EP0709724B1 - Emulsions d'halogénure d'argent à l'épitaxie dotée - Google Patents

Emulsions d'halogénure d'argent à l'épitaxie dotée Download PDF

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Publication number
EP0709724B1
EP0709724B1 EP95202609A EP95202609A EP0709724B1 EP 0709724 B1 EP0709724 B1 EP 0709724B1 EP 95202609 A EP95202609 A EP 95202609A EP 95202609 A EP95202609 A EP 95202609A EP 0709724 B1 EP0709724 B1 EP 0709724B1
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Prior art keywords
carbon
silver halide
emulsion
ircl
photographic
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German (de)
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EP0709724A3 (fr
EP0709724A2 (fr
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Eric Leslie c/o EASTMAN KODAK COMPANY Bell
Traci Y. c/o Eastman Kodak Company Kuromoto
Robert Don C/O Eastman Kodak Company Wilson
Woodrow Gordon C/O Eastman Kodak Company Mcdugle
Raymond Stanley c/o Eastman Kodak Company Eachus
Sherrill Austin Eastman Kodak Company Puckett
Myra Toffolon C/O Eastman Kodak Company Olm
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Eastman Kodak Co
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Eastman Kodak Co
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Priority claimed from US08/316,003 external-priority patent/US5480771A/en
Priority claimed from US08/330,280 external-priority patent/US5462849A/en
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Publication of EP0709724A3 publication Critical patent/EP0709724A3/xx
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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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03517—Chloride content
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03552—Epitaxial junction grains; Protrusions or protruded grains
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C2001/0845—Iron compounds
    • 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
    • G03C2200/00—Details
    • G03C2200/33—Heterocyclic

Definitions

  • the invention relates to photography. More specifically, the invention relates to photographic silver halide emulsions and to processes for their preparation.
  • dopant is employed herein to designate any element or ion other than silver or halide incorporated in a face centered silver halide crystal lattice.
  • metal in referring to elements includes all elements other than those of the following atomic numbers: 2, 5-10, 14-18, 33-36, 52-54, 85 and 86.
  • Group VIII metal refers to an element from period 4, 5 or 6 and any one of groups 8 to 10 inclusive.
  • Group VIII noble metal refers to an element from period 5 or 6 and any one of groups 8 to 10 inclusive.
  • palladium triad metal refers to an element from period 5 and any one of groups 8 to 10 inclusive.
  • platinum triad metal refers to an element from period 6 and any one of groups 8 to 10 inclusive.
  • halide is employed in its conventional usage in silver halide photography to indicate chloride, bromide or iodide.
  • the halides are named in their order of ascending concentrations.
  • halide refers to groups known to approximate the properties of halides--that is, monovalent anionic groups sufficiently electronegative to exhibit a positive Hammett sigma value at least equaling that of a halide--e.g., CN - , OCN - , SCN - , SeCN - , TeCN - , N 3 - , C(CN) 3 - and CH - .
  • C-C, H-C or C-N-H organic refers to groups that contain at least one carbon-to-carbon bond, at least one carbon-to-hydrogen bond or at least one carbon-to-nitrogen-to-hydrogen bond sequence.
  • epitaxial deposition refers to crystal growth onto a substrate of a detectibly different crystal structure wherein the substrate controls the crystalline orientation of the crystal growth. Since each silver halide forms a crystal structure that is either different in kind or in unit cell dimensions from the remaining silver halides, detectable differences in halide composition of the substrate and oriented crystal growth satisfy the "different crystal structure" requirement to qualify as epitaxial deposition.
  • epitaxial deposition is employed to indicate the crystal growth epitaxially deposited.
  • Research Disclosure 308119, sub-section D, proceeds further to point out a fundamental change that occurred in the art between the 1978 and 1989 publication dates of these silver halide photography surveys.
  • Research Disclosure 308118, I-D states further:
  • the metals introduced during grain nucleation and/or growth can enter the grains as dopants to modify photographic properties, depending on their level and location within the grains.
  • a coordination complex such as a hexacoordination complex or a tetracoordination complex
  • the ligands can also be occluded within the grains.
  • Coordination ligands such as halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl ligands are contemplated and can be relied upon to vary emulsion properties further.
  • Patent 4,945,035 were the first to demonstrate that ligands capable of forming coordination complexes with dopant metal ions are capable of entering the grain crystal structure and producing modifications of photographic performance that are not realized by incorporation of the transition metal ion alone.
  • emphasis is placed on the fact that the coordination complex steric configuration allows the metal ion in the complex to replace a silver ion in the crystal lattice with the ligands replacing adjacent halide ions.
  • Ohya et al European patent application 0 513 748 A1 discloses photographic silver halide emulsions precipitated in the presence of a metal complex having an oxidation potential of from -1.34 V to +1.66 V and a reduction potential not higher than -1.34 V and chemically sensitized in the presence of a gold-containing compound.
  • a table of illustrative complexes satisfying the oxidation and reduction potentials are listed. This listing includes, in addition to the complexes consisting of halide and pseudohalide ligands, K 2 [Fe(EDTA)], where EDTA is an acronym for ethylenediaminetetraacetic acid.
  • iridium containing compound in combination with a required metal complex an iridium containing compound.
  • useful iridium compounds include, in addition to simple halide salts and coordination complexes containing halide ligands, hexaamine iridium (III) salt (i.e., a [(NH 3 ) 6 Ir] +3 salt), hexaamine iridium (IV) salt (i.e., a [(NH 3 ) 6 Ir] +4 salt), a trioxalate iridium (III) salt and a trioxalate iridium (IV) salt. While offering a somewhat broader selection of ligands for use with the metals disclosed, Ohya et al does not attach any importance to ligand selection and does not address whether ligands are or are not incorporated into the grain structures during precipitation.
  • Ohkubo et al U.S. Patent 3,672,901 discloses silver halide precipitation in the presence of iron compounds.
  • Hayashi U.S. Patent 5,112,732 discloses useful results to be obtained in internal latent image forming direct positive emulsions precipitated in the presence of potassium ferrocyanide, potassium ferricyanide or an EDTA iron complex salt. Doping with iron oxalate is demonstrated to be ineffective.
  • Photographic emulsions containing composite grains comprised of host grain portions and surface portions epitaxially deposited on the host grain portions are well known in the art.
  • An illustrative listing of emulsions containing composite grains appears in Research Disclosure, Vol. 365, Sept. 1994, Item 36544, I. Emulsion grains and their preparation, A. Grain halide composition, paragraph (5).
  • Prior filed, non-prepublished EP-A-0634689 discloses internally doped silver halide emulsions containing a metal hexacoordination complex having at least one organic ligand containing at least one carbon-to-carbon bond, at least one carbon-to-hydrogen bond or at least one carbon-to-nitrogen-to-hydrogen bond sequence and at least half of the metal coordination sites occupied by halide or pseudohalide ligands.
  • the G-Series examples thereof disclose composite silver halide grains including cubic silver chloride host grain portions, and epitaxially deposited silver bromide surface portions which include K 2 [IrCl 5 (pyrazine)] or K 4 [Ir 2 Cl 10 (pyrazine)] on the cubic silver chloride host grain portions.
  • the present invention has for the first time introduced during epitaxial deposition dopant metal hexacoordination complexes containing one or more organic ligands, other than for the epitaxially deposited silver bromide which includes K 2 [IrCl 5 (pyrazine)] or K 4 [Ir 2 Cl 10 (pyrazine)] on cubic silver chloride host grain portions disclosed in EP-A-0634689, and obtained modifications in photographic performance that can be attributed specifically to the presence of the organic ligand or ligands.
  • the result is to provide the art with additional and useful means for tailoring photographic performance to meet specific application requirements.
  • this invention is directed to a photographic silver halide emulsion comprised of radiation sensitive composite silver halide grains including host grain portions accounting for at least 50 percent of total silver and surface portions epitaxially deposited on the host grain portions characterized in that the epitaxially deposited surface portions on the host grain portions exhibit a face centered cubic crystal lattice structure containing a hexacoordination complex of a metal from periods 4, 5 and 6 of groups 3 to 14 inclusive of the periodic table of elements in which one or more organic ligands each containing at least one carbon-to-carbon bond, at least one carbon-to-hydrogen bond or at least one carbon-to-nitrogen-to-hydrogen bond sequence occupy up to half the metal coordination sites in the coordination complex and at least half of the metal coordination sites in the coordination complex are provided by halogen or pseudohalogen ligands, with the proviso that when the host grain portions comprise cubic silver chloride grains, the hexacoordination complex of a metal contained in the epitaxially deposited surface portion is other
  • the present invention is directed toward the improvement of photographic silver halide emulsions comprised of radiation sensitive composite silver halide grains.
  • the composite grains are formed by epitaxially depositing surface portions onto a host grain population.
  • the host grain portions account for at least 50 percent (preferably at least 90 percent) of the total silver forming the composite grains.
  • the epitaxially deposited surface portions of the composite grains can form a shell, but are preferably nonuniformly distributed on the host grains.
  • the epitaxially deposited surface portions are located principally adjacent at least one of the edges and corners of the host grains.
  • the host grains can be chosen of any convenient conventional silver halide composition.
  • Maskasky U.S. Patent 4,094,684 discloses composite grains in which silver iodide host grains serve as substrates for the epitaxial deposition of silver chloride.
  • the host grain portions and required that the epitaxially deposited grain surface portions be selected from among those individual and mixed silver halides that form a face centered cubic crystal lattice structure, such as silver chloride, silver bromide, silver chlorobromide, silver bromochloride, silver iodobromide, silver iodochloride, silver iodochlorobromide and silver iodobromochloride.
  • the surface portions of the grains must exhibit a detectibly different crystal lattice structure than the host portions of the grains. This is most conveniently satisfied by employing different halide compositions in precipitating the host and surface portions of the grains.
  • the composite grains can take any of the varied forms disclosed by Maskasky U.S. Patents 4,435,501, 4,463,087 and 5,275,930, Ogawa et al U.S. Patent 4,735,894, Yamashita et al U.S. Patent 5,011,767, Haugh et al U.K.
  • Patent 2,038,792 Koitabashi EPO 0 019 917, Ohya et al EPO 0 323 215, Takada EPO 0 434 012, Chen EPO 0 498 302 and Berry and Skillman, "Surface Structures and Epitaxial Growths on AgBr Microcrystals", Journal of Applied Physics , Vol. 35, No. 7, July 1964, pp. 2165-2169.
  • the host grains are formed of silver bromide or iodobromide and the epitaxially deposited surface portions are formed by the precipitation of silver chloride.
  • the silver chloride can then be sited at the edges or corners of the host grains. Corner epitaxy produces higher speed composite grains than edge epitaxy and much higher speed composite grains than simply shelling the host grains.
  • the emulsions of this invention contain high (at least 90 mole percent) chloride grains and contain from 0 to 10 mole percent bromide and from 0 to 2 mole percent iodide.
  • the composite grains contain at least 0.5 mole percent bromide.
  • the host portion of the grains can consist essentially of silver chloride.
  • the epitaxially deposited surface portions of the grains contain a higher proportion of halides other than chloride than the host grains.
  • the surface portions of the grains contain a higher proportion of bromide than the host portions of the grains.
  • Composite grains containing higher portions of the halides other than chloride in the surface portions of the grains are illustrated by Tanaka EPO 0 080 905, Hasebe et al U.S.
  • Patent 4,865,962, Asami EPO 0 295 439 Suzumoto et al U.S. Patent 5,252,454, Ohshima et al U.S. Patent 5,252,456, and Maskasky U.S. Patent 5,275,930.
  • the present invention has achieved modifications of photographic performance that can be specifically attributed to the presence of metal coordination complexes containing one or more C-C, H-C or C-N-H organic ligands during the epitaxial deposition portion of composite grain precipitation.
  • the photographic effectiveness of these C-C, H-C or C-N-H organic ligand metal complexes is attributed to the recognition of criteria for selection never previously appreciated by those skilled in the art. Location of the complexes in epitaxially formed surface portions of composite grains has been observed to be a favored location.
  • the complexes are chosen from among hexacoordination complexes to favor steric compatibility with the face centered cubic crystal structures of silver halide grains.
  • Metals from periods 4, 5 and 6 and groups 3 to 14 inclusive of the periodic table of elements are known to form hexacoordination complexes and are therefore specifically contemplated.
  • Preferred metals for inclusion in the coordination complexes are Group VIII metals.
  • Non-noble Group VIII metals i.e., the period 4 Group VIII metals
  • Noble Group VIII metals (those from the palladium and platinum triads) are contemplated, with ruthenium and rhodium being specifically preferred period 5 metal dopants and iridium being a specifically preferred period 6 dopant.
  • the coordination complexes contain a balance of halide and/or pseudohalide ligands (that is, ligands of types well known to be useful in photography) and C-C, H-C or C-N-H organic ligands.
  • halide and/or pseudohalide ligands that is, ligands of types well known to be useful in photography
  • C-C, H-C or C-N-H organic ligands To achieve performance modification attributable to the presence of the C-C, H-C or C-N-H organic ligands at least half of the coordination sites provided by the metal ions must be satisfied by pseudohalide, halide or a combination of halide and pseudohalide ligands and at least one of the coordination sites of the metal ion must be occupied by an organic ligand.
  • the organic ligands occupy all or even the majority of coordination sites in the complex, photographic modifications attributable to the presence of the organic ligand have not been identified.
  • Metal hexacoordination complexes suitable for use in the practice of this invention have at least one C-C, H-C or C-N-H organic ligand and at least half of the metal coordination sites occupied by halide or pseudohalide ligands.
  • a variety of such complexes are known. The specific embodiments are listed below. Formula acronyms are defined at their first occurrence.
  • MC-1 [Sc(NCS) 3 (py) 3 ] py pyridine Tris (pyridine) tris (thiocyanato) scandium (III) Reported by G. Wilkinson, R.D. Gillard and J.A. McCleverty (eds.), Comprehensive Coordination Chemistry , Pergamon 1987.
  • MC-3 (Et 4 N) [TiCl 4 (MeCN) 2 ]
  • Et ethyl
  • Me methyl Tetraethylammonium bis(acetonitrile) tetrachloro titanium (III) Reported by B. T. Russ and G. W. A.
  • MC-10 (Bu 4 N) [Cr(NCO) 4 (1,2-propanediamine)] Tetrabutylammonium tetra (cyanato) - (1,2-propanediamine) chromate (III) Reported by E. Blasius and G. Klemm, Z. Anorg. Allgem. Chem., 443 , 265 (1978).
  • MC-11 (Bu 4 N) [Cr(NCO) 4 (1,2-cyclohexanediamine)] Tetrabutylammonium tetra (cyanato) - (1,2-cyclohexanediamine) chromate (III) Reported by E. Blasius and G. Klemm, Z. Anorg. Allgem. Chem., 443 , 265 (1978).
  • MC-12 [ReOCl 3 (en)] Trichloro(ethylenediamine)oxo rhenium (V) Reported by D. E. Grove and G. Wilkinson, J. Chem. Soc.(A), 1224 (1966).
  • MC-14h L (4-py)pyridinium Sodium pentacyano(4-pyridylpyridinium) ferrate (II)
  • MC-14i L 1-methyl-4-(4-py)pyridinium Sodium pentacyano[1-methyl-4-(4-pyridyl)pyridium] ferrate (II)
  • MC-14j L N-Me-pyrazinium Sodium pentacyano(N-methyl pyrazinium) ferrate
  • MC-14k L 4-Cl(py) Sodium pentacyano (4-chloro pyridino) ferrate (II) h-k Reported by H.
  • MC-14m L thiourea Sodium pentacyano (thiourea) ferrate (II)
  • MC-14n L pyrazole Sodium pentacyano (pyrazole) ferrate
  • II) MC-14o L imidazole Sodium pentacyano (imidazole) ferrate (II) m-o Reported by C. R. Johnson, W. W. Henderson and R. E. Shepherd, Inorg . Chem ., 23 , 2754 (1984).
  • MC-14z L P(OBu) 3 Sodium pentacyano(tributyl phosphite) ferrate (II)
  • MC-14aa L P(Bu) 3 Sodium pentacyano[(tri butyl)phosphine] ferrate (II) z-aa Reported by V. H. Inouye, E. Fluck, H. Binder and S. Yanagisawa, Z. Anorg. Allgem. Chem ., 483 , 75-85 (1981).
  • MC-14bb L p -nitroso-N,N-dimethylaniline Sodium pentacyano( p -nitroso-N,N-dimethylaniline) ferrate (II)
  • MC-14cc L nitrosobenzene Sodium pentacyano(nitroso benzene) ferrate (II)
  • MC-14dd L 4-CN-(py) Sodium pentacyano(4-cyano pyridine) ferrate (II) bb-dd Reported by Z. Bradic, M. Pribanic and S. Asperger, J. Chem. Soc ., 353 (1975).
  • MC-14oo L 4-Ph(py) Sodium pentacyano(4-phenyl pyridine) ferrate (II)
  • MC-14pp L pyridazine Sodium pentacyano (pyridazine) ferrate (II)
  • MC-14qq L pyrimidine Sodium pentacyano (pyrimidine) ferrate (II) oo-qq Reported by D. K. Lavallee and E. B. Fleischer, J. Am. Chem. Soc ., 94 (8), 2583 (1972).
  • MC-14rr L Me 2 SO Sodium pentacyano(dimethyl sulfoxide) ferrate (II) Reported by H. E. Toma, J. M. Malin and E. Biesbrecht, Inorg. Chem ., 12 , 2884 (1973).
  • MC-15a L (pyz) Potassium pentacyano (pyrazine) ruthenate (II) Reported by C. R. Johnson and R. E. Shepherd, Inorg. Chem ., 22 , 2439 (1983).
  • MC-15b L methylpyrazinium Potassium pentacyano (methylpyrazinium) ruthenate (II)
  • MC-15c L imidazole Potassium pentacyano (imidazole) ruthenate (II)
  • MC-15d L 4-pyridylpyridinium Potassium pentacyano (4-pyridylpyridinium) ruthenate (II)
  • MC-15e L 4,4'-bipyridine Potassium pentacyano (4,4'-bipyridine) ruthenate (II)
  • MC-15f L Me 2 SO Potassium pentacyano (dimethylsulfoxide) ruthenate (II)
  • MC-15g L (py) Potassium pentacyano (pyridine) ruthenate (II)
  • MC-15h L 4-[ - OC(O)](py) Potassium pentacyano (isonicotin
  • dimac N,N-dimethylacetamide Tris(N,N-dimethylacetamide) tris(isothiocyanato) indium (III) Reported by S. J. Patel, D. B. Sowerby and D. G. Tuck, J. Chem. Soc.(A) , 1188 (1967).
  • MC-40a L (pyz) Sodium decacyano ( ⁇ -pyrazine) ferrate (II) cobaltate (III)
  • MC-40b L 4,4'-bipyridine Sodium decacyano ( ⁇ -4, 4'-bipyridine) ferrate (II) cobaltate (III)
  • MC-40c L 4-cyanopyridine Sodium decacyano ( ⁇ -4-cyanopyridine) ferrate (II) cobaltate (III) Reported by K. J. Pfenning, L. Lee, H. D. Wohlers and J. D. Peterson, Inorg. Chem ., 21 , 2477 (1982).
  • any C-C, H-C or C-N-H organic ligand capable of forming a dopant metal hexacoordination complex with at least half of the metal coordination sites occupied by halide or pseudohalide ligands can be employed.
  • This excludes coordination complexes such as metal ethylenediaminetetraacetic acid (EDTA) complexes, since EDTA itself occupies six coordination sites and leaves no room for other ligands.
  • EDTA metal ethylenediaminetetraacetic acid
  • tris(oxalate) and bis(oxalate) metal coordination complexes occupy too many metal coordination sites to allow the required inclusion of other ligands.
  • a ligand must include at least one carbon-to-carbon bond, at least one carbon-to-hydrogen bond or at least one hydrogen-to-nitrogen-to-carbon bond linkage.
  • a simple example of an organic ligand classifiable as such solely by reason of containing a carbon-to-carbon bond is an oxalate (-O(O)C-C(O)O-) ligand.
  • a simple example of an organic ligand classifiable as such solely by reason of containing a carbon-to-hydrogen bond is a methyl (-CH 3 ) ligand.
  • a simple example of a C-C, H-C or C-N-H organic ligand classifiable as such solely by reason of containing a hydrogen-to-nitrogen-to-carbon bond linkage is a ureido [-HN-C(O)-NH-] ligand. All of these ligands fall within the customary contemplation of C-C, H-C or C-N-H organic ligands.
  • the organic ligand definition excludes compounds lacking C-C, H-C or C-N-H organic characteristics, such as ammonia, which contains only nitrogen-to-hydrogen bonds, and carbon dioxide, which contains only carbon-to-oxygen bonds.
  • halide and pseudohalide ligands with one or more C-C, H-C or C-N-H organic ligands to achieve useful photographic effects is consistent with the halide and pseudohalide ligands occupying halide ion lattice sites in the crystal structure.
  • the diversity of size and steric forms of the C-C, H-C or C-N-H organic ligands shown to be useful supports the position that photographic effectiveness extends beyond the precepts of prior substitutional models.
  • C-C, H-C or C-N-H organic ligand effectiveness can be independent of size or steric configuration and is limited only by their availability in metal dopant ion hexacoordination complexes. Nevertheless, since there is no known disadvantage for choosing C-C, H-C or C-N-H organic ligands based on host crystal lattice steric compatibility or approximations of steric compatibility nor have any advantages been identified for increasing ligand size for its own sake, the preferred C-C, H-C or C-N-H organic ligand selections discussed below are those deemed most likely to approximate host crystal lattice compatibility.
  • C-C, H-C or C-N-H organic ligands contain up to 24 (optimally up to 18) atoms of sufficient size to occupy silver or halide ion sites within the grain structure.
  • the C-C, H-C or C-N-H organic ligands preferably contain up to 24 (optimally up to 18) nonmetallic atoms. Since hydrogen atoms are sufficiently small to be accommodated interstitially within a silver halide face centered cubic crystal structure, the hydrogen content of the organic ligands poses no selection restriction.
  • organic ligands can contain metallic ions, these also are readily sterically accommodated within the crystal lattice structure of silver halide, since metal ions are, in general, much smaller than nonmetallic ions of similar atomic number. For example, silver ion (atomic number 47) is much smaller than bromide ion (atomic number 35).
  • the organic ligands consist of hydrogen and nonmetallic atoms selected from among carbon, nitrogen, oxygen, fluorine, sulfur, selenium, chlorine and bromine. The steric accommodation of iodide ions within silver bromide face centered cubic crystal lattice structures is well known in photography.
  • the heaviest non-metallic atoms can be included within the C-C, H-C or C-N-H organic ligands, although their occurrence is preferably limited (e.g., up to 2 and optimally only 1) in any single organic ligand.
  • Organic ligands can be selected from among a wide range of organic families, including substituted and unsubstituted aliphatic and aromatic hydrocarbons, secondary and tertiary amines (including diamines and hydrazines), phosphines, amides (including hydrazides), imides, nitriles, aldehydes, ketones, organic acids (including free acids, salts and esters), sulfoxides, and aliphatic and aromatic heterocycles including chalcogen (i.e., oxygen, sulfur, selenium and tellurium) and pnictide (particularly nitrogen) hetero ring atoms.
  • chalcogen i.e., oxygen, sulfur, selenium and tellurium
  • pnictide particularly nitrogen
  • Aliphatic hydrocarbon ligands containing up to 10 (most preferably up to 6) nonmetallic (e.g., carbon) atoms including linear, branched chain and cyclic alkyl, alkenyl, dialkenyl, alkynyl and dialkynyl ligands.
  • Aromatic hydrocarbon ligands containing 6 to 14 ring atoms (particularly phenyl and naphthyl).
  • Aliphatic azahydrocarbon ligands containing up to 14 nonmetallic (e.g., carbon and nitrogen) atoms.
  • the term "azahydrocarbon” is employed to indicate nitrogen atom substitution for at least one, but not all, of the carbon atoms.
  • the most stable and hence preferred azahydrocarbons contain no more than one nitrogen-to-nitrogen bond. Both cyclic and acyclic azahydrocarbons are particularly contemplated.
  • Aliphatic ether and thioether ligands also being commonly named as thiahydrocarbons in a manner analogous to azahydrocarbon ligands. Both cyclic and acyclic ethers and thioethers are contemplated.
  • Amines including diamines, most preferably those containing up to 12 (optimally up to 6) nonmetal (e.g., carbon) atoms per nitrogen atom organic substituent.
  • the amines must be secondary or tertiary amines when in the form of a ligand, since a primary amine (H 2 N-), designated by the term "amine” used alone, does not satisfy the organic ligand definition.
  • Amides most preferably including up to 12 (optimally up to 6) nonmetal (e.g., carbon) atoms.
  • Aldehydes, ketones, carboxylates, sulfonates and phosphonates including mono and dibasic acids, their salts and esters
  • phosphonates including mono and dibasic acids, their salts and esters
  • up to 12 optically up to 7
  • nonmetal e.g., carbon
  • Aliphatic sulfoxides containing up to 12 (preferably up to 6) nonmetal (e.g., carbon) atoms per aliphatic moiety containing up to 12 (preferably up to 6) nonmetal (e.g., carbon) atoms per aliphatic moiety.
  • the heterocyclic ligands contain at least one five or six membered heterocyclic ring, with the remainder of the ligand being formed by ring substituents, including one or more optional pendant or fused carbocyclic or heterocyclic rings.
  • the heterocycles contain only 5 or 6 non-metallic atoms.
  • heterocyclic ring structures include furans, thiophenes, azoles, diazoles, triazoles, tetrazoles, oxazoles, thiazoles, imidazoles, azines, diazines, triazines, as well as their dihydro (e.g., oxazoline, thiazoline and imidazoline), bis (e.g., bipyridine) and fused ring counterparts (e.g, benzo- and naptho- analogues).
  • a nitrogen hetero atom is present, each of trivalent, protonated and quaternized forms are contemplated.
  • heterocyclic ring moieties are those containing from 1 to 3 ring nitrogen atoms and azoles containing a chalcogen atom.
  • the requirement that at least one of the coordination complex ligands be a C-C, H-C or C-N-H organic ligand and that half of the ligands be halide or pseudohalide ligands permits one or two of the ligands in hexacoordination complexes to be chosen from among ligands other than C-C, H-C or C-N-H organic, halide and pseudohalide ligands.
  • nitrosyl (NO), thionitrosyl (NS), carbonyl (CO), oxo (O) and aquo (HOH) ligands are all known to form coordination complexes that have been successfully incorporated in silver halide grain structures.
  • These ligands are specifically contemplated for inclusion in the coordination complexes satisfying the requirements of the invention.
  • any known dopant metal ion coordination complex containing the required balance of halo and/or pseudohalo ligands with one or more C-C, H-C or C-N-H organic ligands can be employed in the practice of the invention.
  • the coordination complex is structurally stable and exhibits at least very slight water solubility under silver halide precipitation conditions. Since silver halide precipitation is commonly practiced at temperatures ranging down to just above ambient (e.g., typically down to about 30°C), thermal stability requirements are minimal.
  • only extremely low levels of water solubility are required.
  • the C-C, H-C or C-N-H organic ligand containing coordination complexes satisfying the requirements above can be present during silver halide emulsion precipitation in any conventional level known to be useful for the metal dopant ion.
  • Evans U.S. Patent 5,024,931 discloses effective doping with coordination complexes containing two or more Group VIII noble metals at concentrations that provide on average two metal dopant ions per grain. To achieve this, metal ion concentrations of 10 -10 M are provided in solution, before blending with the emulsion to be doped.
  • useful metal dopant ion concentrations, based on silver range from 10 -10 to 10 -3 gram atom per mole of silver. A specific concentration selection is dependent upon the specific photographic effect sought.
  • Dostes et al Defensive Publication T962,004 teaches metal ion dopant concentrations ranging from as low as 10 -10 gram atom/Ag mole for reducing low intensity reciprocity failure and kink desensitization in negative-working emulsions;
  • Spence et al U.S. Patents 3,687,676 and 3,690,891 teach metal ion dopant concentrations ranging as high as 10 -3 gram atom/Ag mole for avoidance of dye desensitization.
  • metal ion dopant concentrations can vary widely, depending upon the halide content of the grains, the metal ion dopant selected, its oxidation state, the specific ligands chosen, and the photographic effect sought, concentrations of less than 10 -6 gram atom/Ag mole are contemplated for improving the performance of surface latent image forming emulsions without significant surface desensitization. Concentrations of from 10 -9 to 10 -6 gram atom/Ag mole have been widely suggested.
  • the metal dopant ion coordination complexes can be introduced during emulsion precipitation employing procedures well known in the art.
  • the coordination complexes can be introduced during precipitation of the host grain portions as well as during precipitation of the epitaxially deposited host grain portions. It is preferred, however, that the metal dopant coordination complexes containing one or more C-C, H-C or C-N-H organic ligands be introduced primarily and, most preferably, entirely during precipitation of the epitaxially deposited surface portions of the grains.
  • the coordination complexes are introduced at least in part during precipitation through one of the halide ion or silver ion jets or through a separate jet.
  • Typical types of coordination complex introductions are disclosed by Janusonis et al, McDugle et al, Keevert et al, Marchetti et al and Evans et al, each cited above.
  • Another technique, demonstrated in the Examples below, for coordination complex incorporation is to precipitate Lippmann emulsion grains in the presence of the coordination complex followed by ripening the doped Lippmann emulsion grains onto host grains.
  • the emulsions prepared can, apart from the features described above, take any convenient conventional form.
  • Conventional emulsion compositions and methods for their preparation are summarized in Research Disclosure, Item 36544, Section I, cited above, as well as in Vol. 308, December 1989, Item 308119, Section I.
  • Other conventional photographic features are disclosed in the following sections of Item 308119:
  • Rhodium hexahalides represent one well known and widely employed class of dopants employed to increase photographic contrast. Generally the dopants have been employed in concentration ranges of 10 -6 to 10 -4 gram atom of rhodium per mole of silver. Rhodium dopants have been employed in all silver halides exhibiting a face centered cubic crystal lattice structure. However, a particularly useful application for rhodium dopants is in graphic arts emulsions. Graphic arts emulsions typically contain at least 50 mole percent chloride based on silver and preferably contain more than 90 mole percent chloride.
  • rhodium hexahalide dopants exhibit limited stability, requiring care in selecting the conditions under which they are employed. It has been discovered that the substitution of an C-C, H-C or C-N-H organic ligand for one or two of the halide ligands in rhodium hexahalide results in a more stable hexacoordination complex. Thus, it is specifically contemplated to substitute rhodium complexes of the type disclosed in this patent application for rhodium hexahalide complexes that have heretofore been employed in doping photographic emulsions.
  • spectral sensitizing dye when adsorbed to the surface of a silver halide grain, allows the grain to absorb longer wavelength electromagnetic radiation.
  • the longer wavelength photon is absorbed by the dye, which is in turn adsorbed to the grain surface. Energy is thereby transferred to the grain allowing it to form a latent image.
  • spectral sensitizing dyes provide the silver halide grain with sensitivity to longer wavelength regions, it is quite commonly stated that the dyes also act as desensitizers.
  • the native sensitivity of the silver halide grains with and without adsorbed spectral sensitizing dye it is possible to identify a reduction in native spectral region sensitivity attributable to the presence of adsorbed dye. From this observation as well as other, indirect observations it is commonly accepted that the spectral sensitizing dyes also are producing less than their full theoretical capability for sensitization outside the spectral region of native sensitivity.
  • the surprising effectiveness of the pseudohalide ligand containing complexes as compared to those that contain halide ligands is attributed to the greater electron withdrawing capacity of the pseudohalide ligands satisfying the stated Hammett sigma values. Further, the sensitizing effect has shown itself to be attainable with spectral sensitizing dyes generally accepted to have desensitizing properties either as the result of hole or electron trapping. On this basis it has been concluded that the dopants are useful in all latent image forming spectrally sensitized emulsions. The dopant can be located either uniformly or non-uniformly within the grains.
  • the dopants are preferably present within 500 ⁇ (50nm) of the grain surface, and are optimally separated from the grain surface by at least 50 ⁇ (5nm).
  • Preferred metal dopant ion concentrations are in the range of from 10 -5 to 10 -8 gram atom/Ag mole.
  • cobalt coordination complexes satisfying the requirements of the invention to reduce photographic speed with minimal ( ⁇ 5%) or no alteration in photographic contrast.
  • One of the problems that is commonly encountered in preparing photographic emulsions to satisfy specific aim characteristics is that, in adjusting an emulsion that is objectionable solely on the basis of being slightly too high in speed for the specific application, not only speed but the overall shape of the characteristic curve is modified.
  • Preferred cobalt complexes are those that contain, in addition to one or two organic ligands occupying up to two coordination sites, pseudohalide ligands that exhibit Hammett sigma values of that are more positive than 0.50.
  • the cobalt complex can be uniformly or non-uniformly distributed within the grains. Cobalt concentrations are preferably in the range of from 10 -6 to 10 -9 gram atom/Ag mole.
  • group 8 metal coordination complexes satisfying the requirements of the invention that contain as the C-C, H-C or C-N-H organic ligand an aliphatic sulfoxide are capable of increasing the speed of high (>50 mole %) chloride emulsions and are capable of increasing the contrast of high (>50 mole %) bromide emulsions.
  • Preferred aliphatic sulfoxides include those containing up to 12 (most preferably up to 6) nonmetal (e.g., carbon) atoms per aliphatic moiety.
  • the coordination complex can occupy any convenient location within the grain structure and can be uniformly or non-uniformly distributed.
  • Preferred concentrations of the group 8 metal are in the range of from 10 -6 to 10 -9 gram atom/Ag mole.
  • anionic [MX x Y y L z ] hexacoordination complexes where M is a group 8 or 9 metal (preferably iron, ruthenium or iridium), X is halide or pseudohalide (preferably Cl, Br or CN), x is 3 to 5, Y is H 2 O, y is 0 or 1, L is a C-C, H-C or C-N-H organic ligand, and z is 1 or 2, are surprisingly effective in reducing high intensity reciprocity failure (HIRF), low intensity reciprocity failure (LIRF) and thermal sensitivity variance and in improving latent image keeping (LIK).
  • HIRF high intensity reciprocity failure
  • LIRF low intensity reciprocity failure
  • LIK latent image keeping
  • HIRF is a measure of the variance of photographic properties for equal exposures, but with exposure times ranging from 10 -1 to 10 -4 second.
  • LIRF is a measure of the variance of photographic properties for equal exposures, but with exposure times ranging from 10 -1 to 100 seconds.
  • C-C, H-C or C-N-H organic ligands are azoles and azines, either unsubstituted or containing alkyl, alkoxy or halide substituents, where the alkyl moieties contain from 1 to 8 carbon atoms.
  • Particularly preferred azoles and azines include thiazoles, thiazolines and pyrazines. Further advantages of complexes containing these ligands are demonstrated in the Examples below.
  • anionic [MX x Y y L z ] hexacoordination complexes are anionic [MZ 5 L'M'Z' 5 ] hexacoordination complexes, where M and M' are group 8 or 9 metals (preferably iron, ruthenium or iridium or any combination), Z and Z' are independently selected from among X, Y and L with the proviso that in at least three occurrences of each of Z and Z' they are X and in zero or 1 occurrence of each of Z and Z' they are H 2 O, and L' is a C-C, H-C or C-N-H organic bridging ligand, such as a substituted or unsubstituted aliphatic or aromatic diazahydrocarbon.
  • M and M' are group 8 or 9 metals (preferably iron, ruthenium or iridium or any combination)
  • Z and Z' are independently selected from among X, Y and L with the proviso that in at least three occurrences of
  • Suitable bridging C-C, H-C or C-N-H organic ligands include H 2 N-R-NH 2 , where R is a substituted or unsubstituted aliphatic or aromatic hydrocarbon containing from 2 to 12 nonmetal atoms, as well as substituted or unsubstituted heterocycles containing two ring nitrogen atoms, such as pyrazine, 4,4'-bipyridine, 3,8-phenanthroline, 2,7-diazapyrene and 1,4-[bis(4-pyridyl)]butadiyne.
  • the preferred substituents of the heterocyclic ring atoms are alkyl, alkoxy or halide substituents, where the alkyl moieties contain from 1 to 8 carbon atoms.
  • the anionic [MX x Y y L z ] or [MZ 5 L'M'Z' 5 ] hexacoordination complex can be located either uniformly or non-uniformly within the grains; however, in the practice of this invention it is contemplated that the iridate complexes will be located either primarily or exclusively in the epitaxially deposited surface portions of the grains. Concentrations preferably range from 10 -9 to 10 -3 gram atom group 8 or 9 metal/Ag mole. When only group 8 metal is present, such as iron and/or ruthenium, preferred concentrations are in the range of from 10 -7 to 10 -3 gram atom/Ag mole. When a group 9 metal, such as iridium is present, preferred concentrations are in the range of from 10 -5 to 10 -9 gram atom/Ag mole.
  • Na 3 K 2 [IrCl 5 (pyrazine)Fe(CN) 5 ] was prepared by reacting equimolar amounts of K 2 [IrCl 5 (pyrazine)] and Na 3 [Fe(CN) 5 (NH 3 )] ⁇ 3H 2 O in a small amount of H 2 O at room temperature for 24 hours. The volume was decreased with flowing nitrogen, and ethyl alcohol added to precipitate the final product. The product was assigned a formula of Na 3 K 2 [IrCl 5 (pyrazine)Fe(CN) 5 ] by IR, UV/VIS and NMR spectroscopies and by CHN chemical analyses.
  • K 5 [IrCl 5 (pyz)Ru(CN) 5 ] 5- The mixed metal dimer K 5 [IrCl 5 (pyrazine)Ru(CN) 5 ] was prepared by reacting equimolar amounts of K 3 [Ru(CN) 5 (pyrazine)] and K 2 [IrCl 5 (H 2 O)] in a small amount of H 2 O in a hot water bath at 80 C for 2 hours. The volume was partially reduced with flowing nitrogen, and ethyl alcohol was added to precipitate the final product. The dimer was recrystallized by dissolving in a minimum amount of water and precipitated with ethyl alcohol. The product was assigned as K 5 [IrCl 5 (pyrazine)Ru(CN) 5 ] by IR, UV/VIS, and NMR spectroscopies and by CHN chemical analyses.
  • RhCl 3 (oxazole) 3 0.5 g of (NH 4 ) 2 [RhCl 5 (H 2 O)] was reacted with 0.5 ml oxazole in 15 ml H 2 O for 3 days. The solution was then added to a large amount of acetone whereupon a white precipitate appeared. The precipitate (NH 4 Cl) was filtered off. A yellow solid was obtained after evaporating the solvent from the filtrate. This yellow solid was washed with cold acetone in which it was slightly soluble. Slow evaporation of the acetone solution provided bright yellow crystals. The yellow product was assigned as RhCl 3 (oxazole) 3 by Infrared, UV/Vis, and NMR spectroscopies and CHN chemical analysis.
  • the oil was dissolved in a small amount of water and added to a large excess of ethanol. This afforded more brown precipitate.
  • the precipitates were washed with ethanol and analyzed using IR, UV/Vis and NMR spectroscopies and CHN chemical analysis.
  • K 3 IrBr 6 was the iridium source for the preparation of the monothiazole complex K 2 IrBr 5 (thiazole). 2 grams of K 3 IrBr 6 and 0.9 grams of thiazole were dissolved in a minimum amount of water and allowed to set at room temperature for 24 hours. During this time the solution assumed a light green color and the addition of an equal volume of acetone precipitated a lustrous green precipitate. This was filtered, washed with 50% water/50% acetone, acetone, and air dried. The material was characterized as K 2 IrBr 5 (thiazole).
  • reaction flask After 1 hour at 85° C, the reaction flask was placed in the refrigerator to quench the reaction and precipitate more of the bis-thiazole complex. The reaction flask was removed after about an hour and the volume decreased about 30% with a N 2 flow and then put back into the refrigerator overnight. The precipitated material was filtered off the next morning and washed with about 20 ml of ice cold water and then acetone and air dried. This orange colored material is quite soluble in water and assumed to be the cis isomer.
  • KIrBr 4 (thiazole) 2 was recrystallized by dissolving the material in a minimum amount of warm water (ca. 60° C) and filtering. The filtrate was then decreased in volume by 50% and pure KIrBr 4 (thiazole) 2 precipitated with an equal volume of acetone.
  • reaction times were limited to four hour units to keep the reaction from getting too far above room temperature.
  • One of the reaction runs was in D 2 O, and 1 H NMR was used to monitor both the disappearance of the starting material K 2 IrCl 5 (thiazole) and the appearance of the monoaquated product K 2 IrCl 4 (H 2 O)(thiazole). It was found that in ca. 16 hours, 100% of K 2 IrCl 5 (thiazole) had reacted under our experimental conditions.
  • the main photochemical reaction products are KIrCl 4 (H 2 O)(thiazole) and KCl, but a few other NMR peaks are observed that are weak and not identified.
  • Ag(CF 3 COO) silver trifluoroacetate, AgTFA
  • AgTFA silver trifluoroacetate
  • the solution was filtered after the addition of AgTFA to remove the AgCl, and the filtrate evaporated to near dryness. Either acetone or ethyl alcohol was then added to precipitate KIrCl 4 (H 2 O) (tz) which was filtered, washed with acetone, and allowed to air dry.
  • the material that results from using AgTFA to precipitate the free chloride is further purified by passing a concentrated solution of the material through a column of Sephadex. 2.5 grams of material were dissolved in 5 ml water and passed through ca. 25.4 cm (10 inch) of Sephadex G-25 in a 100 ml buret. The material separated into observable bands although there were no clear separations between the bands. The first band collected was small and the color was greenish. This band amounted to about 2 ml. The second band was reddish and amounted to only about 2 ml also.
  • the third band was the major band and with elution with water gave about 20 ml of a reddish brown solution which was evaporated to dryness with N 2 , redissolved in a minimum amount of water, and precipitated with ethyl alcohol to give pure KIrCl 4 (H 2 O) (thiazole).
  • the orange solid was filtered and washed with a 50% water/50% acetone solution and then acetone and air dried.
  • the orange precipitate is not very soluble in water but may be recrystallized by dissolving the orange material in a minimum amount of water at ca. 50° C and precipitating with acetone.
  • the recrystallized orange material was KIrCl 5 (4-methylthiazole) 2 .
  • KIrCl 4 (4-methylthiazole) 2 can also be readily synthesized in aqueous solution at 70° C. Due to its low solubility, the material was assumed to be the trans-isomer.
  • the material was recrystallized by dissolving the material in a minimum amount of water at ambient temperature, filtering the material through a fine frit filter, and then reprecipitating with acetone.
  • the pale orange colored material is the monosubstituted complex K 2 IrCl 5 (5-methylthiazole).
  • [IrCl 4 (5-methylthiazole) 2 ] 1- When the reaction between K 3 IrCl 6 and 5-methylthiazole was carried out at 60° C for a period of 8 hours, an orange crystalline material precipitated when the solution was cooled to room temperature. This has been identified as the bis-substituted complex KIrCl 4 (5-methylthiazole) 2 .
  • KIrCl 4 (2-bromothiazole) 2 was synthesized by the room temperature reaction of 5 grams of K 3 IrCl 5 and 5 grams of 2-bromothiazole in a 5% acetone/95 % water mixture. The mixture was allowed to set for 3 weeks during which time a pale orange material slowly formed and precipitated out of solution. Additional material was precipitated with an equal volume of acetone, filtered, washed with a 50% acetone/50% water mixture, then acetone, and air dried. The material was identified as KIrCl 5 (2-bromothiazole) 2 .
  • [IrCl 5 L] 2- An aqueous solution of K 3 IrCl 6 was stirred at ambient temperature with an excess of the organic liquid ligand L for several days. The K 2 IrCl 5 L complex was precipitated by adding the aqueous solution to a water miscible organic solvent, such as acetone or ethyl alcohol. The materials were filtered, washed with a 50:50 volume ratio of water and acetone, then acetone, and air dried.
  • a water miscible organic solvent such as acetone or ethyl alcohol
  • Substrate Emulsion A was prepared as follows: A reaction vessel containing 5.7 l of a 3.9% by weight gelatin solution and 1.2 g 1,8-dihydroxy-3,6-dithiaoctane was adjusted to 46°C, pH of 5.8 and a pAg of 7.51 by addition of a NaCl solution. A 2 M solution of AgNO 3 and a 2 M solution of NaCl were simultaneously run into the reaction vessel with rapid stirring, each at constant flow rates of 249 ml/min while controlling the pAg at 7.51. The emulsion was then washed to remove excess salts. The cubic emulsion grains had an edge length of about 0.38 ⁇ m.
  • Substrate Emulsion B was prepared as follows: A reaction vessel containing 8.5 liters of a 2.8% by weight gelatin aqueous solution and 1.9 g 1,8-dihydroxy-3,6-dithiaoctane were adjusted to 68.3°C, pH of 5.8 and pAg of 7.35 by addition of NaCl solution. A 3.75 M solution of AgNO 3 and a 3.75 M solution of NaCl were added simultaneously with rapid stirring. The silver potential was controlled at 7.35 pAg. The emulsion was then washed to remove excess salts. The cubic emulsion grains had an average edge length of 0.6 ⁇ m.
  • Substrate Emulsion C was prepared as follows: A reaction vessel containing 7.15 liters of a 2.7% by weight gelatin solution and 1.9 g 1,8-dihydroxy-3,6-dithiaoctane was adjusted to 68.3°C. A 4 M solution of AgNO 3 and a 4 M solution of NaCl were added simultaneously with flow rates increasing from 48 ml/min. to 83 ml/min. The silver potential was controlled at 7.2 pAg. The emulsion was then washed to remove excess salts. The cubic emulsion grains had an edge length of 0.78 ⁇ m.
  • Substrate Emulsion D was prepared as follows: A reaction vessel containing 4.67 liters of a 2.7% by weight gelatin solution and 1.4 g 1,8-dihydroxy-3,6-dithiaoctane was adjusted to 68.3°C. A 1.35 M solution of AgNO 3 and a 1.8 M solution of NaCl were added simultaneously with flow rates increasing from 54 ml/min. to 312 ml/min. The silver potential was controlled at 7.2 pAg. The emulsion was then washed to remove excess salts. The cubic emulsion grains had an edge length of 1.0 ⁇ m.
  • This example illustrates the use of a preformed fine grain silver halide (Lippmann) emulsion as a carrier of the dopant (termed a grain surface modifier), and as a source of the epitaxially deposited silver halide material.
  • a preformed fine grain silver halide (Lippmann) emulsion as a carrier of the dopant (termed a grain surface modifier), and as a source of the epitaxially deposited silver halide material.
  • Undoped Lippmann Emulsion L1 was prepared as follows: A reaction vessel containing 4.0 liters of a 5.6% by weight gelatin aqueous solution was adjusted to a temperature of 40°C, pH of 5.8 and a pAg of 8.86 by addition of AgBr solution. A 2.5 molar solution containing 1698.7 grams of AgNO 3 in water and a 2.5 molar solution containing 1028.9 grams of NaBr in water were simultaneously run into the reaction vessel with rapid stirring, each at a constant flow rate of 200 ml/min. The double jet precipitation continued for 3 minutes at a controlled pAg of 8.86, after which the double jet precipitation was continued for 17 minutes during which the pAg was decreased linearly from 8.86 to 8.06. A total of 10 moles of silver bromide (Lippmann bromide) was precipitated, the silver bromide having average grain sizes of 0.05 ⁇ m.
  • Emulsion L5 was prepared exactly as Emulsion L1, except a solution of 0.533 gram of MC-41 in 25 ml water was added at a constant flow rate beginning at 50% and ending at 90% of the precipitation. This triple jet precipitation produced 10 moles of a 0.05 ⁇ m grain size emulsion.
  • Control Emulsion 1a was prepared as follows: a 50 millimole (mmole) sample of substrate Emulsion B was heated to 40°C and spectrally sensitized by the addition of 14 milligrams of the blue spectral sensitizing dye Dye D, anhydro-5-chloro-3,3'-di(3-sulfopropyl)naphtho[1,2-d]thiazolothiacyanine hydroxide triethylammonium salt.
  • Dye D anhydro-5-chloro-3,3'-di(3-sulfopropyl)naphtho[1,2-d]thiazolothiacyanine hydroxide triethylammonium salt.
  • Emulsion L1 This was followed by the addition of 0.45 mmole of Emulsion L1.
  • Emulsion 1b was prepared and sensitized exactly as Emulsion 1a, except that 0.045 mmole of Emulsion L5 and 0.405 mmole of Emulsion L1 were added during the sensitization process instead of 0.45 mmole of Emulsion L1 alone.
  • Emulsion 1c was prepared and sensitized exactly as Emulsion 1a, except that 0.0675 mmole of Emulsion L5 and 0.3825 mmole of Emulsion L1 were added during the sensitization process instead of 0.45 mmole of Emulsion L1 alone.
  • epitaxially deposited silver chlorobromide regions of Emulsions 1b and 1c were doped with a total of 0.09 mppm and 0.135 mppm of MC-41, respectively.
  • the emulsions were coated on paper support using sizing methods disclosed in U.S. Patent 4,994,147. Specifically, they were coated at 0.28 gram/m 2 silver with 0.002 gram/m 2 of 2,4-dihydroxy-4-methyl-1-piperidinocyclopenten-3-one, 0.02 gram/m 2 of KCl, 0.78 mg/m 2 of potassium p-tolylsulfonate, 7.8 mg/m 2 of sodium p-tolylsulfinate, 1.08 grams/m 2 yellow dye-forming coupler C2, and with 0.166 gram/m 2 gelatin.
  • a gelatin protective overcoat layer 1.1 grams/m 2 was applied along with bis(vinylsulfonylmethyl)ether gelatin hardener.
  • the coatings were exposed through a step tablet to a 3000°K light source for various exposure times and processed as recommended in "Using KODAK EKTACOLOR RA Chemicals", Publication No. Z-130, cited above. After processing, the Status A reflection densities of each coating were measured.
  • Control Emulsion 2a was prepared as follows: a 0.3 mole sample of substrate Emulsion C was heated to 40°C and chemically sensitized by the addition of a colloidal dispersion of gold sulfide followed by digestion at 60°C, and spectrally sensitized by the addition of blue sensitizing dye Dye D.
  • Emulsion 2b was prepared and sensitized exactly as Emulsion 2a, except that 0.003 micromole of MC-41 was added prior to the addition of KBr during the finishing operation.
  • the emulsions were coated, exposed, processed and the sensitometry read as described above in Example 1.
  • Examples 3-7 demonstrate the effectiveness of adding coordination complexes of iridium and at least one organic ligand into epitaxial regions of cubic AgCl emulsions coated in a tricolor multilayer format. These emulsions demonstrate improved reciprocity, heat sensitivity, and latent image keeping.
  • Control Emulsion 3a was prepared as follows: a 10 mole sample of substrate Emulsion B was heated to 40°C, adjusted to a pH of 5.6, and chemically sensitized by the addition of a colloidal dispersion of gold sulfide followed by digestion at 65°C.
  • Emulsions 3b, 3c and 3d were prepared and sensitized exactly as Emulsion 3a, except that 11.1, 43.5, and 168.0 micromoles of MC-41, respectively, were added prior to the KBr addition during the finishing operation. Doped epitaxial regions were thereby produced.
  • the emulsions were coated in a conventional tricolor multilayer format along with the blue sensitive and green sensitive emulsions described below.
  • a high chloride silver halide emulsion was precipitated by equimolar addition of silver nitrate and sodium chloride solutions into a well-stirred reactor containing gelatin peptizer and thioether ripener.
  • the resultant emulsion contained cubic shaped grains of 0.78 ⁇ m average edgelength.
  • the emulsion was optimally sensitized by the addition of a colloidal suspension of gold sulfide and heat treated at 60°C, during which time blue spectral sensitizing dye Dye D; 1-(3-acetamidophenyl)-5-mercaptotetrazole and KBr were added.
  • Green Emulsion A high chloride silver halide emulsion was precipitated by equimolar addition of silver nitrate and sodium chloride solutions into a well-stirred reactor containing gelatin peptizer and thioether ripener.
  • the resultant emulsion contained cubic shaped grains of 0.30 ⁇ m average edgelength.
  • the emulsion was optimally sensitized by the addition of green sensitizing dye anhydro-5-chloro-9-ethyl-5'-phenyl-3'-(3-sulfobutyl)-3-(sulfopropyl)oxacarbocyanine hydroxide, sodium salt (Dye E), a colloidal suspension of gold sulfide, heat digestion followed by the addition of 1-(3-acetamidophenyl)-5-mercaptotetrazole and KBr.
  • green sensitizing dye anhydro-5-chloro-9-ethyl-5'-phenyl-3'-(3-sulfobutyl)-3-(sulfopropyl)oxacarbocyanine hydroxide, sodium salt (Dye E), a colloidal suspension of gold sulfide, heat digestion followed by the addition of 1-(3-acetamidophenyl)-5-mercaptotetrazole and KBr.
  • Coupler dispersions were emulsified by methods well known to the art, and the following layers were coated on a polyethylene resin coated paper support, sized as described in U.S. Patent 4,994,147 and pH adjusted as described in U.S. Patent 4,917,994.
  • the polyethylene layer coated on the emulsion side of the support contained a mixture of 0.1% (4,4'-bis(5-methyl-2-benzoxazolyl)stilbene and 4,4'-bis(2-benzoxazolyl) stilbene, 12.5% TiO 2 , and 3% ZnO white pigment.
  • the layers were hardened with bis(vinylsulfonylmethyl)ether at 1.95% of the total gelatin weight.
  • Layer 1 Blue Sensitive Layer Gelatin 1.530 g/m 2 Blue Sensitive Silver 0.280 g Ag/m 2 Yellow Dye-Forming Coupler C2 1.080 g/m 2 Dibutyl phthalate 0.260 g/m 2 2-(2-butoxyethoxy)ethyl acetate 0.260 g/m 2 2, 5-Dihydroxy-5-methyl-3-(1-piperidinyl)-2-cyclopenten-1-one 0.002 g/m 2 Potassium 2,5-dihydroxy-4-(1-methylheptadecyl)phenylsulfonate 0.009 g/m 2
  • Layer 2 Interlayer Gelatin 0.753 g/m 2 Dioctyl hydroquinone 0.094 g/m 2 Dibutyl phthalate 0.282 g/m 2 Disodium 4,5 Dihydroxy- m -benzenedisulfonate 0.065 g/m 2 Sodium isopropylnaphthylsulf
  • the multilayer coating described above was evaluated by exposure to a 3000°K color temperature light source through a neutral density step tablet having an exposure range of 0 to 3 logE, and processing as recommended in "Using KODAK EKTACOLOR RA Chemicals", Publication No. Z-130, cited above.
  • the Status A reflection densities of each coating were measured, and the sensitometric response of the red sensitive layer containing the doped epitaxial emulsions of the invention are shown in Table 3-I.
  • Example 3 was repeated, except that the Layer 3, the green sensitive layer, was replaced with alternate green sensitive layer I.
  • Alternate Green Sensitive Layer I Gelatin 1.230 g/m 2 Green Sensitive Silver 0.160 g Ag/m 2 Magenta Dye-Forming Coupler C6 0.260 g/m 2 Tris(2-ethylhexyl)phosphate 0.520 g/m 2 2-Butoxy-1-(N,N-dibutylamino)-5-(1,1,3,3-tetramethylbutyl)benzene 0.360 g/m 2 ST-4 2,5-Dioctylhydroquinone 0.060 g/m 2
  • Example 3 was repeated, except that the Layer 3, the green sensitive layer, was replaced with alternate green sensitive layer II.
  • Example 3 was repeated, except that the Layer 3, the green sensitive layer, was replaced with alternate green sensitive layer III.
  • Alternate Green Sensitive Layer III Gelatin 1.230 g/m 2 Green Sensitive Silver 0.108 g Ag/m 2 Magenta Dye-Forming Coupler C9 0.140 g/m 2 Tritolyl phosphate 1.119 g/m 2 1,1'-Bis(3,3-dimethyl-5,5',6,6'-tetrapropoxyindane) 0.129 g/m 2 2-Methyl-1,1-bis(2-hydroxy-3,5-dimethylphenyl)propane 0.054 g/m 2 2,6-Dichloro-4-ethoxycarbonylphenyl hexadecanoate 0.097 g/m 2 Sodium 3,5-bis ⁇ 3-[2,4-bis(1,1-dimethylpropyl)phenoxy]propylcarbamoyl ⁇ -phenylsulfinate 0.011 g/m 2
  • Example 3 was repeated, except that the Layer 3, the blue sensitive layer, was replaced with alternate blue sensitive layer I.
  • Alternate Blue Sensitive Layer I Gelatin 1.042 g/m 2 Blue Sensitive Silver 0.243 g Ag/m 2 Yellow Dye-Forming Coupler C10 0.539 g/m 2 Bis(3- tert -butyl-2-hydroxy-5-methylphenyl)methane hemiacetate 0.237 g/m 2 Sodium 2,5-dihydroxy-4-isooctadecylphenylsulfonate 0.009 g/m 2 Dibutyl phthalate 0.301 g/m 2 Glycerol 0.162 g/m 2
  • Example 3 was repeated, except that the Layer 3, the blue sensitive layer, was replaced with alternate blue sensitive layer II.
  • Alternate Blue Sensitive Layer II Gelatin 1.042 g/m 2 Blue Sensitive Silver 0.243 g Ag/m 2 Yellow Dye-Forming Coupler C11 0.645 g/m 2 Poly (N- tert -butylacrylamide) 0.538 g/m 2 Dibutyl phthalate 0.269 g/m 2
  • Control Emulsion 9a was prepared as follows: a 10 mole sample of substrate Emulsion A was heated to 40°C, adjusted to a pH of 4.3, and chemically sensitized by the addition of a colloidal dispersion of gold sulfide followed by digestion at 65°C.
  • Control Emulsions 9b, 9c and 9d were prepared and sensitized exactly as Emulsion 9a, except that 3.7, 11.1, and 22.2 micromoles of K 2 IrCl 6 (CD-3), respectively; were added prior to the KBr addition during the finishing operation. Doped epitaxial regions were thereby produced.
  • Emulsions 9e, 9f and 9g were prepared and sensitized exactly as Emulsion 9a, except that 3.7, 11.1, and 22.2 micromoles of K 2 IrCl 5 (thiazole) (MC-41), respectively; were added prior to the KBr addition during the finishing operation. Doped epitaxial regions were thereby produced.
  • the emulsions were coated and evaluated in a conventional tricolor multilayer format, along with blue sensitive and green sensitive emulsions, as described above in Example 3.
  • the sensitometric response of the red sensitive layers containing the doped epitaxial emulsions of the invention are shown in Table 9-I. Emuls. # Dopant Complex Nominal Dopant Level (mppm) Speed for a 0.5" exp.
  • Control Emulsion 10a was prepared as follows: a 10 mole sample of substrate Emulsion A was heated to 40°C, adjusted to a pH of 4.9 and a pAg of 8.05, and spectrally and chemically sensitized by the addition of spectral sensitizing dye Dye E, a colloidal dispersion of gold sulfide, followed by digestion at 65°C.
  • Control Emulsions 10b, 10c and 10d were prepared and sensitized exactly as Emulsion 10a, except that 3.7, 11.2, and 22.4 micromoles of K 2 IrCl 6 (CD-3), respectively; were added prior to the KBr addition during the finishing operation. Doped epitaxial regions were thereby produced.
  • Emulsions 10e, 10f and 10g were prepared and sensitized exactly as Emulsion 10a, except that 3.7, 11.2, and 22.4 micromoles of K 2 IrCl 5 (thiazole) (MC-41), respectively; were added prior to the KBr addition during the finishing operation. Doped epitaxial regions were thereby produced.
  • the emulsions were coated and evaluated in a conventional tricolor multilayer format, along with blue sensitive and green sensitive emulsions, as described above in Example 3.
  • the sensitometric response of the red sensitive layers containing the doped epitaxial emulsions of the invention are shown in Table 10-I. Emuls. # Dopant Complex Nominal Dopant Level (mppm) Speed for a 0.5" exp.
  • Table 10-I demonstrate that emulsions containing epitaxial regions doped at a range of amounts of a coordination complex containing iridium and a thiazole ligand have improved reciprocity and contrast LIK performance relative to an undoped control. Relative to a K 2 IrCl 6 doped control, the emulsions of the invention have improved reciprocity, speed LIK and contrast LIK performance.
  • Control Emulsion 11a was prepared as follows: a 10 mole sample of substrate Emulsion B was heated to 40°C, adjusted to a pH of 4.5, and chemically sensitized by the addition of a colloidal dispersion of gold sulfide, followed by digestion at 60 C.
  • Control Emulsions 11b and 11c were prepared and sensitized exactly as Emulsion 11a, except that 0.8 and 9.2 micromoles of K 2 IrCl 6 (CD-3), respectively; were added prior to the KBr addition during the finishing operation. Doped epitaxial regions were thereby produced.
  • Emulsions 11d and 11e were prepared and sensitized exactly as Emulsion 11a, except that 0.8 and 9.2 micromoles of K 2 IrCl 5 (thiazole) (MC-41), respectively; were added prior to the KBr addition during the finishing operation. Doped epitaxial regions were thereby produced.
  • the emulsions were coated in the conventional tricolor multilayer format described above in Example 3, except that the blue sensitive emulsions of this example were used along with the red sensitive emulsion described below.
  • a high chloride silver halide emulsion was precipitated be equimolar addition of silver nitrate and sodium chloride solutions into a well-stirred reactor containing gelatin peptizer and thioether ripener.
  • the resultant emulsion contained cubic shaped grains of 0.38 mm average edgelength.
  • the emulsion was optimally sensitized by the addition of a colloidal suspension of aurous sulfide, heat digestion followed by the addition of 1-(3-acetamidophenyl)-5-mercaptotetrazole, potassium bromide, KBr, and the red spectral sensitizing dye anhydro-3-ethyl-9,11-neopentalene-3'-(3-sulfopropyl)thiadicarbocyanine hydroxide (Dye I).
  • Control Emulsion 12a was prepared as follows: a 10 mole sample of substrate Emulsion D was heated to 40°C, adjusted to a pH of 5.6, chemically sensitized by the addition of a colloidal dispersion of gold sulfide, followed by digestion at 60°C.
  • Control Emulsions 12b, 12c and 12d were prepared and sensitized exactly as Emulsion 12a, except that 0.8, 4.6 and 9.2 micromoles of K 2 IrCl 6 (CD-3), respectively; were added prior to the Lippmann bromide addition during the finishing operation. Doped epitaxial regions were thereby produced.
  • Emulsions 12e, 12f and 12g were prepared and sensitized exactly as Emulsion 12a, except that 0.8, 4.6 and 9.2 micromoles of K 2 IrCl 5 (thiazole) (MC-41), respectively; were added prior to the Lippmann bromide addition during the finishing operation. Doped epitaxial regions were thereby produced.
  • the emulsions were coated and evaluated in the conventional tricolor multilayer format described above in Example 11.
  • the sensitometric response of the blue sensitive layers containing the doped epitaxial emulsions of the invention are shown in Table 12-I. Emuls. # Dopant Complex Nominal Dopant Level (mppm) Speed for a 0.5" exp.
  • Control Emulsion 13a was prepared as follows: a 0.3 mole sample of substrate Emulsion C was heated to 40°C and chemically sensitized by the addition of a colloidal dispersion of gold sulfide followed by digestion at 60°C, and spectrally sensitized by the addition of blue spectral sensitizing dye Dye D.
  • Emulsions 13b-h were prepared and sensitized exactly as Emulsion 13a, except that 0.126 micromole of the dopant complex listed in Table 13-I for these emulsions were added prior to the addition of KBr during the finishing operation.
  • the emulsions were coated, exposed, processed and the sensitometry read as described above in Example 1.
  • Control Emulsion 14a was prepared as follows: a 0.3 mole sample of substrate Emulsion C was heated to 40°C and chemically sensitized by the addition of a colloidal dispersion of gold sulfide followed by digestion at 60°C, and spectrally sensitized by the addition of blue spectral sensitizing dye Dye D.
  • Emulsions 14b-d were prepared and sensitized exactly as Emulsion 14a, except that 0.126 micromole of the dopant complex listed in Table 14-I for these emulsions were added prior to the addition of KBr during the finishing operation.
  • the emulsions were coated, exposed, processed and the sensitometry read as described above in Example 1.
  • Control Emulsion 15a was prepared as follows: a 0.3 mole sample of substrate Emulsion C was heated to 40°C and chemically sensitized by the addition of a colloidal dispersion of gold sulfide followed by digestion at 60°C, and spectrally sensitized by the addition of blue spectral sensitizing dye Dye D.
  • Emulsions 15b and 15c were prepared and sensitized exactly as Emulsion 15a, except that 0.126 micromole of the dopant complex listed in Table 15-I for these emulsions were added prior to the addition of KBr during the finishing operation.
  • the emulsions were coated, exposed, processed and the sensitometry read as described above in Example 1.
  • Control Emulsion 16a was prepared as follows: a 0.3 mole sample of substrate Emulsion C was heated to 40°C and chemically sensitized by the addition of a colloidal dispersion of gold sulfide followed by digestion at 60°C, and spectrally sensitized by the addition of blue spectral sensitizing dye Dye D.
  • Emulsions 16b was prepared and sensitized exactly as Emulsion 16a, except that the dopant complex listed in Table 16-I for these emulsions were added prior to the addition of KBr during the finishing operation.
  • the emulsions were coated, exposed, processed and the sensitometry read as described above in Example 1.
  • Control Emulsion 17a was prepared as follows: a 0.3 mole sample of substrate Emulsion C was heated to 40°C and chemically sensitized by the addition of bis (1,4,5-triethyl-1,2,4-triazolium-3-thiolate gold(I) tetrafluroborate followed by digestion at 60°C, and spectrally sensitized by the addition of blue dye Dye D.
  • Emulsions 17b and 17c prepared and sensitized exactly as Emulsion 17a, except that 0.31 micromoles of K 2 IrCl 6 (CD-3) and K 2 IrCl 5 (thiazole) (MC-41), respectively; were added prior to the addition of the dye during the finishing operation. Doped epitaxial regions were thereby produced.

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  • Spectroscopy & Molecular Physics (AREA)
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Claims (10)

  1. Emulsion photographique aux halogénures d'argent comprenant des grains composites d'halogénures d'argent sensibles aux rayonnements contenant des portions de grains hôtes représentant au moins 50% de la quantité totale d'argent et des portions superficielles déposées épitaxialement sur les portions de grains hôtes
    caractérisée en ce que les portions superficielles déposées épitaxialement sur les portions de grains hôtes présentent une structure de réseau cristallin cubique à faces centrées contenant un complexe hexacoordiné d'un métal des périodes 4, 5 et 6 des groupes 3 à 14 inclus dans le tableau périodique des éléments dans lequel un ou plusieurs ligands organiques contenant chacun au moins une liaison carbone-carbone, au moins une liaison carbone-hydrogène ou au moins une séquence de liaison carbone-azote-hydrogène occupe(nt) jusqu'à la moitié des sites de coordination métalliques du complexe de coordination et où au moins la moitié des sites de coordination métalliques du complexe de coordination sont formés par des ligands halogène ou pseudohalogène, à la condition que lorsque les portions de grains hôtes comprennent des grains cubiques de chlorure d'argent, le complexe hexacoordiné du métal incorporé dans la portion superficielle déposée épitaxialement soit autre que K2[IrCl5(pyrazine)] ou K4[Ir2Cl10(pyrazine)].
  2. Emulsion photographique aux halogénures d'argent selon la revendication 1, caractérisée en outre en ce que les portions superficielles déposées épitaxialement sont principalement adjacentes à au moins l'un des bords et coins des portions de grains hôtes.
  3. Emulsion photographique aux halogénures d'argent selon la revendication 1 ou 2, caractérisée en outre en ce que les grains composites d'halogénures d'argent contiennent au moins 90% en moles de chlorure, de 0 à 10% en moles de bromure et de 0 à 2% en moles d'iodure, les portions superficielles déposées épitaxialement contenant une concentration en halogénures autres que le chlorure supérieure aux portions des grains hôtes.
  4. Emulsion photographique aux halogénures d'argent selon l'une quelconque des revendications 1 à 3 incluse, caractérisée en outre en ce que l'on choisit les ligands organiques parmi les hydrocarbures aliphatiques et aromatiques substitués et non substitués, les amines, les phosphines, les amides, les imides, les nitriles, les aldéhydes, les éthers, les cétones, les acides organiques, les sulfoxydes et les hétérocycles aliphatiques et aromatiques comprenant un ou une combinaison d'hétéroatomes cycliques pnictide et chalcogène.
  5. Emulsion photographique aux halogénures d'argent selon l'une quelconque des revendications 1 à 4 incluse, caractérisée en outre en ce que l'on choisit le dopant de l'ion métallique parmi les dopants métalliques du groupe VIII.
  6. Emulsion photographique aux halogénures d'argent selon l'une quelconque des revendications 1 à 5 incluse, caractérisée en outre en ce que le complexe hexacoordiné est un complexe anionique répondant à la formule (I)   [MXxYyLz]    ou (II)   [MZ5L'Z'5M'] où
    M et M' sont indépendamment choisis parmi les métaux des groupes 8 ou 9 ;
    X est Cl, Br ou CN ;
    x est de 3 à 5 ;
    Y est H2O ;
    y est 0 ou 1 ;
    L est un ligand organique contenant au moins une liaison carbone-carbone, au moins une liaison carbone-hydrogène ou au moins une séquence de liaison carbone-azote-hydrogène ;
    L' est un ligand pontant organique contenant au moins une liaison carbone-carbone, au moins une liaison carbone-hydrogène ou au moins une séquence de liaison carbone-azote-hydrogène ;
    z est 1 ou 2 ; et
    Z et Z' sont indépendamment choisis parmi X, Y et L, à la condition que dans au moins 3 cas pour chacun des groupes Z et Z', ils soient X et que dans zéro ou un cas pour chacun des groupes Z et Z', ils soient H2O.
  7. Emulsion photographique selon la revendication 6, caractérisée en outre en ce que L est un groupe thiazole, thiazoline ou pyrazine.
  8. Emulsion photographique aux halogénures d'argent selon la revendication 6 ou 7, caractérisée en outre en ce que l'on utilise une concentration de métal formant le complexe de coordination comprise entre 10-9 et 10-3 moles d'atomes par mole d'argent, par rapport à la quantité totale d'argent.
  9. Emulsion photographique aux halogénures d'argent selon l'une quelconque des revendications 6 à 8 incluse, caractérisée en outre en ce que M de la formule (I) et au moins l'un des groupes M et M' de la formule (II) est l'iridium et où l'on utilise une concentration en iridium comprise entre 10-9 et 10-5 moles d'atomes par mole d'argent.
  10. Emulsion photographique aux halogénures d'argent selon l'une quelconque des revendications 6 à 8 incluse, caractérisée en outre en ce que M et M' sont choisis parmi les métaux du groupe 8 que sont le fer et le ruthénium et que l'on utilise une concentration en métaux du groupe 8 comprise entre 10-7 et 10-3 moles d'atomes par mole d'argent.
EP95202609A 1994-09-30 1995-09-28 Emulsions d'halogénure d'argent à l'épitaxie dotée Expired - Lifetime EP0709724B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US330280 1981-12-14
US316003 1994-09-30
US08/316,003 US5480771A (en) 1994-09-30 1994-09-30 Photographic emulsion containing transition metal complexes
US08/330,280 US5462849A (en) 1994-10-27 1994-10-27 Silver halide emulsions with doped epitaxy

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EP0709724A2 EP0709724A2 (fr) 1996-05-01
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0634689A1 (fr) * 1993-07-13 1995-01-18 Eastman Kodak Company Emulsions à l'halogénure d'argent dopés internement et procédés pour leur préparation

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US4933272A (en) * 1988-04-08 1990-06-12 Eastman Kodak Company Photographic emulsions containing internally modified silver halide grains
US5037732A (en) * 1989-08-28 1991-08-06 Eastman Kodak Company Photographic emulsions containing internally modified silver halide grains

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0634689A1 (fr) * 1993-07-13 1995-01-18 Eastman Kodak Company Emulsions à l'halogénure d'argent dopés internement et procédés pour leur préparation

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EP0709724A3 (fr) 1996-05-08
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EP0709724A2 (fr) 1996-05-01
DE69526624T2 (de) 2002-11-21

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