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
• • 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 ⁇ , N3 ⁇ , 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, K2[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 [(NH3)6Ir]+3 salt), hexaamine iridium (IV) salt (i.e., a [(NH3)6Ir]+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).
• the present invention has for the first time introduced during epitaxial deposition dopant metal hexacoordination complexes containing one or more organic ligands 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.
• 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-4 (R4N)[TiCl4(EtO)(MeCN)] EtO CH3CH2O
• MC-4a R Me Tetramethylammonium (acetonitrile) ethoxytetrachloro titanate (IV)
• MC-4b R Et Tetraethylammonium (acetonitrile) ethoxytetrachloro titanate (IV) a-b Reported by F. Von Adalbert, Z. Anorg. Allgem. Chem . , 338 , 147 (1965).
• MC-7 (Et4N)[VCl4(MeCN)2] Tetraethylammonium bis(acetonitrile) tetrachloro vanadate (III) Reported by R. J. H. Clark, Comprehensive Inorganic Chemistry , Vol. 3, pp. 544-545, edited by A. F. Trotman-Dickerson, Pergoman Press, Oxford, 1973.
• MC-8 [WCl4(en)] en ethylenediamine (Ethylenediamine)tetrachloro tungsten (IV) Reported by C. D. Kennedy and R. D. Peacock, J. Chem. Soc ., 3392 (1963).
• MC-10 (Bu4N)[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 (Bu4N)[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 [ReOCl3(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-14p L MeNH2 Sodium pentacyano (methylamine) ferrate (II)
• MC-14q L Me2NH Sodium pentacyano (dimethylamine) ferrate
• MC-14r L Me3NH Sodium pentacyano (trimethylamine) ferrate
• MC-14s L EtNH2 Sodium pentacyano (ethylamine) ferrate
• MC-14t L BuNH2 Sodium pentacyano (butylamine) ferrate
• MC-14u L cyclohexylamine Sodium pentacyano (cyclohexylamine) ferrate (II)
• MC-14v L piperidine Sodium pentacyano (piperidine) ferrate
• MC-14w L aniline Sodium pentacyano (aniline) ferrate
• MC-14x L morpholine Sodium pentacyano (morpholine) ferrate (II)
• 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 Me2SO Sodium pentacyano(dimethyl sulfoxide) ferrate (II) Reported by H. E. Toma, J. M. Malin and E. Biesbrecht, Inorg. Chem ., 12 , 2884 (1973).
• MC-15 K3[Ru(CN)5L] 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 Me2SO Potassium pentacyano (dimethylsulfoxide) ruthenate (II)
• MC-15g L (py) Potassium pentacyano (pyridine) ruthenate (II)
• MC-15h L 4-[ ⁇ OC(O)](py) Potassium pentacyano (isonicotinato
• MC-35 [In(dimac)3(NCS)3] 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).
• 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 (-CH3) 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. Note that the amines must be secondary or tertiary amines, since a primary amine (H2N-), designated by the term "amine” used alone, does not satisfy the organic ligand definition.
• H2N- primary amine
• 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 and here incorporated by reference.
• 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 H2O, 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 [MZ5L'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 H20, 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 each of
• Suitable bridging C-C, H-C or C-N-H organic ligands include H2N-R-NH2, 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 [MZ5L'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.
• Na3K2[IrCl5(pyrazine)Fe(CN)5] was prepared by reacting equimolar amounts of K2[IrCl5(pyrazine)] and Na3[Fe(CN)5(NH3)] ⁇ 3H2O in a small amount of H2O 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 Na3K2[IrCl5(pyrazine)Fe(CN)5] by IR, UV/VIS and NMR spectroscopies and by CHN chemical analyses.
• [IrCl5(pyz)Ru(CN)5]5 ⁇ The mixed metal dimer K5(IrCl5(pyrazine)Ru(CN)5] was prepared by reacting equimolar amounts of K3[Ru(CN)5(pyrazine)] and K2[IrCl5(H2O)] in a small amount of H2O 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 K5[IrCl5(pyrazine)Ru(CN)5] by IR, UV/VIS, and NMR spectroscopies and by CHN chemical analyses.
• Na4[Rh2Cl10(pyrazine)] was prepared by reacting Na3RhCl6 ⁇ 12H2O with pyrazine in a 2 to 1.05 (5% excess pyrazine) molar ratio at 100 C in a minimum amount of H2O for 1 hour.
• Acetone was added to the cooled solution to give an oil and an orange colored liquid with some suspended solid material which was decanted. The oil was washed several times with acetone and decanted. The acetone was removed with a N2 flow to give a sticky red substance which was then air dried in an oven at 100 C for 1 hour to give a dark red material.
• Na3K3[Ru(CN)5(pyrazine)Fe(CN)5] was similarly prepared by stirring equimolar amounts of K3[Ru(CN)5(pyrazine)] and Na3[Fe(CN)5(NH3)] ⁇ 3H2O in a small amount of H2O 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 as Na3K3[Ru(CN)5(pyrazine)Fe(CN)5] by IR, UV/VIS and NMR spectroscopies and by CHN chemical analyses.
• 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.
• K3IrBr6 was the iridium source for the preparation of the monothiazole complex K2IrBr5(thiazole). 2 grams of K3IrBr6 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 K2IrBr5(thiazole).
• reaction flask After 1 hour at 85 o 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 N2 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.
• KIrBr4(thiazole)2 was recrystallized by dissolving the material in a minimum amount of warm water (ca. 60 o C) and filtering. The filtrate was then decreased in volume by 50% and pure KIrBr4(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 D2O, and 1H NMR was used to monitor both the disappearance of the starting material K2IrCl5(thiazole) and the appearance of the monoaquated product K2IrCl4(H2O)(thiazole). It was found that in ca. 16 hours, 100% of K2IrCl5(thiazole) had reacted under our experimental conditions.
• the main photochemical reaction products are KIrCl4(H2O)(thiazole) and KCl, but a few other NMR peaks are observed that are weak and not identified.
• Ag(CF3COO) 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 KIrCl4(H2O)(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. 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 N2, redissolved in a minimum amount of water, and precipitated with ethyl alcohol to give pure KIrCl4(H2O)(thiazole).
• KIrCl4(4-methylthiazole)2 was synthesized by the room temperature reaction of excess 4-methylthiazole with K3IrCl6. Typically, 5 grams of K3IrCl6 and 5 grams of 4-methylthiazole were added together in ca. 100 ml of water in a 250 ml round bottom flask. The mixture was stirred until all the iridium salt dissolved, and then the solution was allowed to stand for 12 days. An orange precipitate slowly formed, and after the 12 days, an equal volume of acetone (100 ml) was added to the flask to precipitate additional orange material.
• 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 o C and precipitating with acetone.
• the recrystallized orange material was KIrCl5(4-methylthiazole)2.
• KIrCl4(4-methylthiazole)2 can also be readily synthesized in aqueous solution at 70 o C. Due to its low solubility, the material was assumed to be the trans-isomer.
• KIrCl4(2-bromothiazole)2 was synthesized by the room temperature reaction of 5 grams of K3IrCl5 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 KIrCl5(2-bromothiazole)2.
• [IrCl5L]2 ⁇ An aqueous solution of K3IrCl6 was stirred at ambient temperature with an excess of the organic liquid ligand L for several days. The K2IrCl5L 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
• CD-7 and CD-8 the comparative dopant (CD) complexes listed in Table I below were purchased from commercial sources.
• CD-7 and CD-8 were prepared as reported by M. Delephine, Ann. Chim ., 19 , 145 (1923).
• EDTA ethylenediaminetetraacetic acid Table I CD-1 EDTA CD-2 [Fe(EDTA)] ⁇ 1 CD-3 [IrCl6] ⁇ 2 CD-4 K2C2O4.H2O CD-5 [Fe(CN)6] ⁇ 4 CD-6 [Fe(C2O4)3] ⁇ 3 CD-7 [ cis -IrCl2(C2O4)2] ⁇ 3 CD-8 [Ir(C2O4)3] ⁇ 3
• the purpose of this example is to demonstrate the incorporation of C-C, H-C or C-N-H organic ligands within a silver halide grain structure.
• An emulsion F19 was prepared as described below in the F Series Examples, doped with 43.7 molar parts per million (mppm) of dopant MC-14c.
• Electron paramagnetic resonance spectroscopic measurements were made on emulsion F19 at temperatures between 5 and 300°K, using a standard X-band homodyne EPR spectrometer and standard cryogenic and auxiliary equipment, such as that described in Electron spin Resonance, 2nd Ed., A Comprehensive Treatise on Experimental Techniques , C. P. Poole, Jr., John Wiley & Sons, New York, 1983.
• EPR signals were observed from the doped sample unless it was exposed to light or strong oxidants, such as gaseous chlorine. After exposure to band-to-band light excitation (365 nm) between 260°K and room temperature, EPR signals were observed at 5-8°K. These signals were not observed from the undoped control sample after light exposure. Discernible in these signals were powder pattern lineshapes like those typically observed from a randomly oriented ensemble of low symmetry paramagnetic species in a powder or frozen solution.
• the strongest powder patterns had g1 features at 2.924 (Site I), 2.884 (Site II) and 2.810 (Site III), each with a linewidth at half maximum of 1.0 ⁇ 0.1 mT, shown below to be from four distinct kinds of [Fe(CN)5(bipyridyl)]2 ⁇ complexes in which the metal ions have low spin d5 electronic configurations.
• the powder pattern EPR spectrum was also observed after the doped, unexposed silver chloride emulsion was placed in an oxidizing atmosphere of chlorine gas.
• the observations that this pattern was absent before exposure and was produced by the oxidizing atmosphere confirmed that the [Fe(CN)5(bipyridyl)] complex dopant was incorporated with the metal ion in the Fe(II) state, which is invisible to EPR measurements, and that the Fe(II) ion trapped a hole (was oxidized) to produce the Fe(III) oxidation state during exposure to chlorine or light.
• the dopant was incorporated primarily as [Fe(CN)5(bipyridyl)]3 ⁇ with the ligands surrounding the ferrous ion intact by comparing the observed EPR spectra with those obtained upon doping silver chloride powders with the most chemically-feasible, ligand-exchanged contaminants of the dopant salt that might be produced during synthesis of the dopant or precipitation of the emulsion.
• the species [Fe(CN)6]4 ⁇ , [Fe(CN)5(H2O)]3 ⁇ [Fe(CN)5Cl]4 ⁇ and [Fe2(CN)10]6 ⁇ were investigated.
• Solution A Gelatin (bone) 40 g D. W. 1500 g
• Solution B 2.5N Sodium bromide Solution
• Gelatin (phthalated) 50 g D. W. 300 g
• Solution E Gelatin (bone) 119 g D. W. 1000 g
• Emulsion A1 was prepared as follows: Solution A was adjusted to a pH of 3 at 40 o C with 2N HNO3 and the temperature was adjusted to 70 o C. The pAg of solution A was adjusted to 8.19 with solution B. Solutions B and C were run into solution A with stirring at a constant rate of 1.25 ml/min for four minutes. The addition rate was accelerated to 40 ml/min over the next 40 minutes. The resulting mixture was cooled to 40 o C. Solution D was then added with stirring and the mixture was held for 5 minutes. The pH was then adjusted to 3.35 and the gel was allowed to settle. The temperature was dropped to 15 o C for 15 minutes and the liquid layer was decanted.
• Doped emulsion A1a was prepared as described for emulsion A1 except that during the accelerated portion of the reagent addition, after 603 cc of solution B had been added, a dopant solution was substituted for solution B. After the dopant solution was depleted, it was replaced by solution B.
• Dopant Anion Dopant Solution for Emulsion A1a CD-5 K4Fe(CN)6 12.04 mg Solution B 181 cc
• Doped emulsions prepared in this fashion were monodispersed in size and shape and had octahedral edge lengths of 0.5 microns +/- 0.05 microns.
• the resulting doped emulsion A1a nominally contained a total of 11 molar parts per million (mppm) of dopant in the outer 72% to 93.5% of the grain volume; i.e., the emulsion had an undoped shell of approximate thickness 40 to 100 ⁇ .
• Doped emulsion A1b was prepared as described for emulsion A1, except that the dopant solution was modified to introduce a total of 55 molar parts per million (mppm) of (comparison dopant CD-5) in the outer 72% to 93.5% of the grain volume.
• Doped emulsion A2 was prepared as described for emulsion A1, except that the dopant solution was modified to introduce a total of 5.2 molar parts per million (mppm) of dopant MC-14b and 2.6 mppm of MC-37 in the outer 72% to 93.5% of the grain volume. The initial 0 to 72% of the grain volume and the final 93.5% to 100% of the grain volume were undoped.
• mppm 5.2 molar parts per million
• Doped emulsion A3 was prepared as described for emulsion A2, except that the dopant solution was modified to introduce 11 mppm of dopant MC-37 into the outer 72% to 93.5% of the grain volume.
• Doped emulsion A4 was prepared as described for emulsion A2, except that the dopant solution was modified to introduce 2.6 mppm of dopant MC-14c and 3.9 mppm of dopant MC-38 into the outer 72% to 93.5% of the grain volume.
• Doped emulsion A5 was prepared as described for emulsion A2, except that the dopant solution was modified to introduce 12.9 mppm of dopant MC-14c and 19.4 mppm of dopant MC-38 into the outer 72% to 93.5% of the grain volume.
• Doped emulsion A6 was prepared as described for emulsion A2, except that the dopant solution was modified to introduce 6.6 mppm of dopant MC-38 into the outer 72% to 93.5% of the grain volume.
• Doped emulsion A7 was prepared as described for emulsion A2, except that the dopant solution was modified to introduce 28.9 mppm of dopant MC-38 into the outer 0.5% to 93.5% of the grain volume. Analysis of this emulsion by inductively coupled plasma atomic emission spectropscopy (ICP-AES) showed that the Fe level was, within experimental error, the same as in emulsions prepared like A7 but doped with the conventional dopant anion (Fe(CN)6)4 ⁇ (60.7% +/- 4.6% vs 73.6% +/- 9.8%).
• ICP-AES inductively coupled plasma atomic emission spectropscopy
• Doped emulsion A8 was prepared as described for emulsion A2, except that the dopant was modified to introduce 5.6 mppm of dopant MC-48 into the outer 72% to 93.5% of the grain volume.
• Doped emulsion A9 was prepared as described for emulsion A2, except that the dopant solution was modified to introduce 10.3 mppm of dopant MC-15a into the outer 72% to 93.5% of the grain volume.
• Doped emulsion A10 was prepared as described for emulsion A2, except that the dopant was dissolved in 181 cc of water, and this was added to the emulsion through a third jet so as to introduce 6.6 mppm of dopant MC-38 into the outer 72% to 93.5% of the grain volume.
• Doped emulsion A11 was prepared as described for emulsion A2, except that the dopant solution was modified to introduce 55.3 mppm of dopant MC-14l into the outer 50% to 93.5% of the grain volume.
• Doped emulsion A12 was prepared as described for emulsion A2, except that the dopant solution was modified to introduce 26 mppm of dopant MC-39 into the outer 72% to 93.5% of the grain volume.
• Doped emulsion A13 was prepared as described for emulsion A2, except that the dopant solution was modified to introduce 55 mppm of dopant MC-14n into the outer 72% to 93.5% of the grain volume.
• Doped emulsion A14 was prepared as described for emulsion A2, except that the dopant solution was modified to introduce 11 mppm of dopant [Fe(EDTA)] ⁇ 1 (CD-2) into the outer 72% to 93.5% of the grain volume.
• Doped emulsion A15 was prepared as described for emulsion A2, except that the dopant solution was modified to introduce 55.3 mppm of dopant [Fe(C2O4)3]3 ⁇ (CD-6) into the outer 50% to 93.5% of the grain volume.
• Doped emulsion A16 was prepared as described for emulsion A2, except that the dopant solution was modified to introduce 55 mppm of dopant MC-15a into the outer 50% to 93.5% of the grain volume.
• ICP-MS Ion coupled plasma mass spectrometry
• emulsions A1, A1a, A1b, A4, A5 and A6 were sensitized by the addition of 28 micromole/mole Ag of sodium thiosulfate and 22 micromole/mole Ag of bis (1,4,5-triethyl-1,2,4-triazolium-3-thiolate gold(I) tetrafluroborate, followed by a digestion for 40 minutes at 70 o C.
• the chemically sensitized emulsions were divided into 3 portions.
• the red spectral sensitizing dye (DYE A) (5,5'-dichloro-3,3',9-triethylthiacarbocyanine p -toluenesulfonate) was added from methanolic solution at levels of 0.50 and 0.75 millimole per Ag mole to two of the portions after which the samples were held at 40 o C for one hour.
• Coatings of each of emulsion were made at 21.5 mg Ag/dm2 and 54 mg gelatin/dm2 with a gelatin overcoat layer containing 10.8 mg gelatin/dm2 a surfactant and a hardener, on a cellulose acetate support.
• Some coatings of each sensitized emulsion were exposed for 0.1 second to 365 nm on a standard sensitometer and then developed for 6 minutes in Kodak Rapid X-Ray TM developer, a hydroquinone-ElonTM(N-methyl- p -aminophenol hemisulfate) surface developer at 21°C.
• ⁇ Dmin is the difference in minimum optical density between the undoped control and the doped emulsion, x 100. Smaller values indicate less increase in Dmin attributable to doping.
• ⁇ speed is the difference in speed (measured at 0.15 optical density) between the undoped control and the doped emulsion, x100. Larger values indicate larger speed increases attributable to doping.
• Table A-II shows that emulsions doped with the invention compounds, MC-14c (discussed in the example above) and MC-38, show improved resistance to dye desensitization, and also show either improved resistance to dye desensitization or lower Dmin or both when compared to the comparison emulsion A1a.
• Table A-III demonstrates that an emulsion doped with the invention compound MC-38 does not exhibit increased Dmin at high dopant levels, unlike the emulsion doped with (CD-5).
• each of the emulsions described above was optimally chemically sensitized by the addition of sodium thiosulfate and bis (1,4,5-triethyl-1,2,4-triazolium-3-thiolate gold(I) tetrafluroborate, followed by a digestion for 40 minutes at 70 o C.
• the chemically sensitized emulsions were divided into 4 portions.
• the red spectral sensitizing dye (DYE A) (5,5'-dichloro-3,3',9-triethylthiacarbocyanine p -toluenesulfonate) was added from methanolic solution at levels of 0.25, 0.50 and 0.75 millimole per Ag mole to three of the portions after which the samples were held at 40°C for one hour.
• Doped Emulsion A6 and control Emulsion A1 were also chemically and spectrally sensitized as described above, except that the green spectral sensitizer 5,6,5',6'-dibenzo-1,1'-diethyl-2,2'-tricarbocyanine iodide (Dye B) was used in place of Dye A at levels of 0.0375 and 0.075 mmole/mole of silver.
• Dye B green spectral sensitizer
• Emulsion Dopant 0.0375 mmole dye/Ag mole 0.075 mmole dye/Ag mole A1 None 0 0 A6 MC-38 49 55
• the speed increases of the dyed doped invention emulsions relative to the dyed undoped control are shown in Table A-IV and Table A-VI.
• the level of Dye A or Dye B was increased in the sensitized control emulsion, the overall speed of the emulsion decreased.
• the dyed doped invention emulsions showed higher speed than the dyed undoped control emulsion in all cases.
• high intensity reciprocity failure was improved in the doped invention emulsions compared to the undoped control emulsion.
• Comparative Emulsions A14 and A15 were doped with dopant anions [Fe(EDTA)] ⁇ 1 (CD-2) and [Fe(C2O4)3]3 ⁇ (CD-6), respectively.
• Dopant anions (CD-2) and (CD-6) do not satisfy the requirements of this invention.
• ICP-AES measurements of the Fe content in degelled emulsion A14 showed no significant increase in Fe level above background levels despite the addition of the iron -containing comparative dopant [Fe(EDTA)] ⁇ 1 (CD-2). This failure to incorporate Fe was reflected by the failure to see a significant change in undyed speed as a result of doping with (CD-2) and the observation of significantly reduced dyed speeds in the doped emulsion A14.
• Emulsion B1 The double jet precipitation method described in Example A was modified to produce AgBr 0.97 I 0.03 octahedral emulsions with edge lengths of 0.5 ⁇ m +/- 0.05 ⁇ m and with the iodide distributed uniformly throughout the emulsion grain.
• Emulsion B2 was precipitated like Emulsion B1, except that 13.4 mppm total of dopant anion MC-38 was introduced into the outer 72 to 93.5% of the grain volume. The initial 0 to 72% of the grain volume and the final 93.5% to 100% of the grain volume was undoped.
• each of these emulsions was optimally chemically sensitized by the addition of 100 mg/Ag mole of sodium thiocyanate, 16 ⁇ mole/ Ag mole of sodium thiosulfate and bis (1,4,5-triethyl-1,2,4-triazolium-3-thiolate gold(I) tetrafluroborate at 40 o C, followed by a digestion for 22 minutes at 70 o C.
• the chemically sensitized emulsions were divided into 3 portions.
• the red spectral sensitizing dye (DYE A) (5,5'-dichloro-3,3',9-triethylthiacarbocyanine p -toluenesulfonate) was added, from methanolic solution at levels of 0.50 and 0.75 millimoles per Ag mole to two of the portions after which the samples were held at 40 o C for one hour.
• Emulsions B were coated and exposed as described for Emulsions A. TABLE B-I Difference in Log Relative Speed times 100, between Doped, Dyed Emulsion and Undoped, Dyed Control* Emulsion Dopant 0.50 mmole dye/Ag mole 0.75 mmole dye/Ag mole B1 none 0 0 B2 MC-38 36 43 *The larger the speed number the greater the improvement in dyed speed in the doped emulsion over the undoped control.
• Emulsion C1 The double jet precipitation method used for Emulsion A7 was used to produce the monodispersed, 0.5 ⁇ m edge length, octahedral AgBr grains, except that the dopant solution was modified to introduce a total of 11 mppm of dopant anion MC-17 into the outer 72-92.5% of the grain volume.
• This emulsion was chemically sensitized by the addition of sodium thiosulfate and bis (1,4,5-triethyl-1,2,4-triazolium-3-thiolate gold(I) tetrafluroborate, followed by a digestion for 40 minutes at 70 o C.
• the levels of these sensitizers necessary to give optimum speed and minimum density were determined for emulsions C1 and A1 and these were used for the coatings described below.
• Emulsion C1 was coated and exposed as described for Emulsions A.
• emulsion C1 The photographic parameters of emulsion C1 are compared to those of a control emulsion A1 in Table C-I. It can be seen that this level and placement of dopant MC-17 is useful for decreasing the speed of the emulsion without modifying curve shape.
• Emulsion Dopant D min Speed Contrast A1 none 0.10 306 1.58 C1 MC-17 0.10 237 1.57
• Emulsion D1 The double jet precipitation method used for Emulsion A2 was used to produce the monodispersed, 0.5 ⁇ m edge length, octahedral AgBr grains, except that the dopant solution was modified to introduce a total of 46.7 mppm of dopant anion MC-14rr into the outer 0.5 to 93.5% of grain volume.
• This emulsion was optimally sulfur and gold chemically sensitized employing a digestion for 40 minutes at 70 o C.
• Emulsion D2 was prepared like emulsion D1, except that the dopant solution was modified to introduce a total of 100 mppm of dopant anion MC-14rr into the outer 72% to 93.5% of the grain volume.
• This emulsion was optimally sulfur and gold chemically sensitized employing a digestion for 40 minutes at 70 o C.
• Emulsions D1 and D2 were coated and exposed as described for the A Series Emulsions.
• Emulsion E1 was prepared as follows: Solution A: Gelatin (bone) 180 g D. W. 7200 g Solution B: 1.2 N in Sodium bromide 2.8 N in Sodium chloride Solution C 2.0 N Silver nitrate Solution D Gelatin (bone) 180 g D. W. 1000 g
• Solution A was adjusted to a pH of 3 at 35 o C, and pAg was adjusted to 7.87 with a NaCl solution.
• Solutions B and C were run into solution A with stirring. Solutions B and C were run in at rates of about 17.3 and 30 ml/min, respectively, for the first 3 minutes. The addition rate of solution C was then ramped from 30 to 155 ml/min and solution B was ramped from 17.3 to 89.3 ml/min in 12.5 min. Solutions C and B were then run in at 155 ml/min and 89.3 ml/min respectively for 21 min.
• the pAg was controlled at 7.87 during the addition of solutions B and C. The temperature was then raised to 40°C and the pAg adjusted to 8.06. The emulsion was washed until the pAg measured 7.20. The emulsion was concentrated and solution D was added. The pAg was adjusted to 7.60 and the pH adjusted to 5.5.
• the AgCl 0.70 Br 0.30 emulsions prepared had a narrow distribution of grain sizes and morphologies; emulsion grains were cubic shape with edge lengths of 0.17 ⁇ m.
• Emulsion E1 was chemically sensitized by the addition of 0.812 mg/Ag mole of 4,4'-phenyl- disulfide diacetanilide from methanolic solution, 13.35 x 10 ⁇ 6 mole/Ag mole of 1,3-di(carboxymethyl)-1,3-dimethyl-2-thiourea disodium monohydrate and 8.9 x 10 ⁇ 6 mole/Ag mole potassium tetrachloroaurate(III), followed by a digestion for 10 minutes at 65 o C.
• Emulsion E2 was prepared and sensitized as for emulsion E1, except that the salt solution was modified so as to introduce a total of 0.14 mppm of dopant anion MC-46 through the entire emulsion grain.
• Coatings of each of the above optimally sensitized emulsions were made at 21.5 mg Ag/dm2 and 54 mg gelatin/dm2 with a gelatin overcoat layer made at 10.8 mg gelatin/dm2 a surfactant and a hardener, on a cellulose acetate support.
• Some coatings of each sensitized emulsion were exposed for 0.1 second to 365 nm on a standard sensitometer and then developed for 6 minutes in a hydroquinone-Elon TM (N-methyl- p -aminophenol hemisulfate) surface developer at 21 o C.
• Control Emulsion F1 was prepared in the absence of any dopant salt.
• a reaction vessel containing 5.7 liters of a 3.95% by weight gelatin solution was adjusted to 46°C, pH of 5.8 and a pAg of 7.51 by addition of a NaCl solution.
• a solution of 1.2 grams of 1,8-dihydroxy-3,6-dithiaoctane in 50 ml of water was then added to the reaction vessel.
• a 2 M solution of AgNO3 and a 2 M solution of NaCl were simultaneously run into the reaction vessel with rapid stirring, each at a flow rate of 249 ml/min. with controlled pAg of 7.51.
• Emulsion F2 was prepared similarly as Emulsion F1, except as follows: During the precipitation, an iridium containing dopant was introduced via dissolution into the chloride stream in a way that introduced a total of 0.32 mppm of dopant MC-27a into the outer 93% to 95% of the grain volume. A shell of pure silver chloride (5 % of the grain volume) was then precipitated to cover the doped band.
• Emulsion F3 was precipitated as described for Emulsion F2, except that dopant MC-27a was added at a level of 0.16 ppm into the outer 93% to 95% of the grain volume.
• Emulsion F4 was precipitated as described for Emulsion F2, except that dopant MC-32d was introduced at a total level of 0.32 mppm into the outer 93% to 95% of the grain volume.
• Analyses for iridium incorporation were performed by ICP-MS. The iridium levels in this emulsion were at least as high as those detected in a comparative emulsion doped with the conventional iridium dopant anions, (IrCl6)3 ⁇ or (IrCl6)2 ⁇ .
• Emulsion F5 was precipitated as described for Emulsion F2, except that dopant MC-32d was introduced at a total level of 0.10 mppm into the outer 93% to 95% of the grain volume.
• Emulsion F6 was precipitated as described for Emulsion F2, except that MC-41 was introduced at a total level of 0.32 mppm into the outer 93% to 95% of the grain volume.
• Analyses for iridium incorporation were performed by ICP-MS.
• the iridium levels in this emulsion were at least as high as those detected in comparative emulsions prepared doped with the conventional iridium dopant anions, (IrCl6)3 ⁇ or (IrCl6)2 ⁇ .
• Emulsion F7 was precipitated as described for Emulsion F2, except that dopant MC-41 was introduced at a total level of 0.16 mppm into the outer 93% to 95% of the grain volume.
• Emulsion F8 was precipitated as described for Emulsion F2, except that dopant MC-31 was introduced at a total level of 0.16 mppm into the outer 93% to 95% of the grain volume.
• Emulsion F9 was precipitated as described for Emulsion F2, except that dopant MC-29a was introduced at a total level of 0.32 mppm into the outer 93% to 95% of the grain volume.
• the iridium levels in this emulsion were at least as high as those detected in a comparative emulsions doped with the conventional iridium dopant anions, (IrCl6)3 ⁇ or (IrCl6)2 ⁇ .
• Emulsion F10 was precipitated as described for Emulsion F2, except that dopant MC-29b was introduced at a total level of 0.32 mppm into the outer 93% to 95% of the grain volume.
• Emulsion F11 was precipitated as described for Emulsion F2, except that dopant MC-29c was introduced at a total level of 0.32 mppm into the outer 93% to 95% of the grain volume.
• Emulsion F12 was precipitated as described for Emulsion F2, except that dopant MC-42 was introduced at a total level of 0.32 mppm into the outer 93% to 95% of the grain volume.
• Emulsion F13 was precipitated as described for Emulsion F2, except that dopant MC-43 was introduced at a total level of 0.32 mppm into the outer 93% to 95% of the grain volume.
• Emulsion F14 was precipitated as described for Emulsion F2, except that dopant MC-14rr was introduced at a total level of 25 mppm into the outer 79.5% to 92% of the grain volume.
• Emulsion F15 was precipitated as described for Emulsion F2, except that dopant MC-14rr was introduced at a total level of 43.7 mppm into the outer 7.9% to 95% of the grain volume. Analysis of this emulsion by ICP-AES showed that, within experimental error, the incorporated Fe level was the same as in similarly prepared emulsions doped with the conventional dopant anion [Fe(CN)6]4 ⁇ .
• Emulsion F16 was precipitated as described for Emulsion F2, except that EDTA (CD-1) was introduced as a dopant at a total level of 43.7 mppm into the outer 7.9% to 95% of the grain volume. Analysis of this emulsion by ICP-AES showed that the Fe level was less than the detection limit of this technique (3 mppm Fe in AgCl).
• Emulsion F17 was precipitated as described for Emulsion F2, except that dopant Fe(EDTA)(CD-2) was introduced at a total level of 43.7 mppm into the outer 7.9% to 95% of the grain volume. Analysis of this emulsion by ICP-AES showed-that the Fe level was less than the detection limit of this technique (3 mppm Fe in AgCl).
• Emulsion F18 was precipitated as described for Emulsion F2, except that dopant [Fe(CN)6]4 ⁇ (CD-5) was introduced at a total level of 21.8 mppm into the outer 7.9% to 95% of the grain volume.
• Emulsion F19 was precipitated as described for Emulsion F2, except that dopant MC-14c was introduced through a third jet from a 0.1 molar aqueous KClO4 solution and at a total level of 43.7 mppm into the outer 7.9% to 95% of the grain volume.
• the emulsion was studied by EPR spectroscopy, and the results were as described above in Example 1.
• Emulsion F20 was precipitated as described for emulsion F2, except that dopant MC-41 was introduced at a total level of 21.8 mppm into the outer 7.9 to 95% of the grain volume. This emulsion was examined by EPR spectroscopy, as described in Example 1, in order to demonstrate the incorporation of organic ligands within the silver halide grain structure. Exposure of the emulsion F20 at between 180 and 240°K produced a distinct EPR spectrum, with well resolved iridium and chlorine hyperfine structure. The spectrum could unequivocally be assigned to an iridium (II) ion at a silver position in the silver halide lattice.
• II iridium
• Emulsion F21 was precipitated as described for emulsion F2, except that dopant MC-29a was introduced at a total level of 21.8 mppm into the outer 7.9 to 95% of the grain volume.
• the emulsion was examined by EPR spectroscopy, as described in Example 1. Exposure of emulsion F21 at 210°K produced a distinctive EPR spectrum with well resolved indium and chlorine hyperfine structure. The spectrum could unequivocally be assigned to an iridium (II) ion at a silver position the silver halide lattice.
• the resulting emulsions were each divided into several portions.
• portions designated portions (I) were chemically and spectrally sensitized by the addition of 30 mg/Ag mole of a colloidal dispersion of gold sulfide followed by digestion at 60°C for 30 minutes. Following digestion each portion I was cooled to 40° and 300 mg/mole of 1-(3-acetamidophenyl)-5-mercaptotetrazole were added and held for 10 minutes, followed by 20 mg/mole of red spectral sensitizing dye anhydro3-ethyl-9,11-neopentylene-3'-(3-sulfopropyl)thiadicarbocyanine hydroxide (Dye C) and a 20 minute hold.
• Dye C anhydro3-ethyl-9,11-neopentylene-3'-(3-sulfopropyl)thiadicarbocyanine hydroxide
• portions (Ia) were treated as for portions (I), except that no dye was added and the final 20 minute hold was eliminated.
• portions designated portions (II) were chemically and spectrally sensitized as described for portions (I), except that 50 rather than 30 mg/Ag mole of a colloidal dispersion of gold sulfide was added for each emulsion.
• portions designated portions (III) were chemically and spectrally sensitized by the addition of aurous bis(1,4,5,-triazolium-1,2,4- trimethyl-3-thiolate) tetrafluoroborate, at 5, 7.5 or 10 mg per silver mole and di(carboxymethyl)-dimethyl thiourea, at 0.75 mg per silver mole followed by heat digestion and antifoggant and dye addition as described for portions (I).
• Portions (IV) were chemically and spectrally sensitized by the addition of 8.4 mg/Ag mole of a colloidal dispersion of gold sulfide, followed by digestion at 30 minutes at 60°C. The emulsion was then treated as for portion I, except that 1.3 grams of KBr per silver mole were added prior to the dye addition.
• Sensitized portions (I, Ia, II and III) of the F series emulsions described above were coated onto cellulose acetate film support at 21.53 mg/dm2 silver chloride and 53.92 mg/dm2 gelatin.
• a gelatin overcoat layer comprised of 10.76 mg/dm2 gelatin and a hardener, bis(vinylsulfonylmethyl) ether, at a level of 1.5% by wt., based of total gelatin.
• Samples of these coated photographic elements were evaluated by exposure for 1/10 second to 365 nm radiation, followed by development for 12 minutes in Kodak DK-50 TM developer. Additionally, samples of the coatings were evaluated for reciprocity failure by giving them a series of calibrated (total energy) white light exposures ranging from 1/10,000th of a second to 10 seconds, followed by development as above.
• Sensitized portions (IV) of the F series emulsions described above were coated onto a photographic paper support at silver and gel levels of 1.83 and 8.3 mg/dm2, respectively.
• a gelatin overcoat containing 4.2 mg/dm2 of Coupler C1 and 1.5% by weight based on total gelatin of the hardener bis(vinylsulfonylmethyl) ether was applied over the emulsion.
• These coated photographic elements were evaluated by exposure for 1/10 second followed by development for 45 seconds in Kodak Ektacolor RA-4 TM developer.
• the coatings were evaluated for reciprocity by giving them a series of calibrated (total energy) white light exposures ranging from 1/10,000th of a second to 10 seconds, followed by development as above.
• Tables F-I, F-II and F-III high intensity reciprocity failure (HIRF) and low intensity reciprocity failure (LIRF) are reported as the difference between relative log speeds times 100 measured a minimum density plus 0.15 optical density obtained at exposures of 10 ⁇ 4 and 10 ⁇ 1 second for HIRF and 10 ⁇ 1 and 10 seconds for LIRF.
• ideal performance is for no speed difference--e.g., HIRF or LIRF are ideally zero or as near zero as attainable.
• Zero is the ideal difference.
• b Shoulder ⁇ density is the difference in density at a point 0.3 log E slow of the 1.0 optical density speed point for two equivalent exposures, the first of 0.1 sec duration and the second of 100 sec duration. Zero is the ideal difference.
• c Toe ⁇ density is the difference in density at a point 0.3 log E fast of the 1.0 optical density speed point for two equivalent exposures, the first of 0.1 sec duration and the second of 100 sec duration. Zero is the ideal difference.
• Tables F-I, F-II and F-III show significant reductions in HIRF to be produced by the incorporation as a grain dopant of iridium complexes containing an acetonitrile, pyridazine, thiazole or pyrazine ligand. Additionally these complexes are capable of significantly reducing LIRF.
• Substrate Emulsion S1 was prepared as follows: A reaction vessel containing 8.5 liters of a 2.8% by weight gelatin aqueous solution and 1.8 grams of 1,8-dihydroxy-3,6-dithiaoctane was adjusted to a temperature of 68.3°C, pH of 5.8 and a pAg of 7.35 by addition of NaCl solution. A 3.75 molar solution containing 1658.0 grams of AgNO3 in water and a 2.75 molar solution containing 570.4 grams of NaCl in water were simultaneously run into the reaction vessel with rapid stirring, each at a flow rate of 84 ml/min. The double jet precipitation continued for 31 minutes at a controlled pAg of 7.35. A total of 9.76 moles of silver chloride were precipitated, the silver chloride having a cubic morphology of 0.6 ⁇ m average cube length.
• Lippmann bromide carrier emulsions were prepared as a means of introducing the dopant complex into the emulsion grain during the chemical/spectral sensitization step.
• Undoped Lippmann control 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 AgNO3 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 L2 was prepared exactly as Emulsion L1, except a solution of 0.217 gram of [IrCl6]2 ⁇ (CD-3) 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 particle diameter emulsion.
• Emulsion L3 was prepared exactly as Emulsion L1, except a solution of 0.528 gram of MC-29a 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 particle diameter emulsion.
• Emulsion L4 was prepared exactly as Emulsion L1, except a solution of 0.488 gram of MC-31 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 particle diameter emulsion.
• Control Emulsion G1 was prepared as follows: A 50 millimole (mmole) sample of Emulsion S1 was heated to 40°C and spectrally sensitized by the addition of 14 milligrams (mg) 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 mmoles of Emulsion L1.
• Comparative and example emulsions were prepared as described for emulsion G1, except that the 0.45 mmole of Emulsion L1 used for emulsion G1 was replaced by equivalent amounts of a combination of emulsion L1 and emulsions L2, L3 or L4 as outlined in Table G-I.
• Table G-I Component Emulsions used in preparation of G Series Emulsions Emulsion Total amount of Lippmann Emulsion (mmole) Amount of L1 (mmole) Amount of L# (mmole) Dopant complex incorporated Nominal Dopant level in Epitaxy (mppm) G2a comp. 0.45 0.40 0.05, L2 CD-3 5 G2b comp.
• the emulsions were coated on a photographic paper support as disclosed in U.S. Patent 4,994,147 at 0.28 gram/m2 silver with 0.002 gram/m2 of 2,4-dihydroxy-4-methyl-1-piperidinocyclopenten-3-one and 0.02 gram/m2 of KCl and 1.08 gram/m2 yellow dye-forming coupler C2: to give a layer with 0.166 gram/m2 gelatin.
• a 1.1 gram/m2 gelatin protective overcoat 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, published by Eastman Kodak Co., 1990, the disclosure of which is here incorporated by reference.
• Speed is based on the light exposure required to obtain an optical density of 1.0.
• b Incubation ⁇ speed is the speed difference between a coating stored for 3 weeks at 49°C and 50% relative humidity conditions and a check coating stored at -18°C and 50% relative humidity conditions. Ideally the difference should be zero.
• a Heat sensitivity ⁇ measures the effect of temperature differences (40°C versus 20°C) at the time of exposure, taken as the difference in sensitometry.
• b Speed and Toe measured for a 0.1 sec exposure
• c Toe is the density of the sensitometric curve at an exposure scale value 0.3 log E less than that of the 1.0 optical density speed point.
• d Latent Image keeping Change is the effect of delay time between exposure and processing, taken as the (30′ vs. 30 ⁇ ) difference in sensitometry.
• Each of the emulsions in this series contained AgBr 95.9 I 4.1 tabular grains exhibiting a mean equivalent circular diameter of approximately 2.7 ⁇ m and a mean thickness of 0.13 ⁇ m.
• Emulsion H1 an undoped control emulsion, was prepared as follows: Solution A: gelatin (bone) 10 g NaBr 30 g H2O 5000 ml Solution B: 0.393N AgNO3 514 ml Solution C: 2N NaBr 359 ml Solution D: 0.1286N (NH4)2SO4 350 ml Solution E: 2.5N NaOH 40 ml Solution F: 4N HNO3 25ml Solution G: gelatin (bone) 140.14 g H2O add to 1820 ml Solution H: 2.709N NaBr 0.0413N KI Solution I: 2.75N AgNO3 4304 ml Solution J: 4.06N NaBr 720 ml Solution K: AgI 0.36 mole H2O 760 ml
• Solution A was added to a reaction vessel.
• the pH of the reaction vessel was adjusted to 6 at 40°C.
• the temperature was raised to 65°C and solutions B and C were added at rates of 64 ml/min and 15.3 ml/min, respectively for 1 min.
• Solutions D, E, F and G were then added consecutively.
• Solutions B and H were added at rates of 87 ml/min and 13.9 ml/min for 5 min while pAg was controlled at 9.07.
• Solution J and K were then added consecutively.
• Solution I was then added at a rate of 50 ml/min over 24 min and solution C was used to control the pAg at 8.17.
• the emulsion was cooled to 40°C, washed to reach a pAg of 8.06 and concentrated.
• Doped Emulsion H2 was prepared as described above, except that dopant MC-42 was introduced into the reaction vessel from an aqueous solution in the first part of step c. Dopant MC-42 was added in an amount needed to give a total dopant concentration of 0.025 mppm.
• Doped Emulsion H3 was prepared as described above, except that dopant MC-31 was introduced into the reaction vessel from an aqueous solution in the first part of step c. Dopant MC-31 was added in an amount needed to give a total dopant concentration of 0.013 mppm.
• Dope Emulsion H4 was prepared as described above, except that dopant MC-41 was introduced into the reaction vessel from an aqueous solution in the first part of step c. Dopant MC-41 was added in an amount needed to give a dopant concentration of 0.025 mppm.
• Samples of emulsions H1 to H3 were sensitized by melting at 40°C , adding NaSCN at 100 mg/Ag mole, adding benzothiazolium tetrafluoroborate finish modifier at 30 mg/Ag mole, adding green sensitizing dyes Dye E and Dye F in an amount sufficient to provide from 65%-80% monolayer dye coverage in a 3:1 molar ratio of Dye E:Dye F, adding gold sensitizer in the form of sodium aurous (I) dithiosulfate dihydrate at 1.75 mg/Ag mole, adding sulfur sensitizer in the form of sodium thiosulfate at 0.87 mg/Ag mole. This mixture was then brought to 60° C and held for 7 min. then chill set.
• Dye E was anhydro-5-chloro-9-ethyl-5'-phenyl-3'-(3-sulfobutyl)-3-(sulfopropyl)oxacarbocyanine hydroxide, sodium salt.
• Dye F was anhydro-6,6'-dichloro-1,1'-diethyl-3,3'-bis(3-sulfopropyl)-5,5'-bis(trifluoromethyl)benz-imidazole carbocyanine hydroxide, sodium salt.
• the sensitized emulsion was combined with a coupler melt made up to provide a coating lay down of 53.82 mg/dm2 gelatin, 21.53 mg/dm2 Ag, 7.5 mg/dm2 dye-forming coupler C3 and 1.75 g/Ag mole 5-methyl-s-triazole-[2-3-a]-pyrimidine-7-ol sodium salt onto a cellulose acetate photographic film support.
• the support had been previously coated with 3.44 mg/dm2 Ag for antihalation and a 24.4 mg/dm2 gelatin pad.
• the coupler containing emulsion layer was overcoated with 9.93 mg/dm2 gelatin and bis(vinylsulfonylmethyl)ether hardener at 1.75% by weight, based on gelatin.
• the coated photographic film samples were evaluated for reciprocity response by giving them a series of calibrated (total energy) exposures ranging from 1/10,000th of a second to 10 seconds, followed by development for 6 minutes in Kodak KRX TM developer, a hydroquinone-Elon TM (N-methyl- p -aminophenol hemisulfate) developer.
• the sensitized emulsion portions were combined with a coupler melt made up to provide a coating laydown of 32.29 mg/dm2, 10.76 mg/dm2 Ag, 9.69 mg/dm2 dye-forming coupler C4 onto a cellulose acetate photographic support.
• the support had been previously coated with 3.44 mg/dm2 Ag for antihalation and a 24.4 mg/dm2 gelatin pad.
• the coupler containing emulsion layer was overcoated with 9.93 mg/dm2 gelatin and bis-(vinylsulfonylmethyl) ether hardener at 1.75% by weight, based on gelatin.
• the coated photographic film samples were evaluated for reciprocity response by giving them a series of calibrated (total energy) exposures ranging from 1/100,000th of a second to 1 second, followed by development for 2 minutes 15 seconds in Kodak Flexicolor C-41 TM developer.
• the emulsions prepared for comparison in this example series were silver bromide regular octahedra that were doped by pAg cycling to produce a thin shell of doped silver bromide on the surface of the host grains.
• Emulsion I1 A monodispersed one ⁇ m edge-length octahedral AgBr emulsion was prepared by the double-jet technique described in Example series A, modified to produce the larger grain size by the presence of 500 mppm of the ripening agent 1,10-dithia-4,7,13,16-tetraoxacyclooctadecane in the reaction vessel at the start of precipitation.
• the pAg of the emulsion, measured at 40 O C was increased from 8.2 to 9.8 by the addition of 1.5 mole % NaBr (aq).
• the dopant salt was added from dilute aqueous solution in the amounts described in Table I-I.
• the emulsion was held at 40 O C for 15 minutes.
• Aqueous AgNO3 was added in the amount of 1.5 mole %.
• the emulsion was held 15 minutes and then chilled. This procedure was designed to bury the dopant complex within a thin shell of AgBr.
• the emulsion resulting from the above procedure was coated at 26.9 mg/dm2 Ag and 75.35 mg/dm2 gelatin on a cellulose acetate photographic film support.
• the resulting photographic element was exposed for 1/10th second to a 5500°K color temperature light source through a graduated density filter and developed for 12 minutes in Kodak Rapid X-Ray TM developer, a hydroquinone-ElonTM (N-methyl- p -aminophenol hemisulfate) developer.
• 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 o C, pH of 5.8 and a pAg of 7.51 by addition of a NaCl solution. A 2 M solution of AgNO3 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 o C, pH of 5.8 and pAg of 7.35 by addition of NaCl solution. A 3.75 M solution of AgNO3 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 o C. A 4 M solution of AgNO3 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 o C. A 1.35 M solution of AgNO3 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.
• Substrate Emulsion E-I were precipitated as described for substrate Emulsion A, except that the appropriate iridium containing dopant for Emulsions 11b-11f in Table 11-I, respectively, was introduced at a total of 0.28 mppm (mole part per million) into the outer 93% to 95% of the grain volume. A shell of pure silver chloride (5% of the grain volume) was then precipitated to cover the doped band.
• Control Emulsion 11a was prepared as follows: a 0.3 mole sample of substrate Emulsion A was heated to 40 o C and chemically and spectrally sensitized by the addition of a colloidal dispersion of gold sulfide followed by digestion at 65 o C, addition of 1-(3-acetamidophenyl)-5-mercaptotetrazole and KBr. The portion was then cooled to 40 o C, and red spectral sensitizing dye Dye C was added.
• Emulsions 11b-11f were prepared as Emulsion 11a, except that substrate Emulsions E-I were used in place of Emulsion A.
• the emulsions were coated on paper support using sizing methods disclosed in U.S. Patent 4,994,147. Specifically, they were coated at 0.18 gram/m2 silver, 0.422 gram/m2 cyan-dye forming coupler C1, and with 0.166 gram/m2 gelatin. A gelatin protective overcoat layer 1.1 grams/m2 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, published by Eastman Kodak Co., 1990, the disclosure of which is here incorporated by reference. After processing, the Status A reflection densities of each coating were measured.
• Sensitivity (speed) of the coatings is taken as the reciprocal of the relative amount of light in LogE x 100 to produce a 1.0 optical density, where E is exposure in lux-seconds.
• Emulsion 12 was precipitated as described for substrate Emulsion A, except that MC-54 was introduced at a total level of 50 mppm into 3.5-95% of the grain volume. This emulsion was examined by EPR spectroscopy, in order to demonstrate the incorporation of organic ligands within the silver halide grain structure.
• Emulsion 12 Exposure of Emulsion 12 to above-bandgap light at 140°K produced a distinctive EPR spectrum.
• the spectrum could unequivocally be assigned to an iridium (II) ion in the silver halide lattice.
• 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.
• 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 13a 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.
• Emulsion L1 This was followed by the addition of 0.45 mmole of Emulsion L1.
• Emulsion 13a was prepared and sensitized exactly as Emulsion 13a, except that 0.045 mmole of Emulsion 15 and 0.405 mmole of Emulsion L1 were added during the sensitization process instead of 0.45 mmole of Emulsion L1 alone.
• Emulsion 13b was prepared and sensitized exactly as Emulsion 13a, 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.
• Emulsions 13b and 13c 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/m2 silver with 0.002 gram/m2 of 2,4-dihydroxy-4-methyl-1-piperidinocyclopenten-3-one, 0.02 gram/m2 of KCl, 0.78 mg/m2 of potassium p-tolylsulfonate, 7.8 mg/m2 of sodium p-tolylsulfinate, 1.08 grams/m2 yellow dye-forming coupler C2, and with 0.166 gram/m2 gelatin.
• a gelatin protective overcoat layer 1.1 grams/m2 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.
• Table 13-I The photographic parameters obtained for these emulsions are shown in Table 13-I.
• the results in Table 13-I demonstrate that emulsions with epitaxial regions doped with MC-41 have improved reciprocity and heat sensitivity performance.
• Speed HIRF is taken as the speed difference of equivalent exposures (intensity x time) of 0.031 and 0.5 sec duration. Zero is the ideal.
• c Heat Sensitivity Delta Speed measures the effect of temperature differences (40 C versus 20 C) at the time of exposure, taken as the difference in sensitometry. Zero is the ideal.
• 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 sensitizing dye Dye D.
• Emulsions 14b, 14c and 14d were prepared and sensitized exactly as Emulsion 14a, except that 0.003 micromole of MC-41, MC-29a, MC-31, respectively, were added prior to the addition of KBr during the finishing operation.
• Table 14-I The photographic parameters obtained for these emulsions are shown in Table 14-I.
• the results in Table 14-I demonstrate that emulsions with epitaxial regions doped with coordination complexes containing iridium and either a thiazole or pyrazine ligand have improved reciprocity performance.
• Table 14-I Emuls. # Dopant Complex/Solution Addition Nominal Dopant Level (mppm) Speed for a 2 sec.
• Speed HIRF b (0.01 ⁇ -2.0 ⁇ ) 14a none 0 184 -14 14b MC-41 0.01 183 -11 14c MC-29a 0.01 147 -4 14d MC-31 0.01 169 -12
• Speed is taken as the reciprocal of the relative amount of light (LogE x 100) required to obtain an optical density of 1.0.
• Speed HIRF is taken as the speed difference of equivalent exposures (intensity x time) of 0.31 and 2.0 sec duration. Zero is the ideal.
• Examples 15-19 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 15a 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 o C.
• Emulsions 15b, 15c and 15d were prepared and sensitized exactly as Emulsion 15a, 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 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 0.78 ⁇ m average edgelength.
• the emulsion was optimally sensitized by the addition of a colloidal suspension of gold sulfide and heat treated at 60 o 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 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 0.30 ⁇ m average edgelength. The emulsion was optimally sensitized by the addition of green sensitizing 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% TiO2, and 3% ZnO white pigment.
• the layers were hardened with bis(vinylsulfonylmethyl)ether at 1.95% of the total gelatin weight.
• 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 15-I.
• b Speed LIRF is taken as the speed difference of equivalent exposures (intensity x time) of 0.5 and 128 sec duration. Zero is the ideal.
• c Speed HIRF is taken as the speed difference of equivalent exposures (intensity x time) of 0.031 and 0.5 sec duration. Zero is the ideal.
• d Delta toe density is the difference in density at a point 0.3 log E fast of the 1.0 optical density speed point for two equivalent exposures, the first of 0.5 sec duration and the second of 128 sec duration. Zero is the ideal difference.
• Example 15 was repeated, except that the Layer 3, the green sensitive layer, was replaced with alternate green sensitive layer I.
• Example 15 was repeated, except that the Layer 3, the green sensitive layer, was replaced with alternate green sensitive layer II.
• Example 15 was repeated, except that the Layer 3, the green sensitive layer, was replaced with alternate green sensitive layer III.
• Example 15 was repeated, except that the Layer 3, the blue sensitive layer, was replaced with alternate blue sensitive layer I.
• Example 15 was repeated, except that the Layer 3, the blue sensitive layer, was replaced with alternate blue sensitive layer II.
• Control Emulsion 21a 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 21b, 21c and 21d were prepared and sensitized exactly as Emulsion 21a, except that 3.7, 11.1, and 22.2 micromoles of K2IrCl6 (CD-3), respectively; were added prior to the KBr addition during the finishing operation. Doped epitaxial regions were thereby produced.
• Emulsions 21e, 21f and 21g were prepared and sensitized exactly as Emulsion 21a, except that 3.7, 11.1, and 22.2 micromoles of K2IrCl5(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 15.
• the sensitometric response of the red sensitive layers containing the doped epitaxial emulsions of the invention are shown in Table 21-I.
• b Speed LIRF is taken as the speed difference of equivalent exposures (intensity x time) of 0.5 and 128 sec duration. Zero is the ideal.
• c Latent Image Keeping (LIK) change is the effect of delay time between exposure and processing, taken as the (5′ vs. 30 ⁇ ) difference in sensitometry. Zero is the ideal.
• Control Emulsion 22a 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 22b, 22c and 22d were prepared and sensitized exactly as Emulsion 22a, except that 3.7, 11.2, and 22.4 micromoles of K2IrCl6 (CD-3), respectively; were added prior to the KBr addition during the finishing operation. Doped epitaxial regions were thereby produced.
• Emulsions 22e, 22f and 22g were prepared and sensitized exactly as Emulsion 22a, except that 3.7, 11.2, and 22.4 micromoles of K2IrCl5(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 15.
• the sensitometric response of the red sensitive layers containing the doped epitaxial emulsions of the invention are shown in Table 22-I Table 22-I Emuls. # Dopant Complex Nominal Dopant Level (mppm) Speed for a 0.5 ⁇ exp.
• b Speed LIRF is taken as the speed difference of equivalent exposures (intensity x time) of 0.5 and 512 sec duration. Zero is the ideal.
• c Latent Image Keeping (LIK) change is the effect of delay time between exposure and processing, taken as the (5′ vs. 30 ⁇ ) difference in sensitometry. Zero is the ideal.
• Table 21-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 K2IrCl6 doped control, the emulsions of the invention have improved reciprocity, speed LIK and contrast LIK performance.
• Control Emulsion 23a 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 23b and 23c were prepared and sensitized exactly as Emulsion 23a, except that 0.8 and 9.2 micromoles of K2IrCl6 (CD-3), respectively; were added prior to the KBr addition during the finishing operation. Doped epitaxial regions were thereby produced.
• Emulsions 23d and 23e were prepared and sensitized exactly as Emulsion 23a, except that 0.8 and 9.2 micromoles of K2IrCl5(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 15, 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).
• the coatings were evaluated as described in Example 15 above.
• the sensitometric response of the blue sensitive layers containing the doped epitaxial emulsions of the invention are shown in Table 23-I.
• a Speed LIRF (0.5 ⁇ -512 ⁇ ) b Heat Sensitivity Speed c 23a none 0 140 -28 -3.1 23b CD-3 0.08 137 -24 -2.8 23c CD-3 0.92 103 -5 3.5 23e MC-41 0.08 134 -20 -0.8 23f MC-41 0.92 110 1 -0.6
• Speed is taken as the reciprocal of the relative amount of light (LogE x 100) required to obtain an optical density of 1.0.
• b Speed LIRF is taken as the speed difference of equivalent exposures (intensity x time) of 0.5 and 512 sec duration. Zero is the ideal.
• c Heat sensitivity delta speed measures the effect of temperature differences (40 o C vs. 20 o C) at the time of exposure (128 sec), taken as the difference in sensitometry.
• Control Emulsion 24a 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 24b, 24c and 24d were prepared and sensitized exactly as Emulsion 24a, except that 0.8, 4.6 and 9.2 micromoles of K2IrCl6 (CD-3), respectively; were added prior to the Lippmann bromide addition during the finishing operation. Doped epitaxial regions were thereby produced.
• Emulsions 24e, 24f and 24g were prepared and sensitized exactly as Emulsion 24a, except that 0.8, 4.6 and 9.2 micromoles of K2IrCl5(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 23.
• the sensitometric response of the blue sensitive layers containing the doped epitaxial emulsions of the invention are shown in Table 24-I.
• b Speed LIRF is taken as the speed difference of equivalent exposures (intensity x time) of 0.5 and 512 sec duration. Zero is the ideal.
• c Latent Image Keeping (LIK) change is the effect of delay time between exposure and processing, taken as the (5′vs. 30 ⁇ ) difference in sensitometry. Zero is the ideal.
• Control Emulsion 25a 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 25b-h were prepared and sensitized exactly as Emulsion 25a, except that 0.126 micromole of the dopant complex listed in Table 25-I for these emulsions were added prior to the addition of KBr during the finishing operation.
• Table 25-I The photographic parameters obtained for these emulsions are shown in Table 25-I.
• Table 25-I demonstrate that emulsions with epitaxial regions doped with coordination complexes containing iridium and either a thiazole derivative or pyrazine derivative ligand have improved reciprocity performance.
• Table 25-I Emuls. # Dopant Complex/Solution addition Nominal Dopant Level (mppm) Contrast HIRF-delta toe dens. a (.02-2 ⁇ ) Contrast LIRF-delta toe dens.
• b Delta toe density is the difference in density at a point 0.3 log E fast of the 1.0 optical density speed point for two equivalent exposures, the first of 2 sec duration and the second of 100 sec duration. Zero is the ideal difference.
• c Speed HIRF is taken as the speed difference of equivalent exposures (intensity x time) of 0.02 and 2 sec duration. Zero is the ideal.
• Control Emulsion 26a 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 26b-d were prepared and sensitized exactly as Emulsion 26a, except that 0.126 micromole of the dopant complex listed in Table 26-I for these emulsions were added prior to the addition of KBr during the finishing operation.
• Table 26-I The photographic parameters obtained for these emulsions are shown in Table 26-I.
• the results in Table 26-I demonstrate that emulsions with epitaxial regions doped with coordination complexes containing iridium and either a thiazole derivative or pyrazine derivative ligand have improved reciprocity performance.
• Control Emulsion 27a 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 27b and 27c were prepared and sensitized exactly as Emulsion 27a, except that 0.126 micromole of the dopant complex listed in Table 27-I for these emulsions were added prior to the addition of KBr during the finishing operation.
• Control Emulsion 28a 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 28b was prepared and sensitized exactly as Emulsion 28a, except that the dopant complex listed in Table 28-I for these emulsions were added prior to the addition of KBr during the finishing operation.
• Control Emulsion 29a 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 29b and 29c prepared and sensitized exactly as Emulsion 29a, except that 0.31 micromoles of K2IrCl6 (CD-3) and K2IrCl5(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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