EP0590715B1 - Emulsionsherstellung mittels gleichzeitig durchgeführten chemischer und spektraler Sensibilisierung in Anwesenheit eines Salzes - Google Patents

Emulsionsherstellung mittels gleichzeitig durchgeführten chemischer und spektraler Sensibilisierung in Anwesenheit eines Salzes

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Publication number
EP0590715B1
EP0590715B1 EP19930202730 EP93202730A EP0590715B1 EP 0590715 B1 EP0590715 B1 EP 0590715B1 EP 19930202730 EP19930202730 EP 19930202730 EP 93202730 A EP93202730 A EP 93202730A EP 0590715 B1 EP0590715 B1 EP 0590715B1
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EP
European Patent Office
Prior art keywords
salt
emulsion
dye
water
spectral sensitization
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EP19930202730
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English (en)
French (fr)
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EP0590715A1 (de
Inventor
Lode c/o Agfa-Gevaert N.V. Deprez
René c/o Agfa-Gevaert N.V. De Keyzer
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Agfa Gevaert NV
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Agfa Gevaert NV
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Publication of EP0590715B1 publication Critical patent/EP0590715B1/de
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/015—Apparatus or processes for the preparation of emulsions
    • 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
    • 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
    • G03C1/08—Sensitivity-increasing substances
    • 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
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • 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
    • G03C2001/03511—Bromide content
    • 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
    • G03C2001/03576—Containing no iodide
    • 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
    • G03C2200/00—Details
    • G03C2200/43—Process

Definitions

  • the present invention relates to a method for the preparation of a photographic silver halide emulsion with improved characteristics.
  • sensitivity can apply to the intrinsic blue or near-ultraviolet sensitivity or to the sensitivity in a defined spectral region.
  • emulsion technology Another more recent goal of emulsion technology is providing emulsions which are suitable for so-called rapid processing. This means emulsions which can be processed in a relative short time without disadventageous side-effects like unsufficiently developed exposed silver halide, unfixed rest silver halide or residual dye stain.
  • Still another goal of emulsion technology consists in performing the consecutive steps of emulsion preparation starting from the precipitation stage up to the final coating in a rapid, efficient and cost-effective way, in the ideal case even in a continuous on-line way.
  • EP-A-291 339 claims the addition of a spectral sensitising dye during the desalting step after silver halide precipitation.
  • US-A-5 141 846 discloses the advantageous effect achieved by the addition of a spectral sensitising dye and a silver halide complexing agent during the chemical ripening of silver halide (111) grains.
  • US 2,839,405 discloses the use of several metal salts for improvement of fog and stability of bromoiodide emulsions. The salt is added after chemical and spectral sensitization.
  • Jones US 2,843,490 describes the addition of a divalent metal salt during spectral sensitization by a meso-substituted carbocyanine dye ; sensitivity and stability are claimed to be improved.
  • US 3,804,634 discloses the combination of a merocyanine dye and a divalent cadmium salt.
  • US 3,837,862 claims a combination of a cyanine and a merocyanine dye ; some particular inorganic salts can be present.
  • US 3,865,598 deals with the addition of bromides or iodides to an emulsion containing a J-band forming green sensitizer. The salt is added after the chemical ripening and before the spectral sensitization. It is believed that a halide conversion takes place, whereafter the sensitizer adsorbs better at the newly formed conversion zones.
  • Unexamined Japanese patent publication (Kokai) 57-104926 claims increased sensitivity and lower fog by the combined presence of some specified salts and some particular thioethers.
  • US 5,130,212 discloses a process combining the presence of a water-soluble calcium salt with a cyanine and a merocyanine dye.
  • the present invention constitutes a further extension and improvement on the teachings of the use of water-soluble salts during emulsion preparation.
  • the objects of the present invention are realized by providing a method for the preparation of a photographic silver halide emulsion comprising the steps of precipitation, chemical ripening and spectral sensitization, characterized in that said chemical ripening step and said spectral sensitization step are performed simultaneously and in the presence of a water-soluble metal salt the anion of which can form with a silver cation a salt with a solubility product higher than 10 -7.5 .
  • the salts resulting from the precipitatation e.g. potassium nitrate
  • a water-soluble metal salt is added in order to establish a desired optimal concentration.
  • the cation of the metal salt is divalent or polyvalent.
  • the advantages of the present invention are most perspicuous when cyanine dyes are used as spectral sensitizers.
  • the soluble salts produced during emulsion precipitation can be used as the water-soluble metal salt of the present invention and stay present while performing the simultaneous chemical ripening and spectral sensitization steps.
  • the precipition salts are removed by a conventional washing procedure, e.g. a procedure involving flocculation, several washings and redispersion, or an ultrafiltration procedure. Thereafter the concentration of the water-soluble metal salt present during the simultaneous chemical and spectral sensitization step can he freely chosen in order to establish a desired optimal ionic strenght of the reaction mixture.
  • the chemical ripening and the spectral sensitization are really performed simultaneously, and that the water-soluble metal salt is also present from the start of that simultaneous process.
  • the spectral sensitizing dye(s), the chemical ripening agent(s) and the water-soluble salt(s) are added together to the emulsion or, to work more practically, with short intervals after each other.
  • any addition order can be followed.
  • preferred sequences are (a) first adding sensitizing dye(s), then salt(s) and finally ripening agent(s), or (b) first salt(s), then dye(s) and finally ripening agent(s).
  • 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, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • the preferred class of sensitizing dyes for use in accordance with the present invention is the class of cyanine dyes, and most preferably polar cyanine dyes poorly adsorbing on a silver halide grain surface.
  • Suitable supersensitizers are i.a. heterocyclic mercapto compounds containing at least one electronegative substituent as described e.g. in US 3,457,078, nitrogen-containing heterocyclic ring-substituted aminostilbene compounds as described e.g. in US 2,933,390 and US 3,635,721, aromatic organic acid/formaldehyde condensation products as described e.g. in US 3,743,510, cadmium salts, and azaindene compounds.
  • the water-soluble salt in connection with the present invention can be all kinds of salt the anion of which can form with a silver cation a salt with a solubility product higher than 10 -7.5 , which is considerably higher than the solubility products of the silver halides. By doing so no anion conversion can occur at the emulsion grain surface.
  • useful salts include magnesium sulphate, calcium nitrate, lithium sulphate, sodium sulphate, potassium sulphate, sodium nitrate and potassium nitrate, in decreasing order of preference.
  • Salts with an divalent or polyvalent cation are preferred, because salts of this type need to be added in a lower molar concentration in order to reach a desired level of ionic strenght or conductivity than it is the case with monovalent cations. In this way the finally coated emulsion layer in not overloaded with salt.
  • the most preferred salts are magnesium sulphate and calcium nitrate.
  • mixtures of two or more salts can be used.
  • the salts are added as an aqueous solution, e.g. a 0.5 M to 1.3 M solution.
  • the optimal concentration of sensitizing dye and water-soluble salt shell be established by experiment for each particular combination of dye and salt under consideration. Usualy a dye concentration is chosen as to obtain a theoretical grain coverage between 10 and 200 percent. Preferably the amount added of the water-soluble salt is established as to obtain a concentration between 0.001 and 1.5 M, and most preferably between 0.01 M and 1.0 M.
  • the formation of the silver halide grains itself occurs according to well-known conventional techniques. They can be prepared by mixing the halide and silver solutions in partially or fully controlled conditions of temperature, concentrations, sequence of addition, and rates of addition.
  • the silver halide can be precipitated according to the single-jet method, the double-jet method, or the conversion method.
  • the resulting silver halide particles may have a regular crystalline form such as a cubic or octahedral form or they may have a transition form. They may also have an irregular crystalline form such as a spherical form or a tabular form, or may otherwise have a composite crystal form comprising a mixture of said regular and irregular crystalline forms.
  • the silver halide grains may have a multilayered grain structure.
  • the grains may comprise a core and a shell, which may have different halide compositions and/or may have undergone different modifications such as the addition of dopes.
  • the silver halide grains may also comprise different phases inbetween.
  • the average size of the silver halide grains may range from 0.05 to 1.0 micron, preferably from 0.2 to 0.5 micron.
  • the size distribution of the silver halide particles of the photographic emulsion can be homodisperse or heterodisperse. A homodisperse size distribution is obtained when 95% of the grains have a size that does not deviate more than 30% from the average grain size.
  • the silver halide emulsion can be chemically ripened as described i.a. in "Chimie et Physique Photographique” by P. Glafkides, in “Photographic Emulsion Chemistry” by G.F. Duffin, in “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).
  • chemical sensitization can be carried out by effecting the ripening in the presence of small amounts of compounds containing sulphur e.g.
  • the emulsions can be sensitized also by means of gold-sulphur ripeners or by means of reductors e.g. tin compounds as described in GB 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
  • reductors e.g. tin compounds as described in GB 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
  • conventional gold-sulphur ripening agents are used.
  • the halide composition of the silver halide emulsions prepared according to the method of this invention is not specifically limited and may be any composition selected from silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, and silver chlorobromoiodide.
  • the method of the present invention is particularly suited for the preparation of emulsions containing substantially no iodide, and most particularly for rather sensitive silver bromide emulsions containing substantially no iodide.
  • the presence of small mole percents of iodide (1 % to 5 %) in the grain and especially at the grain surface promotes the adsorption of sensitizing dyes.
  • the practice of the present invention offers the possibility of preparing emulsions substantially free of iodide, suited for rapid processing, and yet obtaining a spectral sensitivity equal to a comparable emulsion containing iodide, as will proved by the examples furtheron.
  • the silver halide emulsion for use in accordance with the present invention may comprise compounds preventing the formation of fog or stabilizing the photographic characteristics during the production or storage of photographic elements or during the photographic treatment thereof.
  • Many known compounds can be added as fog-inhibiting agent or stabilizer to the silver halide emulsion. Suitable examples are i.a.
  • heterocyclic nitrogen-containing compounds such 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, tetrazaindenes and pentazaindenes, especially those described by Birr in Z.
  • benzothiazolium salts such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlor
  • the fog-inhibiting agents or stabilizers can be added to the silver halide emulsion prior to, during, or after the ripening thereof and mixtures of two or more of these compounds can be used.
  • the binder is a hydrophilic colloid, preferably gelatin.
  • Gelatin can, however, be replaced in part or integrallly by synthetic, semi-synthetic, or natural polymers.
  • Synthetic substitutes for gelatin are e.g. polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyvinyl imidazole, polyvinyl pyrazole, polyacrylamide, polyacrylic acid, and derivatives thereof, in particular copolymers thereof.
  • Natural substitutes for gelatin are e.g. other proteins such as zein, albumin and casein, cellulose, saccharides, starch, and alginates.
  • the semi-synthetic substitutes for gelatin are modified natural products e.g. gelatin derivatives obtained by conversion of gelatin with alkylating or acylating agents or by grafting of polymerizable monomers on gelatin, and cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose, phtaloyl cellulose, and cellulose sulphates.
  • modified natural products e.g. gelatin derivatives obtained by conversion of gelatin with alkylating or acylating agents or by grafting of polymerizable monomers on gelatin
  • cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose, phtaloyl cellulose, and cellulose sulphates.
  • the gelatin can be lime-treated or acid-treated gelatin.
  • the preparation of such gelatin types has been described in e.g. "The Science and Technology of Gelatin", edited by A.G. Ward and A. Courts, Academic Press 1977, page 295 and next pages.
  • the gelatin can also be an enzyme-treated gelatin as described in Bull. Soc. Sci. Phot. Japan, N° 16, page 30 (1966).
  • the gelatin can contain calcium or can be substantially free of calcium.
  • 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
  • the typical ingredients for this type of material are present, e.g. colour forming components, masking compounds, development inhibitor releasing (DIR) compounds, etc. These ingredients are usually added in the form of a dispersion, if needed containing so-called oilformers.
  • the photographic emulsion can be coated on a support by means of any of the conventional coating techniques, e.g. dip coating, air knife coating, extrusion coating, slide hopper coating and curtain coating. Usualy before coating the composition containing the emulsion has to be diluted.
  • the coating composition is preferably diluted, not with mere water, but with a salt solution e.g. the same salt as used during the simultaneous chemical and spectral sensitization. In this way the ionic strenght can be maintained at a constant level so that no desorption of the dye from the grain will occur before coating.
  • the photographic material can contain several non light sensitive layers, e.g. an anti-stress top layer, one or more backing layers, and one or more intermediate layers eventually containing filter dyes or antihalation dyes that absorb scattering light and thus promote the image sharpness. Suitable light-absorbing dyes are described in i.a. US 4,092,168, US 4,311,787, DE 2,453,217, and GB 7,907,440.
  • One or more backing layers can be provided at the non-light sensitive side of the support.
  • This layers which can serve as anti-curl layer can contain i.a. matting agents e.g. silica particles, lubricants, anti static agents, light absorbing dyes, opacifying agents, e.g. titanium oxide and the usual ingredients like hardeners and wetting agents.
  • the photographic material 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
  • 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.
  • Preferred surface-active coating agents are compounds containing perfluorinated alkyl groups.
  • 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 and plasticizers.
  • 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, acryl
  • the support of the photographic material may be opaque or transparent, e.g. a paper support or resin support.
  • a paper support preference is given to one coated at one or both sides with an Alpha-olefin polymer, e.g. a polyethylene layer which optionally contains an anti-halation dye or pigment.
  • an organic resin support e.g. cellulose nitrate film, cellulose acetate film, polyvinylacetal film, polystyrene film, polyethylene terephthalate film, polycarbonate film, polyvinylchloride film or poly-Alpha-olefin films such as polyethylene or polypropylene film.
  • the thickness of such organic resin film is preferably comprised between 0.07 and 0.35 mm.
  • These organic resin supports are preferably coated with a subbing layer which can contain water insoluble particles such as silica or titanium dioxide.
  • the photographic silver halide emulsions can be used in various types of black-and-white or colour photographic elements such as in photographic elements for graphic arts, e.g. camera materials, scan materials, image-setting materials and contact materials, and for so-called general amateur and professional photography, diffusion transfer reversal photographic elements, cinamatographic recording and duplicating films, and radiographic recording and duplicating films.
  • the emulsions prepared according to the present invention are sensitive tabular grain emulsions containing no iodide which are used in an X-ray recording film suited for rapid processing.
  • the photographic materials are to be exposed according to their particular composition and application.
  • Possible exposure sources include tungsten light, xenon light, halogen bulbs, metal-halogen lamps, CRT devices, X-ray sources and laser exposure.
  • the processing cycle of the expose photographic materials conventionally includes a development step, a fixing step, a washing step and a drying step.
  • a bleaching or bleach-fixing step is required.
  • the developing solution, or the material itself in case of so-called "activation development” contains a developing agent, e.g. such well-known substances like 1,4-dihydroxy benzene compounds such as hydroquinone, chlorohydroquinone, bromohydroquinone, toluhydroquinone, morpholinemethyl hydroquinone and sulfohydroquinone.
  • a developing agent e.g. such well-known substances like 1,4-dihydroxy benzene compounds such as hydroquinone, chlorohydroquinone, bromohydroquinone, toluhydroquinone, morpholinemethyl hydroquinone and sulfohydroquinone.
  • an auxiliary developing agent can be used.
  • Typical auxiliary developing agents include 3-pyrazolidone developing agents, e.g. 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4'-hydroxymethyl-3-pyrazolidone, and N-methyl-p-aminophenol sulphate.
  • 3-pyrazolidone developing agents e.g. 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4'-hydroxymethyl-3-pyrazolidone, and N-methyl-p-aminophenol sulphate.
  • p-phenylenediamine derivatives are employed as developing agents.
  • ammonium or sodium thiosulphte is employed as fixing agent.
  • Useful bleaching agents for bleach or bleach-fixing baths are ferricyanide ions, persulphate ions and complexes of iron(III) and polyaminocarboxylic acids, e.
  • the emulsions were chemically and spectrally sensitised in the presence of sensitizing dye anhydro-5,5'-dichloro-3,3'-bis(n.sulfobutyl)-9-ethyloxacarbocyanine hydroxide (dye 1), chloroauric acid, sodium thiosulphate, toluenethiosulfonic acid, carboxy-Phenidone and potassium thiocyanate and in the presence or absence of a salt (see table 1). The order of addition was first salt, then dye and finally ripening agents.
  • sensitizing dye anhydro-5,5'-dichloro-3,3'-bis(n.sulfobutyl)-9-ethyloxacarbocyanine hydroxide (dye 1), chloroauric acid, sodium thiosulphate, toluenethiosulfonic acid, carboxy-Phenidone and potassium thiocyanate and in the presence or absence
  • the emulsion was coated on one side of a polyethylene support at a silver coverage of 3.5 g/m 2 , expressed as AgNO 3 .
  • a protective layer was applied containing gelatin at a coverage of 1.1 g/m 2 , polymethylmethacrylate, formaldehyde hardener and conventional wetting agents.
  • Samples of the photographic materials were exposed by green light of 540 nm during 0.02 seconds using a continuous wedge, and were then processed in a rapid processing cycle composed of following steps : loading (3.4 sec.), developing : 23.4 sec./ 35°C., cross-over : 3.8 sec., fixing : 15.7 sec./ 35°C., cross-over : 3.8 sec., rinsing : 15.7 sec./ 20°C., cross-over + drying : 32.2 sec. : total time : 98.0 sec.
  • composition of developer :
  • concentrated part A potassium hydroxide 55.9 g potassium sulphite (65 % solution) 255 g ethylenediaminetetraacetic acid-tetrasodium-trihydrate 8.4 g diethyleneglycol 111.6 g potassium carbonate 128.5 g hydroquinone 120 g 5-methylbenzotriazole 0.36 g water to make 1 l pH adjusted to 11.8 concentrated part B : acetic acid 39.5 g 1-phenyl-3-pyrazolidone 6.0 g 5-nitro-indazole 1.0 g diethyleneglycol to make 100 ml concentrated part C : glutardialdehyde (50 % solution) 21.5 g potassium metabisulphite 36.0 g water to make 100 ml starter : water 15.0 ml acetic acid (96 % solution) 4.0 ml potassium bromide 4.0 g
  • composition of the fixer :
  • concentrated part A ammoniumthiosulphate (78 % solution) 661 g sodium sulphite 54 g boric acid 25 g sodium acetate trihydrate 70 g acetic acid 40 g water to make 1 l pH adjusted to 5.3 by acetic acid concentrated part B : acetic acid 10 g sulphuric acid 13 g aluminium sulphate (34 % solution) 27 g water to make 250 ml
  • the ready-to-use fixer was made by mixing 200 ml of concentrated part A, 750 ml of water and 50 ml of concentrated part B. The pH of this mixture was 4.3 at 25 °C.
  • emulsions 1, 3 and 5 of example 1 were coated on both sides of the support and subjected to a heat treatment (3 days in 57 °C / 34 RH) for simulation of ageing. Exposure and processing was identicxal to example 1.
  • the sensitometic results of fresh samples (1) were compared to those of the treated samples (2) in table 2 : n o % I salt (mole/l) sens 1 .
  • the relative fog increase is about the same for all three samples. However the absolute fog value and the sensitivity of invention emulsion 1 remain after treatment as good as for the control emulsion 5 with 1 % of iodide.
  • the table illustrates the enormous increase in green sensitivity due to the addition of a salt.
  • the iodide content and the nature of dye and salt cause little additional difference.

Claims (11)

  1. Ein Verfahren zur Herstellung einer fotografischen Silberhalogenidemulsion, das eine Fällungsstufe, eine chemische Reifungsstufe und eine Spektralsensibilisierungsstufe umfaßt, wobei die chemische Reifungsstufe und die Spektralsensibilisierungsstufe gleichzeitig durchgeführt werden, dadurch gekennzeichnet, daß die gleichzeitig durchgeführte chemische und spektrale Sensibilisierungsstufe in Gegenwart von wenigstens einem wasserlöslichen Metallsalz erfolgt, wobei das Anion des Metallsalzes mit einem Silberkation ein Salz mit einem Löslichkeitsprodukt von über 10-7,5 bilden kann.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die während der Fällung gebildeten löslichen Salze vor der chemischen und spektralen Sensibilisierung, die gleichzeitig in Gegenwart von wenigstens einem wasserlöslichen Metallsalz durchgeführt werden, wobei das Anion des Metallsalzes mit einem Silberkation ein Salz mit einem Löslichkeitsprodukt von über 10-7,5 bilden kann, ausgewaschen werden.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die spektrale Sensibilisierung mittels eines spektralen Cyaninsensibilisierungsfarbstoffs vorgenommen wird.
  4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß der spektrale Cyaninsensibilisierungsfarbstoff ein Cyaninfarbstoff mit schwacher Adsorption am Emulsionskorn ist.
  5. Verfahren nach irgendeinem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Kation des wasserlöslichen Metallsalzes, dessen Anion mit einem Silberkation ein Salz mit einem Löslichkeitsprodukt von über 10-7,5 bilden kann, wenigstens zweiwertig ist.
  6. Verfahren nach irgendeinem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das wasserlösliche Salz Magnesiumsulfat, Calciumnitrat, Lithiumsulfat, Natriumsulfat, Kaliumsulfat, Natriumnitrat oder Kaliumnitrat ist.
  7. Verfahren nach irgendeinem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der (die) zur spektralen Sensibilisierung verwendete(n) spektrale(n) Sensibilisierungsfarbstoff(e), das (die) zur chemischen Reifung benutzte(n) Reifungsmittel und das (die) wasserlösliche(n) Metallsalz(e) innerhalb kurzer Intervalle nacheinander in der folgenden Reihenfolge zugesetzt werden : zuerst der (die) Farbstoff(e), dann das (die) Salz(e) und schließlich das (die) Reifungsmittel.
  8. Verfahren nach irgendeinem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der (die) zur spektralen Sensibilisierung verwendete(n) spektrale(n) Sensibilisierungsfarbstoff(e), das (die) zur chemischen Reifung benutzte(n) Reifungsmittel und das (die) wasserlösliche(n) Metallsalz(e) innerhalb kurzer Intervalle nacheinander in der folgenden Reihenfolge zugesetzt werden : zuerst das (die) Salz(e), dann der (die) Farbstoff(e) und schließlich das (die) Reifungsmittel.
  9. Verfahren zur Herstellung eines fotografischen Materials, das die folgenden Stufen umfaßt :
    die Herstellung einer Silberhalogenidemulsion nach dem in irgendeinem der Ansprüche 1 bis 8 beschriebenen Verfahren, und
    den Auftrag der Silberhalogenidemulsion auf einen Träger.
  10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß die Emulsion keine wesentliche Menge Iodid enthält.
  11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß die keine wesentliche Menge Iodid enthaltende Emulsion eine Silberbromidemulsion ist.
EP19930202730 1992-10-02 1993-09-21 Emulsionsherstellung mittels gleichzeitig durchgeführten chemischer und spektraler Sensibilisierung in Anwesenheit eines Salzes Expired - Lifetime EP0590715B1 (de)

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