EP0190625A2 - Photographische Umkehrelemente mit tafelförmige Körner enthaltenden Emulsionen - Google Patents

Photographische Umkehrelemente mit tafelförmige Körner enthaltenden Emulsionen Download PDF

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Publication number
EP0190625A2
EP0190625A2 EP86100953A EP86100953A EP0190625A2 EP 0190625 A2 EP0190625 A2 EP 0190625A2 EP 86100953 A EP86100953 A EP 86100953A EP 86100953 A EP86100953 A EP 86100953A EP 0190625 A2 EP0190625 A2 EP 0190625A2
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Prior art keywords
silver
grains
forming
reversal
photographic element
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EP86100953A
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French (fr)
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EP0190625B1 (de
EP0190625A3 (en
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Allan Francis Sowinski
David Clayton Shuman
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Eastman Kodak Co
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Eastman Kodak Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—Tabular grain emulsions

Definitions

  • This invention relates to improved photographic elements adapted for producing reversal images. More specifically, this invention relates to reversal silver halide photographic elements containing in at least one emulsion layer tabular haloiodide grains.
  • the term "silver haloiodide” is employed in its art recognized usage to designate silver halide grains containing silver ions in combination with iodide ions and at least one of chloride and bromide ions.
  • the term "reversal photographic element” designates a photographic element which produces a photographic image for viewing by being imagewise exposed and developed to produce a negative of the image to be viewed, followed by uniform exposure and/or fogging of residual silver halide and processing to produce a second, viewable image.
  • Color slides such as those produced from Kodachrome * and Ektachrome . films, constitute a popular example of reversal photographic elements. In the overwhelming majority of applications the first image is negative and the second image is positive.
  • Patent 4,082,553 illustrates a conventional reversal photographic element containing silver haloiodide grains modified by the incorporation of a small proportion of fogged silver halide grains.
  • German OLS 3,402,840 is similar to U.S. Patent 4,082,553, but describes the imaging silver halide grains in terms of those larger than and smaller than 0.3 micrometer and additionally requires in addition to the fogged silver halide grains or their metal or metal sulfide equivalent an organic compound capable of forming a silver salt of low solubility.
  • High aspect ratio tabular grain silver haloiodide emulsions have been recognized to provide a variety of photographic advantages, such as improvements in speed-granularity relationships, increased image sharpness, and reduced blue speed of minus blue recording emulsion layers.
  • High aspect ratio tabular grain silver haloiodide emulsions in reversal photographic elements are illustrated by Research Disclosure Vol. 225, January 1983, Item 22534; and U.S. Patents 4,434,226; 4,439,520; 4,433,048; 4,400,463; and 4,435,501. Research Disclosure is published by Kenneth Mason Publications, Ltd., The Old Harbourmaster's, 8 North Street, Emsworth, Hampshire P010 7DD, England.
  • It is an object of this invention to provide a photographic element capable of forming a reversal image comprising a support and, coated on the support, at least one image recording emulsion layer comprised of a dispersing medium and a blend of radiation sensitive tabular silver haloiodide grains having a thickness of less than 0.5 ⁇ m, a diameter of at least 0.6 ⁇ m, and an"average aspect ratio of greater than 8:1 accounting for at least 35 percent of the total grain projected area of said emulsion layer, said reversal photographic element exhibiting increased reversal threshold speed. It is a further object to provide reversal photographic elements as described above which exhibit reduced toe region density in the reversal image as well as increases in maximum density and contrast.
  • blended with the radiation sensitive tabular silver haloiodide grains are relatively fine grains present in a concentration sufficient to improve reversal imaging consisting essentially of a silver salt more soluble than silver iodide.
  • Curve 1 is the reversal characteristic curve produced by an emulsion layer of a conventional reversal photographic element wherein radiation sensitive tabular silver hdloiodide grains are present, but the relatively fine grains are not present.
  • Curve 2 illustrates the reversal characteristic curve produced by the same emulsion layer differing only by the inclusion of the relatively fine grains. It is to be understood that exposure and processing producing both curves are identical.
  • reversal threshold speed exhibited by curve 2 exceeds that of curve 1, where reversal threshold speed is defined as the exposure level corresponding to the threshold (first detectable) decline from maximum density of the reversal characteristic curve.
  • reversal threshold speed is defined as the exposure level corresponding to the threshold (first detectable) decline from maximum density of the reversal characteristic curve.
  • This invention relates to an improvement in silver halide photographic elements useful in reversal imaging.
  • the photographic elements are comprised of a support and one or more image recording silver halide emulsion layers coated on the support. At least one of the image recording emulsion layers contains a dispersing medium and radiation sensitive tabular silver haloiodide grains blended with relatively fine grains consisting essentially of a silver salt more soluble than silver iodide.
  • Tabular grains are herein defined as those having two substantially parallel crystal faces, each of which is clearly larger than any other single crystal face of the grain.
  • the tabular grains employed in the blended grain emulsion layers forming one or more layers of the reversal photographic elements of this invention are chosen so that the tabular grains having a thickness of less than 0.5 ⁇ m and a diameter of at least 0.6 ⁇ m have an average aspect ratio of greater than 8:1 and account for at least 35 percent of the total grain projected area of the blended grain emulsion layer in which they are present.
  • a convenient approach for preparing blended grain emulsion layers satisfying the requirements of this invention is to blend with the relatively fine second grain population a radiation sensitive high aspect ratio tabular grain emulsion.
  • high aspect ratio tabular grain emulsion is herein defined as requiring that tThe tabular silver halide grains having a thickness of less than 0.3 pm and a diameter of at least 0.6 ⁇ m have an average aspect ratio of greater than 8:1 and account for at least 50 percent of the total projected area of the grains present in the emulsion. The term is thus defined in conformity with the usage of this term in the patents relating to tabular grain emulsions cited above.
  • tabular grains are preferred having a thickness of less than 0.3 ⁇ m.
  • the emulsion layer is intended to record blue light as opposed to green or red light, it is advantageous to increase the thickness criterion of the tabular grains to less than 0.5 ⁇ m, instead of less than 0.3 ⁇ m.
  • Such an increase in tabular grain thickness is also contemplated for applications in which the reversal image is to be viewed without enlargement or where granularity is of little importance, although these latter applications are relatively rare in reversal imaging, reversal images being most commonly viewed by projection.
  • Tabular grain emulsions wherein the tabular grains have a thickness of less than 0.5 um intended for recording blue light are disclosed by U.S. Patent 4,439,520, cited above.
  • tabular grains satisfying the 0.3 m thickness and 0.6 ⁇ m diameter criteria account for at least 50 percent of the total projected area of the grains in high aspect ratio tabular grain emulsions, it is appreciated that in blending a second grain population the tabular grain percentage of the total grain projected area is decreased.
  • the tabular grain emulsions contemplated for preparing blended grain emulsion layers satisfying the requirements of this invention must be capable of providing tabular grains satisfying the thickness and diameter criteria which also provide at least 35 percent of the total grain projected area in the blended grain emulsion layer.
  • tabular grain emulsions employed in the practice of this invention preferably provide at least 50 percent of the total grain projected area, at least before blending with the second grain population, this is not essential if the 35 percent of the total grain projected area condition noted above in the blended grain emulsion layer is satisfied.
  • the preferred high aspect ratio tabular grain silver haloiodide emulsions are those wherein the silver haloiodide grains having a thickness of less than 0.3 ⁇ m (optimally less than 0.2 ⁇ m) and a diameter of at least 0.6 ⁇ m have an average aspect ratio of at least 12:1 and optimally at least 20:1.
  • these silver haloiodide grains satisfying the above thickness and diameter criteria account for at least 70 percent and optimally at least 90 percent of the total projected area of the silver halide grains.
  • the blended grain emulsions required by this invention also satisfy the parameters set but for the preferred high aspect ratio tabular grain emulsions.
  • the tabular grains typically have an average thickness of at least 0.03 ⁇ m, although even thinner tabular grains can in principle be employed.
  • High aspect ratio tabular grain emulsions useful in the practice of this invention can have extremely high average aspect ratios.
  • Tabular grain average aspect ratios can be increased by increasing average grain diameters. This can produce sharpness advantages, but maximum average grain diameters are generally limited by granularity requirements for a specific photographic application.
  • Tabular grain average aspect ratios can also or alternatively be increased by decreasing average grain thicknesses. When silver coverages are held constant, decreasing the thickness of tabular grains generally improves granularity as a direct function of increasing aspect ratio.
  • the maximum average aspect ratios of the tabular grain emulsions of this invention are a function of the maximum average grain diameters acceptable for the specific photographic application and the minimum attainable tabular grain thicknesses which can be conveniently produced.
  • the tabular haloiodide grains employed in the practice of this invention contain in addition to iodide at least one of bromide and chloride.
  • the silver haloiodides specifically contemplated are silver bromoiodides, silver chlorobromoiodides, and silver chloroiodides.
  • Silver bromoiodide emulsions generally exhibit higher photographic speeds and are for this reason the preferred and most commonly employed emulsions for candid photography.
  • Iodide must be present in the tabular silver haloiodide grains in a concentration sufficient to influence photographic performance. It is thus contemplated that at least about 0.5 mole percent iodide will be present in the tabular silver haloiodide grains. However, high levels of iodide are not required to achieve the advantages of this invention. Generally the tabular silver haloiodide grains contain less than 8 mole percent iodide. Preferred iodide levels in the tabular silver haloiodide grains are from 1 to 7 mole percent and optimally are from 2 to 6 mole percent. All of the above iodide mole percentages are based on total silver present in the tabular grains.
  • the radiation sensitive tabular haloiodide grains required for the practice of this invention are preferably provided by selecting from among the various high aspect ratio tabular grain emulsions disclosed in Research Disclosure Vol. 225, January 1983, Item 22534; and U.S. Patents 4,434,226; 4,439,520; 4,433,048; 4,400,463; and 4,435,501; each cited above.
  • the blended grain emulsion required for the practice of this invention can be conveniently provided by blending with a tabular grain silver haloiodide emulsion as described above a second grain population consisting essentially of silver salt which is more soluble than silver iodide.
  • the silver salt should be sufficiently insoluble that it is capable of forming a grainrather than being present in a solubilized form.
  • Useful silver salts can be chosen from among those having a solubility product constant in the range 9.5 to less than 16.
  • Preferred silver salts are those having a solubility product constant in the range of from 9.75 to 15.5, optimally from 11 to 13. Unless otherwise stated, all solubility product constants are referenced to a temperature of 20°C.
  • a discussion and listing of solubility product constants for exemplary silver salts is presented by James, Theory of the Photographic Process, 4th Ed., Macmillan, 1977, Chapter 1, Sections F, G, and H, pp. 5-10.
  • the silver salt forming the relatively fine grains be at least as soluble as the most soluble silver halide present in the radiation sensitive tabular grains.
  • the relatively fine grains preferably consist essentially of silver chloride or silver chlorobromide as opposed to silver bromide.
  • the relatively fine grains preferably consist essentially of silver bromide, silver thiocyanate, or a combination of both. Advantages have been realized when silver bromide and silver thiocyanate grains are employed in combination.
  • the relatively fine grains consist essentially of silver salt more soluble than silver iodide
  • less soluble silver salts in small quantities that do not interfere with effectiveness can be present.
  • the grains consisting essentially of a silver salt more soluble than silver iodide are fine as compared to the tabular silver haloiodide grains.
  • the permissible size of this second grain population blended with the radiation sensitive tabular grains is a direct function of the solubility of the silver salt forming these grains.
  • the second grain population in all instances exhibits an average grain diameter of less than 0.5 ⁇ m and preferably exhibits an average grain diameter of less than 0.3 m. Optimally the second grain population exhibits an average grain diameter of less than 0.1 ⁇ m.
  • the second grain population is optimally provided by blending a conventional Lippmann emulsion with the radiation sensitive tabular grain emulsion to produce the blended grain emulsion required for the practice of this invention.
  • the minimum average diameter of the second grain population is limited only by synthetic convenience, typically being at least about 0.05 ⁇ m.
  • any concentration of the second grain population can be employed that is capable of enhancing the photographic properties of the reversal photographic elements.
  • Minimum second grain population concentrations can range from as low as about 0.5 mole percent, based on total silver in the blended grain emulsion layer, with concentrations above about 1 mole percent being preferred and concentrations above about 5 mole percent being optimum for maximizing photographic benefits.
  • maximum concentrations of the second grain population are generally maintained below the concentrations of the silver haloiodide forming the radiation sensitive tabular grains--that is, below 50 mole percent, based on total silver in the blended grain emulsion layer, with most efficient utilization of silver occurring at second grain concentrations below about 40 mole percent.
  • the relatively fine grain emulsion can, for example, take the form of a relatively fine grain silver chloride, silver bromide, or silver thiocyanate emulsion, the preparations of which are well known to those skilled in the art and form no part of this invention.
  • the relatively fine grain emulsion is optimally a Lippmann emulsion. So long as the grain requirements identified above are satisfied, either or both of the tabular grain containing and relatively fine grain containing emulsions can themselves be the product of conventional grain blending.
  • the reversal photographic elements of this invention can take any convenient conventional form.
  • the reversal photographic elements can take the form of either black-and-white or color reversal photographic elements.
  • the reversal photographic elements according to this invention can be comprised of a conventional photographic support, such as a transparent film'support, onto which is coated a blended grain emulsion layer as described above.
  • a conventional photographic support such as a transparent film'support
  • overcoat and subbing layers are preferred, only the blended grain emulsion layer is essential.
  • silver halide is imagewise developed to produce a first silver image, which need not be viewable.
  • the first silver image can be removed by bleaching before further development when a silver or silver enhanced dye reversal image is desired. Thereafter, the residual silver halide is uniformly rendered developable by exposure or by fogging. Development produces a reversal image.
  • the reversal image can be either a silver image, a silver enhanced dye image, or a dye image only, depending upon the specific choice of conventional processing techniques employed.
  • the production of silver reversal images is described by Mason, Photographic Processing Chemistry, 1966, Focal Press Ltd., pp. 160-161. If a dye only image is being produced, silver bleaching is usually deferred until after the final dye image is formed.
  • the reversal photographic elements of this invention are in a preferred form color reversal photographic elements capable of producing multicolor images--e.g., images that at least approximately replicate subject colors.
  • Illustrative of such color reversal photographic elements are those disclosed by U.S. Patents 4,439,520 and 4,082,553, each cited above.
  • a color reversal photographic element can be comprised of a support having coated thereon at least three color forming layer units, including a blue recording yellow dye image forming layer unit, a green recording magenta dye image forming layer unit, and a red recording cyan dye image forming layer unit.
  • Each color forming layer unit is comprised of at least one radiation sensitive silver halide emulsion layer.
  • At least one radiation sensitive emulsion layer in each color forming layer unit is comprised of a blended grain emulsion as described above.
  • the blended grain emulsions in each color forming layer unit can be chemically and spectrally sensitized as taught by U.S. Patent 4,439,520.
  • chemical and spectral sensitization of the tabular grain emulsion is completed before blending with the second grain population, which therefore remains substantially free of sensitizing materials.
  • One or more dye image providing materials, such as couplers, are preferably incorporated in each color forming layer unit, but can alternatively be introduced into the photographic element during processing.
  • Exemplary preferred photographic supports include cellulose acetate and poly(ethylene terephthalate) film supports and photographic paper supports, especially a paper support which is partially acetylated or coated with baryta and/or a-olefin polymer, particularly a polymer of an a-olefin containing 2 to 10 carbon atoms, such as polyethylene, polypropylene, and ethylenebutene copolymers.
  • gelatin or other conventional subbing layer To facilitate coating on the photographic support it is preferred to provide a gelatin or other conventional subbing layer.
  • At least one layer comprised of a red sensitized blended grain high aspect ratio tabular grain silver haloiodide emulsion layer, as described in detail above.
  • a red sensitized blended grain high aspect ratio tabular grain silver haloiodide emulsion layer as described in detail above.
  • at least one conventional cyan dye image forming coupler is included, such as, for example, one of the cyan dye image forming couplers disclosed in U.S.
  • At least one hydrophilic colloid interlayer preferably a gelatin interlayer which includes a reducing agent, such as an aminophenol or an alkyl substituted hydroquinone, is provided to act as an oxidized developing agent scavenger.
  • a reducing agent such as an aminophenol or an alkyl substituted hydroquinone
  • At least one layer comprised of a green sensitized blended grain high aspect ratio tabular grain silver haloiodide emulsion layer, as described in detail above.
  • a conventional magenta dye image forming coupler is included, such as, for example, one of the magenta dye image forming couplers disclosed in U.S.
  • a yellow filter layer is provided for the purpose of absorbing blue light.
  • the yellow filter layer can take any convenient conventional form, such as a gelatino-yellow colloidal silver layer (i.e., a Carey Lea silver layer) or a yellow dye containing gelatin layer.
  • the filter layer contains a reducing agent acting as an oxidized developing agent scavenger, as described above in connection with the Interlayer IV.
  • At least one layer comprised of a blue sensitized blended grain high aspect ratio tabular grain silver haloiodide emulsion layer, as described in detail above.
  • the tabular grains can be thicker than high aspect ratio tabular grains--that is, the thickness criteria for the grains can be increased from 0.3 m to less than 0.5 ⁇ m, as described above.
  • the grains exhibit more native blue speed, which preferably is augmented by the use of blue spectral sensitizers, although this is not essential, except for the highest attainable blue speeds.
  • At least one conventional magenta dye image forming coupler is included, such as, for example, one of the magenta dye image forming couplers disclosed in U.S. Patents 2,875,057; 2,895,826; 2,908,573; 2,920,961; 3,148,062; 3,227,554; 3,253,924; 3,265,506; 3,277,155; 3,369,895; 3,384,657; 3,408,194; 3,415,652; and 3,447,928.
  • At least one overcoat layer is provided.
  • Such layers are typically transparent gelatin layers and contain known addenda for enhancing coating, handling, and photographic properties, such as matting agents, surfactants, antistatic agents, ultraviolet absorbers, and similar addenda.
  • the high aspect ratio tabular grain emulsion layers show sufficient differences in blue speed and green or red speed when substantially optimally sensitized to green or red light that the use of a yellow filter layer is not required to achieve acceptable green or red exposure records. It is appreciated that in the absence of a yellow filter layer the color forming layer units can be coated in any desired order on the support. While only a single color forming layer unit is disclosed for recording each of the blue, green, and red exposures, it is appreciated that two, three, or even more color forming layer units can be provided to record any one of blue, green, and red. It is also possible to employ within any or all of the blue, green, and red color forming layer units multiple radiation sensitive emulsion layers any, some, or all of which satisfy the blended grain emulsion requirements of this invention.
  • the reversal photographic elements can, of course, contain other conventional features known in the art, which can be illustrated by reference to Research Disclosure, Vol. 176, December 1978, Item 17643.
  • the silver halide emulsions other than the blended grain emulsions described can be chosen from among those described in Paragraph I; the silver halide emulsions can be chemically sensitized, as described in Paragraph III; the silver halide emulsions can be spectrally sensitized, as described in Paragraph IV; any portion of the elements can contain brighteners, as described in Paragraph V; the emulsion layers can contain antifoggants and stabilizers, as described in Paragraph VI; the color forming layer units can contain color image forming materials as described in Paragraph VII; the elements can contain absorbing and scattering materials, as described in Paragraph VIII; the emulsion and other layers can contain vehicles, as described in Paragraph IX; the hydrophilic colloid and other layers of the elements can contain
  • the photographic elements can be imagewise exposed with any of various forms of energy, as illustrated by Research Disclosure, Item 17643, cited above, Paragraph XVIII. For multicolor imaging the photographic elements are exposed to visible light.
  • Multicolor reversal dye images can be formed in photographic elements according to this invention having differentially spectrally sensitized silver halide emulsion layers by black-and-white development followed by color development. Reversal processing is demonstrated below employing conventional reversal processing compositions and procedures.
  • a very high speed green sensitized high aspect ratio tabular grain silver bromoiodide emulsion consisting of (a) high aspect ratio tabular bromoiodide grains (1.08) having an average aspect ratio of 18:1, an average tabular grain thickness of 0.1 ⁇ m, and a bromide to iodide mole ratio of 97:3; (b) 0.08 ⁇ m silver bromide grains (0.86) provided by blending a Lippmann emulsion with a high aspect ratio tabular grain silver bromoiodide emulsion providing the grains for (a); (c) gelatin (2.16); and (d) a magenta dye forming coupler, 1-(2,4,6-trichlorophenyl)-3- ⁇ 3-( ⁇ -(2,4,-di-tert-amylphenoxy)acetamido]benz- amido ⁇ -5-pyrazolone (0.86).
  • Element 2 was identical to Element 1, except that no Lippmann emulsion was blended to form Layer 2.
  • Element 3 was identical to Element 1, except that the Lippmann emulsion was not blended in Layer 2, but was partitioned into two equal parts blended into Layers 1 and 3.
  • Element 1 An element identical to Element 1 was prepared, except that instead of blending a high aspect ratio tabular grain emulsion with the silver bromide Lippmann emulsion (a) a single jet precipitated, ammonia digested silver bromoiodide emulsion containing nontabular grains of 0.54 pm in mean diameter and a bromide to iodide mole ratio of 96.5:3.4 was substituted for the high aspect ratio tabular grain silver bromoiodide emulsion and (b) the coating coverage of the silver bromide grains was reduced to 0.43 g/m 2 .
  • a single jet precipitated, ammonia digested silver bromoiodide emulsion containing nontabular grains of 0.54 pm in mean diameter and a bromide to iodide mole ratio of 96.5:3.4 was substituted for the high aspect ratio tabular grain silver bromoiodide emulsion and (b) the coating coverage of the silver bromide grains was reduced to 0.43 g/m 2
  • Element 5 was identical to Element 4, except that no Lippmann emulsion was blended to form Layer 2.
  • Element 6 was identical to Element 4, except that the Lippmann emulsion coverage was increased to 0.86 g/m 2 and was not blended in Layer 2, but was partitioned into two equal parts blended into Layers 1 and 3.
  • Element 7 was identical to Element 4, except that the single jet ammonia digested silver bromoiodide emulsion exhibited a bromide to iodide mole ratio of 93.7:6.3 and a mean grain diameter of 0.70 ⁇ m.
  • Element 8 was identical to Element 7, except that no Lippmann emulsion was blended to form Layer 2.
  • Element 9 was identical to Element 7, except that the Lippmann emulsion coverage was increased to 0.86 g/m 2 and was not blended in Layer 2, but was partitioned into two equal parts blended into Layers 1 and 3.
  • a very high speed green sensitized high aspect ratio tabular grain silver bromoiodide emulsion consisting of (a) high aspect ratio tabular bromoiodide grains having an average aspect ratio of 18:1, an average tabular grain thickness of 0.1 ⁇ m, and a bromide to iodide mole ratio of 97:3 (1.08); (b) gelatin (2.16); and (c) a cyan dye forming coupler, 3-[a-(2,4,- di-tert-amylphenoxy)hexanamido]-2-heptafluorobutyr- amidophenol (0.97).
  • Gelatin (0.97) and bis(vinylsulfonyl)methane hardener at 1.75% by weight, based on total gelatin in both layers.
  • Element 11 was identical to Element 10, except that 0.054 g/m 2 of 0.08 ⁇ m silver bromide grains in the form of a Lippmann emulsion were blended with the high aspect ratio tabular grain silver bromoiodide emulsion.
  • Element 12 was identical to Element 11, except that the coating coverage of the silver bromide grains was approximately doubled to 0.11 g/m 2 .
  • Element 13 was identical to Element 12, except that the coating coverage of the silver bromide grains was doubled to 0.22 g/m 2 .
  • a very high speed green sensitized high aspect ratio tabular grain silver bromoiodide emulsion consisting of (a) high aspect ratio tabular bromoiodide grains having an average aspect ratio of 18:1, an average tabular grain thickness of 0.1 ⁇ m, and a bromide to iodide mole ratio of 97:3 (1.08); (b) gelatin (2.16); and (c) a cyan dye forming coupler, 3-[a-(2,4,- di-tert-amylphenoxy)hexanamido]-2-heptafluorobutyr- amidophenol (0.97).
  • a yellow filter layer comprised of gelatin (0.60); ⁇ -cyano-4-[N,N-bis(isopropoxycarbonylmethyl)]-amino-2-methyl-4'-methanesulfonamidochalcone (0.11); and a-cyano-4-[N-ethyl-N-(2,2,2-trifluoroethoxy- carbonylmethyl]aminc-2-methyl-4'-propanesulfonamido " chalcone (0.08).
  • a very high speed blue sensitized high aspect ratio tabular grain silver bromoiodide emulsion consisting of (a) high aspect ratio tabular bromoiodide grains (1.08) having an average aspect ratio of 11.7:1, an average tabular grain thickness of 0.12 ⁇ m, and a bromide to iodide mole ratio of 97:3; (b) gelatin (2.16); and (c) a yellow dye forming coupler, a-[4-(4-benzyloxyphenylsulfonyl)phenoxy]-a-pivalyl-2-chloro-5-hexadecylsulfonamidoacetanalide (1.61).
  • Ultraviolet absorbers 3-(di-n-hexylamino)allylidene- malonitrile (0.11) and n-propyl-a-cyano-p-methoxycinnamate (0.11), 0.08 ⁇ m silver bromide grains (0.12), gelatin (1.36), and bis(vinylsulfonyl)methane hardener at 1.75% by weight, based on total gelatin in all layers.
  • Elements 19 and 20 were identical to Element 18, except that the green sensitized high aspect ratio tabular grain emulsion forming Layer 1 also contained 0.11 and 0.22 g/m 2 , respectively, of 0.08 ⁇ m silver bromide grains, introduced by blending a Lippmann emulsion. The time of development was four minutes 30 seconds.
  • Element 18 represented by reversal characteristic curve C18
  • Element 20 represented by reversal chracteristic curve E20
  • Figure 7 A very pronounced increase in maximum density, threshold speed, and contrast and a very pronounced decease in toe region density is observed for Element 20.
  • the performance of Element 19 was intermediate between that of Elements 18 and 20, but nearer to that of Element 20.
  • Elements 21 and 22 were identical to Element 18, except that the green sensitized high aspect ratio tabular grain emulsion forming Layer 1 also contained 0.054 and 0.11 g/m 2 , respectively, of 0.2-0.4 ⁇ m average diameter silver thiocyanate grains.
  • Element 22 which contained approximately twice the coating coverage of silver thiocyanate grains exhibited differences from Element 18 that were qualitatively similar to those exhibited by Element 21, but the differences were larger in the case of Element 22.
  • Element 23 was identical to Element 18, except that the green sensitized high aspect ratio tabular grain emulsion forming Layer 1 also contained 0.11 g/m 2 of 0.2-0.4 ⁇ m average diameter silver thiocyanate grains and 0.22 g/m 2 of 0.08 pm
  • the reversal characteristic curve E23 obtained for Element 23 is plotted in Figure 8. It can be seen that a higher maximum density and contrast is realized as compared to corresponding curves C18 and E21 representing Elements 18 and 21, respectively. Also a lower toe region density is realized.
  • Element 14 An element similar to Element 14 was prepared, exposed, and processed, except that the emulsion layer additionally contained silver iodide grains of less than 0.1 pm in average diameter (0.11) as a result of blending in a Lippmann silver iodide emulsion.
  • a control element was made by coating a sulfur and gold chemically sensitized high speed red spectrally sensitized high aspect ratio tabular grain silver bromoiodide emulsion on a gelatin (4.89) subbed film support.
  • the tabular silver bromoiodide grains had an average diameter of 1.6 um and an average thickness of 0.11 pm.
  • the silver coverage was 1.46 g/m 2 and the gelatin coverage of the emulsion layer was 2.15 g/m 2 .
  • the emulsion layer was overcoated with gelatin (0.98), and the element was hardened with 1.57 percent by weight, based on total gelatin, bis(vinylsulfonyl)methane.
  • the film support had a process removable carbon containing antihalation layer of the type disclosed in Simmons U.S. Patent 2,327,828.
  • An element was prepared similar to Element 25, except that the silver coverage was increased 5 percent by weight by blending into the silver bromoiodide emulsion before coating a Lippmann emulsion having silver bromide grains of 0.08 ⁇ m average diameter.
  • An element was prepared similar to Element 25, except that the silver coverage was increased 10 percent by weight by blending into the silver bromoiodide emulsion before coating a Lippmann emulsion having silver bromide grains of 0.08 pm average diameter.
  • An element was prepared similar to Element 25, except that the silver coverage was increased 20 percent by weight by blending into the silver bromoiodide emulsion before coating a Lippmann emulsion having silver bromide grains of 0.08 ⁇ m average diameter.
  • Elements 25, 26, 27, and 28 were identically exposed and processed.
  • the dried elements were exposed (1/50 second, 500 watts/2850 0 K) through a 0.61 neutral density filter and a Daylight V filter plus a Wratten 23A * filter.
  • the elements were processed for 80 seconds in a black-and-white developer of the type disclosed by Battaglini et al U.S. Patent 3,607,263, Example 1, washed, exposed uniformly to red light, and processed in color developer containing a cyan coupler, following a procedure like that of Example 1 of Schwan et al U.S. Patent 2,959,970.
  • the characteristic curves obtained for Elements 25 and 28 are shown in Figure 10 as curves C25 and E28, respectively. It can be seen that curve E28 has a higher maximum density and contrast than curve C25 and exhibits reduced density in the toe region of the characteristic curve.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP86100953A 1985-02-04 1986-01-24 Photographische Umkehrelemente mit tafelförmige Körner enthaltenden Emulsionen Expired - Lifetime EP0190625B1 (de)

Priority Applications (1)

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AT86100953T ATE63009T1 (de) 1985-02-04 1986-01-24 Photographische umkehrelemente mit tafelfoermige koerner enthaltenden emulsionen.

Applications Claiming Priority (2)

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US69805385A 1985-02-04 1985-02-04
US698053 1985-02-04

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EP0190625A2 true EP0190625A2 (de) 1986-08-13
EP0190625A3 EP0190625A3 (en) 1988-07-27
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EP (1) EP0190625B1 (de)
JP (1) JPH07111551B2 (de)
AT (1) ATE63009T1 (de)
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DE (1) DE3678848D1 (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0267483A2 (de) * 1986-11-13 1988-05-18 Minnesota Mining And Manufacturing Company Verfahren und Element zur Herstellung eines photographischen Bildes
EP0312959A1 (de) * 1987-10-16 1989-04-26 Fuji Photo Film Co., Ltd. Photographische Silberhalogenidemulsion
EP0334320A1 (de) * 1988-03-25 1989-09-27 EASTMAN KODAK COMPANY (a New Jersey corporation) Mischemulsionen mit verbessertem Empfindlichkeits-Körnigkeitsverhältnis
EP0599428A2 (de) * 1992-11-27 1994-06-01 Eastman Kodak Company Photographische Elemente zur Herstellung von spektralen Bildaufzeichnungen, die durch Abtasten wiederauffindbar sind, und Verfahren zu ihrer Verwendung
EP0651283A1 (de) * 1993-10-29 1995-05-03 Eastman Kodak Company Verbesserte Umkehr photographischer Elemente, die Emulsionen mit tafelförmigen Körnern enthalten
EP0718676A1 (de) * 1994-12-22 1996-06-26 Eastman Kodak Company Emulsionen mit erhöhter Empfindlichtkeit und kontrollierten Minimaldichten enthaltende photographische Aufnahmeelemente

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3598597A (en) * 1967-05-24 1971-08-10 Gaf Corp Speed and contrast of a silver halide photographic emulsion obtained by addition of silver chloride emuldion to silver bromide emulsion
DE3241643A1 (de) * 1981-11-12 1983-05-19 Eastman Kodak Co., 14650 Rochester, N.Y. Direkt-positives photographisches aufzeichnungsmaterial
DE3241635A1 (de) * 1981-11-12 1983-05-19 Eastman Kodak Co., 14650 Rochester, N.Y. Photographisches aufzeichnungsmaterial
DE3347215A1 (de) * 1982-12-27 1984-06-28 Fuji Photo Film Co., Ltd., Minamiashigara, Kanagawa Lichtempfindliches, photographisches silberhalogenidmaterial

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5816048A (ja) * 1981-07-22 1983-01-29 Res Inst Electric Magnetic Alloys 耐食性の優れた高透磁率非晶質合金およびその製造方法
JPS58111936A (ja) * 1981-11-12 1983-07-04 イ−ストマン・コダツク・カンパニ− 放射線感応性乳剤およびその製法
BE894966A (fr) * 1981-11-12 1983-05-09 Eastman Kodak Co Produit radiographique
JPS6012540A (ja) * 1983-07-01 1985-01-22 Konishiroku Photo Ind Co Ltd リツプマン型ハロゲン化銀写真感光材料

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3598597A (en) * 1967-05-24 1971-08-10 Gaf Corp Speed and contrast of a silver halide photographic emulsion obtained by addition of silver chloride emuldion to silver bromide emulsion
DE3241643A1 (de) * 1981-11-12 1983-05-19 Eastman Kodak Co., 14650 Rochester, N.Y. Direkt-positives photographisches aufzeichnungsmaterial
DE3241635A1 (de) * 1981-11-12 1983-05-19 Eastman Kodak Co., 14650 Rochester, N.Y. Photographisches aufzeichnungsmaterial
DE3347215A1 (de) * 1982-12-27 1984-06-28 Fuji Photo Film Co., Ltd., Minamiashigara, Kanagawa Lichtempfindliches, photographisches silberhalogenidmaterial

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PHOTOGRAPHIC SCIENCE AND ENGINEERING, vol. 28, no. 4, July-August 1984, pages 137-145, Society of Photographic Scientists and Engineers, Springfield, VA, US; T. SUGIMOTO: "Growth mechanism and size distribution of AgBr tabular grains" *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0267483A2 (de) * 1986-11-13 1988-05-18 Minnesota Mining And Manufacturing Company Verfahren und Element zur Herstellung eines photographischen Bildes
EP0267483A3 (en) * 1986-11-13 1988-12-14 Minnesota Mining And Manufacturing Company Process and element for obtaining a photographic image
EP0312959A1 (de) * 1987-10-16 1989-04-26 Fuji Photo Film Co., Ltd. Photographische Silberhalogenidemulsion
US5043258A (en) * 1987-10-16 1991-08-27 Fuji Photo Film Co. Silver halide photographic emulsion
EP0334320A1 (de) * 1988-03-25 1989-09-27 EASTMAN KODAK COMPANY (a New Jersey corporation) Mischemulsionen mit verbessertem Empfindlichkeits-Körnigkeitsverhältnis
EP0599428A2 (de) * 1992-11-27 1994-06-01 Eastman Kodak Company Photographische Elemente zur Herstellung von spektralen Bildaufzeichnungen, die durch Abtasten wiederauffindbar sind, und Verfahren zu ihrer Verwendung
EP0599428A3 (de) * 1992-11-27 1995-03-29 Eastman Kodak Co Photographische Elemente zur Herstellung von spektralen Bildaufzeichnungen, die durch Abtasten wiederauffindbar sind, und Verfahren zu ihrer Verwendung.
EP0651283A1 (de) * 1993-10-29 1995-05-03 Eastman Kodak Company Verbesserte Umkehr photographischer Elemente, die Emulsionen mit tafelförmigen Körnern enthalten
EP0718676A1 (de) * 1994-12-22 1996-06-26 Eastman Kodak Company Emulsionen mit erhöhter Empfindlichtkeit und kontrollierten Minimaldichten enthaltende photographische Aufnahmeelemente
US5728516A (en) * 1994-12-22 1998-03-17 Eastman Kodak Company Photographic print elements containing cubical grain silver iodochloride emulsions

Also Published As

Publication number Publication date
EP0190625B1 (de) 1991-04-24
CA1259845A (en) 1989-09-26
ATE63009T1 (de) 1991-05-15
DE3678848D1 (de) 1991-05-29
JPS61246746A (ja) 1986-11-04
EP0190625A3 (en) 1988-07-27
JPH07111551B2 (ja) 1995-11-29

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