EP0699956B1 - Matériau photographique couleur à l'halogénure d'argent - Google Patents

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

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EP0699956B1
EP0699956B1 EP95113006A EP95113006A EP0699956B1 EP 0699956 B1 EP0699956 B1 EP 0699956B1 EP 95113006 A EP95113006 A EP 95113006A EP 95113006 A EP95113006 A EP 95113006A EP 0699956 B1 EP0699956 B1 EP 0699956B1
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Prior art keywords
silver halide
coupler
alkyl
formula
compounds
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German (de)
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EP0699956A1 (fr
Inventor
Beate Dr. Weber
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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
    • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
    • G03C7/3885—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 solvent
    • 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
    • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
    • G03C7/3005—Combinations of couplers and photographic additives
    • G03C7/3008—Combinations of couplers having the coupling site in rings of cyclic compounds and photographic additives
    • 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
    • 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

Definitions

  • the invention relates to a color photographic silver halide material with a novel coupler solvent.
  • Color photographic silver halide materials which provide color images by the chromogenic process usually contain at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, at least one green-sensitive silver halide emulsion layer containing at least one pupil coupler and at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler.
  • the couplers are usually dissolved or dispersed in fine droplets of a so-called coupler solvent.
  • Suitable and common coupler solvents are e.g. Tricresyl phosphate (TKP), dibutyl phthalate (DBP), but also fatty acid amides such as diethyl lauramide.
  • TKP Tricresyl phosphate
  • DBP dibutyl phthalate
  • fatty acid amides such as diethyl lauramide.
  • the object of the invention was therefore to provide new coupler solvents with which improved maximum densities and steeper gradations can be achieved, but which must not impair the stability of the dye.
  • Alkyl and alkenyl can be straight-chain or branched, unsubstituted or substituted.
  • R 1 is preferably linear or branched alkyl or alkenyl with 8 8 C atoms.
  • R 2 and R 3 are preferably independently of one another hydrogen or methyl.
  • R 4 is preferably straight-chain or branched alkylene having 1 to 8 carbon atoms.
  • l is preferably 1.
  • m is preferably 0.
  • Examples of compounds of the formulas (I) to (III) are: I-1 H 23 C 11 CONH- (CH 2 ) 2 -O- (CH 2 ) 2 -OH I-2 H 35 C 17 CONH- (CH 2 ) 2 -O- (CH 2 ) 2 -OH I-3 H 23 C 11 CONH- (CH 2 CH 2 O) 3 -H I-6 H 23 C 11 CONH- (CH 2 ) 5 -OH I-7 H 23 C 11 CONH- (CH 2 ) 3 -OH
  • the compounds of formula (I) are prepared by known methods from acid chlorides or acid anhydrides and amino alcohols.
  • the couplers are usually used in an amount of 0.1 to 100 mmol / m 2 .
  • the coupler solvents according to the invention can be used in an amount of 0.05 to 3 g / g coupler.
  • a mixture of several compounds according to the invention can also be used.
  • 15 to 50% by weight of the total coupler solvent of at least one coupler is particularly preferably at least one coupler solvent of the formula (I) according to the invention.
  • the coupler solvents according to the invention are used in particular for the purple couplers.
  • Teal couplers are usually phenol or ⁇ -naphthol type couplers.
  • Yellow couplers are usually couplers with an open-chain ketomethylene group, in particular couplers of the ⁇ -acylacetamide type, for example benzoylanilide couplers and ⁇ -pivaloylacetanilide couplers.
  • Pupur couplers are usually 5-pyrazolone, indazolone or pyrazoloazole type couplers.
  • radicals R 4 , R 6 , R 7 and R 8 represent hydrogen, alkyl, aralkyl, aryl, alkoxy, aroxy, alkylthio, arylthio, amino, anilino, Acylamino, cyano, alkoxycarbonyl, carbamoyl, sulfamoyl, where these radicals can be further substituted.
  • R 5 represents hydrogen or a radical which can be split off on color coupling, such as a halogen atom or a preferably cyclic group attached to the coupling point via an oxygen atom, a sulfur atom or a nitrogen atom.
  • the coupling to the coupling point of the coupler molecule can take place either directly via an atom which is part of a ring, for example a nitrogen atom, or indirectly via an intermediate link.
  • split off Groups are known in large numbers, for example as escape groups of 2-equivalent purple couplers.
  • cleavable groups attached via oxygen correspond to the formula -OR 9 , wherein R 9 represents an acyclic or cyclic organic radical, for example alkyl, aryl, a heterocyclic group or acyl, which is derived, for example, from an organic carbon or sulfonic acid.
  • R 15 denotes an optionally substituted phenyl group.
  • these are 5-membered heterocyclic rings which are connected to the coupling site of the purple coupler via a ring nitrogen atom.
  • the heterocyclic rings often contain groups adjacent to the nitrogen atom which mediates binding to the coupler molecule, e.g. Carbonyl or sulfonyl groups or double bonds.
  • the cleavable group is attached to the coupling site of the coupler via a sulfur atom, it can be the remainder of a diffusible carbocyclic or heterocyclic mercapto compound which is capable of inhibiting the development of silver halide.
  • Such inhibitor residues have been widely described as a cleavable group attached to the coupling site of couplers, including magenta couplers, e.g. in US-A 3,227,554.
  • Couplers correspond to formulas IV-D and IV-E.
  • pyrazoloazole couplers of the formula IV are:
  • acyl group also in the context of acylamino, is derived in particular from a carbon, carbamate, carbonic or sulfonic acid.
  • the compounds of formula V are used in particular in an amount of 0.05 to 3 g / g coupler.
  • radicals R 7 or r, t, v, w, x can be the same or different.
  • acyl group contained in the radical X (formula Ve) and for a possible acyl group in the radicals R 7 and R 9 the same applies to R 1 to R 6 .
  • the color photographic recording material according to the invention contains at least one light-sensitive silver halide emulsion layer and preferably a sequence of several such light-sensitive silver halide emulsion layers and, if appropriate, further auxiliary layers such as, in particular, protective layers and non-light-sensitive binder layers arranged between the light-sensitive layers, wherein according to the present invention at least one of the light-sensitive silver halide emulsion layers present is an inventive one Connection in combination with a color coupler, preferably a purple coupler, is assigned.
  • color photographic materials are color negative films, color reversal films, color positive films, color photographic paper, color reversal photographic paper, color sensitive materials for the color diffusion transfer process or the silver color bleaching process.
  • Suitable supports for the production of color photographic materials are e.g. Films and foils of semi-synthetic and synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate and paper laminated with a baryta layer or ⁇ -olefin polymer layer (e.g. polyethylene).
  • These carriers can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light.
  • the surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer.
  • 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, semisynthetic or naturally occurring polymers.
  • 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 methyl groups.
  • the silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide.
  • the halide content of at least one layer can consist of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide.
  • silver bromide iodide emulsions are used, in the case of color negative and color reversal paper usually silver chloride bromide emulsions with a high chloride content up to pure silver chloride emulsions.
  • It can be predominantly compact crystals, which are, for example, regularly cubic or octahedral or can have transitional forms. Platelet-shaped crystals can 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.
  • AgBrCl emulsions with at least 80 mol% AgCl, in particular at least 95 mol% AgCl, are preferably used.
  • the silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as e.g. Doping of the individual grain areas are different.
  • the average grain size of the emulsions is preferably between 0.2 ⁇ m and 2.0 ⁇ m, the grain size distribution can be either homodisperse or heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ⁇ 30%.
  • the emulsions can also contain organic silver salts, e.g. Silver benzotriazolate or silver behenate.
  • Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
  • the photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
  • various methods e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
  • the soluble salts are removed from the emulsion, for example by means of pasta and washing, by flaking 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).
  • the 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), and thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic compounds 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 17643 (Dec. 1978), Chapter III).
  • 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
  • surface-active compounds such as thioethers
  • a reduction sensitization can be carried out with the addition of reducing agents (tin-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidine sulfinic acid) using hydrogen, by means of low pAg (eg less than 5) and / or high pH (eg above 8) .
  • reducing agents titanium-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidine sulfinic acid
  • the photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
  • Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are for example from Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can also 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 also 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 be added to the silver halide emulsions during or after their ripening.
  • the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.
  • the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
  • surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
  • surface-active compounds e.g. Saponin
  • non-ionic surfactants e.g. Alkylene oxide compounds, glycerin compounds or glycidol compounds
  • cationic surfactants e.g.
  • alkyl amines quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing an acid group, e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid or phosphoric ester group, ampholytic surfactants, e.g. Amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters of an amino alcohol.
  • an acid group e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid or phosphoric ester group
  • ampholytic surfactants e.g. Amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters of an amino alcohol.
  • the photographic emulsions can be spectrally sensitized using methine dyes or other dyes.
  • Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
  • Sensitizers can be dispensed with if the intrinsic sensitivity of the silver halide is sufficient for a certain spectral range, for example the blue sensitivity of silver bromides.
  • the 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 which contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue (e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic effectiveness unfolds, e.g. - As a development inhibitor or accelerator.
  • Examples of such 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. Release triazoles and benzotriazoles are described in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281, 28 42 063, 36 26 219, 36 30 564, 36 36 824, 36 44 416.
  • Other advantages for color rendering, i.e. Color separation and color purity, and for detail reproduction, i.e. Sharpness and graininess can be achieved with such DIR couplers, 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-0 167 168 and 0 219 713. 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 are used that split off a development accelerator or an fogging agent.
  • Compounds of this type are, for example, in DE-A-25 34 466, 32 09 110, 33 33 355, 34 10 616, 34 29 545, 34 41 823, in EP-A-0 089 834, 0 110 511, 0 118 087 , 0 147 765 and in U.S.-A-4,618,572 and 4,656,123.
  • the cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (US Pat. No. 4,420,556).
  • the material may further contain compounds other than couplers, which can liberate, for example, a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR hydroquinones and other compounds as described, for example, in US Pat US-A-4 636 546, 4 345 024, 4 684 604 and in DE-A-31 45 640, 25 15 213, 24 47 079 and in EP-A-198 438. These compounds perform the same function as the DIR, DAR or FAR couplers, except that they do not form coupling products.
  • couplers can liberate, for example, a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR hydroquinones and other compounds as described, for example, in US Pat US-A-4 636 546, 4 345 024, 4 684 60
  • High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211.
  • the high molecular weight color couplers are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.
  • the couplers or other compounds can be incorporated into silver halide emulsion layers by first preparing a solution, a dispersion or an emulsion from the compound in question and then adding it to the casting solution for the layer in question.
  • the selection of the suitable solvent or dispersion medium depends on the solubility of the compound.
  • Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-O 043 037.
  • oligomers or polymers instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.
  • the compounds according to the invention are used in particular for the yellow-coupling layer.
  • the compounds can also be introduced into the casting solution in the form of loaded latices.
  • anionic water-soluble compounds e.g. dyes
  • pickling polymers e.g. acrylic acid
  • Suitable oil formers in addition to the compounds according to the invention 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.
  • Each of the differently sensitized, light-sensitive layers can consist of a single layer or can also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470).
  • red-sensitive silver halide emulsion layers are often arranged closer to the support than green-sensitive silver halide emulsion layers and these are in turn closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.
  • the green or Red-sensitive layers can be selected without the yellow filter layer, other layer arrangements in which e.g. the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.
  • the non-light-sensitive intermediate layers which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.
  • Suitable agents which are also called scavengers or EOP-catchers, are described in Research Disclosure 17 643 (Dec. 1978), chapters VII, 17 842 (Feb. 1979) and 18 716 (Nov. 1979), page 650 and in EP A-0 069 070, 0 098 072, 0 124 877, 0 125 522.
  • sub-layers of the same spectral sensitization can differ with regard to their composition, in particular as regards 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, e.g. separated by layers of other spectral sensitization.
  • all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).
  • the photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives to improve dye, coupler and white stabilization and to reduce the color fog, plasticizers (latices), Contain biocides and others.
  • binder layers in particular the layer furthest away from the carrier, but also occasionally intermediate layers, especially if they represent the most distant layer from the support during production, can contain photographically inert particles of inorganic or organic nature, for example as matting agents or as spacers (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643 , (Dec. 1978), Chapter XVI).
  • the average particle diameter of the spacers is in particular in the range from 0.2 to 10 ⁇ m.
  • the spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath.
  • suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
  • Additives to improve dye, coupler and whiteness stability and to reduce the color fog can belong to the following chemical 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.
  • a color photographic recording material suitable for a rapid processing process was produced by applying the following layers in the order given to a support made of 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 11 through 15 corresponded to Sample 10 with the difference that DBP was replaced by the compounds shown in Table 2.
  • the processed samples were then covered with a UV protective film and irradiated in a xenon test device to determine the light fastness (15 ⁇ 10 6 lxh).
  • the UV protective film was produced as follows: a layer of 1.5 g of gelatin, 0.65 g of UV absorber UV-1, 0.07 g of dioctylhydroquinone and 0.36 g of CPM was placed on a transparent cellulose triacetate film provided with an adhesive layer applied. The amounts relate to 1 m 2 .
  • the compounds according to the invention as coupler solvents significantly increase the maximum density of the purple dyes.
  • Comparative sample 11 shows, compared to sample 10, no improvement in the maximum density and drastic deterioration in the light stability of the dye.
  • the compounds according to the invention also improve the light stability.

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

Claims (5)

  1. Matériau photographique couleur à base d'halogénure d'argent contenant au moins un coupleur de couleur, caractérisé en ce que ce coupleur couleur est dissous ou dispersé dans un composé de formule (I)
    Figure imgb0107
     dans laquelle
    R1   représente un groupe alkyle, alcényle, cycloalkyle ou cycloalcényle,
    R2 et R3   représentent chacun, indépendamment l'un de l'autre, H, un groupe alkyle, alcényle, cycloalkyle ou cycloalcényle,
    R4   représente un groupe alkylène ou alcénylène,
    X   représente CO ou SO2,
    m   est égal à 0 ou 1 et
    l   est un nombre allant de 1 à 5.
  2. Matériau photographique couleur à base d'halogénure d'argent selon la revendication 1 caractérisé en ce que le composé de formule (I) répond à l'une des formules (II) ou (III)
    Figure imgb0108

            R1-CO-NH-(CH2-CH2-O)-1H     (III)

    dans lesquelles
    R1 et l ont les significations indiquées dans la revendication 1
  3. Matériau photographique couleur à base d'halogénure d'argent selon la revendication 1 caractérisé en ce que le coupleur dissous ou dispersé dans le composé de formule (I) est un coupleur pourpre de formule (IV)
    Figure imgb0109
     dans laquelle
    R4   représente H, un groupe alkyle, aralkyle ou aryle ;
    R5   représente H ou un groupe libérable par copulation ;
    Za, Zb, Zc   représentent chacun un groupe méthine éventuellement substitué, =N- ou -NH-, l'une des liaisons Za-Zb ou Zb-Zc étant une double liaison et l'autre une liaison simple.
  4. Matériau photographique couleur à base d'halogénure d'argent selon la revendication 3, dans lequel le coupleur répond à l'une des formules IV-D ou IV-E
    Figure imgb0110
     dans lesquelles
    R4, R6 et R7   représentent chacun l'hydrogène, un groupe alkyle, aralkyle, aryle, alcoxy, aroxy, alkylthio, arylthio, amino, anilino, acylamino, cyano, alcoxycarbonyle, carbamoyle, sulfamoyle, ces groupes pouvant porter d'autres substituants, et
    R5   représente l'hydrogène ou un groupe libérable à la copulation couleur.
  5. Matériau photographique couleur à base d'halogénure d'argent selon la revendication 1, pour lequel on utilise en outre un agent de protection contre la lumière répondant à la formule (V)
    Figure imgb0111
     dans laquelle
    R1   représente H, un groupe alkyle, aryle, acyle ;
    R2   représente -OR1, -COOH, un groupe alkyle, aryle, dialkylamino, acylamino, sulfonamido, acyle, sulfonyle ;
    R3, R4, R5, R6 représentent chacun H, un halogène ou un groupe tel que mentionné en référence à R2, ou bien deux groupes voisins parmi les groupes -OR1, R2, R3, R4, R5, R6 complètent ensemble un cycle de 5 à 8 chaînons.
EP95113006A 1994-08-31 1995-08-18 Matériau photographique couleur à l'halogénure d'argent Expired - Lifetime EP0699956B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4430948 1994-08-31
DE4430948A DE4430948A1 (de) 1994-08-31 1994-08-31 Farbfotografisches Silberhalogenidmaterial

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EP0699956A1 EP0699956A1 (fr) 1996-03-06
EP0699956B1 true EP0699956B1 (fr) 1997-07-23

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Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6396656A (ja) * 1986-10-13 1988-04-27 Konica Corp 色再現性にすぐれたハロゲン化銀写真感光材料
JPS63139347A (ja) * 1986-12-02 1988-06-11 Konica Corp 色再現性に優れたハロゲン化銀写真感光材料
IT1228436B (it) * 1987-07-24 1991-06-17 Minnesota Mining & Mfg Materiali fotografici agli alogenuri d'argento sensibili alla luce
JP2964013B2 (ja) * 1990-10-02 1999-10-18 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
EP0486929B1 (fr) * 1990-11-13 1998-10-14 Eastman Kodak Company Compositions de copulants photographiques comprenant alcools avec groupes ballastes et procédés
US5258278A (en) * 1991-07-15 1993-11-02 Eastman Kodak Company Color photographic material containing a coupler composition comprising a pyrazoldtriazole magenta coupler and a carbonamide compound
US5376520A (en) * 1992-12-07 1994-12-27 Konica Corporation Silver halide light sensitive color photographic material

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DE59500416D1 (de) 1997-08-28
US5510234A (en) 1996-04-23
DE4430948A1 (de) 1996-03-07
EP0699956A1 (fr) 1996-03-06
JPH0876330A (ja) 1996-03-22

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