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
  • G03C7/392—Additives
  • G03C7/39208—Organic compounds
  • G03C7/39236—Organic compounds with a function having at least two elements among nitrogen, sulfur or oxygen
• • 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

Definitions

• R1 can be different in a polymer, so that co-, block co- or graft polymers are possible.
• the compounds of the formulas (I) and (II) are preferably water-soluble or water-dispersible. Compounds of formula (I) are preferred.
• the polyaddition, polycondensation or polymerization compounds R5 are, for example, polyesters, preferably aliphatic polyesters, polyacetals, polyethers, polyamides, polyesteramides, polycarbonates, polyurethanes, polystyrenes, poly (meth) acrylates, optionally substituted polyacrylamides, polyalkylene compounds.
• the compounds have a molecular weight of about 300 to 20,000, preferably 500 to 5,000.
• polyethers are the polymerization products of ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide and their mixed or graft polymerization products, and those by condensation of polyvalent ones Alcohols or mixtures thereof obtained condensates and the products obtained by alkoxylation of polyhydric alcohols.
• polyacetals e.g. the compounds that can be prepared from hexanediol and formaldehyde are questionable.
• the predominantly linear condensates obtained from polyvalent saturated carboxylic acids and polyvalent saturated alcohols, amino alcohols, diamines and their mixtures are suitable as polyesters, polyester amides and polyamides.
• poly (meth) acrylates such as polybutyl acrylate, polyethyl acrylate, polyhydroxyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, optionally substituted polyacrylamides or polymethacrylamides, polyvinyl ether, polyethylene, polypropylene, polyisobutylene may be mentioned as polymers.
• JP-OS 78/124 425 they have hitherto been used in the photographic industry as an additive to bleaching baths in order to improve bleachability.
• Suitable supports for the production of color photographic materials are e.g. Films and foils of semi-synthetic and synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate and paper laminated with a baryta layer or ⁇ -olefin polymer layer (e.g. polyethylene).
• These carriers can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light.
• the surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer.
• the color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and, if appropriate, intermediate layers and protective layers.
• Binding agents, silver halide grains and color couplers are essential components of the photographic emulsion layers.
• 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-vinylpyrrolidone, 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, which have been 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. Oxidized gelatin can also be used. The production such gelatins are described, for example, in The Science and Technology of Gelatine, edited by AG Ward and A. Courts, Academic Press 1977, page 295 ff.
• the gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.
• the silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide.
• the halide content of at least one layer can consist of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide.
• silver bromide iodide emulsions are usually used; in the case of color negative and color reversal paper, silver chloride bromide emulsions with a high chloride content are used up to pure silver chloride emulsions.
• platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.
• 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 e.g. Doping of the individual grain areas are different.
• the average grain size of the emulsions is preferably between 0.2 ⁇ m and 2.0 ⁇ m, the grain size distribution can be either homodisperse or heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ⁇ 30%.
• the emulsions can also contain organic silver salts, e.g. 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 combined either in succession by the single-jet process or simultaneously by the double-jet process or by any combination of the two 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 method is used, in which a certain pAg value is kept constant or a defined pAg profile is traversed during the precipitation.
• so-called inverse precipitation with an excess of silver ions is also possible.
• 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.
• Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe may also be present during the precipitation and / or physical ripening of the silver halide grains.
• 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.
• the soluble salts are removed from the emulsion, e.g. by pasta and washing, by flakes and washing, by ultrafiltration or by ion exchangers.
• the silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog are reached.
• the procedure is e.g. described by H. Frieser "The basics of photographic processes with silver halides" page 675-734, Akademische Verlagsgesellschaft (1968).
• a reduction sensitization can be carried out with the addition of reducing agents (tin-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidine sulfinic acid) using hydrogen, by means of low pAg (eg less than 5) and / or high pH (eg above 8) .
• reducing agents titanium-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidine sulfinic acid
• 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 for example from 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 can also be used as antifoggants such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts.
• metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles
• antifoggants such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts.
• Heterocycles containing mercapto groups for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
• mercaptobenzthiazoles for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines
• mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
• Other suitable compounds are published in Research Disclosure 17643 (Dec. 1978), Chapter VI.
• 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 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.).
• 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.).
• surface-active compounds e.g. saponin
• non-ionic surfactants e.g. alkylene oxide compounds, glycerol compounds or glycidol compounds
• cationic surfactants e.g.
• Acid group for example carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, for example amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters of an amino alcohol.
• the photographic emulsions can be spectrally sensitized using methine dyes or other dyes.
• Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
• 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.
• the red-sensitive layers become cyan couplers, assigned to the green-sensitive layers of purple couplers and the blue-sensitive layers of yellow couplers.
• Color couplers for producing the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type; Color couplers for producing 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 ⁇ -benzoylacetanilide or ⁇ -pivaloylacetanilide type.
• the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers.
• the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling point, which is split off during the coupling.
• the 2-equivalent couplers include those that are colorless, as well as those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler), and the white couplers that react with color developer oxidation products yield essentially colorless products.
• the 2-equivalent couplers also include those couplers which contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and either directly or after one or after the residue from the primary cleavage group several other groups have been split off (e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic effectiveness unfolds, for example as Development inhibitor or accelerator.
• Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.
• DIR couplers the development inhibitors of the azole type, e.g. Release triazoles and benzotriazoles are described in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281.28 42 063, 36 26 219, 36 30 564, 36 36 824, 36 44 416.
• Other advantages for color rendering, i.e. Color separation and color purity, and for detail reproduction, i.e. Sharpness and graininess can be achieved with such DIR couplers, e.g. do not split off the development inhibitor directly as a result of the coupling with an oxidized color developer, but only after a further subsequent reaction, which is achieved, for example, with a timing group.
• DIR couplers which release a development inhibitor which is decomposed into essentially photographically ineffective products in the developer bath are described, for example, in DE-A-32 09 486 and in EP-A-0 167 168 and 0 219 713. This measure ensures trouble-free development and processing consistency.
• DIR couplers in particular those which release an easily diffusible development inhibitor
• suitable measures can be taken to improve the color rendering, e.g. achieve a more differentiated color rendering, as described, for example, in EP-A-0 115 304, 0 167 173, GB-A-2 165 058, DE-A-37 00 419 and US-A-4 707 436.
• the DIR couplers can be added to a wide variety of layers in a multilayer photographic material, e.g. also light-insensitive or intermediate layers. However, they are preferably added to the photosensitive silver halide emulsion layers, the characteristics of the silver halide emulsion, e.g. whose iodide content, the structure of the silver halide grains or their grain size distribution influence the photographic properties achieved.
• the influence of the inhibitors released can be limited, for example, by incorporating an inhibitor scavenger layer in accordance with DE-A-24 31 223. For reasons of reactivity or stability, it can be advantageous to use a DIR coupler which forms a color in the coupling in the respective layer in which it is introduced, which color differs from the color to be produced in this layer.
• DAR or FAR couplers can be used, which release a development accelerator or an fogger.
• links of this type are, for example, in DE-A 25 34 466, 32 09 110, 33 33 355, 34 10 616, 34 29 545, 34 41 823, in EP-A-0 089 834, 0 110 511, 0 118 087, 0 147,765 and in U.S.-A-4,618,572 and 4,656,123.
• DIR, DAR or FAR couplers mainly the effectiveness of the residue released during coupling is desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, which give essentially colorless products on coupling (DE-A-15 47 640).
• the cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (US Pat. No. 4,420,556).
• the material may further contain compounds other than couplers, which can, for example, release a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR-hydroquinones and other compounds, as described for example in US-A-4 636 546, 4 345 024, 4 684 604 and in DE-A-31 45 640, 25 15 213, 24 47 079 and in EP-A-198 438. These compounds perform the same function as the DIR, DAR or FAR couplers, except that they do not form coupling products.
• couplers can, for example, release a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR-hydroquinones and other compounds, as described for example in US-A-4 636 546, 4 345 024, 4 684 604 and in DE
• High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211.
• the high molecular weight color couplers are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.
• the couplers or other compounds can be incorporated into silver halide emulsion layers 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. Choosing the right one Solvent or dispersant 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-O 043 037.
• oligomers or polymers instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.
• the compounds can also be introduced into the casting solution in the form of loaded latices.
• anionic water-soluble compounds eg dyes
• pickling polymers e.g. acrylic acid
• Suitable oil formers are e.g. Alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.
• oil formers 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-t-amylphenol, dioctylacelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-octoxy-5-butyl-2-butyl
• Each of the differently sensitized, light-sensitive layers can consist of a single layer or can also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470).
• red-sensitive silver halide emulsion layers are often arranged closer to the support than green-sensitive silver halide emulsion layers and these are in turn closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.
• the green or Red-sensitive layers can be selected without the yellow filter layer, other layer arrangements in which e.g. the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.
• the non-light-sensitive intermediate layers which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.
• Suitable agents which are also called scavengers or EOP-catchers, are described in Research Disclosure 17 643 (Dec. 1978), chapters VII, 17 842 (Feb. 1979) and 18 716 (Nov. 1979), page 650 and in EP A-0 069 070, 0 098 072, 0 124 877, 0 125 522.
• sub-layers of the same spectral sensitization they can be distinguished with regard to their composition, in particular with regard to the type and amount of the silver halide grains.
• the sublayer with higher sensitivity will be located further away from the support than the sublayer with lower sensitivity.
• Partial layers of the same spectral sensitization can be adjacent to one another or through other layers, for example through Layers of other spectral sensitization must be separated.
• all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).
• the photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives to improve dye, coupler and white stabilization and to reduce the color fog, plasticizers (latices), Contain biocides and others.
• Compounds that absorb UV light are intended on the one hand to protect the image dyes from fading by UV-rich daylight and, on the other hand, as filter dyes to absorb the UV light in daylight upon exposure and thus improve the color rendering of a film.
• Connections of different structures are usually used for the two tasks. Examples are aryl substituted benzotriazole compounds (US-A-3 533 794), 4-thiazolidone compounds (US-A-3 314 794 and 3 352 681), benzophenone compounds (JP-A-2784/71), cinnamic acid ester compounds (US-A-3 705 805 and 3,707,375), butadiene compounds (US-A-4,045,229) or benzoxazole compounds (US-A-3,700,455).
• Ultraviolet absorbing couplers such as ⁇ -naphthol type cyan couplers
• ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.
• Filter dyes suitable for visible light include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.
• Suitable whiteners are e.g. in Research Disclosure 17,643 (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 insoluble in water and can be insoluble in alkali or be alkali-soluble, the alkali-soluble generally being removed from the photographic material in the alkaline development bath.
• suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
• Additives to improve dye, coupler and whiteness stability and to reduce the color fog can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromanes, spiroindanes , p-alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.
• the layers of the photographic material can be hardened with the usual hardening agents.
• Suitable curing agents include formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds, the reactive halogen contain (US-A-3 288 775, US-A-2 732 303, GB-A-974 723 and GB-A-1 167 207), divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro-1,3, 5-triazine and other compounds containing a reactive olefin bond (US-A-3 635 718, US-A-3 232 763 and GB-A-994 869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A-2 732 316 and
• the hardening can be effected in a known manner by adding the hardening agent to the casting solution for the layer to be hardened, or by overlaying the layer to be hardened with a layer which contains a diffusible hardening agent.
• Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed to such an extent immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours, that no further change in the sensitometry and the swelling of the layer structure occurs as a result of the crosslinking reaction .
• Swelling is understood to mean the difference between the wet layer thickness and the dry layer thickness during the aqueous processing of the film (Photogr. Sci., Eng. 8 (1964), 275: Photogr. Sci. Eng. (1972), 449).
• hardening agents which react very quickly with gelatin are, for example, carbamoylpyridinium salts which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin with the formation of peptide bonds and crosslinking of the gelatin.
• Color photographic negative materials are usually processed by developing, bleaching, fixing and washing or by developing, bleaching, fixing and stabilizing without subsequent washing, whereby bleaching and fixing can be combined into one processing step.
• All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine or indophenol dyes can be used as the color developer compound.
• Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
• Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3106 (1951) and G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, page 545 ff.
• bleaching agents e.g. Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used.
• Iron (III) complexes of aminopolycarboxylic acids are particularly preferred, especially e.g. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids.
• Persulfates and peroxides e.g. Hydrogen peroxide.
• the bleach-fixing bath or fixing bath is usually followed by washing, which is designed as countercurrent washing or consists of several tanks with their own water supply.
• the washing can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent.
• this stabilizing bath also acts as a final bath.
• Emulsion 1 (EM 1)
• the emulsion was then cooled, flocculated by acidification and with the addition of a flocculant.
• the flocculate was washed out several times and redispersed with the addition of inert bone gelatin, so that a silver / gelatin weight ratio of 1: 0.3 (based on silver nitrate) resulted.
• the emulsion thus obtained had an average grain diameter of 0.8 ⁇ m and an iodide content of 3 mol%.
• EM 1 is a comparative emulsion.
• EM 2 was prepared like EM 1 with the change that the initial charge additionally contained 0.34 g of compound P 3.
• the proportion of tabular crystals in the total projection area was 85% and the average aspect ratio of the tabular crystals was 7.5.
• EM 3 was prepared like EM 1 with the change that the initial charge additionally contained 1.36 g of compound P 3.
• the proportion of tabular crystals in the total projection area was 95% and the average aspect ratio of the tabular crystals was 17.
• EM 4 was prepared like EM 1 with the change that the initial charge additionally contained 3.4 g of compound P 3.
• the proportion of tabular crystals in the total projection area was 97% and the average aspect ratio of the tabular crystals was> 25.
• Example 2 (Experiments 1-4, Table 2)
• the emulsions were poured onto the antihalation layer of a cellulose acetate support consisting of a silver dispersion with a silver coating corresponding to 4.6 g AgNO3 / m2.
• a protective layer containing a hardening agent of the formula was applied to each of the emulsion layers and containing a wetting agent, applied at a coating thickness of 2 g gelatin / m2 and 340 mg hardening agent / m2.
• the further processing includes the following baths: Stop bath 1 minute at 38 ° C; Bleach bath 3 1/4 minutes at 38 ° C; Water 3 1/2 minutes at 38 ° C; Fixer 3 1/4 minutes at 38 ° C; Water 5 minutes at 38 ° C.
• the stop, bleaching and fixing baths used correspond to those commonly used (British Journal of Photography, 1974 , pages 597 and 598).
• the yellow coupler GB 1 had the following structure:
• Example 3 corresponds in its embodiment to Example 2 with the difference that a silver bromide iodide emulsion with 9 mol% iodide and an average grain diameter of 1.1 ⁇ m (emulsion B), and the amounts of the compound given in Table 2 for experiments 5 to 7 P 3 / mol AgNO3 were used.
• the emulsion A used in Example 2 was after the addition of 5 mmol of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per mole of AgNO3 with 300 ⁇ mol red sensitizer S 1 per mole of AgNO3 and then in each case with those in Table 2 for experiments 8 to 10 specified amounts of the compound P 3 / Mol AgNO3 added.
• 700 g of a 10% by weight gelatin solution and 300 g of a 9.8% by weight coupler from the blue-green coupler BG 1 as well as wetting agent and water were added to each kg of emulsion.
• the emulsions were poured onto the antihalation layer of a cellulose acetate support consisting of a silver dispersion with a silver coating corresponding to 5.5 g AgNO3 / m2.
• a protective layer containing a hardening agent of the formula was applied to each of the emulsion layers and containing a wetting agent, applied at a coating thickness of 2 g gelatin / m2 and 340 mg hardening agent / m2.
• the compounds P-1, P-4 and P-5 and the magenta couplers PP1 and PP2 are mixed into various samples of a silver bromide iodide emulsion with 3 mol% iodide and an average particle diameter of 0.75 ⁇ m spectrally sensitized with the green sensitizer S 2, the 75th g of silver bromide iodide and 72 g of gelatin based on 1 kg of emulsion.
• the emulsions prepared in this way were applied to cellulose triacetate layer supports provided with an adhesive layer and dried.
• the stop, bleach and fix baths are common bath compositions. A final bath free of formalin was used.
• the green sensitizer S 2 had the structure: Coupler PP1
• Coupler PP2 a / b / c 20/40/40% by weight, Mn ⁇ 40,000
• a core / shell plasticizer latex is produced according to the method given in US Pat. No. 4,714,671 in Example 1.
• the latex obtained shows good plasticizer properties, but is unstable when electrolytes are added.
• the colloid stability of the latex is significantly improved (Table 4).
• the test is carried out by dropping 0.5 ml of the electrolyte solution into 100 ml of the latex in a 150 ml beaker and then assessing the latex stability.
• the example shows that photographically useful latices can be significantly improved in their stability by adding the polymers according to the invention.

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• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1993
  • 1993-03-16 DE DE4308323A patent/DE4308323A1/de not_active Withdrawn
• 1994
  • 1994-03-03 DE DE59408758T patent/DE59408758D1/de not_active Expired - Fee Related
  • 1994-03-03 EP EP94103198A patent/EP0616256B1/fr not_active Expired - Lifetime
  • 1994-03-11 JP JP6066412A patent/JPH0728210A/ja active Pending

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