EP0722117B1 - Matériau photographique couleur à l'halogénure d'argent - Google Patents

Matériau photographique couleur à l'halogénure d'argent Download PDF

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Publication number
EP0722117B1
EP0722117B1 EP95119066A EP95119066A EP0722117B1 EP 0722117 B1 EP0722117 B1 EP 0722117B1 EP 95119066 A EP95119066 A EP 95119066A EP 95119066 A EP95119066 A EP 95119066A EP 0722117 B1 EP0722117 B1 EP 0722117B1
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EP
European Patent Office
Prior art keywords
layer
color
sensitive
silver
coupler
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EP95119066A
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German (de)
English (en)
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EP0722117A3 (fr
EP0722117A2 (fr
Inventor
Ralf Dr. Büscher
Peter Dr. Bell
Johannes Dr. Willsau
Hans-Ulrich Dr. Borst
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Agfa Gevaert NV
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Agfa Gevaert NV
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Classifications

    • 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
    • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03594—Size of the grains
    • 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

Definitions

  • the invention relates to a color photographic silver halide material with corrected Differences in the copy density of the three colors, its sensitivity due the correction is not reduced.
  • DE-A-2421068 describes a light-sensitive color photographic material with four Silver halide layers, of which the first three layers each predominantly against red, green and blue light are sensitive and colorless couplers for generation contain a blue-green, purple and yellow partial color image and the fourth Silver halide emulsion layer as a color correction layer for masking the unwanted secondary densities in at least two partial color images spontaneously is veiled developable, has a lower sensitivity than that photosensitive silver halide emulsion layers for the production of Partial color images and at least one colorless coupler to produce a yellow to contains purple mask image.
  • the object of the invention was the possibility of a difference correction Color density in a layer that is above photosensitive layers, in particular above the top layer spectrally sensitized to green light, preferably over all light-sensitive layers of a color photographic material, which is on a support as photosensitive layers at least one red sensitive, at least a silver halide emulsion layer containing a cyan coupler, at least a green sensitive, containing at least one purple coupler Silver halide emulsion layer and at least one blue-sensitive, at least one silver halide emulsion layer containing yellow coupler contains, in particular a color negative film is arranged to create, but the Sensitivity of the material does not diminish.
  • this is the leuco form (colorless form) of a dye caused by the conditions of a processing bath, in particular of the bleaching or bleach-fixing bath is converted into the dye form.
  • this is the combination of one colorless color coupler that combines with the developer oxidation product Dye couples of the desired color and density, and a non-spectrally sensitized, fogged silver halide emulsion.
  • Color couplers which are preferred in the material in the photosensitive Color couplers used layers are used. Mixtures can also be used multiple couplers are used, which are the same but also different Couple dyes.
  • the veiled silver halide emulsion is preferably a particularly fine-grained emulsion, in particular one with a high chloride content, for example an AgCl 0.9-1 Br 0.1-0.1 emulsion, the particles of which have a diameter of the same volume of 0.05 to 0.12 ⁇ m exhibit.
  • the combination is preferably used in a layer which is characterized by the Developer oxidation product of the next adjacent photosensitive layer is not reached and their developer oxidation product is the closest neighboring photosensitive layer not reached. This can e.g. happen in that an intermediate layer is provided between these two layers if necessary, a so-called EOP catcher, i.e. a reducing one Contains connection.
  • the combination of coupler and veiled emulsion used according to the invention is preferably used in the following amounts: 0.01 to 0.08 mmol coupler / m 2 and 0.2 to 0.6 mmol silver halide / m 2 .
  • a leuco dye is used, it is used in an amount of 0.01 to 0.08 mmol / m 2 .
  • the color densities generated by the further layer should be 0.01 to 0.1.
  • the material according to the invention is in particular a color photographic silver halide material with a carrier, at least one red-sensitive, silver halide emulsion layer containing at least one cyan coupler, at least one green sensitive, containing at least one purple coupler Silver halide emulsion layer, at least one blue sensitive, at least a yellow coupler containing silver halide emulsion layer, all green sensitive Silver halide emulsion layers arranged closer to the carrier than all blue sensitive silver halide emulsion layers and all red sensitive ones Silver halide emulsion layers arranged closer to the carrier than all green sensitive silver halide emulsion layers.
  • Between blue and green sensitive silver halide emulsion layers usually a yellow filter layer. This can be an effective ingredient contain colloidal silver or a yellow dye that can be decolorized or must be waterable. Such dyes are known from the literature.
  • the material preferably contains 2 or 3 sensitive to blue, green and red Layers.
  • Suitable transparent supports for the production of color photographic materials are e.g. Films and foils of semi-synthetic and synthetic polymers, such as Cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, Polyethylene terephthalate, polyethylene naphthalate and polycarbonate. These carriers can also be colored black for the purpose of shielding light.
  • the surface of the support is generally subjected to a treatment in order to To improve the adhesion of the photographic emulsion layer, for example one Corona discharge with subsequent application of a substrate layer.
  • the backside the carrier can be provided with a magnetic layer and an antistatic layer his.
  • Essential components of the photographic emulsion layers are binders, Silver halide grains and color couplers.
  • Gelatin is preferably used as the binder. However, this can be done entirely or partly by other synthetic, semi-synthetic or also naturally occurring Polymers to be replaced.
  • Synthetic gelatin substitutes are for example polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyacrylamides, polyacrylic acid and their derivatives, especially 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 are reacted with alkylating or acylating agents or obtained by grafting polymerizable monomers are examples of this.
  • the binders should have a sufficient amount of functional groups have so that sufficient by reaction with suitable curing agents resistant layers can be produced.
  • Such 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 acidic or alkaline Be informed. Oxidized gelatin can also be used. The Production of such gelatins is described, for example, in The Science and Technology of Gelatine, published by A.G. Ward and A. Courts, Academic Press 1977, Page 295 ff.
  • the gelatin used should be as possible contain low levels of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.
  • Silver halide can be used as halide, chloride, bromide or iodide or mixtures of which included.
  • the halide content of at least one layer 0 to 15 mol% from iodide, 0 to 20 mol% from chloride and 65 to 100 mol% consist of bromide.
  • It can be mostly compact crystals act, e.g. are regular cubic or octahedral or transitional forms can have.
  • platelet-shaped crystals can also preferably be used are present, whose average ratio of diameter to thickness is preferred 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 have the ratio of diameter to thickness is significantly larger than 5: 1, e.g. 12: 1 to 30: 1.
  • the silver halide grains can also have a multi-layered grain structure have, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as. Doping of the individual grain areas are different.
  • the average grain size of the emulsions is preferably between 0.2 ⁇ m and 2.0 ⁇ m, the grain size distribution can be both homo- and heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not exceed Deviate ⁇ 30% from the average grain size.
  • the emulsions can besides the silver halide also contain organic silver salts, e.g. Silver benzotriazolate or silver behenate.
  • the photographic emulsions can be prepared using various methods (e.g. P. Glafkides, 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) made from soluble silver salts and soluble halides become.
  • the soluble salts are removed from the emulsion, e.g. through pasta and washing, by flaking and washing, by ultrafiltration or by Ion exchanger.
  • the silver halide emulsion generally undergoes chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the sensitivity and subjected to optimum veils.
  • the procedure is e.g. at H. Frieser "The Basics of Photographic Processes with Silver Halides” Pages 675-734, Akademische Verlagsgesellschaft (1968).
  • the chemical sensitization with the addition of compounds of Sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII of the periodic table (e.g. gold, platinum, palladium, iridium) continue to occur can thiocyanate compounds, surface-active compounds, such as thioethers, heterocyclic nitrogen compounds (e.g. imidazoles, azaindenes) or also spectral sensitizers (described e.g. by F. Hamer "The Cyanine Dyes and Related Compounds ", 1964, or Ullmann's Encyclopedia of Chemical Engineering, 4th edition, vol. 18, p. 431 ff. And Research Disclosure 17643 (Dec. 1978), chapter III) are added.
  • thiocyanate compounds e.g. gold, platinum, palladium, iridium
  • surface-active compounds such as thioethers
  • heterocyclic nitrogen compounds e.g. imidazoles, azaindenes
  • a reduction sensitization can with the addition of reducing agents (tin-II salts, amines, hydrazine derivatives, Aminoborane, silane, formamidine sulfinic acid) by hydrogen, by low pAg (e.g. less than 5) and / or high pH (e.g. above 8) become.
  • reducing agents tin-II salts, amines, hydrazine derivatives, Aminoborane, silane, formamidine sulfinic acid
  • the photographic emulsions can be used to prevent the compounds Fog formation or to stabilize the photographic function during the Production, storage or photographic processing included.
  • Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, especially those which are substituted by hydroxyl or amino groups. Such connections are for example from Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. 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 also 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 also be used as antifoggants.
  • Heterocycles containing mercapto groups for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly 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 the silver halide emulsions before, during or after their maturation are added. Of course you can do the connections also other photographic layers associated with a halogen silver layer are to clog.
  • the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surfactants for various purposes, such as coating aids, to prevent electrical charge, to improve the Sliding properties, for emulsifying the dispersion, for preventing the Adhesion and to improve the photographic characteristics (e.g. acceleration of development, high contrast, sensitization).
  • Next natural surface active compounds e.g. Saponin, mainly synthetic surface-active compounds (surfactants)
  • non-ionic Surfactants e.g. Alkylene oxide compounds, glycerol compounds or Glycidol compounds
  • cationic surfactants e.g.
  • alkylamines quaternary Ammonium salts, pyridine compounds and other heterocyclic compounds, Sulfonium compounds or phosphonium compounds, anionic surfactants, containing an acid group, e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, Sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, e.g. Amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters an amino alcohol.
  • an acid group e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, Sulfuric acid ester or phosphoric acid ester group
  • ampholytic surfactants e.g. Amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters an amino alcohol.
  • the photographic emulsions can be made using methine dyes or other dyes are spectrally sensitized.
  • Particularly suitable Dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
  • the differently sensitized emulsion layers do not become diffusing assigned monomeric or polymeric color couplers that are in the same Layer or in a layer adjacent to it.
  • the red-sensitive layers become cyan couplers, the green-sensitive ones Layers of purple couplers and the blue-sensitive layers of yellow couplers assigned.
  • Color couplers for generating the blue-green partial color image are usually Phenol or ⁇ -naphthol type couplers.
  • Color couplers for generating the purple partial color image are usually Pyrazolone or pyrazolotriazole type couplers.
  • Color couplers for generating the yellow partial color image are usually couplers of the acylacetanilide type.
  • the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers act.
  • the latter are derived from the 4 equivalent couplers characterized in that they contain a substituent in the coupling site which at the clutch is split off.
  • the 2-equivalent couplers also include couplers that: contain a detachable residue in the coupling site, which reacts with Color developer oxidation products are set free and either directly or after the primary split off one or more more Groups have been split off (e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic activity unfolded, e.g. as a development inhibitor or accelerator.
  • Examples of such 2-equivalent couplers are the well-known DIR couplers as well as DAR and FAR couplers.
  • DIR couplers the development inhibitors of the azole type, e.g. Triazoles and Release benzotriazoles are described in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281.28 42 063, 36 26 219, 36 30 564, 36 36 824, 36 44 416.
  • Other advantages for color rendering, i.e. Color separation and color purity, and for detail reproduction, i.e. Sharpness and graininess are with such DIR couplers to achieve, e.g. the development inhibitor is not immediately considered Split off the coupling with an oxidized color developer, but first after a further follow-up reaction, for example with a timing group is achieved.
  • DIR couplers that release a development inhibitor that in the developer bath essentially ineffective photographically decomposed products are for example in DE-A-32 09 486 and in EP-A-0 167 168 and 0 219 713 described. With this measure, a trouble-free development and Processing consistency reached.
  • DIR couplers especially those that do a good job cleavable development inhibitor can be eliminated by suitable Measures for optical sensitization, improvements in color rendering, e.g. achieve a more differentiated color rendering, such as in EP-A-0 115 304, 0 167 173, GB-A-2 165 058, DE-A-37 00 419 and US-A-4 707 436.
  • the DIR couplers can be in a multi-layer photographic material various layers can be added, e.g. also insensitive to light or intermediate layers. However, they are preferably the photosensitive one Silver halide emulsion layers added, the characteristic Properties of the silver halide emulsion, e.g. their iodide content, the structure the silver halide grains or their grain size distribution influences the photographic properties achieved.
  • the influence of the released Inhibitors can, for example, by incorporating an inhibitor scavenger layer be limited according to DE-A-24 31 223. For reasons of reactivity or Stability, it may be advantageous to use a DIR coupler that is in the respective layer in which it is introduced, one of that in this layer producing color deviating color forms when coupling.
  • contrast and maximum density DAR or FAR couplers can be used, which one Split off development accelerator or an fogger. Connections this Type are for example in DE-A-25 34 466, 32 09 110, 33 33 355, 34 10 616, 34 29 545, 34 41 823, in EP-A-0 089 834, 0 110 511, 0 118 087, 0 147 765 and in U.S.-A-4,618,572 and 4,656,123.
  • BAR couplers (Bleach Accelerator Releasing Coupler) is referred to EP-A-193 389.
  • DAR and FAR couplers mainly the effectiveness of the released in the clutch rest is desired and less on the color-forming properties of these couplers are also such DIR, Suitable DAR or FAR couplers, which are essentially colorless when coupling Products result (DE-A-15 15 47 640).
  • the cleavable residue can also be a ballast residue, so that in the reaction with Color developer oxidation products coupling products are obtained that are diffusible are or at least weak or limited mobility (US-A-4 420 556).
  • the material may also contain compounds other than couplers, which, for example, a development inhibitor, a development accelerator, a bleach accelerator, a developer, a silver halide solvent Can release fogging or an anti-fogging agent, for example So-called DIR hydroquinones and other compounds, such as those described in US-A-4 636 546, 4 345 024, 4 684 604 and in DE-A-31 45 640, 25 15 213, 24 47 079 and in EP-A-198 438 are described. Meet these connections the same function as the DIR, DAR or FAR couplers, except that they do not Form coupling products.
  • a development inhibitor for example, a development inhibitor, a development accelerator, a bleach accelerator, a developer, a silver halide solvent Can release fogging or an anti-fogging agent, for example So-called DIR hydroquinones and other compounds, such as those described in US-A-4 636 546, 4 345 024, 4 684 604 and in DE-A-31 45 640,
  • 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 described.
  • the high molecular color couplers are usually through Polymerization of ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.
  • Incorporation of the couplers or other compounds in silver halide emulsion layers can be done in such a way that first of the Compound and then a solution, dispersion or emulsion is added to the casting solution for the layer in question.
  • the selection of the suitable solvent or dispersant depends on the solubility the connection.
  • Methods for introducing compounds which are essentially insoluble in water by grinding processes are, for example, in DE-A-26 09 741 and DE-A-26 09 742.
  • Hydrophobic compounds can also be made using high-boiling Solvents, so-called oil formers, are introduced into the casting solution. Appropriate methods are described, for example, in US Pat. No. 2,322,027, US Pat. No. 2 801 170, US-A-2 801 171 and EP-A-O 043 037.
  • polymeric oil formers are used instead of the high-boiling solvents.
  • the compounds can also be in the form of loaded latices in the casting solution be introduced.
  • anionic water-soluble compounds e.g. of dyes
  • cationic polymers so-called Pickling polymers take place.
  • 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 examples include dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, Decyl phthalate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, Tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, Tridecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl p-hydroxybenzoate, Diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-t-amylphenol, dioctylacelate, glycerol
  • the usually between layers of different spectral sensitivity arranged non-light-sensitive intermediate layers can contain agents which an undesirable diffusion of developer oxidation products from a photosensitive to another photosensitive layer with different prevent spectral sensitization.
  • Suitable agents also called scavengers or EOP-catchers, are described in Research Disclosure 17,643 (Dec. 1978), Chapter 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 Partial layer with higher sensitivity from the carrier can be arranged as the sublayer with less sensitivity.
  • Sub-layers of the same spectral Sensitization can be adjacent to one another or through other layers, e.g. separated by layers of other spectral sensitization. For example, all highly sensitive and all low sensitive layers in one Layer package can be summarized (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).
  • 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.
  • Ultraviolet absorbing couplers such as ⁇ -naphthol type cyan couplers
  • ultraviolet absorbing polymers can be used. This Ultraviolet absorbents can be fixed in a special layer by pickling his.
  • Filter dyes suitable for visible light include oxonol dyes, Hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes are oxonol dyes, hemioxonol dyes and merocyanine dyes 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 described.
  • Certain layers of binder especially those furthest from the carrier removed layer, but also occasionally intermediate layers, especially if the most distant layer during manufacture can represent photographically inert particles of inorganic or organic Contain nature, e.g. as a matting agent or as a spacer (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 Range from 0.2 to 10 m.
  • the spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble in general alkaline developing bath can be removed from the photographic material.
  • suitable polymers are polymethyl methacrylate, copolymers of Acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
  • Additives to improve dye, coupler and white stability as well as Reduction of the color fog can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromanes, 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 photographic material can be used with the usual Hardening agents are hardened.
  • Suitable curing agents are e.g. Formaldehyde, Glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and Similar ketone compounds, bis (2-chloroethyl urea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds containing reactive halogen (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, which contain 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
  • the curing can be effected in a known manner in that the Hardening agent is added to the casting solution for the layer to be hardened, or in that the layer to be hardened is overlaid with a layer containing a contains diffusible curing agent.
  • Hardening agents There are slow-acting and fast-acting among the classes listed Hardening agents and so-called instant hardeners, which are particularly advantageous.
  • Immediate hardeners are understood to be compounds that are suitable binders network, preferably immediately after watering, at the latest after 24 hours after 8 hours at the latest the hardening is complete to the extent that none further changes in the sensitometry caused by the crosslinking reaction and the swelling of the layer structure occurs.
  • the difference between Wet film thickness and dry film thickness in the aqueous processing of Films understood (Photogr. Sci. Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).
  • hardeners react very quickly with gelatin e.g. to carbamoylpyridinium salts with free carboxyl groups of gelatin able to react so that the latter with free amino groups of the gelatin react to form peptide bonds and crosslink the gelatin.
  • Color photographic negative materials are usually developed, Bleaching, fixing and watering or by developing, bleaching, fixing and Stabilize processed without subsequent watering, bleaching and Fixing can be combined into one processing step.
  • a color developer compound you can use all developer connections that have the ability to use color couplers in the form of their oxidation product To react azomethine or indophenol dyes.
  • Suitable color developer compounds are aromatic, containing at least one primary amino group P-Phenylenediamine type compounds such as N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfonamidoethyl) -3-methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
  • P-Phenylenediamine type compounds such as N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfonamidoethyl) -3-methyl-p
  • the material is usually bleached immediately after color development and fixed.
  • 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-hydroxyethylethylenediamine triacetic acid, Alkyliminodicarboxylic acids and corresponding Phosphonic acids.
  • the bleach-fixing bath or fixing bath is usually followed by a wash, which is called Countercurrent irrigation is carried out or from several tanks with their own Water supply exists.
  • Example 2 In addition 0.04 g coupler C-1 0.04 g CPM
  • Example 3 In addition 0.05 g AgNO 3 of a veiled AgClBr emulsion with 8 mol% AgBr, average grain diameter 0.1 ⁇ m, not spectrally sensitized
  • Example 4 In addition 0.05 g AgNO 3 of the emulsion mentioned in Example 3 0.04 g coupler C-1 0.04 g CPM
  • Example 5 In addition 0.05 g AgNO 3 of the emulsion mentioned in Example 3 0.04 g coupler M-2 0.04 g CPM
  • Example 6 In addition 0.05 g AgNO 3 of the emulsion mentioned in Example 3 0.04 g coupler Y-1 0.04 g CPM

Landscapes

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

Claims (5)

  1. Matériau à l'halogénure d'argent pour photographie en couleurs qui contient, sur un support, à titre de couches photosensibles, au moins une couche d'émulsion à l'halogénure d'argent sensible au rouge contenant au moins un copulant pour le bleu-vert, au moins une couche d'émulsion à l'halogénure d'argent sensible au vert contenant au moins un copulant pour le magenta, et au moins une couche d'émulsion à l'halogénure d'argent sensible au bleu contenant au moins un copulant pour le jaune, caractérisé en ce qu'on prévoit, au-dessus d'une couche photosensible (lorsqu'on regarde par rapport au support), au moins une couche supplémentaire qui contient un composé incolore ou une combinaison de composés incolores qui donne lieu, via le traitement, après l'exposition, à une densité chromatique uniforme sur toute la surface, de couleur prédéfinie et de densité prédéfinie.
  2. Matériau à l'halogénure d'argent pour photographie en couleurs selon la revendication 1, caractérisé en ce que la couche supplémentaire contient la combinaison d'un copulant chromogène incolore qui copule avec le produit d'oxydation de révélateur pour donner un colorant et d'une émulsion à l'halogénure d'argent voilée qui n'a pas été soumise à une sensibilisation spectrale.
  3. Matériau à l'halogénure d'argent pour photographie en couleurs selon la revendication 1, caractérisé en ce que la couche supplémentaire est disposée au-dessus de la couche la plus supérieure soumise à une sensibilisation spectrale pour la lumière verte.
  4. Matériau à l'halogénure d'argent pour photographie en couleurs selon la revendication 1, caractérisé en ce que la couche supplémentaire est disposée au-dessus de la couche photosensible la plus supérieure.
  5. Matériau à l'halogénure d'argent pour photographie en couleurs selon la revendication 2, caractérisé en ce que l'émulsion à l'halogénure d'argent voilée qui n'a pas été soumise à une sensibilisation spectrale est une émulsion au AgCl0,9-1Br0-0,1 dont les particules présentent un diamètre de la sphère à volume égal de 0,05 à 0,12 µm.
EP95119066A 1994-12-16 1995-12-04 Matériau photographique couleur à l'halogénure d'argent Expired - Lifetime EP0722117B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4444867 1994-12-16
DE4444867A DE4444867A1 (de) 1994-12-16 1994-12-16 Farbfotografisches Silberhalogenidmaterial

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EP0722117A2 EP0722117A2 (fr) 1996-07-17
EP0722117A3 EP0722117A3 (fr) 1997-03-12
EP0722117B1 true EP0722117B1 (fr) 2001-03-28

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US (1) US5679504A (fr)
EP (1) EP0722117B1 (fr)
DE (2) DE4444867A1 (fr)

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
US6593042B1 (en) * 2001-12-21 2003-07-15 Eastman Kodak Company Expansion of color gamut for silver halide media

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2421068A1 (de) * 1974-05-02 1975-11-13 Agfa Gevaert Ag Lichtempfindliches farbphotographisches material

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2328014A1 (de) * 1973-06-01 1974-12-19 Agfa Gevaert Ag Lichtempfindliches farbphotographisches material
DE2411105C3 (de) * 1974-03-08 1982-01-14 Agfa-Gevaert Ag, 5090 Leverkusen Verfahren zur Herstellung farbphotographischer Bilder
US4749641A (en) * 1986-09-15 1988-06-07 Eastman Kodak Company Imaging element containing dye masking coupler
JP2724353B2 (ja) * 1988-01-29 1998-03-09 富士写真フイルム株式会社 ハロゲン化銀写真感光材料

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2421068A1 (de) * 1974-05-02 1975-11-13 Agfa Gevaert Ag Lichtempfindliches farbphotographisches material

Also Published As

Publication number Publication date
EP0722117A3 (fr) 1997-03-12
DE59509131D1 (de) 2001-05-03
US5679504A (en) 1997-10-21
DE4444867A1 (de) 1996-06-20
EP0722117A2 (fr) 1996-07-17

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