EP0257515A2 - 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

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Publication number
EP0257515A2
EP0257515A2 EP87111926A EP87111926A EP0257515A2 EP 0257515 A2 EP0257515 A2 EP 0257515A2 EP 87111926 A EP87111926 A EP 87111926A EP 87111926 A EP87111926 A EP 87111926A EP 0257515 A2 EP0257515 A2 EP 0257515A2
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EP
European Patent Office
Prior art keywords
layer
layers
alkyl
hardening
aryl
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EP87111926A
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German (de)
English (en)
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EP0257515B1 (fr
EP0257515A3 (en
Inventor
Heinz Dr. Reif
Prem Dipl.-Ing. Lalvani
Hans Dr. Buschmann
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Agfa Gevaert AG
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Agfa Gevaert AG
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • 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 reactive substances in dispersed form, 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 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, in photographic ones Recording materials change important parameters of the cast layers 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 and the swelling of the layer structure occurs due to the crosslinking reaction.
  • 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 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 hardener, being applied to the layers to be hardened, characterized in that a first 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 effected by overlaying with an at least two-layer hardening system, the hardening agent being contained essentially in one part layer, preferably in the bottom part, while the other part layer contains practically no hardening agent.
  • the layers to be hardened including those partial layers of the hardening casting which did not contain any hardening agent, are hardened quickly without any appreciable degree of intracatenary crosslinking of the binder.
  • the intracatenary crosslinking cannot normally be completely avoided if the partial layer containing the hardening agent also contains hardenable binding agent, so that a reaction between binding agent and hardening agent occurs before the coating entry.
  • the heteroaromatic ring represented by R51 is, for example, a triazole, thiadiazole, oxadiazole, pyridine, pyrrole, quinoxaline, thiophene, furan, pyrimidine or triazine ring. In addition to the at least two vinylsulfonyl groups, it may optionally contain further substituents and optionally fused-on benzene rings, which in turn may also be substituted. Examples of heteroaromatic rings (R51) are listed below. wherein r is a number from 0 to 3 and R52 is C1-C4-alkyl, C1-C4-alkoxy or phenyl.
  • 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-C2 Alk 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 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 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 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 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 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 which does not contain a hardening agent but which may contain additives which are usually added to the uppermost protective layer of a photographic recording material is applied simultaneously with or after the application of the hardening coating solution.
  • the application of the hardening pouring layer comprising hardening agent and at least one further binding agent layer can take place simultaneously or in quick succession by means of cascade or curtain coaters.
  • the casting temperature can be varied within a wide range, e.g. 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 hardening agent is preferably applied with the lower partial layer and the main amount 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, anti Static and inorganic or organic solid particles, which are used, for example, as matting agents or spacers, can be added to the outermost hardener-free partial layer of the double-layer or multilayer hardening casting; however, depending on the function, they can also be contained in whole or in part in the lower hardener-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 oxide, magnesium oxide, titanium dioxide and calcium carbonate are suitable, for example, as organic 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 curing coating 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 hardening agent contained in the partial layer should be such that it is sufficient for the hardening of the overlaid layers including the partial layer of the hardening casting containing no hardening agent.
  • the binder layers to be cured 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 give essentially colorless product when reacted with color developer oxidation products.
  • the 2-equivalent couplers also include those couplers that contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue (e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic activity unfolds, 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, 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.
  • a color photographic recording material for color negative development was prepared by applying the following layers in the order given to a transparent cellulose triacetate support. The quantities given relate to 1 m2. For the silver halide application, the corresponding amounts of AgNO3 are given. All silver halide emulsions were stabilized per 100 g of AgNO3 with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.
  • red-sensitized silver bromide iodide emulsion from 3.5 g AgNO3, with 1.7 g gelatin and 0.7 g of a mixture of various couplers to produce a blue-green partial color image (emulsified with tricresyl phosphate in a weight ratio of 1: 1.)
  • red-sensitized silver bromide iodide emulsion from 2.0 g AgNO3, with 2.0 g gelatin and 0.2 g of a cyan coupler (emulsified with tricresyl phosphate in a weight ratio of 1; 1,)
  • Silver bromide iodide emulsion from 0.6 g AgNO3, with 1.4 g of gelatin and 0.85 g of a mixture of different couplers to produce the yellow partial color image (emulsified with tricresyl phosphate in a weight ratio of 1: 1)
  • the total layer thickness of all applied layers was 24.3 ⁇ m.
  • Impranil® DLN dispersion (Trading product of BAYER AG, Leverkusen)
  • 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 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.
  • a color photographic recording material for reverse color development was produced by applying the following layers in the order given on a transparent cellulose triacetate layer support.
  • the quantities given relate to 1 m2.
  • the corresponding amounts of AgNO3 are given. All silver halide emulsions were stabilized per 100 g of AgNO3 with 0.5 g of 4-hydroxy-6-methoxy-1,3,3a, 7-tetraazaindene.
  • red-sensitized silver bromide iodide emulsion (5.5 mol% iodide; average grain diameter 0.25 ⁇ m) from 0.98 g AgNO3, with 0.81 g gelatin and 0.26 g coupler C-1
  • red-sensitized silver bromide iodide emulsion (6.5 mol% iodide; average grain diameter 0.6 ⁇ m) from 0.85 g AgNO3, with 0.7 g gelatin and 0.58 g coupler C-1
  • Silver bromide iodide emulsion (4.9 mol% iodide; average grain diameter 0.35 ⁇ m) from 0.76 g AgNO3, with 0.56 g gelatin 0.47 g coupler Y-1 0.4 g connection WM - 1
  • Silver bromide iodide emulsion (3.3 mol% iodide; average grain diameter 0.78 ⁇ m) from 1.3 g AgNO3, with 0.76 g gelatin 1.42 g coupler Y-1 0.3 g connection WM - 1
  • M-1 coupler 7 from US-A-2,000,788 Y-1 coupler 16 from US-A-3,933,501
  • the wet scratch resistance, the coefficient of friction and the rewinding torque were determined.

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  • 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)
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
DE19863629388 DE3629388A1 (de) 1986-08-29 1986-08-29 Verfahren zur haertung proteinartige bindemittel enthaltender schichten
DE3629388 1986-08-29

Publications (3)

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

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EP87111926A Expired - Lifetime EP0257515B1 (fr) 1986-08-29 1987-08-18 Procédé de durcissement de couches contenant un liant de type protéinique

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

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2212288A (en) * 1987-09-10 1989-07-19 Agfa Gevaert Ag A silver halide photographic recording material
DE4001784A1 (de) * 1990-01-23 1991-07-25 Agfa Gevaert Ag Farbfotografisches silberhalogenidmaterial
DE4119982A1 (de) * 1991-06-18 1992-12-24 Du Pont Deutschland 1,3-bis-carbamoylimidazoliumverbindungen und verfahren zum haerten von gelatine enthaltenden schichten
US5919906A (en) * 1998-11-05 1999-07-06 Eastman Kodak Company Protease produced gelatin
US5972591A (en) * 1990-12-20 1999-10-26 Eastman Kodak Company Thickener for delivery of photographic emulsions
US6100381A (en) * 1998-11-03 2000-08-08 Eastman Kodak Company Enzyme method of manufacturing gelatin

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Publication number Priority date Publication date Assignee Title
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
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
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

Citations (1)

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Publication number Priority date Publication date Assignee Title
GB2101758A (en) * 1981-06-16 1983-01-19 Fuji Photo Film Co Ltd Silver halide photographic light-sensitive materials

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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

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Publication number Priority date Publication date Assignee Title
GB2101758A (en) * 1981-06-16 1983-01-19 Fuji Photo Film Co Ltd Silver halide photographic light-sensitive materials

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2212288A (en) * 1987-09-10 1989-07-19 Agfa Gevaert Ag A silver halide photographic recording material
GB2212288B (en) * 1987-09-10 1991-01-02 Agfa Gevaert Ag A photographic recording material
DE4001784A1 (de) * 1990-01-23 1991-07-25 Agfa Gevaert Ag Farbfotografisches silberhalogenidmaterial
US5972591A (en) * 1990-12-20 1999-10-26 Eastman Kodak Company Thickener for delivery of photographic emulsions
DE4119982A1 (de) * 1991-06-18 1992-12-24 Du Pont Deutschland 1,3-bis-carbamoylimidazoliumverbindungen und verfahren zum haerten von gelatine enthaltenden schichten
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

Also Published As

Publication number Publication date
US5034249A (en) 1991-07-23
JPS6361243A (ja) 1988-03-17
DE3629388A1 (de) 1988-03-03
EP0257515B1 (fr) 1992-05-13
EP0257515A3 (en) 1990-02-07
DE3779014D1 (de) 1992-06-17

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