EP0586974B1 - Matériau photographique couleur à l'halogénure d'argent - Google Patents

Matériau photographique couleur à l'halogénure d'argent Download PDF

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Publication number
EP0586974B1
EP0586974B1 EP93113652A EP93113652A EP0586974B1 EP 0586974 B1 EP0586974 B1 EP 0586974B1 EP 93113652 A EP93113652 A EP 93113652A EP 93113652 A EP93113652 A EP 93113652A EP 0586974 B1 EP0586974 B1 EP 0586974B1
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EP
European Patent Office
Prior art keywords
color
acid
silver halide
compounds
alkyl
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.)
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EP93113652A
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German (de)
English (en)
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EP0586974A1 (fr
Inventor
Beate Dr. Weber
Günter Dr. Helling
Klaus Dr. Walz
Markus Dr. Geiger
Kaspar Wingender
Jörg Dr. Hagemann
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Agfa Gevaert AG
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Agfa Gevaert AG
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Priority claimed from DE19924229928 external-priority patent/DE4229928A1/de
Priority claimed from DE19934307439 external-priority patent/DE4307439A1/de
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Publication of EP0586974A1 publication Critical patent/EP0586974A1/fr
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
    • G03C7/3882—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor characterised by the use of a specific polymer or latex
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/39212—Carbocyclic
    • G03C7/39216—Carbocyclic with OH groups

Definitions

  • the invention relates to a color photographic silver halide material based on a Carrier has at least one yellow-coupling silver halide emulsion layer and improved light stability of the generated by the processing Azomething yellow dye.
  • the object of the invention was therefore to improve the light stability of the yellow dyes, so that the longer exposure of light to color photos with initially balanced Colors do not cause uneven fading of the dyes, what that would result in a color cast.
  • the to improve light resistance The agents proposed for the purple dyes are for the stabilization of the Yellow dyes are only suitable to a limited extent and, moreover, often with others Disadvantages that they appear to be unsuitable for practical use to let. As hydroquinones or hydroquinone derivatives, they are easily oxidizable and often give rise to an undesirable coloring (yellowing) of the image whites. With longer storage, they are often caused by the action of atmospheric oxygen or other oxidizing agents oxidize and lose their effectiveness.
  • the compounds of formula (I) can also be in oligomeric or polymeric form available.
  • the yellow coupler can preferably be in an oligomeric or polymeric Oil formers should be distributed.
  • Oligomers or polymeric oil formers are soluble in organic solvents Compounds with a unit which is repeated at least twice in the molecule, whose boiling point is above 200 ° C, in which color couplers are dissolved or dispersed can be.
  • the two radicals R 9 are preferably identical, likewise the two radicals R 10 , R 9 is preferably isopropyl, tert-butyl, cyclohexyl, tert-amyl and 1-methylcyclohexyl.
  • R 10 is preferably methyl, ethyl, propyl, isopropyl n-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, tert-amyl, nonyl.
  • R 11 , R 12 , R 13 are in particular H or CH 3 .
  • Suitable examples are the following compounds connection R 10 R 10 ' R 11 R 12 I-1 C 2 H 5 C 2 H 5 H H I-2 tC 4 H 9 tC 4 H 9 H H H I-3 nC 4 H 9 nC 4 H 9 H H I-4 CH 3 CH 3 H H I-5 C 9 H 19 C 9 H 19 H H I-6 C 2 H 5 C 2 H 5 CH 3 H I-7 CH 3 CH 3 CH 3 H I-8 CH 3 CH 3 H CH 3 I-9 CH 3 CH 3 H C 6 H 5 I-10 tC 4 H 9 tC 4 H 9 CH 3 H such as
  • the bisphenol compounds are preferably used in an amount of 0.1 to 2 g / g Color couplers, especially used in an amount of 0.1 to 1 g / g color coupler.
  • the average molecular weight of the oligomeric or polymeric oil formers is preferably not greater than 200,000, preferably 400 to 100,000.
  • the oligomeric or polymeric oil formers are preferably in one Amount of 0.05 to 10 g / g color coupler, especially in an amount of 0.1 to 4 g / g color coupler used.
  • R 9 is preferably hydrogen and R 10 is a C 1 -C 12 -alkyl radical which is in particular p-permanent to the oxygen.
  • R 11 is especially hydrogen; R 12 is especially methyl; o is in particular 1 to 5; p is in particular 0 to 5.
  • oligomeric and polymeric oil formers are polymers with the following structural units
  • the preferred oligomeric and polymeric oil formers are obtained by adding Alkylene oxides produced on phenol adlehyd resins.
  • the compounds according to the invention are preferred in combination with yellow couplers used.
  • Dye stabilization is also possible with other couplers, magenta and cyan couplers of the photographic materials.
  • 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 carriers 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 baryta layer or ⁇ -olefin polymer layer (e.g. polyethylene) laminated paper.
  • These carriers can be mixed with dyes and pigments, for example titanium dioxide. You can also colored black for the purpose of shielding light be.
  • the surface of the carrier is generally subjected to a treatment to improve the adhesion of the to improve photographic emulsion layer, 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 Gelatin, edited by A.G. Ward and A. Courts, Academic Press 1977, page 295 ff. described.
  • the gelatin used in each case should have the lowest possible content of contain photographically active impurities (inert gelatin). Gelatins with high Viscosity and low swelling are particularly advantageous.
  • Silver halide can be used as halide, chloride, bromide or iodide or mixtures of which included.
  • the halide content can be at least one layer 0 to 15 mol% from iodide, 0 to 100 mol% from chloride and 0 to 100 mol% insist on bromide.
  • the silver halide emulsions preferably consist of at least 80 mol% of material according to the invention from AgCl.
  • color negative and color reversal films are usually silver bromoiodide emulsions, usually silver chloride bromide emulsions in the case of color negative and color reversal paper with a high chloride content up to pure silver chloride emulsions.
  • It can be predominantly compact crystals, e.g. regular cubic or are octahedral or can have transitional forms.
  • Preferably can also be platelet-shaped crystals, their average ratio from 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 according to the projected area of the grain.
  • the layers can also have tabular silver halide crystals, where the ratio of diameter to thickness is significantly larger than 5: 1, e.g. 12: 1 to 30: 1.
  • the silver halide grains can also be multi-layered Have 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 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.
  • Two or more types of silver 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 will.
  • 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 will.
  • 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 preferred precipitation with excess halide 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 and / or 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 and / or Compounds of metals of subgroup VIII Periodic table e.g. gold, platinum, palladium, iridium
  • thiocyanate compounds e.g. gold, platinum, palladium,
  • 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 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
  • 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 the blue-sensitive layers of yellow couplers assigned.
  • 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 the type of 5-pyrazolones, indazolone or pyrazoloazoles.
  • Color coupler for generating the yellow partial color image are usually couplers with an open chain ketomethylene grouping, in particular couplers of the type ⁇ -Acylacetamids, for example ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetanilide couplers.
  • 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 will.
  • 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 these couplers are well received 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 will.
  • 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-0 130,115, 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.
  • suitable oil formers are dibutyl phthalate, Dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl 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, Is
  • the invention contains at least one silver halide emulsion layer one distributed in a polymeric oil former Coupler in combination with a connection of the Formula (I).
  • 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-hydroxycoumarans, 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, N-ethyl-N-3-hydroxypropyl-3-methyl-p-phenylenediamine and 1- (N- Ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
  • Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3106 (1951) and G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New
  • 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-hydroxyethylethylenediamine triacetic acid, Alkyliminodicarboxylic acids and of corresponding phosphonic acids.
  • Suitable as Bleaching agents are 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.
  • 8 mmol color coupler are in the same weight Dibutyl phthalate (DBP) and three times the amount by weight Ethyl acetate in the presence of 0.15 g of dioctyl sulfosuccinate dissolved at a temperature of 50 to 70 ° C.
  • the solution may also be used 25% by weight, based on the amount of couplers to be tested added light stabilizing compound.
  • the solution is then in 150 g of 7.5 wt .-% aqueous, about 40 ° C warm gelatin solution stirred in and dispersed therein. Ethyl acetate is distilled off.
  • Dibutyl phthalate is optionally replaced by the same Amount of polymer oil former replaced.
  • the emulsifier produced under a) is mixed with a silver halide emulsion mixed that 8.2 g of silver in shape of silver halide, 9.2 g gelatin and 0.04 g sodium dodecylbenzenesulfonate contains. The total volume is adjusted to 350 ml with water. The so made Pouring solution is on a layer of cellulose triacetate shed.
  • the processed samples are then covered with a UV protective film and irradiated in a Xenotest device to determine the light fastness (40% relative humidity; 25 ° C; 9.6 ⁇ 10 6 1x ⁇ h).
  • the UV protective film was made as follows. A layer of 1.5 g of gelatin, 0.65 g of compound A (UV absorber) of the following formula was placed on a transparent cellulose triacetate film provided with an adhesive layer 0.07 g dioctyl hydroquinone and 0.36 g tricresyl phosphate applied. The amounts relate to 1 m 2 . Density decrease in% No.
  • the compound V-1 (comparative stabilizer) has the formula
  • the experiments show that the compounds of the formula (I) have a stabilizing effect when dibutyl phthalate is used as an oil former, compared to experiments in which no stabilizer is used, but that this effect is not markedly better than the effect of the comparative substance V -1.
  • the compounds of the formula (I) and the polymeric oil formers are used together, a considerable improvement in the stabilizing effect is found.
  • a color photographic recording material was produced by applying the following layers in the order given on a paper coated on both sides with polyethylene. The quantities given relate to 1 m 2 . The corresponding amounts of AgNO 3 are given for the silver halide application.
  • Samples 2 and 8 are according to the invention.
  • the comparison stabilizers had the following formulas
  • the following two layers were applied to a paper coated on both sides with polyethylene.
  • the quantities relate to 1 m 2 each.
  • the processed material was further stored in a climatic oven (80 ° C, 50% relative humidity, 21 days), the yellow dye decomposing into colored products according to the attached table.
  • the densities behind the red and green filters before and after storage in a climatic chamber were determined with a hand densitometer. The percent density increases are given in Table 4.
  • Comparative stabilizer V-6 has the following formula Samples 10 and 16 are according to the invention.
  • Example 3 was repeated with the change that instead of the yellow coupler Y-1 the Yellow coupler Y-2 was used in the same amount.
  • Comparative stabilizer V-7 Samples 18 and 24 are in accordance with the invention.
  • the samples 10 and 16 and 18 and 24 the increase in the secondary densities due to storage in a climatic chamber less than the comparison samples. This keeps the natural color rendering preserved even after storage under unfavorable climatic conditions.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (3)

  1. Matériau pour photographie en couleurs qui contient, sur un support, au moins une couche d'émulsion à l'halogénure d'argent sensible au bleu contenant au moins un copulant pour le jaune, au moins une couche d'émulsion à l'halogénure d'argent sensible au vert contenant au moins un copulant pour le magenta, au moins une couche d'émulsion à l'halogénure d'argent sensible au rouge contenant au moins un copulant pour le bleu-vert, ainsi que des couches habituelles non photosensibles, caractérisé en ce qu'au moins une couche contient un composé de formule (I)
    Figure 00690001
    ou encore un composé oligomère ou polymère obtenu par polymérisation à partir d'un composé de formule (I) dans laquelle
    R9
    représente, de manière identique ou différente, un radical
    Figure 00690002
    R10
    représente, de manière identique ou différente, un groupe alkyle contenant en particulier de 1 à 9 atomes de carbone,
    R11
    représente un atome d'hydrogène ou un groupe alkyle,
    R12
    représente un atome d'hydrogène, un groupe aryle ou un groupe alkyle,
    R13
    représente un atome d'hydrogène, un groupe aryle ou un groupe alkyle,
    R14, R15
    représentent, de manière identique ou différente, un groupe alkyle, contenant en particulier de 1 à 4 atomes de carbone,
    R16
    représente un atome d'hydrogène ou un groupe alkyle, contenant en particulier de 1 à 4 atomes de carbone.
  2. Matériau pour photographie en couleurs selon la revendication 1, caractérisé en ce que les deux radicaux R9 sont identiques et les deux radicaux R10 sont identiques.
  3. Matériau à l'halogénure d'argent pour photographie en couleurs selon la revendication 1, caractérisé en ce que les émulsions à l'halogénure d'argent sont des émulsions de AgCl jusqu'à concurrence d'au moins 80 moles %.
EP93113652A 1992-09-08 1993-08-26 Matériau photographique couleur à l'halogénure d'argent Expired - Lifetime EP0586974B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE4229928 1992-09-08
DE19924229928 DE4229928A1 (de) 1992-09-08 1992-09-08 Farbfotografisches Silberhalogenidmaterial
DE4307439 1993-03-10
DE19934307439 DE4307439A1 (de) 1993-03-10 1993-03-10 Farbfotografisches Aufzeichnungsmaterial

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EP0586974A1 EP0586974A1 (fr) 1994-03-16
EP0586974B1 true EP0586974B1 (fr) 1998-12-09

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DE4322056A1 (de) * 1993-07-02 1995-01-12 Agfa Gevaert Ag Farbfotografisches Material
DE4338105A1 (de) * 1993-11-08 1995-05-11 Agfa Gevaert Ag Farbfotografisches Aufzeichnungsmaterial
US5594047A (en) * 1995-02-17 1997-01-14 Eastman Kodak Company Method for forming photographic dispersions comprising loaded latex polymers
US5582960A (en) * 1995-02-17 1996-12-10 Eastman Kodak Company Photographic print material
US5731134A (en) * 1996-02-09 1998-03-24 Eastman Kodak Company Gelatin and polymer latex dispersion coating compositions
US5891613A (en) * 1997-08-22 1999-04-06 Eastman Kodak Company Silver halide light-sensitive element
US6312881B1 (en) * 2000-01-14 2001-11-06 Eastman Kodak Company Photographic element with yellow dye-forming coupler and stabilizing compounds
US6555306B1 (en) 2001-12-21 2003-04-29 Eastman Kodak Company Photographic element with dye-forming coupler and image dye stabilizing compound
US6846620B1 (en) * 2003-06-27 2005-01-25 Albert J. Mura, Jr. Photographic element with dye-forming coupler and image dye stabilizing coupler solvent
US20230166992A1 (en) * 2021-11-30 2023-06-01 Baker Hughes Oilfield Operations Llc Selective lithium extraction chemistry for geothermal brine

Citations (1)

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Publication number Priority date Publication date Assignee Title
EP0246766A2 (fr) * 1986-04-30 1987-11-25 EASTMAN KODAK COMPANY (a New Jersey corporation) Stabilisation d'images de colorants produites dans des matériaux photographiques

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JPS4831256B1 (fr) * 1969-09-05 1973-09-27
JPS60122936A (ja) * 1983-12-07 1985-07-01 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JPH0677130B2 (ja) * 1984-02-09 1994-09-28 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
JPH0786669B2 (ja) * 1986-05-27 1995-09-20 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
JP2866941B2 (ja) * 1987-11-25 1999-03-08 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
JP2530868B2 (ja) * 1987-11-30 1996-09-04 コニカ株式会社 色素画像の堅牢性が改良されたハロゲン化銀写真感光材料
DE3835202A1 (de) * 1988-10-15 1990-04-19 Agfa Gevaert Ag Farbfotografisches aufzeichnungsmaterial
DE4031159A1 (de) * 1990-10-03 1992-04-09 Agfa Gevaert Ag Farbfotogafisches farbkupplerhaltiges aufzeichnungsmaterial
JPH04340960A (ja) * 1991-05-17 1992-11-27 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料

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Publication number Priority date Publication date Assignee Title
EP0246766A2 (fr) * 1986-04-30 1987-11-25 EASTMAN KODAK COMPANY (a New Jersey corporation) Stabilisation d'images de colorants produites dans des matériaux photographiques

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JPH06208211A (ja) 1994-07-26
EP0586974A1 (fr) 1994-03-16
US5441861A (en) 1995-08-15

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