US3297447A - Stabilization of synergistically sensitized photographic systems - Google Patents

Stabilization of synergistically sensitized photographic systems Download PDF

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US3297447A
US3297447A US486235A US48623565A US3297447A US 3297447 A US3297447 A US 3297447A US 486235 A US486235 A US 486235A US 48623565 A US48623565 A US 48623565A US 3297447 A US3297447 A US 3297447A
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photographic
silver halide
issued
emulsion
selenium
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Patricia A Mcveigh
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to FR25078A priority Critical patent/FR1450841A/fr
Priority to CH1015865A priority patent/CH455505A/fr
Priority to BE667170A priority patent/BE667170A/xx
Priority to DE19651472836 priority patent/DE1472836C/de
Priority to SE9608/65A priority patent/SE344829B/xx
Priority to DK374865AA priority patent/DK124634B/da
Priority to NO159028A priority patent/NO122513B/no
Priority to GB31190/65A priority patent/GB1115038A/en
Priority to NL656509486A priority patent/NL145963B/xx
Priority to BR171519/65A priority patent/BR6571519D0/pt
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US486235A priority patent/US3297447A/en
Priority to GB40300/66A priority patent/GB1154236A/en
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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
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • 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
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
    • 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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/496—Binder-free compositions, e.g. evaporated
    • G03C1/4965—Binder-free compositions, e.g. evaporated evaporated
    • 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
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/725—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing inorganic compounds

Definitions

  • This invention relates to photography and more particularly to the stabilization of photographic systems sensitized with a combination of a noble metal sensitizer, e.g., a gold salt, and a labile selenium sensitizer.
  • a noble metal sensitizer e.g., a gold salt
  • a labile selenium sensitizer e.g., a gold salt
  • photographic systems such as silver halide systems, particularly gelatino silver halide emulsions, can be sensitized chemically with a combination of a noble metal sensitizer, e.g. a gold salt, and a labile sulfur compound. It is, furthermore, known that photographic silver halide emulsions can be sensitized with labile selenium compounds. It has been generally thought that he sensitization of such emulsions by means of labile selenium requires a somewhat larger amount of sensitizer than when a sulfur sensitizer is employed.
  • an object of my invention to provide new stabilized photographic systems sensitized with a combination of a labile selenium sensitizer and a noble metal sensitizer for increasing the speed synergistically of such photographic systems. It is another object of this invention to provide new stabilized synergistically sensitized silver halide emulsions without adversely affecting the speed of such emulsions.
  • Particularly useful labile sulfur compounds for my invention include the well-known class of compounds which have been previously identified as labile sulfur sensitizers. These include the water-soluble thiosulfa-tes such as alkali metal thiosulfates including sodium and potassium thiosulfates, as well as ammonium thiosulfate; thioureas such as thiourea, allylisothiourea, diacetylthiourea; thiosemicarbazide; thiocarbamates such as isopropylthiocarbamate; and the like labile sulfur compounds.
  • Other labile sulfur compounds useful in my invention are described in an article by T. H. James and W. Vanselow in J. Phot. Sci., vol. 1 (1953), page 133, as well as in an article by A Hautot and H. Sauvenier in Sci. Ind. Phot., vol. 27 (1957), No.1.
  • the amount of labile sulfur compound used in my invention can vary considerably depending upon the particular sensitized photographic system employed, finishing conditions, including temperature and time of digestion and ripening, etc. In general, I have found that the unique stabilizing effect of labile sulfur compounds can be accomplished at a somewhat lower concentration than might be required in their use as sulfur sensitizers. With reference to silver halide photographic systems, particularlyuseful results have been obtained at concentrations of about 0.1 to 10 mg. per mole of silver halide. Larger or smaller quantities can be employed without adversely affecting the sensitometric properties of the photographic system. The labile sulfur compounds are efficaciously added to be present during the chemical sensitization of the photographic system.
  • the selenium sensitizers useful in my invention include a wide variety of labile selenium sensitizers, many having been previously suggested for use alone in sensitizing photographic silver halide emulsions. Suitable selenium addenda are disclosed in Sheppard et al. US. Patent 1,623,- 499, issued April 5, 1927, .as well as Sheppard US. Patents 1,574,944, issued March 2, 1926, and 1,602,592, issued October 12, 1926.
  • the labile selenium sensitizers of my invention which have been found to be particularly useful are organic selenium compounds wherein the selenium atom is doubly bonded to a carbon atom of the organic compound through a covalent linkage.
  • Useful groups of selenium sensitizers include aliphatic selenoureas wherein the aliphatic radical is, for example, an alkyl radical such as methyl, ethyl, propyl, isopropyl, butyl, heXyl, octyl, etc.
  • Such selenoureas have at least one hydrogen atom attached to the nitrogen atom thereof, thus making possible the formation of an enol tautomer.
  • analogous selenoureas containing one or more aromatic radicals, such as phenyl, tolyl, etc., or heterocyclic radicals, such as benzothiazolyl,
  • syridyl, etc. and aliphatic isoselenocyanates.
  • Other useful labile selenium sensitizers are selenophosphates such as tri-alkyl and tri-aryl selenophosphates. It has also been found that colloidal selenium itself is a useful sensitizer.
  • Illustrative addenda suitable for furnishing the labile selenium moiety in the stabilized photographic systems of the invention include:
  • N- (fi-carboxyethyl) -N,N'-dimethylselenourea selenoacetamide, diethylselenide, triphenylphosphine selenide, tri-p-tolylselenophosphate, tri-n-butylselenophosphate, 2-selenoproponic acid, 3-selenobutyric acid, methyl-3-selenobutyrate, allyl isoselenocyanate, and dioctylselenourea.
  • the concentration of selenium sensitizer can be varied considerably depending upon the particular selenium addendum employed (some sensitizers being more efficacious than others), the nature of the photographic system, the amount and chemical nature of the noble metal sensitizer, etc.
  • concentration of selenium sensitizer can be varied considerably depending upon the particular selenium addendum employed (some sensitizers being more efficacious than others), the nature of the photographic system, the amount and chemical nature of the noble metal sensitizer, etc.
  • silver halide systems for example, I have found that useful results can be obtained using amounts as small as 0.05 mg. of selenum sensitizer per mole of silver halide although considerably larger amounts can also be employed, such as 5.0 mg. or more per mole of silver halide.
  • labile as used herein has the meaning well understood by those skilled in the art of photography, i.e., a material which yields a silver salenide or sulfide that is insoluble in water at room temperature (20 C.) upon addition to an aqueous silver nitrate solution.
  • selenourea is a labile selenium compound, since silver selenide precipitates when selenourea is added to an aqueous silver nitrate solution.
  • colloidal selenium precipitates silver selenide upon addition to aqueous silver nitrate and is, therefore, a labile selenium addendum or sensi-tizer of invention.
  • sodium thiosulfate is a labile sulfur compound as silver sulfide precipitates when an aqueous sodium thiosulfate solution is added to an aqueous silver nitrate solution.
  • the noble metal sensitizers useful in the photographic systems stabilized in accordance with my invention include the well-known gold sensitizers which have been previously recognized as useful in the photographic art and found to be outstanding intheir sensitizing action, including water-soluble and water-insoluble organic and inorganic gold compounds and salts, although other noble metal sensitizers can be used, including palladium, platinum, etc., sensitizers such as are disclosed in Smith et al., U.S. Patent 2,448,060, issued August 31, 1948. Typical suitable gold sensitizers are described in Waller et al., U.S. Patent 2,399,083, issued April 23, 1946, and Damschroder et al., U.S. Patent 2,642,361, issued June 16, 1953.
  • Illustrative addenda suitable for furnishing the noble metal moiety in the sensitizer combinations of the invention include:
  • ammonium chloroplatinite i.e., (NH PtCl ammonium chloropalladate, i.e., (NI-I PdCl and organic gold sensitizers having the formulas:
  • noble metal sensitizer useful in sensitizing the photographic systems of the invention can likewise be varied as in the case of selenium sensitizer. I have found, for example, that amounts varying from about 0.1 to 5.0 mg. of gold sensitizer per mole of silver halide are quite satisfactory.
  • the noble metal moiety and the labile selenium moiety used in sensitizing the photographic systems stabilized in accordance with the invention are more generally added to the photographic system as separate entities, although such is not necessary.
  • Typical thiocyanates include sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, etc. Other water-soluble thiocyanates can be employed to equal advantage.
  • the amount of thiocyanate compound used can likewise be varied, depending upon the particular system being sensitized, relative amounts of selenium and noble metal sensitizers,
  • the sensitizing addenda used in sensitizing the photographic systems stabilized in accordance with the invention can be added in a variety of ways to photographic systems and at various stages in the preparation of such. In general, with respect to silver halide emulsions, such addenda can be added with useful effects at the completion of the Ostwald ripening and prior to one or more of the final digestion operations.
  • the sensitizing addenda of the invention are preferably added to silver halide emulsions after the silver halide grains are substantially in their final size and shape.
  • the addenda can be added in the form of their aqueous solutions, Where they are soluble in water, or in an innocuous organic solvent where the sensitizer does not have suflicient solubility in water to be used in the form of an aqueous solution.
  • Particulanly useful organic solvents include ethanol, methanol, pyridine, acetone, dioxane, etc. That is, organic solvents which have a rather high degree of polarity are preferred. Where it is desired to add the sensitizing addenda in some other form than a solution, this procedure is also possible, especially where the sensitizer is available in the form of a colloidal suspension.
  • sensitizers suspended in an organic solvent which forms very small suspended particles or globules in the photographic emulsion similar to the type of colloidal particle produced in preparing coupler dispersions.
  • Dispersing media useful for this purpose include tricresyl phosphate, dibutyl phthalate, triphenyl phosphate, etc.
  • the order of addition of sensitizers and stabilizers to the emulsion can be varied.
  • the sensitizers (part or all) can be added before or after the sulfur stabilizer. Especially useful results are obtained where all addenda are added prior to the final digestion.
  • gelatin In the preparation of dispersions of light-sensitive materials such as silver halide and the like, there can be employed as the dispersing agent gelatin or some other colloidal material, such as colloidal albumin, a cellulose derivative or a synthetic resin, for instance, a polyvinyl compound.
  • colloidal colloids which can be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in Lowe U.S. Patent 2,286,215, issued June 16, 1942; a far hydrolyzed cellulose ester such as cellulose acetate hydrolyzed to an acetyl content of 19 to 26% as described in U.S. Patent 2,327,808, of Lowe and Clark,
  • the loss of density sometimes occurring when a photographic emulsion is dried can be prevented or substantially reduced by incorporating in the gelatin silver halide emulsions of my invention a water-soluble, gelatin-compatible vinyl monomer. Only a small amount of such an addendum is generally required, and frequently amounts as small as about 5%, based on total solids in the emulsion are useful, although it is obvious that much larger amounts, such as about can be employed in certain types of emulsions.
  • Typical polymers which can be used in combination with gelatin to prevent loss of density and thereby increase the covering power in the processed, dried layer include the polyvinyl lactams, such as polyvinylpyrrolidone, as well as other polyvinyl lactams described in Du Pont British Patent 867,899, published May 10, 1961.
  • Other useful polymers include polyacrylamide types, such as polyacrylamide itself, or copolymers of acrylic amide with other ethylenically-unsaturated monomers, including acrylic acid, methacrylic acid, methacylamide, acrylonitrile, methyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, or mixtures of these monomers.
  • Other colloids useful in preventing or inhibiting such density losses include natural gums, salicylic acid condensates, etc.
  • Such emulsions can contain speed-increasing compounds of the quaternary ammonium type of CarrollU.S. Patent 2,271,623, issued February 3, 1942; Carroll and Allen U.S. Patent 2,288,226, issued June 30, 1942; and Carroll and Spence U.S. Patent 2,334,864, issued November 23, 1943; or the polyethylene glycol type of Carroll and Beach U.S. Patent 2,708,162, issued May 10, 1955; or the quaternary ammonium salts and polyethylene glycols of Piper U.S. Patent 2,886,437, issued May 12, 1959; as well as the thiopolymers of Graham and Sagal U.S. Patent 3,046,129, issued July 24, 1962, and the Dann and Chechak U.S. Patent 3,046,134, issued July 24, 1962.
  • useful effects can be obtained by adding the aforementioned speed-increasing compounds to the photographic developer solutions instead of, or in addition to, the photographic emulsions.
  • the photographic systems stabilized according to the technique of my invention are especially useful in the preparation of integral screen X-ray materials.
  • Such X-ray materials have the advantage of convenience of handling and improved sharpness, inasmuch as they can be prepared using a single silver halide emulsion coated on but one side of the photographic support, as compared with conventional X-ray materials which have a silver halide emulsion layer coated on each side of the support (i.e., duplitized material). Since an opaque screen is employed in integral X-ray materials, the possibility of using an emulsion on only one side of the support is most desirable, and by using the novel emulsions of my invention, it is possible to use silver halide emulsion having finer grain to reach a given speed.
  • An integral screen X-ray material using the novel emulsions of my invention can have the layer arrangement shown in French Patent 1,324,023, issued March 4, 1963. In such an arrangement the intensifying screen is located on the side opposite to the emulsion so that the screen remains with the positive after stripping.
  • Other arrangements which can be used in the preparation of integral screen materials are described in Blake et al. US. Patent 2,887,379, issued May 19, 1959 (col. 8, lines 4 to 21).
  • a conventional support is coated in succession with an intensifying screen, receiving layer, silver halide emulsion layer containing my novel combination of selenium and noble metal sensitizers, and if desired, a thin protective layer of gelatin (which can be omitted, if desired).
  • intensifying screen receiving layer
  • silver halide emulsion layer containing my novel combination of selenium and noble metal sensitizers
  • a thin protective layer of gelatin which can be omitted, if desired.
  • the stabilized photographic systems of the invention can also be used in orthochromatic, panchromatic, and infrared sensitive systems.
  • Various silver salts can be used as the sensitive salt in sensitized silver halide systems stabilized in accordance with the invention such as silver bromide, silver iodide, silver chloride, or mixed silver halides, such as silver chlorobromide or silver bromoiodide.
  • the present photographic systems can be used for color photography, for example, in silver halide emulsions containing color-forming couplers or emulsions to be developed by solutions containing couplers or other color-generating materials, emulsions of the mixed-packet type, such as described in Godowsky US. Patent 2,698,794, issued January 4, 1955; in silver dye-bleach systems; and emulsions of the mixedgrain type, such as described in Carroll and Hanson US. Patent 2,592,243, issued April 8, 1952.
  • Typical color-forming compounds or couplers which are useful in color photography, according to our invention include the following:
  • amylsulfanilide 2-cyanoacetylcoumarone-5-sulfon-N-n-buty1anilide Z-cyanoacetyl-S-benzoylamino-coumarone Z-cyanoacetylcoumarone--sulfondimethylamide Z-cyanoacetylcoumarone-S-sulfon-N-methylanilide Z-cyanoacetylnaphthalene sulfon-N-methylanilide 2-cyanoacetylcoumarone-5- (N'y-phenylproyl -p-tert.
  • couplers which do have wandering tendencies can be employed in a useful manner according to the technique described in Jelley and Vittum US. Patent 2,322,027, issued June 15, 1943.
  • This method comprises adding the color coupler to a water-immiscible crystalloidal solvent, such as tr icresyl phosphate or dibutyl phthalate and adding the solution to an aqueous emulsion.
  • the couplers are characterized by inherent non-wandering characteristics due to the presence in the coupler molecules of a fatty type radical (e.g., l-(2,4,6-trichlorophenyl)-3-n-pentadecyl-5- pyrazolone; 1 phenyl 3 n-pentadecyl-4-(l-phenyl-S- tetrazolylthio) 5 pyrazolone; 1-phenyl-3-(3,5-disulfobenzamido) 4 (2-hydroXy-4-n-pentadecylphenylazo)-5- pyrazolone dipotassium salt, etc.
  • the coupler can be incorporated in the emulsion simply by dissolving it in a convenient organic solvent which does not have any deleterious effect upon the emulsion.
  • solvents such as pyridine, triethanolamine
  • the present photographic systems intended can also be used in diffusion transfer processes which, for example, utilize undeveloped silver halide in non-image areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a receiving layer in close proximity to the original silver halide emulsion layer.
  • diffusion transfer processes which, for example, utilize undeveloped silver halide in non-image areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a receiving layer in close proximity to the original silver halide emulsion layer.
  • Such processes are described in Rott U.S. Patent 2,352,014, issued June 20, 1944, and Land U.S. Patents 2,584,029, issued January 29, 1952; 2,698,236, issued December 28, 1954; 2,543,181, issued February 27, 1951, and 2,698,245, issued December 28, 1954; and Yackel et al. U.S. Patent 3,020,155, issued February 6, 1962.
  • My photographic systems can be advantageously used in diflusion transfer systems utilized for document copying, and in those wherein a silver halide emulsion layer is coated adjacent to a fogged silver halide emulsion layer or a layer containing silver precipitating nuclei, such as nickel sulfide.
  • the sensitive emulsion following development, is then washed off, leaving the positive image in the light-insensitive layer containing the diffused silver image.
  • the present photographic systems can also be used in color transfer processes which utilize the 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.
  • Color processes of this type are described in Land U.S. Patents 2,559,643, issued July 10, 1951, and 2,698,798, issued January 4, 1955; Land and Rogers Belgian Patents 554,933 and 554,934, granted August 12, 1957; International Polaroid Belgian Patents 554,212, granted July 16, 1957, and 554,935, granted August 12, 1957; Yutzy U.S. Patent 2,756,142, granted July 24, 1956, and Whitmore and Mader Canadian Patent 602,607, issued August 30, 1960.
  • the sensitizing combinations are compatible with a wide variety of dye-developer combinations, including anthraquinone dye developers, such as 4-[1,5'- bis (2",5"-dihydroxyphenyl) 3' pentyl] amino 1- hydroxyanthraquinone, or azo dye developers, such as 2,4 bis (2,5 dimethoxy 3' [2"-(2",5-dihydroxy- 4 methylbenzoyl)isopropyl] phenylazo) 1 naphthol.
  • anthraquinone dye developers such as 4-[1,5'- bis (2",5"-dihydroxyphenyl) 3' pentyl] amino 1- hydroxyanthraquinone
  • azo dye developers such as 2,4 bis (2,5 dimethoxy 3' [2"-(2",5-dihydroxy- 4 methylbenzoyl)isopropyl] phenylazo) 1 naphthol.
  • Such dye developers can be incorporated in the lightsensitive emulsions themselves, or they can be incorporated in a hydrophilic colloid (e.g., gelatin) layer located contiguous to the noble metal-selenium sensitized lightsensitive emulsion.
  • a hydrophilic colloid e.g., gelatin
  • the present photographic systems can be used in the preparation of photographic products wherein a photographic developing agent is incorporated in a light-sensitive emulsion, or in a hydrophilic colloid layer contiguous with the emulsion, for example, in photographic products of the type described in Yutzy et al. U.S. Patent 2,725,298, issued November 29, 1955, or in Yutzy et al. U.S. Patent 2,739,890, issued March 27, 1956.
  • novel photographic systems of my invention can be used in the production of photographic products containing, for example, at least about 5 grams per mole of silver halide of a developing agent, such as 1-phenyl-3-pyrazolidone and wherein the emulsion is coated on a fibrous support which contains sufiicient moisture so that upon heating the exposed element, a negative silver image is obtained directly without the application of liquids.
  • a developing agent such as 1-phenyl-3-pyrazolidone
  • novel photographic systems of the invention can also be used in monobath processes such as are described in Haist et al. U.S. Patent 2,875,048, issued February 24, 1959, and in web-type processes, such as the one described in Tregillus et al. U.S. patent application Serial -No. 835,473, filed August 24, 1958, now U.S. Patent No. 3,179,517.
  • novel photographic systems of the invention can be used in the preparation of lithographic printing plates using, for example, techniques as described in Kodak French Patent 1,280,832, issued November 27, 1961.
  • the photographic systems of my invention can contain, in addition to labile sulfur compounds, certain stabilizers or antifoggants that are particularly useful for reducing incubation fog.
  • Useful stabilizing compounds for the emulsions of my invention include the salts of noble metals, especially palladium and platinum, including such salts as are described in Trivelli and Smith U.S. Patents 2,566,245, issued August 28, 1951, and 2,566,263, issued August 28, 1951.
  • Another group of useful stabilizing compounds include urazole stabilizers, such as urazole, l-phenyl dithiourazole, l-ethyl dithiourazole, etc., including stabilizers disclosed in Howe U.S. Patent 2,538,599, issued December 19, 1950.
  • mercury compounds such as those disclosed in Allen et al. U.S. Patent 2,728,663, issued December 27, 1955; Carroll et al. U.S. Patent 2,728,664, issued December 27, 1955 and Leubner et al. U.S. Patent 2,728,665, issued December 27, 1955. It has also been found that the photographic systems of the invention can be further stabilized with disulfide compounds, including the cyclic disulfides of Kodak Belgian Patent 569,317, or the aliphatic disulfides of Herz and Kalenda U.S. Patent 3,043,696, issued July 10, 1962.
  • Another group of disulfide stabilizing compounds which have useful effects in my invention include those containing a carbamylalkyl radical, wherein the carbamyl radical is aliphatic or cycloaliphatic (e.g., where the nitrogen atom of the carbamyl radical forms a part of a heterocyclic ring, such as pipen'dyl, morpholinyl, etc., as in the case of bis-(N- morpholinylcarbonyloxyethyl)-disulfide).
  • a carbamylalkyl radical wherein the carbamyl radical is aliphatic or cycloaliphatic (e.g., where the nitrogen atom of the carbamyl radical forms a part of a heterocyclic ring, such as pipen'dyl, morpholinyl, etc., as in the case of bis-(N- morpholinylcarbonyloxyethyl)-disulfide).
  • Nitron and similarly constituted tetrazoles are also useful stabilizers in the invention.
  • a salicylic acid such as 5-(1,1,3,3-tetramethylbutyl)salicylic acid.
  • 1-phenyl-5-mercaptotetrazoles are useful stabilizers in the invention.
  • Water-soluble salts of Group H elements of the Periodic Table such as magnesium, calcium, strontium, barium, cadmium and zinc, organic tertiary phosphines and azaindenes such as triazaindenes, tetrazaindenes and pentazaindenes are also useful stabilizers in the photographic systems of the invention.
  • Typical suitable azaindenes are disclosed in Heimbach and Kelly U.S. Patents 2,444,605 and 2,444,606, issued July 6, 1948; Heimbach U.S. Patents 2,444,607, issued July 6, 1948, and 2,450,397, issued September 28, 1948; Heimbach and Clark U.S. Patent 2,444,609, issued July 6, 1948; Allen and Reynolds U.S. Patents 2,713,541, issued July 19, 1955, and 2,743,181, issued April 24, 1956; Carroll and Beach 13 U.S. Patent 2,716,062, issued August 23, 1955; Allen and Beilfuss U.S. Patent 2,735,769, issued February 21, 1956; Reynolds and Sagal U.S. Patent 2,756,147, issued July 24, 1956; Allen and Sagura U.S. Patent 2,772,164, issued November 27, 1956 and Z. Wiss. Phot., vol. 47, 1952, pages 2 to 28.
  • a particularly useful class of stabilizers or antifoggants that can be utilized to control fog in the photographic systems of the invention are the derivatives of hydroxy carboxylic acids described in the copending application of Humphlett, U.S. Serial No. 413,962, filed November 25, 1964, and which stabilizer addenda can be represented by the following Formulas A and B:
  • A. O I! ($11M)... o l (drum and wherein: M and Z are each hydroxy radicals or acyloxy radicals wherein R is an alkyl radical or an aryl radical); X is a hydrogen atom, an acyloxymethyl radical if (-CHgOCR wherein R is an alkyl radical or an aryl radical) or a carbinol radical (CH OH); Y is a carboxy radical II (-0 OH) 21 carbamyl radical II N112) or a radical having the formula II COR wherein R is an alkyl radical (more generally having 1 to 2 carbons, particularly when Z is a hydroxyl radical); A is a carbinol radical, a radical having the formula as described for Y, a carboxy radical, an acyloxymethyl radical or a carbamyl radical; m is an integer of 2 to 3; n is an integer of 1 to 5; and 0 is an integer of O to 2.
  • the subject addenda contain at least one carbamyl or ester moiety including a or 6 lactone or inner ester groups (e.g., Formula A) as Well as the more conventional ester groups described above ii i (e.g., -ocr -oon Hence, at least one of A, Yand Z of Formula B forms a carbamyl or an ester radical.
  • Typical useful antifoggant 'addenda can be represented by the following more subgeneric formulas:
  • R is an alkyl radical having 1 to 2 carbon atoms; R and R are each an alkyl radical which more generally has 1 to 8 carbon atoms or a phenyl radical, including substituted phenyl radicals; R is an alkyl radical which more generally has 1 to 8 carbon atoms or a hydrogen atom; p is an integer of 2 to 3; and q is an integer of 1 to 5.
  • R is an alkyl radical having 1 to 2 carbon atoms
  • R and R are each an alkyl radical which more generally has 1 to 8 carbon atoms or a phenyl radical, including substituted phenyl radicals
  • R is an alkyl radical which more generally has 1 to 8 carbon atoms or a hydrogen atom
  • p is an integer of 2 to 3
  • q is an integer of 1 to 5.
  • Other subgeneric formulas defining antifoggant addenda of the invention included within generic Formulas A and B can be formulated.
  • the alkyl substituents described above suitably have 1 to 20 carbon atoms, and preferably 1 to 8 carbon atoms, including methyl, ethyl, isopropyl, butyl, heptyl, octyl, decyl, octadecyl, eicosyl and the like.
  • the aryl substituents described above include such radicals as phenyl, tolyl, naphthyl and the like, phenyl being preferred.
  • stabilizers or antifoggants can be utilized in conventional antifoggant amounts, the amount utilized varying with the particular stabilizer and the elfect desired in accordance with usual practice. Mixtures or combinations of more than one of the above-described stabilizers can be utilized.
  • Such stabilizers e.g., the azaindenes and mercury salts, which are normally added just prior to coating can, if desired, be included during the chemical sensitization of the silver halide emulsion.
  • the photographic systems stabilized with a labile sulfur compound in accordance with the invention can be any photographic system that is sensitized with noble metals and labile selenium.
  • the invention thus has utility, not only for silver halide photographic systems, but also, for other light-sensitive systems such as other light-sensitive silver salts, thallous halides, cuprous halides, lead halides and related light-sensitive heavy metal salts.
  • Example 1 dimethylselenourea (a labile selenium compound) and 4.0
  • the chemically sensitized emulsion was the Same manner but with the addition of 267 mg. 4- coated on a cellulose acetate film support at a coverage hydroxy-6-methyl-1,3,3a,7-tetraazaindene per mole of TABLE V Coating Amount of Tetraazaindene Relative 7 Speed Fog Similar results as those set out in Table V were obtained when 400 mg. of -acetamido-4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per mole of silver halide or 400 mg.
  • Example 6 A moderately coarsegrained gelatino silver bromoiodide emulsion containing 3.24 mole percent iodide was chemically sensitized by adding, per mole of silver halide, 2 mg. of potassium chloroaurate, 100 mg. of sodium thiocyanate, and 4 mg. of tri-p-tolylselenophosphate and heating for 15 minutes at 65 C. (Coating A). A second portion was chemically sensitized in the same manner, but with the addition of 2 mg. sodium thiosulfate and heated for the same time at 65 C. (Coating B). The chemically sensitized emulsions were coated on cellulose acetate fi-lm supports. A sample of each coating was exposed on an Eastman Ib sensitometer and processed as described in Example 1.
  • R represents an alkyl radical, such as butyl, isopropyl, amyl, isoamyl, etc., or an aromatic radical, such as phenyl, tolyl (o, m or p), etc.
  • alkyl radical such as butyl, isopropyl, amyl, isoamyl, etc.
  • aromatic radical such as phenyl, tolyl (o, m or p), etc.
  • selenium compounds can be used as labile selenium compounds in sensitizing the emulsions of the invention.
  • Example 7 moderately coarse-grained gelatino silver bromo iodide emulsion containing 3.24 mole percent iodide was chemically sensitized by adding, per mole of silver halide, 2 mg. of potassium chloroaurate, 100 mg. of sodium thiocyanate, and 2.6 mg. of selenobenzophenone and heating for 20 minutes at C. (Coating A). Other portions were chemically sensitized in the same manner, but with the addition of sodium thiosulfate in the amounts shown below, and heated at 65 C. for the length of time shown in Table VII (Coatings B and C). The chemically sensitized emulsions were then coated on cellulose acetate filrn supports. A sample of each coating was exposed on an Eastman Ib sensitometer and processed as described in Example 1.
  • Compound I is 4-hydroxy-6-methyl-l,3, 3a,7-tetraazaindene
  • Compound H is methyl-L-arabonate
  • Compound III is D-arabonamide
  • Compound IV is 'glucono-y-lactone.
  • hydroxy carboxylic acid derivates that can also be suitably utilized as antifoggants in the described gelatino silver bromoiodide emulsion at concentrations of 20 grams per mole of silver halide, or in combination with 2 grams per mole of silver halide of 4-hydroxy-6-methyl-l,3,3a,7-tetraazaindene, include: diethyl mucate, methyl D-arabonate, ethyl D-ara-bonate, methyl L-arabonate tetraacetate, D-arabono- -lactone, isopropyl L-arabonate, isobutyl D-arabonate tetraacetate, methyl (tetraacetyl-D-arabonyl)glycolate, D gluco-D- guloheptone- -lactone, D gl-uco-D-gulo heptonoamide, methyl D,L-glycerate, dimethyl D-tartrate, D-
  • Example 9 A coating of vacuum deposited silver bromide is made on a cellulose acetate film support and overcoated with a thin layer of gelatin by the method described in Example 1 of copending Rasch et al. application U.S. Serial No. 415,596, filed December 3, 1964. The resulting photographic element is immersed for five minutes at 68 F. in the following sensitizing solution:
  • the resulting treated photographic element is then allowed to air dry in the dark at 68 F.
  • the resulting dried photographic element is then exposed to roomlight for 10 seconds through a neutral density stepwedge and developed for 10 seconds in Kodak D-72 developing solution, fixed in hypo, washed and dried in the usual manner.
  • the fog level of the resulting processed photographic element is low when compared to a similarly exposed and processed photographic element prepared in the same manner except that the sodium thiosulfate is omitted from the sensitizing solution.
  • Example 10 To a fine-grained gelatino silver chlorobromide emulsion containing 60 mole percent bromide and 40 mole percent chloride was added 4.4 mg. of potassium chloroaurate, 50 mg. of sodium thiocyanate, 2.2 mg. of N,N- dimethylselenourea, and 2 mg. of sodium thiosulfate, and the emulsion heated at about 60 C. for about minutes. Thereafter to separate portions of the emulsion were added the antifoggants listed in Table IX below and the emulsions were coated on cellulose acetate film supports at coverages of 137 mg. of silver and 202 mg. of gelatin per square foot.
  • Example 11 A moderately coarse-grained, gelatino thallous bromoiodide emulsion containing 13 mole percent iodide and 87 mole percent bromide is chemically sensitized by adding, per mole of thallous halide, 10 mg. of potassium chloroaurate, 40 mg. of seleno-DL-cystine and 10 mg.
  • the chemically sensitized emulsion is coated on a cellulose acetate film support at a coverage of 306 mg. of thallium and 450 mg. of gelatin per square foot.
  • a sample of coating is hardened by bathing 5 minutes in a 3 percent solution of potassium chrome alum, washed, and dried. The sample is exposed through a step tablet for 5 minutes with a SOO-watt photoflood lamp at a distance of 9 inches. The exposed sample is processed at 68 F.
  • Example 12 In a manner similar to that described in Table G, column 25 of US. Patent 3,046,129, issued July 24, 1962, a conventional photographic gelatino silver bromoiodide emulsion was divided into three aliquot portions, each portion containing a conventional magenta coupler, such as one of those identified in Fierke et al. US. Patent 2,801,171 (e.g., coupler No. 7). A sample of the emulsion is sensitized to its optimum sensitivity with aurous thiosulfate at 3.3 mg. per mole of silver halide and dimethylselenourea at 0.2 mg. per mole of silver halide, the emulsion containing sodium thiosulfate at 2 mg.
  • a conventional magenta coupler such as one of those identified in Fierke et al. US. Patent 2,801,171 (e.g., coupler No. 7).
  • a sample of the emulsion is sensitized to its optimum sensitivity with aurous
  • the emulsion is coated on a cellulose acetate film support and dried.
  • the film sample is then exposed to daylight quality illumination in an Eastman Ib sensitometer and given a conventional negative development in the developing composition as described in Example 1.
  • the metallic silver is then removed by successive treatments with a ferricyanide bleach bath and fixing bath, followed by water washing in the usual manner. A reversal magenta image is obtained.
  • a photographic silver halide emulsion sensitized with at least two different sensitizers being a noble metal sensitizer and the other being a labile selenium sensitizer, said silver halide emulsion being stabilized by the addition thereto of a labile sulfur compound.
  • a photographic silver halide emulsion sensitized with at least two different sensitizers one of said sensitizers being a gold salt and the other being a labile selenium sensitizer, said silver halide emulsion being stabilized by the addition thereto of a labile sulfur compound.
  • a photographic silver halide emulsion sensitized with a gold salt and a labile selenium sensitizer said silver halide emulsion being stabilized by the addition thereto of a labile sulfur compound and a mercury compound antifoggant.
  • (l) M and Z are each selected from the group consisting of a hydroxy radical and an acyloxy radical having the formula i o CR wherein R is selected from the group consisting of 12.11 alkyl radical and an aryl radical;
  • X is selected from the group consisting of a hydrogen atom, a carbinol radical, a radical having the formula II -OH2OCR wherein R is selected from the group consisting of an alkyl radical and an aryl nadical;
  • Y is selected from the group consisting of a carboxy radical, a carbamyl radical and a radical having the formula ll GOR1 wherein R is an alkyl radical;
  • A is selected from the group consisting of a carbinol radical, a carbamyl radical, a carboxy radical, a radical having the formula u OOR wherein R is an alkyl radical and a radical having the formula i oHzohR wherein R is selected from the group consisting of an alkyl nadical and an aryl radical;
  • m is an integer of 2 to 3;
  • n is an integer of 1 to 5;
  • o is an integer of 0 to 2; except that at least one of A, Y and Z forms a radical selected from the group consisting of a carbamyl radical and an ester radical.

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US486235A 1964-07-22 1965-09-09 Stabilization of synergistically sensitized photographic systems Expired - Lifetime US3297447A (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
FR25078A FR1450841A (fr) 1964-07-22 1965-07-19 Stabilisation d'une émulsion photographique aux halogénures d'argent contenant plusieurs sensibilisateurs présentant un effet de synergie
CH1015865A CH455505A (fr) 1964-07-22 1965-07-20 Procédé de préparation d'une émulsion photographique sensible stabilisée
BE667170A BE667170A (xx) 1964-07-22 1965-07-20
DK374865AA DK124634B (da) 1964-07-22 1965-07-21 Fremgangsmåde til fremstilling af stabiliseret, højfølsom fotografisk sølvhalogenidemulsion.
NO159028A NO122513B (xx) 1964-07-22 1965-07-21
SE9608/65A SE344829B (xx) 1964-07-22 1965-07-21
DE19651472836 DE1472836C (de) 1964-07-22 1965-07-21 Chemisch sensibilisierte photographische Silberhalogenidemulsion
NL656509486A NL145963B (nl) 1964-07-22 1965-07-22 Werkwijze voor het verhogen van de gevoeligheid van lichtgevoelige zilverhalogenide-emulsies en fotografisch materiaal, voorzien van deze emulsies.
GB31190/65A GB1115038A (en) 1964-07-22 1965-07-22 Sensitive photographic materials
BR171519/65A BR6571519D0 (pt) 1964-07-22 1965-07-22 Estabilizacao de emulsoes fotograficas de halogeneto de prata sensibilizadas sinergicamente
US486235A US3297447A (en) 1964-07-22 1965-09-09 Stabilization of synergistically sensitized photographic systems
GB40300/66A GB1154236A (en) 1964-07-22 1966-09-09 Sensitive Photographic Materials

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Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3408197A (en) * 1967-01-03 1968-10-29 Eastman Kodak Co Synergistic sensitization of silver halide emulsions with labile selenium formed in situ
US3408196A (en) * 1967-01-03 1968-10-29 Eastman Kodak Co Sensitization of silver halide emulsion with labile selenium formed in situ
US3420670A (en) * 1965-11-26 1969-01-07 Eastman Kodak Co Stabilization of synergistically sensitized photographic systems
US3442653A (en) * 1964-02-10 1969-05-06 Eastman Kodak Co Sensitized silver halide systems with activated nonlabile selenium compounds
US3619188A (en) * 1968-07-24 1971-11-09 Ilford Ltd Bleach-fix processing
DE2657080A1 (de) * 1975-12-16 1977-06-30 Asahi Chemical Ind Trocken-bildaufzeichnungsmaterial
JPS59180536A (ja) * 1983-03-30 1984-10-13 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真乳剤
US4764457A (en) * 1981-08-17 1988-08-16 Konishiroku Photo Industry Co., Ltd. Silver halide photographic emulsion
EP0506009A1 (en) * 1991-03-25 1992-09-30 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5166045A (en) * 1989-06-19 1992-11-24 Eastman Kodak Company Doping of silver halide emulsions with group VIB compounds to form improved photoactive grains
US5215880A (en) * 1991-05-08 1993-06-01 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material containing tellurium compound
EP0563708A1 (en) 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and light-sensitive material using the same
US5310631A (en) * 1992-04-20 1994-05-10 Fuji Photo Film Co., Ltd. Method of processing a silver halide photosensitive material containing a silver halide sensitized with a selenium sensitizer using a black-and-white developer containing a chelate complex salt of a transition metal
US5393655A (en) * 1992-12-10 1995-02-28 Fuji Photo Film Co., Ltd. Silver halide photographic material containing selenium or tellurium compound
US5397692A (en) * 1990-05-29 1995-03-14 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
EP0693710A1 (en) 1994-07-18 1996-01-24 Konica Corporation Silver halide photographic element and processing method thereof
US5492803A (en) * 1995-01-06 1996-02-20 Minnesota Mining And Manufacturing Company Hydrazide redox-dye-releasing compounds for photothermographic elements
US5492804A (en) * 1994-06-30 1996-02-20 Minnesota Mining And Manufacturing Company Chromogenic leuco redox-dye-releasing compounds for photothermographic elements
US5492805A (en) * 1994-06-30 1996-02-20 Minnesota Mining And Manufacturing Company Blocked leuco dyes for photothermographic elements
US5616446A (en) * 1994-09-29 1997-04-01 Konica Corporation Silver halide photographic light-sensitive material
EP0772079A2 (en) 1995-10-31 1997-05-07 Eastman Kodak Company Light-sensitive silber halide emulsions and processes for their preparation
EP0777153A1 (en) 1995-11-30 1997-06-04 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
EP0777150A1 (en) 1995-11-29 1997-06-04 Konica Corporation Developing composition for silver halide photographic light sensitive material
US5759760A (en) * 1997-06-04 1998-06-02 Eastman Kodak Company Aqueous solid particle dispersions in chemical sensitization
US5763154A (en) * 1996-08-07 1998-06-09 Eastman Kodak Company Palladium chemical sensitizers for silver halides
US5891615A (en) * 1997-04-08 1999-04-06 Imation Corp. Chemical sensitization of photothermographic silver halide emulsions
US5928857A (en) * 1994-11-16 1999-07-27 Minnesota Mining And Manufacturing Company Photothermographic element with improved adherence between layers
US5939249A (en) * 1997-06-24 1999-08-17 Imation Corp. Photothermographic element with iridium and copper doped silver halide grains
US20060121397A1 (en) * 2003-01-31 2006-06-08 Konica Minolata Photo Imaging Inc. Silver halide emulsion silver halide photographic sensitive material and method of image formation
US20070202448A1 (en) * 2004-03-11 2007-08-30 Shigeru Shibayama Silver Halide Color Photographic Light-Sensitive Material
US20070254248A1 (en) * 2004-09-30 2007-11-01 Fujifilm Corporation Silver Halide Color Photographic Light-Sensitive Material
US7468241B1 (en) 2007-09-21 2008-12-23 Carestream Health, Inc. Processing latitude stabilizers for photothermographic materials
US20090075218A1 (en) * 2005-04-28 2009-03-19 Fujifilm Corporation Silver halide color photographic light-sensitive material
US20090081578A1 (en) * 2007-09-21 2009-03-26 Carestream Health, Inc. Method of preparing silver carboxylate soaps
US20090181332A1 (en) * 2008-01-14 2009-07-16 William Donald Ramsden Protective overcoats for thermally developable materials
WO2017123444A1 (en) 2016-01-15 2017-07-20 Carestream Health, Inc. Method of preparing silver carboxylate soaps
US10464362B2 (en) * 2015-10-23 2019-11-05 Nippon Paper Industries Co., Ltd. Thermosensitive recording medium
US10513137B2 (en) 2015-06-16 2019-12-24 Nippon Paper Industries Co., Ltd. Thermosensitive recording medium

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US4565778A (en) * 1983-03-31 1986-01-21 Konishiroku Photo Industry Co., Ltd. Silver halide photographic materials
JP2579689B2 (ja) * 1989-11-06 1997-02-05 富士写真フイルム株式会社 ハロゲン化銀写真乳剤
EP0514675B1 (en) * 1991-04-22 1999-12-08 Fuji Photo Film Co., Ltd. Silver halide photographic materials and method for processing the same
JPH0756257A (ja) * 1993-08-10 1995-03-03 Konica Corp ハロゲン化銀写真感光材料

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Cited By (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3442653A (en) * 1964-02-10 1969-05-06 Eastman Kodak Co Sensitized silver halide systems with activated nonlabile selenium compounds
US3420670A (en) * 1965-11-26 1969-01-07 Eastman Kodak Co Stabilization of synergistically sensitized photographic systems
US3408196A (en) * 1967-01-03 1968-10-29 Eastman Kodak Co Sensitization of silver halide emulsion with labile selenium formed in situ
US3408197A (en) * 1967-01-03 1968-10-29 Eastman Kodak Co Synergistic sensitization of silver halide emulsions with labile selenium formed in situ
US3619188A (en) * 1968-07-24 1971-11-09 Ilford Ltd Bleach-fix processing
DE2657080A1 (de) * 1975-12-16 1977-06-30 Asahi Chemical Ind Trocken-bildaufzeichnungsmaterial
US4764457A (en) * 1981-08-17 1988-08-16 Konishiroku Photo Industry Co., Ltd. Silver halide photographic emulsion
JPS59180536A (ja) * 1983-03-30 1984-10-13 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真乳剤
JPH0466013B2 (xx) * 1983-03-30 1992-10-21 Konishiroku Photo Ind
US5166045A (en) * 1989-06-19 1992-11-24 Eastman Kodak Company Doping of silver halide emulsions with group VIB compounds to form improved photoactive grains
US5397692A (en) * 1990-05-29 1995-03-14 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
EP0506009A1 (en) * 1991-03-25 1992-09-30 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5236821A (en) * 1991-03-25 1993-08-17 Fuji Photo Film Co., Ltd. Silver halide photographic material which contains a selenium sensitizer
US5215880A (en) * 1991-05-08 1993-06-01 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material containing tellurium compound
EP0563708A1 (en) 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and light-sensitive material using the same
US5310631A (en) * 1992-04-20 1994-05-10 Fuji Photo Film Co., Ltd. Method of processing a silver halide photosensitive material containing a silver halide sensitized with a selenium sensitizer using a black-and-white developer containing a chelate complex salt of a transition metal
US5393655A (en) * 1992-12-10 1995-02-28 Fuji Photo Film Co., Ltd. Silver halide photographic material containing selenium or tellurium compound
US5492804A (en) * 1994-06-30 1996-02-20 Minnesota Mining And Manufacturing Company Chromogenic leuco redox-dye-releasing compounds for photothermographic elements
US5492805A (en) * 1994-06-30 1996-02-20 Minnesota Mining And Manufacturing Company Blocked leuco dyes for photothermographic elements
US5696289A (en) * 1994-06-30 1997-12-09 Minnesota Mining And Manufacturing Company Blocked leuco dyes for photothermographic elements
US5705676A (en) * 1994-06-30 1998-01-06 Minnesota Mining And Manufacturing Company Chromogenic leuco redox-dye-releasing compounds for photothermographic elements
EP0693710A1 (en) 1994-07-18 1996-01-24 Konica Corporation Silver halide photographic element and processing method thereof
US5556738A (en) * 1994-07-18 1996-09-17 Konica Corporation Silver halide photographic element and processing method thereof
US5616446A (en) * 1994-09-29 1997-04-01 Konica Corporation Silver halide photographic light-sensitive material
US5928857A (en) * 1994-11-16 1999-07-27 Minnesota Mining And Manufacturing Company Photothermographic element with improved adherence between layers
US5492803A (en) * 1995-01-06 1996-02-20 Minnesota Mining And Manufacturing Company Hydrazide redox-dye-releasing compounds for photothermographic elements
EP0772079A2 (en) 1995-10-31 1997-05-07 Eastman Kodak Company Light-sensitive silber halide emulsions and processes for their preparation
EP0777150A1 (en) 1995-11-29 1997-06-04 Konica Corporation Developing composition for silver halide photographic light sensitive material
EP0777153A1 (en) 1995-11-30 1997-06-04 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US5763154A (en) * 1996-08-07 1998-06-09 Eastman Kodak Company Palladium chemical sensitizers for silver halides
US5891615A (en) * 1997-04-08 1999-04-06 Imation Corp. Chemical sensitization of photothermographic silver halide emulsions
US5759760A (en) * 1997-06-04 1998-06-02 Eastman Kodak Company Aqueous solid particle dispersions in chemical sensitization
US5939249A (en) * 1997-06-24 1999-08-17 Imation Corp. Photothermographic element with iridium and copper doped silver halide grains
US6060231A (en) * 1997-06-24 2000-05-09 Eastman Kodak Company Photothermographic element with iridium and copper doped silver halide grains
US20060121397A1 (en) * 2003-01-31 2006-06-08 Konica Minolata Photo Imaging Inc. Silver halide emulsion silver halide photographic sensitive material and method of image formation
US7220537B2 (en) 2003-01-31 2007-05-22 Konica Minolta Photo Imaging, Inc. Silver halide emulsion silver halide photographic sensitive material and method of image formation
US7527922B2 (en) 2004-03-11 2009-05-05 Fujifilm Corporation Silver halide color photographic light-sensitive material
US20070202448A1 (en) * 2004-03-11 2007-08-30 Shigeru Shibayama Silver Halide Color Photographic Light-Sensitive Material
US20070254248A1 (en) * 2004-09-30 2007-11-01 Fujifilm Corporation Silver Halide Color Photographic Light-Sensitive Material
US7407740B2 (en) 2004-09-30 2008-08-05 Fujifilm Corporation Silver halide color photographic light-sensitive material
US20090075218A1 (en) * 2005-04-28 2009-03-19 Fujifilm Corporation Silver halide color photographic light-sensitive material
US7468241B1 (en) 2007-09-21 2008-12-23 Carestream Health, Inc. Processing latitude stabilizers for photothermographic materials
US7524621B2 (en) 2007-09-21 2009-04-28 Carestream Health, Inc. Method of preparing silver carboxylate soaps
US20090081578A1 (en) * 2007-09-21 2009-03-26 Carestream Health, Inc. Method of preparing silver carboxylate soaps
US20090181332A1 (en) * 2008-01-14 2009-07-16 William Donald Ramsden Protective overcoats for thermally developable materials
US7622247B2 (en) 2008-01-14 2009-11-24 Carestream Health, Inc. Protective overcoats for thermally developable materials
US10513137B2 (en) 2015-06-16 2019-12-24 Nippon Paper Industries Co., Ltd. Thermosensitive recording medium
US10464362B2 (en) * 2015-10-23 2019-11-05 Nippon Paper Industries Co., Ltd. Thermosensitive recording medium
WO2017123444A1 (en) 2016-01-15 2017-07-20 Carestream Health, Inc. Method of preparing silver carboxylate soaps

Also Published As

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NL6509486A (xx) 1966-01-24
NL145963B (nl) 1975-05-15
DE1472836A1 (de) 1969-03-27
CH455505A (fr) 1968-07-15
BE667170A (xx) 1965-11-16
GB1154236A (en) 1969-06-04
NO122513B (xx) 1971-07-05
SE344829B (xx) 1972-05-02
DE1472836B2 (de) 1973-01-18
DK124634B (da) 1972-11-06
GB1115038A (en) 1968-05-22
BR6571519D0 (pt) 1973-09-11

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