EP0377910B1 - Matériau de reproduction photographique couleur négatif - Google Patents

Matériau de reproduction photographique couleur négatif Download PDF

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Publication number
EP0377910B1
EP0377910B1 EP89124180A EP89124180A EP0377910B1 EP 0377910 B1 EP0377910 B1 EP 0377910B1 EP 89124180 A EP89124180 A EP 89124180A EP 89124180 A EP89124180 A EP 89124180A EP 0377910 B1 EP0377910 B1 EP 0377910B1
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EP
European Patent Office
Prior art keywords
layer
sensitive
coupler
dir
agno3
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EP89124180A
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German (de)
English (en)
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EP0377910A2 (fr
EP0377910A3 (fr
Inventor
Reinhart Matejec
Ralf Büscher
Hans Langen
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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
    • G03C7/3029—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
    • 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

Definitions

  • the invention relates to a color photographic negative recording material which has at least three color coupler-containing silver halide emulsion partial layers of different sensitivity for recording light from at least one of the spectral ranges red, green, blue, the color couplers contained in the most sensitive partial layer and in the least sensitive partial layer coupling faster than the color coupler in the medium-sensitive sub-layer.
  • the invention relates to a color photographic negative recording material containing at least one red-sensitive, at least one green-sensitive and at least one blue-sensitive silver halide emulsion layer, each with assigned color couplers for the generation of spectral sensitivity of complementary colored image dyes, for recording light from at least one of the spectral ranges red, green, blue there are at least three color coupler-containing sub-layers of different sensitivity, namely a most sensitive, a medium-sensitive and a least sensitive sub-layer, at least one of which is used contains a DIR coupler in the more sensitive sub-layers, characterized in that the color coupler used solely for color production in the most sensitive sub-layer and the color coupler contained in the least sensitive sub-layer solely for color production serves by at least a factor of 1.5 (preferably by at least the factor 2) couple faster than the color coupler used only for color generation in the medium-sensitive sub-layer.
  • color photographic recording materials for the recording of light from one or more of the three main spectral regions have three or more sub-layers of different sensitivity, then these are usually arranged in such a way that the further away they are from the common substrate, the greater their sensitivity.
  • Color couplers can be assigned to each of the different spectrally related sub-layers, specifically these color couplers can be the same or different.
  • the color couplers are usually selected with regard to their coupling reactivity so that faster coupling couplers are used in a more sensitive sub-layer and slower coupling couplers in a less sensitive sub-layer (DE-A-1 958 709).
  • a color coupler is used which, compared to the color coupler in the middle, medium-sensitive sub-layer, couples not faster, but faster.
  • the color coupler contained in the least sensitive sublayer like the one contained in the most sensitive sublayer, couples faster than the color coupler contained in the middle, medium-sensitive sublayer by at least a factor of 1.5, preferably by at least a factor of 2.0 .
  • a relative clutch speed constant k which can be determined by a method described in DE-A-27 04 797.
  • the ratio of the coupling speeds of couplers in the different sub-layers of the same spectral sensitivity required according to the invention applies in any case to the color couplers and in particular to colorless color couplers.
  • Advanced color photographic recording materials also contain Couplers with other functions, for example so-called mask couplers and so-called DIR couplers.
  • these couplers which are not limited to the color production alone, should differ from the latter in the relative coupling speed by no more than a factor of 5, preferably no more than a factor of 2, if possible.
  • the sharpness can surprisingly be improved without impairing the granularity, and at the same time the amount of silver halide, especially in the least sensitive partial layer, can be reduced, which also has a favorable effect on the sharpness.
  • the color coupler contained in the least sensitive sub-layer not only couples faster than the color coupler contained in the middle medium-sensitive sub-layer, but also faster than the color coupler in the most sensitive sub-layer.
  • the same (fast) color coupler is used in the most sensitive sublayer and in the least sensitive sublayer or different color couplers with approximately the same (high) Coupling speed are used and if the color coupler in the most sensitive sub-layer is further mixed with a color coupler with a lower coupling speed in an amount of up to 90 mol%, based on the total coupler content in the most sensitive sub-layer.
  • the recording materials according to the invention contain at least one DIR coupler in the medium-sensitive partial layer and / or in the most sensitive partial layer of a layer structure consisting of at least three partial layers of the same spectral sensitivity.
  • the use of DIR couplers and the advantages which can thus be achieved based on interimage effects and edge effects, such as improved color rendering and sharpness, are known.
  • the inhibitors released from the DIR couplers can have low diffusibility (D ⁇ 0.4) or high diffusibility (D ⁇ 0.4).
  • the DIR couplers can also be used as a mixture of two or more DIR couplers. Methods for measuring diffusibility are described, for example, in EP-A-0 101 621 and DE-A-37 36 048.
  • the least sensitive partial layer does not contain a DIR coupler.
  • color couplers examples of color couplers, mask couplers and DIR couplers with which the invention can be implemented are given below with their coupling rate constant k [104 ⁇ 1 ⁇ mol ⁇ 1 ⁇ s ⁇ 1].
  • the diffusibility of the released inhibitor is also indicated for the DIR couplers.
  • the invention is not limited to the coupler examples given.
  • the recording material according to the invention has a large number of differently spectrally sensitized silver halide emulsion layers on a transparent layer support, including at least three silver halide emulsion layers of the same or approximately the same spectral sensitivity, which are referred to in the present context as partial layers. These three sub-layers can be directly adjacent to one another or can also be separated from one another by one or more layers of optionally other spectral sensitivity.
  • At least one such layer structure consisting of three sub-layers of the same spectral sensitivity is equipped with the features according to the invention, which essentially consist in the least sensitive sub-layer as well as the most sensitive sub-layer containing a color coupler that couples at least 1.5 times faster than the color coupler in the medium-sensitive layer of the same spectral sensitivity, wherein at least one of the two more sensitive sub-layers of the same spectral sensitivity contains a DIR coupler and preferably no DIR coupler is contained in the least sensitive sub-layer.
  • Such a multiplicity of partial layers, each consisting of a least sensitive partial layer, a medium-sensitive partial layer and a most sensitive partial layer with the features according to the invention are advantageously present for each of the three spectral ranges blue, green and red.
  • the total silver halide content of the color photographic recording material expressed by the equivalent amount of AgNO3, to not more than 10g AgNO3, preferably not more than 9 g AgNO3 per m without impairing the color rendering and granularity, thereby improving the sharpness .
  • the silver halide present as a light-sensitive component in the photographic recording material can contain chloride, bromide or iodide or mixtures thereof as the halide.
  • the halide content of the silver halide in a light-sensitive layer can consist of 0 to 15 mol% of iodide, 0 to 10 mol% of chloride and 0 to 100 mol% of bromide. It can be predominantly compact silver halide crystals, e.g. are regular cubic or octahedral or can have transitional forms.
  • the silver halide grains can also have a multi-layered grain structure, in the simplest case homodisperse emulsions or mixtures thereof in at least one layer are preferred, 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 also be heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ⁇ 30%.
  • Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
  • Gelatin is preferably used as the binder for the light-sensitive and non-light-sensitive layers. 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, polysccharides, cellulose, sugar, starch or alginates.
  • Semi-synthetic gelatin substitutes are usually modified natural products.
  • cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthaloyl cellulose and gelatin derivatives which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers.
  • 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 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 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 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.
  • 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 described, for example, by H. Frieser "The Basics of Photographic Processes with Silver Halides" page 675-734, Akademische Verlagsgesellschaft (1968).
  • the photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
  • 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.
  • Sensitizers can be dispensed with if the intrinsic sensitivity of the silver halide is sufficient for a certain spectral range, for example the blue sensitivity of silver bromides.
  • the differently sensitized emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it.
  • the red-sensitive layers are cyan couplers
  • the green-sensitive layers are magenta couplers
  • the blue-sensitive layers are yellow couplers.
  • Color couplers for producing the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type. Derivatives of ureidophenols or 1,5-aminonaphthols are preferably used.
  • Color couplers for producing the purple partial color image are generally couplers of the 5-pyrazolone, acylaminopyrazolone, indazolone or pyrazoloazole type.
  • Color couplers for generating the yellow partial color image are usually couplers with an open-chain ketomethylene grouping; especially ⁇ -acylacetamide type couplers; suitable examples are ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetanilide couplers.
  • the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers.
  • the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling point, which is split off during the coupling.
  • the 2-equivalent couplers include those that are colorless, as well as those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler), and the white couplers that react with color developer oxidation products yield essentially colorless products.
  • the 2-equivalent couplers also include couplers that contain a detachable residue in the coupling point, the is set free when reacting with color developer oxidation products, either directly or after one or more further groups have been split off from the primarily split off residue (for example DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic effectiveness unfolds, for example as a development inhibitor or accelerator.
  • Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.
  • DIR couplers the mercaptotype development inhibitors, e.g. Release 1-phenyl-5-mercaptotetrazole are described, for example, in US-A-3,227,554 and US-A-3,632,345.
  • DIR couplers which release development inhibitors of the azole type, for example triazoles and benzotriazoles, are described in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281, 27 26 180, 36 26 219, 36 30 564, 36 36 824, 36 44 416, 28 42 063 and EP-A-0 272 573. Further advantages for color reproduction, ie color separation and color purity, and for detail reproduction, ie sharpness and granularity, can be achieved with those DIR couplers which, for example, do not split off the development inhibitor directly as a result of coupling with an oxidized color developer, but only after one further follow-up reaction, which is achieved, for example, with a timing group.
  • DIR couplers which release development inhibitors with a high diffusibility (D ⁇ 0.4) are described, for example, in EP-A-0 101 621 and DE-A-37 36 048.
  • the cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (US Pat. No. 4,420,556).
  • 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 or other compounds can be incorporated into silver halide emulsion layers and other 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.
  • Methods for introducing compounds which are essentially insoluble in water are by grinding processes described for example in DE-A-26 09 741 and DE-A-26 09 742.
  • Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. 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 can also be used as so-called polymeric oil formers.
  • the compounds can also be introduced into the casting solution in the form of loaded latices.
  • 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, Tridecylphosphate, tributoxyethylphosphate, trichloropropylphosphate, di-2-ethylhexylphenylphosphate, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostyl-phenyl-tolate, isostearyl-tolyl-isolate, isostearyl-tol-
  • 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 and 0 125 522.
  • the photographic recording 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.
  • 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).
  • Ultraviolet absorbing couplers such as ⁇ -naphthol type cyan couplers
  • ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.
  • 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 described, for example, 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 most distant layer from the support, but also occasionally intermediate layers, especially if they are the most distant layer from the support during manufacture, may contain photographically inert particles of inorganic or organic 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).
  • photographically inert particles of inorganic or organic 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 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 the stability of dyes, couplers and whites and to reduce 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 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 US
  • 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.
  • the last-mentioned hardening agents which react very quickly with gelatin are, for example, carbamoylpyridinium salts which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin with the formation of peptide bonds and crosslinking of the gelatin.
  • a color photographic recording material for color negative color development was produced (layer structure 1 A - comparison) by applying the following layers in the order given to a transparent cellulose triacetate support. The quantities are based on 1 m.
  • the corresponding amounts of AgNO3 are given. All silver halide emulsions were stabilized per 100 g of AgNO3 with 0.1 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.
  • Table 1b provides an overview of the couplers, DIR couplers and mask couplers contained in the individual layers of the various layer structures.
  • the relative coupling rate constant k is given in brackets in the unit 104 ⁇ 1 ⁇ mol ⁇ 1 ⁇ s ⁇ 1.
  • Table 1c gives an overview of the silver halide deposits contained in the individual layers of the various layer structures in the form of the equivalent amounts of AgNO3. The total order AgNO3 is also given.
  • Layer structures layer (Comparison) (according to the invention) 1A 1B 1C 1D 1E 1 2nd 3rd 1.20 0.82 0.93 0.50 0.50 4th 1.62 1.62 1.62 1.62 5 1.53 1.53 1.53 1.53 1.76 6 7 1.06 0.66 0.73 0.35 0.35 8th 1.25 1.25 1.25 1.25 1.25 9 1.45 1.45 1.45 1.45 1.63 10th 11 0.70 0.52 0.59 0.32 0.32 12th 0.40 0.40 0.40 0.40 0.40 13 0.81 0.81 0.81 1.06 14 total 10.02 9.06 9.31 8.23 8.89
  • a sample of the layer structures 1A to 1E was exposed behind a gray step wedge with white light (exposure time: 0.01 s) and according to a color negative processing method, as in "The British Journal of Photography, (1974), pages 597 and 598 described, processed.
  • the RMS values mean fluctuation squares
  • the measurement method is described in: TH James, The Theory of the Photographic Process, 4th ed., Mac Millan Publ. Co., New York (1977) p. 619. Numerical values for the five layer structures 1A to 1E are given in Table 1d .
  • modulation transfer function (MTF) on the five layer structures was determined as a measure of the sharpness. This method is described e.g. at T.H. James, p. 604.
  • the spatial frequency ( ⁇ in [mm ⁇ 1] at which the MTF still has a value of 50% is given in Table 1d. The larger this value, the better the sharpness of the image.
  • the structures 1D and 1E according to the invention have a significantly better sharpness compared to the comparative structures 1A to 1C without deterioration in the color granularity, in particular in the blue-green and purple-colored partial color image.
  • the sensitivity to light was the same for the setups 1A to 1E within the test fluctuations ( ⁇ 0.2 DIN).
  • Table 2a provides an overview of the couplers, DIR couplers and mask couplers contained in the individual layers of the various layer structures.
  • the relative coupling rate constant k is given in brackets in the unit 104 ⁇ 1 ⁇ mol ⁇ 1 ⁇ s ⁇ 1.
  • Table 2b provides an overview of the silver halide deposits in the individual layers of the various layer structures in the form of the equivalent amounts of AgNO3. The total order AgNO3 is also given.
  • Table 2b AgNO3 orders [g / m] Layer structures layer (Comparison) (according to the invention) 2A 2 B 2C 2D 2E 3rd 1.26 0.78 0.90 0.45 0.45 4th 1.55 1.55 1.55 1.55 1.55 6 1.02 0.71 0.82 0.42 0.42 7 0.96 0.96 0.96 0.96 0.96 0.96 9 0.65 0.65 0.65 0.65 0.65 11 1.47 1.47 1.47 1.47 1.62 13 1.18 1.18 1.18 1.35 15 0.91 0.91 0.91 0.91 1.15 total 9.00 8.21 8.44 7.59 8.15
  • the measures according to the invention improve the sharpness, especially in blue-green and purple, without a deterioration in the color granularity.
  • the sensitivities for the setups 2A to 2E were the same within the test fluctuations ( ⁇ 0.2 DIN).
  • Table 3b provides an overview of the couplers, DIR couplers and mask couplers contained in the individual layers of the layer structures 3A and 3B.
  • the relative coupling rate constant k is given in brackets in the unit 104 ⁇ 1 ⁇ mol ⁇ 1 ⁇ s ⁇ 1.

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Claims (4)

  1. Matériau d'enregistrement négatif pour photographie en couleurs, contenant au moins une couche d'émulsion à l'halogénure d'argent sensible au rouge, au moins une couche d'émulsion à l'halogénure d'argent sensible au vert et au moins une couche d'émulsion à l'halogénure d'argent sensible au bleu, contenant des copulants chromogènes qui leur sont respectivement attribués pour obtenir des colorants d'image de couleurs complémentaires pour la sensibilité spectrale, dans lequel sont présents, pour l'enregistrement de la lumière à partir d'au moins un des domaines spectraux rouge, vert, bleu, au moins trois couches partielles à sensibilité différente contenant des copulants chromogènes, notamment une couche partielle très sensible, une couche partielle moyennement sensible et une couche partielle à sensibilité minimale, au moins une des deux couches partielles les plus sensibles contenant un copulant DIR, caractérisé en ce que le copulant chromogène contenu dans la couche partielle la plus sensible, servant uniquement pour la formation des couleurs, et le copulant chromogène correspondant contenu dans la couche partielle la moins sensible copulent au moins du facteur 1,5 plus vite que le copulant chromogène correspondant dans la couche partielle moyennement sensible.
  2. Matériau d'enregistrement selon la revendication 1, caractérisé en ce que la couche partielle la moins sensible ne contient pas de copulant DIR.
  3. Matériau d'enregistrement selon la revendication 1, caractérisé en ce que le copulant DIR contenu dans une des deux couches partielles les plus sensibles se distingue du copulant chromogène contenu dans la même couche partielle, quant à la vitesse de copulation, d'un facteur qui n'est pas supérieur à 5.
  4. Matériau d'enregistrement selon la revendication 1, caractérisé par une application totale d'halogénure d'argent de toutes les couches photosensibles, exprimée par la quantité équivalente en AgNO₃, qui n'est pas supérieure à 10 g de AgNO₃ par m.
EP89124180A 1989-01-12 1989-12-30 Matériau de reproduction photographique couleur négatif Expired - Lifetime EP0377910B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3900681 1989-01-12
DE3900681 1989-01-12

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EP0377910A2 EP0377910A2 (fr) 1990-07-18
EP0377910A3 EP0377910A3 (fr) 1991-08-14
EP0377910B1 true EP0377910B1 (fr) 1996-02-21

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EP89124180A Expired - Lifetime EP0377910B1 (fr) 1989-01-12 1989-12-30 Matériau de reproduction photographique couleur négatif

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US (1) US4963465A (fr)
EP (1) EP0377910B1 (fr)
JP (1) JPH02259754A (fr)
DE (1) DE58909608D1 (fr)

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Publication number Priority date Publication date Assignee Title
JPH03132651A (ja) * 1989-10-18 1991-06-06 Konica Corp 広ラチチュードを有するハロゲン化銀カラー写真感光材料
JPH04114151A (ja) * 1990-09-04 1992-04-15 Konica Corp 色再現性等にすぐれるハロゲン化銀カラー写真感光材料
US5258270A (en) * 1990-10-04 1993-11-02 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0492443B1 (fr) * 1990-12-21 1997-05-14 Eastman Kodak Company Elément photographique couleur copiant à l'halogénure d'argent et procédé
DE4101179A1 (de) * 1991-01-17 1992-07-23 Agfa Gevaert Ag Farbfotografisches negativ-aufzeichnungsmaterial mit dir-verbindungen
US5283164A (en) * 1992-06-19 1994-02-01 Eastman Kodak Company Color film with closely matched acutance between different color records
CA2093841C (fr) * 1992-07-17 1996-12-03 Elbert D. Edgar Film couleur
JP2788831B2 (ja) * 1992-10-20 1998-08-20 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
US5387500A (en) * 1993-06-24 1995-02-07 Eastman Kodak Company Color photographic elements containing a combination of pyrazoloazole couplers
EP0889358B1 (fr) * 1997-06-30 2002-04-10 Tulalip Consultoria Comercial Sociedade Unipessoal S.A. Eléments photographiques couleur à l'halogénure d'argent sensible à la lumière contenant des coupleurs magenta 5-pyrazolone à 2 équivalents
US6030758A (en) * 1997-08-18 2000-02-29 Konica Corporation Silver halide light sensitive photographic material
GB9827966D0 (en) * 1998-12-19 1999-02-10 Eastman Kodak Co Photographic element containing a dir coupler
US20010040701A1 (en) * 2000-02-03 2001-11-15 Edgar Albert D. Photographic film having time resolved sensitivity distinction

Family Cites Families (10)

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Publication number Priority date Publication date Assignee Title
US3620747A (en) * 1968-05-20 1971-11-16 Eastman Kodak Co Photographic element including superimposed silver halide layers of different speeds
BE758971A (fr) * 1969-11-22 1971-05-17 Agfa Gevaert Nv
JPS588501B2 (ja) * 1975-01-08 1983-02-16 富士写真フイルム株式会社 多層カラ−感光材料
DE3029209A1 (de) * 1980-08-01 1982-03-18 Agfa-Gevaert Ag, 5090 Leverkusen Lichtempfindliches fotografisches aufzeichnungsmaterial und dessen verwendung zur herstellung fotografischer bilder
JPS5960437A (ja) * 1982-09-30 1984-04-06 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料
DE3346621A1 (de) * 1983-12-23 1985-07-04 Agfa-Gevaert Ag, 5090 Leverkusen Farbfotografisches aufzeichnungsmaterial und entwicklungsverfahren
USH567H (en) * 1985-11-21 1989-01-03 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive materials containing cyan coupler and specific compound
IT1188553B (it) * 1986-02-24 1988-01-20 Minnesota Mining & Mfg Materiale fotografico multistrato a colori agli alogenuri d'argento
JP2550331B2 (ja) * 1986-11-15 1996-11-06 コニカ株式会社 ハロゲン化銀カラ−写真感光材料
EP0285176B1 (fr) * 1987-04-02 1994-06-08 Fuji Photo Film Co., Ltd. Matériau photographique à l'halogénure d'argent

Also Published As

Publication number Publication date
EP0377910A2 (fr) 1990-07-18
DE58909608D1 (de) 1996-03-28
EP0377910A3 (fr) 1991-08-14
JPH02259754A (ja) 1990-10-22
US4963465A (en) 1990-10-16

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