EP0616256B1 - Matériau photographique couleur d'enregistrement - Google Patents

Matériau photographique couleur d'enregistrement Download PDF

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Publication number
EP0616256B1
EP0616256B1 EP94103198A EP94103198A EP0616256B1 EP 0616256 B1 EP0616256 B1 EP 0616256B1 EP 94103198 A EP94103198 A EP 94103198A EP 94103198 A EP94103198 A EP 94103198A EP 0616256 B1 EP0616256 B1 EP 0616256B1
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Prior art keywords
compounds
color
layer
alkyl
couplers
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EP94103198A
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German (de)
English (en)
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EP0616256A1 (fr
Inventor
Günter Dr. Helling
Klaus Dr. Wagner
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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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/39236—Organic compounds with a function having at least two elements among nitrogen, sulfur or oxygen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/392—Additives
    • G03C7/396—Macromolecular additives

Definitions

  • R 1 can be different in one polymer, so that co-, block-co- or graft polymers are possible.
  • the compounds of formulas (I) and (II) are preferred water soluble or water dispersible. links of formula (I) are preferred.
  • the polyaddition, polycondensation or polymerization compounds R 5 are, for example, polyesters, preferably aliphatic polyesters, polyacetals, polyethers, polyamides, polyesteramides, polycarbonates, polyurethanes, polystyrenes, poly (meth) acrylates, optionally substituted polyacrylamides, polyalkylene compounds.
  • the compounds have a molecular weight of 300 to 20,000, preferably 500 to 5,000.
  • polyethers e.g. the polymerization products of Ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide as well as their mixed or graft polymerization products, as well as the condensation of polyvalent ones Alcohols or mixtures of the same condensates obtained and that by alkoxylation of polyhydric alcohols won products called.
  • polyesters e.g. those made from hexanediol and Formaldehyde-producible compounds in question.
  • polyester amides and polyamides are made of polyvalent saturated carboxylic acids and polyvalent saturated alcohols, amino alcohols, diamines and their mixtures obtained, mostly linear Suitable for condensates.
  • Polystyrene, substituted may be mentioned as polymers Polystyrenes, poly (meth) acrylates such as polybutyl acrylate, Polyethyl acrylate, polyhydroxyethyl acrylate, polymethyl methacrylate, Polyethyl methacrylate, optionally substituted Polyacrylamides or polymethacrylamides, polyvinyl ethers, Polyethylene, polypropylene, polyisobutylene.
  • polymers Polystyrenes poly (meth) acrylates such as polybutyl acrylate, Polyethyl acrylate, polyhydroxyethyl acrylate, polymethyl methacrylate, Polyethyl methacrylate, optionally substituted Polyacrylamides or polymethacrylamides, polyvinyl ethers, Polyethylene, polypropylene, polyisobutylene.
  • JP-OS 781124 425 they were used in the photographic Industry previously used as an additive to bleach baths to improve bleachability.
  • Suitable supports for the production of color photographic materials are e.g. Films and foils of semi-synthetic and synthetic polymers such as cellulose nitrate, Cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, Polyethylene terephthalate and polycarbonate and with a barite layer or ⁇ -olefin polymer layer (e.g. polyethylene) laminated paper.
  • These carriers can with dyes and pigments, for example titanium dioxide, be colored. They can also be used for shielding purposes be colored black by light.
  • the surface the carrier is generally subjected to a treatment, the adhesion of the photographic emulsion layer to improve, for example a corona discharge with subsequent application for a substrate layer.
  • the color photographic materials usually contain at least one red sensitive, green sensitive and blue sensitive silver halide emulsion layer and optionally intermediate layers and Protective layers.
  • Essential components of the photographic emulsion layers are binders, silver halide grains and Color coupler.
  • Gelatin is preferably used as the binder. However, this can be done in whole or in part by others synthetic, semi-synthetic or also naturally occurring Polymers to be replaced. Synthetic gelatin substitutes Examples include polyvinyl alcohol, poly-N-vinyl pyrrolidone, Polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers. Naturally occurring gelatin substitutes are, for example other proteins like 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, which by implementation with alkylating or acylating agents or by Grafting polymerizable monomers obtained are examples of this.
  • the binders should have a sufficient amount of functional groups so that by implementation sufficiently resistant with suitable hardening agents Layers can be created.
  • Such functional Groups are especially amino groups, but also Carboxyl groups, hydroxyl groups and active methylene groups.
  • the gelatin which is preferably used can be acidic or alkaline digestion. It can also oxidized gelatin can be used. The production such gelatin 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 should be as possible low level of photographically active impurities included (inert gelatin). Gelatin with high viscosity and low swelling are special advantageous.
  • Halide chloride bromide or iodide or mixtures of which included.
  • the halide content at least one layer of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% consist of bromide.
  • silver bromide iodide emulsions in the case of color negative and color reversal paper usually high silver chloride bromide emulsions
  • platelet-shaped crystals are regular cubic or octahedral or can have transitional forms.
  • platelet-shaped crystals can also be present, their average ratio of diameter to Thickness is preferably at least 5: 1, the diameter a grain is defined as the diameter of a Circle with a circle content corresponding to the projected Area of the grain.
  • the silver halide grains can also be multi-layered Have grain structure, in the simplest case with an inner and an outer grain area (corel shell), the halide composition andloder other modifications, such as Endowments of the individual Grain areas are 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 both be homo- and heterodisperse. Homodisperse grain size distribution means 95% of the grains are not deviate more than ⁇ 30% from the average grain size.
  • the emulsions can also contain organic silver salts, e.g. Silver benzotriazolate or silver behenate.
  • silher halide emulsions Two or more types of silher halide emulsions, which are made separately, as a mixture be used.
  • the photographic emulsions can be different Methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), V.L. Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) soluble silver salts and soluble halides become.
  • the silver halide is preferably precipitated in Presence of the binder, e.g. the gelatin and can carried out in the acidic, neutral or alkaline pH range are, preferably silver halide complexing agents can also be used.
  • the latter belong e.g. Ammonia, thioether, imidazole, ammonium thiocyanate or excess halide.
  • the merge the water-soluble silver salts and the halides optionally takes place one after the other after the single-jet or simultaneously using the double-jet process or by any combination of both methods.
  • the pAg range can be changed during the Precipitation can vary within wide limits, preferably uses the so-called pAg-controlled method, in which a certain pAg is kept constant or on Run through the defined pAg profile during the precipitation becomes.
  • a certain pAg is kept constant or on Run through the defined pAg profile during the precipitation becomes.
  • the so-called inverse Precipitation possible with excess of silver ions is also the so-called inverse Precipitation possible with excess of silver ions.
  • the silver halide crystals can also be precipitated by physical ripening (Ostwald ripening), in the presence of excess halide and / or silver halide complexing agent to grow.
  • the growth of the emulsion grains can even predominantly through Ostwald ripening take place, preferably a fine-grained, so-called Lippmann emulsion, with a less soluble Emulsion mixed and redissolved on the latter.
  • the silver halide grains can also contain salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe to be available.
  • the precipitation can also be carried out in the presence of sensitizing dyes respectively.
  • Complexing agent and / or dyes can be any Deactivate the point in time, e.g. by changing the pH or by an oxidative treatment.
  • the soluble salts are removed at an earlier point in time removed from the emulsion, e.g. by pasta and washing, by flaking and washing, by ultrafiltration or through ion exchangers.
  • the silver halide emulsion generally becomes one chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until it is reached of the optimum sensitivity and fog.
  • the procedure is e.g. with H. Frieser "The basics of the photographic processes with silver halides " Pages 675-734, Academic Publishing Company (1968).
  • the chemical sensitization can add of compounds of sulfur, selenium, tellurium andloder Compounds of metals of subgroup VIII Periodic table (e.g. gold, platinum, palladium, iridium) can take place, furthermore thiocyanate compounds, surface-active Compounds such as thioethers, heterocyclic Nitrogen compounds (e.g. imidazoles, azaindenes) or spectral sensitizers (described e.g. with F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmann's Encyclopedia of Technical Chemistry, 4th edition, vol. 18, p. 431 ff. And Research Disclosure 17643 (Dec. 1978), Chapter III) can be added.
  • compounds of sulfur, selenium, tellurium andloder Compounds of metals of subgroup VIII Periodic table e.g. gold, platinum, palladium, iridium
  • thiocyanate compounds e.g. gold, platinum, palladium, i
  • a reduction sensitization with the addition of reducing agents (tin-II salts, Amines, hydrazine derivatives, aminoboranes, silanes, Formamidine sulfinic acid) by hydrogen, by low pAg (e.g. less than 5) and / or high pH (e.g. above 8) be carried out.
  • reducing agents tin-II salts, Amines, hydrazine derivatives, aminoboranes, silanes, Formamidine sulfinic acid
  • the photographic emulsions can be compounds to Prevention of fog or for stabilization the photographic function during production, the Storage or photographic processing included.
  • Azaindenes are particularly suitable, preferably tetra and pentaazaindenes, 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 can also be used as antifoggants. Nitroindazole, optionally substituted benzotriazoles or benzthiazolium salts can be used.
  • 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 the silver halide emulsions before, during or after their ripening.
  • the connections can also be made to others photographic layers that are a layer of halogen silver are assigned.
  • the photographic emulsion layers or other hydrophilic Colloid layers of the one produced according to the invention Photosensitive material can be surface active Contain funds for various purposes, such as coating aids, to prevent electrical charging Improvement of the sliding properties, for emulsifying the Dispersion, to prevent adhesion and to improve the photographic characteristics (e.g. acceleration of development, high contrast, sensitization etc.).
  • surface active compounds e.g. Saponin
  • surfactants mainly synthetic surface-active compounds (surfactants) Use: non-ionic surfactants, e.g. Alkylene oxide compounds, Glycerin compounds or glycidol compounds, cationic Surfactants, e.g.
  • alkylamines quaternary ammonium salts
  • Pyridine compounds and other heterocyclic Compounds sulfonium compounds or phosphonium compounds, anionic surfactants containing one Acid group, e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, Sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, e.g. Amino acid and Aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters an amino alcohol.
  • Acid group e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, Sulfuric acid ester or phosphoric acid ester group
  • ampholytic surfactants e.g. Amino acid and Aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters an amino alcohol.
  • the photographic emulsions can be made using spectral of methine dyes or other dyes be sensitized.
  • Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex Merocyanine dyes.
  • the differently sensitized emulsion layers become non-diffusing monomeric or polymeric color couplers assigned which is in the same shift or in a layer adjacent to it.
  • the red-sensitive layers become cyan couplers
  • the green-sensitive layers of purple couplers and assigned to the blue-sensitive layers yellow couplers.
  • Color coupler for generating the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type; Color coupler for the generation of the purple Partial color images are usually couplers of 5-pyrazolone, Indazolone or pyrazoloazole type; Color coupler to generate the yellow partial color image are in the Usually couplers with an open chain ketomethylene grouping, in particular couplers of ⁇ -benzoylacetanilide or ⁇ -pivaloylacetanilide type,
  • the color couplers can be 4-equivalent couplers, but also act as 2-equivalent couplers. Latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling point, which is split off at the clutch. To the 2 equivalent couplers colorless ones are to be expected are, as well as those that have an intense intrinsic color have, which disappears with the color coupling or replaced by the color of the image dye generated becomes (mask coupler), and the white couplers that react with color developer oxidation products essentially result in colorless products.
  • Couplers are also to be expected, which in the Coupling point contain a removable residue that when reacting with color developer oxidation products in Freedom is set, either directly or after one or several other groups have been split off (e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic Effectiveness unfolds, e.g. as a development inhibitor or accelerator.
  • 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.
  • DIR couplers the development inhibitors of the azole type, e.g. Triazoles and benzotriazoles are released in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281.28 42 063, 36 26 219, 36 30 564, 36 36 824, 36 44 416.
  • Other advantages for color rendering, i.e. Color separation and color purity, and for detail reproduction, i.e. Sharpness and graininess are with such DIR couplers to achieve, e.g. the development inhibitor not immediately as a result of coupling with one split off oxidized color developer, but only after a further follow-up reaction, for example with a timing group is reached.
  • DIR couplers that release a development inhibitor which in the developer bath is essentially photographically ineffective Products are decomposed, for example in DE-A-32 09 486 and in EP-A-0 167 168 and 0 219 713 described. With this measure, a trouble-free Development and processing consistency achieved.
  • DIR couplers especially those that split off a diffusible development inhibitor, can be taken by taking suitable measures at the optical sensitization improvements in color rendering, e.g. a more differentiated color rendering, achieve, such as 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 used in a multi-layer photographic Material added to different layers e.g. also light-insensitive or intermediate layers. However, they are preferably the photosensitive silver halide emulsion layers added, the characteristic properties the silver halide emulsion, e.g. their iodide content, the Structure of the silver halide grains or their grain size distribution of influence on the photographic achieved Properties are.
  • the influence of the released Inhibitors can be installed, for example an inhibitor scavenger layer according to DE-A-24 31 223 limited become.
  • the one in the respective layer in which it is introduced is one of those to be generated in this layer Color deviates from the color of the coupling.
  • contrast and DAR or FAR couplers can achieve maximum density be used, which is a development accelerator or split off an fogger.
  • links of this type are described, 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.
  • BAR couplers (Bleach Accelerator Releasing Coupler) is on EP-A-193 389 referred.
  • Coupler split off photographically effective group by modifying an intermolecular reaction this group after their release with a another group according to DE-A-35 06 805.
  • DAR or FAR couplers mainly the effectiveness of the released at the clutch The rest is desirable and it is less on the color-forming Properties of this coupler that arrives are also such DIR, DAR or FAR couplers suitable for the Coupling result in essentially colorless products (DE-A-15 47,640).
  • the detachable residue can also be a ballast residue, see above that in the reaction with color developer oxidation products Coupling products are obtained that are diffusible are or at least a weak or restricted one Have mobility (US-A-4 420 556).
  • the material can still be different from couplers Contain compounds which contain, for example, a development inhibitor, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, an fogger or a Free antifoggants, for example so-called DIR hydroquinones and other compounds, as 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 are described.
  • This Connections perform the same function as the DIR, DAR or FAR couplers, except that they are not coupling products form.
  • High molecular weight color couplers are 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 described.
  • the high molecular color couplers are used in usually by polymerization of ethylenically unsaturated monomeric color couplers. You can but also obtained by polyaddition or polycondensation become.
  • Hydrophobic compounds can also be made using high-boiling solvents, so-called oil formers, be introduced into the casting solution.
  • Appropriate methods are for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-O 043 037.
  • the compounds can also be in the form of loaded latices be introduced into the casting solution. Is referred for example on DE-A-25 41 230, DE-A-25 41 274, DE-A-28 35 856, EP-A-0 014 921, EP-A-0 069 671, EP-A-O 130,115, U.S. 4,291,113.
  • anionic water-soluble Compounds e.g. from dyes
  • cationic polymers so-called pickling polymers respectively.
  • Suitable oil formers are e.g. Alkyl phthalate, 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-ethyl-hexyldiphenyl phosphate, Tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, Tridecyl phosphate, tributoxyethyl phosphate, Trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl p-hydroxybenzoate, Diethyldodecanamide, N-tetradecylpyrrolidone, Isostearyl alcohol, 2,4-di-t-amylphenol, Dioctyl acylate,
  • Each of the differently sensitized, photosensitive Layers can consist of a single layer or two or more partial silver halide emulsion layers include (DE-C-1 121 470).
  • Layer supports are often arranged closer than green-sensitive ones Silver halide emulsion layers and these again closer than blue-sensitive, whereby in general between green sensitive layers and blue sensitive layers a non light sensitive yellow filter layer.
  • the yellow filter layer choose other layer arrangements, where on the carrier e.g. the blue sensitive, then the red sensitive and finally the green-sensitive layers follow.
  • Spectral sensitivity arranged non-photosensitive Intermediate layers can contain agents which is an undesirable diffusion of developer oxidation products from a photosensitive to a other photosensitive layer with different prevent spectral sensitization.
  • sub-layers of the same spectral sensitization can look at their Composition, especially what type and amount of silver halide grains concerns differentiate. In general becomes the sub-layer with higher sensitivity be arranged further away from the support than the partial layer with less sensitivity. Sub-layers same spectral sensitization can each other adjacent or through other layers, e.g. by Separate layers of other spectral sensitization be. For example, all highly sensitive and all low-sensitivity layers to form a layer package be summarized (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.
  • Ultraviolet absorbing couplers such as Cyan couplers of the ⁇ -naphthol type
  • ultraviolet absorbing Polymers are used. These ultraviolet absorbents can be done by pickling in a special Layer fixed.
  • filter dyes suitable for visible light Oxonol dyes include hemioxonol dyes, styryl dyes, Merocyanine dyes, cyanine dyes and azo dyes.
  • oxonol dyes, Hemioxonol dyes and merocyanine dyes 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 described.
  • Certain layers of binder especially that of Carrier most distant layer, but also occasionally Intermediate layers, especially if they during the manufacturing process the furthest from the wearer represent removed layer, can be photographically inert Contain particles of inorganic or organic nature, e.g. as a matting agent or as a spacer (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), Chapter XVI).
  • the average particle diameter of the spacers is in particular in the range from 0.2 to 10 ⁇ m.
  • the spacers are insoluble in water and insoluble in alkali or be alkali-soluble, the alkali-soluble generally in an alkaline development bath the photographic material are removed.
  • suitable polymers are polymethyl methacrylate, copolymers from acrylic acid and methyl methacrylate as well Hydroxypropylmethyl cellulose hexahydrophthalate.
  • Additives to improve the dye, coupler and White stability and to reduce the color fog can belong to the following chemical substance classes: Hydroquinones, 6-hydroxychromanes, 5-hydroxy-coumarans, Spirochromanes, spiroindanes, p-alkoxyphenols, steric 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 with the usual hardening agents are hardened.
  • Suitable Hardening agents are e.g. 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 others 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-di-acryloylhexahydro-1,3,5-triazine and other connections, which contain a reactive olefin bond (US-A-3 635,718, U.S.-A-3,232,763 and GB-A-994,869); N-hydroxymethylphthalimide and
  • the hardening can be effected in a known manner by that the hardening agent of the casting solution for the hardening layer is added, or in that the Layer to be hardened is covered with a layer which contains a diffusible hardening agent.
  • hardening agents that react very quickly with gelatin is it e.g. carbamoylpyridinium salts, those with free carboxyl groups of gelatin able to react, so that the latter with free amino groups gelatin to form peptide bonds and crosslinking of the gelatin react.
  • Color photographic negative materials are usually processed by developing, bleaching, fixing and washing or by developing, bleaching, fixing and stabilizing without subsequent washing, whereby bleaching and fixing can be combined into one processing step.
  • All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine or indophenol dyes can be used as the color developer compound.
  • Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfonamidoethyl) -3-methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
  • Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3106 (1951) and G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York. Page 545 ff.
  • the material is immediately after the Color development bleached and fixed.
  • a bleach can e.g. Fe (III) salts and Fe (III) complex salts such as Ferricyanides, dichromates, water-soluble cobalt complexes be used.
  • Iron (III) complexes are particularly preferred of aminopolycarboxylic acids, especially e.g. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid> Diethylenetriaminepentaacetic acid, Nitrilotriacetic acid, iminodiacetic acid; N-hydroxyethyl-ethylenediamine triestric acid; Alkyliminodicarboxylic acids and of corresponding phosphonic acids.
  • Suitable as Bleaching agents are also persulfates and peroxides; e.g. Hydrogen peroxide.
  • the bleach-fixing bath or fixing bath is usually followed by one Irrigation, which is carried out as countercurrent irrigation or consists of several tanks with their own water supply.
  • the watering can be completed by a stabilizing bath to be replaced, usually in countercurrent to be led.
  • This stabilizing bath takes over when formaldehyde is added also the function of a final bath.
  • Emulsion 1 (EM 1)
  • the emulsion was then cooled, by acidification and flocculated with the addition of a flocculant.
  • the flocculate was washed out several times and with the addition of inert bone gelatin redispersed, so that a Silver / gelatin weight ratio of 1: 0.3 (referred on silver nitrate).
  • the emulsion thus obtained had an average grain diameter of 0.8 ⁇ m and an iodide content of 3 mole%.
  • EM 2 was produced like EM 1 with the change that the template additionally contained 0.34 g of compound P 3.
  • the proportion of tabular crystals in the total projection area was 85% and the average aspect ratio of tabular crystals 7.5.
  • EM 3 was produced like EM 1 with the change that the template additionally contained 1.36 g of compound P 3.
  • the proportion of tabular crystals in the total projection area was 95% and the mean aspect ratio of tabular crystals 17.
  • EM 4 was produced like EM 1 with the change that the template additionally contained 3.4 g of compound P 3.
  • the proportion of tabular crystals in the total projection area was 97% and the average aspect ratio of tabular crystals) 25.
  • Example 2 (Experiments 1-4. Table 2)
  • the emulsions were poured onto the antihalation layer of a cellulose acetate support consisting of a silver dispersion with a silver coating corresponding to 4.6 g AgNO 3 / m 2 .
  • a protective layer containing a hardening agent of the formula was applied to each of the emulsion layers and containing a wetting agent, applied with an application thickness of 2 g gelatin / m 2 and 340 mg hardening agent / m 2 .
  • the samples were placed in a sensitometer behind a Step wedge exposed in the following developer 38 ° C 195 seconds developed and further processing subject.
  • the further processing includes the following baths: Stop bath 1 minute at 38 ° C: Bleach bath 3 1/4 minutes at 38 ° C: Water 3 1/2 minutes at 38 ° C: Fixer 3 1/4 minutes at 38 ° C: Water 5 minutes at 38 ° C.
  • the stop, bleaching and fixing baths used correspond to those commonly used (British Journal of Photography, 1974 , pages 597 and 598).
  • the yellow coupler GB 1 had the following structure:
  • Example 3 corresponds in its embodiment to Example 2 with the difference that a silver bromide iodide emulsion with 9 mol% iodide and an average grain diameter of 1.1 ⁇ m (emulsion B), and the amounts of the compound given in Table 2 for experiments 5 to 7 P 3 / mol AgNO 3 were used.
  • the emulsion A used in Example 2 was after adding 5 mmol of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per mole of AgNO 3 with 300 ⁇ mol red sensitizer S 1 per mole of AgNO 3 and then each with the in Table 2 for the experiments 8 to 10 specified amounts of compound P 3 / mol AgNO 3 added.
  • the emulsions were poured onto the antihalation layer of a cellulose acetate support consisting of a silver dispersion with a silver coating corresponding to 5.5 g AgNO 3 / m 2 .
  • a protective layer containing a hardening agent of the formula was applied to each of the emulsion layers and containing a wetting agent, applied with an application thickness of 2 g gelatin / m 2 and 340 mg hardening agent / m 2 .
  • Table 2 shows, the veils are reduced by the substances according to the invention and the storage stability of the photographic material is significantly improved.
  • connections P-1, P-4 and P-5 and the purple couplers PP1 and PP2 are different samples one with the Green sensitizer S 2 spectrally sensitized silver bromoiodide emulsion with 3 mol% iodide and one mixed average particle diameter of 0.75 ⁇ m, the 75 g of silver bromide iodide and 72 g of gelatin based on Contains 1 kg of emulsion.
  • the emulsions prepared in this way were coated with a Cellulose triacetate substrates provided with an adhesive layer applied and dried.
  • the green sensitizer S 2 had the structure: Coupler PP1
  • Coupler PP2 a / b / c 20/40/40 wt%, Mn - 40,000
  • Example 4 According to the procedure given in Example 4,7 in US 4,714,671 a core / shell plasticizer latex is made.
  • the latex obtained shows good plasticizer properties, but is with the addition of electrolytes unstable.
  • compounds P-4 or P-5 By adding compounds P-4 or P-5 the colloidal stability of the latex is significantly improved (Table 4).
  • the test is carried out by dropping 0.5 ml of the electrolyte solution into 100 ml of the latex in a 150 ml beaker and then assessing the latex stability.
  • the example shows that photographically useful latices can be significantly improved in their stability by adding the polymers according to the invention.

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

Claims (2)

  1. Matériau photographique couleurs à base d'halogénure d'argent avec au moins une couche d'émulsion d'halogénure d'argent, caractérisé en ce qu'il contient avant traitement un composé de la formule I :
    Figure 00570001
    dans laquelle
    R1
    est H ou un groupe alkyle, aralkyle ou cycloalkyle le cas échéant substitué,
    R2
    est H ou un groupe alkyle, aryle ou aralkyle le cas échéant substitué ou une chaíne polymère,
    R3
    est OH,
    R4
    est un groupe alkyle, aryle ou aryle le cas échéant substitué,
    m
    vaut 2 ou 3, de préférence 2,
    n
    vaut 2 à 10 000, de préférence 5 à 2 000,
    ou bien en ce qu'il contient un composé de la formule générale II :
    Figure 00570002
    dans laquelle R1, R3, n et m ont la signification indiquée ci-dessus et peuvent être identiques ou différents, et R5 est un groupe alkylène, arylène, aralkylène le cas échéant substitué ou une chaíne de polyaddition, polycondensation ou polymérisation.
  2. Matériau photographique couleurs à base d'halogénure d'argent selon la revendication 1, caractérisé en ce qu'au moins une couche contient avant traitement un composé de la formule (I), dans laquelle :
    R1
    est un alkyle en C1 à C4,
    R2
    est un alkyle en C1 à C20 le cas échéant substitué.
EP94103198A 1993-03-16 1994-03-03 Matériau photographique couleur d'enregistrement Expired - Lifetime EP0616256B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4308323 1993-03-16
DE4308323A DE4308323A1 (de) 1993-03-16 1993-03-16 Farbfotografisches Aufzeichnungsmaterial

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EP0616256A1 EP0616256A1 (fr) 1994-09-21
EP0616256B1 true EP0616256B1 (fr) 1999-09-22

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