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
  • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
  • G03C7/3882—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor characterised by the use of a specific polymer or latex
• • 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
  • G03C7/39212—Carbocyclic
  • G03C7/39216—Carbocyclic with OH groups

Definitions

• the invention relates to a color photographic silver halide material which has at least one yellow-coupling silver halide emulsion layer on a support and is characterized by improved light stability of the azomething yellow dye produced by the processing.
• the image dyes produced by chromogenic development undergo certain changes to varying degrees under the influence of environmental conditions.
• the influence of light is of particular influence.
• the yellow azomethine dyes produced from the open-chain ketomethylene compounds bleach particularly strongly, while the cyan dyes produced from phenolic or naphtholic couplers prove to be quite stable and the magenta dyes produced from pyrazolone couplers have now been approximated in their light stability to the cyan couplers by adding suitable stabilizers.
• the object of the invention was therefore to improve the light stability of the yellow dyes, so that the prolonged exposure to light on color photos with initially balanced colors does not cause uneven bleaching of the dyes, which would result in the appearance of a color cast.
• the agents proposed for improving the lightfastness of the purple dyes are only suitable to a limited extent for the stabilization of the yellow dyes and, moreover, often have other disadvantages which make them appear unsuitable for practical use.
• hydroquinones or hydroquinone derivatives they are easily oxidizable and often give rise to undesirable coloring (yellowing) of the image whites. When stored for a long time, they are often oxidized by the action of atmospheric oxygen or other oxidizing agents and thus lose their effectiveness.
• Polymeric oil formers are compounds which are soluble in organic solvents and have a unit which repeats at least twice in the molecule and whose boiling point is above 200 ° C., in which color couplers can be dissolved or dispersed.
• Suitable bridge members R1 are e.g. Alkylene, alkylidene or sulfonyl groups and heteroatoms such as O and S.
• Examples of R are methyl, ethyl, propyl, butyl, cyclohexyl, phenyl, acetyl and benzyl.
• the two radicals R9 are identical, as are the two radicals R10.
• R9 is preferably isopropyl, tert-butyl, cyclohexyl, tert-amyl and 1-methylcyclohexyl.
• R10 is preferably methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-amyl, tert-amyl, nonyl.
• R11, R12, R13 are in particular H or CH3.
• the bisphenol compounds are preferably used in an amount of 0.1 to 2 g / g color coupler, in particular in an amount of 0.1 to 1 g / g color coupler.
• the average molecular weight of the polymeric oil formers is preferably not greater than 200,000, preferably 400 to 100,000.
• the polymeric oil formers are preferably used in an amount of 0.05 to 10 g / g color coupler, in particular in an amount 0.1 to 4 g / g color coupler.
• polymeric oil formers of the present invention include the following:
• Acrylates such as methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, t-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, t-octyl acrylate, cyanoethylacrylate, 2-acetoxyethyl acrylate, dimethyl acrylate, cycloethyl acrylate, cycloethyl acrylate, methacrylate, hydroxypropyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-isopropoxyacrylate, 2- (2-methoxyethoxy) ethyl acrylate; Methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl
• Monomers containing urea and / or urethane groups may also be present.
• the polymeric oil formers can be homopolymers of the abovementioned monomers or copolymers of two or more of the abovementioned monomers.
• the polymers can contain monomers with acid groups in an amount that does not render them water-soluble.
• Examples of monomers with acid groups are acrylic acid, methacrylic acid, itaconic acid, maleic acid, itaconic acid monoalkyl esters, maleic acid monoalkyl esters, citraconic acid, styrenesulfonic acid, vinylbenzylsulfonic acid, acryloyloxyalkylsulfonic acid, methacryloyloxyalkylsulfonic acid, acrylamidalkylsulfonic acid and methacrylamidealkylloxyphosphate, methacrylamide alkylsulfoyl phosphate.
• These acids can also be used in salt form with an alkali metal such as sodium and potassium or with an ammonium ion.
• Acrylates, acrylamides and methacrylates are the preferred monomers for forming the polymeric oil formers of this invention.
• the polymers can be prepared by solution polymerization, bulk polymerization, suspension polymerization and emulsion polymerization.
• the free radical polymerization of an ethylenically unsaturated monomer is initiated by the addition of a free radical which is formed by thermal decomposition of a chemical initiator by action of a reducing agent on an oxidizing compound (redox initiator) or by physical action, such as radiation with ultraviolet rays or other high-energy radiation, high frequencies, etc.
• a free radical which is formed by thermal decomposition of a chemical initiator by action of a reducing agent on an oxidizing compound (redox initiator) or by physical action, such as radiation with ultraviolet rays or other high-energy radiation, high frequencies, etc.
• chemical initiators include persulfates (e.g. ammonium persulfate or potassium persulfate, hydrogen peroxide, organic peroxides (e.g. benzoyl peroxide or t-butyl peroctoate) and azonitrile compounds (e.g. 4,4'-azobis-4-cyanovaleric acid or azobisisobutyronitrile).
• persulfates e.g. ammonium persulfate or potassium persulfate
• hydrogen peroxide e.g. benzoyl peroxide or t-butyl peroctoate
• azonitrile compounds e.g. 4,4'-azobis-4-cyanovaleric acid or azobisisobutyronitrile
• Examples of conventional redox initiators include hydrogen peroxide iron (II) salt, potassium persulfate, sodium metabisulfite and cerium IV salt alcohol, etc.
• a compound with a surface-active effect is used as the emulsifier which can be used in the emulsion polymerization.
• Preferred examples thereof include soap, a sulfonate, a sulfate, a cationic compound, an amphoteric compound and a high molecular weight protective colloid.
• Specific examples of the emulsifiers and their functions are described in Belgische Chemische Industrie, vol. 28, pages 16 to 20, 1963.
• Polyester resins produced by polycondensation of a polyhydric alcohol and a polybasic acid are identical to each other.
• Polyhydric alcohols are glycols with a hydrocarbon chain of 2 to 12 carbon atoms, especially with an aliphatic hydrocarbon chain or polyalkylene glycols.
• Polybasic acids are dicarboxylic acids whose carboxyl groups are separated from each other by a hydrocarbon chain with 1 to 12 carbon atoms.
• polyhydric alcohols examples include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, trimethylolpropane, 1,4-butanediol, isobutylenediol, 1,5-pentanediol, neopentylglycol, 1,6-hexanediol, 1,8-octanediol , 1,9-nonanediol, 1,10-decanediol, glycerol, diglycerol, triglycerol, 1-methylglycerol, pentaerythritol, mannitol and sorbitol.
• polybasic acids examples include oxalic acid, succinic acid, glutaric acid, adipic acid, pimellic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalenedioic acid, from terephthalenedic acid, from terephthalic acid phthalic acid, from terephthalic acid phthalic acid, from terephthalic acid phthalic acid from terephthalic acid phthalic acid Maleic anhydride.
• polyesters are made from ⁇ -propiolactone, ⁇ -caprolactone and dimethylpropiolactone.
• epihalohydrin e.g. epichlorohydrin
• R9 is hydrogen and R10 is a C1-C12 alkyl radical, which is in particular p-to the oxygen.
• R11 is especially hydrogen; R12 is especially methyl; o is in particular 1 to 5; p is in particular 0 to 5.
• Examples of preferred polymeric oil formers are polymers with the following structural units
• the preferred polymeric oil formers are made by adding alkylene oxides to phenol aldehyde resins.
• the compounds according to the invention are preferably used in combination with yellow couplers.
• Dye stabilization of the photographic materials is also achieved with other couplers, magenta and cyan couplers.
• color photographic materials are color negative films, color reversal films, color positive films, color photographic paper, color reversal photographic paper, color sensitive materials for the color diffusion transfer process or the silver color bleaching process.
• 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 Gelatin, published 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
• silver chloride bromide emulsions with a high chloride content are usually used up to pure silver chloride emulsions.
• These can be predominantly compact crystals which are, for example, regularly cubic or octahedral or can have transitional forms.
• 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 layers can also have tabular silver halide crystals, where the ratio of diameter to thickness is much 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 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 formed, should not be exceeded.
• the pAg range can vary within wide limits during precipitation, the so-called pAg-controlled method is preferably 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, so-called inverse precipitation in the case of excess silver ions is also possible, in addition to precipitation, the silver halide crystals can also be physically ripened ( Ostwald ripening), grow 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 the like nd is redeemed 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.
• 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, for example ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetanilide couplers.
• Suitable yellow couplers include the following:
• the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers.
• the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site which is split off during the coupling.
• the 2-equivalent couplers include those that are colorless and those that have an intense inherent color, which disappears during the color coupling or is replaced by the color of the image dye produced (mask coupler), and the white couplers which, when reacted with color developer oxidation products, essentially give 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 thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue (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 activity unfolds, for example as a development inhibitor or accelerator.
• Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR and FAR couplers.
• DIR couplers which release development inhibitors of the azole type, for example triazoles and benzotriazoles, are described in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281, 28 42 063, 36 26 219, 36 30 564, 36 36 824, 36 44 416.
• DIR couplers of this type provide further advantages for color reproduction, ie color separation and color purity, and for detail reproduction, ie sharpness and graininess to achieve, for example, the cleavage of the development inhibitor not 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, for example also light-insensitive or intermediate layers. However, they are preferred to the photosensitive silver halide emulsion layers added, the characteristic properties of the silver halide emulsion, for example its iodide content, the structure of the silver halide grains or their grain size distribution having an influence on the photographic properties achieved.
• the influence of the inhibitors released can be limited, for example, by incorporating an inhibitor scavenger layer in accordance with DE-A-24 31 223. For reasons of reactivity or stability, it 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.
• Compounds 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 liberate, for example, 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 Pat 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 liberate, for example, 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 Pat US-A-4 636 546, 4 345 024, 4 684 60
• 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-t-amylphenol, dioctyl acylate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-dibutyl-2-butoxy-5-
• At least one silver halide emulsion layer contains a coupler distributed in a polymeric oil former in combination with a compound of the formula (I).
• 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 ones which are generally arranged between layers of different spectral sensitivity Intermediate layers can contain agents which prevent undesired diffusion of developer oxidation products from one photosensitive to another photosensitive 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 can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains.
• the sub-layer with higher sensitivity will be arranged further away from the support than the sub-layer with lower sensitivity.
• Partial layers of the same spectral sensitization can be adjacent to one another or separated by other layers, for example by layers of different spectral sensitization.
• 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.
• 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 classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromanes, spiroindanes , p-alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.
• the layers of the photographic material can be hardened with the usual hardening agents.
• Suitable curing agents are, for example, formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis- (2-chloroethylurea), 2-Hydroxy-4,6-dichloro-1,3,5-triazine and other compounds containing reactive halogen (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
• the curing can be effected in a known manner in that the curing agent of the casting solution for the hardening layer is added, or by covering the layer to be hardened with a layer containing 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 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.
• 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, N-ethyl-N-3-hydroxypropyl-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
• 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.
• Dibutyl phthalate is optionally replaced by the same amount of polymeric oil former.
• the emulsifier produced under a) is mixed with a silver halide emulsion which contains 8.2 g of silver in the form of silver halide, 9.2 g of gelatin and 0.04 g of sodium dodecylbenzenesulfonate. The total volume is adjusted to 350 ml with water. The casting solution thus produced is poured onto a layer of cellulose triacetate.
• the processed samples are then covered with a UV protective film and irradiated in a Xenotest device to determine the light fastness (40% relative humidity; 25 ° C; 9.6 ⁇ 106 1x ⁇ h).
• the UV protective film was made as follows. A layer of 1.5 g of gelatin, 0.65 g of compound A (UV absorber) of the following formula was placed on a transparent cellulose triacetate film provided with an adhesive layer 0.07 g dioctyl hydroquinone and 0.36 g tricresyl phosphate applied. The quantities refer to 1 m2.
• the compound V-1 (comparative stabilizer) has the formula
• the experiments show that the compounds of the formula (I) have a stabilizing effect when dibutyl phthalate is used as an oil former, compared to those in which no stabilizer is used, but that this effect is not markedly better than the effect of the comparative substance V -1.
• the compounds of the formula (I) and the polymeric oil formers are used together, a considerable improvement in the stabilizing effect is found.
• a color photographic recording material was produced by applying the following layers in the order given to a paper coated on both sides with polyethylene.
• the amounts given relate in each case to 1 m 2.
• the corresponding amounts of AgNO3 are given.
• Samples 2 and 8 are according to the invention.
• the comparison stabilizers had the following formulas
• the following two layers were applied to a paper coated on both sides with polyethylene.
• the quantities refer to 1 m2 each.
• the processed material was further stored in a climatic oven (80 ° C, 50% relative humidity, 21 days), the yellow dye decomposing into colored products according to the attached table.
• the densities behind the red and green filters before and after storage in a climatic chamber were determined with a hand densitometer. The percent density increases are given in Table 4.
• Comparative stabilizer V-6 has the following formula Samples 10 and 16 are according to the invention.
• Example 3 was repeated with the change that the yellow coupler Y-2 was used in the same amount instead of the yellow coupler Y-1.
• Examples 3 and 4 show, in the samples 10 and 16 or 18 and 24 according to the invention, the increase in the secondary densities due to storage in a climatic oven is considerably less than in the comparative samples. As a result, the natural color rendering is retained even after storage under unfavorable climatic conditions.

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• 1993
  • 1993-08-26 US US08/112,192 patent/US5441861A/en not_active Expired - Fee Related
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