US3539350A - Photographic elements and emulsions stabilized against thermal fog - Google Patents

Photographic elements and emulsions stabilized against thermal fog Download PDF

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Publication number
US3539350A
US3539350A US650211A US3539350DA US3539350A US 3539350 A US3539350 A US 3539350A US 650211 A US650211 A US 650211A US 3539350D A US3539350D A US 3539350DA US 3539350 A US3539350 A US 3539350A
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United States
Prior art keywords
silver halide
silver
emulsion
photographic
fog
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US650211A
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English (en)
Inventor
Maurice Fizar Pfaff
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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
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression

Definitions

  • This invention relates to photographic materials, their preparation and use.
  • One aspect of the invention relates to new and improved stabilizers against thermal fog for photographic elements.
  • Another aspect of the invention relates to photographic silver halide emulsions containing the stabilizers therein.
  • U.S. Fat. 2.839,405 of Jones issued June 7, 1958 discloses various emulsion stabilizers such as the watersoluble inorganic acid salts of cadmium, cobalt, manganese and zinc. While these fog inhibitors are effective at temperatures which are ordinarily encountered, these and other prior art emulsion stabilizers will not stabilize an emulsion for very long when the emulsion is heated to 100 C. It would be desirable to have an emulsion stabilizer which would protect a photographic emulsion exposed to temperatures over 100 C. A photographic element with great heat resistance could be commercially used in airplanes to record all the characteristics of the flight and could be kept intact even though the airplane has crashed and the photographic element has been heated for a long time.
  • a fogstabilizing amount of cadmium chloride and an acid selected from the group consisting of citric acid, tartaric acid or mixtures thereof is incorporated into the silver halide emulsion of a photographic element or in a layer contiguous to the silver halide emulsion.
  • This particular emulsionstabilizer combination is a synergistic stabilizer combination as will be shown by the examples hereinafter.
  • the emulsion stabilizers of this invention may be incorporated into the silver halide emulsion of a photographic element or in a layer contiguous to the silver halide emulsion, in any amount which will stabilize the silver halide emulsion against thermal fog.
  • a concentration of the cadmium chloride in an amount of from about 10 to about grams per mole of silver in the silver halide emulsion and a concentration of the acid in an amount of from about 5 to about 55 grams per mole of silver in the silver halide emulsion can be used with good results.
  • the cadmium chloride is employed in a concentration of from about 12 to about 60 grams per mole of silver in the silver halide emulsion and the acid is employed in a concentration of from about 7 to about 20 grams per mole of silver in the silver halide emulsion.
  • the preparation of photographic silver halide emulsions such as are suitably stabilized with the emulsion stabilizers of this invention typically involves three separate operations:
  • the emulsion stabilizers of the invention can be added to the emulsion before this final digestion or after ripening or it can be added immediately prior to the coating step.
  • the silver halide emulsion of a photographic element containing the stabilizers of 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.
  • Spectral sensitizers which can be used are the cyanines, merocyanines, complex (trinuclear) cyanines, complex (trinuclear) merocyanines, styryls, and hemicyanines.
  • Sensitizing dyes useful in sensitizing such emulsions are described, for example, in US. Pat. 2,526,632 of Brooker and White issued Oct. 24, 1950, and 2,503,776 of Sprague issued Apr. 11, 1950.
  • Developing agents can also be incorporated into the silver halide emulsion if desired or can be contained in a contiguous layer.
  • Various silver salts can be used as the sensitive salt such as silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide or silver bromoiodide.
  • the silver halides used can be those which form latent images predominantly on the surface of the silver halide grains or those which form latent images inside the silver halide crystals such as described in US. Pat. 2,592,250 of Davey and Knott issued Apr. 8, 1952.
  • the silver halide emulsion layer of a photographic element containing the stabilizers of the invention can contain any of the hydrophilic, water-permeable binding materials suitable for this purpose. Suitable materials include gelatin, colloidal albumin, polyvinyl compounds, cellulose derivatives, acrylamide polymers, etc. Mixtures of these binding agents can also be used.
  • the binding agents for the emulsion layer of the photographic element can also contain dispersed polymerized vinyl compounds. Such compounds are disclosed, for example, in US. Pats. 3,142,568 of Nottorf issued July 28, 1964; 3,193,386 of White issued July 6, 1965; 3,062,674 of Houck, Smith and Yudelson issued Nov.
  • the silver halide emulsion of a photographic element containing the stabilizers of the invention can be used on a wide variety of supports.
  • Typical supports are cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polystyrene film, poly(ethylene terephthaate) film and related films or resinous materials as well as glass, paper, metal and the like.
  • Supports such as paper which are coated with a-olefin polymers, particularly polymers of a-olefins containing two or more carbon atoms, as exemplified by polyethylene, polypropylene, ethylene-butene copolymers and the like can also be employed.
  • the speed of the photographic emulsions containing the stabilizers of the invention can be further enhanced by including in the emulsions a variety of hydrophilic colloids such as carboxymethyl protein of the type described in U.S. Pat. 3,011,890 of Gates, Jr., Miller and Koller issued Dec. 5, 1961, and polysaccharides of the type described in Canadian Pat. 635,206 of Koller and Russell issued Jan. 23, 1962.
  • hydrophilic colloids such as carboxymethyl protein of the type described in U.S. Pat. 3,011,890 of Gates, Jr., Miller and Koller issued Dec. 5, 1961, and polysaccharides of the type described in Canadian Pat. 635,206 of Koller and Russell issued Jan. 23, 1962.
  • Photographic emulsions containing the stabilizers of the invention can also contain speed-increasing compounds such as quaternary ammonium compounds, polyethylene glycols or thioethers. Frequently, usefui effects can be obtained by adding the aforementioned speedincreasing compounds to the photographic developer solutions instead of, or in addition to, the photographic emulsions.
  • speed-increasing compounds such as quaternary ammonium compounds, polyethylene glycols or thioethers.
  • Photographic elements containing the stabilizers of the instant invention can be used in various kinds of photographic systems. In addition to being useful in X-ray and other non-optically sensitized systems, they can also be used in orthochromatic, panchromatic and infrared sen sitive systems.
  • the sensitizing addenda can be added to photographic systems before or after any sensitizing dyes which are used.
  • Silver halide emulsions containing the stabilizers of the invention can be used in color photography, for example, emulsions containing color-forming couplers or emulsions to be developed by solutions containing couplers or other color-generating materials, emulsions of the mixedpacket type such as described in U.S. Pat. 2,698,794 of Godowsky issued Jan. 4, 1955; in silver dye-bleach systerns; and emulsions of the mixed-grain type such as described in U.S. Pat. 2,592,243 of Carroll and Hanson issued Apr. 8, 1952.
  • the emulsions can also be used in diffusion transfer color processes which utilize a diffusion transfer of an imagewise distribution of developer, coupler or dye, from a light-sensitive layer to a second layer, while the two layers are in close proximity to one another.
  • Silver halide emulsions containing the stabilizers of the invention can be processed in stabilization processes such as the ones described in U.S. Pat. 2,614,927 of Broughton and Woodward issued Oct. 21, 1952, and as described in the article Stabilization Processing of Films and Papers by H. D. Russell, E. C. Yackel and J. S. Bruce in PSA Journal, Photographic Science and Technique, volume 16B, October 1950.
  • the stabilizers of this invention can be incorporated to advantage during manufacture in silver halide emulsions representing the variations described above. Moreover, fog control in binderless silver halide films prepared by vapor deposition of silver halide on a suitable support can be achieved by coating the stabilizing agents of the invention over the vapor deposited layer of silver halide.
  • Example 1 A coarse-grain, ammonical, gelatinosilver bromoiodide emulsion is prepared containing about 99 mole percent bromide and 1 mole percent iodide. The emulsion is sensitized with conventional sulfur and gold compounds and then a portion of it coated on a baryta paper support (250 grams baryta per square decimeter) at a silver coverage of about 40 milligrams per square decimeter and a gelatin coverage of about 80 milligrams per square decimeter. Similar portions of the emulsion are coated in the same manner containing the stabilizers listed in the following table. The coated elements are then exposed on an intensity scale sensitometer and enclosed in an impervious package of a composite aluminum-polyethylene sheet.
  • the invention can be sensitized using any of the well- 60 known techniques in emulsion making, for example, by digesting with naturally active gelatin or various sulfur, selenium, tellurium compounds and/ or gold compounds.
  • the emulsions can also be sensitized with salts of noble metals of Group VH1 of the Periodic Table which have an atomic weight greater than 100.
  • Silver halide emulsions containing the stabilizers of the invention can be used in diffusion transfer processes which utilize the undeveloped silver halide in non-image areas of the negative to form a positive by dissolving the 7 undeveloped silver halide and precipitating it on a silver layer in close proximity to the original silver halide emulsion layer.
  • diffusion transfer processes which utilize the undeveloped silver halide in non-image areas of the negative to form a positive by dissolving the 7 undeveloped silver halide and precipitating it on a silver layer in close proximity to the original silver halide emulsion layer.
  • Such processes are described in U.S. Pats. 2,352,014 of Rott issued June 20, 1944; 2,543,181 of Water at 125 F.500 cc. N-methyl-p-aminophenol sulfate2 grams Sodium sulfite (desiccated)--72 grams Hydroquinone8 grams Sodium carbonate (monohydrated)56 grams Potassium bromide4 grams Land issued Feb
  • the stabilizer combination of the invention is a synergistic combination in providing protection for the longest period of time.
  • Example 4 Although a cellulose triacetate film support undergoes deformation at 100 C., it is still possible to study changes of characteristics of an emulsion coated on such a support. To illustrate, an emulsion similar to that of Example 1 is prepared and the various stabilizers listed in the following table are added. The various samples are then coated on a cellulose triacetate support, 0.2 millimeter thick, at the same coverage as in Example 1 and then processed in the same manner as in Example 1 with the following results:
  • a composition comprising a photographic silver halide emulsion containing a fog-stabilizing amount of cadmium chloride and an acid selected from the group consisting of citric acid, tartaric acid or mixtures thereof.
  • composition of claim 1 wherein said cadmium chloride is present in a concentration of from about 10 to about 150 grams per mole of silver in said silver halide emulsion and said acid is present in a concentration of from about to about 55 grams per mole of silver in said silver halide emulsion.
  • composition of claim 2 wherein said acid is citric acid.
  • composition of claim 2 wherein said acid is tartaric acid.
  • a photographic element comprising a support coated with a silver halide layer, said element containing a fogstabilizing amount of cadmium chloride and an acid selected from the group consisting of citric acid, tartaric acid or mixtures thereof.
  • Thermal fog stabilizers (grams per silver mole) 0 hrs. 1 hr. 2 hrs. 4 hrs. 5 hrs. 6 hrs.
  • Citric acid (8.8) 0. 18 0. 17 0. 17
  • the stabilizer combination of the invention is a synergistic combination and also point out the unobviousness of the invention in that acids other than citric and tartaric acid are not efiective, chlorides other than cadmium chloride are not effective and cadmium salts other than cadmium chloride are not efiective.
  • Example 5 Coated elements similar to those of Example 4 are prepared but are not exposed before enclosing in the impervious package. Instead, the coated elements are heated for various times and then exposed on an intensity scale sensitometer, developed, washed and fixed as in Example 4 with the following results:
  • Thermal tog stabilizers (grams Rel. Rel. per silver mole) speed Fog Hours speed Fog None 100 0. 18 1 100 0. CdCl (14) 126 0. 16 1 145 0. 24 Citric acid (8.8) 50 0. 18 4 100 0. 36 CdCla (14) plus citric acid (8.8). 71 0. 16 4 100 0. 2O CdClz (14) plus 2N Sulfuric acid (26 ml.) 112 0.16 2 159 0. 30 Citric acid (8.8) plus KCl (5.6) 0. 17 2 63 0.
  • said silver halide layer comprises coarse grain silver bromoiodide, sensitized with sulfur or gold.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US650211A 1966-08-05 1967-06-30 Photographic elements and emulsions stabilized against thermal fog Expired - Lifetime US3539350A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR72203A FR1498513A (fr) 1966-08-05 1966-08-05 Nouvelles émulsions photographiques stabilisées contre le voile thermique et produits photographiques contenant ces nouvelles émulsions

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US3539350A true US3539350A (en) 1970-11-10

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BE (1) BE700303A (ref)
DE (1) DE1597532A1 (ref)
FR (1) FR1498513A (ref)
GB (1) GB1161264A (ref)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6078155A (en) * 1999-01-18 2000-06-20 Mitsubishi Denki Kabushiki Kaisha Electric power steering circuit assembly
US20110200809A1 (en) * 2010-02-12 2011-08-18 Eastman Chemical Company Sulfite softwood based cellulose triacetate for lcd films

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2042533C3 (de) * 1970-08-27 1981-10-01 Agfa-Gevaert Ag, 5090 Leverkusen Verfahren zur Herstellung photographischer Silberhalogenidemulsionen

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2384663A (en) * 1943-08-21 1945-09-11 Eastman Kodak Co Method of preventing aerial oxidation and color stain
US2839405A (en) * 1955-03-08 1958-06-17 Eastman Kodak Co Inorganic salt antifoggants for photographic emulsions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2384663A (en) * 1943-08-21 1945-09-11 Eastman Kodak Co Method of preventing aerial oxidation and color stain
US2839405A (en) * 1955-03-08 1958-06-17 Eastman Kodak Co Inorganic salt antifoggants for photographic emulsions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6078155A (en) * 1999-01-18 2000-06-20 Mitsubishi Denki Kabushiki Kaisha Electric power steering circuit assembly
US20110200809A1 (en) * 2010-02-12 2011-08-18 Eastman Chemical Company Sulfite softwood based cellulose triacetate for lcd films

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Publication number Publication date
FR1498513A (fr) 1967-10-20
GB1161264A (en) 1969-08-13
DE1597532A1 (de) 1970-06-04
BE700303A (ref) 1967-12-01

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