US3297446A - Synergistic sensitization of photographic systems with labile selenium and a noble metal - Google Patents

Synergistic sensitization of photographic systems with labile selenium and a noble metal Download PDF

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US3297446A
US3297446A US468972A US46897265A US3297446A US 3297446 A US3297446 A US 3297446A US 468972 A US468972 A US 468972A US 46897265 A US46897265 A US 46897265A US 3297446 A US3297446 A US 3297446A
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silver halide
photographic
emulsion
selenium
sensitized
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Dunn Joseph Stanley
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to DK64865AA priority Critical patent/DK130897B/da
Priority to DE19651472818 priority patent/DE1472818A1/de
Priority to BE659479A priority patent/BE659479A/xx
Priority to NL656501562A priority patent/NL144403B/xx
Priority to CH176765A priority patent/CH441997A/fr
Priority to SE01685/65A priority patent/SE333096B/xx
Priority to NO156718A priority patent/NO120009B/no
Priority to FR4940A priority patent/FR1428087A/fr
Priority to GB5713/65A priority patent/GB1098466A/en
Priority to US468972A priority patent/US3297446A/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to GB29373/66A priority patent/GB1150573A/en
Priority to CH1636266A priority patent/CH476325A/fr
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Publication of US3297446A publication Critical patent/US3297446A/en
Priority to US717396A priority patent/US3442653A/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
    • G03C1/494—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
    • 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
    • G03C1/7253—Lead salts
    • 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
    • G03C2001/091—Gold
    • 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
    • G03C2001/095—Disulfide or dichalcogenide compound
    • 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
    • G03C2001/097—Selenium

Definitions

  • This invention relates to photography and more particularly to noble metal sensitized photographic systems.
  • 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.
  • a noble metal sensitizer e.g., a gold salt and a labile sulfur compound.
  • gold-sulfur sensitizer con1 binations are, there is a need in the art for photographic systems having greater speeds without concurrent increases a grain size, or reduced grain size for a given speed.
  • gelatino silver halide emulsions sensitized with novel synergistic gold-containing sensitizer combinations therefor.
  • noble metal sensitized systems wherein vthe speed sensitivity of the system is increased with labile selenium.
  • the noble metal moiety and the labile selenium moiety cooperate or synergize to impart substantially increased sensitivity to photographic systems that can be sensitized with noble metals.
  • the noble metal moiety and the labile selenium moiety are more generally added to the emulsion as separate entities, although such is not necessary.
  • 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.
  • especially useful compounds include selenoamides, selenoketones (especially ketones having an alkyl radical attached to the moiety), selenocarboxylic acids and esters, etc.
  • 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, pyridyl, etc., and aliphatic isoselenocyanates. It has also been found that colloidal selenium itself is a useful sensitizer, and this discovery was quite surprising in view of the disadvantageous effects of colloidal sulfur in silver halide emulsions.
  • Illustrative addenda suitable for furnishing the labile selenium moiety in the sensitizer combinations of the invention include:
  • concentration of selenium sensitizer can be varied considerably depending upon the particular selenium addendum employed (some sensitizers being more efiicacious than others), the nature of the photographic system, the amount and chemical nature of the noble metal sensitizer, etc.
  • labile as used herein has the meaning well understood by those skilledfin the art of photography, i.e., a material which yields a silver selenide that is insoluble in water at room temperature (20C.) 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 sensitizer of invention.
  • the noble metale sensitizers useful in my invention include the Well known gold sensitizers which have been previously recognized as useful in the photographic art and found to be outstanding in their sensitizing action,
  • noble metal sensitizers including palladium, platinum, etc.
  • sensitizers such as are disclosed in Smith et al. US. Patent 2,448,060, issued August 31, 1948.
  • Typical suitable gold sensitizers are described in Waller et al. US. Patent 2,399,083, issued April 23, 1946, and Damschroder et al. US. 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:
  • C-C CCH CH'N CHz C-C /N ⁇ H: H: CH AuCh (VII) f /O gH; C 415 AuCh (VIII) S S
  • the quantity of noble metal sensitizer useful in my 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.
  • 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, etc.
  • the sensitizing addenda used in my 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 sufficient solubility in water to be used in the form of an aqueous solution.
  • Particularly 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. In some cases, it is possible to add the present sensitizers suspended in an organic solvent which forms very small suspended particles 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.
  • Vacuum deposited photographic systems substantially free of conventional vehicles, binders or dispersing agents can also be sensitized in accordance with the invention.
  • Such vacuum deposited photographic systems can be sensitized in accordance with the invention by incorporating the subject sensitizers in a coating or layer contiguous to the vacuum deposited light-sensitive material.
  • Suitable vacuum deposited silver halide systems that can be sensitized in accordance with the invention are disclosed in Rasch et a1. application, U.S. Serial No. 415,596, filed December 3,
  • 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 US. 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 US.
  • Typical polymers which can be used'in combination with gelatin to prevent loss of density and thereby increase the covering power in the processed, dn'ed layer include the polyvinyl lactams, such as polyvinyl-pyrrolidone, 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, methacrylamide, 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, salicyclic acid condensates, etc.
  • Such emulsions can contain speed increasing compounds of the quaternary ammonium type of Carroll US. Patent 2,271,623, issued February 3, 1942; Carroll and Allen US. Patent 2,288,226, issued June 30, 1942; and Carroll and Spence US. Patent 2,334,864, issued November 23,
  • the photographic silver halide systems sensitized according to the novel 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 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).
  • 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 emulsions having finer grain to reach a given speed. This results in higher contrast for such a material, since finer grain emulsions inherently produce higher contrast. Thus, for the same grain size, it is possible to obtain higher speeds with the selenium-gold sensitized emulsions of my invention.
  • 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, dlivr March 4, 1963.
  • 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 typical integral screen X-ray material of my invention 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).
  • Other arrangements will become apparent to those skilled in the art.
  • the chemical sensitizing addenda which I have described can be used in various kinds of photographic systems. In addition to being useful in X-ray and other nonoptically sensitized systems, they can also be used in orthochromatic, panchromatic, and infrared sensitive systems.
  • the sensitizing addenda can be added to photographic systems before or after any sensitizing dyes which are used.
  • Various silver salts can be used as the sensitive salt in silver halide systems such as silver bromide, silver iodide, silver chloride, or mixed silver halides, such as silver chlorobromide or silver bromoiodide.
  • the present sensitizing agents can be used in emulsions intended for color photograph, for example, 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 mixed-grain type, such as described in Carroll and Hanson US. Patent 2,592,243, issued April 8, 1952.
  • V I My synergistic sensitizing combinations can also be used in photographic systems intended for use in diifusion transfer processes which, for example, utilize undeveloped silver halide in non-irnage 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.
  • diifusion transfer processes which, for example, utilize undeveloped silver halide in non-irnage 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 US. 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,
  • My photographic systems can be advantageously used in diffusion 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 image-wise 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]p'henylaso)-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]p'henylaso)-1-nap
  • Such dye developers can be incorporated in the light-sensitive emulsions themselves, or they can be incorporated in a hydrophilic colloid (e.g., gelatin) layer located contiguous to the noble metalselenium sensitized light-sensitive emulsion.
  • a hydrophilic colloid e.g., gelatin
  • Photographic emulsions sensitized by the novel means described herein can be used in the preparation of photographic products wherein a photographic developing agent is incorporated in the emulsion itself, 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.
  • 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, dlivr November 27, 1961.
  • 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 stabilizers which are quite useful in my invention comprise the alkane, areneand heterocyclic sulfinic acids and their water-soluble salts (sodium benzene sulfinate, sodium anthraquinone sulfonates, ethane disulfinic acid, etc., including stabilizers disclosed in Brunken U.S. Patent 2,057,764, issued October 20, 1936).
  • Another group of useful stabilizing compounds include urazole stabilizers, such as urazole, 4- phenyl urazole, l-ethyl dithiourazole, etc., including stabilizers disclosed in Howe U.S. Patent 2,538,599, issued December 19, 1950.
  • 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 teterocyclic ring, such as piperidyl, 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 teterocyclic ring, such as piperidyl, morpholinyl, etc., as in the case of bis-(N-morpholinylcarbonyloxyethyl)-disulfide).
  • 1-phenyl-5 mercaptotetrazoles are useful stabilizers in the invention.
  • Water-soluble salts of Group II elements of the Periodic Table such as magnesium, calcium, strontium, barium, cadmium and zinc, organic tertiary phosphines and azaindenes such as triazindenes, 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 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 Hum-phlett, U.S. Serial No. 413,962, filed November 25, 1964, and which stabilizer addenda can be represented by the following Formulas A and B,
  • M and Z are each hydroxy radicals or acyloxy radicals ll C R wherein R is an alkyl radical or an aryl radical)
  • X is a hydrogen atom, an acyloxymethyl radical I (-CHgO (J) R2 wherein R2 is an alkyl radical or an aryl radical) or a carbinol radical (CH OH);
  • Y is a carboxy radical a carbamyl radical I!
  • 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
  • o is an integer of 0 to 2.
  • the subject addenda contain at least one carbamyl or ester moiety including 7 or 6 lactone or inner ester groups (e.g., Formula A) as well as the more conventional ester groups described above II (as, o R, 0 OR Hence, at least one of A, Y and 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.
  • 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 effect desired in accordance with usual practice. Mixtures or combinations of more than one of the abovedescribed stabilizers can be utilized.
  • Such stabilizers e.g., the azaindenes, which are normally added just prior to coating may, if desired, be included during the chemical sensitization of the silver halide emulsion.
  • novel sensitizer combinations of a noble metal and a labile selenium described herein can be utilized to sensitize any photographic system that can be sensitized with noble metals.
  • 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 A coarse-grained, gelatino silver bromoiodide emulsion containing about 6 mole percent iodide was chemically sensitized by adding 2 mg. per mole of silver halide of sodium thiosulfate (a labile sulfur compound), 20 mg. per mole of silver halide of potassium thiocyanate and 0.75 mg. per mole of silver halide of the gold salt, potassium chloroaurate. These addenda were intimately incorporated in the emulsion after ripening but prior to digestion. The emulsion was then heated for 15 minutes at 60 C.
  • sodium thiosulfate a labile sulfur compound
  • a second portion of the same unsensitized emulsion was chemically sensitized exactly as described, except that the sodium thiosulfate was replaced with 0.2 mg. per mole of silver halide of N,N-dimethylsele-nourea (a labile selenium compound). After sensitization, the emulsion was heated for about 24 minutes at 60 C. Each batch of chemically sensitized emulsion was separately coated'on conventional cellulose acetate film support and then dried. The dried coatings were then exposed to daylight quality illumination on an Eastman Ib sensitometer and developed for 5 minutes in a developer having the following composition:
  • EXAMPLE 2 11 larly finished by heating for a few minutes at 60 C. Each batch of emulsion was then separately coated on a cellulose acetate film support, dried and exposed, developed, fixed, washed and dried as described in Example 1. The following results were obtained.
  • EXAMPLE 3 A coarse-grained, gelatino silver bromoiodide emulsion of the type used in medical radiography, or conventional high speed negative photography, was chemically sensitized with compounds identified in Table III and at the concentrations (mg/silver mole) shown in Table HI. Each portion of sensitized emulsion contain 40 mg. of potassium thiocyanate per mole of silver halide, and each was separately coated on conventional cellulose acetate film support and dried. The dried coatings were then separately exposed to daylight quality illumination on an Eastman lb sensitometer and developed in a conventional hydroquinone-Elon (N-methyl-p-aminophenol sulfate) developing composition, such as described in Example 1. The developed coatings were then fixed, washed and dried in the usual manner. The following sensitometric data were obtained:
  • Sulfur means sodium thiosulfate
  • Gold means potassium chloroaurate
  • Selenium-1 means dimethylselenourea
  • Selenium-2 means colloidal selenium
  • Selenium-3 means diethylselenourea
  • Selenium-4 means selenourea
  • Example 4 below illustrates the use of my novel sensitizing combinations in a photographic silver halide emulsion designed especially for use in a lithographic process.
  • An emulsion suitable for this purpose can be prepared as described in U.S. Patent 2,756,148.
  • EXAMPLE 4 A fine grain high contrast gelatino silver chlorobromide emulsion containing 90 mole percent chloride was chemically sensitized by adding, per mole of silver halide, 1.78 mg. of sodium thiosulfate and 1.72 mg. of potassium chloroaurate and heating for 12 minutes at 65 C. A second portion of this emulsion was chemically sensitized TABLE IV Coating No. Type of Sensitizer Relative 7 Fog Speed :1 Sulfur-Gold 100 13. 0 01 b Selenium-Gold 191 13.0 01
  • the developer has the following composition:
  • a second aliquot portion (b) was sensitized with the same gold chloride salt and with dimethylselenourea at 0.2 mg. per mole of silver halide.
  • Aliquot sample (c) was 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.
  • Each of the coatings contained the tetrazole stabilizing compound, 5-(4-cyanophenyl)tetrazole monohydrate, at a concentration of about 5 grams per mole of silver halide.
  • the three samples of emulsions were coated on separate cellulose acetate film supports and dried.
  • the film samples were then exposed to daylight quality illumination in an Eastman type Ib sensitometer and given a conventional negative development in a hydroquinone, N-methyl-p-aminophenol sulfate developer as described in Example 1.
  • the coatings were then flashed to white light and developed once again in an alkaline color developing composition containing 4-amino- N,N-diethyl-3-methylaniline hydrochloride as the active developing agent.
  • the metallic silver was then removed by successive treatments with a ferricyanide bleach bath and fixing bath, followed by conventional water washing. The following results were obtained:
  • Couplers producing cyan images 5- (p-amylphenoxybenzenesulfonamino -l -naphthol 5- (N-benzyl-N-naphthalenesulfonamino) 1 -naphthol 5-(n-benzyl-N-n-valerylamino) -1-naphthol 5 -caproylamino-1 -n aphth ol Z-chloro -5 (N-n-valeryl-N-p-isopro pylb enzyl amino) -1- naphthol V 2,4-dichloro-5 p-nitrobenzoyl-;3-o'hydroxyethyl-arnino l-naphthol 2,4-dichloro-5-palmitylamino-1 -naphthol 2,2'-dihydroxy-5 ,5 -dibromostilbene S-diphenylethersulfonamid
  • amylsulfonanilide 1-p-laurylphenyl-3 -methyl-5-pyrazolone l-li-n aphthyl-3 -amyl-5 -p yrazol one 1-p-nitrophenyl-3-n-amyl-5-pyrazolone 1-p-phenoxyphenyl-3 -n-amyl-5-pyrazolone 1-phenyl-3 -n-amyl-5-pyrazolone 1,4-phenylene bis-3 1-phenyl-5-pyrazolone) 1-phenyl-3 -acetylamino-S-pyrazolone 1-phenyl-3 -propionylamino-S-pyrazolone 1-phenyl-3 -n-valerylamino-5-pyrazolone 1-phenyl-3 -cl1loro acetylamino-S-pyrazolone 1-phenyl-3-dichloroacetylamino-S-pyrazolone 1-phenyl-3 -
  • amylbenzoylamino -5-pyrazolone 1-phenyl-3 -diarnylbenzoylamino-S-pyrazolone 1-phenyl-3 -fl-naphthoylamino-S-pyrazolone 1-phenyl-3-phenylcarbarnylamino-S-pyrazolone 1-phenyl-3 -palmitylamino-S-pyrazolone 1-pheny1-3 -benzenesulfonylamino-S-pyrazolone 1- (p-phenoxyphenyl) -3-(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 couplier to a water-immiscible crystalloidal solvent, such as tricresyl 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., 1-(2,4,6 trichlorophenyl)-3-n-pentadecyl-S-pyrazolone; l-phenyl-3-n-pentadecyl-4-(1-phenyl-5-tetrazolylthio) 5- pyrazol one; 1-phe11y1-3-( 3,5 d sulfobelnz'amido -4-( 2-hydroxy-4-n-pentadencylphenylazo) S-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, e
  • EXAMPLE 7 A coarse-grained silver bromoiodide emulsion of the type described in Example 1 above was divided into several aliquot portions and each portion was then chemically sensitized as described below. The emulsions were then coated on separate supports and processed as described in Example 1 above. The following results were obtained:
  • EXAMPLE 8 An emulsion of the type described in Example 7 above was coated and processed as described in Example 1. Aliquot portions of the emulsion were treated with sensitizer addenda before coating, these addenda being identified in the following table in mg. per mole of silver halide.
  • the seleniumgold sensitized emulsions of my invention can be further improved in speed by adding to the emulsion a conventional polyethylene glycol sensitizer, alone or in combination with an onium salt of the type described in U.S. Patents 2,400,532; 2,423,549; 2,441,389; 2,944,898; 2,944,900; or 3,062,645.
  • Quaternary ammonium salts of the type described in U.S. Patent 3,017,271 can also be used. This effect is illustrated in the following example.
  • EXAMPLE 9 A selenium-gold sensitized, gelantino silver bromoiodide emulsion was prepared and coated as described in Example 1 above. A separate portion of the same emulsion was prepared and then modified by the addition of 0.66 g. of a olyethylene glycol sensitizer (referred to in Table IX as PEG) having an average molecular weight of 1500 and 0.4 g. per mole of silver halide of tetradecamethylene bis (pyridinium perchlorate) (referred to in Table IX as Q-salt). The modified emulsion was then coated and dried.
  • a olyethylene glycol sensitizer referred to in Table IX as PEG
  • PEG olyethylene glycol sensitizer having an average molecular weight of 1500 and 0.4 g. per mole of silver halide of tetradecamethylene bis (pyridinium perchlorate)
  • the speed of my seleniumgold sensitized emulsions can be further increased by including therein a thioether sensitizer of the type described in U.S. Patents 3,046,134; 3,021,215; 3,062,646; or 3,038,- 805.
  • the control emulsion of Example 9 was increased in speed from to by including therein a thioether sensitizer of the type described in U.S. Patent 3,046,132. While a 55 percent increase in speed was obtained, the fog level only rose from .05 to .15.
  • EXAMPLE 10 A selenium-gold-sensitized, gelatino silver bromoiodide emulsion was prepared as described in Example 1 of this application, and the emulsion was coated on a conventional cellulose acetate film'support and dried. A second sample of the same emulsion was prepared and then modified by the addition of 33 g. per mole of silver halide of a carboxyrnethyl protein of the type described in U.S. Patent 3,011,890. This sample was also coated on cellulose acetate film support and dried. The samples, numbered a and b respectively in the following table, were then exposed and processed as described in Example 7 above. The following results were obtained:
  • a selenium-gold-sensitized, gelatino silver bromoiodide emulsion was prepared as described in Example 1 of this application, and the emulsion was coated on a conventional cellulose acetate film support and dried.
  • a second sample of the same emulsion was prepared and then modified by the addition of 40 g. per mole of silver halide of polyacrylamide (e.g., a polymer of the type described in U.S. application Serial No. 301,177, filed August 9, 1963). This sample was also coated on cellulose acetate film support and dried.
  • the samples, numbered a and b respectively in the following table, were then exposed and processed as described in Example 1 above. The following results were obtained:
  • Compound I is 4-hydroxy-6-methyl- 1,3,3a,7-tetrazaindene
  • Compound II is methyl-L-arabonate
  • Compound III is D-arabonamide
  • Compound IV is glucono-y-lactone.
  • Other related hydroxy carboxylic acid derivates that can also be suitably utilized as antifoggants in the described gelatino silver bromoioemulsion samples were coated on a cellulose acetate film support at a coverage of 540 mg. silver and 500 mg. gelatin per square foot. Portions of the films were exposed in an Eastman type Ib sensitometer, developed for 5 minutes in the developer described in Example 1, fixed in hypo, washed and dried in the usual way.
  • B B-carboxyethyl-diphenylphosphine.
  • C B-cyanoet hyl-diphenylphosphine.
  • D bis-(fl-oyanoethyl)-pl1e11y1phosphine.
  • dide 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-1,3,3a,7- tetrazaindene include: diethyl mucate, methyl D-arabonate, ethyl D-arabonate, methyl L-arabonate tetraacetate, D-arabono y-lactone, isobutyl D-arabonate tetra acetate, methyl (tetraacetyl-D-arabonyl)glycolate, D- gluco-D-gulo-'heptano-yslactone, D gluco-D-gulo-heptonoamide, methyl D,L-glycerate, dimethyl D-tartrate, D- glucono-S-lactone, Dgluconamide, D-gluco-D-gulo-heptonic acid hexaacetate monohydrate, D-galactonic acid pen
  • EXAMPLE 13 A medium-grain gelatino silver bromoiodide emulsion containing about 3 mole percent iodide and about 97 mole percent bromide was sensitized by adding 2.75 mg. potassium chloroaurate, 100 mg. sodium thiocyanate and 0.8 mg. N,N-dimethylselenourea, and thereafter heating Such organic tertiary phosphine antifoggants can be utilized in a wide range of antifoggant concentrations althrough about .5 to 25 grams per mole of silver halide are more generally utilized.
  • EXAMPLE 14 A moderately coarse-grain, gelatino thallous bromoiodide emulsion containing 13 mole percent iodide and 87 mole percent bromide was chemically sensitized by adding, per mole of thallous halide, 10 mg. potassium chloroaurate and 40 mg. DL-cystine and thereafter heating for 10 minutes at 40 C., then cooling to 35 C. A second portion was chemically sensitized with 10 mg. potassium chloroaurate and 40 mg. seleno-DL-cystine and heated in the same manner. The chemically sensitized emulsion was coated on a cellulose acetate support at a coverage of 306 mg. thallium and 450 mg. gelatin per square foot.
  • each coating was hardened by bathing 5 minutes in a 3 percent solution of potassium chrome alum, washed, and dried. Each sample was exposed through a step tablet for 5 minutes with a 500- watt photoflood lamp at a distance of 9 inches. Each exposed sample was processed at 68 F. by bathing 5 minutes in a 10 percent silver nitrate Solution, Washing 21 1 minute in distilled water, bathing minutes in a 2 percent potassium bromide solution, washing 1 minute in distilled Water, developing 4 minutes in the developer described below, followed by the usual fixing in hypo,
  • the develop utilized had the 5 Various salts of Group 11 elements were incorporated following formula: into the emulsions as antifoggants.
  • the emulsions were Water about F C) 5000 coated on cellulose acetate film sup-ports at coverages N methyl p aminophenol Sulfate 2'0 of 459 mg. of silver and 1040 mg. of gelatin per square Sodium sulfite desiccated 900 foot. Each coating was exposed on an Eastman Ib Hydroquinone sensitometer, before and after an incubation, and then Sodium carbonate, monohydrated 525 developed for 3 minutes in the developer described below, Potassium bromide 50 and thereafter fixed in hypo, Washed and dried in the Water to make one mgr.
  • Control 100 1.77 .08 105 1 20 0. 48 0.72
  • Control plus strontium nitrate g. 95 1.91 10 83 1. 51 0.32 83 1. 17 0. 48
  • Control 100 1.94 .10 1.0 1.0 Control plus magnesium sulfate (30 g.)- 105 1. 83 22 105 1.60 0.30 110 1. 0.36 Control plus cadmium sulfate (40 g.) 73 2. 08 06 53 1. 41 0.24 1. 40 0.18 Control plus zinc sulfate (30 g.) 80 2. 06 12 69 1. 70 0. 14 63 1. 59 0. 14
  • Control 100 1. 96 12 0.90 1. 0 Control plus zinc sulfate (20 g.) 91 2. 10 12 91 1. 67 0. 14 73 1. 75 0. 26
  • Control 100 1.96 .10 1 0 1 0 Control plus 3-hydroxy-1-propane sulionic acid.
  • Calcium salt (40 g.) 105 1.86 08 174 1. 84 U. 24 115 1.65 0.38
  • Control 100 1.94 .10 1 0 1 0 Control plus 3-hydroxy-1-propa ulionio acid.
  • Barium salt (30 g.) 100 1. 90 12 105 1.63 0. 32 105 1. 25 0.50 Control plus 3-hydroxy-1-propan fouic acid.
  • Strontium salt (40 g.) 115 2. 08 10 100 1. 71 0.20 83 1. 55 0.42
  • Control 100 1. 51 08 0. 60 1. 0 Control plus cadmium nitrate (30 g.)- 91 1. 73 07 105 0. 98 0.38 105 1. 16 0.26
  • Control 100 1. 70 10 105 1. 20 0.40 0.90 Control plus barium nitrate (20 g.) 105 1. 65 10 105 1. 40 0. 16 112 1. 26 0.24
  • Control 100 1. 43 08 115 1. 00 0. 34 0.62
  • Control plus magnesium nitrate (20 g.) 100 1. 58 06 105 1. 23 0.14 97 1. 16 0. 15
  • water-soluble salts of Group 11 elements with atomic weights of about 10 to 200 can be utilized. Generally about 5 to 75 grams, and preferably about 15 to 50 grams, of such water-soluble salts per mole of silver halide are utilized as antifoggants.
  • the resulting treated photographic element is then allowed to air dry in the dark at 68 F.
  • the dried photographic element and a control element not immersed in the abovedescribed solution are then exposed to roomlight for seconds through a neutral density stepwedge and developed for 10 seconds in Kodak D-72 developing solution which is modified by the addition of 2.5 grams of sodium thiosulfate per liter, fixed in hypo, washed and dried in the usual manner.
  • Comparison of the exposed and processed photographic elements indicates that the photographic element immersed in the solution containing the gold and selenium salts had substantially greater sensitivity to roomlight than does the photographic element not treated with such salt solution.
  • EXAMPLE 17 A series of coarse-grain gelatino silver bromoiodide emulsions sensitized with gold chloride and N-N-dimethylselenourea were prepared and coated as described in Example 1.
  • Various antifoggants and combinations of antifoggants as described below in Table XVII were incorporated into portions of the silver halide emulsion before coating, exposed on an Eastman Ib sensitometer, both before and after incubation for 2 weeks at 120 F. and 50% relative humidity, developed as described in Example 1, fixed in hypo, washed and dried in the usual manner.
  • the incubated coatings containing the antifoggant addenda showed substantially less fog than control coatings containing no antifoggant addenda.
  • Table XVII below tabulates the various antifoggant addenda utilized and typical concentrations utilized in terms of grams per mole of silver halide.
  • Urazole 6 EXAMPLE 18 A coarse-grain gelatino bromoiodide emulsion (98 mole percent bromide and 2 mole percent iodide) containing 40 g. gelatin per silver mole, to which was added mg. potassium thiocyanate, 0.45 mg. dimethyl selenourea and 1.78 mg. aurous sulfide per silver mole, was split into portions. Gelatin or synthetic polymer were added as indicated in Table XVIII below and the emulsion was after-ripened by heating as indicated in the table. Further gelatin was added as indicated and the emulsions were coated at 452 mg. silver per square foot on a cellulose acetate film support.
  • Polymer 1 100 Polymer 1 The polymer is a copolymer consisting of 90 weight percent butyl acrylate, 10 weight percent acrylic acid.
  • e-Bromocaproamide EXAMPLE 19 To a fine-grain gelatino silver chlorobromide emulsion containing 60 mole percent bromide and 40 mole percent chloride was added 4.4 mg. potassium chloroaurate, 50 mg. sodium thiocyanate, 2.2 mg. N,N-dimethylselenourea, and 2 mg. sodium thiosulfate. After adding the compounds listed in Table XIX below, the emusion was coated on a cellulose acetate film support at a coverage of 137 mg. silver and 202 mg. gelatin per square foot.
  • a photographic silver halide emulsion sensitized with at least two difierent sensitizers one of said sensitizers being a noble metal sensitizer and the other of said sensitizers being a labile selenium sensitizer.
  • 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.
  • a photographic silver halide emulsion sensitized with a gold salt and colloidal selenium 9.
  • a photographic silver halide emulsion sensitized with a gold salt and a selenourea 10.
  • a photographic silver halide emulsion containing a color'forming coupler, a gold salt and labile selenium sensitizer containing a color'forming coupler, a gold salt and labile selenium sensitizer.
  • a photographic gelatino silver halide emulsion sensitized with a gold salt and N,N-dimethylselenourea 14.
  • a photographic gelatino silver halide emulsion sensitized with a gold salt and selenourea 15.
  • X is selected from the group consisting of a hydrogen atom, a carbinol radical, a radical having the formula II CH2OCR7 wherein R is selected from the group consisting of an alkyl radical and an aryl radical;
  • Y is selected from the group consisting of a carboxy radical, a carbamyl radical and a radical having the formula i -COR 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 wherein R is an alkyl radical and a radical having the formula 0 OHzO C R whereni R is selected from the group consisting of an alkyl radical and an aryl radical;
  • m is an integer of 2 to 3;
  • n is an integer of 1 to 5;
  • 0 is an integer of 0 to 2;

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BE659479A BE659479A (US07943777-20110517-C00090.png) 1964-02-10 1965-02-09
NL656501562A NL144403B (nl) 1964-02-10 1965-02-09 Werkwijze voor het verhogen van de gevoeligheid van lichtgevoelige zilverhalogenide-emulsies en fotografisch materiaal, voorzien van deze emulsies.
DK64865AA DK130897B (da) 1964-02-10 1965-02-09 Fremgangsmåde til forøgelse af sensibiliteten af en ædelmetalsensibiliserbar fotografisk sølvhalogenidemulsion.
DE19651472818 DE1472818A1 (de) 1964-02-10 1965-02-09 Photographisches Material
NO156718A NO120009B (US07943777-20110517-C00090.png) 1964-02-10 1965-02-10
FR4940A FR1428087A (fr) 1964-02-10 1965-02-10 Nouvelle émulsion aux halogénures d'argent et nouveaux produits photographiques contenant une telle émulsion
CH176765A CH441997A (fr) 1964-02-10 1965-02-10 Matériel photographique sensible
SE01685/65A SE333096B (US07943777-20110517-C00090.png) 1964-02-10 1965-02-10
GB5713/65A GB1098466A (en) 1964-02-10 1965-02-10 Sensitive photographic materials
US468972A US3297446A (en) 1964-02-10 1965-07-01 Synergistic sensitization of photographic systems with labile selenium and a noble metal
GB29373/66A GB1150573A (en) 1964-02-10 1966-06-30 Sensitive Photographic Materials
CH1636266A CH476325A (fr) 1964-02-10 1966-11-15 Matériel photographique sensible stabilisé
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US3396028A (en) * 1964-11-25 1968-08-06 Eastman Kodak Co Silver halide emulsions containing hydroxy carboxylic acid derivatives as fog inhibitors
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
US3442653A (en) * 1964-02-10 1969-05-06 Eastman Kodak Co Sensitized silver halide systems with activated nonlabile selenium compounds
US3655407A (en) * 1969-03-10 1972-04-11 Eastman Kodak Co Method of coating dilute aqueous emulsions
FR2154582A1 (US07943777-20110517-C00090.png) * 1971-09-27 1973-05-11 Fuji Photo Film Co Ltd
US3769017A (en) * 1972-03-29 1973-10-30 Konishiroku Photo Ind Photosensitive silver halide element containing a thiosugar antifoggant
US3976489A (en) * 1972-03-24 1976-08-24 Polaroid Corporation Silver halide photographic products with semiconductor sensitizers
US4003746A (en) * 1975-07-01 1977-01-18 E. I. Du Pont De Nemours And Company Organic heterocyclic and thioaryl phosphines in silver halide emulsions and developers therefor
DE2657080A1 (de) * 1975-12-16 1977-06-30 Asahi Chemical Ind Trocken-bildaufzeichnungsmaterial
US4138256A (en) * 1975-11-17 1979-02-06 Ciba-Geigy Ag Method of processing photographic silver dye bleach materials
US4411985A (en) * 1981-09-17 1983-10-25 Eastman Kodak Company Heat stabilizable photographic silver halide material and process
JPS59180536A (ja) * 1983-03-30 1984-10-13 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真乳剤
US5112733A (en) * 1989-05-31 1992-05-12 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
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US5210002A (en) * 1991-07-25 1993-05-11 Eastman Kodak Company Nucleated high contrast photographic elements containing urea compounds which enhance speed and increase contrast
US5213944A (en) * 1991-10-17 1993-05-25 Eastman Kodak Company Nucleated high contrast photographic elements containing substituted thioureas which enhance speed and increase contrast
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US5415991A (en) * 1991-05-10 1995-05-16 Fuji Photo Film Co., Ltd. Stable, rapidly-developable silver halide photographic material
US5415992A (en) * 1993-11-30 1995-05-16 Eastman Kodak Company Heat stabilized silver chloride photographic emulsions containing phosphine compounds
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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
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
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
US6100021A (en) * 1998-12-15 2000-08-08 Agfa-Gevaert N.V. Sensitization of silver halide
EP1624337A2 (en) 2004-08-02 2006-02-08 Fuji Photo Film Co., Ltd. Silver halide holographic sensitive material and system for taking holographic images by using the same
EP1691237A2 (en) 2005-02-15 2006-08-16 Fuji Photo Film Co., Ltd. Holographic recording material and holographic recording method
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
EP1980908A1 (en) 2007-04-13 2008-10-15 FUJIFILM Corporation Silver halide photographic material and image forming method using the same
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
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EP0562476A1 (en) 1992-03-19 1993-09-29 Fuji Photo Film Co., Ltd. A silver halide photographic emulsion and a photographic light-sensitive material
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EP0590715A1 (en) * 1992-10-02 1994-04-06 Agfa-Gevaert N.V. Emulsion preparation using simultaneous chemical and spectral sensitization in the presence of a salt
EP0626614A1 (en) * 1993-05-26 1994-11-30 Agfa-Gevaert N.V. A red-sensitive silver halide photographic material
US5415992A (en) * 1993-11-30 1995-05-16 Eastman Kodak Company Heat stabilized silver chloride photographic emulsions containing phosphine compounds
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
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
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
US6100021A (en) * 1998-12-15 2000-08-08 Agfa-Gevaert N.V. Sensitization of silver halide
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
EP1624337A2 (en) 2004-08-02 2006-02-08 Fuji Photo Film Co., Ltd. Silver halide holographic sensitive material and system for taking holographic images by using the same
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
EP1691237A2 (en) 2005-02-15 2006-08-16 Fuji Photo Film Co., Ltd. Holographic recording material and holographic recording method
US20090075218A1 (en) * 2005-04-28 2009-03-19 Fujifilm Corporation Silver halide color photographic light-sensitive material
EP1980908A1 (en) 2007-04-13 2008-10-15 FUJIFILM Corporation Silver halide photographic material and image forming method using the same
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
WO2017123444A1 (en) 2016-01-15 2017-07-20 Carestream Health, Inc. Method of preparing silver carboxylate soaps

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DK130897C (US07943777-20110517-C00090.png) 1975-09-29
NL6501562A (US07943777-20110517-C00090.png) 1965-08-11
NO120009B (US07943777-20110517-C00090.png) 1970-08-10
SE333096B (US07943777-20110517-C00090.png) 1971-03-01
DE1472818A1 (de) 1969-12-04
GB1098466A (en) 1968-01-10
NL144403B (nl) 1974-12-16
CH441997A (fr) 1967-08-15
DK130897B (da) 1975-04-28
BE659479A (US07943777-20110517-C00090.png) 1965-05-28
GB1150573A (en) 1969-04-30

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