EP0616255B1 - Elément photographique en couleurs à basse teneur d'argent et procédé de formation d'une image en couleurs - Google Patents

Elément photographique en couleurs à basse teneur d'argent et procédé de formation d'une image en couleurs Download PDF

Info

Publication number
EP0616255B1
EP0616255B1 EP94200669A EP94200669A EP0616255B1 EP 0616255 B1 EP0616255 B1 EP 0616255B1 EP 94200669 A EP94200669 A EP 94200669A EP 94200669 A EP94200669 A EP 94200669A EP 0616255 B1 EP0616255 B1 EP 0616255B1
Authority
EP
European Patent Office
Prior art keywords
silver
grain
emulsion
dye image
color photographic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94200669A
Other languages
German (de)
English (en)
Other versions
EP0616255A1 (fr
Inventor
John Arthur c/o Kodak Limited Bee
Peter Douglas C/O Kodak Limited Marsden
Joe Edward C/O Eastman Kodak Company Maskasky
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kodak Ltd
Eastman Kodak Co
Original Assignee
Kodak Ltd
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB939305578A external-priority patent/GB9305578D0/en
Application filed by Kodak Ltd, Eastman Kodak Co filed Critical Kodak Ltd
Publication of EP0616255A1 publication Critical patent/EP0616255A1/fr
Application granted granted Critical
Publication of EP0616255B1 publication Critical patent/EP0616255B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • G03C1/0051—Tabular grain emulsions
    • G03C1/0053—Tabular grain emulsions with high content of silver chloride
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3017—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials with intensification of the image by oxido-reduction
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX 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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03594—Size of the 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
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/047—Proteins, e.g. gelatine derivatives; Hydrolysis or extraction products of proteins
    • G03C2001/0478—Oxidising agent
    • 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
    • G03C2200/01—100 crystal face

Definitions

  • the invention is directed color photographic elements containing silver halide emulsions and to processes for producing dye images.
  • tabular grain equivalent circular diameter ECD
  • t tabular grain thickness
  • tabular grain emulsions from those that contain only incidental tabular grain inclusions it is also the recognized practice of the art to require that a significant percentage (e.g., greater than 30 percent and more typically greater than 50 percent) of total grain projected area be accounted for by tabular grains having an aspect ratio of at least 2 and more typically an average aspect ratio of at least 5.
  • tabular grain emulsions satisfying grain thickness ( t ), aspect ratio ( ECD/t ), and projected area aims have been formed by introducing two or more parallel twin planes into octahedral grains during their preparation.
  • Regular octahedral grains are bounded by ⁇ 111 ⁇ crystal faces.
  • the predominant feature of tabular grains formed by twinning are opposed parallel ⁇ 111 ⁇ major crystal faces.
  • the major crystal faces have a three fold symmetry, typically appearing triangular or hexagonal.
  • Patent 4,063,951 Mignot U.S. Patent 4,386,156, EP-A-0 584 815 and EP-A-0 534 395, both documents do not belong to the state-of-the-art by virtue of Article 54(2)EPC, disclose high chloride tabular grain emulsions, wherein the grains exhibit ⁇ 100 ⁇ crystal faces.
  • Redox amplification processing From time to time interest has been expressed in redox amplification processing to produce dye images in color photographic elements containing silver halide emulsions.
  • the principal advantage of redox amplification processing is that lower silver coverages can be employed in construction of the color photographic elements.
  • Redox amplification processing and color photographic elements particularly structured for such processing are disclosed by Research Disclosure, Vol. 308, December 1989, Item 308119, Section XIX, Sub-sections G and H. Research Disclosure is published by Kenneth Mason Publications, Ltd., Dudley House, 12 North St., Emsworth, Hampshire P010 7DQ, England.
  • High chloride silver halide grains prefer grain forms having ⁇ 100 ⁇ crystallographic faces--e.g., cubic and, less commonly, cubo-octahedral forms.
  • the grains Prior to the present invention in those instances in which redox amplification processing has been undertaken employing high chloride emulsions the grains have typically been high chloride cubic grains.
  • the present invention is directed to a color photographic element containing a dye image forming layer unit comprised of at least one silver halide emulsion and a dye image providing compound characterized in that total silver in the dye image forming layer unit is less than 200 mg/m 2 and the emulsion contains a silver halide grain population comprised of at least 50 mole percent chloride, based on total silver forming the grain population, and greater than 30 percent of the grain population projected area is accounted for by tabular grains each having an aspect ratio of at least 2, a mean thickness of less than 0.3 ⁇ m, and parallel major faces lying in ⁇ 100 ⁇ crystallographic planes.
  • this invention is directed to a process of producing a dye image in an imagewise exposed color photographic element, containing a dye image forming layer unit comprised of at least one silver halide emulsion and a dye image providing compound, by developing the silver halide emulsion to produce silver imagewise and employing the developed silver to catalyze the reaction of an oxidizing agent and a reducing agent that are inert to oxidation-reduction interaction in the absence of developed silver, and reacting oxidized reducing agent with the dye image providing compound to form the dye image, characterized in that total silver in the dye image forming layer units is less than 200 mg/m 2 and the emulsion contains a silver halide grain population comprised of at least 50 mole percent chloride, based on total silver forming the grain population, and greater than 30 percent of the grain population projected area is accounted for by tabular grains each having an aspect ratio of at least 2, a mean thickness of less than 0.3 ⁇ m, and parallel major faces lyihg in ⁇ 100 ⁇
  • the present invention offers a combination of advantages not previously realized.
  • Employing tabular grain emulsions realizes the known advantages, including improved sensitivity and increased image sharpness of these emulsions.
  • By employing high aspect ratio tabular grains that are high chloride grains the advantages of more rapid processing and improved environmental compatibility of spent processing solutions are realized.
  • By employing high chloride tabular grains having major faces lying in ⁇ 100 ⁇ crystallographic planes tabular grains (hereinafter referred to as ⁇ 100 ⁇ tabular grains) have been provided that are inherently more stable than ⁇ 111 ⁇ tabular grains.
  • the ⁇ 100 ⁇ tabular grains show no tendency to revert to nontabular forms, thereby eliminating any necessity of resorting to adsorbed grain shape stabilizers employed in combination with high chloride ⁇ 111 ⁇ tabular grains.
  • the extremely low levels of total silver typical of redox amplification processing can be combined with the remaining advantages to achieve color photographic elements and redox amplification processing and systems that are superior to those that have heretofore been available within the art.
  • the color photographic elements of the invention have the capability of producing dye images with lower levels of granularity than have heretofore been realized in producing dye images by redox amplification imaging using high chloride emulsions.
  • the color photographic elements also have the capability of producing dye images of conventional quality employing lower levels of total silver than have been employed using high chloride emulsions. Finally, despite the known higher covering power of tabular grains, the color photographic elements can be employed to form retained dye images without bleaching. This offers advantages in silver coverages, in simplifying processing and in improving the environmental compatibility of spent processing solutions.
  • a color photographic element satisfying the requirements of the invention can be constructed as follows:
  • the support ( S ) can be either a transmissive or reflective support and can take any conventional form, such as any of the forms disclosed in Research Disclosure, Item 308119, cited above, Section XVII.
  • the support is preferably a transparent film support, preferably provided with a processing solution removable or decolorizable antihalation backing layer, not shown.
  • the support is preferably a reflective support of the type found in a conventional photographic print.
  • the protective overcoat ( OC ) is a preferred, but non-essential feature provided to protect physically the underlying layer units from physical damage during handling and processing.
  • the protective overcoat is a transparent layer preferably constructed of a photographic vehicle of type disclosed in Research Disclosure, Item 308119, cited above, Section IX, and typically contains one or more of the following: coating aids, such as those disclosed in Section XI; plasticizers and/or lubricants, such as those disclosed in Section XII; antistatic agents, such as those disclosed in Section XIII; and matting agents, such as those disclosed in Section XVI.
  • the magenta ( M ) dye image forming layer unit is coated farthest from the support to receive first imagewise exposing light.
  • the magenta dye image forming layer unit contains at least one silver halide emulsion.
  • the emulsion is most typically a green sensitized emulsion and preferably contains high chloride grains to minimize blue light contamination of the record of green light exposure formed by this emulsion layer.
  • the cyan ( C ) dye image forming layer unit is located to receive imagewise exposing light after it has passed through the magenta dye image forming layer unit.
  • the emulsion is most typically a red sensitized emulsion and preferably contains high chloride grains to minimize blue light contamination of the record of red light exposure formed by this emulsion layer.
  • the yellow ( Y ) dye image forming layer unit is typically blue-sensitized and is coated nearest the support, since the human eye is least sensitive to this image. Hence the lower image sharpness during exposure received by this dye image forming layer unit afforded by this coating location can be best accommodated with less perceived image degradation.
  • the yellow dye image forming layer unit record preferably contains high chloride grains, but for an entirely different reason than the remaining dye image forming layer units. Since processing solutions must penetrate both of the overlying dye image forming layer units to reach the yellow dye image forming layer unit, the selection of high chloride grains, which can be processed more rapidly, for this layer unit offsets this disadvantage. Blue sensitization is relied upon to offset the low native blue sensitivity of the high chloride grains in the yellow dye image forming layer unit.
  • each dye image providing compound can be blended with the emulsion or emulsions within the layer unit or coated in a contiguously adjacent layer.
  • the interlayers ( IL ) contain conventional oxidized developing agent scavengers to prevent inter-unit migration of oxidized developing agent during process that would otherwise produce color contamination of the layer unit dye images.
  • conventional yellow filter materials are necessarily absent from the interlayers, but in the remaining coating sequences yellow filter materials can be present in any inter-layer underlying the blue sensitized dye image forming layer unit.
  • the six dye image forming layer unit sequences described above are exemplary of numerous known dye image forming layer unit sequences.
  • Kofron et al U.S. Patent 4,439,520 discloses a variety of dye image forming layer unit sequences made possible by providing plural dye image layer units responsive to the same region of the spectrum.
  • one or any combination of the dye image forming layer units can be sensitized to a different portion of the spectrum, including one or more portions of the spectrum that lie outside the visible--e.g., the near ultraviolet and the near infrared.
  • At least three dye image forming layer units are required. However, for specific photographic applications only two or even one dye image forming layer unit is sufficient to provide the dye image required. For example, for forming color separation images a single dye image forming layer unit per element is sufficient. For the simplest multicolor imaging at least two dye image forming layer units are required.
  • the color photographic elements of the invention contain less than 400 mg/m 2 of total silver, preferably less than 220 mg/m 2 and optimally less than 170 mg/m 2 .
  • Each dye image forming layer unit whether employed singly or in combination, contains less than 200 mg/m 2 of total silver, preferably less than 133 mg/m 2 , most preferably less than 110 mg/m 2 and optimally less than 85 mg/m 2 .
  • the color photographic elements preferably contain at least 30 mg/m 2 total silver and most preferably at least 40 mg/m 2 total silver.
  • the total silver in the color photographic element can be proportionately reduced.
  • a minimum of 1 mg/m 2 of silver is preferred, a minimum of 10 mg/m 2 of silver is most preferred and a minimum of at least 20 mg/m 2 of silver is generally optimum.
  • the color photographic elements of the invention contain at least one high chloride ⁇ 100 ⁇ tabular grain emulsion in at least one dye image forming layer unit.
  • a high chloride ⁇ 100 ⁇ tabular grain emulsion is present in each dye image forming layer unit, and optimally each of the emulsions is a high chloride ⁇ 100 ⁇ tabular grain emulsion.
  • the remaining emulsions can take any conventional form known to be useful in redox amplification imaging. In a specifically preferred form they are high chloride cubic or cubo-octahedral grain emulsions.
  • they are tabular grain silver bromide or iodobromide emulsions. It is also possible to employ high chloride ⁇ 100 ⁇ tabular grain emulsions in combination with high chloride ⁇ 111 ⁇ tabular grain emulsions; however, since high chloride ⁇ 100 ⁇ tabular grain emulsions can satisfy the same application requirements as high chloride ⁇ 111 ⁇ tabular grain emulsions and offer the additional advantage of inherent grain shape stability, it is specifically preferred that all high chloride tabular grain emulsions employed be high chloride ⁇ 100 ⁇ tabular grain emulsions.
  • the incorporation of blended emulsions in the dye image forming layer units is specifically contemplated to achieve known adjustments of imaging characteristics. It is, however, generally preferred that the high chloride emulsion or emulsions present in a dye image forming layer be the sole latent image forming emulsion or emulsions present.
  • the high chloride ⁇ 100 ⁇ tabular grain emulsions incorporated within the color photographic elements and in the processes of the invention each contain a silver halide grain population comprised of at least 50 mole percent chloride, based on total silver forming the grain population, and greater than 30 percent of the grain population projected area is accounted for by tabular grains each having an aspect ratio of at least 2, a thickness of less than 0.3 ⁇ m, and parallel major faces lying in ⁇ 100 ⁇ crystallographic planes.
  • the highest conveniently attainable proportion of total grain projected area be accounted for by high chloride ⁇ 100 ⁇ tabular grains having an aspect ratio of at least 2 and a thickness of less than 0.3 ⁇ m, hereinafter referred to as the selected high chloride ⁇ 100 ⁇ tabular grain population.
  • the selected high chloride ⁇ 100 ⁇ tabular grain population preferably accounts for at least 50 percent, most preferably at least 70 percent and optimally at least 90 percent of the total high chloride grain population present within a dye image forming layer unit.
  • the selected high chloride ⁇ 100 ⁇ tabular grain population preferably exhibits an average aspect ratio of at least 5 and most preferably at least 8.
  • ECD maximum useful average of a photographic emulsion
  • the average aspect ratio of the tabular grains just exceeds 33.3.
  • the high chloride ⁇ 100 ⁇ tabular grains are selected on the basis of a preferred thickness of less than 0.2 ⁇ m (the thickness criterion for thin tabular grains)
  • the average aspect ratio rises to greater than 50.
  • an optimum tabular grain thickness of less than 0.1 ⁇ m average aspect ratios can range in excess of 100.
  • high chloride ⁇ 100 ⁇ tabular grains can form the selected tabular grain population.
  • Ultrathin, less than 0.07 ⁇ m in thickness, high chloride ⁇ 100 ⁇ tabular grain populations satisfying the above projected areas can be prepared.
  • maximum average ECD's rarely exceed 6 ⁇ m and more commonly are less than 4 ⁇ m.
  • average aspect ratios of from 5 to 100 and more commonly from 8 to 50 are typical of the selected high chloride ⁇ 100 ⁇ tabular grain populations contemplated for use in the practice of the invention.
  • the high chloride ⁇ 100 ⁇ tabular grain emulsions containing at least 50 mole percent chloride and less than 2 mole percent iodide, with any remaining halide being bromide.
  • Silver chloride, iodochloride, bromochloride, iodobromochloride and bromoiodochloride emulsions are specifically contemplated.
  • the high chloride ⁇ 100 ⁇ tabular grains are internally free of iodide and most preferably internally free of iodide at the grain nucleation site. When the grains are nucleated in the absence of iodide, pure silver chloride ⁇ 100 ⁇ tabular grains can be produced. Emulsions of this type can be produced by the precipitation techniques taught by Maskasky U.S. Patent 5,264,337, cited above. Further descriptions of the preparation of emulsions of this type are provided in the examples and in the discussion that follows.
  • An alternative approach is to nucleate the high chloride ⁇ 100 ⁇ tabular grains in the presence of iodide.
  • grain nucleation occurs in a high chloride environment in the presence of iodide ion under conditions that favor the emergence of ⁇ 100 ⁇ crystal faces.
  • iodide ion the inclusion of iodide into the cubic crystal lattice being formed by silver ions and the remaining halide ions is disruptive because of the much larger diameter of iodide ion as compared to chloride ion.
  • the incorporated iodide ions introduce crystal irregularities that in the course of further grain growth result in tabular grains rather than regular (cubic) grains.
  • a reaction vessel containing a dispersing medium and conventional silver and reference electrodes for monitoring halide ion concentrations within the dispersing medium.
  • Halide ion is introduced into the dispersing medium that is at least 50 mole percent chloride--i.e., at least half by number of the halide ions in the dispersing medium are chloride ions.
  • the pCl of the dispersing medium is adjusted to favor the formation of ⁇ 100 ⁇ grain faces on nucleation--that is, within the range of from 0.5 to 3.5, preferably within the range of from 1.0 to 3.0 and, optimally, within the range of from 1.5 to 2.5.
  • the grain nucleation step is initiated when a silver jet is opened to introduce silver ion into the dispersing medium.
  • Iodide ion is preferably introduced into the dispersing medium concurrently with or, optimally, before opening the silver jet.
  • Effective tabular grain formation can occur over a wide range of iodide ion concentrations ranging up to the saturation limit of iodide in silver chloride.
  • the saturation limit of iodide in silver chloride is reported by H. Hirsch, "Photographic Emulsion Grains with Cores: Part I. Evidence for the Presence of Cores", J . of Photog. Science, Vol. 10 (1962), pp. 129-134, to be 13 mole percent.
  • iodide grains in which equal molar proportions of chloride and bromide ion are present up to 27 mole percent iodide, based on silver, can be incorporated in the grains. It is preferred to undertake grain nucleation and growth below the iodide saturation limit to avoid the precipitation of a separate silver iodide phase and thereby avoid creating an additional category of unwanted grains. It is generally preferred to maintain the iodide ion concentration in the dispersing medium at the outset of nucleation at less than 10 mole percent. In fact, only minute amounts of iodide at nucleation are required to achieve the desired tabular grain population. Initial iodide ion concentrations of down to 0.001 mole percent are contemplated. However, for convenience in replication of results, it is preferred to maintain initial iodide concentrations of at least 0.01 mole percent and, optimally, at least 0.05 mole percent.
  • silver iodochloride grain nuclei are formed during the nucleation step. Minor amounts of bromide ion can be present in the dispersing medium during nucleation. Any amount of bromide ion can be present in the dispersing medium during nucleation that is compatible with at least 50 mole percent of the halide in the grain nuclei being chloride ions.
  • the grain nuclei preferably contain at least 70 mole percent and optimally at least 90 mole percent chloride ion, based on silver.
  • Grain nuclei formation occurs instantaneously upon introducing silver ion into the dispersing medium.
  • silver ion introduction during the nucleation step is preferably extended for a convenient period, typically from 5 seconds to less than a minute. So long as the pCl remains within the ranges set forth above no additional chloride ion need be added to the dispersing medium during the nucleation step. It is, however, preferred to introduce both silver and halide salts concurrently during the nucleation step.
  • the advantage of adding halide salts concurrently with silver salt throughout the nucleation step is that this permits assurance that any grain nuclei formed after the outset of silver ion addition are of essentially similar halide content as those grain nuclei initially formed.
  • Iodide ion addition during the nucleation step is particularly preferred. Since the deposition rate of iodide ion far exceeds that of the other halides, iodide will be depleted from the dispersing medium unless replenished.
  • Silver ion is preferably introduced as an aqueous silver salt solution, such as a silver nitrate solution.
  • Halide ion is preferably introduced as alkali or alkaline earth halide, such as lithium, sodium and/or potassium chloride, bromide and/or iodide.
  • the dispersing medium contained in the reaction vessel prior to the nucleation step is comprised of water, the dissolved halide ions discussed above and a peptizer.
  • the dispersing medium can exhibit a pH within any convenient conventional range for silver halide precipitation, typically from 2 to 8. It is preferred, but not required, to maintain the pH of the dispersing medium on the acid side of neutrality (i.e., ⁇ 7.0). To minimize fog a preferred pH range for precipitation is from 2.0 to 5.0.
  • Mineral acids such as nitric acid or hydrochloride acid, and bases, such as alkali hydroxides, can be used to adjust the pH of the dispersing medium. It is also possible to incorporate pH buffers.
  • the peptizer can take any convenient conventional form known to be useful in the precipitation of photographic silver halide emulsions and particularly tabular grain silver halide emulsions.
  • a summary of conventional peptizers is provided in Research Disclosure, Item 308119, cited above, Section IX. While synthetic polymeric peptizers of the type disclosed by Maskasky I, cited above and here incorporated by reference, can be employed, it is preferred to employ gelatino peptizers (e.g., gelatin and gelatin derivatives).
  • gelatino peptizers e.g., gelatin and gelatin derivatives.
  • gelatino peptizers typically contain significant concentrations of calcium ion, although the use of deionized gelatino peptizers is a known practice.
  • peptizers are low methionine gelatino peptizers (i.e., those containing less than 30 micromoles of methionine per gram of peptizer), optimally less than 12 micromoles of methionine per gram of peptizer.
  • the grain growth modifiers of the type taught for inclusion in the emulsions of Maskasky I and II are not appropriate for inclusion in the dispersing media, since these grain growth modifiers promote twinning and the formation of tabular grains having ⁇ 111 ⁇ major faces.
  • adenine e.g., adenine
  • the grain growth modifiers promote twinning and the formation of tabular grains having ⁇ 111 ⁇ major faces.
  • at least about 10 percent and typically from 20 to 80 percent of the dispersing medium forming the completed emulsion is present in the reaction vessel at the outset of the nucleation step. It is conventional practice to maintain relatively low levels of peptizer, typically from 10 to 20 percent of the peptizer present in the completed emulsion, in the reaction vessel at the start of precipitation.
  • the concentration of the peptizer in the dispersing medium be in the range of from 0.5 to 6 percent by weight of the total weight of the dispersing medium at the outset of the nucleation step. It is conventional practice to add gelatin, gelatin derivatives and other vehicles and vehicle extenders to prepare emulsions for coating after precipitation. Any naturally occurring level of methionine can be present in gelatin and gelatin derivatives added after precipitation is complete.
  • the nucleation step can be performed at any convenient conventional temperature for the precipitation of silver halide emulsions. Temperatures ranging from near ambient--e.g., 30°C up to about 90°C are contemplated, with nucleation temperatures in the range of from 35 to 70°C being preferred.
  • a grain growth step follows the nucleation step in which the grain nuclei are grown until tabular grains having ⁇ 100 ⁇ major faces of a desired average ECD are obtained.
  • the objective of the nucleation step is to form a grain population having the desired incorporated crystal structure irregularities
  • the objective of the growth step is to deposit additional silver halide onto (grow) the existing grain population while avoiding or minimizing the formation of additional grains. If additional grains are formed during the growth step, the polydispersity of the emulsion is increased and, unless conditions in the reaction vessel are maintained as described above for the nucleation step, the additional grain population formed in the growth step will not have the desired tabular grain properties described herein for use in the invention.
  • the process of preparing emulsions can be performed as a single jet precipitation without interrupting silver ion introduction from start to finish.
  • a spontaneous transition from grain formation to grain growth occurs even with an invariant rate of silver ion introduction, since the increasing size of the grain nuclei increases the rate at which they can accept silver and halide ion from the dispersing medium until a point is reached at which they are accepting silver and halide ions at a sufficiently rapid rate that no new grains can form.
  • single jet precipitation limits halide content and profiles and generally results in more polydisperse grain populations.
  • the emulsions are held within the temperature ranges described herein for nucleation for a period sufficient to allow reduction in grain dispersity.
  • a holding period can range from a minute to several hours, with typical holding periods ranging from 5 minutes to an hour.
  • relatively smaller grain nuclei are Ostwald ripened onto surviving, relatively larger grain nuclei, and the overall result is a reduction in grain dispersity.
  • the rate of ripening can be increased by the presence of a ripening agent in the emulsion during the holding period.
  • a conventional simple approach to accelerating ripening is to increase the halide ion concentration in the dispersing medium. This creates complexes of silver ions with plural halide ions that accelerate ripening.
  • ripening can be accelerated and the percentage of the grain population projected area accounted for by ⁇ 100 ⁇ tabular grains can be increased by employing conventional ripening agents.
  • Preferred ripening agents are sulfur containing ripening agents, such as thioethers.
  • Typical thioether ripening agents are disclosed by McBride U.S. Patent 3,271,157, Jones U.S. Patent 3,574,628 and Rosencrantz et al U.S. Patent 3,737,313. More recently crown thioethers have been suggested for use as ripening agents.
  • Ripening agents containing a primary or secondary amino moiety, such as imidazole, glycine or a substituted derivative, are also effective. Sodium sulfite has been demonstrated to be effective in increasing the percentage of total grain projected area accounted by the ⁇ 100 ⁇ tabular grains.
  • grain growth can proceed according to any convenient conventional precipitation technique for the precipitation of silver halide grains bounded by ⁇ 100 ⁇ grain faces.
  • iodide and chloride ions are required to be incorporated into the grains during nucleation and are therefore present in the completed grains at the internal nucleation site, any halide or combination of halides known to form a cubic crystal lattice structure can be employed during the growth step.
  • iodide nor bromide ions need be incorporated in the grains during the growth step, since the irregular grain nuclei faces that result in tabular grain growth, once introduced, persist during subsequent grain growth independently of the halide being precipitated, provided the halide or halide combination is one that forms a cubic crystal lattice.
  • silver bromide or silver iodobromide When silver bromide or silver iodobromide is being deposited during the growth step, it is preferred to maintain a pBr within the dispersing medium in the range of from 1.0 to 4.2, preferably 1.6 to 3.4.
  • a pBr When silver chloride, silver iodochloride, silver bromochloride or silver iodobromochloride is being deposited during the growth step, it is preferred to maintain the pCl within the dispersing medium within the ranges noted above in describing the nucleation step.
  • both silver and halide salts are preferably introduced into the dispersing medium.
  • double jet precipitation is contemplated, with added iodide salt, if any, being introduced with the remaining halide salt or through an independent jet.
  • the rate at which silver and halide salts are introduced is controlled to avoid renucleation--that is, the formation of a new grain population. Addition rate control to avoid renucleation is generally well known in the art, as illustrated by Wilgus German OLS No. 2,107,118, Irie U.S. Patent 3,650,757, Kurz U.S. Patent 3,672,900, Saito U.S. Patent 4,242,445 and Wey "Growth Mechanism of AgBr Crystals in Gelatin Solution", Photographic Science and Engineering, Vol. 21, No. 1, Jan./Feb. 1977, p. 14, et seq.
  • the nucleation and growth stages of grain precipitation occur in the same reaction vessel. It is, however, recognized that grain precipitation can be interrupted, particularly after completion of the nucleation stage. Further, two separate reaction vessels can be substituted for the single reaction vessel described herein.
  • the nucleation stage of grain preparation can be performed in an upstream reaction vessel (herein also termed a nucleation reaction vessel) and the dispersed grain nuclei can be transferred to a downstream reaction vessel in which the growth stage of grain precipitation occurs (herein also termed a growth reaction vessel).
  • an enclosed nucleation vessel can be employed to receive and mix reactants upstream of the growth reaction vessel, as illustrated by Posse et al U.S.
  • peptizers that exhibit reduced adhesion to grain surfaces.
  • low methionine gelatin of the type disclosed by Maskasky II is less tightly absorbed to grain surfaces than gelatin containing higher levels of methionine.
  • Further moderated levels of grain adsorption can be achieved with so-called “synthetic peptizers"--that is, peptizers formed from synthetic polymers.
  • the maximum quantity of peptizer compatible with limited coalescence of grain nuclei is, of course, related to the strength of adsorption to the grain surfaces.
  • Dopants in concentrations of up to 10 -2 mole per silver mole and typically less than 10 -4 mole per silver mole, can be present in the grains.
  • Compounds of metals such as copper, thallium, lead, mercury, bismuth, zinc, cadmium, rhenium, and Group VIII metals (e.g., iron, ruthenium, rhodium, palladium, osmium, iridium and platinum) can be present during grain precipitation, preferably during the growth stage of precipitation.
  • the modification of photographic properties is related to the level and location of the dopant within the grains.
  • the ligands can also be included within the grains and the ligands can further influence photographic properties.
  • Coordination ligands such as halo, aquo, cyano cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl ligands are contemplated and can be relied upon to modify photographic properties.
  • Patent 3,790,390 Ohkubo et al U.S. Patent 3,890,154; Iwaosa et al U.S. Patent 3,901,711; Habu et al U.S. Patent 4,173,483; Atwell U.S. Patent 4,269,927; Janusonis et al U.S. Patent 4,835,093; McDugle et al U.S. Patents 4,933,272, 4,981,781, and 5,037,732; Keevert et al U.S. Patent 4,945,035; and Evans et al U.S. Patent 5,024,931.
  • B. H. Carroll "Iridium Sensitization: A Literature Review", Photographic Science and Engineering, Vol. 24, NO. 6, Nov./Dec. 1980, pp. 265-257, and Grzeskowiak et al published European Patent Application 264 288.
  • a further procedure that can be employed to maximize the population of high chloride ⁇ 100 ⁇ tabular grains is to incorporate an agent capable of restraining the emergence of non- ⁇ 100 ⁇ grain crystal faces in the emulsion during its preparation.
  • the restraining agent when employed, can be active during grain nucleation, during grain growth or throughout precipitation.
  • Useful restraining agents under the contemplated conditions of precipitation are organic compounds containing a nitrogen atom with a resonance stabilized ⁇ electron pair. Resonance stabilization prevents protonation of the nitrogen atom under the relatively acid conditions of precipitation.
  • Aromatic resonance can be relied upon for stabilization of the ⁇ electron pair of the nitrogen atom.
  • the nitrogen atom can either be incorporated in an aromatic ring, such as an azole or azine ring, or the nitrogen atom can be a ring substituent of an aromatic ring.
  • the restraining agent can satisfy the following formula: where Z represents the atoms necessary to complete a five or six membered aromatic ring structure, preferably formed by carbon and nitrogen ring atoms.
  • Preferred aromatic rings are those that contain one, two or three nitrogen atoms.
  • Specifically contemplated ring structures include 2H-pyrrole, pyrrole, imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, 1,3,5-triazole, pyridine, pyrazine, pyrimidine, and pyridazine.
  • Selection of preferred restraining agents and their useful concentrations can be accomplished by the following selection procedure:
  • the compound being considered for use as a restraining agent is added to a silver chloride emulsion consisting essentially of cubic grains with a mean grain edge length of 0.3 ⁇ m.
  • the emulsion is 0.2 M in sodium acetate, has a pCl of 2.1, and has a pH that is at least one unit greater than the pKa of the compound being considered.
  • the emulsion is held at 75°C with the restraining agent present for 24 hours.
  • the compound introduced is performing the function of a restraining agent.
  • the significance of sharper edges of intersection of the ⁇ 100 ⁇ crystal faces lies in the fact that grain edges are the most active sites on the grains in terms of ions reentering the dispersing medium.
  • the restraining agent is acting to restrain the emergence of non- ⁇ 100 ⁇ crystal faces, such as are present, for example, at rounded edges and corners.
  • Optimum restraining agent activity occurs when the new grain population is a tabular grain population in which the tabular grains are bounded by ⁇ 100 ⁇ major crystal faces.
  • the emulsions used in this invention can be chemically sensitized with active gelatin as illustrated by T. H. James, The Theory of the Photographic Process, 4th Ed., Macmillan, 1977, pp. 67-76, or with sulfur, selenium, tellurium, gold, platinum, palladium, iridium, osmium, rhenium or phosphorus sensitizers or combinations of these sensitizers, (particularly combinations of sulfur with gold or selenium), such as at pAg levels of from 5 to 10, pH levels of from 5 to 8 and temperatures of from 30 to 80°C, as illustrated by Research Disclosure, Vol. 120, April, 1974, Item 12008, Research Disclosure, Vol.
  • Patent 3,984,249 by low pAg (e.g., less than 5), high pH (e.g., greater than 8) treatment, or through the use of reducing agents such as stannous chloride, thiourea dioxide, polyamines and amineboranes as illustrated by Allen et al U.S. Patent 2,983,609, Oftedahl et al Research Disclosure, Vol. 136, August, 1975, Item 13654, Lowe et al U.S. Patents 2,518,698 and 2,739,060, Roberts et al U.S. Patents 2,743,182 and '183, Chambers et al U.S. Patent 3,026,203 and Bigelow et al U.S. Patent 3,361,564.
  • reducing agents such as stannous chloride, thiourea dioxide, polyamines and amineboranes as illustrated by Allen et al U.S. Patent 2,983,609, Oftedahl et al Research Disclosure,
  • Chemical sensitization can take place in the presence of spectral sensitizing dyes as described by Philippaerts et al U.S. Patent 3,628,960, Kofron et al U.S. Patent 4,439,520, Dickerson U.S. Patent 4,520,098, Maskasky U.S. Patent 4,435,501, Ihama et al U.S. Patent 4,693,965 and Ogawa U.S. Patent 4,791,053. Chemical sensitization can be directed to specific sites or crystallographic faces on the silver halide grain as described by Haugh et al U.K. Patent Application 2,038,792A and Mifune et al published European Patent Application 302 528.
  • the sensitivity centers resulting from chemical sensitization can be partially or totally occluded by the precipitation of additional layers of silver halide using such means as twin-jet additions or pAg cycling with alternate additions of silver and halide salts as described by Morgan U.S. Patent 3,917,485, Becker U.S. Patent 3,966,476 and Research Disclosure, Vol. 181, May, 1979, Item 18155.
  • the chemical sensitizers can be added prior to or concurrently with the additional silver halide formation. Chemical sensitization can take place during or after halide conversion as described by Hasebe et al published European Patent Application 273 404.
  • epitaxial deposition onto selected tabular grain sites e.g., edges or corners
  • epitaxial deposition onto selected tabular grain sites can either be used to direct chemical sensitization or to itself perform the functions normally performed by chemical sensitization.
  • the emulsions used in the invention can be spectrally sensitized with dyes from a variety of classes, including the polymethine dye class, which includes the cyanines, merocyanines, complex cyanines and merocyanines (i.e., tri-, tetra- and polynuclear cyanines and merocyanines), styryls, merostyryls, streptocyanines, hemicyanines, arylidenes, allopolar cyanines and enamine cyanines.
  • the polymethine dye class which includes the cyanines, merocyanines, complex cyanines and merocyanines (i.e., tri-, tetra- and polynuclear cyanines and merocyanines), styryls, merostyryls, streptocyanines, hemicyanines, arylidenes, allopolar cyanines and enamine cyanines.
  • the cyanine spectral sensitizing dyes include, joined by a methine linkage, two basic heterocyclic nuclei, such as those derived from quinolinium, pyridinium, isoquinolinium, 3H-indolium, benzindolium, oxazolium, thiazolium, selenazolinium, imidazolium, benzoxazolium, benzothiazolium, benzoselenazolium, benzotellurazolium, benzimidazolium, naphthoxazolium, naphthothiazolium, naphthoselenazolium, naphtotellurazolium, thiazolinium, dihydronaphthothiazolium, pyrylium and imidazopyrazinium quaternary salts.
  • two basic heterocyclic nuclei such as those derived from quinolinium, pyridinium, isoquinolinium, 3H-indolium, benzin
  • the merocyanine spectral sensitizing dyes include, joined by a methine linkage, a basic heterocyclic nucleus of the cyanine-dye type and an acidic nucleus such as can be derived from barbituric acid, 2-thiobarbituric acid, rhodanine, hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-pyrazolin-5-one, 2-isoxazolin-5-one, indan-1,3-dione, cyclohexan-1,3-dione, 1,3-dioxane-4,6-dione, pyrazolin-3,5-dione, pentan-2,4-dione, alkylsulfonyl acetonitrile, benzoylacetonitrile, malononitrile, malonamide, isoquinolin-4-one, chroman-2,4-dione, 5H-furan-2-one
  • One or more spectral sensitizing dyes may be employed. Dyes with sensitizing maxima at wavelengths throughout the visible and infrared spectrum and with a great variety of spectral sensitivity curve shapes are known. The choice and relative proportions of dyes depends upon the region of the spectrum to which sensitivity is desired and upon the shape of the spectral sensitivity curve desired.
  • An example of a material which is sensitive in the infrared spectrum is shown in Simpson et al., U.S. Patent 4,619,892, which describes a material which produces cyan, magenta and yellow dyes as a function of exposure in three regions of the infrared spectrum (sometimes referred to as "false" sensitization).
  • Dyes with overlapping spectral sensitivity curves will often yield in combination a curve in which the sensitivity at each wavelength in the area of overlap is approximately equal to the sum of the sensitivities of the individual dyes.
  • Combinations of spectral sensitizing dyes can be used which result in supersensitization--that is, spectral sensitization greater in some spectral region than that from any concentration of one of the dyes alone or that which would result from the additive effect of the dyes.
  • Supersensitization can be achieved with selected combinations of spectral sensitizing dyes and other addenda such as stabilizers and antifoggants, development accelerators or inhibitors, coating aids, brighteners and antistatic agents. Any one of several mechanisms, as well as compounds which can be responsible for supersensitization, are discussed by Gilman, Photographic Science and Engineering, Vol. 18, 1974, pp. 418-430.
  • Spectral sensitizing dyes can also affect the emulsions in other ways. For example, spectrally sensitizing dyes can increase photographic speed within the spectral region of inherent sensitivity. Spectral sensitizing dyes can also function as antifoggants or stabilizers, development accelerators or inhibitors, reducing or nucleating agents, and halogen acceptors or electron acceptors, as disclosed in Brooker et al U.S. Patent 2,131,038, Illingsworth et al U.S. Patent 3,501,310, Webster et al U.S. Patent 3,630,749, Spence et al U.S. Patent 3,718,470 and Shiba et al U.S. Patent 3,930,860.
  • Examples of useful supersensitizing-dye combinations, of non-light-absorbing addenda which function as supersensitizers or of useful dye combinations are found in McFall et al U.S. Patent 2,933,390, Jones et al U.S. Patent 2,937,089, Motter U.S. Patent 3,506,443 and Schwan et al U.S. Patent 3,672,898.
  • Spectral sensitizing dyes can be added at any stage during the emulsion preparation. They may be added at the beginning of or during precipitation as described by Wall, Photographic Emulsions, American Photographic Publishing Co., Boston, 1929, p. 65, Hill U.S. Patent 2,735,766, Philippaerts et al U.S. Patent 3,628,960, Locker U.S. Patent 4,183,756, Locker et al U.S. Patent 4,225,666 and Research Disclosure, Vol. 181, May, 1979, Item 18155, and Tani et al published European Patent Application 301 508. They can be added prior to or during chemical sensitization as described by Kofron et al U.S. Patent 4,439,520, Dickerson U.S.
  • the dyes can be mixed in directly before coating as described by Collins et al U.S. Patent 2,912,343. Small amounts of iodide can be adsorbed to the emulsion grains to promote aggregation and adsorption of the spectral sensitizing dyes as described by Dickerson cited above. Postprocessing dye stain can be reduced by the proximity to the dyed emulsion layer of fine high iodide grains as described by Dickerson.
  • the spectral-sensitizing dyes can be added to the emulsion as solutions in water or such solvents as methanol, ethanol, acetone or pyridine; dissolved in surfactant solutions as described by Sakai et al U.S. Patent 3,822,135; or as dispersions as described by Owens et al U.S. Patent 3,469,987 and Japanese published Patent Application (Kokai) 24185/71.
  • the dyes can be selectively adsorbed to particular crystallographic faces of the emulsion grain as a means of restricting chemical sensitization centers to other faces, as described by Mifune et al published European Patent Application 302 528.
  • the spectral sensitizing dyes may be used in conjunction with poorly adsorbed luminescent dyes, as described by Miyasaka et al published European Patent Applications 270 079, 270 082 and 278 510.
  • Instability which increases minimum density in negative-type emulsion coatings can be protected against by incorporation of stabilizers, antifoggants, antikinking agents, latent-image stabilizers and similar addenda in the emulsion and contiguous layers prior to coating.
  • Most of the antifoggants effective in the emulsions used in this invention can also be used in developers and can be classified under a few general headings, as illustrated by C.E.K. Mees, The Theory of the Photographic Process, 2nd Ed., Macmillan, 1954, pp. 677-680.
  • stabilizers and antifoggants can be employed, such as halide ions (e.g., bromide salts); chloropalladates and chloropalladites as illustrated by Trivelli et al U.S. Patent 2,566,263; water-soluble inorganic salts of magnesium, calcium, cadmium, cobalt, manganese and zinc as illustrated by Jones U.S. Patent 2,839,405 and Sidebotham U.S. Patent 3,488,709; mercury salts as illustrated by Allen et al U.S. Patent 2,728,663; selenols and diselenides as illustrated by Brown et al U.K.
  • halide ions e.g., bromide salts
  • chloropalladates and chloropalladites as illustrated by Trivelli et al U.S. Patent 2,566,263
  • water-soluble inorganic salts of magnesium, calcium, cadmium, cobalt, manganese and zinc as illustrated by Jones
  • Patent 1,336,570 and Pollet et al U.K. Patent 1,282,303 quaternary ammonium salts of the type illustrated by Allen et al U.S. Patent 2,694,716, Brooker et al U.S. Patent 2,131,038, Graham U.S. Patent 3,342,596 and Arai et al U.S. Patent 3,954,478; azomethine desensitizing dyes as illustrated by Thiers et al U.S. Patent 3,630,744; isothiourea derivatives as illustrated by Herz et al U.S. Patent 3,220,839 and Knott et al U.S. Patent 2,514,650; thiazolidines as illustrated by Scavron U.S.
  • Patent 3,565,625 peptide derivatives as illustrated by Maffet U.S. Patent 3,274,002; pyrimidines and 3-pyrazolidones as illustrated by Welsh U.S. Patent 3,161,515 and Hood et al U.S. Patent 2,751,297; azotriazoles and azotetrazoles as illustrated by Baldassarri et al U.S. Patent 3,925,086; azaindenes, particularly tetraazaindenes, as illustrated by Heimbach U.S. Patent 2,444,605, Knott U.S. Patent 2,933,388, Williams U.S. Patent 3,202,512, Research Disclosure, Vol. 134, June, 1975, Item 13452, and Vol.
  • High chloride emulsions can be stabilized by the presence, especially during chemical sensitization, of elemental sulfur as described by Miyoshi et al European published Patent Application 294 149 and Tanaka et al published European Patent Application 297 804 and thiosulfonates as described by Nishikawa et al published European Patent Application 293 917.
  • useful stabilizers for gold sensitized emulsions are water-insoluble gold compounds of benzothiazole, benzoxazole, naphthothiazole and certain merocyanine and cyanine dyes, as illustrated by Yutzy et al U.S. Patent 2,597,915, and sulfinamides, as illustrated by Nishio et al U.S. Patent 3,498,792.
  • tetraazaindenes particularly in combination with Group VIII noble metals or resorcinol derivatives, as illustrated by Carroll et al U.S. Patent 2,716,062, U.K. Patent 1,466,024 and Habu et al U.S. Patent 3,929,486; quaternary ammonium salts of the type illustrated by Piper U.S. Patent 2,886,437; water-insoluble hydroxides as illustrated by Maffet U.S. Patent 2,953,455; phenols as illustrated by Smith U.S. Patents 2,955,037 and '038; ethylene diurea as illustrated by Dersch U.S.
  • Patent 3,582,346 barbituric acid derivatives as illustrated by Wood U.S. Patent 3,617,290; boranes as illustrated by Bigelow U.S. Patent 3,725,078; 3-pyrazolidinones as illustrated by Wood U.K. Patent 1,158,059 and aldoximines, amides, anilides and esters as illustrated by Butler et al U.K. Patent 988,052.
  • the high chloride ⁇ 100 ⁇ tabular grain emulsions described herein can be protected from fog and desensitization caused by trace amounts of metals such as copper, lead, tin, iron and the like by incorporating addenda such as sulfocatechol-type compounds, as illustrated by Kennard et al U.S. Patent 3,236,652; aldoximines as illustrated by Carroll et al U.K. Patent 623,448 and meta- and polyphosphates as illustrated by Draisbach U.S. Patent 2,239,284, and carboxylic acids such as ethylenediamine tetraacetic acid as illustrated by U.K. Patent 691,715.
  • addenda such as sulfocatechol-type compounds, as illustrated by Kennard et al U.S. Patent 3,236,652; aldoximines as illustrated by Carroll et al U.K. Patent 623,448 and meta- and polyphosphates as illustrated by Draisbach U.S. Patent 2,239,
  • stabilizers useful in layers containing synthetic polymers of the type employed as vehicles and to improve covering power are monohydric and polyhydric phenols as illustrated by Forsgard U.S. Patent 3,043,697; saccharides as illustrated by U.K. Patent 897,497 and Stevens et al U.K. Patent 1,039,471, and quinoline derivatives as illustrated by Dersch et al U.S. Patent 3,446,618.
  • stabilizers useful in protecting the emulsion layers against dichroic fog are addenda such as salts of nitron as illustrated by Barbier et al U.S. Patents 3,679,424 and 3,820,998; mercaptocarboxylic acids as illustrated by Willems et al U.S. Patent 3,600,178; and addenda listed by E. J. Birr, Stabilization of Photographic Silver Halide Emulsions, Focal Press, London, 1974, pp. 126-218.
  • stabilizers useful in protecting emulsion layers against development fog are addenda such as azabenzimidazoles as illustrated by Bloom et al U.K. Patent 1,356,142 and U.S. Patent 3,575,699, Rogers U.S. Patent 3,473,924 and Carlson et al U.S. Patent 3,649,267; substituted benzimidazoles, benzothiazoles, benzotriazoles and the like as illustrated by Brooker et al U.S. Patent 2,131,038, Land U.S. Patent 2,704,721, Rogers et al U.S.
  • Patent 3,265,498 mercapto-substituted compounds, e.g., mercaptotetrazoles, as illustrated by Dimsdale et al U.S. Patent 2,432,864, Rauch et al U.S. Patent 3,081,170, Weyerts et al U.S. Patent 3,260,597, Grasshoff et al U.S. Patent 3,674,478 and Arond U.S. Patent 3,706,557; isothiourea derivatives as illustrated by Herz et al U.S. Patent 3,220,839, and thiodiazole derivatives as illustrated by von Konig U.S. Patent 3,364,028 and von Konig et al U.K. Patent 1,186,441.
  • mercapto-substituted compounds e.g., mercaptotetrazoles, as illustrated by Dimsdale et al U.S. Patent 2,432,864, Rauch et al U.S. Patent
  • the emulsion layers can be protected with antifoggants such as monohydric and polyhydric phenols of the type illustrated by Sheppard et al U.S. Patent 2,165,421; nitro-substituted compounds of the type disclosed by Rees et al U.K. Patent 1,269,268; poly(alkylene oxides) as illustrated by Valbusa U.K. Patent 1,151,914, and mucohalogenic acids in combination with urazoles as illustrated by Allen et al U.S. Patents 3,232,761 and 3,232,764, or further in combination with maleic acid hydrazide as illustrated by Rees et al U.S. Patent 3,295,980.
  • antifoggants such as monohydric and polyhydric phenols of the type illustrated by Sheppard et al U.S. Patent 2,165,421; nitro-substituted compounds of the type disclosed by Rees et al U.K. Patent 1,269,268;
  • addenda can be employed such as parabanic acid, hydantoin acid hydrazides and urazoles as illustrated by Anderson et al U.S. Patent 3,287,135, and piazines containing two symmetrically fused 6-member carbocyclic rings, especially in combination with an aldehyde-type hardening agent, as illustrated in Rees et al U.S. Patent 3,396,023.
  • Kink desensitization of the emulsions can be reduced by the incorporation of thallous nitrate as illustrated by Overman U.S. Patent 2,628,167; compounds, polymeric lattices and dispersions of the type disclosed by Jones et al U.S. Patents 2,759,821 and '822; azole and mercaptotetrazole hydrophilic colloid dispersions of the type disclosed by Research Disclosure, Vol. 116, December, 1973, Item 11684; plasticized gelatin compositions of the type disclosed by Milton et al U.S. Patent 3,033,680; water-soluble interpolymers of the type disclosed by Rees et al U.S.
  • Patent 3,536,491 polymeric lattices prepared by emulsion polymerization in the presence of poly(alkylene oxide) as disclosed by Pearson et al U.S. Patent 3,772,032, and gelatin graft copolymers of the type disclosed by Rakoczy U.S. Patent 3,837,861.
  • pressure desensitization and/or increased fog can be controlled by selected combinations of addenda, vehicles, hardeners and/or processing conditions as illustrated by Abbott et al U.S. Patent 3,295,976, Barnes et al U.S. Patent 3,545,971, Salesin U.S. Patent 3,708,303, Yamamoto et al U.S. Patent 3,615,619, Brown et al U.S. Patent 3,623,873, Taber U.S. Patent 3,671,258, Abele U.S. Patent 3,791,830, Research Disclosure, Vol. 99, July, 1972, Item 9930, Florens et al U.S.
  • Patent 3,843,364 Priem et al U.S. Patent 3,867,152, Adachi et al U.S. Patent 3,967,965 and Mikawa et al U.S. Patents 3,947,274 and 3,954,474.
  • latent-image stabilizers can be incorporated, such as amino acids, as illustrated by Ezekiel U.K. Patents 1,335,923, 1,378,354, 1,387,654 and 1,391,672, Ezekiel et al U.K. Patent 1,394,371, Jefferson U.S. Patent 3,843,372, Jefferson et al U.K. Patent 1,412,294 and Thurston U.K. Patent 1,343,904; carbonyl-bisulfite addition products in combination with hydroxybenzene or aromatic amine developing agents as illustrated by Seiter et al U.S.
  • Patent 3,424,583 cycloalkyl-1,3-diones as illustrated by Beckett et al U.S. Patent 3,447,926; enzymes of the catalase type as illustrated by Matejec et al U.S. Patent 3,600,182; halogen-substituted hardeners in combination with certain cyanine dyes as illustrated by Kumai et al U.S. Patent 3,881,933; hydrazides as illustrated by Honig et al U.S. Patent 3,386,831; alkenyl benzothiazolium salts as illustrated by Arai et al U.S.
  • Patent 3,954,478 hydroxy-substituted benzylidene derivatives as illustrated by Thurston U.K. Patent 1,308,777 and Ezekiel et al U.K. Patents 1,347,544 and 1,353,527; mercapto-substituted compounds of the type disclosed by Sutherns U.S. Patent 3,519,427; metal-organic complexes of the type disclosed by Matejec et al U.S. Patent 3,639,128; penicillin derivatives as illustrated by Ezekiel U.K. Patent 1,389,089; propynylthio derivatives of benzimidazoles, pyrimidines, etc., as illustrated by von Konig et al U.S.
  • Patent 3,910,791 combinations of iridium and rhodium compounds as disclosed by Yamasue et al U.S. Patent 3,901,713; sydnones or sydnone imines as illustrated by Noda et al U.S. Patent 3,881,939; thiazolidine derivatives as illustrated by Ezekiel U.K. Patent 1,458,197 and thioether-substituted imidazoles as illustrated by Research Disclosure, Vol. 136, August, 1975, Item 13651.
  • the dye image providing compounds incorporated in the color photographic elements of this invention can take any convenient conventional form.
  • a general description of dye image providing compounds useful in color photographic elements is provided in Research Disclosure, Item 308119, cited above, Section VII.
  • the dye image providing compound is typically a dye image forming coupler (hereinafter referred to as a coupler), although other dye image providing compounds, such as a dye redox releaser compound, a dye developer compound, an oxichromic developer compound, or a bleachable dye or dye precursor compound are also contemplated.
  • Dye redox releaser, dye developer, and oxichromic developer compounds useful in color photographic elements are described in The Theory of the Photographic Process, 4th edition, T.H.
  • a coupler compound contains a coupler moiety COUP, which is combined with oxidized developing agent a coupling reaction to form an image dye.
  • a coupler compound can additionally contain a group, called a coupling-off group, that is attached to the coupler moiety by a bond that is cleaved upon reaction of the coupler compound with oxidized color developing agent.
  • Coupling-off groups can be halogen, such as chloro, bromo, fluoro, and iodo, or organic radicals that are attached to the coupler moieties by atoms such as oxygen, sulfur, nitrogen, and phosphorus.
  • Couplers which form cyan dyes upon reaction with oxidized color developing agents are described in such representative patents and publications as: U.S. Patent Nos. 2,772,162; 2,895,826; 3,002,836; 3,034,892; 2,474,293; 2,423,730; 2,367,531; 3,041,236; 4,333,999, "Farbkuppler-eine Literaturubersicht,” published in Agfa Mitannonen, Band III, pp. 156-175 (1961), and Section VII D of Research Disclosure, Item 308119, cited above.
  • couplers are phenols and naphthols.
  • Couplers which form magenta dyes upon reaction with oxidized color developing agent are described in such representative patents and publications as: U.S. Patent Nos. 2,600,788; 2,369,489; 2,343,703; 2,311,082; 3,152,896; 3,519,429; 3,062,653; 2,908,573, "Farbkuppler-eine Literaturubersicht,” published in Agfa Mitannonen, Band III, pp. 126-156 (1961), and Section VII D of Research Disclosure, Item 308119, cited above.
  • couplers are pyrazolones or pyrazolotriazoles.
  • Couplers which form yellow dyes upon reaction with oxidized and color developing agent are described in such representative patents and publications as: U.S. Patent Nos. 2,875,057; 2,407,210; 3,265,506; 2,298,443; 3,048,194; 3,447,928, "Farbkuppler-eine Literaturubersicht,” published in Agfa Mitannonen, Band III, pp. 112-126 (1961), and Section VII D of Research Disclosure, Item 308119, cited above.
  • couplers are acylacetamides, such as benzoylacetamides and pivaloylacetamides.
  • the color photographic elements of the invention are employed to form color prints for viewing.
  • the color photographic elements of the invention are intended to be used as taking films (i.e., to form a image that is subsequently printed employing a separate element)
  • the color photographic elements can contain an applied magnetic layer, such as described in Research Disclosure, Vol. 343, Item Nov. 1992, Item 34390.
  • the color photographic elements can be imagewise exposed by any conventional technique employed. Contemplated exposures include those set out in Research Disclosure, Item 308119, cited above, Section XVIII.
  • color photographic elements and their processing following imagewise exposure can take any convenient conventional form known to be useful in redox amplification dye imaging.
  • Color photographic elements particularly intended for redox amplification dye imaging and redox amplification dye imaging processes are disclosed by Bissonette U.S. Patents 3,748,138, 3,826,652, 3,847,619, 3,856,524, 3,862,842, 3,923,511, 3,989,526, 4,002,477, 4,088,486, 4,089,685, 4,097,278 and 4,146,395; Travis U.S. Patent 3,765,891; Matejec U.S.
  • Patents 3,674,490 and 3,776,730 discloses a preferred reversal process.
  • redox amplification dye imaging an oxidizing agent and a reducing agent are employed that are reactively inert in the absence of silver, but are catalyzed by developed silver to enter into a oxidation-reduction action.
  • the oxidized reducing agent produced by the oxidation-reduction reaction then reacts with the dye image providing compound to form a dye image.
  • the reducing agent is a color developing agent (e.g., a p -phenylene-diamine).
  • Typical preferred color developing agenda include 4-amino-3-methyl-N,N-diethylaniline hydro-chloride, 4-amino-3-methyl-N-ethyl-N-(methanesulfonamido)ethylaniline sulfate hydrate, 4-amino-3-methyl-N-ethyl-N-hydroxyethylaniline sulfate, 4-amino-3-(methanesulfonamido)ethyl-N,N-diethylaniline hydrochloride, and 4-amino-N-ethyl-N-(2-methoxyethyl)- m -toluidine di- p -toluenesulfonic acid.
  • the oxidized color developing agent produced by the oxidation-reduction reaction then reacts with the dye image providing compound, usually a coupler, to form the dye image.
  • the dye image providing compound is a redox dye releaser
  • the reducing agent is an electron transfer agent (e.g., an aminophenol, 3-pyrazolidinone, a p-phenylenediamine or a reductone).
  • Typical preferred redox dye releasers and electron transfer agents are set out in Research Disclosure, Vol. 151, Nov. 1976, Item 15162.
  • Useful oxidizing agents can be selected from among transition metal ion complexes (e.g., cobalt(III) and ruthenium(III) complexes containing ammine and/or amine ligands). Cobalt hexammine is a specifically preferred transition metal ion complex useful as an oxidizing agent.
  • Peroxy compounds e.g., hydrogen peroxide and compounds that provide hydrogen peroxide, such as alkali metal perborates, percarbonates and periodates
  • Hydrogen peroxide is a specifically preferred oxidizing agent. Mixtures of oxidizing agents can be employed, if desired.
  • the fixing step can also be omitted. However, because this step is generally not burdensome, it is preferred to include fixing within the overall process. Since the reducing agents employed in the redox amplification dye imaging step are themselves silver halide developing agents in many instances, it is recognized that the development and redox amplification dye imaging can take place in the same processing solution, thereby simplifying the process. It is, in fact, possible to conduct the processing entirely within a single bath, referred to as a monobath.
  • the patents cited above to illustrate redox amplification processing provide specific examples of monobaths and their use. The relatively high solubility and development rates of high chloride emulsions as well as the higher environmental tolerance of chloride ion than bromide or iodide ion, offer additional important advantages to the practice of the invention.
  • Emulsion 1 High-Aspect-Ratio High-Chloride ⁇ 100 ⁇ Tabular Grain Emulsion
  • Emulsion 1A Emulsion 1A
  • a stirred reaction vessel containing 400 mL of a solution which was 0.5% in bone gelatin, 6mM in 3-amino-1H-1,2,4-triazole, 0.040 M in NaCl, and 0.20 M in sodium acetate was adjusted to pH 6.1 at 55°C.
  • To this solution at 55°C were added simultaneously 5.0 mL of 4 M AgNO 3 and 5.0 mL of 4 M NaCl at a rate of 5 mL/min each. The temperature of the mixture was then increased to 75°C at a constant rate requiring 12 min and then held at this temperature for 5 min.
  • the pH was adjusted to 6.2 and held to within ⁇ 0.1 of this value, and the flow of the AgNO 3 solution was resumed at 5 mL/min until 0.8 mole of Ag had been added.
  • the flow of the NaCl solution was also resumed at a rate needed to maintain a constant pAg of 6.64.
  • the resulting AgCl emulsion consisted of tabular grains having ⁇ 100 ⁇ major faces which made up 65% of the projected area of the total grain population. This tabular grain population had a mean equivalent circular diameter of 1.95 ⁇ m and a mean thickness of 0.165 ⁇ m. The average aspect ratio of the emulsion tabular grains was 11.8.
  • This emulsion was prepared similar to Emulsion 1A, except that the precipitation was stopped when 0.4 mole of Ag had been added.
  • the resulting emulsion consisted of tabular grain having ⁇ 100 ⁇ major faces which made up 65% of the projected area of the total grain population.
  • This tabular grain population had a mean equivalent circular diameter of 1.28 ⁇ m and a mean thickness of 0.130 ⁇ m.
  • the average aspect ratio of the emulsion tabular grains was 9.8.
  • Emulsion 2 pH 6.1 Nucleation, pH ⁇ 3.6 Growth
  • This emulsion was prepared similar to Emulsion 1B, except that the pH of the reaction vessel was adjusted to 3.6 for the last 95% of the AgNO 3 addition.
  • the resulting emulsion consisted of ⁇ 100 ⁇ tabular grains making up 60% of the projected area of the total grain population.
  • This tabular grain population had a mean equivalent circular diameter of 1.39 ⁇ m, and a mean thickness of 0.180 ⁇ m.
  • the average aspect ratio of the emulsion tabular grains was 7.7.
  • Emulsion 3 High-Aspect-Ratio AgBrCl (10% Br) ⁇ 100 ⁇ Tabular-Grain Emulsion
  • Emulsion was prepared similar to Emulsion 1B, except that the salt solution was 3.6 M in NaCl and 0.4 M in NaBr.
  • the resulting AgBrCl (10% Br) emulsion consisted of ⁇ 100 ⁇ tabular grain making up 52% of the projected area of the total grain population. This tabular grain population had a mean equivalent circular diameter of 1.28 ⁇ m, and a mean thickness of 0.115. The average aspect ratio of the emulsion tabular grains was 11.1.
  • Emulsion 4 3,5-Diamino-1,2,4-Triazole as ⁇ 100 ⁇ Tabular Grain Nucleating Agent
  • This emulsion was prepared similar to Emulsion 1A, except that 3,5-diamino-1,2,4-triazole (2.4 mmole) was used as the ⁇ 100 ⁇ tabular grain nucleating agent.
  • the resulting AgCl emulsion consisted of tabular grains having ⁇ 100 ⁇ major faces which made up 45% of the projected area of the total grain population.
  • This tabular grain population had a mean equivalent circular diameter of 1.54 ⁇ m and a mean thickness of 0.20 ⁇ m.
  • the average aspect ratio of the emulsion tabular grains was 7.7.
  • Emulsion 5 Imidazole as ⁇ 100 ⁇ Tabular Grain Nucleating Agent
  • This emulsion was prepared similar to Emulsion 1A, except that imidazole (9.6 mmole) was used as the ⁇ 100 ⁇ tabular grain nucleating agent.
  • the resulting AgCl emulsion consisted of tabular grains having ⁇ 100 ⁇ major faces which made up 40% of the projected area of the total grain population.
  • This tabular grain population had a mean equivalent circular diameter of 2.20 ⁇ m and a mean thickness of 0.23 ⁇ m.
  • the average aspect ratio of the tabular grain emulsion was 9.6.
  • Emulsion 6 AgCl ⁇ 100 ⁇ Tabular Grain Emulsion Made Without Aromatic Amine Restraining Agent
  • the resulting AgCl emulsion consisted of tabular grains having ⁇ 100 ⁇ major faces which made up 40% of the projected area of the total gain population. This tabular grain population had a mean equivalent circular diameter of 2.18 ⁇ m and a mean thickness of 0.199 ⁇ m. The average aspect ratio of the tabular grain emulsion was 11.0.
  • Emulsion 7 High-Aspect-Ratio High-Chloride ⁇ 100 ⁇ Tabular Grain Emulsion
  • a reaction vessel contained 2 L of a solution that was 3.5% in low methionine (oxidized) gelatin, 5.6 mM in NaCl and 0.15 mM in KI. To this stirred solution at 40°C was added simultaneously and at 60 mL/min each, 30 mL of a solution 2 M in AgNO 3 and 30 mL of a solution 1.99 M in NaCl and 0.01 M in KI. The mixture was stirred for 10 min and then 1.88 L of a solution 0.5 M in AgNO 3 was added first at 8.0 mL/min for 40 min, then the flow rate was accelerated 2X requiring 130 min. A solution 0.5 M in NaCl was concurrently added as needed to maintain a constant pCl of 2.32.
  • the emulsion consisted of a ⁇ 100 ⁇ tabular grain population making up 75% of the projected area of the emulsion grains. This population had a mean diameter of 1.66 ⁇ m, and a mean thickness of 0.11 ⁇ m.
  • a control emulsion was prepared which was an AgBr tabular grain emulsion consisting of grains having a mean diameter of 1.7 ⁇ m and a mean thickness of 0.085 ⁇ m.
  • This emulsion was a silver chloride emulsion containing cubic grains having an average grain edge length of 0.6 ⁇ m.
  • This emulsion was a silver chloride emulsion containing cubic grains having an average grain edge length of 0.75 ⁇ m.
  • a 2030 mL solution containing 3.52% by weight low methionine gelatin, 0.0056 M sodium chloride, and 3.35 X 10 -4 potassium iodide was provided in a stirred reaction vessel.
  • the iodide was incorporated to facilitate tabular grain nucleation, but was maintained well below that required to significantly increase blue absorption.
  • the contents of the reaction vessel were maintained at 40°C and the pCl was 2.25.
  • the mixture was then held four minutes with the temperature remaining at 40°C. Following the hold, a 0.5 M silver nitrate solution and a 0.5 M sodium chloride solution were then added simultaneously at 10.83 mL/min for 40 minutes with the pCl maintained at 2.25. The 0.5 M silver nitrate and the 0.5 M sodium chloride solutions were then added simultaneously with a ramped linearly increasing flow from 10.83 mL/min to 16.73 mL/min over 70 minutes with the pCl maintained at 2.25. Following this, a 0.75 M silver nitrate solution and a 0.75 M sodium chloride solution were added simultaneously at 16.73 mL/min over 90 minutes with the pCl maintained at 2.25.
  • the resulting emulsion was a tabular grain emulsion having ⁇ 100 ⁇ major faces with an average ECD of 1.524 ⁇ m and an average thickness of 0.148 ⁇ m.
  • Emulsion 7 A stirred 50 g portion (0.05 mole) of Emulsion 7 at 25°C was adjusted to pH 5.3 with H 2 SO 4 and pCl of 2.06 with NaCl. To this emulsion was added 5 ml of a solution of 0.2 M NaBr at 0.5 mL/min. Then a solution containing 0.7 mmole/Ag mole of the green spectral sensitizing dye, anhydro-5-chloro-9-ethyl-5'-phenyl-3'-(3-sulfobutyl)-3-(3-sulfopropyl)oxacarbocyanine hydroxide, triethyl amine salt, Dye A, was added.
  • Example Coating 1 The temperature was increased to 40°C and 4 x 10 -6 mole/Ag mole of sodium thiosulfate and 2.6 x 10 -6 /Ag mole of potassium tetrachloroaurate were added. The mixture was heated for 15 min at 60°C. A portion of this emulsion was mixed with cyan color coupler dispersion, gelatin, surfactant, and, hardener, and made 5 x 10 -3 M in NaCl. It was coated at 0.011 g Ag/m 2 , 1.1 g coupler/m 2 and 2.2 g gelatin/m 2 onto paper support to make Example Coating 1.
  • Control Emulsion 8 was added 0.7 mmole Dye A/Ag mole and then 20 x 10 -6 mole/Ag mole of sodium thiosulfate and 13 x10 -6 mole/Ag mole of potassium tetrachloroaurate were added. The mixture was heated for 15 min at 60°C. A portion of this emulsion was mixed with cyan color coupler dispersion, gelatin, surfactant, and hardener, and made 5 x 10 -3 M in NaCl. It was coated at 0.011 g Ag/m 2 , 1.1 g coupler/m 2 and 2.2 g gelatin/m 2 onto paper support to make Control Coating 2.
  • Example Coating 1 and Control Coating 2 were exposed for 0.1 sec to a 600 W, 3,000 K tungsten light source through a 0-4.0 density step-tablet.
  • the exposed coatings were developed for 10 sec. at 20°C in a developer having the following composition: 10 g 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine p-toluenesulfonate, 20 g potassium carbonate, 4 g potassium sulfite, distilled water to 2 L and just before use 20 mL of 30 % hydrogen peroxide was added.
  • the coatings were then put into a 1% acetic acid stop bath and then water washed. No bleach or fix baths were needed.
  • Table I Coating D min D max Relative Speed Example 1 0.36 1.0 140 Control 2 0.12 0.4 100
  • Example Coating 1 provided a significantly higher D max and photographic speed than Control Coating 2. This demonstrated the superiority of the redox amplification dye imaging process employing a color photographic element containing a high chloride ⁇ 100 ⁇ tabular grain emulsion.
  • Emulsions 9, 10 and 11 were each optimally chemically and blue sensitized and then dual coated with an incorporated dispersion of a yellow dye forming coupler to give yellow single records suitable for redox amplification processing.
  • the silver laydowns used are given in Table II.
  • the prepared coatings were subject to sensitometric graduation exposures; exposure time of 0.1 sec with neutral density filter of 0.62 and a Wratten TM 98 filter.
  • the coatings were processed in a redox amplification process using the redox amplifier formulation and process sequence given below.
  • the high chloride ⁇ 100 ⁇ tabular grain Emulsion 11 produced a higher speed than either of the control cubic grain Emulsions 9 and 10, which were chosen to otherwise provide coating and performance parameters just above and just below those of Emulsion 11.
  • Emulsion 11 gave higher speed than that achieved with the Control Emulsions 9 and 10.
  • a comparison of Control Emulsion 10 with the two levels of Emulsion 11 indicates higher Dmax and similar contrast.
  • a conventional red sensitized cubic grain silver chloride emulsion of edge length 0.38 ⁇ m was used for the cyan dye image forming layer unit of these coatings at a silver laydown of 32.3 mg/m 2 ; similarly a conventional green sensitized cubic grain silver chloride emulsion of edge length 0.31 micrometers was used for the magenta layer at a silver laydown of 37.7 mg/m 2 .

Claims (10)

  1. Elément photographique couleur contenant une unité de couches formatrices d'image de colorant comprenant au moins une émulsion aux halogénures d'argent et un composé formateur d'image de colorant
       CARACTERISE EN CE QUE
    l'argent total contenu dans l'unité de couches formatrices d'image de colorant est inférieur à 200 mg/m2 et
    l'émulsion contient une population de grains d'halogénures d'argent comprenant au moins 50 pourcent en moles de chlorure, par rapport à l'argent total formant la population de grains, et plus de 30 pourcent de la surface projetée de la population de grains sont représentés par des grains tabulaires ayant chacun un indice de forme d'au moins 2, une épaisseur inférieure à 0,3 µm et des faces principales parallèles reposant dans des plans cristallographiques {100}.
  2. Elément photographique couleur selon la revendication 1, caractérisé aussi en ce que plus de 50 pourcent de la surface projetée des grains sont représentés par des grains tabulaires.
  3. Elément photographique couleur selon la revendication 1 ou 2, caractérisé aussi en ce que les grains tabulaires ont une épaisseur moyenne inférieure à 0,2 µm.
  4. Elément photographique couleur selon l'une quelconque des revendications 1 à 3 incluse, caractérisé aussi en ce que les grains tabulaires contiennent moins de 2 pourcent en moles d'iodure.
  5. Elément photographique couleur selon l'une quelconque des revendications 1 à 4 incluse, caractérisé aussi en ce que l'unité de couches formatrices d'image de colorant contient moins de 133 mg/m2 d'argent total.
  6. Elément photographique couleur selon la revendication 5, caractérisé aussi en ce que l'unité de couches formatrices d'image de colorant contient moins de 110 mg/m2 d'argent total.
  7. Elément photographique couleur selon la revendication 6, caractérisé aussi en ce que l'unité de couches formatrices d'image de colorant contient moins de 85 mg/m2 d'argent total.
  8. Elément photographique couleur selon l'une quelconque des revendications 1 à 7 incluse, caractérisé aussi en ce que l'élément photographique comprend au moins deux unités de couches formatrices d'image de colorant et contient moins de 400 mg/m2 d'argent total.
  9. Procédé de production d'une image de colorant dans un élément photographique exposé conformément à l'image, selon l'une quelconque des revendications 1 à 8 incluse, en développant l'émulsion aux halogénures d'argent afin de produire de l'argent conformément à l'image et en employant l'argent développé pour catalyser la réaction d'un agent oxydant et d'un agent réducteur qui sont inertes à l'interaction oxydation-réduction en l'absence d'argent développé, et en faisant réagir l'agent réducteur oxydé avec le composé formateur d'image de colorant pour former l'image de colorant.
  10. Procédé selon la revendication 9, caractérisé aussi en ce que le composé formateur d'image de colorant est un coupleur, l'agent réducteur est un développateur chromogène et l'agent oxydant est un peroxyde ou un complexe de colbalt(III).
EP94200669A 1993-03-18 1994-03-16 Elément photographique en couleurs à basse teneur d'argent et procédé de formation d'une image en couleurs Expired - Lifetime EP0616255B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US188171 1980-09-17
GB939305578A GB9305578D0 (en) 1993-03-18 1993-03-18 Photographic silver halide image forming process
GB9305578 1993-03-18
US18817194A 1994-01-26 1994-01-26

Publications (2)

Publication Number Publication Date
EP0616255A1 EP0616255A1 (fr) 1994-09-21
EP0616255B1 true EP0616255B1 (fr) 1999-09-15

Family

ID=26302609

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94200669A Expired - Lifetime EP0616255B1 (fr) 1993-03-18 1994-03-16 Elément photographique en couleurs à basse teneur d'argent et procédé de formation d'une image en couleurs

Country Status (2)

Country Link
EP (1) EP0616255B1 (fr)
DE (1) DE69420605T2 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5665530A (en) * 1994-08-30 1997-09-09 Fuji Photo Film Co., Ltd. Silver halide emulsion and photographic material using the same
DE69525516T2 (de) * 1994-12-24 2002-10-31 Eastman Kodak Co Fotografisches Silberhalogenidmaterial mit verbesserter Körnigkeit und verbessertem Farbton
US5707793A (en) * 1995-04-19 1998-01-13 Fuji Photo Film Co., Ltd. Silver halide emulsion and silver halide photographic material using the same
GB9605245D0 (en) * 1996-03-13 1996-05-15 Kodak Ltd Method of photographic colour processing
US5837430A (en) * 1996-06-17 1998-11-17 Konica Corporation Image forming method

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2529853B2 (ja) * 1987-06-12 1996-09-04 富士写真フイルム株式会社 ハロゲン化銀写真乳剤の製造方法
DE69122717T2 (de) * 1990-05-14 1997-05-07 Eastman Kodak Co Fotografische filme enthaltend silberhalogenidkörner mit geringen zwillingsebenenabständen
JPH0566510A (ja) * 1991-09-06 1993-03-19 Konica Corp ハロゲン化銀写真乳剤
AU2599492A (en) * 1991-09-24 1993-04-27 Eastman Kodak Company High tabularity high chloride emulsions of exceptional stability
US5275930A (en) * 1992-08-27 1994-01-04 Eastman Kodak Company High tabularity high chloride emulsions of exceptional stability

Also Published As

Publication number Publication date
EP0616255A1 (fr) 1994-09-21
DE69420605D1 (de) 1999-10-21
DE69420605T2 (de) 2000-04-06

Similar Documents

Publication Publication Date Title
US5314798A (en) Iodide banded tabular grain emulsion
US5320938A (en) High chloride tabular grain emulsions and processes for their preparation
US5264337A (en) Moderate aspect ratio tabular grain high chloride emulsions with inherently stable grain faces
US5292632A (en) High tabularity high chloride emulsions with inherently stable grain faces
US5356764A (en) Dye image forming photographic elements
CA1175698A (fr) Emulsions de chlorobromure d'argent comprenant des grains tabulaires, et avec du chlorure et du bromure disposes en couches annulaires
CA1175700A (fr) Procedes d'obtention d'emulsions de bromoiodure d'argent a allongement eleve
EP0617318B1 (fr) Formation numérique d'image avec émulsions à grains tabulaires
EP0772079B1 (fr) Emulsions à l'halogénure d'argent sensible à la lumière et procédé pour leur préparation
US5618656A (en) Method of processing originating and display photographic elements using common processing solutions
US5310635A (en) Photographic camera film containing a high chloride tabular grain emulsion with tabular grain {100} major faces
EP0616255B1 (fr) Elément photographique en couleurs à basse teneur d'argent et procédé de formation d'une image en couleurs
EP0617320A2 (fr) Emulsions à grains tabulaires contenant des antivoiles et des stabilisants
EP0645022B1 (fr) Procedes de preparation d'emulsions a grains tabulaires
EP0641459B1 (fr) Elements photographiques formant une image couleur
US5672467A (en) Higher speed color photographic element and a method for high speed imaging
US5395746A (en) Inherently stable high chloride tabular grains with improved blue absorption
JP3268109B2 (ja) 低銀カラー写真要素および色素画像生成方法
JP3270614B2 (ja) 中位アスペクト比平板状粒子乳剤
EP0617317A1 (fr) Emulsions à grains tabulaires modifiés par oligomères
JP2002341478A (ja) 放射線感受性高塩化物乳剤の製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB

17P Request for examination filed

Effective date: 19950314

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 19981016

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

RBV Designated contracting states (corrected)

Designated state(s): DE FR GB

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EASTMAN KODAK COMPANY

Owner name: KODAK LIMITED

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REF Corresponds to:

Ref document number: 69420605

Country of ref document: DE

Date of ref document: 19991021

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20050207

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20050302

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20050331

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060316

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061003

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20060316

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20061130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060331