Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials

Definitions

• the invention relates to a highly sensitive color photographic recording material with several silver halide emulsion layers of improved sharpness.
• three silver halide emulsion partial layers of the same spectral sensitivity but different general sensitivity are to be used to improve the granularity of a partial color image, with each more sensitive partial layer being arranged further away from the substrate than each less sensitive sub-layer.
• a maximum color density of at most 0.6 and altogether at most 1.0 is achieved in the middle and in the upper sub-layer, which can be achieved by reducing the coupler content, i.e. can be achieved by increasing the ratio of silver halide to coupler.
• color photographic materials in particular color negative materials, have a structure in which at least one red-sensitive layer, one green-sensitive layer, one yellow filter layer and one blue-sensitive layer are applied to a support in the order given. Since the human eye has the greatest sensitivity in the green spectral range, the image generated in the green-sensitive layer has the greatest influence with regard to the subjectively perceived Sharpness. The sharpness of the image produced in the green-sensitive layer, however, suffers from the light scattering within the blue-sensitive layers located above the green-sensitive layer in the conventional structure specified above. In order to improve the sharpness, it has therefore already been proposed to arrange the green-sensitive layer above the blue-sensitive layers. Such structures are described for example in DE-OS 2 427 491, DE-AS 1 128 291 and US Pat.
• DE-AS 1 128 291 there is a blue-sensitive layer (B) on a support (T), a red-sensitive layer (R), a green-sensitive layer (G) and a yellow filter layer (F) as the top layer.
• B blue-sensitive layer
• R red-sensitive layer
• G green-sensitive layer
• F yellow filter layer
• the object of the invention was to provide photographic recording materials with improved sharpness and improved color rendering.
• a color photographic recording material with at least one green, blue and red-sensitive silver halide emulsion layer and associated color couplers, in which a green-sensitive silver halide emulsion layer is arranged such that it is closest to the object to be imaged on exposure to all light-sensitive silver halide emulsion layers contains at least 50%, preferably at least 90%, silver halide grains, which consist of at least 50 mol%, preferably at least 80 mol%, of silver chloride, have a layered grain structure and have a crystal shape in which the ratio of diameter to thickness is at most 5 is.
• the recording material contains at least two blue, two green and two red-sensitive silver halide emulsion layers and no blue light absorbing filter layer.
• the following layers are applied to a layer support (structures 1 to 7). Additional layers can be arranged between, above and below the individual layers, in particular auxiliary layers such as antihalation layers, hardening layers and filter layers:
• the silver chloride-rich silver halide emulsions to be used according to the invention are known per se.
• Such grains have a core and at least one layer which surrounds the core and whose properties differ from the core (core / shell emulsions). It is known from DE-AS 1 169 290 and GB 1 027 146 to drop a silver chloride shell onto a silver bromide core.
• DE-OS 2 308 239 and US 3 935 014 relate on emulsions for producing directly positive images with silver halide grains which have a localized phase with a high silver chloride content.
• the zone Z Br rich in silver bromide can be present as a core or as a layer within the silver halide grain. Preferably 20% by volume of the silver halide of the grain is further from the crystal center than the zone Z Br rich in silver bromide.
• the silver halide grains in the bromide-rich zone Z Br and in areas other than halide can have chloride, bromide, iodide or mixtures thereof.
• the transition from the bromide-rich zone Z Br to an adjacent zone of a different composition can be sharp or continuous.
• the chloride content of the total halide content is at least 85, in particular at least 90 mol%.
• the zone Z Br rich in silver bromide consists essentially, for example at least 90%, or exclusively of silver bromide.
• the area B can be present both as a core and as a shell around a core.
• the grains preferably contain a core enveloped by at least one region B.
• region B can be present as a shell within the silver halide grain or on the surface of the crystal.
• the crystal nucleus is successively provided with two shells containing silver bromide, the bromide content of the two shells being significantly different.
• a bromide-containing shell with a local concentration of 30 to 45 mol% bromide is preferably located on the crystal surface of the chloride-rich silver halide crystal.
• the bromide concentration is 3 to 8 mol%, based on the total halide.
• the silver halide grains in the green-sensitive layer in the core and in areas other than halide can have chloride, bromide, iodide or mixtures thereof.
• the transition from one area to an adjacent area of a different composition can be sharp or continuous.
• the chloride content of the total halide content is at least 85, in particular at least 90 mol%.
• the silver halide emulsions for the green-sensitive layer to be used according to the invention can be prepared by means of the customary procedures (e.g. single entry, double entry, with constant or accelerated material flow). It is particularly preferred to use the double-inlet process under control of the pAg value.
• the silver halide emulsions can be precipitated in the presence of dopants such as cadmium, lead, copper or zinc, such as are used e.g. is described in EP-OS 17 148.
• Substances that are usually used as ripening agents can also be present during the precipitation: e.g. Compounds of sulfur, selenium, tellurium, iridium, gold, palladium, platinum, thiourea derivatives, formamidine sulfonic acid, tin (II) chloride.
• the silver halide precipitation can be carried out in the presence of divalent and / or polyvalent cations such as La3+, Tl3+, Co2+, Rh3+.
• the silver halide grains can be designed, for example, as cubes, octahedra or tetradecahedra.
• the grain size is preferably between 0.1 and 2.5 ⁇ m, in particular between 0.2 and 1.0 ⁇ m.
• the emulsion has a narrow grain size distribution.
• at least 95% by weight of the grains have a diameter which does not deviate from the average grain diameter by more than 40%.
• the emulsions can also have a broad grain size distribution.
• at least 10%, preferably 20%, of the silver halide grains have a diameter which deviates from the average grain diameter by at least 40%.
• the silver halide emulsion to be used according to the invention in the green-sensitive layer contains essentially silver chloride-rich silver halides which have an aspect ratio of at most 5. It is therefore predominantly compact crystals that e.g. are cubic or octahedral or have transitional forms. They can be characterized in that they essentially have a thickness of more than 0.2 ⁇ m and a maximum diameter of 2.5 ⁇ m.
• All emulsions are preferably chemically sensitized to a high surface sensitivity on the grain surface. They can be chemically sensitized by known methods, for example with active gelatin or with compounds of sulfur, selenium, tellurium, gold, palladium, Platinum, iridium, where the pAg values can vary between 4 and 10, the pH values between 3.5 and 9 and the temperatures between 30 ° C and 90 ° C; chemical sensitization can be carried out in the presence of heterocyclic nitrogen compounds such as imidazoles, azaindenes, azapyridazines and azapyrimidines and thiocyanate derivatives, thioethers and other silver halide solvents.
• heterocyclic nitrogen compounds such as imidazoles, azaindenes, azapyridazines and azapyrimidines and thiocyanate derivatives, thioethers and other silver halide solvents.
• the emulsions according to the invention can be subjected to a reduction sensitization, for example by hydrogen, by low pAg (for example less than 5) and / or high pH (for example above 8), by reducing agents such as tin (II) chloride, thiourea dioxide and aminoboranes.
• a reduction sensitization for example by hydrogen, by low pAg (for example less than 5) and / or high pH (for example above 8), by reducing agents such as tin (II) chloride, thiourea dioxide and aminoboranes.
• the surface ripening nuclei can also be present as troglodyte nuclei (sub-surface nuclei) according to DE-OS 2 306 447 and US Pat. No. 3,966,476. Other methods are described in the above. Research Disclosure No. 17643 in Section III.
• the emulsions can contain antifoggants and stabilizers.
• Azaindenes are particularly suitable, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are, for example, in the article by Birr, Z.Wiss. Phot. 47 , (1952), pp. 2-58.
• Other suitable stabilizers and antifoggants are given in Research Disclosure No. 17643 of December 1978, Section VI, published by Industrial Opportunities Ltd., Homewell Havant, Hampshire, PO9 1 EF in Great Britain.
• the antifoggants and stabilizers can be added to the photosensitive silver halide emulsions before chemical ripening, chemical ripening or after chemical ripening. In a preferred embodiment, they are added to the finished casting solution after chemical ripening.
• the emulsions can be optically sensitized in a manner known per se, e.g. with the usual polymethine dyes, such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
• polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
• Such sensitizers are from F.M. Hamer in "The Cyanine Dyes and related Compounds", (1964). In this regard, reference is made in particular to Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 18, pages 431 ff and to Research Disclosure No. 17 643, section IV, given above.
• the color photographic recording materials each contain at least one silver halide emulsion layer unit for recording light from each of the three spectral ranges red, green and blue.
• Each of the silver halide emulsion layer units mentioned can comprise a single silver halide emulsion layer or also a plurality of silver halide emulsion layers.
• Color photographic recording materials with double layers for the different spectral ranges are known, for example, from US Pat. Nos. 3,663,228, 3,849,138 and 4,184,876.
• Color photographic on Drawing materials with triple layers are known from DE-OS 2 018 341 and DE-OS 3 413 800.
• formalin scavengers e.g. the iminopyrazolones known from DE-OS 3 148 108 and US Pat. No. 4,414,309.
• non-light-sensitive auxiliary layers can be present in the color photographic recording material according to the invention, for example adhesive layers, antihalation layers or cover layers, in particular intermediate layers between the light-sensitive layers, as a result of which the diffusion of developer oxidation product from one layer into another is to be effectively prevented.
• intermediate layers of this type can furthermore contain certain compounds which are able to react with developer oxidation product.
• Such layers are preferably arranged between adjacent light-sensitive layers of different spectral sensitivity.
• a less sensitive silver halide emulsion with an average grain diameter of about 0.8 ⁇ m or smaller, which contains chloride, bromide and optionally iodide, can also be embedded in intermediate layers. Such a layer has a particularly beneficial effect on the sensitivity of the adjacent layers.
• the less sensitive silver halide emulsion can, however, also be introduced directly into the light-sensitive layers.
• the layers can additionally contain the usual constituents, such as scavengers, DIR couplers and also DAR couplers.
• Color couplers which can react with color developer oxidation product to form a dye are preferably assigned to the light-sensitive silver halide emulsion layers.
• the color couplers are preferably directly adjacent to and in particular contained in the silver halide emulsion layer.
• the red-sensitive layer can contain a color coupler for producing the blue-green partial color image, usually a coupler of the phenol or ⁇ -naphthol type.
• the green-sensitive layer can contain, for example, at least one color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone type usually being used.
• the blue-sensitive layer can contain, for example, at least one color coupler for producing the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping.
• the color couplers can be, for example, 6-, 4- or 2-equivalent couplers.
• Suitable couplers are, for example, from the publications "Color Coupler” by W. Pelz in “Messages from the Research Laboratories of Agfa, Leverkusen / Kunststoff", Volume III, page 111 (1961), K. Venkataraman in “The Chemistry of Synthetic Dyes", Vol 4, 341 to 387, Academic Press (1971) and TH James, "The Theory of the Photographic Process", 4th Ed., Pp. 353-362, and from Research Disclosure No. 17643 December 1978 Section VII, published by Industrial Opportunities Ltd., Homewell Havant, Hampshire, PO9 1 EF in the UK.
• the usual mask couplers can be used to improve the color rendering.
• the recording material can also contain DIR compounds and white couplers which do not give any dye when reacted with color developer oxidation products.
• the inhibitors which can be split off from the DIR compounds can be split off directly or from non-inhibiting intermediate compounds.
• the pyrazoloazole couplers correspond to one of the formulas II or III wherein R1 is hydrogen or a removable group R2 to R4, which are the same or different, represent a hydrogen atom, a halogen atom, an alkyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an acyl group, a sulfonyl group, a carboxyl group, a sulfo group, a hydroxyl group, an amino group, a Carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an ureido group, a sulfinyl group, an alkylthio group,
• the cleavable group represented by R 1 is preferably a halogen atom (for example F, Cl, Br, I) or an organic group which is generally attached to the coupling point of the coupler molecule via an oxygen, sulfur or nitrogen atom . If the cleavable group is a cyclic group, the coupling to the coupling point of the coupler molecule can either take place directly via an atom which is part of a ring, for example a nitrogen atom, or indirectly via an intermediate link. Such cleavable groups are known in large numbers, for example as escape groups of 2-equivalent yellow couplers. With regard to useful cleavable groups, reference is made in particular to DE-OS 31 21 955 and DE-OS 3 516 996.
• Suitable mask couplers are given below:
• Suitable DIR couplers have the following structure, for example:
• the components of the photographic material can be incorporated using customary, known methods. If the compounds are soluble in water or alkali, they can be added in the form of aqueous solutions, optionally with the addition of water-miscible organic solvents such as ethanol, acetone or dimethylformamide. If they are insoluble in water or alkali, they can be incorporated into the recording materials in dispersed form in a manner known per se. For example, a solution of these compounds in a low-boiling organic solvent can be mixed directly with the silver halide emulsion or initially with an aqueous gelatin solution and the organic solvent can then be removed. The dispersion of the respective compound thus obtained can then be mixed with the silver halide emulsion. If necessary, so-called oil formers are also used, generally higher-boiling organic compounds, which include the compounds to be dispersed in the form of oily droplets.
• hydrophilic film-forming agents are suitable as protective colloid or binder for the layers of the recording material, e.g. Proteins, especially gelatin. Casting aids and plasticizers can be used. Reference is made to the compounds indicated in Research Disclosure 17,643 above in Sections IX, XI and XII.
• the layers of the photographic material can be hardened in the usual manner, for example with hardeners of the epoxy type, the heterocyclic ethylene imine and the acryloyl type. Furthermore, it is also possible to harden the layers according to DE-OS 2 218 009 in order to achieve color photographic materials which are suitable for high-temperature processing. It is also possible to harden the photographic layers with hardeners of the diazine, triazine or 1,2-dihydroquinoline series or with hardeners of the vinyl sulfone type.
• Suitable color developer substances for the material according to the invention are in particular those of the p-phenylenediamine type, for example 4-amino-N, N-diethyl-aniline hydrochloride; 4-amino-3-methyl-N-ethyl-N- ⁇ - (methanesulfonamido) ethylaniline sulfate hydrate; 4-amino-3-methyl-N-ethyl-N- ⁇ -hydroxyethylaniline sulfate; 4-amino-N-ethyl-N- (2-methoxyethyl) -m-toluidine-di-p-toluenesulfonic acid and N-ethyl-N- ⁇ -hydroxyethyl-p-phenylenediamine. Further useful color developers are described, for example, in J.Amer.Chem.Soc. 73 , 3100 (1951) and in G. Haist, Modern Photographic Processing, 1979, John Wiley and
• the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together.
• the usual compounds can be used as bleaching agents, for example Fe3+ salts and Fe3+ complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes etc.
• Iron-III complexes of aminopolycarboxylic acids in particular, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, are particularly preferred. N-hydroxyethylethylenediamine triacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids.
• Persulphates are also suitable as bleaching agents.
• Silver chloride emulsion to be used according to the invention A silver chlorobromide emulsion of the core / shell type was prepared by pAg-controlled double entry. So much AgCl / AgBr was struck on a monodisperse AgCl core emulsion that a volume ratio core: shell of 2.6: 97.4 was obtained. The emulsion had cubic crystal garb with an average particle size of 0.81 ⁇ m and a total chloride content of 95 mol%. The emulsion was ripened with a gold-sulfur ripening to the maximum sensitivity, special attention being paid to a good sensitivity / fog ratio.
• Anti-inhalation layer made of black colloidal silver
• a blue-sensitive silver halide emulsion layer consisting of a silver bromide iodide emulsion (5.5 mol% iodide, average grain diameter 0.5 ⁇ m) with a yellow coupler of the formula Y 1 and a DIR coupler of the formula DIR 5.
• Silver application 10.4 mmol AgNO3 per m2
• Yellow coupler 1.4 mmol per m2
• DIR coupler 0.2 mmol per m2
• DIR 4 0.001 mmol per m2
• Protective layer of gelatin thickness 1 ⁇ m, the layer being the UV absorber of the formula contains.
• Gelatin top layer containing an instant hardening agent which is introduced into the photographic recording material by "diffusion hardening".
• the top layer has the following composition: Gelatin solution, 5% by weight in water 100 g Water, desalted 770 g Hardening agent of the formula 10% by weight in water 100 g
• Anti-inhalation layer made of black colloidal silver
• a blue-sensitive silver halide emulsion layer consisting of a silver bromide iodide emulsion (5.5 mol% iodide, average grain diameter 0.5 ⁇ m) with a yellow coupler of the formula Y 1 and a DIR coupler of the formula DIR 5.
• Silver application 10.4 mmol AgNO3 per m2
• Yellow coupler 1.4 mmol per m2
• DIR coupler 0.2 mmol per m2
• Protective layer made of gelatin, 1 ⁇ m thick, the layer containing a UV absorber.
• Gelatin top layer containing an instant hardening agent which is introduced into the photographic recording material by "diffusion hardening".
• the top layer has the following composition: Gelatin solution, 5% by weight in water 100 g Water, desalted 770 g Hardening agent of the formula 10% by weight in water 100 g Wetting agent as example 1, layer 9 4% by weight in water 30 g Wet application of layer 9 60 g / m2
• a layer structure was produced as in Example 2, with the change that the pyrazoloazole PA 11 is used in the green-sensitive layer instead of the purple coupler specified there and that no mask coupler is used in this layer.
• Good color rendering, especially for blue colors, is achieved when the sensitivity difference ⁇ F between the blue and green sensitive (and between blue and red sensitive) layer is at least 1.0 lg H for the blue separation.

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• 1986
  • 1986-02-26 DE DE19863606086 patent/DE3606086A1/de not_active Withdrawn
• 1987
  • 1987-02-14 EP EP87102112A patent/EP0234460B1/fr not_active Expired - Lifetime
  • 1987-02-14 DE DE8787102112T patent/DE3768527D1/de not_active Expired - Fee Related
  • 1987-02-17 US US07/015,738 patent/US4788133A/en not_active Expired - Fee Related
  • 1987-02-26 JP JP62041593A patent/JPS62205334A/ja active Pending

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