EP1014175A1 - Verfahren zur Herstellung einer homogenen und dünne tafelförmige Körner enthaltenden Silberhalogenidemulsion - Google Patents

Verfahren zur Herstellung einer homogenen und dünne tafelförmige Körner enthaltenden Silberhalogenidemulsion Download PDF

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EP1014175A1
EP1014175A1 EP98204367A EP98204367A EP1014175A1 EP 1014175 A1 EP1014175 A1 EP 1014175A1 EP 98204367 A EP98204367 A EP 98204367A EP 98204367 A EP98204367 A EP 98204367A EP 1014175 A1 EP1014175 A1 EP 1014175A1
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Prior art keywords
silver halide
silver
crystals
dispersion
emulsion
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EP98204367A
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English (en)
French (fr)
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Dirk c/o Agfa-Gevaert N.V. Bollen
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Agfa Gevaert NV
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Agfa Gevaert NV
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Priority to EP98204367A priority Critical patent/EP1014175A1/de
Priority to US09/460,377 priority patent/US6214532B1/en
Priority to JP11360123A priority patent/JP2000187294A/ja
Publication of EP1014175A1 publication Critical patent/EP1014175A1/de
Withdrawn legal-status Critical Current

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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
    • G03C1/0051—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
    • G03C1/015—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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49818—Silver halides
    • 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
    • G03C2001/0156—Apparatus or processes for the preparation of emulsions pAg value; pBr value; pCl value; pI value
    • 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
    • G03C2001/0157—Ultrafiltration
    • 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
    • G03C2001/03529—Coefficient of variation
    • 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 controlling several parallel running processes and an apparatus to realize it. More specifically the invention is related to a method for preparing specially designed silver halide crystals which can be used in photosensitive materials.
  • inorganic salts For the formation of inorganic salts a variety of conventional precipitation techniques are known which are mostly allways batch-wise processes. This can be easily demonstrated with procedures which are used for the preparation of silver halide salts dispersed in a hydrophilic protective colloid.
  • the most common approach of the batch preparation technique is the single-jet (or single-run) procedure where a silver salt solution is added in a controlled or uncontrolled way into a reaction vessel containing a halide salt.
  • silver halide nuclei are formed in a first reaction step which is followed by a growth process for the formation of the ultimate silver halide grains.
  • An alternative and more widely used batch process for the formation of silver halide crystals is the double jet precipitation technique whereby a silver salt and a halide salt solution are concurrently added to a reaction vessel containing a dispersing protective colloid.
  • a silver salt and a halide salt solution are concurrently added to a reaction vessel containing a dispersing protective colloid.
  • the double-jet method offers silver halide crystals with narrower grain size distribution and allows free alteration of the halide composition of crystals according to their growth.
  • Double-jet precipitation techniques are described, for example, in US-P 3,801,326, US-P 4,046,376, US-P 4,147,551, and US-P 4,171,224.
  • One of the methods starts with the formation of small instable nuclei which are formed in a nucleation chamber outside the precipitation vessel as, for instance, described in JN-A 02.172.815, JN-A 02.172.816 and JN-A 02.172.817.
  • Increased uniformity of crystals can be realized if the nuclei are prepared in a low molecular gelatin (MW ⁇ 25000) (EP-A 0 610 597) or if the soluble silver and halide salts are mixed together in the nucleation room via a membrane as proposed by Saito (JN-A 05.061.134 and JN-A 06.086.923).
  • thin tabular crystals formed in this way can be kept homogene if the growth takes place at very low concentration of the silver and halide salt reactants which means that the preparation procedure itself is time-consuming and very inefficient while the emulsion has to be concentrated afterwards.
  • This extra working-step can be carried out with, for instance, ultrafiltration or dialysis and gives the emulsion with the requested characteristics. Combining this concentration step together with the precipitation as described in JN-A 02.172.816 and JN-A 02.172.817 does not give the wanted results and leads to a tabular emulsion with thicker emulsion crystals.
  • Figure 1 gives a schematic view of the method for preparing tabular silver halide crystals as used in the present invention. It shows the essential parts of the preparation system and their internal relationship which will be described hereinafter in detail.
  • This invention describes a method for the formation of silver halide crystals which are responsible for the photo- sensitivity of silver halide photographic material.
  • These silver halide crystals can be prepared by mixing together a soluble silver and a soluble halide salt in the presence of a dispersing polymer as a binder. This procedure is normally carried out under well-defined circumstances of pH, pAg, temperature, flow rate profile of the reactant solutions, etc.. However the precipitation of a silver halide emulsion of the present invention has to be carried out by controlling the same parameters but in a new system configuration.
  • This system is constituted out of a growth chamber (c) for the precipitation of silver halide crystals, a buffer vessel (a) for collecting the silver halide emulsion formed, a mixing chamber (b) for diluting the silver halide dispersion, a concentration unit (d) and some other small system units necessary for supporting the different system processes.
  • the soluble silver salt (Ag + ) and soluble halide (X - ) solutions are stored in containers which are connected with the precipitation system via flow-controlled valves in order to regulate the amount of silver and halide which have to be supplied.
  • These containers are directly connected to a main vessel (a) wherein both reactants can be added to form silver halide nuclei.
  • a protective colloid In order to get a dispersion of the nuclei a protective colloid have to be preferably present in vessel (a) before starting the precipitation or can be simultaneously added together with both reactants. Principally many different protective colloids can be used which are described in Res.Disclosure, No.38957 (1996), section IIA.
  • the most preferred protective colloid which can be used in the present invention is gelatine that in turn can be mixed with a lot of other products that are compatible with gelatine and that improve the photographic quality, the film handling, convenience, etc. of the photosensitive materials containing said dispersion (see Res.Disclosure,No.38957 (1996), section IIC).
  • the stability of the nuclei which are initially formed depends on the conditions that are used during the precipitation and the physical ripening which can take place.
  • the silver halide nuclei can be formed in growth chamber (c) before the transfer to vessel (a).
  • the silver halide nuclei can also be formed in an external nucleation unit before introduction in vessel (a) as described for instance in WO 90/01462, JN-A 05.341.414, JN-A 05.061.134.
  • the dispersion of said nuclei is transferred from vessel (a) to a mixing chamber (b) wherein the dispersion is diluted by an aqueous solution.
  • This aqueous solution is a regeneration product of the production process of the present invention as will be described later.
  • the nuclei dispersion is diluted by adding between 0.2 and 10 parts of the aqueous solution mentioned hereinbefore per part of the dispersion.
  • this dilution factor is preferably situated between 0.3 and 5 and most preferably between 0.5 and 3.
  • Mixing chamber (b) can be equipped with a special inlet system in order to optimize the mixing conditions or can even contain a special mixing device but such configurations for mixing charter (b) are not necessary to give optimal results.
  • the diluted nuclei dispersion is transferred to a growth chamber (c) where silver halide is precipitated on the nuclei introduced from mixing chamber (b) via a silver salt and a halide salt inlet. While mixing in this chamber is very important additional arrangements can be taken to optimize the mixing efficiency. This can for instance be realized by improving the position of the silver salt and halide salt inlet or by positioning a special mixing device or arrangement.
  • the growth of the diluted nuclei dispersion in chamber (c) can be executed by adding silver halide crystals formed in an external mixer or precipitating unit as for instance is described in WO 90/01462.
  • the fine grains formed in this mixer have to be immediately introduced in growth chamber (c) because these grains dissolve readily due to their fineness of grain size to again form silver and halide ions which in turn deposit on the minute amount of nuclei introduced from the diluting unit (b).
  • This way of working is interesting because of the possibility to form homogeneous crystals which are also uniform in halide composition. Mixing the different solutions coming together in growth chamber (c) is important in order to increase the homogeneity of the reaction mixture and to minimize the thickness growth.
  • the silver halide crystal dispersion formed in the growth chamber (c) is than transferred to vessel (a) before it is pumped to the next processing steps namely diluting and growing.
  • the continueous production of the tabular silver halide dispersion coming from growth chamber (c) will increase the amount of dispersion and therefor the level of the dispersion in vessel (a).
  • vessel (a) is built in a closed circuitry together with an special unit (d) in which the dispersion can be concentrated.
  • the most preferred way of concentrating the dispersion of the present invention is using an ultra-filtration or a dialysis unit.
  • This ultra-filtration or dialysis unit is started automatically if the dispersion in vessel (a) is exceeding a certain restricted level which is detected by a float positioned in vessel (a) in order to keep the volume constant.
  • the eluate coming from concentrating unit (d) can be collected in vessel (e) which in turn can be used for the dilution of the nuclei or crystal dispersion in mixing chamber (b). It have to be remembered that this eluate is containing the salts left after the precipitation of silver halide.
  • a float in vessel (e) is controlling the amount of water and discharge the superfluous amount of aequeous solution to a drain.
  • the way the homogeneous thin tabular emulsions of the present invention is prepared, is quite different from the method used in JN-A 02.172.816 where the crystals formed in a growth chamber were first fed through an ultra-filtration unit before collection in a buffer vessel and transfer to the same growth chamber.
  • This can also be said for both systems described in JN-A 02.172.817 where together with the growth chamber a second mixing chamber is used.
  • This second chamber is used to mix a dispersion of freshly prepared crystals together with a dispersion produced in an earlier production cycle which is first concentrated by ultra-filtration.
  • the difference between the production systems described in the last mentioned Japanese patents and the system of the present invention is the fact that the formation of the crystals in the growth chamber is not executed on a diluted dispersion of silver halide crystals.
  • the concentration of the reactants used for the precipitation of the silver halide crystals in growth chamber (c) is not limited and can be as high as 5 or 6 mole per liter. A more preferred concentration range of the reactants can go up to 3 mole per liter.
  • the silver halide dispersion can be contineously withdrawn out of vessel (a) during the contineous crystal production process for feeding the ultra-filtration unit where the prepared silver halide crystals are simultaneously separated from the soluble salts accumulated in (a) during crystal formation.
  • the concentration of the silver halide in vessel (a) can increase during the preparation process of the present invention till 5 but it will be preferably situated between 0.1 and 4 and most preferably between 0.1 and 3 mole per liter.
  • the photographic emulsions prepared in this way for use in the image-forming element of the present invention can contain silver-halide crystals comprising chloride, bromide or iodide alone or combinations thereof.
  • Other silver salts which can be incorporated into a limited amount in the silver halide lattice are silver phosphate, silver thiocyanate and some other silver salts including organic silver salts like silver citrate and others.
  • the chloride and bromide salts can be combined in all ratios in order to form a silver chlorobromide salt.
  • Iodide ions however can be coprecipitated with chloride and/or bromide ions in order to form a iodohalide with a iodide amount depending on the saturation limit of iodide in the lattice with the given halide composition; i.e. up to a maximum amount of about 40 mole % in silver iodobromide and up to at most 13 mole % in silver iodochloride both based on silver.
  • the composition of the silver halide in the crystal volume can change in a continuous or in a discontinuous way.
  • Emulsions containing crystals composed of various sections with different halide compositions are used for several different photographic applications.
  • Such a structure with a difference in halide composition between the centre and the rest of the crystal known as so-called “core-shell” emulsion) or with more than two crystal parts differing in halide composition (called a "band” emulsion) may occur.
  • the changes in halide composition can be realized by direct precipitation or in an indirect way by conversion wherein fine silver halide grains of a certain predetermined halide composition are dissolved in the presence of the so-called host grains forming a "shell” or "band” on the given grain.
  • the crystals formed by the methods described above have a morphology which can be described as tabular.
  • the aspect ratio (ratio of equivalent circular diameter to thickness) of the grains can vary from low ( ⁇ 2) over "medium” or “intermediate” (from 2 up to 8) to "high” (> 8).
  • the aspect ratio of the tabular silver halide crystals of the present invention is preferably ⁇ 2.
  • the thickness of the last mentioned emulsions can be very low and is preferably situated between 0.03 and 0.30 ⁇ m with a variation coefficient preferably ⁇ 40% and most preferably between 0.07 and 0.22 ⁇ m with a variation coefficient of not more than 30 %.
  • high aspect ratios can be realized.
  • the major faces of the tabular grains may have a (111) or a (100)-habit, the structure of which is stable or should be stabilized (for instance by a "crystal habit modifying agent") respectively.
  • any excess of aqueous soluble salts can be removed via the concentration step where the emulsion is separated in an ultra-filtrating or dialysing system. It means that the emulsion produced in this way immediately can be used in the next step of the production process. Although less efficient in the precipitation system of the present invention the more classical methods of emulsion washing can also be used. All the procedures which can be used for removing any excess of salt without any problem, including the methods like the dia- or ultrafiltration and ion-exchange techniques, are described in Research Disclosure No. 38957(1996), section III.
  • the silver halide emulsions of the present invention that are prepared in one of the ways described hereinbefore contain crystals having a spherical equivalent diameter (SED) of not more than 1.5 ⁇ m while the minimum spherical equivalent diameter is not less than 0.01 ⁇ m.
  • the spherical equivalent diameter (SED) of the crystal represents the diameter of the sphere having the same volume as the average volume of the silver halide crystals of said emulsion.
  • the silver halide emulsions can be chemically sensitized in many different ways. It can be carried out in the presence of a chalcogen as sulphur, selenium or tellurium, in the presence of a noble metal as e.g. gold or in combination with a chalcogen and noble metal. Sometimes it can be necessary to add a sulphur sensitizer in the form of a dispersion of solid particles as described in EP-A 0 752 614. Reduction sensitization is another method of sensitizing a photosensitive silver halide emulsion that can be combined with the chalcogen/noble metal sensitization if desired.
  • Reduction sensitization should be mentioned as a way of introducing hole traps into the silver halide crystals for use in the image-forming elements according to the present invention in order to optimize the efficiency of latent image formation. It is clear that the incorporation of hole traps into silver halide can also be realized in other ways e.g. by the introduction of Cu (+) , Ni (2+) , etc.. Reduction sensitization can be performed by decreasing the pAg of the emulsion or by adding thereto reducing agents as e.g. tin compounds (see GB-Patent 789,823), amines, hydrazine derivatives, formamidine-sulphinic acids, silane compounds, ascorbic acid, reductic acid and the like. Care should however be taken in order to avoid generation of fog in an uncontrollable way.
  • reducing agents e.g. tin compounds (see GB-Patent 789,823), amines, hydrazine derivatives, formamidine-sul
  • the silver halide emulsions used in the image-forming elements according to the present invention are spectrally sensitized with dyes from different classes which include polymethine dyes comprising cyanines, merocyanines, tri-, tetra- and polynuclear cyanines and merocyanines, oxonols, hemioxonols, styryls, merostyryls, etc.. Sometimes more than one spectral sensitizer may be used in case a larger part of the spectrum should be covered.
  • Combinations of several spectral sensitizers are sometimes used to get supersensitization, meaning that in a certain region of the spectrum the sensitization is greater than that from any concentration of one of the dyes alone or that which would result from the additive effect of the dyes.
  • supersensitization can be attained by using selected combinations of spectral sensitizing dyes and other addenda such as stabilizers, development accelerators or inhibitors, brighteners, coating aids, etc..
  • the photographic elements comprising said silver halide emulsions may include various compounds which should play a role of interest in the material itself or afterwards as e.g. in processing, finishing or storing the photographic material.
  • the silver halide material can also contain different types of couplers that can be incorpated as described in the same Res.Disclosure, section X.
  • the photographic elements can be coated on a variety of supports as described in Res.Disclosure,No. 38957(1996), section XV, and the references cited therein.
  • the photographic elements may be exposed to actinic radiation, especially in the visible, near-ultraviolet and near-infrared region of the spectrum, in order to form a latent image (see Res.Disclosure, No.38957(1996) section XVI).
  • actinic radiation especially in the visible, near-ultraviolet and near-infrared region of the spectrum
  • the irradiation of the doped materal with X-rays is also part of the present invention.
  • the latent-image formed can be processed in many different ways in order to form a visible image as described in Res.Disclosure, No.38957(1996), section XIX.
  • the present invention is also especially focusing on automatic processing photosensitive silver halide materials, which is advantageously used in order to get rapid and convenient processing.
  • the materials of the present invention can preferably be processed as described in EP-A 0 732 619.
  • the developer mentioned in the last reference contains a combination of hydroquinone and ascorbic acid or one of its isomers or derivatives as an auxiliary developing agent. In more general terms this has already been described for silver halide systems as those mentioned e.g. in EP-A 0 552 650 and EP-A 0 752 614, but it is recommended to apply the method and to use the various ascorbic acid analogues as described in EP-A 0 732 619.
  • Processing to form a visible dye image for colour materials means contacting the element with a colour developing agent in order to reduce developable silver halide and to oxidize the colour developing agent which in turn normally reacts with a coupler to form a dye.
  • photothermographic application which is also an important part of the present invention.
  • a photosensitive agent is present which after exposure to UV, visible or IR light is capable of catalysing or participating in a thermographic process bringing about changes in optical density or colour.
  • photothermographic materials are the so called “Dry Silver” photographic materials of the 3M Company, which are reviewed by D.A. Morgan in “Handbook of Imaging Science", edited by A.R. Diamond, page 43, published by Marcel Dekker in 1991.
  • the photo-addressable thermosensitive element comprises photosensitive silver halide, a reducing agent for silver ions and a binder.
  • the thermosensitive element may further comprise a substantially light-insensitive organic silver salt in catalytic association with the photosensitive silver halide and in thermal working relationship with the reducing agent for silver ions.
  • the element may comprise a layer system with the silver halide in catalytic association with the substantially light-insensitive organic silver salt ingredients, a spectral sensitiser optionally together with a supersensitiser in intimate sensitising association with the silver halide particles and the other ingredients active in the thermal development process or pre- or post-development stabilization of the element being in the same layer or in other layers with the proviso that the organic reducing agent and the toning agent, if present, are in thermal working relationship with the substantially light-insensitive organic silver salt, i.e. during the thermal development process the reducing agent and the toning agent, if present, are able to diffuse to the substantially light-insensitive organic silver salt, e.g. a silver salt of a fatty acid.
  • a spectral sensitiser optionally together with a supersensitiser in intimate sensitising association with the silver halide particles and the other ingredients active in the thermal development process or pre- or post-development stabilization of the element being in the same layer or in
  • thermographic element comprising a substantially light-insensitive organic silver salt, an organic reducing agent therefor in thermal working relationship therewith and a binder.
  • substantially light-insensitive organic silver salts are silver salts of organic carboxylic acids in particular aliphatic carboxylic acids known as fatty acids wherein the aliphatic carbon chain has preferably at least 12 C-atoms, e.g.
  • silver laurate, silver palmitate, silver stearate, silver hydroxystearate, silver oleate and silver behenate which silver salts are also called “silver soaps", silver dodecyl sulphonate described in US-A 4,504,575 and silver di-(2-ethylhexyl)-sulfosuccinate described in EP-A 0 227 141.
  • Modified aliphatic carboxylic acids with thioether groups as described e.g. in GB-P 1,111,492 and other organic silver salts as described in GB-P 1,439,478, e.g. silver benzoate and silver phthalazinone may be used likewise to produce a thermally developable silver image.
  • a suspension of particles containing a substantially light-insensitive organic silver salt may be obtained by using a process comprising simultaneously metered addition of an aqueous solution or suspension of an organic carboxylic acid or its salt and an aqueous solution of a silver salt to an aqueous liquid as described in EP-A 0 754 969.
  • the silver halide emulsion grains described hereinbefore may be added to the photo-addressable thermally developable element in any way which places it in catalytic proximity to the substantially light-insensitive organic silver salt.
  • Silver halide and the substantially light-insensitive organic silver salt being separately formed (i.e. ex-situ or "preformed") in a binder can be mixed prior to use to prepare a coating solution, but it is also effective to blend both of them for a long period of time which is especially important in cases where tabular silver halide grains are present so that an intimate contact with the large specific surface of said tabular grains is realized.
  • it is effective to use a process which comprises adding a halogen-containing compound to the organic silver salt to partially convert the substantially light-insensitive organic silver salt into silver halide as disclosed in US-A 3,457,075.
  • a particularly preferred mode of preparing the emulsion of organic silver salt and photosensitive silver halide for coating the photo-addressable thermally developable element from solvent media according to the present invention is disclosed in US-A 3,839,049, but other methods such as those described in Research Disclosure, June 1978, item 17029 and US-A 3,700,458 may also be used for producing the emulsion.
  • WO97/48014 discloses a production method for a photothermographic recording material comprising the steps of: (i) providing a support; (ii) coating the support with a photo-addressable thermally developable element comprising a substantially light-insensitive organic silver salt, photosensitive silver halide in catalytic association with the substantially light-insensitive organic silver salt, a reducing agent in thermal working relationship with the substantially light-insensitive organic silver salt and a binder, characterised in that the photosensitive silver halide is formed by reacting an aqueous emulsion of particles of the substantially light-insensitive organic silver salt with at least one onium salt with halide or polyhalide anion(s) and that the photo-addressable thermally developable element is coated from an aqueous dispersion medium.
  • Suitable organic reducing agents for the reduction of the substantially light-insensitive organic silver salts in photo-addressable thermosensitive elements are organic compounds containing at least one active hydrogen atom linked to O, N or C, such as is the case with mono-, bis-, tris- or tetrakis-phenols, mono- or bis-naphthols, di- or polyhydroxy-naphthalenes, di- or polyhydroxybenzenes, hydroxymonoethers such as alkoxynaphthols, e.g. 4-methoxy-1-naphthol described in US-A 3,094,41; pyrazolidin-3-one type reducing agents, e.g.
  • PHENIDONE (tradename), pyrazolin-5-ones, indan-1,3-dione derivatives, hydroxytetrone acids, hydroxytetronimides, 3-pyrazolines, pyrazolones, reducing saccharides, aminophenols e.g. METOL (tradename), p-phenylenediamines, hydroxylamine derivatives such as for example described in US-A 4,082,901, reductones e.g. ascorbic acids, hydroxamic acids, hydrazine derivatives, amidoximes, n-hydroxyureas and the like; see also US-A 3,074,809, US-A 3,080,254, US-A 3,094,417 and US-A 3,887,378.
  • Polyphenols such as the bisphenols used in the 3M Dry SilverTM materials, sulfonamide phenols such as used in the Kodak DacomaticTM materials, and naphthols are particularly preferred for photothermographic recording materials with photo-addressable thermally developable elements on the basis of photosensitive silver halide/organic silver salt/reducing agent.
  • the reducing agent must be present in such a way that it is able to diffuse to the photosensitive silver halide and, if present, the substantially light-insensitive organic silver salt particles so that reduction thereof can take place.
  • auxiliary reducing agents may be used in conjunction with so-called auxiliary reducing agents.
  • Auxiliary reducing agents that may be used in conjunction with the above mentioned primary reducing agents are sulfonyl hydrazide reducing agents such as disclosed in US-A 5,464,738, trityl hydrazides and formyl-phenyl-hydrazides such as disclosed in US-A 5,496,695 and organic reducing metal salts, e.g. stannous stearate described in US-A 3,460,946 and 3,547,648.
  • the film-forming binder for the photo-addressable thermosensitive element according to the present invention may be coatable from a solvent or aqueous dispersion medium.
  • a solvent dispersion medium any kinds of natural, modified natural or synthetic resins or mixtures of such resins in which the organic silver salt can be dispersed homogeneously may be used; e.g.
  • polymers derived from a,b-ethylenically unsaturated compounds such as polyvinyl chloride, after-chlorinated polyvinyl chloride, copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and vinyl acetate, polyvinyl acetate and partially hydrolyzed polyvinyl acetate, polyvinyl acetals that are made from polyvinyl alcohol as starting material in which only a part of the repeating vinyl alcohol units may have reacted with an aldehyde, preferably polyvinyl butyral, copolymers of acrylonitrile and acrylamide, polyacrylic acid esters, polymethacrylic acid esters, polystyrene and polyethylene or mixtures thereof.
  • a,b-ethylenically unsaturated compounds such as polyvinyl chloride, after-chlorinated polyvinyl chloride, copolymers of vinyl chloride and vinylidene chloride, copolymers of
  • the film-forming binder for the photo-addressable thermosensitive developable element coatable from an aqueous dispersion medium according to the present invention may be all kinds of transparent or translucent water-dispersible or water soluble natural, modified natural or synthetic resins or mixtures of such resins in which the organic silver salt can be dispersed homogeneously, for example proteins such as gelatin and gelatin derivatives (e.g.
  • phthaloyl gela-tin cellulose derivatives such as carboxymethylcellulose, poly-saccharides such as dextran, starch ethers, galactomannan, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, homo-or copolymerized acrylic or methacrylic acid, latexes of water dispersible polymers, with or without hydrophilic groups, or mixtures thereof.
  • Polymers with hydrophilic functionality for forming an aqueous polymer dispersion (latex) are described in US-A 5,006,451, but serve therein for forming a barrier layer preventing unwanted diffusion of vanadium pentoxide present as an antistatic agent.
  • the binder to organic silver salt weight ratio is preferably in the range of 0.2 to 6, while the thickness of the photo-addressable thermally developable element is preferably in the range of 5 to 50 ⁇ m.
  • binders or mixtures thereof may be used in conjunction with waxes or "heat solvents", also called “thermal solvents” or “thermosolvents”, improving the reaction speed of the redox-reaction at elevated temperature.
  • heat solvent in this invention is meant a non-hydrolyzable organic material which is in solid state in the recording layer at temperatures below 50°C but becomes a plasticizer for the recording layer in the heated region and/or liquid solvent for at least one of the redox-reactants, e.g. the reducing agent for the organic silver salt, at a temperature above 60°C.
  • compounds such as urea, methyl sulfonamide and ethylene carbonate being heat solvents described in US-A 3,667,959, and compounds such as tetrahydro-thiophene-1,1-dioxide, methyl anisate and 1,10-decanediol being described as heat solvents in Research Disclosure, December 1976, (item 15027) pages 26-28.
  • Still other examples of heat solvents have been described in US-A 3,438,776, and 4,740,446, and in published EP-A 0 119 615 and 0 122 512 and DE-A 3 339 810.
  • the photo-addressable thermosensitive material comprising said substantially light-insensitive organic silver salt and said light-sensitive silver halide crystals may include various other compounds which should play a role of interest in the material itself or afterwards as e.g. in the processing, finishing or conservation stage of the material. These compounds can be 'toning agents', also stabilizers and anti-foggants, surfactants (specially for coating photo-addressable thermosensitive elements from aqueous media), anti-halation dyes and other additives (like free fatty acids, antistatic agents, surface active agents, etc.) that are described in EP-A 0 844 514.
  • the support used for the photo-addressable thermosensitive material, the function and composition of the protective and antistatic layers, the coating of the various layers of the photothermographic recording material are also disclosed in EP-A 0 844 514.
  • a reaction vessel having a volume of 6 liter was filled with 1500 ml of demineralized water, further adding thereto 14.2 ml of a solution of sulphuric acid 6 N (in order to get a starting pH of 1.7), 6.8 ml of an aqueous solution of potassium bromide 2.94 N (in order to provide a potential difference between a silver electrode and a silver/silver chloride reference elctrode of 6 mV.
  • a temperature of 40°C an amount of 7.5 g of oxidized gelatine (having less than 40 ppm of methionin.
  • Silver halide nuclei were formed by reaction of a silver nitrate solution and a halide salt solution run by double-jet in the reaction vessel at a rate of 80 ml/min. at 40°C and at 40 mV during 9 seconds.
  • silver halide emulsion crystals were grown at the same potential value by increasing the double jet precipitation rate up from 5 ml/min. up to 33.4 ml/min. during 7587 seconds for the silver nitrate solution, while continuously adapting the running velocity of the halide salt solution in order to have a constant potential value of + 30 mV. A total amount of 500 g of silver nitrate was thus precipitated.
  • Tabular silver halide emulsion crystal characteristics are following:
  • Tabular silver halide emulsion crystal characteristics are following:
  • Tabular silver halide emulsion crystal characteristics are following:
  • Tabular silver halide emulsion crystal characteristics are following:

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP98204367A 1998-12-21 1998-12-21 Verfahren zur Herstellung einer homogenen und dünne tafelförmige Körner enthaltenden Silberhalogenidemulsion Withdrawn EP1014175A1 (de)

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Application Number Priority Date Filing Date Title
EP98204367A EP1014175A1 (de) 1998-12-21 1998-12-21 Verfahren zur Herstellung einer homogenen und dünne tafelförmige Körner enthaltenden Silberhalogenidemulsion
US09/460,377 US6214532B1 (en) 1998-12-21 1999-12-13 Method of preparing silver halide emulsion containing homogeneous and thin tabular crystals
JP11360123A JP2000187294A (ja) 1998-12-21 1999-12-20 均質で薄い平板状結晶を含有するハロゲン化銀乳剤の製造方法

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0102320A2 (de) * 1982-07-23 1984-03-07 Ciba-Geigy Ag Verfahren zur Herstellung von Silberhalogenidemulsionen
JPH02172816A (ja) * 1988-12-26 1990-07-04 Fuji Photo Film Co Ltd ハロゲン化銀粒子の製造方法及び装置
US5145768A (en) * 1988-12-22 1992-09-08 Fuji Photo Film Co., Ltd. Process of forming silver halide grains
US5270159A (en) * 1988-12-26 1993-12-14 Fuji Photo Film Co., Ltd. Process of producing silver halide grains and apparatus therefor
EP0697618A1 (de) * 1994-07-14 1996-02-21 Fuji Photo Film Co., Ltd. Verfahren zur Herstellung von Silberhalogenidkorn und Silberhalogenidemulsion unter Verwendung dieses Korns
EP0816911A1 (de) * 1996-06-26 1998-01-07 Konica Corporation Photographische Silberhalogenidemulsion und photographisches lichtempfindliches Silberhalogenidmaterial

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0102320A2 (de) * 1982-07-23 1984-03-07 Ciba-Geigy Ag Verfahren zur Herstellung von Silberhalogenidemulsionen
US5145768A (en) * 1988-12-22 1992-09-08 Fuji Photo Film Co., Ltd. Process of forming silver halide grains
JPH02172816A (ja) * 1988-12-26 1990-07-04 Fuji Photo Film Co Ltd ハロゲン化銀粒子の製造方法及び装置
US5270159A (en) * 1988-12-26 1993-12-14 Fuji Photo Film Co., Ltd. Process of producing silver halide grains and apparatus therefor
EP0697618A1 (de) * 1994-07-14 1996-02-21 Fuji Photo Film Co., Ltd. Verfahren zur Herstellung von Silberhalogenidkorn und Silberhalogenidemulsion unter Verwendung dieses Korns
EP0816911A1 (de) * 1996-06-26 1998-01-07 Konica Corporation Photographische Silberhalogenidemulsion und photographisches lichtempfindliches Silberhalogenidmaterial

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Low Silver Halide Concentration Process", RESEARCH DISCLOSURE., vol. 340, no. 37, August 1992 (1992-08-01), HAVANT GB, pages 612 - 615, XP000328072 *

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