US3761266A - Silver halide emulsions predominantly chloride containing silver halide grains with surfaces chemically sensitized and interiors free fromchemical sensitization and the use thereof in reversal processes - Google Patents

Silver halide emulsions predominantly chloride containing silver halide grains with surfaces chemically sensitized and interiors free fromchemical sensitization and the use thereof in reversal processes Download PDF

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US3761266A
US3761266A US00123006A US3761266DA US3761266A US 3761266 A US3761266 A US 3761266A US 00123006 A US00123006 A US 00123006A US 3761266D A US3761266D A US 3761266DA US 3761266 A US3761266 A US 3761266A
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silver halide
silver
emulsion
developer
grains
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K Milton
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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
    • G03C1/485—Direct positive emulsions

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  • This invention relates to unfogged silver halide emulsions and methods of forming positive images in unfogged silver halide emulsions wherein the halide is predominantly chloride.
  • this invention relates to a process of obtaining positive images in a silver halide emulsion, wherein the halide is predominantly chloride, said process comprising (1) imagewise exposure of said silver halide emulsion and then (2) either (a) developing said exposed silver halide emulsion in a silver halide surface developer in the presence of a fogging agent, (b) light-flashing said exposed silver halide emulsion during development in a surface developer, (0) developing in a silver halide aerial fogging surface developer or (d) bathing the imagewise-exposed silver halide emulsion in a surface-image stabilizer bath followed by light-flashing before or during development in a silver halide surface developer.
  • the silver halide emulsions of this invention comprise silver
  • certain unfogged silver halide emulsions wherein the halide is predominantly chloride, can be imagewise-exposed and then (a) developed in a surface developer in the presence of a fogging agent, (b) light-flashed during development in a surface developer, (c) developed in a silver halide aerial fogging surface developer or (d) bathed in a surface-image stabilizer bath followed by light-flashing before or during development in a silver halide surface developer.
  • the silver halide emulsions of this invention contain internal sensitivity such as internal sensitivity resulting from internal structural defects, metal dopants occluded in the grain, and the like.
  • the silver halide emulsions of this invention can be characterized by the following tests when coated at about 200 mg. silver/ft. wherein it will produce a good reversal in Process A if it will give a D less than 0.3 in Process B, a D greater than 1.0 in Process C and a relative speed in Process D which is less than the relative speed obtained in Process C.
  • PROCESS A (l) Image-expose for A second on an intensity-scale sensitometer.
  • PRO-CESS B (l) Image-expose for /s second in an intensity-scale sensitometer.
  • PROCESS C (1) Soak for 30 seconds in an aqueous solution containing 6.67 g. cadmium chloride per liter.
  • PROCESS D (l) Uniform-flash for 6 seconds using a Colight Flash Model 919 having the light intensity set at 70 wherein the bulb is 53 inches from the film support.
  • the silver halide emulsions of this invention which can be characterized by the above test are those wherein the halide is predominantly chloride and wherein the grains of said emulsion comprise internal sites for the deposition of photolytic silver.
  • the halide of the silver halide comprises at least 50 mole percent chloride and prefarbly at least 2 percent and, more preferably, 5 mole percent of bromide or iodide.
  • the internal sites for the deposition of photolytic silver can be formed by several procedures.
  • halide ions such as iodide or bromide ions or in an excess of silver ions; generally, at least 5 percent excess of the respective anion or cation is present above that necessary to precipitate the counter-silver or halide ion respectively.
  • interrupted precipitations are used to form sites in the grains for the deposition of photolytic silver.
  • the halide constituency is changed as the halide grows to provide the sites.
  • the silver halide grains have foreign metal dopants occluded therein such as polyvalent metal ions or metal compounds.
  • the silver halide emulsions of this invention do not require chemical sensitization on the surface of the grains to form reversal images by the process of this invention; however, in certain preferred embodiments, a low amount of chemical sensitization is present on the surface of the grain.
  • the emulsions are sensitized to a level which will provide a density of less than 0.3 in Process B above when coated at 200 mg. silver/ftF.
  • the surface sensitivity is preferably balanced with the internal sensitivity to provide internal sites for the deposition of photolytic silver which are more efficient than surface sites during the imagewise exposure, but less efiicient in the unexposed regions than the surface sites during the fogging step.
  • the silver halide emulsions are imagewise-exposed and then developed in a silver halide surface developer in the presence of a silver fogging agent such as a reactive N- substituted, cycloammonium quaternary salt.
  • a silver fogging agent such as a reactive N- substituted, cycloammonium quaternary salt.
  • the silver halide emulsions of this invention are imagewiseexposed and then developed in a silver halide surface developer in the presence of a fogging agent such as a hydrazine compound.
  • the silver halide emulsions of this invention are imageWise-exposed and then lightflashed during development in a silver halide surface developer.
  • the silver halide emulsions of this invention are imagewise-exposed and then developed in a surface, aerial fogging developer such as a developer composition with air bubbled through it, or developed in in the presence of an oxidizing agent such as hydrogen peroxide, sodium perborate, including aerial fogging with the use of metal catalysts such as cupric ion and the like.
  • aerial fogging developer such as a developer composition with air bubbled through it, or developed in in the presence of an oxidizing agent such as hydrogen peroxide, sodium perborate, including aerial fogging with the use of metal catalysts such as cupric ion and the like.
  • the oxidizing agents and/ or metal catalysts can be present in the developer composition or in at least one layer of the photographic element wherein they can be activated or brough in active contact with the silver halide after imagewise exposure.
  • the silver halide emulsions of this invention are imagewise-exposed, bathed in the presence of a surface-image stabilizer and then light flashed before or during development in a surface developer.
  • a surface-image stabilizer is one which enables exposed silver halide grains to become developable in a surface-image developer, said grains being undevelopable to a substantial density in Process B, above, in the absence of said surface-image stabilizer.
  • Typical useful surfaceimage stabilizers include cadmium salts, amines such as dialkanol amines, developing agents, tetrazaindenes, sodium sulfite, bromide salts and the like.
  • the imagewiseexposed silver halide emulsions of this invention are developed in the above processes in the presence of an alkylene oxide polymer.
  • the silver halide emulsions of this invention are unfogged, silver halide emulsions wherein the halide is predominantly chloride and wherein said emulsion comprises a halogen-accepting organic compound.
  • the internal-image emulsions which are useful according to this invention are those which contain grains having a foreign metal dopant occluded therein.
  • the metal dopants can be occluded within the grain, for example, by precipitating in the presence of foreign metal ions (i.e., other than silver ions).
  • the metal dopants can be introduced 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 U.S. Pats.
  • the silver halides used in the present invention are unfogged. Such emulsions contain only minimal developable surface latent images wherein procesing for 5 minutes at 27 C. in Kodak Developer DK- will provide a density of less than 0.30.
  • the internal-image emulsions useful in this invention comprise silver halide grains having chemical or physical sites internal to the grain for the deposition of photolytic silver.
  • the physical sites can be obtained by employing precipitation conditions which will result in the formation of physical defects in the crystal lattice such as, for example, changing the conditions of the precipitation medium to promote a change in crystal shape, interrupted precipitations, and the like.
  • the chemical sites can be obtained by incorporating metal dopants into the silver halide grain.
  • the dopant is a foreign metal ion or a metallic compound.
  • the silver halide grains containing occluded metallic compounds can be obtained by precipitating in the presence of the metallic compound or preferably depositing the metal on a core of silver halide and then continuing formation of the grain to build a shell or outer region over the metallic deposit. Typical emulsions of this type are disclosed in Porter et al., US. Pats. 3,206,313 and 3,317,322.
  • the silver halide grains comprise occluded sulfur and noble metal compounds.
  • the silver halide grains are formed in the presence of foreign metal ions and preferably polyvalent metal ions.
  • 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 divalent metal ions such as lead ions, 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 or iridium ions.
  • the silver halide grains contain at least 10- and preferably at least 10 mole percent dopant based on silver halide.
  • the surface of the grains of the doped emulsions of this invention can be chemically sensitized to a level below that which would produce substantial density (i.e., a density of less than 0.30) in a surface developer such as Kodak Developer DK-85 after imagewise exposure when coated at a coverage of about 200 mg. Ag/ft.
  • a surface developer such as Kodak Developer DK-85 after imagewise exposure when coated at a coverage of about 200 mg. Ag/ft.
  • Such chemical sensitization includes three major classes, viz., gold or noble-metal sensitization, sulfur sensitization such as by a labile sulfur compound, and reduction sensitization, i.e., treatment of the silver halide with a strong reducing agent which does not fog appreciably the silver halide but introduces small specks of metallic silver into the silver halide crystal or grain.
  • gold or noble-metal sensitization sulfur sensitization such as by a labile sulfur compound
  • reduction sensitization i.e., treatment of the silver halide with a strong reducing agent which does not fog appreciably the silver halide but introduces small specks of metallic silver into the silver halide crystal or grain.
  • reduction sensitization i.e., treatment of the silver halide with a strong reducing agent which does not fog appreciably the silver halide but introduces small specks of metallic silver into the silver halide crystal or grain.
  • the silver halide grains can be chemically sensitized by any of the accepted procedures.
  • the silver halide grains can be digested with naturally active gelatin, or sulfur compounds can be added, such as those described in U.S. Pats. 1,574,944 by Sheppard issued Mar. 2, 1926, 1,623,499 by Sheppard et al. issued Apr. 5, 1927, and 2,410,689 by Sheppard issued Nov. 5, 1946, or selenium compounds can be used such as those described in U.S. Pats. 3,297,447 by McVeigh, 3,297,446 by Dunn, and the like.
  • the silver halide grains can also be treated with salts of the noble metals, such as ruthenium, palladium and platinum.
  • Representative compounds are ammonium chloropalladate, potassium chloroplatinate and sodium chloropalladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli, U.S. Pat. 2,448,060 issued Aug. 31, 1948, and as antifoggants in higher amounts, as described in Trivelli and Smith, U.S. Pats. 2,566,245 issued Aug. 28, 1951, and 2,566,263 issued Aug. 28, 1951.
  • the silver halide grains can also be chemically sensitized with gold salts as described in U.S. Pats. 2,399,083 by Waller et a1. issued Apr. 23, 1946, and 2,642,361 by Damschroder et a1. issued June 16, 1953.
  • Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and 2-aurosulfobenzothiazole methochloride.
  • the silver halide grains can also be chemically sensitized with reducing agents, such as stannous salts (Carroll, U.S. Pat. 2,487,850 issued Nov. 15, 1949), polyamines, such as diethylene triamine (Lowe et al., U.S. Pat. 2,518,698 issued Aug. 15, 1950), polyamines, such as spermine (Lowe et al., U .S. Pat. 2,521,925 issued Sept. 12, 1950), or bis(p-aminoethyl)sulfide and its watersoluble salts (Lowe et al., U.S. Pat. 2,521,926 issued Sept.
  • reducing agents such as stannous salts (Carroll, U.S. Pat. 2,487,850 issued Nov. 15, 1949), polyamines, such as diethylene triamine (Lowe et al., U.S. Pat. 2,518,698 issued Aug. 15, 1950), polyamines, such as spermine (Lowe et al
  • the silver halide grains can also be spectrally sensitized with cyanine and merocyanine dyes, such as those described in U.S. Pats. 1,846,301 and 1,846,302, both issued Feb. 23, 1932, and 1,942,854 issued Jan. 9, 1934, all by Brooker; 1,990,507 by White issued Feb. 12, 1935; 2,112,140 issued Mar. 22, 1938, 2,165,338 issued July 11, 1939, 2,493,747 issued Jan. 10, 1950, and 2,739,964 issued Mar. 27, 1956, all by Brooker et al.; 2,493,748 by Brooker et a1. issued Jan. 10, 1950; 2,503,776 issued Apr. 11, 1950, and 2,519,001 issued Aug.
  • cyanine and merocyanine dyes such as those described in U.S. Pats. 1,846,301 and 1,846,302, both issued Feb. 23, 1932, and 1,942,854 issued Jan. 9, 1934, all by Brooker; 1,990,507 by White issued Feb.
  • the silver halide emulsions of this invention can contain halogen-accepting compounds characterized by an anodic halfwave potential which is less than 0.62 and a cathodic halfwave potential which is more negative than l.3.
  • a preferred class of halogen-accepting organic compounds that can be used in the practice of this invention comprises the spectral-sensitizing merocyanine dyes having the formula:
  • A represents the atoms necessary to complete an acid heterocyclic nucleus, e.g., rhodanine, 2-thiohydantoin and the like
  • B represents the atoms necessary to complete a basic nitrogen-containing heterocyclic nucleus, e.g., benzothiazole, naphthothiazole, benzoxazole and the like
  • each L represents a methine linkage, e.g.,
  • n is an integer from 0 to 2, i.e., 0, 1 or 2.
  • Typical useful halogen-accepting compounds are disclosed in Wise, U.S. Pat. 3,537,858 issued Nov. 3, 1970.
  • iodidereleasing compounds in the silver halide element or to use a developer containing iodide ions to obtain certain desired image characteristics.
  • level of chemical sensitization is increased, the use of iodide-releasing compounds or iodide in the developer becomes less desirable.
  • a simple exposure and development process can be used to form a positive image.
  • a photographic element comprising at least one layer of a silver halide composition as described above can be imagewise-exposed and then developed in the presence of a fogging agent in a silver halide surface developer.
  • the element can be given a flash over-all exposure during surface development to provide a positive image.
  • the term surface developer encompasses those developers which will reveal the surface latent image on a silver halide grains, but will not reveal substantial internal latent image in an internal image-forming emulsion with conditions generally used to develop a surface-sensitive silver halide emulsion.
  • the surface developers can generally utilize any of the silver halide developing agents or reducing agents, but the developing bath or composition is generally substantially free of a silver halide solvent (such as water-soluble thiocyanates, water soluble thioethers, thiosulfates, ammonia and the like) which will solubilize or crack the grain to reveal substantial internal image.
  • a silver halide solvent such as water-soluble thiocyanates, water soluble thioethers, thiosulfates, ammonia and the like
  • Low amounts of excess halide are sometimes desirable in the developer or incorporated in the emulsion as halide-releasing compounds, but high amounts are generally avoided to prevent substantial cracking of the grain, especially with respect to io
  • Typical silver halide developing agents which can be used in the developing compositions of this invention include hydroquinones, catechols, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones, phen ylenediamines and the like or combinations thereof.
  • the developing agents can be incorporated in the photographic elements wherein they are brought in contact with the silver halide after imagewise exposure; however, in cerembodiments they are preferably employed in a developing bath along with a silver halide fogging agent.
  • a Colight contact printing lamp having a tungsten light source such as Model 919 available from Colwell Litho Products, Inc., Minneapolis, Minn, can be used to provide a light flash during development.
  • the developing compositions used in the process of this invention can also contain certain antifoggants and development restrainers, or optionally they can be incorporated in layers of the photographic element.
  • Typical useful antifoggants include benzotriazoles and benzothiazoles such as S-methylbenzothiazole, S-nitrobenzotriazole and the like; nitrobenzimidazoles; heterocyclic thiones such as 1-methyl-2-tetrazoline-S-thione and the like; aromatic and aliphatic mercapto compounds, etc.
  • Kodak Developer DK-85 The surface developer referred to herein as Kodak Developer DK-85 is described in the Handbook of Chemistry and Physics, 39th Ed., 1957, Chemical Rubber Publishing C0., Cleveland, Ohio, page 3062, and has the followlng composition:
  • the silver halide emulsions of this invention can be developed in a silver halide surface developer in the presence of a fogging agent to provide good positive images.
  • the fogging agent can be incorporated in at least one layer of the silver halide element, which layer is in Waterpermeable association with the silver halide emulsion, or it can be contacted with said silver halide emulsion by a separate bath or simultaneously with the surface developer composition by incorporating the fogging agent into the developer composition.
  • the useful fogging agents of this invention are those which provide nucleation or fog specks which initiate development of the silver halide in the unexposed areas before initiating substantial development in the exposed areas of an internal-image emulsion in a surface developer.
  • selective fogging agents Compounds of this type are generally not practical developing agents by themselves for silver halides and are referred to as selective fogging agents; in some documents they have been referred to generally as silver halide fogging agents or nucleating agents.
  • Typical useful selective fogging agents include hydrazine compounds, reactive N-substituted cycloammonium salts and the like.
  • hydrazines are used as the fogging agent, such as the compounds disclosed in US. Pats. 2,588,982 by Ives issued Mar. 11, 1952, and 3,227,552 by Whitmore issued Ian. 4, 1966.
  • the fogging agents are reactive N-substituted cycloammonium quaternary salts.
  • Typical useful fogging agents of this type are disclosed in US. Ser. Nos. 28,041 by Lincoln and Heseltine filed Apr. 13, 1970, 85,706 by Kurtz and Heseltine filed Oct. 30, 1970, and 85,709 by Kurtz and Harbison filed Oct. 1970, which are incorporated herein by reference.
  • these compounds can be represented by the formula:
  • (A) Z represents the atoms necessary to complete a heterocyclic nucleus containing a heterocyclic ring of 5 to 6 atoms including the quaternary nitrogen atoms, with the additional atoms of said heterocyclic ring being selected from carbon, nitrogen, oxygen, sulfur and selenium;
  • (C) a represents a positive integer of from 2 to 6;
  • (D) X represents an acid anion;
  • (E) R represents a member selected from:
  • each of T and T when taken alone, represents a member selected from an alkoxy radical and an alkylthio radical
  • R represents either a hydrogen atom, an alkyl radical, an aralkyl radical, an alkylthio radical or an aryl radical such as phenyl and naphthyl, and including substituted aryl radicals.
  • the N-substituted, cycloammonium quaternary salts are those which contain N-substituted alkyl radicals having the terminal carbon atom substituted with a hydrozono radical, an acyl radical such as a formyl radical, an acetyl radical or a benzoyl radical, and those which have a dihydroaromatic ring nucleus such as, for example, a dihydropyridinium nucleus.
  • the fogging agents can be incorporated in at least one layer of the photographic element in waterpermeable association with the silver halide emulsion or they can be contacted with the emulsion before or during development such as by a pre-bath or incorporating the fogging agent in the developer composition; however, the fogging agents are preferably located in at least one layer of the element and in a highly preferred embodiment they are located in the silver halide emulsion layer. Concentrations of from about 75 to about 1500 mg. of the subject fogging agents per mole of silver in the silver halide emulsion are useful, with from about to about 1200 mg.
  • Typical useful selective fogging agents include 2-methyl-3- [3- (p-sulfophenylhydrazone) propyl]benzothiazolium bromide,
  • the silver halide emulsions of this invention can be made by any of the precipitation and ripening procedures used for making silver halide grains and preferably procedures for making grains having metal dopants or metal ions occluded therein.
  • Typical procedures include singlejet procedures, double-jet procedures, procedures utilizing automatic proportional control means to maintain specified pAg and pH, procedures using ripening agents such as thiocyanates, thioether and/or ammonia, procedures utilizing an increase in flow rates as disclosed in Wilgus, U.S. Ser. No. 11,838 filed Feb. 16, 1970; hot nucleation procedures as disclosed in Musliner, U.S. Ser. No. 31,351 filed Apr. 23, 1970, and the like.
  • the silver halide compositions made for use in the systems of this invention are preferably monodispersed, and in some embodiments are preferably large-grain emulsions made according to Wilgus, U.S. Ser. No. 11,838, which is incorporated herein by reference.
  • the monodispersed emulsions are those which comprise silver halide grains having a substantially uniform diameter. Generally, in such emulsions, no more than about by weight, of the silver halide grains smaller than the mean grain size and/or no more than about 5%, by number, of the silver halide grains larger than the mean grain size vary in diameter from the mean grain diameter 'by more than about 40%.
  • Preferred photographic emulsions of this invention comprise silver halide grains, at least 95%, by weight, of said grains having a diameter which is within 40%, preferably within about 30%, of the mean grain diameter.
  • Mean grain diameter i.e., average grain size, can be determined using conventional methods, e.g., such as projective area as shown in an article by Trivelli and Smith entitled Empirical Relations between Sensitometric and Size-Frequency Characteristics in Photographic Emulsion Series in The Photographic Journal, vol. LXXIX, 1939, pp. 330-338.
  • the aforementioned uniform size distribution of silver halide grains is a characteristic of the grains in monodispersed photographic silver halide emulsions
  • Silver halide grains having a narrow size distribution can be obtained by controlling the conditions at which the silver halide grains are prepared using a doublerun procedure.
  • the silver halide grains are prepared by simultaneously running an aqueous solution of a water-soluble silver salt, for example, silver nitrate, and a water-soluble halide, for example, an alkali metal halide such as potassium chloride, into a rapidly agitated aqueous solution of a silver halide peptizer, preferably gelatin, a gelatin derivative or some other protein peptizer.
  • the pH and the pAg employed in this type of procedure are interrelated. For example, changing one while maintaining the other constant at a given temperature can change the size frequency distribution of the silver halide grains which are formed.
  • the temperature is about 30 to about 90 C.
  • the pH is up to about 9, preferably 4 or less
  • the pAg is up to about 9.8.
  • Suitable methods for preparing photographic silver halide emulsions having the required uniform particle size are disclosed in an article entitled Ia: Properties of Photographic Emulsion Grains, by Klein and Moisar, The Journal of Photographic Science, vol. 12, 1964, pp.
  • the photographic emulsions and elements described in the practice of this invention can contain various colloids alone or in combination as vehicles, binding agents and various layers.
  • Suitable hydrophilic materials include both naturally occurring substances such as proteins, for example, gelatin, gelatin derivatives, cellulose derivatives, polysaccharides such as dextran, gum arabic and the like; and synthetic polymeric substances such as water-soluble polyvinyl compound like poly(vinylp-yrrolidone), acrylamide polymers and the like.
  • 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. Pats. 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 Ream et al. issued Nov.
  • elfective are those water-insoluble polymers or latex copolymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates, those which have cross-linking sites which facilitate hardening or curing, those having recurring sulfobetaine units as described in Canadian Pat. 774,054 by Dykstra, and those described in U.S. Pat. 3,488,708 by Smith issued Jan. 6, 1970..
  • the photographic elements of this invention can also contain certain onium salts, such as quaternary ammonium salts, sulfonium salts and phosphonium salts in order to increase the development rate without adversely affecting the improved dot quality and contrast.
  • onium salts such as quaternary ammonium salts, sulfonium salts and phosphonium salts.
  • Such compounds are disclosed, for example, in U.S. Pats. 2,271,623 by Carroll issued Feb. 3, 1942; 2,944,898 by Beavers et al. issued July 12, 1960; 2,944,900 by Carroll et al. issued July 12, 1960; 2,288,226 by Carroll et al. issued June 30, 1942, 2,275,727 issued Mar. 10, 1942; 2,271,622 issued Feb. 3, 1942; and 2,886,437 by Piper issued May 12, 1959; and Agfa British Pat. 1,067,958 published May 10, 1967. Concentrations ranging from about 0.01 to about 2.0 grams of onium salt per mole of silver in
  • the silver halide emulsion of a photographic element useful in this invention can contain conventional addenda such as gelatin plasticizers, coating aids, and hardeners such as aldehyde hardeners, e.g., formaldehyde, mucochloric acid, glutaraldehyde bis(sodium bisulfite), maleic dialdehyde, aziridines, dioxane derivatives and oxypolysaccharides.
  • aldehyde hardeners e.g., formaldehyde, mucochloric acid, glutaraldehyde bis(sodium bisulfite), maleic dialdehyde, aziridines, dioxane derivatives and oxypolysaccharides.
  • R represents a heterocyclic group or an aryl group of the benzene or naphthalene series and R represents hydrogen, an alkyl group or an aryl group of the benzene or naphthalene series, and R and R each represents hydrogen or an alkyl group.
  • Examples within this formula includes l-phenyl- 3-pyrazolidone, 5 methyl 3 pyrazolidone, l-phenyl- 5 phenyl 3 pyrazolidone, l-phenyl 5 methyl 3- pyrazolidone, l-phenyl 4,4 dimethyl 3 pyrazolidone, l-p-hydroxyphenyl 4,4 dimethyl 3 pyrazolidone, 4- methyl 1 phenyl 3 pyrazolidone, etc.
  • the above 3- pyrazolidones can also be contained in a contiguous layer instead of the silver halide emulsion, if desired.
  • Alkylene oxides can also be utilized in the processes of this invention.
  • Typical useful compounds include polyethylene glycol, polyethylene glycol oleyl ether, polyethylene glycol cetyl ether, polyethylene oxide derivatives, block copolymers such as those comprising blocks of polyoxypropylene, polyoxyethylene and the like, Watersoluble organosilicone polyalkyleneoxide polymers and the like.
  • the alkylene oxide polymer can be used in any concentration effective for the intended purpose. When the alkylene oxide polymer is present in the photographic element, good results are obtained when the concentration is less than about 2 grams per mole of silver in the silver halide emulsion. A preferred concentration range for the polymer in this embodiment is from about to about 800 mg. per mole of silver in the silver halide emulsion. When the alkylene oxide polymer is present in the photographic developer, good results are generally obtained when the polymer is employed in a concentration of from about 0.1 to about 10 grams per liter of developer composition.
  • 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, prticularly a polymer of an alpha-olefin containing 2 to 10 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. Pat. 2,716,059 by Yutzy et al.; silver salt diffusion transfer processes such as described in U.S. Pats. 2,352,014 by Rott, 2,543,181 by Land, 3,020,155 by Yackel et al, and 2,861,885 by Land; color image transfer processes such as described in U.S. Pats.
  • This invention may be used with elements designed for color photography, for example, elements containing color-forming couplers such as those described in U.S. Pats. 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 al. and 3,046,129 by Graham et al.; or elements to be developed in solutions containing color-forming couplers such as those described in U.S. Pats. 2,252,718 by Mannes et al., 2,592,243 by Carroll et al. and 2,950,970 by Schwan et al.; and in false-sensitized color materials such as those described in U.S. Pat. 2,763,549 by Hanson.
  • elements containing color-forming couplers such as those described in U.S. Pats. 2,376,679 by Frohlich et al.
  • a silver chlorobromoiodide (:9.75:0.25) emulsion is prepared by simultaneously adding over a period of 35 minutes at 55 C. 0.4875 mole of potassium bromide, 0.0125 mole of potassium iodide and 0.50 mole of silver nitrate to a solution containing 21 grams of gelatin. An additional 19 grams of gelatin are added and the emulsion is chill-set and washed with cold water. An additional 61.5 grams of gelatin are added, the emulsion is melted at 60 C., and 4.5 moles of sodium chloride and 4.5 moles of silver nitrate are simultaneously added over a period of 24 minutes at 60 C. An additional 50 grams of gelatin are added and the emulsion is chill-set and Washed.
  • the emulsion is chemically sensitized at the surface of the grains by adding 1.78 mg. of sodium thiosulfate/ silver mole and 1.72 mg. of potassium chloroaurate/ silver mole and heated for 10 minutes at 65 C.
  • EXAMPLE 2 A chlorobromoiodide (90:9.75:0.25) emulsion is prepared similar to the emulsion described in Example 1 except after the first precipitation the emulsion is chemically sensitized by adding 33 mg. of sodium thiosulfate/ silver mole and 6.6 mg. of potassium chloroaurate/silver mole and heated for 30 minutes at 65 C. A silver chloride shell is then precipitated on the core emulsion and chemically sensitized and heated for 50 minutes at 65 C. as described in Example 1.
  • a silver chlorobromoiodide (90:9.75:0.25) emulsion is prepared by simultaneously adding over a period of 24 minutes at 60 C. an aqueous solution containing 0.4875 mole of potassium bromide, 0.0125 mole of potassium iodide and 4.5 mole of sodium chloride and an aqueous solution containing 5.0 mole of silver nitrate to a rapidly agitated, aqueous gelatin solution. After the emulsion is chill-set and washed, the silver chlorobromoiodide grains are chemically sensitized by adding 1.78 mg. of sodium thiosulfate/silver mole and 1.72 mg. of potassium chloroaurate/silver mole and heated for 10 minutes at 65 C.
  • EXAMPLE 4 A chlorobromide (90: 10) emulsion is prepared similar to Example 1 except 0.0125 mole of potassium iodide is replaced with an additional 0.0125 mole of potassium bro mide.
  • EXAMPLE 5 A silver chlorobromoiodide (90:9:1) emulsion is prepared similar to that described in Example 3 except the precipitation is over a period of 6% minutes at 78 C. Excess halide ion is present throughout the precipitation. The emulsion is then chemically sensitized at the surface of the grains as described in Example 3.
  • EXAMPLE 6 A chlorobromoiodide (90:9: 1) is prepared similar to Example 5 except 0.000044 g. of ammonium chlororhodate per silver mole is added to the silver nitrate solution. The emulsion is not chemically sensitized.
  • EXAMPLE 7 A chlorobromide (65:35) emulsion is prepared by simultaneously adding an aqueous silver nitrate solution and an aqueous sodium chloride and potassium bromide solution to a rapidly agitated gelatin solution. A 4% excess silver ion is maintained during precipitation. After the emulsion is chill-set and washed, the silver halide grains are chemically sensitized by adding 4 mg. of sodium thiosulfate/ silver mole.
  • Example 3 except no potassium iodide is present during precipitation.
  • EXAMPLE 9 I A chlorobromide (90: emulsion is prepared as described in Example 8 except to the precipitation vessel prior to precipitation are added 10.7 mg. of potassium chloroiridate per silver mole. The emulsion grains are then chemically sensitized at the surface by adding 1.78 mg. of sodium thiosulfate/ silver mole and 1.72 mg. of potassium chloroaurate/ silver mole and heated 60 minutes at 65 C.
  • the above emulsions are then coated on a film support in the presence of 125 mg. of oleyl ether of polyethylene glycol/silver mole, appropriate spreading and hardening agents, and the spectral-sensitizing dye l-carboxymethyl-S- 3 ethyl 2 benzoxazolinylidene)ethylidene]-3-phenyl- '2-thiohydantoin.
  • Example IO-C (incorporated oxidizing agents) Over the emulsion layer is coated the following composition:
  • Process C and a relative speed in Process D which' is less than the relative speed obtained in Process C.
  • EXAMPLE 10 An emulsion is prepared as described in Example 1 and coated with the previously described addenda on a film support at 200 mg./ft. Various coated samples are then processed as described.
  • EXAMPLE 10-A (Aerial fog) (a) Image-expose for ,5 second in an intensity-scale sensitometer.
  • EXAMPLE 10-B (Oxidizing agent) (a) Image-expose second in an intensity-scale sensitometer.
  • the photographic element is then processed as follows:
  • Example 10-D Fix, wash and dry
  • Example 10-E incorporated reactive N-substituted cycloammonium quaternary salts
  • Example -E fluorescence-sensitive silver quaternary salts
  • EXAMPLE 11 In Examples 1 through 9, a light flash is applied during development, but it is possible to flash the element prior to development by using stabilizing baths.
  • Example 1 An emulsion as described in Example 1 is coated on a film support and processed as described.
  • Example ll-G Results similar to Example ll-G are obtained when the stabilizing bath contains an amine such as 2,2-iminodiethanol and an alkali metal salt such as potassium bromide followed by development in a conventional lithtype developer.
  • an amine such as 2,2-iminodiethanol
  • an alkali metal salt such as potassium bromide
  • EXAMPLE 12 An emulsion is prepared as described in Example 1 and processed in a manner similar to Process A except Kodak Developer D-85 is substituted by Kodak Developer D-ll. The following results are observed:
  • EXAMPLE 14 An emulsion is prepared as described in Example 1 except to the emulsion layer are added g. of gelatin/ mole of silver and 80 g. of a polymeric latex/mole of silver. The coated emulsion is then processed by the procedure described in Process A.
  • EXAMPLE 15-A To the emulsion of Example 1 are added appropriate spreading and hardening agents and the dye 3-carboxymethyl-5-[3-methy1 2(3) thiazolinylideneJisopropylidene rhodanine.
  • the emulsion After coating on a film support, the emulsion is exposed on an intensity-scale sensitometer. The exposed emulsion is then bathed in an aqueous solution containing 3.37 g. of cadmium chloride per liter. After drying, the emulsion is uniformly flashed using a Colight lamp exposure at a distance of 4 /2 feet for 4 seconds with the dial on the rheostat set at 50 and then developed for 2% minutes at 70 C. in Kodak Developer D-85 as described in Example 1 of U.S. Ser. No. 758,582 by Milton filed Sept. 9, 1968.
  • EXAMPLE 15-B This example follows the same procedure as Example 15-A except the emulsion is not bathed in cadmium chloride.
  • EXAMPLE 15-C This example is similar to Example l5-A except the emulsion is not bathed in cadmium chloride and the overall flash exposure is given during development.
  • EXAMPLE 15-D This example is similar to Example 15-A except the emulsion is bathed in cadmium chloride before image exposure.
  • EXAMPLE 15-E This example is similar to Example 15-D except the uniform flash and development are simultaneous.
  • Photographic results Example Relative number Procedure Results speed Dmin- 'y Du CdClz after image exposure, uniform flash prior to development..- Positive image 08 11. 4 5. 91 15-B No CdClz uniform flash prior to development- No image" 15-0 No CdClz uniform flash during development" Positive image 162 .06 9.6 5.00 15-D CdClz prior to image exposure, uniform flash prior to development. Total grain development;
  • a photographic silver halide element comprising a support and at least one layer coated thereon of a silver halide emulsion which contains unfogged silver halide grains having internal sites for the deposition of photolytic silver, said grains having beenprepared by adding a soluble bromide salt or a mixture of soluble bromide and iodide salts to silver nitrate and thereafter adding a soluble chloride salt and additional silver nitrate to the emulsion so formed such that the chloride comprises at least 50 mole percent of the total halide of the silver halide grain; said grains being chemically sensitized on the surface thereof and essentially free from chemical sensitization in the interior thereof; wherein said silver halide emulsion is characterized as one which when coated at a coverage of about 200 mg./ft.
  • a photographic element according to claim 1 comprising at least one layer containing a hydrazine compound, which layer is in water-permeable association with said silver halide emulsion.
  • a photographic element according to claim 1 comprising at least one layer containing a reactive N-substituted cycloammonium salt, which layer is in water-permeable association with said silver halide emulsion.
  • a silver halide element according to claim 1 wherein said silver halide emulsion comprises a halogen-accepting compound having an anodic halfwave potential which is less than 0.62 and a cathodic halfwave potential which is more negative than 1.3.
  • a silver halide element according to claim 1 comprising at least one layer containing a metal catalyst for producing aerial fog.
  • a photographic element according to claim 1 comprising at least one layer containing an oxidizing agent.
  • a photographic element according to claim 1 comprising at least one layer containing a water-soluble alkylene oxide polymer.
  • a process for producing a positive image in a silver halide, photographic element comprising a support and at least one layer coated thereon of a silver halide emulsion which contains unfogged silver chlorobromide or chlorobromoiodide grains having internal sites for the deposition or photolytic silver, said grains having been prepared'by adding a soluble bromide salt or a mixture of soluble bromide and iodide salts to silver nitrate and thereafter adding a soluble chloride salt and additional silver nitrate to the emulsion so formed such that the chloride comprises at least 50 mole percent of the total halide of the silver halide grain; said grains being chemically sensitized on the surface thereof and essentially free from chemical sensitization in the interior thereof; said emulsion when coated at a coverage of about 200 mg./ft.
  • said photographic element comprises at least one layer containing a metal catalyst or an oxidizing agent and said emulsion is developed after imagewise exposure in a silver halide surface developer to provide aerial fogging.
  • said silver halide emulsion layer comprises a polymeric latex.

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US00123006A 1971-03-10 1971-03-10 Silver halide emulsions predominantly chloride containing silver halide grains with surfaces chemically sensitized and interiors free fromchemical sensitization and the use thereof in reversal processes Expired - Lifetime US3761266A (en)

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Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3890154A (en) * 1969-12-24 1975-06-17 Fuji Photo Film Co Ltd Light-sensitive silver halide photographic materials
US3901711A (en) * 1972-08-31 1975-08-26 Mitsubishi Paper Mills Ltd Silver halide photographic emulsion containing a gold salt and a polyalkylene oxide
US3935014A (en) * 1973-02-20 1976-01-27 Agfa-Gevaert Aktiengesellschaft Direct-positive photographic emulsion containing, unfogged, monodispersed silver halide grains having a layered grain structure of specific silver chloride content
US3957488A (en) * 1973-06-28 1976-05-18 Agfa-Gevaert, A.G. Photographic emulsion containing unfogged, heterodisperse layered silver halide grains having a prodominantly bromide core and total chloride content less than 30 mole percent
US3966476A (en) * 1973-02-09 1976-06-29 Agfa-Gevaert, A.G. Spectrally sensitized silver halide emulsion containing more than 50% of the grains with ripening nuclei in cavities
US4030920A (en) * 1976-04-12 1977-06-21 Eastman Kodak Company Processing compositions containing glycols for color transfer processes comprising direct positive silver halide developement
US4040839A (en) * 1975-05-19 1977-08-09 Fuji Photo Film Co., Ltd. Direct-positive process utilizing a supersensitized silver halide emulsion
US4075020A (en) * 1975-07-30 1978-02-21 Agfa-Gevaert Aktiengesellschaft Process for the preparation of silver halide emulsions
US4139387A (en) * 1977-10-19 1979-02-13 Agfa-Gevaert Aktiengesellschaft Process for the production of direct-positive photographic images
US4263396A (en) * 1974-04-06 1981-04-21 Agfa-Gevaert Ag Direct-positive photographic material
US4268621A (en) * 1978-07-29 1981-05-19 Konishiroku Photo Industry Co., Ltd. Direct positive photographic material
US4279987A (en) * 1978-11-14 1981-07-21 Konishiroku Photo Industry Co., Ltd. Light-sensitive, direct positive silver halide photographic material
US4440851A (en) * 1981-10-22 1984-04-03 Konishiroku Photo Industry Co., Ltd. Method for the formation of a direct positive image
US4564591A (en) * 1981-12-02 1986-01-14 Konishiroku Photo Industry Co., Ltd. Silver halide color photographic material
EP0204530A2 (en) 1985-05-31 1986-12-10 Konica Corporation Method for forming direct positive color image
EP0318987A1 (en) 1987-12-02 1989-06-07 Fuji Photo Film Co., Ltd. Direct positive photographic lightsensitive material
US4863838A (en) * 1979-03-26 1989-09-05 Konishiroku Photo Industry Co., Ltd. Direct positive type light-sensitive silver halide photographic materials
US4868089A (en) * 1984-12-30 1989-09-19 Konishiroku Photo Industry Co., Ltd. Positive image forming method
US4910130A (en) * 1986-11-25 1990-03-20 Konica Corporation Direct positive light-sensitive silver halide photographic material
US5166043A (en) * 1990-07-27 1992-11-24 Agfa-Gevaert, N.V. Light-sensitive silver halide material for making direct-positive images
US5190853A (en) * 1988-11-22 1993-03-02 Fuji Photo Film Co., Ltd. Silver halide color photosensitive material
USH1242H (en) 1990-03-03 1993-10-05 Konica Corporation Silver halide photographic light-sensitive material
US5279920A (en) * 1991-11-01 1994-01-18 Konica Corporation Silver halide photographic light sensitive material
US5292611A (en) * 1991-12-17 1994-03-08 Konica Corporation Dye image forming method
US5424170A (en) * 1993-08-31 1995-06-13 Konica Corporation Silver halide photographic light sensitive material
US5547810A (en) * 1994-09-16 1996-08-20 Konica Corporation Image forming method with alkali precursor
EP0754967A1 (en) 1995-07-14 1997-01-22 Agfa-Gevaert N.V. Photographic direct positive material containing a particular stabilizer

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58120248A (ja) * 1982-01-12 1983-07-18 Konishiroku Photo Ind Co Ltd 直接ポジ画像形成方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE550907A (enrdf_load_stackoverflow) *
US2497875A (en) * 1947-10-17 1950-02-21 Eastman Kodak Co Direct positive photographs using aerial fogging developer
FR1484742A (fr) * 1965-04-30 1967-06-16 Agfa Gevaert Nv Méthode pour la production d'images photographiques positives directes
US3574625A (en) * 1967-04-07 1971-04-13 Eastman Kodak Co Photographic systems with polyvalent metal ions contiguous to the silver halide grains

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3890154A (en) * 1969-12-24 1975-06-17 Fuji Photo Film Co Ltd Light-sensitive silver halide photographic materials
US3901711A (en) * 1972-08-31 1975-08-26 Mitsubishi Paper Mills Ltd Silver halide photographic emulsion containing a gold salt and a polyalkylene oxide
US3966476A (en) * 1973-02-09 1976-06-29 Agfa-Gevaert, A.G. Spectrally sensitized silver halide emulsion containing more than 50% of the grains with ripening nuclei in cavities
US3935014A (en) * 1973-02-20 1976-01-27 Agfa-Gevaert Aktiengesellschaft Direct-positive photographic emulsion containing, unfogged, monodispersed silver halide grains having a layered grain structure of specific silver chloride content
US3957488A (en) * 1973-06-28 1976-05-18 Agfa-Gevaert, A.G. Photographic emulsion containing unfogged, heterodisperse layered silver halide grains having a prodominantly bromide core and total chloride content less than 30 mole percent
US4263396A (en) * 1974-04-06 1981-04-21 Agfa-Gevaert Ag Direct-positive photographic material
US4040839A (en) * 1975-05-19 1977-08-09 Fuji Photo Film Co., Ltd. Direct-positive process utilizing a supersensitized silver halide emulsion
US4075020A (en) * 1975-07-30 1978-02-21 Agfa-Gevaert Aktiengesellschaft Process for the preparation of silver halide emulsions
US4030920A (en) * 1976-04-12 1977-06-21 Eastman Kodak Company Processing compositions containing glycols for color transfer processes comprising direct positive silver halide developement
US4139387A (en) * 1977-10-19 1979-02-13 Agfa-Gevaert Aktiengesellschaft Process for the production of direct-positive photographic images
US4268621A (en) * 1978-07-29 1981-05-19 Konishiroku Photo Industry Co., Ltd. Direct positive photographic material
US4279987A (en) * 1978-11-14 1981-07-21 Konishiroku Photo Industry Co., Ltd. Light-sensitive, direct positive silver halide photographic material
US4863838A (en) * 1979-03-26 1989-09-05 Konishiroku Photo Industry Co., Ltd. Direct positive type light-sensitive silver halide photographic materials
US4440851A (en) * 1981-10-22 1984-04-03 Konishiroku Photo Industry Co., Ltd. Method for the formation of a direct positive image
US4564591A (en) * 1981-12-02 1986-01-14 Konishiroku Photo Industry Co., Ltd. Silver halide color photographic material
US4868089A (en) * 1984-12-30 1989-09-19 Konishiroku Photo Industry Co., Ltd. Positive image forming method
EP0204530A2 (en) 1985-05-31 1986-12-10 Konica Corporation Method for forming direct positive color image
US4898807A (en) * 1985-05-31 1990-02-06 Konishiroku Photo Industry Co., Ltd. Method for forming direct positive color image using an N-hydroxy alkyl-substituted-P-phenyldiamine derivative at elevated temperatures for a short period of time
US4910130A (en) * 1986-11-25 1990-03-20 Konica Corporation Direct positive light-sensitive silver halide photographic material
EP0318987A1 (en) 1987-12-02 1989-06-07 Fuji Photo Film Co., Ltd. Direct positive photographic lightsensitive material
US5190853A (en) * 1988-11-22 1993-03-02 Fuji Photo Film Co., Ltd. Silver halide color photosensitive material
USH1242H (en) 1990-03-03 1993-10-05 Konica Corporation Silver halide photographic light-sensitive material
US5166043A (en) * 1990-07-27 1992-11-24 Agfa-Gevaert, N.V. Light-sensitive silver halide material for making direct-positive images
US5279920A (en) * 1991-11-01 1994-01-18 Konica Corporation Silver halide photographic light sensitive material
US5292611A (en) * 1991-12-17 1994-03-08 Konica Corporation Dye image forming method
US5424170A (en) * 1993-08-31 1995-06-13 Konica Corporation Silver halide photographic light sensitive material
US5547810A (en) * 1994-09-16 1996-08-20 Konica Corporation Image forming method with alkali precursor
EP0754967A1 (en) 1995-07-14 1997-01-22 Agfa-Gevaert N.V. Photographic direct positive material containing a particular stabilizer

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AU3976472A (en) 1973-09-13
BE780539A (fr) 1972-07-03
DE2211771A1 (de) 1972-09-28
FR2128756A1 (enrdf_load_stackoverflow) 1972-10-20
DE2211771B2 (de) 1977-01-27
CA970197A (en) 1975-07-01
FR2128756B1 (enrdf_load_stackoverflow) 1976-01-16

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