EP0257515B1 - Procédé de durcissement de couches contenant un liant de type protéinique - Google Patents

Procédé de durcissement de couches contenant un liant de type protéinique Download PDF

Info

Publication number
EP0257515B1
EP0257515B1 EP87111926A EP87111926A EP0257515B1 EP 0257515 B1 EP0257515 B1 EP 0257515B1 EP 87111926 A EP87111926 A EP 87111926A EP 87111926 A EP87111926 A EP 87111926A EP 0257515 B1 EP0257515 B1 EP 0257515B1
Authority
EP
European Patent Office
Prior art keywords
layers
alkyl
layer
aryl
hardened
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
EP87111926A
Other languages
German (de)
English (en)
Other versions
EP0257515A2 (fr
EP0257515A3 (en
Inventor
Heinz Dr. Reif
Prem Dipl.-Ing. Lalvani
Hans Dr. Buschmann
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 EP0257515A2 publication Critical patent/EP0257515A2/fr
Publication of EP0257515A3 publication Critical patent/EP0257515A3/de
Application granted granted Critical
Publication of EP0257515B1 publication Critical patent/EP0257515B1/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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • 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
    • G03C1/30—Hardeners

Definitions

  • the invention relates to a method for hardening layers containing proteinaceous binders by using an immediate hardening agent, in particular hardening agent activating carboxyl groups.
  • Layers containing proteinaceous binders are used in a wide variety of fields, e.g. as protective coatings for objects or as binder layers which contain dispersed reactive substances, for example in materials for analytical or diagnostic purposes or in photographic recording materials. Such layers must be hardened for practical use.
  • a variety of curing agents have been known for this purpose.
  • the hardening agents 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, in photographic ones Recording materials important parameters of the cast layers change with increasing storage time.
  • sensitometric data such as sensitivity, gradation and maximum density can drift 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 hardening 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 testing 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).
  • instant 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.
  • 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) (for example DE-A-3 307 506, Example 2). By diffusion it reaches the other gelatin-containing layers to be hardened and crosslinks the gelatin so quickly that the hardening is almost complete after drying and the parameters characteristic of the physical and photographic properties have reached their final values.
  • the invention has for its object to provide an improved method for hardening layers containing proteinaceous binders using instant hardeners.
  • the invention relates to a method for curing layers containing proteinaceous binders, an instant hardener, in particular a carboxyl group-activating instant hardening agent, being applied to the layers to be hardened, characterized in that a lower layer containing the instant hardener is applied to the layers to be hardened, and at least one further layer, which contains proteinaceous binder, but essentially no instant hardener, is applied simultaneously or in succession.
  • the hardening of the binder layers is thus brought about by overlaying with an at least two-layer hardening system, the instant hardener being essentially contained in the lower part-layer when pouring, while the other part-layers contain practically no instant hardener.
  • the layers to be hardened including those partial layers of the hardening casting which did not contain an instant hardening agent, are hardened rapidly without any intracatenary crosslinking of the binder occurring.
  • the intracatenary crosslinking cannot normally be completely avoided if the partial layer containing the instant hardener also contains hardenable binder, so that a reaction between the binder and the instant hardener occurs even before the coating entry.
  • 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 C7-C20-aralkyl substituted by halogen, C1-C2-alkoxy, sulfo or C1-C2-alkyl.
  • Alkoxy unless otherwise defined, is a particular C1-C20 alkoxy.
  • X ⁇ is preferably a halide ion such as Cl ⁇ , Br ⁇ or BF4 ⁇ , NO3 ⁇ , (SO42 ⁇ ) 1/2 , ClO4 ⁇ , CH3OSO3 ⁇ , PF6 ⁇ , CF3SO3 ⁇ .
  • Alkenyl is especially C2-C20 alkenyl.
  • Alkylene is especially C2-C20 alkylene; Arylene in particular phenylene, aralkylene in particular benzylene and alkaralkylene in particular 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 attached, in particular form a pyrrolidine or piperidine ring bonded by 2 oxo groups in the o- and o ⁇ -position, which may be benzo, cyclohexeno- or [2.2.1] -bicyclohexenocondensed.
  • 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.
  • Hardeners are preferably listed below:
  • 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 absence of light.
  • 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 compounds (a) are particularly preferred.
  • the binder to be cured used in the layers which are subjected to the curing process according to the invention is a proteinaceous 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. Hardening using instant hardeners is usually done in the way carried out that the instant hardening agent is applied in excess as the last layer on the layers to be hardened, it being possible to add further substances, such as UV absorbers, antistatic agents, matting agents and polymeric organic particles, to the hardening coating solution.
  • At least one further binder layer is applied simultaneously with the application of the hardening coating solution or subsequently, which does not contain an instant hardener, but can contain additives which are usually added to the top protective layer of a photographic recording material.
  • the application of the layers containing immediate hardening agent and at least one further binder layer can be done simultaneously or in quick succession using 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. If little binder is used, the casting temperature can be below 25 ° C.
  • the layer additives are divided in such a way that the instant hardening agent is applied with the lower partial layer and the majority of the binder is preferably applied with the upper partial layer or layers.
  • the total 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 outermost instant hardener-free partial layer of the double- or multilayer hardening casting; however, depending on their function, they can also be contained in whole or in part in the lower partial hardening agent-containing partial layer of the hardening pour.
  • 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.
  • Silicon dioxide, magnesium dioxide, titanium dioxide and calcium carbonate are suitable, for example, as inorganic solid particles which can be incorporated into one of the partial layers of the multilayer hardening casting according to the invention. Such materials are widely used to matt the outermost layers of photographic recording materials and thus reduce their stickiness.
  • Solid particles of an organic nature which can be alkali-soluble or alkali-insoluble, are also 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 about 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 hardening agents to one or more partial layers of the multilayer hardening casting according to the invention.
  • the multilayer hardening casting is poured onto the binder layers to be hardened, in particular gelatin layers, by the method according to the invention.
  • the amount of the instant hardening agent contained in the one partial layer should be such that it is sufficient for the hardening of the overlaid layers, including the partial layers of the hardening casting which contain no instant hardening agent, in order for the casting solution for the instant hardening agent-containing partial layer, which contains comparatively little binder, to have the required casting viscosity to lend, it is expedient to add thickeners such as polystyrene sulfonic acid or hydroxyethyl cellulose.
  • the binder layers to be hardened can contain reagents, in particular color reagents for analytical and diagnostic purposes, with which, for example, certain substances in human or animal body fluids can be quickly detected.
  • Photographic, in particular color photographic, recording materials to which the method of the present invention can advantageously be applied are preferably multilayer materials which have a plurality of silver halide emulsion layers or emulsion layer units with different spectral sensitivity.
  • Emulsion layer units are understood to mean laminates of 2 or more silver halide emulsion layers of the same spectral sensitivity.
  • Layers of the same spectral sensitivity do 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.
  • non-proteinaceous binders such as polyvinyl alcohol, N-vinylpyrrolidone, polyacrylic acid and their derivatives, in particular copolymers, or cellulose derivatives.
  • each of the light-sensitive silver halide emulsion layers or emulsion layer units mentioned is at least one color-imparting compound, as a rule Color coupler, assigned, which is able to react with color developer oxidation product to form a non-diffusing or temporally or locally diffusible dyes.
  • 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 consequently 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 usually a coupler of the phenol or ⁇ -naphthol type.
  • Particularly noteworthy are, for example, 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 thoroughly 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-pyrazolonsi or indazolone type usually being used. Cyanoacetyl compounds, oxazolones and pyrazoloazoles are also suitable as magenta couplers. Especially to be emphasized are, for example, purple couplers, as described in US Pat. Nos. 2,600,788, 4,383,027, 1,557,803, 1,810,464, 24,066,655, DE-A-32 26 163.
  • 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 obvious ketomethylene grouping.
  • a color coupler with an obvious 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. As is known, 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 by the color of the one produced Image dye is replaced (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 that contain a cleavable residue in the coupling point, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue (e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic effectiveness unfolds, e.g. as a development inhibitor or accelerator.
  • Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR 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, who at the Coupling essentially colorless products, 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 weight color couplers are generally obtained by polymerizing ethylenically unsaturated monomeric color couplers produced. 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 total layer thickness of all applied layers was 24.3 ⁇ m.
  • the wet scratch resistance, the parallel breaking strength, the coefficient of friction and the torque were determined.
  • a metal tip of a defined size was passed over the wet layer and loaded with increasing weight.
  • the wet scratch resistance is indicated by the weight [N] at which the tip leaves a visible scratch mark on the layer.
  • a high weight corresponds to a high wet scratch resistance.
  • the measurement was carried out with a sample of the respective material which had previously been at 38 ° C. for 5 min. was swollen in water with a hardness of 10 ° DH.
  • the parallel breaking strength was characterized by the parameters breaking diameter [mm] and breaking strength [N].
  • breaking diameter is the distance between the two jaws and breaking force is the force with which the two jaws act on the loop at the moment when the loop breaks along the perforation line. The method is described in Research Disclosure 25254 (April 1985).
  • coefficient of friction tensile force / normal force x 100
  • the rewinding torque [mN ⁇ cm] during forward and backward transport was determined as follows.
  • the ready-made films were matched to the test climate (35 ° C, 90% r.h.) in the cartridge without a container for 7 d, then placed in an Orthomat cassette from Leitz and transported further by one small picture length every second.
  • the torque required for the transport, from which the contribution to the friction of the cassette mechanism was subtracted, is given as a measure of the pre-transport.
  • the film was transported back within 7 s. The torque from the beginning of the transport and the maximum torque occurring at the end of the transport are measured and specified as a measure of the return transport.
  • Example 1 As in Example 1, the wet scratch resistance, the coefficient of friction and the rewinding torque were determined.

Landscapes

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

Claims (9)

  1. Procédé de durcissement de couches contenant des liants de type protéiné, un revêtement de durcissement contenant un durcisseur instantané étant appliqué sur les couches à durcir, caractérisé en ce qu'une couche inférieure qui contient le durcisseur instantané et au moins une autre couche qui contient le liant de type protéiné, mais essentiellement pas de durcisseur instantané, sont appliquées simultanément ou successivement sur les couches à durcir.
  2. Procédé, selon la revendication 1, caractérisé en ce que les couches à durcir sont les couches d'un matériau d'enregistrement photographique à plusieurs couches.
  3. Procédé, selon la revendication 2, caractérisé en ce que les couches à durcir sont les couches d'un matériau d'enregistrement photographique en couleur en plusieurs couches.
  4. Procédé, selon une des revendications 1, 2 et 3, caractérisé en ce que les couches à durcir sont des couches de gélatine.
  5. Procédé, selon une des revendications 1 à 4, caractérisé en ce qu'au moins une couche partielle du revêtement de durcissement à plusieurs couches contient des particules solides organiques ou inorganiques.
  6. Procédé, selon une des revendications 1 à 4, caractérisé en ce que la couche partielle contenant le durcisseur instantané du revêtement de durcissement à plusieurs couches contient au moins un composé augmentant la viscosité.
  7. Procédé, selon une des revendications 1 à 6, caractérisé en ce que les couches partielles sans durcisseur instantané du revêtement de durcissement à plusieurs couches sont appliquées sur celle-ci avant le séchage de la couche partielle contenant le durcisseur instantané.
  8. Procédé, selon la revendication 7, caractérisé en ce que les couches partielles du revêtement de durcissement en plusieurs couches sont appliquées simultanément sur les couches à durcir.
  9. Procédé, selon une des revendications 1 à 8, caractérisé en ce que le durcisseur instantané de formule suivante est utilisé:
    Figure imgb0058
     dans laquelle
    R₁ désigne un radical alkyle, aryle ou aralkyle,
    R₂ a la même signification que R₁ ou désigne un radical alkylène, arylène, aralkylène ou alkaralkylène, la deuxième liaison étant liée avec un radical de formule
    Figure imgb0059
     ou
    R₁ et R₂ désignent ensemble les atomes nécessaires pour compléter un cycle hétérocylique éventuellement substitué,
    R₃ désigne l'hydrogène, un radical alkyle, aryle, alcoxy, -NR₄-COR₅, -(CH₂)m-NR₈R₉, -(CH₂)n-CONR₁₃R₁₄ ou
    Figure imgb0060
     ou un élément de pontage ou une liaison directe à une chaîne polymère,
    R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈ et R₁₉ désignant l'hydrogène ou un radical alkyle C₁-C₄,
    R₅ désigne l'hydrogène, un radical alkyle C₁-C₄ ou NR₆R₇,
    R₈ désigne -COR₁₀-,
    R₁₀ désigne NR₁₁R¹²
    R₁₁ désigne un radical alkyle C₁-C₄ ou aryle,
    R₁₂ désigne l'hydrogène, un radical alkyle C₁-C₄ ou aryle,
    R₁₃ désigne l'hydrogène, un radical alkyle C₁-C₄ ou aryle,
    R₁₆ désigne l'hydrogène, un radical alkyle C₁-C₄, COR₁₈ ou CONHR₁₉,
    m désigne un chiffre de 1 à 3,
    n désigne un chiffre de 0 à 3,
    p désigne un chiffre de 2 à 3 et
    Y désigne O ou NR₁₇ ou
    R₁₃ et R₁₄ désignent ensemble les atomes nécessaires pour compléter un cycle hétérocyclique éventuellement substitué,
    Z désigne les atomes C nécessaires pour compléter un cycle hétérocyclique aromatique à 5 ou 6 éléments, éventuellement avec un cycle benzène en anneau et
    X(-) désigne un anion manquant si un radical anionique est déjà lié avec le reste de la molécule.
EP87111926A 1986-08-29 1987-08-18 Procédé de durcissement de couches contenant un liant de type protéinique Expired - Lifetime EP0257515B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3629388 1986-08-29
DE19863629388 DE3629388A1 (de) 1986-08-29 1986-08-29 Verfahren zur haertung proteinartige bindemittel enthaltender schichten

Publications (3)

Publication Number Publication Date
EP0257515A2 EP0257515A2 (fr) 1988-03-02
EP0257515A3 EP0257515A3 (en) 1990-02-07
EP0257515B1 true EP0257515B1 (fr) 1992-05-13

Family

ID=6308453

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87111926A Expired - Lifetime EP0257515B1 (fr) 1986-08-29 1987-08-18 Procédé de durcissement de couches contenant un liant de type protéinique

Country Status (4)

Country Link
US (1) US5034249A (fr)
EP (1) EP0257515B1 (fr)
JP (1) JPS6361243A (fr)
DE (2) DE3629388A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3730319C2 (de) * 1987-09-10 1996-05-09 Agfa Gevaert Ag Fotografisches Aufzeichnungsmaterial
DE4001784C2 (de) * 1990-01-23 1994-11-10 Agfa Gevaert Ag Farbfotografisches Silberhalogenidmaterial
DE69126775T2 (de) * 1990-12-20 1998-01-29 Eastman Kodak Co Verfahren zur Beschichtung photographischer Mehrschichtmaterialien
US5229260A (en) * 1991-03-13 1993-07-20 Konica Corporation Silver halide photographic light sensitive material
US5601971A (en) * 1991-06-18 1997-02-11 Sterling Diagnsotic Imaging, Inc. Hardening of hydrophilic colloids with imidazolium and triazine combinations
DE4119982C2 (de) * 1991-06-18 1993-09-30 Du Pont Deutschland 1,3-Bis-carbamoylimidazoliumverbindungen und Verfahren zum Härten von Gelatine enthaltenden Schichten
US5547832A (en) * 1992-07-07 1996-08-20 Eastman Kodak Company Method for hardening photographic materials
US5368894A (en) * 1993-06-08 1994-11-29 Minnesota Mining And Manufacturing Company Method for producing a multilayered element having a top coat
US5378842A (en) * 1993-12-21 1995-01-03 E. I. Du Pont De Nemours And Company Imidazolium hardeners for proteinaceous materials
US6100381A (en) * 1998-11-03 2000-08-08 Eastman Kodak Company Enzyme method of manufacturing gelatin
US5919906A (en) * 1998-11-05 1999-07-06 Eastman Kodak Company Protease produced gelatin
US6419987B1 (en) * 1999-12-17 2002-07-16 Eastman Kodak Company Method for providing a high viscosity coating on a moving web and articles made thereby
DE50201681D1 (de) * 2002-07-01 2005-01-05 Ilford Imaging Ch Gmbh Verfahren zur Beschichtung eines bewegten Trägers

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3880665A (en) * 1972-05-24 1975-04-29 Agfa Gevaert Ag Hardening with a heterocyclic carbamoyl ammonium compound of a photographic material containing a silver halide layer
US4055427A (en) * 1974-02-23 1977-10-25 Agfa-Gevaert Aktiengesellschaft Process of hardening a silver halide photographic material with a 1-carbamoyloxypyridinium salt
DE2439551C2 (de) * 1974-08-17 1985-11-21 Agfa-Gevaert Ag, 5090 Leverkusen Verfahren zur Härtung photographischer Schichten
DE2439553A1 (de) * 1974-08-17 1976-02-26 Agfa Gevaert Ag Verfahren zur haertung photographischer schichten
GB1528163A (en) * 1975-02-10 1978-10-11 Agfa Gevaert Process for the hardening of photographic layers
DE2545755A1 (de) * 1975-10-11 1977-04-21 Agfa Gevaert Ag Verfahren zur haertung photographischer schichten
DE2547589A1 (de) * 1975-10-24 1977-04-28 Agfa Gevaert Ag Haertung photographischer schichten
DE2625026A1 (de) * 1976-06-03 1977-12-22 Agfa Gevaert Ag Verfahren zur haertung photographischer gelatinehaltiger schichten
JPS5473871A (en) * 1977-11-24 1979-06-13 Fuji Photo Film Co Ltd Undercoating of polyester film
JPS5565949A (en) * 1978-11-13 1980-05-17 Fuji Photo Film Co Ltd Subbing method for photographic material
DE2924035A1 (de) * 1979-06-13 1981-01-08 Agfa Gevaert Ag Verfahren zur kettenverlaengerung von gelatine durch partielle haertung
JPS57207243A (en) * 1981-06-16 1982-12-18 Fuji Photo Film Co Ltd Photographic sensitive silver halide material

Also Published As

Publication number Publication date
JPS6361243A (ja) 1988-03-17
EP0257515A2 (fr) 1988-03-02
EP0257515A3 (en) 1990-02-07
US5034249A (en) 1991-07-23
DE3629388A1 (de) 1988-03-03
DE3779014D1 (de) 1992-06-17

Similar Documents

Publication Publication Date Title
EP0257515B1 (fr) Procédé de durcissement de couches contenant un liant de type protéinique
EP0395956A2 (fr) Matériau photographique de reproduction
EP0027988B1 (fr) Matériau photographique d'halogénure d'argent sensible à la lumière
EP0282865B1 (fr) Agents durcisseurs pour protéines, couche liante durcie à l'aide de ces agents et matériau d'enregistrement photographique contenant une telle couche
DE3626221A1 (de) Farbfotografisches aufzeichnungsmaterial zur herstellung farbiger aufsichtsbilder
EP0345514B1 (fr) Matériau photographique couleur à l'halogénure d'argent
EP0237887B1 (fr) Procéde de préparation d'un matériau d'enregistrement photographique
EP0317825B1 (fr) Matériau de reproduction photographique couleur
EP0286913B1 (fr) Matériau d'enregistrement photographique couleur
EP0207399B1 (fr) Couche de liant durcie
DE3730319C2 (de) Fotografisches Aufzeichnungsmaterial
DE3836945A1 (de) Fotografisches silberhalogenidmaterial und verfahren zu seiner verarbeitung
DE4318438A1 (de) Fotografisches Aufzeichnungsmaterial
DE4001784C2 (de) Farbfotografisches Silberhalogenidmaterial
EP0267523B1 (fr) Matériau photographique couleur à l'halogénure d'argent sensible à la lumière
EP0262504B1 (fr) Préparation de matériaux photographiques multicouches
DE4213869A1 (de) Fotografisches material
DE3835467A1 (de) Farbfotografisches silberhalogenidmaterial
EP0257452A2 (fr) Durcisseurs pour protéines, couche de liant durcie par ces composés et matériau d'enregistrement photographique contenant une telle couche
DE4320828A1 (de) Farbfotografisches Aufzeichnungsmaterial
EP0318799B1 (fr) Matériau de reproduction photographique couleur avec un coupleur phénolique bleu vert
DE3936827A1 (de) Farbfotografisches silberhalogenidmaterial
DE3913404A1 (de) Farbfotografisches aufzeichnungsmaterial mit einem farbkuppler vom pyrazoloazol-typ
DE3721503A1 (de) Fotografisches aufzeichnungsmaterial
DE3914947A1 (de) Fotografisches silberhalogenidmaterial und verfahren zu seiner verarbeitung

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: 19870818

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE DE FR GB

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

17Q First examination report despatched

Effective date: 19910812

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

REF Corresponds to:

Ref document number: 3779014

Country of ref document: DE

Date of ref document: 19920617

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
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
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19930729

Year of fee payment: 7

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

Ref country code: GB

Payment date: 19930730

Year of fee payment: 7

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

Ref country code: BE

Payment date: 19930818

Year of fee payment: 7

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

Ref country code: DE

Payment date: 19940714

Year of fee payment: 8

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

Ref country code: GB

Effective date: 19940818

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

Ref country code: BE

Effective date: 19940831

BERE Be: lapsed

Owner name: AGFA-GEVAERT A.G.

Effective date: 19940831

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

Effective date: 19940818

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

Ref country code: FR

Effective date: 19950428

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: DE

Effective date: 19960501