EP0326161B1 - Matériaux photographiques couleurs à l'halogénure d'argent - Google Patents

Matériaux photographiques couleurs à l'halogénure d'argent Download PDF

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Publication number
EP0326161B1
EP0326161B1 EP19890101457 EP89101457A EP0326161B1 EP 0326161 B1 EP0326161 B1 EP 0326161B1 EP 19890101457 EP19890101457 EP 19890101457 EP 89101457 A EP89101457 A EP 89101457A EP 0326161 B1 EP0326161 B1 EP 0326161B1
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EP
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Prior art keywords
group
silver halide
aliphatic
aromatic
substituted
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German (de)
English (en)
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EP0326161A3 (en
EP0326161A2 (fr
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Yasuhito Fuji Photo Film Co. Ltd. Momoki
Shigeru Fuji Photo Film Co. Ltd. Ohno
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • 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
    • G03C7/34—Couplers containing phenols
    • G03C7/346—Phenolic couplers
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/83—Organic dyestuffs therefor
    • G03C1/832—Methine or polymethine dyes

Definitions

  • This invention relates to silver halide color photographic materials, particularly to silver halide color photographic materials for prints, and more particularly to silver halide photographic materials which give stable color images in long storage, sharp color image quality (which is called sharpness hereinafter), high photographic sensitivity and low photographic fog.
  • Silver halide color photographic materials are usually spectrally sensitized by adding spectral sensitizers to silver halides according to the subtractive primary colors.
  • a yellow dye-forming coupler, a magenta dye-forming coupler and a cyan dye-forming coupler are contained in the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer, respectively.
  • the silver halide color photographic materials are then processed with a color developing solution comprising an aromatic primary amine color developing agent and then with a bleach-fix bath to obtain an image.
  • the resulting color image is not always stable to light, heat or moisture.
  • the cyan dye image has a larger dark discoloration caused by heat or moisture than both the yellow dye image and the magenta dye image, which changes the color balance. This is a great problem in practical use (for example, the print is turned reddish-brown when preserved in an album).
  • JP-A-56-80045 (GB-B-2,066,494; the term “JP-A” as used herein means an "unexamined published Japanese patent application")
  • JP-A-56-104333 (GB-B-2,068,943)
  • JP-B-57-37857 (US-A-4,333,999)
  • JP-B as used herein means an "examined Japanese patent publication”
  • JP-A-58-105229 US-A-4,430,423
  • JP-A-60-24547 (US-A-4,565,777)
  • couplers substituted at the 2 and 5 positions of the benzene ring of phenol with acyl amino groups i.e., "2,5-diacylaminophenolic” couplers
  • phenolic cyan couplers are quite useful for producing color photographic images which are very fast against heat and are preserved well.
  • the photographic materials using these couplers are stable in processing and excellent in reproducing colors, particularly because of preservation of cyan density in bleach-fix processing.
  • phenolic couplers are favorable compounds to be used as the cyan-dye-forming couplers in color photographic materials.
  • the standard conditions for selecting the cyan couplers include, for example, light resistance, spectral absorption characteristics of dyes, and effect on photographic properties. Cyan couplers which satisfy all these properties are desired.
  • One is to prevent unsharpening of an image caused by the halation caused by reflecting the light scattered during or after transmission through silver halide emulsion layers on the interface between a silver halide emulsion and a base or on the surface of a photographic material opposite to silver halide emulsion layers and inducing again the reflecting light into the silver halide emulsion layers; and the other is to prevent unsharpening of an image caused by the irradiation caused by the scattering of light on the surface of silver halide in the silver halide emulsion layers.
  • Silver halide color photographic materials for prints usually employ the method of preventing irradiation.
  • silver halide emulsion layers are colored.
  • these layers to be colored consist of hydrophilic colloids, therefore, water-soluble dyes are usually contained in the layers for coloring.
  • the dyes should satisfy the following conditions.
  • the oxonol dyes having two pyrazolone nuclei have been used for coloring photographic materials as useful dyes which are decolored in a developing solution containing sulfite and exert little harmful influence on photographic emulsions.
  • JP-A-60-225155 discloses that photographic materials prepared by combining 2,5-diacylaminophenolic couplers and specific oxonol dyes have high resistance to dark discoloration, excellent sharpness, good latent image stability and high whiteness (low fog), but it has been found that the above combinations are not satisfactory in respect of sharpness and fog.
  • a method for processing light-sensitive silver halide color photographic materials comprising carrying out processing of a light-sensitive silver halide color photographic material with a water washing-substitutive stabilizing solution which has been subjected to concentration regulating treatment in the presence of a compound of the following general formula: wherein R6 and R6′ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; R7 and R7′ each represent a hydroxy group, an alkoxy group, a substituted alkoxy group, a cyano group, a trifluoromethyl group, -COOR8, -CONHR8, -NHCOR8, an amino group, a substituted amino group substituted with an alkyl group having 1 to 4 carbon atoms or a cyclic amino group represented by the formula: (where p and q each represent 1 or 2, and X represents an oxygen atom, a sulfur atom or -CH2- ); R8 represents
  • EP-A- 0 186 169 thus suggests an improved system for overcoming problems occurring in a processing method wherein a stabilizing solution is used instead of a water washing process.
  • EP-A- 0 322 702 which represents a state of the art by virtue of Article 54 (3)
  • EPC describes a direct positive photographic material having at least one previously-not-fogged internal latent image-type silver halide emulsion layer on a support having incorporated therein an irradiation-preventing dye and a cyan coupler for preventing a change of photographic performance during preservation and giving images of improved sharpness.
  • a silver halide color photographic material comprising a support having at least one silver halide color photographic emulsion layer coated thereon and containing at least one compound represented by the following general formula (I) and at least one compound represented by the following general formula (II) in at least one hydrophilic colloid layer provided on the support: wherein each of R1 and R2 represents -COOR5 or each of R3 and R4 represents hydrogen or an alkyl group; each of R5 and R6 represents hydrogen, an alkyl group, an aryl group, or R5 and R6 together form a 5- or 6-membered ring; each of Q1 and Q2 represents an aryl group (2- or 3-valent); each of X1 and X2 represents a divalent bonding group or a bond; each of Y1 and Y2 represents a sulfonic acid group or a carboxylic acid group; each of L1, L2 and L3 represents a methine group; each of m1 and
  • alkyl group or alkyl moiety
  • aryl group or aryl moiety
  • aromatic group each represents substituted and unsubstituted.
  • each of R1 and R2 represents -COOR5 or each of R3 and R4 represents hydrogen or an alkyl group (e.g., methyl, ethyl); each of R5 and R6 represents hydrogen, an unsubstituted alkyl group (e.g., methyl, ethyl, isopropyl, butyl); a substituted alkyl group [examples of the substituents include a sulfo group (e.g., sufomethyl, sulfoethyl), a carboxyl group (e.g., carboxymethyl, carboxyethyl), a hydroxy group (e.g., hydroxyethyl, 1,2-dihydroxypropyl), an alkoxy group (e.g., methoxyethyl, ethoxyethyl), a halogen atom [e.g., fluorine, chlorine, bromine (e.g., 2-chloroethy
  • R1 and R2 represent -COOR5 and R5 represents hydrogen
  • R1 and R2 represent carboxyl groups, which may form not only a free acid but a salt (e.g., sodium salt, potassium salt, ammonium salt, tetraammonium salt).
  • R5 and R6 may form a 5 to 6 membered ring (e.g., morpholino, piperidino).
  • Each of Q1 and Q2 represents a 2- or 3-valent unsubstituted aryl group (e.g., phenyl, naphthyl), a 2- or 3-valent substituted phenyl group [examples of the substituents include a C1 to C4 alkyl group, a C1 to C4 alkoxy group, a halogen atom (chlorine, bromine, fluorine), an aliphatic or aromatic carbamoyl group (e.g., ethylcarbamoyl), an aliphatic or aromatic sulfamoyl group (e.g., ethylsulfamoyl), a cyano group, a nitro group, an alkylsulfonyl group (e.g., methanesulfonyl), an aryls
  • Each of X1 and X2 represents a divalent bonding group and more particularly, -O-, -SO2, or a bond, wherein R7 represents hydrogen, a C1 to C5 alkyl group, or a C1 to C5 (total) substituted alkyl group
  • R7 represents hydrogen, a C1 to C5 alkyl group, or a C1 to C5 (total) substituted alkyl group
  • substituents include a C1 to C3 alkoxy group, a sulfo group (e.g., sulfoethyl, sulfopropyl), a carboxyl group (e.g., carboxylethyl), a cyano group, a hydroxy group (e.g., hydroxyethyl), an amino group unsubstituted or substituted with an alkyl group such as a methyl group and an ethyl group, an aliphatic or aromatic sulfonamido group
  • Each of Y1 and Y2 represents a sulfonic acid group or a carboxylic acid group, which may form not only a free acid but a salt (e.g., sodium salt, potassium salt, ammonium salt, tetraammonium salt).
  • Each of L1, L2 and L3 represents a methine group, or a substituted methine group (where the substituents include a methyl group, an ethyl group and a phenyl group).
  • Each of m1 and m2 represents 1 or 2; n represents 0, 1, or 2; each of p1 and p2 represents 0, 1, 2, 3 or 4; each of s1 and s2 represents 1 or 2.
  • each of R3 and R4 is preferably hydrogen or a methyl group; each of R5 and R6 is preferably hydrogen, a C1 to C4 alkyl group, a C1 to C6 substituted alkyl group [examples of the substituents preferably include a sulfo group, a carboxyl group, a hydroxy group, a C1 to C2 alkoxy group, a chlorine atom, a cyano group, an amino group, and a C1 to C4 alkylamino group], a phenyl group or a substituted phenyl group [examples of the substituents preferably include a sulfo group, a carboxyl group, a C1 to C4 alkoxy group, a chlorine atom, a cyano group, a C1 to C4 alkyl group, an amino group, and a C1 to C4 alkyl group, an amino group, and a C1 to C4 alkyl group, an amino group
  • R5 and R6 preferably form a 5-membered ring or a 6-membered ring (e.g., a morpholino ring, a pyrolidine ring, a piperidine ring).
  • Each of Q1 and Q2 preferably is a phenylene group, a substituted phenylene group [where the substituents preferably include a C1 to C4 alkyl group, a C1 to C4 alkoxy group, a halogen atom (e.g., chlorine, bromine, fluorine) and a C1 to C4 dialkylamino group].
  • each set of groups may be the same or different.
  • Each of X1 and X2 preferably represents -O-, or a bond wherein R7 preferably represents hydrogen, a C1 to C5 alkyl group, or a C1 to C5 substituted alkyl group [examples of the substituents include a C1 to C3 alkoxy group, a cyano group, a hydroxy group and a C1 to C4 alkylamino group].
  • the dyes according to the present invention are preferably those which are able to dissolve into a processing solution easily thereby come out from the photographic material, the carbon numbers of an alkyl group and an aryl group preferably are small.
  • the compounds of formula (I) can be synthesized by various methods, for example, by carrying out the condensation of a pyrazolone represented by formula (III) and a compound represented by formula (IVa), (IVb), (IVc), (IVd) or (IVe) in the presence of bases: (IVb) HC (OC2H5)3 wherein R1, R3, Q1, X1, Y1, L1, L2, L3, m1, n, p1 and s1 have the same definition as given above; Z represents hydrogen, a nitro group, or a halogen atom (e.g., chlorine, bromine); R8 represents hydrogen, an alkyl group (e.g., methyl, ethyl), or a phenyl group; and X represents an anion (e.g., chloride, bromide, iodide, perchlorate, methyl sulfate, ethyl sulfate, p-toluene sulfonate).
  • bases which are used in the condensation reaction include pyridine, piperidine, triethylamine, triethanol amine, sodium acetate, and potassium acetate.
  • solvents which are used for carrying out the condensation reaction include alcohols (e.g., methanol, ethanol, isopropanol), amides (e.g., dimethylformamide, dimethylacetamide, N-methylpyrrolidone), nitriles (e.g., acetonitrile), dimethylsulfoxide, ethylene glycol, ethers (e.g., ethylene glycol monomethylether, ethylene glycol diethylether), water, and a mixture of water and the above-described solvents.
  • the amount of the solvent in the mixture is preferably from 1 to 100 parts by volume per part by volume of water.
  • the reaction temperature may be selected from the range of from 0°C to the boiling point of the solvent.
  • the reaction time is decided depending on the reaction temperature, and it is usually selected from the range of from about 30 min to about 3 d.
  • a pyrazolone represented by formula (III) is used in the condensation reaction in an amount of from 0.1 to 3 mol per mol of a compound represented by formula (IVa), (IVb), (IVC), (IVd) or (IVe).
  • Compound 12 was obtained by using 3-ethoxycarbonyl-1-(2,4-disulfobenzyl)pyrazoline-5-one in the same manner as Synthesis Example 2. Melting point: higher than 300°C ⁇ H2O max : 640 nm ⁇ : 7.02 ⁇ 104
  • the compounds which are represented by formula (II) are nondiffusible cyan couplers.
  • R8 represents a chain or cyclic aliphatic group, preferably having from 1 to 32 (total) carbon atoms (e.g., methyl, butyl, pentadecyl, cyclohexyl), an aromatic group, preferably having from 6 to 32 (total) carbon atoms (e.g., phenyl, naphthyl), a heterocyclic group, preferably 5 ⁇ 7-membered ring containing at least one of N, O and S atoms as hetero atom (e.g., 2-pyridyl, 3-pyridyl, 2-furanyl, 2-oxazolyl) or a substituted amino group, preferably substituted with at least one of an alkyl and aryl groups.
  • 1 to 32 (total) carbon atoms e.g., methyl, butyl, pentadecyl, cyclohexyl
  • an aromatic group preferably having from 6 to 32 (total) carbon atoms (e
  • These groups may be substituted by a substituent selected from an alkyl group, an aryl group, an alkoxy or aryloxy group, (e.g., methoxy, dodecyloxy, methoxyethoxy, phenyloxy, 2,4-di-tert-amylphenoxy, 3-tertbutyl-4-hydroxyphenyloxy, naphthyloxy), a carboxyl group, an alkylcarbonyl or arylcarbonyl group (e.g., acetyl, tetradecanoyl, benzoyl), an alkoxycarbonyl or aryloxycarbonyl group (e.g., methoxycarbonyl, benzyloxycarbonyl, phenoxycarbonyl), an aliphatic or aromatic acyloxy group (e.g., acetyl, benzoyloxy, phenylcarbonyloxy), an aliphatic or aromatic sulfamoyl group (e.g
  • an aliphatic group means a straight-chain, branched-chain, or cyclic aliphatic hydrocarbon group, which may be a saturated or unsaturated group such as an alkyl, alkenyl or alkynyl group.
  • R7 represents a C2 to C20 (total) alkyl group (e.g., ethyl, butyl, pentadecyl)
  • X3 represents hydrogen, a halogen atom (e.g., Cl, Br, F), an aliphatic group (e.g., methyl, propyl, allyl), an alkoxy group (e.g., methoxy, butoxy), or an aliphatic or aromatic acylamino group (e.g., acetoamide).
  • a halogen atom e.g., Cl, Br, F
  • an aliphatic group e.g., methyl, propyl, allyl
  • an alkoxy group e.g., methoxy, butoxy
  • an aliphatic or aromatic acylamino group e.g., acetoamide
  • Z represents hydrogen or a coupling-releasing group, such as a halogen atom (e.g., fluorine, chlorine, bromine), an alkoxy group (e.g., ethoxy, dodecyloxy, methoxycarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy), an aryloxy group (e.g., 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy), an aliphatic or aromatic acyloxy group (e.g., acetoxy, tetradecanoyloxy, benzoyloxy), an aliphatic or aromatic sulfonyloxy group (e.g., methanesulfonyloxy, toluenesulfonyloxy), an amido group (e.g., dichloroacetylamino, heptabutyrylamino, methanesulfonylamin
  • R7 is preferably a C2 to C15 alkyl group, more preferably a C2 to C4 alkyl group.
  • Z is preferably hydrogen or a halogen atom, more preferably a halogen atom.
  • X3 is preferably a halogen atom.
  • the dyes of formula (I) can be used as filter dyes, irradiation-preventing dyes or antihalation dyes in any effective amount, preferably in such an amount that the dye provides optical density (of whole hydrophilic colloid layers) of 0.05 to 3.0.
  • the addition thereof is conducted in any step of processing before coating a photographic layer coating composition onto a support.
  • the dyes according to the present invention can be dispersed in at least one of hydrophilic colloidal layers, i.e., emulsion layers and the other hydrophilic colloidal layers (intermediate layer, protective layer, antihalation layer including backing layer, and filter layers) by various known methods.
  • hydrophilic colloidal layers i.e., emulsion layers and the other hydrophilic colloidal layers (intermediate layer, protective layer, antihalation layer including backing layer, and filter layers) by various known methods.
  • the cyan coupler represented by formula (II) can be employed in an amount of 0.1 to 1 mol, preferably 0.2 to 0.5 mol per mol of silver halide in the photographic silver halide emulsion layer containing the cyan coupler.
  • the cyan couplers represented by formula (II) are dissolved in high-boiling organic solvents (e.g., phthalic acid ester solvents, phosphate solvents, fatty acid ester solvents) and the resulting solutions are dispersed in hydrophilic colloidal media to be added to silver halide emulsions.
  • high-boiling organic solvents e.g., phthalic acid ester solvents, phosphate solvents, fatty acid ester solvents
  • benzotriazole ultraviolet absorbing agents In order to improve the properties of the silver halide color photographic materials in storage, there can be added benzotriazole ultraviolet absorbing agents and substantially water-insoluble, organic solvent-soluble polymers. In particular, the use of these polymers is effective for improving dark discoloration. As the most useful polymers, there are mentioned those described in JP-A- 71262.
  • the hydrophilic colloids include typically gelatin and also any other conventionally known ones to be used for photographic materials.
  • the present invention can employ any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride as a silver halide.
  • silver chlorobromide containing 90 mol% or more of silver chloride (preferably 98 mol% or more) is favorable.
  • This silver chlorobromide may contain a little silver iodide but preferably contains no silver iodide.
  • the grains of silver halide according to the present invention may be in the form of regular crystals such as a cube and an octahedron or irregular crystals such as a sphere and a tabular or combinations thereof. Also, a mixture of grains having various forms of crystals can be used, but those in the form of regular crystals are preferably used.
  • the silver halide grains according to the present invention may consist of different phases or a uniform phase as to the inside layer and the surface layer.
  • the grains may be those which form latent images mainly on the surface thereof (e.g., negative emulsion) or mainly in the inside thereof (e.g., internal latent image emulsion, previously fogged direct reversal emulsion).
  • the grains are those which can form latent images mainly on the surface thereof.
  • the silver halide emulsions to be used in the present invention are preferably tabular grain emulsions in which the grains having a thickness of 0.5 »m or less, preferably 0.3 »m or less, a diameter of preferably 0.6 »m or more and an average aspect ratio of 5 or more occupy 50% or more of the whole projected area, or monodisperse emulsions such that the statistical coefficient of variation (a value of s/ d obtained by dividing the standard deviation s by a diameter d in the distribution represented by a diameter of a circle approximate to the projected areas) is 20% or less.
  • two or more of tabular grain emulsions and monodisperse emulsions may be mixed.
  • the photographic emulsions to be used in the present invention can be prepared by the methods described in P. Glafkides, “Chimie er physique Photographique”, (Paul Montel Co., Ltd., 1967), G.F. Duffin, “Photographic Emulsion Chemistry” (Focal Press, 1966), and V.L. Zelikman, “Making and Coating Photographic Emulsion” (Focal Press, 1964).
  • silver halide solvents for example, ammonia, potassium thiocyanate, ammonium thiocyanate, thioether compounds (e.g., US-A-3,271,157; US-A-3,574,628; US-A-3,704,130; US-A-4,297,439; US-A-4,276,374), thion compounds (e.g., JP-A-53-144319, JP-A-53-82408, JP-A-55-77737), and amine compounds (e.g., JP-A-54-100717).
  • ammonia, potassium thiocyanate, ammonium thiocyanate, thioether compounds e.g., US-A-3,271,157; US-A-3,574,628; US-A-3,704,130; US-A-4,297,439; US-A-4,276,374
  • thion compounds e.g., JP-A-53-144319, JP-
  • a cadmium salt zinc salt, thallium salt, iridium salt or complex salt thereof, rhodium salt or complex salt thereof, or ferric salt or ferric complex salt thereof.
  • Silver halide emulsions are usually chemically sensitized, for example, by the methods described in "Die Grundlagen der Photographischen Sawe mit Silberhalogeniden” edited by H. Frieser, (Akademisch Verlagsgesellshaft, 1968) pp. 675 to 734.
  • a method of sulphur sensitization using compounds containing sulphur which can react with active gelatin or silver e.g., thiosulfates, thioureas, mercapto compounds, rhodanines
  • a method of reduction sensitization using reducible materials e.g., stannous salt, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds
  • noble metal sensitization using noble metal compounds e.g., gold complexes and other complexes of metals belonging to Group VIII in the periodic table such as Pt, Ir and Pd
  • noble metal compounds e.g., gold complexes and other complexes of metals belonging to Group VIII in the periodic table such as Pt, Ir and Pd
  • the silver halide photographic emulsions to be used in the present invention can contain various compounds, for example, azoles such as benzothiozolium salt, nitroindazoles, triazoles, benzotriazoles, and benzimidazoles (particularly, those with nitro- or halogen-substituents); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadioazoles, mercaptotetrazoles (particularly, 1-phenyl-5-meratptotetrazole), and mercaptopyrimidines; these heterocyclic mercapto compounds having water-soluble groups such as carboxyl group and sulfone group; thioketo compounds such as oxazolinethion; azaindenes such as tetraa
  • the silver halide photographic emulsions according to the present invention can contain color couplers such as a cyan coupler, magenta coupler, yellow coupler and compounds for dispersing couplers.
  • the silver halide photographic emulsions according to the present invention may contain compounds which form color by oxidation coupling with an aromatic primary amine developing agent (e.g., phenylenediamine derivatives, aminophenol derivatives) in color development.
  • aromatic primary amine developing agent e.g., phenylenediamine derivatives, aminophenol derivatives
  • 5-pyrazolone couplers e.g., 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcumarone couplers, pyrazolotriazole couplers, and open-chain acylacetonitrile couplers as magenta couplers and acylacetoamide couplers (e.g., benzoyl acetanilides, pivaloyl acetanilides) as yellow couplers.
  • couplers are preferably nondiffusible couplers having hydrophobic groups called ballast groups in the molecule.
  • the couplers may be 4 equivalent or 2 equivalent to a silver ion, or colored couplers having the effect of color correction, or couplers releasing development restrainers along with the development (the so-called DIR couplers).
  • the couplers other than DIR couplers may contain colorless DIR coupling compounds which form colorless products from the coupling reaction and release development restrainers. Also, there may be added ultraviolet absorbing agents and discoloration-preventing agents such as cinnamic acid esters and 2-(2-hydroxyphenyl)benzotriazole.
  • discoloration-preventing agents include compounds described in the following patent specifications: US-A-3,432,300, US-A-3,573,045; US-A-3,574,627; US-A-3,700,455; US-A-3,764,337; US-A-3,935,016; US-A-4,254,216; US-A-4,268,593; US-A-4,430,425; US-A-4,465,757; US-A-4,465,765; US-A-4,518,679; GB-B-1,347,556; GB-B-2,066,975; JP-A-52-152225; JP-A-53-17729; JP-A-53-20327; JP-A-54-145530; JP-A-55-6321; JP-A-55-21004; JP-A-61-72246; JP-A-61-73152; JP-A-61-90155; JP-A-61-90156;
  • the photographic emulsions according to the present invention may contain, for example, polyalkylene oxide or derivatives thereof, such as ether, ester and amine; thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives and 3-pyrazolidones so as to increase sensitivity and contrast or accelerate development.
  • polyalkylene oxide or derivatives thereof such as ether, ester and amine
  • thioether compounds, thiomorpholines, quaternary ammonium salt compounds such as urethane derivatives, urea derivatives, imidazole derivatives and 3-pyrazolidones
  • the silver halide photographic emulsions according to the present invention can employ known water-soluble dyes (e.g., oxonol dye; hemioxonol dye and merocyanine dye) in addition to the dyes disclosed in the present invention as filter dyes or irradiation-preventing dyes.
  • known cyanine dyes, merocyanine dyes and hemicyanine dyes other than the dyes disclosed in the present invention may be used as spectral sensitizers.
  • the photographic emulsions according to the present invention may contain various surfactants for the use as coating aids and antistatic agents, improving slipping-propertiers, emulsion-dispersing, preventing adhesion, and improving photographic characteristics (for example, accelerating development, providing high contrast, sensitizing).
  • the photographic materials of the present invention can contain various additives such as discoloration-preventing agents, hardening agents, color antifoggants, ultraviolet-absorbing agents, and protective colloids such as gelatin, which are described particularly in Research Disclosure Vol. 176 (1978, XII) RD-17643.
  • the finished emulsions are coated on a suitable support, for example, baryta paper, resin-coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, or other plastic supports or glass plates.
  • a suitable support for example, baryta paper, resin-coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, or other plastic supports or glass plates.
  • the silver halide photographic materials of the present invention include color positive film, color paper, color negative film, color reversal film (which may contain couplers or may not), photographic materials for plate making processes (e.g., lith film, lith dupe film), photosensitive materials for cathode ray tube display (e.g., photosensitive materials for emulsion X-ray recording, direct or indirect photographing materials using a screen), photographic materials for a silver salt diffusion transfer process, photographic materials for a color diffusion transfer process, photographic materials for a dye transfer process, an inhibition transfer process, photographic materials for a silver dye bleach process, photographic materials for recording print-out images, photographic materials for direct printing of images, photographic materials for heat development and photographic materials for physical development.
  • photographic materials for plate making processes e.g., lith film, lith dupe film
  • photosensitive materials for cathode ray tube display e.g., photosensitive materials for emulsion X-ray recording, direct or indirect photographing materials using a screen
  • Exposure for forming photographic images can be carried out by using various well-known light sources, for example, natural light (sun light), or a tungsten lamp, fluorescent lamp, mercury vapor lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp and cathode ray tube flying spot.
  • the exposure time is usually in a range of 1/1000 to 30 s, but can be shorter than 1/1000 s, e.g., in a range of 1/104 to 1/106 s when using a xenon flash lamp or a cathode-ray tube, or longer than 30 s.
  • the spectral composition of light to be used for exposure can be controlled with color filters if desired.
  • Laser rays can be used for exposure.
  • exposure may be conducted by light excited from phosphors by an X-ray, ⁇ -ray or ⁇ -ray.
  • the photographic processing of the photographic materials of the present invention can be carried out by known processes and processing solutions as described, for example, in Research Disclosure No. 176, pp. 28 to 30 (RD-17643). This photographic processing may be carried out for forming silver images (black and white photographic processing) or color images (color photographic processing).
  • the processing temperature is usually in a range of 18 to 50°C, but may be lower than 18°C or higher than 50°C.
  • the present invention has no limitation with respect to methods of processing color photographic images.
  • conventional methods include a method of carrying out exposure, color development, bleach-fixing and, if necessary, washing and stabilizing; a method of carrying out exposure, color development, bleaching, fixing, and if necessary, washing and stabilizing; and a method of carrying out exposure, development with a developing solution containing a black and white developing agent, uniform exposure, color development, bleach-fixing and, if necessary, washing and stabilizing; and a method of carrying out exposure, development with a developing solution containing a black and white developing agent, further development with a color developing solution containing a fogging agent (e.g., sodium borohydride), bleach-fixing, and, if necessary, washing and stabilizing.
  • a fogging agent e.g., sodium borohydride
  • aromatic primary amine color developing agents to be used in the color-developing solutions according to the present invention include those which are known and widely used in various color photographic processes, for example, amino phenolic and p-phenylenediamine derivatives.
  • amino phenolic and p-phenylenediamine derivatives Preferably, p-phenylenediamine derivatives are used, and the following are the typical examples thereof.
  • these p-phenylenediamine derivatives may be in the form of salts such as a sulfate, hydrochloride, sulfite and p-toluenesulfonate.
  • salts such as a sulfate, hydrochloride, sulfite and p-toluenesulfonate.
  • Thse aromatic primary amine color developing agents are used in an amount of about 0.1 g to about 20 g, preferably about 0.5 g to about 10 g per 1 l of a developing solution.
  • the color developing solutions to be used in the present invention can contain hydroxylamines, as is well known.
  • Hydroxylamines can be used in the form of free amines in the color-developing solutions, but generally are in the form of aqueous solutions of acid salts, such as sulfate, oxalate, chloride, phosphate, carbonate, and acetate thereof. Hydroxylamines may be substituted or unsubstituterd. The nitrogen atoms of hydroxylamines may be substituted with alkyl groups.
  • Hydroxylamines are added in an amount of preferably 0 to 10 g, more preferably 0 to 5 g, per 1 l of a color developing solution. As far as the stability of a color developing solution is kept, the smaller amount is better.
  • sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite and potassium metasulfite and carbonyl sulfite additives in an amount of preferably 0 g to 20 g per 1 l, more preferably 0 g to 5 g per 1 l. As far as the stability of a color developing solution is kept, the smaller amount is better.
  • aromatic polyhydroxy compounds described in JP-A-52-49828, JP-A-56-47038, JP-A-56-32140, JP-A-59-160142, and US-A-3,746,544 hydroxyacetones described in US-A-3,615,503; and GB-B-1,306,176
  • ⁇ -aminocarbonyl compounds described in JP-A-52-143020 and JP-A-53-89425 various metals described in JP-A-57-44148 and JP-A-57-53749
  • hydrazine-N,N-diacetic acid is preferred. These preservatives can be used in a combination of two or more, if desired. Particularly, 4,5-dihydroxy-m-benzenedisulfonic acid, poly(ethylene imine) and triethanol amine are preferably added.
  • the color developing solutions to be used in the present invention has a pH value of preferably 9 to 12, more preferably 9 to 11, and can contain other compounds known as components of developing solutions.
  • the color developing solution are preferably used at a processing temperature in a range of 20 to 50°C, preferably 30 to 40°C, a processing period of time in a range of 20 s to 5 min, preferably 30 s to 4 min, and is replenished in an amount of 30 to 1000 ml, preferably 60 to 400 ml per 1 m2 of a photographic material, though the smaller amount is better.
  • Desilvering process in the present invention is usually conducted as follows.
  • the desilvering process may generally include any of bleaching step-fixing step; fixing step-bleach-fixing step; bleaching step-bleach-fixing step; and bleach-fixing step.
  • the silvering step is carried out for 2 min or less, more preferably for 15 s to 90 s.
  • the present invention can employ such bleaching solutions, bleach-fixing solutions, fixing solutions, and additives given to the solutions in the amounts described, for example, in JP-A-63-229457, pp. 20 to 25.
  • washing and/or stabilizing after desilvering can be carried out in the same way as described in said JP-A-63-229457, pp. 25 to 29 line 12.
  • Specimen (1) for multi-layered color print having the following structure of layers was prepared on a paper support laminated with polyethylene on both sides.
  • composition of each layer is shown hereinafter. Numerical figures indicate the amounts of coatings (g/m2), and the amounts of silver halide emulsions are calculated in terms of silver. However, the amounts of cyan couplers and dyes are given in mol/m2.
  • Polyethylene-laminated paper where the polyethylene on the first layer side contained a white pigment (TiO2) and a blue dye (ultramarine).
  • the silver halide emulsion (EM-1) used in the above specimen was prepared as follows:
  • Solution 1 was heated to 74°C, to which solutions 2 and 3 were added. Then, solutions 4 and 5 were added thereto at the same time in 9 min. After further 10 min, solutions 6 and 7 were added at the same time in 45 min. Then the mixed solution was allowed to stand for 5 min after the addition thereof, and then cooled and desalted.
  • Water and dispersion gelatin were added to adjust the pH to 6.2, to obtain a monodisperse cubic silver chlorobromide emulsion having an average particle size of 0.96 »m, a coefficient of variation (a value obtained by dividing standard deviation by an average particle size: s/ d ) of 0.08, and 80 mol% of silver bromide. This emulsion was optimumly chemically sensitized with sodium thiosulfate.
  • the other silver chlorobromide emulsions (EM-2) to (EM-6) were prepared in a manner similar to the above emulsion (EM-1) except for changing the amounts of chemicals, temperature and time.
  • Specimens (2) to (7) were prepared in the same manner as the above specimen (1) except for changing the dyes of the 4th layer and the cyan coupler of the 5th layer.
  • the compositions of dyes and cyan couplers were shown in Table 2. It is to be noted that the numbers of dyes and cyan couplers correspond to those given in Examples. The following cyan coupler (C) was used for comparison.
  • composition of each processing solution was given as follows:
  • the above specimens (1) to (7) were developed and then evaluated as to sensitivity, fogging, sharpness and discoloration.
  • the values of relative sensitivity in a density of 1.0 were obtained with using the relative sensitivity value of specimen (1) of 100 for convenience; the values of fogging were obtained in the developing times of 3 min 30 s and also in the forced development time of 7 min; and the values of sharpness were obtained by determining C.T.F. (contrast transfer function) (%) in a spatial frequency of 15 cycles/mm, in which the higher value of sharpness was better.
  • the specimens of the present invention prepared by combining cyan couplers and dyes are good photographic materials having high sensitivity, less fogging, high sharpness and good resistance to dark discoloration.
  • Specimen (8) having the following composition was prepared in the same manner as Example 1.
  • Specimens (8) to (11) were prepared by changing the dyes of the 4th layer and the cyan couplers of the 5th layer in the above specimen. The compositions thereof were shown in Table 5.
  • the specimens (8) to (11) were exposed to light and treated by the following steps to obtain the evaluation thereof the same as Example 1. (A 3-tank countercurrent system of rinse (4) ⁇ (1) was employed).
  • composition of each processing solution is given as follows:
  • Ion exchange water (each of calcium and magnesium in 3 ppm or less).
  • the specimens (8) to (11) were developed and evaluated in the same manner as Example 1, with the sensitivity values were obtained when the relative sensitivity of specimen (8) was considered as 100, and the values of fog formed by forced development were obtained when the development time was 90 s. The results are shown in Table 6.
  • the specimens containing the combinations of cyan couplers and dyes are good photographic materials which have high sensitivity, low fogging values, high sharpness and good resistance to dark discoloration.
  • the present invention can provide silver halide color photographic materials having hydrophilic colloidal layers containing new dyes which are easily decolored by processing and are stable even after the lapse of time without exerting any harmful effect on the photographic properties of photographic emulsions, particularly on sensitivity and fog. Moreover, the present invention can provide silver halide color photographic materials including a red-sensitive emulsion layer which has good resistance to dark discoloration, high sharpness, high sensitivity and low fog.

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Claims (11)

  1. Matériau photographique couleur à l'halogénure d'argent qui comprend un support portant au moins une couche d'émulsion photographique couleur à l'halogénure d'argent et contenant au moins un composé représenté par la formule générale (I) suivante et au moins un composé représenté par la formule générale (II) suivante dans au moins une couche colloïdale hydrophile disposée sur le support :
    Figure imgb0157
     dans laquelle R₁ et R₂ représentent chacun -COOR₅ ou
    Figure imgb0158
     R₃ et R₄ représentent chacun un atome d'hydrogène ou un groupe alkyle, R₅ et R₆ représentent chacun un atome d'hydrogène, un groupe alkyle non substitué, un groupe aryle ou bien R₅ et R₆ forment ensemble un noyau à 5 ou 6 chaînons ; Q₁ et Q₂ représentent chacun un groupe aryle ; X₁ et X₂ représentent chacun un groupe de liaison divalent ou une liaison ; Y₁ et Y₂ représentent chacun un groupe acide sulfonique ou un groupe acide carboxylique ; L₁, L₂ et L₃ représentent chacun un groupe méthine ; m₁ et m₂ représentent chacun 1 ou 2 ; n représente 0, 1 ou 2 ; p₁et p₂ représentent chacun 0, 1, 2, 3 ou 4 ; et s₁ et s₂ représentent chacun 1 ou 2 ; et
    Figure imgb0159
     dans laquelle Y₃ représente -NHCO- ou -CONH- ; R₈ représente un groupe aliphatique, un groupe aromatique, un groupe hétérocyclique ou un groupe arylamino qui peut être substitué ; X₃ représente un atome d'hydrogène, un atome d'halogène, un groupe alcoxy ou un groupe acylamino ; R₇ représente un groupe alkyle (contenant 2 atomes de carbone ou plus) ; et Z représente un atome d'hydrogène ou un groupe qui peut être éliminé par couplage avec un agent développateur chromogène oxydé, ledit matériau photographique ne contenant pas une couche d'émulsion d'halogénure d'argent du type à image latente interne précédemment non voilée.
  2. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel ledit composé représenté par la formule (I) est utilisé en quantité telle que le composé produise une densité optique de 0,05 à 3,0.
  3. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1 ou 2, dans lequel ledit composé représenté par la formule (I) est incorporé dans au moins une couche colloïdale hydrophile.
  4. Matériau photographique couleur à l'halogénure d'argent selon l'une quelconque des revendications 1 à 3, dans lequel la quantité dudit composé représenté par la formule (II) est de 0,1 à 1 mol par mole d'halogénure d'argent dans la couche d'émulsion d'halogénure d'argent photographique contenant le composé.
  5. Matériau photographique couleur à l'halogénure d'argent selon l'une quelconque des revendications 1 à 4, dans lequel le groupe alkyle représenté par R₅ ou R₆ porte un substituant choisi parmi un groupe sulfo, un groupe carboxyle, un groupe hydroxyle, un groupe alcoxy, un atome d'halogène, un groupe cyano, un groupe sulfonyle aliphatique ou aromatique, un groupe nitro, un groupe amino substitué ou non par un groupe aikyle et un groupe aryle.
  6. Matériau photographique couleur à l'halogénure d'argent selon l'une quelconque des revendications 1 à 4, dans lequel le groupe aryle représenté par R₅ ou R₆ est un groupe phényle non substitué ou portant un substituant choisi parmi un groupe sulfo, un groupe carboxyle, un groupe hydroxyle, un groupe alcoxy, un atome d'halogène, un groupe cyano, un groupe nitro, un groupe amino substitué ou non par un groupe alkyle et un groupe alkyle.
  7. Matériau photographique couleur à l'halogénure d'argent selon l'une quelconque des revendications 1 à 6 dans lequel R₁ et R₂ forment chacun un sel de sodium, un sel de potassium, un sel d'ammonium ou un sel d'ammonium quaternaire.
  8. Matériau photographique couleur à l'halogénure d'argent selon l'une quelconque des revendications 1 à 7, dans lequel le groupe aryle représenté par Q₁ ou Q₂ est un groupe phényle ou naphtyle di- ou trivalent ou un groupe phényle portant un substituant choisi parmi un groupe alkyle en C₁-C₄, un groupe alcoxy en C₁-C₄, un atome d'halogène, un groupe carbamoyle aliphatique ou aromatique, un groupe sulfamoyle aliphatique ou aromatique, un groupe cyano, un groupe nitro, un groupe alkylsulfonyle, un groupe arylsulfonyle, un groupe amino non substitué ou substitué par un groupe alkyle, un groupe acylamino aliphatique ou aromatique et un groupe sulfonamido aliphatique ou aromatique.
  9. Matériau photographique couleur à l'halogénure d'argent selon l'une quelconque des revendications 1 à 8, dans lequel X₁ et X₂ représentent chacun
    Figure imgb0160
     ou une liaison, dans lesquels R₇ représente l'hydrogène, un groupe alkyle en C₁-C₅ ou un groupe alkyle substitué en C₁-C₅ (au total) ayant un substituant choisi parmi un groupe alcoxy en C₁-C₃, un groupe sulfo, un groupe carboxyle, un groupe cyano, un groupe hydroxyle, un groupe amino non substitué ou substitué par un groupe alkyle, un groupe sulfonamido aliphatique ou aromatique, un groupe carbonamido aliphatique ou aromatique, un groupe carbamoyle aliphatique ou aromatique et un groupe sulfamoyle aliphatique ou aromatique.
  10. Matériau photographique couleur à l'halogénure d'argent selon l'une quelconque des revendications 1 à 9, dans lequel Y₁ et Y₂ représentent chacun un groupe acide sulfonique ou un groupe acide carboxylique qui peut former un acide libre ou un sel.
  11. Matériau photographique couleur à l'halogénure d'argent selon l'une quelconque des revendications 1 à 10, dans lequel L₁, L₂ et L₃ représentent chacun un groupe méthine ou un groupe méthine substitué par un substituant choisi parmi un groupe méthyle, un groupe éthyle et un groupe phényle.
EP19890101457 1988-01-28 1989-01-27 Matériaux photographiques couleurs à l'halogénure d'argent Expired - Lifetime EP0326161B1 (fr)

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JP17771/88 1988-01-28
JP63017771A JPH0693093B2 (ja) 1988-01-28 1988-01-28 ハロゲン化銀カラー写真感光材料

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JPH0830865B2 (ja) * 1986-04-23 1996-03-27 コニカ株式会社 ハロゲン化銀カラ−写真感光材料
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JPH0812398B2 (ja) * 1987-12-28 1996-02-07 富士写真フイルム株式会社 直接ポジ写真感光材料

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JPH01193733A (ja) 1989-08-03
JPH0693093B2 (ja) 1994-11-16
EP0326161A3 (en) 1990-06-13
CN1030010C (zh) 1995-10-11
EP0326161A2 (fr) 1989-08-02
DE68922120D1 (de) 1995-05-18

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