EP0895121B1 - Elément photosensible contenant une émulsion à l'halogénure d'argent sensibilisée chimiquement avec un composé chalcogénure - Google Patents

Elément photosensible contenant une émulsion à l'halogénure d'argent sensibilisée chimiquement avec un composé chalcogénure Download PDF

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Publication number
EP0895121B1
EP0895121B1 EP98202305A EP98202305A EP0895121B1 EP 0895121 B1 EP0895121 B1 EP 0895121B1 EP 98202305 A EP98202305 A EP 98202305A EP 98202305 A EP98202305 A EP 98202305A EP 0895121 B1 EP0895121 B1 EP 0895121B1
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EP
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Prior art keywords
silver halide
photosensitive element
chalcogenic
halide emulsion
group
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EP98202305A
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German (de)
English (en)
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EP0895121A1 (fr
Inventor
Johan Loccufier
René De Keyzer
Antonius Rutges
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
Agfa Gevaert AG
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Priority to EP98202305A priority Critical patent/EP0895121B1/fr
Publication of EP0895121A1 publication Critical patent/EP0895121A1/fr
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—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
    • G03C2001/097—Selenium
    • 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
    • G03C2001/098—Tellurium
    • 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
    • G03C2200/33—Heterocyclic

Definitions

  • the invention also provides a method for chemically sensitizing a silver halide emulsion by means of a chalcogenic compound according to the formula (1) at least partly in the presence of a silver halide solvent and a spectral sensitizer at a pH-value situated between 3 and 10, a pAg-value situated between 6 and 11 and a temperature in the range of from 40 °C up to 95 °C.
  • the chemical sensitization has also to be carried out in the presence of a spectral sensitizer.
  • This can be a dye out of different classes including polymethine dyes comprising cyanines, merocyanines, tri-, tetra- and polynuclear cyanines and merocyanines, oxanols, hemioxanols, styryls, merostyryls and so on.
  • Many representitive examples of these dye-classes can be found in EP-A 0 618 492, EP-A 0 638 841, US-A 5,308,748, US-A 5,310,645 and 5 US-A 5,338,656.
  • Some types of spectral sensitizers are preferably used for this invention. It concerns the symmetrical or the unsymmetrical cyanine dyes containing a benzoxazole, benzthiazole or benzimidazole nucleus.
  • additional chemical metal salts can be added for occlusion in the crystal lattice.
  • Such compound is replacing an appropiate of silver and halide ions in the silver halide lattice.
  • dopants can be distinguished from the metal complexes which are added just before coatingas an additive by EPR- or ENDOR-technique. These dopants can be used to modify the crystal structure or the crystal properties and can therefore be employed to influence many photographical properties like sensitivity, reciprocity failure, gradation, pressure sensitivity, fog, stability, etc.
  • Gelatin may, however, be replaced in part or integrally by synthetic, semi-synthetic, or natural polymers.
  • Synthetic substitutes for gelatin are e.g. polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyvinyl imidazole, polyvinyl pyrazole, polyacrylamide, polyacrylic acid, and derivatives thereof, in particular copolymers thereof.
  • Natural substitutes for gelatin are e.g. other proteins such as zein, albumin and casein, cellulose, saccharides, starch, and alginates.
  • the semi-synthetic substitutes for gelatin are modified natural products e.g.
  • This example demonstrates the possibilities of a silver halide. emulsion comprising tabular AgBr(I)-crystals which have been chemically sensitized with a chalcogenic chemical sensitizer of the present invention compared with a chemical sensitizer which lack the neighbouring group participating action. It also illustrates the influence of other chemical sensitizers like sulphur and gold salts.
  • the emulsion was flocculated after addition of a small amount of polystyrene sulphonic acid and the acidification to a pH value of 3.4. After sedimentation the mother liquid was removed, distilled water added and remaining salts were washed out after repeating this procedure.
  • the AgBr(I) crystals of the emulsion prepaired in this way were containing 1 mol % of iodide and had a spherical equivalent diameter (SED) of 0.93 ⁇ m while the thickness was 0.22 ⁇ m.

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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. Elément photosensible comportant sur un support au moins une couche d'émulsion aux halogénures d'argent ainsi qu'une couche colloïdale hydrophile non sensible à la lumière, caractérisé en ce que la couche d'émulsion aux halogénures d'argent comprend un composé chalcoaène répondant à la formule (1) :
    Figure 00380001
    dans laquelle:
    Nu est un groupe nucléophile,
    L est un groupe de liaison bivalent,
    R1 représente un groupe alkyle, aryle, aralkyle ou hétéroaryle substitués ou non, ou un ou plusieurs substituants R1 représentent ensemble les atomes nécessaires pour constituer un noyau saturé ou insaturé substitué ou non;
    n est égal à 0, 1, 2, 3 ou 4.
  2. Elément photosensible selon la revendication 1, caractérisé en ce que ledit groupe nucléophile Nu dans la formule générale (1) est un groupe nucléophile formant une liaison hétérolytique avec son doublet électronique libre.
  3. Elément photosensible selon la revendication 1, caractérisé en ce que ledit groupe de liaison bivalent L dans la formule générale (1) représente un groupe pouvant disposer un atome cédant des électrons en l'une quelconque des positions 5 à 8 par rapport à l'atome de carbone de la double liaison carbone-chalcogêne.
  4. Elément photosensible selon l'une quelconque des revendications 1 à 3, caractérisé en ce que ladite émulsion aux halogénures d'argent est sensibilisée par voie chimique au moyen d'un composé chalcogène répondant à la formule (1) en une quantité de 10-8 à 10-4 mole par rapport à 1 mole d'halogénure d'argent.
  5. Procédé de sensibilisation chimique pour émulsions aux halogénures d'argent caractérisé par les étapes consistant à ajouter un sensibilisateur sulfuré et/ou aurique ainsi qu'un composé chalcogène tel que défini dans l'une quelconque des revendications 1 à 4, caractérisé par l'étape consistant à ajouter un solvant des halogénures d'argent au composé chalcogène et à ajouter un sensibilisateur spectral, dans les conditions suivantes:
    un pAg compris entre 6 et 11,
    un pH compris entre 3 et 10,
    une température dans l'intervalle de 40 à 95 °C.
  6. Procédé selon la revendication 5, caractérisé en ce que ledit solvant des halogénures d'argent est un sel de thiocyanate.
  7. Procédé selon la revendication 5 ou 6, caractérisé en ce que ledit solvant des halogénures d'argent est contenu en une quantité de 10-6 à 10-1 mole par mole d'halogénure d'argent.
  8. Procédé selon l'une quelconque des revendications 5 à 7, caractérisé en ce que le sensibilisateur spectral est un colorant cyanine symétrique ou asymétrique contenant un noyau benzoxazole, benzothiazole ou benzimidazole.
EP98202305A 1997-08-01 1998-07-08 Elément photosensible contenant une émulsion à l'halogénure d'argent sensibilisée chimiquement avec un composé chalcogénure Expired - Lifetime EP0895121B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP98202305A EP0895121B1 (fr) 1997-08-01 1998-07-08 Elément photosensible contenant une émulsion à l'halogénure d'argent sensibilisée chimiquement avec un composé chalcogénure

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP97202395 1997-08-01
EP97202395 1997-08-01
EP98202305A EP0895121B1 (fr) 1997-08-01 1998-07-08 Elément photosensible contenant une émulsion à l'halogénure d'argent sensibilisée chimiquement avec un composé chalcogénure

Publications (2)

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EP0895121A1 EP0895121A1 (fr) 1999-02-03
EP0895121B1 true EP0895121B1 (fr) 2004-01-21

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Country Status (1)

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Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3049335B2 (ja) * 1990-05-21 2000-06-05 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
DE19635098A1 (de) * 1996-08-30 1998-03-05 Agfa Gevaert Ag Lichtempfindliche Silberhalogenidemulsion und fotografisches Material
DE19648008A1 (de) * 1996-11-20 1998-05-28 Agfa Gevaert Ag Farbfotografisches Silberhalogenidmaterial

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