EP0528480B1 - Un matériau photographique à l'halogénure d'argent - Google Patents

Un matériau photographique à l'halogénure d'argent Download PDF

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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
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EP
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Prior art keywords
silver halide
emulsion
photographic
photographic material
material according
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EP19920202407
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German (de)
English (en)
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EP0528480A1 (fr
Inventor
Luc Julius Heremans
Rudi August Goedeweeck
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Agfa Gevaert NV
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Agfa Gevaert NV
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    • 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
    • G03C1/42—Developers or their precursors
    • 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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • 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
    • G03C1/34—Fog-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. Matériau photographique photosensible à l'halogénure d'argent comprenant un support et une ou plusieurs couches colloïdales hydrophiles englobant au moins une couche photosensible d'émulsion à l'halogénure d'argent, caractérisé en ce que
    - ladite couche d'émulsion est une couche d'une émulsion au bromure d'argent ou au bromoiodure d'argent sensibilisée à l'or et au soufre, possédant un faciès cristallin cubique, et
    - ladite couche d'émulsion et/ou une couche colloïdale hydrophile en relation de perméabilité à l'eau avec cette dernière comprend, à titre de composé de 3-pyrazolidin-1-one la 1-p-carboxyphényl-4,4'-diméthyl-3-pyrazolidin-1-one.
  2. Matériau photographique selon la revendication 1, dans lequel la distribution des cristaux d'halogénure d'argent est homogène dans le sens où le diamètre d'au moins 95% en poids ou en nombre des grains se situe en deçà de 40% du diamètre moyen des grains.
  3. Matériau photographique selon la revendication 1, dans lequel la distribution des cristaux d'halogénure d'argent est homogène dans le sens où le diamètre d'au moins 95% en poids ou en nombre des grains se situe en deçà de 30% du diamètre moyen des grains.
  4. Matériau photographique selon la revendication 1, dans lequel la distribution des cristaux d'halogénure d'argent est homogène dans le sens où le diamètre d'au moins 95% en poids ou en nombre des grains se situe en deçà de 10% à 20% du diamètre moyen des grains.
  5. Matériau photographique selon l'une quelconque des revendications précédentes, dans lequel ladite émulsion à l'halogénure d'argent est une émulsion à l'halogénure d'argent sensibilisée par voie spectrale.
  6. Matériau photographique selon l'une quelconque des revendications précédentes, dans lequel le matériau photographique est un matériau radiographique.
  7. Matériau photographique selon l'une quelconque des revendications précédentes, dans lequel la 3-pyrazolidin-1-one est présente dans une couche protectrice coulée par-dessus la couche d'émulsion à l'halogénure d'argent.
  8. Matériau photographique selon l'une quelconque des revendications précédentes, dans lequel la 3-pyrazolidin-1-one est présente en une quantité de 1 à 25 mmoles par mole d'halogénure d'argent de l'émulsion.
EP19920202407 1991-08-16 1992-08-04 Un matériau photographique à l'halogénure d'argent Expired - Lifetime EP0528480B1 (fr)

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EP91202099 1991-08-16
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DE69324791T2 (de) * 1993-02-12 1999-10-28 Agfa Gevaert Nv Lichtempfindliches, photograhisches Silberhalogenidmaterial mit gesteigerter Bildqualität für Schnellverarbeitung zur Anwendung in der Mammographie

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US2691589A (en) * 1953-08-03 1954-10-12 Eastman Kodak Co Photographic developer compositions
EP0196705B1 (fr) * 1985-03-26 1988-08-10 Agfa-Gevaert N.V. Méthode pour effectuer le développement contrasté d'un matériau photographique à couche d'émulsion à l'halogénure d'argent exposé sous forme d'image
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

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