EP0933671B1 - Photoempfindliches bilderzeugendes Material, das tafelförmige Silber(iodo)bromidkristalle enthält, die mit einem Metall-Ligandenkomplex dotiert sind, der tiefe Elektronenfallen erzeugt - Google Patents

Photoempfindliches bilderzeugendes Material, das tafelförmige Silber(iodo)bromidkristalle enthält, die mit einem Metall-Ligandenkomplex dotiert sind, der tiefe Elektronenfallen erzeugt Download PDF

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Publication number
EP0933671B1
EP0933671B1 EP99200087A EP99200087A EP0933671B1 EP 0933671 B1 EP0933671 B1 EP 0933671B1 EP 99200087 A EP99200087 A EP 99200087A EP 99200087 A EP99200087 A EP 99200087A EP 0933671 B1 EP0933671 B1 EP 0933671B1
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EP
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Prior art keywords
silver
forming element
silver halide
crystals
iod
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EP99200087A
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French (fr)
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EP0933671A1 (de
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Dirk Vandenbroucke
Kathy Elst
Gina De Lamper
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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
    • G03C1/005—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
    • G03C2001/093—Iridium
    • 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
    • G03C2001/094—Rhodium

Definitions

  • the present invention relates to a photosensitive silver halide emulsion and a photosensitive material containing said emulsion. More specifically the present invention is related to a tabular silver brom(iod)ide emulsion with enhanced image contrast.
  • a silver halide material used for industrial applications needs a very high flexibility in its practical properties for use, like for instance 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 deep electron trap in the silver halide crystal which can be arranged by doping with certain metal ligand complexes. Such an electron trap is called deep if it easily holds a captured electron.
  • the LUMO lowest unoccupied molecular orbital
  • the incorporated molecular entity (related complex) should be situated at least 0.5 eV below the conduction band while the trapping lifetime should be longer than 0.2 s (R.S.Eachus, M.T.Olm in "Cryst.Latt.Def.and Amorph.Mat.”, 1989(18), 297-313).
  • the LUMO of the related complex thus has the ability to trap an electron from the conduction band (D.F.Shriver, P.W.Atkins, C.H.Langford in “Inorganic Chemistry”- Oxford Univ.Press (1990), Oxford-Melbourne-Tokyo).
  • a general property of a deep electron trapping agent (here further called 'DETA') is that it always creates loss in sensitivity which is inherent in this created lattice defect.
  • the DETA lowers the efficiency of the latent image formation process at the surface of the crystal by capturing a photo electron. Because the amount of these molecules is equally distributed over the solid silver halide the larger and intrinsically most sensitive emulsion grains will contain the most DETA-molecules (compared with the smaller less sensitive emulsion grains). These intrinsically most sensitive emulsion grains are therefore desensitized to a larger extent than the smaller and intrinsically less sensitive grains. This results in an overall desensitization and an increase of the overall gradation which can be most markedly seen in the so-called 'toe' of the sensitimetric curve, wherefrom the terminolgy 'toe-gradation' has been derived.
  • Ligands set forth therein differing from pure halides as (CN), (NO), (CO) and (NH 3 )are (SCN), (SecN) and (TeCN), which have also been mentioned as ligands for the same metal atoms as in JP-A's 04-125629 and 06-059365_wherein high sensitivity, low fog and good reciprocity and latent image storage stability are envisaged respectively.
  • RhCl 6 3- -complex in aqueous solutions which is especially active in a matrix rich in silver chlorobromide as has been demonstrated in EP-A 0 557 616 and in JP-A 6,035,093 and which is cheaper than the other complexes.
  • disadvantages related therewith are the formation of a chloro-aquo complex which is less active as a DETA, the activity decrease in a bromide or bromoiodide matrix and the impracticability in a silver chloride matrix.
  • a still further object of the present invention is to provide a DETA as a dopant for photosensitive silver halide emulsions which can easily be prepared with relative low costs.
  • the precipitation of a photosensitive silver halide emulsion is conducted in an aqueous dispersing medium including, at least during grain growth, a peptizer wherein silver ions and halide ions are brought together.
  • Grain structure and properties can be selected by control of several parameters like precipitation temperature, pH and relative proportion of the silver and halide ions in the dispersing medium.
  • the precipitation is commonly conducted 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 current invention are prepared in the presence of compounds which can be occluded in the crystal structure.
  • a compound also called dopant
  • the dopant can be distinguished from the metal-complex introduced in the emulsion as an additive 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.
  • dopants are modifying the crystal structure and are further influencing the properties of the crystal.
  • a lot of parameters like sensitivity, gradation, pressure sensitivity, high or low intensity reciprocity failure (LIRF), stability, dye desensitization, and several other sensitometric aspects of a photosensitive silver halide emulsion can be modified by selection of the dopant, including its concentration, its valency and its location in the crystal in case of incorporation of the single metal ion.
  • 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.
  • the dopant utilized in accordance with the present invention is a rhodium complex be defined by the general formula (1) as described hereinbefore and which is applied as a deep electron trapping agent or DETA.
  • the complex satisfying formula (1) contains at least one chalcogenic cyanate complex and differs from the other known chalcogenic cyanate complexes in different ways.
  • SCN- or NCS-containing complexes described as in EP-A 0 336 425, EP-A 0 606 895, US-A 5,278,041 and US-A 5,609,997) which are used in silver halide materials as SET (shallow electron trap) and which cannot be applied for sensitivity decrease or gradation increase.
  • EP-A 0 336 427 EP-A 0 415 481 and US-A 4,981,781 other DET-producing complexes containing a NCS- or SCN-ligand are known and described but these do not contain halogen-ligands.
  • the ligand L in formula (1) is a chalcogenic cyanate group represented by YCN or NCY wherein Y represents a chalcogene atom selected from the group consisting of S, Se and Te.
  • n an integer having a value from 1 up to less than 6, while m equals a value of 1, 2 or 3.
  • a survey of possible structures for complex ions of Rh has been summarized in the Table 1 hereinafter, RhCl 5 (SCN) 3- RhCl 5 (SeCN) 3- RhCl 5 (TeCN) 3- RhCl 5 (NCS) 3- RhCl 5 (NCSe) 3- RhCl 5 (NCTe) 3- RhCl 4 (H 2 O)(SCN) 2- RhCl 4 (H 2 O)(SeCN) 2- RhCl 4 (H 2 O)(TeCN) 2- RhCl 4 (H 2 O)(NCS) 2- RhCl 4 (H 2 O)(NCSe) 2- RhCl 4 (H 2 O) (NCTe) 2- RhCl 4 (SCN) 2 3- RhCl 4 (SeCN) 2 3- RhCl 4 (TeCN) 2 3- RhCl 4 (NCS) 2 3- RhCl 4 (NCS) 2 3- RhCl
  • the complexes of the present invention satisfying formula (1) and which are used as deep electron trapping agents (DETA), can be prepared in different ways as described for instance for the CNS- or SCN-ligand complexes in 'Gmelins Handbuch der Anorganische Chemie' (Verlag Chemie,Germany), Vol.64(1955), p.70,71 and in US 3,507,928 (Rh-complexes).
  • Rh-complexes used as dopants for tabular silver brom(iod)ide crystals in photosensitive layers in a photosensitive image-forming element of the present invention, said Rh-complexes being represented by formula (1), the following procedure was executed as described hereinafter for the RhCl 6 3(-) -complex with a SCN - or a NCS - -ligand.
  • the said mixture of complexes is the result of an exchange between the Cl- and the SCN-ligand which forms a more strongly bond with the metal atom(s) of the mixture of complexes and which is therefore also more stable.
  • the amount of dopant which can effectively be incorporated in the emulsion grains in order to get the desired effect as described in the present invention should be situated in the range between 10 -10 and 10 -2 mole per mole of silver halide, preferably in the range between 10 -9 and 10 -4 mole per mole of silver halide and even more preferrably between 10 -8 and 5.10 -6 mole per mole of silver halide.
  • the location of the dopant may play a dominant role in fine-tuning the sensitometric characteristics of the material comprising emulsion grains containing one or more dopants. This is utilized advantageously in several applications where the dopant is non-uniformly distributed in the silver halide crystal.
  • the complex(es) or dopant(s) according to formula (1) is(are) preferably concentrated in the inner portion of the silver halide crystals, wherein said inner portion is defined as the portion which contains less than 50 mole % of the silver present in each crystal, more preferably less than 25 mole % of the silver present in each crystal.
  • Dopants according to the formula (1) are essentially those which act as a deep and permanent electron trap in the silver halide crystal and which satisfy (as already taught hereinbefore) two conditions:
  • the doping procedure itself can normally be performed at any stage during the grain growth phase of the emulsion preparation where the reactants are added to the reaction vessel in the form of solutions of silver and halide salts or in the form of preformed silver halide nuclei or fine grains which easily dissolve in the precipitation medium. It is important to know that the dopants can also be added in an indirect way by addition of a dispersion containing very fine soluble silver halide grains or nuclei already comprising the dopant. Individual reactants for the formation of silver halide can be added 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.
  • 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.
  • the solution containing the dopants is preferentially introduced making use of a third jet, in a zone in the reactor wherein the compounds are rapidly incorporated in the growing microcrystals.
  • the advantage of the use of such a third jet is that a solvent can be used for the given dopant which is most suitable for the stability of that compound. Further the temperature of the dopant solution can be adjusted in order to maximize the stability too. 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 can be added at a constant rate or at any rate profile as has e.g. been described in JP-A 03163438, wherein the dopant is occluded in two different concentrations in the silver halide grains of a direct positive emulsion, thereby having the highest dopant concentration closest to the grain centre.
  • the said JP-Application describes a method to get a silver halide emulsion with improved gradation without paying attention to the sensitivity level, which, contrary thereto, is also one of the targets of the present invention.
  • the photographic emulsions prepared in this way for use in the image-forming element of the present invention contain tabular silver brom(iod)ide.
  • Other silver salts which can be incorporated in a limited amount in the silver halide lattice are silver phosphate, silver thiocyanate, silver citrate and some other silver salts.
  • Iodide ions can be coprecipitated with bromide ions in order to form a iodobromide with an iodide amount which depends on the saturation limit of iodide in the lattice with the given halide composition: this means up to a maximum amount of about 40 mole percent in silver iodobromide based on silver.
  • the activity of the complex(es) or dopant(s) satisfying formula (1) is almost not influenced by the brom(iod)ide composition of the silver brom(iod)ide 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 differing photographic applications.
  • Such a structure with a difference in halide composition between the center 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 have a morphology which is 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) where especially in the case of the ultrathin 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 ⁇ -habitus, the structure of which is (respectively) stable or has to be stabilized (for instance by a "crystal habit modifying agent").
  • dopants which are deep electron traps as described by formula (1) can be added to the silver halide emulsion. These are optionally introduced, essentially because of their specific influence on the photographic characteristics.
  • Different classes of dopants are known: dopants resulting in a non-permanent trapping behaviour or a shallow electron trap or SET (such as IrCl 6 3- or Ru(CN) 6 2- , described in Research Disclosure No 36736 (1994), p. 657, or a recombination or hole trapping center. These dopants are essentially all those not obeying the conditions for creating a deep electron trap. Many examples of this category have already been described in the patent literature but cover different silver halide systems like e.g.
  • the tabular silver brom(iod)ide emulsions coated in at least one photosensitive layer of the photosensitive image-forming element according to the present invention which are prepared in one of the ways described hereinbefore contain crystals which have a spherical equivalent diameter (SED) which is situated between 0.01 ⁇ m and 1.5 ⁇ m, more preferably between 0.01 ⁇ m and 1.0 ⁇ m and even more preferably between 0.01 ⁇ m and 0.9 ⁇ m.
  • SED spherical equivalent diameter
  • the spherical equivalent diameter (SED) of the crystal represents the diameter of the sphere which has the same volume as the average volume of the silver halide crystals of the said emulsion.
  • the emulsions can be surface-sensitive emulsions which form 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. Further emulsions.
  • 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 surface-sensitized by chemical sensitization which can be done in many different ways, in presence of a chalcogen as sulfur, selenium or tellurium, in 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 has been described in EP-A 0 752 614.
  • Reduction sensitization is another method of sensitizing a photosensitive silver halide emulsion which if desired can be combined with the chalcogen/noble metal-sensitization.
  • Reduction sensitization should especially be mentioned with respect to the present invention as a way of introducing hole traps in the silver brom(iod)ide crystals for use in the image-forming elements according to the present invention in order to optimize the efficiency of latent image formation.
  • Reduction sensitization can be performed by decreasing pAg of the emulsion or by adding thereto reducing agents as e.g. tin compounds (see GB-Patent 789,823), amines, hydrazinederivatives, 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.
  • hole traps in silver halide can also be realized by incorporating special dopants like for instance Cu (+) and Ni (2+) .
  • the silver brom(iod)ide 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 and so on. Sometimes more than one spectral sensitizer may be used in the case that a larger part of the spectrum should be covered.
  • desensitizers should be used, as for instance in pre-fogged direct-positive or in daylight handling materials, various chemical compounds are proposed for practical use. Principally all these compounds which are used as desensitizers in silver halide materials and which are for instance summarized in EP-A 0 477 436 can be used in combination with the elements of the present invention.
  • the photographic elements comprising the 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 the processing, finishing or warehousing the photographic material.
  • the silver brom(iod)ide material can also contain different types of couplers, which can be incorpated as described in the same RD, section X.
  • the photographic elements can be coated on a variety of supports as described in RD 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 RD No. 38957(1996) section XVI).
  • the latent-image formed can be processed in many different ways in order to form a visible image (same RD, section XIX).
  • 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 the coupler to form a dye (RD. No. 38957(1996), section XX).
  • Example 1 Application to a tabular silver bromide emulsion.
  • the pH of the solution C1 was adjusted at a value of 1.8 with a sulphuric acid solution and pBr adjusted at 2.39 with Kbr.
  • the solutions C2, C3 and C4 were kept at room temperature while solutions C1 and C5 were heated to 45° Celsius.
  • the thus prepared silver bromoiodide emulsion has hexagonal tabular crystals in a numerical amount of about 95 % with a thickness of 210 nm and an average volumetric diameter d of 0.7 ⁇ m.
  • Emulsion (2) was prepared in the same way, except that 1 ml of solution Dot 5, containing a Rhodium complex, was added to solution C1 at a constant rate using a third jet.
  • the position of the dopant in the emulsion grains was expressed as amitual amount of the crystal volume at the moment where the addition of the third jet was started and as amitual amount of the crystal volume at the moment where the addition of the third jet was stopped. In this particular case it was situated between 20 and 25 %.
  • Emulsion (3) was prepared in the same way, except that 1 ml of the solution Dot 6, containing a Rhodium complex, was added to solution C1 at a constant rate using a third jet.
  • the position of the dopant in the emulsion grains was expressed as thetempo amount of the crystal volume at the moment where the addition of the third jet was started and thetempoual amount of the crystal volume at the moment where the addition of the third jet was stopped. In this inventive emulsion it was situated between 20 and 25 % too.
  • Emulsion (4) was prepared in the same way as in the inventive emulsion, except that 1 ml of the solution C7, containing only the KSCN salt, was added to solution C1 at a constant rate using a third jet.
  • the position of the salt in the emulsion grains was expressed as thetempoual amount of the crystal volume at the moment where the addition of the third jet was started and thetempoual amount of the crystal volume at the moment where the addition of the third jet was stopped. Also in this emulsion the KSCN salt was also situated between 20 and 25 %.
  • the tabular bromoiodide emulsions were ripened at a pAg and pH equal to 7.38 and 5.5 respectively with 8.9*10 -3 mole per mole of silver of anhydro 5,5'-dichloro-3,3'-bis(n-sulphobutyl)-9-ethyl-oxacarbocyanine hydroxide as a spectral sensitizer, 1.4*10 -3 mole of a potassium thiocyanate solution per mole of silver, 3.24*10 -7 mole of a toluene sodium thiosulphonate solution per mole of silver, 1.5*10 -5 mole of a sodium thiosulphate solution per mole of silver, 1.35*10 -6 mole of a gold trichloride solution per mole of silver and 1.3 *10 -4 mole of a mercaptotetrazole compound per mole of silver, at 55 °C for 200 minutes.
  • the emulsions were coated on a substrated PET base at 1.7 g gelatine/m2 and 5 g AgNO3/m2.
  • the emulsions were image-wise exposed through a step-wedge originally using a 10 -3 sec Xenon flash.
  • the exposed photographic materials were developed in a surface developer at room temperature for 5 minutes and fixed for 5 minutes in a commercial fixer G333C (Trademark of AGFA) which was 1/3 diluted with demineralized water.
  • the fog levels for the materials were situated at about 0.07 for the ripened emulsions.
  • the speed S measured was the logaritm of the energy of the illumination needed in order to obtain an optical density equal to 1 above fog level.
  • the contrast G is measured around this point. All the values which are summarized in Table 2 are relative to the values of comparative emulsion (1) which is taken 100 % each time. For the sensitivity S a decrease of 50 % means a sensitivity loss with a factor of 2 while a decrease in gradation G is always proportional.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (8)

  1. Ein strahlungsempfindliches Bilderzeugungselement, das auf einem Träger zumindest eine strahlungsempfindliche Schicht mit tafelförmigen Silberbromid(iodid)körnern enthält, die durch einen Übergangsmetallkomplex innendotiert sind, wodurch eine tiefe und permanente Elektronenfalle gebildet wird, wobei der Übergangsmetallkomplex der folgenden allgemeinen Formel (1) entspricht : RhCl6-n(H2O)n1(L)n2 m- in der bedeuten :
    L ein Ligand der Formel YCN(-) oder NCY(-), wobei Y S, Se oder Te bedeutet,
    n, n1 und n2 ganze Zahlen, die den folgenden Gleichungen entsprechen : 1 ≤ n < 6 und n = n1 + n2, wobei n2 ≥ 1,
    m die ganze Zahl 1, 2 oder 3,
    und wobei der Metallkomplex der Formel (1) in einem inneren Bereich der Silberhalogenidkristalle, der nicht mehr als 50 mol% des in jedem Kristall enthaltenen Silbers enthält, eingebettet ist.
  2. Ein strahlungsempfindliches Bilderzeugungselement nach Anspruch 1, dadurch gekennzeichnet, daß das Verhältnis des Dotiermittels der Formel (1) zwischen 10-10 und 10-2 Mol pro Mol Silber liegt.
  3. Ein strahlungsempfindliches Bilderzeugungselement nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Metallkomplex der Formel (1) in einem inneren Bereich der Silberhalogenidkristalle, der weniger als 25 mol-% des in jedem Kristall enthaltenen Silbers enthält, eingebettet ist.
  4. Ein strahlungsempfindliches Bilderzeugungselement nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Silberbromid(iodid)kristalle ein oder mehrere zusätzliche Dotiermittel, die sich durch ihre nicht-permanente elektroneneinfangende Aktivität zum Dotiermittel der Formel (1) unterscheiden, enthalten.
  5. Ein strahlungsempfindliches Bilderzeugungselement nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Silberbromid(iodid)kristalle durch Reduktion sensibilisiert sind.
  6. Ein strahlungsempfindliches Bilderzeugungselement nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Silberbromid(iodid)kristalle einen Durchmesser eines sphärischen Äquivalenten (SED) zwischen 0,01 µm und 1,50 µm aufweisen.
  7. Ein strahlungsempfindliches Bilderzeugungselement nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der Komplex der Formel (1) nach Zugabe von 20% der Gesamtmenge Silber in einem inneren Bereich der tafelförmigen Silberbromid(iodid)kristalle vorliegt.
  8. Ein strahlungsempfindliches Bilderzeugungselement nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß der Komplex der Formel (1) vor Zugabe von 25% der Gesamtmenge Silber in einem inneren Bereich der tafelförmigen Silberbromid(iodid)kristalle vorliegt.
EP99200087A 1998-01-30 1999-01-11 Photoempfindliches bilderzeugendes Material, das tafelförmige Silber(iodo)bromidkristalle enthält, die mit einem Metall-Ligandenkomplex dotiert sind, der tiefe Elektronenfallen erzeugt Expired - Lifetime EP0933671B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP99200087A EP0933671B1 (de) 1998-01-30 1999-01-11 Photoempfindliches bilderzeugendes Material, das tafelförmige Silber(iodo)bromidkristalle enthält, die mit einem Metall-Ligandenkomplex dotiert sind, der tiefe Elektronenfallen erzeugt

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP98200280 1998-01-30
EP98200280 1998-01-30
EP99200087A EP0933671B1 (de) 1998-01-30 1999-01-11 Photoempfindliches bilderzeugendes Material, das tafelförmige Silber(iodo)bromidkristalle enthält, die mit einem Metall-Ligandenkomplex dotiert sind, der tiefe Elektronenfallen erzeugt

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EP0933671A1 EP0933671A1 (de) 1999-08-04
EP0933671B1 true EP0933671B1 (de) 2001-11-21

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EP99200087A Expired - Lifetime EP0933671B1 (de) 1998-01-30 1999-01-11 Photoempfindliches bilderzeugendes Material, das tafelförmige Silber(iodo)bromidkristalle enthält, die mit einem Metall-Ligandenkomplex dotiert sind, der tiefe Elektronenfallen erzeugt

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Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4835093A (en) * 1988-04-08 1989-05-30 Eastman Kodak Company Internally doped silver halide emulsions
US5037732A (en) * 1989-08-28 1991-08-06 Eastman Kodak Company Photographic emulsions containing internally modified silver halide grains
JPH04125629A (ja) * 1990-09-18 1992-04-27 Konica Corp ハロゲン化銀カラー写真感光材料
JPH0659365A (ja) * 1992-08-05 1994-03-04 Konica Corp ハロゲン化銀写真乳剤
US5616446A (en) * 1994-09-29 1997-04-01 Konica Corporation Silver halide photographic light-sensitive material
US5462849A (en) * 1994-10-27 1995-10-31 Eastman Kodak Company Silver halide emulsions with doped epitaxy
US5576172A (en) * 1995-05-15 1996-11-19 Eastman Kodak Company Elevated iodide surface laminae tabular grain emulsions

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