EP0320776B1 - Matériau photographique couleur à l'halogénure d'argent - Google Patents

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

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EP0320776B1
EP0320776B1 EP88120447A EP88120447A EP0320776B1 EP 0320776 B1 EP0320776 B1 EP 0320776B1 EP 88120447 A EP88120447 A EP 88120447A EP 88120447 A EP88120447 A EP 88120447A EP 0320776 B1 EP0320776 B1 EP 0320776B1
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Prior art keywords
alkyl
aryl
silver halide
couplers
group
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EP88120447A
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German (de)
English (en)
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EP0320776A3 (en
EP0320776A2 (fr
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Erich Dr. Wolff
Dieter Lowski
Harry Elias
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/39236—Organic compounds with a function having at least two elements among nitrogen, sulfur or oxygen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3003—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
    • G03C7/301—Combinations of couplers having the coupling site in pyrazoloazole rings 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
    • G03C7/388—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

Definitions

  • the invention relates to a color photographic silver halide material with high sensitivity and high color density, which has good spectral absorption properties, particularly in the purple range.
  • EP-A-145 342 which contains a number of further references, proposes to disperse pyrazolotriazole magenta couplers of a certain structure in certain phenolic compounds (so-called oil formers) and thus into them Silver halide emulsion to incorporate.
  • the alkyl radicals R1 and R2 have in particular 1 to 16 carbon atoms, e.g. Methyl, ethyl, butyl, dodecyl, iso-propyl, tert-butyl, iso-amyl, and can be substituted by halogen atoms, C1-C4 alkylsulfonyl groups or phenoxy groups, e.g. CF3, C3F7, CH3-SO2-CH2-CH2-CH2-.
  • the aryl radicals R1 and R2 are in particular optionally substituted by C1-C4-alkyl, halogen, C1-C4-alkoxi, C1-C4-alkylcarbonylamino, C1-C4-alkylsulfonylamino, C1-C4-alkylsulfonyl, C1-C4-alkoxycarbonyl, phenyl or naphthyl radicals .
  • R1 or R2 is a ballast group.
  • the leaving group Z is preferably halogen, for example chlorine, bromine, iodine or fluorine, an aryloxy group, for example phenoxy, p-methoxyphenoxy, p-butanesulfonamidophenoxy or p-tert.-butylcarboamidophenoxy, an arylthio group, for example phenylthio or a heterocyclic thio group, e.g. 1-ethyltetrazole-5-thiolyl.
  • Z is preferably a halogen atom, in particular chlorine.
  • Such residues are to be regarded as ballast residues, which make it possible to incorporate the compounds according to the invention in a diffusion-resistant manner in the hydrophilic colloids usually used in photographic materials.
  • Organic radicals which generally contain straight-chain or branched aliphatic groups and optionally also isocyclic or heterocyclic aromatic groups with generally 8-20 C atoms are preferably suitable for this purpose. With the rest of the molecule, these radicals are either directly or indirectly, for example connected via one of the following groups: -NHCO-, -NHSO2-, -NR-, where R is hydrogen or alkyl, -O- or -S-.
  • the diffusion-proofing residue can also contain water-solubilizing groups, such as sulfo groups or carboxyl groups, which can also be in anionic form. Since the diffusion properties depend on the molecular size of the total compound used, it is sufficient in certain cases, for example if the total molecule used is large enough, to use shorter-chain residues as ballast residues.
  • L is preferably a number 0 to 3
  • p is a number 1 to 3
  • q is 1 or 2.
  • Alkyl R3, R5, R7, R8, R9, R10 and R11 is especially C1-C6 alkyl; Alkoxy R3 is especially C1-C4 alkoxy; Aryl R3, R5, R7 and R8 is in particular phenyl and phenyl substituted by C1-C4-alkyl, C1-C4-alkoxy or halogen.
  • Optionally substituted amino R3 is especially amino, C1-C16-alkylamino, di-C1-C12-alkylamino, -NHCO-R8, NHCO-heterocycle, -NH-CO-NHR8 and -NHSO2-R8, where R8 is the above and heterocycle has the following meaning.
  • Suitable heterocycle residues are in particular pyridyl and morpholinyl.
  • Typical examples of pyrazolotriazole magenta couplers according to the invention are listed below.
  • the production of the purple couplers is known for example from EP-A-145 342.
  • the phenolic compounds of the formula (III) are prepared by known methods. A typical method is described in the examples.
  • the silver halide 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 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.
  • 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 is preferably precipitated in the presence of the binder, for example 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, for example, 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, the so-called pAg-controlled method is preferably 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 through 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 can 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 silver halides can be, for example, silver bromide, silver bromide iodide with iodide contents from 0.1 to 40 mol%, silver chloride, silver chloride bromide with bromide contents from 1 to 80 mol% and silver bromide iodide chloride with a predominant proportion of bromide.
  • 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 generally modified natural products.
  • Cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose as well as 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.
  • the preparation of such gelatins is published, for example, in The Science and Technology of Gelatine AG 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 gelatin can be partially or completely oxidized.
  • 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 e.g. B. von 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, (subst.) Benzotriazoles or benzothiazolium salts can also be used as antifoggants.
  • mercaptobenzthiazoles can also 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 silver halide emulsions are usually chemically ripened, for example by the action of gold compounds or compounds of divalent sulfur.
  • 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.).
  • the photographic emulsions can be spectral using methine dyes or other dyes be sensitized.
  • 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 bromide.
  • Color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive emulsion layer. These 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. Usually, cyan couplers are assigned to the red-sensitive layers, purple couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers, purple couplers of the formula (I) or (II) being used according to the invention exclusively or as a mixture with other purple couplers described below.
  • Color couplers for producing the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type; suitable examples of this are known in the literature.
  • Color couplers for producing the yellow partial color field are usually couplers with an open-chain ketomethylene grouping, in particular couplers of the type ⁇ -acylacetamids; Suitable examples of this are ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetanilide couplers, which are also known from the literature.
  • Color couplers for producing the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type; Suitable examples of this are described in large numbers in the literature.
  • 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 site which is split off during the coupling.
  • the 2-equivalent couplers include those that are colorless. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.
  • DIR, DAR or FAR couplers Since with DIR, DAR or FAR couplers the effectiveness of the residue released during coupling is mainly desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, which give essentially colorless products on coupling (DE-A-1 547 640).
  • 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).
  • 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 incorporation of the couplers or other compounds in silver halide emulsion layers can be done in this way take place that a solution, a dispersion or an emulsion is first prepared from the compound in question and then added 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-0 043 037.
  • 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.
  • couplers of the formula (I) or (II) according to the invention using compounds of the formula (III) are introduced into a casting solution and thus into an emulsion layer.
  • anionic water-soluble compounds e.g. dyes
  • pickling polymers e.g. acrylic acid
  • Suitable oil formers for other couplers and other compounds are e.g. Alkyl phthalates, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters and trimesic acid esters.
  • Color photographic material typically comprises at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on a support.
  • the order of these layers can be varied as desired. Couplers which form blue-green, purple and yellow dyes are usually incorporated into the red, green or blue-sensitive emulsion layers. However, different combinations can also be used.
  • Each of the 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 in turn are closer than blue-sensitive layers, with generally green-sensitive ones Layers and blue-sensitive layers there is a non-light-sensitive yellow filter layer.
  • the green or Red-sensitive layers can be chosen 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.
  • 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 from the support than the sublayer with lower sensitivity.
  • Partial layers of the same spectral sensitization can be adjacent to one another or separated by other layers, for example by layers of different 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 may further contain UV light absorbing compounds, whites, spacers, filter dyes, formalin scavengers and others.
  • Compounds that absorb UV light are intended on the one hand to protect the image dyes from fading by UV-rich daylight and, on the other hand, as filter dyes to absorb the UV light in daylight upon exposure and thus improve the color rendering of a film.
  • Connections of different structures are usually used for the two tasks. Examples are aryl-substituted benzotriazole compounds (US Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat. Nos. 3,314,794 and 3,352,681), benzophenone compounds (JP-A 2784/71), cinnamic acid ester compounds (US Pat. Nos. 3,705,805 and 3,707) 375), butadiene compounds (US-A 4 045 229) or benzoxazole compounds (US-A 3 700 455).
  • Ultraviolet absorbing couplers such as ⁇ -naphthol type cyan couplers
  • ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.
  • Filter dyes suitable for visible light include oxonol dyes, hemioxonol dyes, styrene dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.
  • Suitable white toners are e.g. in Research Disclosure December 1978, page 22 ff, Unit 17 643, Chapter V.
  • binder layers in particular the most distant layer from the support, but also occasionally intermediate layers, especially if they are the most distant layer from the support during manufacture, may contain photographically inert particles of inorganic or organic nature, e.g. as a matting agent or as a spacer (DE-A 3 331 542, DE-A 3 424 893, Research Disclosure December 1978, page 22 ff, Unit 17 643, Chapter XVI).
  • photographically inert particles of inorganic or organic nature e.g. as a matting agent or as a spacer (DE-A 3 331 542, DE-A 3 424 893, Research Disclosure December 1978, page 22 ff, Unit 17 643, 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.
  • binders of the material according to the invention are hardened with suitable hardnesses, for example with hardeners of the epoxy type, the ethyleneimine type, the acryloyl type or the vinylsulfone type. Diazine, triazine or 1,2-dihydroquinoline series hardeners are also suitable.
  • the binders of the material according to the invention are preferably hardened with instant hardeners.
  • 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.
  • the materials according to the invention are processed in the usual manner according to the processes recommended for this.
  • Salicylic acid isoamyl ester 4-sulfochloride were found in 650 ml m-xylene heated to 30 ° C and in portions with 97 g Iron (III) chloride added. The temperature was kept between 30 and 40 ° C.
  • the emulsifier was 6 min. stirred at 1000 U / min, where it heated to about 50 ° C and EA was suctioned off in a water jet vacuum (200-300 mbar).
  • the quality of the fresh coupler emulgate is assessed as follows using a phase contrast or polarization microscope:
  • Emulgate prepared according to Example 1 were mixed with a silver bromide iodide emulsion (0.7 mol% iodide) in a ratio of 1 mol coupler: 5.2 mol AgNO3, applied to a layer of cellulose acetate and with a protective layer of a 3 wt .-% Layered gelatin solution containing a carbamoylpyridinium betaine (CAS. Reg. No. 65411-60-1) as hardening agent. After drying and slicing, the samples thus produced were exposed behind a step wedge and processed in the negative AP 70 process (38 ° C.). bath min Color developer (CD 70) 3.25 Bleach bath 6.5 Watering 3.0 Fixer 6.5 splashdown 6.0
  • Table 2 shows that the combination according to the invention, in comparison to the couplers or oil formers of the prior art, is distinguished by high sensitivity, steep gradation and high color yield with comparable fresh fog values.
  • Example 2 Individual layers produced according to Example 2 of the couplers and oil formers listed in Table 3 were exposed to a formalin concentration of 10 ppm at 70% rel. Before exposure and processing according to Example 2 for 0, 3, 7, 14 and 21 days. Exposed to humidity.

Claims (5)

  1. Matériau d'halogénure d'argent pour photographie en couleurs, qui contient, dans au moins une couche d'émulsion à l'halogénure d'argent, un copulant magenta répondant aux formules (I) ou (II)
    Figure imgb0044
     dans lesquelles
    R₁   représente un groupe alkyle, un groupe aryle ou un radical de ballast,
    R₂   représente un radical de ballast, un groupe alkyle ou un groupe aryle,
    Z   représente un atome d'hydrogène ou un groupe qui peut se libérer lors de la réaction avec le produit d'oxydation du révélateur,
    ainsi qu'un composé de formule (III)
    Figure imgb0045
     dans laquelle
    R₃   représente un groupe alkyle, un groupe alcoxy, un groupe aryle, un groupe amino éventuellement substitué ou encore le radical d'un composé hétérocyclique,
    R₄   représente COR₅, NHR₆, S(O)nR₇
    R₅   représente OR₈, NHR₈, un groupe alkyle, un groupe aryle ou un composé hétérocyclique,
    R₆   représente SO₂R₈, COR₈ ou CONHR₈
    R₇   représente un groupe alkyle, un groupe aryle ou NHR₈
    R₈   représente un groupe alkyle ou un groupe aryle et
    n   représente 0, 1 ou 2,
    à l'exception des composés dans lesquels R₃ représente un radical carboxyméthoxyphényle, un radical carboxyméthoxy, un radical alcoxycarbonylméthoxy ou un radical alcoxycarbonylméthoxyphényle substitué sur le groupe méthylène.
  2. Matériau d'halogénure d'argent pour photographie en couleurs selon la revendication 1, dans lequel Z représente un atome d'halogène, un groupe aryloxy, un groupe arylthio ou un groupe thio hétérocyclique.
  3. Matériau d'halogénure d'argent pour photographie en couleurs selon la revendication 1, dans lequel le copulant magenta répond à la formule (IV)
    Figure imgb0046
     dans laquelle
    Z'   représente un groupe qui se sépare par la mise en réaction avec le produit d'oxydation du révélateur,
    R₉ et R₁₀   représentent un atome d'hydrogène ou un groupe alkyle,
    R₁₁   représente un groupe alkyle, un atome d'halogène ou un groupe hydroxyle,
    l, p et q   représentent un nombre de 0 à 4 et
    r   représente 0 ou 1.
  4. Matériau d'halogénure d'argent pour photographie en couleurs selon la revendication 3, dans lequel
    l   représente un nombre de 0 à 3,
    p   représente un nombre de 1 à 3 et
    q   représente 1 ou 2.
  5. Matériau d'halogénure d'argent pour photographie en couleurs selon la revendication 1, dans lequel le phénol répond à la formule
    Figure imgb0047
     et R₃ et R₄ ont la signification indiquée.
EP88120447A 1987-12-18 1988-12-07 Matériau photographique couleur à l'halogénure d'argent Expired - Lifetime EP0320776B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873743006 DE3743006A1 (de) 1987-12-18 1987-12-18 Farbfotografisches silberhalogenidmaterial
DE3743006 1987-12-18

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EP0320776A2 EP0320776A2 (fr) 1989-06-21
EP0320776A3 EP0320776A3 (en) 1990-05-16
EP0320776B1 true EP0320776B1 (fr) 1993-03-31

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Application Number Title Priority Date Filing Date
EP88120447A Expired - Lifetime EP0320776B1 (fr) 1987-12-18 1988-12-07 Matériau photographique couleur à l'halogénure d'argent

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US (1) US4898811A (fr)
EP (1) EP0320776B1 (fr)
JP (1) JPH021843A (fr)
DE (2) DE3743006A1 (fr)

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EP0361427B1 (fr) * 1988-09-27 1994-06-08 Fuji Photo Film Co., Ltd. Matériau photographique couleur
US4948722A (en) * 1988-10-31 1990-08-14 Eastman Kodak Company Photographic material and process comprising a pyrazoloazole dye-forming coupler
DE3918547A1 (de) * 1989-06-07 1990-12-13 Agfa Gevaert Ag Farbfotografisches silberhalogenidmaterial
JP2670859B2 (ja) * 1989-06-30 1997-10-29 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およびカラー画像形成法
US5089380A (en) * 1989-10-02 1992-02-18 Eastman Kodak Company Methods of preparation of precipitated coupler dispersions with increased photographic activity
US4970139A (en) * 1989-10-02 1990-11-13 Eastman Kodak Company Methods of preparation of precipitated coupler dispersions with increased photographic activity
JPH03126031A (ja) * 1989-10-12 1991-05-29 Konica Corp ハロゲン化銀カラー写真感光材料
GB9010966D0 (en) * 1990-05-16 1990-07-04 Kodak Ltd Photographic material comprising a magenta dye image forming coupler combination
US5164288A (en) * 1990-05-29 1992-11-17 Eastman Kodak Company Photographic element containing pyrazoloazole coupler and oxidized developer competitor
JP2687257B2 (ja) * 1990-06-01 1997-12-08 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
DE4038965A1 (de) * 1990-12-06 1992-06-11 Agfa Gevaert Ag Farbfotografisches aufzeichnungsmaterial mit einem farbkuppler vom pyrazoloazol-typ
US5232821A (en) * 1991-04-01 1993-08-03 Eastman Kodak Company Photographic coupler compositions containing ballasted sulfoxides and sulfones and methods
JP3089579B2 (ja) * 1993-01-11 2000-09-18 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及びカラー画像形成方法
JPH06230534A (ja) * 1993-02-05 1994-08-19 Konica Corp ハロゲン化銀カラー写真感光材料
GB9828867D0 (en) 1998-12-31 1999-02-17 Eastman Kodak Co Photographic addenda

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JPS60108847A (ja) * 1983-11-18 1985-06-14 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料
JPH0656483B2 (ja) * 1986-01-29 1994-07-27 富士写真フイルム株式会社 カラ−画像形成法

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Title
RESEARCH DISCLOSURE, Nr. 245, September 1984, S. 442-454, Havant, Hampshire, GB, Abschnitt Nr. 24531: "Image-forming process" *

Also Published As

Publication number Publication date
US4898811A (en) 1990-02-06
EP0320776A3 (en) 1990-05-16
EP0320776A2 (fr) 1989-06-21
DE3879901D1 (de) 1993-05-06
DE3743006A1 (de) 1989-06-29
JPH021843A (ja) 1990-01-08

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