
    L Monodisperse tetradecahedral grains 0.33 10 4.5
    M Monodisperse (111) tabular grains with mean aspect ratio of 5.0 0.33 9 6.0
    N Monodisperse (111) tabular grains with mean aspect ratio of 3.0 0.43 9 2.5
    O Monodisperse (111) tabular grains with mean aspect ratio of 6.0 0.75 9 3.0
    P Monodisperse (111) tabular grains with mean aspect ratio of 6.0 0.90 8 2.8
    Spectral sensitization of Emulsions A to P
    Emulsion Added spectral sensitizer Added amount per 1 mol of silver halide (g)
    A S-1 0.01
    S-2 0.35
    S-3 0.02
    S-8 0.03
    S-13 0.015
    S-14 0.01
    B S-2 0.35
    S-3 0.02
    S-8 0.03
    S-13 0.015
    S-14 0.01
    C S-2 0.45
    S-3 0.04
    S-8 0.04
    S-13 0.02
    D S-2 0.5
    S-3 0.05
    S-8 0.05
    S-13 0.015
    E S-1 0.01
    S-2 0.45
    S-3 0.05
    S-8 0.05
    S-13 0.01
    F S-2 0.4
    S-3 0.04
    S-8 0.04
    G S-4 0.3
    S-5 0.05
    S-12 0.1
    H S-4 0.2
    S-5 0.05
    S-9 0.15
    S-14 0.02
    I S-4 0.3
    S-9 0.2
    S-12 0.1
    Spectral sensitization of Emulsions A to P (continued from Table 2)
    Added spectral sensitizer Added amount per 1 mol of silver halide (g)
    J S-4 0.35
    S-5 0.05
    S-12 0.1
    K S-4 0.3
    S-9 0.05
    S-12 0.1
    S-14 0.02
    L S-6 0.1
    S-10 0.2
    S-11 0.05
    M S-6 0.05
    S-7 0.05
    S-10 0.25
    S-11 0.05
    N S-10 0.4
    S-11 0.15
    O S-6 0.05
    S-7 0.05
    S-10 0.3
    S-11 0.1
    P S-6 0.05
    S-7 0.05
    S-10 0.2
    S-11 0.25
    Figure 01040001
    Figure 01040002
    Figure 01040003
    Figure 01040004
    Figure 01050001
    Figure 01050002
    Figure 01050003
    Figure 01060001
    Figure 01060002
    Figure 01060003
    Figure 01060004
    • Oil-1
    Tri-n-hexyl phosphate
    Oil-2
    Tricresyl phosphate
    Oil-3
    Figure 01070001
    Oil-4
    Tricyclohexyl phosphate
    Oil-5
    Di-2-ethylhexyl succinate
    Oil-6
    Figure 01070002
    Oil-7
    Figure 01070003
    Oil-8
    Figure 01070004
    Oil-9
    Figure 01070005
    Figure 01080001
    Figure 01080002
    Figure 01080003
    Figure 01090001
    Figure 01090002
    Figure 01090003
    Figure 01090004
    Figure 01090005
    Figure 01100001
    Figure 01100002
    Figure 01100003
    Figure 01100004
    Figure 01100005
    Figure 01110001
    Figure 01110002
    Figure 01110003
    Figure 01110004
    Figure 01120001
    Figure 01120002
    Figure 01120003
    Figure 01120004
    Figure 01120005
    Figure 01120006
    Figure 01130001
    Figure 01130002
    Figure 01130003
    Figure 01130004
    Figure 01140001
    Figure 01140002
    Figure 01140003
    Figure 01140004
    Figure 01150001
    Figure 01150002
    Figure 01150003
    Figure 01150004
    Figure 01150005
    Figure 01150006
    Figure 01160001
    Figure 01160002
    Figure 01160003
    Figure 01160004
    Figure 01170001
    Figure 01170002
    Figure 01170003
    Figure 01170004
    Figure 01170005
    Figure 01180001
    Figure 01180002
    Figure 01180003
    Figure 01180004
    Figure 01190001
    Figure 01190002
    Figure 01190003
    Figure 01190004
    Figure 01190005
    W-7   C8F17SO3Li
    Figure 01190006
    Figure 01190007
    Figure 01190008
    Figure 01200001
    Figure 01200002
    Figure 01200003
    Preparation of dispersion of organic solid dispersion dyes:
  • Dye E-1 was dispersed by the following process. To 1430 g of a wet cake of dye E-1 containing 30% of methanol, 200 g of Pluronic F88, (an ethylene oxide-propylene oxide block copolymer) made by BASF Corp. were added together with water to give a slurry with a dye content of 6%. Then, an Ultra-viscomill (UVM-2, a product of Imex Corp.) was charged with 1700 ml of zirconia beads having a mean diameter of 0.5 mm. The slurry was passed through the mill, and subjected to grinding for 8 hours at a peripheral speed of about 10 m/sec and a discharge rate of 0.5 L/min. After the removal of the beads by filtration, the resulting dispersion was diluted with water to give a dye concentration of 3%. The diluted dispersion was then heated at 90°C for 10 hours for stabilization. The average size of the obtained dye particles was 0.60 µm with a distribution width of 18% in terms of standard deviation of (particle size x 100/average particle size).
  • In a similar manner, a solid dispersion of dye E-2 was prepared having an average particle size of 0.54 µm.
    • (2) Exposure and development processing
  • The photographic material prepared above (Sample No. 101) was exposed to a CIE D50 light source through an optical wedge designed for live scene shooting photographic materials (neutral color, density gradient of 0.4/cm and density range of 4.8) ; thereafter the material was processed by the following processing procedures (development treatment A)
    Process step Duration (min) Temp. (°C) Tank volume (L) Replenished amount (ml/m2)
    First development 6 38 165 2,200
    First washing 2 38 50 7,500
    Image reversal 2 38 86 1,100
    Color-forming development 6 38 165 2,200
    Pre-bleaching 2 38 65 1,100
    Bleaching 4 38 150 220
    Fixing 4 38 108 1,100
    Second washing 4 38 55 7,500
    Final rinsing 1 25 44 1,100
  • The composition of each processing bath was as follows.
    [First developer]
    Tank solution Replenisher
    Nitrilo-N,N,N-trimethylenephosphoric acid pentasodium salt 1.5 g 1.5 g
    Diethylenetriaminepentaacetic acid pentasodium salt 2.0 g 2.0 g
    Sodium sulfite 28 g 30 g
    Hydroquinone potassium monosulfonate 18 g 20 g
    Potassium carbonate 20 g 20 g
    Potassium bicarbonate 15 g 15 g
    1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrrazolidone 1.5 g 2.0 g
    Potassium bromide 2.5 g 1.4 g
    Potassium thiocyanate 1.2 g 1.2 g
    Potassium iodide 4.0 mg 1.5 mg
    Diethylene glycol 15 g 15 g
    Water to make 1000 ml 1000 ml
    PH 9.65 9.70
    The pH was adjusted with sulfuric acid or potassium hydroxide.
    [Reversal bath]
    Tank solution Replenisher
    Nitrilo-N,N,N-trimethylenephosphoric acid pentasodium salt 3.0 g The same as tank sol.
    Stannous chloride dihydrate 2.0 g
    p-Aminophenol 0.001 g
    Sodium hydroxide 8 g
    Acetic acid 15 ml
    Water to make 1000 ml
    PH 6.00
    The pH was adjusted with acetic acid or sodium hydroxide.
    [Color-forming developer]
    Tank solution Replenisher
    Nitrilo-N,N,N-trimethylenephosphoric acid pentasodium salt 2.0 g 2.0 g
    Sodium sulfite 7.0 g 7.0 g
    Trisodium phosphate dodecahydrate 36 g 36 g
    Potassium bromide 0.7 g -
    Potassium iodide 40 mg -
    Sodium hydroxide 3.0 g 3.0 g
    Citrazinic acid 0.5 g 0.5 g
    N-ethyl-N-( β-methanesulfoneamide-ethyl)-3-methyl-4-aminoaniline 3/2 sulfuric acid monohydrate 11 g 11 g
    3,6-Dithiaoctane-1,8-diol 1.0 g 1.0 g
    Water to make 1000 ml 1000 ml
    PH 11.00 12.10
    The pH was adjusted with sulfuric acid or sodium hydroxide.
    [Pre-bleaching]
    Tank solution Replenisher
    Ethylenediaminetetraacetic acid disodium salt dihydrate 8.0 g 8.0 g
    Sodium sulfite 5.0 g 6.0 g
    1-Thioglycerol 0.4 g 0.5 g
    Formaldehyde-sodium bisulfite adduct 20 g 25 g
    Water to make 1000 ml 1000 ml
    PH 6.30 6.10
    The pH was adjusted with acetic acid or sodium hydroxide.
    [Bleaching solution]
    Tank solution Replenisher
    Bleaching agent (shown in Table 4) 0.15 mol 0.30 mol
    Added compound (shown in Table 4) 0.02 mol 0.04 mol
    Compound VI Iron (III) complex (shown in Table 4) 0.03 mol 0.06 mol
    Potassium bromide 100 g 200 g
    Ammonium nitrate 10 g 20 g
    Water to make 1000 ml 1000 ml
    PH 5.0 4.8
    The pH was adjusted with nitric acid or ammonium hydroxide.
  • In the incorporation of the bleaching agent, the complex-forming compound and the iron compound had been reacted in advance to form a complex, which was added to the bath along with the adjustment of the quantity of ammonium nitrate so as to give the composition shown in Table 4. The pH value in Table 4 indicates that of the tank solution, and the pH value for the replenisher was set at 0.3 lower than that of the tank solution.
    [Fixing solution] [Tank solution] [Replenisher]
    Ammonium thiosulfate 80 g The same as tank sol.
    Sodium sulfite 5.0 g The same as tank sol.
    Sodium bisulfite 5.0 g The same as tank sol.
    Compound (a) 0.05 g The same as tank sol.
    Compound (b) 0.05 g The same as tank sol.
    Water to make 1000 ml The same as tank sol.
    pH 6.6
    The pH value was adjusted with acetic acid or aqueous ammonia.
    Figure 01250001
    Figure 01250002
    [Stabilizing sol.] [Tank solution] [Replenisher]
    1,2-Benzoisothiazoline-3-on 0.06 g The same as tank sol.
    Dipropylene glycol 0.3 g The same as tank sol.
    Polyoxyethylene-tridecyl ether (average degree of polymerization = 10) 5.0 g The same as tank sol.
    Water to make 1000 ml The same as tank sol.
    pH 7.0
    • (2) Evaluation
  • On each sample obtained by the above processing, the amount of residual silver, the deposition of ferric compound (i.e., iron (III) compound, stain formation and failure of color restoration were evaluated by the following methods. Amount of residual silver: the silver amount remaining in the processed photosensitive material was quantitatively measured by fluorescent X-ray analysis. By measuring the silver amount of the sample for which the treatment with a bleaching solution was omitted and subtracting the weight of the colloidal silver from the measured value, the amount of developed silver was determined to be 4.5 g/m2.
    Failure of color destoration: the photographic characteristic (HD) curve was obtained for each photosensitive material that had been processed in the above-described manner with a transmission densitometer having a measuring optical system in conformity with International Standard ISO 5. From the HD curve thus obtained, the Dmax(R) which indicates the maximum density measured with red light was read. Separately, a reference sample for comparison was prepared by repeating the same processing as above except that the bleaching solution was replaced to the following reference bleaching solution having a sufficiently high bleaching activity and that the bleaching time was changed to 6 min. The corresponding Dmax(R) was similarly obtained and designated Ref. Dmax(R). Then, the degree of color restoration failure was defined and evaluated by the following equation. Degree of color restoration failure = [Dmax(R)/Ref. Dmax(R)] x 100
    [Reference bleaching solution]
    Tank solution Replenisher
    Ethylenediaminetetraacetic acid disodium salt dihydrate 2.0 g 4.0 g
    Ethylenediaminetetraacetic acid ferric ammonium salt dihydrate 120 g 240 g
    Potassium bromide 100 g 200 g
    Ammonium nitrate 10 g 20 g
    Water to make 1000 ml 1000 ml
    PH 5.70 5.50
    The pH was adjusted with nitric acid or ammonium hydroxide.
  • Stain formation: After the minimum density of the HD curve measured with green light (Dmin(G)) was read, the sample was kept in an atmosphere of 60°C and 70% RH for 2 weeks, and then Dmin(G) was measured again. By using the two Dmin(G) values before and after the storage, the magenta stain was defined and evaluated by the following equation. Stain (ΔDmin(G)) = Dmin(G) after storage - Dmin(G) before storage Precipitation formation of ferric compound: each bleaching tank solution after 2 round treatments (One round treatment corresponds to the processing amount for the replenishing volume integral equal to the tank volume.) was poured in a beaker, and the turbidity of the solution was visually inspected. At the same time, the existence of precipitate on the bottom of the beaker was checked.
    The following evaluation criteria were adopted.
  • O: No turbidity is observed in the bleaching solution, nor precipitate is formed at all.
  • Δ: Slight turbidity is observed in the bleaching solution but within an allowable limit, and no precipitate is formed.
  • x: Turbidity is obvious, but no precipitate is formed.
  • xx: Turbidity is obvious, and precipitate is formed.
  • Table 4 shows the evaluation results obtained by the methods described above. In the table, the term "turbidity" has the same meaning as "precipitate formation".
    Test No. (I) Added compound (VI) Amount of residual Ag (mg/m2) Color restoration failure (%) Stain Turbidity Note
    1 I-8 - - 7.0 92 0.28 xx Compar. example
    2 I-8 Compar. comp. (1) - 6.5 90 0.21 xx Compar. example
    3 I-8 Compar. comp. (2) - 15.6 85 0.09 O Compar. example
    4 I-8 II-1 - 4.4 95 0.03 O The present invention
    5 I-8 II-3 - 4.1 96 0.02 O The present invention
    6 I-8 III-1 - 4.9 98 0.03 O The present invention
    7 I-8 IV-1 - 3.9 98 0.05 O The present invention
    8 I-8 V-1 - 3.8 99 0.04 O The present invention
    9 I-8 II-3 - 4.6 97 0.03 O The present invention
    10 I-8 II-3 VI-1 2.1 99 0.02 O The present invention
    Comparative compound (1) = iminodiacetic acid
    Comparative compound (2) = 1-hydroxyethylidene-1, 1-diphosphonic acid
    (I) and (VI) in the top line each indicates the iron (III) complex of the compound represented by formula (I) or (VI) , respectively.
  • Table 4 indicates the following facts. For the systems where the conventional iron (III) PDTA (Compounds (1) to (3)) complex salts now in practical use in the market are used as the bleaching agent, precipitation and stain formation tends to occur, and the amount of residual silver is comparatively large when an additive is not used <Test No. 1>. Though the addition of Comparative Compound (1) is effective to suppress stain formation, precipitate deposition still takes place <Test No. 2>. When Comparative Compound (2) was added, both precipitate and stain formations were suppressed, but the amount of residual silver further increased <Test No. 3>. In the three comparative examples (Test Nos. 1 to 3), in particular in Test No. 3, color development was also incomplete. In a clear contrast to these results, the examples of the present invention wherein the compounds represented by formulae (II) to (V) were incorporated, no precipitate deposition occurred, and desilvering, stain characteristic and color development were satisfactorily good. By comparing Test No. 5 with No. 9, one can conclude that the advantageous features of the present invention are exhibited even when the bleaching agent is replaced to the iron (III) complex represented by formula (I). And by comparing Test No. 5 with No. 10, one can conclude that desilvering and stain-suppression are further enhanced when the iron (III) complex represented by formula (VI) was incorporated in addition to the bleaching agent.
    • EFFECT OF THE INVENTION
  • According to the present invention wherein a bleaching solution containing at least one iron (III) complex salt represented by formula (I) and at least one compound represented by formulae (II) to (V) is used for the processing of color photographic materials, precipitate deposition in the time-elapsed bleaching solution, stain formation and incomplete color development are difficult to occur even when a color-forming developer containing phosphate ion at a concentration of from 0.05 to 0.25 mol/L is used and the photographic material to be processed is a color reversal material that develops a large quantity of silver. Hence, such a bleaching solution can achieve a photographic processing of desirable developing quality.
    Furthermore, by adding the iron (III) complex salt of the iminocarboxylic acid represented by formula (VI) to the bleaching solution described above, the advantageous features of the present invention are enhanced.

Claims (16)

  1. A method of processing a silver halide color photographic Material, wherein the color-forming developer used for the color-forming development step comprises phosphate ion at a concentration of from 0.05 to 0.25 mol/L, and the bleaching solution used for the bleaching step comprises at least one iron (III) complex salt of the compound represented by the following formula (I) , and at least one of compounds represented by the following formulae (II), (III), (IV) and (V):
    Figure 01320001
    wherein A1, A2, A3 and A4 may be the same or different, each represents -CH2OH, -PO3(M2)2 or -COOM1; M1 and M2 each represents a hydrogen atom, an alkali metal atom, an ammonium group or an organic ammonium group; X1 represents a straight-chain or branched-chain alkylene group containing 3 to 6 carbon atoms, a ring-forming, saturated or unsaturated divalent organic group, or -(B1O)n5-B2-; n5 represents an integer of 1 to 8; B1 and B2 may be the same or different, each represents an alkylene group having 1 to 5 carbon atoms; and n1, n2, n3 and n4 may be the same or different, each represents an integer not more than 10;
    Figure 01330001
    wherein R1 represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, a carboxyalkyl group or an alkoxyalkyl group; R2 and R3 each represents a hydrogen atom, an alkyl group or an alkoxyalkyl group; and M6, M7 and M8 each represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an onium group;
    Figure 01330002
    wherein L0 represents a divalent alkylene group having 2 to 8 carbon atoms, and M9 and M10 each represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an onium group; M11OOC―X2―NH―X3―NH―X4―COOM12 wherein X2, X3 and X4 each represents a substituted or unsubstituted alkylene group having 1 to 3 carbon atoms, and M11 and M12 each represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an onium group; and
    Figure 01340001
    wherein Z represents a nitrogen-containing heterocyclic ring; R4 represents a hydrogen atom, an alkyl group or an alkoxyalkyl group; M13 represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an onium group; and m represents an integer of 1 to 3.
  2. The method of processing a silver halide color photographic material as in claim 1, wherein the bleaching solution further contains at least one iron (III) complex salt of the compound represented by formula (VI):
    Figure 01340002
    wherein G1 and G2 each represents a carboxyl group, a phosphono group, a sulfo group, a hydroxy group, a mercapto group, an aryl group, a heterocyclic group, an alkylthio group, an amidino group, a guanidino group or a carbamoyl group; L1, L2 and L3 each represents a divalent aliphatic or aromatic group or a divalent linking group comprising a combination thereof; m and n each represents 0 or 1; X represents a hydrogen atom, an aliphatic or aromatic group; and M represents a hydrogen atom or a cation.
  3. The method of processing a silver halide color photographic material as in claim 2, wherein the content ratio of the iron (III) complex salt of the compound represented by formula (VI) to the iron (III) complex salt of the compound represented by formula (I) is in the range of from 0.1 to 0.8.
  4. The method of processing a silver halide color photographic material as in claim 2 or 3 wherein the compound represented by formula (VI) is a compound represented by formula (VII) :
    Figure 01350001
    wherein L2' represents a divalent aliphatic or aromatic group or a divalent linking group comprising a combination thereof; G2' represents a carboxyl group, a phosphono group, a sulfo group, a hydroxy group, a mercapto group, an aryl group, a heterocyclic group, an alkylthio group, an amidino group, a guanidino group or a carbamoyl group; and M' and M" represents a hydrogen atom or a cation.
  5. The method of processing a silver halide color photographic material as in claim 1, wherein the compound represented by formula (I) is Compound (I-3), Compound (I-4), Compound (I-8), Compound (I-11) or Compound (I-16).
    Figure 01360001
    Figure 01360002
    Figure 01360003
    Figure 01370001
    Figure 01370002
  6. The method of processing a silver halide color photographic material as in any one of claims 1 to 5, wherein the compound represented by formula (I) is Compound (I-3).
    Figure 01370003
  7. The method of processing a silver halide color photographic material as in any one of claims 1 to 6, wherein the compound represented by formula (II) is selected from the group consisting of iminodisuccinic acid, N-carboxymethylaspartic acid and N,N'-dicarboxymethylaspartic acid.
  8. The method of processing a silver halide color photographic material as in any one of claims 1 to 7, wherein the compound represented by formula (III) is N-(2-hydroxyethyl)aminodiacetic acid.
  9. The method of processing a silver halide color photographic material as in any one of claims 1 to 8, wherein the compound represented by formula (IV) is ethylenediamine-N,N'-diacetic acid.
  10. The method of processing a silver halide color photographic material as in any one of claims 1 to 9, wherein the compound represented by formula (V) is pyridine-2-carboxylic acid.
  11. The method of processing a silver halide color photographic material as in claim 2, wherein the compound represented by formula (VI) is N-carboxymethylaspartic acid.
  12. The method of processing a silver halide color photographic material as in claim 1, wherein the compound represented by formula (I) is used in an amount of 30 to 95% based on the total amount of the complex-forming compound capable of forming an iron (III) complex salt in the bleaching solution, and the compounds represented by formulae (II) to (V) are used in an amount of 5 to 70% based on the total amount of the complex-forming compound capable of forming an iron (III) complex salt in the bleaching solution.
  13. The method of processing a silver halide color photographic material as in any one of claims 1 to 12, wherein the bleaching solution further contains a compound represented by formula [A]: A5(-COOM5)n51 wherein A5 represents an n51-valent organic group, provided that A5 never represents an unsubstituted methyl, ethyl or ethylene group; n51 represents an integer of 1 to 6; and M5 represents an ammonium group, an organic ammonium group, an alkali metal or a hydrogen atom.
  14. The method of processing a silver halide color photographic material as in claim 13, wherein the compound represented by formula [A] is Compound (A-3), Compound (A-4), Compound (A-15) or Compound (A-16):
    (A-3)
    HOOCCH (OH) CH2COOH
    (A-4)
    HOOCCH=CHCOOH
    (A-15)
    Glutaric acid
    (A-16)
    HOOCCH2COOH
  15. The method of processing a silver halide color photographic material as in claim 13, wherein the compound represented by formula [A] is contained in an amount of 0.01 to 0.25 mol per 1liter of the processing tank solution.
  16. The method of processing a silver halide color photographic material as in any one of claims 1 to 15, wherein the black-and-white development is carried out before a color development.
EP02005892A 2001-03-14 2002-03-14 Processing method for silver halide color photographic material Withdrawn EP1241522A1 (en)

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