EP0447657A1 - Matériau d'enregistrement photographique - Google Patents

Matériau d'enregistrement photographique Download PDF

Info

Publication number
EP0447657A1
EP0447657A1 EP90124876A EP90124876A EP0447657A1 EP 0447657 A1 EP0447657 A1 EP 0447657A1 EP 90124876 A EP90124876 A EP 90124876A EP 90124876 A EP90124876 A EP 90124876A EP 0447657 A1 EP0447657 A1 EP 0447657A1
Authority
EP
European Patent Office
Prior art keywords
silver halide
compounds
color
couplers
recording material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP90124876A
Other languages
German (de)
English (en)
Other versions
EP0447657B1 (fr
Inventor
Hans Dr. Öhlschläger
Bernhard Dr. Morcher
Lothar Dr. Rosenhahn
Friedhelm Sommer
Thomas Dr. Stetzer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert AG
Original Assignee
Agfa Gevaert AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Publication of EP0447657A1 publication Critical patent/EP0447657A1/fr
Application granted granted Critical
Publication of EP0447657B1 publication Critical patent/EP0447657B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium

Definitions

  • the invention relates to a photographic recording material with a layer support and at least one photosensitive silver halide emulsion layer arranged thereon.
  • the material contains special triazoles as antifoggants and special heterocyclic mercapto compounds as stabilizers.
  • antifoggants or stabilizers to photographic silver halide emulsions to reduce fog formation, e.g. B. heterocyclic compounds containing sulfur, for example in the form of a mercapto group.
  • German interpretation documents 1 183 371 (GB 1 067 066), 1 189 380 (US 3 364 028 and 3 365 294), 1 597 503 (US 3 615 617>, DE 1 979 027) to the German published documents 1 522 363 (GB 1 186 441), 2 042 533 (US 3 761 278), 2 130 031 and 2 308 530.
  • the object of the invention was to develop a photographic recording material in which the sensitivity and the gradation of the silver halide emulsions can be controlled independently of one another.
  • heterocyclic compounds can be further substituted, for example by fluorine, chlorine, bromine, optionally also by substituted alkyl groups having preferably up to 8 carbon atoms such as methyl, ethyl, isopropyl, alkenyl such as allyl, cycloalkyl such as cyclohexyl, optionally substituted aryl such as phenyl or Naphthyl, hydroxy, alkoxy with preferably up to 6 carbon atoms such as methoxy or butoxy, mercapto, alkylthio with preferably up to 6 carbon atoms such as methylthio, butylthio, carboxyl, alkoxycarbonyl, sulfo, optionally substituted sulfonamide, nitro, amino, with alkyl , Aryl or acyl substituted amino, such as butylamino or acetylamino.
  • substituted alkyl groups having preferably up to 8 carbon atoms such as methyl, e
  • Examples of cations of a metal atom according to group X are Na ⁇ , K ⁇ , Mg2 ⁇ and Zn2 ⁇ ; a cation of a non-metal radical represents, for example, NH4 ⁇ .
  • Suitable heteroaryl radicals are, for example: thiophene, furan, 1,2,4-triazole and pyridine.
  • Suitable substituents of the radicals R1, R2 and R3 are common substituents in the field of photographic antifoggants, such as halogen, in particular chlorine or bromine, C1-C4-alkoxy groups, C1-C4-alkoxycarbonyl, C6-C10-aryloxycarbonyl and C1-C4-alkylcarbonyloxy.
  • Aryl and heteroaryl can also be substituted with C1-C8 alkyl.
  • the antifoggants according to the invention are used in an amount of 10 ⁇ 5 to 10 ⁇ 2, preferably 0.5 to 5 x 10 ⁇ 3 mol per mol of silver halide.
  • the compounds are prepared by known methods, as described, for example, in the literature:
  • the alcohol component of the ester can be exchanged by transesterification with sodium alcoholate catalysis at 60 to 100 ° C.
  • alkylthio-1,2,3-triazoles are accessible, for example, by alkylation with alkyl bromides.
  • 1,2,4-triazole-substituted 1,2,3-triazoles can be prepared in a conventional manner by ring-closing reaction of a 1,2,3-triazolecarboxylic acid ester with thiosemicarbazide.
  • the stabilizers (11) according to the invention are preferably used in an amount of from 10 ⁇ 5 to 10 ⁇ 2 mol per mol of silver halide. Suitable examples are the following compounds:
  • photographic materials are black and white films, black and white paper, black and white reversal photographic paper, 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.
  • Color photographic recording materials with a layer support and at least three light-sensitive silver halide emulsion layers of different spectral sensitivity, to which a yellow coupler, a magenta coupler and a cyan coupler are each spectrally assigned, in particular color reversal materials, are preferred.
  • Suitable supports for the production of color photographic materials are, for example, films and foils of semisynthetic and synthetic polymers, such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate, and paper laminated with a barite layer or ⁇ -olefin polymer layer (eg polyethylene).
  • These supports 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 the support is generally subjected to a treatment 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 as well as, if necessary, 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, 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.
  • the binders should have a sufficient amount of functional groups so that sufficient resistant layers can be produced by reaction with suitable curing agents.
  • Such 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 of such gelatins is described, for example, in The Science and Technology of Gelatine, published by A.G. Ward and A. Courts, Academic Press 1977, page 295 ff.
  • the gelatin used in each case should contain the lowest possible 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 be 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol%. consist of bromide.
  • silver bromide iodide emulsions are usually used; in the case of color negative and color reversal paper, silver chloride bromide emulsions are usually used.
  • It can be predominantly compact crystals that are, for example, regular cubic or octahedral or Transitional shapes can preferably also be platelet-shaped crystals, 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 in which the ratio of diameter to thickness is substantially greater than 5: 1, for example 12: 1 to 30: 1.
  • the silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as doping of the individual grain areas, being different.
  • the average grain size of the emulsions is preferably between 0.2 ⁇ m and 2.0 ⁇ m, the grain size distribution can be both homo- and heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate more than + 30% from the mean grain size.
  • the emulsions can also contain organic silver salts, for example silver benzotriazolate or silver behenate.
  • Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
  • the photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsions, The Focal Press, London (1966) from soluble silver salts and soluble halides will.
  • 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 be physically ripened (Ostwald ripened) in the presence of excess halide and / or silver halide complexing agent to grow. The growth of the emulsion grains can even take place predominantly by Ostwald ripening, a fine-grained, so-called Lippmann emulsion preferably being mixed with a less soluble emulsion and being redissolved on the latter.
  • Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe can 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 have been reached.
  • chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog have been reached.
  • the procedure is described, for example, by H. Frieser "The Basics of Photographic Processes with Silver Halides" page 675-734, Akademische Verlagsgesellschaft (1968).
  • Chemical sensitization can be carried out with the addition of compounds of sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII of the periodic table (for example gold, platinum, palladium, iridium).
  • Thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic compounds can also be used Nitrogen compounds (e.g. imidazoles, azaindenes) or spectral sensitizers (described, for example, by F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmanns Encyclopedia of Industrial Chemistry, 4th edition, vol. 18, pp. 431 ff. and Research Disclosure No. 17643, Section III).
  • a reduction sensitization with the addition of reducing agents (tin-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidinesulfinic acid) by hydrogen, by low pAg (z, B, less than 5) and / or high pH (e.g. above 8 ) be performed.
  • reducing agents titanium-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidinesulfinic acid
  • azaindenes preferably tetra- and penta-azaindenes
  • azaindenes are suitable, 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 such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can be used.
  • 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.).
  • non-ionic surfactants for example alkylene oxide compounds, glycerol compounds or glycidol compounds
  • cationic surfactants for example higher alkylamines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds
  • sulfonium compounds or phosphonium compounds anionic surfactants containing an acid group, eg carboxylic acid, sulfonic acid, a phosphonium compound
  • anionic surfactants containing an 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 and 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.
  • Sensitizers can be dispensed with if the intrinsic sensitivity of the silver halide is sufficient for a certain spectral range, for example the blue sensitivity of silver bromides.
  • 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 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 ⁇ -acylacetamide type; Suitable examples are ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetanilide couplers.
  • the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers.
  • the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site which is split off during the coupling.
  • the 2-equivalent couplers include colorless ones are, as well as those that have an intense intrinsic 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 essentially result in colorless products when reacted with color developer oxidation products.
  • the 2-equivalent couplers also include those couplers that contain a cleavable residue in the coupling point, 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 (eg 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, 27 26 180, 36 26 219, 36 30 564, 36 36 824, 36 44 416 and 28 42 063. Further advantages for color reproduction, that is, color separation and color purity, and for detail reproduction, that is, sharpness and granularity, can be achieved with those DIR couplers which, for example, do not split off the development inhibitor directly as a result of coupling with an oxidized color developer, but only after a further follow-up 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-167 168 and 219 713. This measure ensures trouble-free development and processing consistency.
  • 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 preferably added to the light-sensitive silver halide emulsion layers, 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 caused, for example, by incorporation an inhibitor capture layer according to DE-A-24 31 223 are limited. For reasons of reactivity or stability, it may 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-89 834, 110 511, 118 087, 147 765 and described in US-A-4,618,572 and 4,656,123.
  • DIR, DAR or FAR couplers Since with DIR, DAR or FAR couplers the effectiveness of the residue released during the coupling is mainly desired and the color-forming properties of these couplers are less important, these are also DIR, DAR or FAR couplers are suitable which, when coupled, result in essentially colorless products (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. You can but 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 dispersion medium 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. Is referred for example on DE-A-25 41 230, DE-A-25 41 274, DE-A-28 35 856, EP-AO 014 921, EP-A-0 069 671, EP-AO 130 115, US-A- 4,291,113.
  • 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 examples include dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecoxy phosphate, 2-ethylhexyl phosphate, tridecoxy phosphate, 2-ethylhexyl phylate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-tert-amylphenol, dioctyl acylate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N,
  • Each of the differently sensitized, light-sensitive layers can consist of a single layer or 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, with a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.
  • green or red-sensitive layers are suitably low in their own sensitivity, other layer arrangements can be selected without the yellow filter layer, 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, 17 842/1979, pages 94-97 and 18.716 / 1979, page 650 and in EP-A- 69,070, 98,072, 124,877, 125,522 and in US-A-463,226.
  • 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 sublayer with higher sensitivity will be located further 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, e.g. separated by layers of other 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.
  • 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 white toners 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 layer furthest away from the support, but also occasionally intermediate layers, especially if they represent the layer furthest away from the support during production, can contain photographically inert particles of an inorganic or organic nature, for example as matting agents or as spacers (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 haze can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromans, 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-chloroethyl urea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds, the reactive halogen included (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 7
  • 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 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 and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
  • Further 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.
  • Persulphates 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 functions as a final bath.
  • This example shows the advantages of the antifoggants according to the invention and the stabilizers when used in color reversal materials.
  • Color photographic recording materials for reverse processing are produced by successively applying the layers listed below on a cellulose triacetate support provided with an adhesive layer.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP90124876A 1990-03-10 1990-12-20 Matériau d'enregistrement photographique Expired - Lifetime EP0447657B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4007731A DE4007731A1 (de) 1990-03-10 1990-03-10 Fotografisches aufzeichnungsmaterial
DE4007731 1990-03-10

Publications (2)

Publication Number Publication Date
EP0447657A1 true EP0447657A1 (fr) 1991-09-25
EP0447657B1 EP0447657B1 (fr) 1995-09-06

Family

ID=6401950

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90124876A Expired - Lifetime EP0447657B1 (fr) 1990-03-10 1990-12-20 Matériau d'enregistrement photographique

Country Status (2)

Country Link
EP (1) EP0447657B1 (fr)
DE (2) DE4007731A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3157509A (en) * 1962-03-20 1964-11-17 Eastman Kodak Co Photographic emulsions containing novel fog-inhibiting addenda
EP0107488A2 (fr) * 1982-10-22 1984-05-02 Konica Corporation Emulsions aux halogénures d'argent
EP0369235A1 (fr) * 1988-11-12 1990-05-23 Agfa-Gevaert AG Matériau d'enregistrement photographique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3157509A (en) * 1962-03-20 1964-11-17 Eastman Kodak Co Photographic emulsions containing novel fog-inhibiting addenda
EP0107488A2 (fr) * 1982-10-22 1984-05-02 Konica Corporation Emulsions aux halogénures d'argent
EP0369235A1 (fr) * 1988-11-12 1990-05-23 Agfa-Gevaert AG Matériau d'enregistrement photographique

Also Published As

Publication number Publication date
DE59009635D1 (de) 1995-10-12
DE4007731A1 (de) 1991-09-12
EP0447657B1 (fr) 1995-09-06

Similar Documents

Publication Publication Date Title
EP0358071B1 (fr) Matériau de reproduction photographique
DE3736410A1 (de) Farbfotografisches silberhalogenidmaterial
EP0464409B1 (fr) Matériau de reproduction photographique pour la couleur
EP0351588B1 (fr) Matériau de reproduction photographique couleur
DE3830522A1 (de) Fotografisches aufzeichnungsmaterial
DE4039022A1 (de) Farbfotografisches aufzeichnungsmaterial
EP0370226B1 (fr) Matériel photographique à l'halogénure d'argent et sa méthode de traitement
EP0369235B1 (fr) Matériau d'enregistrement photographique
EP0377889B1 (fr) Matériel d'enregistrement à l'halogénure d'argent
EP0652474B1 (fr) Matériau photographique couleur d'enregistrement
EP0413204A2 (fr) Matériau photographique couleur à l'halogénure d'argent
EP0447656A1 (fr) Matériau photographique couleur à l'halogénure d'argent et son développement
EP0447657B1 (fr) Matériau d'enregistrement photographique
EP0373339B1 (fr) Matériau d'enregistrement photosensible à l'halogénure d'argent
EP0377181A2 (fr) Matériau photographique couleur
EP0550907B1 (fr) Matériau d'enregistrement photographique
EP0363820A2 (fr) Matériau photographique couleur à l'halogénure d'argent
EP0616256B1 (fr) Matériau photographique couleur d'enregistrement
EP0345514A2 (fr) Matériau photographique couleur à l'halogénure d'argent
EP0697624B1 (fr) Matériau d'enregistrement photographique couleur
DE3838467C2 (de) Fotografisches Aufzeichnungsmaterial
EP0722117B1 (fr) Matériau photographique couleur à l'halogénure d'argent
DE4008067A1 (de) Farbfotografisches aufzeichnungsmaterial zur herstellung farbiger aufsichtsbilder
EP0709731A2 (fr) Produit photographique couleur à l'halogénure d'argent
DE3833387A1 (de) Farbfotografisches silberhalogenidmaterial

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19901220

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB IT

17Q First examination report despatched

Effective date: 19940817

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB IT

REF Corresponds to:

Ref document number: 59009635

Country of ref document: DE

Date of ref document: 19951012

ITF It: translation for a ep patent filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19951102

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19971230

Year of fee payment: 8

REG Reference to a national code

Ref country code: GB

Ref legal event code: 746

Effective date: 19980721

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981231

BERE Be: lapsed

Owner name: AGFA-GEVAERT A.G.

Effective date: 19981231

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20011105

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20011108

Year of fee payment: 12

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021220

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20021220

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030901

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20031027

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050701

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051220