US3457078A - Supersensitized silver halide emulsions - Google Patents

Supersensitized silver halide emulsions Download PDF

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US3457078A
US3457078A US436460A US43646065A US3457078A US 3457078 A US3457078 A US 3457078A US 436460 A US436460 A US 436460A US 43646065 A US43646065 A US 43646065A US 3457078 A US3457078 A US 3457078A
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emulsion
mercapto
sensitivity
silver halide
emulsions
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Oskar Riester
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Agfa Gevaert NV
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Agfa AG
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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
    • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/20—Methine and polymethine dyes with an odd number of CH groups with more than three CH groups

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  • OSKAR R/ESTER Y [M M QM A r IORNE Y5 United States Patent 3,457,078 SUPERSENSITIZED SILVER HALIDE EMULSIONS Oskar Riester, Leverkusen, Germany, assignor to Agfa Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany Filed Mar. 2, 1965, Ser. No. 436,460 Claims priority, application Germany, Mar. 11, 1964, A 45,450 Int. 'Cl. G03c 1/28 U.S. Cl.
  • This invention relates to silver halide emulsions which are sensitized by symmetrical and unsymmetrical pentamethine cyanines and their higher vinylene homologues which are simultaneously supersensitized and stabilized by addition of heterocyclic mercapto compounds.
  • Optical sensitization of silver halide emulsions results in an increase of the optical range of sensitivity and speed.
  • the action of sensitizing dyes is usually influenced by another compound adsorbed to the surface of the silver halide grains. Generally, the result is diminished sensitizing, but certain materials produce a considerable increase in the sensitization, and this is called supersensitization.
  • optical sensitizers used according to the invention comprise symmetrical and unsymmetrical pentamethine cyanines and their higher vinylene homologues such as heptaor nonamethine cyanines.
  • These sensitizing dyes are known and described, for example, by F. M. Hamer in Quarterly Reviews 4 (1950), pages 335-339 or by Gotze and Socher in Beihefte Kunststoff Angewandte Chemie," 40 (1940), pages 9-13 or in the handbook The Cyanine Dyes and Related Compounds, by F. M. Hamer, published by Interscience Publishers 1964.
  • the heterocyclic rings may be substituted with radicals including alkyl, preferably lower alkyl groups up to 5 carbon atoms, aryl, preferably phenyl, alkoxy, with preferably up to 5 carbon atoms.
  • the methine chain can also be substituted, for example, with alkyl, particularly lower alkyl up to 6 carbon atoms, such as methyl and ethyl, aryl, preferably phenyl, cycloalkyl such as cyclohexyl or heterocyclic compounds, such as imidazole and thiazole, which can also be substituted with the substituents mentioned hereinbefore.
  • polymethine dyes with a relatively long methine chain can be easily supersensitized by simple rinsing with water or by treatment with solutions of ammonia, amines or silver salts.
  • This increase in sensitivity is, however, not stable, so that a material treated in this way must be processed in a few weeks or even days.
  • the combination with the heterocyclic mercapto compounds according to the present invention provides a stable supersensitization with a concomitant reduction in fogging.
  • the silver halide emulsions of the invention are also stable with respect to fogging under the conditions of high temperature and humidity occurring for example in tropical climates.
  • the concentration of the polymethine sensitizing dyes in the emulsion can vary from about 1 to about 30 mg. per liter emulsion.
  • the suitable and most economical concentration for any given emulsion will be apparent to 3 one skilled in the art upon making the tests customary applied in the art of emulsion making.
  • a quantity of the sensitizing dye is dissolved in a suitable solvent and a volume of this solution is added to about 1 liter of the silver halide gelatine emulsion. With most of the ordinary emulsions 3 to 20 mg. of the sensitizing dye suffice to produce the maximum sensitization.
  • Suitable heterocyclic rings are for instance the following: oxazine, oxazole, thiazole, thiodiazole, imidazole or tetrazole.
  • the heterocyclic mercapto compounds must further contain electronegative substituents, such as halogens, preferably chlorine or bromine, trifluoromethyl, sulphonic groupings of the formula SO -R, R representing alkyl, preferably with up to carbon atoms, or aryl, preferably phenyl, sulfonamide radicals which can be substituted by alkyl groups, preferably lower alkyl groups having up to 5 carbon atoms, or aryl groups, preferably phenyl, sulfonic acid, carboxyl groups, phenyl radicals or fused benzene rings.
  • electronegative substituents such as halogens, preferably chlorine or bromine, trifluoromethyl, sulphonic groupings of the formula SO -R, R representing alkyl, preferably with up to carbon atoms, or aryl, preferably phenyl, sulfonamide radicals which can be substituted by alkyl groups, preferably lower alkyl groups having up
  • heterocyclic mercapto compounds which are watersoluble and which are substituted by watersolubilizing groups, such as sulfonic acid, carboxyl or sulfonamide groups in addition to the mercapto group.
  • suitable compounds are the following heterocyclic compounds: oxazine, oxazole, thiazole, thiodiazole, imidazole and tetrazole.
  • Suitable substances includes the following:
  • the axis of ordinates represents the sensitivity or speed of the emulsions in steps of the wedge image plotted against the quantity of the heterocyclic mercapto compound in mg. per liter of emulsion as axis of abscisses.
  • the concentration of the heterocyclic mercapto compound in the emulsion can vary widely, i.e., from about 30 mg. to about 500 mg. per liter of flowable emulsion. The specific concentration will depend very much on the type of light-sensitive emulsion and the effects desired. Generally the concentration of the heterocyclic mercapto compound is several times the concentration customarily employed if the compounds are used as antifoggants. Preferred are concentrations of 2-l0 times the usual concentrations. With most ordinary silver halide emulsions 250 mg. of heterocyclic mercapto compounds per liter of emulsion suffice to produce the stabilized supersensitization. With highly sensitive emulsions to which customarily no or only some mgs.
  • stabilizers of the heterocyclic mercapto compound type can be added, somewhat lower concentrations between 30-100 mgs. of the supersensitizer may be sufficient to obtain supersensitization. Preferred are concentrations of between 60-200 mgs. of the heterocyclic mercapto compound.
  • the optical range of the sensitivity of the supersensitized emulsions is approximately the same the optical sensitivity of the original emulsion.
  • the supersensitization results in an increase of speed.
  • silver halide As light-sensitive silver compounds can be used silver halide, silver bromide, or silver chlorobromides, which may contain a small amount up to 10 mol percent of silver iodide.
  • the silver halide emulsions can be prepared with any hydrophilic colloids.
  • Known to be satisfactory for dispersing silver halides are for example natural materials, such as gelatine, albumine, alginic acid or derivatives thereof, such as salts particularly of alkali metals, amides or esters and hydrophilic synthetic resins such as polyvinyl alcohol, polyvinyl pyrrolidone, cellulose esters or cellulose ethers, such as carboxymethyl cellulose.
  • the emulsions stabilized in accordance with the present invention can be chemically sensitized by any of the accepted procedures.
  • the emulsions can be treated with salts of the noble metals such as ruthenium, rhodium, palladium, iridium and platinum. Suitable compounds are well known in the art.
  • the emulsions can also be sensitized with gold salts as described by R. Koslowsky, Z. wiss. Phot. 46, pages 65-72 (1951).
  • the emulsions can also be chemically sensitized with reducing agents such as stannous salts, polyamines, sulfur compounds, such as described in the US. Patent 1,574,944, polyethylene oxides and the like.
  • reducing agents such as stannous salts, polyamines, sulfur compounds, such as described in the US. Patent 1,574,944, polyethylene oxides and the like.
  • the emulsions may contain another known stabilizer such as mercury compounds, triazoles and azaindenes, such as disclosed by Birr in Z. wiss. Phot. vol. 47 (1952), pages 2-28.
  • another known stabilizer such as mercury compounds, triazoles and azaindenes, such as disclosed by Birr in Z. wiss. Phot. vol. 47 (1952), pages 2-28.
  • the emulsions may be hardened by any suitable hardener, such as formaldehyde, halogen substituted aliphatic acids such as mucobromic acid.
  • suitable hardener such as formaldehyde, halogen substituted aliphatic acids such as mucobromic acid.
  • EXAMPLE 1 10 mg. of bis-(3 ethyl benzthiazole)-pentamethine cyanine perchlorate are dissolved in the ratio 112000 in methanol and added to 1 liter of a gelatino-silver chlorobromide emulsion of medium sensitivity.
  • a wetting agent such as 30 ml. of a. 7.5 percent aqueous solution of saponin per liter emulsion and hardening agent such as 15 ml. of a 10 percent aqueous formaldehyde solution
  • 10 g. of a cyan coupler are also added, for example sodium-l-hydroxy-Z-(carboxylic stearyl amide)-naphthalene 4 sulfonate as a 5 percent aqueous solution.
  • a layer of this emulsion applied to paper shows in the spectrograph an optical sensitization in the deep red with a .maximum at approximately 695 m,u.
  • the material is exposed through a stepped wedge. with a factor of per step in a common sensitometer behind an Agfa 45 red filter which transmits only red light above approximately 610 m and, after development in a color forming developer, this wedge shows 16 steps.
  • EXAMPLE 2 6 mg. of bis-(3 ethyl benzselenazole)-pentamethine cyanine perchlorate are added in methanolic solution to 1 liter of a gelatine-silver chlorobromide emulsion, such as that used for the production of photographic copy papers. Wetting and hardening agents and g. of the cyan color coupler as described in Example 1 are also added. The above emulsion is then coated onto a paper support and dried. A spectral sensitization is obtained with a maximum at about 717 me.
  • the spectral sensitivity is initially reduced down to a minimum at about mg. per liter of emulsion.
  • an optimum is reached at 180' to 200 mg.
  • the control emulsion which does not contain the stabilizer yields upon exposure through a stepped wedge in a sensitometer as described in Example 1 and after the customary colorphotographic processing a colored wedge with 10 steps.
  • the sample containing the optimum concentration of the stabilizer yields upon identical processing a colored wedge with 20 steps, corresponding to an increase by about 9 times.
  • the dependence of the number of reproduced wedge steps on the added quantity of stabilizer is illustrated in FIGURE 2.
  • EXAMPLE 3 2 mg. of bis-(3 ethyl benzthiazole) heptamethine cyanine iodide are added to 1 kg. of a silver chlorobromide emulsion of medium sensitivity and the aforementioned additives are also added. The above emulsion is then coated onto a paper support and dried. The resulting light-sensitive layer has a spectral sensitivity with a sensitisation maximum at 810 m The unstabilized emulsion yields after usual exposure through a stepped wedge in a sensitometer and processing with a color-forming developer a wedge image with 7 ste s.
  • the sensitivity initially decreases at 50 mg. per kg. to 3 steps.
  • the sensitivity then rises sharply and reaches the optimum value at about 150 mg. with 16.5 steps.
  • the sensitivity is obtained in this way.
  • EXAMPLE 4 An emulsion sensitized with the dye described in Example 1 and provided with the said additives and containing 1 (4' phenoxy 3' sulfonic acid-phenyl)-3 heptadecyl-S-pyrazolone as red color coupler is brought to about 6 times the sensitivity by adding 120 mg. of sodium 2 mercapto-naphtho 1'-8:4,6 oxazine-3- sulfonate.
  • a similar efiect is obtained if l-hydroxy 2 naphthoic acid-2'-(methyl octadecyl amino) 5' sulfonic acid anilide is used as cyan color coupler.
  • An emulsion sensitized in the same way is increased in sensitivity by about 4 times using 200 mg. of 2 mercapto-benzoxazole-S-carboxylic acid.
  • EXAMPLE 5 26 mg. of bis-(3-ethyl benzthiazole) 9,11 (2',2-dimethylcyclotrimethylene 1,3) pentamethine cyanine 6 iodide and the said additives are added to 1 kg. of a silver chlorobromide emulsion.
  • the sensitization maximum is at about 693 my and, on addition of sodium-2- mercapto 5 chlorobenzoxazole 7 sulfonate, the sensitization is reduced to less than half at 50-60 mg. per kg.
  • the sensitization increases to twice the original height at an addition of 100420 mg. of the above stabilizer per kg. of emulsion.
  • EXAMPLE 6 A highly sensitive silver bromide gelatine emulsion containing about 4 mol percent of silver iodide is sensitized with a methanolic solution of 3 mg. of bis-(3-ethyl- S-methyl benzthiazole)-pentamethine cyanide bromide.
  • the above emulsion is coated onto a transparent support of cellulose acetate and dried.
  • the resulting light-sensitive material is sensitive to red light with a maximum in the infrared region at about 709 III/L.
  • EXAMPLE 7 A supported silver chlorobromide gelatine emulsion layer containing the additives described in Example 1 and 3 mg. of bis-(3-ethyl-benzthiazole)-l0-[meso] phenyl pentamethine perchlorate per kg. emulsion shows a sensitization in the deep red with a maximum at about 700 mu.
  • EXAMPLE 8 A supported silver chlorobromide gelatine emulsion layer containing the additives of Example 1 and 20 mg. of bis-(1-methyl-3-ethy1 benzimidazole) 10 (2'-[1'- methyl-3'-ethyl-benzimidazolium]-pentamethine) cyanine diodide per kg. emulsion shows a broad spectral sensitivity with a maximum at 560 m After exposure in a sensitometer behind a yellow separation wedge and usual processing a wedge image showing 6 steps is produced. On addition of 200 mg. of 2-mercapto-5-chlorobenzoxazole-7-sulfonate, this speed is increased to 24 steps, i.e. by about 60 times.
  • EXAMPLE 9 A supported silver chlorobromide gelatine emulsion layer containing 12 mg. of bis-(3-propionic acid benzthiazole)-pentamethine cyanine iodide per kg. of emulsion and containing the additives described in Example 1 shows a sensitization with a maximum at 704 III/1., and a sensitivity of 8 X i-steps behind a red separation wedge and usual processing. On adding 200 mg. of sodium-2-mercapto-naphtho- 3',2:4,S-oxazole-7'-sulfonate, the speed is increased to 20 steps, i.e. by about 16 times.
  • the sensitivity increases to 19 steps, i.e. by about 2 /2 times.
  • EXAMPLE 11 A supported silver chlorobromide gelatine emulsion layer containing a cyan color coupler, wetting agents and hardening agents as described in Example 1 and 10 mg. of 3-ethyl benzoxazole-3-ethyl-benzthiazole pentamethine cyanine iodide shows a sensitization maximum at 667 mg.
  • the unstabilized emulsion yields after usual exposure in a sensitometer behind a stepped wedge and processing with a color-forming developer, for instance of the primary aromatic amine type, a wedge image with 17 /2 steps.
  • a color-forming developer for instance of the primary aromatic amine type
  • a wedge image with 23 steps is produced, that is to say, an increase in speed by about 4 times.
  • EXAMPLE 12 An emulsion sensitized as in Example 1 and provided with the other additives is brought to a sensitivity 4 times higher on addition of 180 mg. of 1-methyl-2-mercapto-5- ethylsulfone benzimidazole. Approximately the same increase is achieved on adding 100 mg. of 2-mercapto-5- phenyl benzoxazole or 45 mg. of 1-phenyl-2-mercapto tetrazole or 60 mg. of 1-methyl-2-mercapto-S-trifluoromethyl benzimidazole.
  • EXAMPLE 13 6 mg. of bis(3-ethyl-6-methoxybenzthiazole)-pentamethine cyanine ethyl sulfate are added with the previously described additives to 1 kg. of a silver chlorobromide emulsion. The above emulsion is then coated onto a paper support and dried. The sensitivity of the emulsion is increased by 2 /2 times by addition of 90 mg. of 2-mercapto- -(p-chlorophenylaminosulfone)-benzthiazo1e.
  • EXAMPLE 14 A supported silver chloride gelatine emulsion layer of medium sensitivity, containing the usual wetting agents and hardening agents as described in Example 1 and also containing 3 mg. of bis-(3-ethyl-5,6-benzobenzthiazole)- pentamethine cyanine bromide is exposed behind a stepped wedge in an ordinary sensitometer. The resulting image obtained upon usual processing shows a red sensitivity of 14 steps. An otherwise identical emulsion which however additionally contains 120 mg. of 2-mercapto-5-(p-chlorophenyl aminosulfone)-benzthiazole shows after identical processing an increased sensitivity of 22 /2 steps, i.e. by about 7 times.
  • EXAMPLE 15 A supported silver chlorobromide gelatine emulsion layer which contains 6 g. of bis-(3-ethyl benzthiazole)- pentamethine perchlorate and 10 g. of sodium-l-hydroxy- Z-(carboxy stearyl-amido)-napthalene-4-sulfonate per kg. emulsion is exposed behind a stepped wedge in an ordinary sensitometer. The resulting image obtained upon usual processing shows a sensitivity of 16 steps behind a red filter.
  • Heterocyclic mercapto compounds which can be used in accordance with the invention are described, for example, in the handbook Photographic Chemistry by P. Glafkides vol. 1, pages 374-380, published by Fountain Press, London 195 8.
  • optical sensitizing dye is a pentamethine cyanine dye.
  • optical sensitizing dye is a heptamethine cyanine dye.

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3753719A (en) * 1970-03-20 1973-08-21 Konishiroku Photo Ind Light-sensitive color photographic material
US4030927A (en) * 1975-01-16 1977-06-21 Fuji Photo Film Co., Ltd. Supersensitizing combinations of halogen substituted benzotriazoles and cyanine dyes
US4060420A (en) * 1976-08-06 1977-11-29 Eastman Kodak Company Sulfonylacetate activator-stabilizer precursor
US4097284A (en) * 1974-11-26 1978-06-27 Fuji Photo Film Co., Ltd. Method for supersensitizing silver halide photographic emulsions
US4105451A (en) * 1976-12-22 1978-08-08 Eastman Kodak Company Photothermographic material, composition and process
US4125403A (en) * 1976-06-25 1978-11-14 Fuji Photo Film Co., Ltd. Heat developable light sensitive material
US4307187A (en) * 1974-12-28 1981-12-22 Fuji Photo Film Co., Ltd. Thermally developable light-sensitive materials
US4596767A (en) * 1983-04-13 1986-06-24 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US4603104A (en) * 1985-05-31 1986-07-29 Minnesota Mining And Manufacturing Company Supersensitization of silver halide emulsions
US4607006A (en) * 1983-10-06 1986-08-19 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material containing non-spectral sensitizing electron donative silver halide adsorptive compound
US4780404A (en) * 1987-06-09 1988-10-25 Minnesota Mining And Manufacturing Company Supersensitization of silver halide emulsion
US5192653A (en) * 1989-01-23 1993-03-09 Fuji Photo Film Co., Ltd. Method for spectrally sensitizing silver halide photographic emulsions
US5246828A (en) * 1991-04-16 1993-09-21 Konica Corporation Light-sensitive silver halide photographic material
US5441866A (en) * 1994-02-28 1995-08-15 Minnesota Mining And Manufacturing Company Sensitizers for photothermographic elements
US5543278A (en) * 1990-02-01 1996-08-06 Minnesota Mining And Manufacturing Company Infrared sensitive silver halide photographic elements
EP0786690A2 (en) 1996-01-26 1997-07-30 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
EP0786691A1 (en) 1996-01-26 1997-07-30 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
EP0786692A1 (en) 1996-01-26 1997-07-30 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
US5994051A (en) * 1997-07-25 1999-11-30 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
US6010841A (en) * 1996-01-26 2000-01-04 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
US6054260A (en) * 1997-07-25 2000-04-25 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
US6153371A (en) * 1997-07-25 2000-11-28 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
US6514682B1 (en) 2001-06-20 2003-02-04 Eastman Kodak Company Speed addendum for photographic emulsions

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Publication number Priority date Publication date Assignee Title
US5013622A (en) * 1986-12-12 1991-05-07 Minnesota Mining And Manufacturing Company Supersensitization of silver halide emulsions
DE3739474A1 (de) * 1987-11-21 1989-06-01 Agfa Gevaert Ag Farbfotografisches aufzeichnungsmaterial
US4914015A (en) * 1988-10-17 1990-04-03 Minnesota Mining And Manufacturing Company Red and infrared films containing 5-substituted-thio-1,2,3,4-thiatriazoles and 5-substituted-oxy-1,2,3,4-thiatriazoles
EP0465730B1 (en) * 1990-07-10 1996-06-05 Agfa-Gevaert N.V. Photographic infrared sensitized material containing a speed enhancing agent

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US2177635A (en) * 1937-05-29 1939-10-31 Eastman Kodak Co Photographic emulsion
US2546642A (en) * 1941-09-05 1951-03-27 Gevaert Photo Prod Nv Light-sensitive photographic emulsion
US2734900A (en) * 1953-12-28 1956-02-14 Chxgh
US2824001A (en) * 1956-01-16 1958-02-18 Eastman Kodak Co Stabilized photographic silver halide emulsions
US3266897A (en) * 1964-03-02 1966-08-16 Eastman Kodak Co Antifoggant agents for photography
US3305362A (en) * 1962-03-08 1967-02-21 Agfa Ag Process for developing silver halide and compositions therefor

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US2177635A (en) * 1937-05-29 1939-10-31 Eastman Kodak Co Photographic emulsion
US2546642A (en) * 1941-09-05 1951-03-27 Gevaert Photo Prod Nv Light-sensitive photographic emulsion
US2734900A (en) * 1953-12-28 1956-02-14 Chxgh
US2824001A (en) * 1956-01-16 1958-02-18 Eastman Kodak Co Stabilized photographic silver halide emulsions
US3305362A (en) * 1962-03-08 1967-02-21 Agfa Ag Process for developing silver halide and compositions therefor
US3266897A (en) * 1964-03-02 1966-08-16 Eastman Kodak Co Antifoggant agents for photography

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3753719A (en) * 1970-03-20 1973-08-21 Konishiroku Photo Ind Light-sensitive color photographic material
US4097284A (en) * 1974-11-26 1978-06-27 Fuji Photo Film Co., Ltd. Method for supersensitizing silver halide photographic emulsions
US4307187A (en) * 1974-12-28 1981-12-22 Fuji Photo Film Co., Ltd. Thermally developable light-sensitive materials
US4030927A (en) * 1975-01-16 1977-06-21 Fuji Photo Film Co., Ltd. Supersensitizing combinations of halogen substituted benzotriazoles and cyanine dyes
US4125403A (en) * 1976-06-25 1978-11-14 Fuji Photo Film Co., Ltd. Heat developable light sensitive material
US4060420A (en) * 1976-08-06 1977-11-29 Eastman Kodak Company Sulfonylacetate activator-stabilizer precursor
US4105451A (en) * 1976-12-22 1978-08-08 Eastman Kodak Company Photothermographic material, composition and process
US4596767A (en) * 1983-04-13 1986-06-24 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US4607006A (en) * 1983-10-06 1986-08-19 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material containing non-spectral sensitizing electron donative silver halide adsorptive compound
US4603104A (en) * 1985-05-31 1986-07-29 Minnesota Mining And Manufacturing Company Supersensitization of silver halide emulsions
US4780404A (en) * 1987-06-09 1988-10-25 Minnesota Mining And Manufacturing Company Supersensitization of silver halide emulsion
US5192653A (en) * 1989-01-23 1993-03-09 Fuji Photo Film Co., Ltd. Method for spectrally sensitizing silver halide photographic emulsions
US5543278A (en) * 1990-02-01 1996-08-06 Minnesota Mining And Manufacturing Company Infrared sensitive silver halide photographic elements
US5246828A (en) * 1991-04-16 1993-09-21 Konica Corporation Light-sensitive silver halide photographic material
US5441866A (en) * 1994-02-28 1995-08-15 Minnesota Mining And Manufacturing Company Sensitizers for photothermographic elements
EP0786690A2 (en) 1996-01-26 1997-07-30 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
EP0786691A1 (en) 1996-01-26 1997-07-30 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
EP0786692A1 (en) 1996-01-26 1997-07-30 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
US5747236A (en) * 1996-01-26 1998-05-05 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
US5747235A (en) * 1996-01-26 1998-05-05 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
US6010841A (en) * 1996-01-26 2000-01-04 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
US5994051A (en) * 1997-07-25 1999-11-30 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
US6054260A (en) * 1997-07-25 2000-04-25 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
US6153371A (en) * 1997-07-25 2000-11-28 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
US6306570B1 (en) 1997-07-25 2001-10-23 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
US6514682B1 (en) 2001-06-20 2003-02-04 Eastman Kodak Company Speed addendum for photographic emulsions

Also Published As

Publication number Publication date
CH453887A (de) 1968-03-31
DE1447577B1 (de) 1970-05-14
FR1426623A (fr) 1966-01-28
BE660948A (en)) 1965-09-13
GB1108745A (en) 1968-04-03

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