EP0429240B1 - Photographisches Silberhalogenidmaterial - Google Patents

Photographisches Silberhalogenidmaterial Download PDF

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Publication number
EP0429240B1
EP0429240B1 EP90312399A EP90312399A EP0429240B1 EP 0429240 B1 EP0429240 B1 EP 0429240B1 EP 90312399 A EP90312399 A EP 90312399A EP 90312399 A EP90312399 A EP 90312399A EP 0429240 B1 EP0429240 B1 EP 0429240B1
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group
represented
general formula
hydrogen atom
photographic material
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EP0429240A1 (de
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Takahiro Ogawa
Shun Takada
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Konica Minolta Inc
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Konica Minolta Inc
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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
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/3225—Combination of couplers of different kinds, e.g. yellow and magenta couplers in a same layer or in different layers of the photographic material

Definitions

  • This invention relates to a silver halide photographic material, more particularly to a silver halide photographic material that is capable of faithful color reproduction and that has improved raw stockstability.
  • Japanese Patent Application (kokai) No. 123047/1988 describes a silver halide photographic material containing a yellow coupler of the general formula (I) on a support.
  • Japanese Patent Application (kokai) No. 231451/1988 which corresponds with EP-A-0283329, describes a silver halide photographic material containing on a support a yellow and a magenta coupler represented by the general formulas (I) and (II) and a phenolic cyan coupler having a substituent ethyl group on 3-position.
  • EP-A-0 330 093 describes a silver halide color photographic material containing at least one compound of the general formulae (I), (II), (III), and (IV) as an anti-bacterial agent.
  • An object, therefore, of the present invention is to provide a silver halide photographic material that is capable of faithful color reproduction and which yet has good raw stock stability.
  • a silver halide color photographic material having on a support a yellow coupler represented by the following general formula (Y-I), a magenta coupler represented by the following general formula (M-I) and a cyan coupler represented by the following general formula (C-I), which photographic material is characterized by containing at least one of the compounds represented by the following general formulas (I), (II), (III) and (IV): where R1 is an alkyl group, a cycloalkyl group or an aryl group; R2 is an alkyl group, a cycloalkyl group, an aryl group or an acyl group; R3 is an optional substituent on the benzene ring; n is 0 or 1; X1 is a group capable of leaving upon coupling with the oxidation product of a developing agent; and Y1 is an organic group; where Z is the nonmetallic group necessary to form a nitrogenous hetero ring which may optionally have a substituents (I), (III) and (
  • the yellow coupler represented by the general formula (Y-I) Is first described.
  • alkyl group represented by R1 in the general formula (Y-I) include methyl, ethyl, isopropyl, t-butyl and dodecyl.
  • These alkyl groups may further contain substituents such as a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an acylamino group and a hydroxy group.
  • Examples of the cyaloalkyl group represented by R1 include a cyclopropyl group, a cyclohexyl group and an adamantyl group.
  • Examples of the aryl group represented by R1 include a phenyl group.
  • a branched alkyl group is preferred as R1.
  • the alkyl and cycloalkyl groups represented by R2 in the general formula (Y-I) may be exemplified by the same groups as listed for R1, and an illustrative aryl group is a phenyl group.
  • the alkyl, cycloalkyl and aryl groups represented by R2 may have the same substituents as in R1.
  • Examples of the acyl group represented by R2 include an acetyl group, a propionyl group, a butyryl group, a hexanoyl group and a benzoyl group.
  • An alkyl or aryl group is preferred as R2, with an alkyl group being more preferred.
  • a particularly preferred example of R2 is a lower alkyl group having no more than 5 carbon atoms.
  • Examples of the optional substituent on the benzene ring which is represented by R3 in the general formula (Y-I) include: a halogen atom (e.g. chlorine), an alkyl group (e.g. ethyl, i-propyl or t-butyl), an alkoxy group (e.g. methoxy), an aryloxy group (e.g. phenyloxy), an acyloxy group (e.g. methylcarbonyloxy or benzoyloxy), an acylamino group (e.g. acetamino or phenylcarbonylamino), a carbamoyl group (e.g.
  • a halogen atom e.g. chlorine
  • an alkyl group e.g. ethyl, i-propyl or t-butyl
  • an alkoxy group e.g. methoxy
  • an aryloxy group e.g. phenyloxy
  • N-methylcarbamoyl or N-phenylcarbamoyl an alkylsulfonamido group (e.g. ethylsulfonamido), an arylsulfonamido group (e.g. phenylsulfonamido), a sulfamoyl group (e.g. N-propylsulfamoyl or N-phenylsulfamoyl), and an imido group (e.g. succinylimido or glutarimido).
  • alkylsulfonamido group e.g. ethylsulfonamido
  • an arylsulfonamido group e.g. phenylsulfonamido
  • a sulfamoyl group e.g. N-propylsulfamoyl or N-phenylsulfamoyl
  • Y1 represents an organic group. While Y1 is not limited in any other way, it is preferably a group represented by the following general formula (Y-II): - J - R 4
  • R4 is an organic group containing one linkage group having a carbonyl or sulfonyl unit.
  • Illustrative groups having a carbonyl unit include an ester group, an amido group, a carbamoyl group, a ureido group and a urethane group
  • illustrative groups having a sulfonyl unit include a sulfonyl group, a sulfonamido group, a sulfamoyl group and an aminosulfonamido group.
  • J is where R5 is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
  • Examples of the alkyl group represented by R5 include methyl, ethyl, isopropyl, t-butyl and dodecyl, and examples of the aryl group represented by R5 include phenyl and naphthyl.
  • the alkyl or aryl group represented by R5 may have a substituent. While there is no particular limitation on the substituent, typical examples include: a halogen atom (e.g. chlorine), an alkyl group (e.g. ethyl or t-butyl), an aryl group (e.g. phenyl, p-methoxyphenyl or naphthyl), an alkoxy group (e.g. ethoxy or benzyloxy), an aryloxy group (e.g. phenoxy), an alkylthio group (e.g. ethylthio), an arylthio group (e.g.
  • a halogen atom e.g. chlorine
  • an alkyl group e.g. ethyl or t-butyl
  • an aryl group e.g. phenyl, p-methoxyphenyl or naphthyl
  • an alkoxy group e.g.
  • phenylthio an alkylsulfonyl group (e.g. ⁇ -hydroxyethylsulfonyl), an arylsuflonyl (e.g. phenylsulfonyl), as well as an acylamino such as an alkylcarbonylamino (e.g. acetamido) or an arylcarbonylamino (e.g. phenylcarbonylamino).
  • Other useful substituents include carbamoyl groups having an alkyl or aryl (preferably phenyl) as a substituent, such as an N-methylcarbamoyl group and an N-phenylcarbamoyl group.
  • alkylcarbonyl group such as acyl (e.g. acetyl) and an arylcarbonyl group such as benzoyl
  • sulfonamido groups such as an alkylsulfonamido (e.g. methylsulfonamido) and an arylsulfonamido (e.g. benzenesulfonamido).
  • Sulfamoyl groups having an alkyl or aryl (preferably phenyl) as a substituent can also be used as substituents and specific examples include N-methylsulfamoyl and N-phenylsulfamoyl groups.
  • the yellow coupler represented by the general formula (Y-I) may take on a his form, with two molecules bonded at site R1, R3 or Y1.
  • Y-V Compounds represented by the following general formula (Y-V) are preferred yellow couplers for use in the present invention: where R1, R2, R3 and J are the same as R1, R2 and R3 in the general formula (Y-I) and J in the general formula (Y-II); n is 0 or 1; R7 is an alkylene group, an arylene group, an alkylenearylene group, an arylenealkylene group or -A-V1-B (where A and B are each an alkylene group, an arylene group, an alkylenearylene group or an arylenealkylene group; and V1 is a divalent linkage group); R8 is an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group; P is a bonding group having a carbonyl or sulfonyl unit; and X1 is a group capable of leaving upon coupling with the oxidation product of a developing agent.
  • Examples of the alkylene group represented by R7 in the general formula (Y-V) include a methylene group, an ethylene group, a propylene group, a butylene group and a hexylene group. These alkylene groups may have substituents such as an alkyl group, as in methyl-methylene, ethyl-ethylene, 1-methyl-ethylene, 1-methyl-2-ethyl-ethylene, 2-decyl-ethylene, 3-hexyl-propylene or 1-benzyl-ethylene, or an aryl group, as in 2-phenyl-ethylene or 3-naphthyl-propylene.
  • Examples of the arylene group represented by R7 include a phenylene group and a naphthylene group.
  • Examples of the alkylarylene group represented by R7 include a methylenephenylene group, and examples of the arylenealkylene group represented by R7 include a phenylenemethylene group.
  • alkylene group, arylene group, alkylenearylene and arylenealkylene groups represented by A and B are the same as the alkylene group, arylene group, alkylenearylene group and arylenealkylene groups represented by R7 in the general formula (Y-V).
  • Examples of the divalent linkage group represented by V1 include groups such as -O- and -S-.
  • alkylene arylene, alkylenearylene and arylenealkylene groups and -A-V1-B which are represented by R7
  • an alkylene group is particularly preferred.
  • Examples of the alkyl group represented by R8 in the general formula (Y-V) include an ethyl group, a butyl group, a hexyl group, an octyl group, a dodecyl group, a hexadecyl group and an octadecyl group. These alkyl groups may be straight or branched.
  • Examples of the cycloalkyl group represented by R8 include a cyclohexyl group.
  • Examples of the aryl group represented by R8 include a phenyl group and a napthyl group.
  • Examples of the heterocyclic group represented by R8 include a pyridyl group.
  • alkyl, cycloalkyl, aryl and heterocyclic groups represented by R8 may contain substituents.
  • Illustrative substituents are not limited in any way and may include the same substituents as listed for R5, except that organic groups having a dissociative hydrogen atom having a pKa value of no more than 9.5 (e.g. a phenolic hydrogen atom) are not preferred as substituents in R8.
  • P represents a bonding group having a carbonyl or sulfonyl unit, preferably a group within the following class (Y-VI), more preferably a bonding group having a sulfonyl unit:
  • R and R' which may be the same or different each represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
  • Examples of the groups represented by R and R' may be the same as those listed for R5. Those groups may have substituents which are the same as those listed for R5.
  • a hydrogen atom is preferred as R and R'.
  • the yellow coupler represented by the general formula (Y-I) is preferably used in an amount ranging from 1 x 10 ⁇ 3 to 1 mole, more preferably from 1 x 10 ⁇ to 8 x 10 ⁇ 1 moles, per mole of silver halide.
  • magenta coupler represented by the general formula (M-I) is next described below.
  • Z represents the nonmetallic atomic group necessary to form a nitrogenous hetero ring which may have a substituent.
  • X represents a hydrogen atom or a group capable of leaving upon reaction with the oxidation product of a color developing agent.
  • R represents a hydrogen atom or a substituent. While there is no particular limitation on the substituent represented by R, typical examples include groups such as alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl and cycloalkyl.
  • halogen cycloalkenyl, alkynyl, hetero ring, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycloxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imido, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl and heterocyclic thio; as well as spiro compound residues and bridged hydrocarbon compound residues.
  • the alkyl group represented by R in the general formula (M-I) preferably contains 1 - 32 carbon atoms and it may be straight or branched.
  • the aryl group represented by R is preferably a phenyl group.
  • acylamino group represented by R examples include alkylcarbonylamino and arylcarbonylamino.
  • Examples of the sulfonamido group represented by R include alkylsulfonamido and arylsulfonamido.
  • alkyl and aryl moieties in the alkylthio and arylthio groups, respectively, represented by R may be the same as the alkyl and aryl groups listed above for R.
  • the alkenyl group represented by R preferably contains 2 - 32 carbon atoms, and the cycloalkyl group represented by R preferably contains 3 - 12 carbon atoms, more preferably 5 - 7 carbon atoms.
  • the alkenyl group may be straight or branched.
  • the cycloalkenyl group represented by R preferably contains 3 - 12 carbon atoms, more preferably 5 - 7 carbon atoms.
  • Examples of the sulfonyl group represented by R include alkylsulfonyl and arylsulfonyl; examples of the sulfinyl group represented by R include alkylsulfinyl and arylsulfinyl; examples of the phosphonyl group represented by R include alkylphosphonyl, alkoxyphosphonyl, aryloxyphosphonyl and arylphosphonyl; examples of the acyl group represented by R include alkylcarbonyl and arylcarbonyl; examples of the carbamoyl group represented by R include alkylcarbamoyl and arylcarbamoyl; examples of the sulfamoyl group represented by R include alkylsulfamoyl and arylsulfamoyl; examples of the acyloxy group represented by R include alkylcarbonyloxy and arylcarbonyloxy; examples of the carbamoyloxy group represented by R include
  • Examples of the group represented by X which is capable of leaving upon reaction with the oxidation product of a color developing agent include: a halogen atom (e.g. Cl, Br or F), as well as alkoxy, aryloxy, heterocycloxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxycarbonylthio, acylamino, sulfonamido, N-bound nitrogenous hetero ring, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, and (where R1′ has the same meaning as R; Z′ has the same meaning as Z; R2′ and R3′ each represents a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group).
  • X is a halogen
  • Examples of the nitrogenous hetero ring formed by Z or Z′ include a pyrazole ring, an imidazole ring, a triazole ring and a tetrazole ring. These rings may have substituents that are exemplified by those which are listed for R.
  • the compounds represented by the general formula (M-I) may be more specifically represented by the following general formulas (M-II) to (M-VII):
  • R1 - R8 and X have the same meanings as R and X.
  • R1 - R8 and X have the same meanings as R and X.
  • R1 - R8 and X have the same meanings as R and X.
  • R1 - R8 and X have the same meanings as R and X.
  • R1 - R8 and X have the same meanings as R and X.
  • M-VIII general formula (M-VIII) are particularly preferred: where R1, X and Z1 have the same meanings as defined for R, X and Z in the general formula (M-I).
  • magenta couplers represented by the general formulas (M-II) to (M-VII) those which are represented by the general formula (M-II) are particularly preferred.
  • R9, R10 and R11 have the same meaning as R. Any two of R9, R10 and R11, say, R9 and R10 may combine to form a saturated or unsaturated ring (e.g. cycloalkane, cycloalkene or hetero ring), and R11 may further bind to said ring to form a bridged hydrocarbon compound residue.
  • R9, R10 and R11 may combine to form a saturated or unsaturated ring (e.g. cycloalkane, cycloalkene or hetero ring), and R11 may further bind to said ring to form a bridged hydrocarbon compound residue.
  • R9 - R11 are an alkyl group
  • R9 - R11 is a hydrogen atom
  • R9 and R10 combining to form a cycloalkyl together with the room carbon atoms
  • the ring that is formed by Z in the general formula (M-I), the substituent that may be possessed by the ring formed by Z1 in the general formula (M-VIII), and R2 - R8 in the general formulas (M-II) to (M-VI) are preferably represented by the following general formula (M-X): - R 1 - SO 2 - R 2 where R1 is an alkylene group; and R is an alkyl group, a cycloalkyl group or an aryl group.
  • the alkylene group represented by R1 preferably contains at least two, more preferably 3 - 6, carbon atoms in the straight portion, and it may be either straight or branched.
  • the cycloalkyl group represented by R is preferably 5- or 6-membered.
  • magenta coupler represented by the general formula (M-I) are listed below.
  • Magenta couplers that can be used in the present invention in addition to the magenta couplers described above are the compounds identified under Nos. 1 - 4, 6, 8 - 17, 19 - 24, 26 - 43, 45 - 59, 61 - 104, 106 - 121, 123 - 162 and 164 - 223 on pages 66 - 122 in the specification of Japanese Patent Application No. 9791/1986.
  • couplers described herein can be synthesized with reference being made to Journal of the Chemical Society, Perkin I (1977), 2047 - 2052, U.S. Patent No. 3,725,067, as well as Japanese Patent Application (kokai) Nos. 99437/1984, 42045/1983, 162548/1984, 171956/1984, 33552/1985, 43659/1985, 172982/1985 and 190770/1985.
  • the coupler of the general formula (M-I) can be used in amounts that preferably range from 1 x 10 ⁇ 3 to 1 mole, more preferably from 1 x 10 ⁇ to 8 x 10 ⁇ 1 moles, per mole of silver halide.
  • the coupler of the general formula (M-I) may be used in combination with other magenta couplers.
  • the alkyl group represented by R12 may be straight or branched and it may optionally have a substituent.
  • R12 is an alkyl group having 2 - 6 carbon atoms.
  • the ballast group represented by R11 in the general formula (C-I) is an organic group having such a size and shape as to provide the coupler molecule with a sufficient degree of bulkiness to effectively prevent the coupler from diffusing from the layer where it is incorporated to another layer.
  • This ballast group is preferably represented by the following general formula: where R n1 is an alkyl group having 1 - 12 carbon atoms, and Ar is an aryl group such as phenyl that may optionally contain a substituent.
  • the cyan dye forming coupler represented by the general formula (C-I) can be used in amounts that preferably range from 1 x 10 ⁇ 3 to 1 mole, more preferably from 1 x 10 ⁇ to 8 x 10 ⁇ 1 moles, per mole of silver halide.
  • the lower alkyl group represented by R10 may be exemplified by methylene, ethylene and propylene.
  • the halogen atom represented by X may be exemplified by chlorine, bromime or iodine.
  • the alkyl group represented by X is preferably a straight or branched alkyl group having 1 - 8 carbon atoms.
  • the cycloalkyl group represented by X is preferably a cycloalkyl group having 1 - 8 carbon atoms.
  • the aryl group represented by X is preferably a phenyl or naphthyl group.
  • the alkoxycarbonyl group preferably has 1 - 5 carbon atoms.
  • Each of the groups listed above may have a substituent such as an alkyl group having 1 - 4 carbon atoms, a halogen atom, a hydroxyl group, a sulfo group, a nitro group, an amino group, a cyano group, a carboxyl group or a phenyl group.
  • a substituent such as an alkyl group having 1 - 4 carbon atoms, a halogen atom, a hydroxyl group, a sulfo group, a nitro group, an amino group, a cyano group, a carboxyl group or a phenyl group.
  • the alkyl or alkenyl group represented by R20 in the general formula (II) preferably has 1 - 36 carbon atoms, more preferably 1 - 18 carbon atoms.
  • the cycloalkyl group represented by R20 preferably has 3 - 12 carbon atoms, more preferably 3 - 6 carbon atoms.
  • the alkyl, alkenyl, cycloalkyl, aralkyl, aryl and heterocyclic groups represented by R20 may have substituents which are selected from among the following: a halogen atom, nitro, cyano, thiocyano, aryl, alkoxy, aryloxy, carboxy, sulfoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, sulfo, acyloxy, sulfamoyl, carbamoyl, acylamino, diacylamino, ureido, thioureido, urethane, thiourethane, sulfonamido, hetero ring, arylsulfonyloxy, alkylsulfonyloxy, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkyl
  • the alkyl group represented by R30 and R40 in the general formula (II) preferably contains 1 - 18 carbon atoms, more preferably 1 - 9 carbon atoms.
  • the cycloalkyl group represented by R30 and R40 preferably has 3 - 12 carbon atoms, more preferably 3 - 6 carbon atoms.
  • the alkyl, cycloalkyl and aryl groups represented by R30 and R40 may have substituents such as halogen, nitro, sulfone, aryl and hydroxy.
  • the benzene ring may have substituents such as hydrogen, halogen, alkyl, alkoxy, cyano and nitro.
  • the lower alkyl having 1 - 5 carbon atoms which is represented by R50, R60 and R70 in the general formula (III) and the hydroxymethyl group represented by R70 may have a substituent.
  • R80 is preferably a hydrogen atom
  • R90 is preferably a hydrogen atom, an alkyl group having 1 - 3 carbon atoms, an amino group, a nitro group, a sulfo group, a halogen atom, or a hydroxy group
  • m is preferably 1
  • the thiazolyl group represented by Z is preferably
  • Some of the compounds represented by the general formulas (I), (II), (III) and (IV) are known as preservatives for hydrophilic colloids in silver halide photographic materials. Part of the compounds represented by the general formula (I) are described in Japanese Patent Application (kokai) Nos. 22847/1984 and 257747/1988; part of the compounds represented by the general formula (II) are described in Japanese Patent Application (kokai) Nos. 27424/1979, 131929/1984, 142543/1984, 166343/1983, 131929/1984, 142543/1984 and 226343/1984; part of the compounds represented by the general formula (III) are described in Japanese Patent Application Nos. 119547/1985 and 231936/1987; and part of the compounds represented by the general formula (IV) are described in Japanese Patent Application (kokai) Nos. 274944/1988 and 263938/1985.
  • One or more members that are selected from among the compounds illustrated above may be used in the present invention. These compounds are well known in the art and are commercially available from ICI, Japan, Dainippon Ink & Chemicals, Inc., Rohm & Haas, Japan, San-ai oil Co., Ltd..
  • the amounts in which the compounds of the general formulas (I), (II), (III) and (IV) are used are not limited to any particular values but they are preferably in the range of 1 x 10 ⁇ 4 to 1 x 10 ⁇ g/m. Those compounds may be incorporated in either silver halide emulsion layers or non-emulsion layers or both. There also is no particular limitation on the method by which those compounds are added.
  • Compounds such as dye forming couplers to be used in the silver halide photographic material of the present invention are usually dissolved in high-boiling point ( ⁇ ca. 150°C) organic solvents or water-insoluble high-molecular weight compounds, optionally in combination with low-boiling point and/or water-insoluble organic solvents, and the resulting solutions are emulsified or dispersed in hydrophilic binders such as aqueous solutions of gelatin with the aid of surfactants, followed by addition to a hydrophilic colloidal layer of interest.
  • hydrophilic binders such as aqueous solutions of gelatin with the aid of surfactants, followed by addition to a hydrophilic colloidal layer of interest.
  • the low-boiling point organic solvent may be removed simultaneously with the step of dispersion.
  • the high-boiling point organic solvents to be used in the present invention are preferably those compounds which have dielectric constants of no more than 6.5 and which may be exemplified by esters (e.g. phthalate esters and phosphate esters), organic acid amides, ketones and hydrocarbon compounds that have dielectric constants of no more than 6.5. More preferred are those high-boiling point organic solvents which have dielectric constants of 1.9 - 6.5 and vapor pressures of up to 0.5 mmHg at 100°C. Among those organic solvents, phthalate esters and phosphate esters are particularly preferred. The most preferred are dialkyl phthalates having an alkyl group with at least 9 carbon atoms. Two or more high-boiling point organic solvents may be used in admixture.
  • dielectric constant means a dielectric constant at 30°C.
  • the high-boiling point organic solvents described above are generally used in amounts ranging from 0 to 400 wt% of coupler, preferably from 10 to 100 wt% of coupler.
  • the silver halide photographic material of the present invention may be a color negative or positive film or a color paper.
  • the advantage of the present invention is particularly noticeable when said photographic material is used as a color paper for direct viewing.
  • Color papers and other examples of the silver halide photographic material of the present invention may be monochromatic or multicolored.
  • Silver halides that can be used in the silver halide photographic material of the present invention include silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride and any other types that are customarily used in silver halide emulsions.
  • the silver halide emulsion to be used in the present invention may be chemically sensitized by any known technique such as sulfur sensitization, selenium sensitization, reduction sensitization or noble metal sensitization.
  • the silver halide emulsion to be used in the present invention may be optically sensitized to have sensitivity in a desired wavelength range using dyes that are known as spectral sensitizers in the art.
  • Gelatin is used advantageously as a binder (or protective colloid) in the silver halide photographic material of the present invention.
  • Other hydrophilic colloids may also be used, such as gelatin derivatives, graft polymers of gelatin and other high-molecular weight compounds, proteins, sugar derivatives, cellulosic derivatives, and synthetic hydrophilic high-molecular weight materials such as homopolymers and copolymers.
  • Photographic emulsion layers and other hydrophilic colloidal layers in the silver halide photographic material of the present invention are hardened by using, either independently or in combination, those hardeners which crosslink the molecules of binders (or protective colloids) to increase the film strength.
  • Hardeners are desirably added in amounts that are capable of hardening photographic materials to such an extent that there is no need to incorporate hardeners in processing solutions. If desired, hardeners may be incorporated in processing solutions.
  • the silver halide photographic material of the present invention may have uv absorbers contained in protective layers, inter mediates and other hydrophilic colloidal layers in order to prevent fogging due to the discharge of static buildup that occurs in the photographic material on account of triboelectrification or other phenomena, as well as to prevent image deterioration due to ultraviolet radiation.
  • the silver halide photographic material of the present invention may be provided with auxiliary layers such as a filter layer, an anti-halo layer and an anti-irradiation layer. These layers and/or emulsion layers may contain dyes that flow out of the color photographic material during development or which are bleachable.
  • Silver halide emulsion layers and/or other hydrophilic colloidal layers in the silver halide photographic material of the present invention may have matting agents incorporated therein in order to reduce the gloss of the photographic material, enhance its writability or to prevent one unit of the photographic material from sticking to another.
  • the silver halide photographic material of the present invention may have lubricants incorporated therein in order to reduce sliding friction.
  • the silver halide photographic material of the present invention may have antistats incorporated therein in order to prevent static buildup.
  • Antistats may be incorporated in an anti static layer on the side of a support where no emulsion layers are provided, or they may be incorporated in emulsion layers and/or protective colloids on the side of the support where emulsion layers are provided.
  • Photographic emulsion layers and/or other hydrophilic colloidal layers in the silver halide photographic material of the present invention may incorporate various surfactants for achieving multiple purposes including improved coatability, prevention of static buildup, improved slip property, efficient emulsification and dispersion, anti-blocking and improved photographic characteristics such as accelerated development, contrastiness and increased sensitivity.
  • Photographic emulsion layers and other layers in the silver halide photographic material of the present invention are coated various supports including: flexible reflective supports such as baryta paper, paper laminated with ⁇ -olefinic polymers, paper supports that permit ⁇ -olefinic polymer layer to be readily released, and synthetic papers; reflective supports having white pigments coated on synthetic or semi-synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate and polyamide; and rigid supports such as glass, metal and ceramic sheets. Reflective supports as thin as 120 - 160 ⁇ m can also be used.
  • the supports to be used in the present invention may be of a reflection or transmission type.
  • white pigments may be incorporated in the supports or the latter may be coated with a hydrophilic colloidal layer containing a white pigment.
  • White pigments may be inorganic or organic, with inorganic white pigments being preferred.
  • Illustrative inorganic white pigments include alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, silicas such as fine particulate silicic acid and synthetic silicates, as well as calcium silicate, alumina, alumina hydrates, titanium oxide, zinc oxide, talc and clay. Barium sulfate and titanium oxide are preferred.
  • the support of the silver halide photographic material or the present invention may be subjected to surface treatments such as corona discharge, irradiation with ultraviolet rays and flame treatment before emulsion layers and other photographic layers are applied either directly or with one or more subbing layers being provided in order to improve various properties such as adhesion to the surface of the support, antistatic property, dimensional stability, friction resisting property, hardness, anti-halo property, and friction characteristics.
  • surface treatments such as corona discharge, irradiation with ultraviolet rays and flame treatment before emulsion layers and other photographic layers are applied either directly or with one or more subbing layers being provided in order to improve various properties such as adhesion to the surface of the support, antistatic property, dimensional stability, friction resisting property, hardness, anti-halo property, and friction characteristics.
  • Thickeners may be used in order to improve the coatability of silver halide emulsions in the production of the silver halide photographic material of the present invention.
  • Particularly advantageous coating methods are extrusion coating and curtain coating which are capable of simultaneous application of two or more layers.
  • color developing agents that are extensively used in various color photographic processes may be incorporated in color developing solutions for processing the silver halide photographic material of the present invention.
  • the color developed photographic material of the present invention may be immediately processed with processing solutions having a bleaching capability; alternatively, it may be processed with a "bleach-fixing solution" which has both bleaching and fixing capabilities.
  • Metal complex salts of organic acids are typically used as bleaching agents in the bleaching step.
  • Paper supports each laminated with polyethylene on one side and with TiO2 containing polyethylene on the other side were coated with seven layers (see below) to prepare samples of multi-layered silver halide color photographic material.
  • the coating solutions for the seven layers were prepared in the following manner.
  • a yellow coupler (26.7 g; see Table 2), 10.0 g of a dye image stabilizer (ST-1), 6.67 g of ST-2, 0.67 g of an anti-stain agent (HQ-1), 6.67 g of a high-boiling point organic solvent (DNP) and 60 ml of ethyl acetate were mixed to form a solution.
  • the solution was emulsified and dispersed in 220 ml of a 10% aqueous solution of gelatin containing 7 ml of a 20% solution of surfactant (SU-1) by means of an ultrasonic: homogenizer, to thereby prepare a yellow coupler dispersion.
  • This dispersion was mixed with a blue-sensitive silver halide emulsion (silver content, 8.67 g; for the method of its preparation, see below) to prepare the coating solution for the first layer.
  • the coating solutions for the second to the seventh layers were prepared in substantially the same manner. Preservatives were added as required.
  • the layer arrangement is shown in Table 1 below.
  • DOP dioctyl phthalate DNP dinonyl phthalate
  • DIDP diisodecyl phthalate PVP polyvinylpyrrolidone compound H-1 shown below was used as a hardener.
  • Solutions A and B were added simultaneously over 30 minutes to 1,000 ml of a 2% aqueous solution of gelatin held at 40°C, with the pAg and pH being held at 6.5 and 3.0, respectively. Further, solutions C and D (see below) were added simultaneously over 180 minutes, with the pAg and pH being controlled at 7.3 and 5.5, respectively.
  • the pAg was controlled by the method described in Japanese Patent Application (kokai) No. 45437/1984 and the pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.
  • the emulsion EMP-1 was chemically ripened with the following compounds at 50°C for 90 minutes to prepare a blue-sensitive silver halide emulsion (EmA).
  • EmA blue-sensitive silver halide emulsion
  • Sodium thiosulfate 0.8 mg/mol AgX
  • Chloroauric acid 0.5 mg/mol AgX Stabilizer (SB-5) 6 x 10 ⁇ 4 mol/mol AgX Sensitizing dye (D-1) 5 x 10 ⁇ 4 mol/mol AgX
  • EMP-2 The procedure for preparing EMP-1 was repeated except that the times over which solutions A/B and solutions C/D were added were varied. Thus, a monodispersed cubic emulsion EMP-2 was prepared: it had an average grain size of 0.43 ⁇ m, a variation coefficient ( ⁇ /r) of 0.08 and a AgCl content of 99.5 mol%.
  • the emulsion EMP-2 was chemically ripened with the following compounds at 55°C for 120 minutes to prepare a green-sensitive silver halide emulsion (EmB).
  • EmB green-sensitive silver halide emulsion
  • Sodium thiosulfate 1.5 mg/mol AgX
  • Chloroauric acid 1.0 mg/mol AgX Stabilizer (SB-5) 6 x 10 ⁇ 4 mol/mol AgX Sensitizing dye (D-2) 4 x 10 ⁇ 4 mol/mol AgX
  • EMP-1 The procedure for preparing EMP-1 was repeated except that the times over which solutions A/B and solutions C/D were added were varied.
  • a monodispersed cubic emulsion EMP-3 was prepared; it had an average grain size or 0.50 ⁇ m, a variation coefficient ( ⁇ /r) of 0.08 and a AgCl content of 99.5 mol%.
  • the emulsion EMP-3 was chemically ripened with the following compounds at 60°C for 90 minutes to prepare a red-sensitive silver halide emulsion (EmC).
  • Ethylenediaminetetraacetic acid iron (II) ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aq. sol.) 100 ml Ammonium thiosulfate (40% aq. sol.) 27.5 ml Water to make 1,000 ml pH adjusted to 5.7 with potassium carbonate or glacial acetic acid
  • Sensitivity reduction % sensitivity before storage - sensitivity after storage sensitivity before storage x 100
  • the samples of the present invention achieved good color reproduction; furthermore, they experienced substantially small reduction in the sensitivity of blue-sensitive layer when they were stored as raw stock.
  • Example 2 Additional samples were prepared as in Example 1 except that the following AgClBr emulsions were used as blue-, green- and red-sensitive emulsions.
  • a AgClBr emulsion having an average grain size of 0.7 ⁇ m and a AgBr content of 90 mol% was subjected to optimum sensitization with sodium thiosulfate at 57°C, and a sensitizing dye (D-1) and astabilizing agent (Z-1) were added,
  • a AgClBr emulsion having an average grain size of 0.5 ⁇ m and a AgBr content of 70 mol% was subjected to optimum sensitization with sodium thiosulfate at 57°C, and a sensitizing dye (D-2) and a stabilizer (Z-1) were added.
  • a AgClBr emulsion having an average grain size of 0.4 ⁇ m and a AgBr content of 60 mol% was subjected to optimum sensitization with sodium thiosulfate, a sensitizing dye (D-3) and a phenolic resin at 60°C, and a stabilizer (Z-1) was added.
  • Ethylenediaminetetraacetic acid iron (II) ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aq. sol.) 100 ml Ammonium sulfite (40% aq. sol.) 27.5 ml Water to make 1,000 ml pH adjusted to 7.1 with potassium carbonate or glacial acetic acid
  • the samples prepared in accordance with the present invention were satisfactory in terms of both raw stock stability and color reproduction.
  • emulsion A Using the grains in emulsion A as core grains, an aqueous solution of silver nitrate and an aqueous solution of sodium chloride were added simultaneously by a double-jet method with the temperature and pAg being controlled ad 55°C and 6, respectively, thereby obtaining a cubic monodispersed core/shell emulsion EM-1 having an average grain size of 0.6 ⁇ m (the spread of grain size distribution* was 8%).
  • Spread of grain size distribution (%) standard deviation of grain size average grain size ⁇ 100
  • the coat weight is expressed by g/m.
  • the coat weight is expressed in terms of silver.
  • Second layer (intermediate layer)
  • Green-sensitive emulsion prepared by spectral sensitization after addition of green-sensitive sensitizing dye (GD-1) to EM-1 0.27 Gelatin 1.3 Magenta coupler (M-23) 0.24 Image stabilizer (ST-3) 0.20 Solvent (DOP) 0.32
  • Blue-sensitive emulsion prepared by spectral sensitization after addition of blue-sensitive sensitizing dye (BD-1) to EM-1 0.50 Gelatin 1.35 Yellow coupler (Y-6) 0.90 Image stabilizer (ST-1) 0.30 Solvent (DNP) 0.20 Preservative (9) 1 x 10 ⁇ 3
  • UV absorber UV-1) 0.10 UV absorber (UV-2) 0.28 Solvent (DNP) 0.12
  • Diethylenetriaminepentaacetic acid iron (II) ammonium salt 90 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aq. sol.) 180 ml Ammonium sulfite (40% aq. sol.) 27.5 ml 3-Mercapto-1,2,4-triazole 0.15 g Water to make 1,000 ml pH adjusted to 7.1 with potassium carbonate or glacial acetic acid
  • the samples prepared in accordance with the present invention were satisfactory in terms of both raw stock stability and color reproduction.
  • the present invention provides a silver halide photographic material that achieves faithful color reproduction and which yet has good raw stock stability.

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Claims (8)

  1. Farbphotographisches Silberhalogenid-Aufzeichnungsmaterial mit einem Schichtträger und einem darauf befindlichen Gelbkuppler der Formel (Y-I), Purpurrotkuppler der Formel (M-I) und Blaugrünkuppler der Formel (C-I), welches zusätzlich mindestens.eine Verbindung der Formeln (I), (II), (III) und (IV) enthält:
    Figure imgb0156
     worin bedeuten:
    R₁ eine Alkylgruppe, eine Cycloalkylgruppe oder eine Arylgruppe;
    R₂ eine Alkylgruppe, eine Cycloalkylgruppe, eine Arylgruppe oder eine Acylgruppe;
    R₃ einen möglichen Substituenten am Benzolring; n = 0 oder 1;
    X₁ eine bei der Kupplung mit dem Oxidationsprodukt einer Entwicklerverbindung abspaltbare Gruppe und
    Y 1 eine organische Gruppe;
    Figure imgb0157
     worin bedeuten:
    Z diejenige nichtmetallische Gruppe, die zur Bildung eines gegebenenfalls substituierten stickstoffhaltigen Heterorings erforderlich ist;
    X ein Wasserstoffatom oder eine bei der Reaktion mit dem Oxidationsprodukt einer Farbentwicklerverbindung abspaltbare Gruppe und
    R ein Wasserstoffatom oder einen Substituenten;
    Figure imgb0158
     worin bedeuten:
    R₁₁ eine Ballastgruppe;
    R₁₂ eine Alkylgruppe mit 2 oder mehr Kohlenstoffatomen und
    Z₁ ein Wasserstoffatom oder ein(e) bei der Reaktion mit dem Oxidationsprodukt einer Farbentwicklerverbindung abspaltbare(s) Atom oder Gruppe;
    Figure imgb0159
     worin bedeuten:
    R₁₀ eine Niedrigalkylengruppe;
    M ein Wasserstoffatom, ein Alkalimetall oder eine Alkylgruppe;
    X ein Halogenatom, eine Alkylgruppe, eine Cycloalkylgruppe, eine Arylgruppe, eine Carboxylgruppe, eine Aminogruppe, eine Hydroxylgruppe, eine Sulfogruppe, eine Nitrogruppe oder eine Alkoxycarbonylgruppe;
    n = 0 oder 1 und
    m eine ganze Zahl von 1 bis 5;
    Figure imgb0160
     worin bedeuten:
    R₂₀ ein Wasserstoffatom, eine Alkylgruppe, eine Cycloalkylgruppe, eine Alkenylgruppe, eine Aralkylgruppe, eine Arylgruppe, eine Alkoxygruppe, -CONHR mit R gleich einer Alkyl-, Aryl-, Alkylthio-, Arylthio-, Alkylsulfonyl- oder Arylsulfonylgruppe oder eine heterocyclische Gruppe und
    R₃₀ und R₄₀ jeweils ein Wasserstoffatom, ein Halogenatom, eine Alkylgruppe, eine Cycloalkylgruppe, eine Arylgruppe, eine heterocyclische Gruppe, eine Cyanogruppe, eine Alkylthiogruppe, eine Arylthiogruppe, eine Alkylsulfoxidgruppe, eine Alkylsulfonylgruppe oder eine Alkylsulfinylgruppe, wobei R₃₀ und R₄₀ zusammen auch einen gegebenenfalls substituierten Benzolring bilden können;
    Figure imgb0161
     worin bedeuten:
    R₅₀ und R₆₀ jeweils ein Wasserstoffatom, ein Halogenatom, eine Niedrigalkylgruppe mit 1 bis 5 Kohlenstoffatom(en) oder eine Hydroxymethylgruppe und R₇₀ ein Wasserstoffatom oder eine Niedrigalkylgruppe mit 1 bis 5 Kohlenstoffatom(en);
    Figure imgb0162
     worin bedeuten:
    R₈₀ ein Wasserstoffatom, eine Alkylgruppe oder eine Arylgruppe;
    R₉₀ ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Nitrogruppe, eine Carboxylgruppe, eine Sulfogruppe, eine Sulfamoylgruppe, eine Hydroxygruppe, eine Halogenatom, eine Alkoxygruppe oder eine Thiazolylgruppe;
    m = 0 oder 1 und
    Z die zur Bildung eines Thiazolylrings erforderliche Atomgruppe.
  2. Photographisches Aufzeichnungsmaterial nach Anspruch 1, wobei es sich bei dem Gelbkuppler der allgemeinen Formel (Y-I) um eine Verbindung der folgenden allgemeinen Formel (Y-V) handelt:
    Figure imgb0163
     worin R₁, R₂, R₃, X₁ und n die Bedeutung von R₁, R₂, R₃, X₁ und n in der allgemeinen Formel (Y-I) aufweisen,
    J für
    Figure imgb0164
     mit R₅ gleich einem Wasserstoffatom, einer Alkylgruppe, einer Arylgruppe oder einer heterocyclischen Gruppe steht;
    R₇ eine Alkylengruppe, eine Arylengruppe, eine Alkylenarylengruppe, eine Arylenalkylengruppe oder -A-V₁-B mit A und B jeweils gleich einer Alkylengruppe, Arylengruppe, Alkylenarylengruppe oder Arylenalkylengruppe und V₁ gleich einer zweiwertigen verbindenden Gruppe darstellt;
    R₈ einer Alkylgruppe, Cycloalkylgruppe, Arylgruppe oder heterocyclischen Gruppe entspricht und P eine verbindende Gruppe mit einer Carbonyl- oder Sulfonyleinheit bedeutet.
  3. Photographisches Aufzeichnungsmaterial nach Anspruch 1 oder 2, wobei es sich bei dem Purpurrotkuppler der allgemeinen Formel (M-I) um eine Verbindung der folgenden allgemeinen Formel (M-II):
    Figure imgb0165
     worin R₁, R₂ und X die Bedeutung von R und X in der allgemeinen Formel (M-I) aufweisen, handelt.
  4. Photographisches Aufzeichnungsmaterial nach Ansprüchen 1 bis 3, wobei R₁₂ in der allgemeinen Formel (C-I) für eine Alkylgruppe mit 2 bis 6 Kohlenstoffatomen steht und R₁₁ eine Gruppe
    Figure imgb0166
     mit Rn1 gleich einer Alkylgruppe mit 1 bis 12 Kohlenstoffatom(en) und Ar gleich einer Arylgruppe bedeutet.
  5. Photographisches Aufzeichnungsmaterial nach einem der vorhergehenden Ansprüche, wobei die Verbindungen der allgemeinen Formeln (I), (II), (III) und (IV) in Mengen von 1 x 10⁻⁴ bis 1 x 10⁻ g/m eingesetzt sind.
  6. Photographisches Aufzeichnungsmaterial nach einem der vorhergehenden Ansprüche, wobei zum Auflösen farbstoffbildender Kuppler und sonstiger Verbindungen ein hochsiedendes organisches Lösungsmittel verwendet wird.
  7. Photographisches Aufzeichnungsmaterial nach Anspruch 6, wobei das hochsiedende organische Lösungsmittel aus Estern, Amiden, Ketonen und Kohlenwasserstoffverbindungen mit Dielektrizitätskonstanten von nicht mehr als 6,5 ausgewählt ist.
  8. Photographisches Aufzeichnungsmaterial nach einem der vorhergehenden Ansprüche, bei welchem es sich um ein Farbpapier zur direkten Betrachtung handelt.
EP90312399A 1989-11-15 1990-11-14 Photographisches Silberhalogenidmaterial Expired - Lifetime EP0429240B1 (de)

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JP298092/89 1989-11-15

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EP0628866A1 (de) * 1993-06-04 1994-12-14 Konica Corporation Lichtempfindliches, farbphotographisches Silberhalogenid-Material
JPH09166853A (ja) 1995-12-15 1997-06-24 Konica Corp ハロゲン化銀カラー写真感光材料の画像形成方法
FR2786889B1 (fr) 1998-12-03 2001-02-02 Eastman Kodak Co Procede pour empecher la croissance des micro-organismes dans les dispersions photographiques
US6448281B1 (en) 2000-07-06 2002-09-10 Boehringer Ingelheim (Canada) Ltd. Viral polymerase inhibitors
EP2335700A1 (de) 2001-07-25 2011-06-22 Boehringer Ingelheim (Canada) Ltd. Hepatitis C Virus Polymerase Inhibitoren mit heterobicylischer Struktur
SI1718608T1 (sl) 2004-02-20 2013-11-29 Boehringer Ingelheim International Gmbh Inhibitorji virusne polimeraze
WO2007019674A1 (en) 2005-08-12 2007-02-22 Boehringer Ingelheim International Gmbh Viral polymerase inhibitors
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US6911302B2 (en) 2002-07-11 2005-06-28 Eastman Kodak Company Coating composition for photographic materials

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