EP0464409B1 - Matériau de reproduction photographique pour la couleur - Google Patents

Matériau de reproduction photographique pour la couleur Download PDF

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Publication number
EP0464409B1
EP0464409B1 EP91109572A EP91109572A EP0464409B1 EP 0464409 B1 EP0464409 B1 EP 0464409B1 EP 91109572 A EP91109572 A EP 91109572A EP 91109572 A EP91109572 A EP 91109572A EP 0464409 B1 EP0464409 B1 EP 0464409B1
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EP
European Patent Office
Prior art keywords
silver halide
silver
recording material
colour photographic
compounds
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EP91109572A
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German (de)
English (en)
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EP0464409A1 (fr
Inventor
Reinhart Dr. Matejec
Hans Dr. Vetter
Heinrich Dr. Odenwälder
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/39224—Organic compounds with a nitrogen-containing function
    • 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
    • G03C7/3017—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials with intensification of the image by oxido-reduction
    • G03C7/302—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials with intensification of the image by oxido-reduction using peroxides
    • 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
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/144—Hydrogen peroxide treatment

Definitions

  • the invention relates to a color photographic recording material which is characterized by a particularly low silver coating and which is processed in an environmentally friendly manner without an actual color developing bath being necessary.
  • color photographic silver halide materials with a low silver application can be processed into excellent color images by the amplification process without a color developing bath being run through if the color photographic materials in the color coupler-containing layers in dissolved hydrophobic oil droplets contain at least one p-phenylenediamine compound with a primary amino group and at least one ballast residue.
  • the invention relates to a color photographic recording material having at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler and at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler and customary intermediate and protective layers, characterized in that the silver halide is applied all light-sensitive layers, given as AgNO3, is not more than 0.3 g / m and the color coupler-containing layers dissolved in hydrophobic oil droplets contain at least one p-phenylenediamine compound with at least one primary amino group and at least one ballast residue.
  • the color photographic material preferably contains in at least one light-sensitive layer as an emulsion a silver chloride bromide emulsion with 0.05 to 3 mol% of silver bromide.
  • a silver chloride bromide emulsion with 0.05 to 3 mol% of silver bromide.
  • at least 50% of the silver bromide is on the surface of the silver halide grains.
  • Such emulsions are obtained in particular by treating AgCl emulsions and AgClBr emulsions with a lower bromide content than desired after sensitization with the aqueous solution of a bromide.
  • the emulsions of all the light-sensitive layers are preferably AgClBr emulsions of the type mentioned, it being possible for the bromide fractions to differ from layer to layer within the inserted frame.
  • the silver halides preferably have a bromide content of 0.2-2 mol%.
  • the silver halide grains can contain up to 0.5 mol% of silver iodide, but are preferably free of silver iodide.
  • Color coupler and p-phenylene diamine compound are preferably dissolved together in a high-boiling hydrophobic solvent ("oil-forming agent"), and this solution is emulsified in an aqueous gelatin solution.
  • oil-forming agent a high-boiling hydrophobic solvent
  • P-Phenylenediamine compounds with at least one ballast residue are also those p-phenylenediamine compounds with which a latex is loaded.
  • Another possibility is to load latices, identical or different, both with color couplers and with p-phenylenediamine compounds. This technique is described, for example, in DE-A-25 41 230, DE-A 25 41 274, DE-A-28 35 856, EP-A 0 014 921, EP-A 0 069 671, EP-A 0 130 115 and US-A 3,291,113.
  • the color photographic recording material preferably consists of a reflective support on which, in the order given, a layer sensitive to blue, containing at least one yellow coupler, a layer sensitive to green, to some extent containing a purple coupler, and a layer sensitive to red, containing at least one cyan coupler, and customary intermediate and protective layers are applied .
  • the silver halide coating is preferably 0.05 to 0.3 g / m.
  • Another object of the invention is an image forming method for the above material, in which the material is treated with aqueous H2O2 after imagewise exposure.
  • the concentration of H2O2 is preferably 0.5 to 25 g / l.
  • the color photographic material or the intensifying bath contains a black and white developer substance (e.g. Phenidon®, Hydroquinone, Metol®, Amidol® in an amount of 0.01 to 1.0 g / l.
  • a black and white developer substance e.g. Phenidon®, Hydroquinone, Metol®, Amidol® in an amount of 0.01 to 1.0 g / l.
  • the reinforcement can be followed by the usual steps of bleaching, fixing, washing and drying, whereby bleaching and fixing can be carried out in one bath (bleach-fix bath).
  • bleaching and fixing can be carried out in one bath (bleach-fix bath).
  • a particular advantage of the method is that the small amount of silver halide produces such a weak silver image that the color image is no longer disturbed and the silver image therefore does not need to be removed.
  • the bleaching can thus be omitted.
  • Fixing (dissolving the unexposed silver halide) can also be omitted if the silver halide is converted into a light-insensitive silver complex salt by a stabilizing bath. In this case, drying can immediately follow the stabilization.
  • the silver halide emulsion layers essentially contain a binder, which is also the main constituent of the intermediate and protective layers.
  • Gelatin is preferably used as the binder. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers.
  • Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers.
  • Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, cellulose, sugar, starch or alginates.
  • Semi-synthetic gelatin substitutes are usually modified natural products.
  • Cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives, which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers, are examples of this.
  • the binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents.
  • functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.
  • the gelatin which is preferably used can be obtained by acidic or alkaline digestion. Oxidized gelatin can also be used. The preparation of such gelatins is described, for example, in The Science and Technology of Gelatine, published by AG Ward and A. Courts, Academic Press 1977, page 295 ff.
  • the gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.
  • the silver halides used according to the invention can be predominantly compact crystals, which e.g. are regular cubic or octahedral or can have transitional forms.
  • the silver halides can also be in the form of platelet-shaped crystals whose average ratio of diameter to thickness is e.g. is at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.
  • the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is substantially greater than 5: 1, e.g. 12: 1 to 30: 1.
  • the average grain size of the emulsions is preferably between 0.2 ⁇ m and 2.0 ⁇ m, the grain size distribution can be either homodisperse or heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ⁇ 30%. Homodisperse silver halide emulsions or mixtures thereof are preferred. In addition to the silver halide, the emulsions can also contain organic silver salts, for example silver benzotriazolate or silver behenate.
  • Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
  • the photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
  • various methods e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
  • the silver halide is preferably precipitated in the presence of the binder, for example the gelatin, and can be carried out in the acidic, neutral or alkaline pH range, silver halide complexing agents preferably being additionally used.
  • the latter include, for example, ammonia, thioether, imidazole, ammonium thiocyanate or excess halide.
  • the water-soluble silver salts and the halides are combined either in succession by the single-jet process or simultaneously by the double-jet process or by any combination of the two processes. Dosing with increasing inflow rates is preferred, the "critical" feed rate, at which no new germs are being produced, should not be exceeded.
  • the pAg range can vary within wide limits, preferably during the precipitation the so-called pAg-controlled method is used, in which a certain pAg value is kept constant or a defined pAg profile is run through during the precipitation.
  • so-called inverse precipitation with an excess of silver ions is also possible.
  • the silver halide crystals can also grow by physical ripening (Ostwald ripening) in the presence of excess halide and / or silver halide complexing agent.
  • the growth of the emulsion grains can even take place predominantly by Ostwald ripening, preferably a fine-grained, so-called Lippmann emulsion, mixed with a less soluble emulsion and redissolved on the latter.
  • Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe may also be present during the precipitation and / or physical ripening of the silver halide grains.
  • the precipitation can also be carried out in the presence of sensitizing dyes.
  • Complexing agents and / or dyes can be rendered ineffective at any time, e.g. by changing the pH or by an oxidative treatment.
  • the soluble salts are removed from the emulsion, for example by pasta and washing, by flaking and washing, by ultrafiltration or by ion exchangers.
  • the silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog are reached.
  • the procedure is e.g. described by H. Frieser "The basics of photographic processes with silver halides" page 675-734, Akademische Verlagsgesellschaft (1968).
  • Chemical sensitization can be carried out with the addition of compounds of sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII of the periodic table (for example gold, platinum, palladium, iridium).
  • Thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic compounds can also be used Nitrogen compounds (e.g. imidazoles, azaindenes) or spectral sensitizers (described, for example, by F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmanns Encyclopedia of Industrial Chemistry, 4th edition, vol. 18, pp. 431 ff. and Research Disclosure 17643 (Dec.
  • the photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
  • Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are for example from Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Furthermore, salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can be used as antifoggants.
  • metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can be used as antifoggants.
  • Heterocycles containing mercapto groups for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are also suitable, these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
  • mercaptobenzthiazoles for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines
  • mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
  • Other suitable compounds are published in Research Disclosure 17643 (Dec. 1978), Chapter VI.
  • the stabilizers can be added to the silver halide emulsions before, during or after their ripening.
  • the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.
  • the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active agents for various purposes, such as coating aids, for preventing electrical charging, for improving the sliding properties, for emulsifying the dispersion, for preventing adhesion and for improving the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
  • coating aids for preventing electrical charging, for improving the sliding properties, for emulsifying the dispersion, for preventing adhesion and for improving the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
  • non-ionic surfactants for example alkylene oxide compounds, glycerol compounds or glycidol compounds
  • cationic surfactants for example higher alkylamines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds
  • sulfonium compounds or phosphonium compounds anionic surfactants containing an acid group, for example carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group
  • ampholytic surfactants for example amino acid and aminosulfonic acid compounds and sulfur or phosphoric acid esters of an amino alcohol.
  • fluorine-containing surfactants which are known for example from GB-PS 1 330 356, 1 524 631 and US-PS 3 666 478 and 3 689 906.
  • the photographic emulsions can be spectrally sensitized using methine dyes or other dyes.
  • Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
  • Color couplers for producing the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type; Color couplers for generating the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type; Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular of the benzoylacetanilide and ⁇ -pivaloylacetanilide type. Numerous examples of the couplers are described in the literature.
  • the couplers can also be of high molecular weight, so-called latex couplers.
  • High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211.
  • the high molecular weight color couplers are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.
  • the couplers, the p-phenylenediamine derivatives or other compounds can be incorporated into silver halide emulsion layers in such a way that a solution, dispersion or emulsion is first prepared from the compound in question and then added to the casting solution for the layer in question.
  • the selection of the suitable solvent or dispersing agent depends on the solubility of the compound.
  • Hydrophobic compounds can also be used using high-boiling solvents, so-called oil formers, be introduced into the casting solution. Corresponding methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-0 043 037.
  • oligomers or polymers instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.
  • anionic water-soluble compounds e.g. dyes
  • pickling polymers e.g. acrylic acid
  • Suitable oil formers are e.g. Alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.
  • oil formers are dibutylphthalate, dicyclohexylphthalate, di-2-ethylhexylphthalate, decylphthalate, triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, NN-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-t-amylphenol, dioctyl acylate, glycerol tributyrate, isostearyl lactate, Trioctyl citrate, N, N-dibutyl-2-butoxy-5
  • Each of the differently sensitized, light-sensitive layers can consist of a single layer or can also comprise two or more silver halide emulsion partial layers.
  • the non-light-sensitive intermediate layers which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.
  • Suitable agents which are also called scavengers or EOP-catchers, are described in Research Disclosure 17 643 (Dec. 1978), chapters VII, 17 842 (Feb. 1979) and 18 716 (Nov. 1979), page 650 and in EP A-0 069 070, 0 098 072, 0 124 877, 0 125 522.
  • the photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives to improve dye, coupler and white stabilization and to reduce the color fog, plasticizers (latices), Contain biocides and others.
  • Compounds that absorb UV light are intended to protect the image dyes from fading due to UV-rich daylight. Connections of different structures are usually used for the two tasks. Examples are aryl-substituted benzotriazole compounds (US-A-3 533 794), 4-thiazolidone compounds (US-A-3 314 794 and 3 352 681), benzophenone compounds (JP-A-2784/71), cinnamic acid ester compounds (US-A-3 705 805 and 3,707,375), butadiene compounds (US-A-4,045,229) or benzoxazole compounds (US-A-3,700,455).
  • benzotriazole compounds US-A-3 533 794
  • 4-thiazolidone compounds US-A-3 314 794 and 3 352 681
  • benzophenone compounds JP-A-2784/71
  • cinnamic acid ester compounds US-A-3 705 805 and 3,707,375
  • butadiene compounds US-A-4
  • UV absorbers should absorb light up to 400 nm and have a steep drop in their light absorption capacity at wavelengths above 400 nm.
  • Filter dyes suitable for visible light include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.
  • Suitable whiteners are e.g. in Research Disclosure 17,643 (Dec. 1978), Chapter V, in US-A-2,632,701, 3,269,840 and in GB-A-852,075 and 1,319,763.
  • binder layers in particular the layer furthest away from the carrier, but also occasionally intermediate layers, especially if they represent the layer furthest away from the carrier during production, can be photographically inert
  • Contain particles of inorganic or organic nature for example as matting agents or as spacers (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), Chapter XVI).
  • the average particle diameter of the spacers is in particular in the range from 0.2 to 10 ⁇ m.
  • the spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath.
  • suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
  • Additives to improve dye, coupler and whiteness stability and to reduce the color fog can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromans, spiroindanes , p-alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.
  • the layers of the photographic material can be hardened with the usual hardening agents.
  • Suitable curing agents include formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds, the reactive halogen contain (US-A-3 288 775, US-A-2 732 303, GB-A-974 723 and GB-A-1 167 207), divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro-1,3, 5-triazine and other compounds containing a reactive olefin bond (US-A-3 635 718, US-A-3 232 763 and GB-A-994 869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A-2 732 316 and
  • the hardening can be effected in a known manner by adding the hardening agent to the casting solution for the layer to be hardened, or by overlaying the layer to be hardened with a layer which contains a diffusible hardening agent.
  • Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed to such an extent immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours, that no further change in the sensitometry and the swelling of the layer structure occurs as a result of the crosslinking reaction .
  • Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).
  • hardening agents which react very quickly with gelatin are, for example, carbamoylpyridinium salts which contain free carboxyl groups of the gelatin able to react, so that the latter react with free amino groups of the gelatin to form peptide bonds and crosslink the gelatin.
  • bleaching agents e.g. Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used.
  • Iron (III) complexes of aminopolycarboxylic acids are particularly preferred, especially e.g. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-N-hydroxyethyl-ethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids.
  • Persulfates and peroxides e.g. Hydrogen peroxide.
  • the bleach-fixing bath or fixing bath is usually followed by washing, which is designed as countercurrent washing or consists of several tanks with their own water supply
  • the watering can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent.
  • This stabilizing bath also takes on the function of a final bath when formaldehyde is added.
  • a color photographic recording material was produced by applying the following layers in the order given to a support made of paper coated on both sides with polyethylene. The quantities are based on 1 m. For the silver halide application, the corresponding amounts of AgNO3 are given. All emulsions were stabilized with 0.8 g butylbenzotriazole / 100 g AgNO3. Before casting, all casting solutions were adjusted to pH 5.5.
  • layer structure C Like layer structure C, but additionally the amounts of phenidone mentioned in layer structure B for the 2nd, 4th and 6th layers.
  • the layer structures A to F produced in this way were exposed in a sensitometer behind a gray scale wedge for 1/100 s and processed with the following belts:
  • Ammonium thiosulfate 50 G Sodium sulfite 5 G Sodium bisulfite 2nd G make up to 1000 ml with water; pH 6.0

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  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (9)

  1. Matériau d'enregistrement et de reproduction de photographie en couleurs, comportant au moins une couche d'émulsion d'halogénure d'argent sensible au bleu contenant au moins un coupleur pour jaune, au moins une couche d'émulsion d'halogénure d'argent sensible au vert contenant au moins un coupleur pour pourpre et au moins une couche d'émulsion d'halogénure d'argent sensible au rouge contenant au moins un coupleur pour bleu-vert, ainsi que les couches intermédiaires et protectrices usuelles, matériau caractérisé en ce que la quantité d'halogénure d'argent appliquée dans toutes les couches photosensibles, indiquée en AgNO₃, n'excède pas 0,3 g/m et les couches contenant des coupleurs chromogènes, dissoutes dans des gouttelettes d'huile hydrophobe, contiennent au moins une p-phénylènediamine comportant un groupe amino primaire et au moins un reste inerte de charge ou un latex, qui est chargé d'une p-phénylènediamine.
  2. Matériau pour reproduction à enregistrement de photographie en couleurs selon la revendication 1, caractérisé en ce qu'on utilise dans au moins une couche photosensible, à titre d'émulsion, une émulsion de chlorure-bromure d'argent comportant 0,05 à 3 mol % de bromure d'argent.
  3. Matériau d'enregistrement et de reproduction de photographie en couleurs selon la revendication 2, dans lequel au moins 50 % du bromure d'argent se trouvent à la surface des grains d'halogénure d'argent.
  4. Matériau d'enregistrement et de reproduction de photographie en couleurs selon la revendication 2, caractérisé en ce que la teneur en bromure d'argent est de 0,2 à 2 mol % et l'émulsion d'halogénure d'argent est dépourvue d'iodure.
  5. Matériau d'enregistrement et de reproduction de photographie en couleur selon la revendication 1, caractérisé en ce que les émulsions de toutes les couches photosensibles sont des émulsions de AgClBr comportant 0,05 à 3 mol % de bromure d'argent.
  6. Matériau d'enregistrement et de reproduction de photographie en couleurs selon la revendication 4, caractérisé en ce que les proportions de bromure des chlorures-bromures d'argent des diverses couches photosensibles sont différentes (d'une couche à l'autre).
  7. Matériau d'enregistrement et de reproduction de photographie en couleurs selon la revendication 1, caractérisé en ce que la quantité d'halogénure d'argent appliquée, indiquée en AgNO₃, est de 0,05 à 0,2 g/m.
  8. Procédé de développement de photographie en couleurs, caractérisé en ce qu'on soumet un matériau selon la revendication 1, exposé pour formation d'image, à un renforcement par H₂O₂ en présence d'une substance de développement en noir et blanc.
  9. Procédé selon la revendication 8, dans lequel il n'y a pas de blanchiment.
EP91109572A 1990-06-23 1991-06-11 Matériau de reproduction photographique pour la couleur Expired - Lifetime EP0464409B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4020058A DE4020058A1 (de) 1990-06-23 1990-06-23 Farbfotografisches aufzeichnungsmaterial
DE4020058 1990-06-23

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EP0464409A1 EP0464409A1 (fr) 1992-01-08
EP0464409B1 true EP0464409B1 (fr) 1996-01-17

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EP91109572A Expired - Lifetime EP0464409B1 (fr) 1990-06-23 1991-06-11 Matériau de reproduction photographique pour la couleur

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US (1) US5215875A (fr)
EP (1) EP0464409B1 (fr)
JP (1) JPH04233535A (fr)
DE (2) DE4020058A1 (fr)

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US5391443A (en) * 1991-07-19 1995-02-21 Eastman Kodak Company Process for the extraction of spectral image records from dye image forming photographic elements
GB9116930D0 (en) * 1991-08-06 1991-09-18 Kodak Ltd Photosensitive photographic silver halide colour materials
US5223581A (en) * 1992-02-19 1993-06-29 Eastman Kodak Company Polymers for the release of photographically useful groups
DE4211460A1 (de) * 1992-04-06 1993-10-07 Agfa Gevaert Ag Verfahren zur Herstellung eines fotografischen Bildes
US5411840A (en) * 1992-12-21 1995-05-02 Eastman Kodak Company Low volume processing for establishing boundary conditions to control developer diffusion in color photographic elements
GB9315366D0 (en) * 1993-07-24 1993-09-08 Kodak Ltd Method of photographic processing
GB9321648D0 (en) * 1993-10-20 1993-12-08 Kodak Ltd Photographic developer/amplifier compositions
GB9321656D0 (en) * 1993-10-20 1993-12-08 Kodak Ltd Photographic developer/amplifier compositions
DE69700897D1 (de) * 1996-06-17 2000-01-13 Konishiroku Photo Ind Bildererzeugungsverfahren
US5916739A (en) * 1996-11-22 1999-06-29 Konica Corporation Silver halide light sensitive photographic material and image forming method by use thereof
GB9626331D0 (en) * 1996-12-19 1997-02-05 Kodak Ltd Photographic recording materials and their use in redox amplification

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DE1931057C2 (de) * 1969-06-19 1982-05-13 Agfa-Gevaert Ag, 5090 Leverkusen Verfahren zur Herstellung farbphotographischer Bilder
DE2961488D1 (en) * 1978-01-27 1982-01-28 Agfa Gevaert Nv Photographic material suited for the production of multicolour images by means of diffusion transfer of complexed silver halide
JPS5723938A (en) * 1980-07-19 1982-02-08 Konishiroku Photo Ind Co Ltd Formation of dye image
JPS5818629A (ja) * 1981-07-28 1983-02-03 Fuji Photo Film Co Ltd 画像形成方法
GB2117914B (en) * 1982-01-27 1985-07-10 Fuji Photo Film Co Ltd Color intensified image forming process
JPS58200233A (ja) * 1982-05-18 1983-11-21 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
EP0273430B1 (fr) * 1986-12-26 1993-03-17 Fuji Photo Film Co., Ltd. Matériaux photographiques à l'halogénure d'argent et procédé de production de ceux-ci
JPS6444938A (en) * 1987-08-13 1989-02-17 Fuji Photo Film Co Ltd Method for forming amplification of color image
JPH0814682B2 (ja) * 1988-01-18 1996-02-14 富士写真フイルム株式会社 ハロゲン化銀感光材料
JPH087416B2 (ja) * 1988-10-03 1996-01-29 富士写真フイルム株式会社 カラー画像形成方法

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Publication number Publication date
US5215875A (en) 1993-06-01
EP0464409A1 (fr) 1992-01-08
DE59107271D1 (de) 1996-02-29
DE4020058A1 (de) 1992-01-02
JPH04233535A (ja) 1992-08-21

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