EP0945755A1 - Elément photosensible formateur d'images contenant des cristaux d'halogénure d'argent modifiés à l'intérieur d'un complexe metal-halogène-fluor - Google Patents

Elément photosensible formateur d'images contenant des cristaux d'halogénure d'argent modifiés à l'intérieur d'un complexe metal-halogène-fluor Download PDF

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Publication number
EP0945755A1
EP0945755A1 EP99200094A EP99200094A EP0945755A1 EP 0945755 A1 EP0945755 A1 EP 0945755A1 EP 99200094 A EP99200094 A EP 99200094A EP 99200094 A EP99200094 A EP 99200094A EP 0945755 A1 EP0945755 A1 EP 0945755A1
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Prior art keywords
silver halide
emulsion
forming element
silver
photosensitive image
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EP99200094A
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German (de)
English (en)
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EP0945755B1 (fr
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Dirk Vandenbroucke
Matthias Höhling
Ingo Reese
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Agfa Gevaert NV
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Agfa Gevaert NV
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • 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
    • G03C1/06—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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • G03C2005/3007—Ascorbic acid
    • 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
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers

Definitions

  • the present invention relates to a photosensitive silver salt emulsion and a photosensitive material containing said emulsion. More specifically the invention relates to a silver salt emulsion with improved imaging characteristics and to a method for making said emulsion.
  • a silver halide material used for industrial applications requires a very high flexibility in its practical properties for use, e.g. the light temperature range for exposure, the range of development times in which an optimal image quality can be realized, etc..
  • One of the means increasingly used in the art is the introduction of a hole or electron trap in the silver halide crystal, which can be realized by doping with certain metal ligand complexes.
  • dopants influencing the photographic activity of silver halide materials in different ways are known.
  • the type and strength of the effect of the introduction of a dopant is always the result of the formation of ionic crystal defects in the lattice which in turn can influence the path of photocharges initiated by light absorption in the crystal.
  • the following types of active lattice centres for interaction with photocharges can be distinguished: (i) deep and permanent electron traps, (ii) non-permanent electron traps, (iii) shallow electron traps, (iv) hole traps and (v) recombination centres.
  • a description and definition of the centres mentioned can be found in the following references: R.S.Eachus,M.T.Olm, 'Crystal Latt. Def. and Amorph.
  • Transition metal complexes that can be used as dopant are characterized by the positions of the LUMO and HOMO, where LUMO means 'lowest unoccupied molecular orbital' and HOMO 'highest occupied molecular orbital' (see D.F.Shriver, P.W.Atkins, C.H.Langford in 'Inorganic Chemistry', Oxford University Press(1990)-Oxford-Melbourne-Tokyo).
  • the distance between the energy levels of LUMO and HOMO of a metal ion in a given lattice is among other things determined by the electron-withdrawing strength of the different ligands in the complex.
  • metal ligand complexes with at least two different ligands are preferably used in practice. If all the ligands in a metal complex are more electronegative (situated more to the right side of the spectrophotometrical series) the complex is getting more SET ( s hallow electron trap) characteristics; if a ligand is becoming less electronegative the trap depth of the metal complex dopant will increase thereby forming a more permanent trapping centre.
  • SET s hallow electron trap
  • metal ligand complexes with two or more different ligands are used in materials presently sold in the market.
  • 'State of the art' are metal complexes containing halogen ligands used together with another ligand being chosen with respect to the kind of trapping centre needed in the silver halide grains.
  • EP-A 0 336 426 with CN-ligands
  • EP-A 0 336 427 with NO- or NS-ligand
  • EP-A 0 415 480 with oxo-coordination ligands
  • EP-A 0 415 481 with CC-ligand
  • US-A 5,360,712 with organic ligands like azole, diazole, triazole, pyridine, pyrazine, etc.
  • the metal complexes described for the first time in the present invention contain one or more F-ligands next to other halogen ligands. These mixed halogen ligand complexes give sensitometric effects that can be fully attributed to the F-ligand, which is unexpected and new in the art.
  • a metal-halogen-fluorine-complex called hereinafter 'MHF'-complex
  • a photosensitive image-forming element comprising on at least one side of a support a photosensitive layer containing silver halide crystals that are internally doped with a new type of transition metal complex with exclusively halide ligands, more preferably a metal halogen-fluorine-complex (hereinafter called 'MHF'-complex) represented by general formula (1): [ML 6-n F n ] m- wherein:
  • the present invention further provides a method for obtaining a photosensitive image-forming element containing silver halide crystals into which the MHF-complex represented by formula (1) is incorporated.
  • photosensitive silver halide emulsions can be prepared by precipitation in an aqueous dispersing medium including, at least during grain growth, a peptizer in which silver ions and halide ions are brought together. Grain structure and properties are selected by control of several parameters like precipitation temperature, pH and relative proportion of the silver and halide ions in the dispersing medium. In order to avoid fog during the precipitation the grain preparation is commonly carried out on the halide side of the equivalence point which is defined as "the point at which the silver and halide ion activity is equal".
  • the silver halide emulsions of the present invention are prepared in the presence of compounds (generally known as dopants) which can be occluded in the crystal structure.
  • dopants compounds which can be occluded in the crystal structure.
  • Such a dopant is replacing an appropiate amount of silver and halide ions in the silver-halide lattice.
  • the detection of the presence of said dopants in silver halide crystals themselves can be carried out by EPR or ENDOR techniques.
  • the EPR technique and sample preparation has been described in US-A 5,457,021 by Olm et al and by H.Vercammen, T.Ceulemans, D.Schoenmakers, P.Moens and D.Vandenbroucke in Proc.
  • sensitivity sensitivity, gradation, pressure sensitivity, high or low intensity reciprocity failure (HIRF or LIRF), stability, dye desensitization, and several other sensitometric aspects of a photosensitive silver- halide emulsion
  • the dopant including its concentration, its valency and its location in the crystal in case of incorporation of the single metal ion.
  • coordination complexes or even oligomeric coordination complexes are used the different ligands bound at the central metal ion can be occluded in the crystal lattice too and can in this way influence the photographic properties of the silver halide material as well (see Research Disclosure No. 38957 (1996) p. 591, section I-D).
  • the present invention is based on the experimental data obtained with respect to the photographic effect of hexa-coordinated metal-halogen complexes which are incorporated into radiation sensitive silver halide grains which can be strongly enhanced if at least one of the halogen ligands is a fluorine atom.
  • Such complexes are represented by formula (1): [ML 6-n F n ] m- wherein:
  • n an integer having a value satisfying following equation: 1 ⁇ n ⁇ 6, while m equals a value of 1, 2, 3 or 4.
  • Table 1 to 5 A survey of chemical structures that can be used as MHF-complex dopant in the present invention are summarized in Table 1 to 5.
  • Re (IV)-complexes cis -[ReFBrI 4 ] 2- fac- [ReFBr 2 I 3 ] 2- mer -[ReFBr 3 I 2 ] 2- trans -[ReFBr 4 I] 2- [ReFBr 5 ] 2- trans -[ReFCl 4 I] 2- trans -[ReFCl 4 Br] 2- [ReFCl 5 ] 2- cis -[ReF 2 I 4 ] 2- fac- [ReF 2 BrI 3 ] 2- all-cis -[ReF 2 Br 2 I 2 ] 2- cis- [ReF 2 Br 2 t I 2 ] 2- mer -[ReF 2 Br 3 I] 2- cis -[ReF 2 Br 4 ] 2- cis -[ReF 2 Cl 4 ] 2- fac- [ReF 3 I 3 ] 2- fac -[ReF 3 BrI 2 ] 2- fac- [ReF 3 BrI] 2- fac- [ReF 3 Br 3 ] 2- fac- [ReF 3 Cl 3 ]
  • the doping procedure itself can be performed normally at any stage in the grain growth phase of the emulsion preparation during which the reactants for silver halide formation are added to the reaction vessel in the form of solutions of silver and halide salts. This can be carried out by using two different jet-inlets for the individual reactant solutions.
  • the doping can also be executed during the grain growth process wherein the addition of the silver halide components are introduced as preformed silver halide nuclei or fine grains which easily dissolve in the precipitation medium. In the present invention special attention should be paid to the way in which the dopants are introduced during the grain growth process.
  • the addition of the dopants can be carried out in different ways: directly, incorporated into one of the reactant flows for the silver halide formation or as an individual injection next to the reactants, and indirectly by addition of a dispersion of fine soluble silver halide grains or nuclei already comprising the dopant.
  • the solution containing the dopant(s) satisfying formula (1) is preferably introduced by making use of a third jet in addition to said two jets for the introduction of the silver salt and the halide salt solution for the formation of the silver halide grains. This third jet is introduced in a zone of the reactor where the compounds are rapidly incorporated into the growing microcrystals.
  • the advantage of using a third jet is that a solvent which is most suitable for the stability of that compound can be used for the given dopant. Furthermore the temperature of the dopant solution can be adjusted in order to maximize the stability. The most stable conditions for the dopant solution are preferably tested by UV-VIS absorption.
  • the third jet itself can be adjusted automatically or manually.
  • the dopant solution can be added at a constant rate or at any rate profile as has been described e.g. in JP-A 03163438, wherein the dopant is occluded in two different concentrations in the silver halide grains of a direct positive emulsion.
  • the amount of dopant which can be used in the present invention is limited and situated between 10 -10 and 10 -2 mole per mole of silver halide but preferably between 10 -8 and 10 -4 mole per mole of silver halide.
  • concentration of dopant solution can be chosen freely but is determined by various factors like the solubility of the complex, the stability of the desired solution, etc..
  • the position in the silver halide crystals where the dopant is incorporated is also free to choose but depends on the trapping activity of the complex in the crystal.
  • the formation of silver halide can be carried out by adding the individual reactants together.
  • the addition itself can be performed through surface or subsurface delivery tubes by hydrostatic pressure or by an automatic delivery system for maintaining control of pH and/or pAg in the reaction vessel and of the rate of the reactant solutions introduced therein, which method is used in a controlled double-jet precipitation procedure.
  • the reactant solutions or dispersions can be added at a constant rate or a constantly increasing or fluctuating rate in combination with stepwise delivery procedures as desired. More details about possible ways of making a silver halide emulsion that can be principally used in practising this invention are summarized in Research Disclosure No. 38957 (1996), p. 591-639, section I-C.
  • the photographic emulsions prepared in this way for use in the image-forming element of the present invention 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. It should be noted in the context of the present invention that the activity of the complex(es) or dopant(s) satisfying formula (1) is hardly influenced by the halide composition of the silver halide crystals used.
  • 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 tabular or non-tabular like cubic, octahedral, etc..
  • 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); especially in the case of the ultra-thin tabular crystals (from 0.05 up to 0.15 ⁇ m) 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.
  • the emulsions can include silver halide grains of any conventional shape or size. Specifically the emulsions can include coarse, medium or fine silver halide grains.
  • the silver halide emulsions can be either monodisperse or polydisperse after precipitation.
  • the polydispersity can be the result of mixing two or more monodispersed emulsions.
  • dopants represented by formula (1) can be added during the preparation of the silver halide emulsion. These are optionally introduced only if their specific influence on the photographic characteristics is desired. As stated already in the description of the background of the present invention different classes of dopants are known. It is a special feature of the present invention to use combinations of dopants including at least one satisfying formula (1). It means that together with a deep electron trapping metal complex represented by formula (1) another dopant can be present (e.g. Ru(CN) 6 2- ) creating shallow electron traps in silver halide. But it is also possible that for instance RuCl 5 (NO) 3- (as deep electron trap) is used together with PtF 6 2- as SET.
  • Ru(CN) 6 2- e.g. Ru(CN) 6 2-
  • 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 emulsions can be surface-sensitive emulsions forming latent images primarily at the surface of the silver halide grains or they can be emulsions forming their latent-image primarily in the interior of the silver halide grain. Furthermore the emulsions can be negative-working emulsions such as surface-sensitive emulsions or unfogged internal latent image-forming emulsions. However direct-positive emulsions of the unfogged latent-image-forming type which are positive-working by development in the presence of a nucleating agent, and even pre-fogged direct-positive emulsions can be used in the present invention.
  • the silver halide emulsions can be chemically sensitized in many different ways.
  • chalcogen as sulphur, selenium or tellurium
  • a noble metal as e.g. gold or in combination with a chalcogen and noble metal.
  • 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.
  • reducing agents e.g. tin compounds (see GB-Patent 789,823), amines, hydrazine derivatives, formamidine-sulphinic acids, silane compounds, ascorbic acid, reductic acid and the like.
  • 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. These products can be stabilizers and anti-foggants (see RD No.
  • 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.
  • a method for obtaining a photosensitive image-forming element comprising the steps of :
  • 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.
  • a method for obtaining an image comprising the steps of:
  • 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.
  • a point of interest of the present invention is the presence of a dopant or a transition metal complex according to formula (1) in the organic silver salt material or even incorporated in the organic silver salt itself.
  • a dopant or a transition metal complex according to formula (1) in the organic silver salt material or even incorporated in the organic silver salt itself.
  • the silver halide crystals it can also be a combination of dopants satisfying formula (1).
  • this doping possibility can additionally be combined with a dopant of another group.
  • 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.
  • W097/48014 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 gelatin cellulose derivatives such as carboxymethylcellulose, polysaccharides 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), antihalation dyes and other additives (like free fatty acids, antistatic agents, surface active agents, etc.) that are described in unpublished Application EP 96/203269, filed november 21, 1996.
  • 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 disclosed in the same Application EP 96/203269.
  • Example 1 Application of halogen-fluor-complexes of osmium to a silver chloride emulsion.
  • the pH of the solutions A1 and A3 was brought to 2.80 using a sulphuric acid solution.
  • the solutions A2 and A3 were kept at room temperature, whereas solution A1 was heated to 50°C.
  • the pAg was set at 7.05 using a NaCl solution.
  • Solution A2 was added to solution A1 at a constant rate during 3 minutes, while solution A3 was added at a rate in order to keep the pAg constant at a value of 7.05.
  • the addition rate of solution A2 was slightly raised during 3 minutes while the addition rate of solution A3 was varied in order to raise the pAg to 7.5 in 3 minutes.
  • Solution A2 was further added at a constantly accelerating rate starting at 7.86 mmole/min until 25.5 mmole/min during 60 minutes, while solution A3 was simultaneously added at a rate in order to keep the pAg constant at 7.5.
  • the emulsion was ultrafiltrated and desalted by ultrafiltration at constant pAg of 7.7. After the washing procedure 600g of gelatin was added to the precipitate followed by the addition of water in order to make a total of 10 kg of emulsion. The pH was set to 2.8 with a sulphuric acid solution.
  • the thus prepared silver chloride emulsion had a monodisperse grain size distribution with a mean grain size of 0.33 ⁇ m and amitual variation coefficient of about 15% in grain size.
  • the primitive and the chemically sensitized emulsions were coated on a substrated PET base at 1.85 g gelatin per m 2 and 25 mmole AgCl per m 2 .
  • An emulsion containing gelatin (1.0 g per m 2 ), a divinylsulphonyl-hardener and surfactants was coated on top of the emulsion layer.
  • Strips with the coated emulsions were image-wise exposed through a step-wedge original using a 10 -3 sec Xenon flash.
  • the exposed photographic materials were developed in a commercial developer G101 (Trademark of AGFA) for 15 sec at 35°C and fixed for 5 minutes in a commercial fixer G333C (Trademark of AGFA) which was 1/3 diluted with demineralized water.
  • Sensitometric data that were measured on the processed strips are summarized in Table 1.2. For all these samples the fog level was 0.03 to 0.05. Sensitivity was measured at a density level of 0.2 above fog and contrast was evaluated between densities 0.1 and 0.5 above fog, i.e. in the foot of the densitometric curve.
  • the data mentioned in Table 1.2 are the relative data expressed in percentage: for the sensitivity (Rel.Sens.) the light dose necessary to get the indicated density for a doped emulsion relative to the light dose to get the same density with the non-doped (reference) emulsion. A value of 50 means a half of the sensitivity with respect to that of the reference emulsion.
  • the experimental error is of the order of 10 to 12%.
  • the relative contrast (Rel.Contr.) is 100 times the ratio of the contrast for the doped and the non-doped emulsion.
  • the table gives the results of the emulsions without (-) and with (+) chemical sensitization in the column 'Chem.Sens.'
  • ligand structure of the osmate compounds used as a dopant in these AgCl emulsions significant influences on quantum efficiency and contrast were observed.
  • For the primitive emulsions a significant lowering of sensitivity and contrast was observed by doping the AgCl-emulsions with an OsCl 2- 6 - or OsBr 2- 6 -complex.
  • the effect of the dopants on the reciprocity behaviour was tested on the chemically sensitized emulsions.
  • Different film strips were exposed using a 10 -5 sec. Xe-flash pulse and a 10 sec. Xe lamp exposure with equal total light energy dose.
  • the exposed photographic materials were developed in a surface developer at room temperature for 8 minutes and fixed for 5 minutes in a commercial fixer G333C (Trademark of Agfa) which was 1/3 diluted with demineralized water.
  • the relative sensitivity is determined in a similar way as mentionned above at reference density 0.2 above fog.
  • the high intensity reciprocity failure (HIRF) was determined as the difference in sensitivity between the 10 -5 sec. and the 10 sec. exposure.
  • the ⁇ HIRF is the change in reciprocity behaviour due to the dopant. A positive value indicates that the dopant enhances the high intensity reciprocity failure, whereas a negative value indicates that the dopant lowers the HIRF.
  • the detection of electrons trapped at shallow electron traps can be done by employing the electron paramagnetic resonance (EPR) technique.
  • EPR electron paramagnetic resonance
  • This technique is in fact the only technique -apart from derived techniques, such as electron nuclear double resonance (ENDOR)- which enables the unambiguous detection of the functionality of these shallow electron traps, as quoted also in Olm et al U.S. Serial No. 5,503,970.
  • the shallowly trapped photoelectrons give rise to an EPR signal, which is composed of a single line, with a g value that is characteristic for the local grain composition. It is shown in R.S. Eachus, M.T. Olm, R. Janes and M.C.R. Symons, Phys. Stat. Sol.
  • Emulsion N° Dopant Conc. (10 -6 mole/mol Ag) Relative Sens. (10 -5 sec) Relative Sens. (10 sec) ⁇ HIRF E2 none - 100 100 0 Comparat.
  • the g value in EPR is characteristic for each species under study, and can be calculated and measured as described in, e.g., Electron Paramagnetic Resonance: Techniques and Applications, by Raymond S. Alger, (1968) published by Interscience publishers, New York.
  • the width of the line, as a function of temperature and concentration of the added dopant complex, is described by H. Vercammen, D. Schoemaker, D. Vandenbroucke, Proceedings of the 1997 International Symposium on Silver Halide Imaging, Victoria - BC, Canada, 1997, pp. 125.
  • the line width of the EPR signal of shallowly trapped electrons at 20 K is quoted to be 1.0 ⁇ 0.1 mT for a dopant concentration of 1 ppm.
  • the emulsion powders could be routinely measured at 2K. This low temperature is chosen to elimate other electronic or ionic events.
  • the dopant is EPR active (i.e. paramagnetic) before or after the trapping of a photoproduced charge, or the complex remains EPR active before and after, but its EPR spectrum is changed.
  • the first case is observed.
  • the following reference is given for the detection of Rh 2+ after trapping of an electron by a Rh 3+ ion: H. Vercammen, T. Ceulemans, D. Schoemaker, P. Moens, D. Vandenbroucke, Proceedings of the 49 th IS&T Annual Conference, Minneaplis, Minnesota, 1996, pp.54.
  • the Os 3+ -signal was found to reduce to about 20%-70% of the original intensity depending on the temperature of illumination. This can be ascribed to the capture of a photogenerated charge (in this case an electron) which reduces Os 3+ to os 2+ , which is not detectable by EPR, i.e., is not paramangetic. Indeed no extra EPR lines were detected after illumination.
  • a photogenerated charge in this case an electron
  • Emulsion E6 was further characterized using ENDOR techniques. With X-band ENDOR and Triple ENDOR it is possible to prove that, for the osmium related complex, one of the surrounding nuclei is fluor ( 19 F).
  • RF radio-frequency
  • Example 2 Application of halogen-fluor-complexes of platinum as dopants in silver halide emulsion.
  • a reference emulsion was prepared in an identical way as emulsion E2 in the previous example.
  • the emulsion E13 was prepared in an identical way as emulsion E2, except that between seconds 72 and 306 of the precipitation of the silver halide grains 10.06 ml of an aqueous solution containing 1.5 10 -4 mole/l of K 2 PtF 6 was added using a separate jet at a constant flow rate. Further emulsion preparation steps were identical to those in example 1.
  • the primitive and the chemical sensitized emulsions were coated on a substrated PET base at 1.85 g gelatin/m 2 and 25 mmol AgCl/m 2 .
  • An emulsion containing gelatin (1.0 g/m 2 ), a divinylsulphonyl-hardener and surfactants was coated on top of the emulsion layer.
  • Strips with the coated emulsions were image-wise exposed through a step-wedge original using a 10 -3 sec Xenon flash.
  • the exposed photographic materials were developed in a commercial developer G101 for 15 sec. at 35°C and fixed for 5 minutes in a commercial fixer G333C (Trademark of Agfa) which was 1/3 diluted with demineralized water.
  • Sensitometric data are summarized in Table 2.1. Sensitometric data for the none doped and the PtF 6 2- doped emulsions. Emulsion N° Dopant Chem.Sens. (+/-) Rel. Sens. (0.2+Fog) Rel. Contr. (0.2-0.5)+Fog E2 none - 100 100 Comparat. E13 K 2 PtF 6 - 74 119 Invention E2 none + 100 100 Comparat. E13 K 2 PtF 6 + 100 103 Invention
  • the fog level was 0.03 to 0.05.
  • Sensitivity was measured at a density level of 0.2 above fog and contrast was evaluated between densities 0.1 and 0.5 above fog, i.e. in the foot of the densitometric curve. Definition of sensitometric parameters was identical to those in example 1. In the primitive emulsions a limited desensitization and contrast enhancing activity was noticed. In the chemical sensitized emulsions apparently no influence was induced on the photochemical efficiency of the emulsion by the incorporation of the dopant. Powders were prepared in a similar way as explained for the emulsions in example 1. Similar EPR tests were done on these powders to investigate the electron-trapping activity of the fluorine-platinum complexes.
  • halogen-fluorine-platinum complexes are shallow electron trapping agents in AgCl emulsions.
  • Example 3 Application of halogen-fluor complexes of iridium to silver halide emulsion.
  • the primitive and the chemical sensitized emulsions were coated on a substrated PET base at 1.85 g gelatin/m 2 and 25 mmol AgCl/m 2 .
  • An emulsion containing gelatin (1.0 g/m 2 ), a divinylsulphonyl-hardener and surfactants was coated on top of the emulsion layer.
  • Strips of these coated emulsions were image-wise exposed through a step-wedge original using a 10 -5 sec or a 10 sec Xenon flash with an equal energy dose in both exposures.
  • the exposed photographic materials were developed in a commercial developer G101 for 15 sec. at 35°C and fixed for 5 minutes in a commercial fixer G333C (Trademark of Agfa) which was 1/3 diluted with demineralized water.
  • Sensitometric data are summarized in Table 3.1. For all these samples the fog level was 0.03 to 0.05. The relative sensitivity was determined in a similar way as mentionned above and the reference density level was 0.2 above fog.
  • the desensitization is even larger for the primitive emulsion and equal for the sensitized emulsion, whereas for the further F-substituted compounds the desensitizing effect was lowered in the case of the primitive emulsions and even switched to a sensitizing effect while this influence was not noticed on the chemical sensitized emulsions.

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EP99200094A 1998-03-25 1999-01-15 Elément photosensible formateur d'images contenant des cristaux d'halogénure d'argent modifiés à l'intérieur d'un complexe métal-halogène-fluor Expired - Lifetime EP0945755B1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6902879B2 (en) 2001-08-30 2005-06-07 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion, silver halide photosensitive material, and novel iridium complex and preparation process thereof
EP1818718A2 (fr) * 2001-11-05 2007-08-15 Fuji Photo Film Co., Ltd. Matériau photothermographique et procédé de développement thermique correspondant
US10471655B2 (en) 2015-09-04 2019-11-12 Carbon, Inc. Cyanate ester dual resins for additive manufacturing

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2566245A (en) * 1945-08-30 1951-08-28 Eastman Kodak Co Complex compounds of the platinum group as photographic fog inhibitors
EP0572022A2 (fr) * 1992-05-27 1993-12-01 Fuji Photo Film Co., Ltd. Matériau photographique encapsulé
US5474888A (en) * 1994-10-31 1995-12-12 Eastman Kodak Company Photographic emulsion containing transition metal complexes
US5616446A (en) * 1994-09-29 1997-04-01 Konica Corporation Silver halide photographic light-sensitive material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2566245A (en) * 1945-08-30 1951-08-28 Eastman Kodak Co Complex compounds of the platinum group as photographic fog inhibitors
EP0572022A2 (fr) * 1992-05-27 1993-12-01 Fuji Photo Film Co., Ltd. Matériau photographique encapsulé
US5616446A (en) * 1994-09-29 1997-04-01 Konica Corporation Silver halide photographic light-sensitive material
US5474888A (en) * 1994-10-31 1995-12-12 Eastman Kodak Company Photographic emulsion containing transition metal complexes

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6902879B2 (en) 2001-08-30 2005-06-07 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion, silver halide photosensitive material, and novel iridium complex and preparation process thereof
EP1818718A2 (fr) * 2001-11-05 2007-08-15 Fuji Photo Film Co., Ltd. Matériau photothermographique et procédé de développement thermique correspondant
EP1818718A3 (fr) * 2001-11-05 2009-03-04 Fuji Photo Film Co., Ltd. Matériau photothermographique et procédé de développement thermique correspondant
US10471655B2 (en) 2015-09-04 2019-11-12 Carbon, Inc. Cyanate ester dual resins for additive manufacturing
US11040483B2 (en) 2015-09-04 2021-06-22 Carbon, Inc. Cyanate ester dual cure resins for additive manufacturing
US11090859B2 (en) 2015-09-04 2021-08-17 Carbon, Inc. Cyanate ester epoxy dual cure resins for additive manufacturing

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