EP0301477B1 - Matériau photosensible couleur à l'halogénure d'argent et sa méthode de traitement - Google Patents

Matériau photosensible couleur à l'halogénure d'argent et sa méthode de traitement Download PDF

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Publication number
EP0301477B1
EP0301477B1 EP19880112038 EP88112038A EP0301477B1 EP 0301477 B1 EP0301477 B1 EP 0301477B1 EP 19880112038 EP19880112038 EP 19880112038 EP 88112038 A EP88112038 A EP 88112038A EP 0301477 B1 EP0301477 B1 EP 0301477B1
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Prior art keywords
group
acid
carbon atoms
coupler
silver halide
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EP19880112038
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German (de)
English (en)
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EP0301477A3 (en
EP0301477A2 (fr
Inventor
Kei C/O Fuji Photo Film Co. Ltd. Sakanoue
Hidetoshi C/O Fuji Photo Film Co. Ltd. Kobayashi
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • 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
    • 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
    • G03C7/30523—Phenols or naphtols couplers

Definitions

  • the present invention concerns a silver halide color photosensitive material.
  • Silver halide color photosensitive materials are generally processed in a color developing step and a desilvering step.
  • exposed silver halide is reduced by a color developing agent to produce silver, while the oxidized color developing agent reacts with a coupler to provide a dyed image.
  • the thus formed silver is oxidized with a bleaching agent in the succeeding desilvering step and further undergoes the effect of a fixing agent into a soluble silver complex which is then removed by dissolution.
  • JP-A As a method of increasing the bleaching power, Research Disclosure Item Nos. 24241 and 11449 and JP-A-61-201247 (the term “JP-A” as used herein means an "unexamined published Japanese patent application”) describe couplers of a bleach accelerating compound releasing type, and it has been known that the desilvering performance can be improved by using a silver halide color photosensitive material containing such a coupler of the bleach accelerating compound releasing type.
  • JP-A-61-201247 concerning a coupler of the bleach accelerating compound releasing type described above, a phenol type cyan coupler having a 4-cyanophenylureido group at the 2-position is used as a kind of cyan image-forming coupler effective for such a reproducibility.
  • EP-A-0 246 616 belonging to the state of the art according to Art. 54(3)EPC describes a silver halide colour photographic material comprising a support having provided thereon at least one silver halide emulsion layer containing specific cyan couplers.
  • a silver halide colour photosensitive material comprising at least one silver halide emulsion layer on a support, which contains at least one bleaching accelerator releasing type coupler characterised in that said bleaching accelerator releasing type coupler is represented by the following formula (I) : wherein R 1 is selected from the group consisting of a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amidino group, a guanidino group, R 2 is selected from the group consisting of a halogen atom, a hydroxyd group, a carboxyl group, a sulfo group, an amino group, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a carbonamido group, a sulfonamido group, a carbamoyl group,
  • the alkyl group, alkenyl group and alkynyl group of the coupler of formula (I) may be linear, branched or cyclic and may be substituted or unsubstituted.
  • the aryl group of the coupler of formula (1) may be substituted or unsubstituted and includes a condensed ring.
  • Heterocyclic rings may be a substituted or unsubstituted, single or condensed heterocyclic ring.
  • aryl groups suitable for the couplers to be used in the present invention include phenyl, p-tolyl, m-tolyl, o-tolyl, 4-chlorophenyl, 4-nitrophenyl, 4-cyanophenyl, 4-hydroxyphenyl, 3-hydroxyphenyl, 1-naphthyl, 2-naphthyl, o-biphenyl, p-biphenyl, pentafluorophenyl, 2-methoxyphenyl, 2-ethoxyphenyl, 4-methoxyphenyl, 4-t-butylphenyl, 4-t-octylphenyl, 4-carboxyphenyl, 4-methane sulfoneamidophenyl, 4-(4-hydroxyphenylsulfonyl)phenyl, 2-n-tetradecyloxyphenyl, 4-n-tetradecyloxyphenyl, 2-chloro-5-n-dodec
  • R 1 represents a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amidino group, a guanidino group or a group represented by wherein R 4 and R 5 each represents an alkyl, alkenyl or alkynyl group with 1 to 30 carbon atoms.
  • R 4 and R 5 may join with each other to form a ring.
  • the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom oran iodine atom.
  • R represents an amidino group orguanidino group
  • the number of carbon atoms thereof is from 1 to 30 which may be substituted with an aliphatic group, an aromatic group, a hydroxyl group, an aliphatic oxy group, an acyl group, an aliphatic sulfonyl group, an aromatic sulfonyl group, an acyloxy group, an aliphatic sulfonyloxy group or an aromatic sulfonyloxy group, or two nitrogen atoms may join with each other to form a heterocyclic ring such as imidazole or benzimidazole.
  • R z represents a halogen atom, (for example, fluorine, chlorine, bromine or iodine), a hydroxyl group, a carboxyl group, a sulfo group, a cyano group, a nitro group, an amino group with 0 to 30 carbon atoms (for example, amino, methylamino, dimethylamino, pyrrolidino, anilino), an alkyl, alkenyl or alkynyl group with 1 to 30 carbon atoms, an aryl group with 6 to 30 carbon atoms, a carbonamido group with 1 to 30 carbon atoms (for example, formamido, acetoamido, trifluoroacetoamido, benzoamido), a sulfonamido group with 1 to 30 carbon atoms (for example, methane sulfonamido, trifluoromethane sulfonamido, n-butane
  • R 3 represents a hydrogen atom or RaY, in which R e represents a hydrogen atom, an alkyl, alkenyl or alkynyl group with 1 to 30 carbon atoms, an aryl group with 6 to 30 carbon atoms, a heterocyclic group with 1 to 30 carbon atoms, -SO 2 R 7 , -SO 2 OR 7 , or an imido group with 4 to 30 carbon atoms (for example, succinimido, maleinimido, phthalimido, diacetylimido) ; Y represents -CO-, -SO 2 -, -SO- or single bond, R 7 represents an alkyl, alkenyl or alkynyl group with 1 to 30 carbon atoms, an aryl group with 6 to 30 carbon atoms or a heterocyclic group with 1 to 30 carbon atoms ; R 8 represents a hydrogen atom, an alkyl, alkenyl or alkynyl group with 1 to 30 carbon
  • the group represented by LINK may be present or absent. It is preferred that the group LINK is absent but it may also be properly selected depending on the purpose. In the case of using the group represented by LINK, the following known functional linkage groups may be induded :
  • R 15 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group
  • R 16 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.
  • R 11' R 12 , R 13 can represent a divalent group, and any two of R 11 , R 12 and R 13 can be joined to form a cyclic structure.
  • Specific examples of the group represented by formula (T-1) are set forth below.
  • Nu represents a nucleophilic group in which an oxygen atom or a sulfur atom is an example of the nucleophilic species ;
  • E represents an electrophilic group capable of cleaving the bonding with the symbol ** upon nucleophilic attack from Nu.
  • LINK represents a linkage group for sterically relating Nu and E such that they can conduct an intramolecular nucleophilic substitution reaction. Specific examples of the groups represented by Formula (T-2) are described below.
  • L represents a (n + 1) valent group, that is, those groups formed by removing n number of hydrogen atoms from a linear, branched or cyclic alkyl group with 1 to 8 carbon atoms, an aryl group with 6 to 10 carbon atoms which may be substituted with a halogen atom or an alkyl group, or a heterocyclic group with 1 to 10 carbon atoms (for example, tetrazol-1-yl, 1,3,4-triazol-1-yl, 2-methyl-1,3,4-triazol-1-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-triazol-2-yl, 1-methyl-1,3,4-
  • the groups represented by X are those groups with not more than 8 carbon atoms, for example, a carboxyl group, a sulfo group, a hydroxyl group, an amino group, an alkoxy group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a ureido group, a sulfamyl group, an acryl group, an amidino group, an alkylsulfonyl group, a phosphono group, a phosphonooxy group, or those groups containing at least one of these aforementioned groups.
  • R 2 and R 3 or a plurality of R 2 may join with each other to form a ring.
  • R 1 is preferably a halogen atom, -COR 4 or -S0 2 R 4 , and the case in which R 4 represents an amino group is further preferred.
  • Examples of -COR 4 include carbamoyl, N-ethylcarbamoyl, N-n-butylcarbamoyl, N-cyclohexylcarbamoyl, N-(2-ethylhexyl)carbamoyl, N-dodecylcarbamoyl, N-hexadecylcarbamoyl, N-(3-decyloxypropyl)carbamoyl, N-(3-dodecyloxypropyl)carbamoyl, N-(3-(2,4-di-t-pentylphenoxy)propyl)carbamoyl, N-(4-(2,4-di-t-pentyl- phenoxy)butyl)carbamoyl, N,N-dimethylcarbamoyl, N,N-dibutylcarbamoyl, N-methyl-N-d
  • Examples of -S0 2 R 4 include sulfamoyl, N-methylsulfamoyl, N,N-diethylsulfamoyl, N,N-diisopropylsulfamoyl, N-(3-dodecyloxypropyl)sulfamoyl, N-(3-(2,4-di-t-pentylphenoxy)propyl)sulfamoyl, N-(4-(2,4-di-t-pentylphenoxy)butyl)sulfamoyl, pyrrolidinosul- fonyl, N-phenylsulfonyl, N-(2-butoxyphenyl)sulfamoyl and N-(2-tetradecyloxyphenyl)sulfamoyl.
  • R 1 -COR 4 in which R 4 is an amino group is particularly preferred.
  • R 2 is preferably a halogen atom, an aliphatic group, an aliphatic oxy group, a carbonamido group, a sulfonamido group or a cyano group : a fluorine atom, a chlorine atom, a trifluoromethyl group, a methoxy group or a cyano group being particularly preferred.
  • the substitution position of R 2 is preferably at the 2-position or the 4-position relative to R 3 NH-.
  • R s is preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group -OR 7 or -SR7 ; Y is preferably -CO- or -S02-.
  • alkyl group include methyl, trifluoromethyl, trichloromethyl, ethyl, heptafluoropropyl, t-butyl, 1-ethylpentyl, cyclohexyl, benzyl, undecyl, tridecyl and 1-(2,4-di-t-pentylphenoxy)propyl.
  • Examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl, 2-chlorophenyl, 4-methoxyphenyl, 4-nitrophenyl and pentafluorophenyl.
  • Examples of-OR 7 include methoxy, ethoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, n-pentyloxy, n-hexyloxy, n-octyloxy, 2-ethylhexyloxy, n-decyloxy, n-dodecyloxy, 2-methoxyethoxy, benzyloxy, trichloroethoxy, trifluoroethoxy, phenoxy and p-methylphenoxy.
  • Examples of -SR 7 include methylthio, ethylthio, allylthio, n-butylthio, benzyl- thio, n-dodecylthio, phenylthio, p-t-octylphenylthio, p-dodecylphenylthio, and p-octyloxyphenylthio.
  • R 3 is, more preferably, an aliphatic oxy carbonyl group in which R e is R 7 0 and Y is -CO-, or an aliphatic or aromatic sulfonyl group in which R e is an alkyl, alkenyl, alkynyl or aryl group and y is -SO z -.
  • R 3 is most preferably an aliphatic oxy carbonyl group.
  • L is preferably an alkylene group or a heterocyclic group, more preferably, an alkylene group.
  • X is, preferably, a substituent in which the ⁇ -substituent constant is 0.5 or less, preferably, the substituent constant has a negative value.
  • the value is determined by the method as described in "Substituent Constants for Correlation Analysis in Chemistry and Biology" written by C. Hansch and A. Leo, published by John Wiley, 1979. Examples of X and ⁇ -substituent constants (within ( )) are shown below.
  • n is preferably 1 or 2 and, more preferably 1.
  • n is represented by the following formula (II) : wherein R 17 and R 18 represent a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, p represents an integer of 1 to 8, and Z represents a hydroxyl group, a carboxyl group, a sulfo group or an amino group with 0 to 8 carbon atoms (for example, amino, methylamino, ethylamino, methoxyethylamino, butylamino, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, piperidino, pyrrolidino, morpholino).
  • p represents an integer of 2 to 8
  • each may be identical to or different from the others, and the number of carbon atoms in is from 1 to 8.
  • the carboxyl group the carboxyl group
  • the coupler represented by formula (I) may form a dimer or higher polymer joined with another by way of divalent or higher valent groups at the substituents R 1 , R 2 and R 3 respectively.
  • the range for the number of carbon atoms shown for each of the substituents as described above may be beyond the scope of the above definition.
  • the coupler represented by formula (I) forms a polymer
  • typical examples thereof include a homopolymer or copolymer of addition polymerizable ethylenically unsaturated compounds having a cyan dye forming coupler residue (cyan color forming monomer).
  • the polymer contains repeating units of formula (III) and one or more of cyan color-forming repeating units represented by formula (III) may be contained in the polymer and it may be a copolymer containing one or more of the non-color-forming ethylenic monomer as the copolymerization ingredient.
  • R represents a hydrogen atom, an alkyl group with 1 to 4 carbon atoms or a chlorine atom;
  • A represents -CONH-, -COO- or a substituted or unsubstituted phenylene group ;
  • B represents a substituted or unsubstituted alkylene group, a phenylene group or an aralkylene group;
  • Q represents a cyan coupler residue formed by removing other hydrogen atoms than the hydrogen atom at the hydroxy group on the 1-position of the compound represented by formula (I).
  • a copolymer of the cyan color forming monomer giving the coupler unit of formula (III) with the following non-color-forming ethylenic monomer is preferred.
  • the non-color-forming ethylenic monomer which is not coupled with oxidation products of an aromatic primary amine developing agent, can include acrylic acid ; a-chloroalkylacrylic acid ; a-alkylacrylic acid (for example, methacryl acid), esters or amides derived from these acrylic acids (for example, acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, N-methylolacrylamide, N-(1,1-dimethyl-2-sulfonatoethyl)acrylamide, N-(3-sulfonatopropyl)acrylamide, methylacrylate, ethylacrylate, n-propylacrylate, n-butylacrylate, t-butylacrylate, isobutylacrylate, acetoacetoxyethylacrylate, n-hexylacrylate, 2-ethylhexylacrylate,
  • Acrylic acid ester, methacrylic acid ester and maleic acid esters are particularly preferred.
  • Two or more of the non-color-forming ethylenic monomers can be used together.
  • the following combinations can be used : methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methylacrylate and diacetone acrylamide, N-(1,1-dimethyl-2-sulfonatoethyl)acrylamide and acrylic acid, potassium styrene sulfinate and N-vinylpyrrolidone.
  • the ethylenically unsaturated monomer for copolymerization with a vinylic monomer corresponding to formula (III) described above can be selected such that a preferred effect can be given to the copolymer formed with respect to physical properties and/or chemical properties of the copolymer, such as solubility, compatibility with a binder for the photographic colloid composition (for example, gelatin), flexibility and heat stability.
  • oleophilic polymer coupler soluble in organic solvent
  • the emulsion of the cyan polymer couplerfor use in the material of this invention may be prepared by emulsion-dispersing a solution of the oleophilic coupler obtained by polymerization of the vinylic monomer giving the coupler unit dissolved in an organic solvent in an aqueous gelatin solution in the form of a latex or may be prepared by a direct emulsion polymerization method.
  • hydrophilic non-color-forming ethylenic monomers such as N-(1,1-dimethyl-2-sul- fonatoethyl)acrylamide, 3-sulfonate propylacrylate, sodium styrenesulfonate, potassium 2-styrene sulfinate, propylacrylate, methacrylamide, acrylic acid, methacrylic acid, N-vinylpyrrolidone and N-vinylpyridine.
  • the hydrophilic polymer coupler can be added as an aqueous solution to a coating liquid, and it is also possible to add same after being dissolved in a mixed solvent of a water miscible organic solvent such as a lower alcohol, tetrahydrofuran, acetone, ethyl acetate, cyclohexane, ethyl lactate, dimethyl formamide or dimethylacetoamide and water.
  • a water miscible organic solvent such as a lower alcohol, tetrahydrofuran, acetone, ethyl acetate, cyclohexane, ethyl lactate, dimethyl formamide or dimethylacetoamide and water.
  • the coupler may be added after being dissolved in an aqueous alkali solution or an alkali-containing organic solvent
  • a small amount of a surface active agent may be added.
  • the compounds represented by formula (I) can, for example, be synthesized according to the methods described in EP-A-161626, and JP-A-61-201247. Further, a compound having a functional linkage group can be synthesized according to the methods described in those patent literatures set forth above for the explanation of the functional linkage groups, for example, U.S. Patents 4,146,396, 4,246,962, 4,409,323 and 4,421,845.
  • the addition amount of the bleach accelerator releasing type coupler represented by formula (I) to the photosensitive material is preferably from 1 x 10- 7 mol to 1 x 10- 1 mol, particularly, from 1 x 10 -6 mol to 5x 10- 2 mol per m 2 of the photosensitive material. While the bleach accelerator releasing compound used according to the present invention can be added to any of the layers in the photosensitive material, it is preferred to add same to the photosensitive emulsion layer, particularly, a red-sensitive emulsion layer.
  • silver halide used in the emulsion layer of the photosensitive material is explained in more detail.
  • Any silver halide that is, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, silver chloride and silver chloroiodide may be used, but the use of silver iodobromide is particularly preferred.
  • the silver iodide content is usually less than 40 mol%, preferably, less than 20 mol% and more preferably, less than 10 mol%.
  • the silver halide grains may be so-called regular grains having a regular crystal body such as a hexahed- ron, an octahedron or tetradecahedron or those of irregular crystal forms such as spheres, those having crystal defects such as twine planes or mixed forms thereof. Furthermore, a mixture of grains of various crystal forms may be used.
  • the silver halide may either be a monodispersed emulsion having a narrow distribution or a polydispersed emulsion having a broad distribution.
  • tabular grains with an aspect ratio of 5 or more may be used.
  • the cristal structure of the emulsion grains mav hA uniform or one having a different halogen composition compositions may be joined by epitaxial junction, or may be joined with other compounds than silver halide such as silver rhodanate or lead oxide.
  • the emulsion described above may of a (A) a surface latent image type whereby latent images are formed mainly on the surface of the grains, or of (B) an internal latent image type whereby latent images are formed to the inside of the grains, or of (C) a type whereby the latent images are formed both on the surface as well as on the inner side of the grains. Grains in which the inside thereof is chemically sensitized may be used.
  • Silver halide photographic emulsions usable in the present invention can be produced by properly using known methods.
  • the emulsion can be prepared according to the method described in Research Disclosure vol. 176, No. 17643 (December 1978), pages 22 to 23, "Emulsion Preparation and Types", vol 187, No. 18716 (November 1979), page 648.
  • typical silver halide grains have an average grain size of not less than 0.1 pm in which at least 95% by weight thereof is within ⁇ 40% of the average grain size.
  • Those emulsions with average grain size from 0.25 to 2 ⁇ m in which at least 95% by weight of the number of silver halide grains are within the range of an average grain size ⁇ 20% can be used.
  • a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex thereof, a rhodium salt or a complex thereof, an iron salt or a complex salt may be present alone or with other of the above mentioned salts.
  • the emulsion used in the present invention is usually subjected to chemical ripening and spectral sensitization after the physical ripening.
  • various color couplers can be used in addition to the cyan image forming coupler of formula (I) and specific examples thereof are described in patent literatures set forth in Research Disclosure (RD) No. 17643, VII-C to G.
  • the color forming coupler those couplers giving three primary colors by a subtractive color process (that is, yellow, magenta and cyan) by color development are important, and the following couplers can be used preferably in the material of the present invention in addition to the diffusion resistant 4-equivalent or 2-equivalent couplers specifically described in the patent literatures set forth in Research Disclosure No. 17643, VII-C and D.
  • Typical examples of the yellow couplers usable herein include known oxygen atom releasing type yellow couplers or nitrogen atom releasing type yellow couplers.
  • a-Pivaloyl acetoanilide type couplers are excellent in the fastness of the color forming dye, particularly, light fastness, whereas a-benzoyl acetoanilide type couplers can provide a high color forming density.
  • magenta couplers usable in the present invention include hydrophobic 5-pyrazolone type and pyrazoloazole type couplers having ballast groups.
  • the 5-pyrazolone type couplers those substituted at the 3-position with an aryl amino group or an acyl amino group are preferred in view of the hue and the color forming density of the color forming dye.
  • the cyan coupler usable in the present invention further includes hydrophobic and diffusion resistant naphthol and phenol type couplers, and 2-equivalent naphthol type couplers of the oxygen atom releasing type can be mentioned as preferred typical examples.
  • those couplers capable of forming a cyan dye fast to humidity and temperature are preferably used and typical examples thereof include phenol type cyan couplers having an ethyl or a higher alkyl group at the metaposition of the phenol nuclei and 2,5-diacrylamino substituted phenol type couplers, phenol type couplers having a phenyl ureido group at the 2-position and a diacylamino group at the 5-position as described in U.S. Patent 3,772,002, and 5-amidonaphthol type cyan couplers as described in EP-A-161626.
  • a coupler in which the color forming dye has an adequate diffusing property may be used to improve the granular property.
  • specific examples of a magenta coupler are found in U.S. Patent 4,366,237, and specific examples of a yellow, magenta or cyan coupler are found in European Patent 96,570.
  • the dye-forming couplers and the particular couplers described above may form a dimer or a higher polymer.
  • Typical examples of polymerized dye-forming couplers are described in U.S. Patent 3,451,820.
  • Specific examples of polymerized magenta couplers are described in U.S. Patent 4,367,282.
  • Couplers releasing a photographically useful residual group upon coupling can also be used preferably in the present invention.
  • DIR coupler releasing development inhibitors those patented couplers described in RD 17643, VII-F (described above) are useful.
  • Couplers releasing a nucleating agent, a development accelerator or a precursor thereof upon development imagewise can be used for the photosensitive material according to the present invention. Specific examples of such compounds are described in British Patents 2,097,140 and 2,131,188. In addition, it is possible to use DIR redox compound releasing couplers as described in JP-A-60-185950, and couplers releasing dyes restoring color after splitting as described in EP-A-173302.
  • the coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods.
  • Examples of high boiling point organic solvents used for the oil-in-water droplet dispersion method are described in U.S. Patent 2,322,027.
  • the steps and the effect of the latex dispersion method and specific examples of latices for impregnation are described in U.S. Patent 4,199,363, German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.
  • the photosensitive material of the present invention may also contain hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, non- coloring couplers, an sulfonamido phenol derivatives as an anti-color fogging agent or an anti-color mixing agent
  • Known anti-discoloration agents may be used for the photosensitive material of the present invention.
  • Typical examples of known anti-discoloration agents include hydroquinones, 6-hydroxychromans, 5-hydroxycuma- rans, spirochromans, p-alkoxyphenols, hindered phenols such as bisphenols, gallic acid derivatives, methylene dioxybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by silylating or alkylating phenolic hydroxy groups in each of the compounds.
  • metal complexes typically represented by a (bissalicylaldoxymato)nickel complex and a (bis-N,N-dialkyldithiocarbamato)nickel complex may also be used.
  • the photographic emulsion layer and other layers are coated on a typical flexible support such as plastic films.
  • the photographic emulsion layer and other hydrophilic colloid layers can be coated by utilizing various known coating methods, for example, dip coating, roller coating, curtain coating and extrusion coating.
  • the present invention can be applied to various color photosensitive materials. Typical examples thereof include general-purpose or cinema use color negative films, color reversal films for slide or television use, color papers, color positive films, and color reversal papers.
  • the colordeveloper used forthe development of the photosensitive material according to the present invention is an aqueous alkaline solution using an aromatic primary amine color developing agent as the main ingredient.
  • an aminophenol type compound is also useful as the color developing agent, a p-phenylene diamine compound is preferably used and typical examples thereof include 3-methyl-4-amino-N,N-diethylaniline, 3-methy)-4-amino-N-ethyt-N-p-hydroxyethy)aniiine, 3-methyl-4-amino-N-ethyl-N-fi-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-J3-methoxyethyl aniline, as well as a sulfate, a hydrochloride, a phosphate, a p-toluene sulfonate, a tetraphenyl borate, a p-(t-
  • the aminophenol derivative includes, for example, o-aminophenol, p-aminophenol, 4-amino-2-methylphenol, 2-amino-3-methylphenol and 2-oxy-3-amino-1,4-dimethylbenzene.
  • the color developer may also contain a pH buffer such as an alkali metal carbonate, a borate or a phosphate ; a development inhibitor or an anti-foggant such as a bromide, a iodide, benzoimidazoles, benzothiazoles, and mercapto compounds; a preservative such as hydroxylamine, triethanol amine, compounds described in German Patent Application (OLS) No.
  • a pH buffer such as an alkali metal carbonate, a borate or a phosphate
  • a development inhibitor or an anti-foggant such as a bromide, a iodide, benzoimidazoles, benzothiazoles, and mercapto compounds
  • a preservative such as hydroxylamine, triethanol amine, compounds described in German Patent Application (OLS) No.
  • sulfite or hypersulfite an organic solvent such as diethylene glycol ; a development promoter such as a benzyl alcohol, polyethylene glycol, a quaternary ammonium salt, amines, a thiocyanate and, 3,6-thiaoctane-1,8-diol ; a dye-forming coupler ; a competing coupler; a nucleating agent such as sodium boronhydride; an auxiliary developing agent such as 1-phenyl-3-pyrazolidone ; a tackifier ; and a chelating agent such as ethylenediamine tetraacetic acid, nitrilotriacetic acid, cyclohexane diamine tetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediamine triacetic acid, diethylenetriamine pentaacetic acid, triethylenetetramine hexaneacetic acid and aminopolycarboxylic acid represented
  • aminophosphonic acid such as aminotris(methylene phosphonic acid), ethylenediamine-N,N,N',N'-tetramethylene phosphonic acid, phosphono carboxylic acid as described in Research Disclosure No. 18170 (May, 1979).
  • the color developing agent is used in a concentration of 0.1 g to 30 g per 1 I of the usual color developer solution, more preferably, in a concentration of from 1 g to 15 g per 1 I of the color developer solution.
  • the pH value of the color developer is usually 7 or higher and, most generally, 9 to 13.
  • the silver halide color photographic material is color developed as described above after imagewise exposure, and then processed with a processing solution having a bleaching performance.
  • a processing solution having a bleaching performance designates processing solutions having a performance of oxidizing metal silver resulting from the developing reaction and colloidal silver contained in the photosensitive material thereby converting them into a soluble silver salt such as a silver thiosulfate complex or an insoluble silver salt such as silver bromide, and they include, a bleaching solution, or a bleach-f l xing solution.
  • a processing solution having a bleach-fixing performance directly after processing with the color development.
  • the bleaching agent used in the processing solution having the bleaching performance includes a ferric complex salt such as ferricyanate ferric complex salts or citrate ferric salts, and a peroxide such as a persulfate or hydrogen peroxide.
  • a ferric complex salt such as ferricyanate ferric complex salts or citrate ferric salts
  • a peroxide such as a persulfate or hydrogen peroxide.
  • a aminopolycarboxylic acid ferric complex salt which is a complex of ferric ions with an aminopolycarboxylic acid or a sait thereof.
  • aminocarboxylic acids and salts thereof include:
  • (1), (2), (6), (7), (10), (11), (16), (18) are particularly preferred.
  • the aminocarboxylic acid ferric complex salt may be used in the form of a complex salt, or a ferric ion complex salt may be formed in a solution using a ferric salt, for example, ferric sulfate, ferric chloride, ferric sulfate, ammonium ferric sulfate and ferric phosphate with aminocarboxylic acid.
  • a ferric salt for example, ferric sulfate, ferric chloride, ferric sulfate, ammonium ferric sulfate and ferric phosphate with aminocarboxylic acid.
  • the complex salt may be used alone or as a mixture of two or more of them.
  • ferric salts in the case of forming a complex salt in a solution using a ferric salt and an aminocarboxylic acid, one or more ferric salts may be used.
  • one or more aminocarboxylic acids may be used.
  • aminopolycarboxylic acid may be used in excess amounts for forming the ferric
  • an aminopolycarboxylic acid Fe (III) complex salt described above, except for (19), and an ethylenediamine tetraacetic acid Fe (111) complex salt may be used in combination.
  • the processing solution having the bleaching function containing the ferric complex salt described above may contain metal ion complex salts such as of cobalt, nickel and copper other than iron ions.
  • the amount of the bleaching agent per one liter of the processing solution having the bleaching performance is from 0.1 mol to 1 mol, preferably, from 0.2 mol to 0.5 mol.
  • the pH value of the bleaching solution is preferably from 4.0 to 8.0, particularly, from 5.0 to 7.5 and more preferred 5,7 or less.
  • the processing bath having the bleaching performance can contain, in addition to the bleaching agent and the compound as described above, a re-halogenating agent such as a bromide, (for example, potassium bromide, sodium bromide, ammonium bromide) ora chloride, (forexample, potassium chloride, sodium chloride and ammonium chloride).
  • a re-halogenating agent such as a bromide, (for example, potassium bromide, sodium bromide, ammonium bromide) or a chloride, (forexample, potassium chloride, sodium chloride and ammonium chloride).
  • additives known to be used for a tin bleach-fixing solution such as one or more inorganic acids, organic acids and salts thereof having pH buffering performance can be added, for example, a nitrate (such as sodium nitrate and ammonium nitrate), boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate and tartaric acid.
  • a nitrate such as sodium nitrate and ammonium nitrate
  • boric acid borax
  • sodium metaborate sodium metaborate
  • acetic acid sodium acetate
  • sodium carbonate potassium carbonate
  • phosphorous acid phosphoric acid
  • sodium phosphate citric acid
  • citric acid sodium citrate and tartaric acid
  • the fixing bath subsequent to the bleaching bath or a processing bath having bleach-fixing performance can be incorporated with those compounds known as fixing agents such as a thiosulfate, (for example, sodium thiosulfate, ammonium thiosulfate, ammonium sodium thiosulfate and potassium thiosulfate), a thiocyanate (such as ammonium thiocyanate and potassium thiocyanate), thiourea and a thioether.
  • the addition amount of these fixing agents is preferably less than 3 mol and, particularly preferably less than 2 mol per 1 of the processing solution having the fixing performance or the processing solution having the bleach-fixing performance.
  • the processing solution having the bleach-fixing performance can contain so-called sulfite ion releasing compounds such as a sulfite, (for example, sodium sulfite and ammonium sulfite), a hydrogensulfite or an aldehyde and a hypersulfite addition product (for example, carbonyl-bisulfite).
  • a sulfite for example, sodium sulfite and ammonium sulfite
  • hydrogensulfite or an aldehyde for example, carbonyl-bisulfite
  • aminopolycarboxylic acid salts as shown from (1) to (19), or organic phosphonic acid compounds such as ethylenediamine tetrakismethylenephosphonic acid, diethylenetriamine pentakismethylenephos- phonic acid, 1,3-diaminopropane tetrakis methylenephosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid and 1-hydroxyethyiidene-1,1'-diphosphonic acid.
  • organic phosphonic acid compounds such as ethylenediamine tetrakismethylenephosphonic acid, diethylenetriamine pentakismethylenephos- phonic acid, 1,3-diaminopropane tetrakis methylenephosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid and 1-hydroxyethyiidene-1,1'-diphosphonic acid.
  • At least one bleaching accelerator selected from compounds having a mercapto group or a disulfide bond, isothiourea derivatives and thiazolidine derivatives may be incorporated in the processing solution having the bleaching function for conducting the processing.
  • the amount of such compounds per 1 I of the processing solution having the bleach-fixing performance is preferably from 1 x 10 -5 to 1 x 10- 1 mol and, more preferably, from 1 x 1 Q-4 to 5 x 10- 2 .
  • the bleaching accelerator incorporated in the processing solution having the bleaching performance is selected from the compounds having a mercapto group or a disulfide bond, a thiazolidine derivative, a thiourea derivative and isothio derivatives, as long as they are effective in bleaching acceleration. These compounds and specific examples are preferably described in JP-A-63-163853.
  • the compound For adding the compound into the processing solution, it is generally preferred to previously dissolve same in water or an alkaline organic acid organic solvent. If the compound is added in the form of powder directly to the processing bath having the bleaching function, this causes no undesired effect at all for the bleaching acceleration.
  • the bleaching accelerator can be incorporated into the photosensitive material of the present invention.
  • the bleaching accelerator can be incorporated into any one of the blue-sensitive, green-sensitive and red-sensitive emulsion layers, or a gelatin layer at the uppermost, intermediate or the lowermost layer.
  • the processing bath having the bleach-fixing performance according to the method of the present invention may be a step including one vessel.
  • it may be constituted as a step including two or more vessels in which replenishing solution is supplied to the group of vessels in a multi-stage countercurrent system.
  • the processing solutions in the group of the vessels may be circulated to form a uniform processing solution as the whole and the replenishing solution may be supplied to one of the vessels of the group.
  • the silver halide color photosensitive material according to the present invention is usually applied to desilvering processing such as fixing or bleach-fixing and, thereafter, subjected to a water washing and/or stabilizing step.
  • the amount of washing water in the water washing step can be set within a wide range depending on the characteristics of the photosensitive material, for example, the material used such as coupler, the application use and, further, the temperature of the washing water, the number ofwaterwashing vessels (number of steps), the replenishing system such as countercurrent or normal current type as well as other various conditions.
  • the relationship between the number of water washing vessels and the amount of water in the multi-stage countercurrent system can be determined by the method described in "Journal of the Society of Motion Picture and Television Engineers", Vol. 64, pages 248 to 253 (May, 1955).
  • an isothiazolone compound or cyabendazoles chlorine type fungicides such as chlorinated sodium isocyanurate or other benzotriazole, as described in JP-A-57-8542, as well as bacteriocides described in "Chemistry of Bacteriocide and Fungicide” written by Hiroshi Horiuchi, "Microorganism Fungicide, Bacteriocide and Fungicide Technology” edited by Eisei Gijutsukai, "Bacteria and Fungi Control Encyclopedia” edited by Nippon Bacteria and Fungi Controlling Society can be used.
  • the pH value forthe washing water in the processing of the photosensitive material according to the present invention is from 4 to 9, preferably, 5 to 8.
  • the temperature and the time for water washing can also be set variously depending on the characteristics and the application uses of the photosensitive material and it is generally selected within a range from 20 to 10 min at 15 to 45°C, preferably, from 30 to 5 min at 25 to 40°C.
  • the photosensitive material according to the invention can be processed directly with a stabilizing solution instead of water washing.
  • a stabilizing processing any known method can be used as described in JP-A-57-8543, JP-A-58-14834, JP-A-59-184343, JP-A-60-220345, JP-A-60-238832.
  • stabilizing baths containing 1-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2-methyl-4-isothiazolin-3-one, a bismuth compound or an ammonium compound can preferably be used.
  • a stabilizing bath containing formalin and a surface active agent used as the final bath for the camera film type color photosensitive material can be mentioned as an example.
  • Specimen 101 which is a multi-layered color photosensitive material comprising each of the layers of the composition shown below was prepared. (Composition of the photosensitive layer)
  • the coating amount was shown, for the silver-halide and colloidal silver by the amount of silver represented by g/m 2 unit, for the coupler, additive and gelatin, by the amount represented by g/m 2 unit and, for the sensitizing dye, by the mol number per one mol of silver halide in one identical layer.
  • Tenth Layer (Yellow filter layer).
  • Specimen 101 The specimen prepared as described above is referred to as Specimen 101.
  • Specimens 102 to 110 were prepared in the same manner as Specimen 101 by using comparative compounds A, B and C and compounds of the formula (1) each in an equal molar amount instead of the coupler EXC-6 added to the fifth layer in Specimen 101.
  • specimens passed through the processing were stored under 80°C, 70% relative humidity atmosphere for 30 days in a dark place to examine the color image fastness.
  • the stabilization steps (1), (2) and (3) were conducted as a countercurrent system of (3) ⁇ (2) ⁇ (1).
  • the amount of the fixing solution carried to the water washing vessel was 2 ml per 1 m.
  • Bleaching solution In common with the mother liquid and
  • the tap water was processed by using a strongly acidic cationic exchange resin (Na type) manufactured by Mitsubishi Chemical Industries Ltd. to adjust the water quality as described below.
  • a strongly acidic cationic exchange resin Na type manufactured by Mitsubishi Chemical Industries Ltd.
  • Disodium ethylenediamine tetraacetate was added to 500 mgll of the tap water described above. pH 6.8
  • Specimens 101 to 110 were processed in the same manner as in the processing step (III) exceptfor changing the replenishing amount in the water washing step from 10 ml to 125 ml (referred to as Processing step (IV)).
  • the coupler of formula (l) shows remarkable effects in the reduction of the residual silver amount and the fastness of cyan color image, with no side effect such as increase in Dmin and has sufficient sensitivity as well.
  • Example 2 The same running processing was carried out as in Example 1 while changing the pH value of the bleach-fixing bath used in the processing step (III) to 6.0, 5.7, 5.5. Then the residual silver amount and the density of the cyan dye image were measured for Specimens 101 to 110 subjected to wedge exposure.
  • the use of the coupler of formula (I) provides a sufficient cyan concentration even when passed through a bleach-fixing bath at a low pH effective for the improvement of the desilvering rate, and it can satisfy both the improvement of the desilvering property when using a bleach-fixing bath at a low pH and the stability of the cyan dye image (resistivity to the reduction in color restorability).
  • Specimen 201 that is, a multi-layered color photosensitive material comprising each of the layers of the composition shown below was prepared. (Composition of the photosensitive layer)
  • the coating amount was shown, for the silver-halide and colloidal silver, by the amount of silver represented by g/m 2 unit, for the coupler, additive and gelatin by the amount represented by glm 2 unit and, for the sensitizing dye, by the mol number per one mol of silver halide in one identical layer.
  • stabilizer Cpd-3 for the emulsion (0.04 g/m 2 ) and surface active agent Cpd-4 (0.01 g/m 2 ) were added as coating aid to each of the layers.
  • Specimens 202 to 210 were prepared by replacing coupler EXC-6 added to the fourth layer in Specimen 201 by the comparative coupler and the coupler of formula (I) used in Example 1.

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Claims (7)

1. Un matériau photosensible en couleur à l'halogénure d'argent comprenant au moins une couche d'émulsion d'halogénure d'argent sur un support, qui contient au moins un coupleur du type libérant un accélérateur de blanchiment, caractérisé en ce que ledit coupleur du type libérant un accélérateur de blanchiment est représenté par la forme suivante (1) :
Figure imgb0319
dans laquelle R1 est choisi dans le groupe comprenant un atome d'halogène, un groupe alkyle, un groupe alcényle, un groupe alcynyle, un groupe aryle, un groupe hétérocyclique, un groupe
Figure imgb0320
Figure imgb0321
comprenant un atome d'halogène, un groupe hydroxyle, un groupe carboxyle, un groupe sulfo, un groupe amino, un groupe cyano, un groupe nitro, un groupe alkyle, un groupe alcényle, un groupe alcynyle, un groupe aryle, un groupe carbonamido, un groupe sulfonamido, un groupe carbamoyle, un groupe sulfamoyle, un groupe uréido, un groupe acyle, un groupe acyloxy, un groupe oxy aliphatique, un groupe oxy aromatique, un groupe thio aliphatique, un groupe thio aromatique, un groupe sulfonyle aliphatique, un groupe sulfonyle aromatique, un groupe sulfinyle aliphatique, un groupe sulfinyle aromatique, un groupe oxycarbonyle aliphatique, un groupe oxycarbonyle aromatique, un groupe oxycarbonylamino aliphatique, un groupe oxycarbonylamino aromatique, un groupe sulfamoylamino, un groupe hétérocyclique et un groupe imido ; 1 représente un nombre entier de 0 à 3 ; R3 est choisi dans le groupe comprenant un atome d'hydrogène, et RgY, ou bien R2 et R3 peuvent être reliés l'un à l'autre pour former un cycle ; LINK représente un groupe de liaison fonctionnel attaché par l'intermédiaire d'un hétéroatome à la position 4 d'un noyau naphtol ; m représente 0 ou 1 ; L est choisi dans le groupe comprenant un groupe de valence (n + 1) c'est-à-dire un groupe alkyle ayant 1 à 8 atomes de carbone, un groupe aryle ayant 6 à 10 atomes de carbone et un groupe hétérocyclique ayant de 1 à 10 atomes de carbone à partir duquel n atomes d'hydrogène ont été enlevés, X représente un substituant soluble dans l'eau ; n représente un nombre entier de 1 à 3, R4 et R5 sont tous les deux choisis indépendamment dans le groupe comprenant un groupe alkyle, un groupe alcényle, un groupe alcynyle, un groupe aryle, un groupe hétérocyclique, un groupe amino, un groupe oxy aliphatique ou un groupe oxy aromatique, ou bien R4 et R5 peuvent être reliés l'un à l'autre pour former un cycle ; R6 est choisi dans le groupe comprenant un atome d'hydrogène, un groupe alkyle, un groupe alcényle, un groupe alcynyle, un groupe aryle, un groupe hétérocyclique,
Figure imgb0322
Figure imgb0323
-SO2R7 -S02OR7 et un groupe imido ; Y est choisi dans le groupe comprenant N-Rg, -CO-, -S02, -SO et une liaison simple ; et R7 est choisi dans le groupe comprenant un groupe alkyle, un groupe alcényle, un groupe alcynyle, un groupe aryle et un groupe hétérocyclique ; Rg est choisi dans le groupe comprenant un atome d'hydrogène, un groupe alkyle, un groupe alcényle, un groupe alcynyle, un groupe aryle et un groupe hétérocyclique ; R9 et R10 sont tous les deux choisis indépendamment dans le groupe comprenant un atome d'hydrogène, un groupe alkyle, un groupe alcényle, un groupe alcynyle, un groupe aryle, un groupe hétérocyclique, un groupe acyle, un groupe sulfonyle aliphatique, et un groupe sulfonyle aromatique ou bien Rg et R10 peuvent être réunis l'un à l'autre pour former un cycle et à la condition que lorsque 1 est égal à 2 ou plus, chaque R2 peut être identique à ou différent d'un autre R2, ou bien un R2 quelconque peut être lié à un autre R2 pourformer un cycle, et un R2 pourformer un dimère ou un polymère supérieur qui est obtenu au moyen d'un groupe divalent ou de valence supérieure dans l'un des R1, R2 ou R3 et à la condition que le coupleur de formule (I) ne soit pas :
Figure imgb0324
Figure imgb0325
Figure imgb0326
Figure imgb0327
ou
Figure imgb0328
2. Le matériau selon la revendication 1, dans lequel Re représente un groupe alkyle, un groupe alcényle, un groupe alcynyle, un groupe aryle, -OR7 ou SR7 et Y représente -CO- ou -SO2-.
3. Le matériau selon la revendication 1, selon lequel X est un substituant dans lequel la constante de substituant π est de 0,5 ou moins.
4. Une méthode de traitement d'un matériau photosensible en couleur à l'halogénure d'argent selon laquelle un matériau photosensible en couleur à l'halogénure d'argent selon l'une quelconque des revendications 1 à 3 est traité par fixage ou par fixage-blanchiment après le développement en couleur.
5. La méthode selon la revendication 4, selon laquelle la valeur du pH du bain de fixage ou de fixage-blanchiment est de 5,7 ou moins.
6. La méthode selon la revendication 4, selon laquelle l'agent de blanchiment utilisé dans ledit bain de fixage ou de fixage-blanchiment est choisi dans le groupe comprenant les suivants :
(1) acide diéthylènetriamine pentaacétique,
(2) sel pentasodique de l'acide diéthylènetriamine pentaacétique,
(3) acide éthylènediamine-N-(β-oxyéthyl)-N,N',N'-triacétique,
(4) éthylènediamine-N-(β-oxyéthyl)-N,N',N'-triacétate trisodique,
(5) éthylènediamine-N-(β-oxyéthyl)-N,N',N'-triacétate triammonique,
(6) acide 1,2-diaminopropane tétraacétique,
(7) 1,2-diaminopropane tétraacétate disodique,
(8) acide nitrilotriacétique,
(9) sel de sodium de l'acide nitrilotriacétique,
- (10) tétraacétate de cyclohexanediamine
(11) sel disodique de l'acide cyclohexanediamine tétraacétique,
(12) acide N-méthyliminodiacétique,
(13) acide iminodiacétique,
(14) dihydroxyéthyl glycine,
(15) éther éthylique de l'acide diamine tétraacétique,
(16) éther glycolique de l'acide diamine tétraacétique,
(17) acide éthylènediamine tétrapropionique,
(18) acide 1,3-diaminopropane tétraacétique et
(19) acide éthylènediamine tétraacétique.
7. La méthode selon l'une quelconque des revendications 4 à 6 qui comprend une étape de lavage à l'eau ou de stabilisation directe après le fixage ou le fixage-blanchiment, l'étape de lavage à l'eau ou l'étape de stabilisation incluant une pluralité de récipients et, lors du réapprovisionnement d'une solution de traitement dans un système à contre-courant à étapes multiples, la quantité de réapprovisionnement étant de 0,1 à 50 fois la quantité de la solution de traitement transférée du bain précédent par unité de surface du matériau photosensible en couleur à l'halogénure d'argent à traiter.
EP19880112038 1987-07-27 1988-07-26 Matériau photosensible couleur à l'halogénure d'argent et sa méthode de traitement Expired EP0301477B1 (fr)

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US5585228A (en) 1994-11-30 1996-12-17 Eastman Kodak Company Benzotriazole based UV absorbing compounds and photographic elements containing them
US5561031A (en) * 1995-03-23 1996-10-01 Eastman Kodak Company Color reversal elements with incorporated bleach accelerator
DE69610541T2 (de) 1995-08-02 2001-06-07 Eastman Kodak Co., Rochester Filterfarbstoffe enthaltende photographische Elemente
US5723280A (en) 1995-11-13 1998-03-03 Eastman Kodak Company Photographic element comprising a red sensitive silver halide emulsion layer
US6183944B1 (en) 1995-11-30 2001-02-06 Eastman Kodak Company Aggregated dyes for radiation-sensitive elements
US5747236A (en) 1996-01-26 1998-05-05 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
US5747235A (en) 1996-01-26 1998-05-05 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
EP0786692B1 (fr) 1996-01-26 2004-11-17 Eastman Kodak Company Couche d'émulsion à l'halogénure d'argent sensible à la lumière ayant sensibilité photographique renforcée
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CA1287765C (fr) * 1985-02-28 1991-08-20 Eastman Kodak Company Materiau photographique colorant et methode englobant un compose a decharge d'agent accelerateur de blanchiment
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JPS61179438A (ja) * 1986-02-03 1986-08-12 Fuji Photo Film Co Ltd 写真色素像の形成方法
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