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
  • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/392—Additives
  • G03C7/396—Macromolecular additives
• • 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
  • G03C2007/3034—Unit 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
  • G03C2200/27—Gelatine content

Definitions

• the invention relates to a photographic recording material with improved sensitometric properties.
• Photographic recording materials are required to have high sensitivity, good sharpness and fine grain.
• Synthetic polymers can also be used as peptizers or as carriers for hydrophobic substances, e.g. in the form of loaded latices, see US 4 199 363. In some cases excellent granularity is achieved, reference is made to DE-A 3 036 846 and EP-A 93 924.
• Such polymers can be loaded with color couplers, e.g. is known from DE-A 2 541 274, DE-A 2 541 230, DE-A 2 541 276, EP-A 0 014 921, US-A 4 133 687, EP-A 0 069 671, DD 144 129, EP -A 0 130 115, DD 138 831, DE-A 2 820 092, DE-A 1 597 467, US-A 4 291 113, GB-A 2 072 365, DE-A 2 835 856, GB-A 1 516 855, DE-A 30 36 846, DE-A 2 815 635.
• color couplers e.g. is known from DE-A 2 541 274, DE-A 2 541 230, DE-A 2 541 276, EP-A 0 014 921, US-A 4 133 687, EP-A 0 069 671, DD 144 129, EP -A 0 130 115
• the invention was therefore based on the object of specifying a color photographic recording material with improved properties, which in particular should have improved sharpness but also good fluency and sensitivity.
• a color photographic recording material with at least one silver halide emulsion layer has now been found, which is split into a relatively insensitive sub-layer L and at least one more sensitive sub-layer H, the sub-layers H and L being assigned at least one color coupler.
• at least one synthetic polymer P and gelatin is contained in at least one partial layer H, the weight ratio of all synthetic polymers P and gelatin in this partial layer being between 30:70 and 80:20.
• the weight ratio is at least 40:60 and in a further embodiment it is between 40:60 and 60:40.
• the color developer preferably contains a p-phenylenediamine.
• synthetic polymers are preferably understood to mean synthetic high-molecular compounds from the group of the polymerization products, the polycondensation products and the polyaddition products.
• Polymerization products are preferably polymers made from ethylenically unsaturated low-molecular compounds and polymers made from low-molecular compounds which have a ring structure.
• ethylenically unsaturated compounds are ethylene, butadiene, isoprene, vinyl aromatics such as styrene, ⁇ -methylstyrene, divinylbenzene, chloromethylstyrene, vinyltoluene, (meth) acrylic acid derivatives such as optionally substituted (meth) acrylic acid esters, (meth) acrylic acid amides, (meth) acrylic acid , Vinyl esters, vinyl amides, vinyl ethers, vinyl heterocycles and others Vinyl pyridine, vinyl imidazole, vinyl sulfones, vinyl sulfonamides, vinyl ketones, maleic acid derivatives, fumaric acid derivatives, itaconic acid derivatives, (meth) allyl compounds, vinyl thioethers, vinyl silanes, vinyl chloride, vinylidene chloride, (meth) acrylonitrile ..
• Low molecular weight compounds which have a ring structure are e.g. Ethylene oxide, propylene oxide, butylene oxide, aziridines, tetrahydrofuran, caprolactam, epichlorohydrin.
• Polycondensation products and polyaddition products are e.g. Polyesters, polyamides, polycarbonates, polysulfones, polyurethanes, polysiloxanes, polyureas, phenol-formaldehyde resins, polyimides, polyphenylene oxide, epoxy resins, urea-formaldehyde resins. Examples of the compounds are described in Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, Verlag Chemie, Weinheim 1980.
• Particularly preferred synthetic polymers are the nonionic polyurethanes known from German patent 1,522,387, the anionic polyurethanes known from German patent 1,522,393, which contain a group of phosphonic acid, phosphoric ester or phosphoric acid amide capable of salt formation, and those from the German patent 1 472 746 anionic polyurethanes.
• Polymers are preferably used which are in dispersion form, i.e. have a particulate character.
• the mean particle size is in the range of 20-2000 nm, preferably in the range of 20-500 nm.
• Polymers whose glass transition temperature Tg is below + 25 ° C. are also preferred.
• Polymer dispersions which are nonionic or have an anionic charge are also preferred.
• Polymers are also preferred which show a certain solvency for the color coupler used.
• the color coupler is soluble in the polymer if a polymer / coupler mixture, produced by evaporating a solution of polymer and coupler, has no enthalpy of fusion of the coupler in a differential thermal analysis measurement. Polymers that can dissolve more than 5% color couplers are preferred.
• the polymers are used in such a way that they enable a limited diffusion of the dye which is formed in the color coupling from the color coupler.
• Latices that can be loaded are preferably suitable.
• the polymers described in DE-A 3 036 846, DE-A 1 522 387, DE-A 1 472 746 are particularly suitable.
• Preferred examples of polymers are L1 to L180 from Research Disciosure 19 551, polymer I to polymer V from DE-A 3 036 846, polyester p. 6 line 33 -S. 7 line 22 of EP 0 069 671.
• Particularly preferred polymers are given below. Some of them are loaded with couplers.
• the above-mentioned polymers are added in particular to the highly sensitive partial layers of a color negative material.
• the highly sensitive partial layers can contain: color masks, white couplers, scavangers, DIR couplers and also DAR couplers.
• a combination of the polymers mentioned here in the highly sensitive partial layers with DIR couplers is particularly advantageous because the sharpness is increased by means of edge effects.
• a combination of these polymers with DAR couplers (Development Accelerator Release) counteracts a grain enlargement.
• the highly sensitive partial layers can also contain casting aids such as wetting agents and thickeners, etc.
• At least some of the polymers to be used according to the invention are used as carriers for a color coupler.
• a latex loaded with a kuppler there is a latex loaded with a kuppler. It can be particularly advantageous to use a mixture of loaded and unloaded latex.
• the low-sensitivity layer L contains the polymers P to be used according to the invention, or at least to a much lesser extent. Otherwise, the sublayer L may contain the usual constituents, that is, in addition to the silver halide emulsion, color couplers, masks, white couplers, scavangers, DIR couplers and / or DAR couplers. These components, in particular the color couplers, can also be applied to a latex in the low-sensitivity layer, which is then present as a loaded latex. It is also possible to fix the couplers in the form of polymeric couplers.
• the ratio of polymer to gelatin in the sublayer L is preferably less than 25:75.
• the coupler / silver ratio in the low-sensitivity layer L is larger than in the more sensitive sublayer H.
• the recording material according to the invention has at least one blue, green and red sensitive layer. Of these, at least one layer is split into two sub-layers L and H according to the invention. It is particularly preferred to divide all spectrally sensitized layers into at least two sub-layers of different sensitivity.
• the sub-layers of the same spectral sensitivity can be combined adjacent to form double or multiple-layer packets, but the sub-layers of one spectral sensitivity can alternate with the layers of another spectral sensitivity, but also in any order that achieves the most advantageous constellation.
• At least one blue-sensitive layer is preferably located above the green and red-sensitive layers and is separated from them by a yellow filter layer.
• further protective and intermediate layers can be used.
• Layer structures in which at least one emulsion layer is split into sub-layers of different sensitivity are e.g. known from DE-A 1 958 709 (Pankow).
• the effective sensitivity When assessing the sensitivity of the individual sub-layers, it is not the absolute sensitivity that is important, but the effective sensitivity, taking into account the respective position within the color photographic multilayer material.
• the difference in the effective sensitivity is expediently between 0.1 and 1.0 relative log Ixt units. In individual cases, the difference in sensitivity is chosen so that a balanced gradation curve results without perceptible distortion during color photographic processing.
• auxiliary layers can be present in the color photographic recording material according to the invention, e.g. 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 products 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 products.
• 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 0.1 ⁇ m or smaller, which contains chloride, bromide and optionally iodide, can also be embedded in these 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.
• Color couplers which can react with color developer oxidation products 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 a-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-pyrazo ion 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- and 2- Act equivalent coupler.
• Suitable couplers are known, 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.
• the usual mask couplers can be used to improve the color reproduction.
• the recording material can furthermore contain DIR compounds and white couplers which do not give any dye on reaction with color developer oxidation products.
• the inhibitors which can be split off from the DIR compounds can be split off directly or via non-inhibiting intermediate compounds.
• the light-sensitive silver halide emulsions used can contain chloride, bromide and iodide or mixtures thereof as the halide.
• the halide content of at least one layer consists of 0 to 12 mol% of Agl, 0 to 50 mol% of AgCl and 50 to 100% of AgBr.
• the crystals are predominantly compact, 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.
• the average ratio of diameter to thickness is preferably less than 8: 1, it being true that the diameter of a come is defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.
• all or individual emulsions can also have essentially tabular silver halide crystals in which the ratio of diameter to thickness is greater than 8: 1.
• the emulsions can be monodisperse emulsions, which preferably have an average grain size of 0.3 ⁇ m to 1.2 ⁇ m.
• the silver halide grains can have a layered grain structure.
• the emulsions can be chemically sensitized.
• the usual sensitizers are suitable for chemical sensitization of the silver halide grains. Sulfur-containing compounds, for example allyl isothiocyanate, allyl thiourea and thiosulfates, are particularly preferred.
• Also suitable as chemical sensitizers are noble metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium. This method of chemical sensitization is described in the article by R. Koslowsky, Z.Wiss.Phot .. 46, 65-72 (1951). It is also possible to sensitize the emulsions with polyalkylene oxide derivatives. Reference is also made to Research Disclosure No. 17 643, section III.
• 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 Ullman's Encyclopedia of Industrial Chemistry, 4th edition, volume 18, pages 431 ff and to Research Disclosure No. 17 643, section IV, given above.
• antifoggants and stabilizers can be used.
• Particularly suitable stabilizers are azaindenes, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are e.g. in the article by Birr, Z.Wiss.Phot. 47, 1952), pp. 2-58.
• Other suitable stabilizers and antifoggants are given in Research Disclosure No. 17 643 above in Section IV. Suitable compounds for improving the resistance to formalin are given in US-A 464 463.
• the recording material can contain stabilizers against visible and UV light and to improve the storage stability, which may optionally be in polymeric form. Particularly good stabilizers in this sense are e.g. Amino allyl malonitriles.
• the additional components of the photographic material can be incorporated by 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 water or. are insoluble in alkali, they can be incorporated into the recording materials in a known manner in dispersed form. 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.
• layer supports can be used for the materials according to the invention, for example supports made of cellulose esters, for example cellulose acetate and made of polyesters. Also suitable are paper supports, which may be coated can, for example, with polyolefins, in particular with polyethylene or polypropylene. In this regard, reference is made to Research Disclosure No. 17 643, Section XVII.
• 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 in accordance with the process of German laid-open specification 2 218 009 in order to obtain color photographic materials which are suitable for high-temperature processing. It is also possible to harden the photographic layers or the color photographic multilayer materials with hardeners of the diazine-triazine or 1,2-dihydroquinoline series or with hardeners of the vinylsulfone type. Further suitable hardening agents are known from German laid-open documents 2 439 551, 2 225 230, 2 317 672 and from Research Disclosure 17 643, section XI, specified above.
• the curing is preferably adjusted so that the swelling of the layers in water (10 ° DH) at 38 ° C (5 min) does not drop below 2.3-2.6 and there is sufficient wet scratch resistance for processing.
• Suitable color developer substances for the material according to the invention are in particular those of the p-phenylenediamine type, e.g. 4-amino-N, N-diethyl-aniline hydrochloride: 4-amino-3-methyl-N-ethyl-N-ß- (methanesulfonamido) ethyl-aniline 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-ß-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
• 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 Fe 3 + salts and Fe 3 + 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, N, are particularly preferred -Hydroxyethylethylenediamintriessigkla, alkyliminodicarboxylic acids and corresponding phosphonic acids.
• Persulphates are also suitable as bleaching agents.
• the quantities given relate to 1 m 2 .
• the corresponding amounts of AgNO 3 are given for the silver halide application.
• 3rd layer (low-sensitivity, red-sensitized layer)
• This third layer also contained 0.6 g of blue-green coupler C1, emulsified (1 part by weight of coupler with 0.5 part by weight of oil-forming agent), also 50 mg of red mask CC1 and 25 mg of DlR1.
• the third layer contained the components mentioned here in order to achieve the same gradation in a quantity reduced by a factor of 0.8, and this layer also contained 1.6 g of P8.
• 6th layer (low-sensitivity, green-sensitized layer)
• This 6th layer also contained 0.6 g of the purple coupler M1 as an emulsifier (1 part by weight of color coupler emulsified with 1 part by weight of tricresyl phosphate), 20 mg of the yellow mask CC2 and 7.5 mg of the DIR coupler DIR2.
• the 6th layer contained the constituents mentioned here in order to achieve the same gradation in a quantity reduced by a factor of 0.85, and this layer also contained 1.3 g of P8.
• This 10th layer also contained 0.7 g of yellow coupler Y1, emulsified in the weight ratio 1: 1 with tricresyl phosphate and 0.15 g of the DIR coupler DIR3.
• the 10th layer contained these components in a quantity reduced by a factor of 0.75 to achieve the same gradation, but additionally 0.6 g of P8.
• Table B1 / I shows the color granularity of the layer structure variants measured at 0.5, 1.0 and 1.5 via fog. Determination of sharpness
• MTF modulafions transfer function
• the spatial frequencies (in lines per mm) at which the MTF has a value of 75%, 50% and 25% are specified here.
• the higher sharpness of the structures according to the invention can be seen from the higher spatial frequencies at which the MTF reaches these percentages.
• Table B1 / II shows the sharpness data for the layer structure variants of Example 1.
• the eight layer structure variants 2A to 2H described here are produced.
• the four layer structure variants 2E to 2H corresponded to these four variants 2A to 2D, but they contain, according to the invention, addition of the above-mentioned polymers in the highly sensitive partial layers, specifically mixtures of unloaded with those which were loaded with color couplers.
• the medium and low-sensitive sub-layers as well as the separation and filter layers are the same for all eight variants. There are differences only from the 13th shift.
• the quantities given relate to 1 m 2 .
• the corresponding amounts of AgNO 3 are given for the silver halide application.
• 3rd layer (low-sensitivity, red-sensitized layer)
• 4th layer intermediate layer containing 0.6 g of gelatin and 0.2 g of the same cyan coupler C1 as in the 3rd layer.
• 5th layer (medium-sensitive, red-sensitized layer)
• intermediate layer containing 0.6 g of gelatin, 0.2 g of the purple coupler M1 and 0.05 g of the yellow mask CC2.
• the yellow silver sol was stabilized with a phenyl mercaptotetrazole.
• 11th layer low-sensitivity, blue-sensitive layer.

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• 1985
  • 1985-06-11 DE DE19853520845 patent/DE3520845A1/de not_active Withdrawn
• 1986
  • 1986-05-30 US US06/868,947 patent/US4724197A/en not_active Expired - Fee Related
  • 1986-06-03 EP EP86107522A patent/EP0205075B1/fr not_active Expired - Lifetime
  • 1986-06-03 DE DE8686107522T patent/DE3677822D1/de not_active Expired - Fee Related
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