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EP0651284A1 - Fällung von Silberhalogenidkristallen, die lodid enthalten - Google Patents

Fällung von Silberhalogenidkristallen, die lodid enthalten Download PDF

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Publication number
EP0651284A1
EP0651284A1 EP93203040A EP93203040A EP0651284A1 EP 0651284 A1 EP0651284 A1 EP 0651284A1 EP 93203040 A EP93203040 A EP 93203040A EP 93203040 A EP93203040 A EP 93203040A EP 0651284 A1 EP0651284 A1 EP 0651284A1
Authority
EP
European Patent Office
Prior art keywords
iodide
silver
group
crystals
emulsion
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.)
Withdrawn
Application number
EP93203040A
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English (en)
French (fr)
Inventor
Ann Verbeeck
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Agfa Gevaert NV
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Agfa Gevaert NV
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Filing date
Publication date
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Priority to EP93203040A priority Critical patent/EP0651284A1/de
Publication of EP0651284A1 publication Critical patent/EP0651284A1/de
Withdrawn legal-status Critical Current

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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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • 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
    • G03C1/0051—Tabular grain 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
    • G03C1/035—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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03541—Cubic grains
    • 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
    • G03C2001/03558—Iodide 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
    • G03C2200/00—Details
    • G03C2200/52—Rapid processing

Definitions

  • the present invention relates to the preparation of silver halide emulsions, to X-ray silver halide photographic materials in which the said emulsions can be used and to the processing of said materials.
  • Intrinsic sensitivity may be enhanced e.g. by enriching the iodide content of silver halide crystals to a certain extent. Moreover an enhanced amount of iodide will offer the possibility to get a better adsorption of certain spectral sensitizer.
  • dye stain may become more important and the development may be inhibited as the lower solubility may make the kinetics of development and fixation decrease. This occurs in particular in rapid processing conditions due to the very short development, fixing and rinsing times which do not allow the total destruction and/or rinsing out of those sensitizing or non-sensitizing dyes.
  • iodide ions have been built into the crystal volume and more particularly in the vicinity of and/or at the crystal surface is very critical to get a suitable compromise between high sensitivity (as a result of intrinsic sensitivity of the silver halide crystal and improved adsorption of spectral sensitizer) and rapid processability.
  • a solution to provide a more homogenous micromixing has been found by the preparation of the initial nuclei in a reaction vessel that is smaller and separated from the bulk vessel as has e.g. been described in DE 1 472 745, DE 2 116 157 and DE 2 556 885, in US-Patents Nos. 3,705,034; 4,334,012; 4,336,328; 4,684,607 and 5,004,679 as well as in EP-Applications Nos. 326 852, 326 853, 370 116, 407 576, 355 535, 408 752, 368 275, 374 852, 374 853, 374 954.
  • initial nuclei in a small separate reaction vessel is followed by growth of the said initial nuclei by means of further single or double jet precipation but also by means making use of the Ostwald ripening technique wherein the driving force for growing the silver halide crystals is the difference in crystal diameter between the initial nuclei and the added "feeding crystals" and/or the differences in solubility between both types of crystals.
  • the initial crystals also called “nuclei”
  • Ostwald ripening in the reaction vessel being separated from the vessel where the said nuclei are formed. Growth may occur by a difference in pAg between those two separated vessels, so that the dissolution step is fully determining the way in which silver iodide may be built in.
  • a method for the preparation of a silver halide crystals comprising iodide in an amount of up to 3 mole % in the lattice of said crystals comprising the step of reacting a silver salt solution with a metal halide solution in the presence of at least one organic compound releasing iodide represented by the formula: A-L-I (I) wherein A represents a group with a positive Hammett ⁇ p value, commonly known as an electron-accepting or electon-withdrawing group, and L is a divalent linking group.
  • a photographic material comprising a support and at least one silver halide emulsion layer on at least one side of said support coated from an emulsion containing silver iodohalide crystals prepared according to the method described hereinbefore.
  • A is an electron-accepting or electron withdrawing, also called a group with a positive Hammett ⁇ p -Hammett value.
  • Hammett ⁇ p values have been defined e.g. on p. 96 of "Structure/Activity Correlations for Drugs” published by Nankodo (1979).
  • electron witdrawing groups are -COOH, -SO2R, -SO3R', etc. wherein R represents a substituted or unsubstituted aliphatic or aromatic group and R' represents an inorganic cation or an organic cationic group.
  • a groups include a carboxylic acid group, a cyano group, a carbamoyl group, an acyl group, a sulphonyl group, an oxycarbonyl group, a sulphamoyl group.
  • the organic compounds releasing iodide are preferably corresponding to the above formula wherein the divalent linking group is chosen from unsubstituted or substituted alkylene, unsubstituted or substituted oxyalkylene, unsubstituted or substituted aralkylene, or combinations of two or more thereof, wherein several atoms of L, or of A and L, can combine to form a ring, and wherein the iodine atom is not bound to an aromatic moiety or to an atom bearing a double bond, or to a hetero-atom.
  • iodide ion slow releasers include following compounds : ICH2COOH (I-1) I(CH2)2COOH (I-2) I(CH2)3COOH (I-3) CH3CHICOOH (I-4) CH3CH2CHICOOH (I-5) CH3CHICH2COOH (I-6) HOOC-CHI-COOH (I-7) HOOC-CH2-CHI-COOH (I-8) ICH2CN (I-9) I(CH2)2CONH2 (I-10) ICH2COCH3 (I-11) I(CH2)2SO2CH3 (I-12) ICH2COOCH3 (I-13) ICH2CH2SO3Na (I-14) ICH2CONH2 (I-15) ICH2-CO-NH-C(CH2OH)3 (I-16) ICH2-CO-NH-C2H4-SO3Na (I-17) ICH2-CO-NH-CH2-(CHOH)4-CH2OH (I-18) In a particular preferred embodiment the following compounds ICH2
  • the choice of a compound releasing iodide ions is mainly determined by its activity observed in real circumstances. E.g. the pH value of the medium and the presence of highly active nucleophilic ions have an important role therein.
  • the iodide releaser is preferably used in aqueous solution in a concentration between 0.1 and 1 molar.
  • a preferred compound present in the precipitation vessel is ammonia.
  • the emulsions according to this invention can be prepared by the known methods like the single-jet method, wherein a iodohalide salt solution can be added to the solution containing a protective colloid in the reaction vessel before the start of the precipitation.
  • a silver salt solution can be added during a predetermined time while stirring.
  • Iodide ions may be distributed in a homogenous or heterogenous way over the silver iodohalide volume.
  • a core-shell structure is typical for a crystal structure with a heterogenous distribution over its crystal volume.
  • a (iodo)halide containing solution may consecutively be added to the reaction vessel after addition of a silver salt solution.
  • This consecutive addition may be repeated in the presence of at least one organic compound releasing iodide in order to obtain different internal shell(s) containing silver iodide built up around the core.
  • the core may be rich or poor in iodide ion concentration or may even be iodide free provided that at the start of the precipitation no iodide ions are present in the reaction vessel.
  • the silver iodohalide crystals thus formed may have an outermost shell with a lower or a higher iodide concentration in comparison with an adjacent shell, depending on the precipitation conditions.
  • the size distribution of the silver halide particles prepared according to this invention may be homodisperse or heterodisperse. Homodisperse distributions are obtained when 95 % of the grains have a size that does not deviate for more than 30 % from the average grain size. Average particle size diameters may vary over a wide range e.g. from 0.1 to 2.0 ⁇ m.
  • the double-jet technique wherein a protective colloid solution is added to the reaction vessel before and wherein solutions of silver salts and halide salts are added simultaneously.
  • the silver halide composition may be varied during the additions and especially when shells obtained by conversion with iodide ions are present, a combination of single and double jet precipitation techniques may be useful.
  • said iodide ions are namely able to displace bromide and/or chloride ions from the grain, a technique known in the art as conversion.
  • the said conversion step can also be performed at the silver halide crystal surface.
  • a further precipitation technique may be the triple-jet technique to enhance the possibility to vary the halide composition in the volume of the crystals during precipitation. Combinations of single-jet, double-jet and triple-jet precipitation techniques are possible.
  • iodide ions that are incorporated in the lattice of iodohalide crystals during precipitation are released from at least one organic compound releasing iodide ions. It may be useful to replace the said organic compound(s) partially by an inorganic iodide salt if required e.g. from kinetic considerations during precipitation.
  • variable concentrations of solutions providing respectively silver and halide ions may be used during the different precipitation steps.
  • Variable flow rates for the said solutions may be available during precipitation while controlling the pAg value and the temperature in the reaction vessel.
  • the silver halide particles of the photographic emulsions according to the present invention may further have a regular crystalline form, e.g. cubic or octahedral or a transition form. Also an irregular crystalline form such as a spherical form or a tabular form may be obtained. Otherwise the emulsion crystals may have a composite crystal form comprising a mixture of said regular and irregular crystalline forms.
  • the crystals may be doped with whatever a dope, as e.g. with Rh3+, Ir4+, Cd2+, Zn2+, Pb2+.
  • the halide composition is chloroiodide, chlorobromoiodide or bromoiodide.
  • the amount of iodide at certain sites within the crystal volume can vary between wide limits.
  • cubic or tabular silver (chloro)bromoiodide or chloroiodide are preferred.
  • chemical and/or spectral sensitizers can be added to the emulsion vessel. Further during precipitation grain growth restrainers or accelerators may be added.
  • gelatin which is a thermoreversible polymer, showing a sufficient gel strength after coating.
  • Conventional lime-treated or acid treated gelatin can be used. 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).
  • Other types of protective colloids for use instead of or in addition to gelatin include various natural film-forming substances and synthetic resins, e.g.
  • Coagulation in gelatineous medium can e.g. be effected by an alcohol or a salt or if the emulsion contains a sufficient amount of acid-coagulable gelatin derivatives or hydrogen bridge forming anionic polymeric compounds by addition of an acid to lower the pH value to the isoelectric point.
  • Hydro bridge forming anionic polymeric compounds are polystyrene sulphonic acid and sulphonated copolymers of styrene, which are commonly used.
  • Acid coagulable gelatin derivatives as phtaloyl or N-phenyl carbamoyl gelatin can be used, requiring only adjustment of the pH to the right value to cause the emulsion to coagulate.
  • Suitable coagulation techniques have been described e.g. in U.S. Patent Specifications 2,614,928; 2,614,929 and 2,728,662.
  • the silver halide emulsions can be precipitated in silica medium in the presence of a compound releasing iodide whereupon it is possible to apply the flocculation method as described in EP-A 517 961.
  • Separately formed two or more different silver halide emulsions may be mixed for use in silver halide photographic materials in accordance with the present invention.
  • the light-sensitive silver halide emulsion prepared according to the present invention can be chemically sensitized 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 Sawe 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. thiosulphate, thiocyanate, thioureas, sulphites, mercapto compounds, and rhodanines.
  • sulphur e.g. thiosulphate, thiocyanate, thioureas, sulphites, mercapto compounds, and rhodanines.
  • 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-A 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
  • Chemical sensitization can also be performed with small amounts of Ir, Rh, Ru, Pb, Cd, Hg, Tl, Pd, Pt, or Au.
  • One of these chemical sensitization methods or a combination thereof can be used.
  • a mixture can also be made of two or more separately precipitated emulsions being chemically sensitized before mixing them.
  • spectral sensitizer(s) may be added to the redispersed silver halide emulsion. This may be performed 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, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes, complex merocyanine dyes.
  • a survey of useful chemical classes of spectral sensitizing dyes and specific useful examples in connection with tabular grains is given in the already cited Research Disclosure Item 22534.
  • Especially preferred green sensitizer in connection with the present invention are anhydro-5,5'-dichloro-3,3'-bis(n.sulfobutyl)-9-ethyloxacarbo-cyanine hydroxide and anhydro-5,5'-dichloro-3,3'-bis(n.sulfopropyl)-9-ethyloxacarbo-cyanine hydroxide.
  • spectral sensitization In classical emulsion preparation spectral sensitization traditionally follows the completion of chemical sensitization. However, especially in connection with tabular grains having a large specific surface, it is specifically considered that spectral sensitization may occur simultaneously with or may even precede completely the chemical sensitization step: the chemical sensitization after spectral sensitization is believed to occur at one or more ordered discrete sites of tabular grains. This may also be done with emulsions, wherein the chemical sensitization proceeds in the presence of one or more phenidone and derivatives, a dihydroxy benzene as hydroquinone, resorcinol, catechol and/or a derivative(s) therefrom, one or more stabilizer(s) as e.g. 1-p-carboxyphenyl, 4,4' dimethyl-3-pyrazolidine-1-one, auxiliary agent(s) or antifoggant(s), one or more spectal sensitizer(s) or combinations of said ingredients
  • 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 as described e.g. in US-A 3,743,510, cadmium salts, and azaindene compounds.
  • To the silver halide emulsion prepared in accordance with the present invention may be added 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 chemical ripening thereof and mixtures of two or more of these compounds can be used.
  • the silver halide emulsions prepared in accordance with the present invention can be used to form one or more silver halide emulsion layers coated on a support to form a photographic silver halide element according to well known techniques.
  • the photographic element of the present invention may 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, and plasticizers as described below.
  • additives such as e.g. compounds improving the dimensional stability of the photographic element, UV-absorbers, spacing agents, hardeners, and plasticizers as described below.
  • the gelatin binder of the photographic elements can be forehardened with appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. di-vinyl-sulphonyl-methane, ethylene di-(vinyl-sulphone), 1,3-vinylsulphonyl-2-propanol, bis-(vinylsulphonyl-methyl)-ether, chromium salts e.g. chromium acetate and chromium alum, aldehydes e.g. formaldehyde, glyoxal, and glutaraldehyde, N-methylol compounds e.g.
  • appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. di-vinyl-sulphonyl-methane, ethylene
  • dimethylolurea and methyloldimethylhydantoin dioxan derivatives e.g. 2,3-dihydroxy-dioxan, active vinyl compounds as 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.
  • These hardeners can be used alone or in combination.
  • the binder can also be hardened with fast-reacting hardeners such as carbamoylpyridinium salts as disclosed in US Patent 4,063,952 and with the onium compounds as disclosed in EU Patent Application 408,143.
  • the emulsion may be coated on any suitable substrate such as, preferably, a thermoplastic resin e.g. polyethyelenterephtalate or a polyethylene coated paper support.
  • a thermoplastic resin e.g. polyethyelenterephtalate or a polyethylene coated paper support.
  • suitable additives for improving the dimensional stability of the photographic element may be added, i.a. dispersions of a water-soluble or hardly soluble synthetic polymer e.g.
  • Plasticizers suitable for incorporation in the emulsions according to the present invention are e.g. glycol, glycerine, or the latexes of neutral film forming polymers including polyvinylacetate, acrylates and methacrylates of lower alkanols, e.g. polyethylacrylate and polybutylmethacrylate.
  • 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 ⁇ m and 10 ⁇ m.
  • 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 silver halide emulsions prepared according to the present invention can be used in various types of photographic elements such as i.a. in photographic elements for graphic arts and for so-called amateur and professional photography, diffusion transfer reversal photographic elements, low-speed and high-speed photographic elements, colour materials, X-ray materials, materials for micrographic applications etc..
  • the said photographic silver halide emulsions are used in single side or double side coated X-ray materials.
  • the photographic element with (an) emulsion(s) according to the present invention may contain one single emulsion layer, as it is the case for many applications, or it can be built up by two or even more emulsion layers.
  • a material with a single or a duplitized emulsion layer coated on one or both sides of the support may contain silver halide emulsions according to this invention.
  • duplitized emulsions differing in photographic speed by at least 0.15 log E a gain in cross-over in double side coated materials can be obtained.
  • the material contains blue, green and red sensitive layers each of which can be single coated, but merely consist of double or even triple layers.
  • the photographic material can contain several non-light sensitive layers, e.g. an antistress topcoat layer, one or more backing layers, and one or more intermediate layers eventually containing filter- or antihalation dyes that absorb scattering light and thus promote the image sharpness.
  • Suitable light-absorbing dyes used in these intermediate layers are described in e.g. US Patents 4,092,168, US 4,311,787, DE 2,453,217, and GB Patent 7,907,440.
  • One or more backing layers can be provided at the non-light sensitive side of the support of materials coated with at least one emulsion layer at only one side of the support.
  • These layers which can serve as anti-curl layer can contain e.g. matting agents like silica particles, lubricants, antistatic agents, light absorbing dyes, opacifying agents, e.g. titanium oxide and the usual ingredients like hardeners and wetting agents.
  • 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, poly(vinyl acetal) film, polystyrene film, poly(ethylene 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 material with silver halide grains prepared according to the present invention can be image-wise exposed by any convenient radiation source in accordance with its specific application.
  • processing conditions and composition of processing solutions are dependent from the specific type of photographic material in which the silver iodohalide grains prepared according to the present invention are applied.
  • materials for X-ray diagnostic purposes said materials may be adapted to rapid processing conditions.
  • an automatically operating processing apparatus is used provided with a system for automatic regeneration of the processing solutions.
  • the forehardened material may be processed using one-part package chemistry or three-part package chemistry, depending on the processing application determining the degree of hardening required in said processing cycle.
  • the developing and/or fixing step may proceed in hardener free processing solutions and replenishment of the developer and/or fixer solution may proceed by concentrate regeneration.
  • reaction vessel 61.0 ml of solutions 1 and 2 were introduced into a reaction vessel in 28 seconds using the double jet technique.
  • Said reaction vessel initially contained 2.16 liter of destilled water at 45°C, 12.6 grams of potassium bromide and 12.5 grams of gelatin. After one minute the reaction temperature of this mixture was raised to 70°C in 20 minutes and 47.5 grams of phthalated gelatin in 475 ml destilled water were added. After 10 minutes the neutralization step was started.
  • a double jet precipitation was started using solutions 1 and 2 which continued for 40 minutes 51 seconds. During this precipitation, the pBr value was kept constant at 1.63. The flowing rate of solution 1 was 7.5 ml per minute at the start, linearly increasing to 22.2 ml per minute at the end of the precipitation. Thereafter the second neutralisation phaze was started.
  • Second growth step (during which 62.0 mole % of the total amount of AgNO3 was used):
  • This emulsion was prepared in the same way as comparative emulsion No. 1 with the only difference that after the second neutralization step 100 ml of solution 6 were added to the reaction vessel and that in the second growth step solution 7 was used instead of solution 3.
  • This emulsion was prepared in the same way as inventive emulsion No. 1 with the only difference that after the second neutralization step 200 ml of solution 6 were added to the reaction vessel and that in the second growth step solution 8 was used instead of solution 7.
  • This emulsion was prepared in the same way as inventive emulsion No. 1 with the only difference that after the second neutralization step 300 ml of solution 6 were added to the reaction vessel and that in the second growth step solution 9 was used instead of solution 7.
  • Emulsions Nos. 1 to 3 were each optimally sulphur and gold sensitized in the presence of sodium thiocyanate and anhydro-5,5'-dichloro-3,3'-bis(n.sulfobutyl)-9-ethyloxacarbo-cyanine hydroxide in an amount of 660 mg per mole of silver nitrate.
  • Each emulsion was stabilized with 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene and after addition of the normal coating additives the solutions were coated simultaneously together with a protective layer on both sides of a polyethylene terephthalate film support having a thickness of 175 ⁇ m.
  • the resulting photographic material contained per side an amount of silver halide corresponding to 3.5 grams of AgNO3 per m2.
  • the coating weight expressed in grams per square meter per side was 1.1 g of gelatin, 0.023 g of polymethylmethacrylate having a mean particle size of 3.5 ⁇ m and 0.1 g of formaldehyde as a hardening agent.
  • CURIX HT530 (Agfa-Gevaert trademarked name) with the following time (in seconds) and temperature (in °C) characteristics: loading 0.2 sec. developing 9.3 sec. 35°C in developer I described below cross-over 1.4 sec. rinsing 0.9 sec. cross-over 1.5 sec. fixing 6.6 sec. 35°C in fixer I described below cross-over 2.0 sec. rinsing 4.4 sec. 20°C cross-over 4.6 sec. drying 6.7 sec. total 37.6 ⁇ sec.
  • composition of the developer is composition of the developer:
  • composition of the fixer ready-for-use is Composition of the fixer ready-for-use:
  • Chemically sensitized fast monodisperse negative working silver bromoiodide emulsions having a varying iodide content were prepared in the following manner.
  • the next 500 ml of silver nitrate were added at an increasing flow rate going from 15.5 ml/min. to 21.0 ml/min.
  • the pAg was kept constant at the same value of 7.9 as for the core precipitation, but the halide composition was changed from a 100% KBr composition to a composition of 98 mole % KBr and 2 mole % KI for the shell. Over the whole silver bromoiodide crystal an average amount of 1 mole % of iodide ions was incorporated in this way.
  • the redispersed emulsion was chemically sensitized for a period of 4 hours at 48°C in the presence of p-toluene thiosulphonate, sodium thiosulphate, sodium sulphite and a mixture of gold(III)-chloride and ammoniumthiocyanate so as to obtain an optimum in the relationship between fog and sensitivity.
  • the emulsion was spectrally sensitized with anhydro-5,5'-dichloro-3,3'-bis(n.sulfobutyl)-9-ethyloxacarbo-cyanine hydroxide in an amount of 375 mg per mole of silver halide and stabilized with 4-hydroxy-6-methyl-1,3,3a-tetrazaindene before coating on a polyester support of 175 ⁇ m thickness.
  • the emulsion layers were coated at a ratio of 6.8g/m2 of silver halide expressed as the equivalent amount of AgNO3.
  • the whole precipitation, flocculation, redispersing and sensitization procedure was performed in the same way as for comparative emulsion No. 4, except for the presence instead of potassium iodide of monoiodoacetic acid in an equivalent amount as KI that was added so as to convert the silver bromide core after precipitation of 50 mole % of the total amount of silver nitrate.
  • the whole precipitation, flocculation, redispersing and sensitization procedure was performed in the same way as for comparative emulsion No. 5, except for the presence instead of potassium iodide of monoiodoacetic acid in an equivalent amount as KI that was added so as to convert the silver bromide core after precipitation of 50 mole % of the total amount of silver nitrate.
  • the emulsions were chemically sensitized for a period of 4 hours at 48°C in the presence of p-toluene thiosulphonate, sodium thiosulphate, sodium sulphite and of a mixture of gold(III)-chloride and ammoniumthiocyanate.
  • the emulsions were spectrally sensitized with anhydro-5,5'-dichloro-3,3'-bis(n.sulfobutyl)-9-ethyloxacarbo-cyanine hydroxide in an, amount of 375 mg per mole of silver halide and stabilized with 4-hydroxy-6-methyl-1,3,3a-tetrazaindene before coating on a polyester support of 175 ⁇ m thickness.
  • the emulsion layers were coated with silver halide crystals at a ratio of 6.8g/m2 of silver halide expressed as the equivalent amount of AgNO3.
  • the photographic material samples were made by coating the emulsion on a polyethylene terephthalate support together with a composition for forming a protective gelatin layer.
  • the amount of gelatin per square meter in the emulsion layers was 3.0 g, whereas in the protective layers it was 1.1 g.
  • 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 given in table III.
  • This table shows the sensitometric results in terms of fog, sensitivity (log E(xposure)) and overall contrast of the photographic strips prepared and exposed 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 gradation is measured from the characteristic curve over a density range of 1.75 starting from a density value of 0.25 to 2.00 above fog.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP93203040A 1993-10-29 1993-10-29 Fällung von Silberhalogenidkristallen, die lodid enthalten Withdrawn EP0651284A1 (de)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0881530A1 (de) * 1997-05-30 1998-12-02 Eastman Kodak Company Emulsion von hohem Chloridgehalt hergestellt mittels Dimethylamine-Silberchlorojodid-Komplexverbindungen und Antischleiermittel
EP0881531A1 (de) * 1997-05-30 1998-12-02 Eastman Kodak Company Herstellung einer Dimethylamin-Silberchlorjodid-Komplexverbindung und deren Verwendung als einzige Quelle für die Einbringung von Jodid in Silberchloridkristalle
EP0881532A1 (de) * 1997-05-30 1998-12-02 Eastman Kodak Company Herstellung einer Dimethylamin-Silberbromojodid-Komplexverbindung und deren Verwendung als einzige Quelle für die Einbringung von Jodid in Silberbromidkristalle
EP1150160A1 (de) * 2000-04-25 2001-10-31 Fuji Photo Film B.V. Verfahren zur Herstellung einer photographischen Silberhalogenidemulsion
US6630292B2 (en) 2000-04-25 2003-10-07 Fuji Photo Film B.V. Method for producing a silver halide photographic emulsion

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0341728A2 (de) * 1988-05-13 1989-11-15 Fuji Photo Film Co., Ltd. Photographische Silberhalogenidmaterialien
EP0542354A1 (de) * 1991-11-14 1993-05-19 Agfa-Gevaert N.V. Verfahren zum Entwickeln photographischer Röntgenmaterialien
EP0561415A1 (de) * 1992-03-19 1993-09-22 Fuji Photo Film Co., Ltd. Verfahren zur Herstellung einer photographischen Silberhalogenidemulsion, Emulsion und lichtempfindliches Material
EP0563701A1 (de) * 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Photographisches lichtempfindliches Silberhalogenidmaterial

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0341728A2 (de) * 1988-05-13 1989-11-15 Fuji Photo Film Co., Ltd. Photographische Silberhalogenidmaterialien
EP0542354A1 (de) * 1991-11-14 1993-05-19 Agfa-Gevaert N.V. Verfahren zum Entwickeln photographischer Röntgenmaterialien
EP0561415A1 (de) * 1992-03-19 1993-09-22 Fuji Photo Film Co., Ltd. Verfahren zur Herstellung einer photographischen Silberhalogenidemulsion, Emulsion und lichtempfindliches Material
EP0563701A1 (de) * 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Photographisches lichtempfindliches Silberhalogenidmaterial

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0881530A1 (de) * 1997-05-30 1998-12-02 Eastman Kodak Company Emulsion von hohem Chloridgehalt hergestellt mittels Dimethylamine-Silberchlorojodid-Komplexverbindungen und Antischleiermittel
EP0881531A1 (de) * 1997-05-30 1998-12-02 Eastman Kodak Company Herstellung einer Dimethylamin-Silberchlorjodid-Komplexverbindung und deren Verwendung als einzige Quelle für die Einbringung von Jodid in Silberchloridkristalle
EP0881532A1 (de) * 1997-05-30 1998-12-02 Eastman Kodak Company Herstellung einer Dimethylamin-Silberbromojodid-Komplexverbindung und deren Verwendung als einzige Quelle für die Einbringung von Jodid in Silberbromidkristalle
EP1150160A1 (de) * 2000-04-25 2001-10-31 Fuji Photo Film B.V. Verfahren zur Herstellung einer photographischen Silberhalogenidemulsion
US6630292B2 (en) 2000-04-25 2003-10-07 Fuji Photo Film B.V. Method for producing a silver halide photographic emulsion

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