EP1241522A1 - Entwicklungsverfahren für farbphotographisches Silberhalogenidmaterial - Google Patents

Entwicklungsverfahren für farbphotographisches Silberhalogenidmaterial 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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Prior art keywords
group
acid
formula
compound
processing
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English (en)
French (fr)
Inventor
Hiroyuki Seki
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Fujifilm Corp
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Fuji Photo Film Co Ltd
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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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EP2216083A3 (de) * 2003-06-27 2010-11-24 Invitrogen Dynal AS Konjugate aus magnetischen polymerteilchen und carboxymethylierter asparaginsäure
US10287373B2 (en) 2015-10-21 2019-05-14 Lg Chem, Ltd. Ligand compound, catalyst system for olefin oligomerization, and method for oligomerizing olefins using the same

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Publication number Priority date Publication date Assignee Title
EP2216083A3 (de) * 2003-06-27 2010-11-24 Invitrogen Dynal AS Konjugate aus magnetischen polymerteilchen und carboxymethylierter asparaginsäure
AU2004251492B2 (en) * 2003-06-27 2011-03-17 Invitrogen Dynal As Conjugates of magnetic polymer particles and carboxymethylated aspartic acid
US10287373B2 (en) 2015-10-21 2019-05-14 Lg Chem, Ltd. Ligand compound, catalyst system for olefin oligomerization, and method for oligomerizing olefins using the same

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