EP0409019A2 - 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
EP0409019A2
EP0409019A2 EP90112994A EP90112994A EP0409019A2 EP 0409019 A2 EP0409019 A2 EP 0409019A2 EP 90112994 A EP90112994 A EP 90112994A EP 90112994 A EP90112994 A EP 90112994A EP 0409019 A2 EP0409019 A2 EP 0409019A2
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Prior art keywords
color
spectral sensitivity
layer
recording material
silver halide
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EP90112994A
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German (de)
English (en)
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EP0409019B1 (fr
EP0409019A3 (en
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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 present invention relates to a color photographic recording material (color negative or color reversal) at least one blue-sensitive layer which produces a yellow image dye during color development, - At least one layer sensitive to green and producing a purple image dye during color development and at least one red-sensitive layer which produces a blue-green image dye during color development, in which the reproduction of different color nuances is decisively improved by a special spectral sensitization.
  • the newer color photographic recording materials are - on the one hand equipped with powerful so-called interimage effects (IIE), - on the other hand, so spectrally sensitized with regard to the color layers sensitive to the main spectral ranges blue, green, red that the flanks of the sensitization curves to the neighboring areas in the spectrum each fall steeply and thus come fairly close to the ideal of rectangular sensitization (see Fig. 2).
  • IIE interimage effects
  • 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 External sensitization described causes spectral sensitivity for the two other main spectral ranges; moreover, only the silver halide grains with the lowest photosensitivity are spectrally sensitized to foreign substances. This improves the density gradation.
  • the invention relates to a color photographic recording material which contains at least one light-sensitive silver halide emulsion layer for each of the three main spectral ranges blue, green and red Light of the main spectral range in question is sensitive (main spectral sensitivity) and contains at least one coloring compound for producing a partial color image complementary to the main spectral sensitivity, characterized by one or more silver halide emulsion layers with additional sensitization to light from the gap extending between two adjacent main spectral ranges (secondary spectral sensitivity) and the ability , after exposure to light from this gap by development to produce a partial color image complementary to the secondary spectral sensitivity.
  • the main spectral sensitivity usually corresponds to the following wavelength ranges (main spectral ranges): Blue: ⁇ ⁇ 480 nm Green: 520 ⁇ ⁇ 580 nm Red: 620 ⁇ the lower sensitivity limit of the blue main spectral range and the upper sensitivity limit of the red main spectral range do not require precise definition, but coincide with the limits of the visible spectral range.
  • the present invention is concerned with sensitization in the area of the gaps between the main spectral ranges defined above.
  • 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.
  • 3A shows (schematically) how the sensitivity range of the layer system providing green-sensitive purple dye according to the present invention is expanded from G0 on the short-wave side by G S and on the long-wave side by G L.
  • FIGS. 3A and 3B shows schematically the extension 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.
  • B L / G S that is to say in the range of the gap between the main spectral ranges blue and green, both yellow and purple dye , so overall "red” and when exposed to light in the range of G L / R S , that is in the region of the gap between the main spectral ranges green and red, both purple and cyan dye, so overall "blue” is generated.
  • 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 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 colored 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 coordination 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 maximum of sensitization between 480 and 520 nm (blue / green LS dyes) or between 580 and 620 nm (green / red LS dyes) and sufficiently steep sensitizing edges
  • formulas I to XV mean R1, R2, R3, R4 H, -CH3 or -OCH3, at least one of the radicals R1 to R4 being -OCH3, R5, R6 -CH3, -C2H5, -CH2CH2SO3H, -CH2CH2CH2SO3H, -CH2CH2CH2SO3H or -CH2CH2CH (CH3) SO3H, at least one of the radicals R5 and R6 being sulfoalkyl.
  • 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 generally by Ag+ 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, for example also light-insensitive or intermediate layers. However, they are preferred 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 on 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 the 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.
  • red sensitizers RS examples, in particular for negative and reversal film, are the red sensitizers RS, green sensitizers GS and blue sensitizers BS, which can be used individually or in combination with one another, for example RS-1 and RS-2, and GS-1 and GS -2.
  • 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 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-A -26 22 922).
  • Color photographic recording materials for producing 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 with the silver halide emulsion layer that an interaction between them is possible, which is 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 a possibly non-light-sensitive binder layer adjacent to it.
  • One or more color couplers can be assigned to each of the differently spectrally sensitized silver halide emulsion layers. If there are several silver halide emulsion layers of the same spectral sensitivity, 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, for which the silver halide emulsion layers in question are predominantly sensitive.
  • Color couplers for producing the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type; suitable examples are
  • Color couplers for producing the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type; suitable examples are
  • Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the ⁇ -acylacetamide type; suitable examples of this are ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetanilide couplers of the formulas
  • 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 site 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 site, 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 that develop a Release accelerating agent or a fogging agent and can be used to increase sensitivity, contrast and maximum density.
  • DIR, DAR or FAR couplers Since with DIR, DAR or FAR couplers the effectiveness of the residue released during coupling is mainly 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 diffuse are obtained in the reaction with color developer oxidation products are capable of ionizing or at least have poor or restricted mobility (US Pat. No. 4,420,556).
  • the material may further contain compounds other than couplers, which can, for example, release a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a foggant or an antifoggant, for example so-called DIR-hydroquinones and other compounds, for example as 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. These compounds perform the same function as the DIR, DAR or FAR couplers, except that they do not form coupling products.
  • couplers can, for example, release a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a foggant or an antifoggant, for example so-called DIR-hydroquinones and other compounds, for example as described in US-A-4 636 546, 4 345 024, 4 684 604 and in DE
  • 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 eg dyes
  • pickling polymers e.g. acrylic acid
  • Suitable oil formers are e.g. Alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.
  • oil formers 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, tridecoxy phosphate, 2-ethylhexyl phosphate, tridecoxy phosphate, 2-ethylhexyl phylate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-diamylphenol, dioctylacelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-dibutyl
  • 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 and 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 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 white toners 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.
  • binder layers in particular the layer furthest away from the carrier, but also occasionally intermediate layers, especially if they represent the layer furthest away from the carrier during production, can 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, 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 are, for example, 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, the reactive halogen included (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 7
  • 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 caused by the crosslinking reaction and the swelling of the layer structure occurs .
  • 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.
  • Further 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.
  • Persulphates 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 functions as a final bath.
  • a color photographic recording material for color negative color development was produced (layer structure 1A comparison) by applying the following layers in the order given to a transparent cellulose triacetate support.
  • the quantities given relate to 1 m2.
  • 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.
  • Layer 3 (1st red-sensitized layer, slightly sensitive) Silver bromide iodide emulsion, red-sensitized (as indicated in Table 1) (4.0 mol% iodide; average grain diameter 0.45 ⁇ m) from 2.2 g AgNO3, with 2.0 g gelatin 0.60 g cyan coupler C-19 0.05 g RM-1 red mask 0.03 g DIR coupler DIR-1 0.52 g CPM
  • Layer 6 (1st green-sensitized layer, slightly sensitive) Silver bromide iodide emulsion, green-sensitized (as indicated in Table 1) (4.5 mol% iodide; average grain diameter 0.4 ⁇ m) from 1.8 g AgNO3, with 1.6 g gelatin 0.60 g magenta coupler M-23 0.05 g yellow mask YM-1 0.03 g DIR coupler DIR-2 0.08 g DIR coupler DIR-3 0.11 g CPM 0.12 g DBP
  • Layer 7 (2nd green-sensitized layer, highly sensitive) Silver bromide iodide emulsion, sensitized to green (as indicated in Table 1) (7.0 mol% iodide; average grain diameter 0.7 ⁇ m) from 2.2 g AgNO3, with 1.4 g gelatin 0.15 g magenta coupler M-18 0.03 g yellow mask YM-1 0.75 g CPM
  • Layer 11 (2nd blue-sensitive layer, highly sensitive), Silver bromide iodide emulsion, blue-sensitized (as indicated in Table 1) (9.0 mol% iodide; average grain diameter 0.9 ⁇ m) from 1.0 g of AgNO3, with 0.85 g gelatin 0.30 g yellow coupler Y-2 0.30 g CPM
  • Example 1 the following compounds are used in addition to the couplers already mentioned:
  • the dyes specified below are used here and in the following examples as sensitizing dyes for the main spectral ranges.
  • samples of the layer structures 1A and 1B were 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 copied onto color-negative paper as described in DE-A-37 00 419 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 at 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.
  • Layer 3 (1st red-sensitized layer, slightly sensitive) Core / shell type silver bromide iodide emulsion (4.5 mol% iodide, 1.5 mol% chloride; average grain diameter 0.4 ⁇ m), red-sensitized as indicated in Table 2, from 2.6 g of AgNO3, with 1.8 g gelatin 0.30 g cyan coupler C-1 0.20 g cyan coupler C-9 0.06 g RM-1 red mask 0.04 g DIR coupler DIR-1 0.25 g CPM 0.25 g DBP
  • Layer 5 (1st green-sensitized layer, slightly sensitive) Core / shell type silver bromide iodide emulsion, 5.0 mol% iodide; average grain diameter 0.38 ⁇ m), green sensitized as indicated in table 2, from 2.0 g of AgNO3, with 1.8 g gelatin 0.40 g M-12 magenta coupler 0.18 g yellow mask YM-1 0.03 g DIR coupler DIR-2 0.60 g CPM
  • Layer 7 (1st blue-sensitive layer, slightly sensitive) Core / shell type silver bromide iodide emulsion 5.5 mol% iodide; average grain diameter 0.32 ⁇ m), blue-sensitized as indicated in table 2, from 0.6 g AgNO3, with 1.8 g gelatin 0.90 g yellow coupler Y-17 0.10 g DIR coupler DIR-3 0.25 g CPM 0.65 g of polyethyl acrylate
  • Layer 9 (2nd red sensitive layer, highly sensitive) Silver bromide emulsion (T-grains); (1.65 mol% iodide; average grain diameter (area) 2.4 ⁇ m; medium aspect ratio 1:12), red-sensitized as indicated in Table 2, from 2.0 g of AgNO3, with 1.8 g gelatin 0.18 g cyan coupler C-8 0.03 g RM-1 red mask 0.01 g DIR dome DIR-3 0.10 g CPM
  • Layer 11 (2nd green-sensitive layer, highly sensitive) Silver bromide iodide emulsion (T-grains as in layer 9), green sensitized as indicated in table 2, from g AgNO3, with g gelatin g M-17 magenta coupler g YM-1 yellow mask g DIR coupler DIR-4 g CPM g DBP
  • Layer 13 (2nd blue-sensitive layer, highly sensitive), Silver bromoiodide emulsion 9.5 mol% iodide; average grain diameter 0.95 ⁇ m) blue-sensitized as indicated in table 2, from 1.0 g AgNO3, with 1.2 g gelatin 0.12 g yellow coupler Y-21 0.02 g DIR coupler DIR-3 0.30 g CPM
  • Layer 15 (hardening layer) 1.5 g gelatin 0.7 g hardener (CAS Reg.-No. 65411-60-1)
  • 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 m2 each.
  • 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.
  • Layer 6 (1st green-sensitized layer, slightly sensitive) Silver bromide iodide emulsion (4.8 mol% iodide; average grain diameter 0.28 ⁇ m), green sensitized as indicated in table 3, from 0.94 g AgNO3, with 0.77 g gelatin 0.30 g magenta coupler M-12
  • 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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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP90112994A 1989-07-20 1990-07-07 Matériau d'enregistrement photographique en couleurs au rendu chromatique amélioré Expired - Lifetime EP0409019B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3924111 1989-07-20
DE3924111A DE3924111A1 (de) 1989-07-20 1989-07-20 Farbfotografisches aufzeichnungsmaterial mit verbesserter wiedergabe von farb-nuancen

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EP0409019A2 true EP0409019A2 (fr) 1991-01-23
EP0409019A3 EP0409019A3 (en) 1993-01-13
EP0409019B1 EP0409019B1 (fr) 1996-02-14

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JP (1) JPH0364747A (fr)
DE (2) DE3924111A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0607801A1 (fr) * 1993-01-18 1994-07-27 Agfa-Gevaert AG Matériau photographique couleur d'enregistrement
EP0607800A1 (fr) * 1993-01-18 1994-07-27 Agfa-Gevaert AG Matériau photographique couleur d'enregistrement
FR2716546A1 (fr) * 1994-02-18 1995-08-25 Eastman Kodak Co Produit photographique aux halogénures d'argent en couleurs ayant un contraste amélioré dans les hautes densités et des couleurs lumineuses dans les faibles densités.
EP0809140A1 (fr) * 1996-05-06 1997-11-26 Agfa-Gevaert AG Matériau photographique couleur d'enregistrement ayant une sensibilité plus élevée et reproduction des couleurs améliorée
EP0866363A1 (fr) * 1997-03-18 1998-09-23 Agfa-Gevaert AG Matériau d'enregistrement photographique en couleurs à haute sensibilité avec une sensibilité accrue dans la région spectrale rouge
EP0866368A2 (fr) * 1997-03-18 1998-09-23 Agfa-Gevaert AG Matériau d'enregistrement photographique en couleurs à haute sensibilité avec une sensibilité accrue dans la région spectrale verte
EP0901042A1 (fr) * 1997-09-05 1999-03-10 Eastman Kodak Company Une amélioration aux pellicules négatives couleur adaptés pour balayage numérique
EP0978761A1 (fr) * 1998-08-05 2000-02-09 Eastman Kodak Company Elément de pellicule photographique contenant une émulsion à sensibilité au vert et au rouge
US6040125A (en) * 1997-03-18 2000-03-21 Agfa-Gevaert Nv High-speed color photographic recording material having increased sensitivity in the blue spectral region
EP1033619A2 (fr) * 1999-03-01 2000-09-06 Eastman Kodak Company Pellicule photographique comprenant une émulsion ayant une sensibilité accrue pour le vert
EP1113321A1 (fr) * 1999-12-28 2001-07-04 Eastman Kodak Company Elément photographique amélioré pour formation d' image couleur
EP1116996A2 (fr) * 1999-12-28 2001-07-18 Eastman Kodak Company Elément photographique pour l'imagerie en couleur
EP1116995A2 (fr) * 1999-12-28 2001-07-18 Eastman Kodak Company Elément photographique pour l'imagerie en couleur
US6296994B1 (en) 1999-03-01 2001-10-02 Eastman Kodak Company Photographic elements for colorimetrically accurate recording intended for scanning
US6485897B1 (en) 2001-05-22 2002-11-26 Eastman Kodak Company Spectral sensitized silver halide element for electronic filmwriter device

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2038870A5 (fr) * 1969-10-09 1971-01-08 Fuji Photo Film Co Ltd
DE2026560A1 (en) * 1969-11-26 1971-05-27 Photographic colour material
DE3700419A1 (de) * 1986-01-08 1987-07-09 Fuji Photo Film Co Ltd Lichtempfindliche farbphotographische materialien
JPS62160449A (ja) * 1986-01-08 1987-07-16 Fuji Photo Film Co Ltd カラ−写真感光材料
EP0262567A2 (fr) * 1986-10-03 1988-04-06 Agfa-Gevaert AG Film photographique couleur négatif

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2038870A5 (fr) * 1969-10-09 1971-01-08 Fuji Photo Film Co Ltd
DE2026560A1 (en) * 1969-11-26 1971-05-27 Photographic colour material
DE3700419A1 (de) * 1986-01-08 1987-07-09 Fuji Photo Film Co Ltd Lichtempfindliche farbphotographische materialien
JPS62160449A (ja) * 1986-01-08 1987-07-16 Fuji Photo Film Co Ltd カラ−写真感光材料
EP0262567A2 (fr) * 1986-10-03 1988-04-06 Agfa-Gevaert AG Film photographique couleur négatif

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0607801A1 (fr) * 1993-01-18 1994-07-27 Agfa-Gevaert AG Matériau photographique couleur d'enregistrement
EP0607800A1 (fr) * 1993-01-18 1994-07-27 Agfa-Gevaert AG Matériau photographique couleur d'enregistrement
US5437969A (en) * 1993-01-18 1995-08-01 Agfa-Gevaert Ag Color photographic recoding material
US5445928A (en) * 1993-01-18 1995-08-29 Agfa-Gevaert Ag Color photographic recording material
FR2716546A1 (fr) * 1994-02-18 1995-08-25 Eastman Kodak Co Produit photographique aux halogénures d'argent en couleurs ayant un contraste amélioré dans les hautes densités et des couleurs lumineuses dans les faibles densités.
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
EP0809140A1 (fr) * 1996-05-06 1997-11-26 Agfa-Gevaert AG Matériau photographique couleur d'enregistrement ayant une sensibilité plus élevée et reproduction des couleurs améliorée
US5856076A (en) * 1996-05-06 1999-01-05 Agfa-Gevaert Aktiengesellschaft Color photographic recording material having elevated sensitivity and improved color reproduction
EP0866363A1 (fr) * 1997-03-18 1998-09-23 Agfa-Gevaert AG Matériau d'enregistrement photographique en couleurs à haute sensibilité avec une sensibilité accrue dans la région spectrale rouge
EP0866368A2 (fr) * 1997-03-18 1998-09-23 Agfa-Gevaert AG Matériau d'enregistrement photographique en couleurs à haute sensibilité avec une sensibilité accrue dans la région spectrale verte
EP0866368A3 (fr) * 1997-03-18 1998-10-07 Agfa-Gevaert AG Matériau d'enregistrement photographique en couleurs à haute sensibilité avec une sensibilité accrue dans la région spectrale verte
US6040125A (en) * 1997-03-18 2000-03-21 Agfa-Gevaert Nv High-speed color photographic recording material having increased sensitivity in the blue spectral region
EP0901042A1 (fr) * 1997-09-05 1999-03-10 Eastman Kodak Company Une amélioration aux pellicules négatives couleur adaptés pour balayage numérique
EP0978761A1 (fr) * 1998-08-05 2000-02-09 Eastman Kodak Company Elément de pellicule photographique contenant une émulsion à sensibilité au vert et au rouge
US6143482A (en) * 1998-08-05 2000-11-07 Eastman Kodak Company Photographic film element containing an emulsion with green-red responsivity
US6251578B1 (en) 1998-08-05 2001-06-26 Eastman Kodak Company Photographic film element containing an emulsion with green-red responsivity
EP1033619A2 (fr) * 1999-03-01 2000-09-06 Eastman Kodak Company Pellicule photographique comprenant une émulsion ayant une sensibilité accrue pour le vert
EP1033619A3 (fr) * 1999-03-01 2001-05-02 Eastman Kodak Company Pellicule photographique comprenant une émulsion ayant une sensibilité accrue pour le vert
US6296994B1 (en) 1999-03-01 2001-10-02 Eastman Kodak Company Photographic elements for colorimetrically accurate recording intended for scanning
EP1113321A1 (fr) * 1999-12-28 2001-07-04 Eastman Kodak Company Elément photographique amélioré pour formation d' image couleur
EP1116996A2 (fr) * 1999-12-28 2001-07-18 Eastman Kodak Company Elément photographique pour l'imagerie en couleur
EP1116995A2 (fr) * 1999-12-28 2001-07-18 Eastman Kodak Company Elément photographique pour l'imagerie en couleur
EP1116996A3 (fr) * 1999-12-28 2002-03-27 Eastman Kodak Company Elément photographique pour l'imagerie en couleur
EP1116995A3 (fr) * 1999-12-28 2002-03-27 Eastman Kodak Company Elément photographique pour l'imagerie en couleur
US6485897B1 (en) 2001-05-22 2002-11-26 Eastman Kodak Company Spectral sensitized silver halide element for electronic filmwriter device

Also Published As

Publication number Publication date
EP0409019B1 (fr) 1996-02-14
EP0409019A3 (en) 1993-01-13
DE3924111A1 (de) 1991-01-31
DE59010128D1 (de) 1996-03-28
JPH0364747A (ja) 1991-03-20

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