EP0703493B1 - 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
EP0703493B1
EP0703493B1 EP95114105A EP95114105A EP0703493B1 EP 0703493 B1 EP0703493 B1 EP 0703493B1 EP 95114105 A EP95114105 A EP 95114105A EP 95114105 A EP95114105 A EP 95114105A EP 0703493 B1 EP0703493 B1 EP 0703493B1
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Prior art keywords
silver halide
sensitive
layers
layer
compounds
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EP95114105A
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German (de)
English (en)
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EP0703493A1 (fr
Inventor
Jörg Dr. Siegel
Peter Dr. Hankofer
Hans-Ulrich Dr. Borst
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/3924—Heterocyclic
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—Tabular grain emulsions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03535—Core-shell grains
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03558—Iodide content

Definitions

  • the invention relates to a negative-developing color photographic silver halide material which contains at least 2 blue-sensitive, yellow-coupling, at least 2 green-sensitive, purple-coupling, at least 2 red-sensitive, cyan-coupling silver halide emulsion layers and a yellow filter layer on a transparent support, the layers having the same spectral sensitivity having different photographic sensitivities, the blue-sensitive layers are arranged further away from the support than the yellow filter layer and the green- and red-sensitive layers are arranged closer to the support than the yellow filter layer, and this is characterized by improved development kinetics.
  • the material according to the invention is characterized in that at least one of the highly sensitive green-sensitive and the highly sensitive red-sensitive layers contains an effective amount of a compound which is referred to as crown ether and the said highly sensitive layers contain silver bromide iodide emulsions, the iodide content of which is 1 to 15 mol%.
  • photosensitive silver halide materials which have good storage stability, excellent stability against security light and high sensitivity.
  • the effects are achieved by the combined use of a red sensitizer and a crown ether called a supersensitizer in photographic materials which have a reflective support and a red-sensitive silver halide emulsion layer which is arranged further away from the support than the blue-sensitive silver halide emulsion layer.
  • the silver halide emulsions are silver bromide chloride emulsions with high levels of chloride. The claimed effects cannot be confirmed with the silver bromide iodide emulsions also mentioned but not tested.
  • the crown ether can be added at any time prior to casting the layer. It is preferably added before or during chemical ripening. It is particularly preferably added together with the corresponding sensitizer (sensitive to green or red) before the chemical ripening of the silver halide emulsion. In this case, small amounts of crown ether are sufficient to achieve the effect according to the invention.
  • the chemical ripening preferably consists of a so-called gold / sulfur (selenium) ripening, that is to say a treatment of the silver halide emulsion with gold compounds on the one hand and sulfur and / or selenium compounds on the other hand at elevated temperature.
  • crown ethers which are added in an amount of 10 -5 to 1 mol / mol of silver bromide iodide to the layer in question correspond to the formulas (I), (II) and (III):
  • Suitable elements X 1 are, for example, nitrogen, phosphorus, arsenic, oxygen and sulfur, preferably oxygen.
  • Hydrocarbon radicals L 1 have 2 to 4 carbon atoms in the main chain, preferably 2 carbon atoms and can be substituted, for example, by alkyl, alkoxy, oxo or carboxy or be part of a carbocyclic or heterocyclic aromatic ring.
  • Bridgehead atoms L 2 are preferably nitrogen atoms.
  • Nitrogen, phosphorus and arsenic atoms L 1 carry, in particular, hydrogen atoms or phenyl groups as third substituents or are linked by double bonds to an adjacent group L 1 , the double bond being able to be part of a fused pyridine ring.
  • the compounds of the formulas (I), (II) and (III) are known from the literature and are usually referred to as crown ethers, even if the oxygen atoms of the ether groups can be replaced by other elements of the 6th or by the 5th main group (see above).
  • Suitable compounds of the formulas (I) to (VI) are:
  • the macrocyclic polyethers mentioned can preferably be combined with sensitizer dyes whose oxidation potential is between +1.8 and +0.5 V, preferably between +1.6 and +0.7 V and whose excitation energies are 1.7 to 2.7 eV, preferably 1.9 to 2.6 eV.
  • the effective amount of dye is increased to up to 250% of the originally optimal concentration by adding the polyethers.
  • the mean diameter of the equal-volume sphere of the emulsion grains is preferably 0.3 to 2.0 ⁇ m, in particular 0.5 to 1.5 ⁇ m.
  • Silver halide emulsions are preferred in which tabular hexagonal crystals with an aspect ratio of at least 5 make up at least 50%, in particular at least 70%, of the projection area, the adjacent edge ratio preferably being between 1: 1 and 2: 1.
  • Monodisperse emulsions are preferred.
  • the compounds of the formulas (I), (II) and (III) are added before or during chemical ripening, they are preferably added in an amount of 10 -5 to 1 mol / mol of silver bromide iodide to the layer in question.
  • the use of the compounds of the formulas (I), (II) and (III) is not restricted to the red or green-sensitized layers of the highest sensitivity. They can also be used in one or more of the blue-sensitive layers and in layers which are green- or red-sensitized but do not have the highest sensitivity. Depending on the time of addition, the optimal amounts correspond to the previously mentioned ranges.
  • the silver halide materials according to the invention are particularly suitable as color photographic recording materials.
  • color photographic recording materials are color negative films, color reversal films and color positive films.
  • 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. They can 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 In addition to the red, green and blue sensitive silver halide emulsion layers and the yellow filter layer, the color photographic materials contain customary 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 also 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 methylene groups.
  • the silver halide present as a light-sensitive component in the layers which are not the red- or green-sensitive layers of the highest sensitivity 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 20 mol% of chloride and 65 to 100 mol% of bromide.
  • silver bromoiodide emulsions are commonly used. It can be predominantly compact crystals, e.g. are regular cubic or octahedral or can have transitional forms.
  • platelet-shaped crystals may preferably also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, in particular 5: 1 to 20: 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.
  • Such platelet-shaped silver halide grains can be contained in particular in the layers which contain the crown ether.
  • 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) can be prepared from soluble silver salts and soluble halides.
  • the silver halide is preferably precipitated in the presence of the binder, e.g. the gelatin and can be carried out in the acidic, neutral or alkaline pH range, silver halide complexing agents preferably being additionally used.
  • the latter include e.g. Ammonia, thioether, imidazole, ammonium thiocyanate or excess halide.
  • the water-soluble silver salts and the halides are combined either in succession by the single-jet process or simultaneously by the double-jet process or by any combination of the two processes. Dosing with increasing inflow rates is preferred, the "critical" feed rate, at which no new germs are being produced, should not be exceeded.
  • the pAg range can vary within wide limits during the precipitation, preferably the so-called pAg-controlled method is used, in which a certain pAg value is kept constant or a defined pAg profile is traversed during the precipitation.
  • so-called inverse precipitation with an excess of silver ions is also possible.
  • the silver halide crystals can also grow by physical ripening (Ostwald ripening) in the presence of excess halide and / or silver halide complexing agent.
  • the growth of the emulsion grains can even take place predominantly by Ostwald ripening, preferably a fine-grained, so-called Lippmann emulsion, mixed with a more difficult to dissolve emulsion and redissolved on the latter.
  • 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 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
  • 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 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, for preventing electrical charging, for improving the sliding properties, for emulsifying the dispersion, for preventing adhesion and for improving the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
  • coating aids for preventing electrical charging, for improving the sliding properties, for emulsifying the dispersion, for preventing adhesion and for improving the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
  • non-ionic surfactants for example alkylene oxide compounds, glycerol compounds or glycidol compounds
  • cationic surfactants for example higher alkylamines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds
  • sulfonium compounds or phosphonium compounds anionic surfactants containing an acid group, eg carboxylic acid, Sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group
  • ampholytic surfactants for example amino acid and aminosulfonic acid compounds, and sulfuric or phosphoric acid esters of an amino alcohol.
  • Cyanine dyes, merocyanine dyes and complex merocyanine dyes are particularly suitable as sensitizing dyes.
  • the color couplers added to the differently sensitized silver halide emulsion layers are non-diffusing monomeric or polymeric compounds.
  • the color photographic material can furthermore contain compounds which react with the developer oxidation product and thereby split off a photographically active group, for example a development inhibitor, so-called DIR couplers.
  • 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 dispersing agent 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 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.
  • 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.
  • Layers of the same spectral sensitization can differ with regard to their composition, particularly with regard to the type and amount of the silver halide grains.
  • the sub-layer with higher sensitivity will be arranged further away from the support than the sub-layer 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.
  • highly sensitive layers on the one hand and low-sensitivity layers on the other hand can each 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.
  • the layers of the photographic material can be hardened with the usual hardening agents.
  • 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 such an extent immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours, that no further change in the sensitometry and the swelling of the layer structure occurs as a result of the crosslinking reaction .
  • Swelling is understood to mean the difference between the wet film thickness and the dry film thickness 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 are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
  • Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3106 (1951) and G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, page 545 ff.
  • bleaching agents e.g. Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used.
  • Iron (III) complexes of aminopolycarboxylic acids are particularly preferred, especially e.g. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids.
  • Persulfates and peroxides e.g. Hydrogen peroxide.
  • 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.
  • the optimal amount of gold / sulfur was used for the chemical ripening.
  • the complementary colored couplers dissolved in a coupler solvent, were added to the emulsions and poured onto a transparent layer support made of cellulose triacetate.
  • a tabular emulsion (88 mol% AgBr, 12 mol% AgI) with an average grain size of 1.2 ⁇ m and an aspect ratio of 6: 1 was used. 73% of the projection area takes up hexagonal plates with a neighboring edge ratio between 1: 1 and 2: 1; the coefficient of variation is 25%.
  • a core-shell emulsion was used; (91 mol% AgBr, 9 mol% AgI) mean grain diameter 1.0 ⁇ m, core and shell AgBr, in between a layer of AgBrI with 40 mol% AgI.
  • a tabular emulsion (88 mol% AgBr, 12 mol% AgI) was used, average grain diameter 1.2 ⁇ m, aspect ratio 6: 1. 73% of the projection area takes up hexagonal plates with a neighboring edge ratio between 1: 1 and 2: 1; the coefficient of variation is 25%.
  • a core-shell emulsion (91 mol% AgBr, 9 mol% AgI) with an average grain diameter of 1.0 ⁇ m was used, core and shell AgBr, in between a layer of AgBrI with 40 mol% AgI.
  • a tabular emulsion (88 mol% AgBr, 12 mol% AgI) with an average grain size of 1.2 ⁇ m and an aspect ratio of 6: 1 was used; 73% of the projection area takes up hexagonal plates with a neighboring edge ratio between 1: 1 and 2: 1; the coefficient of variation is 25%.
  • a core-shell emulsion (91 mol% AgBr, 9 mol% AgI) with an average grain size of 1.0 ⁇ m was used, core and shell AgBr, in between a layer of AgBrI with 40 mol% AgI.
  • a tabular emulsion (88 mol% AgBr, 12 mol% AgI) was used, average grain size 1.2 ⁇ m, aspect ratio 6: 1; 73% of the projection area takes up hexagonal plates with a neighboring edge ratio between 1: 1 and 2: 1; the coefficient of variation is 25%.
  • Sensitizers 1 to 6 sensitize for the red area, sensitizers 7 to 9 for the green area.
  • a color photographic recording material for color negative color development was prepared by applying the following layers in the order given to a transparent cellulose triacetate support. 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 / g of AgNO 3 .
  • the fourth layer contained 2.2 g of a spectrally red-sensitized Ag (Br, I) emulsion with 12 mol% iodide, average grain diameter 1.0 ⁇ m.
  • the 7th layer contained 1.25 g of AgNO 3 of the spectrally green-sensitized Ag (Br, I) emulsion according to Example 2, which was ripened in the presence of the compound K 52.
  • the 7th layer was changed according to Example 9.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (6)

  1. Matériau photographique couleur à l'halogénure d'argent à développement négatif qui contient sur un support transparent au moins deux couches d'émulsion d'halogénure d'argent sensibles au bleu, à couplage jaune, au moins deux couches d'émulsion d'halogénure d'argent sensibles au vert, à couplage pourpre, au moins deux couches d'émulsion d'halogénure d'argent sensibles au rouge, à couplage bleu-vert et une couche filtrante jaune,
    les couches de même sensibilité spectrale présentant des sensibilités photographiques différentes,
    les couches sensibles au bleu étant disposées à plus grande distance du support que la couche filtrante jaune et les couches sensibles au vert et au rouge étant situées à plus faible distance du support que la couche filtrante jaune,
    caractérisé en ce qu'au moins l'une des couches sensibles au vert à plus haute sensibilité et des couches sensibles au rouge à plus haute sensibilité contient en une quantité efficace un composé qui correspond à l'une des formules (I), (II) ou (III)
    Figure imgb0094
    Figure imgb0095
    Figure imgb0096
    où
    les symboles X1   représentent indépendamment les uns des autres un élément du cinquième ou sixième groupe principal du système périodique des éléments,
    les symboles L1   représentent indépendamment les uns des autres un reste hydrocarboné non substitué ou substitué ayant au moins deux atomes de carbone dans la chaîne principale, la chaîne principale étant la succession d'atomes entre deux atomes X1 voisins ou entre un atome X1 et un atome de tête de pont L2 voisin du précédent,
    les symboles L2   représentent indépendamment les uns des autres un atome de tête de pont et
    n   représente un nombre de 1 à 10,
    et les couches à plus haute sensibilité citées contiennent des émulsions de bromoiodure d'argent dont la proportion d'iodure est de 1 à 15 mol %.
  2. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, caractérisé en ce que
    les symboles X1   représentent l'oxygène
    les symboles L1   représentent un reste hydrocarboné ayant 2 à 4 atomes de carbone dans la chaîne principale, qui peut être substitué,
    les symboles L2   représentent l'azote.
  3. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, caractérisé en ce que les composés des formules I, II et III correspondent aux formules IV, V et VI :
    Figure imgb0097
    Figure imgb0098
    Figure imgb0099
     où
    les symboles X2   représentent indépendamment les uns des autres l'azote ou l'oxygène et
    les symboles n2 et n3   représentent indépendamment les uns des autres un nombre de 1 à 10 et chaque angle représente un groupe -CH2- ou - CH-, 2 groupes -CH- voisins pouvant faire partie d'un cycle benzénique condensé.
  4. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, caractérisé en ce que les composés des formules (I), (II) ou (III) sont ajoutés à l'émulsion d'halogénure d'argent de la couche sensible au vert à plus haute sensibilité ou de la couche sensible au rouge à plus haute sensibilité avant la maturation chimique.
  5. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1, caractérisé en ce qu'au moins une couche qui contient l'un des composés des formules (I), (II) ou (III) contient des cristaux d'halogénure d'argent en forme de plaquettes dont le rapport moyen du diamètre à l'épaisseur est d'au moins 5:1.
  6. Matériau photographique couleur à l'halogénure d'argent selon la revendication 5, caractérisé en ce que les cristaux d'halogénure d'argent hexagonaux en forme de plaquettes ayant un indice de forme d'au moins 5 représentent au moins 50 % de la surface de projection.
EP95114105A 1994-09-21 1995-09-08 Matériau photographique couleur à l'halogénure d'argent Expired - Lifetime EP0703493B1 (fr)

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DE4433637A DE4433637A1 (de) 1994-09-21 1994-09-21 Farbfotografisches Silberhalogenidmaterial
DE4433637 1994-09-21

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EP0703493B1 true EP0703493B1 (fr) 1997-08-20

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JP3736180B2 (ja) * 1999-03-01 2006-01-18 コニカミノルタホールディングス株式会社 熱現像感光材料、画像記録方法及び画像形成方法
JP3736204B2 (ja) * 1999-06-03 2006-01-18 コニカミノルタホールディングス株式会社 熱現像ハロゲン化銀写真感光材料、画像記録方法及び画像形成方法
US20050274274A1 (en) * 2004-06-14 2005-12-15 Gore Makarand P Methods and compositions for dying a substrate

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DE4433637A1 (de) 1996-03-28
US5571664A (en) 1996-11-05
EP0703493A1 (fr) 1996-03-27
JPH0895189A (ja) 1996-04-12

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