EP0317825B1 - Matériau de reproduction photographique couleur - Google Patents

Matériau de reproduction photographique couleur Download PDF

Info

Publication number
EP0317825B1
EP0317825B1 EP88118632A EP88118632A EP0317825B1 EP 0317825 B1 EP0317825 B1 EP 0317825B1 EP 88118632 A EP88118632 A EP 88118632A EP 88118632 A EP88118632 A EP 88118632A EP 0317825 B1 EP0317825 B1 EP 0317825B1
Authority
EP
European Patent Office
Prior art keywords
alkyl
denotes
mol
aryl
recording material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP88118632A
Other languages
German (de)
English (en)
Other versions
EP0317825A3 (en
EP0317825A2 (fr
Inventor
Walter Dr. Pätzold
Armin Dr. Voigt
Helmut Dr. Mäder
Sieghart Dipl.-Ing. Klötzer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert AG
Original Assignee
Agfa Gevaert AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Publication of EP0317825A2 publication Critical patent/EP0317825A2/fr
Publication of EP0317825A3 publication Critical patent/EP0317825A3/de
Application granted granted Critical
Publication of EP0317825B1 publication Critical patent/EP0317825B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • 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
    • G03C1/127—Methine and polymethine dyes the polymethine chain forming part of a carbocyclic ring

Definitions

  • the invention relates to a color photographic recording material which contains at least one blue-sensitive, at least one green-sensitive and at least one red-sensitive silver halide emulsion layer on a reflective layer support and optionally further non-light-sensitive binder layers, the binder of which is hardened with an instant hardener.
  • the hardeners generally react with free amino, imino or hydroxyl groups of the proteinaceous binder with crosslinking thereof.
  • slow-reacting hardeners are disadvantageous in that, for example, important parameters of the cast layers in photographic recording materials remain over a longer period of time change.
  • sensitometric data such as sensitivity, gradation and maximum density can change slowly, and the final properties of the layer or layer structure are often only achieved after a considerable period of storage. This necessitates increased testing effort during production.
  • fast-acting curing agents because with them the final properties are achieved within a short time after the casting, so that the required storage or waiting times can be shortened and the test effort can be reduced.
  • Very useful fast-acting curing agents hereinafter also called instant hardeners, are described in DE-A-22 25 230, DE-A-23 17 677 and DE-A-24 39 551.
  • Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed immediately after casting or at the latest after 24 hours, preferably after 8 hours, to the extent that no further change in the sensitometry caused by the crosslinking reaction and the swelling of the layer structure occurs.
  • Swelling is understood to mean the difference between the wet layer thickness and the dry layer thickness during the aqueous processing of the film (Photogr. Sci. Eng. 8 (1964), 275; Photogr. Sci. Eng. 16 (1972), 449).
  • hardening agents which react very quickly with gelatin are, for example, carbamoylpyridinium salts which presumably are able to react with free carboxyl groups of the proteinaceous binder, so that the latter can react with free amino groups to form peptide bonds and crosslink the binder.
  • carbamoylpyridinium salts which presumably are able to react with free carboxyl groups of the proteinaceous binder, so that the latter can react with free amino groups to form peptide bonds and crosslink the binder.
  • the instant hardeners mentioned may generally only be added to casting solutions containing gelatin shortly before the casting, since otherwise the casting properties, in particular the viscosity of the casting solutions, would be changed quickly and sustainably by premature reaction.
  • the immediate hardener is added to the top layer (protective layer). By diffusion, it reaches the other gelatin-containing layers to be hardened and crosslinks the gelatin so quickly that the hardening is almost complete immediately after drying and the parameters characteristic of the physical and photographic properties have reached their final values
  • red-sensitive silver halide emulsion layers of which are sensitized with the usual sulfo-containing sensitizers have a decrease in sensitivity if moisture acts on these materials before exposure (moisture defects).
  • the invention was based on the object of providing a color photographic recording material which is produced using instant hardeners but does not show any moisture defects.
  • red-sensitive Layers sensitized with at least one special sensitizer and at least one special potentizer.
  • the sensitizer I is preferably used in an amount of 0.05 to 0.25, in particular 0.075 to 0.20 mmol / mol Ag, the potentizer II in an amount of 0.45 to 3.00, in particular 0.70 to 1 , 40 mmol / mol Ag used.
  • the instant hardener is preferably used in an amount of 0.1 to 5 mmol / m2, preferably 0.5 to 1.7 mmol / m2.
  • alkyl is in particular C1-C2 Hydrox-alkyl optionally substituted by halogen, hydroxy, sulfo, C1-C20-alkoxy.
  • Aryl unless otherwise defined, is in particular optionally substituted by halogen, sulfo, C1-C20-alkoxy or C1-C20-alkyl C6-C14-aryl.
  • Aralkyl unless otherwise defined, is in particular C Halogen-C20-aralkyl substituted by halogen, C1-C20-alkoxy, sulfo or C1-C20-alkyl.
  • Alkoxy unless otherwise defined, is in particular C1-C20 alkoxy.
  • X ⁇ is preferably a halide ion such as Cl ⁇ , Br ⁇ or BF4 ⁇ , NO3 ⁇ , (SO42 ⁇ ) 1/2 , ClO4 ⁇ , CH3OSO3 ⁇ , PF6 ⁇ , CF3SO3 ⁇ and in particular a -SO3 ⁇ - covalently linked to the hardener molecule Group, where the -SO3 ⁇ group can be directly connected to the heterocycle via a substituent (see definitions alkyl, aryl, aralkyl) or in the formulas (a), (b), (c).
  • a substituent see definitions alkyl, aryl, aralkyl
  • Alkenyl is especially C2-C20 alkenyl.
  • Alkylene is especially C2-C20 alkylene; Arylene especially phenylene, aralkylene especially benzylene and alkaralkylene especially xylylene.
  • Suitable N-containing ring systems that can represent Z are shown on the previous page.
  • the pyridine ring is preferred.
  • R36 and R37 together with the nitrogen atom to which they are bonded, in particular form a pyrrolidine or piperidine ring substituted by 2 oxo groups bonded in the o- and o'-position, and the benzo, cyclohexeno- or [2.1.1] -bicyclohexeno-condensed can.
  • Acyl is especially C1-C10 alkylcarbonyl or benzoyl; Carbalkoxy is especially C1-C10 alkoxycarbonyl; Carbamoyl is especially mono- or di-C1-C4 alkylaminocarbonyl; Carbaroxy is especially phenoxycarbonyl.
  • Groups R24 which can be split off by nucleophilic agents are, for example, halogen atoms, C1-C15 alkylsulfonyloxy groups, C7-C15 aralkylsulfonyloxy groups, C6-C15 arylsulfonyloxy groups and 1-pyridinyl radicals.
  • the compounds can be prepared in a simple manner known from the literature.
  • the secondary amines are e.g. with phosgene the carbamic acid chlorides, which are then reacted with aromatic, heterocyclic nitrogen-containing compounds in the dark.
  • the preparation of compound 3 is described in Chemical Reports 40, (1907), page 1831. Further information on the synthesis can be found in DE-OS 2 225 230, DE-OS 2 317 677 and DE-OS 2 439 551.
  • JP-OSs 44 140/82 and 46 538/82 and JP-PS 50 669/83 Methods for the synthesis of these compounds are described in more detail in JP-OSs 44 140/82 and 46 538/82 and JP-PS 50 669/83.
  • the binder to be cured used in the layers which are subjected to the curing process according to the invention is a porten-like binder which contains free amino groups and free carboxyl groups.
  • Gelatin is a preferred example. Gelatin is mainly used in photographic recording materials as a binder for the light-sensitive substances, the coloring compounds and, if appropriate, other additives. Such recording materials often have a large number of different layers.
  • the hardening by means of an instant hardener is usually carried out in such a way that the hardening agent is applied in excess as the last layer on the layers to be hardened is, wherein the hardening coating solution further substances such as UV absorbers, antistatic agents, matting agents and polymeric organic particles can be added.
  • the layer containing the hardening agent can be applied simultaneously with or after the casting of the remaining layers by means of cascade or curtain coaters.
  • the casting temperature can be varied over a wide range, e.g. B. between 45 and 5 ° C, preferably between 38 and 18 ° C.
  • the layer thickness of the hardening casting is, for example, between 0.2 and 2.5 ⁇ m.
  • Other additives such as UV absorbers, color correction dyes, antistatic agents and inorganic or organic solid particles, which are used, for example, as matting agents or spacers, can be added to the hardener-containing layer.
  • Suitable UV absorbers are described, for example, in US Pat. No. 3,253,921, DE-C-20 36 719 and EP-A-0 057 160.
  • suitable inorganic solid particles are silicon dioxide, magnesium dioxide, titanium dioxide and calcium carbonate. Such materials are widely used to matt the outermost layers of photographic recording materials and thus reduce their stickiness.
  • solid particles Organic in nature which can be alkali-soluble or alkali-insoluble, are suitable for this purpose. Such particles, also referred to as spacers, generally roughen the surface, so that the surface properties, in particular the adhesive or sliding properties, can be modified thereby.
  • Polymethyl methacrylate is an example of alkali-insoluble spacers. Alkali-soluble spacers are described, for example, in DE-A-34 24 893.
  • Particulate organic polymers with reactive groups in particular those reactive groups which react with the binder, as described, for example, in DE-A-35 44 212, can also be added as so-called hardeners.
  • the hardener-containing partial layer which contains comparatively little or no binding agent
  • its thickening agent such as polystyrene sulfonic acid or hydroxyethyl cellulose.
  • the color photographic recording materials according to the present invention are multilayer materials which have a plurality of silver halide emulsion layers or emulsion layer units with different spectral sensitivity.
  • the emulsion layer unit is understood to mean layer packages of 2 or more silver halide emulsion layers of the same spectral sensitivity. Layers of the same However, spectral sensitivity does not necessarily have to be arranged adjacent to one another, but can also be separated from one another by other layers, in particular also by layers of different spectral sensitivity.
  • the binder in these layers is usually a protein-like binder with free carboxyl groups and free amino groups, preferably gelatin.
  • the layered binder can contain up to 50% by weight of non-proteinaceous binders such as polyvinyl alcohol, N-vinylpyrrolidone, polyacrylic acid and their derivatives, in particular copolymers, or cellulose derivatives and gelatin derivatives.
  • non-proteinaceous binders such as polyvinyl alcohol, N-vinylpyrrolidone, polyacrylic acid and their derivatives, in particular copolymers, or cellulose derivatives and gelatin derivatives.
  • each of the light-sensitive silver halide emulsion layers or emulsion layer units mentioned is assigned at least one color-imparting compound, usually a color coupler, which can react with color developer oxidation products to form a non-diffusing dye.
  • the color couplers are expediently non-diffusing and accommodated in the light-sensitive layer itself or in close proximity to it.
  • the color couplers assigned to the two or more partial layers of an emulsion layer unit do not necessarily have to be identical. They are only intended to give the same color in color development, usually a color that is complementary to the color of the light to which the photosensitive silver halide emulsion layers are sensitive.
  • the red-sensitive silver halide emulsion layers are assigned at least one non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the phenol or ⁇ -naphthol type.
  • a coupler of the phenol or ⁇ -naphthol type is particularly noteworthy.
  • cyan couplers as described in US-A-2,474,293, US-A-2,367,531, US-A-2,895,826, US-A-3,772,002, EP-A-0 028 099 , EP-A-0 112 514.
  • the green-sensitive silver halide emulsion layers are generally assigned at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone or indazolone type usually being used. Cyanoacetyl compounds, oxazolones and pyrazoloazoles are also suitable as magenta couplers. Particularly noteworthy are, for example, purple couplers, as described in US Pat. Nos. 2,600,788, 4,383,027, 1,547,803, 1,810,464, 24,066,665, DE -A-32 26 163 are described.
  • the blue-sensitive silver halide emulsion layers are normally assigned at least one non-diffusing color coupler to produce the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping.
  • a color coupler with an open-chain ketomethylene grouping are particularly noteworthy.
  • yellow couplers as described in US Pat. No. 3,408,194, US Pat. No. 3,933,501, DE-A-23 29 587, DE-A-24 56 976.
  • Color couplers of these types are known in large numbers and are described in a large number of patents. Examples include the publications “Color Coupler” by W. Pelz, "Messages from the research laboratories of Agfa, Leverkusen / Kunststoff", Volume III (1961) p. 111, and by K. Venkataraman in “The Chemistry of Synthetic Dyes” , Vol. 4., 341 to 387, Academic Press (1971).
  • 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 both those that are practically colorless and 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).
  • the known white couplers are also to be counted among the 2-equivalent couplers, but they essentially result in colorless products on reaction with color developer oxidation 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 develops certain desired photographic effectiveness, for example as a development inhibitor or accelerator.
  • Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR and FAR couplers.
  • Suitable DIR couplers are described, for example, in GB-A-953 454, DE-A-1 800 420, DE-A-20 15 867, DE-A-24 14 006, DE-A-28 42 063, DE-A- 34 27 235.
  • Suitable DAR or FAR couplers are described, for example, in DE-A-32 09 110, EP-A-0 089 834, EP-A-0 117 511, EP-A-0 118 087.
  • 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, the products which are essentially colorless upon coupling, as described, for example, in DE-A-1 547 640.
  • the cleavable residue can also be a ballast residue, so that when reacting with color developer oxidation products coupling products e.g. Dyes can be obtained which are diffusible or at least have a weak or restricted mobility, as described, for example, in 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-0 027 284, US-A-4 080 211.
  • the high molecular color coupler are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.
  • the layers of the color photographic recording material to be hardened by the process according to the invention may contain further additives, for example antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties.
  • the layers to be hardened can also contain compounds which absorb UV light.
  • 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 silver halide preferably consists of 15 to 100 mol% of chloride, 0 to 85 mol% of bromide and 0 to 2 mol% of iodide.
  • the average particle diameter is preferably 0.2 to 0.6 ⁇ m.
  • the silver halides can be doped with Rh, Ir, Cd or Pb and ripened with sulfur compounds or a combination of sulfur and gold compounds.
  • the silver halide emulsions can also contain at least 80 mol% of chloride, preferably 95 to 100 mol% of chloride, 0 to 5 mol% of bromide and 0 to 1 mol% of iodide.
  • Example 1 corresponded to Example 1 with the difference that a silver chloride emulsion (100 mol% chloride) was used in the 3rd layer.
  • the emulsion was prepared by double inlet with a grain size of 0.40 ⁇ m, flocculated in the usual way, washed and redispersed with gelatin.
  • the weight ratio gelatin-silver (as AgNO3) was 0.5.
  • the emulsion was then ripened with 20 ⁇ mol thiosulfate, 1.5 ⁇ mol HAuCl4 and 15 ⁇ mol NH4SCN per mol Ag for optimal sensitivity, sensitized to the blue spectral range and stabilized.
  • the same emulsion was used in the 5th and 7th layers, but sensitized to the green and red spectral range.
  • Example 1 The samples were then exposed through a step wedge.
  • the samples of Example 1 and the comparison to Example 1 were developed in the EP2 process, samples of Example 2 and the comparison to 2 in the RA-4 process.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Materials For Photolithography (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Plural Heterocyclic Compounds (AREA)

Claims (8)

  1. Matériau d'enregistrement pour la photographie en couleurs, qui contient, sur un support de couches réfléchissant, au moins une couche d'émulsion à l'halogénure d'argent sensible au bleu, au moins une couche d'émulsion à l'halogénure d'argent sensible au vert et au moins une couche d'émulsion à l'halogénure d'argent sensible au rouge et éventuellement d'autres couches de liants non photosensibles, dont le liant est durci à l'aide d'un agent procurant un durcissement instantané, la ou les couches sensibles au rouge étant sensibilisées avec au moins un composé de formule I
    Figure imgb0072
     dans laquelle
    R₅₃ et R₅₄   représentent un groupe alkyle,
    R₅₅, R₅₆, R₅₇ et R₅₈   représentent un atome d'hydrogène, un atome d'halogène, un groupe alkyle, un groupe alcoxy, un radical de formule
    Figure imgb0073
     un groupe aryle ou bien R₅₅ et R₅₆ représentent ensemble ou encore R₅₇ et R₅₈ représentent ensemble un groupe méthylènedioxy ou bien les membres restants d'un noyau benzénique condensé,
    R₅₉ et R₆₀   représentent un groupe alkyle,
    R₆₁   représente un atome d'hydrogène ou un groupe méthyle,
    X-   représente un anion et
    n   représente un nombre de 1 à 5,
    le cation ne contenant pas de groupes d'acides sulfoniques liés de manière covalente,
    et au moins un composé mercapto (composé II) de l'oxazine, de l'oxazole, du thiazole, du thiadiazole, de l'imidazole ou du tétrazole, qui peut être substitué par un atome d'halogène, par un groupe d'acide sulfonique, par un groupe sulfonamide, par un groupe carboxyle, par un groupe alkylsulfonique ou par un groupe phényle ou encore par un radical benzénique condensé qui peut, à son tour, être substitué par les groupes mentionnés.
  2. Matériau d'enregistrement pour la photographie en couleurs selon la revendication 1, caractérisé en ce que l'agent procurant un durcissement instantané est mis en oeuvre en une quantité de 0,1 à 5 mmoles/m².
  3. Matériau d'enregistrement pour la photographie en couleurs selon la revendication 1, caractérisé en ce que l'agent procurant un durcissement instantané est mis en oeuvre en une quantité de 0,5 à 1,7 mmole/m².
  4. Matériau d'enregistrement pour la photographie en couleurs selon la revendication 1, caractérisé en ce que l'halogénure d'argent est constitué par 15 à 100 moles % de chlorure, 0 à 85 moles % de bromure et 0 à 2 moles % d'iodure et présente une granulométrie moyenne de 0,2 à 0,6 µm.
  5. Matériau d'enregistrement pour la photographie en couleurs selon la revendication 1, caractérisé en ce que l'agent procurant un durcissement instantané répond à la formule
    Figure imgb0074
     dans laquelle
    R₁   représente un groupe alkyle, un groupe aryle ou un groupe aralkyle,
    R₂   a la même signification que celle donnée pour R₁ ou bien représente un groupe alkylène, un groupe arylène, un groupe aralkylène ou un groupe alkaralkylène, la deuxième liaison étant liée à un groupe de formule
    Figure imgb0075
     ou bien,
    R₁ et R₂   représentent ensemble les atomes requis pour compléter un noyau hétérocyclique éventuellement substitué, par exemple un noyau pipéridine, un noyau pipérazine ou un noyau morpholine, le noyau pouvant être substitué par exemple par un groupe alkyle en C₁-C₃ ou par un atome d'halogène,
    R₃   représente un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcoxy, -NR₄-COR₅, -(CH₂)m-NR₈R₉, -(CH₂)n-CONR₁₃R₁₄ ou
    Figure imgb0076
     ou encore un élément faisant office de pont ou bien une liaison directe à une chaîne polymère,
    R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈ et R₁₉   représentant un atome d'hydrogène ou un groupe alkyle en C₁-C₄
    R₅   représentant un atome d'hydrogène, un groupe alkyle en C₁-C₄ ou NR₆R₇
    R₈   représentant -COR₁₀
    R₁₀   représentant NR₁₁R₁₂
    R₁₁   représentant un groupe alkyle en C₁-C₄ ou un groupe aryle, en particulier un groupe phényle,
    R₁₂   représentant un atome d'hydrogène, un groupe alkyle en C₁-C₄ ou un groupe aryle, en particulier un groupe phényle,
    R₁₃   représentant un atome d'hydrogène, un groupe alkyle en C₁-C₄ ou un groupe aryle, en particulier un groupe phényle,
    R₁₆   représentant un atome d'hydrogène, un groupe alkyle en C₁-C₄, COR₁₈ ou CONHR₁₉
    m   représentant un nombre de 1 à 3,
    n   représentant un nombre de 0 à 3,
    o   représentant le nombre 1 ou 2,
    p   représentant le nombre 2 ou 3 et
    y    représentant O ou NR₁₇ ou bien
    R₁₃ et R₁₄   représentant ensemble les atomes reguis pour compléter un noyau hétérocyclique éventuellement substitué, par exemple un noyau pipéridine, un noyau pipérazine ou un noyau morpholine, le noyau pouvant être substitué par exemple par un groupe alkyle en C₁-C₃ ou par un atome d'halogène,
    Z   représente les atomes de carbone requis pour compléter un noyau hétérocyclique aromatique penta- ou hexagonal, éventuellement avec un noyau benzénique condensé, et
    X-   représente un anion qui peut être lié à la molécule restante à l'intervention d'une liaison covalente;
  6. Matériau d'enregistrement pour la photographie en couleurs selon la revendication 1, caractérisé en ce qu'on met en oeuvre le composé I en une quantité de 0,05 à 0,25 µmole/mole de Ag et le composé II en une quantité de 0,45 à 3,00 µmoles/mole de Ag.
  7. Matériau d'enregistrement pour la photographie en couleurs selon la revendication 1, caractérisé en ce que l'halogénure d'argent est constitué par au moins 80 moles % de chlorure.
  8. Matériau d'enregistrement pour la photographie en couleurs selon la revendication 7, caractérisé en ce que l'halogénure d'argent est constitué par 95 à 100 modes % de chlorure, 0 à 5 modes % de bromure et 0 à 1 mole % d'iodure.
EP88118632A 1987-11-21 1988-11-09 Matériau de reproduction photographique couleur Expired - Lifetime EP0317825B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873739474 DE3739474A1 (de) 1987-11-21 1987-11-21 Farbfotografisches aufzeichnungsmaterial
DE3739474 1987-11-21

Publications (3)

Publication Number Publication Date
EP0317825A2 EP0317825A2 (fr) 1989-05-31
EP0317825A3 EP0317825A3 (en) 1990-05-16
EP0317825B1 true EP0317825B1 (fr) 1993-07-21

Family

ID=6340954

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88118632A Expired - Lifetime EP0317825B1 (fr) 1987-11-21 1988-11-09 Matériau de reproduction photographique couleur

Country Status (3)

Country Link
EP (1) EP0317825B1 (fr)
JP (1) JPH01155334A (fr)
DE (2) DE3739474A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69303356T2 (de) * 1992-12-16 1997-01-23 Eastman Kodak Co Rotsensibilisatoren für silberchloridreiche Emulsionen

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1447577B1 (de) * 1964-03-11 1970-05-14 Agfa Ag Stabilisierte Supersensibilisierung von Halogensilberemulsionen
US4618570A (en) * 1984-03-27 1986-10-21 Konishiroku Photo Industry Co., Ltd. Silver halide photographic materials
DE3606086A1 (de) * 1986-02-26 1987-08-27 Agfa Gevaert Ag Farbfotografisches aufzeichnungsmaterial

Also Published As

Publication number Publication date
JPH01155334A (ja) 1989-06-19
DE3739474A1 (de) 1989-06-01
DE3882492D1 (de) 1993-08-26
EP0317825A3 (en) 1990-05-16
EP0317825A2 (fr) 1989-05-31

Similar Documents

Publication Publication Date Title
EP0257515B1 (fr) Procédé de durcissement de couches contenant un liant de type protéinique
DE3736410A1 (de) Farbfotografisches silberhalogenidmaterial
DE4320444A1 (de) Farbfotografisches Aufzeichnungsmaterial
EP0358071A2 (fr) Matériau de reproduction photographique
DE3586555T2 (de) Lichtempfindliches photographisches silberhalogenidmaterial.
EP0345514B1 (fr) Matériau photographique couleur à l'halogénure d'argent
EP0317825B1 (fr) Matériau de reproduction photographique couleur
DE3626221A1 (de) Farbfotografisches aufzeichnungsmaterial zur herstellung farbiger aufsichtsbilder
EP0286913B1 (fr) Matériau d'enregistrement photographique couleur
DE3836945A1 (de) Fotografisches silberhalogenidmaterial und verfahren zu seiner verarbeitung
DE4318438A1 (de) Fotografisches Aufzeichnungsmaterial
EP0267523B1 (fr) Matériau photographique couleur à l'halogénure d'argent sensible à la lumière
EP0282865A1 (fr) Agents durcisseurs pour protéines, couche liante durcie à l'aide de ces agents et matériau d'enregistrement photographique contenant une telle couche
EP0364807A2 (fr) Matériau de reproduction photographique couleur
EP0363820A2 (fr) Matériau photographique couleur à l'halogénure d'argent
DE3730319A1 (de) Fotografisches aufzeichnungsmaterial
DE4320828A1 (de) Farbfotografisches Aufzeichnungsmaterial
DE4001784C2 (de) Farbfotografisches Silberhalogenidmaterial
EP0377889A1 (fr) Matériel d'enregistrement à l'halogénure d'argent
EP0257452A2 (fr) Durcisseurs pour protéines, couche de liant durcie par ces composés et matériau d'enregistrement photographique contenant une telle couche
DE3806629A1 (de) Verfahren zur erzeugung von colorbildern
EP0369235A1 (fr) Matériau d'enregistrement photographique
DE3721503A1 (de) Fotografisches aufzeichnungsmaterial
DE3914947A1 (de) Fotografisches silberhalogenidmaterial und verfahren zu seiner verarbeitung
EP0318799B1 (fr) Matériau de reproduction photographique couleur avec un coupleur phénolique bleu vert

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19881109

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE DE FR GB IT NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): BE DE FR GB IT NL

17Q First examination report despatched

Effective date: 19920902

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB IT NL

ITF It: translation for a ep patent filed

Owner name: SOCIETA' ITALIANA BREVETTI S.P.A.

REF Corresponds to:

Ref document number: 3882492

Country of ref document: DE

Date of ref document: 19930826

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19930913

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19931013

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19931101

Year of fee payment: 6

ET Fr: translation filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19931112

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19931117

Year of fee payment: 6

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19931130

Year of fee payment: 6

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19941109

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19941130

BERE Be: lapsed

Owner name: AGFA-GEVAERT A.G.

Effective date: 19941130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19950601

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19941109

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19950731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19950801

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051109