EP0226849B1 - Procédé de préparation d'une image en couleur - Google Patents

Procédé de préparation d'une image en couleur Download PDF

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Publication number
EP0226849B1
EP0226849B1 EP19860116345 EP86116345A EP0226849B1 EP 0226849 B1 EP0226849 B1 EP 0226849B1 EP 19860116345 EP19860116345 EP 19860116345 EP 86116345 A EP86116345 A EP 86116345A EP 0226849 B1 EP0226849 B1 EP 0226849B1
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European Patent Office
Prior art keywords
group
coupler
substituted
couplers
layer
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EP19860116345
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German (de)
English (en)
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EP0226849A2 (fr
EP0226849A3 (en
Inventor
Tadahisa Fuji Photo Film Co. Ltd. Sato
Nobuo Fuji Photo Film Co. Ltd. Furutachi
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP24271286A external-priority patent/JPS62209457A/ja
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Publication of EP0226849A3 publication Critical patent/EP0226849A3/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/36—Couplers containing compounds with active methylene groups
    • G03C7/38—Couplers containing compounds with active methylene groups in rings
    • G03C7/381—Heterocyclic compounds
    • G03C7/382—Heterocyclic compounds with two heterocyclic rings
    • G03C7/3825—Heterocyclic compounds with two heterocyclic rings the nuclei containing only nitrogen as hetero atoms
    • G03C7/3835—Heterocyclic compounds with two heterocyclic rings the nuclei containing only nitrogen as hetero atoms four nitrogen atoms
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
    • G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
    • G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
    • G03C7/30529—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution having the coupling site in rings of cyclic compounds

Definitions

  • the present invention relates to a process for forming a color image comprising developing a silver halide photographic material using a developer containing an aromatic primary amine in the presence of at least one coupler. Said process can increase the photographic speed, improve the gradation (gamma) and heighten the color density of the developed image.
  • color developing agents of the aromatic primary amine type which have been oxidized with exposed silver halides as oxidants react with couplers to produce indophenol, indoaniline, indamine azomethine, phenoxazine, phenazine and their analogous dyes, thus forming color images.
  • a magenta color image is formed by using couplers of a 5-pyrazolone, cyanoacetophenone, indazolone, pyrazolobenzimidazole or pyrazolotriazole type.
  • magenta color image-forming couplers which have so far been widely used are 5-pyrazolones.
  • the dyes formed from 5-pyrazolone couplers have an unnecessary absorption containing a yellow component in the neighborhood of 430 nm to cause color turbidity.
  • magenta couplers described in the foregoing patent specifications also have such undesirable properties that when mixed with a silver halide emulsion in a condition that they are dispersed in a hydrophilic protective colloid like gelatin, some of them provide only unsatisfactory color images, have low solubility in high boiling organic solvents, are difficult to synthesize, have relatively low coupling activity in an ordinary developer or provide dyes of extremely poor fastness to light.
  • R and R 1 are each H, halogen or various aliphatic or cyclic substituents;
  • X is H or a coupling releasable group or R 1 .
  • R 2 or X may form a bis-coupler; or R 1 or R 2 may link to a vinyl group of a vinyl monomer to form a polymer coupler.
  • a coupling split-off group (X) is a group which facilitates the synthesizing of the resulting coupler, e.g. a halogen atom, an alkylthio group or an arylthio group
  • couplers having an aryloxy group as a coupling split-off group can solve the above-described problem.
  • the aryloxy group-releasing couplers suffer from disadvantages that they are obtained in a low yield to be unsuitable for large-scaled synthesis and that they have low stability.
  • pyrazoloazoles described in the above-cited U.S. Patent 3,725,067 have similar defects. These couplers are also disclosed in GB-A-2135788.
  • Said object is achieved by a process for forming a color image comprising developing a silver halide photographic material using a developer containing an aromatic primary amine in the presence of at least one coupler characterized in that said coupler is represented by the following formula (I) or (II): wherein R 1 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group; R 2 represents a hydrogen atom or a substituent group; and X represents a split-off group linked through a nitrogen or sulfur atom; wherein R 1 and X have the same meanings as in formula (I), respectively; and R' 2 represents an alkyl group, an aryl group, an alkylthio group, an arylthio group, or a hetercyclic thio group.
  • R represents an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a trifluoromethyl group, a phenylmethyl group, a methoxyethyl group, a 2-phenoxyethyl group, a 2-methylsulfonylethyl group, a 2-hydroxyethyl group, a 3,3,3-trifluoropropyl group, a 2-fluoroethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 2-cyanoethyl group, or a 3-oxobutyl group; an aryl group such as a phenyl group, a 4-methylphenyl group, a 4-t-butylphenyl group, a 4- acylaminophenyl group, a 4-halogenophenyl group, or a 4-alkoxyphenyl group
  • R 2 represents a hydrogen atom, a halogen atom (e.g., a chlorine atom or a bromine atom), an alkyl group [including substituted alkyl groups such as a sulfonamido substituted alkyl group (e.g., a sulfonamidomethyl group, a 1-sulfonamidoethyl group, a 2-sulfonamidoethyl group, a 1-methyl-2-sulfonamidoethyl group or a 3-sulfonamidopropyl group), an acylamino-substituted alkyl group (e.g., an acylaminomethyl group, a 1-acylaminoethyl group, a 2-acylaminoethyl group, a 1-methyl-2-acylaminoethyl group, or a 3-acylaminopropyl), a sulfonamido-substituted phen
  • a methoxy group e.g., an ethoxy group, a 2-methoxyethoxy group, a 2-dodecylethoxy group, or a 2-methanesulfonylethoxy group
  • an aryloxy group e.g.
  • a phenoxy group a 2-methylphenoxy group, or a 4-t-butylphenoxy group
  • an acylamino group e.g., an acetamido group, a benzamido group, a tetradecanamido group, an «-(2,4-di-t-amyl-phenoxy)butylamido group, a y-(3-t-butyl-4-hydroxyphenoxy)butylamido group, or an a-(4-(4-hydroxyphenylsulfonyl)phenoxy) decanamido group) an anilino group (e.g.
  • a phenylamino group a 2-chloroanilino group, a 2-chloro-5-tetradecanamidoanilino group, a 2-chloro-5-dodecyloxycarbonylanilino group, a N-acetylanilino group, or a 2-ch!oro-5- ⁇ m-(3-t-butyt-4-hydroxyphenoxy) dodecanamidolanilino group), a ureido group (e.g., a phenylureido group, a methylureido group, or a N,N-dibutylureido group), a sulfamoylamino group (e.g., a N,N-dipropylsulfamoylamino group, or a N-methyl-N-decylsulfamoylamino group), an alkylthio group (e.g., a methylthi
  • an alkyl group, an aryl group, an alkylthio group and a arylthio group, especially an alkyl group and an aryl group, are preferred over others.
  • R' 2 represents a substituted alkyl group such as a sulfonamido-substituted alkyl group (e.g., a sulfonamidomethyl group, a 1-sulfonamidoethyl group, a 2-sulfonamidoethyl group, a 1-methyl-2-sulfonamidoethyl group, or a 3-sulfonamidopropyl group), an acylamino-substituted alkyl group (e.g., an acylaminomethyl group, a 1-acylaminoethyl group, a 2-acylaminoethyl group, a 1-methyl-2-acylaminoethyl group, or a 3-acylamino-propyl group), a sulfonamido-substituted phenylalkyl group (e.g., a p-sul- fonamidophenyl
  • X represents a group linked through a nitrogen atom (e.g., a benzenesulfonamido group, a N-ethyltoluenesulfonamido group, a heptafluorobutanamido group, a 2,3,4,5,6-pentafluorobenzamido group, an octanesulfonamido group, a p-cyanophenylureido group, a N,N.diethylsulfamoylamino group, a 1-piperidyl group, a 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl group, a 1-benzylethoxy-3-hydantoinyl group, a 2N-1,1-dioxo-3(2H)-oxo-1,2-benzoisothiazolyl group, a 2-oxo-1,2-dihydro-1-pyridiny
  • a phenylthio group a 2-carboxyphenylthio group, a 2-methoxy-5-t-octylphenylthio group, a 4-methanesulfonyl- phenylthio group, a 4-octanesulfonamidophenylthio group, a 2-cyanoethylthio group, a 1-ethoxycarbonyl- tridecylthio group, a 5-phenyl-2,3,4,5- tetrazolythio group, or a 2-benzothiazolyl group),
  • R 1 , R 2 , R' 2 , or X is a divalent group and, thus, the coupler (I) or (II) forms a bis compound
  • Ri, R 2 or R' 2 represents a substituted or unsubstututed alkylene group (e.g., a methylene group, an ethylene group, a 1,10-decylene group, or -CH 2 CH 2 -0-CH 2 CH 2 -), or a substituted or unsubstituted phenylene group (e.g., a 1,4-phenylene group, a 1,3-phenylene group or and X represents a divalent group obtained by converting any of the above-cited monovalent groups into the corresponding divalent group at a proper position.
  • a substituted or unsubstututed alkylene group e.g., a methylene group, an ethylene group, a 1,10-decylene group, or -CH 2 CH 2 -0-CH 2
  • a linkage group represented by Ri, R 2 , or R' 2 includes groups formed by connecting some groups selected from substituted or unsubstituted alkylene groups (e.g., a methylene group, ethylene group, a 1,10-decylene group or a -CH 2 CH 2 0CH 2 CH 2 -), substituted or unsubstituted phenylene groups (e.g., a 1,4-phenylene group, a 1,3-phenylene group or -NHCO-, -CONH-, -O-, -OCO-, and aralkylene groups or Suitable examples of such linkage groups include and
  • the vinyl group may further have a substituent group.
  • substituent groups include a hydrogen atom, a chlorine atom, and a lower alkyl group containing I to 4 carbon atoms (e.g., a methyl group or an ethyl group).
  • a monomer having a moiety represented by the general formula (I) or (II) may form a copolymer together with a non-color-forming ethylenic monomer which is not coupled with an oxidation product of an aromatic primary amine developing agent.
  • non-color-forming ethylenic monomers which are not coupled with an oxidation product of an aromatic primary amine developing agent, are acrylic acid, «-chloroacrylic acid, a-alkylacrylic acids (e.g., methacrylic acid), esters and amides derived from acrylic acids as described above (e.g., acrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and Q-hydroxy methacrylate), methylenebisacrylamide, vinyl esters and
  • non-color-forming ethylenic unsaturated monomers can be used in combination with two or more thereof.
  • a combination of n-butyl acrylate with methyl acrylate, of styrene with methacrylic acid, of methacrylic acid with acrylamide or of methyl acrylate with diacetoneacrylamide can be employed.
  • non-color-forming ethylenic unsaturated monomers to be copolymerized with water-insoluble solid monomer couplers can be selected to exert a favorable influence upon the physical properties and/or the chemical properties of the resulting copolymers, such as solubility, compatibility with binders of photographic colloidal compositions, e.g., gelatin, flexibility or thermal stability.
  • the polymer couplers which can be used in the process of the present invention may be either watersoluble or water-insoluble. However, particularly preferred are polymer coupler latexes.
  • magenta couplers which can be used in the process of the present invention are illustrated below. Unless otherwise indicated, all fractions of constituent monomers in the polymer couplers instanced below are by weight.
  • a general process for synthesizing the couplers used in the process of the present invention is described below. Some of the inventors have disclosed in Japanese Patent Application (OPI) No. 197688/85 a process for synthesizing 1 H-pyrazolo-[1,5-b]-1,2,4-triazoles which have a hydrogen atom or an alkyl group at the 6-position.
  • the couplers of the present invention (formula (I)) can be synthesized in basically the same manner as those described above except that different starting materials are used. The synthesis scheme is illustrated below.
  • the substituent X may be introduced at the start as shown above, or the synthesis may be conducted using the compound wherein X is a hydrogen atom as a starting material and various substituents for X may be introduced after synthesis of the skeleton as described hereinafter.
  • the 1H-pyrazolo[5,1-c]-1,2,4-triazole couplers can be synthesized using 3-alkoxy (or aryloxy)-5-hydrazinopyrazoles as a starting material according to the method described in Japanese Patent Publication No. 30895/73.
  • the polymer couplers can be synthesized using a solution polymerization process or an emulsion polymerization process.
  • the solution polymerization can be carried out using the processes described in U.S. Patent 3,451,820 and Japanese Patent Application (OPI) No. 28745/83.
  • a monomer coupler having the moiety represented by formula (I) and a non-color-forming ethylenic monomer e.g., acrylic acid, «-chloroacrylic acid, alacrylic acid such as methacrylic acid, or an ester or amide derived from such an acrylic acid (e.g., acrylamide, n-butyl acrylamide, n-butyl methacrylate, methyl methacrylate or ethyl methacrylate))
  • a soluble organic solvent e.g., dioxane or methyl cellosolve
  • polymerization can be initiated at a proper temperature (about 30 to 100°C) through formation of free radicals by applying thereto a physical means such as UV irradiation or high energy irradiation, or by applying chemical means such as use of initiators (e.g., persulfates, hydrogen peroxide, benzoyl peroxide or azobis
  • the polymer After completion of the polymerization reaction, the polymer can be isolated by extracting the product into an organic organic solvent, concentrating the product, or pouring the product into water.
  • the emulsion polymerization can be effected using the method described in U.S. Patent 3,370,952.
  • Linking a nitrogen atom is divided roughly into three groups. Processes falling into the first group involve, as described in U.S. Patent 3,419,391, nitrosifying the coupling active site of a coupler with an appropriate nitrosifying agent, reducing the nitroso group by a suitable process (for example, a hydrogenation process using a catalyst like Pd-on-carbon or a chemical reduction process using, for example, stannous chloride) and then allowing the resulting 7-amino compound to react with a halide to yield predominantly the amide compound.
  • a suitable process for example, a hydrogenation process using a catalyst like Pd-on-carbon or a chemical reduction process using, for example, stannous chloride
  • Processes falling into the second group involve, as described in U.S. Patent 3,725,067, halogenating the 7-position of a coupler with an appropriate halogenating agent such as sulfuryl chloride, chlorine gas, bromine, N-chlorosuccinimide or N-bromosuccinimide, and then replacing the halogen with a nitrogen-containing hetero ring in the presence of an appropriate base catalyst such as triethylamine, sodium hydroxide, diazabicyclo[2,2,2]octane or anhydrous potassium carbonate, according to the process described in Japanese Patent Publication No. 45135/81, thus the coupler which is linked to a nitrogen atom at the 7- position being synthesized.
  • an appropriate halogenating agent such as sulfuryl chloride, chlorine gas, bromine, N-chlorosuccinimide or N-bromosuccinimide
  • an appropriate base catalyst such as triethylamine, sodium hydroxide, diazabicyclo[2,2,2]o
  • Processes falling into the third group are effective in introducing a 6; or 10 7 r-electron system aromatic nitrogen-containing hetero ring to a coupler at the 7-position and involve, as described in Japanese Patent Publication No. 36577/82, adding 2 moles or more of a 6; or low-electron system aromatic nitrogen-containing hetero ring to 1 mole of a 7-halogenated coupler synthesized in the course of the second group process described above and heating the mixture at a temperature of from 50°C to 150°C without using any solvent, or heating it at a temperature of from 30° C to 150°C in an aprotic polar solvent such as dimethylformamide, sulfolane or hexamethylphosphotriamide, to introduce the aromatic nitrogen-containing heterocyclic group to the 7-position of the coupler via the nitrogen atom.
  • aprotic polar solvent such as dimethylformamide, sulfolane or hexamethylphosphotriamide
  • Couplers substituted by an aromatic mercapto or heterocyclic mercapto group at the 7-position can be synthesized using the process described in U.S. Patent 3,227,554, which involves dissolving an arylmercap- tane, a heterocyclic mercaptane, or a disulfide corresponding thereto in a halogenated hydrocarbon solvent, converting the mercaptane or disulfide into a sulfenyl chloride with chlorine or sulfuryl chloride, and then adding the sulfenyl chloride a 4-equivalent coupler dissolved in an aprotic solvent.
  • hydrochlorides or hydrobromides are employed effectively.
  • Magenta dye images produced from the magenta couplers to be employed in the process of the present invention are enhanced in fastness to light by a combined use with color image stabilizers represented by the following formula: wherein R 10 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group; R 11 , R12, R 14 , and R 15 each represents a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an acylamino group, an alkoxycarbonyl group, or a sulfonamido group; and R 13 represents an alkyl group, a hydroxyl group, an aryl group, or an alkoxy group, provided that R 10 and R 11 may combine with each other to form a 5- or 6-membered ring or a methylenedioxy ring, and that R 13 and R 14 may combine with each other to form a 5-membered hydrocarbon ring.
  • the couplers used in the process of the present invention are incorporated in a silver halide color photographic material.
  • the couplers may be incorporated in a light-sensitive material or may be added to a color developing bath.
  • a suitable content of the coupler in the light-sensitive material ranges from 2 x 10- 3 mole to 5 x 10- 1 mole, preferably from 1 x 10- 2 mole to 5 x 10- 1 mole, per mole of silver halide.
  • the coupler is a polymeric coupler, its amount is adjusted such that the amount of the color-forming moiety falls into the above-described range.
  • a suitable amount of the coupler to be added to a color developing agent ranges from 0.001 mole to 0.1 mole, preferably from 0.01 mole to 0.05 mole, per I of the bath containing the same.
  • the pyrazoloazole couplers of the process of the present invention can be introduced into a light-sensitive material using various known methods of dispersing.
  • the dispersion can be effected by a solid dispersion method, an alkaline dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method.
  • couplers are dissolved in either a high boiling organic solvent having a boiling point of 175°C or above or a so-called auxiliary solvent having a low boiling point, or in a mixture of these solvents and then dispersed finely into an aqueous medium like water or an aqueous gelatin solution in the presence of a surface active agent.
  • Suitable examples of high boiling organic solvents are described for example, in U.S. Patent 2,322,027.
  • the dispersion may be accompanied by phase inversion. Further, the auxiliary solvent used may be removed from the dispersion or decreased in content therein through distillation, noodle washing or ultrafiltration, if desired, in preference to coating of the dispersion.
  • high boiling organic solvents which can be used include phthalic acid esters (e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate or decyl phthalate), phosphoric or phosphonic acid esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, tributoxyethyl phosphate, trich- loropropyl phosphate or di-2-ethylhexylphenyl phosphate), benzoic acid esters (e.g., 2-ethylhexyl benzoate, dodecyl benzoate, or 2-ethylhexyl-p-hydroxy benzoate), amides (e.
  • diethyldodecanamide or N-tetradecyl- pyrrolidone diethyldodecanamide or N-tetradecyl- pyrrolidone
  • alcohols and phenols e.g., isostearyl alcohol or 2,4-di-tert-amylphenol
  • aliphatic carboxylic acid esters e.g., dioctyl azelate, glycerol tributyrate, isostearyl lactate or trioctyl citrate
  • aniline derivatives e.g., N,N-dibutyl-2-butoxy-5-tertoctylaniline
  • hydrocarbons e.g., paraffins, dodecylbenzene or diisopropyl- naphthalene).
  • organic solvents having a boiling point of from about 30 C or more, preferably from 50 °C to about 160°C can be used, with typical examples including ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.
  • Silver halide emulsions which can be employed in the process of the present invention include not only a silver chloride emulsion and a silver bromide emulsion but also mixed silver halide emulsions.
  • Typical examples of mixed silver halides which can be used include silver chlorobromide, silver chloroiodobromide and silver iodobromide.
  • silver chloroiodobromide, silver iodochloride, or silver iodobromide each having an iodide content of 3 mole% or less silver chloride, silver bromide, and silver chlorobromide are more preferred.
  • the interior and the surface of the silver halide grain may differ, the silver halide grain may have a multiphase structure with epitaxial faces, or the silver halide grain may be uniform throughout.
  • the silver halide grains of the above-described kinds may be present as a mixture.
  • a mean grain size of the silver halide grains employed in the process of the present invention refers to a grain diameter in case of grains which are spherical or approximately spherical in shape, while it refers to an edge length in case of cubic grains, and in both cases, it is represented by a mean value based on the projected area of the grains) ranges preferably from 0.1 flm to 2 wm, particularly preferably from 0.15 ⁇ m to 1 fl m.
  • the distribution of the grain size may be either narrow or broad.
  • a so-called monodispersed silver halide emulsion having a narrow grain size distribution such that at least 90%, preferably at least 95%, of the grains fall within the range of ⁇ 40% of the number or weight average grain size can be used.
  • monodispersed silver halide emulsions having substantially the same color sensitivity but differing in grain size can be coated in a single layer as a mixture, or they can be coated separately in a multilayer.
  • two or more polydispersed silver halide emulsions or a combination of monodispersed and polydispersed emulsions may be coated as a mixture or separately in a multilayer.
  • the silver halide grains to be employed in the process of the present invention may have a regular crystal form such as that of a cube, an octahedron, a dodecahedron, or a tetradecahedron, or an irregular crystal form, such as that of the sphere. Also, the grains may have a composite form of these crystal forms. Moreover, the grains may have a tabular form in which a grain diameter is greater than a grain thickness by a factor of 5 or more, particularly 8 or more. Emulsions in which such tabular grains account for 50% or more of the total projected area of the grains may be employed in the process of this invention. Emulsions which contain silver halide grains having various kinds of crystal forms as a mixture may be employed. These various kinds of emulsions may be either those which form a latent image predominantly at the surface of the grain (surface latent image type) or those which mainly form a latent image inside the grains (internal latent image type).
  • photographic emulsions can be prepared using various methods as described, e.g., in P. Grafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), V.L. Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966), so on. More specifically, any processes, e.g., the acid process, the neutral process or the ammoniacal process can be employed.
  • a method in which silver halide grains are produced in the presence of excess silver ions (the so-called reverse mixing method) can be employed.
  • the so-called controlled double jet method in which the pAg of the liquid phase where silver halide grains are to be precipitated is maintained constant may be employed. According to this method, silver halide emulsions having a regular crystal form and an almost uniform grain size can be obtained.
  • emulsions used in the process of the present invention are, in general, those that are subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in these steps are described in Research Disclosure, No. 17643 and ibid., No. 18716, and the relevant parts therein are listed in the following Table.
  • Important dye-forming couplers are those capable of forming three primary colors (of yellow, magenta, and cyan) in a subtractive color process by color development, and specific examples of non-diffusible four-equivalent or two-equivalent couplers which may be used in the present invention are described in the patent specifications referred to in Research Disclosure, No. 17643, VII-C and D.
  • other couplers as mentioned below may also preferably be used in the process of the present invention.
  • yellow couplers which may be used in the process of the present invention are hydrophobic acylacetamide type couplers having a ballast group. Specific examples thereof are described, for example, in U.S. Patents 2,407,210, 2,875,057, and 3,265,506.
  • Two-equivalent yellow couplers are particularly preferably used in the process of the present invention; and typical examples thereof are oxygen atom-releasing type yellow couplers as described in U.S. Patents 3,408,194, 3,447,928, 3,933,501, and 4,022,620; and nitrogen atom-releasing type yellow couplers as described in Japanese Patent Publication No. 10739/83, U.S. Patents 4,401,752 and 4,326,024, Research Disclosure, No.
  • a-Pivaloylacetanilide type couplers are good in fastness, especially to light, of the formed dyes; and, on the other hand, a-benzoylacetanilide type couplers are high in color density of the formed dyes.
  • Magenta couplers which may be used in combination with the pyrazoloazole type coupler in the process of the present invention are ballast group-containing hydrophobic indazolone type or cyanoacetyl type couplers, preferably 5-pyrazolone type or pyrazoloazole type couplers.
  • the 5-pyrazolone type couplers those whose 3-position is substituted by an arylamino group or an acylamino group are preferred because of hue and color density of the formed dyes.
  • Typical examples of these couplers are described in U.S. Patents 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896, and 3,936,015.
  • ballast group-containing 5-pyrazolone type couplers as described in European Patent 73,636 are preferred because they provide a high color density.
  • cyan couplers which can be used in the process of the present invention
  • hydrophobic and diffusion- resistant naphthol type and phenol type couplers are exemplified.
  • Typical examples thereof include naphthol type couplers as described in U.S. Patent 2,474,293 and preferably oxygen atom-releasing type two-equivalent naphthol type couplers as described in U.S. Patents 4,052,212, 4,146,396, 4,228,233 and 4,296,200, etc.
  • Specific examples of phenol type couplers are described in U.S. Patents 2,369,929, 2,801,171, 2,772,162 and 2,895,826.
  • Cyan couplers capable of forming cyan dyes fast to humidity and temperature are preferably used in the process of the present invention.
  • Typical examples thereof include phenol type cyan couplers having an alkyl group more than a methyl group at the meta-position of the phenol nucleus as described in U.S. Patent 3,772,002, 2,5-diacylamino-substituted phenol type couplers as described in U.S. Patents 2,772,162, 3,758,308, 4,126,396, 4,334,011 and 4,327,173, West German Patent Application (OLS) No.
  • couplers capable of forming appropriately diffusible dyes can be used together in order to improve the graininess.
  • Specific examples of such types of magenta couplers are described in U.S. Patent 4,366,237 and British Patent 2,125,570, and those of yellow, magenta and cyan couplers are described in European Patent 96,570 and West German Patent Application (OLS) No. 3,234,533.
  • Dye forming couplers and the above described special couplers may form polymers including dimers or more.
  • Typical examples of polymerized dye forming couplers are described in U.S. Patents 3,451,820 and 4,080,211.
  • Specific examples of polymerized magenta couplers are described in British Patent 2,102,173 and U.S. Patent 4,367,282.
  • Couplers capable of releasing a photographically useful residue during the course of coupling can also be preferably employed in the process of the present invention.
  • Specific examples of useful DIR couplers capable of releasing a development inhibitor are described in the patents cited in Research Disclosure, No. 17643 (December, 1978), "VII-F" as mentioned above.
  • the color photographic materials used in the process of the present invention may be developed by means of a conventional developing means as described, for example, in the aforesaid Research Disclosure, NO. 17643, pp. 28-29 and ibid., No. 18716, page 651, from left-hand column to right-hand column.
  • the color photographic light-sensitive material used in the present invention is generally subjected to washing or stabilization.
  • the washing step is, in general, carried out using two or more tanks according to the countercurrent washing method for the purpose of saving water.
  • the stabilizing step mention may be made of a multistage countercurrent stabilization processing which is to be carried out in place of the washing step, as described in Japanese Patent Application (OPI) No. 8543/82.
  • OPI Japanese Patent Application
  • a countercurrent bath having 2 to 9 tanks is required.
  • To the stabilizing bath used in the present invention are added various kinds of compounds in order to stabilize the developed images.
  • Typical examples of such additives include various buffering agents for adjusting the pH of the film to a proper value (ranging, e.g., from 3 to 8), such as those prepared by combining properly acids and alkalis selecting from borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, and formaldehyde.
  • the stabilizing bath may further contain a water softener (e.g., inorganic phosphoric acids, aminopolycarboxylic acids, organic phosphoric acids, aminopolyphosphonic acids or phosphonocarboxylic acids), a fertilizer (e.g., benzisothiazolinone, isothiazolone, 4-thiazolinebenzimidazole or halogenated phenols), a surface active agent, a fluorescent whitening agent, a hardener, and various kinds of additives, if desired. Two or more kinds of compounds may be used for the same purpose or different purposes.
  • a water softener e.g., inorganic phosphoric acids, aminopolycarboxylic acids, organic phosphoric acids, aminopolyphosphonic acids or phosphonocarboxylic acids
  • a fertilizer e.g., benzisothiazolinone, isothiazolone, 4-thiazolinebenzimidazole or halogenated phenols
  • ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite or ammonium thiosulfate, are added to the stabilizing bath in order to control the pH of the processed film.
  • the process of the present invention can be applied to various kinds of color photographic materials.
  • Representatives of such materials are color negative films for general use or motion picture use, color reversal films for slide use or television use, color paper, color positive films or color reversal paper.
  • Coupler (1) 17 ml of tri(2-ethylhexyl) phosphate and 25 ml of ethyl acetate were added to 14,3 g of Coupler (1) as a magenta coupler, and the mixture was heated for dissolution.
  • the solution was added to 100 ml of an aqueous solution containing 10 g of gelatin and 1.0 g of sodium dodecylbenzenesulfonate, followed by stirring at an elevated temperature to prepare a finely emulsified dispersion.
  • the whole amount of the emulsion dispersion was added to 100 g of a silver chlorobromide emulsion having a bromide content of 50 mole% (containing 6.5 g of silver), and 10 ml of a 2% aqueous solution of 2,4-dihydroxy-6-chloro-s-triazine sodium salt was further added thereto as a hardener.
  • the thus prepared composition was coated on a paper support laminated with polyethylene on both the sides thereof in such an amount that the silver coverage was 200 mg/m 2.
  • a gelatin layer was provided on the coated layer to prepare a sample. This sample is referred to as Sample A.
  • Sample A and the comparative sample were subjected to 1000 C.M.S. wedge exposure and then processed using the following processing solutions.
  • the coupler used in the present invention is superior in both sensitivity and gradation to the coupler having an alkyl group at the 6-position. This is attributable to introduction of an alkoxy group or an aryloxy group at the 6-position, whereby the coupling activity is enhanced and the color-forming efficiency is improved.
  • a first layer (undermost layer) to a seventh layer (uppermost layer) were coated in sequence on a paper support laminated with polyethylene on both sides thereof to prepare color photographic materials B and C.
  • each third layer in which an emulsion dispersion of magenta coupler and a silver halide emulsion were contained were prepared in the same manner as in Example 1.
  • Example 2 B and C were exposed in the same manner as in Example 1 through a B-G-R three-color separation filter and then processed in the same manner as in Example 1 except that the color development time employed was 2 min, 3 min and 30 s, or 6 min.
  • the couplers of the present invention can contribute to attainment of photographic characteristics with less fluctuation by short-time development.
  • High activity and high color-forming efficiency of the couplers used in the present invention as compared with those of conventional pyrazoloazole couplers are advantageous in designing photographic materials.
  • the couplers used in the present invention have excellent properties.
  • Coupler (2) as a magenta coupler
  • the solution was added to 100 ml of an aqueous solution containing 10 g of gelatin and 1.0 g of sodium dodecylbenzenesulfonate, followed by stirring at an elevated temperature to prepare a finely emulsified dispersion.
  • the whole amount of the emulsion dispersion was added to 100 g of a silver chlorobromide emulsion having a bromide content
  • Comparative Sample (1) was prepared in the same manner as described above except that 8.9 g (16.8 mmol) of the following Comparative Compound (1):
  • magenta coupler (described in European Patent Application No. 176,804A) was used as the magenta coupler and that tri(2-ethylhexyl) phosphate was used in an amount of 18 ml instead of 20 ml.
  • Coating compositions for the second to seventh layers were prepared in a similar manner as described above.
  • 1-oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardener.
  • Spectral sensitizers employed in the respective emulsion layers are illustrated below.
  • the following dyes were incorporated in the emulsion layers as their respective irradiation preventing dyes.
  • the compositions were simultaneously coated to prepare a multilayered silver halide color photographic material.
  • Various coating compositions for the third layer were prepared using the couplers represented by the formula (I) or (II) of the present invention and the comparative couplers as the magenta coupler and changing the formulation variously as shown in Table 6. Using these coating compositions respectively, multilayered color photographic materials were prepared and referred to as Samples II-A to II-G.
  • the sensitivity is a relative value, taking the sensitivity of Sample II-A 1 and Sample B attained by 1.5 min development as 100 (comparison was carried out using samples having the same volume).
  • the gradation (y) is expressed in terms of a slope of the characteristic curve in the straight line portion corresponding to the density range of from 0.6 to 2.0.
  • the maximum density means a maximum density of magenta dye image.
  • Samples II-C to II-G had enhanced sensitivity and improved gradation (y) and produced high color density of the developed image.
  • Example 8 For the purpose of sensitometry evaluation, the samples prepared in Example 4, Samples II-A to II-G, were subjected to wedge exposure in a conventional manner and processed according to the following processing steps using processing solutions having formulations described below. The results obtained are shown in Table 8.
  • the sensitivity is a relative value, taking the sensitivity of Samples II-A 1 and II-B attained by 30 s development as 100.
  • the gradation ( ⁇ ) is expressed in terms of a slope of the characteristic curve in the straight line portion corresponding to the density range of from 0.6 to 2.0.
  • Gamma values in parentheses are slopes of individual straight line portions because image densities did not go up to 2.0 under such conditions.
  • the maximum density means a maximum density of magenta dye image.
  • Second Layer (antihalation layer):
  • Samples III-B to III-F were prepared in the same manner as Sample III-A 1 or III-A 2 except that the comparative magenta coupler (*15) was replaced by an equimolar amount of each of Couplers (2), (7), (8), (11), and (13). These samples III-A to III-F were subjected to wedge exposure in a conventional manner and then processed according to the following processing steps using processing solutions having the formulations described below.
  • Samples III-B to III-F in which the couplers of the process of the present invention are employed had improved gradation ( ⁇ ) and produced high color density of the developed image.
  • Second Layer (Gelatin interlayer):
  • Emulsion (c) was mixed with a I kg portion of a red-sensitive silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin and having an iodide content of 2.5 mol%), and the mixture was coated in a dry thickness of 2.5 pm (silver coverage: 0.8 g/m 2 ).
  • Emulsion (d) A 300 g portion of Emulsion (d) was mixed with a I kg portion of a green-sensitive silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin and having an iodide content of 3 mol%), and the mixture was coated in a dry thickness of 2.0 ⁇ m (silver coverage: 0.7 g/m 2 ).
  • Samples IV-B to IV-G were prepared in the same manner as the Sample IV-A, or IV-A 2 except that Comparative Magenta Coupler (I) or (2) was replaced by an equimolar amount of each of Couplers (2), (7), (8), (11), (13) and (14) respectively.
  • Samples IV-B to IV-G in which the couplers of the process of present invention are employed had improved gradation ( ⁇ ) and produced high color density of the developed image.
  • Gelatin Hardener H-I and a surface active agent were incorporated in each of the foregoing layers.
  • Samples V-B to V-G were prepared in the same manner as Sample V-Ai or V-A 2 except that Comparative Magenta Coupler (I) or (2) was replaced by an equimolar amount of each of Couplers (2), (7), (8), (11), (13) and (14), respectively. These Samples V-A to V-G were subjected to wedge exposure in a conventional manner and then processed according to the following processing steps using processing solutions having the formulations described below.
  • the photographic processing employed herein included the following steps and was carried out at a temperature of 38°C.
  • compositions of the processing solutions used were as follows.
  • the couplers of the process of the present invention have less dependence of sensitivity, gradation and maximum density upon color development time and can exhibit photographic characteristics with smaller fluctuation by short-time development as compared with the conventional couplers having an alkyl group at the 6-position.
  • the couplers of the process of the present invention possess higher activity and higher color-forming efficiency as compared with conventional pyrazoloazole couplers, they are advantageous in designing photographic materials.
  • the couplers of the process of the present invention are found to have excellent properties.

Claims (16)

1. Un procédé pour former une image couleur comprenant le développement d'un matériau photographique à l'halogénure d'argent en utilisant un révélateur contenant une amine primaire aromatique en présence d'au moins un coupleur, caractérisé en ce que ledit coupleur est représenté par la formule (I) ou (II) suivante :
Figure imgb0144
dans laquelle R1 représente un groupe alkyle substitué ou non, un groupe aryle substitué ou non ou un groupe hétérocyclique ; R2 représente un atome d'hydrogène ou un substituant ; et X représente un groupe éliminable relié par un atome d'azote ou de soufre ;
Figure imgb0145
dans laquelle R1 et X ont les mêmes significations que dans la formule (I), respectivement ; et R'2 représente un groupe alkyle substitué ou non, un groupe aryle substitué ou non, un groupe alkylthio, un groupe arylthio ou un groupe thio hétérocyclique.
2. Le procédé selon la revendication 1, dans lequel le substituant représenté par R2 est un atome d'hydrogène ou d'halogène, un groupe alkyle, un groupe aryle, un groupe hétérocyclique, un groupe cyano, un groupe alcoxy, un groupe aryloxy, un groupe acylamino, un groupe anilino, un groupe uréido, un groupe sulfamoylamino, un groupe alkylthio, un groupe arylthio, un groupe alcoxycarbonyla- mino, un groupe sulfonamido, un groupe carbamoyle, un groupe sulfamoyle, un groupe sulfonyle ou un groupe alcoxycarbonyle.
3. Le procédé selon la revendication 2, dans lequel le substituant représenté par R2 est un groupe alkyle, un groupe aryle, un groupe alkylthio ou un groupe arylthio.
4. Le procédé selon la revendication 1, dans lequel le substituant représenté par R2 est un groupe alkyle ou un groupe aryle.
5. Le procédé selon la revendication 1, dans lequel R'2 est un groupe alkyle substitué ou un groupe aryle substitué.
6. Le procédé selon la revendication 5, dans lequel R'2 est un groupe alkyle substitué.
7. Un procédé selon la revendication 1, dans lequel Ri, R2, R'2 ou X est un groupe divalent pour former un bis-composé, Ri, R2 ou R'2 représente un groupe alkylène substitué ou non ou un groupe phénylène substitué ou non et X représente un groupe divalent obtenu en transformant l'un quelconque des groupes monovalents cités dans la revendication 1 en un groupe divalent correspondant dans une position convenable.
8. Un procédé selon la revendication 1, dans lequel le coupleur représenté par la formule (I) ou (II) constitue une partie d'un monomère vinylique, un groupe de liaison représenté par Ri, R2 ou R'2 comprend des groupes formés en reliant des groupes choisis parmi un groupe alkylène substitué ou non, un groupe phénylène substitué ou non, -NHCO-, -CONH-, -O-, -OCO- et un groupe aralkylène.
9. Le procédé selon la revendication 1, dans lequel un monomère ayant un reste représenté par la formule (I) ou (II) forme un copolymère avec un monomère éthylénique non chromogène qui ne copule pas avec un produit d'oxydation d'un développateur du type amine primaire aromatique.
10. Le procédé selon la revendication 1, dans lequel le coupleur représenté par la formule (I) ou (II) est incorporé dans le matériau photographique à l'halogénure d'argent.
11. Le procédé selon la revendication 1, dans lequel le coupleur représenté par la formule (I) ou (II) est ajouté à un bain de développement chromogène.
12. Le procédé selon la revendication 10, dans lequel le coupleur représenté par la formule (I) ou (II) est ajouté en quantité de 2 x 10-3 mole à 5 x 10-1 mole par mole de l'halogénure d'argent.
13. Le procédé selon la revendication 12, dans lequel le coupleur représenté par la formule (I) ou (II) est ajouté en quantité de 1 x 10-2 mole à 5 x 10-1 mole par mole de l'halogénure d'argent.
14. Le procédé selon la revendication 11, dans lequel le coupleur représenté par la formule (I) ou (II) est ajouté en quantité de 0,001 mole à 0,1 mole par litre du bain de développement chromogène.
15. Le procédé selon la revendication 14, dans lequel le coupleur représenté par la formule (I) ou (II) est ajouté en quantité de 0,01 à 0,05 mole par litre du bain de développement chromogène.
16. Le procédé selon la revendication 1, dans lequel on incorpore dans ledit matériau photographique à l'halogénure d'argent un stabilisant de l'image couleur représenté par la formule suivante :
Figure imgb0146
dans laquelle R10 représente un atome d'hydrogène, un groupe alkyle, un groupe aryle, ou un groupe hétérocyclique ; R11, R12, R14 et R15 représentent chacun un atome d'hydrogène, un groupe hydroxyle, un groupe alkyle, un groupe aryle, un groupe alcoxy, un groupe acylamino, un groupe alcoxycarbonyle ou un groupe sulfonamido ; et R1 représente un groupe alkyle, un groupe hydroxyle, un groupe aryle ou un groupe alcoxy, à la condition que R10 et R11 puissent se combiner entre eux pour former un cycle à 5-6 chaînons ou un cycle méthylènedioxy et que R13 et R14 puissent se combiner entre eux pour former un cycle hydrocarboné à 5 chaînons.
EP19860116345 1985-11-25 1986-11-25 Procédé de préparation d'une image en couleur Expired EP0226849B1 (fr)

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JP24271286A JPS62209457A (ja) 1985-11-25 1986-10-13 カラ−画像形成方法

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EP0285274B1 (fr) * 1987-03-09 1990-11-07 EASTMAN KODAK COMPANY (a New Jersey corporation) Matériaux photographiques à l'halogénure d'argent et procédé comprenant un coupleur pyrazoloazole
JPH0693105B2 (ja) * 1987-06-10 1994-11-16 富士写真フイルム株式会社 マゼンタ色素形成カプラ−
JPS647041A (en) * 1987-06-30 1989-01-11 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material
US5149828A (en) * 1987-09-30 1992-09-22 Ciba-Geigy Ag Stabilizers for color photography recording materials
DE3871062D1 (de) * 1987-09-30 1992-06-17 Ciba Geigy Ag Stabilisatoren fuer farbphotographische aufzeichnungsmaterialien.
JPH01108546A (ja) 1987-10-22 1989-04-25 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
JPH01250955A (ja) 1987-12-09 1989-10-05 Fuji Photo Film Co Ltd カラー写真感光材料
JPH02217845A (ja) * 1989-02-20 1990-08-30 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
JP2665628B2 (ja) * 1990-11-22 1997-10-22 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
DE4211479A1 (de) * 1992-04-06 1993-10-07 Agfa Gevaert Ag Verfahren zur Herstellung von Pyrazolo [5,1-c][1,2,4]triazolen
JPH0675343A (ja) 1992-07-06 1994-03-18 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料及びカラー画像形成方法
EP1709483A4 (fr) 2004-01-30 2007-06-27 Fujifilm Corp Materiau photographique couleur photosensible a base d'halogenure d'argent et procede de formation d'une image couleur

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