EP0697624B1 - Matériau d'enregistrement photographique couleur - Google Patents

Matériau d'enregistrement photographique couleur Download PDF

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Publication number
EP0697624B1
EP0697624B1 EP95112192A EP95112192A EP0697624B1 EP 0697624 B1 EP0697624 B1 EP 0697624B1 EP 95112192 A EP95112192 A EP 95112192A EP 95112192 A EP95112192 A EP 95112192A EP 0697624 B1 EP0697624 B1 EP 0697624B1
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EP
European Patent Office
Prior art keywords
silver halide
compounds
layer
color
couplers
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EP95112192A
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German (de)
English (en)
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EP0697624A2 (fr
EP0697624A3 (fr
Inventor
Johannes Dr. Willsau
Heinrich Dr. Odenwälder
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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
    • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
    • 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
    • G03C2200/00—Details
    • G03C2200/35—Intermediate layer
    • 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
    • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/156—Precursor compound

Definitions

  • the invention relates to a negative type color photographic silver halide material with improved sensitivity.
  • DAR and FAR couplers development accelerator releasing or fogging agent releasing couplers
  • DAR and FAR couplers which are used in the coupler-containing silver halide emulsion layer and split off either a development accelerator or a fogging agent in the coupling reaction with the developer oxidation product
  • the sensitivity of increase photographic silver halide materials is not yet sufficient for many applications.
  • fog and graininess are undesirably increased (e.g. DE-3 333 355).
  • the object of the present invention was to provide additives for photographic materials with which an increase in sensitivity can be achieved without a simultaneous increase in graininess and fog.
  • the compound residue which splits off the 4-equivalent coupler preferably carries a ballast group which makes the compound diffusion-resistant, while the splitted-off coupler has a group which has a silver halide affinity and with which it is adsorbed on the silver halide grain.
  • the silver halide-affine group can be linked directly or via an intermediate member Z to the 4-equivalent coupler.
  • Preferred divalent intermediate members Z are alkylene groups, arylene groups, -COCH 2 -, -COCH 2 -S-, -COCH 2 -O-, -CONH-, -S-, -O-, (COUP-D) can be connected to T 1 via a bond to COUP or to D. The same applies to M 2 .
  • the group AB can be a coupler residue, a redox compound or a residue which can split off the group (T 1 ) m - (COUP-D) - (T 2 ) n in a non-imagewise manner, for example solely through the alkali of the developer.
  • Suitable redox compounds are oxidizable compounds which, after their oxidation, can split off the group (T 1 ) m - (COUP-D) - (T 2 ) n .
  • T 1 can also be a coupler residue.
  • T 2 can be a hydrolyzable group such as -OCOCH 2 Cl, -OCO-phenyl, -OSO 2 -CH 3 , or a coupler residue.
  • the group AB is preferably the remainder of a 2-equivalent coupler which contains the remainder (T 1 ) m - (COUP-D) - (T 2 ) n bound to the coupling point.
  • (COUP-D) is preferably linked to B via the silver halide affinity group D.
  • (COUP-D) preferably does not contain any diffusion-resistant ballast residue.
  • B and COUP can be the residues of yellow, purple or cyan couplers or the residues of couplers that do not produce color.
  • the compounds of the formula I are used in particular in an amount of 0.0005 to 0.05 mmol / m 2 of photographic material, it being possible for the total amount to be used in one layer or distributed over several layers.
  • the compounds of the formula I are preferably used in the case of double or triple-layer packages adjacent to the highly sensitive layers. Instead of a compound of the formula I, mixtures of several compounds of this formula can also be used, the amount given above also being the total amount in this case.
  • Examples of negative type color photographic materials are color negative films, color photographic paper, color reversal films and color reversal paper.
  • the invention is particularly valuable for color negative films.
  • Suitable supports for the production of such color photographic materials are e.g. Films and sheets of semisynthetic and synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate and paper laminated with a baryta layer or a-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.
  • the color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and, if appropriate, intermediate layers and protective layers.
  • Binding agents, silver halide grains and color couplers are essential components of the photographic emulsion layers.
  • Gelatin is preferably used as the binder. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers.
  • Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers.
  • Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, cellulose, sugar, starch or alginates.
  • Semi-synthetic gelatin substitutes are usually modified natural products.
  • Cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives, which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers, are examples of this.
  • the binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents.
  • functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.
  • the gelatin which is preferably used can be obtained by acidic or alkaline digestion. Oxidized gelatin can also be used. The production of such gelatins is described, for example, in The Science and Technology of Gelatine, published by A.G. Ward and A. Courts, Academic Press 1977, page 295 ff.
  • the gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.
  • the silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide.
  • the halide content of at least one layer can consist of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide.
  • the color photographic material according to the invention preferably contains silver bromide iodide emulsions with 5 to 15 mol% of silver iodide.
  • It can be predominantly compact crystals, e.g. are regular cubic or octahedral or can have transitional forms.
  • platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.
  • the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is substantially greater than 5: 1, e.g. 12: 1 to 30: 1.
  • the silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as doping of the individual grain areas, being different.
  • the average grain size of the emulsions is preferably between 0.2 m and 2.0 m, the grain size distribution can be both homo- and heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ⁇ 30%.
  • the emulsions can also contain organic silver salts, for example silver benzotriazolate or silver behenate.
  • Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
  • the photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
  • various methods e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
  • the silver halide crystals can also grow by physical ripening (Ostwald ripening) in the presence of excess halide and / or silver halide complexing agent.
  • the growth of the emulsion grains can even take place predominantly by Ostwald ripening, preferably a fine-grained, so-called Lippmann emulsion, mixed with a less soluble emulsion and redissolved on the latter.
  • Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe may also be present during the precipitation and / or physical ripening of the silver halide grains.
  • the precipitation can also be carried out in the presence of sensitizing dyes.
  • Complexing agents and / or dyes can be rendered ineffective at any time, e.g. by changing the pH or by an oxidative treatment.
  • the soluble salts are removed from the emulsion, e.g. by pasta and washing, by flakes and washing, by ultrafiltration or by ion exchangers.
  • the silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog are reached.
  • Chemical sensitization can be carried out with the addition of compounds of sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII of the periodic table (for example gold, platinum, palladium, iridium).
  • Thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic compounds can also be used Nitrogen compounds (e.g. imidazoles, azaindenes) or spectral sensitizers (described, for example, by F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmanns Encyclopedia of Industrial Chemistry, 4th edition, vol. 18, pp. 431 ff. and Research Disclosure No. 17643, Section III).
  • a reduction sensitization 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. Furthermore, salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can be used as antifoggants.
  • metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can be used as antifoggants.
  • Heterocycles containing mercapto groups for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
  • mercaptobenzthiazoles for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines
  • these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
  • a water-solubilizing group for example a carboxyl group or sulfo group.
  • the stabilizers can be added to the silver halide emulsions before, during or after their ripening.
  • the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.
  • the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
  • 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 ester or phosphoric acid 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 ester or phosphoric acid 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 differently sensitized emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it.
  • cyan couplers are assigned to the red-sensitive layers, purple couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers.
  • Color couplers for producing the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type.
  • Color couplers for generating the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type.
  • Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the ⁇ -acylacetamide type; suitable examples are ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetanilide couplers.
  • the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers.
  • the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling 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, for example as a development inhibitor (DIR coupler).
  • DIR coupler development inhibitor
  • DIR couplers the development inhibitors of the azole type, e.g. Triazoles and benzotriazoles are released in DE-A-2 414 006, 2 610 546, 2 659 417, 2 754 281, 2 726 180, 3 626 219, 3 630 564, 3 636 824, 3 644 416 and 2 842 063 described.
  • Further advantages for color rendering, i.e. color separation and color purity, and for detail rendering i.e. sharpness and granularity can be achieved with such DIR couplers which e.g. do not split off the development inhibitor directly as a result of the coupling with an oxidized color developer, but only after a further subsequent reaction, which is achieved, for example, with a timing group.
  • DIR couplers which release a development inhibitor which is decomposed into essentially photographically ineffective products in the developer bath are described, for example, in DE-A-32 09 486 and in EP-A-167 168 and 219 713. This measure ensures trouble-free development and processing consistency.
  • the DIR couplers can be added to a wide variety of layers in a multilayer photographic material, for example also light-insensitive or intermediate layers. However, they are preferably added to the light-sensitive silver halide emulsion layers, the characteristic properties of the silver halide emulsion, for example its iodide content, the structure of the silver halide grains or their grain size distribution having an influence on the photographic properties achieved.
  • the influence of the inhibitors released can be limited, for example, by incorporating an inhibitor scavenger layer in accordance with DE-A-24 31 223. For reasons of reactivity or stability, it may be advantageous to use a DIR coupler which is in the respective layer in which he is introduced forms a color different from the color to be produced in this layer in the coupling.
  • the material may further contain compounds other than couplers, which can, for example, release a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR hydroquinones and other compounds, as described for example in US-A-4 636 546, 4 345 024, 4 684 604 and in DE-A-3 145 640, 2 515 213, 2 447 079 and in EP-A-198 438. These compounds perform the same function as the DIR, DAR or FAR couplers, except that they do not form coupling products.
  • couplers can, for example, release a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR hydroquinones and other compounds, as described for example in US-A-4 636 546, 4 345 024, 4 684 604 and in DE-A
  • 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.
  • Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-O 043 037.
  • oligomers or polymers instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.
  • the compounds can also be introduced into the casting solution in the form of loaded latices.
  • anionic water-soluble compounds e.g. dyes
  • pickling polymers e.g. acrylic acid
  • Suitable oil formers are e.g. Alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.
  • oil formers examples include dibutylphthalate, dicyclohexylphthalate, di-2-ethylhexylphthalate, decylphthalate, triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-tert-amylphenol, dioctyl acylate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-doxy-5-butyl-2-butyl
  • Each of the differently sensitized, light-sensitive layers can consist of a single layer or two or more silver halide emulsion partial layers include (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 scavengers, are described in Research Disclosure 17.643 / 1978, Chapter VII, 17.842 / 1979, pages 94-97 and 18.716 / 1979, page 650 and in EP-A-69 070, 98 072 , 124 877, 125 522 and in US-A-463 226.
  • sub-layers of the same spectral sensitization can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains.
  • the sublayer with higher sensitivity will be located further away from the support than the sublayer with lower sensitivity.
  • Partial layers of the same spectral sensitization can be adjacent to one another or through other layers, 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 1 958 709, DE-A 2 530 645, DE-A 2 622 922).
  • 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 the dye, Coupler and white stabilization, as well as to reduce color fog and others included.
  • the layers of the photographic material can be hardened with the usual hardening agents.
  • Suitable curing agents are e.g. Formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other 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-diacryloylhexahydro-1,3,5-triazine and other compounds, which contain a reactive olefin bond (US-A 3 635 718, US-A-3 232 763 and GB-A 994 869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A 2
  • the hardening can be effected in a known manner by adding the hardening agent to the casting solution for the layer to be hardened, or by overlaying the layer to be hardened with a layer which contains a diffusible hardening agent.
  • Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed to the extent that none immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours further changes in the sensitometry and the swelling of the layer structure occur due to the crosslinking reaction.
  • Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).
  • hardening agents that react very quickly with gelatin are e.g. to carbamoylpyridinium salts, which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin to form peptide bonds and crosslink the gelatin.
  • Color photographic negative materials are usually processed by developing, bleaching, fixing and washing or by developing, bleaching, fixing and stabilizing without subsequent washing, whereby bleaching and fixing can be combined into one processing step.
  • All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine or indophenol dyes can be used as the color developer compound. Suitable color developer compounds.
  • aromatic compounds containing at least one primary amino group of the p-phenylenediamine type 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.
  • Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used as bleaching agents.
  • Iron (III) complexes of aminopolycarboxylic acids in particular, for example, ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids are particularly preferred.
  • Persulphates are also suitable as bleaching agents.
  • the bleach-fixing bath or fixing bath is usually followed by washing, which is designed as countercurrent washing or consists of several tanks with their own water supply.
  • the washing can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent.
  • this stabilizing bath also acts as a final bath.
  • a color photographic recording material for color negative color development was produced (layer structure 1A) by applying the following layers in the order given to a transparent layer support made from cellulose triacetate. The quantities given relate to 1 m 2 .
  • the corresponding amounts of AgNO 3 are stabilized with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.
  • compound I-1 was additionally added to the 8th layer in an amount of 1 mg / m 2 .
  • the results are shown below.

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  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (3)

  1. Matériau à l'halogénure d'argent de type négatif pour la photographie en couleurs, comprenant un support et au moins une couche d'émulsion à l'halogénure d'argent photosensible contenant un copulant chromogène et au moins une couche non photosensible voisine de cette dernière, caractérisé en ce que la couche voisine non photosensible contient un composé qui réagit avec le produit d'oxydation du révélateur au cours du développement en libérant un copulant à 4 équivalents présentant un groupe adhésif manifestant une affinité pour l'halogénure d'argent.
  2. Matériau à l'halogénure d'argent pour la photographie en couleurs selon la revendication 1, caractérisé en ce que le composé qui réagit avec le produit d'oxydation du révélateur au cours du développement en libérant un copulant à 4 équivalents présentant un groupe adhésif manifestant une affinité pour l'halogénure d'argent est mis en oeuvre en une quantité de 0,0005 à 0,05 mmole/m du matériau photographique.
  3. Matériau à l'halogénure d'argent pour la photographie en couleurs selon la revendication 1, caractérisé en ce que le composé qui réagit avec le produit d'oxydation du révélateur au cours du développement en libérant un copulant à 4 équivalents présentant un groupe adhésif manifestant une affinité pour l'halogénure d'argent répond à la formule I

            A-B-(T1)m-(COUP-D)-(T2)n     (I)

    dans laquelle
    A   représente un résidu de ballast,
    B   représente le résidu d'un composé qui réagit au cours du développement avec libération de (T1)m-(COUP-D)-(T2)n,
    T1 et T2   représentent des éléments de synchronisation qui peuvent être libérés lors du développement,
    m, n   représentent 0 ou 1,
    COUP   représente le résidu d'un copulant à 4 équivalents et
    D   représente un groupe manifestant une affinité pour l'halogénure d'argent.
EP95112192A 1994-08-16 1995-08-03 Matériau d'enregistrement photographique couleur Expired - Lifetime EP0697624B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4429030 1994-08-16
DE4429030A DE4429030A1 (de) 1994-08-16 1994-08-16 Farbfotografisches Aufzeichnungsmaterial

Publications (3)

Publication Number Publication Date
EP0697624A2 EP0697624A2 (fr) 1996-02-21
EP0697624A3 EP0697624A3 (fr) 1996-09-11
EP0697624B1 true EP0697624B1 (fr) 1997-11-05

Family

ID=6525817

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95112192A Expired - Lifetime EP0697624B1 (fr) 1994-08-16 1995-08-03 Matériau d'enregistrement photographique couleur

Country Status (4)

Country Link
US (1) US5622817A (fr)
EP (1) EP0697624B1 (fr)
JP (1) JPH0862796A (fr)
DE (2) DE4429030A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19733524A1 (de) * 1997-08-02 1999-02-04 Agfa Gevaert Ag Farbnegativfilm
US6197488B1 (en) * 1999-07-21 2001-03-06 Eastman Kodak Company Color photographic element containing a coupler releasing derivative with at least three heteroatoms with specific hydrophobicity

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5950439A (ja) * 1982-09-16 1984-03-23 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JPS59157638A (ja) * 1983-02-25 1984-09-07 Fuji Photo Film Co Ltd ハロゲン化銀カラ−感光材料
JPS60107029A (ja) * 1983-11-15 1985-06-12 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
DE3605713A1 (de) * 1986-02-22 1987-08-27 Agfa Gevaert Ag Farbfotografisches aufzeichnungsmaterial
JPS6444937A (en) * 1987-08-14 1989-02-17 Fuji Photo Film Co Ltd Direct positive color photosensitive material
JPH01106052A (ja) * 1987-10-20 1989-04-24 Fuji Photo Film Co Ltd ハロゲン化銀カラー反転感光材料
US5213942A (en) * 1987-12-22 1993-05-25 Fuji Photo Film Co., Ltd. Silver halide color reversal photographic maerial having silver halide emulsions with different grain diameters
JP2899626B2 (ja) * 1989-05-24 1999-06-02 富士写真フイルム株式会社 ハロゲン化銀写真感光材料

Also Published As

Publication number Publication date
EP0697624A2 (fr) 1996-02-21
DE4429030A1 (de) 1996-02-22
US5622817A (en) 1997-04-22
JPH0862796A (ja) 1996-03-08
DE59500943D1 (de) 1997-12-11
EP0697624A3 (fr) 1996-09-11

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