US4276364A
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US
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Acylhydrazinophenylthiourea nucleating agents and photographic emulsions and elements containing such agents
Assignee: Eastman Kodak Co
•
Filing: 1980-06-23
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Granted: 1981-06-30
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Expires: 2000-06-23
Abstract
Abstract Novel 3,3-disubstituted acylhydrazinophenylthiourea nucleating agents are disclosed as well as silver halide photographic emulsions and elements containing silver halide grains capable of forming an internal latent image having the nucleating agents adsorbed to the surface of the silver halide grains. Imaging processes in which these materials participate are also disclosed.
Inventors
- 👤 Ronald E. Leone
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 03:50
CPC Classifications
C; C07; C07D; C07D295/00; C07D295/16; C07D295/20; C07D295/215; G; G03; G03C; G03C1/00; G03C1/005; G03C1/485; G03C1/48538; G03C1/48546; G03C1/48561
Claims Analysis
Total Claims: 30
Claim 1
Independent Claim
168 words
A silver halide emulsion comprised of silver halide grains capable of forming an internal latent image and, adsorbed to the surface of said silver halide grains, a nucleating amount of a 3,3-disubstituted acylhydrazinophenylthiourea of the formula ##STR13## wherein R is hydrogen or an alkyl, cycloalkyl, haloalkyl, alkoxyalkyl or phenylalkyl substituent, R 1 is a phenylene or alkyl, halo-, or alkoxysubstituted phenylene group, and R 2 and R 3 are independently selected from among alkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituents having from 1 to 18 carbon atoms, a cycloalkyl substituent; a phenyl nucleus having a Hammett sigma value-derived electron-withdrawing characteristic less positive than +0.50, and naphthyl, or R 2 and R 3 together form a heterocyclic nucleus forming a 5- or 6-membered ring, wherein the ring atoms are chosen from the class consisting of nitrogen, carbon, oxygen, sulfur and selenium atoms, the alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms and the cycloalkyl moieties have from 3 to 10 carbon atoms.
Claim 2
Dependent Claim
168 words
A silver halide emulsion comprised of silver halide grains capable of forming an internal latent image and, adsorbed to the surface of said silver halide grains, a nucleating amount of a 3,3-disubstituted acylhydrazinophenylthiourea of the formula ##STR13## wherein R is hydrogen or an alkyl, cycloalkyl, haloalkyl, alkoxyalkyl or phenylalkyl substituent, R 1 is a phenylene or alkyl, halo-, or alkoxysubstituted phenylene group, and R 2 and R 3 are independently selected from among alkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituents having from 1 to 18 carbon atoms, a cycloalkyl substituent; a phenyl nucleus having a Hammett sigma value-derived electron-withdrawing characteristic less positive than +0.50, and naphthyl, or R 2 and R 3 together form a heterocyclic nucleus forming a 5- or 6-membered ring, wherein the ring atoms are chosen from the class consisting of nitrogen, carbon, oxygen, sulfur and selenium atoms, the alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms and the cycloalkyl moieties have from 3 to 10 carbon atoms.
Claim 3
Dependent Claim
103 words
A silver halide emulsion according to claim 1 wherein said 3,3-disubstituted acylhydrazinophenylthiourea is of the formula ##STR14## wherein R is hydrogen or methyl and R 2 and R 3 are independently selected from among alkyl and phenylalkyl substituents, wherein the alkyl moieties are in each instance from 1 to 6 carbon atoms, and a phenyl nucleus having a Hammett sigma value-derived electron-withdrawing characteristic less positive than +0.50, or R 2 and R 3 together form a saturated heterocyclic nucleus forming a 5- or 6-membered ring, wherein the ring atoms are chosen from the class consisting of nitrogen, carbon, oxygen, sulfur, and selenium atoms.
Claim 4
Dependent Claim
27 words
A silver halide emulsion according to claim 2 wherein said 3,3-disubstituted acylhydrazino-phenylthiourea is present in a concentration of from 0.1 to 500 mg per mole of silver.
Claim 5
Dependent Claim
131 words
A silver halide emulsion according to claims 1, 2 or 3 wherein said silver halide grains are predominantly silver bromide and contain metal dopants occluded therein, which grains when coated on a photographic support, exposed to a light intensity scale, and developed for 5 minutes at 25° C. in test surface developer provide (a) a density of less than 0.4 and (b) a density of at least 0.5 less than when this testing procedure is repeated modifying the test surface developer by the inclusion of 0.5 gram per liter of potassium iodide, the test surface developer being of the following composition: ______________________________________
Water 500.0 cc
N-methyl-p-aminophenol sulfate
2.5 g
Sodium sulfite, desiccated
30.0 g
Hydroquinone 2.5 g
Sodium metaborate 10.0 g
Potassium bromide 0.5 g
Water to make 1.0 liter.
______________________________________
Claim 6
Dependent Claim
176 words
A photographic element comprised of a support bearing a silver halide emulsion layer comprising silver halide grains capable of forming an internal latent image and, adsorbed to the surface of said silver halide grains, a nucleating amount of a 3,3-disubstituted acylhydrazinophenylthiourea of the formula ##STR15## wherein R is hydrogen or an alkyl, cycloalkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituent, R 1 is a phenylene or alkyl, halo-, or alkoxysubstituted phenylene group, and R 2 and R 3 are independently selected from among alkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituents having from 1 to 18 carbon atoms, a cycloalkyl substituent, a phenyl nucleus having a Hammett sigma value-derived electron-withdrawing characteristic less positive than +0.50, and naphthyl, or R 2 and R 3 together form a heterocyclic nucleus forming a 5- or 6-membered ring, wherein the ring atoms are chosen from the class consisting of nitrogen, carbon, oxygen, sulfur, and selenium atoms, the alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms and the cycloalkyl moieties have from 3 to 10 carbon atoms.
Claim 7
Dependent Claim
176 words
A photographic element comprised of a support bearing a silver halide emulsion layer comprising silver halide grains capable of forming an internal latent image and, adsorbed to the surface of said silver halide grains, a nucleating amount of a 3,3-disubstituted acylhydrazinophenylthiourea of the formula ##STR15## wherein R is hydrogen or an alkyl, cycloalkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituent, R 1 is a phenylene or alkyl, halo-, or alkoxysubstituted phenylene group, and R 2 and R 3 are independently selected from among alkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituents having from 1 to 18 carbon atoms, a cycloalkyl substituent, a phenyl nucleus having a Hammett sigma value-derived electron-withdrawing characteristic less positive than +0.50, and naphthyl, or R 2 and R 3 together form a heterocyclic nucleus forming a 5- or 6-membered ring, wherein the ring atoms are chosen from the class consisting of nitrogen, carbon, oxygen, sulfur, and selenium atoms, the alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms and the cycloalkyl moieties have from 3 to 10 carbon atoms.
Claim 8
Dependent Claim
102 words
A photographic element according to claim 5 wherein the 3,3-disubstituted acylhydrazinophenylthiourea is of the formula ##STR16## wherein R is hydrogen or methyl and R 2 and R 3 are independently selected from among alkyl and phenylalkyl substituents, wherein the alkyl moieties are in each instance from 1 to 6 carbon atoms, and a phenyl nucleus having a Hammett sigma value-derived electron-withdrawing characteristic less positive than +0.50, or R 2 and R 3 together form a saturated heterocyclic nucleus forming a 5- or 6-membered ring, wherein the ring atoms are chosen from the class consisting of nitrogen, carbon, oxygen, sulfur, and selenium atoms.
Claim 9
Dependent Claim
28 words
A photographic element according to claims 5 or 6 wherein said 3,3-disubstituted acylhydrazinophenylthiourea is present in a concentration of from 1.0 to 100 mg per mole of silver.
Claim 10
Dependent Claim
121 words
A photographic element according to claim 6 wherein said silver halide grains contain a metal dopant, which grains when coated on a photographic support, exposed to a light intensity scale, and developed for 5 minutes at 25° C. in test surface developer provide (a) a density of less than 0.25 and (b) a density of at least 5 times greater when this testing procedure is repeated modifying the test surface developer by the inclusion of 0.5 gram per liter of potassium iodide, the test surface developer being of the following composition: ______________________________________
Water 500.0 cc
N-methyl-p-aminophenol sulfate
2.5 g
Sodium sulfite, desiccated
30.0 g
Hydroquinone 2.5 g
Sodium metaborate 10.0 g
Potassium bromide 0.5 g
Water to make 1.0 liter.
______________________________________
Claim 11
Dependent Claim
200 words
A process of obtaining a direct-positive image comprising imagewise exposing a photographic element comprised of a support and coated on the support, a silver halide emulsion layer comprising silver halide grains capable of forming an internal latent image and, adsorbed to the surface of the silver halide grains, a nucleating amount of a 3,3-disubstituted acylhydrazinophenylthiourea of the formula ##STR17## wherein R is hydrogen or an alkyl, cycloalkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituent, R 1 is a phenylene or alkyl, halo-, or alkoxysubstituted phenylene group, and R 2 and R 3 are independently selected from among alkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituents having from 1 to 18 carbon atoms, a cycloalkyl substituent; a phenyl nucleus having a Hammett sigma value-derived electron-withdrawing characteristic less positive than +0.50, and naphthyl, or R 2 and R 3 together form a heterocyclic nucleus forming a 5- or 6-membered ring, wherein the ring atoms are chosen from the class consisting of nitrogen, carbon, oxygen, sulfur, and selenium atoms, the alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms and the cycloalkyl moieties have from 3 to 10 carbon atoms, and selectively surface developing the silver halide grains remaining unexposed.
Claim 12
Dependent Claim
200 words
A process of obtaining a direct-positive image comprising imagewise exposing a photographic element comprised of a support and coated on the support, a silver halide emulsion layer comprising silver halide grains capable of forming an internal latent image and, adsorbed to the surface of the silver halide grains, a nucleating amount of a 3,3-disubstituted acylhydrazinophenylthiourea of the formula ##STR17## wherein R is hydrogen or an alkyl, cycloalkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituent, R 1 is a phenylene or alkyl, halo-, or alkoxysubstituted phenylene group, and R 2 and R 3 are independently selected from among alkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituents having from 1 to 18 carbon atoms, a cycloalkyl substituent; a phenyl nucleus having a Hammett sigma value-derived electron-withdrawing characteristic less positive than +0.50, and naphthyl, or R 2 and R 3 together form a heterocyclic nucleus forming a 5- or 6-membered ring, wherein the ring atoms are chosen from the class consisting of nitrogen, carbon, oxygen, sulfur, and selenium atoms, the alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms and the cycloalkyl moieties have from 3 to 10 carbon atoms, and selectively surface developing the silver halide grains remaining unexposed.
Claim 13
Dependent Claim
258 words
In an image transfer film unit which comprises a photographic element comprising a support bearing at least one silver halide emulsion layer containing radiation-sensitive internal latent image-forming silver halide grains and, adsorbed to the surface of said silver halide grains, a nucleating agent, said photographic element including an image dye-providing material within or in contact with said silver halide emulsion layer, an image-receiving means positioned to receive image dye from said photographic element, an alkaline processing composition, means containing and adapted to release said alkaline processing composition for contact with said emulsion layer, and a silver halide developing agent located in at least one of the photographic element and the alkaline processing composition, the improvement wherein said nucleating agent is a 3,3-disubstituted acylhydrazinophenylthiourea of the formula ##STR18## wherein R is hydrogen or an alkyl, cycloalkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituent, R 1 is a phenylene or alkyl, halo-, or alkoxysubstituted phenylene group, and R 2 and R 3 are independently selected from among alkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituents having from 1 to 18 carbon atoms, a cycloalkyl substituent, a phenyl nucleus having a Hammett sigma value-derived electron-withdrawing characteristic less positive than +0.50, and naphthyl, or R 2 and R 3 together form a heterocyclic nucleus forming a 5- or 6-membered ring, wherein the ring atoms are chosen from the class consisting of nitrogen, carbon, oxygen, sulfur, and selenium atoms, the alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms and the cycloalkyl moieties have from 3 to 10 carbon atoms.
Claim 14
Dependent Claim
258 words
In an image transfer film unit which comprises a photographic element comprising a support bearing at least one silver halide emulsion layer containing radiation-sensitive internal latent image-forming silver halide grains and, adsorbed to the surface of said silver halide grains, a nucleating agent, said photographic element including an image dye-providing material within or in contact with said silver halide emulsion layer, an image-receiving means positioned to receive image dye from said photographic element, an alkaline processing composition, means containing and adapted to release said alkaline processing composition for contact with said emulsion layer, and a silver halide developing agent located in at least one of the photographic element and the alkaline processing composition, the improvement wherein said nucleating agent is a 3,3-disubstituted acylhydrazinophenylthiourea of the formula ##STR18## wherein R is hydrogen or an alkyl, cycloalkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituent, R 1 is a phenylene or alkyl, halo-, or alkoxysubstituted phenylene group, and R 2 and R 3 are independently selected from among alkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituents having from 1 to 18 carbon atoms, a cycloalkyl substituent, a phenyl nucleus having a Hammett sigma value-derived electron-withdrawing characteristic less positive than +0.50, and naphthyl, or R 2 and R 3 together form a heterocyclic nucleus forming a 5- or 6-membered ring, wherein the ring atoms are chosen from the class consisting of nitrogen, carbon, oxygen, sulfur, and selenium atoms, the alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms and the cycloalkyl moieties have from 3 to 10 carbon atoms.
Claim 15
Dependent Claim
17 words
An improved image transfer film unit according to claim 10 wherein said film unit incorporates an antifoggant.
Claim 16
Dependent Claim
17 words
An improved image transfer film unit according to claim 11 wherein said antifoggant is a benzotriazole antifoggant.
Claim 17
Dependent Claim
105 words
An improved image transfer film unit according to claim 10 wherein said 3,3-disubstituted acylhydrazinophenylthiourea is of the formula ##STR19## wherein R is hydrogen or methyl and R 2 and R 3 are independently selected from among alkyl and phenylalkyl substituents, wherein the alkyl moieties are in each instance from 1 to 6 carbon atoms, and a phenyl nucleus having a Hammett sigma value-derived electron-withdrawing characteristic less positive than +0.50, or R 2 and R 3 together form a saturated heterocyclic nucleus forming a 5- or 6-membered ring, wherein the ring atoms are chosen from the class consisting of nitrogen, carbon, oxygen, sulfur, and selenium atoms.
Claim 18
Dependent Claim
375 words
An image transfer film unit comprising (a) a photographic element comprising a support bearing (1) a layer containing a blue-sensitive silver halide emulsion having in contact therewith an immobile material capable of releasing a mobile yellow image dye, (2) a layer containing a green-sensitized silver halide emulsion having in contact therewith an immobile material capable of releasing a mobile magenta image dye, and (3) a layer containing a red-sensitized silver halide emulsion having in contact therewith an immobile material capable of releasing a mobile cyan image dye, wherein each of said silver halide emulsions comprises silver halide grains having metal dopants occluded therein, which grains when coated on a photographic support, exposed to a light intensity scale, and developed for 5 minutes at 25° C. in test surface developer provide (a) a density of less than 0.4 and (b) a density of at least 0.5 less than when this testing procedure is repeated modifying the test surface developer by the inclusion of 0.5 gram per liter of potassium iodide, (b) an image-receiving means positioned to receive image dye from said photographic element, (c) an aqueous alkaline processing composition, (d) means containing and adapted to release said alkaline processing composition into contact with said silver halide emulsions, (e) a silver halide surface developing agent located in said processing composition, and (f) from 1 to 100 mg per mole of silver of a nucleating agent adsorbed to said silver halide grains within at least one of said silver halide emulsion layers, said nucleating agent having the formula ##STR20## wherein R 2 and R 3 are independently selected from among alkyl and phenylalkyl substituents, wherein the alkyl moieties are in each instance from 1 to 6 carbon atoms, and a phenyl nucleus having a Hammett sigma value-derived electron-withdrawing characteristic less positive than +0.50, or R 2 and R 3 together form a saturated heterocyclic nucleus forming a 5- or 6-membered ring, wherein the ring atoms are chosen from the class consisting of nitrogen, carbon, oxygen, sulfur, and selenium atoms, the test surface developer consisting essentially of ______________________________________
Water (52° C.) 500.0 cc
N-methyl-p-aminophenol sulfate
2.5 g
Sodium sulfite, desiccated
30.0 g
Hydroquinone 2.5 g
Sodium metaborate 10.0 g
Potassium bromide 0.5 g
Water to make 1 liter.
______________________________________
Claim 19
Dependent Claim
375 words
An image transfer film unit comprising (a) a photographic element comprising a support bearing (1) a layer containing a blue-sensitive silver halide emulsion having in contact therewith an immobile material capable of releasing a mobile yellow image dye, (2) a layer containing a green-sensitized silver halide emulsion having in contact therewith an immobile material capable of releasing a mobile magenta image dye, and (3) a layer containing a red-sensitized silver halide emulsion having in contact therewith an immobile material capable of releasing a mobile cyan image dye, wherein each of said silver halide emulsions comprises silver halide grains having metal dopants occluded therein, which grains when coated on a photographic support, exposed to a light intensity scale, and developed for 5 minutes at 25° C. in test surface developer provide (a) a density of less than 0.4 and (b) a density of at least 0.5 less than when this testing procedure is repeated modifying the test surface developer by the inclusion of 0.5 gram per liter of potassium iodide, (b) an image-receiving means positioned to receive image dye from said photographic element, (c) an aqueous alkaline processing composition, (d) means containing and adapted to release said alkaline processing composition into contact with said silver halide emulsions, (e) a silver halide surface developing agent located in said processing composition, and (f) from 1 to 100 mg per mole of silver of a nucleating agent adsorbed to said silver halide grains within at least one of said silver halide emulsion layers, said nucleating agent having the formula ##STR20## wherein R 2 and R 3 are independently selected from among alkyl and phenylalkyl substituents, wherein the alkyl moieties are in each instance from 1 to 6 carbon atoms, and a phenyl nucleus having a Hammett sigma value-derived electron-withdrawing characteristic less positive than +0.50, or R 2 and R 3 together form a saturated heterocyclic nucleus forming a 5- or 6-membered ring, wherein the ring atoms are chosen from the class consisting of nitrogen, carbon, oxygen, sulfur, and selenium atoms, the test surface developer consisting essentially of ______________________________________
Water (52° C.) 500.0 cc
N-methyl-p-aminophenol sulfate
2.5 g
Sodium sulfite, desiccated
30.0 g
Hydroquinone 2.5 g
Sodium metaborate 10.0 g
Potassium bromide 0.5 g
Water to make 1 liter.
______________________________________
Claim 20
Dependent Claim
110 words
A photographic element according to claim 14 wherein said silver halide grains contain a metal dopant, provide a maximum optical density less than 0.25 when coated on a support at a density of from 3 to 4 grams per square meter, exposed to a light intensity scale for a fixed time of from 1×10 2 to 1 second and developed for 5 minutes at 25° C. in the surface developer, and provide a maximum optical density at least 5 times greater than the above maximum density when the above procedure is repeated additionally including in the surface developer 0.5 gram per liter of potassium iodide to form an internal developer.
Claim 21
Dependent Claim
20 words
A photographic element according to claim 14 wherein the immobile materials capable of releasing mobile image dye are redox dye-releasers.
Claim 22
Dependent Claim
217 words
In a process of producing a visible image in an imagewise exposed photographic element having a support and, coated on the support, a silver halide emulsion layer comprising silver halide grains capable of forming an internal latent image and, adsorbed to the surface of the silver halide grains, a nucleating agent in an amount sufficient to promote development of unexposed silver halide grains comprising processing in an aqueous alkaline surface developer, the improvement comprising developing in the presence of a 3,3-disubstituted acylhydrazinophenylthiourea of the formula ##STR21## wherein R is hydrogen or an alkyl, cycloalkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituent, R 1 is a phenylene or alkyl, halo-, or alkoxysubstituted phenylene group, and R 2 and R 3 are independently selected from among alkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituents having from 1 to 18 carbon atoms, a cycloalkyl substituent, a phenyl nucleus having a Hammett sigma value-derived electron-withdrawing characteristic less positive than +0.50, and naphthyl, or R 2 and R 3 together form a heterocyclic nucleus forming a 5- or 6-membered ring, wherein the ring atoms are chosen from the class consisting of nitrogen, carbon, oxygen, sulfur, and selenium atoms, the alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms and the cycloalkyl moieties have from 3 to 10 carbon atoms.
Claim 23
Dependent Claim
217 words
In a process of producing a visible image in an imagewise exposed photographic element having a support and, coated on the support, a silver halide emulsion layer comprising silver halide grains capable of forming an internal latent image and, adsorbed to the surface of the silver halide grains, a nucleating agent in an amount sufficient to promote development of unexposed silver halide grains comprising processing in an aqueous alkaline surface developer, the improvement comprising developing in the presence of a 3,3-disubstituted acylhydrazinophenylthiourea of the formula ##STR21## wherein R is hydrogen or an alkyl, cycloalkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituent, R 1 is a phenylene or alkyl, halo-, or alkoxysubstituted phenylene group, and R 2 and R 3 are independently selected from among alkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituents having from 1 to 18 carbon atoms, a cycloalkyl substituent, a phenyl nucleus having a Hammett sigma value-derived electron-withdrawing characteristic less positive than +0.50, and naphthyl, or R 2 and R 3 together form a heterocyclic nucleus forming a 5- or 6-membered ring, wherein the ring atoms are chosen from the class consisting of nitrogen, carbon, oxygen, sulfur, and selenium atoms, the alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms and the cycloalkyl moieties have from 3 to 10 carbon atoms.
Claim 24
Dependent Claim
27 words
In a process according to claim 17 the further improvement in which the surface developer is at a pH in the range of from 13.9 to 11.8.
Claim 25
Dependent Claim
27 words
In a process according to claim 17 the further improvement in which the surface developer is at a pH in the range of from 12.0 to 13.0.
Claim 26
Dependent Claim
326 words
In a process of producing by surface development a visible image in an imagewise exposed photographic element having a support and, coated on the support, a silver halide emulsion layer comprising silver halide grains and a nucleating agent in an amount sufficient to promote surface development of unexposed silver halide grains, the silver halide grains having metal dopants occluded therein and which grains when coated on a photographic support, exposed to a light intensity scale, and developed for 5 minutes at 25° C. in test surface developer provide (a) a density of less than 0.4 and (b) a density of at least 0.5 less than when this testing procedure is repeated modifying the test surface developer by the inclusion of 0.5 gram per liter of potassium iodide, the test surface developer being of the following composition: ______________________________________
Water 500.0 cc
N-methyl-p-aminophenol sulfate
2.5 g
Sodium sulfite, desiccated
30.0 g
Hydroquinone 2.5 g
Sodium metaborate 10.0 g
Potassium bromide 0.5 g
Water to make 1.0 liter,
______________________________________ the improvement wherein the nucleating agent is a 3,3-disubstituted acylhydrazinophenylthiourea of the formula ##STR22## wherein r is hydrogen or an alkyl, cycloalkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituent, R 1 is a phenylene or alkyl, halo-, or alkoxysubstituted phenylene group, and R 2 and R 3 are independently selected from among alkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituents having from 1 to 18 carbon atoms, a cycloalkyl substituent, a phenyl nucleus having a Hammett sigma value-derived electron-withdrawing characteristic less positive than +0.50, and naphthyl, or R 2 and R 3 together form a heterocyclic nucleus forming a 5- or 6-membered ring, wherein the ring atoms are chosen from the class consisting of nitrogen, carbon, oxygen, sulfur and selenium atoms. the alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms and the cycloalkyl moieties have from 3 to 10 carbon atoms, and surface development occurring at a pH in the range of from 12.0 to 13.0.
Claim 27
Dependent Claim
326 words
In a process of producing by surface development a visible image in an imagewise exposed photographic element having a support and, coated on the support, a silver halide emulsion layer comprising silver halide grains and a nucleating agent in an amount sufficient to promote surface development of unexposed silver halide grains, the silver halide grains having metal dopants occluded therein and which grains when coated on a photographic support, exposed to a light intensity scale, and developed for 5 minutes at 25° C. in test surface developer provide (a) a density of less than 0.4 and (b) a density of at least 0.5 less than when this testing procedure is repeated modifying the test surface developer by the inclusion of 0.5 gram per liter of potassium iodide, the test surface developer being of the following composition: ______________________________________
Water 500.0 cc
N-methyl-p-aminophenol sulfate
2.5 g
Sodium sulfite, desiccated
30.0 g
Hydroquinone 2.5 g
Sodium metaborate 10.0 g
Potassium bromide 0.5 g
Water to make 1.0 liter,
______________________________________ the improvement wherein the nucleating agent is a 3,3-disubstituted acylhydrazinophenylthiourea of the formula ##STR22## wherein r is hydrogen or an alkyl, cycloalkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituent, R 1 is a phenylene or alkyl, halo-, or alkoxysubstituted phenylene group, and R 2 and R 3 are independently selected from among alkyl, haloalkyl, alkoxyalkyl, or phenylalkyl substituents having from 1 to 18 carbon atoms, a cycloalkyl substituent, a phenyl nucleus having a Hammett sigma value-derived electron-withdrawing characteristic less positive than +0.50, and naphthyl, or R 2 and R 3 together form a heterocyclic nucleus forming a 5- or 6-membered ring, wherein the ring atoms are chosen from the class consisting of nitrogen, carbon, oxygen, sulfur and selenium atoms. the alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms and the cycloalkyl moieties have from 3 to 10 carbon atoms, and surface development occurring at a pH in the range of from 12.0 to 13.0.
Claim 28
Dependent Claim
100 words
In a process according to claim 20 the further improvement in which the nucleating agent is of the formula ##STR23## wherein R 2 and R 3 are independently selected from among alkyl and phenylalkyl substituents, wherein the alkyl moieties are in each instance from 1 to 6 carbon atoms, and a phenyl nucleus having a Hammett sigma value-derived electron-withdrawing characteristic less positive than +0.50, or R 2 and R 3 together form a saturated heterocyclic nucleus forming a 5- or 6-membered ring, wherein the ring atoms are chosen from the class consisting of nitrogen, carbon, oxygen, sulfur, and selenium atoms.
Claim 29
Dependent Claim
19 words
In a process according to claim 20 the further improvement wherein a visible image is transferred to a receiver.
Claim 30
Dependent Claim
49 words
In a process according to claim 22 the further improvement wherein the photographic element is a dye image transfer photographic element containing in contact with the silver halide emulsion layer an initially immobile dye releasing material and image dye is transferred to the receiver to form a visible image.
References Cited (Backward Citations)
US4030925A
Cited
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1984-06-29 | 1984-12-29 | 1985-06-30 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-06-29 | 1988-12-29 | 1989-06-30 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-06-29 | 1992-12-29 | 1993-06-30 | $7700.00 | Window Closed / Lapsed |