Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/407—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
  • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
  • G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
  • G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
  • G03C7/30529—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution having the coupling site in rings of cyclic compounds
• • 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
  • G03C7/32—Colour coupling substances
  • G03C7/36—Couplers containing compounds with active methylene groups
  • G03C7/38—Couplers containing compounds with active methylene groups in rings
  • G03C7/381—Heterocyclic compounds
  • G03C7/382—Heterocyclic compounds with two heterocyclic rings
  • G03C7/3825—Heterocyclic compounds with two heterocyclic rings the nuclei containing only nitrogen as hetero atoms

Definitions

• This invention relates to a method for processing a silver halide color photographic material and, more particularly, to a method which is excellent in processing properties, color-forming properties, and color fading resistance and, further, provides a color developer having excellent stability.
• Magenta couplers represented by the following general formula (I) are known from, for example, JP-A No. 59-162548 (The term "JP-A” as used herein means an "unexamined published Japanese patent application"), JP-A No. 60-43659, JP-A No. 59-171956, JP-A No. 60-172982, and JP-A No. 60-33552, and U.S. Pat. No.
• R 11 represents a hydrogen atom or a substituent
• X represents a hydrogen atom or a group capable of being eliminated by a coupling reaction with an oxidation product of an aromatic primary amine developing agent
• Za, Zb, and Zc each represents a methine group, a substituted methine group, ⁇ N-- or --NH--, provided that one of the Za--Zb bond and the Zb--Zc bond is a double bond and the other is a single bond and, when Zb--Zc is a carbon-to-carbon double bond, it may be a part of an aromatic ring, and a dimer or higher polymer may be formed at R 11 or X, or, when Za, Zb or Zc represents a substituted methine group, a dimer or higher polymer may be formed at the substituted methine group.
• magenta couplers of general formula (I) have the defect that, when processed with a conventional color developer, they show poor color-forming properties, a serious variation in photographic properties and, after being processed, are liable to cause magenta stain with time.
• anti-fading techniques include adding various compounds such as hydroquinone derivatives described in, for example, U.S. Pat. Nos. 2,360,290, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300, 2,735,765, 2,710,801, and 2,816,028, British Pat. No. 1,363,921, and JP-A No. 58-24141, gallic acid derivatives described in U.S. Pat. Nos. 3,457,079 and 3,069,262, p-alkoxyphenols described in U.S. Pat. Nos.
• JP-B No. 49-20977 (the term "JP-B” as used herein means an "examined Japanese patent publication") and JP-B No. 52-6623, p-hydroxyphenol derivatives described in U.S. Pat. Nos. 3,432,300, 3,573,050, 3,574,627 and 3,764,337, JP-A No. 52-35633, JP-A No. 52-147434 and JP-A No. 52-152225, and bisphenols described in U.S. Pat. No. 3,700,455; and the stain-preventing techniques described in, for example, JP-A No. 49-11330, JP-A No. 50-57223, JP-A No. 56-85747, and JP-B No. 56-8346) have failed to provide sufficient results.
• a method for processing a silver halide color photographic material which comprises processing a silver halide light-sensitive material containing at least one pyrazoloazole type magenta coupler represented by following general formula (I), after imagewise exposure, with a color developer containing an aromatic primary amine color developing agent and at least one member selected from among hydrazines and hydrazides represented by following general formula (II): ##STR4## wherein R 11 represents a hydrogen atom Or a substituent, X represents a hydrogen atom or a group capable of being eliminated by a coupling reaction with an oxidation product of an aromatic primary amine developing agent, Za, Zb, and Zc each represents a methine group, a substituted methine group, ⁇ N-- or --NH--, provided that one of the Za--Zb bond and
• Magenta couplers represented by general formula (I) are described in detail below.
• polymer means one which contains two or more groups represented by general formula (I) per molecule, and the polymer includes bis derivatives and polymer couplers.
• the polymer coupler may be a homopolymer composed of only monomers (preferably those containing a vinyl group, which are hereinafter referred to as "vinyl monomers") having the moiety represented by general formula (I) or a copolymer with a non-color forming, ethylenic monomer not coupling with an oxidation product of an aromatic amine developing agent.
• the compounds represented by general formula (I) are 5-membered ring/5-membered ring condensation type nitrogen-containing heterocyclic couplers, whose color-forming matrix nucleus shows an aromaticity electronically equal to naphthalene and has a chemical structure usually given a generic name of azapentalene.
• couplers represented by general formula (I) preferable couplers are 1H-imidazo-(1,2-b)pyrazoles, 1H-pyrazolo(1,5-b)pyrazoles, 1 H-pyrazolo(5,1-c)(1,2,4-triazoles, 1H-pyrazolo(1,5-b)(1,2,4)triazoles, 1H-pyrazolo(1,5-d)tetrazoles, and 1H-pyrazolo(1,5-a)benzimidazoles, which are respectively represented by the following general formulae (Ia), (Ib), (Ic), (Id), (Ie) and (If). Of these, compounds represented by (Ia), (Ic) and (Id) are particularly preferable, with (Id) being more particularly preferable. ##
• R 12 , R 13 and R 14 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbomoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group, an anilino group, a ureido group, an imido group, a sulfamoylamino group, a carbomoylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, a carbomoyl group, an acyl
• R 12 , R 13 , R 14 or X may be a divalent group to form a bis derivative.
• R 12 , R 13 , R 14 or X may be a divalent group to form a bis derivative.
• R 12 , R 13 or R 14 represents a single bond or a linking group through which the moiety represented by general formula (Ia) to (If) is bound to the vinyl group.
• R 12 , R 13 and R 14 each represents a hydrogen atom, a halogen atom (for example chlorine or bromine), an alkyl group (for example, methyl, propyl, i-propyl, t-butyl, trifluoromethyl, tridecyl, 3-(2,4-di-tamylphenoxy)propyl, 2-dodecyloxyethyl, 3-phenoxypropyl, 2-hexylsulfonyl-ethyl, cyclopentyl or benzyl), an aryl group (for example, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl), a heterocyclic group (for example, 2-furyl, 2-thienyl, 2-pyrimidinyl or 2-benzothiazolyl), a cyano group, an alkoxy group (for example, methoxy, ethoxy,
• X represents a hydrogen atom, a halogen atom (for example, chlorine, bromine or iodine), a carboxyl group or a group bound through an oxygen atom (for example, acetoxy, prapanoyloxy, benzoyloxy, 2,4-dichlorobenzoyloxy, ethoxyoxaloyloxy, pyruvinyloxy, cinnamoyloxy, phenoxy, cyanophenoxy, 4-methanesulfonamidophenoxy, 4-methanesulfonylphenoxy, ⁇ -naphthoxy, 3-pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy, benzyloxy, phenethyloxy, 2-phenoxyethoxy, 5-phenyltetrazolyloxy, or 2-benzothiazolyloxy), a group bound through a nitrogen atom (for example, benzenes
• R 12 , R 13 , R 14 or X is a divalent group to form a bis derivative
• examples of the divalent group include a substituted or unsubstituted alkylene group (for example, methylene, ethylene, 1,10-decylene or --CH 2 CH 2 --O--CH 2 CH 2 --), a substituted or unsubstituted phenylene group (for example, 1,4-phenylene, 1,3-phenylene, ##STR7## and --NHCO--R 15 --CONH--- (wherein R 15 represents a substituted or unsubstituted alkylene or a substituted or unsubstituted phenylene group).
• Examples of the linking group represented by R 12 , R 13 and R 14 in the case where the moiety represented by general formula (Ia) to (If) constitutes a part of vinyl monomer include those which are formed by combining those selected from among an alkylene group (substituted or unsubstituted alkylene group of, for example, methylene, ethylene, 1,10-decylene or --CH 2 CH 2 OCH 2 CH 2 --), a phenylene group substituted or unsubstituted phenylene group of, for example, 1,4-phenylene, 1,3-phenylene, ##STR8## --NHCO--, --CONH--, --O--, --OCO-- and an aralkylene group (for example, ##STR9##
• an alkylene group substituted or unsubstituted alkylene group of, for example, methylene, ethylene, 1,10-decylene or --CH 2 CH 2 OCH 2 CH 2 --
• the vinyl group of the vinyl monomer includes those which posses a substituent or substituents in addition to those represented by general formulae (Ia) to (If).
• Preferable substituents are a hydrogen atom, a chlorine atom or a lower alkyl group containing 1 to 4 carbon atoms.
• non-color forming ethylenic monomers not coupling with an oxidation product of an aromatic primary amine developing agent there are illustrated, for example, acrylic acid, ⁇ -chloroacrylic acid, alkylacrylic acid (e.g., methacrylic acid), esters or amides of these acrylic acids (for example, acrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacryllate, n-butyl methacrylate and ⁇ -hydroxymethacrylate), methylenedibisacrylamide, vinyl esters (for example,
• High color-forming ballast groups described in, for example, JP-A No. 58-42045, JP-A No. 59-214854, JP-A No. 59-177553, JP-A No. 59-177544 and JP-A No. 59-177557 may be substituted with any group of the above-described compounds of general formulae (Ia) to (If).
• couplers of general formula (I) are generally added to a silver halide emulsion layer in amounts of 2 ⁇ 10 -3 mol to 5 ⁇ 10 -1 mol, preferably 1 ⁇ 10 -2 mol to 5 ⁇ 10 -1 mol, per mol of silver in the emulsion layer.
• two or more of the above-described couplers may be used together in one and the same layer, or one and the same compound may of course be added to two or more different layers.
• couplers are dissolved in an alkyl phthalate (for example, dibutyl phthalate or dioctyl phthalate), a phosphoric acid ester (for example, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), a citric acid ester (for example, tributyl acetylcitrate), a benzoic acid ester (for example, octyl benzoate), an alkylamide (for example, diethyllaurylamide), an fatty acid ester (for example, dibutoxyethyl succinate or diethyl azelate), a trimesic acid ester (for example tributyl trimesate) or in an organic solvent having a
• a lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secbutyl alcohol, methyl isobutyl ketone, ⁇ -ethoxyethyl acetate or methylcellosolve acetate
• a hydrophilic colloid for example, a lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secbutyl alcohol, methyl isobutyl ketone, ⁇ -ethoxyethyl acetate or methylcellosolve acetate.
• the above-described high-boiling organic solvent and the low-boiling organic solvent may be used as a mixture.
• R 1 , R 2 and R 3 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group (preferably containing 1 to 20 carbon atoms; for example, methyl, ethyl, sulfopropyl, carboxybutyl, hydroxyethyl, cyclohexyl, benzyl or phenethyl), a substituted or unsubstituted aryl group (preferably containing 6 to 20 carbon atoms; for example, phenyl, 2,5-dimethoxyphenyl, 4-hydroxyphenyl or 2-carboxyphenyl) or a substituted or unsubstituted heterocyclic group (preferably containing 1 to 20 carbon atoms and preferably being a 5- to 6-membered ring containing at least one of oxygen, nitrogen and sulfur as hetero atom; for example, pyridin-4-yl or N-acetylpiperidin-4-yl).
• R 4 represents a hydrogen atom, a hydroxy group, a substituted or unsubstituted hydrazino group (for example, hydrazino, methylhydrazino or phenylhydrazino), a substituted or unsubstituted alkyl group (preferably containing 1 to 20 carbon atoms; for example, methyl, ethyl, sulfopropyl, carboxybutyl, hydroxyethyl, cyclohexyl, benzyl, t-butyl or n-octyl), a substituted or unsubstituted aryl group (preferably containing 6 to 20 carbon atoms; for example, phenyl, 2,5-dimethoxyphenyl, 4-hydroxyphenyl, 2-carboxyphenyl, 2-carboxyphenyl or 4-sulfophenyl), a substituted or unsubstituted heterocyclic group (preferably containing 1 to 20 carbon atoms and being
• a halogen atom for example, chlorine or bromine
• a hydroxy group for example, chlorine or bromine
• a carboxy group for example, a sulfo group, an amino group, an alkoxy group, an amido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkyl group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, a nitro group, a cyano group, a sulfonyl group or a sulfinyl group are preferable, and these may further be substituted.
• a halogen atom for example, chlorine or bromine
• X 1 preferably represents a divalent organic residual group, and specifically represents, for example, --CO--, --SO 2 -- or ##STR11## n represents 0 or 1, provided that, when n is 0, R 4 represents a group selected from among a substituted or unsubstituted alkyl, aryl and heterocyclic groups. R 1 and R 2 , and R 3 and R 4 may optionally together form a heterocyclic group.
• R 1 to R 4 preferably represents a substituted or unsubstituted alkyl group.
• R 1 , R 2 , R 3 and R 4 each represents a hydrogen atom or a substituted or unsubstituted alkyl group are preferable (provided that R 1 , R 2 , R 3 and R 4 do not all represent a hydrogen atom at the same time).
• R 1 , R 2 and R 3 represent a hydrogen atom and R 4 a substituted or unsubstituted alkyl group; those wherein R 1 and R 3 represent a hydrogen atom, and R 2 and R 4 a substituted or unsubstituted alkyl group; or those wherein R 1 and R 2 represent a hydrogen atom, and R 3 and R 4 a substituted or unsubstituted alkyl group (R 3 and R 4 optionally together forming a hetero ring).
• X 1 preferably represents --CO--
• R 4 preferably represents a substituted or unsubstituted amino group
• R 1 to R 3 each preferably represents a hydrogen atom or a substituted or unsubstituted alkyl group.
• the alkyl group represented by R 1 to R 4 more preferably contains 1 to 10 carbon atoms, and most preferably 1 to 7 carbon atoms.
• Preferable substituents for the alkyl group include a hydroxy group, a carboxylic acid group, a sulfo group and a phosphonic acid group. When two or more substituents exist, they may be the same or different from each other.
• the compounds represented by the general formula (II) may form a bis derivative, a tris derivative or a polymer bound through R 1 , R 2 , R 3 or R 4 .
• JP-A No. 63-146041 Japanese Patent Application No. 61-170756
• JP-A No. 63-146042 Japanese Patent Application No. 6-171682
• JP A-63-146043 Japanese Patent Application No. 61-173468
• the compounds of general formula (II) are added in amounts of 0.01 g to 50 g, preferably 0.1 g to 30 g, more preferably 0.5 g to 10 g, per liter of color developer.
• Color developers used in the present invention contain known aromatic primary amine color developing agents.
• Preferable examples thereof are p-phenylenediamine derivatives, and typical examples thereof are illustrated below which, however, are not limitative.
• p-phenylenediamine derivatives may be in a salt form such as sulfates, hydrochlorides, sulfites or p-toluenesulfonates.
• the aromatic primary amine developing agents are used in amounts of, preferably about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g, per liter of color developing solution.
• color-developing agent D-4 in the presence of the compounds of general formula (I) depresses an increase of fog and, therefore, serves to provide good photographic properties, thus being preferable.
• Sulfite ion known as preservative is not substantially incorporated in the color developer of the present invention.
• the term "not substantially” permits one to add in an amount not influencing photographic properties, specifically in an amount of 0 to 0.005 mol/liter, preferably 0 to 0.002 mol/liter.
• JP-A No. 63-25654 diamines described in JP-A No. 63-43139 and JP-A No. 63-30845, polyamines described in JP-A No. 63-26655, polyamines described in JP-A No. 63-44655, nitroxy radicals described in JP-A No. 63-53551, alcohols described in JP-A No. 63-43140 and JP-A No. 63-53549, oximes described in JP-A No. 63-56654, and tertiary amines described in EP-A-266797.
• the color developer of the present invention preferably does not substantially contain benzyl alcohol in view of preventing an increase in fog and stain after processing. That is, "not substantially containing” means to contain benzyl alcohol in an amount of up to 5.0 ml, preferably up to 2 ml, per liter of the color developer, more preferably 0 ml.
• the color developer used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11, and may further contain known developer components.
• buffer agents are preferably used.
• the buffer agents carbonic acid salts, phosphoric acid salts, boric acid salts, tetraboric 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, 2-amino-2-methyl-1,3-propanediol salts, valine salts, proline salts, trishydroxyaminomethane salts, lysine salts, etc. may be used.
• carbonic acid salts, phosphoric acid salts, tetraboric acid salts and hydroxybenzoic acid salts are excellent in solubility and buffering ability in the higher pH region of more than 9.0, do not exert detrimental influences (for example, fogging) on photographic properties when added to color developers, and are inexpensive. Thus, their use is particularly preferable.
• buffer agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), etc.
• these buffer agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (s
• buffer agents are added to color developers in amounts of preferably not less than 0.1 mol/liter, particularly preferably 0.1 mol/liter to 0.4 mol/liter.
• various chelating agents may be used in the color developer as agents for preventing precipitation of calcium or magnesium or for improving the stability of the color developer.
• organic acid compounds are preferable, which are exemplified by the aminopolycarboxylic acids described in JP-B No. 48-30496 and JP-B No. 44-30232, organophosphonic acids described in JP-A No. 56-97347, JP-B No. 56-39359 and West German Pat. No. 2,227,639, phosphonocarboxylic acids described in JP-A No. 52-102726, JP-A No. 53-42730, JP-A No. 54-121127, JP-A No. 55-126241 and JP-A No. 55-659506, and compounds described in JP-A No. 58-195845, JP-A No. 58-203440 and JP-B No. 53-40900. Specific examples thereof are illustrated below which, however, are not limitative.
• Nitrilotriacetic acid diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephophosphonic acid, ethylenediamine-N,N,N',N'-tetramethylene phosphonic acid, trans-cyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine-o-hydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, etc.
• Two or more of these chelating agents may be used in combination as the case demands.
• chelating agents are added in a sufficient amount to mask metal ions in the color developer, for example, about 0.1 g to about 10 g per liter.
• An arbitrary development accelerator may be added to the color developer as the case demands.
• the color developer of the present invention preferably does not substantially contain benzyl alcohol.
• the compounds to be used in the present invention represented by the foregoing general formula (II) provide remarkable effects as to stability of color developers not substantially containing benzyl alcohol.
• thioether compounds described in JP-B No. 37-16088, JP-B No. 37-5987, JP-B No. 38-7826, JP-B No. 44-12380, JP-B No. 45-9019 and U.S. Pat. No. 3,813,247 p-phenylenediamine compounds described in JP-A No. 52-49829 and JP-A No. 50-15554, quaternary ammonium salts described in JP-A No. 50-137726, JP-B No. 44-30074, JP-A No. 56-156826 and JP-A No. 52-43429, amine compounds described in U.S. Pat. Nos.
• any antifogging agent(s) may be added as the case demands.
• alkali metal halides such as sodium chloride, potassium bromide and potassium iodide
• organic antifogging agents may be used.
• nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolidine and adenine.
• the color developer used in the present invention preferably contains a fluorescent brightening agent.
• a fluorescent brightening agent 4,4'-diamino-2,2-disulfostilbene compounds are preferable. They are added in amounts of 0 g to 5 g/liter, preferably 0.1 g to 4 g /liter.
• Various surface active agents such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, aromatic carboxylic acids, etc., may be added as the case demands.
• the processing temperature of the color developer of the present invention is generally 20° to 50 ° C. and more preferably 30° to 40 ° C.
• the processing time is generally 20 seconds to 5 minutes, and more preferably 30 seconds to 2 minutes.
• the replenishing amount is desirably minimized, and is generally 20 to 600 ml, preferably 50 to 300 ml, more preferably 100 to 200 ml, per m 2 of light-sensitive material.
• the color photographic material used in the present invention is generally subjected to bleaching or bleach-fixing after developing.
• a bleaching solution, a bleach-fixing solution, and a fixing solution used in the present invention are described below.
• any conventional bleaching agents may be used, with iron(III) organic complex salts (for example, complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid or diethylenetriaminepentaacetic acid, aminopolyphosphonic acid, phosphonocarboxylic acid and organophosphonic acid) or iron(III) salts of organic acids (for example, citric acid, tartaric acid and malic acid); persulfates; and hydrogen peroxide being preferable.
• iron(III) organic complex salts for example, complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid or diethylenetriaminepentaacetic acid, aminopolyphosphonic acid, phosphonocarboxylic acid and organophosphonic acid
• iron(III) salts of organic acids for example, citric acid, tartaric acid and malic acid
• persulfates for example, citric acid, tartaric acid and malic acid
• hydrogen peroxide being preferable.
• iron(III) organic complex salts are particularly preferable in view of rapid processing and prevention of environmental pollution.
• Aminopolycarboxylic acids, aminopolyphosphonic acids or organophosphonic acids, or their salts useful for forming the iron(III) organic complex salts are illustrated below: ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid, etc.
• These compounds may be in the form of sodium salts, potassium salts, lithium salts and ammonium salts.
• iron(III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred due to their high bleaching ability.
• ferric ion complex salts may be used in complex salt form, or may be formed in solution by using a ferric salt such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate or ferric phosphate and a chelating agent such as an aminopolycarboxylic acid, aminopolyphosphonic acid or phosphonocarboxylic acid.
• the chelating agent may be added in an amount more than that amount necessary for forming the ferric ion complex salt.
• aminopolycarboxylic acid/iron complexes are preferable, which are added in amounts of 0.01 to 1.0 mol/liter, preferably 0.05 to 0.50 mol/liter.
• Various compounds may be used as bleaching accelerator in the bleaching solution, bleach-fixing solution and/or pre-baths thereof.
• mercapto group- or disulfido bond-containing compounds described in U.S. Pat. No. 3,893,858, West German Pat. No. 1,290,812, JP-A No. 53-95630 and Research Disclosure, 17129 (July 1978), thiourea compounds described in JP-B No. 45-8506, JP-A No. 52-20832, JP-A No. 53-32735 and U.S. Pat. No. 3,706,561, and halides such as iodine ion and bromine ion are preferable due to their excellent bleaching ability.
• the bleaching or bleach-fixing solution used in the present invention may contain bromide (for example, potassium bromide, sodium bromide or ammonium bromide), chloride (for example, potassium chloride, sodium chloride or ammonium chloride) or iodide (for example, ammonium iodide) as a rehalogenating agent.
• bromide for example, potassium bromide, sodium bromide or ammonium bromide
• chloride for example, potassium chloride, sodium chloride or ammonium chloride
• iodide for example, ammonium iodide
• one or more inorganic acids, organic acids and alkali metal salts or ammonium salts thereof having a buffering ability such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate and tartaric acid, or anti-corrosives such as ammonium nitrate and guanidine may be added thereto.
• Fixing agents used in the bleach-fixing or fixing solution used in the method of the present invention are known conventional fixing agents, i.e., water-soluble silver halide dissolving agents such as thiosulfates (e.g., sodium thiosulfate and ammonium thiosulfate), thiocyanates (e.g., sodium thiocyanate and ammonium thiocyanate) , thioether compounds (e.g., ethylenebisthioglycolic acid and 3,6-dithia-1,8-octanediol) and thioureas. These may be used alone or as a combination of two or more.
• thiosulfates e.g., sodium thiosulfate and ammonium thiosulfate
• thiocyanates e.g., sodium thiocyanate and ammonium thiocyanate
• thioether compounds e.g., ethylenebisthio
• Special bleach-fixing solutions comprising a combination of a fixing agent and a large amount of halide such as potassium iodide described in JP-A No. 55-155354 may also be used.
• a fixing agent such as potassium iodide described in JP-A No. 55-155354
• the amount of fixing agent ranges from 0.3 to 2 mols, preferably 0.5 to 1.0 mol, per liter.
• the bleach-fixing solution or fixing solution used in the present invention preferably has a pH of 3 to 10, more preferably 5 to 9.
• the bleach-fixing solution may further contain various fluorescent brightening agents, defoaming agents, surfactants, polyvinyl pyrrolidone and organic solvents (e.g., methanol).
• the bleach-fixing or fixing solution of the present invention can contain, as a preservative, sulfite ion-releasing compounds such as sulfites (e.g., sodium sulfite, potassium sulfite and ammonium sulfite), bisulfites (e.g., ammonium bisulfite, sodium bisulfite and potassium bisulfite), and metabisulfites (e.g., potassium metabisulfite, sodium metabisulfite, and ammonium metabisulfite). These compounds are incorporated in amounts of preferably about 0.02 to about 0.50 mol/liter, more preferably 0.04 to 0.40 mol/liter, calculated as sulfite ion.
• sulfite ion-releasing compounds such as sulfites (e.g., sodium sulfite, potassium sulfite and ammonium sulfite), bisulfites (e.g., ammonium bisulfite, sodium bisulfite and
• sulfite salts are commonly added.
• ascorbic acid carbonyl-bisulfite adducts, carbonyl compounds, etc., may also be added.
• buffering agents may be added as the case demands.
• fluorescent brightening agents may be added as the case demands.
• chelating agents may be added as the case demands.
• defoaming agents may be added as the case demands.
• the silver halide color photographic material used in the present invention is generally subjected to water-washing and/or stabilizing.
• the amount of washing water used in the water-washing washing step can be selected from a wide range depending upon the characteristics of light-sensitive materials (for example, the kinds of used materials such as couplers), uses, and, further, conditions such as the temperature of the washing water, number of washing tanks (or steps), replenishing manner (such as counter current or direct current), and the like.
• the relationship between the number of water-washing tanks and the amount of water in a multi-stage counter current process can be determined according to Journal of the Society of Motion Picture and Television Engineers, Vol. 64, pp. 248-253 ( May 1955).
• the number of steps in multi-stage counter current process is usually 2 to 6, preferably 2 to 4.
• the multi-stage counter current process enables one to greatly reduce the amount of washing water.
• the amount of washing water may be 0.5 liter to 1 liter per m 2 of light-sensitive materials.
• various problems such as the propagation of bacteria caused by a prolonged residence time of the washing water in a tank leads to the production of suspended matter which adheres to light-sensitive materials.
• reducing the concentration of calcium and magnesium ions described in JP-A No. 62-288838 intended to solve the problem is extremely effective.
• the washing water may contain a surfactant as a draining agent and may contain a chelating agent represented by ethylenediaminetetraacetic acid as a hard-water softener.
• the pH of the washing water used in processing the light-sensitive material of the present invention generally ranges from 4 to 9, preferably 5 to 8.
• the temperature and time of washing may be varied depending upon the characteristics of the light-sensitive material, end use, etc., but, in general, a washing temperature of 15° to 45° C. and a washing time of 20 seconds to 10 minutes, preferably a washing temperature of 25° to 40° C. and a washing time of 30 seconds to 5 minutes, are employed.
• the light-sensitive material may be processed with a stabilizing solution subsequent to the above-described water-washing step or directly without the water-washing step.
• a stabilizing solution subsequent to the above-described water-washing step or directly without the water-washing step.
• compounds having image-stabilizing ability For example, there are illustrated aldehyde compounds represented by formalin, buffering agents for adjusting the film pH to a level suited for stabilizing dyes, and ammonium compounds.
• various bactericides and fungicides hereinbefore described may be used.
• a surfactant may be added thereto.
• known techniques described in JP-A No. 57-8543, JP-A No. 58-14834, JP-A No. 59-184343, JP-A No. 60-220345, JP-A No. 238832, JP-A No. 60-239784, JP-A No. 60-239749, JP-A No. 61-4054, JP-A No. 61-118749, etc. may be employed.
• chelating agents such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediamine-tetramethylenephosphonic acid, and magnesium or bismuth compounds is also a preferable embodiment for the stabilizing solution.
• the solution used int he washing and/or stabilizing step may be used in the prior step.
• an over-flow of washing water whose amount is decreased by the multi-stage counter current manner is introduced into its pre-bath of bleach-fixing bath, into which a concentrated solution is replenished, thus the amount of waste solution being reduced.
• the method of the present invention may be applied in any processing that uses a color developer.
• it may be applied to the processing of color papers, color reversal papers, color direct positive light-sensitive materials, color positive films, color negative films, color reversal films, etc., particularly preferably color papers and color reversal papers.
• silver halide emulsions for the light-sensitive material to be used in the present invention those emulsions which have any halide composition, such as silver iodobromide, silver bromide, silver chlorobromide and silver chloride, may be used.
• silver chlorobromide emulsions containing 60 mol % or more silver chloride or silver chloride emulsions are preferable, with the content of silver chloride being particularly preferably 80 to 100 mol %.
• silver chlorobromide emulsions containing 50 mol % or more silver bromide or silver bromide emulsions (optionally containing up to 3 mol % silver iodide) are preferable, with the content of silver bromide being particularly preferably 70 mol % or more.
• silver iodobromide and silver chloroiodobromide are preferable, with the silver iodide content preferably being 3 to 15 mol %.
• the silver halide grains used in the present invention may have an inner portion and a surface layer different from each other in phase composition, may be of a multi-phase structure having a conjunction structure, or may wholly comprise a uniform phase. Further, mixtures thereof can be used.
• Average grain size (presented in terms of diameter of grains with respect to spherical or approximately spherical grains or, with cubic grains, calculated based on projected area taking the edge length as grain size) of silver halide grains used in the present invention is preferably 0.1 ⁇ m to 2 ⁇ m, particularly preferably 0.15 ⁇ m to 1.5 ⁇ m.
• Grains size distribution may be narrow or broad, but monodispersed emulsions which have a coefficient of variation (standard deviation value/average grain size in the grain size distribution curve of silver halide emulsion) of within ⁇ 20%, particularly preferably with ⁇ 15%, are preferably used in the present invention.
• two or more kinds of monodispersed silver halide emulsions may be used as a mixture in one and the same layer or separately coated as superposed layers to provide emulsion layers having substantially the same color sensitivity.
• two or more polydispersed silver halide emulsions or a combination of a monodispersed emulsion and a polydispersed emulsion may be used as a mixture or by coating as separate and superposed layers.
• Silver halide grains used in the present invention may be in a regular crystal form such as cubic, octahedral, rhombic dodecahedral or tetradecahedral form or a mixture thereof, in an irregular crystal form such as spherical, or in a composite form thereof.
• tabular grains are also usable. Emulsions wherein tabular grains having a length-to-thickness ratio of 5 to 8, or 8 or more, account for 50% or more of the total projected area of the grains may also be used. Emulsions comprising a mixture of these various crystal forms may be used as well. Either surface latent image-forming type silver halide grains forming a latent image mainly on the surface thereof or internal latent image-forming type grains forming a latent image in the interior thereof may be used.
• the photographic emulsions used in the present invention can be prepared according to processes described in Research Disclosure (RD), vol. 170, Item No. 17643 (I, II, III) (December, 1978).
• the silver halide emulsions to be used in the present invention are usually subjected to physical ripening, chemical ripening, and spectral sensitization before use. Additives used in these steps are described in Research Disclosure, vol. 176, No. 17643 (December, 1978) and Research Disclosure, vol. 187, No. 18716 (November, 1979). Places where such additives are described are tabulated in the table to be shown hereinafter.
• couplers may be used in the present invention other than the magenta couplers of general formula (I).
• color couplers as used herein means those compounds which undergo a coupling reaction with an oxidation product of aromatic primary amine developing agent to produce dyes.
• Typical examples of useful color couplers include naphtholic or phenolic couplers, pyrazolone or pyrazoloazole type compounds, and open-chain or heterocyclic ketomethylene compounds.
• Specific examples of such cyan, magenta, and yellow couplers used in the present invention are described in those patents which are cited in Research Disclosure, (RD), 17643 (December, 1978), Item VII-D and ibid., 18717 (November, 1979).
• Color couplers incorporated in the light-sensitive materials preferably have a ballast group or are polymerized to acquire diffusion resistance.
• two equivalent color couplers substituted by coupling-off groups in coupling active sites permit one to reduce the amount of coated silver.
• Couplers which can form color dyes with suitable diffusibility, non-color forming couplers, DIR couplers capable of releasing a development inhibitor upon coupling reaction, or couplers capable of releasing a development accelerator may also be used.
• the use of two equivalent yellow couplers is preferable, and typical examples thereof include yellow couplers of the oxygen atom coupling-off type described in U.S. Pat. Nos. 3,408,194, 3,447,928, 3,933,501 and 4,022,620, etc., and yellow couplers of the nitrogen atom coupling-off type described in JP-B No. 55-10739, U.S. Pat. Nos.
• ⁇ -Pivaloylacetanilide type couplers are excellent in fastness, particularly light fastness, of colored dyes, whereas ⁇ -benzoylacetanilide type couplers provide high coloration density.
• Magenta couplers which can be used in the present invention include oil protected type indazolone or cyanoacetyl, preferably pyrazoloazole type (e.g., pyrazolone) couplers.
• pyrazoloazole type e.g., pyrazolone
• those which are substituted by an arylamino group or an acylamino group in the 3-position are preferable in view of the hue and coloration density of the colored dyes. Typical examples thereof are described in U.S. Pat. Nos. 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896 and 3,936,015.
• ballast group-containing 5-pyrazolone couplers described in European Pat. No. 73,636 provide high coloration density.
• Cyan couplers which can be used in the present invention include oil protected type naphtholic and phenolic couplers. Typical examples thereof include naphtholic couplers described in U.S. Pat. No. 2,474,293, preferably oxygen atom coupling-off type 2-equivalent naphtholic couplers described in U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233 and 4,296,200. Specific examples of the phenolic couplers are described in U.S. Pat. Nos. 2,369,929, 2,801,171, 2,772,162, 2,895,826, etc.
• Cyan couplers capable of forming dyes fast against high humidity and high temperature are preferably used in the present invention, and typical examples thereof include phenolic cyan couplers having an alkyl group containing 2 or more carbon atoms at the m-position of the phenol nucleus described in U.S. Pat. No. 3,772,002, 2,5-diacylamino-substituted phenolic couplers described in U.S. Pat. Nos. 2,772,162, 3,758,308, 4,126,396, 4,334,011, and 4,327,173, West German Patent Application (OLS) No. 3,329,729, and JP-A No.
• OLS West German Patent Application
• Graininess can be improved by using those couplers which form dyes with proper diffusibility.
• couplers forming diffusible dyes U.S. Pat. No. 4,366,237 and British Pat. No. 2,125,570 describe specific examples of magenta couplers, and European Pat. No. 96,570 and West German Patent Application (OLS) No. 3,234,533 describe specific examples of yellow, magenta, or cyan couplers.
• the dye-forming couplers and the above-described special couplers may form a dimer or higher polymer.
• Typical examples of polymerized dye-forming couplers are described in U.S. Pat. Nos. 3,451,820 and 4,080,211.
• Specific examples of polymerized magenta couplers are described in British Pat. No. 2,102,173 and U.S. Pat. No. 4,367,282.
• Two or more of the various couplers used in the present invention may be used in one and the same light-sensitive layer, or one and the same compound may be used in two or more layers for obtaining photographic characteristics required for light-sensitive materials.
• the couplers used in the present invention may be introduced into light-sensitive materials according to various known dispersing processes. Examples of high-boiling organic solvents to be used in the oil-in-water dispersing process are described in, for example, U.S. Pat. No. 2,322,027. Steps and effects of latex dispersing processes, and specific examples of latexes for impregnation are described in U.S. Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.
• OLS West German Patent Application
• Standard amounts of color couplers other than the magenta couplers of general formula (I) are 0.001 to 1 mol per mol of light-sensitive silver halide and, preferably, 0.01 to 0.5 mol with respect to yellow couplers, 0.003 to 0.3 mol with respect to magenta couplers, and 0.002 to 0.3 mol with respect to cyan couplers.
• the photographic light-sensitive material used in the present invention is coated on a conventional flexible support such as a plastic film (for example, cellulose nitrate, cellulose acetate, or polyethylene terephthalate) or paper or on a rigid support such as glass.
• a plastic film for example, cellulose nitrate, cellulose acetate, or polyethylene terephthalate
• a rigid support such as glass. Supports and coating processes are described in detail in Research Disclosure, vol. 176, Item 17643, XV (p. 27) and XVII (p. 28) (December 1978).
• a reflective support is preferably used.
• "Reflective supports” serve to raise reflectivity to make distinct the dye image formed in the silver halide emulsion layers.
• Such reflective supports include those which are prepared by coating a hydrophobic resin containing dispersed therein a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate or calcium sulfate on a support and those which comprise a hydrophobic resin containing dispersed therein the light-reflecting substance.
• Multi-layer color photographic print papers having the stratum structure shown in Table A on a paper support double-laminated with polyethylene were prepared with changing the magenta couplers used. Coating solutions were prepared as follows.
• the aforesaid emulsion dispersion and this emulsion were mixed with each other according to the formulation in Table A to prepare a coating solution for forming the first layer.
• Coating solutions for forming the second to seventh layers were also prepared in the same manner as with the coating solution for forming the first layer.
• gelatin hardener for each layer sodium salt of 1-hydroxy-2,5-dichloro-s-triazine was used.
• 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the blue-sensitive emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer in amounts of 8.5 ⁇ 10 -5 mol, 7.7 ⁇ 10 -4 mol, and 2.5 ⁇ 10 -4 mol, respectively, per mol of silver halide.
• 4-hydroxy-6-methyl-1,2,3a,7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in amounts of 1.2 ⁇ 10 -2 mol and 1.1 ⁇ 10 -2 mol, respectively, per mol of silver halide.
• Color photographic printing papers containing varying magenta couplers as shown in Table 1 were prepared. The resulting photographic papers were exposed through an optical wedge, then processed according to the following steps.
• Photographic properties are presented in terms of D min and gradation of magenta density.
• D min represents a minimum density
• gradation is presented in terms of the change in density from the point of 0.5 in density to the point on 0.3 in log E higher exposure side.
• Example 1 The same experiments as with No. 12 in Example 1 were conducted except for changing the magenta coupler M-37 to M-58, M-70, M-71, M-72 or M-74 to obtain preferable results as in Example 1.
• Multi-layer color photographic printing papers having the stratum structures shown below on a paper support double-laminated with polyethylene were prepared while changing the magenta coupler. Coating solutions were prepared as follows.
• Coating solutions for forming the second to seventh layers were also prepared in the same manner as with the coating solution for the first layer.
• a gelatin hardener for each layer the sodium salt of 1-hydroxy-3,5-dichloro-s-triazine was used.
• each layer is shown below. Numerals represent coated amounts (g/m 2 ). Amounts of silver halide emulsions are represented as amounts of coated silver.
• Cpd-12 and Cpd-13 were used as irradiation-preventing dyes.
• each layer were further used, as emulsifying and dispersing agents or coating aids, Alkanol XC (made by duPont), sodium alkylbenzenesulfonate, succinic ester, and Magefacx F-120 (made by Dainippon Ink & Chemicals, Inc.). Further, Cpd-14 and Cpd-15 were used as stabilizers for silver halides.
• Magenta couplers used are as follows.
• Running testing was conducted according to the following steps while changing the formulation of the color developers.
• the processing steps were as follows. Processing amount was 15 m 2 /day in respective processings, and the processing was conducted for 30 days.
• Running testing (continuous processing) was conducted under each condition until the amount of replenishing color developer became three times as much as the tank volume (17 liters). Change in stain and in G (green density) of gradation portion were measured at the start and the .end of the running processing using an automatic recording densitometer (type of Fuji Photo Film Co., Ltd.). Further, samples at the end of the running processing were allowed to stand at 60° C. (5-10% RH) for 4 months, and again subjected to measurement of change in G density in stained areas.
• Table 2 shows that, in the comparative examples, an increase in D min ⁇ D min ), an increase in gradation ( ⁇ gradation) and an increase in D min after agin ⁇ D min after aging) were very high when II-(b) was used as the additive (compound B) to the color developer, and that, in the case of using Sample A or B (containing magenta couplers outside the scope of the present invention),D min , gradation and change in ⁇ D min after aging were very high even when color developers of the present invention were used.

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