EP0409019B1 - Matériau d'enregistrement photographique en couleurs au rendu chromatique amélioré - Google Patents

Matériau d'enregistrement photographique en couleurs au rendu chromatique amélioré Download PDF

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Publication number
EP0409019B1
EP0409019B1 EP90112994A EP90112994A EP0409019B1 EP 0409019 B1 EP0409019 B1 EP 0409019B1 EP 90112994 A EP90112994 A EP 90112994A EP 90112994 A EP90112994 A EP 90112994A EP 0409019 B1 EP0409019 B1 EP 0409019B1
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Prior art keywords
color
colour
spectral sensitivity
layer
dye
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EP0409019A3 (en
EP0409019A2 (fr
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Reinhart Dr. Matejec
Helmut Dr. Kampfer
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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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • 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
    • G03C7/3041—Materials with specific sensitometric characteristics, e.g. gamma, density

Definitions

  • the color "jumps" from blue to green and then remains fairly constant in the wavelength range up to 580 nm. The reproduction of the color shades between blue and green is poorly differentiated.
  • color-negative recording material In order to remedy this deficiency, it was proposed for color-negative recording material to provide intermediate layers between layers of different spectral sensitivity, which contain silver halide and DIR couplers (possibly also color couplers) and whose silver halide is sensitized to the silver halide of the main color layers in a spectrally shifted manner (cf. DE-A-29 02 681, EP-A 0 167 173 and DE-A 3 700 419).
  • Color photographic recording material with a high IIE on the one hand, in which, on the other hand, silver halide grains in the light-sensitive, image dye-providing layers not only have spectral main sensitization in their own spectral range (main spectral sensitivity) but also color sensitization in foreign spectral ranges are known from DE-A-36 21 764. Those there described external sensitization causes a spectral sensitivity for the two other main spectral ranges; otherwise only the silver halide grains with the lowest photosensitivity are spectrally externally sensitized. This improves the density gradation.
  • the present invention is concerned with sensitization in the area of the gaps between the main spectral ranges defined above.
  • B O , G O and R O are the spectral sensitivity curves for the main spectral sensitivities blue , Denote green and red, each referring to the same energy spectrum.
  • the inventive step essentially consists in spectrally sensitizing the color photographic recording material in such a way that the spectral sensitivities of the relevant color layers or color sub-layers overlap more strongly with the main spectral sensitivity blue, green or red, while maintaining steep sensitization edges.
  • This principle will be explained by way of example with the aid of the (schematic) illustrations in FIGS. 3A and 3B.
  • FIG. 3A shows (schematically) how the sensitivity range of the layer system providing green-sensitive purple dye according to the present invention is expanded by G O on the short-wave side by G S and on the long-wave side by G L.
  • FIGS. 3A and 3B shows schematically the expansion of the long-wave flank of the blue sensitivity of the yellow dye-providing layer system by B L and the short-wave flank of the red sensitivity of the cyan dye layer system by R S , combination of the measures described in FIGS. 3A and 3B leads to this desired effect, because when exposed to light in the range of B L / G S , that is in the area of the gap between the main spectral ranges blue and green, both yellow and purple dye, that is to say “red” overall, and when exposed to light in the range of G L / R S , that is to say in the region of the gap between the main spectral ranges green and red, both purple and cyan dye, that is to say "blue” in total.
  • the spectral sensitivity curves of the layers with a spectral sensitivity in the region of the two adjacent main spectral regions, measured by the color density of the color image produced, are increased in the region of the secondary spectral sensitivity, and thus the intersection of these two sensitivity curves is also increased. This is explained in more detail below with reference to FIGS. 2 and 2A.
  • the recording material according to the invention is characterized in that in order to produce a color density of the complementary partial color image by exposure to light in the region of the secondary spectral sensitivity, no more than 0.6, preferably no more than 0.4 logarithmic exposure units I ⁇ t are required more than when exposed to light in the range of the main spectral sensitivity.
  • the value ⁇ S E as defined above is not greater than 0.6, preferably not greater than 0.4 (log I ⁇ t units).
  • the additional spectral sensitization according to the invention can preferably be implemented with those spectral sensitizing dyes which, individually or in a mixture of several sensitizers (according to the schematic illustration in FIG. 4), in the gaps between blue and green sensitivity or between green and red - Provide sensitivity to spectrally narrow sensitization bands with steep flanks, for example by forming appropriate dye aggregates.
  • spectral sensitizing dyes are referred to here as "gap dyes" (LS dyes).
  • the amount in which these LS dyes are used depends on the one hand on the type of silver halide grains (size, halide composition and the like), on the type and amount of the adsorption competitors present on the grain surfaces (stabilizers, halide ions, other sensitizers and the like .) as well as according to the desired color matching and strength of the color nuance differentiation. The latter also depends on the subjective perception of color.
  • Such intermediate layers can additionally contain mask couplers, DIR couplers, DAR couplers and / or other couplers which are capable of releasing "photographically useful groups” (PUG).
  • PUG photographically useful groups
  • Suitable LS dyes according to the present invention are all spectral sensitizers which can generate a sensitization maximum between 480 and 520 nm (blue / green LS dyes) or between 580 and 620 nm (green / ROL LS dyes and sufficiently steep sensitizing edges
  • This means that especially I-aggregate-forming cyanine dyes are suitable as well as combinations of I-aggregate-forming dyes, provided they have "mixing aggregates" with sensitization maxima between 480 and 520 nm or on the silver halide crystal surfaces form between 580 and 620 nm.
  • the dyes with a sulfoalkyl group are in betaine form, the dyes with two sulfoalkyl groups as a salt with any cation.
  • LS dyes according to the invention are further illustrated by the following examples:
  • the dyes according to the invention are prepared by known methods customary in the chemistry of cyanine dyes, as described, for example, in the monograph by F.M. Hamer, "The Cyanine Dyes and Related Compounds", Interscience Publishes 1964.
  • the recording materials according to the invention are equipped with high interimage effects, or if such high interimage effects can be produced by suitable processing conditions.
  • the interimage effect is measured as a percentage distribution of the color gradation in the case of color separation exposure with light of the corresponding main spectral range in relation to that color gradation which is obtained when exposed to white light.
  • the IIE is generally produced by DIR couplers, and in the case of color reversal material usually by Agkomp complexing agents such as SCN ⁇ in the reversal first developer.
  • 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, 28 42 063, 27 26 180, 36 26 219, 36 30 564, 36 36 824 and 36 44 416. Further advantages for color reproduction, ie, color separation and color purity, and for detail reproduction, ie, sharpness and graininess, are also included to achieve such DIR couplers which, for example, do not split off the development inhibitor directly as a result of the coupling with an oxidized color developer, but only after a further subsequent reaction, which is achieved, for example, with a timing group.
  • DIR couplers which release a development inhibitor which is decomposed into essentially photographically ineffective products in the developer bath are described, for example, in DE-A-32 09 486 and in EP-A-0 167 168 and EP-A-0 219 713. This measure ensures trouble-free development and processing consistency.
  • the DIR couplers can be added to a wide variety of layers in a multilayer photographic material, for example also light-insensitive or intermediate layers. However, they are preferably the added light-sensitive silver halide emulsion layers, the characteristic properties of the silver halide emulsion, for example its iodide content, the structure of the silver halide grains or their grain size distribution having an influence on the photographic properties achieved.
  • the influence of the inhibitors released can be limited, for example, by incorporating an inhibitor scavenger layer in accordance with DE-A-24 31 223. For reasons of reactivity or stability, it may be advantageous to use a DIR coupler which forms a color during the coupling which is different from the color which is to be formed in the layer containing the DIR coupler.
  • Suitable light-sensitive silver halide emulsions are emulsions of silver chloride, silver bromide or mixtures thereof, possibly with a silver iodide content of up to 20 mol% in one of the commonly used hydrophilic binders.
  • Gelatin is preferably used as a binder for the photographic layers. However, this can be replaced in whole or in part by other natural or synthetic binders.
  • the emulsions can be chemically and spectrally sensitized in the usual way, and the emulsion layers as well as other non-light-sensitive layers can be hardened in the usual way with known hardening agents.
  • Color photographic recording materials usually contain at least one silver halide emulsion layer for the recording of light from the three spectral ranges red, green and blue.
  • the light-sensitive layers are spectrally sensitized in a known manner by means of suitable sensitizing dyes.
  • suitable sensitizing dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
  • 9-ethyl carbocyanines with benzthiazole, benzselenazole or naphthothiazole as basic end groups which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl and 9-ethyl-naphthoxathia or -selencarbocyanines and 9- Ethyl naphthothiaoxa or benzimidazocarbocyanines, provided that the dyes carry at least one sulfoalkyl group on the heterocyclic nitrogen.
  • Blue-sensitive silver halide emulsion layers do not necessarily have to contain a spectral sensitizer, since in many cases the intrinsic sensitivity of the silver halide is sufficient for the recording of blue light.
  • Each of the light-sensitive layers mentioned can consist of a single layer or, in a known manner, for example in the case of the so-called double-layer arrangement, also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470).
  • Red-sensitive silver halide emulsion layers are usually arranged closer to the layer support than green-sensitive silver halide emulsion layers and these are in turn closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.
  • a non-photosensitive intermediate layer is usually arranged, which may contain means for accommodating the incorrect diffusion of developer oxidation products.
  • silver halide emulsion layers of the same spectral sensitivity can be directly adjacent to one another or be arranged such that there is a light-sensitive layer with a different spectral sensitivity between them (DE-A-1 958 709, DE-A-25 30 645, DE-A26 22 922).
  • Color photographic recording materials for the production of multicolored images usually contain, in spatial and spectral assignment to the silver halide emulsion layers of different spectral sensitivity, coloring compounds, here in particular color couplers, for producing the different partial color images cyan, purple and yellow.
  • Spatial and spectral assignment is understood to mean that the color coupler is in such a spatial relationship to the silver halide emulsion layer that an interaction between them is possible, an image-like correspondence between the silver image formed during development and the color image generated from the color coupler permits so that each silver halide emulsion layer with a certain spectral sensitization is assigned a color coupler for generating a partial color image complementary to the respective spectral sensitivity can. This is usually achieved by the fact that the color coupler is contained in the silver halide emulsion layer itself or in an adjacent, possibly non-light-sensitive binder layer.
  • Each of the differently spectrally sensitized silver halide emulsion layers can be assigned one or more color couplers. If several silver halide emulsion layers of the same spectral sensitivity are present, each of them can contain a color coupler, which color couplers need not necessarily be identical. They should only result in at least approximately the same color during color development, normally a color that is complementary to the color of the light to which the silver halide emulsion layers in question are predominantly sensitive.
  • 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 those couplers that contain a cleavable residue in the coupling point, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue (e.g.
  • a certain desired photographic activity unfolds, for example as a development inhibitor or accelerator.
  • 2-equivalent couplers are the already mentioned DIR couplers as well as DAR or.
  • FAR couplers which are a development accelerator or release an haze and can be used to increase sensitivity, contrast and maximum density.
  • DIR, DAR or FAR couplers mainly the effectiveness of the residue released during coupling is desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, which give essentially colorless products on coupling (DE-A-15 47 640).
  • the cleavable residue can also be a ballast residue, so that coupling products which are diffusible are obtained in the reaction with color developer oxidation products are or at least have a weak or limited mobility (US-A-4 420 556).
  • the material may further contain compounds other than couplers, which can liberate, for example, a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR hydroquinones and other compounds as described, for example, in US Pat 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. These compounds perform the same function as the DIR, DAR or FAR couplers, except that they do not form coupling products.
  • couplers can liberate, for example, a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR hydroquinones and other compounds as described, for example, in US Pat US-A-4 636 546, 4 345 024, 4 684 60
  • 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 in such a way that a solution, a dispersion or an emulsion is first prepared from the compound in question and then the casting solution for the compound in question Layer is added.
  • the selection of the suitable solvent or dispersing agent depends on the solubility of the compound.
  • 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 instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.
  • the compounds can also be introduced into the casting solution in the form of loaded latices.
  • anionic water-soluble compounds for example dyes
  • pickling polymers for example dyes
  • 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, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-diamylphenol, dioctylacelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-dibutyl-2-butoxy-5-paroxy-5-aniline
  • 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 also called scavengers or EOP scavengers, are described in Research Disclosure 17,643 (Dec. 1978), chapters VII, 17/842 (February 1979), and 18/716 (November 1979), page 650 as well as in EP-A-0 069 070, 0 098 072, 0 124 877 and 0 125 522 226 described.
  • sub-layers of the same spectral sensitization can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains.
  • the sublayer with higher sensitivity will be located further away from the support than the sublayer with lower sensitivity.
  • 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 on the one hand to protect the image dyes from fading by UV-rich daylight and, on the other hand, as filter dyes to absorb the UV light in daylight upon exposure and thus improve the color rendering of a film.
  • 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).
  • 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 e.g. in Research Disclosure 17,643, Chapter V, in US-A-2,632,701, 3,269,840 and in GB-A-852,075 and 1,319,763.
  • Certain layers of binder 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 contain photographically inert particles of an inorganic or organic nature, e.g. as matting agents or as spacers ( DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, 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 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.
  • 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.
  • Color photographic negative materials are usually processed by developing, bleaching, fixing and washing or by developing, bleaching, fixing and stabilizing without subsequent washing, whereby bleaching and fixing can be combined into one processing step.
  • All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine or indophenol dyes can be used as the color developer compound.
  • Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example 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.
  • Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3106 (1951) and G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, page 545 ff.
  • 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-hydroxyethylethylenediaminetriacetic 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 washing can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent.
  • this stabilizing bath also acts as a final bath.
  • 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.
  • Example 1 the following compounds are used in addition to the couplers already mentioned:
  • UV absorber UV-1 UV absorber UV-1
  • the dyes specified below are used here as sensitizing dyes for the main spectral ranges and in the examples below.
  • samples of the layer structures 1A and 1B were each exposed to light of different wavelengths (from 400 to 700 nm) through a green step wedge using very narrow-band spectral filters (e.g. interference filters, spectral width ⁇ ⁇ 10 nm) and then processed in a color negative processing process described in "The British Journal of Photography", 1974, pages 597 and 598.
  • the density level with color density 1.0 (measured via fog) of the color negative was then, as described in DE-A-37 00 419, copied onto color-negative paper and the dominant wavelength of the positive copy against the wavelength of that onto the samples 1A and 1B applied to exposed light. (see Fig. 5A and 5B).
  • Deviations from the straight line rising by 45 ° in these diagrams indicate deviations from "realistic color rendering"; It can be seen from these figures that the deviations in material 1B according to the invention are significantly smaller than in comparison material 1A.
  • FIG. 6A compare layer structure 2A
  • 6B layer structure 2B according to the invention
  • Table 2 Layer structure 2A (comparison) 2B (invention) main awareness only Main sensitization like 1A gap awareness additional Gap B L / G S Gap G L / R S Col. ⁇ mol / mol Ag Col. ⁇ mol / mol Ag Col.
  • a color photographic recording material for reverse color development was produced (layer structure 3A - comparison) by applying the following layers in the order given to a transparent layer support made of cellulose triacetate.
  • the Quantities refer to 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.
  • layers 3, 4, 6, 7, 10 and 11 were additionally "gap-sensitized" as indicated in Table 3.
  • FIG. 7A compare layer structure 3A
  • FIG. 7B layer structure 3B according to the invention
  • Table 3 Layer structure 3A (comparison) 3B (invention) main awareness only Main sensitization like 3A gap sensitization additionally Gap B L / G S Gap G L / R S Col. ⁇ mol / mol Ag Col. ⁇ mol / mol Ag Col.

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  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (8)

  1. Matériau de reproduction photographique en couleurs qui contient pour chacune des trois plages spectrales principales bleu, vert et rouge, au moins chaque fois une couche d'émulsion à l'halogénure d'argent photosensible, sensible à la lumière de la plage spectrale principale concernée (sensibilité spectrale principale) et au moins un composé chromophore pour produire une image couleur partielle en couleurs complémentaires par rapport à la sensibilité spectrale principale, caractérisé par une ou plusieurs couches d'émulsion à l'halogénure d'argent possédant une sensibilisation supplémentaire à la lumière provenant du vide de 480 à 520 nm et/ou de 580 à 620 nm s'étendant entre deux plages spectrales principales adjacentes (sensibilité spectrale secondaire) et par la capacité de produire par le développement, après exposition à la lumière provenant de ce vide, une image couleur partielle en couleurs complémentaires par rapport à la sensibilité spectrale secondaire, la sensibilisation supplémentaire dans la plage des longueurs d'onde de 480 à 520 nm et/ou de 580 à 620 nm (sensibilité spectrale secondaire) entraînant une superposition des courbes de sensibilité spectrales mesurées à une densité des couleurs de 1,0, correspondantes aux deux plages spectrales principales chaque fois directement adjacentes, de sorte que, en vue de la production d'une densité des couleurs de 1,0 par exposition dans la plage de la sensibilité spectrale secondaire, tout au plus 0,6 unité d'exposition logarithmique (log I.t) est davantage requise qu'en vue de la production de la même densité des couleurs (densité des couleurs = 1,0), en cas de spectre de même énergie, par exposition dans une des plages des sensibilités spectrales principales adjacentes.
  2. Matériau de reproduction photographique en couleurs selon la revendication 1, caractérisé en ce que des coupleurs de couleur sont affectés à la ou aux couches d'émulsion d'halogénure d'argent présentant la sensibilité spectrale secondaire, de sorte qu'après exposition à la lumière à partir d'une des plages de longueurs d'onde correspondant à la sensibilité spectrale secondaire, une image couleur partielle en couleurs complémentaires par rapport à la sensibilité spectrale secondaire est produite par développement chromogène.
  3. Matériau de reproduction selon l'une quelconque des revendications 1 ou 2, caractérisé par un effet interimage en cyan (EIIC) d'au moins 20 %, un effet interimage en magenta (EIIM) d'au moins 20 % et un effet interimage en jaune (EIIY) d'au moins 10 %.
  4. Matériau de reproduction selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la sensibilisation supplémentaire dans la plage de longueurs d'onde 480-520 nm est provoquée par un colorant de sensibilisation aux vides (colorant LS) d'une des formules générales I à IX
    Figure imgb0174
    Figure imgb0175
    Figure imgb0176
    Figure imgb0177
    Figure imgb0178
    Figure imgb0179
    Figure imgb0180
    Figure imgb0181
    Figure imgb0182
     dans lesquelles
    R¹ , R , R³ , R⁴ ,   désignent H, - CH₃ ou - OCH₃ , au moins un des résidus R¹ à R⁴ désignant -OCH₃;
    R⁵, R⁶   désignent -CH₃, -C₂H₅, -CH₂CH₂SO₃H, -CH₂CH₂CH₂SO₃H, - CH₂CH₂CH₂CH₂SO₃H ou -CH₂CH₂CH(CH₃)SO₃H, au moins un des résidus R⁵ et R⁶ désignant un radical sulfo-alkyle;
    R⁷, R¹⁰   désignent -CH₃, -C₂H₅ ou -(CH₂)₃SO₃H,
    R⁸, R⁹   désignent H, -CH₃, -OCH₃ ou Cl,
    R¹¹, R¹   désignent un radical alkyle inférieur,
    R¹³   désigne -CH₃, -C₂H₅, -CH₂CH₂OH, - (CH₂)nCOOH ou - CH₂CH₂SO₃H, n désignant 1-3,
    R¹⁴   désignent H, -CH₃, Cl ou -OCH₃,
    R¹⁵, R¹⁶   désignent H, Cl, -CN, F ou -CF₃, au moins un des résidus R¹⁵ et R¹⁶ désignant un substituant différent de H,
    X, Y   désignent S, Se
    Z   désigne O, S
    W   désigne O, S, Se,
    dans chacune des formules générales II, III et IV, au moins un des résidus R⁵, R⁷ et R¹⁰ qu'elles comportent désignant un radical sulfopropyle.
  5. Matériau de reproduction selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la sensibilisation supplémentaire dans la plage de longueurs d'onde 580-620 nm est provoquée par un colorant de sensibilisation aux vides (colorant LS) d'une des formules générales X à XV
    Figure imgb0183
    Figure imgb0184
    Figure imgb0185
    Figure imgb0186
    Figure imgb0187
    Figure imgb0188
     dans lesquelles
    R5 , R⁶   désignent -CH₃, -C₂H₅, -CH₂CH₂SO₃H, -CH₂CH₂CH₂SO₃H, - CH₂CH₂CH₂CH₂SO₃H ou -CH₂CH₂CH(CH₃)SO₃H, au moins un des résidus R⁵ et R⁶ désignant un radical sulfo-alkyle;
    R⁷   désignent -CH₃, -C₂H₅ ou -(CH₂)₃SO₃H,
    R¹⁷, R¹⁹   désignent Cl ou -CN,
    R¹⁸, R⁰   désignent Cl, -CN, -CF₃, ainsi que H, uniquement si R¹⁷, R¹⁹ = CN,
    R¹⁴, R¹   désigne H, Cl, -CH₃ ou -OCH₃,
    R   désigne Cl, -C₆H₅ ou -OCH₃;
    dans chacune des formules générales XII, XIII, XIV et XV, au moins un des résidus R⁵ et R⁷ qu'elles comportent, désignant un radical sulfopropyle.
  6. Matériau de reproduction selon l'une quelconque des revendications 4 et 5, caractérisé en ce que le colorant LS est contenu dans une couche d'émulsion d'halogénure d'argent, qui contient au moins un coupleur de couleur en vue de la production d'une image couleur partielle en couleurs complémentaires par rapport à la sensibilité spectrale secondaire provoquée par le colorant LS.
  7. Matériau de reproduction selon la revendication 6, caractérisé en ce que la couche d'émulsion d'halogénure d'argent contenant le colorant LS contient un mélange de coupleurs de couleur en vue de la production des deux images couleur partielles qui sont en couleurs complémentaires par rapport aux deux sensibilités spectrales principales adjacentes par rapport à la sensibilité spectrale secondaire provoquée par le colorant LS.
  8. Matériau de reproduction selon l'une quelconque des revendications 1 à 6, caractérisé en ce que sont sensibilisées au moins une couche d'émulsion d'halogénure d'argent présentant une sensibilité à la lumière d'une première plage spectrale principale (première sensibilité spectrale principale) et présentant au moins un coupleur de couleur en vue de la production d'une image couleur partielle en couleurs complémentaires par rapport à la première sensibilité spectrale principale et au moins une couche d'émulsion d'halogénure d'argent présentant une sensibilité à la lumière d'une deuxième plage spectrale principale adjacente à la première (deuxième sensibilité spectrale principale) et présentant au moins un coupleur de couleur en vue de la production d'une image couleur partielle en couleurs complémentaires par rapport à la deuxième sensibilité spectrale principale comportant au moins un colorant LS en vue de la sensibilisation à la lumière à partir du vide s'étendant entre les deux plages spectrales principales (sensibilité spectrale secondaire).
EP90112994A 1989-07-20 1990-07-07 Matériau d'enregistrement photographique en couleurs au rendu chromatique amélioré Expired - Lifetime EP0409019B1 (fr)

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DE3924111A DE3924111A1 (de) 1989-07-20 1989-07-20 Farbfotografisches aufzeichnungsmaterial mit verbesserter wiedergabe von farb-nuancen
DE3924111 1989-07-20

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EP0409019A3 EP0409019A3 (en) 1993-01-13
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DE4301106A1 (de) * 1993-01-18 1994-07-21 Agfa Gevaert Ag Farbfotografisches Aufzeichnungsmaterial
DE4301105A1 (de) * 1993-01-18 1994-07-21 Agfa Gevaert Ag Farbfotografisches Aufzeichnungsmaterial
US5512103A (en) * 1994-02-18 1996-04-30 Eastman Kodak Company Silver halide color photography element with improved high density contrast and bright low density colors
EP0809140B1 (fr) * 1996-05-06 2002-01-16 Agfa-Gevaert Matériau photographique couleur d'enregistrement ayant une sensibilité plus élevée et reproduction des couleurs améliorée
DE19711142A1 (de) * 1997-03-18 1998-09-24 Agfa Gevaert Ag Hochempfindliches farbfotografisches Aufzeichnungsmaterial mit erhöhter Empfindlichkeit im blauen Spektralbereich
DE19711144A1 (de) * 1997-03-18 1998-09-24 Agfa Gevaert Ag Hochempfindliches farbfotografisches Aufzeichnungsmaterial mit erhöhter Empfindlichkeit im grünen Spektralbereich
DE19711143A1 (de) * 1997-03-18 1998-09-24 Agfa Gevaert Ag Hochempfindliches farbfotografisches Aufzeichnungsmaterial mit erhöhter Empfindlichkeit im roten Spektralbereich
US6045983A (en) * 1997-09-05 2000-04-04 Eastman Kodak Company Color negative films adapted for digital scanning
US6143482A (en) * 1998-08-05 2000-11-07 Eastman Kodak Company Photographic film element containing an emulsion with green-red responsivity
US6296994B1 (en) 1999-03-01 2001-10-02 Eastman Kodak Company Photographic elements for colorimetrically accurate recording intended for scanning
US6093526A (en) * 1999-03-01 2000-07-25 Eastman Kodak Company Photographic film element containing an emulsion with broadened green responsivity
US6197489B1 (en) * 1999-12-28 2001-03-06 Eastman Kodak Company Photographic element for color imaging
US6180328B1 (en) * 1999-12-28 2001-01-30 Eastman Kodak Company Photographic element for color imaging
US6159674A (en) * 1999-12-28 2000-12-12 Eastman Kodak Company Photographic element for color imaging
US6485897B1 (en) 2001-05-22 2002-11-26 Eastman Kodak Company Spectral sensitized silver halide element for electronic filmwriter device

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JPS4925901B1 (fr) * 1969-10-09 1974-07-04
DE2026560A1 (en) * 1969-11-26 1971-05-27 Photographic colour material
JPS62160449A (ja) * 1986-01-08 1987-07-16 Fuji Photo Film Co Ltd カラ−写真感光材料
JPH0690463B2 (ja) * 1986-01-08 1994-11-14 富士写真フイルム株式会社 カラ−写真感光材料
DE3633713A1 (de) * 1986-10-03 1988-04-14 Agfa Gevaert Ag Farbfotografischer negativ-film

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DE3924111A1 (de) 1991-01-31
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EP0409019A2 (fr) 1991-01-23
JPH0364747A (ja) 1991-03-20

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