US5320938A — High chloride tabular grain emulsions and process…

Claim 1

Independent Claim 69 words

A radiation sensitive emulsion comprised of a dispersing medium and silver halide grains, wherein at least 50 percent of total grain projected area is accounted for by tabular grains (1) bounded by {100} major faces having adjacent edge ratios of less than 10, (2) each having an aspect ratio of at least 2, and (3) internally at their nucleation site containing iodide and at least 50 mole percent chloride.

Claim 2

Dependent Claim 69 words

A radiation sensitive emulsion comprised of a dispersing medium and silver halide grains, wherein at least 50 percent of total grain projected area is accounted for by tabular grains (1) bounded by {100} major faces having adjacent edge ratios of less than 10, (2) each having an aspect ratio of at least 2, and (3) internally at their nucleation site containing iodide and at least 50 mole percent chloride.

Claim 3

Dependent Claim 21 words

A radiation sensitive emulsion according to claim 1 wherein the tabular grains have an average aspect ratio of at least 5.

Claim 4

Dependent Claim 33 words

A radiation sensitive emulsion according to claim 1 wherein the tabular grains accounting for at least 50 percent of total grain projected area have adjacent major face edge ratios of less than 5.

Claim 5

Dependent Claim 21 words

A radiation sensitive emulsion according to claim 1 wherein at least the tabular grains contain at least 70 mole percent chloride.

Claim 6

Dependent Claim 17 words

A radiation sensitive emulsion according to claim 1 wherein the tabular grains contain a transition metal dopant.

Claim 7

Dependent Claim 15 words

A radiation sensitive emulsion according to claim 5 wherein the transition metal dopant is iridium.

Claim 8

Dependent Claim 25 words

A radiation sensitive emulsion according to claim 6 wherein iridium is incorporated in the emulsion in an amount sufficient to reduce low intensity reciprocity failure.

Claim 9

Dependent Claim 23 words

A radiation sensitive emulsion according to claim 7 wherein the emulsion contains from 1×10 -9 to 1×10 -6 mole per silver mole iridium.

Claim 10

Dependent Claim 23 words

A radiation sensitive emulsion according to claim 8 wherein the emulsion contains from 1×10 -8 to 1×10 -7 mole per silver mole iridium.

Claim 11

Dependent Claim 29 words

A radiation sensitive emulsion according to claim 1 wherein the emulsion is sensitized with at least one sensitizer chosen from the class consisting of sulfur, selenium and gold sensitizers.

Claim 12

Dependent Claim 18 words

A radiation sensitive emulsion according to claim 1 wherein the emulsion contains at least one spectral sensitizing dye.

Claim 13

Dependent Claim 109 words

A radiation sensitive emulsion comprised of a dispersing medium and silver halide grains which are at least in part tabular silver halide grains bounded by {100} major faces wherein, of the tabular grains bounded by {100} major faces a portion accounting for 50 percent of total grain projected area selected on the criteria of adjacent major face edge ratios of less than 10 and thicknesses of less than 0.3 μm and having higher aspect ratios than any remaining tabular grains satisfying these criteria (1) have an average aspect ratio of greater than 8 and (2) internally at their nucleation site contain iodide and at least 50 mole percent chloride.

Claim 14

Dependent Claim 109 words

A radiation sensitive emulsion comprised of a dispersing medium and silver halide grains which are at least in part tabular silver halide grains bounded by {100} major faces wherein, of the tabular grains bounded by {100} major faces a portion accounting for 50 percent of total grain projected area selected on the criteria of adjacent major face edge ratios of less than 10 and thicknesses of less than 0.3 μm and having higher aspect ratios than any remaining tabular grains satisfying these criteria (1) have an average aspect ratio of greater than 8 and (2) internally at their nucleation site contain iodide and at least 50 mole percent chloride.

Claim 15

Dependent Claim 25 words

A radiation sensitive emulsion according to claim 12 wherein the selected portion of the tabular grains have an average aspect ratio of greater than 12.

Claim 16

Dependent Claim 26 words

A radiation sensitive emulsion according to claim 12 wherein the selected portion of the tabular grains have adjacent major face edge ratios of less than 2.

Claim 17

Dependent Claim 27 words

A radiation sensitive emulsion according to claim 12 wherein the selected portion of the tabular grains are thin tabular grains having thicknesses of less than 0.2 μm.

Claim 18

Dependent Claim 27 words

A radiation sensitive emulsion according to claim 12 wherein the selected portion of the tabular grains are ultrathin tabular grains having thicknesses of less than 0.06 μm.

Claim 19

Dependent Claim 25 words

A radiation sensitive emulsion according to claim 12 wherein at least the selected portion of the tabular grains contain at least 90 mole percent chloride.

Claim 20

Dependent Claim 22 words

A radiation sensitive emulsion according to claim 12 wherein at least the selected portion of the tabular grains are silver iodochloride grains.

Claim 21

Dependent Claim 20 words

A radiation sensitive emulsion according to claim 12 wherein the emulsion is gold sensitized and contains a benzothiazolium salt stabilizer.

Claim 22

Dependent Claim 18 words

A radiation sensitive emulsion according to claim 12 wherein the emulsion contains gold sulfide as a chemical sensitizer.

Claim 23

Dependent Claim 37 words

A radiation sensitive emulsion according to claim 1 or 12 wherein the tabular grains internally contain transition metal ion dopants and performance modifying ion dopants capable of forming coordination complex ligands with the transition metal ion dopants.

Claim 24

Dependent Claim 18 words

A radiation sensitive emulsion according to claim 21 wherein the performance modifying ion dopant is a cyano ion.

Claim 25

Dependent Claim 23 words

A radiation sensitive emulsion according to claim 22 wherein the cyano ion and the transition metal ion dopant together form a hexacoordination complex.

Claim 26

Dependent Claim 21 words

A radiation sensitive emulsion according to claim 23 wherein the transition metal ion dopant is a period 4 metal ion dopant.

Claim 27

Dependent Claim 15 words

A radiation sensitive emulsion according to claim 24 wherein the transition metal ion dopant is

Claim 28

Dependent Claim 23 words

A radiation sensitive emulsion according to claim 23 wherein the transition metal ion dopant is a period 5 or 6 metal ion dopant.

Claim 29

Dependent Claim 21 words

A radiation sensitive emulsion according to claim 26 wherein the transition metal ion is chosen from groups 8, 9 and 10.

Claim 30

Dependent Claim 51 words

A radiation sensitive emulsion according to claim 26 wherein the dopants are introduced in the form of a hexacoordination complex satisfying the formula: [M(CN).sub.6-y L.sub.y ].sup.m where M is rhenium, ruthenium or osmium, L is a bridging ligand, y is zero, 1 or 2, and m is -2, -3 or -4.

Claim 31

Dependent Claim 20 words

A radiation sensitive emulsion according to claim 21 wherein the performance modifying ion dopant is a nitrosyl or thionitrosyl dopant.

Claim 32

Dependent Claim 57 words

A radiation sensitive emulsion according to claim 29 wherein the grains are formed in the presence of a hexacoordination complex satisfying the formula: [M'L.sub.4 (NY)L'].sup.n where M' is a transition metal ion dopant, L is a bridging ligand, L' is L or (NY), Y is oxygen or sulfur, and n is zero, -1, -2 or 31 3.

Claim 33

Dependent Claim 43 words

A radiation sensitive emulsion according to claim 30 wherein M' is chromium, rhenium, ruthenium, osmium or iridium and L and L' are one or a combination of halogen and cyano ligands or a combination of these ligands with up to two aquo ligands.

Claim 34

Dependent Claim 45 words

A radiation sensitive emulsion according to claim 1 or 12 wherein the tabular grains internally contain on average at least one pair of metal ions chosen from groups 8, 9 and 10 and periods 5 and 6 at adjacent cation sites in their crystal lattice.

Claim 35

Dependent Claim 30 words

A radiation sensitive emulsion according to claim 32 wherein on average the metal ions occupy at least five pairs of adjacent cation lattice sites within each of the tabular grains.

Claim 36

Dependent Claim 30 words

A radiation sensitive emulsion according to claim 33 wherein on average the metal ions occupy at least ten pairs of adjacent cation lattice sites within each of the tabular grains.

Claim 37

Dependent Claim 15 words

A radiation sensitive emulsion according to claim 32 wherein the metal ions are iridium ions.

Claim 38

Dependent Claim 152 words

A radiation sensitive emulsion according to claim 1 or 12 wherein the emulsion contains a photographic stabilizer that protects the emulsion against changes in sensitivity and fog upon aging, the stabilizer being chosen from one or a combination of the following: (A) a mercapto heterocyclic nitrogen compound containing a mercapto group bonded to a carbon atom which is linked to an adjacent nitrogen atom in a heterocyclic ring system, (B) a quaternary aromatic chalcogenazolium salt wherein the chalcogen is sulfur, selenium or tellurium, (C) a triazole or tetrazole containing an ionizable hydrogen bonded to a nitrogen atom in a heterocyclic ring system, (D) a dichalcogenide compound comprising an --X--X-- linkage between carbon atoms wherein each X is divalent sulfur, selenium or tellurium, (E) an organic compound containing a thiosulfonyl group having the formula --SO 2 SM where M is a proton or cation, (F) a mercuric salt, or (G) a quinone compound.

Claim 39

Dependent Claim 39 words

A radiation sensitive emulsion according to claim 36 wherein the photographic stabilizer is a mercapto heterocyclic nitrogen compound containing a mercapto group bonded to a carbon atom which is linked to an adjacent nitrogen atom in a heterocyclic ring.

Claim 40

Dependent Claim 15 words

A radiation sensitive emulsion according to claim 37 wherein the photographic stabilizer is a 5-mercaptotetrazole.

Claim 41

Dependent Claim 15 words

A radiation sensitive emulsion according to claim 38 wherein the photographic stabilizer is an aryl-5-mercaptotetrazole.

Claim 42

Dependent Claim 15 words

A radiation sensitive emulsion according to claim 39 wherein the photographic stabilizer is a phenyl-5-mercaptotetrazole.

Claim 43

Dependent Claim 14 words

A radiation sensitive emulsion according to claim 40 wherein the photographic stabilizer is 1-(3-acetamidophenyl)-5-mercaptotetrazole.

Claim 44

Dependent Claim 14 words

A radiation sensitive emulsion according to claim 40 wherein the photographic stabilizer is 1-(3-ureidophenyl)-5-mercaptotetrazole.

Claim 45

Dependent Claim 26 words

A radiation sensitive emulsion according to claim 36 wherein the photographic stabilizer is a quaternary aromatic chalcogenazolium salt wherein the chalcogen is sulfur, selenium or tellurium.

Claim 46

Dependent Claim 20 words

A radiation sensitive emulsion according to claim 43 wherein the photographic stabilizer is a benzothiazolium salt or a benzoselenazolium salt.

Claim 47

Dependent Claim 32 words

A radiation sensitive emulsion according to claim 36 wherein the photographic stabilizer is a triazole or a tetrazole containing an ionizable hydrogen bonded to a nitrogen atom in a heterocyclic ring system.

Claim 48

Dependent Claim 18 words

A radiation sensitive emulsion according to claim 45 wherein the photographic stabilizer is a benzotriazole or a tetraazaindene.

Claim 49

Dependent Claim 32 words

A radiation sensitive emulsion according to claim 36 wherein the stabilizer is a dichalcogenide compound comprising an --X--X-- linkage between carbon atoms wherein each X is a divalent sulfur, selenium or tellurium.

Claim 50

Dependent Claim 13 words

A radiation sensitive emulsion according to claim 47 wherein each X is selenium.

Claim 51

Dependent Claim 156 words

A process of preparing silver halide emulsions in which tabular grains of less than 0.3 μm in thickness exhibiting {100} major faces with adjacent edge ratios of less than 10 account for at least 50 percent of total grain projected area and internally at their nucleation site contain iodide and at least 50 mole percent chloride, comprised of the steps of (1) introducing silver and halide salts and a dispersing medium into a continuous double jet reactor so that nucleation of the tabular grains occurs in the presence of iodide with chloride accounting for at least 50 mole percent of the halide present in the dispersing medium and the pCl of the dispersing medium being maintained in the range of from 0.5 to 3.5 and (2) following nucleation completing grain growth in a reaction vessel which receives emulsion from the continuous double jet reactor under conditions that maintain the {100} major faces of the tabular grains.

Claim 52

Dependent Claim 156 words

A process of preparing silver halide emulsions in which tabular grains of less than 0.3 μm in thickness exhibiting {100} major faces with adjacent edge ratios of less than 10 account for at least 50 percent of total grain projected area and internally at their nucleation site contain iodide and at least 50 mole percent chloride, comprised of the steps of (1) introducing silver and halide salts and a dispersing medium into a continuous double jet reactor so that nucleation of the tabular grains occurs in the presence of iodide with chloride accounting for at least 50 mole percent of the halide present in the dispersing medium and the pCl of the dispersing medium being maintained in the range of from 0.5 to 3.5 and (2) following nucleation completing grain growth in a reaction vessel which receives emulsion from the continuous double jet reactor under conditions that maintain the {100} major faces of the tabular grains.

Claim 53

Dependent Claim 18 words

A process according to claim 49 wherein bromide ion is present in the dispersing medium following grain nucleation.

Claim 54

Dependent Claim 59 words

A process according to claim 49 wherein grain nucleation is undertaken in the presence of halide ions consisting essentially of chloride and iodide ions with the pCl of the dispersing medium being in the range of from 1.0 to 3.0 and a gelatino peptizer being present having a methionine content of less than 30 micromoles per gram of peptizer.

Claim 55

Dependent Claim 58 words

A process according to claim 51 wherein grain nucleation is undertaken in the presence of halide ions consisting essentially of chloride and iodide ions with the pCl of the dispersing medium being in the range of from 1.5 to 2.5 and a gelatino peptizer being present having a methionine content of less than micromoles per gram of peptizer.

Claim 56

Dependent Claim 23 words

A process according to claim 49 wherein silver and halide salt solutions are introduced into the dispersing medium during grain nucleation and growth.

Claim 57

Dependent Claim 31 words

A process according to claim 53 wherein the addition of the silver and halide salt solutions is suspended after grain nucleation to allow Ostwald ripening of grain nuclei and then resumed.

Claim 58

Dependent Claim 21 words

A process according to claim 54 wherein chloride and iodide salt solutions are introduced into the dispersing medium during grain nucleation.

Claim 59

Dependent Claim 42 words

A process according to claim 55 wherein bromide salt solution is introduced into the dispersing medium after salt solution introduction is resumed after the addition of the silver and halide salt solutions has been suspended to allow Ostwald ripening of grain nuclei.

Claim 60

Dependent Claim 26 words

A process according to claim 49 wherein grain growth is continued until said portion of the tabular grains have an average tabularity of greater than 25.

Claim 61

Dependent Claim 23 words

A process according to claim 49 wherein a silver halide ripening agent is introduced into the dispersing medium in the growth reaction vessel.

Claim 62

Dependent Claim 13 words

A process according to claim 58 wherein the ripening agent is a thioether.

Claim 63

Dependent Claim 13 words

A process according to claim 59 wherein the thioether is a crown thioether.

Claim 64

Dependent Claim 13 words

A process according to claim 58 wherein the ripening agent is a thiocyanate.

Claim 65

Dependent Claim 12 words

A process according to claim 58 wherein the ripening agent is methionine.

Claim 66

Dependent Claim 17 words

A process according to claim 58 wherein the ripening agent contains a primary or secondary amino moiety.

Claim 67

Dependent Claim 15 words

A process according to claim 63 wherein the ripening agent is an imidazole ripening agent.

Claim 68

Dependent Claim 13 words

A process according to claim 63 wherein the ripening agent is a glycine.

Claim 69

Dependent Claim 28 words

A process according to claim 49 wherein bromide ion in a concentration of from 0.5 to 15 mole percent is present in the reaction vessel during grain growth.

Claim 70

Dependent Claim 28 words

A process according to claim 66 wherein bromide ion in a concentration of from 1 to 10 mole percent is present in the reaction vessel during grain growth.

Claim 71

Dependent Claim 30 words

A process according to claim 49 wherein iodide ion in a concentration of from 0.001 to less than 1 mole percent is present in the reaction vessel during grain growth.

Claim 72

Dependent Claim 18 words

A process according to claim 49 wherein precipitation occurs in a pH range of from 2.0 to 8.0.

Claim 73

Dependent Claim 16 words

A process according to claim 69 wherein precipitation occurs at a pH of less than 7.0.

Claim 74

Dependent Claim 18 words

A process according to claim 70 wherein precipitation occurs in a pH range of from 2.0 to 5.0.

Claim 75

Dependent Claim 35 words

A process according to claim 49 wherein precipitation occurs in the presence of a mild oxidizing agent chosen from the class consisting of a mercuric salt, an alkali tetrahaloaurate and an elemental sulfur releasing compound.

Claim 76

Dependent Claim 237 words

A process of preparing a radiation sensitive emulsion containing a dispersing medium and silver halide grains, wherein at least 50 percent of total grain projected area is accounted for by tabular grains (1) bounded by {100}major faces having adjacent edge ratios of less than 10, (2) each having an aspect ratio of at least 2, (3) containing on average at least one pair of metal ions chosen from groups 8, 9 and 10, periods 5 and 6, at adjacent cation sites in their crystal lattice, and (4) internally at their nucleation site containing iodide and at least 50 mole percent chloride are prepared by the steps comprised of (a) introducing silver and halide salts into a dispersing medium so that nucleation of the tabular grains occurs in the presence of iodide with chloride accounting for at least 50 mole percent of the halide present in the dispersing medium and the pCl of the dispersing medium being maintained in the range of from 0.5 to 3.5, (b) following nucleation completing grain growth under conditions that maintain the {100} major faces of the tabular grains, and (c) during at least one of steps (a) and (b) introducing into the dispersing medium oligomers of group 8, 9 or 10, period 5 or 6, metal, wherein each oligomer contains at least two metal ions and on average at least two metal ions are incorporated in each grain in adjacent cation sites.

Claim 77

Dependent Claim 237 words

A process of preparing a radiation sensitive emulsion containing a dispersing medium and silver halide grains, wherein at least 50 percent of total grain projected area is accounted for by tabular grains (1) bounded by {100}major faces having adjacent edge ratios of less than 10, (2) each having an aspect ratio of at least 2, (3) containing on average at least one pair of metal ions chosen from groups 8, 9 and 10, periods 5 and 6, at adjacent cation sites in their crystal lattice, and (4) internally at their nucleation site containing iodide and at least 50 mole percent chloride are prepared by the steps comprised of (a) introducing silver and halide salts into a dispersing medium so that nucleation of the tabular grains occurs in the presence of iodide with chloride accounting for at least 50 mole percent of the halide present in the dispersing medium and the pCl of the dispersing medium being maintained in the range of from 0.5 to 3.5, (b) following nucleation completing grain growth under conditions that maintain the {100} major faces of the tabular grains, and (c) during at least one of steps (a) and (b) introducing into the dispersing medium oligomers of group 8, 9 or 10, period 5 or 6, metal, wherein each oligomer contains at least two metal ions and on average at least two metal ions are incorporated in each grain in adjacent cation sites.

Claim 78

Dependent Claim 18 words

A process according to claim 73 wherein bromide ion is present in the dispersing medium following grain nucleation.

Claim 79

Dependent Claim 59 words

A process according to claim 73 wherein grain nucleation is undertaken in the presence of halide ions consisting essentially of chloride and iodide ions with the pCl of the dispersing medium being in the range of from 1.0 to 3.0 and a gelatino peptizer being present having a methionine content of less than 30 micromoles per gram of peptizer.

Claim 80

Dependent Claim 59 words

A process according to claim 75 wherein grain nucleation is undertaken in the presence of halide ions consisting essentially of chloride and iodide ions with the pCl of the dispersing medium being in the range of from 1.5 to 2.5 and a gelatino peptizer being present having a methionine content of less than 12 micromoles per gram of peptizer.

Claim 81

Dependent Claim 24 words

A process according to claim 73 wherein said oligomers each provide from 2 to 20 of the group 8, 9 or 10 metal ions.

Claim 82

Dependent Claim 24 words

A process according to claim 77 wherein said oligomers each provide from 6 to 10 of the group 8, 9 or 10 metal ions.

Claim 83

Dependent Claim 37 words

A process according to claim 73 wherein the oligomers are introduced into the face centered cubic crystal lattice structure as anionic hexacoordination complexes consisting essentially of the group 8, 9 or 10 metal ions and bridging ligands.

Claim 84

Dependent Claim 13 words

A process according to claim 79 wherein the bridging ligands are halide ions.

Claim 85

Dependent Claim 48 words

A process according to claim 79 wherein the anionic hexacoordination complexes are selected from among those satisfying the formulae: M.sub.2 L.sub.10 M.sub.6 L.sub.24 M.sub.8 L.sub.32 and M.sub.10 L.sub.38 where M represents a group 8, 9 or 10, period 5 or 6, element and L represents a bridging ligand.

Claim 86

Dependent Claim 14 words

A process according to claim 81 wherein L is chosen from among halide ligands.

Claim 87

Dependent Claim 10 words

A process according to claim 81 wherein M is iridium.

Claim 88

Dependent Claim 21 words

A process according to claim 73 wherein at least five group 8, 9 or 10 metal ions are introduced per grain.

Claim 89

Dependent Claim 21 words

A process according to claim 84 wherein at least ten group 8, 9 or 10 metal ions are introduced per grain.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1997-06-13	1997-12-13	1998-06-14	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	2001-06-13	2001-12-13	2002-06-14	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2005-06-13	2005-12-13	2006-06-14	$7700.00	Window Closed / Lapsed

High chloride tabular grain emulsions and processes for their preparation

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