EP0528480B1 - Ein photographisches Silberhalogenidmaterial - Google Patents

Ein photographisches Silberhalogenidmaterial Download PDF

Info

Publication number
EP0528480B1
EP0528480B1 EP19920202407 EP92202407A EP0528480B1 EP 0528480 B1 EP0528480 B1 EP 0528480B1 EP 19920202407 EP19920202407 EP 19920202407 EP 92202407 A EP92202407 A EP 92202407A EP 0528480 B1 EP0528480 B1 EP 0528480B1
Authority
EP
European Patent Office
Prior art keywords
silver halide
emulsion
photographic
photographic material
material according
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
EP19920202407
Other languages
English (en)
French (fr)
Other versions
EP0528480A1 (de
Inventor
Luc Julius Heremans
Rudi August Goedeweeck
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 NV
Original Assignee
Agfa Gevaert NV
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 NV filed Critical Agfa Gevaert NV
Priority to EP19920202407 priority Critical patent/EP0528480B1/de
Publication of EP0528480A1 publication Critical patent/EP0528480A1/de
Application granted granted Critical
Publication of EP0528480B1 publication Critical patent/EP0528480B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/42Developers or their precursors
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression

Definitions

  • the present invention relates to silver halide emulsions and their use in a photographic material.
  • an important aim in the photographic art in general is to develop emulsion making processes suitable for being used on an industrial scale which yield photographic materials with a maximum speed and a minimum overall fog even after long storage periods of said photographic materials.
  • sensitometric values and the image quality of a photographic light-sensitive material do not only depend on the characteristics of the emulsion but are determined also to a considerable extent by the processing conditions, in particular the type of developer selected and the degree of development.
  • the slope of the characteristic curve of a photographic material increases with increasing degree of development. However once a particular limit has been reached, the slope decreases with higher degrees of development as the fog caused by development rises considerably. The same phenomenon can also occur in short development times with more active developing baths having a minimum concentration of stabilizer.
  • the sensitometric properties of a photographic film and their dependence from the processing conditions are determined to a large extent by the size, the crystal form and the crystal structure of the silver halide crystals, which in their turn are determined by the conditions of precipitation and subsequent ripening of the silver halide crystals.
  • Regular-shaped silver halide crystals useful in photography e.g. may be prepared by employing a technique known as balanced double jet precipitation wherein separate streams of silver nitrate and alkali metal halide are introduced into a stirred gelatin solution and the process is controlled to regulate the form of the resulting silver halide crystals.
  • a photographic light-sensitive silver halide material comprising a support and one or more hydrophylic colloid layers including at least one light-sensitive silver halide emulsion layer characterised in that said emulsion layer is a layer of a gold and sulphur sensitized silver bromide or silver bromoiodide emulsion having cubic crystal habit and in that said emulsion layer and/or a hydrophylic colloid layer in water-permeable relationship therewith comprises 1-p-carboxyphenyl-4,4'-dimethyl-3-pyrazolidone the preparation of which has been described in US Patent 2,772,282, so that the material has an exceptionally good fog to speed relation.
  • This 3-pyrazolidinone compound as fog preserving agent is unexpected especially as it is known as a developing agent. It is preferably used in amounts comprised between 1 and 25 mmole per mole of silver nitrate per square meter.
  • the parameter determining whether cubic or octahedral crystals are formed during the precipitation stage of the photographic emulsion making is the pAg of the solution.
  • the pAg of the solution may be regulated by any of the means known in the art of emulsion making, such as the electronic control apparatus and method disclosed in U.S. Patent 3,821,002.
  • the pAg-values yielding cubic, resp. octahedral crystals depend on the temperature.
  • Table I the pAg-neutrality values are set forth for various temperatures, as well as the values for the formation of resp. cubic and octahedral crystals at these temperatures, which are above the pAg-neutrality values.
  • the last column gives the 'change-over pAg values', i.e. the pAg values below which cubic crystals and above which octahedral crystal formation is taking place. Around these pAg values the crystal formation balances between cubic and octahedral structure.
  • Table I Temperature pAg neutrality pAg for cubic pAg for octahedral change-over pAg-value crystal formation 80°C 5.0 6.5 8.8 8.1 60°C 5.4 7.0 9.4 8.7 40°C 5.8 7.5 10.1 9.2 20°C 6.3 8.0 10.9 9.9
  • the silver halide emulsions formed according to the present invention comprise silver bromide or silver bromoiodide.
  • Preferred silver bromoiodide emulsions comprise at most 10 mole% of iodide.
  • a preferred embodiment of making the emulsions used according to the present invention involves the preparation of high-sensitive silver bromide or silver bromoiodide emulsions e.g. X-ray emulsions, by precipitation under balanced double jet conditions.
  • the average grain-size of the silver halide emulsions made according to the present invention may vary between wide limits and depends on the intended use for the emulsion.
  • Fine grain as well as coarse-grain emulsions with an average crystal diameter between 0.1 and 2 ⁇ m, preferably below 1 ⁇ m, can be made according to the present invention, depending on the use of grain-growth restrainers or accelerators, the flow rate and concentration of the solutions, the temperature, pAg etc..
  • Particle size of silver halide grains can be determined using conventional techniques e.g. as described by Trivelli and M.Smith, The Photographic Journal, vol. 69, 1939, p. 330-338, Loveland “ASTM symposium on light microscopy” 1953, p. 94-122 and Mees and Jones “The Theory of the photographic process” (1977), Chapter II.
  • Monodispersed as well as heterodispersed emulsions can be made according to the present invention, depending on the initial conditions during precipitation, monodispersed emulsions being, however, preferred.
  • Monodispersed emulsions in contrast to heterodispersed emulsions have been characterized in the art as emulsions of which at least 95 % by weight or number of the grains have a diameter which is within 40 %, preferably within 30 % of the mean grain-diameter and more preferably within 10% to 20%.
  • Silver halide grains having a narrow grain-size distribution can be obtained by controlling the conditions at which the silver halide grains are prepared using a double jet procedure.
  • the silver halide grains are prepared by simultaneously running an aqueous solution of a water-soluble silver salt for example, silver nitrate, and watersoluble halide, for example, potassium bromide, into a rapidly agitated aqueous solution of a silver halide peptizer, preferably gelatin, a gelatin derivative or some other protein peptizer.
  • a silver halide peptizer preferably gelatin, a gelatin derivative or some other protein peptizer.
  • colloidal silica may be used as a protective colloid as has been described in EP 0392092.
  • the rates of addition of the silver nitrate and halide salt solutions is steadily increased in such a way that no renucleation appears in the reaction vessel.
  • This procedure is especially recommended, not only to save time but also to avoid physical ripening of the silver halide crystals during precipitation, the so-called Ostwald ripening phenomenon, which gives rise to the broadening of the silver halide crystal distribution.
  • the emulsions are generally washed to remove the by-products of grain-formation and grain-growth.
  • the emulsions may be chill-set, shredded and washed by leaching in cold water, or they may be washed by coagulation.
  • the emulsions are preferably washed by acid-coagulation techniques using acid-coagulable gelatin derivatives or anionic polymeric compounds or, when precipitation occurred in silica medium, by certain polymers capable of forming hydrogen bridges with silica, in an amount sufficient to form coagulable aggregates with the silica particles as has been described in EP Application 91201426.3.
  • the acid-coagulable gelatin derivatives are reaction products of gelatin with organic carboxylic or sulphonic acid chlorides, carboxylic acid anhydrides, aromatic isocyanates or 1,4-diketones.
  • the use of these acid-coagulable gelatin derivatives generally comprises precipitating the silver halide grains in an aqueous solution of the acid coagulable gelatin derivative or in an aqueous solution of gelatin to which an acid coagulable gelatin derivative has been added in sufficient proportion to impart acid-coagulable properties to the entire mass.
  • the gelatin derivative may be added after the stage of emulsification in normal gelatin, and even after the physical ripening stage, provided it is added in an amount sufficient to render the whole coagulable under acid conditions.
  • acid-coagulable gelatin derivatives suitable for use in accordance with the present invention can be found e.g. in the United States Patent Specifications referred to above. Particularly suitable are phthaloyl gelatin and N-phenylcarbamoyl gelatin.
  • anionic polymeric compounds are polystyrene sulphonic acid and sulphonated copolymers of styrene.
  • the anionic polymers can be added to the gelatin solution before precipitation of the silver halide grains or after the stage of emulsification. They are preferably added after the grains have reached their ultimate size and shape, i.e. just before washing. It is also possible to use anionic polymers in combination with acid-coagulable gelatin derivatives as described in the published German Patent Specification No. 2,337,172 (DOS).
  • polystyrene sulphonic acid having a molecular weight of at most 30,000.
  • the polystyrene sulphonic acid can be added to the gelatin solution from aqueous solutions preferably comprising from 5 to 20 % by weight of polystyrene sulphonic acid.
  • the amounts used suffice to impart coagulation properties to the emulsion and can easily be determined by those skilled in the art.
  • the silver halide emulsion comprising acid-coagulable gelatin derivative or anionic polymer is acidified e.g. by means of dilute sulphuric acid, citric acid, acetic acid, etc. so as to effect coagulation.
  • Coagulation generally occurs at a pH value comprised between 3 and 4.
  • the coagulum formed may be removed from the liquid by any suitable means, for example the supernatant liquid is decanted or removed by means of a siphon, where upon the coagulum is washed out once or several times.
  • washing of the coagulum may occur by rinsing with mere cold water.
  • the first wash water is preferably acidified to lower the pH of the water to the pH of the coagulation point.
  • Anionic polymer e.g. polystyrene sulphonic acid may be added to the wash water even when an acid coagulable gelatin derivative has been used e.g. as described in published German Patent Specification (DOS) 2,337,172 mentioned hereinbefore.
  • washing may be effected by redispersing the coagulum in water at elevated temperature using a small amount of alkali, e.g. sodium or ammonium hydroxide, recoagulating by addition of an acid to reduce the pH to the coagulation point and subsequently removing the supernatant liquid. This redispersion and recoagulation operation may be repeated as many times as is necessary.
  • the coagulum is redispersed to form a photographic emulsion suitable for the subsequent finishing and coating operations by treating, preferably at a temperature within the range of 35 to 70°C, with the required quantity of water, normal gelatin and, if necessary, alkali for a time sufficient to effect a complete redispersal of the coagulum.
  • photographic hydrophilic colloids can also be used for redispersion e.g. a gelatin derivative as referred to above, albumin, agar-agar, sodium alginate, hydrolysed cellulose esters, polyvinyl alcohol, hydrophilic polyvinyl copolymers, colloidal silica etc.
  • the light-sensitive silver bromide or silver bromoiodide emulsions are chemically sensitized with a sulphur and gold sensitizer. This can be done as described i.a. in the above-mentioned "Chimie et Physique Photographique” by P. Glafkides, in the above-mentioned “Photographic Emulsion Chemistry” by G.F. Duffin, in the above-mentioned “Making and Coating Photographic Emulsion” by V.L. Zelikman et al, and in "Die Grundlagen der Photographischen mit Silberhalogeniden” edited by H. Frieser and published by Akademische Verlagsgesellschaft (1968).
  • sulphur sensitization can be carried out by effecting the ripening in the presence of small amounts of compounds containing sulphur e.g. thiosulphate, thiocyanate, thioureas, sulphites, mercapto compounds, and rhodamines.
  • Gold sensitization occurs by means of gold compounds.
  • small amounts of compounds of Ir, Rh, Ru, Pb, Cd, Hg, Tl, Pd or Pt can be used.
  • the emulsions can be sensitized in addition by means of reductors e.g. tin compounds as described in GB-A 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
  • the light-sensitive silver halide emulsions can be spectrally sensitized with methine dyes such as those described by F.M. Hamer in "The Cyanine Dyes and Related Compounds", 1964, John Wiley & Sons.
  • Dyes that can be used for the purpose of spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, homopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes, complex merocyanine dyes.
  • Suitable supersensitizers are i.a. heterocyclic mercapto compounds containing at least one electronegative substituent as described e.g. in US-A 3,457,078, nitrogen-containing heterocyclic ring-substituted aminostilbene compounds as described e.g. in US-A 2,933,390 and US-A 3,635,721, aromatic organic acid/formaldehyde condensation products.
  • 3-pyraolidinone stabilizing compounds used in accordance with the present invention
  • other compounds for preventing the formation of fog or stabilizing the photographic characteristics during the production or storage of photographic elements or during the photographic treatment thereof may be supplementary added.
  • stabilizers are heterocyclic nitrogen-containing stabilizing compounds as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles (preferably 5-methyl-benzotriazole), nitrobenzotriazoles, mercaptotetrazoles, in particular 1-phenyl-5-mercapto-tetrazole, mercaptopyrimidines, mercaptotriazines, benzothiazoline-2-thione, oxazoline-thione, triazaindenes,
  • the binders of the photographic element can be hardened with appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. 1,3-vinylsulphonyl-2-propanol, chromium salts e.g. chromium acetate and chromium alum, aldehydes e.g. formaldehyde, glyoxal, and glutaraldehyde, N-methylol compounds e.g. dimethylolurea and methyloldimethylhydantoin, dioxan derivatives e.g.
  • appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. 1,3-vinylsulphonyl-2-propanol, chromium salts e.g. chromium acetate and
  • 2,3-dihydroxy-dioxan active vinyl compounds e.g. 1,3,5-triacryloyl-hexahydro-s-triazine, active halogen compounds e.g. 2,4-dichloro-6-hydroxy-s-triazine, and mucohalogenic acids e.g. mucochloric acid and mucophenoxychloric acid.
  • active vinyl compounds e.g. 1,3,5-triacryloyl-hexahydro-s-triazine
  • active halogen compounds e.g. 2,4-dichloro-6-hydroxy-s-triazine
  • mucohalogenic acids e.g. mucochloric acid and mucophenoxychloric acid.
  • the photographic element of the present invention may further comprise various kinds of surface-active agents in the photographic emulsion layer or in at least one other hydrophilic colloid layer.
  • Suitable surface-active agents include non-ionic agents such as saponins, alkylene oxides e.g.
  • polyethylene glycol polyethylene glycol/polypropylene glycol condensation products, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or alkylamides, silicone-polyethylene oxide adducts, glycidol derivatives, fatty acid esters of polyhydric alcohols and alkyl esters of saccharides; anionic agents comprising an acid group such as a carboxy, sulpho, phospho, sulphuric or phosphoric ester group; ampholytic agents such as aminoacids, aminoalkyl sulphonic acids, aminoalkyl sulphates or phosphates, alkyl betaines, and amine-N-oxides; and cationic agents such as alkylamine salts, aliphatic, aromatic, or heterocyclic quaternary ammonium salts, aliphatic or heterocyclic ring
  • Such surface-active agents can be used for various purposes e.g. as coating aids, as compounds preventing electric charges, as compounds improving slidability, as compounds facilitating dispersive emulsification, as compounds preventing or reducing adhesion, and as compounds improving the photographic characteristics e.g higher contrast, sensitization, and development acceleration.
  • Development acceleration can be accomplished with the aid of various compounds, preferably polyalkylene derivatives having a molecular weight of at least 400 such as those described in e.g. US-A 3,038,805 - 4,038,075 - 4,292,400.
  • the photographic element of the present invention may further comprise various other additives such as e.g. compounds improving the dimensional stability of the photographic element, UV-absorbers, spacing agents, hardeners, plasticizers, antistatic agents etc...
  • additives such as e.g. compounds improving the dimensional stability of the photographic element, UV-absorbers, spacing agents, hardeners, plasticizers, antistatic agents etc...
  • Suitable additives for improving the dimensional stability of the photographic element are i.a. dispersions of a water-soluble or hardly soluble synthetic polymer e.g. polymers of alkyl (meth)acrylates, alkoxy(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters, acrylonitriles, olefins , and styrenes, or copolymers of the above with acrylic acids, methacrylic acids, Alpha-Beta-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulphoalkyl (meth)acrylates, and styrene sulphonic acids.
  • a water-soluble or soluble synthetic polymer e.g. polymers of alkyl (meth)acrylates, alkoxy(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters,
  • Suitable UV-absorbers are i.a. aryl-substituted benzotriazole compounds as described in US-A 3,533,794, 4-thiazolidone compounds as described in US-A 3,314,794 and 3,352,681, benzophenone compounds as described in JP-A 2784/71, cinnamic ester compounds as described in US-A 3,705,805 and 3,707,375, butadiene compounds as described in US-A 4,045,229, and benzoxazole compounds as described in US-A 3,700,455.
  • the average particle size of spacing agents is comprised between 0.2 and 10 um.
  • Spacing agents can be soluble or insoluble in alkali. Alkali-insoluble spacing agents usually remain permanently in the photographic element, whereas alkali-soluble spacing agents usually are removed therefrom in an alkaline processing bath.
  • Suitable spacing agents can be made i.a. of polymethyl methacrylate, of copolymers of acrylic acid and methyl methacrylate, and of hydroxypropylmethyl cellulose hexahydrophthalate. Other suitable spacing agents have been described in US-A 4,614,708.
  • the photographic element can comprise an antistatic layer e.g. to avoid static discharges during coating, processing and other handlings of the material.
  • antistatic layer can be an outermost coating or stratum of one or more antistatic agents or a coating applied directly to the film support or other support and overcoated with a barrier or gelatin layer.
  • Antistatic compounds suitable for use in such layers are e.g. vanadium pentoxide sols, tin oxide sols or conductive polymers such as polyethylene oxides and the like.
  • a fully chemically sensitized fast monodisperse negative bromoiodide emulsion of 1 mole percent iodide content was prepared in the following manner.
  • the emulsion was further chemically sensitized for a period of 3 hours at 45°C in the presence of p-toluene thiosulphonate, sodium thiosulphate and gold(III)chloride as noble-metal sensitizer.
  • a series of photographic material samples were made by coating the emulsion on polyethylene terephthalate together with a composition for forming a protective gelatin layer.
  • the emulsion layers were coated at a ratio of 7g/m 2 expressed as the equivalent amount of AgNO 3 .
  • the amount of gelatin per square meter in the emulsion layers was 3.3 g, whereas in the protective layers it was 1.1 g.
  • Example 5 As a comparison sample(example 5) no compound was added. In another comparative sample(example 1) a mercury salt (Hg(CN) 2 in an amount of 0.012 mg/m 2 ) was added to the emulsion layer. For all samples TAI was always incorporated as an emulsion stabilizer to the coating solutions in an amount of 35 mg/m 2 .
  • the developed photographic strips were fixed in a conventional fixing bath comprising e.g. sodium thiosulfate and potassium metabisulfite, and then rinsed in water and allowed to dry.
  • a conventional fixing bath comprising e.g. sodium thiosulfate and potassium metabisulfite
  • Sensitometric properties of these film strips are indicated in Table II.
  • the values figuring in the different columns have the following meaning : the values set forth in the first three columns show the sensitometric results in terms of fog, speed, and gradation of the photographic strips prepared as set forth above and developed in the developing bath of the composition set forth above during an overall developing time of 12 seconds.
  • the values for the speed are absolute values corresponding to density 1 above fog, expressed in log Ixt, a lower value indicating that the material is more sensitive (a difference in log Ixt of -0.30 means a doubling of the speed).
  • the values given for gamma are the values of gradation measured from the characteristic curve over a density range of 0.80 starting from a density value of 0.80 to 1.60 above fog.
  • Table II Example Fog Speed Gradation Difference in fog speed gradation comp1 0.048 200 3.09 +0.019 +0.04 -0.010 2 0.012 200 3.38 +0.008 +0.02 -0.059 3 0.013 201 3.43 +0.006 +0.03 -0.074 4 0.011 200 3.57 +0.007 +0.06 -0.095 comp5 0.049 193 3.02 +0.114 +0.30 -0.062
  • Comparative example 1 shows that a mercury salt is giving rise to better preservation results, but that the best results are obtained with 1-p-carboxyphenyl-4,4'-dimethyl-3-pyrazolidine-1-one in an amount of several hundreds of milligrams per square meter, being an amount that is not very critical.

Claims (8)

  1. Ein fotografisches lichtempfindliches Silberhalogenidmaterial, das einen Träger und eine oder mehrere hydrophile Kolloidschichten, von denen wenigstens eine eine lichtempfindliche Silberhalogenidemulsionsschicht ist, enthält, dadurch gekennzeichnet, daß
    - die Emulsionsschicht eine eine mit Gold und Schwefel sensibilisierte Silberbromid- oder Silberbromidiodidemulsion mit einer kubischen Kristallstruktur enthaltende Schicht ist und
    - die Emulsionsschicht und/oder eine hydrophile, in wasserdurchlässigem Verhältnis dazu stehende Kolloidschicht als 3-Pyrazolidin-1-on-Verbindung 1-p-Carboxyphenyl-4,4'-dimethyl-3-pyrazolidin-1-on enthält.
  2. Ein fotografisches Material nach Anspruch 1, dadurch gekennzeichnet, daß die Silberhalogenidkristalle eine homogene Korngrößenverteilung aufweisen, wobei der Durchmesser von wenigstens 95 Gew.-% oder Zahlen-% der Körner um höchstens 40% vom durchschnittlichen Korndurchmesser abweicht.
  3. Ein fotografisches Material nach Anspruch 1, dadurch gekennzeichnet, daß die Silberhalogenidkristalle eine homogene Korngrößenverteilung aufweisen, wobei der Durchmesser von wenigstens 95 Gew.-% oder Zahlen-% der Körner um höchstens 30% vom durchschnittlichen Korndurchmesser abweicht.
  4. Ein fotografisches Material nach Anspruch 1, dadurch gekennzeichnet, daß die Silberhalogenidkristalle eine homogene Korngrößenverteilung aufweisen, wobei der Durchmesser von wenigstens 95 Gew.-% oder Zahlen-% der Körner um höchstens 10% bis 20% vom durchschnittlichen Korndurchmesser abweicht.
  5. Ein fotografisches Material nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die Silberhalogenidemulsion eine spektral sensibilisierte Silberhalogenidemulsion ist.
  6. Ein fotografisches Material nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das fotografische Material ein Röntgenmaterial ist.
  7. Ein fotografisches Material nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das 3-Pyrazolidin-1-on in einer auf die SilberhalogenidEmulsionsschicht aufgetragenen Schutzschicht eingearbeitet ist.
  8. Ein fotografisches Material nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das 3-Pyrazolidin-1-on in einer Menge zwischen 1 und 25 Mmol pro Mol Silberhalogenid der Emulsion enthalten ist.
EP19920202407 1991-08-16 1992-08-04 Ein photographisches Silberhalogenidmaterial Expired - Lifetime EP0528480B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19920202407 EP0528480B1 (de) 1991-08-16 1992-08-04 Ein photographisches Silberhalogenidmaterial

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP91202099 1991-08-16
EP91202099 1991-08-16
EP19920202407 EP0528480B1 (de) 1991-08-16 1992-08-04 Ein photographisches Silberhalogenidmaterial

Publications (2)

Publication Number Publication Date
EP0528480A1 EP0528480A1 (de) 1993-02-24
EP0528480B1 true EP0528480B1 (de) 1997-11-19

Family

ID=26129362

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19920202407 Expired - Lifetime EP0528480B1 (de) 1991-08-16 1992-08-04 Ein photographisches Silberhalogenidmaterial

Country Status (1)

Country Link
EP (1) EP0528480B1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69324791T2 (de) * 1993-02-12 1999-10-28 Agfa Gevaert Nv Lichtempfindliches, photograhisches Silberhalogenidmaterial mit gesteigerter Bildqualität für Schnellverarbeitung zur Anwendung in der Mammographie

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2688548A (en) * 1953-08-03 1954-09-07 Eastman Kodak Co Photographic developer composition
EP0196705B1 (de) * 1985-03-26 1988-08-10 Agfa-Gevaert N.V. Verfahren zur Durchführung der kontrastreichen Entwicklung eines bildmäsig belichteten photographischen Silberhalogenidemulsionsschichtmaterials
JP2873852B2 (ja) * 1990-03-03 1999-03-24 コニカ株式会社 ハロゲン化銀写真感光材料

Also Published As

Publication number Publication date
EP0528480A1 (de) 1993-02-24

Similar Documents

Publication Publication Date Title
US5449599A (en) Silver halide light-sensitive photographic material with enhanced image quality for rapid processing applications in mammography
EP0528476B1 (de) Verfahren zur Herstellung eines photographischen Silberhalogenidmaterials
EP0532094B1 (de) Verfahren zur Herstellung eines Gelatine enthaltenden Aufzeichnungsmaterials
US5286621A (en) Method for the preparation of tabular emulsion grains rich in chloride
EP0503700B1 (de) Verfahren zur Herstellung von Jodobromid-Emulsionen, die monodisperse tabulare Körner enthalten
US5601969A (en) Preparation of tabular emulsion grains rich in chloride
EP0528480B1 (de) Ein photographisches Silberhalogenidmaterial
EP0555897B1 (de) Photographisches Silberhalogenidröntgenmaterial mit passenden Bildton und Oberflächenglanz
US5017468A (en) Process for the preparation of silver halide emulsions
EP0712034A1 (de) Verfahren zur spektralen Sensibilisierung von tafelförmigen Silberhalogenidkörnern
US5447817A (en) Processing of silver halide photographic industrial x-ray films
US5447826A (en) Photographic silver halide material
EP0712036B1 (de) Lichtempfindliches photographisches Schirm/Silberhalogenidfilmsystem mit verbesserter Bildqualität für Schnellverarbeitungsanwendungen in der Mammographie
US5445927A (en) Silver halide photographic industrial radiography suitable for various processing applications
US5476761A (en) Preparation method of regular silver (halide) bromide or silver bromoiodide light-sensitive emulsions and material comprising said emulsions
US5620836A (en) Assortment of silver halide photographic industrial x-ray films and method of processing said assortment
EP0620483A1 (de) Verarbeitung von photographischen industriellen Silberhalogenid-Röntgenfilmen
EP0651284A1 (de) Fällung von Silberhalogenidkristallen, die lodid enthalten
EP0682287A1 (de) Verfahren zur Herstellung von lichtempfindlichen Silberhalogenidemulsionen, die chloridreiche Kristalle enthalten; und diese Emulsionen enthaltendes Material
EP0590715B1 (de) Emulsionsherstellung mittels gleichzeitig durchgeführten chemischer und spektraler Sensibilisierung in Anwesenheit eines Salzes
EP0610608B1 (de) Photographisches, lichtempfindliches Silberhalogenidmaterial zur Wiedergabe von medizinischen laseraufgezeichneten Bildern und Verfahren zur Verarbeitung
EP0653669A1 (de) Chloridreiche Tafelkornemulsion mit (100)-Hauptflächen
US6733947B2 (en) Diagnostic radiographic silver halide photographic film material
US5523197A (en) Multilayer direct-positive photographic material and process for preparing the same
EP0649051A1 (de) Herstellungsverfahren für lichtempfindliche Silberhalogenidemulsion und diese Emulsionen enthaltendes Material

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

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB NL

17P Request for examination filed

Effective date: 19930707

17Q First examination report despatched

Effective date: 19960903

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

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

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19971119

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19971119

REF Corresponds to:

Ref document number: 69223192

Country of ref document: DE

Date of ref document: 19980102

ET Fr: translation filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
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
REG Reference to a national code

Ref country code: GB

Ref legal event code: 746

Effective date: 19990812

REG Reference to a national code

Ref country code: FR

Ref legal event code: D6

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

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: 12

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: 12

Ref country code: DE

Payment date: 20030620

Year of fee payment: 12

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: 20040804

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: 20040804

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