EP0515873B1 - Matériau de reproduction photographique couleur - Google Patents

Matériau de reproduction photographique couleur Download PDF

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Publication number
EP0515873B1
EP0515873B1 EP92107601A EP92107601A EP0515873B1 EP 0515873 B1 EP0515873 B1 EP 0515873B1 EP 92107601 A EP92107601 A EP 92107601A EP 92107601 A EP92107601 A EP 92107601A EP 0515873 B1 EP0515873 B1 EP 0515873B1
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EP
European Patent Office
Prior art keywords
silver halide
halide emulsion
layer
green
sensitized
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EP92107601A
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German (de)
English (en)
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EP0515873A1 (fr
Inventor
Arno Dr. Schmuck
Manfred Dr. Peters
Helmut Dr. Kampfer
Wolfgang Dr. Schmidt
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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
    • G03C2200/00—Details
    • G03C2200/11—Blue-sensitive layer
    • 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
    • G03C2200/00—Details
    • G03C2200/20—Colour paper
    • 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
    • G03C2200/00—Details
    • G03C2200/35—Intermediate layer

Definitions

  • the invention relates to a color photographic recording material with a reflective support and an expanded range of gradations in the range of maximum densities and thus a significantly improved tracing at high densities.
  • EP 304 297 A certain improvement of this defect is achieved according to EP 304 297 in that in the case of a color photographic material with a first and a second silver halide emulsion layer which are sensitized to a first and a second region of the visible spectrum and each contain color-forming couplers, the second emulsion layer in one limited Extent is also sensitized to the first range of the visible spectrum. If, for example, the red-sensitive layer also contains a green sensitizer, 15 visible levels are now being developed in the purple area instead of the previous 11. Similar solutions are described in EP 368 271 and US 4 806 460.
  • this measure creates, for example, a secondary density of a different color in the purple region, for example blue-green, but only in regions of high density. In areas of high red density, the eye perceives this false color density not as a color distortion, but as a deepening of the main color. However, the measure can only be used for red tones without a color falsification actually being visible. However, the number of additionally obtained gradation levels is not sufficient.
  • a color coupler is provided in a non-light-sensitive intermediate layer between two light-sensitive silver halide emulsion layers.
  • the exposure latitude of the first layer is expanded if the color coupler forms a dye in the intermediate layer depending on the development, which is complementary to the color of the first layer. Therefore, there is a gradual increase in a secondary density over the entire gradation range. This increase is proportional to the increase in the secondary density of the photosensitive layer and leads to an undesirable color distortion.
  • the object of the present invention is to provide a color photographic material with a reflective support which has an extended range of gradations for the color separations in the range of the maximum densities and thus a significantly improved tracing at high densities, which is also distinguished by great color purity and its gradation in Shadow areas can be set flat or steep depending on the requirements, without changing the gradation of the actual color-forming layer.
  • a spectrally sensitized silver halide emulsion which contains at least one sensitizer for spectral region B is provided in a color coupler-free layer ("sensory layer"), adjacent to at least one coloring silver halide emulsion layer which is sensitized for spectral region A, wherein the sensitivity of the spectrally sensitized silver halide emulsion of the sensory layer is 0.6 to 2.5 log H units lower than the sensitivity of the sensitized silver halide emulsion of the color-providing silver halide emulsion layer.
  • the sensory layer is provided in particular as an intermediate layer between two color-giving silver halide emulsion layers, which are sensitized for the spectral ranges A and B, respectively.
  • it contains both a sensitizer for spectral range A and for spectral range B.
  • the color-imparting layers are preferably sensitized to green or red and contain the complementary couplers, namely purple or cyan couplers, in the usual way.
  • the intermediate layer between A and B contains at least one spectrally sensitized silver halide emulsion which has at least one sensitizer for at least one which contains areas A, B or C and the intermediate layer between B and C contains at least one spectrally sensitized silver halide emulsion which contains at least one sensitizer for at least one of the areas A, B or C
  • the sensitivity of the spectrally sensitized silver halide emulsions of the color coupler-free intermediate layers being around 0 , 6 to 2.5 log H units is lower than the sensitivity of the sensitized silver halide emulsions of the coloring silver halide emulsion layers.
  • the intermediate layer between the silver halide emulsion layers which are sensitized for spectral regions A and B contains both a sensitizer for spectral region A or B and for spectral region C.
  • the intermediate layer between the silver halide emulsion layers which are sensitized for the spectral regions B and C contains both a sensitizer for the spectral region B or C and for the spectral region A.
  • the color-imparting layers are preferably sensitized to red, green or blue and contain the complementary couplers, namely cyan, magenta or yellow couplers, in the usual way.
  • the sensor layers can also be arranged above or below the color-providing silver halide emulsion layers.
  • Sensory layer is a layer that contains no couplers that only contribute to the color structure of the image.
  • the sensory layer can contain compounds which split off photographically active groups, such as development inhibitors and development accelerators, in an imagewise coupling reaction, so-called DIR or DAR couplers, and DIR or DAR compounds in the amounts which are typical and effective for them. The latter are those that do not produce any dye during the coupling reaction.
  • the sensory layer may otherwise contain conventional components of an intermediate layer, e.g. Binders and so-called EOP scavengers are substances that react with the developer oxidation product to form stable, colorless substances, and scavengers that reduce EOP.
  • Binders and so-called EOP scavengers are substances that react with the developer oxidation product to form stable, colorless substances, and scavengers that reduce EOP.
  • the material according to the invention is particularly preferably a material which, in the order given, has at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, one intermediate layer, at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler, one intermediate layer, at least one contains red-sensitive silver halide emulsion layer containing at least one cyan coupler and at least one protective layer, characterized in that the intermediate layer between the green- and the red-sensitive silver halide emulsion layer and the intermediate layer between the blue- and green-sensitive silver halide emulsion layer is designed independently of one another in the manner according to the invention and either a green - or a red or a blue sensitized or a green and red or a red and blue or contains a green and blue sensitized or a green and red and blue sensitized silver halide emulsion.
  • Both intermediate layers of the material described in the preceding paragraph are very particularly preferably red, green and blue sensitized.
  • AgBr, AgBrCl, AgBrClI and AgCl can be considered as silver halides of the color coupler-containing and the color coupler-free silver halide emulsion layers.
  • the silver halides of all light-sensitive layers preferably contain at least 80 mol% of chloride, in particular 95 to 100 mol% of chloride, 0 to 5 mol% of bromide and 0 to 1 mol% of iodide.
  • the silver halide emulsions can be directly positive-working or preferably negative-working emulsions.
  • the silver halide can be predominantly compact crystals, e.g. are regular cubic or octahedral or can have transitional forms.
  • twins e.g. B. are platelet-shaped crystals, the average ratio of diameter to thickness is preferably at least 5: 1, wherein the diameter of a grain is defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.
  • the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is greater than 5: 1, e.g. 12: 1 to 30: 1.
  • the silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as doping of the individual grain areas, being different.
  • the average grain size of the emulsions is preferably between 0.2 »m and 2.0» m, the grain size distribution can be both homo- and heterodisperse.
  • the emulsions can also contain organic silver salts, for example silver benzotriazolate or silver behenate.
  • Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
  • the photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
  • various methods e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
  • the silver halide is preferably precipitated in the presence of the binder, for example the gelatin, and can be carried out in the acidic, neutral or alkaline pH range, silver halide complexing agents preferably being additionally used.
  • the latter include, for example, ammonia, thioether, imidazole, ammonium thiocyanate or excess halide.
  • the water-soluble silver salts and the halides are optionally combined one after the other after the single-jet or simultaneously according to the double-jet process or any combination of both processes. Dosing with increasing inflow rates is preferred, the "critical" feed rate, at which no new germs are being produced, should not be exceeded.
  • the pAg range can vary within wide limits during the precipitation, preferably the so-called pAg-controlled process is used, in which a certain pAg value is kept constant or a defined pAg profile is run through during the precipitation, in addition to the preferred precipitation in the case of excess halide But so-called inverse precipitation is also possible with excess silver ions.
  • the silver halide crystals can also grow by physical ripening (Ostwald ripening) in the presence of excess halide and / or silver halide complexing agent. The growth of the emulsion grains can even take place predominantly by Ostwald ripening, preferably a fine-grained, so-called Lippmann emulsion, mixed with a less soluble emulsion and redissolved on the latter.
  • the silver halide grains can be precipitated in the presence of "growth modifiers", which are substances which influence growth in such a way that special grain shapes and grain surfaces (for example 111 surfaces in AgCl) are formed.
  • growth modifiers are substances which influence growth in such a way that special grain shapes and grain surfaces (for example 111 surfaces in AgCl) are formed.
  • silver halide grains are preferably used, the metal ions in the grain interior or on the surface, especially Contain transition metal ions or their complexes.
  • Salts or complexes of Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe, Pt, Pd, Ru or Os are preferably used for doping the silver halides. This enables a targeted adjustment of the sensitivity and contrast of the intermediate layer.
  • the precipitation can also be carried out in the presence of sensitizing dyes.
  • Complexing agents and / or dyes can be rendered ineffective at any time, e.g. by changing the pH or by an oxidative treatment.
  • Gelatin is preferably used as the binder. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers.
  • Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers.
  • Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, cellulose, sugar starch or alginates.
  • Semi-synthetic gelatin substitutes are usually modified natural products. Cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers are examples of this.
  • the binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents.
  • functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.
  • the gelatin which is preferably used can be obtained by acidic or alkaline digestion.
  • 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 amount of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.
  • the gelatin can be partially or completely oxidized.
  • the soluble salts are removed from the emulsion, for example by pasta and washing, by flaking and washing, by ultrafiltration or by ion exchangers.
  • the photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
  • Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups.
  • Such connections are e.g. B. von Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58.
  • Salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, (subst.) Benzotriazoles or benzothiazolium salts can also be used as antifoggants.
  • Heterocycles containing mercapto groups e.g. B.
  • mercaptobenzthiazoles mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, these mercaptoazoles also containing a water-solubilizing group, for example a carboxyl group or sulfo group.
  • a water-solubilizing group for example a carboxyl group or sulfo group.
  • the stabilizers can be added to the silver halide emulsions before, during or after their ripening.
  • the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.
  • the silver halide emulsions are usually chemically ripened, for example by the action of gold compounds or compounds of divalent sulfur.
  • the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
  • 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 bromide iodides.
  • 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.
  • cyan couplers are assigned to the red-sensitive layers, purple couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers.
  • Color couplers for producing the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type.
  • Color couplers for generating the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type.
  • Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the ⁇ -acylacetamide type; 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 couplers usually contain a ballast residue to prevent diffusion within the material, i.e. both within a layer or from layer to layer, to make impossible.
  • a ballast residue instead of couplers with a ballast residue, high molecular weight couplers can also be used.
  • 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 by first preparing a solution, a dispersion or an emulsion of the compound in question and then adding it to the casting solution for the layer in question.
  • the selection of the suitable solvent or dispersing agent depends on the solubility of the compound.
  • Hydrophobic compounds can also be 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 e.g. dyes
  • pickling polymers e.g. acrylic acid
  • Suitable oil formers are e.g. Alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.
  • oil formers are dibutylphthalate, dicyclohexylphthalate, di-2-ethylhexylphthalate, decylphthalate, triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-tert.-amylphenol, dioctylacelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-doxy-5-butyl-2-butyl
  • the photographic material can also contain compounds that absorb UV light, white toners, spacers, Filter dyes, formalin scavengers, light stabilizers, antioxidants, D Min dyes, additives to improve the dye, coupler and white stabilization and to reduce the color fog, plasticizers (latices), biocides and others.
  • UV light-absorbing compounds are intended to protect the image dyes from fading due to UV-rich daylight and, on the other hand, as filter dyes, absorb UV light in daylight during exposure and thus improve the color rendering of a film.
  • compounds of different structures are 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 (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 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, steric 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, which contain a reactive olefin linkage (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
  • 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 that react very quickly with gelatin are e.g. to 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 to form peptide bonds and crosslink the gelatin.
  • the color photographic materials according to the invention are usually processed by developing, bleaching, fixing and washing or stabilizing without subsequent washing, whereby bleaching and fixing can be combined into one processing step.
  • All developing compounds which have the ability to coexist in the form of their oxidation product can be used as the color developer compound Color couplers to react to azomethine or indophenol dyes.
  • 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.
  • the material is usually bleached and fixed after color development.
  • bleaching agents for example, Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used become.
  • Iron (III) complexes of aminopolycarboxylic acids in particular, for example, ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediamine triacetic acid, alkyliminodicarboxylic acids and alkyliminodicarboxylic acids and are particularly preferred.
  • Persulphates and peroxides for example hydrogen peroxide, are also suitable as bleaching agents.
  • the bleach-fixing bath or fixing bath is usually followed by a watering, 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.
  • the material according to the invention is preferably a material to be processed negatively.
  • a color photographic recording material which is suitable for a rapid processing process was produced by applying the following layers in the order given to a paper coated on both sides with polyethylene.
  • the quantities given relate to 1 m2.
  • the corresponding amounts of AgNO3 are given.
  • the emulsions used in Examples 4 to 7 and 9 in the intermediate layers were 1.3 log H units less sensitive than the emulsions in the color-imparting layers.
  • a color photographic recording material was produced which differs from Example 1 in that layer 5 1.90 g gelatin and additionally 0.1 g purple coupler M-1 contains.
  • a color photographic recording material was produced which differs from Example 1 in that the red-sensitive emulsion in layer 6 was additionally green-sensitized with GS 1 (50 »mol / mol Ag).
  • a color photographic recording material was produced which differs from that described in Example 1 in that layer 5 contains an additional green-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.14 »m) contains from 0.28 AgNO3, which was sensitized with 30 mg GS 1/100 g AgNO3.
  • layer 5 contains an additional green-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.14 »m) contains from 0.28 AgNO3, which was sensitized with 30 mg GS 1/100 g AgNO3.
  • a green-exposed color separation wedge was made from this material and processed in the specified process.
  • the comparative samples of Examples 1 and 2 develop 17 visible steps in the purple, the material according to Example 3 15 visible steps and the material according to the invention 21 visible steps. Accordingly, the material according to the invention has an extended range of gradation and better differentiation at high purple densities than the comparative samples according to Examples 1 to 3 and a greater color purity at high densities than the comparative sample according to Example 3.
  • Comparative sample and material according to the invention were exposed with a color negative (image motif) and processed in the specified process.
  • the material according to the invention shows a significantly better tracing in the area of high red densities than the comparative samples of examples 1 to 3 and less color distortion at high purple densities than the comparative sample according to example 3.
  • a color photographic recording material was produced which differs from that described in Example 1 in that layer 5 contains an additional red-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.14 »m) contains from 0.28 g AgNO3, which was sensitized with 20 mg RS1 / 100 g AgNO3.
  • layer 5 contains an additional red-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.14 »m) contains from 0.28 g AgNO3, which was sensitized with 20 mg RS1 / 100 g AgNO3.
  • a red-exposed color separation wedge was made from this material and processed in the specified process.
  • the comparative sample of example 1 develops 14 visible levels in the cyan 14, the comparative sample of example 2 15 and the comparative sample of example 3 develops 14 visible levels, the material according to the invention develops 20 visible levels. Accordingly, the material according to the invention has an extended range of gradation and better differentiation at high color densities than the comparative samples from Examples 1 to 3.
  • the inventive In contrast to the comparative sample from Example 2, material shows no discernible color shift from cyan to blue in the linear gradation range.
  • Comparative sample and material according to the invention were exposed with a color negative (image motif) and processed in the specified process.
  • the material according to the invention shows a significantly better tracing in the area of high green densities than the comparative sample from example 2 and no blue shift of the green tones.
  • a color photographic recording material was produced which differs from the comparative sample described in Example 1 in that layer 5 contains an additional red and green-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0 , 14 »m) from 0.28 g AgNO3, which was sensitized with 30 mg GS1 / 100 g AgNO3 and 20 mg RS1 / 100 g AgNO3.
  • layer 5 contains an additional red and green-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0 , 14 »m) from 0.28 g AgNO3, which was sensitized with 30 mg GS1 / 100 g AgNO3 and 20 mg RS1 / 100 g AgNO3.
  • a red-exposed and a green-exposed color separation wedge was made from this material and processed in the specified process.
  • the comparative sample of Example 2 develops 15 levels in blue-green, 17 levels visible in purple
  • the comparison sample of Example 3 develops levels in blue-green 14, 15 levels visible in purple
  • the material according to the invention develops in blue-green 20 and purple 21 visible steps. Accordingly, the material according to the invention has an expanded range of gradations and better differentiation at high magenta and blue green densities with simultaneously greater color purity in the linear gradation range than the comparison sample of example 2 and a greater color purity at high purple densities than the comparison sample of example 3.
  • Comparative sample and material according to the invention were exposed with a color negative (image motif) and processed in the specified process.
  • the material according to the invention shows a significantly better tracing with at the same time greater color purity in red, green and blue as well as purple and blue-green than the comparative samples of examples 2 and 3.
  • a color photographic recording material was produced which differs from the comparative sample described in Example 1 in that layer 3 contains an additional red, blue and green-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.35 »m) from 0.28 g AgNO3, which was sensitized with 10 mg GS 1/100 g AgNO3 and 5 mg RS 1 and 65 mg BS 1/100 g AgNO3 and that layer 5 was an additional contains red, blue and green sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.35 »m) from 0.28 g AgNO3, with 20 mg GS 1/100 g AgNO3 and 70 mg BS 1 and 15 mg RS 1/100 g AgNO3 was sensitized.
  • layer 3 contains an additional red, blue and green-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.35 »m) from 0.28
  • a red-exposed, a green-exposed and a blue-exposed color separation wedge was made from this material and processed in the specified process.
  • a color photographic recording material was produced, which differs from the comparative sample described in Example 8 in that the 6th layer contains an additional red and green-sensitive silver halide emulsion (silver bromide chloride emulsion with 20 mol% chloride) from 0.40 g of AgNO 3, which contains 25 mg GS 1/100 gAgNO3 and 18 mg RS 1/100 g AgNO3 was sensitized.
  • additional red and green-sensitive silver halide emulsion silver bromide chloride emulsion with 20 mol% chloride
  • a red and a green exposed color separation wedge was made from this material and processed in the specified process.
  • the comparative sample from Example 8 develops visible steps in blue-green 17 and 16 in purple
  • the material according to the invention develops visible steps in blue-green 20 and 20 in purple. Accordingly, the material according to the invention has an extended range of gradation and better differentiation at high magenta and cyan color densities than the comparative sample in Example 8.
  • Comparative sample and material according to the invention were exposed with a color negative (image motif) and processed in the specified process.
  • the material according to the invention shows a significantly better tracing in red, green and blue as well as purple and blue-green than the comparison sample in example 8.
  • the processing baths were produced according to the following recipes:

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

Claims (10)

  1. Matériau pour reproduction ou enregistrement de photographies en couleur comportant un support réfléchissant qui contient, dans une couche dépourvue de copulant chromogène et voisine d'au moins une couche d'émulsion d'halogénure d'argent chromogène, qui a été sensibilisé au domaine spectral A, une émulsion d'halogénure d'argent sensibilisée spectralement, qui contient au moins un sensibilisant pour le domaine spectral B, la sensibilité de l'émulsion d'halogénure d'argent sensibilisée spectralement de la couche dépourvue de copulant chromogène se situant à 0,6 à 2,5 unités de logarithme H plus bas que la sensibilité de l'émulsion d'halogénure d'argent sensibilisée de la couche d'émulsion d'halogénure d'argent chromogène.
  2. Matériau de reproduction d'enregistrement de photographies en couleur selon la revendication 1, caractérisé en ce que la couche dépourvue de copulant chromogène est une couche intermédiaire située entre deux couches d'émulsion d'halogénure d'argent chromogène, qui sont sensibilisées pour les domaines spectraux A ou B.
  3. Matériau d'enregistrement ou de reproduction de photographies en couleur selon la revendication 2, caractérisé en ce que la couche intermédiaire dépourvue de copulant chromogène contient aussi bien un sensibilisateur pour le domaine spectral A que, également, un sensibilisateur pour le domaine spectral B.
  4. Matériau de reproduction d'enregistrement de photographies en couleur selon la revendication 1, caractérisé en ce qu'il s'agit, pour les domaines spectraux A et B, du domaine spectral vert et rouge ou rouge et vert.
  5. Matériau d'enregistrement ou de reproduction de photographies en couleur comportant un support réfléchissant et trois émulsions d'halogénure d'argent chromogènes qui sont sensibilisées pour les domaines spectraux A, B et C, et des couches intermédiaires dépourvues de copulant chromogène, matériau caractérisé en ce que la couche intermédiaire entre A et B contient au moins une émulsion d'halogénure d'argent à sensibilisation spectrale et contient au moins un sensibilisateur pour au moins l'un des domaines A, B ou C et la couche intermédiaire entre B et C contient au moins une émulsion d'halogénure d'argent à sensibilisation spectrale, qui contient au moins un sensibilisateur pour au moins l'un des domaines A, B ou C, la sensibilité des émulsions d'halogénure d'argent sensibilisées spectralement des couches intermédiaires dépourvues d'un copulant chromogène étant inférieure de 0,6 à 2,5 unités de logarithme H à la sensibilité des émulsion d'halogénure d'argent sensibilisées des couches d'émulsion d'halogénure d'argent chromogènes.
  6. Matériau pour reproduction ou enregistrement photographique en couleur selon la revendication 5, caractérisé en ce que la couche intermédiaire entre les couches d'émulsion d'halogénure d'argent, qui sont sensibilisées pour les domaines spectraux A et B, contient aussi bien un sensibilisateur pour le domaine spectral A ou B que, également, un sensibilisateur pour le domaine spectral C.
  7. Matériau d'enregistrement et de reproduction de photographies en couleur selon la revendication 5, caractérisé en ce que la couche intermédiaire entre les couches d'émulsion d'halogénure d'argent, qui sont sensibilisées pour les domaines spectraux B et C, contient aussi bien un sensibilisateur pour le domaine spectral B ou C que, également, un sensibilisateur pour le domaine spectral A.
  8. Matériau d'enregistrement ou de reproduction de photographies en couleur selon la revendication 5, caractérisé en ce que les domaines spectraux A, B et C représentent dans un ordre quelconque le domaine spectral rouge, vert et bleu.
  9. Matériau d'enregistrement et de reproduction photographique en couleur selon les revendications 1 et 5, caractérisé en ce que les halogénures d'argent de toutes les couches photosensibles, y compris les couches intermédiaires selon l'invention, contiennent au moins 80 mol% de chlorure, notamment 95 à 100 mol% de chlorure, 0 à 5 mol% de bromure et 0 à 1 mol% d'iodure.
  10. Matériau pour enregistrement ou reproduction de photographies en couleur selon la revendication 5, qui contient dans l'ordre indiqué, sur un support réfléchissant, au moins une couche d'émulsion d'halogénure d'argent sensible au bleu et contenant au moins un copulant pour jaune, une couche intermédiaire, au moins une couche d'émulsion d'halogénure d'argent sensible au vert et contenant au moins un copulant pour pourpre, une couche intermédiaire, au moins une couche d'halogénure d'argent sensible au rouge, contenant au moins un copulant pour bleu-vert et au moins une couche protectrice, matériau caractérisé en ce que la couche intermédiaire entre la couche d'émulsion d'halogénure d'argent sensible au vert et au rouge et la couche intermédiaire entre la couche d'émulsion d'halogénure d'argent sensible au bleu et au vert et réalisées, chacune indépendamment l'une l'autre de la façon selon l'invention et contient une émulsion d'halogénure d'argent sensibilisée au vert ou une couche sensibilisée au rouge ou une couche sensibilisée au bleu ou une couche sensibilisée au vert et au rouge ou une couche sensibilisée au rouge et au bleu ou une couche sensibilisée au vert et au bleu ou une émulsion sensibilisée au vert et au rouge et au bleu, la sensibilité de l'émulsion d'halogénure d'argent à sensibilisation spectrale des couches intermédiaires dépourvues de copulant chromogène étant inférieure de 0,6 à 2,5 unités de log H à la sensibilité des émulsions d'halogénure d'argent sensibilisées des couches d'émulsion d'halogénure d'argent chromogène.
EP92107601A 1991-05-16 1992-05-06 Matériau de reproduction photographique couleur Expired - Lifetime EP0515873B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE4115972U 1991-05-16
DE4115972 1991-05-16
DE4123601A DE4123601A1 (de) 1991-05-16 1991-07-17 Farbfotografisches aufzeichnungsmaterial
DE4123601 1991-07-17

Publications (2)

Publication Number Publication Date
EP0515873A1 EP0515873A1 (fr) 1992-12-02
EP0515873B1 true EP0515873B1 (fr) 1995-03-15

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EP92107601A Expired - Lifetime EP0515873B1 (fr) 1991-05-16 1992-05-06 Matériau de reproduction photographique couleur

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US (1) US5266451A (fr)
EP (1) EP0515873B1 (fr)
JP (1) JPH05181237A (fr)
DE (2) DE4123601A1 (fr)

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Publication number Priority date Publication date Assignee Title
DE4301105A1 (de) * 1993-01-18 1994-07-21 Agfa Gevaert Ag Farbfotografisches Aufzeichnungsmaterial
EP0684511B1 (fr) * 1994-05-20 2001-02-28 Eastman Kodak Company Pellicule à contraste bas
US5576128A (en) * 1994-12-05 1996-11-19 Eastman Kodak Company Color negative films with low mid-scale contrast for telecine transfer applications
US5561012A (en) * 1994-12-05 1996-10-01 Eastman Kodak Company Process of forming a telecine transfer image having enhanced shadow detail
US5576159A (en) * 1995-02-17 1996-11-19 Eastman Kodak Company Photographic element with color enhancing layer adjacent to an emulsion layer and an oxidized developer scavenger layer
US5750320A (en) * 1996-02-16 1998-05-12 Eastman Kodak Company Color motion picture print films for telecine transfer applications

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR959734A (fr) * 1943-04-06 1950-04-04
US3819372A (en) * 1972-06-13 1974-06-25 Minnesota Mining & Mfg Film element and method for production of spatially distinct dye and silver photographic images
JPS5969754A (ja) * 1982-10-14 1984-04-20 Fuji Photo Film Co Ltd ハロゲン化銀カラ−感光材料
DE3411966A1 (de) * 1983-03-31 1984-10-04 Konishiroku Photo Industry Co., Ltd., Tokio/Tokyo Lichtempfindliches farbphotographisches silberhalogenidmaterial
JPS6191657A (ja) * 1984-10-11 1986-05-09 Fuji Photo Film Co Ltd 多層ハロゲン化銀カラ−感光材料
JPS6299748A (ja) * 1985-10-25 1987-05-09 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
US4902609A (en) * 1987-08-20 1990-02-20 Eastman Kodak Company Photographic print material with increased exposure latitude
US4946765A (en) * 1988-08-15 1990-08-07 Eastman Kodak Company Photographic material with increased exposure latitude

Also Published As

Publication number Publication date
EP0515873A1 (fr) 1992-12-02
DE59201631D1 (de) 1995-04-20
DE4123601A1 (de) 1992-11-19
JPH05181237A (ja) 1993-07-23
US5266451A (en) 1993-11-30

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