US3690891A - Infrared-sensitized silver halide systems - Google Patents

Infrared-sensitized silver halide systems Download PDF

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US3690891A
US3690891A US56700A US3690891DA US3690891A US 3690891 A US3690891 A US 3690891A US 56700 A US56700 A US 56700A US 3690891D A US3690891D A US 3690891DA US 3690891 A US3690891 A US 3690891A
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silver halide
infrared
emulsion
dye
silver
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John Spence
Paul Brewster Gilman Jr
Cynthia Geer Ulbing
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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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • 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
    • G03C1/015—Apparatus or processes for the preparation of emulsions
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • 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
    • G03C2200/06—Additive
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G03C5/164—Infrared processes

Definitions

  • this invention relates to internal-image, silver halide emulsions comprising unfogged, silver halide grains which contain chemically formed internal sensitivity sites and wherein said grains have adsorbed to the surface thereof an infrared-sensitizing dye.
  • this invention relates to an improved process for making negative-image records from infrared exposures.
  • the preferred internal-image silver halide emulsions used in the improved combination of this invention contain unfogged silver halide grains which contain chemically treated sites for the deposition of photolytic or latent image silver internal to the grains, preferably formed by occluding polyvalent metal ions inside the grain.
  • this invention relates to infraredsensitized silver halide emulsion systems with improved photographic properties.
  • Another embodiment of this invention relates to internal-image emulsions containing polymethine infrared-absorbing dyes.
  • the silver halide emulsions comprise organic infrared-sensitizing dyes which have their primary absorption peak in the infrared region of the spectrum wherein said dyes are dicarbocyanines, tricarbocyanines, tetracarbocyanines, pentacarbocyanines, merocyanines, merodicarbocyanines, merotricarbocyanines, polynuclear merocyanines, complex merocyanines and the like.
  • the internalimage emulsions of this invention comprise unfogged sil- 3,690,891 Patented Sept. 12, 1972 ver halide grains which are chemically sensitized internally and wherein said emulsion comprises an infraredabsorbing dye in a concentration sufiicient to cover at least 50% of the total available surface of the silver halide grains and preferably at least 70% of the total available surface.
  • the infrared-sensitizing dyes are used in a concentration above that which would produce a loss in blue sensitivity in a sulfur and gold surfacesensitized silver bromoiodide emulsion (6 mole percent iodide) of at least 0.3 log E when developed in a surface developer such as Kodak D-l9.
  • internal-image emulsion refers to those emulsions wherein a predominant amount of the blue sensitivity is internal to the grains of said emulsion.
  • Such internal-image emulsions are those which, when tested according to normal photographic testing techniques by coating a test portion of the emulsion on a transparent support, exposing to a light-intensity scale for a fixed time between 1 10- and 1 second, bleaching 5 minutes in a 0.3% potassium ferricyanide solution at 65 F. and developing for about 5 minutes at 65 F.
  • Developer B below an internal-type developer
  • Developer A below a surfacetype developer
  • the internal-image radiation emulsions have a predominant amount of sensitivity internal to the grain and preferably have a ratio of total sensitivity to surface sensitivity of greater than 10.
  • Developer A is the usual type of surface-image developer and Developer B is an internal developer having high silver halide solvent activity.
  • Developer A G. N-methyl-p-aminophenol sulfate 2. Ascorbic acid 10.0 Potassium metaborate 35- Potassium bromide 1.0 Water to make 1 liter. pH of 96.
  • the internal-image emulsions which are useful according to this invention are those which contain grains having a metal dopant occluded therein.
  • the metal dopants can be occluded within the grain, for example, by precipitating in the presences of foreign ions (i.e., other than silver ions); by chemically sensitizing a core of a silver halide grain to form a metal or metal salt thereon and then forming a shell or outer region on the core occluding the chemically sensitized site within the grain; etc.
  • Typical useful silver halide emulsions containing grains having metal dopants occluded therein can be prepared by the procedures disclosed in Porter et al., US. Pat. 3,206,- 313 issued Sept.
  • the silver halides used in the present invention are unfogged or at least they are bleached before chemical development to provide an unfogged emulsion.
  • Such silver halide emulsions contain no visible or substantial developable surface latent image.
  • the silver halide emulsions may be coarseor finegrain emulsions and can be prepared by many of the procedures available for making silver halide emulsions, e.g., single-jet emulsion procedures, double-jet emulsion procedures, ammonical emulsions, thiocyanate and/ or thioether ripened emulsions, emulsions prepared using increased flow rates as disclosed in U.S. Ser. No. 11,838 by Wilgus filed Feb. 16, 1970, hot nucleation procedures as disclosed in U.S. Ser. No. 31,351 by Musliner filed Apr. 23, 1970, and the like.
  • the silver halide grains are formed in the presence of foreign metal ions, i.e., metal ions exclusive of silver, and preferably polyvalent metal ions.
  • metal ions exclusive of silver
  • polyvalent metal ions i.e., silver ions exclusive of silver
  • the silver halide grains are formed in the presence of the water-soluble salts of the respective metal, preferably in an acidic medium.
  • Typical useful polyvalent metal ions include trivalent metal ions such as antimony, bismuth, arsenic, gold, iridium, rhodium and the like and tetravalent metal ions such as platinum, osmium, iridium and the like.
  • the grains are formed in the presence of bismuth, lead, iridium or osmium ions.
  • the silver halide grains contain at least about and preferably at least 10- mole percent dopant based on silver halide.
  • the internal-image emulsions can also be formed by other methods which will yield a metal dopant occluded within the grain.
  • metal dopant refers to any metal, metal ion or metalcontaining compound which disrupts or changes the orderly silver ion-halide ion lattice in the silver halide grain or crystal. Therefore, the metal dopants useful according to this invention include such compounds as silver sulfide, silver telluride, silver selenide, mtallic silver, metallic gold, selenium, tellerium, gold sulfide and the like.
  • any of the methods which are useful to produce centers which promote the deposition of photolytic silver can be used to provide the metal dopants within the silver halide grain.
  • preferred metal dopants occluded within the grain contain at least one metal or metal ion other than silver (i.e., a foreign metal atom) and, in certain highly preferred embodiments, the metal of the metal dopant is a trivalent or tetravalent metal ion.
  • the silver halide grains of this invention can additionally be surface-sensitized as long as they contain a strong metal dopant occluded therein, such as a trivalent or tetravalent metal ion or the equivalent thereof.
  • a strong metal dopant occluded therein such as a trivalent or tetravalent metal ion or the equivalent thereof.
  • Typical useful techniques for surface-sensitizing an imulsion are disclosed in Porter et al., U.S. Patent 3,317,322 issued May 2, 1967.
  • the infrared-absorbing dyes are utilized in combination with the doped emulsions of this invention in concentrations of generally above 100 mg./per mole of silver halide.
  • the dyes are used in a concentration above that which would produce a loss in blue sensitivity in a sulfur and gold surface-sensitized, silver bromoiodide emulsion (6 mole percent iodide) of at least 0.3 log E when developed in a surface developer such as Kodak D-19.
  • the infrared-sensitizing dyes which are especially useful according to this invention are those which have a primary absorption peak at a wave length of above 700 millimicrons and preferably above 800 millimicrons.
  • Typical dyes which produce improved photographic properties, such as improved sensitivity, when used in combination with the internal-image emulsions of this invention include:
  • the silver halide emulsions of this invention can be protected against the production of fog and can be stabilized against loss of sensitivity during keeping.
  • Suitable antifoggants and stabilizers each used alone or in combination include thiazolium salts described in U.S. Patents 2,131,038 by Brooker et al. and 2,694,716 by Allen et al.; the azaindenes described in U.S. Patents 2,886,437 by Piper and 2,444,605 by Heimbach et al.; the mercury salts as described in U.S. Patent 2,728,663 by Allen et al.; the
  • the photographic elements of this invention may contain incorporated developing agents such as hydroquinones, catechols, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones and phenylenediamines. Combinations of developing agents can be employed in the practice of the invention.
  • the developing agents can be in a silver halide emulsion and/ or in another suitable location in the photographic element.
  • the developing agents may be added from suitable solvents or in the form of dispersions as described in Yackel, U.S. Patent 2,592,- 368, and Dunn et al., French Patent 1,505,778.
  • the photographic and other hardenable layers used in the practice of this invention can be hardened by various organic or inorganic hardeners, alone or in combination, such as the aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, mixed-function hardeners and polymeric hardeners such as oxidized polysaccharides like dialdehyde starch and oxyguargum and the like.
  • various organic or inorganic hardeners such as the aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines
  • Suitable hydrophilic materials include both naturally occurring substances such as proteins, for example, gelatin, gelatin derivatives, cellulose derivatives, polysacchardies such as dextran, gum arabic and the like; and
  • the described photographic emulsion layers and other layers of a photographic element employed in the practice of this invention can also contain, alone or in combination with hydrophilic, water-permeable colloids, other synthetic polymeric compounds such as dispersed vinyl compounds such as in latex form and particularly those which increase the dimensional stability of the photographic materials.
  • Suitable synthetic polymers include those described, for example, in U.S. Patents 3,142,568 by Nottorf issued July 28, 1964; 3,193,386 by White issued July 6, 1965; 3,062,674 by Houck et al. issued Nov. 6, 1962; 3,220,844 by Houck et al. issued Nov. 30, 1965; 3,287,289 by lRearn et al. issued Nov.
  • Typical supports include cellulose nitrate film, cellulose ester film, poly- (vinyl acetal) film, polystyrene film, poly (ethylene terephthalate) film, polycarbonate film and related films or resinous materials, as well as glass, paper, metal and the like.
  • a flexible support is employed, especially a paper support, which can be partially acetylated or coated with baryta and/or an alpha-olefin polymer, particularly a polymer of an alpha-olefin containing 2 to carbon atoms such as polyethylene, polypropylene, ethylenebutene copolymers and the like.
  • This invention may be used with elements designed for colloid transfer processes such as described in U.S. Patent 2,716,059 by Yutzy et al.; silver salt diffusion transfer processes such as described in U.S. Patents 2,352,014 by Rott, 2,543,181 by Land, 3,020,155 by Yackel et a1. and 2,861,885 by Land; color image transfer processes such as described in U.S.
  • This invention may be used with elements designed for color photography, for example, elements containing colorforming couplers such as those described in U.S. Patents 2,376,679 by Frohlich et al., 2,322,027 by Jelley et al., 2,801,171 by Fierke et al., 2,698, 794 by Godowsky, 3,227,- 554 by Barr et a1. and 3,046,129 by Graham et al.; or elements to be developed in solutions containing colorforming couplers such as those described in U.S. Patents 2,252,718 by Mannes et al., 2,592,243 by Carroll et a1. and 2,950,970 by Schwan et al.; and in false-sensitized color materials such as those described in U.S. Patent 2,763,549 by Hanson.
  • elements containing colorforming couplers such as those described in U.S. Patents 2,376,679 by Frohlich et al., 2,322,
  • Photographic elements prepared according to this invention can be processed by various methods which utilize internal-image silver halide developing compositions containing silver halide solvents and developing agents such as hydroquinones, catechols, aminophenols, 3-pyrazolidones, phenylenediamines, ascorbic acid derivatives, hydroxylamines, hydrazines, reductones and the like including procedures such as web processing as described in U.S. Patent 3,179,517 by Tregillus et al.; stabilization processing as described in Russell et al., Stabilization Processing of Films and Papers, PSA Journal, vol. 16B, August 1950; monobath processing as described in Levy, Combined Development and Fixation of Photographic Images With Monobaths, Phot. Sci, and Eng, vol. 2,
  • the photographic elements of this invention can be processed in hardening developers such as those described in U.S. Patent 3,232,761 by Allen et al.; in roller transport processors such as those described in U .8. Patent 3,025,779 by Russell et al.; or by surface application processing as described in Example 3 of U.S. Patent 3,418,132 by Kitze.
  • EXAMPLE l-A An iridium cored emulsion prepared as described by Berriman in U.S. Pat. 3,367,778, except without surface fogged grains, is used for the spectral-sensitizing experi-' ments.
  • the emulsion is prepared to the following specifications:
  • Coatings .004" wet thickness are made on cellulose acetate subbed support. The dried coatings are exposed in a Bausch and Lomb spectrograph. Blue exposures are made at /2 sec. with a slit width of 1.0 mm. When the exposed strips are processed in an Elon-hydroquinone developer, no image is obtained until 1 g./l. of potassium iodide is added to cause the internal image to develop.
  • EXAMPLE l-B 1.50 ml. of a 1.0% aqueous silver nitrate solution ml. of a 28% aqueous ammonium hydroxide soluion distilled water to ml.
  • the strip is rinsed in water for 1 minute, placed for 15 seconds in ethyl alcohol and then dried.
  • EXAMPLE 2 A variety of sensitizing dyes which range in sensitizing power from very good to strong desensitization in surfacesensitized emulsions are evaluated with the iridium cored emulsion.
  • Example 1-A To 31 g. of the emulsion described in Example 1-A are added 75 ml. of 5% gelatin, 1.0 ml. of a 7 /2% saponin solution and 0.5 ml. of a 10% formaldehyde solution. To 10 ml. of the above emulsion mixture is added the dye solution described in Example 1-A and a 5% gelatin solution to make a total of ml. The mixture is held for 15 minutes at 40 C. and coated at .004" wet thickness on subbed cellulose acetate support.
  • a repeat coating is made using Dye III, 3,3-diethyl-9,11- neopentylenethiatetracarbocyanine iodide, at a level of 100 mg. of dye/mole of silver.
  • a second coating is made similar to the first coating described next above with the addition of 100 mg. of Calcofluor White (triazine-stilbene brightening agent manufactured by American Cyanamid Co.) added per mole of silver.
  • EXAMPLE 4 A radiation-sensitive gelatin silver chlorobromide photographic emulsion is prepared in the presence of bismuth ions as described in Example 18 of U.S. Pat. 3,447,- 927. The dyes are added to portions of the emulsion at the concentrations indicated (mg/Ag mole). All of the emulsion samples are coated with 34 g. of dithiourazole methyl vinyl ketone adduct as described in Wise et al., U.S. Ser. No. 816,867 filed Apr. 4, 1969 corresponding to 8 U.S. Pat. 3,615,618, issued Oct. 26, 1971, and coated on a paper support at mg. Ag/ft.
  • Exposure (1) 20" /1, mm. slit width on Horton Spectrograph (this gives wave length scale wedge spectrogram) (sensitizing maximum and range of sensitivity).
  • Samples of the coatings are heated on an aluminum block with a Teflon surface at a block temperature of 230 C., then photodeveloped for 5 under UV light. Speed is determined as the last step visible in the region of low exposure. Note that any B speel with an is unreliable as the 35 +38A filter transmits infrared radiation.
  • Example 4 An emulsion is prepared according to Example 4 containing 3,3'-diethylsulfodicarbocyanine ethyl sulfate. The emulsion is exposed and developed with 5 seconds of heating at 230 C. as in Example 4 with the following results:
  • EXAMPLE4C An emulsion is prepared as described in Example 4 containing Dyes VII and VIII.
  • Dye VII3,3-diethylthiatricarbocyanine iodide Dye VIII3,3'-diethyl-10, 1 Z-ethylene-l-(4-methyl-1- piperazinyl oxatricarbocyanine perchlorate
  • the emulsions are exposed and developed with seconds of heating at 230 C. as in Example 4 with the following results:
  • EXAMPLE 4-D An emulsion is prepared as lescribed in Example 4 The emulsion, exposure and procesisng are as described in Example 4 with the exception that a sample of each coating is also exposed on an infrared sensitometer through an Interference Flter Set 'Filter No. 1.0 (Optics Technology, Inc.)
  • EXAMPLE 5 An internal-image emulsion, a bromoiodide emulsion .(2.5 mole percent iodide) having an average grain size of 0.2 micron, is prepared by adding 106 mg. of potassium hexachloroiridate/mole of silver to the gelatin solution prior to the precipitation of the silver halide. The emulsion is divided into separate aliquot portions and to the portions are added 250, 500, 700 and 900 mg. of the infrared sensitizing dye 3,3'-diethylthiatricarbocyanine iodide per silver mole. The emulsion samples are then coated on a film support at 100 mg. of silver/ftF. After exposing the coated samples on an Eastman 1B Sensitometer, the samples are developed in the internal-image developer of the following composition:
  • N 0TE.-A 3-earboxymethyl-5-[4-(lethylnaphtho[1,2-d]thiazolin-2 ylldene) -2-butenylrdenelrhodanine;
  • B 1-carb0xymethyl-5-l(3-ethy1- 2(3H):naphtho[2,11-thiazolylidene)-2-butenylidene]-3-phenyl-2-thiohydantom, pyridine salt;
  • O 1,3-diethyl-5-[6-(3-ethyl-2(3)-benzothiazolyhdene)hexadienylidene]barbituric acid;
  • D 3-ethyl-5-[(2-ethyl-1(2)- benzothiazylidene)hexadienylidene]rhodanine.
  • the samples exhibit very high spectral sensitivity with little or no loss in blue-speed sensitivity.
  • EXAMPLE 7 An internal-image emulsion is prepared as described in Example 5. The emulsion is then chemically sensitized at the surface of the grains by adding 2.0 mg. of thiourea dioxide/ silver mole and then finished to optimum. To the emulsion is added 500 mg. of the infrared-sensitizing dye 3,3-diethylthiatric-arbocyanine iodide per silver mole. After exposing and processing as described in Example 5, a 0.3 log E speed increase is noticed over an undyed control.
  • EXAMPLE 8 An internal-image emulsion is prepared with 900 mg. of the dye as described in Example 5. The emulsion is then coated at mg. silver/ft. on a film support and exposed to 20 foot candles of illumination for 5 seconds through a line image. The coating is then rolled in contact with a receiver and pod with a Viscous developer solution of the type described in U.S. Pat. 2,823,122. After 10 seconds, the receiver is separated from the film support and on the receiving layer is noticed a high-quality directpositive image.
  • a photographic element comprising a support and at least one layer containing an internal-image silver halide emulsion comprising silver halide grains having metal dopants occluded therein and a concentration of an organic, sensitizing dye on the surface of said grain above the concentration which would produce a loss in blue sensitivity in a control sulfur and gold surface-sensitized silver bromoiodide emulsion, containing 6 mole percent iodide, of at least 0.3 log E when developed in Kodak Developer D19 of the composition:
  • a photographic element according to claim 1 wherein said silver halide grains are core-shell grains wherein the core has been sulfurand gold-sensitized before forming a shell thereon.
  • a photographic element comprising a support and at least one layer containing a silver halide emulsion having a ratio of total sensitivity to surface sensitivity of greater than 10, comprising silver halide grains having metal dopants occluded therein and a concentration of an organic, sensitizing dye on the surface of said grains above the concentration which would produce a loss in blue sensitivity in a control sulfur and gold surface-sensitized silver bromoiodide emulsion, containing 6 mole percent iodide, of at least 0.3 log E when developed in Kodak Developer D-l9 of the composition:
  • said silver halide grains are core-shell grains wherein the core has been sulfurand gold-sensitized before forming a shell thereon.
  • a photographic internal-image, silver halide emulsion comprising silver halide grains having metal dopants occluded therein and a concentration of an organic, sensitizing dye on the surface of said grains above the concentration which would produce a loss in blue sensitivity in a control sulfur and gold surface-sensitized silver bromoiodide emulsion, containing 6 mole percent iodide, of at 12 least 0.3 log E when developed in Kodak Developer D-l9 of the composition:
  • a photographic silver halide emulsion comprising silver halide grains having a ratio of total sensitivity to surface sensitivity of greater than 10 and having metal dopants occluded therein, and a concentration of an organic, sensitizing dye on the surface of said grains above the concentration which would produce a loss in blue sensitivity in a control sulfur and gold surface-sensitized silver bromoiodide emulsion, containing 6 mole percent iodide, of at least 0.3 log E when developed in Kodak Developer D-l9 of the composition:
  • said dye having a radiation adsorption peak in the infrared region of the electromagnetic spectrum.
  • a photographic element comprising a support having thereon at least one layer containing an internal-image silver halide emulsion comprising silver halide grains, the surface of said grains being free of intentional chemical sensitization, said grains having occluded therein a metal dopant selected from the group consisting of antimony, bismuth, rhodium, platinum, osmium, iridium, and lead ions, and on the surface of said grains a concentration of organic, sensitizing dye having a radiation adsorption peak in the infra-red region of the electromagnetic spectrum, above that which would produce a loss in blue sensitivity in a control sulfur and gold surface-sensitized silver bromoiodide emulsion, containing 6 mole percent iodide, of at least 0.3 log E when developed in Kodak Developer D-19 having the composition:

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852067A (en) * 1971-11-04 1974-12-03 Polaroid Corp Photosensitive element with silver halide, a semiconductor and a sensitizing dye
US3852071A (en) * 1971-11-09 1974-12-03 Fuji Photo Film Co Ltd Process of producing positive images
US3852066A (en) * 1971-11-04 1974-12-03 Polaroid Corp Silver halide with an orthorhombic lead monoxide and sensitizing dye
US3932292A (en) * 1972-08-17 1976-01-13 Ciba-Geigy Ag Process for the manufacture of doped silver halides
US3963493A (en) * 1972-02-18 1976-06-15 Agfa-Gevaert N.V. Direct-positive silver halide emulsion fogged to low level and the use thereof in energetic-surface development
US3993490A (en) * 1974-02-12 1976-11-23 E. I. Du Pont De Nemours And Company Direct positive photographic elements containing developers
US4011083A (en) * 1974-12-10 1977-03-08 Eastman Kodak Company Surface sensitive silver halide emulsion containing a silver complexing azaindene to reduce desensitization of optical sensitizing dye incorporated therein
US4596767A (en) * 1983-04-13 1986-06-24 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US4713316A (en) * 1984-12-05 1987-12-15 Fuji Photo Film Co., Ltd. Heat-developable photographic materials

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8422069D0 (en) * 1984-08-31 1984-10-31 Minnesota Mining & Mfg Photographic elements
US6942960B2 (en) * 2003-08-12 2005-09-13 Eastman Kodak Company Photothermographic materials containing doped high iodide emulsions

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852067A (en) * 1971-11-04 1974-12-03 Polaroid Corp Photosensitive element with silver halide, a semiconductor and a sensitizing dye
US3852066A (en) * 1971-11-04 1974-12-03 Polaroid Corp Silver halide with an orthorhombic lead monoxide and sensitizing dye
US3852071A (en) * 1971-11-09 1974-12-03 Fuji Photo Film Co Ltd Process of producing positive images
US3963493A (en) * 1972-02-18 1976-06-15 Agfa-Gevaert N.V. Direct-positive silver halide emulsion fogged to low level and the use thereof in energetic-surface development
US3932292A (en) * 1972-08-17 1976-01-13 Ciba-Geigy Ag Process for the manufacture of doped silver halides
US3993490A (en) * 1974-02-12 1976-11-23 E. I. Du Pont De Nemours And Company Direct positive photographic elements containing developers
US4011083A (en) * 1974-12-10 1977-03-08 Eastman Kodak Company Surface sensitive silver halide emulsion containing a silver complexing azaindene to reduce desensitization of optical sensitizing dye incorporated therein
US4596767A (en) * 1983-04-13 1986-06-24 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US4713316A (en) * 1984-12-05 1987-12-15 Fuji Photo Film Co., Ltd. Heat-developable photographic materials

Also Published As

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GB1347716A (en) 1974-02-27
DE2136017A1 (de) 1972-02-03
CA976407A (en) 1975-10-21
BE770223A (fr) 1971-12-01
FR2101859A5 (2) 1972-03-31
DE2136017B2 (de) 1974-07-18
AU3141271A (en) 1973-01-25
AU456564B2 (en) 1974-12-19
JPS5226125B1 (2) 1977-07-12

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