EP0436938B1 - Produit photographique couleur à l'halogénure d'argent contenant un coupleur cyan coloré en jaune - Google Patents

Produit photographique couleur à l'halogénure d'argent contenant un coupleur cyan coloré en jaune Download PDF

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Publication number
EP0436938B1
EP0436938B1 EP90125645A EP90125645A EP0436938B1 EP 0436938 B1 EP0436938 B1 EP 0436938B1 EP 90125645 A EP90125645 A EP 90125645A EP 90125645 A EP90125645 A EP 90125645A EP 0436938 B1 EP0436938 B1 EP 0436938B1
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EP
European Patent Office
Prior art keywords
group
silver halide
coupler
photographic material
groups
Prior art date
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EP90125645A
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German (de)
English (en)
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EP0436938A3 (en
EP0436938A2 (fr
Inventor
Keiji Fuji Photo Film Co. Ltd. Miyahashi
Takayoshi Fuji Photo Film Co. Ltd. Kamio
Atsuhiro Fuji Photo Film Co. Ltd. Ohkawa
Masuzi Fuji Photo Film Co. Ltd. Motoki
Hidetoshi Fuji Photo Film Co. Ltd. Kobayashi
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP2276774A external-priority patent/JP2699218B2/ja
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Publication of EP0436938A3 publication Critical patent/EP0436938A3/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • 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
    • G03C7/3225—Combination of couplers of different kinds, e.g. yellow and magenta couplers in a same layer or in different layers of the photographic material
    • 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
    • G03C7/30541—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the released group
    • G03C7/30547—Dyes
    • 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
    • G03C7/333—Coloured coupling substances, e.g. for the correction of the coloured image
    • G03C7/3335—Coloured coupling substances, e.g. for the correction of the coloured image containing an azo chromophore

Definitions

  • This invention relates to a silver halide color photographic material. More particularly, it relates to a photographic material which has excellent color reproducibility and sharpness as well as printability due to the incorporation of a yellow colored cyan coupler and a diffusing development inhibitor-releasing coupler therein.
  • JP-A-54-145135 As means for improving color reproducibility and sharpness, it is known to use the DIR compounds described in JP-A-54-145135 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"), JP-A-56-114946 and JP-A-57-151944 (corresponding to U.S. Patents 4,248,962, 4,409,323 and 4,477,563, respectively). Interlaminar and edge effects are improved, and color reproducibility and sharpness are also improved to some degree by these compounds.
  • JP-A-61-221748 and West German Patent Laid-Open No. 3815469A disclose that effects similar (with respect to photographic performance) to interlaminar effect of from a red-sensitive emulsion layer to a blue-sensitive emulsion layer can be obtained by using a yellow colored cyan coupler in the red-sensitive emulsion layer.
  • a yellow colored cyan coupler in the red-sensitive emulsion layer.
  • Conventional yellow colored cyan couplers have problems in that the molecular extinction coefficients of their yellow dyes are low and their coupling activity is also low.
  • EP-A-0208502 reveals that an interlaminar interimage effect which results in improved colour saturation can be obtained by using diffusible inhibitors or precursors thereof along with enhanced sharpness due to the edge effect. Suitable inhibiting groups and timing groups are revealed.
  • Japanese patent application JP-A-63304242 concerns itself with thermally developable colour photosensitive materials.
  • a silver halide emulsion along with a reducing agent, a binder and a dye providing substance are revealed as are certain yellow coloured cyan couplers which are employed in the emulsion.
  • a first object of the present invention is to provide a photographic material which has excellent color reproducibility.
  • a second object of the present invention is to provide a photographic material which has excellent sharpness.
  • a third object of the present invention is to provide a photographic material which has excellent printability in auto-printers.
  • a fourth object of the present invention is to provide a photographic material which is highly sensitive.
  • a silver halide color photographic material comprising a support having thereon at least one red-sensitive silver halide emulsion layer containing a cyan coupler, at least one green-sensitive silver halide emulsion layer containing a magenta coupler and at least one blue-sensitive silver halide emulsion layer containing a yellow coupler, wherein the photographic material contains at least one compound represented by the following general formula (I) and at least one yellow colored cyan coupler: A-(TIME) n -B (I) wherein A represents a coupler moiety which is released from (TIME) n -B by a coupling reaction with an oxidation product of an aromatic primary amine developing agent; TIME represents a timing group which is bonded to the active coupling site of A and which is releases B after release from A by the coupling reaction; B represents a group represented by the following general formulas (IIa), (IIb), (IIc), (IId), (
  • X 1 represents a substituted or unsubstituted aliphatic group having 1 to 4 carbon atoms (including no carbon atoms in the substituent: the same hereinafter (unless otherwise defined) or a substituted phenyl group, substituent groups being a hydroxyl group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, a sulfonyl group, a sulfonamido group, a sulfamoyl group, an acyloxy group, a ureido group, a carboxyl group, a cyano group, a nitro group, an amino group, an alkoxycarbonyl amino group and an acyl group, the number of carbon atoms in these substituent groups being not more than 3, the phenyl group may have one or more substituent X 2 represents a hydrogen atom, an aliphatic group, a halogen atom, a hydroxyl
  • X 1 is a substituted or unsubstituted aliphatic group having 1 to 4 carbon atoms (examples of substituent groups being an alkoxy group, an alkoxycarbonyl group, a hydroxyl group, an arylamino group, a carbamoyl group, a sulfonyl group, a sulfonamido group, a sulfamoyl group, an amino group, an acyloxy group, a cyano group, a ureido group, an acyl group, a halogen atom and an alkylthio group, the number of carbon atoms in these substituent groups being not more than 3; the aliphatic group may have one or more substituent groups; and these groups may be further substituted with these groups, an aliphatic group or an aromatic group) or a substituted phenyl group (substituent groups being a hydroxyl group, an alkoxycarbonyl group, an
  • aliphatic group means an aliphatic hydrocarbon group which may be a saturated or unsaturated hydrocarbon group or a straight-chain, branched or cyclic hydrocarbon group such as an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, etc.
  • aryl group means at least a substituted or unsubstituted phenyl and naphthyl groups.
  • An acyl moiety (in acyl group, acylamino group, etc.) means an aliphatic and aromatic acyl moiety.
  • a sulfonyl moiety (in sulfonyl group, sulfonamido group) means an aliphatic and aromatic sulfonyl moieties.
  • a carbamoyl group, sulfamoyl group, amino group and ureido group include unsubstituted and substituted groups thereof.
  • a heterocyclic group is a 3- to 8-membered having at least one of N, O and S atoms as hetero atom.
  • the coupler moiety represented by A in formula (I) includes a coupler moiety which is coupled with an oxidation product of an aromatic primary amine developing agent to form a dye (e.g., yellow, magenta, cyan, etc.) and a coupler moiety which forms a coupling reaction product having substantially no absorption in the region of visible light.
  • a dye e.g., yellow, magenta, cyan, etc.
  • yellow dye image-forming coupler moiety represented by A examples include pivaloylacetanilide, benzoylacetanilide, malondiester, malondiamide, dibenzoylmethane, benzothiazolylacetamide, malonestermonoamide, benzothiazolyl acetate, benzoxazolylacetamide, benzoxazolylacetate, malondiester, benzimidazolylacetamide and benzimidazolylacetate coupler moieties; coupler moieties derived from heterocyclic ring-substituted acetamides or heterocyclic ring-substituted acetates described in U.S.
  • Patent 3,841,880 coupler moieties derived from acylacetamides described in U.S. Patent 3,770,446, U.K. Patent 1,459,171, West German Patent (OLS) 2,503,099, JP-A-50-139738 and Research Disclosure 15737; and heterocyclic coupler moieties described in U.S. Patent 4,046,574.
  • magenta dye image-forming coupler moieties represented by A include coupler moieties having a 5-oxo-2-pyrazoline nucleus, a pyrazolo[1,5-a]benzimidazole nucleus, a pyrazoloimidazole nucleus, a pyrazolotriazole nucleus or a pyrazolotetrazole nucleus, and cyanacetophenone coupler moieties.
  • Preferred examples of cyan dye image-forming coupler moieties represented by A include coupler moieties having a phenol nucleus or an ⁇ -naphthol nucleus.
  • couplers having the same effect as that of DIR couplers even when said couplers do not form substantially any dye after the release of a restrainer by a coupling with an oxidation product of a developing agent.
  • coupler moieties represented by A include the coupler moieties described in U.S. Patents 4,052,213, 4,088,491, 3,632,345, 3,958,993 and 3,961,959.
  • TIME in formula (I) include the following groups.
  • R 3 and R 4 each represents a hydrogen atom or a substituent group
  • B is as defined above in formula (I).
  • R 3 include an alkyl group having 1 to 24 carbon atoms (e.g., methyl, ethyl, benzyl, dodecyl) or an aryl group having 6 to 24 carbon atoms (e.g., phenyl, 4-tetradecyloxyphenyl, 4-methoxyphenyl, 2,4,6-trichlorophenyl, 4-nitrophenyl, 4-chlorophenyl, 2,5-dichlorophenyl, 4-carboxyphenyl, p-tolyl).
  • R 3 include an alkyl group having 1 to 24 carbon atoms (e.g., methyl, ethyl, benzyl, dodecyl) or an aryl group having 6 to 24 carbon atoms (e.g., phenyl, 4-tetradecyloxyphenyl, 4-me
  • R 4 examples include a hydrogen atom, an alkyl group having 1 to 24 carbon atoms (e.g., methyl, ethyl, undecyl, pentadecyl), an aryl group having 6 to 36 carbon atoms (e.g., phenyl, 4-methoxyphenyl), a cyano group, an alkoxy group having 1 to 24 carbon atoms (e.g., methoxy, ethoxy, dodecyloxy), an amino group having 0 to 36 carbon atoms (e.g., amino, dimethylamino, piperidino, dihexylamino, anilino), a carbonamido group having 1 to 24 carbon atoms (e.g., acetamido, benzamido, tetradecaneamido), a sulfonamido group having 1 to 24 carbon atoms (e.g., methylsulfonamido, phenylsul
  • Examples of X 1 include methyl, ethyl, propyl, butyl, methoxyethyl, ethoxyethyl, isobutyl, allyl, dimethylaminoethyl, propargyl, chloroethyl, methoxycarbonylmethyl, methylthioethyl, 4-hydroxyphenyl, 3-hydroxyphenyl, 4-sulfamoylphenyl, 3-sulfamoylphenyl, 4-carbamoylphenyl, 3-carbamoylphenyl, 4-dimethylaminophenyl, 3-acetamidophenyl, 4-propaneamidophenyl, 4-methoxyphenyl, 2-hydroxyphenyl, 2,5-dihydroxyphenyl, 3-methoxycarbonylaminophenyl, 3-(3-methylureido)phenyl, 3-(3-ethylureido)phenyl, 4-hydroxyethoxypheny
  • Examples of X 2 include methyl, ethyl, benzyl, n-propyl, i-propyl, n-butyl, i-butyl, cyclohexyl, fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxylmethyl, hydroxyethyl, hydroxy, methoxy, ethoxy, butoxy, allyloxy, benzyloxy, methylthio, ethylthio, methoxycarbonyl, ethoxycarbonyl, acetamido, propaneamido, butaneamido, octaneamido, benzamido, dimethylcarbamoyl, methylsulfonyl, methylsulfonamido, phenylsulfonamido, dimethylsulfamoyl, acetoxy, ureido, 3-methylureido, cyano, nitro
  • the groups represented by formulas (IIa) to (IIp) are preferred. Particularly preferred are the groups represented by formulas (IIa), (IIi), (IIj) and (IIk).
  • Examples of the groups represented by B in formula (I) include the following groups.
  • the compound represented by formula (I) is incorporated into at least one of blue-, green- and red-sensitive layer and a light-insensitive intermediate layer adjacent thereto, preferably into a red-sensitive layer.
  • the couplers are used together as a mixture with principal couplers.
  • the ratio of the coupler of general formula (I) to the principal coupler is 0.1 to 100 mol%, preferably 1 to 50 mol%.
  • the proportion of the coupler of general formula (I) to silver halide is 0.01 to 20 mol%, preferably 0.5 to 10 mol% per mol of silver halide in the same layer when the compound is incorporated into a silver halide emulsion layer, or silver halide in the adjacent silver halide emulsion layer containing a larger amount of silver halide contained in adjacent silver halide emulsion layers when the compound is incorporated into a light-insensitive intermediate layer.
  • a in formula (I) is a coupler moiety represented by the following general formulas (Cp-1), (Cp-2), (Cp-3), (Cp-4), (Cp-5), (Cp-6), (C-7), (Cp-8), (Cp-9), (Cp-10) or (Cp-11).
  • These couplers are preferable, because the coupling rate thereof is high.
  • the free bond derived from the coupling site represents the position where the coupling moiety is bonded to the group which is eliminated by coupling.
  • R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 , R 60 or R 61 in the above formulas has a non-diffusing group, each substituent group is so chosen that the total of carbon atoms thereof is 8 to 32, preferably 10 to 22. In other case, the total of carbon atoms is preferably not more than 15.
  • R 51 is an aliphatic group, an aromatic group, an alkoxy group or a heterocyclic group, and R 52 and R 53 are each an aromatic group or a heterocyclic group.
  • the aliphatic group represented by R 51 is an aliphatic hydrocarbon group having preferably 1 to 22 carbon atoms, which may be a substituted or unsubstituted straight-chain, branched or cyclic hydrocarbon group and may optionally have one or more substituent groups.
  • substituent groups for the aliphatic group include an alkoxy group, an aryloxy group, an amino group, an acylamino group and a halogen atom.
  • these substituent groups may be further substituted with at least one substituent such as a hydroxy group, a nitro group, a cyano group, a group having from 0 to 32 carbon atoms, such as an amino group, a sulfo group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a ureido group, an alkoxycarbonyl group, and an aryloxycarbonyl group.
  • substituent such as a hydroxy group, a nitro group, a cyano group, a group having from 0 to 32 carbon atoms, such as an amino group, a sulfo group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a ureido group, an alkoxycarbonyl group, and an aryloxy
  • R 51 Specific examples of useful aliphatic groups for R 51 include isopropyl, isobutyl, tert-butyl, isoamyl, tert-amyl, 1,1-dimethylbutyl, 1,1-dimethylhexyl, 1,1-diethylhexyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, 2-methoxyisopropyl, 2-phenoxyisopropyl, 2-p-tert-butylphenoxyisopropyl, ⁇ -aminoisopropyl, ⁇ -(diethylamino)isopropyl, ⁇ -(succinimido)isopropyl, ⁇ -(phthalimido)isopropyl and ⁇ -(benzenesulfonamido)isopropyl.
  • R 51 , R 52 or R 53 is an aromatic group (particularly a phenyl group)
  • the aromatic group may be substituted.
  • the aromatic group (such as a phenyl group) may be substituted by an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonyamino group, an aliphatic amido group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkylureido group or an alkyl-substituted succinimido group, each group having not more than 32 carbon atoms.
  • the alkyl moiety in these groups may be substituted with an aromatic group such as an alkyl-substituted phenylene group.
  • the phenyl group represented by R 51 , R 52 or R 53 may be substituted by an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamido group or an arylureido group.
  • the aryl portion of these substituent groups may be further substituted with one or more alkyl groups (the total of carbon atoms being 1 to 22).
  • the phenyl group represented by R 51 , R 52 or R 53 may be substituted by an unsubstituted or C 1 to C 6 lower alkyl-substituted amino group, hydroxy group, carboxy group, sulfo group, nitro group, cyano group, thiocyano group or a halogen atom.
  • R 51 , R 52 or R 53 may be a condensed group wherein a phenyl group is condensed with an other ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group and a tetrahydronaphthyl group. These groups themselves may be further substituted.
  • R 51 is an alkoxy group
  • the alkyl moiety of the alkoxy group is a straight chain or branched alkyl or alkenyl group or a cyclic alkyl or alkenyl group, each group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms. These groups may be substituted by a halogen atom, an aryl group or an alkoxy group.
  • R 51 , R 52 or R 53 is a heterocyclic group
  • the heterocyclic group is bonded through one carbon atom as a member of the ring to the carbon atom of the carbonyl group of the acyl group in ⁇ -acylacetamido or to the nitrogen atom of an amido group.
  • heterocyclic rings include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine and oxazine.
  • These rings may have substituent such as a hydroxy group, a nitro group, a cyano group, a group having from 1 to 32 carbon atoms, such as an amino group, a sulfo group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a ureido group, an alkoxycarbonyl group, and an aryloxycarbonyl group.
  • substituent such as a hydroxy group, a nitro group, a cyano group, a group having from 1 to 32 carbon atoms, such as an amino group, a sulfo group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a ureido group, an alkoxycarbonyl group, and an aryloxycarbonyl group.
  • R 55 has 1 to 32 carbon atoms (including carbon atoms of the substituent if it has any), preferably 1 to 22 carbon atoms
  • R 55 is a straight-chain or branched alkyl group (e.g., methyl, isopropyl, tert-butyl, hexyl, dodecyl), a straight-chain or branched alkenyl group (e.g., allyl), a cyclic alkyl group (e.g., cyclopentyl, cyclohexyl, norbornyl), an aralkyl group (e.g., benzyl, ⁇ -phenethyl) or a cyclic alkenyl group (e.g., cyclopentenyl, cyclohexenyl), each of which may have one or more substituent groups.
  • R 55 is a straight-chain or branched alkyl group (e.g., methyl, isopropyl, ter
  • substituent groups include a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an alkylthiocarbonyl group, an arylthiocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a thiourethane group, a sulfonamido group, a heterocyclic group, an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an alkylthio group, an alkylamino group, a dialkylamino group, an anilino group, an N-ary
  • R 55 may be an aryl group (e.g., phenyl, ⁇ - or ⁇ -naphthyl) which may have one or more substituent groups preferably having 1 to 18 carbon atoms.
  • substituent groups include an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, an aminocarbonyloxy group, an alkoxycarbonylamino group, an aryloxycarbonyla
  • R 55 may be a heterocyclic group (e.g., a 5-membered or 6-membered heterocyclic ring containing at least one hetero-atom selected from nitrogen, oxygen and sulfur, and a condensed heterocyclic group such as pyridyl, quinolyl, furyl, benzothiazolyl, oxazolyl, imidazolyl, and naphthoxazolyl), a substituted heterocyclic group (examples of substituent groups being those described above in the description of the substituent groups for the aryl group), an aliphatic or aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group.
  • a heterocyclic group e.g., a 5-membered or 6-membered
  • R 54 is a hydrogen atom, or a group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms and is a straight-chain or branched alkyl, alkenyl, cyclic alkyl, aralkyl or cyclic alkenyl group (these groups may have one or more substituent groups; examples of the substituent groups are those described above in the description of the substituent groups for R 55 ), an aryl group or a heterocyclic group (these groups may have one or more substituent groups; examples of the substituent groups are those described above in the description of the substituent groups for R 55 ), an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, stearyloxycarbonyl), an aryloxycarbonyl group (e.g., phenoxycarbonyl, naphthoxycarbonyl), an aralkyloxycarbonyl group (e.g., benzyloxycarbonyl), an alkoxy group (
  • R 56 is a hydrogen atom, a straight-chain or branched alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group or a cyclic alkenyl group, each having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms. These groups may be substituted. Examples of substituent groups are those described above in the description of the substituent groups for R 55 .
  • R 56 may represent an aryl group or a heterocyclic group, each of which may have one or more substituent groups. Examples of the substituent groups are those described above in the description of the substituent groups for R 55 .
  • R 56 may represent a cyano group, an alkoxy group, an aryloxy group, a halogen, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, an aminocarbonyloxy group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an alkylthio group, an alkylamino group, a dialkylamino group, an anilino group, an N-arylanilino group, an N-alkylanilino group, an N-acylanilin
  • R 57 , R 58 and R 59 are each a group used in conventional four equivalent type phenol or ⁇ -naphthol couplers.
  • R 57 represents a hydrogen atom, a halogen atom, an alkoxycarbonylamino group, an aliphatic hydrocarbon group, an N-arylureido group, an acylamino group or a group of -O-R 62 or -S-R 62 (wherein R 62 is an aliphatichydrocarbon groups).
  • the carbon number of the groups represented by R 57 is preferably from 1 to 32. When the two or more R 57 groups per molecule exist, two or more R 57 groups may be different.
  • the aliphatic hydrocarbon residue may have one or more substituent groups such as those described above in the description of the substituents for the alkyl group.
  • the carbon numbers of these substituents is preferably from 1 to 28.
  • R 57 may be substituted at any position on the nucleus.
  • the aryl group may have one or more substituent groups.
  • substituent groups are those described above in the description of the substituent for R 55 .
  • R 58 and R 59 are each a group selected from the group consisting of an aliphatic hydrocarbon group, an aryl group and a heterocyclic group.
  • the carbon number of these groups is preferably from 1 to 32. Alternatively, one of them may be hydrogen atom.
  • These groups may have one or more substituent groups. If desired, R 58 and R 59 may be combined together to form a nitrogen-containing heterocyclic nucleus which may have further at least one of N, O, and S atoms.
  • the aliphatic hydrocarbon group may be a saturated or unsaturated hydrocarbon group or a straight-chain, branched or cyclic hydrocarbon group.
  • the hydrocarbon group is an alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclopropyl, cyclohexyl) or an alkenyl group (e.g., allyl, octenyl).
  • alkyl group e.g., methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclopropyl, cyclohexyl
  • an alkenyl group e.g., allyl, octenyl
  • Typical examples of a heterocyclic group include pyridinyl, quinolyl, thienyl, piperidyl and imidazolyl.
  • substituent groups which may be introduced into the aliphatic hydrocarbon group, the aryl group and the heterocyclic group include a halogen atom, a nitro group, a hydroxy group, a carboxyl group, an amino group, a substituted amino group, a sulfo group, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an arylthio group, an arylazo group, an acylamino group, a carbamoyl group, an ester group (including an alkoxycarbonyl group, and an aryloxycarbonyl group), acyl group, an acyloxy group, a sulfonamido group, a sulfamoyl group, a
  • l is an integer of 1 to 4
  • m is an integer of 1 to 3
  • p is an integer of 1 to 5.
  • R 60 represents an arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an alkoxycarbonyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, or an aryloxycarbonyl group, each of which may have one or more substituent groups.
  • substituent groups include an alkoxy group, an alkoxycarbonyl group, an acylamino group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkylsuccinimido group, a halogen atom, a nitro group, a carboxyl group, a nitrile group, an alkyl group and an aryl group.
  • R 61 represents an arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an alkoxycarbonyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, an aryloxycarbonyl group, an alkylsulfonyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, an arylsulfonyl group, an aryl group or a 5-membered or 6-membered heterocyclic group (the hetero-atom being selected from nitrogen, oxygen and sulfur) such as a triazolyl group, an imidazolyl group, a phthalimido group, a succinimido group, a furyl group, a pyridyl group or a benztriazolyl
  • moieties are those of formula (Cp-1) where R 51 is a t-butyl group or a substituted or unsubstituted aryl group and R 52 is a substituted or unsubstituted aryl group, and those of formula (Cp-2) where R 52 and R 53 are each a substituted or unsubstituted aryl group.
  • moieties are those of formula (Cp-3) where R 54 is an acylamino group, a ureido group or an arylamino group and R 55 is a substituted aryl group; those of formula (Cp-4) where R 54 is an acylamino group, a ureido group or an arylamino group and R 56 is a hydrogen atom; and those of formulas (Cp-5) and (Cp-6) where R 54 and R 55 are each a straight-chain or branched alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group or a cyclic alkenyl group.
  • moieties are those the group of formula (Cp-7) where R 57 is an acylamino group or a ureido group at the 2 position, an acylamino group or an alkyl group at the 5 position and a hydrogen atom or a chlorine atom at the 6 position, and those of formula (Cp-9) where R 57 is a hydrogen atom, an acylamino group, a sulfonamido group or an alkoxycarbonyl group at the 5 position, R 58 is a hydrogen atom and R 59 is a phenyl group, an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group or a cyclic alkenyl group.
  • preferred moieties are those of formula (Cp-10) where R 57 is an acylamino group, a sulfonamido group or a sulfamoyl group, and those of formula (Cp-11) where R 60 and R 61 are each an alkoxycarbonyl group.
  • a compound having at least two coupler moiety such as bis-, tris- or tetrakis compound, or polymer may be formed through any one of R 51 to R 61 .
  • the polymer may be a polymer of a monomer having an ethylenically unsaturated group at any one of these groups or a copolymer thereof with a non-color forming monomer.
  • the coupler is a polymer
  • the polymer is either (1) a polymer derived from a monomer coupler represented by the following general formula (Cp-12) and composed of a repeating unit represented by the following general formula (Cp-13); or (2) a copolymer of said monomer coupler with at least one non-color forming monomer having at least one ethylene group and incapable of coupling with an oxidation product of an aromatic primary amine developing agents.
  • Two or more monomer couplers may be polymerized simultaneously.
  • R is a hydrogen atom, a lower alkyl having 1 to 4 carbon atoms or a chlorine atom;
  • a 1 is -CONR'-, -NR'CONR'-, -NR'COO-, -COO-, -SO 2 -, -CO-, -NRCO-, -SO 2 NR'-, -NR'SO 2 -, -OCO-, -OCONR'- -NR'-or -O-;
  • a 2 is -CONR'- or -COO-;
  • R' is a hydrogen atom, an aliphatic group or an aryl group; when two or more R groups per molecule exist, the two or more R' groups may be the same or different groups;
  • a 3 is an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group or an unsubstituted or substituted arylene group (the alkylene group may be a straight-
  • substituent groups for the alkylene group, the aralkylene group or the arylene group represented by A 3 include an aryl group (e.g., phenyl), a nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group (e.g., methoxy), an aryloxy group (e.g., phenoxy), an acyloxy group (e.g., acetoxy), an acylamino group (e.g., acetylamino), a sulfonamido group (e.g., methanesulfonamido), a sulfamoyl group (e.g., methylsulfamoyl), a halogen atom (e.g., fluorine, chlorine, bromine), carboxyl group, a carbamoyl group (e.g., methylcarbamoyl), an alkoxycarbony
  • the compounds described herein can be synthesized according to the methods described in JP-A-54-145135, JP-A-63-37346, JP-A-56-114946, JP-A-57-154234, JP-A-58-162949 (corresponding to U.S. Patents 4,248,962, 4,861,701, 4,409,323, 4,421,845, and 4,482,629, respectively), JP-A-63-37350, JP-A-57-151944 (corresponding to U.S. Patent 4,477,563), JP-A-58-205150, JP-A-60-218645, the literature and other patent specifications.
  • the yellow colored cyan couplers refer to cyan couplers which have an absorption maximum at 400 nm to 500 nm in the visible absorption region of the couplers and form cyan dyes having an absorption maximum at 630 nm to 750 nm in the visible absorption region by the coupling thereof with the oxidation product of an aromatic primary amine developing agent.
  • cyan couplers which release a moiety of a water soluble compound having a 6-hydroxy-2-pyridone-5-ylazo group, a water-solubilizing group pyrazolone-4-ylazo group, a water-solubilizing group 2-acylaminophenylazo group, a 2-sulfonamidophenylazo group, and a 5-aminopyrazol-4-ylazo group by a coupling reaction with the oxidation product of an aromatic primary amine developing agent.
  • the water soluble compound should be dissolved out from the photographic material during a development processing.
  • the compound is preferably soluble in a developing solution of pH 9 to 12 in an amount of at least 1 g/l , more preferably at least 3 g/l at 25°C.
  • the colored cyan couplers can be represented by the following general formulas (CI) and (CII).
  • Cp represents a cyan coupler moiety (T is bonded to the coupling site thereof); T represents a timing group; k represents 0 or 1; X represents an N-, O- or S-containing bivalent group which is bonded to (T) k through the N, O or S atom and which also is bonded to Q; an Q represents an arylene group or a bivalent heterocyclic group.
  • R 1 and R 2 are independently a hydrogen atom, a carboxyl group, a sulfo group, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a carbamoyl group, a sulfamoyl group, a carbonamido group, a sulfonamido group or an alkylsulfonyl group; R 3 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group; and at least one of T, X, Q, R 1 , R 2 and R 3 has a water-soluble group (e.g., hydroxyl, carboxyl, sulfo, amino, ammonium, phosphono, phosphino, hydroxysulfonyloxy).
  • a water-soluble group e.g., hydroxyl, carboxyl,
  • R 4 is an acyl group or a sulfonyl group
  • R 5 is a group which can be attached to the benzene ring
  • j is an integer of 0 to 4; when j is 2 or greater, the two or more R 5 groups may be the same or different
  • at least one of T, X, Q, R 4 and R 5 has a water-soluble group (e.g., hydroxyl, carboxyl, sulfo, phosphono, phosphino, hydroxysulfonyloxy, amino, ammonium).
  • Examples of the coupler moiety represented by Cp include conventional cyan coupler moieties (e.g., moieties of phenol type and naphthol type couplers).
  • Cp coupler moieties represented by general formulas (Cp-6), (Cp-7) and (Cp-8) among those exemplified in the description of the compounds of formula (I).
  • the timing group represented by T in formulas (CI) and (CII) is a group which is cleaved from X after the cleavage of the bond between Cp and T by the coupling reaction of the couplers with an oxidation product of an aromatic primary amine developing agent.
  • the timing group is used for various purposes, e.g., controlling of coupling reactivity, stabilizing the couplers, controlling the release timing of X, etc.
  • Examples of the timing group include conventional timing groups represented by formulas (T-1) to (T-7) exemplified in the description of the compounds of formula (I).
  • k may be an integer of 0 or 1, the case where k is 0 is generally preferred, that is, Cp is directly bonded to X.
  • X is a bivalent group which is bonded to (T) k through an N, O or S atom.
  • X is -O-, -S-, -OSO 2 -, -OSO 2 NH- or a bivalent group which is bonded to (T) k through N, such as a heterocyclic group (e.g., a group derived from pyrrolidine, piperidine, morpholine, piperazine, pyrrole, pyrazole, imidazole, 1,2,4-triazole, benztriazole, succinimide, phthalimide, oxazolidine-2,4-dione, imidazolidine-2,4-dione, 1,2,4-triazolidine-3,5-dione or the like) or a composite group of these groups and an alkylene group (e.g., methylene, ethylene, propylene), a cycloalkylene group (e.g., 1,4-cyclohe
  • the mark * represents the position where the group is bonded to (T) k ; the mark ** represents the position where the group is bonded to Q;
  • X 1 represents -O- or -S-;
  • L represents an alkylene group;
  • X 2 represents a single bond, -O-, -S-, -CO-, -SO 2 -, -SO 2 NH-, -NHSO 2 -, -SO 2 O-, -OSO 2 -, -NHSO 2 NH-, -OSO 2 NH- or NHSO 2 O-; and
  • m represents an integer of 0 to 3.
  • the total of carbon atoms (hereinafter referred to as the carbon number) in X is preferably 0 to 12, more preferably 0 to 8. Most preferably, X is -OCH 2 CH 2 O-.
  • Q in formula (I) is an arylene group or a divalent heterocyclic group.
  • the arylene group may be a condensed ring, and the arylene group may have one or more substituent groups (e.g., halogen atom, hydroxyl, carboxyl, sulfo, nitro, cyano, amino, ammonium, phosphono, phosphino, alkyl, cycloalkyl, aryl, carbonamido, sulfonamido, alkoxy, aryloxy, acyl, sulfonyl, carboxyl, carbamoyl, sulfamoyl).
  • the C-number is preferably 6 to 15, more preferably 6 to 10.
  • the heterocyclic group is a 3-membered to 8-membered (preferably 5-membered to 7-membered) monocyclic or condensed ring heterocyclic group containing at least one hetero-atom selected from the group consisting of N, O, S, P, Se and Te as a member of the heterocyclic ring (e.g., a group derived from pyridine, thiophene, furan, pyrrole, pyrazole, imidazole, thiazole, oxazole, benzothiazole, benzoxazole, benzofuran, benzothiophene, 1,3,4-thiadiazole, indole, or quinoline).
  • the heterocyclic group may have one or more substituent groups (examples of the substituent groups include those already described above in the definition of the substituent groups for the arylene group of Q).
  • the C-number is preferably 2 to 15, more preferably 2 to 10.
  • R 1 , R 2 or R 3 in formula (I) is an alkyl group
  • the alkyl group includes both straight-chain and branched chain alkyl groups which may have unsaturated bonds and one or more substituent groups (e.g., halogen, hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammonium, acyl, carbonamido, sulfonamido, carbamoyl, sulfamoyl, or sulfonyl).
  • substituent groups e.g., halogen, hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammonium, acyl, carbonamido, sulfonamido, carbamoyl, sulfamoyl
  • R 1 , R 2 or R 3 is a cycloalkyl group
  • the cycloalkyl group is a 3-membered to 8-membered cycloalkyl group which may have crosslinking groups, unsaturated bonds or substituent groups (examples of the substituent groups include those already described above in the definition of the substituent groups for the alkyl group of R 1 , R 2 or R 3 ).
  • R 1 , R 2 or R 3 is an aryl group
  • the aryl group may be a condensed ring and may have substituent groups (examples of the substituent groups include alkyl, cycloalkyl and those already described above in the definition of the substituent groups for the alkyl group of R 1 , R 2 or R 3 ).
  • the heterocyclic group is a 3-membered to 8-membered (preferably 5-membered to 7-membered) monocyclic or condensed ring heterocyclic group containing at least one hetero-atom selected from the group consisting of N, S, O, P, Se and Te as a member of the heterocyclic ring.
  • the heterocyclic group include imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl and quinolinyl.
  • the heterocyclic group may have one or more substituent groups (examples of the substituent groups are the same as those for the aryl group of R 1 , R 2 or R 3 ).
  • the carboxyl group includes a carboxylate group; the sulfo group includes a sulfonato group; the phosphino group includes a phosphinato group; and the phosphono group includes a phosphonato group.
  • Those groups may include any counter ions, including Li + , Na + , K + or ammonium.
  • R 1 is a hydrogen atom, a carboxyl group, an alkyl group having 1 to 10 carbon atoms (e.g., methyl, t-butyl, sulfomethyl, 2-sulfoethyl, carboxymethyl, 2-carboxyethyl, 2-hydroxyethyl, benzyl, ethyl, isopropyl) or an aryl group having 6 to 12 carbon atoms (e.g., phenyl, 4-methoxyphenyl, 4-sulfophenyl) with a hydrogen atom, a methyl group or a carboxyl group being particularly preferred.
  • an alkyl group having 1 to 10 carbon atoms e.g., methyl, t-butyl, sulfomethyl, 2-sulfoethyl, carboxymethyl, 2-carboxyethyl, 2-hydroxyethyl, benzyl, ethyl, isopropyl
  • R 2 is a cyano group, carboxyl group, a carbamoyl group having 1 to 10 carbon atoms, a sulfamoyl group having 0 to 10 carbon atoms, a sulfo group, an alkyl group having 1 to 10 carbon atoms (e.g., methyl, sulfomethyl), a sulfonyl group having 1 to 10 carbonatoms (e.g., methylsulfonyl, phenylsulfonyl), a carbonamido group having 1 to 10 carbon atoms (e.g., acetamido, benzamido) or a sulfonamido group having 1 to 10 carbon atoms (e.g., methanesulfonamido, toluenesulfonamido) with a cyano group, carbamoyl group or carboxyl group being particularly preferred.
  • a cyano group e.g.
  • R 3 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (e.g., methyl, sulfomethyl, carboxyethyl, 2-sulfoethyl, 2-carboxyethyl, ethyl, n-butyl, benzyl, 4-sulfobenzyl) or an aryl group having 6 to 15 carbon atoms (e.g., phenyl, 4-carboxyphenyl, 3-carboxyphenyl, 4-methoxyphenyl, 2,4-dicarboxyphenyl, 2-sulfophenyl, 3-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 2,4-disulfophenyl). More preferably, R 3 is an alkyl group having 1 to 7 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • R 3 is an alkyl group having 1 to 7 carbon atom
  • R 4 is an acyl group represented by the following general formula (III) or a sulfonyl group represented by the following general formula (IV): R 11 SO 2 - (IV)
  • R 11 is an alkyl group
  • the alkyl group includes both straight-chain and branched groups, and may contain unsaturated bonds and may have one or more substituent groups (examples of the substituent groups include halogen atom, hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammonium, acyl, carbonamido, sulfonamido, carbamoyl, sulfamoyl, sulfonyl).
  • substituent groups include halogen atom, hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammonium, acyl, carbonamido, sulfonamido, carbamoyl, sulfamoyl, sulfonyl).
  • the cycloalkyl group is a 3-membered to 8-membered cycloalkyl group which may contain crosslinking groups and unsaturated bonds and may have one or more substituent groups (examples of the substituent groups being those described above in the description of the substituent groups for the alkyl group of R 11 ).
  • R 11 is an aryl group
  • the aryl group may be a condensed ring or may have one or more substituent groups (examples of the substituent groups include an alkyl group, a cycloalkyl group and those described above in the description of the substituent groups for the alkyl group of R 11 ).
  • the heterocyclic group is a 3-membered to 8-membered (preferably 5-membered to 7-membered) monocyclic or condensed ring heterocyclic group containing at least one hetero-atom selected from the group consisting of N, S, O, P, Se and Te as a member of the heterocyclic ring (e.g., imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, quinolynyl) and may have one or more substituent groups (examples of the substituent groups being those described above in the description of the substituent groups for the aryl group of R 11 ).
  • carboxyl group may include carboxylato group
  • sulfo group may include sulfonato group
  • phosphino group may include phosphinato group
  • phosphono group may include phosphonato group.
  • Counter ions are Li + , Na + , K + , ammonium, etc.
  • R 11 is an alkyl group having 1 to 10 carbon atoms (e.g., methyl, carboxymethyl, sulfoethyl, cyanoethyl), a cycloalkyl group having 5 to 8 carbon atoms (e.g., cyclohexyl, 2-carboxycyclohexyl) or an aryl group having 6 to 10 carbon atoms (e.g., phenyl, 1-naphthyl, 4-sulfophenyl) among which an alkyl group having 1 to 3 carbon atoms and an aryl group having 6 carbon atoms are particularly preferred.
  • 1 to 10 carbon atoms e.g., methyl, carboxymethyl, sulfoethyl, cyanoethyl
  • a cycloalkyl group having 5 to 8 carbon atoms e.g., cyclohexyl, 2-carboxycyclohexyl
  • R 5 is a group which can be substituted and is preferably an electron donative group. Particularly preferably, R 5 is a group of -NR 12 R 13 or -OR 14 which is preferably attached to the 4-position.
  • R 12 , R 13 and R 14 are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group and hence each has the same meaning as R 11 .
  • R 12 and R 13 may be combined together to form a ring. As the ring to be formed, an alicyclic nitrogen-containing heterocyclic ring is preferred.
  • j is an integer of 0 to 4, preferably 1 to 2, particularly preferably 1.
  • Cp, X, Q, in formulas (CI) and (CII) include the following groups:
  • the colored couplers represented by formula (CI) can be generally synthesized by the diazo coupling reaction of a 6-hydroxy-2-pyridone compound with an aromatic diazonium salt or heterocyclic diazonium salt having a coupler structure.
  • the former 6-hydroxy-2-pyridone compounds can be synthesized by methods described in Klinsberg, Heterocyclic Compound - Pyridine and Its Derivatives , Part 3 (Interscience 1962); J. Am. Chem. Soc. , Vol. 65, page 449 (1943); J. Chem. Tech. Biotechnol. , Vol. 36, page 410 (1986); Tetrahedron , Vol. 22, page 445 (1966); JP-B-61-52827 (the term "JP-B” as used herein means an "examined Japanese patent publication”); West German Patents 2,162,612, 2,349,709 and 2,902,486; and U.S. Patent 3,763,170.
  • the latter diazonium salts can be synthesized according to the methods described in U.S. Patents 4,004,929 and 4,138,258, JP-A-61-72244 and JP-A-61-273543.
  • the diazo coupling reaction of the 6-hydroxy-2-pyridone compounds with the diazonium salts can be carried out in a solvent such as methanol, ethanol, methyl cellosolve, acetic acid, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dioxane, water or the like or a mixture thereof.
  • reaction temperature is generally from -78 to +60°C, preferably from -20 to +30°C.
  • the resulting crude crystal was purified from hot methanol in the same manner as in Synthesis Example 1 to give 14.8 g of the desired coupler (YC-3) with a melting point of 246 to 251°C (decomposition).
  • the structure of the compound was confirmed by 1 HNMR spectrum, mass spectrum and elemental analysis.
  • the compound exhibited a maximum absorption wavelength in methanol at 457.6 nm and had a molecular extinction coefficient of 42700.
  • the compound was found to have good spectral absorption characteristics as a yellow colored coupler.
  • the coupler (YC-30) had a melting point of 154-6°C. The structure thereof was confirmed by 1 HNMR spectrum, mass spectrum and elemental analysis. The compound exhibited a maximum absorption wavelength in methanol at 458.2 nm and had a molecular extinction coefficient of 42800. The compound was found to have good spectral absorption characteristics as a yellow colored coupler.
  • the yellow colored cyan couplers represented by formulas (CII) to (CIV) can be synthesized by methods described in JP-B-58-6939 (the term "JP-B” as used herein means an "examined published Japanese patent publication") and JP-A-1-197563.
  • the couplers represented by general formula (CI) can be synthesized by the methods described in patent specifications cited above.
  • the couplers represented by formulas (CI) and (CII) are more preferred, and the couplers of formula (CI) are particularly preferred.
  • the yellow colored cyan couplers of the present invention be added to sensitive silver halide emulsion layers or adjoining layers in the photographic materials. It is particularly preferred that the yellow colored cyan couplers be added to the red-sensitive emulsion layer.
  • the total amount of the couplers to be added to the photographic material is 0.005 to 0.30 g/m 2 , preferably 0.02 to 0.20 g/m 2 , more preferably 0.03 to 0.15 g/m 2 .
  • the yellow colored couplers used in the present invention can be added in the same manner as in the addition of conventional couplers described hereinafter.
  • benzoylacetanilide type yellow couplers represented by the following general formula (A) be used in the silver halide color photographic materials of the present invention.
  • the yellow couplers represented by formula (A) have high ⁇ (molecular extinction coefficient) values so that the thickness of the photographic layers can be reduced. As a result, not only sharpness is improved, but also color reproducibility is improved, because the interlaminar effect is enhanced.
  • the yellow colored cyan couplers represented by formulas (CI) and (CII) and the developed dyes of these yellow couplers are similar in terms of the spectral absorption wave forms. Accordingly, printability in various auto-printers using color filters having various spectral characteristics, various light sources and various density sensors manufactured by various companies is good (because stability can be kept even when photographing conditions and exposure amount are varied).
  • M and Q each represents a group or an atom which can be attached to the benzene ring;
  • L represents a hydrogen atom, a halogen atom or an aliphatic oxy group;
  • m represents an integer of 0 to 5;
  • n represents an integer of 0 to 4;
  • X represents a group which can be eliminated by a coupling reaction with an oxidation product of an aromatic primary amine developing agent; when m is 2 or greater, the two or more M groups may be the same or different groups; when n is 2 or greater, the two or more Q groups may be the same or different groups; and
  • M, Q, L or X may be a single bond, or a bivalent to tetravalent bonding group forming a bis-, tris- or tetrakis compound having 2 to 4 moieties of the yellow coupler represented by formula (A).
  • M and Q examples include a halogen atom (e.g., fluorine, chlorine, bromine), an aliphatic group having 1 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an aliphatic oxy group having 1 to 20 carbon atoms, an aromatic oxy group having 6 to 20 carbon atoms, a carbonamide group having 2 to 24 carbon atoms, a sulfonamide group having 0 to 20 carbon atoms, a carbamoyl group having 1 to 24 carbon atoms, a sulfamoyl group having 0 to 20 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an aliphatic oxycarbonyl group having 2 to 20 carbon atoms, a substituted amino group having 2 to 24 carbon atoms, an aliphatic thio group having 1 to 24 carbon atoms, a ureido group having 1 to 20 carbon atoms, a sulfamoylamino group
  • L is a hydrogen atom, a halogen atom (fluorine, chlorine, bromine) or an aliphatic oxy group having 1 to 24 carbon atoms, which may be substituted.
  • X is a group which is eliminated by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. More specifically, X is a group represented by the following general formula (B), (C) or (D). -O-R' (B) -S-R" (C)
  • R' is an aromatic group having 2 to 30 carbon atoms, a heterocyclic group having 1 to 28 carbon atoms, an acyl group having 2 to 28 carbon atoms, an aliphatic sulfonyl group having 1 to 24 carbon atoms or an aromatic sulfonyl group having 6 to 24 carbon atoms.
  • R" is an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms or a heterocyclic group having 1 to 28 carbon atoms.
  • Y is a non-metallic atomic group required for forming a monocyclic or condensed 5-membered to 7-membered heterocyclic ring together with N.
  • heterocyclic ring formed by Y together with N include pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, indazole, benzimidazole, benztriazole, tetraazaindene, succinimide, phthalimide, saccharin, oxazolidine-2,4-dione, imidazolidine-2,4-dione, thiazolidine-2,4-dione, urazol, parabanic acid, maleinimide, 2-pyridone, 4-pyridone, 6-pyridazone, 6-pyrimidone, 2-pyrazolone, 1,3,5-triazine-2-one, 1,2,4-triazine-6-one, 1,3,4-tri
  • substituent groups include a halogen atom, a hydroxy group, a nitro group, a cyano group, a carboxyl group, an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic oxy group, an aromatic oxy group, an aliphatic thio group, an aromatic thio group, an aliphatic oxycarbonyl group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a ureido group, a sulfamoylamino group, an aliphatic oxycarbonylamino group and a substituted amino group.
  • the aliphatic group includes straight chain, branched and cyclic alkyl, alkenyl and alkynyl groups. These groups may be substituted with, for example, an aryl group, a halogen atom, an alkoxycarbonyl group, an alkoxy group or an aryloxy group.
  • Examples of the aliphatic group include methyl, ethyl, isopropyl, n-butyl, t-butyl, t-amyl, n-hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, 2-hexyldecyl, n-octadecyl, allyl, benzyl, phenethyl, undecenyl, octadecenyl, trifluoromethyl, chloromethyl, cyanoethyl, 1-(ethoxycarbonyl)ethyl, methoxyethyl, butoxyethyl, 3-dodecyloxypropyl and phenoxyethyl.
  • the heterocyclic group includes substituted or unsubstituted monocyclic or condensed ring heterocyclic rings.
  • examples of the heterocyclic group include 2-furyl, 2-thienyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-quinolyl, oxazole-2-yl, thiazole-2-yl, benzoxazole-2-yl, benzthiazole-2-yl, 1,3,4-thiadiazole-2-yl, 1,3,4-oxadiazole-2-yl and groups derived from the compounds of formula (wherein is the same as that in formula (D)).
  • the aromatic group includes substituted or unsubstituted monocyclic or condensed ring aryl groups.
  • substituents include an alkyl group, a halogen atom, and an alkoxy group.
  • aromatic group include phenyl, tolyl, 4-chlorophenyl, 4-methoxyphenyl, 1-naphthyl, 2-naphthyl and 4-t-butylphenoxyphenyl.
  • M is an aliphatic group (e.g., methyl, ethyl, n-propyl, t-butyl), an aliphatic oxy group (e.g., methoxy, ethoxy, n-butoxy, n-dodecyloxy), a halogen atom (e.g., fluorine, chlorine, bromine), a carbonamido group (e.g., acetamido, n-butaneamido, n-tetradecaneamido, benzamido) or a sulfonamido group (e,g., methylsulfonamido, n-butylsulfonamido, n-octylsulfonamido, n-dodecylsulfonamido, toluenesulfonamido).
  • an aliphatic group e.g., methyl, e
  • L is a chlorine atom or an aliphatic oxy group (methoxy, ethoxy, methoxyethoxy, n-octyloxy, 2-ethylhexyloxy, n-tetradecyloxy).
  • Q is, in addition to those groups described above as preferred examples for M, an aliphatic oxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, n-butoxycarbonyl, n-hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, 1-(ethoxycarbonyl)ethyloxycarbonyl, 3-dodecyloxypropyloxycarbonyl, n-decyloxycarbonyl, n-dodecyloxycarbonyl, phenethyloxycarbonyl) or a carbamoyl group (e.g., dimethylcarbamoyl, dibutylcarbamoyl, dihexylcarbamoyl, di-2-ethylhexylcarbamoyl, n-dodecylcarbamoyl).
  • an aliphatic oxycarbonyl group e.g.,
  • X is the group of formula (B) where R' is an aromatic group (e.g., 4-methoxycarbonylphenoxy, 4-methylsulfonylphenoxy, 4-cyanophenoxy, 4-dimethylsulfamoylphenoxy, 2-acetamido-4-ethoxycarbonylphenoxy, 4-ethoxycarbonyl-2-methylsulfonamidophenoxy) or a group of formula (D).
  • R' is an aromatic group (e.g., 4-methoxycarbonylphenoxy, 4-methylsulfonylphenoxy, 4-cyanophenoxy, 4-dimethylsulfamoylphenoxy, 2-acetamido-4-ethoxycarbonylphenoxy, 4-ethoxycarbonyl-2-methylsulfonamidophenoxy) or a group of formula (D).
  • R' is an aromatic group (e.g., 4-methoxycarbonylphenoxy, 4-methylsulfonylphenoxy, 4-cyanophenoxy, 4-d
  • V is a substituted or unsubstituted methylene group or a substituted or unsubstituted imino group
  • W is an oxygen atom, a sulfur atom, a substituted or unsubstituted methylene group or an unsubstituted imino group
  • V is an imino group
  • W is neither an oxygen atom nor a sulfur atom.
  • Examples of the group represented by formula (E) include succinimido, phthalimido, 1-methyl-imidazolidine-2,4-dione-3-yl, 1-benzyl-imidazolidine-2,4-dione-3-yl, 5-ethoxy-1-methylimidazolidine-2,4-dione-3-yl, 5-methoxy-1-methylimidazolidine-2,4-dione-3-yl, 5,5-dimethyloxazolidine-2,4-dione-3-yl, thiazolidine-2,4-dione-3-yl, 1-benzyl-2-phenyltriazolidine-3,5-dione-4-yl, 1-n-propyl-2-phenyltriazolidine-3,5-dione-4-yl and 5-ethoxy-1-benzylimidazolidine-2,4-dione-3-yl.
  • any one of the groups M, Q, L and X of the yellow coupler represented by formula (A) may be a single bond or a bivalent to tetravalent bonding group forming bi-, tris-, tetrakis-compound of the yellow coupler.
  • compound having one or two yellow coupler moieties are preferable.
  • the yellow coupler of formula (A) is in the form of a bis- to tetrakis compound, the number of carbon atoms of M, Q, L or X may be beyond the extent described above.
  • yellow couplers of formula (A) which can be used in the present invention include, but are not limited to, the following compounds.
  • the above-described yellow couplers which can be preferably used can be synthesized by conventional methods such as synthesis methods described in U.S. Patents 3,227,554, 3,408,194, 3,415,652, 3,447,928 and 4,401,752, U.K.
  • the photographic material of the present invention has a support having thereon at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer.
  • a support having thereon at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer.
  • a typical example is a silver halide photographic material having at least one sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity, but different light sensitivity, the sensitive layer being a unit sensitive layer having color sensitivity to any one of blue light, green light and red light.
  • the unit sensitive layers are generally arranged in the order of a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer from the support.
  • the arrangement may be in the reverse order to that described above according to purpose. Further, the arrangement may be such that a different light-sensitive layer is inserted into the same color sensitive layers.
  • Non-sensitive layers such as various interlayers may be provided between silver halide sensitive layers, or on the uppermost layer or lowermost layer thereof.
  • the interlayers may contain couplers, or DIR compounds described in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037 and JP-A-61-20038.
  • the interlayers may also contain color mixing inhibitors as used conventionally.
  • a plurality of silver halide emulsion layers which constitute each unit sensitive layer preferably include a two-layer structure consisting of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent 1,121,470 and U.K. Patent 923,045. It is preferred that the layers are disposed such that light sensitivity is lower toward the support.
  • a non-sensitive layer may be provided between silver halide emulsion layers.
  • the low-sensitivity emulsion layer may be provided on the farther side from the support and the high-sensitivity emulsion layer may be provided on the side nearer to the support as described in JP-A-57-112751, JP-A-62-200350, JP-A-62-206541 and JP-A-62-206543.
  • the layer may be arranged in order of low-sensitivity blue-sensitive layer (BL)/high-sensitivity blue-sensitive layer (BH)/ high-sensitivity green-sensitive layer (GH)/low-sensitivity green-sensitive layer (GL)/high-sensitivity red-sensitive layer (RH)/low-sensitivity red-sensitive layer (RL) from the outermost layer, or in order of BH/BL/GL/GH/RH/RL, or in order of BH/BL/GH/GL/RL/RH.
  • BL low-sensitivity blue-sensitive layer
  • BH high-sensitivity blue-sensitive layer
  • GH high-sensitivity green-sensitive layer
  • GL low-sensitivity green-sensitive layer
  • RH high-sensitivity red-sensitive layer
  • RL low-sensitivity red-sensitive layer
  • the arrangement may be made in order of blue-sensitive layer/GH/RH/GL/RL from the outermost layer as described in JP-B-55-34932. Further, the arrangement may be made in order of blue-sensitive layer/GL/RL/GH/RH from the outermost layer as described in JP-A-56-25738 and JP-A-62-63936.
  • the layer structure contains three layers having different light sensitivity in such an arrangement that the upper layer is a silver halide emulsion layer having the highest light sensitivity, the medium layer is a silver halide emulsion layer having a light sensitivity lower than that of the upper layer and the lower layer is a silver halide emulsion layer having a light sensitivity lower than that of the medium layer so that light sensitivity becomes lower toward the support in order as described in JP-B-49-15495.
  • the arrangement may be made in order of medium-sensitive emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer from the outermost layer as described in JP-A-59-202464.
  • the arrangement may be made in order of high-sensitivity emulsion layer/low sensitivity emulsion layer/medium-sensitivity emulsion layer or in order of low sensitivity emulsion layer/medium-sensitivity emulsion layer/high-sensitivity emulsion layer.
  • the layer structure is composed of four or more layers, the above-described various arrangements can be made.
  • a donor layer (CL) having a multilayer effect and different in spectral sensitivity distribution from the principal sensitive layers such as BL, GL and RL are provided adjacent to or near the principal sensitive layers to improve color reproducibility, said donor layer being described in U.S. Patents 4,663,271, 4,705,744 and 4,707,436, JP-A-62-160448 and JP-A-63-89850.
  • the preferred silver halide contained in the photographic emulsions of the photographic materials of the present invention is silver iodobromide, silver iodochloride or silver iodochlorobromide, each having a silver iodide content of not higher than about 30 mol%. Particularly preferred is silver iodobromide or silver iodochlorobromide, each having a silver iodide content of about 2 mol% to about 25 mol%.
  • Silver halide grains in the photographic emulsions may have a regular crystal form such as cube, octahedron or tetradecahedron, an irregular crystal form such as a sphere or tabular form, a crystal having a defect such as a twinning plane or a composite form thereof.
  • the size of silver halide grains may be in the range of from fine grains having a grain size of not larger than about 0.2 ⁇ m to large-size grains having a grain size of about 10 ⁇ m in terms of the diameter of projected area. Any of a polydisperse emulsion and monodisperse emulsion may be used.
  • the silver halide photographic emulsions of the present invention can be prepared according to the methods described in Research Disclosure (RD) No. 17643 (December 1978) pp 22-23 I. Emulsion Preparation and Types ; ibid. No. 18716 (November 1979), p. 648; ibid. No. 307105 (November 1989), pp 863-865; P. Glafkides, Chimie et Phisique Photoqraphique (Paul Montel 1967), G.F. Duffin, Photoqraphic Emulsion Chemistry (Focal Press 1966) and V.L. Zelikman et al, Making and Coating Photographic Emulsion (Focal Press 1964).
  • Tabular grains having an aspect ratio of not lower than about 5 can be used in the present invention.
  • the tabular grains can be easily prepared by the methods described in Gutoff, Photoqraphic Science and Engineering , Vol. 14, pp 248-257 (1970), U.S. Patents 4,434,226, 4,414,310, 4,433,048 and 4,439,520 and U.K. Patent 2,112,157.
  • Grains having a uniform crystal structure or a crystal structure different in halogen composition between the interior thereof and the surface thereof can be used.
  • Grains having a laminar crystal structure may be used.
  • Silver halide having a different composition may be joined to the grains by epitaxial growth.
  • a compound such as silver rhodanide or lead oxide other than silver halide may be joined to the grains.
  • a mixture of grains having various crystal forms may be used.
  • Silver halide emulsions are usually subjected to physical ripening, chemical ripening and spectral sensitization and then used. Additives used for these stages are described in Research Disclosure No. 17643, ibid. No. 18716 and ibid. No. 30716 and listed in a Table below.
  • non-light-sensitive finely divided silver halide grains are used in the present invention.
  • non-sensitive finely divided silver halide grains refers to finely divided silver halide grains which are not light-sensitive during imagewise exposure for obtaining a dye image and are substantially not developed in the processing stage. Grains which are previously not fogged are preferable.
  • Finely divided silver halide grains have a silver bromide content of 0 to 100 mol% and may optionally contain silver chloride and/or silver iodide. Grains containing 0.5 to 10 mol% of silver iodide are preferred.
  • Finely divided silver halide grains have a mean grain size (the mean value of diameters of the circles having areas corresponding to projected areas) of preferably 0.01 to 0.5 ⁇ m, more preferably 0.02 to 0.2 ⁇ m.
  • Finely divided silver halide grains can be prepared in the same manner as in the preparation of usual light-sensitive silver halides. In the preparation of finely divided silver halide grains, it is not necessary that the surfaces of silver halide grains be optically sensitized or spectrally-sensitized. However, it is preferred that a conventional stabilizer such as triazole, azaindene, benzthiazolium, a mercapto compound or a zinc compound be added before the finely divided silver halide grains are added to coating solutions. Colloidal silver is preferably incorporated in layers containing the finely divided silver halide grains.
  • color couplers can be used in the present invention. Examples thereof are described in patent specifications cited in the above-described Research Disclosure No. 17643, VII-C to G and ibid. No. 307105, VII-C to G.
  • yellow couplers include those described in U.S. Patents 3,933,501, 4,022,620, 4,326,024, 4,401,752 and 4,248,961, JP-B-58-10739, U.K. Patents 1,425,020 and 1,476,760, U.S. Patents 3,973,968, 4,314,023 and 4,511,649 and European Patent 249,473A.
  • magenta couplers are preferred as magenta couplers. Particularly preferred are magenta couplers described in U.S. Patents 4,310,619 and 4,351,897, European Patent 73,636, U.S. Patents 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, JP-A-60-185951, U.S. Patents 4,500,630, 4,540,654 and 4,556,630 and WO88/04795.
  • cyan couplers phenol couplers and naphthol couplers may be used.
  • Preferred cyan couplers include those described in U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011 and 4,327,173, West German Patent Application (Laid-Open) No. 3,329,729, European Patents 121,365A and 249,453A, U.S. Patents 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4,690,889, 4,254,212 and 4,296,199 and JP-A-61-42658.
  • couplers which release imagewise nucleating agents or development accelerators during development there are preferred those described in U.K. Patents 2,097,140 and 2,131,188, JP-A-59-157638 and JP-A-59-170840.
  • Couplers used in the present invention can be introduced into photographic materials by various known dispersion methods.
  • Examples of the high-boiling organic solvents which have a boiling point of not lower than 175°C at normal pressure used in the oil-in-water dispersion method include phthalic esters (e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-diethylpropyl) phthalate), phosphoric or phosphonic esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate,
  • Organic solvents having a boiling point of not lower than about 30°C, preferably not lower than about 50°C, but not higher than about 160°C can be used as co-solvents.
  • the co-solvents include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.
  • antiseptic and antifungal agents such as 1,2-benzoisothiazoline-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol and 2-(4-thiazolyl)benzimidazole described in JP-A-63-257747, JP-A-62-272248 and JP-A-1-80941 and phenethyl alcohol are added to the color photographic materials of the present invention.
  • antiseptic and antifungal agents such as 1,2-benzoisothiazoline-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol and 2-(4-thiazolyl)benzimidazole described in JP-A-63-257747, JP-A-62-272248 and JP-A-1-80941 and phenethyl alcohol are added to the color photographic materials of the present invention.
  • the present invention can be applied to various color photographic materials.
  • Typical examples of the color photographic materials according to the present invention include general-purpose and movie color negative films, reversal color films for slide or TV, color paper, color positive films and reversal color paper.
  • Examples of supports which can be used in the present invention include those described in the above-described RD No. 17643 (page 28), RD No. 18716 (right column of page 647 to left column of page 648) and RD No. 307105 (page 879).
  • the total of the layer thicknesses of the entire hydrophilic colloid layers on the emulsion layer side thereof is preferably not more than 28 ⁇ m, more preferably not more than 23 ⁇ m, still more preferably not more than 18 ⁇ m, particularly preferably not more than 16 ⁇ m.
  • the layer-swelling rate T 1/2 is preferably not longer than 30 seconds, more preferably not longer than 20 seconds.
  • the layer thickness refers to a layer thickness obtained by measuring the thickness of a layer at 25°C and 55% RH under air conditioning (2 days).
  • the layer-swelling rate T 1/2 can be measured by known method in the field of photography, for example, by using a swellometer described in A. Green et al., Photogr. Sci. Eng.
  • T 1/2 is defined as the time taken until layer thickness reaches 1/2 of saturated layer thickness when processing is conducted with a color developing solution at 30°C for 3 min 15 sec and 90% of the attainable maximum swollen layer thickness is referred to as saturated layer thickness.
  • the layer-swelling rate T 1/2 can be controlled by adding a hardening agent to gelatin as a binder or by changing conditions with time after coating.
  • a swelling ratio of 150 to 400% is preferred.
  • the swelling ratio can be calculated from the maximum swollen layer thickness under the above conditions by using the formula (maximum swollen layer thickness - layer thickness)/layer thickness.
  • the color photographic materials of the present invention can be developed according to conventional methods described in RD No. 17643 (pp 28-29), RD No. 18716 (left column to right column of page 651) and RD No. 307105 (pp 880-881).
  • Color developing solutions which can be used in the processing of the photographic materials of the present invention are preferably aqueous alkaline solutions mainly composed of aromatic primary amine color developing agents. Aminophenol compounds are useful as the color developing agents and p-phenylenediamine compounds are preferred as the color developing agents.
  • Typical examples thereof include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline and salts thereof such as sulfate, hydrochloride and p-toluenesulfonate.
  • 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline sulfate is particularly preferred. These compounds may be used either alone or in combination of two or more of them according to purpose.
  • the color developing solutions contain pH buffering agents such as alkali metal carbonates, borates and phosphates, developed restrainers such as chlorides, bromides, iodides, benzimidazoles, benzothiazoles and mercapto compounds and anti-fogging agents.
  • pH buffering agents such as alkali metal carbonates, borates and phosphates
  • developed restrainers such as chlorides, bromides, iodides, benzimidazoles, benzothiazoles and mercapto compounds and anti-fogging agents.
  • the color developing solutions may optionally contain preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazine such as N,N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, catecholsulfonic acids; organic solvents such as ethylene glycol and diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts and amines; color forming couplers, competitive couplers; auxiliary developing agents such as 1-phenyl-3-pyrazolidone; tackifiers; and chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyeth
  • Black-and-white developing solutions may contain conventional developing agents such as dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone) and aminophenols (e.g., N-methyl-p-aminophenol). These developing agents may be used either alone or in combination of two or more of them.
  • dihydroxybenzenes e.g., hydroquinone
  • 3-pyrazolidones e.g., 1-phenyl-3-pyrazolidone
  • aminophenols e.g., N-methyl-p-aminophenol
  • the pH of the color developing solutions and the black-and-white developing solutions is generally in the range of 9 to 12.
  • the replenishment rate of these developing solutions varies depending on the types of the color photographic materials, but is usually not more than 3 l per m 2 of the photographic material.
  • the replenishment rate can be reduced to 500 ml or less when the concentration of bromide ion in the replenisher is reduced.
  • the opening ratio is preferably not higher than 0.1, more preferably 0.001 to 0.05.
  • Methods for reducing the opening ratio include a method wherein a cover such as a floating lid is provided on the surface of the photographic processing solution in the processing tank; a method wherein a movable lid is used as described in JP-A-1-82033; and a slit development method described in JP-A-63-216050. It is preferred the opening ratio be reduced not only for color development and black and white development stages, but also all of the subsequent stages such as bleaching, bleaching-fixing, fixing, rinsing and stabilization stages. The replenishment rate can be reduced by inhibiting the accumulation of bromide ion in the developing solution.
  • Color development is usually 2 to 5 minutes. However, when a higher temperature and a higher pH are used and the color developing agents are used at a higher concentration, processing time can be shortened.
  • the photographic emulsion layer is generally bleached.
  • Bleaching may be carried out simultaneously with fixing (bleaching-fixing treatment) or separately carried out.
  • a bleaching-fixing treatment may be conducted to expedite processing. Processing may be conducted with a bleaching-fixing bath composed of two consecutive baths. Fixing may be conducted before the bleaching-fixing treatment.
  • bleaching may be conducted according to purpose. Examples of bleaching agents include compounds of polyvalent metals such as iron(III), peracids, quinones and nitro compounds.
  • Typical examples of the bleaching agents include organic complex salts of iron(III) such as complex salts of aminopolycarboxylic acids (e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid), citric acid, tartaric acid, and malic acid.
  • aminopolycarboxylic acids e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid
  • citric acid tartaric acid
  • malic acid e.g., citric acid, tartaric acid, and malic acid
  • iron(III) complex salts of aminopolycarboxylic acids such as (ethylenediaminetetraacetonato)-iron(III) complex and (1,3-diaminopropanetetraacetonato)iron(III) complex are preferred for rapid processing and prevention of environmental pollution.
  • iron(III) complex salts of aminopolycarboxylic acids are useful for bleaching solutions and bleaching-fixing solutions.
  • the pH of the bleaching solutions containing the iron(III) complex salts of aminopolycarboxylic acids and the bleaching-fixing solutions containing the iron(III) complex salts is generally in the range of 4.0 to 8. A lower pH may be used to expedite processing.
  • the bleaching solution, the bleaching-fixing solution and the pre-bath thereof may contain bleaching accelerators.
  • the bleaching accelerators include compounds having a mercapto group or disulfide group described in U.S. Patent 3,893,858, West German Patents 1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426 and Research Disclosure No.
  • the compounds having a mercapto group or disulfide group are preferred for their high accelerating effect.
  • Patent 3,893,858, West German Patent 1,290,812 and JP-A-53-95630 are preferred. Further, the compounds described in U.S. Patent 4,552,834 are preferred. These bleaching accelerators may be incorporated in the photographic materials. These bleaching accelerators are particularly effective in conducting bleaching-fixing of the color photographic materials for photographing.
  • the bleaching solution and the bleaching-fixing solution contain organic acids to prevent stain from being caused by bleaching.
  • organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5.
  • the organic acids include acetic acid and propionic acid.
  • fixing agents used in the fixing solution and the bleaching-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of an iodide.
  • the thiosulfates are widely used as the fixing agents. Particularly, ammonium thiosulfate is most widely used.
  • a combination of a thiosulfate with a thiocyanate, a thioether compound or a thiourea is also preferred.
  • Sulfites, bisulfites, carbonyl bisulfite adducts and sulfinic acid compounds described in European Patent 294769A are preferred as preservatives for the fixing solution and the bleaching-fixing solution. It is also preferred that aminopolycarboxylic acids or organic phosphonic acids are added to the fixing solution or the bleaching-fixing solution to stabilize the solution.
  • compounds having a pKa of 6.0 to 9.0 preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methylimidazole, in an amount of 0.1 to 10 mol/l are added to the fixing solution or the bleaching-fixing solution to adjust the pH.
  • imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methylimidazole
  • Desilvering time is preferably 1 to 3 min, more preferably 1 to 2 min.
  • Processing temperature is 25 to 50°C, preferably 35 to 45°C.
  • agitation in the desilvering stage be intensified as much as possible.
  • Methods for intensifying agitation include a method wherein a jet of the processing solution collides with the surfaces of the emulsions of photographic materials as described in JP-A-62-183460; a method wherein stirring is improved by a rotating means as described in JP-A-62-183461; a method wherein a wiper blade provided in the solution is brought into contact with the surfaces of the emulsions, the photographic material is transferred to thereby form a turbulent flow, whereby a stirring effect is improved; and a method wherein the whole amount of the processing solution circulated is increased.
  • Such means for improving agitation are effectively applicable to any of the bleaching solution, the bleaching-fixing solution and the fixing solution. It is believed that an improvement agitation accelerates the feed of the bleaching solution and the fixing solution into the emulsion layers and as a result, the desilvering rate is enhanced.
  • the above-described means for improving agitation is more effective when the bleaching accelerators are used. The accelerating effect can be greatly increased and the problem of inhibiting fixation caused by the bleaching accelerators can be solved.
  • automatic processors for use in the processing of the photographic materials of the present invention be provided with photographic material conveying means described in JP-A-60-191257, JP-A-60-191258 and JP-A-60-191259.
  • the conveying means can greatly reduce the amount of the processing solution brought over from the previous bath to the subsequent bath so that preservation of the performance of the processing solution is very high. This is particularly effective in shortening the processing time in each stage or reducing the replenishment rate of the processing solution.
  • the silver halide color photographic materials of the present invention are subjected to washing and/or stabilization after desilvering.
  • the amount of rinsing water in the washing stage varies widely depending on the characteristics (e.g., depending on materials used such as couplers) of the photographic materials, their use, the temperature of rinsing water, the number of rinsing tanks (the number of stages), replenishing system (countercurrent, direct flow) and other conditions.
  • the relationship between the amount of water and the number of rinsing tanks in the multi-stage countercurrent system can be determined by the method described in Journal of the Society of Motion Picture and Television Engineers , Vol. 64, p. 248-253 ( May 1955).
  • the amount of rinsing water can be greatly reduced.
  • the residence time of water in the tanks is prolonged and as a result, bacteria are grown and the resulting suspended matter is deposited on the photographic material.
  • a method for reducing calcium ion and magnesium ion concentrations described in JP-A-62-288838 can be effectively used for the color photographic materials of the present invention to solve this problem.
  • isothiazolone compounds thiabendazole compounds, chlorine-containing germicides such as sodium chlorinated isocyanurate and benztriazole described in JP-A-57-8542 and germicides described in Chemistry of Germicidal Antifungal Agent , (1986) written by Hiroshi Horiguchi (Sankyo Shuppan), Sterilization, Disinfection, Antifungal Technique , edited by Sanitary Technique Society and Antibacterial and Antifungal Cyclopedie , (1986) edited by Nippon Antibacterial Antifungal Society, can be used.
  • germicides such as sodium chlorinated isocyanurate and benztriazole described in JP-A-57-8542 and germicides described in Chemistry of Germicidal Antifungal Agent , (1986) written by Hiroshi Horiguchi (Sankyo Shuppan), Sterilization, Disinfection, Antifungal Technique , edited by Sanitary Technique Society and Antibacterial and Antifungal Cyclopedie , (1986
  • the pH of rinsing water in the treatment of the photographic materials of the present invention is in the range of 4 to 9, preferably 5 to 8.
  • the temperature of rinsing water and washing time vary depending on the characteristics of the photographic materials and use, but the temperature and time of washing are generally 15 to 45°C for 20 seconds to 10 minutes, preferably 25 to 40°C for 30 seconds to 5 minutes.
  • the photographic materials of the present invention may be processed directly with stabilizing solutions in place of rinsing water. Such stabilizing treatment can be carried out by conventional methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345.
  • a stabilizing treatment subsequent to rinsing may be conducted.
  • the stabilizing treatment may be used as the final bath for the color photographic materials for photographing.
  • An example thereof include a stabilizing bath containing a dye stabilizer and a surfactant.
  • the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehydesulfite adducts.
  • the stabilizing bath may contain various chelating agents and antifungal agents.
  • Overflow solution from the replenishment of rinsing water and/or stabilizing can be reused in other stages such as desilvering stage.
  • the color developing agents may be incorporated in the silver halide color photographic materials of the present invention for the purpose of simplifying and expediting processing. It is preferred that precursors for the color developing agents are used for the incorporation thereof in the photographic materials. Examples of the precursors include indoaniline compounds described in U.S. Patent 3,342,597; Schiff base compounds described in U.S. Patent 3,342,599 Research Disclosure No. 14850 and ibid. , No. 15159; aldol compounds described in Research Disclosure No. 13924; metal complex salts described in U.S. Patent .3,719,492; and urethane compounds described in JP-A-53-135628.
  • 1-phenyl-3-pyrazolidones may be incorporated in the silver halide color photographic materials of the present invention for the purpose of accelerating color development.
  • Typical examples of the compounds include those described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.
  • various processing solutions are used at a temperature of 10 to 50°C. Generally, a temperature of 33 to 38°C is used. However, a higher temperature can be used to accelerate processing and to shorten processing time, while a lower temperature is used to improve image quality and to improve the stability of the processing solutions.
  • the silver halide photographic materials of the present invention include heat developable photo sensitive materials described in U.S. Patent 4,500,626, JP-A-60-133449, JP-A-59-218443, JP-A-61-238056 and European Patent 210,660A2.
  • the coating weights of silver halide and colloidal silver are represented by g/m 2 in terms of silver.
  • the coating weights of couplers, additives and gelatin are represented by g/m 2 .
  • the amounts of sensitizing dyes are represented by moles per mole of silver halide in the same layer.
  • Cpd-3, Cpd-5, Cpd-6, Cpd-7, Cpd-8, P-1, P-2, W-1, W-2, W-3 were added to improve preservability, processability, pressure resistance, mildewproofing and antifungal properties, antistatic properties, and coatability.
  • Each of Samples 102, 103 and 104 was prepared in the same way as in the preparation of Sample 101 except that a twice molar amount of Compound (D-14) or (D-29) or an equimolar amount of (D-7) was used in place of ExC-13 in each of the third layer, the fourth layer, the eleventh layer and the twelfth layer of Sample 101.
  • Each of Samples 105 to 108 was prepared in the same way as in the preparation of each of Samples 101 to 104 except that the yellow colored cyan coupler (YC-28) in an amount of 0.02 g/m 2 and 0.01 g/m 2 was added to the third layer and the fourth layer of each of Samples 101 to 104, respectively. Similarly, (YC-32) and (YC-47) were added to prepare Samples 109 to 116.
  • YC-28 yellow colored cyan coupler in an amount of 0.02 g/m 2 and 0.01 g/m 2
  • Each of Samples 117 to 120 was prepared in the same way as in the preparation of Sample 107 except that (YC-24), (YC-26), (YC-30) or (YC-3) was used in place of (YC-28).
  • Each of Samples 121 and 122 was prepared in the same way as in the preparation of Sample 107 except that ExY-15 in an amount of 1.10 g/m 2 or 1.20 g/m 2 was used in place of (Y-1) in the eleventh layer of Sample 107; the amount of gelatin was changed to 1.50 g/m 2 ; the amount of Solv-l was changed to 0.40 g/m 2 ; and further ExY-15 or ExY-16 in an amount of 0.18 g/m 2 was used in place of (Y-1) in the twelfth layer of Sample 107.
  • Relative sensitivity was determined from the logarithm of the reciprocal of exposure amount giving a density of (Fog+0.2) under the Condition A.
  • Color turbidity was determined from a value obtained by subtracting the yellow density in the red unexposed area from the yellow density in an exposure amount giving a cyan density of (Fog+0.5) and (Fog+1.0) under the Conditions A and B.
  • Each processing solution used in each stage had the following composition.
  • the samples of the present invention are highly sensitive in comparison with the samples which are outside the scope of the present invention.
  • all of the samples of the present invention are high in sensitivity in comparison with Sample 113 which is suggested as a photographic material in West German Patent 3815469.
  • the samples of the present invention exhibit low color turbidity in any exposure amount under both the conditions A and B in comparison with Samples 102 to 104 using only a DIR compound and Samples 105, 109 and 113 using only a yellow colored coupler.
  • the effect of the present invention on color turbidity is remarkable under the Condition B under which there is color turbidity during exposure and an improvement in chromaticity is desired, rather than under the Condition A under which exposure is only pure red exposure.
  • the effect of the present invention is high in the high density region where exposure amount is increased. Namely, Table 1 shows that an improvement in color reproducibility under various exposure conditions has been achieved by the present invention.
  • Sample 107 using yellow coupler (Y-1) is high-sensitive, exhibits low turbidity and is excellent in sharpness in comparison with Samples 121 and 122 using ExY-15 and ExY-16.
  • Each of Samples 107, 121 and 122 was slit into films of 35 mm in width and processed into 135 size patrone (24 exposures) to prepare each of photographic materials 201, 202 and 203.
  • a half-length of a person was photographed through a color checker (manufactured by Macbeth) with a Canon EOS-630 camera using these photographic materials under each setting condition of ISO speed 400, 100 and 12.
  • the same subject was photographed using commercially available super HG-400 under each setting condition of ISO speed 1600, 400 and 50.
  • the replenishment rate of each processing solution was such that the replenishment rate in the color development stage was 1200 ml per m 2 of color photographic material and that in each of the other stages including the rinses was 800 ml.
  • the amount of the processing solution carried over from the previous bath to the rinse stage was 50 ml per m 2 of color photographic material.
  • Drying temperature was 50°C.
  • An auto-printer FAP-3500 manufactured by Fuji Photo Film Co., Ltd. was set so that each density of B, G and R of neutral 5 of the Macbeth color checker became 0.75 ⁇ 0.02 in printing under three conditions of super HG400.
  • the printing of the photosensitive materials 201 to 203 was done under the above conditions.
  • Fuji color paper HG was used for printing.
  • the Macbeth color checker density of these samples was measured on paper. The results are shown in Table 2.
  • a yellow colored cyan coupler (YC-1) in an amount of 0.015 g/m 2 and 0.005 g/m 2 was added to the fourth layer and the fifth layer, respectively, of Sample 105 (the coupler Ex-10 being the same as D-29 of the present invention) of JP-A-1-214849 to prepare Sample 301.
  • (YC-85), (YC-86), (YC-88) and (YC-89) were added to prepare Samples 302 to 308.
  • the samples for use in the evaluation of performance were processed after imagewise exposed samples were processed until the amount of replenisher added to the color developing solution was three times the tank capacity of mother solution.
  • Rinsing water was supplied by a system running countercurrent from (2) to (1). All of the overflow solution of rinsing water was introduced into the fixing bath.
  • the replenishment to the bleaching-fixing bath was conducted in such a manner that the upper part of the bleaching bath in the automatic processor was connected with the bottom of the bleaching-fixing bath through a pipe, the upper part of the fixing bath was connected with the bottom of the bleaching-fixing bath through a pipe and all of the overflow solution resulting from the feeding of the replenisher to the bleaching bath and the fixing bath was allowed to flow into the bleaching-fixing bath.
  • the amount of the developing solution brought into the bleaching stage, that of the bleaching solution brought into the bleaching-fixing stage, that of the bleaching-fixing solution brought into the fixing stage and that of the fixing solution brought into the rinse stage were 2.5 ml, 2.0 ml, 2.0 ml and 2.0 ml, respectively, each amount being per 35 mm wide x 1 m long of the photographic material.
  • Cross-over time was 5 seconds in each of these stages. The cross-over time was included within the processing time of the previous stage.
  • Each process bath was provided with a means for allowing the jet stream of each processing solution to collide with the surfaces of the emulsion layers as described in JP-A-62-183460.
  • Each processing solution had the following composition.
  • a mixed solution of the mother solution of the above bleaching solution and the mother solution of the following fixing solution (15:85 by volume).
  • Tap water was passed through a mixed-bed column packed with an H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rhom & Haas Co.) and an OH-type strongly basic anion exchange resin (Amberlite IRA-400) to reduce the concentrations of calcium and magnesium ions to 3 mg/l or lower.
  • H-type strongly acidic cation exchange resin Amberlite IR-120B, manufactured by Rhom & Haas Co.
  • Amberlite IRA-400 OH-type strongly basic anion exchange resin

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Claims (14)

  1. Matériau photographique couleur à l'halogénure d'argent, comprenant un support sur lequel se présente au moins une couche d'émulsion d'halogénure d'argent sensible au rouge contenant un copulant du cyan, au moins une couche d'émulsion d'halogénure d'argent sensible au vert contenant un couplant du magenta et au moins une couche d'émulsion d'halogénure d'argent sensible au bleu contenant un copulant du jaune, caractérisé en ce que le matériau photographique contient au moins un composé représenté parla formule générale suivante (I) et au moins un copulant du cyan coloré en jaune:

            A-(TIME)n-B     (I)

    dans laquelle A représente une fraction du copulant qui est libérée de (TIME)n-B par une réaction de couplage avec un produit d'oxydation d'un agent de développement amine primaire aromatique; TIME représente un groupe de temporisation qui est lié au site de couplage actif de A et qui libère B après la libération de A par la réaction de couplage; B représente un groupe représenté par les formules générales (IIa), (IIb), (IIc), (IId), (IIe), (IIf), (IIg), (IIh), (IIi), (IIj), (IIk), (IIℓ), (IIm), (IIn), (IIo), (IIp) ci-dessous; et n représente 0 ou 1, et lorsque n vaut 0, B est directement lié à A:
    Figure imgb0401
    Figure imgb0402
    Figure imgb0403
    Figure imgb0404
    Figure imgb0405
    Figure imgb0406
    Figure imgb0407
    Figure imgb0408
    Figure imgb0409
    Figure imgb0410
    Figure imgb0411
    Figure imgb0412
    Figure imgb0413
    Figure imgb0414
    Figure imgb0415
    Figure imgb0416
     dans lesquelles X1 représente un groupe aliphatique substitué ou non substitué présentant de 1 à 4 atomes de carbone ou un groupe phényle substitué,
       des groupes de substitution étant un groupe hydroxyle, un groupe alcoxycarbonyle, un groupe acylamino, un groupe carbamoyle, un groupe sulfonyle, un groupe sulfonamido, un groupe sulfamoyle, un groupe alcoxy, un groupe uréido, un groupe carboxyle, un groupe cyano, un groupe nitro, un groupe amino, un groupe alcoxycarbonylamino et un groupe acyle, le nombre d'atomes de carbone dans ces groupes de substitution n'étant pas supérieur à 3, le groupe phényle pouvant présenter un ou plusieurs substituants; X2 représente un atome d'hydrogène, un groupe aliphatique, un atome d'halogène, un groupe hydroxyle, un groupe alcoxy, un groupe alkylthio, un groupe alcoxycarbonyle, un groupe acylamino, un groupe carbamoyle, un groupe sulfonyle, un groupe sulfonamido, un groupe sulfamoyle, un groupe acyloxy, un groupe uréido, un groupe cyano, un groupe nitro, un groupe amino, un groupe alcoxycarbonylamino, un groupe aryloxycarbonyle ou un groupe acyle; X3 représente un atome d'oxygène, un atome de soufre ou un groupe imine ne présentant pas plus de 4 atomes de carbone, m représente un entier valant 1 ou 2; le total des atomes de carbone dans les groupes X2 ou (X2)m n'est pas supérieur à 8; et lorsque m vaut 2, les deux groupes X2 peuvent être identiques ou différents, dans lequel ledit copulant du cyan coloré en jaune est capable de libérer une fraction d'un colorant soluble dans l'eau, présentant un groupe sélectionné parmi l'ensemble constitué d'un groupe 6-hydroxy-2-pyridone-5-ylazo, d'un groupe 2-acylaminophénylazo, et d'un groupe 2-sulfonamidophénylazo, par une réaction de couplage avec un produit d'oxydation d'un agent de développement amine primaire aromatique.
  2. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel A dans la formule (I) est une fraction d'un copulant sélectionné parmi l'ensemble constitué d'une fraction d'un copulant du jaune, d'une fraction d'un copulant du magenta, d'une fraction d'un copulant du cyan et d'une fraction d'un copulant qui forme un produit de réaction de couplage ne présentant essentiellement pas d'absorption dans la région de la lumière visible.
  3. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel le composé représenté par la formule (I) est incorporé dans au moins une des couches d'émulsion d'halogénure d'argent et dans une couche intermédiaire, insensible à la lumière, adjacente à celle-ci.
  4. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel la proportion du composé représenté par la formule (I) par rapport au copulant principal dans la même couche, lorsque le composé est incorporé dans une couche d'émulsion d'halogénure d'argent, ou dans cette couche d'émulsion d'halogénure d'argent adjacente contenant une plus grande quantité d'halogénure d'argent lorsque le composé est incorporé dans une couche intermédiaire insensible à la lumière, est de 0,1 à 100% molaires.
  5. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel la proportion du composé représenté par la formule (I) par rapport à l'halogénure d'argent est de 0,01 à 20% molaire par mole d'halogénure d'argent, dans la même couche lorsque le composé est incorporé dans une couche d'émulsion d'halogénure d'argent, ou dans cette couche d'émulsion d'halogénure d'argent adjacente contenant une plus grande quantité d'halogénure d'argent lorsque le composé est incorporé dans une couche intermédiaire insensible à la lumière.
  6. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel le copulant du cyan coloré en jaune présente une absorption maximale entre 400 nm et 500 nm et forme un colorant cyan présentant une absorption maximale entre 630 nm et 750 nm par couplage avec le produit d'oxydation d'un agent de développement amine primaire aromatique.
  7. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel ledit copulant du cyan coloré en jaune est sélectionné parmi l'ensemble constitué des copulants représentés par les formules (CI) et (CII):
    Figure imgb0417
    Figure imgb0418
     dans lesquelles Cp représente une fraction d'un copulant du cyan (T est lié au site de couplage de celui-ci); T représente un groupe de temporisation; k représente 0 ou 1; X représente un groupe bivalent contenant N-, O- ou S- qui est lié à (T)k par l'intermédiaire de l'atome de N, O ou S et qui est également lié à Q; Q représente un groupe arylène ou un groupe hétérocyclique bivalent;
    R1 et R2 représentent chacun un atome d'hydrogène, un groupe carboxyle, un groupe sulfo, un groupe cyano, un groupe alkyle, un groupe cycloalkyle, un groupe aryle, un groupe hétérocyclique, un groupe carbamoyle, un groupe sulfamoyle, un groupe carbonamide, un groupe sulfonamide ou un groupe alkylsuflonyle; R3 est un atome d'hydrogène, un groupe alkyle, un groupe cycloalkyle, un groupe aryle ou un groupe hétérocyclique;
    le groupe de
    Figure imgb0419
     peut présenter la forme d'au moins un autre tautomère de celui-ci;
    R4 est un groupe acyle ou un groupe sulfonyle; R5 est un groupe qui peut être attaché à un cycle benzénique; j est un entier valant de 0 à 4; lorsque j est supérieur ou égal à 2, les deux ou plusieurs groupes R5 peuvent être identiques ou différents; et
    ledit copulant présente au moins un groupe de solubilisation dans l'eau en T, X, Q, R1, R2, R3, R4 et R5.
  8. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel ledit copulant du cyan coloré en jaune est ajouté à une couche d'émulsion d'halogénure d'argent ou à une couche intermédiaire, insensible à la lumière, adjacente à celle-ci.
  9. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel ledit copulant du cyan coloré en jaune est ajouté à une couche d'émulsion d'halogénure d'argent sensible au rouge.
  10. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel ledit copulant du cyan coloré en jaune est ajouté en quantité de 0,005 à 0,30 g/m2.
  11. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel au moins un copulant du jaune contenu dans la couche d'émulsion d'halogénure d'argent sensible au bleu est un composé représenté par la formule générale suivante (A):
    Figure imgb0420
     dans laquelle M et Q représentent chacun un groupe ou un atome qui peut être attaché au cycle benzénique; L représente un atome d'hydrogène, un atome d'halogène ou un groupe oxy aliphatique; m représente un entier valant de 0 à 5; n représente un entier valant de 0 à 4; X représente un groupe qui peut être éliminé par une réaction de couplage avec un produit d'oxydation d'un agent de développement amine primaire aromatique; lorsque m est supérieur ou égal à 2, deux ou plusieurs groupes M peuvent être identiques ou différents; lorsque n est supérieur ou égal à 2, deux ou plusieurs groupes Q peuvent être identiques ou différents; et M, Q, L ou X peuvent être une liaison simple ou un groupe de liaison bivalent, trivalent ou tétravalent formant un composé présentant 2 à 4 fractions du copulant du jaune représenté par la formule (A).
  12. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel le composé représenté par la formule (I) est incorporé dans la couche présentant la même sensibilité à la couleur que celle de la couche contenant le copulant du cyan coloré en jaune.
  13. Matériau photographique couleur à l'halogénure d'argent selon la revendication 12, dans lequel la couche contenant le composé représenté par la formule (I) est une couche sensible au rouge.
  14. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel le composé représenté par la formule (I) et le copulant du cyan coloré en jaune sont contenus dans la même couche sensible au rouge.
EP90125645A 1989-12-29 1990-12-28 Produit photographique couleur à l'halogénure d'argent contenant un coupleur cyan coloré en jaune Expired - Lifetime EP0436938B1 (fr)

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JP343587/89 1989-12-29
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DE69031679T2 (de) * 1989-12-29 1998-06-04 Fuji Photo Film Co Ltd Farbphotographisches Silberhalogenidmaterial, das einen gelb gefärbten Cyan-Kuppler enthält
JP2709226B2 (ja) * 1991-06-06 1998-02-04 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
US5656418A (en) 1994-09-12 1997-08-12 Fuji Photo Film Co., Ltd. Silver halide color photographic material
JPH08202001A (ja) 1995-01-30 1996-08-09 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料

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EP0208502A2 (fr) * 1985-07-01 1987-01-14 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière

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JPH0670711B2 (ja) * 1986-09-29 1994-09-07 富士写真フイルム株式会社 ハロゲン化銀カラ−ネガ写真感光材料
JPS63304242A (ja) * 1987-06-04 1988-12-12 Fuji Photo Film Co Ltd 熱現像カラ−感光材料
DE3815469C2 (de) * 1988-05-06 1993-12-09 Agfa Gevaert Ag Farbfotografisches Aufzeichnungsmaterial mit neuen farbigen Blaugrünkupplern

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EP0208502A2 (fr) * 1985-07-01 1987-01-14 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière

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DE69027521D1 (de) 1996-07-25

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