US3574625A - Photographic systems with polyvalent metal ions contiguous to the silver halide grains - Google Patents

Photographic systems with polyvalent metal ions contiguous to the silver halide grains Download PDF

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Publication number
US3574625A
US3574625A US629091A US3574625DA US3574625A US 3574625 A US3574625 A US 3574625A US 629091 A US629091 A US 629091A US 3574625D A US3574625D A US 3574625DA US 3574625 A US3574625 A US 3574625A
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United States
Prior art keywords
silver halide
halide grains
contiguous
silver
trivalent
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US629091A
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English (en)
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Robert E Bacon
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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
    • G03C1/49—Print-out and photodevelopable 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
    • 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
    • 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
    • G03C1/48538—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure

Definitions

  • This invention relates to radiation-sensitive silver halide materials.
  • this invention relates to a silver halide emulsion containing silver halide grains with occluded polyvalent ions therein and having a halogen acceptor and a metal salt contiguous to said silver halide grains.
  • this invention relates to an improved photographic emulsion which has increased maximum density and increased contrast upon chemical development.
  • this invention relates to an emulsion having good print-out characteristics which can also be chemically developed to an image record with high D and good contrast.
  • Emulsions which have good print-out characteristics and which can be chemically developed to provide a permanent record are known in the art. These emulsions generally contain silver halide grains which have been precipitated in the presence or trivalent or tetravalent metal ions. French patent 1,456,581 made available October 28, 1966, discloses several emulsions of this type. However, it is desirable to further improve the chemical developing-out characteristics of good print-out emulsions.
  • the polyvalent metal ions are used in the precipitation or formation of the silver halide.
  • Silver halide crystals are formed with polyvalent ions or atoms occluded therein.
  • suitable polyvalent metal ions include the trivalent metal ions such as those of antimony, bismuth, arsenic, gold, iridium, rho- "ice dium and the like, and tetravalent metal ions such as those of platinum, osmium, iridium and the like.
  • the polyvalent metal ions or mixtures thereof can be suitably added with the water-soluble salt (e.g. silver nitrate) or the water-soluble halide (e.g.
  • polyvalent ions can also be introduced into the silver halide precipitation vessel with a hydrophilic colloid such as gelatin.
  • the polyvalent metal ions can be added to the system as watersoluble inorganic salts, as organo-metallic materials, as
  • the amount of polyvalent metal utilized can be widely varied, though at least 1 10- and more generally about 1X10 to about 2 mole percent based on the silver halide is used.
  • the presence of the polyvalent metal ions in the silver halide grain can be observed analytically by successively washing the precipitated silver halide grains with a silver halide solvent such as an organic thioether or an alkali metal thiocyanate. If the polyvalent metal ions are only contiguous to the surface, substantially all of the ions will be observed in the analysis of the first washings while substantial amounts of polyvalent ions will be found in washings just prior to complete dissolution of the silver halide when the ions are occluded therein.
  • the emulsion containing the silver halide grains containing the polyvalent 'ions occluded therein is washed and the following addenda are added in accordance with the invention.
  • a halogen acceptor and a trivalent or tetravalent metal ion salt are added to the emulsion.
  • the trivalent or tetravalent metal ion salts, thus added, are contiguous to the silver halide grains and can be readily distinguished from the polyvalent ions occluded within the crystalline grain; for identification the trivalent or tetravalent metal ion salts can be removed by washing in an aqueous solutionfollowed by washing quickly with a silver halide solvent to remove the respective metal salts contiguous to the silver halide grains.
  • Typical trivalent metal ion salts which can be added to the emulsion contiguous to the silver halide grains are those of antimony, bismuth, arsenic, gold, iridium, rhodium and the like.
  • Typical tetravalent metal ion salts which can be added to the emulsion contiguous to the silver halide grains are those of platinum, osmium, iridium and the like.
  • metal salts of rhodium, iridium and platinum are placed contiguous to the silver halide grains to achieve very high D and maximum contrast.
  • the concentration of the trivalent or tetravalent metal ion salts utilized contiguous to the silver halide grains of this invention can be widely varied. Generally about 10 to about 500 mg./mole of silver and preferably about to 250 rug/mole of silver in the emulsion is utilized in the emulsion.
  • the water-soluble silver salt and the water-soluble halide are reacted to precipitate the silver halide preferably under acidic conditions.
  • the pH of the silver halide precipitation is typically less than 6 and preferably less than 5.
  • Such acids as phosphoric, trifluoracetic, hydrobromic, hydrochloric, sulfuric and nitric are typically utilized in the silver halide precipitating media to maintain acidic conditions.
  • the silver halide grains useful in the invention generally have an average grain size of about .01 to 10 microns, and more generally about .05 to 2 microns, in diameter.
  • Suitable silver halides include silver chloride, silver bromide, silver bromoiodide, silver chloroiodide, and silver chlorobromoiodide.
  • the silver halide preferably is unfogged and contains at least 50% bromide, less than 10% iodide and less than 50% chloride on a molar basis.
  • Both silver halide that forms latent image predominantly on the surface of the silver halide crystal or those that form latent images predominantly inside the silver halide crystal, such as those described in Davey and Knott, US. Pat. 2,592,250 issued Apr. 8, 1952, can be used in the materials of the present invention.
  • halogen acceptors can be used in the emulsion.
  • nitrogen containing halogen acceptors are particularly useful in the invention.
  • Typical nitrogencontaining halogen acceptors include the thioureas, hydrazines, urazoles, thiourazoles, and the like. Halogen acceptors of this type are disclosed in McBride, US. Pat. 3,287,137 issued Nov. 22, 1966.
  • the preferred halogen accceptors are those such as Z-imidazolidinethione, 1- phenyl-S-mercaptotetrazole, thiosemicarbazide, tetramethylthiourea, 2-thiouracil, hydrazine, l-phenyl-2-imidazolidinethione, 1-methyl-2-mercaptoimidazole, thiourea, urazole, 3-thiourazole, 3,5-dithiourazole hydrazine salt, urazole sodium salt, 4-ethylurazole, 1,4-dibutylurazole and 3-thio-5-iminourazole.
  • Such ureas which include thioureas, urazoles, etc., as well as cyclic forms thereof, are merely illustrative halogen acceptors.
  • halogen acceptors that can be used in the invention include aromatic mercaptans such as thiosalicylic acid; hydroquinones such as hydroquinone, chlorohydroquinone, gentisic acid and t-butylhydroquinone; catechols such as phenyl catechol and t-butylcatechol; p-aminophenols such as N-methyl-p-aminophenol sulfate; 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, 4-methyl-1- phenyl-3-pyrazolidone and 1phenyl-4,4-dimethyl-3-pyrazolidone; phenylenediamines; nitriles; phenols; glycine; sodium sulfite; alkaline materials such as borax, alkali metal hydroxide, etc.; and the like halogen acceptors well known to those skilled in the art.
  • aromatic mercaptans such as thiosalicylic acid
  • concentration of halogen acceptor utilized in the emulsions of the invention can be widely varied in accordance with usual practice. Usually, about .01 to 100 mole percent, and more generally about .1 to 25 mole percent, based on the silver halide in the emulsion is utilized.
  • halogen acceptors are utilized contiguous to the silver halide in the present photographic system.
  • Such halogen acceptors can be incorporated in the same photographic layer as the silver halide such as in the same emulsion layer, or in a layer adjacent to the silver halide.
  • the photographic silver halide system of the invention can comprise layers coated on a wide variety of supports in accordance with usual practice.
  • suitable supports include paper, polyethylene-coated paper, polypropylene-coated paper, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyester films such as polyethylene terephthalate film, polycarbonate films, polyimide films and related films of resinous materials, as well as glass, metals and others.
  • any method of imagewise halogen acceptor formation in the element followed by over-all light exposure also gives a stable record if the silver halide emulsion layer was coated without a halogen acceptor. In either case, image fading does not occur with continued exposure.
  • a radiation-sensitive gelatino silver chlorobromide (5 mole percent chloride and mole percent bromide) photographic emulsion is prepared by slowly adding simultaneously an aqueous silver nitrate solution and an aqueous alkali metal halide solution to an agitated aqueous gelatin solution at 50 C. at a pH of about 1.8 adjusted with nitric acid.
  • the gelatin solution and the alkali metal halide solution also contain 7.5 mg. of (NH RhCl per mole of silver.
  • the emulsion is washed in the usual manner. Five mole percent of the halogen acceptor, dithiourazole hydrazine salt, is added to the emulsion.
  • the emulsion is divided into three portions; one portion is coated on a polyester (polyethylene terephthalate) film support with no further addenda; to the other portions is added respectively and mg. of rhodium trichloride per mole of silver before coating on a similar support.
  • the coatings are exposed through a step wedge with light from a high pressure mercury arc lamp through a Wratten 2C Filter, and developed for 4 minutes in Kodak 13-85 Developer, fixed, washed and dried.
  • the following comparative results show the improvement in the emulsions of this invention.
  • Rhodium trichloride as a coating addendum Contrast Dmnx N one 1. 66 2. 12 100 mg./mole Ag 4. 6O 3. 24 150 mgJmole Ag 4. 60 3. 26
  • Example 2 Two emulsions of the type described in Example 1 are prepared containing 5 and 15 mg. of (NH RhCl per mole of silver in the gelatin solution and the alkali metal halide solution respectively. Five mole percent of the halogen acceptor, dithiourazole hydrazine salt, is added to each emulsion which is then respectively split again into two portions. One portion of each emulsion is coated on a photographic paper support with no further addenda; to the remaining portion is added 100 mg. of rhodium trichloride per mole of silver before coating on a similar support. Processing and exposure are carried out by the procedure of Example 1 except that the development is for 7 minutes in Kodak D-85 Developer. The following results show that increasing the amount of rhodium salt in the precipitation with or without additional rhodium salt as coating addendum does not give the improvements in developability.
  • a radiation-sensitive gelatino silver chlorobromide (5 mole percent chloride and 95 mole percent bromide) photographic emulsion is prepared by slowly adding simultaneously an aqueous solution of silver nitrate and an aqueous solution of alkali metal halides to an agitated aqueous gelatin solution containing 1.5 g. bismuth trinitrate pentahydrate per mole of silver at 30 C. at a pH of about 1.8 adjusted with nitric acid.
  • 0.7 mole percent of the halogen acceptor, dithiourazole hydrazine salt is added to the emulsion, which is then split into portions; one portion is coated on a polyester, polyethyleneterephthalate film support with no further addenda; to the other portions were added the coating addenda as listed in the table before coating on a similar support.
  • the coatings were exposed through a stepwedge with light from a high pressure mercury arc lamp through a Wratten Filter, and developed for 2 /2 minutes in Kodak D85 developer, tfixed, washed and dried.
  • the following results show the improvement in the emulsions of my invention.
  • An improved radiation-sensitive, photographic silver halide system containing silver halide grains having polyvalent metal ions occluded therein, the improvement comprising the combination of at least .01 mole percent, based on silver, of a halogen acceptor other than gelatin contiguous to said grains and at least 75 mg. per mole, based on silver, of a trivalent or tetravalent metal ion salt contiguous to said silver halide grains.
  • a radiation-sensitive system according to claim 1 wherein said silver halide grains have trivalent or tetravalent metal ions occluded therein.
  • a radiation-sensitive system wherein said silver halide grains have osmium, platinum, iridium, antimony, arsenic, bismuth, gold or rhodium ions or mixtures thereof occluded therein.
  • a radiation-sensitive system according to claim 1 wherein said halogen acceptor is a nitrogen-containing halogen acceptor.
  • a radiation-sensitive system wherein said metal ions contiguous to said grains are antimony, bismuth, arsenic, gold, iridium, rhodium, osmium or platinum ions or mixtures thereof.
  • a radiation-sensitive system wherein said trivalent or tetravalent metal ions are water-soluble rhodium, iridium or platinum salts or mixtures thereof which have been added to the system after the formation of the silver halide grains.
  • halogen acceptor is a direct-print halogen acceptor.
  • a radiation-sensitive system according to claim 1 wherein the halide of said silver halide grains is predominantly bromide.
  • a radiation-sensitive photographic system comprising silver halide grains formed in an acidic medium in the presence of water-soluble osmium, platinum, iridium, antimony, arsenic, bismuth, gold or rhodium salts or mixtures thereof and wherein at least about .01 mole percent, based on silver, of a direct-print halogen acceptor and at least about mg. per mole of silver of a water-soluble trivalent or tetravalent metal ion salt have been added to the system after the formation of said silver halide grains.
  • a radiation-sensitive system wherein said water-soluble trivalent or tetravalent metal ion salts are osmium, platinum or iridium salts or mixtures thereof.
  • a radiation-sensitive system wherein said trivalent or tetravalent metal ions are antimony, arsenic, bismuth, gold, iridium or rhodium salts or mixtures thereof.
  • a radiation-sensitive system comprising silver halide grains having trivalent or tetravalent metal ions occluded therein, at least 75 mg. per mole of silver of a water-soluble trivalent or tetravalent metal ion salt contiguous to said silver halide grains, gelatin and at least .01 mole percent, based on silver, of one other compound which is a halogen acceptor.
  • a photographic element comprising the radiationsensitive system of claim 1.'

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US629091A 1967-04-07 1967-04-07 Photographic systems with polyvalent metal ions contiguous to the silver halide grains Expired - Lifetime US3574625A (en)

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US62909167A 1967-04-07 1967-04-07

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US (1) US3574625A (enrdf_load_stackoverflow)
BE (1) BE713272A (enrdf_load_stackoverflow)
FR (1) FR1558883A (enrdf_load_stackoverflow)
GB (1) GB1225526A (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050037297A1 (en) * 2003-08-12 2005-02-17 Eastman Kodak Company Photothermographic materials containing doped high iodide emulsions

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3761266A (en) * 1971-03-10 1973-09-25 Eastman Kodak Co 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
US3761276A (en) * 1971-03-10 1973-09-25 Eastman Kodak Co Photographic element containing monodispersed unfogged silver halide grains chemically sensitized internally and externally
US3761267A (en) * 1971-03-10 1973-09-25 Eastman Kodak Co Photographic element containing monodispersed unfogged dye sensitizedsilver halide grains metal ions sensitized internally and the use theeof in reversal process
DE3507830A1 (de) * 1985-03-06 1986-09-11 Agfa-Gevaert Ag, 5090 Leverkusen Farbfotografisches aufzeichnungsmaterial mit einer silberhalogenidemulsion und verfahren zu deren herstellung

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050037297A1 (en) * 2003-08-12 2005-02-17 Eastman Kodak Company Photothermographic materials containing doped high iodide emulsions
US6942960B2 (en) 2003-08-12 2005-09-13 Eastman Kodak Company Photothermographic materials containing doped high iodide emulsions

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DE1622931B2 (de) 1975-07-17
FR1558883A (enrdf_load_stackoverflow) 1969-02-28
BE713272A (enrdf_load_stackoverflow) 1968-08-16
DE1622931A1 (de) 1972-02-24
GB1225526A (enrdf_load_stackoverflow) 1971-03-17

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