EP0370226B1 - Matériel photographique à l'halogénure d'argent et sa méthode de traitement - Google Patents

Matériel photographique à l'halogénure d'argent et sa méthode de traitement Download PDF

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Publication number
EP0370226B1
EP0370226B1 EP89119134A EP89119134A EP0370226B1 EP 0370226 B1 EP0370226 B1 EP 0370226B1 EP 89119134 A EP89119134 A EP 89119134A EP 89119134 A EP89119134 A EP 89119134A EP 0370226 B1 EP0370226 B1 EP 0370226B1
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denotes
alkyl
silver halide
layer
photographic
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German (de)
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EP0370226A1 (fr
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Günter Dr. Helling
Frank Dipl.-Ing. Sievers
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • 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
    • G03C1/30—Hardeners

Definitions

  • the invention relates to a photographic silver halide material comprising a support, at least one light-sensitive silver halide emulsion layer applied to the support, a hardening layer and optionally further light-sensitive and light-insensitive layers, which shows a reduction in dirt acceptance during processing.
  • EP-A-259 855 it is known to process photographic materials, in particular X-ray materials in automatically working processing machines, which contain an organic compound in one layer, in particular the gelatin-containing protective layer, for example polyacrylamide, sucrose or dextran, of which at least 10% by weight. -% are washed out during processing.
  • This measure is intended to speed up drying, scratch resistance and sensitivity the material is improved and the residual staining is reduced by the sensitizer.
  • Research Disclosure 13 433 discloses using immediate hardeners together with polystyrene sulfonic acid in a top layer.
  • FR-A-2 267 569 describes the use of certain cellulose sulfates together with instant hardeners in a top layer. These combinations are intended to achieve other tasks than the present invention.
  • 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 in the aqueous processing of the film (Photogr. Sci. Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).
  • Alkyl is especially C1-C20-alkyl optionally substituted by halogen, hydroxy, sulfo, C1-C20-alkoxy.
  • Aryl unless otherwise defined, is in particular optionally substituted by halogen, sulfo, C1-C20-alkoxy or C1-C20-alkyl C6-C14 aryl.
  • Aralkyl unless otherwise defined, is in particular C Halogen-C20-aralkyl substituted by halogen, C1-C20-alkoxy, sulfo or C1-C20-alkyl.
  • Alkoxy unless otherwise defined, is in particular C1-C20 alkoxy.
  • X ⁇ is preferably a halide ion such as Cl ⁇ , Br ⁇ or BF4 ⁇ , NO3 ⁇ , (SO4 2 ⁇ ) 1/2 , ClO4 ⁇ , CH3OSO3 ⁇ , PF6 ⁇ , CF3SO3 ⁇ .
  • Alkylene is especially C2-C20 alkylene; Arylene in particular phenylene, aralkylene in particular benzylene and alkaralkylene in particular xylylene.
  • Suitable N-containing ring systems that can represent Z are shown below.
  • the pyridine ring is preferred.
  • the compounds can be prepared in a simple manner known from the literature.
  • the carbamic acid chlorides are produced from the secondary amines, for example with phosgene, which are then reacted with aromatic, heterocyclic nitrogen-containing compounds in the absence of light.
  • the preparation of compound 3 is described in Chemical Reports 40, (1907), page 1831. Further information on the synthesis can be found in DE-OS 2 225 230, DE-OS 2 317 677 and DE-OS 2 439 551.
  • the casting solution for the hardening layer has in particular a viscosity of 1 to 30 mPa.s; the hardening layer in particular a wet layer thickness of 3 to 30 microns.
  • the thickener should not react with the hardening agent or other substances present in the casting solution or only to such a limited extent that no flocculation or cloudiness greater than 50 NTU (Nephelometric Turbidity Unit; LABO, March 1987), preferably greater than 20 NTU occur.
  • NTU Nephelometric Turbidity Unit
  • Viscosity-increasing agents which do not meet these requirements are unsuitable because of a reduction in the hardening activity, insufficient increase in viscosity or deterioration in the surface properties of the finished material, such as, for example, wet scratch resistance and dirt acceptance.
  • surfactants are: Alkyl esters of sugar; anionic surface-active agents which contain acidic groups, for example a carboxy group, a sulfo group, a phospho group, a sulfate group and a phosphate group, for example alkylcarboxylic acid salts, alkylsulfonic acid salts, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, alkylsulfates, alkylphosphates, nuccinate, n-acylates, n-acylates, n-acylates Sulfoalkyl polyoxyethylene alkylphenyl ether and polyoxyethylene alkyl phosphates; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl s
  • anionic surface active agents having a sulfo group and fluorinated surface active agents are particularly preferred.
  • the hardening layer is preferably applied to a carrier material together with other layers using a so-called V-caster.
  • V casters are e.g. known from DE-A-32 38 905.
  • the casting solution for the hardening layer preferably only meets the casting solutions for the other layers at the pouring edge on which the free-falling curtain forms.
  • a gelatin-containing protective layer is preferably provided between the hardening layer and the uppermost light-sensitive layer.
  • 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, 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 baryta layer or ⁇ -olefin polymer layer (eg 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 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. According to the invention, it is in particular color-negative paper.
  • the color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and, in addition to the hardening layer, optionally 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-vinylpyrolidone, 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, as well as gelatin derivatives, by reaction with alkylating or acylating agents or by grafting 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 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.
  • the photographic material according to the invention is a color photographic material with a reflective base (color paper), the silver halide emulsions of which are either silver bromide chlorides with ⁇ 25 mol% silver chloride or silver halides with at least 90 mol% silver chloride, preferably at least 95 mol% silver chloride and 0 to 10 mol% preferably contain 0 to 5 mol% of silver bromide.
  • the silver halides are preferably free of iodide. It can be predominantly compact crystals, e.g. are regular cubic or octahedral or can have transitional forms. However, 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. However, the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is substantially 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 doping of the individual grain areas, being different.
  • the middle The 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, 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 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 halide silver 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 optionally combined one after the other after the single-jet or simultaneously according to the double-jet process or any combination of both 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 added to any Make the time ineffective, for example by changing the pH value 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).
  • 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 by hydrogen, by low pAg (eg less than 5) and / or high pH (eg above 8).
  • 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. Furthermore, 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 as antifoggants.
  • 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 as antifoggants.
  • 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
  • these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
  • a water-solubilizing group for example a carboxyl group or sulfo group.
  • 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, 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 sulfur 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 partial 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 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 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 the development inhibitors of the azole type, e.g. Triazoles and benzotriazoles are released in DE-A-2 414 006, 2 610 546, 2 659 417, 2 754 281, 2 726 180, 3 626 219, 3 630 564, 3 636 824, 3 644 416 and 2 842 063 described.
  • Further advantages for color rendering, i.e. color separation and color purity, and for detail rendering i.e. sharpness and granularity can be achieved with such DIR couplers which 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-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, 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.
  • Compounds of this type are, for example, in DE-A-2 534 466, 3 209 110, 3 333 355, 3 410 616, 3 429 545, 3 441 823, 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 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-1 547 640).
  • 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-3 145 640, 2 515 213, 2 447 079 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 6
  • 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 Solvents or dispersants depend 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 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-tert.-amylphenol, dioctylacelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-doxy-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.
  • 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 an 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 scavengers, are described in Research Disclosure 17.643 / 1978, Chapter 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 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 1 958 709, DE-A 2 530 645, DE-A 2 622 922).
  • the photographic material may further contain UV light absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives for improving the stabilization of dyes, couplers and whites, and for reducing the color fog 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 December 1978, page 22 ff, Unit 17,643, Chapter V, in US-A-2,632,701, 3,269,840 and in GB-A-852,075 and 1,319,763.
  • Certain layers of binder in particular the layer furthest away from the carrier, but also occasionally intermediate layers, especially if they represent the layer furthest away from the carrier during production, can contain photographically inert particles of an inorganic or organic nature, e.g. as matting agents or as spacers ( DE-A 3 331 542, DE-A 3 424 893, Research Disclosure December 1978, page 22 ff, Unit 17 643, Chapter XVI).
  • photographically inert particles of an inorganic or organic nature e.g. as matting agents or as spacers
  • 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 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 invention further relates to a processing method in which the material according to the invention is imagewise exposed, developed, bleached, fixed, washed or stabilized and finally dried, characterized in that the development is free of benzyl alcohol and preferably in less than two and a half minutes, in particular in less than one Minute.
  • 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.
  • compositions and processing times of the development and bleach-fix bath in which the material according to the invention is processed are given below:
  • a color photographic recording material which is suitable for a rapid processing process was produced by applying the following layers in the order given to a layer support on 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.
  • the layers are applied by means of a curtain coater according to DE-A-32 38 905, the pouring solution for the 8th layer only meeting the layer package of the other casting solutions at the coater edge.
  • the layer structures were exposed behind a gray wedge and subjected to a rapid processing process, the literature-known RA-4 process.

Claims (6)

  1. Film photographique à l'halogénure d'argent constitué d'un support, d'au moins une couche d'émulsion photosensible à l'halogénure d'argent appliquée sur le support, d'une couche durcissante et le cas échéant d'autres couches photosensibles et insensibles à la lumière, caractérisé en ce que parmi toutes les couches, la couche durcissante est appliquée le plus loin de leur support, contient
    a) un durcisseur de formule
    Figure imgb0027
     dans laquelle
    R₁   désigne un groupe alkyle, aryle ou aralkyle,
    R₂   a la même définition que R₁ ou désigne un groupe alkylène, arylène, aralkylène ou alkaralkylène, la seconde liaison étant attachée à un groupe de formule
    Figure imgb0028
     ou bien
    R₁ et R₂   représentent ensemble les atomes nécessaires pour compléter un noyau hétérocyclique éventuellement substitué, le noyau pouvant être substitué par exemple par un radical alkyle en C₁ à C₃ ou un halogène,
    R₃   représente l'hydrogène, un groupe alkyle, aryle, alkoxy, -NR₄-COR₅, -(CH₂)m-NR₈R₉, -(CH₂)n-CONR₁₃R₁₄ ou
    Figure imgb0029
     ou un pont ou une liaison directe à une chaîne polymérique,
    R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈ et R₁₉   représentant de l'hydrogène ou des groupes alkyle en C₁ à C₄,
    R₅   est de l'hydrogène, un groupe alkyle en C₁ à C₄ ou NR₆R₇,
    R₈   est un groupe -COR₁₀,
    R₁₀   est un groupe NR₁₁R₁₂
    R₁₁   est un groupe alkyle en C₁ à C₄ ou aryle,
    R₁₂   est de l'hydrogène, un groupe alkyle en C₁ à C₄ ou aryle,
    R₁₃   est de l'hydrogène, un groupe alkyle en C₁ à C₄ ou aryle,
    R₁₆   est de l'hydrogène, un groupe alkyle en C₁ à C₄, COR₁₈ OU CONHR₁₉,
    m   est un nombre de 1 à 3
    n   est un nombre de 0 à 3
    p   est un nombre de 2 à 3 et
    Y   représente O ou un groupe NR₁₇, ou bien
    R₁₃ et R₁₄   forment conjointement les atomes nécessaires pour compléter un noyau hétérocyclique éventuellement substitué, le noyau pouvant être substitué par un radical alkyle en C₁ à C₃ ou un halogène,
    Z   représente les atomes de carbone nécessaires pour compléter un noyau hétérocyclique aromatique pentagonal ou hexagonal, comprenant le cas échéant un noyau benzénique condensé et
    X⊖   désigne un anion qui disparaît lorsqu'un groupe anionique est déjà lié au reste de la molécule,
    b) un agent épaississant hydrosoluble, pratiquement inerte vis-à-vis de la substance durcissante, les agents épaississants utilisés comprenant un polyacrylamide, des sels d'acides polyméthacryliques ou polyacryliques, des copolymères d'acrylamide et de sels d'acide méthacrylique ou acrylique, des copolymères d'acides 2-acrylamido-2-méthylpropanesulfoniques et de leurs sels, en une quantité de 2 à 500 mg/m² de film photographique, ces agents épaississants étant non ioniques ou anioniques, et possédant sous forme d'une solution aqueuse à 0,5 % en poids une viscosité apparente de 2 à 200 mPa.s pour D = 100 s⁻¹, une viscosité à vitesse nulle de 2 à 100 000 mPa.s et un indice d'Ostwald de 0,25 à 1,00,
    c) et moins de 0,5 mg/m² de gélatine.
  2. Film photographique à l'halogénure d'argent suivant la revendication 1, caractérisé en ce que le durcisseur est utilisé en une quantité de 50 à 500 mg/m² de film photographique.
  3. Film photographique à l'halogénure d'argent suivant la revendication 1, caractérisé en ce que la viscosité apparente de l'épaississant en solution aqueuse de 0,5 % en poids a une valeur de 10 à 80 mPa.s pour D = 100 s⁻¹, la viscosité à la vitesse zéro est de 20 à 20 000 mPa.s et l'indice d'Ostwald est de 0,35 à 0,90.
  4. Film à l'halogénure d'argent pour la photographie en couleur suivant la revendication 1, caractérisé en ce qu'il contient sur un support en papier doublé d'une polyoléfine sur les deux faces, au moins une couche sensible au bleu à laquelle est adjoint un coupleur jaune, au moins une couche sensible au rouge à laquelle est adjoint un coupleur cyan et au moins une couche sensible au vert à laquelle est adjoint un coupleur magenta, et dont les halogénures d'argent contiennent au moins 90 moles % de chlorure d'argent.
  5. Procédé de production d'un tirage sur papier en couleur par exposition d'après image, développement, blanchiment, fixage, lavage à l'eau ou stabilisation et séchage d'un film à l'halogénure d'argent pour la photographie en couleur suivant la revendication 4, caractérisé en ce que le développement est effectué en l'absence d'alcool benzylique.
  6. Procédé suivant la revendication 5, caractérisé en ce qu'au moins 90 % en poids de l'épaississant sont dissous pendant le traitement du film.
EP89119134A 1988-10-29 1989-10-14 Matériel photographique à l'halogénure d'argent et sa méthode de traitement Expired - Lifetime EP0370226B1 (fr)

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DE3836945 1988-10-29
DE3836945A DE3836945A1 (de) 1988-10-29 1988-10-29 Fotografisches silberhalogenidmaterial und verfahren zu seiner verarbeitung

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EP0370226B1 true EP0370226B1 (fr) 1994-03-16

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WO1992011570A1 (fr) * 1990-12-20 1992-07-09 Eastman Kodak Company Agent epaississant utilise lors de la production d'emulsions photographiques
EP0534006A1 (fr) * 1991-09-24 1993-03-31 Agfa-Gevaert N.V. Matériau photographique sensible à la lumière, ayant des propriétés antistatiques et une bonne stabilité au stockage
JPH0649434A (ja) * 1992-06-01 1994-02-22 Eastman Kodak Co ゼラチン溶液用迅速作用性増粘剤
US5547832A (en) * 1992-07-07 1996-08-20 Eastman Kodak Company Method for hardening photographic materials
DE4318438A1 (de) * 1993-06-03 1994-12-08 Agfa Gevaert Ag Fotografisches Aufzeichnungsmaterial
DE19723767A1 (de) * 1997-06-06 1997-11-20 Goes Ges Fuer Sanierungsmasnah Fotografische Formulierungen mit viskositätserhöhenden, wasserlöslichen, synthetischen Polymeren

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US3427158A (en) * 1966-06-02 1969-02-11 Polaroid Corp Novel photographic products and processes
DE2417779A1 (de) * 1974-04-11 1975-10-30 Agfa Gevaert Ag Verfahren zur haertung photographischer schichten
DE2547589A1 (de) * 1975-10-24 1977-04-28 Agfa Gevaert Ag Haertung photographischer schichten
EP0259855A3 (fr) * 1986-09-10 1990-04-18 Fuji Photo Film Co., Ltd. Procédé de développement de matériaux photographiques à l'halogénure d'argent

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DE3836945A1 (de) 1990-05-03
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DE58907230D1 (de) 1994-04-21

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