EP0358073B1 - Matériau de reproduction photographique - Google Patents

Matériau de reproduction photographique Download PDF

Info

Publication number
EP0358073B1
EP0358073B1 EP89115801A EP89115801A EP0358073B1 EP 0358073 B1 EP0358073 B1 EP 0358073B1 EP 89115801 A EP89115801 A EP 89115801A EP 89115801 A EP89115801 A EP 89115801A EP 0358073 B1 EP0358073 B1 EP 0358073B1
Authority
EP
European Patent Office
Prior art keywords
acid
layer
compounds
color
silver halide
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
EP89115801A
Other languages
German (de)
English (en)
Other versions
EP0358073A3 (fr
EP0358073A2 (fr
Inventor
Günter Dr. Helling
Wolfgang Dr. Himmelmann
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 EP0358073A2 publication Critical patent/EP0358073A2/fr
Publication of EP0358073A3 publication Critical patent/EP0358073A3/fr
Application granted granted Critical
Publication of EP0358073B1 publication Critical patent/EP0358073B1/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
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/162—Protective or antiabrasion layer

Definitions

  • the invention relates to a photographic recording material with a support, at least one light-sensitive silver halide emulsion layer, a protective layer and optionally further layers, which exhibits improved properties, in particular an improved maximum density.
  • the object of the present invention was to provide photographic recording materials with improved properties, in particular improved maximum densities.
  • polyester carboxylic acids according to the invention have a block-like structure; hydrophobic polyester blocks with a molecular weight of 500 alternate with hydrophilic blocks which carry two free carboxyl groups.
  • polyester carboxylic acids according to the invention preferably have acid numbers of 30 to 340 mg KOH / g, in particular 50 to 200 mg KOH / g.
  • the compounds of the formula I are used in acid form in particular as oil formers and in anionic form as surfactants and emulsifiers.
  • oil formers they are preferably used in an amount of 0.02 to 5.0 g / m 2 , particularly preferably 0.2 to 3 g / m 2 , and as surfactants preferably in an amount of 0.01 to 3.0 g / m 2 2 , particularly preferably 0.05 to 2 g / m 2 used.
  • the compounds according to the invention can be used as oil formers in all layers in which layer components are used in emulsified form. The same applies to the use as a surfactant.
  • the compounds according to the invention can take on both oil formers and emulsifiers.
  • the compounds of the formula I are prepared by reacting polyester diols of the formula II with carboxylic anhydrides of the formula III or corresponding di- and tetracarboxylic acids at temperatures from 20 to 200 ° C. in a molar ratio of 1: 1 to 1: 2, if appropriate in inert solvents:
  • the condensation reaction is preferably carried out without solvent, in particular at temperatures from 50 to 150 ° C.
  • the compounds of the formula I When used as emulsifiers, the compounds of the formula I are neutralized in an aqueous medium with alkali metal hydroxides or amines. Suitable cations are Na + , K + , Li + , ammonium, mono-, di-, tri- or tetraalkylammonium and di- or tri-hydroxyalkylammonium.
  • the alkyl groups have in particular one to four carbon atoms.
  • the polyester diols 11 are known, for example, from Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 19, p. 305 ff. They are produced by polycondensation of one or more diols with one or more dicarboxylic acids and / or one or more oxy acids. Diols and dicarboxylic acids are preferably used. The oxyacids can be used as lactones.
  • Ethylene glycol, 1,2-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol are preferred.
  • Preferred dicarboxylic acids are succinic acid, adipic acid, phthalic acid, sebacic acid, dodecanedicarboxylic acid.
  • the lactone of an oxycarboxylic acid is e.g. Caprolactone into consideration.
  • the average molecular weight, determined from the OH number by the end group method, of the polyester diols of the formula (11) is about 500 to 20,000, preferably 800 to 5,000.
  • the molar ratio of polyhydric alcohol to polybasic carboxylic acid is greater than 1. Examples of polyester diols are listed in Table 1.
  • Carboxylic anhydrides of the formula (III) are, for example
  • the polyester carboxylic acids according to the invention are soluble in ethyl acetate.
  • carboxylates they are soluble in water or form colloidal solutions with an average particle size of up to 100 nm.
  • the polyester emulsifiers of the general formula (I) are particularly suitable as emulsifiers in aqueous emulsion polymerization for the preparation of latices useful for photography. They deteriorate the properties of the latices to a much lesser extent than the usual emulsifiers. Since, in contrast to these, they are relatively high molecular weight and show good polymer compatibility, they can also be obtained from multiphase systems, e.g. B. Mixtures with binders, do not so easily sweat out, the transparency of the coatings with these mixtures is improved.
  • polyester diols which are known to the person skilled in the art as soft segments, are used in polymer emulsifiers of the formula (I).
  • polyester diols which are used as soft segments preferably contain neopentyl glycol and / or ⁇ -hydroxyethylhexanediol as the diol and adipic acid as the dicarboxylic acid.
  • Caprolactone diols are also known as soft segments. (Angew. Makromol. Chem. 14, 75 (1970) and 16/17, 117 (1971)).
  • the usual monomers such as acrylic esters, methacrylic esters, vinyl esters, vinyl aromatics, conjugated dienes, vinyl halides, (meth) acrylonitrile, divinyl compounds and / or (meth) allyl compounds, but in particular monomers with photographically useful groups, can be used for the polymerization in the presence of the emulsifiers according to the invention .
  • water-soluble monomers such as, for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, styrenesulfonic acid, methallylsulfonic acid, acrylamido-2-methylpropanesulfonic acid and acrylamide can be added in amounts of up to 20%, if necessary, in addition to the monomers mentioned Polymers are installed.
  • Latices with photographically useful groups which are advantageously prepared with the compounds of the formula (I) are known from RD 19 551 (1980), US 4,645,735, US 4,576,910, US 4,551,420, US 4,464,463, DE -OS 3 233 186, DE-OS 3 431 192, DE-OS 3 422 455, DE-OS 3 401 455, DE-OS 3 340 376, DE-OS 3 336 582, DE-OS 3 331 743, EP 0 133 262, DE-OS 3 324 932, DE-OS 3 320 079, DE-OS 3 313 800, DE-OS 3 113 574, DE-OS 3 905 718, EP 0 186 869, US 4 608 424, US 4 612 278, EP 210 409, EP 0 190 003, US 4 557 998, US 4 497 929, DD 235 511, EP 0 121 141, EP 0 107 378, EP 0 186 494,
  • Photographically useful groups are, for example, pp, gb, bg color couplers, white couplers, DIR couplers, UV absorbers, optical brighteners, mask couplers, filter dyes.
  • polyester diol 11-2 from adipic acid and neopentyl glycol with an average molecular weight of 1,700 and 2.18 g of benzene-1,2,4,5-tetracarboxylic acid (96% by weight) are mixed, 4 hours to 160 ° C heated with stirring and the water formed was distilled off. After cooling, a clear, homogeneous polyester carboxylic acid with an acid number of 73 mg KOH / g is obtained.
  • polyester carboxylic acids according to Table 2 are obtained by reacting polyester diols II with carboxylic acid anhydrides.
  • color photographic materials are color negative films, color reversal films, color positive films, color photographic paper, color reversal photographic paper, color sensitive materials for the color diffusion transfer process or the silver color bleaching process.
  • Suitable supports for the production of color photographic materials are, for example, films and foils of semisynthetic and synthetic polymers, such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, Polyvinyl chloride, polyethylene terephthalate and polycarbonate and paper laminated with a baryta layer or a-olefin polymer layer (eg polyethylene).
  • These carriers can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light.
  • the surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer.
  • the color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and, if appropriate, intermediate layers and protective layers.
  • Binding agents, silver halide grains and color couplers are essential components of the photographic emulsion layers.
  • Gelatin is preferably used as the binder. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers.
  • Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers.
  • Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, cellulose, sugar, starch or alginates.
  • Semi-synthetic gelatin substitutes are usually modified natural products.
  • Cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives, which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers, are examples of this.
  • the binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents.
  • functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.
  • the gelatin which is preferably used can be obtained by acidic or alkaline digestion. Oxidized gelatin can also be used. The production of such gelatins is described, for example, in The Science and Technology of Gelatine, published by A.G. Ward and A. Courts, Academic Press 1977, page 295 ff.
  • the gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.
  • the 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 halide content of at least one layer can consist of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide.
  • silver bromide iodide emulsions are usually used; in the case of color negative and color reversal paper, silver chloride bromide emulsions are usually used. It can be predominantly compact crystals, e.g. are regular cubic or octahedral or can have transitional forms.
  • platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.
  • the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is substantially greater than 5: 1, e.g. 12: 1 to 30: 1.
  • the silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as e.g. Doping of the individual grain areas are different.
  • the average grain size of the emulsions is preferably between 0.2 .mu.m and 2.0 .mu.m, the grain size distribution can be both homo- and heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ⁇ 30%.
  • the emulsions can also contain organic silver salts, e.g. Silver benzotriazolate or silver behenate.
  • Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
  • the photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
  • various methods e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
  • the silver halide is preferably precipitated in the presence of the binder, for example the gelatin, and can be carried out in the acidic, neutral or alkaline pH range, with preference being given to Silver halide complexing agents can also be used.
  • the latter include, for example, ammonia, thioether, imidazole, ammonium thiocyanate or excess halide.
  • the water-soluble silver salts and the halides are combined either in succession by the single-jet process or simultaneously by the double-jet process or by any combination of the two processes. Dosing with increasing inflow rates is preferred, the "critical" feed rate, at which no new germs are being produced, should not be exceeded.
  • the pAg range can vary within wide limits during the precipitation, preferably the so-called pAg-controlled method is used, in which a certain pAg value is kept constant or a defined pAg profile is traversed during the precipitation.
  • so-called inverse precipitation with an excess of silver ions is also possible.
  • the silver halide crystals can also grow by physical ripening (Ostwald ripening) in the presence of excess halide and / or silver halide complexing agent.
  • the growth of the emulsion grains can even take place predominantly by Ostwald ripening, preferably a fine-grained, so-called Lippmann emulsion, mixed with a less soluble emulsion and redissolved on the latter.
  • Salts or complexes of metals such as Cd, Zn, Pb, TI, Bi, Ir, Rh, Fe can also be present during the precipitation and / or physical ripening of the silver halide grains.
  • the precipitation can also be carried out in the presence of sensitizing dyes.
  • Complexing agents and / or dyes can be rendered ineffective at any time, e.g. by changing the pH or by an oxidative treatment.
  • the soluble salts are removed from the emulsion, e.g. by pasta and washing, by flakes and washing, by ultrafiltration by ion exchangers.
  • the silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog are reached.
  • the procedure is e.g. with H. Frieser "The basics of photographic processes with silver halides" page 675-734, Akademische Verlagsgesellschaft (1968).
  • a reduction sensitization can be carried out with the addition of reducing agents (tin-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidinesulfinic acid) using hydrogen, by means of low pAg (for example less than 5) and / or high pH (for example over 8) .
  • reducing agents titanium-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidinesulfinic acid
  • the photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
  • Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are e.g. by Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can also be used as antifoggants. Heterocycles containing mercapto groups are particularly suitable, e.g.
  • Mercaptobenzthiazoles mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, these mercaptoazoles also being a water-solubilizing group, e.g. may contain a carboxyl group or sulfo group.
  • Other suitable compounds are published in Research Disclosure No. 17643 (1978), Section VI.
  • the stabilizers can be added to the silver halide emulsions before, during or after their ripening.
  • the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.
  • the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
  • non-ionic surfactants for example alkylene oxide compounds, glycerol compounds or glycidol compounds
  • cationic surfactants for example higher alkylamines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing an acid group.
  • carboxylic acid for example carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, for example amino acid and aminosulfonic acid compounds and sulfuric or phosphoric acid esters of an amino alcohol, but in particular also the carboxylates according to the invention.
  • the photographic emulsions can be spectrally sensitized using methine dyes or other dyes.
  • Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
  • the differently sensitized emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it.
  • cyan couplers are assigned to the red-sensitive layers, purple couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers.
  • white couplers are:
  • DIR couplers the development inhibitors of the azole type, e.g. Triazoles and benzotriazoles are described in DE-A-2 414 006, 2 610 546, 2 659 417, 2 754 281, 2 726 180, 3 626 219, 3 630 564 3 636 824, 3 644 416 and 2 842 063 .
  • Further advantages for color rendering, i.e. color separation and color purity, and for detail rendering i.e. sharpness and granularity can be achieved with such DIR couplers which e.g. do not split off the development inhibitor directly as a result of the coupling with an oxidized color developer, but only after a further subsequent reaction, which is achieved, for example, with a timing group.
  • DIR couplers which release a development inhibitor which is decomposed into essentially photographically ineffective products in the developer bath are described, for example, in DE-A-32 09 486 and in EP-A-167 168 and 219 713. This measure ensures trouble-free development and processing consistency.
  • the DIR couplers can be added to a wide variety of layers in a multilayer photographic material, e.g. also light-insensitive or intermediate layers. However, they are preferably added to the photosensitive silver halide emulsion layers, the characteristics of the silver halide emulsion, e.g. whose iodide content, the structure of the silver halide grains or their grain size distribution influence the photographic properties achieved.
  • the influence of the inhibitors released can be limited, for example, by incorporating an inhibitor scavenger layer in accordance with DE-A-24 31 223. For reasons of reactivity or stability, it can be advantageous to use a DIR coupler which forms a color in the coupling in the respective layer in which it is introduced, which color differs from the color to be produced in this layer.
  • DAR or. FAR couplers are used that split off a development accelerator or an fogging agent.
  • Compounds of this type are, for example, in DE-A-2 534 466, 3 209 110, 3 333 355, 3 410 616, 3 429 545, 3 441 823, in EP-A-89 834, 110 511, 118 087, 147 765 and described in US-A-4,618,572 and 4,656,123.
  • DIR couplers examples are:
  • DIR, DAR or FAR couplers mainly the effectiveness of the residue released during coupling is desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, which give essentially colorless products on coupling (DE-A-1 547 640).
  • the cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (US Pat. No. 4,420,556).
  • the material may further contain compounds other than couplers, which can liberate, for example, a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR hydroquinones and other compounds as described, for example, in US Pat US-A-4 636 546, 4 345 024, 4 684 604 and in DE-A-3 145 640, 2 515 213, 2 447 079 and in EP-A-198 438. These compounds perform the same function as the DIR, DAR or FAR couplers, except that they do not form coupling products.
  • couplers can liberate, for example, a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR hydroquinones and other compounds as described, for example, in US Pat US-A-4 636 546, 4 345 024, 4 6
  • High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211.
  • the high molecular weight color couplers are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.
  • the polyester carboxylates according to the invention can be used as emulsifiers in their preparation.
  • the couplers or other compounds can be incorporated into silver halide emulsion layers by first preparing a solution, a dispersion or an emulsion of the compound in question and then adding it to the casting solution for the layer in question.
  • the selection of the suitable solvent or dispersing agent depends on the solubility of the compound.
  • Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-O 043 037.
  • oligomers or polymers instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.
  • the compounds can also be introduced into the casting solution in the form of loaded latices.
  • anionic water-soluble compounds e.g. dyes
  • pickling polymers e.g. acrylic acid
  • Suitable oil formers are e.g. Alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.
  • suitable oil formers are dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, 2-ethylphosphate, tridecoxyphosphate, tri-ethylphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecylphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecoxyphosphat
  • polyester carboxylic acids according to the invention are preferably used as oil formers, optionally in a mixture with other oil formers, the compounds according to the invention making up at least 50% by weight.
  • Each of the differently sensitized, light-sensitive layers can consist of a single layer or can also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470).
  • red-sensitive silver halide emulsion layers are often arranged closer to the support than green-sensitive silver halide emulsion layers and these are in turn closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.
  • the green or Red-sensitive layers can be selected without the yellow filter layer, other layer arrangements in which e.g. the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.
  • the non-light-sensitive intermediate layers which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.
  • Suitable agents which are also called scavengers or EOP-catchers, are described in Research Disclosure 17.643 / 1978, Chapter VII, 17.842 / 1979, pages 94-97 and 18.716/1979, page 650 and in EP-A-69 070, 98 072, 124 877, 125 522 and in US-A-463 226.
  • sub-layers of the same spectral sensitization can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains.
  • the sublayer with higher sensitivity will be located further away from the support than the sublayer with lower sensitivity.
  • Partial layers of the same spectral sensitization can be adjacent to one another or through other layers, e.g. separated by layers of other spectral sensitization.
  • all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A 1 958 709, DE-A 2 530 645, DE-A 2 622 922).
  • the photographic material may further contain UV light absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives for improving the stabilization of dyes, couplers and whites, and for reducing the color fog and others.
  • Compounds that absorb UV light are intended on the one hand to protect the image dyes from fading by UV-rich daylight and, on the other hand, as filter dyes to absorb the UV light in daylight upon exposure and thus improve the color rendering of a film.
  • Connections of different structures are usually used for the two tasks. Examples are aryl-substituted benzotriazole compounds (US-A 3 533 794), 4-thiazolidone compounds (US-A 3 314 794 and 3 352 681), benzophenone compounds (JP-A 2784/71), cinnamic acid ester compounds (US-A 3 705 805 and 3 707) 375), butadiene compounds (US-A 4 045 229) or benzoxazole compounds (US-A 3 700 455).
  • Ultraviolet absorbing couplers such as a-naphthol type cyan couplers
  • ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.
  • Filter dyes suitable for visible light include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.
  • Suitable whiteners are e.g. in Research Disclosure December 1978, page 22 ff, Unit 17,643, Chapter V, in US-A-2,632,701, 3,269,840 and in GB-A-852,075 and 1,319,763.
  • binder layers in particular the most distant layer from the support, but also occasionally intermediate layers, especially if they are the most distant layer from the support during manufacture, may contain photographically inert particles of inorganic or organic nature, e.g. as a matting agent or as a spacer (DE-A 3 331 542, DE-A 3 424 893, Research Disclosure December 1978, page 22 ff, Unit 17 643, Chapter XVI).
  • photographically inert particles of inorganic or organic nature e.g. as a matting agent or as a spacer (DE-A 3 331 542, DE-A 3 424 893, Research Disclosure December 1978, page 22 ff, Unit 17 643, Chapter XVI).
  • the average particle diameter of the spacers is in particular in the range from 0.2 to 10 ⁇ m.
  • the spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath.
  • suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
  • Additives to improve dye, coupler and whiteness stability and to reduce the color fog can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromans, spiroindanes, p- Alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.
  • the layers of the photographic material can be hardened with the usual hardening agents.
  • Suitable curing agents include formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds, the reactive halogen contain (US-A 3 288 775, US-A-2 732 303, GB-A-974 723 and GB-A 1 167 207) divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine and other compounds containing a reactive olefin bond (US-A 3 635 718, US-A-3 232 763 and GB-A 994 869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A 2 732 316 and
  • Acid derivatives (US-A 2 725 294 and US-A 2 725 295); Carbodiimide type compounds (US-A 3 100 704); Carbamoylpyridinium salts (DE-A 2 225 230 and DE-A 2 439 551); Carbamoyloxypyridinium compounds (DE-A-2 408 814); Compounds with a phosphorus-halogen bond (JP-A-113 929/83); N-carbonyloximide compounds (JP-A-43353/81); N-sulfonyloximido compounds (US-A-4 111 926), dihydroquinoline compounds (US-A-4 013 468), 2-sulfonyloxypyridinium salts (JP-A-110 762/81), formamidinium salts (EP-A 0 162 308), Compounds having two or more N-acyloximino groups (US-A-4,052,
  • the hardening can be effected in a known manner by adding the hardening agent to the casting solution for the layer to be hardened, or by overlaying the layer to be hardened with a layer which contains a diffusible hardening agent.
  • Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed to such an extent immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours, that no further change in the sensitometry and the swelling of the layer structure occurs as a result of the crosslinking reaction .
  • Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).
  • hardening agents that react very quickly with gelatin are e.g. to carbamoylpyridinium salts, which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin to form peptide bonds and crosslink the gelatin.
  • Color photographic negative materials are usually processed by developing, bleaching, fixing and washing or by developing, bleaching, fixing and stabilizing without subsequent washing, whereby bleaching and fixing can be combined into one processing step.
  • All developer compounds which have the ability, in the form of their oxidation product, with color couplers to form azomethine or indophenol dyes can be used as the color developer compound react.
  • Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
  • Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73, 3106 (1951) and G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, page 545 ff.
  • bleaching agents e.g. Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used.
  • Iron (III) complexes of aminopolycarboxylic acids are particularly preferred, especially e.g. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids.
  • Persulphates are also suitable as bleaching agents.
  • the bleach-fixing bath or fixing bath is usually followed by washing, which is designed as countercurrent washing or consists of several tanks with their own water supply.
  • the washing can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent.
  • this stabilizing bath also acts as a final bath.
  • Emulgate E-1 to E-5 were mixed in various samples of a red sensitized silver halide emulsion.
  • the silver halide gelatin emulsion consisted of 75 g of silver bromide iodide (iodide content 3 mol%) and 72 g of gelatin, based on 1 kg of emulsion.
  • the emulsions prepared in this way were applied to cellulose triacetate supports provided with an adhesive layer, dried and hardened.
  • the application of silver bromide is 1.65 g / m 2 ; the order for couplers and oil formers each 1.0 g / m 2 .
  • the hardening takes place by covering with a 1% by weight solution of the hardener of the formula
  • the individual samples were exposed by means of a sensitometer and then processed using the following color developer.
  • the stop, bleach and fix baths are common bath compositions. A final bath free of formalin was used.
  • the emulsions were introduced into a green-sensitized silver halide material, processed and hardened. 1.2 g / m 2 of silver bromide and 0.85 g / m 2 of coupler and oil former were applied.
  • the latex couplers L 2, L 3, L 4 were produced in the same way, with the difference that in addition to the oleyl methyl tauride emulsifier, 0.7 g, 1.4 g, 2.8 g of the polyester carboxylic acid 1-2 were used as Na salt were.
  • the latex couplers L 1 to L 4 were mixed into various samples of a green-sensitized silver halide emulsion which consisted of 75 g of silver bromide iodide (iodide content 3 mol%) and 72 g of gelatin, based on 1 kg of emulsion.
  • the emulsions prepared in this way were applied to cellulose triacetate layer supports provided with an adhesive layer, dried and cured as in Example 1. 1.2 g / m 2 of silver bromide and 1.7 g / m 2 of latex couplers were applied.
  • Example 1 As described in Example 1, the samples were exposed, processed and evaluated sensitometrically.
  • a 15 ⁇ m thick red-sensitized cyan emulsion layer was applied to a cellulose triacetate pad with a 4 ⁇ m thick anti-halo layer composed of gelatin and black colloidal silver.
  • polyester carboxylic acid 1-2 Equal amounts of polyester carboxylic acid 1-2 and, as a comparison, polyethyl acrylate were used in further samples.
  • the layers were dried after drying in a climate of 23 ° C and 20% rel. Adjusted air humidity.
  • the fragility was determined using the following apparatus.
  • a film loop with the emulsion turned outwards is clamped in a parallel baking device with a load cell.
  • a squeezing speed of 10 cm / s the movable jaw moves up to the twice the film thickness on the fixed jaw and turns back.
  • Latices were produced using the sodium salts of polyester carboxylic acids (pH 7.8) according to the invention. The preparation for latex 1 is described below.
  • the latices 2-13 were prepared in an analogous manner (Table 7).
  • the latices are distinguished by the fact that they tend to have comparatively little disruptive foam formation in comparison with the latices produced with conventional anionic emulsifiers. They are also very finely divided and very good with the binders used in photographic materials, e.g. Gelatin miscible, so that clear layers are obtained even when mixed with photographic casting solutions.
  • a color photographic recording material for the color negative development was produced by placing the following layers in the specified manner on a transparent layer support made of cellulose triacetate Order were applied. The quantities given relate in each case to 1 m 2. The corresponding quantities of AgNO 3 are indicated for the silver halide application. All silver halide emulsions were stabilized per 100 g of AgNO 3 with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.
  • a yellow coupler emulsifier is produced in the same way as in recipe 7.1, except that instead of the polyester carboxylic acid, the same amount of tricresyl phosphate and an additional 0.42 g of wetting agent dodecylbenzosulfonate are used in I.
  • a yellow coupler emulsate is produced in the same way as for recipe V1.1, but instead of tricresyl phosphate the same amount of polyester diol 11.10, a starting product for the polyester carboxylic acid, is used.
  • a purple emulsate is produced as recipe 7.2, but instead of the polyester carboxylic acid, the same amount of an oil form mixture dibutyl phthalate (DBP) / tricresyl phosphate (TKP) 10: 1 and as a wetting agent 0.32 g of the compound of the formula emulsified in I.
  • DBP dibutyl phthalate
  • TKP tricresyl phosphate
  • a magenta coupler emulsate is produced in the same way as for recipe V2.1, except that the same amount of polyester diol 11.10 was used instead of the oil former mixture DBP / TKP 10: 1.
  • a cyan coupler emulsifier is produced according to recipe 7.3, only the same amount of the oil shaping mixture TBP / TKP 3: 1 and 0.8 g of the wetting agent from V2.1 are added instead of the polyester carboxylic acid.
  • the emulsifier is produced in the same way as for recipe V3.1, except that the same amount of polyester diol 11.10 is used instead of the oil shaping mixture DBP / TKP 3: 1.
  • experimental setup I contains less wetting agent, which can diffuse into the baths and generates foam.
  • polyester diols can be used as oil formers, but also do not give excellent maximum color densities in comparison with the polyester carboxylic acids.
  • a large amount of wetting agent must be added so that the desired small particle size is obtained.
  • the particle size is measured with the Autosizer 11, manufacturer: MALVERN.
  • the digestion stability is checked by allowing the emulsions to stand for 24 hours at 40 ° C. and then comparing the particle size before and after digestion.
  • the cyan emulsified with the polyester carboxylic acid according to the invention has an outstandingly small particle size without the addition of wetting agent, which hardly changes even after the 24-hour digestion.
  • the cyan coupler emulsions produced with the oil former TKP (W1) and with the oil former Polyesterdiol (VV2) have much coarser particles and a higher polydispersity. After digestion, the particles coarsen so much that a measurement is no longer possible.
  • polyester carboxylic acid according to the invention combines both properties: good solution properties for color couplers and very good wetting agent action.

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)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Polyesters Or Polycarbonates (AREA)

Claims (6)

1. Matériau d'enregistrement photographique à l'halogénure d'argent comportant un support, au moins une couche photosensible d'émulsion à l'halogénure d'argent, une couche protectrice et éventuellement des couches supplémentaires, caractérisé en ce que, dans au moins une couche qui est disposée plus près du support que la couche protectrice, est contenu un composé qui, sous forme de l'acide libre, répond à la formule
Figure imgb0220
dans laquelle
R1 représente un groupe alkylène, un groupe arylène, un groupe aralkylène ou un groupe cycloalkylène,
L représente le radical d'un polyesterdiol ayant un poids moléculaire moyen de 500 à 20.000,
m représente 0 ou 1,
n représente de 0 à 30, de préférence de 0 à 10 et
m + n ≧ 1.
2. Matériau d'enregistrement photographique à l'halogénure d'argent selon la revendication 1, caractérisé en ce que les composés de formule 1 possèdent des indices d'acide de 30 à 340 mg KOH/g.
3. Matériau d'enregistrement photographique à l'halogénure d'argent selon la revendication 1, caractérisé en ce que les composés de formule 1 possèdent des indices d'acide de 50 à 200 mg KOH/g.
4. Matériau d'enregistrement photographique à l'halogénure d'argent selon la revendication 1, caractérisé en ce qu'il contient de 0,02 à 5,0 g/m2 du composé de formule I sous forme de l'acide libre.
5. Matériau d'enregistrement photographique à l'halogénure d'argent selon la revendication 1, caractérisé en ce qu'il contient de 0,01 à 3,0 g/m2 du composé de formule I sous forme anionique.
6. Matériau d'enregistrement photographique à l'halogénure d'argent selon la revendication 1, caractérisé en ce que les polyesterdiols de formule
Figure imgb0221
sont formés à partir de diols de formule
Figure imgb0222
et d'acides dicarboxyliques de formule
Figure imgb0223
dans lesquelles
R2 représente un groupe d'hydrocarbure bivalent contenant de 2 à 13 atomes de carbone,
R3 représente un groupe d'hydrocarbure bivalent contenant de 2 à 13 atomes de carbone, et q représente 0 ou 1.
EP89115801A 1988-09-08 1989-08-26 Matériau de reproduction photographique Expired - Lifetime EP0358073B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3830522 1988-09-08
DE3830522A DE3830522A1 (de) 1988-09-08 1988-09-08 Fotografisches aufzeichnungsmaterial

Publications (3)

Publication Number Publication Date
EP0358073A2 EP0358073A2 (fr) 1990-03-14
EP0358073A3 EP0358073A3 (fr) 1991-03-27
EP0358073B1 true EP0358073B1 (fr) 1994-06-01

Family

ID=6362523

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89115801A Expired - Lifetime EP0358073B1 (fr) 1988-09-08 1989-08-26 Matériau de reproduction photographique

Country Status (4)

Country Link
US (1) US4939077A (fr)
EP (1) EP0358073B1 (fr)
JP (1) JP2723628B2 (fr)
DE (2) DE3830522A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3830522A1 (de) 1988-09-08 1990-03-15 Agfa Gevaert Ag Fotografisches aufzeichnungsmaterial
DE4015161A1 (de) * 1990-05-11 1991-11-14 Agfa Gevaert Ag Fotografisches material mit nc-schicht
US5302501A (en) * 1991-10-25 1994-04-12 Fuji Photo Film Co., Ltd. Silver halide photographic material
DE69308741T2 (de) * 1992-11-12 1997-06-26 Eastman Kodak Co Photographische Zusammensetzung enthaltend einen Verdicker
US5610002A (en) * 1992-11-12 1997-03-11 Eastman Kodak Company Photographic composition containing a thickening agent
US5594047A (en) * 1995-02-17 1997-01-14 Eastman Kodak Company Method for forming photographic dispersions comprising loaded latex polymers
US5582960A (en) * 1995-02-17 1996-12-10 Eastman Kodak Company Photographic print material
GB9517912D0 (en) * 1995-09-02 1995-11-01 Kodak Ltd Improved oil-in-water emulsions
US5589322A (en) * 1995-12-12 1996-12-31 Eastman Kodak Company Process for making a direct dispersion of a photographically useful material
US5981159A (en) * 1996-09-27 1999-11-09 Eastman Kodak Company Photographic material

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2234736A1 (de) * 1971-07-16 1973-02-01 Eastman Kodak Co Verfahren zur modifizierung der elektrostatischen aufladungseigenschaften von gegenstaenden

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2565418A (en) * 1947-08-13 1951-08-21 Eastman Kodak Co Method of preparing photographic silver halide emulsions
US3563942A (en) 1967-11-29 1971-02-16 Du Pont Aqueous dispersion of copolyesters modified with a sulfonated aromatic compound
JPS5240979B2 (fr) * 1973-09-17 1977-10-15
JPS5119534A (ja) * 1974-08-09 1976-02-16 Fuji Photo Film Co Ltd Shashinyojukikoroidotofubutsu
JPS51102095A (ja) * 1975-03-05 1976-09-09 Showa Electric Wire & Cable Co Suiyoseihoriesuterukeijushino seiho
JPS5399928A (en) * 1977-02-10 1978-08-31 Konishiroku Photo Ind Co Ltd Preparation of silver halide photosensitive material
US4401787A (en) 1981-07-07 1983-08-30 Eastman Kodak Company Latex compositions for water resistant coating applications
US4879204A (en) * 1985-01-29 1989-11-07 Fuji Photo Film Co., Ltd. Silver halide photographic element containing anhydazine compound and specific dyes
JPS62115436A (ja) * 1985-11-15 1987-05-27 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料
DE3760488D1 (en) * 1986-05-26 1989-10-05 Agfa Gevaert Nv A sheet or web carrying an antistatic layer
DE3830522A1 (de) 1988-09-08 1990-03-15 Agfa Gevaert Ag Fotografisches aufzeichnungsmaterial

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2234736A1 (de) * 1971-07-16 1973-02-01 Eastman Kodak Co Verfahren zur modifizierung der elektrostatischen aufladungseigenschaften von gegenstaenden

Also Published As

Publication number Publication date
DE3830522A1 (de) 1990-03-15
EP0358073A3 (fr) 1991-03-27
JP2723628B2 (ja) 1998-03-09
US4939077A (en) 1990-07-03
JPH02113237A (ja) 1990-04-25
EP0358073A2 (fr) 1990-03-14
DE58907755D1 (de) 1994-07-07

Similar Documents

Publication Publication Date Title
EP0358071B1 (fr) Matériau de reproduction photographique
EP0358073B1 (fr) Matériau de reproduction photographique
EP0464409B1 (fr) Matériau de reproduction photographique pour la couleur
EP0585672B1 (fr) Matériau d'enregistrement photographique
EP0586974B1 (fr) Matériau photographique couleur à l'halogénure d'argent
EP0351588B1 (fr) Matériau de reproduction photographique couleur
EP0370226B1 (fr) Matériel photographique à l'halogénure d'argent et sa méthode de traitement
EP0329016B1 (fr) Matériau de reproduction photographique couleur
EP0652474B1 (fr) Matériau photographique couleur d'enregistrement
EP0447656A1 (fr) Matériau photographique couleur à l'halogénure d'argent et son développement
EP0413204A2 (fr) Matériau photographique couleur à l'halogénure d'argent
EP0377889B1 (fr) Matériel d'enregistrement à l'halogénure d'argent
EP0369235B1 (fr) Matériau d'enregistrement photographique
EP0377181A2 (fr) Matériau photographique couleur
EP0373339B1 (fr) Matériau d'enregistrement photosensible à l'halogénure d'argent
EP0363820A2 (fr) Matériau photographique couleur à l'halogénure d'argent
EP0616256B1 (fr) Matériau photographique couleur d'enregistrement
EP0697624B1 (fr) Matériau d'enregistrement photographique couleur
EP0554756B1 (fr) Produit pour la reproduction photographique en couleur
EP0564910B1 (fr) Matériau d'enregistrement pour la photographie en couleur
EP0330948A2 (fr) Procédé de production d'images colorées
EP0447657B1 (fr) Matériau d'enregistrement photographique
EP0504692B1 (fr) Film photographique inversible couleur
EP0362604A2 (fr) Matériau photographique couleur à l'halogénure d'argent
EP0709731A2 (fr) Produit photographique couleur à l'halogénure d'argent

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: 19890826

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE DE FR GB 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 NL

17Q First examination report despatched

Effective date: 19931123

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 NL

REF Corresponds to:

Ref document number: 58907755

Country of ref document: DE

Date of ref document: 19940707

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

Effective date: 19940805

ET Fr: translation filed
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: BE

Payment date: 20000704

Year of fee payment: 12

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

Ref country code: NL

Payment date: 20000710

Year of fee payment: 12

REG Reference to a national code

Ref country code: GB

Ref legal event code: 746

Effective date: 20000629

REG Reference to a national code

Ref country code: FR

Ref legal event code: D6

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

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010831

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

BERE Be: lapsed

Owner name: AGFA-GEVAERT A.G.

Effective date: 20010831

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

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020301

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20020301

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

Ref country code: FR

Payment date: 20030619

Year of fee payment: 15

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

Ref country code: GB

Payment date: 20030620

Year of fee payment: 15

Ref country code: DE

Payment date: 20030620

Year of fee payment: 15

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

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040826

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

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050301

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

Effective date: 20040826

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

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050429

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST