EP0498302A1 - Silberhalogenidemulsionen für die Verwendung in Entwicklungsverfahren, bei denen eine physikalische Entwicklung in Lösung erfolgt - Google Patents

Silberhalogenidemulsionen für die Verwendung in Entwicklungsverfahren, bei denen eine physikalische Entwicklung in Lösung erfolgt Download PDF

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Publication number
EP0498302A1
EP0498302A1 EP92101544A EP92101544A EP0498302A1 EP 0498302 A1 EP0498302 A1 EP 0498302A1 EP 92101544 A EP92101544 A EP 92101544A EP 92101544 A EP92101544 A EP 92101544A EP 0498302 A1 EP0498302 A1 EP 0498302A1
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EP
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Prior art keywords
silver halide
iodide
protrusions
bromoiodide
substrates
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EP92101544A
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English (en)
French (fr)
Inventor
Benjamin Teh-Kung C/O Eastman Kodak Company Chen
Kenneth Joseph c/o EASTMAN KODAK COMPANY Reed
Jacques c/o EASTMAN KODAK COMPANY Roussilhe
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Eastman Kodak Co
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Eastman Kodak Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • 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
    • G03C1/0051—Tabular grain emulsions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/50—Reversal development; Contact processes

Definitions

  • This invention is related to photography.
  • the invention is related to silver halide emulsions and the processing of photographic materials containing silver halide emulsions.
  • Silver halide is one of the most widely-used radiation-sensitive components in photographic materials.
  • Silver halide is usually incorporated in photographic materials in the form of microscopic grains dispersed in a carrier medium, such as gelatin. This is referred to as a silver halide emulsion.
  • Silver halide grains are known to exist in a wide variety of configurations or crystal structures. These include cubes, hexagonal or wurtzite structures, tetradecahedral structures, octahedral structures, and the like.
  • Silver halide grains having composite crystal structures are also known.
  • GB 1,027,146 describes a technique for forming composite silver halide grains. This reference teaches the formation of silver halide core or nuclei grains, which are then covered with one or more contiguous layers of silver halide having a different halide composition than the core.
  • U.S. Patent 4,463,087 describes silver halide grains having epitaxially-grown silver salts thereon where epitaxial growth is controlled by the use of an adsorbed site director.
  • U.S. Patent 4,814,264 describes a silver halide emulsion wherein at least 50 weight percent of the silver halide grains comprise a silver halide grain matrix having thereon 10 to 10,000 protrusions per square micrometer of grain matrix surface.
  • the protrusions have an average projected are diameter of up to 0.15 ⁇ m and a halogen composition different from that of the grain matrix.
  • the emulsion is chemically and spectrally sensitized after formation is chemically and spectrally sensitized after formation of the protrusions.
  • U.S. Patent 4,888,272 describes silver halide emulsions similar to those of U.S. 4,814,264, but the silver halide is chemically sensitized prior to formation of the protrusions.
  • Imaging methods utilizing radiation-sensitive silver halide emulsions generally utilize a developing step where silver halide grains that have been exposed to light (i.e., a latent image) are reduced to metallic silver during processing with a chemical developing agent.
  • development may occur by direct chemical development, solution physical development, or both.
  • direct chemical development a chemical developing agent reacts directly with silver halide in the grains carrying the latent image to reduce the silver ions to metallic silver.
  • solution physical development silver ions from the silver halide grains pass into solution and subsequently diffuse to a nucleus (usually an exposed silver halide grain undergoing direct chemical development) where they are reduced to metallic silver.
  • the occurrence of solution physical development is usually associated with processing solutions containing a developing agent along with one or more silver solvents, such as sulfite or thiocyanate.
  • color reversal processing generally involves a first black and white development step followed by fogging of undeveloped silver halide and then a color development step.
  • dissolution of silver halide grains during the first development step leads to less silver halide per crystal available for the dye-forming development reaction that takes place during the color development step, thus leading to improved granularity performance of the material.
  • a method of forming an image in a silver halide photographic material that includes a processing step in a developing solution wherein solution physical development occurs is improved by the incorporation in the photographic material of a silver halide emulsion layer comprising silver halide grain substrates having protrusions thereon, the protrusions having a different halide composition than the substrates such that the solubility of the protrusions in the developing solution is greater than the solubility of the substrates in the developing solution.
  • the invention provides photographic materials that can be subjected to processing involving solution physical development, and that will exhibit improved speed. This is accomplished with little degradation of the material's granularity characteristics.
  • the invention also provides photographic materials that exhibit general gamma increases as well as toe sharpening of the reversal sensitometric curve with little degradation of speed/fog position.
  • Solution physical development most often occurs in processes where conditions during development tend to favor the dissolution of silver halide, thus providing the necessary dissolved silver ions.
  • Well-known compounds for promoting silver halide solubility in processing solutions include sulfite salts (e.g., potassium sulfite) and thiocyanate salts (e.g., sodium thiocyanate).
  • Bromide ion in the developer can affect the rate of solution of silver halide, with the rate of solution typically at a minimum at bromide less than 1 g/l.
  • the pH of the developing solution can also affect solution physical development, with the relative amount of solution physical development decreasing as pH increases.
  • the polyethylene oxides and their derivatives can also increase the rate of solution physical development in certain iodide-containing emulsions where a silver halide solvent is present.
  • the substrate silver halide grains are of the type commonly employed in silver halide photography. They exhibit isomorphic face centered cubic rock salt type crystal structures.
  • the substrate grains can comprised of silver bromide, silver chloride, silver chlorobromide, silver chloroiodide, silver bromoiodide, silver chlorobromoiodide, or mixtures thereof.
  • iodide is present in the grains, it is limited to that which can be accommodated by the cubic crystal lattice. In a cubic silver bromide crystal lattice up to about 40 mole percent iodide can be incorporated, depending upon the temperature of precipitation. It is specifically contemplated to employ silver halide substrate grains containing below about 15 mole percent iodide.
  • the iodide distribution may be homogeneous (e.g., as resulting from run iodide precipitation) or discreet (e.g., core/shell emulsions, double and multiple structures, on emulsions resulting from dump iodide precipitation).
  • the substrate grains can include coarse, medium, or fine silver halide grains bounded predominantly by ⁇ 100 ⁇ or ⁇ 111 ⁇ crystal planes and can be regular or irregular in shape, including, for example, cubic and octahedral shapes.
  • the grains can be cubic, octahedral, or tabular.
  • the silver halide grain population is monodisperse having a coefficient of dispersion of less than 30% and more preferably less than 15%.
  • the substrate grains are most conveniently prepared as a separate silver halide emulsion prior to the addition of the epitaxially deposited silver salt forming the overall, composite grain structure.
  • the substrate grain emulsions can be prepared by a variety of techniques - e.g., single-jet, double-jet (including continuous removal techniques), accelerated flow rate, and interrupted precipitation techniques, as illustrated by Trivvelli and Smith, The Photograhic Journal , Vol. LXXIX, May, 1939, pp. 330-338, T. H. James, The Theory of the Photographic Process , 4th Ed., Macmillan, 1977, Chapter 3, U.S. Patent 2,222,264, German OLS No. 2,107,118, U.K.
  • Patents 1,335,925, 1,430,465, and 1,469,480 U.S. Patents 3,650,757, 3,917,485, 3,979,213, Research Disclosure , Item 17643, Vol. 176, Dec. 1978, and Research Disclosure Item 22434, Vol. 225, January 1983.
  • Research Disclosure and its predecessor, Product Licensing Index are publications of Industrial Opportunities Ltd.; Homewell, Havant; Hampshire, P09 1EF, United Kingdom.
  • Modifying compounds can be present during substrate grain precipitation. Such compounds can be initially in the reaction vessel or can be added along with one or more of the salts according to conventional procedures. Modifying compounds, such as compounds of copper, thallium, lead, mercury, bismuth, cadmium, zinc, middle chalcogens (i.e., sulfur, selenium, and tellurium), gold, and Group VIII noble metals (e.g., iridium), can be present during silver halide precipitation, as illustrated by U.S. Patents 1,195,432, 1,951,933, 2,448,060, 2,628,167, 2,950,972, 3,488,709, 3,737,313, 3,772,031, 4,269,927, and Research Disclosure , Vol. 134, June 1975, Item 13452.
  • Modifying compounds such as compounds of copper, thallium, lead, mercury, bismuth, cadmium, zinc, middle chalcogens (i.e., sulfur, selenium, and tellurium), gold
  • the formation of the protrusion is preferably carried out by adding a water-soluble silver salt and water-soluble halogen salts which correspond to the composition of the protrusions to be formed.
  • the addition of the water-soluble silver salt for the formation is preferably carried out at such a speed that formation of a separate nuclei population does not occur.
  • the formation of the protrusions is carried out at a high silver potential level of at least preferably about +110 mV or more, more preferably about +120 mV to +500 mV, most preferably about +350 mV to +500 mV, although the level may vary somewhat depending on the halogen composition of the protrusions to be formed, the procedure for deposition such as double-jet or single-jet (with single jet, the above preferred silver potentials represent the potentials at the end of the run), and/or the temperature during the formation, and/or the additives to be added during the formation, etc.
  • the silver potential is measured by a saturated calomel electrode (SCE) hereinafter, unless specifically stated otherwise.
  • the temperature during the step of the formation of the protrusions is preferably low and is generally below 80°C, preferably below 65°C, and more preferably below 30°C, although this may vary somewhat depending on the other conditions during the formation.
  • a solvent can be used in an amount such that the protrusions are not intermingled with each other more than necessary.
  • the protrusions formed on the grain substrates of the present invention can be of any size and present of any coverage level.
  • the protrusions will generally cover from 0.1 to 100% of the substrate surface area, and preferably at least 25% of the substrate surface area.
  • the halide composition of the substrate grain and the protrusion are chosen so that the aqueous solubility of the protrusion is greater than that of the substrate grain.
  • Useful combinations of halide compositions for the substrate and protrusion are shown below: substrate protrusion bromide chloride bromide chlorobromide chlorobromide chloride chloroiodide chloride chloroiodide chloride chloroiodide chlorobromide bromoiodide chloride bromoiodide chlorobromide bromoiodide chlorobromoiodide iodide chloride iodide bromide iodide chlorobromide iodide chloroiodide bromoiodide iodide chlorobromoiodide
  • the deposition of the protrusion onto the substrate grain can be directed or non-directed.
  • directed it is meant that the growth of the protrusion is substantially confined to selected surface sites on the substrate grain.
  • an adsorbed site director e.g., an aggregating spectral sensitizing dye,
  • iodide in the substrate grain as described in U.S. Patents 4,094,684 and 4,142,900, or by choosing nonisomorphic crystal lattice silver salts for deposition at selected sites on face centered cubic rock salt type crystal lattice silver halide substrate grains.
  • the disclosures of U.S. Patents 4,094,684, 4,142,900, 4,435,501, and 4,463,087 are incorporated herein by reference.
  • Chemical sensitization can be undertaken prior to, during, or after deposition of the protrusion on the substrate grain or as a following step. For example, when silver thiocyanate is deposited on silver bromoiodide, a large increase in sensitivity is realized merely by selective site deposition of the silver salt. Thus, further chemical sensitization steps of a conventional type may not be necessary to obtain photographic speed. On the other hand, an additional increment in speed can generally be obtained when further chemical sensitization is undertaken.
  • the quantity of sensitizers can be reduced, if desired, where (1) protrusion deposition itself improves sensitivity or (2) sensitization is directed to protrusion deposition sites. Spectral sensitization is contemplated before, during, or following chemical sensitization.
  • Chemical sensitization may be undertaken based on the composition of the silver salt deposited or on the composition of the substrate grains.
  • the silver halide emulsions of the present invention can be chemically sensitized before, during, or after protrusion deposition with active gelatin, as illustrated by T. H. James, The Theory of the Photographic Process , 4th Ed., Macmillan, 1977, pp. 67-76, or with sulfur, selenium, tellurium, gold, platinum, palladium, iridium, osmium, rhodium, rhenium, or phosphorus sensitizers or combinations of these sensitizers, such as at pAg levels of from 5 to 10, pH levels of from 5 to 8 and temperatures of from 30 to 80°C, as illustrated by Research Disclosure , Vol. 120, April 1974, Item 12008, Research Disclosure , Vol.
  • Patents 2,521,926, 3,021,215, and 4,054,457 It is specifically contemplated to sensitize chemically in the presence of finish (chemical sensitization) modifiers--that is, compounds known to suppress fog and increase speed when present during chemical sensitization, such as azaindenes, azapyridazines, azapyrimidines, benzothiazolium salts, and sensitizers having one or more heterocyclic nuclei.
  • finish modifiers are described in U.S. Patents 2,131,038, 3,411,914, 3,554,757, 3,565,631, 3,901,714, Canadian Patent 778,723, and Duffin Photographic Emulsion Chemistry , Focal Press (1966), New York, pp. 138-143.
  • the emulsions can be reduction sensitized--e.g., with hydrogen, as illustrated by U.S. Patents 3,891,446 and 3,984,249, by low pAg (e.g., less than 5) and/or high pH (e.g., greater than 8) treatment or through the use of reducing agents, such as stannous chloride, thiourea dioxide, polyamines and amineboranes, as illustrated by U.S. Patent 2,983,609, Research Disclosure , Vol. 136, August 1975, Item 13654, U.S. Patents 2,518,698, 2,739,060, 2,743,182, 2,743,183, 3,026,203, 3,361,564.
  • Surface chemical sensitization, including sub-surface sensitization, illustrated by U.S. Patents 3,917,485 and 3,966,476, is specifically contemplated.
  • the silver halide emulsions of the present invention are preferably also spectrally sensitized. This may be done before, during, or after protrusion deposition. It is specifically contemplated to employ spectral sensitizing dyes that exhibit absorption maxima in the blue and minus blue--i.e., green and red, portions of the visible spectrum. In addition, for specialized applications, spectral sensitizing dyes can be employed which improve spectral response beyond the visible spectrum. For example, the use of infrared absorbing spectral sensitizers is specifically contemplated.
  • the silver halide emulsions of this invention can be spectrally sensitized with dyes from a variety of classes, including the polymethine dye class, which includes the cyanines, merocyanines, complex cyanines and merocyanines (i.e., tri-, tetra- and polynuclear cyanines and merocyanines), oxonols, hemioxonols, styryls, merostyryls and streptocyanines.
  • the polymethine dye class which includes the cyanines, merocyanines, complex cyanines and merocyanines (i.e., tri-, tetra- and polynuclear cyanines and merocyanines), oxonols, hemioxonols, styryls, merostyryls and streptocyanines.
  • the cyanine spectral sensitizing dyes include, joined by a methine linkage, two basic heterocyclic nuclei, such as those derived from quinolinium, pyridinium, isoquinolinium, 3H-indolium, benz[(e]indolium, oxazolium, oxazolinium, thiazolium, thiazolinium, selenazolium, selenazolinium, imidazolium, imidazolinium, benzoxazolium, benzothiazolium, benzoselenazolium, benzimidazolium, naphthoxazolium, naphthothiazolium, naphthoselenazolium, dihydronaphthothiazolium, pyrylium, and imidazopyrazinium quaternary salts.
  • two basic heterocyclic nuclei such as those derived from quinolinium, pyridinium, isoquinolinium, 3
  • the merocyanine spectral sensitizing dyes include, joined by a double bond or methine linkage, a basic heterocyclic nucleus of the cyanine dye type and an acidic nucleus, such as can be derived from barbituric acid, 2-thiobarbituric acid, rhodanine, hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-pyrazolin-5-one, 2-isoxazolin-5-one, indan-1,3-dione, cyclohexane-1,3-dione, 1,3-dioxane-4,6-dione, pyrazolin-3,5-dione, pentane-2,4-dione, alkylsulfonylacetonitrile, malononitrile, isoquinolin-4-one, and chroman-2,4-dione.
  • One or more spectral sensitizing dyes may be used. Dyes with sensitizing maxima at wavelengths throughout the visible spectrum and with a great variety of spectral sensitivity curve shapes are known. The choice and relative proportions of dyes depends upon the region of the spectrum to which sensitivity is desired and upon the shape of the spectral sensitivity curve desired. Dyes with overlapping spectral sensitivity curves will often yield in combination a curve in which the sensitivity at each wavelength in the area of overlap is approximately equal to the sum of the sensitivities of the individual dyes. Thus, it is possible to use combinations of dyes with different maxima to achieve a spectral sensitivity curve with a maximum intermediate to the sensitizing maxima of the individual dyes.
  • Combinations of spectral sensitizing dyes can be used which result in supersensitization--that is, spectral sensitization that is greater in some spectral region than that from any concentration of one of the dyes alone or that which would result from the additive effect of the dyes.
  • Supersensitization can be achieved with selected combinations of spectral sensitizing dyes and other addenda, such as stabilizers and antifoggants, development accelerators or inhibitors, coating aids, brighteners and antistatic agents. Any one of several mechanisms as well as compounds which can be responsible for supersensitization are discussed by Gilman, "Review of the Mechanisms of Supersensitization", Photographic Science and Engineering , Vol. 18, 1974, pp. 418-430.
  • Spectral sensitizing dyes also affect the emulsions in other ways. Spectral sensitizing dyes can also function as antifoggants or stabilizers, development accelerators or inhibitors, and halogen acceptors or electron acceptors, as disclosed in U.S. Patents 2,131,038 and 3,930,860.
  • the emulsions used in the present invention may be used in color or black-and-white photographic materials.
  • Such materials which generally comprise a support having thereon at least one silver halide emulsion layer and, in the case of a color material, having associated therewith one or more dye-forming couplers, may be prepared, exposed, and processed by techniques well-known in the art.
  • the silver halide emulsions used in the practice of the invention may be advantageously stabilized with stabilizers such as acetophenylmercaptotetrazole. This can be provide the emulsions with lower fog and better keeping characteristics.
  • Emulsion A Emulsion A
  • a 20 liter kettle was charged with 4.0 liters of DW, 60 g/l of deionized gelatin and brought to 40°C.
  • An antifoaming agent and a thioether ripener were added before adjusting vAg to 0 mV with NaBr solution.
  • a 20 liter kettle is charged with 6.6 liters of DW, 34 g/l of phthalated deionized gelatin, and brought to 70°C.
  • An anti-foaming agent a thioether ripener were added before adjusting vAg to 50 mV with NaBr solution.
  • This nucleation is followed by an initial growth period lasting 45 minutes in which the following reagents - AgNO3 (1.5 M/l), mixed solution of NaBr (1.425 M/l) and KI (0.075 M/l) - were introduced via an accelerated double jet technique while the temperature and vAg were maintained at 70°C and 50mV respectively.
  • This initial growth segment is followed by a second growth segment lasting 20 minutes in which the following reagents - AgNO3 (1.5 M/l and NaBr (1.5 M/l) - were introduced via the same technique as above with the temperature and vAg maintained at the same values as above.
  • An iridium dopant is added during the growth stages.
  • the emulsion is then washed by an ordinary flocculation method.
  • a 20 liter kettle was charged with 4.0 liters of distilled water, 60 g/l of phthalated deionized gelatin, and brought to 40°C.
  • An antifoaming agent and a thioether ripener were added before adjusting vAg to 0 mV with NaBr solution.
  • This nucleation was followed by a hold period of 2 minutes. This hold period was followed by an initial growth period lasting 42 minutes in which AgNO3 (2 M/l), NaBr (2 M/l) and KI (2.0 M/l) were introduced via a double jet method such as to produce an iodide profile within the precipitated phase while the temperature and vAg were maintained at the same values as above.
  • a final growth segment was precipitated lasting 38 minutes in which AgNO3 (2.0 M/l) and NaBr (2.0 M/1) were introduced via a double jet method while the temperature and vAg were maintained at the same values as above.
  • a stable population of AgBr microcrystals was nucleated by flowing 0.0284 moles of AgNO3 as a single jet over a time period of 1.5 minutes using 0.25 N silver nitrate at 70°C.
  • the emulsion was washed by an ordinary flocculation method.
  • the emulsion had a tabular shape 1.44 x 0.107 ⁇ m with a bulk iodide of 6%.
  • Emulsion A was sensitized with 800 mg/mole sodium thiocyanate, 2.67 mg/mole tetrachloroaurate, 4 mg/mole sodium thiosulfate, heated for 20 minutes at 70°C and dyed at 0.39 mmoles of dye D-1 per silver mole.
  • the chemical sensitization was the same as example 1 except that a protrusion deposition was performed. 0.18 moles of sensitized emulsion was melted at 40°C and the vAg was adjusted with 0.01 M AgNO3 to 140 mV. Then NaCl was added to the extent of 7.8 mole % of the total host emulsion. Finally 0.1 M/l AgNO3 was run in over a period of 20 minutes such that a total of 6% was added relative to the amount of host emulsion. This emulsion was dyed with 0.39 mmole of dye D-1 per silver mole as in example 1.
  • Emulsion B was sensitized with 75 mg/mole sodium thiocyanate, 4.25 mg/mole tetrachloroaurate, 8.5 mg/mole sodium thiosulfate, heated for 20 minutes at 70°C and dyed at 0.34 mmoles dye D-1 per silver mole.
  • Example 3 The chemically-sensitized emulsion described in Example 3 (without the dye) was then subjected to a 6% AgCl deposition with subsequent dying at 0.34 mmoles per silver mole of dye D-1 in exactly the same manner as Example 2.
  • Example 3 The Example 3 procedure was followed, only after the final dye addition, 80 mg/mole of acetamido phenylmercaptotetrazole was added to the melt.
  • Example 4 The Example 4 procedure was followed, only 12% AgCl was deposited (14% NaCl was added and the deposition featured 0.02 M AgNO3). Finally, 80 mg/mole of acetamido phenylmercaptotetrazole was added to the melt.
  • Emulsions C was sensitized with 50 mg/mole sodium thiocyanate, of 0.45 mmoles/Ag mole dye D-1, 2.77 mg/Ag mole tetrachloroaurate, 5.55 mg/Ag mole sodium thiosulfate, 5 mg/Ag mole of a benzothiazolium finish-modifier, and heated for 10 minutes at 70°C.
  • the dye was therefore present at the time of the deposition.
  • emulsion D To one mole of emulsion D was added 100 mg of NaSCN, 1.67 mg of potassium tetrachloroaurate, 5.5 mg of sodium thiosulfate, 1.0 millimole of dye D-1 and 0.38 mmole of dye D-2. This was then heated for 15 minutes at 60°C.
  • the spectrochemically sensitized emulsion in example 9 was adjusted to 140 mV with 0.1M AgNO3 and 0.006M KI. An excess of 10.1% NaCl was added based on the moles of host emulsion. 8 mole percent AgCl was precipitated onto this host over a period of 12 minutes using 0.3M AgNO3.
  • the emulsions were coated at 8.07 mg/dm2 of silver halide, 23.68 mg/dm2 of gelatin, 16.15 mg/dm2 of coupler C-1, with a 23.68 mg/dm2 gelatin overcoat on an acetate support with gel pad.
  • the gelatin layers were hardened with 1.55% bis(vinylsulfonyl methane) hardener.
  • the coated materials were exposed for 1/100 sec at 5500K equivalent color temperature filtered with a Wratten 9 and 1.246 neutral density filter, and processed in well-known standard Kodak E-6 ® color reversal processing, which utilizes 65.8 g/l potassium sulfite and 0.995 g/l sodium thiocyanate in the first developer to stimulate solution physical development.
  • Kodak E-6 ® color reversal processing which utilizes 65.8 g/l potassium sulfite and 0.995 g/l sodium thiocyanate in the first developer to stimulate solution physical development.
  • identical materials were exposed and processed in Kodak C-41 ® color negative processing, in which essentially no solution physical development occurs.
  • portrusions provided gamma increases in the reversal process compared to gamma decreases in the negative process, and greater speed increases (or smaller speed decreases) in the reversal process compared to the negative process.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP92101544A 1991-01-31 1992-01-30 Silberhalogenidemulsionen für die Verwendung in Entwicklungsverfahren, bei denen eine physikalische Entwicklung in Lösung erfolgt Withdrawn EP0498302A1 (de)

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US64826291A 1991-01-31 1991-01-31
US648262 1991-01-31

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Cited By (14)

* Cited by examiner, † Cited by third party
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US5468601A (en) * 1994-04-12 1995-11-21 Eastman Kodak Company Deposition sensitized emulsions and processes for their preparation
EP0699944A1 (de) * 1994-08-26 1996-03-06 Eastman Kodak Company Emulsionen aus tafelförmigen Körnern mit verbesserter Empfindlichkeit
EP0699950A1 (de) * 1994-08-26 1996-03-06 Eastman Kodak Company Emulsionen mit ultradünnen tafelförmigen Körnern und neuer Behandlung von Dotiermitteln
EP0699945A1 (de) * 1994-08-26 1996-03-06 Eastman Kodak Company Emulsionen mit ultradünnen tafelförmigen Körnern verbesserter Empfindlichkeit
EP0699946A1 (de) * 1994-08-26 1996-03-06 Eastman Kodak Company Emulsionen mit ultradünnen tafelförmigen Körnern mit verbesserter Empfindlichkeit (II)
EP0699949A1 (de) 1994-08-26 1996-03-06 Eastman Kodak Company Emulsionen mit ultradünnen tafelförmigen Körnern und Dotierungsmitteln auf ausgewählten Stellen
EP0701165A1 (de) * 1994-08-26 1996-03-13 Eastman Kodak Company Emulsionen aus tafelförmigen Körnern mit verbesserter Empfindlichkeit
US5536632A (en) * 1995-05-15 1996-07-16 Eastman Kodak Company Ultrathin tabular grain emulsions with dopants at selected locations
WO1996030808A1 (en) * 1995-03-29 1996-10-03 Eastman Kodak Company Tabular grain emulsions containing a restricted high iodide surface phase
US5573902A (en) * 1995-05-15 1996-11-12 Eastman Kodak Company Tabular grain emulsions with sensitization enhancements
US5576171A (en) * 1995-05-15 1996-11-19 Eastman Kodak Company Tabular grain emulsions with sensitization enhancements
US5576168A (en) * 1994-08-26 1996-11-19 Eastman Kodak Company Ultrathin tabular grain emulsions with sensitization enhancements
US5582965A (en) * 1994-08-26 1996-12-10 Eastman Kodak Company Ultrathin tabular grain emulsions with sensitization enhancements (II)
US5614358A (en) * 1995-05-15 1997-03-25 Eastman Kodak Company Ultrathin tabular grain emulsions with reduced reciprocity failure

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4814264A (en) * 1986-12-17 1989-03-21 Fuji Photo Film Co., Ltd. Silver halide photographic material and method for preparation thereof
US4888272A (en) * 1987-03-31 1989-12-19 Fuji Photo Film Co., Ltd. Method for preparing silver halide photographic emulsions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4814264A (en) * 1986-12-17 1989-03-21 Fuji Photo Film Co., Ltd. Silver halide photographic material and method for preparation thereof
US4888272A (en) * 1987-03-31 1989-12-19 Fuji Photo Film Co., Ltd. Method for preparing silver halide photographic emulsions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
EASTMAN KODAK COMPANY 'Black-and-White Processing Using KODAK Chemicals' 1985 , KODAK , NEW YORK, US *

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US5468601A (en) * 1994-04-12 1995-11-21 Eastman Kodak Company Deposition sensitized emulsions and processes for their preparation
EP0699949A1 (de) 1994-08-26 1996-03-06 Eastman Kodak Company Emulsionen mit ultradünnen tafelförmigen Körnern und Dotierungsmitteln auf ausgewählten Stellen
US5576168A (en) * 1994-08-26 1996-11-19 Eastman Kodak Company Ultrathin tabular grain emulsions with sensitization enhancements
EP0699945A1 (de) * 1994-08-26 1996-03-06 Eastman Kodak Company Emulsionen mit ultradünnen tafelförmigen Körnern verbesserter Empfindlichkeit
EP0699951A1 (de) * 1994-08-26 1996-03-06 Eastman Kodak Company Emulsionen mit ultradünnen tafelförmigen Körnern und neuer Behandlung von Dotiermitteln
EP0699946A1 (de) * 1994-08-26 1996-03-06 Eastman Kodak Company Emulsionen mit ultradünnen tafelförmigen Körnern mit verbesserter Empfindlichkeit (II)
EP0699944A1 (de) * 1994-08-26 1996-03-06 Eastman Kodak Company Emulsionen aus tafelförmigen Körnern mit verbesserter Empfindlichkeit
EP0701165A1 (de) * 1994-08-26 1996-03-13 Eastman Kodak Company Emulsionen aus tafelförmigen Körnern mit verbesserter Empfindlichkeit
EP0699950A1 (de) * 1994-08-26 1996-03-06 Eastman Kodak Company Emulsionen mit ultradünnen tafelförmigen Körnern und neuer Behandlung von Dotiermitteln
US5582965A (en) * 1994-08-26 1996-12-10 Eastman Kodak Company Ultrathin tabular grain emulsions with sensitization enhancements (II)
WO1996030808A1 (en) * 1995-03-29 1996-10-03 Eastman Kodak Company Tabular grain emulsions containing a restricted high iodide surface phase
US5536632A (en) * 1995-05-15 1996-07-16 Eastman Kodak Company Ultrathin tabular grain emulsions with dopants at selected locations
US5576171A (en) * 1995-05-15 1996-11-19 Eastman Kodak Company Tabular grain emulsions with sensitization enhancements
US5573902A (en) * 1995-05-15 1996-11-12 Eastman Kodak Company Tabular grain emulsions with sensitization enhancements
US5614358A (en) * 1995-05-15 1997-03-25 Eastman Kodak Company Ultrathin tabular grain emulsions with reduced reciprocity failure

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