Photographic compositions and elements including internal latent image silver halide grains and acylhydrazinophenylthiourea nucleating agents therefor

Claim 2

A radiation-sensitive silver halide emulsion comprising silver halide grains capable of forming an internal latent image when coated in a photographic element and exposed to actinic radiation and a nucleating amount of an acylhydrazinophenylthiourea of the formula ##STR45## wherein R is hydrogen; an alkyl, cycloalkyl, haloalkyl, alkoxyalkyl or phenylalkyl substituent or a phenyl nucleus having a Hammett sigma-value-derived electron withdrawing characteristic more positive than -0.3; R 1 is a phenylene or alkyl, halo- or alkoxy-substituted phenylene group; R 2 is an alkyl, haloalkyl, alkoxyalkyl or phenylalkyl substituent 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; naphthyl or ##STR46## R 3 is hydrogen, benzyl, alkoxybenzyl, halobenzyl or alkylbenzyl; said alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms; and said cycloalkyl moieties have from 3 to 10 carbon atoms.

Claim 3

A radiation-sensitive silver halide emulsion comprising silver halide grains capable of forming an internal latent image when coated in a photographic element and exposed to actinic radiation and a nucleating amount of an acylhydrazinophenylthiourea of the formula ##STR47## wherein R is hydrogen, phenyl, alkylphenyl, cyanophenyl, halophenyl, alkoxyphenyl, alkyl, cycloalkyl, haloalkyl, alkoxyalkyl or a phenylalkyl substituent; R 1 is a phenylene or alkyl, halo- or alkoxy-substituted phenylene group; R 2 is an alkyl substitutent having from 1 to 18 carbon atoms; a cycloalkyl substituent; a haloalkyl, alkoxyalkyl or phenylalkyl substituent; phenyl or naphthyl; an alkylphenyl, cyanophenyl, halophenyl or alkoxyphenyl substituent or ##STR48## R 3 is hydrogen, benzyl, alkoxybenzyl, halobenzyl or alkylbenzyl; said alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms; and said cycloalkyl moieties have from 3 to 10 carbon atoms.

Claim 4

A radiation-sensitive silver halide emulsion comprising silver halide grains capable of forming an internal latent image when coated in a photographic element and exposed to actinic radiation and a nucleating amount of an acylhydrazinophenylthiourea of the formula ##STR47## wherein R is hydrogen, phenyl, alkylphenyl, cyanophenyl, halophenyl, alkoxyphenyl, alkyl, cycloalkyl, haloalkyl, alkoxyalkyl or a phenylalkyl substituent; R 1 is a phenylene or alkyl, halo- or alkoxy-substituted phenylene group; R 2 is an alkyl substitutent having from 1 to 18 carbon atoms; a cycloalkyl substituent; a haloalkyl, alkoxyalkyl or phenylalkyl substituent; phenyl or naphthyl; an alkylphenyl, cyanophenyl, halophenyl or alkoxyphenyl substituent or ##STR48## R 3 is hydrogen, benzyl, alkoxybenzyl, halobenzyl or alkylbenzyl; said alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms; and said cycloalkyl moieties have from 3 to 10 carbon atoms.

Claim 5

A radiation-sensitive silver halide emulsion according to claim 2 wherein said alkyl moieties of R consist of from 1 to 4 carbon atoms.

Claim 6

A radiation-sensitive silver halide emulsion according to claim 2 wherein R 1 is a para-phenylene group.

Claim 7

A radiation-sensitive silver halide emulsion comprising silver halide grains capable of forming an internal latent image when coated in a photographic element and exposed to actinic radiation and a nucleating amount of an acylhydrazinophenylthiourea of the formula ##STR49## wherein R is hydrogen, phenyl, alkylphenyl, cyanophenyl, halophenyl, alkoxyphenyl, alkyl, cycloalkyl, haloalkyl, alkoxyalkyl or a phenylalkyl substituent; R 1 is a phenylene or alkyl, halo- or alkoxy-substituted phenylene group; R 2 is an alkyl, haloalkyl, alkoxyalkyl or phenylalkyl substitutent having from 1 to 18 carbon atoms; a cycloalkyl substituent; phenyl or naphthyl; or an alkylphenyl, cyanophenyl, halophenyl or alkoxyphenyl substituent; R 3 is benzyl, alkoxybenzyl, halobenzyl or alkylbenzyl; said alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms; and said cycloalkyl moieties have from 3 to 10 carbon atoms.

Claim 8

A radiation-sensitive silver halide emulsion comprising silver halide grains capable of forming an internal latent image when coated in a photographic element and exposed to actinic radiation and a nucleating amount of an acylhydrazinophenylthiourea of the formula ##STR49## wherein R is hydrogen, phenyl, alkylphenyl, cyanophenyl, halophenyl, alkoxyphenyl, alkyl, cycloalkyl, haloalkyl, alkoxyalkyl or a phenylalkyl substituent; R 1 is a phenylene or alkyl, halo- or alkoxy-substituted phenylene group; R 2 is an alkyl, haloalkyl, alkoxyalkyl or phenylalkyl substitutent having from 1 to 18 carbon atoms; a cycloalkyl substituent; phenyl or naphthyl; or an alkylphenyl, cyanophenyl, halophenyl or alkoxyphenyl substituent; R 3 is benzyl, alkoxybenzyl, halobenzyl or alkylbenzyl; said alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms; and said cycloalkyl moieties have from 3 to 10 carbon atoms.

Claim 9

A radiation-sensitive silver halide emulsion according to claim 5 wherein said alkyl moieties of R consist of from 1 to 4 carbon atoms; R 1 is para-phenylene or para-phenylene substituted in the 3 ring position with an alkyl, halo- or alkoxy substituent; R 2 is an alkyl substituent having from 1 to 12 carbon atoms, a cyclohexyl substituent, phenyl or phenyl having a 4-alkyl, 4-halo- or 4-alkoxy substituent and R 3 is benzyl or 4-alkoxy, 4-halo- or 4-alkyl-benzyl.

Claim 10

A radiation-sensitive silver halide emulsion according to claim 5 wherein said acylhydrazinophenylthiourea is chosen from the group consisting of 1-[4-(2-acetylhydrazino)phenyl]-1-benzyl-3-phenylthiourea and 1-[4-(2-acetylhydrazino)phenyl]-1-(4-methoxybenzyl)-3-phenylthiourea.

Claim 11

A radiation-sensitive silver halide emulsion comprising silver halide grains capable of forming an internal latent image when coated in a photographic element and exposed to actinic radiation and a nucleating amount of an acylhydrazinophenylthiourea of the formula ##STR50## wherein R is hydrogen, phenyl, alkylphenyl, cyanophenyl, halophenyl, alkoxyphenyl, alkyl, cycloalkyl, haloalkyl, alkoxyalkyl or a phenylalkyl substituent; R 1 is a phenylene or alkyl, halo- or alkoxy-substituted phenylene group; R 2 is an alkyl, haloalkyl, alkoxyalkyl or phenylalkyl substitutent having from 1 to 18 carbon atoms; a cycloalkyl substituent; phenyl or naphthyl; or an alkylphenyl, cyanophenyl, halophenyl or alkoxyphenyl substituent or ##STR51## said alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms; and said cycloalkyl moieties have from 3 to 10 carbon atoms.

Claim 12

A radiation-sensitive silver halide emulsion comprising silver halide grains capable of forming an internal latent image when coated in a photographic element and exposed to actinic radiation and a nucleating amount of an acylhydrazinophenylthiourea of the formula ##STR50## wherein R is hydrogen, phenyl, alkylphenyl, cyanophenyl, halophenyl, alkoxyphenyl, alkyl, cycloalkyl, haloalkyl, alkoxyalkyl or a phenylalkyl substituent; R 1 is a phenylene or alkyl, halo- or alkoxy-substituted phenylene group; R 2 is an alkyl, haloalkyl, alkoxyalkyl or phenylalkyl substitutent having from 1 to 18 carbon atoms; a cycloalkyl substituent; phenyl or naphthyl; or an alkylphenyl, cyanophenyl, halophenyl or alkoxyphenyl substituent or ##STR51## said alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms; and said cycloalkyl moieties have from 3 to 10 carbon atoms.

Claim 13

A radiation-sensitive silver halide emulsion comprising silver halide grains capable of forming an internal latent image when coated in a photographic element and exposed to actinic radiation and a nucleating amount of an acylhydrazinophenylthiourea of the formula ##STR52## wherein R is a hydrogen, phenyl, 4-alkylphenyl, 4-cyanophenyl, 4-halophenyl, 4-alkoxyphenyl, alkyl, cyclohexyl or phenylalkyl substituent, wherein said alkyl moieties have from 1 to 4 carbon atoms; R 1 is a para-phenylene or a 3 position alkyl, halo-, or alkoxy-substituted para-phenylene group; and R 2 is an alkyl, haloalkyl, alkoxyalkyl or phenylalkyl substituent having up to 12 carbon atoms, a cyclohexyl substituent; phenyl or a 4-alkylphenyl, 4-halophenyl or 4-alkoxyphenyl substituent; wherein said alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms.

Claim 14

A radiation-sensitive silver halide emulsion comprising silver halide grains capable of forming an internal latent image when coated in a photographic element and exposed to actinic radiation and a nucleating amount of an acylhydrazinophenylthiourea of the formula ##STR52## wherein R is a hydrogen, phenyl, 4-alkylphenyl, 4-cyanophenyl, 4-halophenyl, 4-alkoxyphenyl, alkyl, cyclohexyl or phenylalkyl substituent, wherein said alkyl moieties have from 1 to 4 carbon atoms; R 1 is a para-phenylene or a 3 position alkyl, halo-, or alkoxy-substituted para-phenylene group; and R 2 is an alkyl, haloalkyl, alkoxyalkyl or phenylalkyl substituent having up to 12 carbon atoms, a cyclohexyl substituent; phenyl or a 4-alkylphenyl, 4-halophenyl or 4-alkoxyphenyl substituent; wherein said alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms.

Claim 15

A radiation-sensitive silver halide emulsion according to claim 9 wherein said acylhydrazinophenylthiourea is chosen from the group consisting of 1-[4-(2-formylhydrazino)phenyl]-3-phenylthiourea; 1-[4-(2-acetylhydrazino)phenyl]-3-phenylthiourea; 1-[4-(2-benzoylhydrazino)phenyl]-3-phenylthiourea; 1-[4-(2-formylhydrazino)phenyl]-3-methylthiourea; 1-[4-(2-acetylhydrazino)phenyl]-3-ethylthiourea; 1-[4-(2-formylhydrazino)phenyl]-3-butylthiourea; 1-[4-(2-formylhydrazino)phenyl]-3-cyclohexylthiourea; 1-[4-(2-formylhydrazino)phenyl]-3-benzylthiourea; 1-[4-(2-formylhydrazino)phenyl]-3-heptylthiourea; 1-[4-(2-formylhydrazino)phenyl-3-decylthiourea; 1-[4-(2-formylhydrazino)phenyl]-3-(4-cyanophenyl)thiourea; 1-[4-(2-formylhydrazino)phenyl]-3-(4-methoxyphenyl)thiourea; 1-[4-(2-formylhydrazino)-3-methoxyphenyl]-3-phenylthiourea; 1-[4-(2-formylhydrazino)-3-methoxyphenyl]-3-butylthiourea; 1-[4-(2-formylhydrazino)-3-methoxyphenyl]-3-cyclohexylthiourea; 1-[4-(2-formylhydrazino)-3-methoxyphenyl]-3-(4-methoxyphenyl)thiourea; 1-[4-(2-trifluoroacetylhydrazino)phenyl]-3-phenylthiourea; 1-{4-[2-(4-cyanobenzoyl)hydrazino]phenyl}-3-phenylthiourea; 1-{4-[2-(4-chlorobenzoyl)hydrazino]phenyl}-3-phenylthiourea; 1-{4-[2-(4-fluorobenzoyl)hydrazino]phenyl}-3-phenylthiourea; 1-{4-[2-(4-methylbenzoyl)hydrazino]phenyl}-3-phenylthiourea; 1-{4-[2-(4-methoxybenzoyl)hydrazino]-phenyl }-3-phenylthiourea; 1-{4-[2-(4-chlorobenzoyl)hydrazino]phenyl}-3-benzylthiourea; and 1-{4-[2-(4-fluorobenzoyl)hydrazino]phenyl}-3-benzylthiourea.

Claim 16

A radiation-sensitive silver halide emulsion comprising silver halide grains capable of forming an internal latent image when coated in a photographic element and exposed to actinic radiation and a nucleating amount of an acylhydrazinophenylthiourea of the formula ##STR53## wherein R is a hydrogen, phenyl, 4-alkylphenyl, 4-cyanophenyl, 4-alkoxyphenyl, alkyl, cyclohexyl or phenylalkyl substituent; R 1 is a para-phenylene or a 3 ring position alkyl, halo- or alkoxy substituted para-phenylene group; and said alkyl moieties in each instance include from 1 to 4 carbon atoms.

Claim 17

A radiation-sensitive silver halide emulsion comprising silver halide grains capable of forming an internal latent image when coated in a photographic element and exposed to actinic radiation and a nucleating amount of an acylhydrazinophenylthiourea of the formula ##STR53## wherein R is a hydrogen, phenyl, 4-alkylphenyl, 4-cyanophenyl, 4-alkoxyphenyl, alkyl, cyclohexyl or phenylalkyl substituent; R 1 is a para-phenylene or a 3 ring position alkyl, halo- or alkoxy substituted para-phenylene group; and said alkyl moieties in each instance include from 1 to 4 carbon atoms.

Claim 18

A radiation-sensitive silver halide emulsion according to claim 9 wherein said acylhydrazinophenylthiourea is chosen from the group consisting of 1,3-bis[ 4-(2-formylhydrazino)phenyl]thiourea; 1,3-bis[4-(2-acetylhydrazino)phenyl]thiourea; and 1,3-bis[4-(2-benzoylhydrazino)phenyl]thiourea.

Claim 19

A radiation-sensitive silver halide emulsion according to claim 1 wherein said acylhydrazinophenylthiourea nucleating agent is present in a concentration of from 0.1 to 200 mg per mole of silver.

Claim 20

A radiation-sensitive silver halide emulsion according to claim 1 wherein said acyhydrazinophenylthiourea nucleating agent is adsorbed to the surface of said silver halide grains.

Claim 21

A photographic emulsion comprising a. a hydrophilic colloid, b. radiation-sensitive silver halide grains which when coated on a support at a density from 3 to 4 grams/m 2 , exposed to a light intensity scale for a fixed time of from 1 × 10.sup. -2 to 1 second and developed for 5 minutes at 25° C in a surface developer of the composition indicated below produce a maximum optical density of less than 0.4 and which provide an optical density of at least 0.5 optical density units less than 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 and c. from 0.5 to 25 mg per mole of silver of acylhydrazinophenylthiourea of the following formula: ##STR54## wherein R is hydrogen, phenyl, alkylphenyl, cyanophenyl, halophenyl, alkoxyalkyl, alkyl, cycloalkyl, haloalkyl, alkoxyalkyl or phenylalkyl substituent; R 1 is a para-phenylene or a 3-alkyl, 3-halo- or 3-alkoxy para-phenylene substituent; R 2 is an alkyl substituent having from 1 to 18 carbon atoms; a cycloalkyl substituent; a haloalkyl, alkoxyalkyl or phenylalkyl substituent; phenyl or naphthyl; an alkylphenyl, halophenyl or alkoxyphenyl substituent or ##STR55## R 3 is hydrogen, benzyl or a 4-alkyl, 4-halo- or 4-alkoxybenzyl group; said alkyl moieties of R have from 1 to 4 carbon atoms; said cycloalkyl moieties have from 3 to 10 carbon atoms; and said alkyl moieties, except as otherwise indicated, have from 1 to 6 carbon atoms; and wherein the surface developer composition consists essentially of ______________________________________ water (53° C) 500.0 cc N-methyl-p-aminophenol sulfate 2.5 grams sodium sulfite, desiccated 30.0 grams hydroquinone 2.5 grams sodium metaborate 10.0 grams potassium bromide 0.5 gram water to make 1.0 liter. ______________________________________

Claim 22

A photographic emulsion comprising a. a hydrophilic colloid, b. radiation-sensitive silver halide grains which when coated on a support at a density from 3 to 4 grams/m 2 , exposed to a light intensity scale for a fixed time of from 1 × 10.sup. -2 to 1 second and developed for 5 minutes at 25° C in a surface developer of the composition indicated below produce a maximum optical density of less than 0.4 and which provide an optical density of at least 0.5 optical density units less than 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 and c. from 0.5 to 25 mg per mole of silver of acylhydrazinophenylthiourea of the following formula: ##STR54## wherein R is hydrogen, phenyl, alkylphenyl, cyanophenyl, halophenyl, alkoxyalkyl, alkyl, cycloalkyl, haloalkyl, alkoxyalkyl or phenylalkyl substituent; R 1 is a para-phenylene or a 3-alkyl, 3-halo- or 3-alkoxy para-phenylene substituent; R 2 is an alkyl substituent having from 1 to 18 carbon atoms; a cycloalkyl substituent; a haloalkyl, alkoxyalkyl or phenylalkyl substituent; phenyl or naphthyl; an alkylphenyl, halophenyl or alkoxyphenyl substituent or ##STR55## R 3 is hydrogen, benzyl or a 4-alkyl, 4-halo- or 4-alkoxybenzyl group; said alkyl moieties of R have from 1 to 4 carbon atoms; said cycloalkyl moieties have from 3 to 10 carbon atoms; and said alkyl moieties, except as otherwise indicated, have from 1 to 6 carbon atoms; and wherein the surface developer composition consists essentially of ______________________________________ water (53° C) 500.0 cc N-methyl-p-aminophenol sulfate 2.5 grams sodium sulfite, desiccated 30.0 grams hydroquinone 2.5 grams sodium metaborate 10.0 grams potassium bromide 0.5 gram water to make 1.0 liter. ______________________________________

Claim 23

A photographic emulsion according to claim 15 wherein said radiation-sensitive silver halide grains contain a metal dopant therein; provide a maximum optical density less than 0.25 when coated on a support at a density of from 3 to 4 grams/m 2 , exposed to a light intensity scale for a fixed time of from 1 × 10.sup. -2 to 1 second and developed for 5 minutes at 25° C in the surface developer; and provide a maximum optical density at least five times greater than the above maximum optical 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 24

A photographic emulsion according to claim 15 wherein said acylhydrazinophenylthiourea is present in a concentration of from 1 to 15 mg per mole of silver.

Claim 25

A photographic emulsion according to claim 15 wherein said acylhydrazinophenylthiourea is adsorbed to the surface of said silver halide grains and at least one other hydrazide, hydrazone or N-substituted cycloammonium quaternary salt nucleating agent is dispersed within said hydrophilic colloid.

Claim 26

A photographic emulsion according to claim 15 wherein said silver halide grains have metal dopants occluded therein and wherein said halide is predominantly bromide, which grains have been chemically sensitized on the surface thereof to a level which would produce a density of less than 0.4 when imagewise exposed and developed in a test surface developer for five minutes at 27° C, and to at least a level which would provide a density of greater than 0.5 in an undoped silver halide emulsion of the same grain size and halide composition when exposed and developed in the test surface developer, provided said emulsions are coated at a coverage of between about 3 and 4 grams per square meter.

Claim 27

A photographic emulsion comprising a. gelatin; b. silver halide grains have metal dopants occluded therein and wherein said halide is predominantly bromide, which grains have been chemically sensitized on the surface thereof to a level which would produce a density of less than 0.4 when imagewise exposed and developed in a test surface developer for five minutes at 27° C, and to at least a level which would provide a density of greater than 0.5 in an undoped silver halide emulsion of the same grain size and halide composition when exposed and developed in the test surface developer, provided said emulsions are coated at a coverage of between about 3 and 4 grams per square meter; c. from 0.5 to 25 mg per mole of silver of acylhydrazinophenylthiourea of the following formula: ##STR56## wherein R is hydrogen, phenyl or methyl and R 2 is phenyl or ##STR57## d. an image dye-providing means, e. at least one nucleating agent chosen from the class consisting of hydrazides and hydrazones having the formulas ##STR58## wherein T is a phenyl, naphthyl or diphenyl radical, T 1 is an acyl or sulfonyl radical, T 2 is an alkylidene radical which contains from 1 to 22 carbon atoms; and f. the surface developer composition consists essentially of ______________________________________ water (53° C) 500.0 cc N-methyl-p-aminophenol sulfate 2.5 grams sodium sulfite, desiccated 30.0 grams hydroquinone 2.5 grams sodium metaborate 10.0 grams potassium bromide 0.5 gram water to make 1.0 liter. ______________________________________

Claim 28

A photographic emulsion comprising a. gelatin; b. silver halide grains have metal dopants occluded therein and wherein said halide is predominantly bromide, which grains have been chemically sensitized on the surface thereof to a level which would produce a density of less than 0.4 when imagewise exposed and developed in a test surface developer for five minutes at 27° C, and to at least a level which would provide a density of greater than 0.5 in an undoped silver halide emulsion of the same grain size and halide composition when exposed and developed in the test surface developer, provided said emulsions are coated at a coverage of between about 3 and 4 grams per square meter; c. from 0.5 to 25 mg per mole of silver of acylhydrazinophenylthiourea of the following formula: ##STR56## wherein R is hydrogen, phenyl or methyl and R 2 is phenyl or ##STR57## d. an image dye-providing means, e. at least one nucleating agent chosen from the class consisting of hydrazides and hydrazones having the formulas ##STR58## wherein T is a phenyl, naphthyl or diphenyl radical, T 1 is an acyl or sulfonyl radical, T 2 is an alkylidene radical which contains from 1 to 22 carbon atoms; and f. the surface developer composition consists essentially of ______________________________________ water (53° C) 500.0 cc N-methyl-p-aminophenol sulfate 2.5 grams sodium sulfite, desiccated 30.0 grams hydroquinone 2.5 grams sodium metaborate 10.0 grams potassium bromide 0.5 gram water to make 1.0 liter. ______________________________________

Claim 29

In a photographic element comprised of a support, and as a coating thereon, a radiation-sensitive silver halide emulsion layer comprised of silver halide grains capable of forming an internal latent image, the improvement comprising an acylhydrazinophenylthiourea nucleating agent incorporated within said radiation-sensitive layer of the formula ##STR59## wherein R is hydrogen; an alkyl, cycloalkyl, haloalkyl, alkoxyalkyl or phenylalkyl substituent or a phenyl nucleus having a Hammett sigma-value-derived electron withdrawing characteristic more positive than -0.3; R 1 is a phenylene or alkyl, halo- or alkoxy-substituted phenylene group; R 2 is an alkyl, haloalkyl, alkoxyalkyl or phenylalkyl substituent 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; naphthyl or ##STR60## R 3 is hydrogen, benzyl, alkoxybenzyl, halobenzyl or alkylbenzyl; said alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms; and said cycloalkyl moieties have from 3 to 10 carbon atoms.

Claim 30

In a photographic element comprised of a support, and as a coating thereon, a radiation-sensitive silver halide emulsion layer comprised of silver halide grains capable of forming an internal latent image, the improvement comprising an acylhydrazinophenylthiourea nucleating agent incorporated within said radiation-sensitive layer of the formula ##STR59## wherein R is hydrogen; an alkyl, cycloalkyl, haloalkyl, alkoxyalkyl or phenylalkyl substituent or a phenyl nucleus having a Hammett sigma-value-derived electron withdrawing characteristic more positive than -0.3; R 1 is a phenylene or alkyl, halo- or alkoxy-substituted phenylene group; R 2 is an alkyl, haloalkyl, alkoxyalkyl or phenylalkyl substituent 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; naphthyl or ##STR60## R 3 is hydrogen, benzyl, alkoxybenzyl, halobenzyl or alkylbenzyl; said alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms; and said cycloalkyl moieties have from 3 to 10 carbon atoms.

Claim 31

In a photographic element comprised of a support, and as a coating thereon. a radiation-sensitive silver halide emulsion layer comprised of silver halide grains capable of forming an internal latent image, the improvement comprising from 0.1 to 200 mg per mole of silver of acylhydrazinophenylthiourea nucleating agent included with said radiation-sensitive layer, said acylhydrazinophenylthiourea nucleating agent having the formula ##STR61## wherein R is a hydrogen, phenyl, alkylphenyl, cyanophenyl, halophenyl, alkoxyphenyl, alkyl, cycloalkyl, haloalkyl, alkoxyalkyl or a phenylalkyl substituent; R 1 is a para-phenylene or 3-alkyl, 3-halo- or 3-alkoxy-substituted para-phenylene group; R 2 is an alkyl substituent having from 1 to 12 carbon atoms; a cycloalkyl substituent; a haloalkyl, alkoxyalkyl or phenylalkyl substituent; phenyl or naphthyl; or an alkylphenyl, halophenyl or alkoxyphenyl substituent; R 3 is hydrogen, benzyl, 4-alkoxybenzyl, 4-halo-benzyl or 4-alkylbenzyl; said alkyl moieties of R have from 1 to 4 carbon atoms; said alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms; and said cycloalkyl moieties have from 3 to 10 carbon atoms.

Claim 32

In a photographic element comprised of a support, and as a coating thereon. a radiation-sensitive silver halide emulsion layer comprised of silver halide grains capable of forming an internal latent image, the improvement comprising from 0.1 to 200 mg per mole of silver of acylhydrazinophenylthiourea nucleating agent included with said radiation-sensitive layer, said acylhydrazinophenylthiourea nucleating agent having the formula ##STR61## wherein R is a hydrogen, phenyl, alkylphenyl, cyanophenyl, halophenyl, alkoxyphenyl, alkyl, cycloalkyl, haloalkyl, alkoxyalkyl or a phenylalkyl substituent; R 1 is a para-phenylene or 3-alkyl, 3-halo- or 3-alkoxy-substituted para-phenylene group; R 2 is an alkyl substituent having from 1 to 12 carbon atoms; a cycloalkyl substituent; a haloalkyl, alkoxyalkyl or phenylalkyl substituent; phenyl or naphthyl; or an alkylphenyl, halophenyl or alkoxyphenyl substituent; R 3 is hydrogen, benzyl, 4-alkoxybenzyl, 4-halo-benzyl or 4-alkylbenzyl; said alkyl moieties of R have from 1 to 4 carbon atoms; said alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms; and said cycloalkyl moieties have from 3 to 10 carbon atoms.

Claim 33

In a photographic element comprised of a support and, coated thereon, a photographic emulsion containing silver halide grains which are substantially unfogged on their surface and which are capable of forming an internal latent image, the improvement comprising a nucleating amount of at least one acylhydrazinophenylthiourea of the following formulas incorporated within said photographic emulsion ##STR62## wherein R is a hydrogen, phenyl, alkylphenyl, cyanophenyl, halophenyl, alkoxyphenyl, alkyl, cycloalkyl, haloalkyl, alkoxyalkyl or phenylalkyl substituent; R 1 is a para-phenylene or 3-alkyl, 3-halo- or 3-alkoxy-substituted para-phenylene group; R 2 is an alkyl substituent having from 1 to 12 carbon atoms; a cycloalkyl substituent; a haloalkyl, alkoxyalkyl or phenylalkyl substituent phenyl or naphthyl; or an alkylphenyl, halophenyl or alkoxyphenyl substituent; R 3 is hydrogen, benzyl, 4-alkoxybenzyl, 4-halobenzyl or 4-alkylbenzyl; said alkyl moieties of R have from 1 to 4 carbon atoms; said alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms; and said cycloalkyl moieties have from 3 to 10 carbon atoms.

Claim 34

In a photographic element comprised of a support and, coated thereon, a photographic emulsion containing silver halide grains which are substantially unfogged on their surface and which are capable of forming an internal latent image, the improvement comprising a nucleating amount of at least one acylhydrazinophenylthiourea of the following formulas incorporated within said photographic emulsion ##STR62## wherein R is a hydrogen, phenyl, alkylphenyl, cyanophenyl, halophenyl, alkoxyphenyl, alkyl, cycloalkyl, haloalkyl, alkoxyalkyl or phenylalkyl substituent; R 1 is a para-phenylene or 3-alkyl, 3-halo- or 3-alkoxy-substituted para-phenylene group; R 2 is an alkyl substituent having from 1 to 12 carbon atoms; a cycloalkyl substituent; a haloalkyl, alkoxyalkyl or phenylalkyl substituent phenyl or naphthyl; or an alkylphenyl, halophenyl or alkoxyphenyl substituent; R 3 is hydrogen, benzyl, 4-alkoxybenzyl, 4-halobenzyl or 4-alkylbenzyl; said alkyl moieties of R have from 1 to 4 carbon atoms; said alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms; and said cycloalkyl moieties have from 3 to 10 carbon atoms.

Claim 35

In a photographic element according to claim 23 the further improvement wherein the acylhydrazinophenylthiourea is present in an amount of from 1 to 25 mg per mole of silver.

Claim 36

In a photographic element according to claim 24 the further improvement wherein the acylhydrazinophenylthiourea is present in an amount of from 1 to 15 mg per mole of silver.

Claim 37

In a photographic element according to claim 23 the further improvement in which said photographic emulsion additionally contains at least one other hydrazide nucleating means, hydrazone nucleating means or N-substituted cycloammonium quaternary salt nucleating means dispersed therein.

Claim 38

In an image transfer film unit which comprises an image-receiving layer, at least one layer of a photographic emulsion containing silver halide grains which are substantially unfogged on their surfaces and which are capable of forming an internal latent image, means containing and capable of selectively introducing an alkaline processing composition into contact with said photographic emulsion layer, and a silver halide developing agent, the improvement comprising a nucleating amount of an acylhydrazinophenylthiourea of the formula ##STR63## wherein R is hydrogen; an alkyl, cycloalkyl, haloalkyl, alkoxyalkyl or phenylalkyl substituent or a phenyl nucleus having a Hammett sigma-value-derived electron withdrawing characteristic more positive than -0.3; R 1 is a phenylene or alkyl, halo- or alkoxy-substituted phenylene group; R 2 is an alkyl, haloalkyl, alkoxyalkyl or phenylalkyl substituent 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; naphthyl or ##STR64## R 3 is hydrogen, benzyl, alkoxybenzyl, halobenzyl or alkylbenzyl; said alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms; and said cycloalkyl moieties have from 3 to 10 carbon atoms.

Claim 39

In an image transfer film unit which comprises an image-receiving layer, at least one layer of a photographic emulsion containing silver halide grains which are substantially unfogged on their surfaces and which are capable of forming an internal latent image, means containing and capable of selectively introducing an alkaline processing composition into contact with said photographic emulsion layer, and a silver halide developing agent, the improvement comprising a nucleating amount of an acylhydrazinophenylthiourea of the formula ##STR63## wherein R is hydrogen; an alkyl, cycloalkyl, haloalkyl, alkoxyalkyl or phenylalkyl substituent or a phenyl nucleus having a Hammett sigma-value-derived electron withdrawing characteristic more positive than -0.3; R 1 is a phenylene or alkyl, halo- or alkoxy-substituted phenylene group; R 2 is an alkyl, haloalkyl, alkoxyalkyl or phenylalkyl substituent 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; naphthyl or ##STR64## R 3 is hydrogen, benzyl, alkoxybenzyl, halobenzyl or alkylbenzyl; said alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms; and said cycloalkyl moieties have from 3 to 10 carbon atoms.

Claim 40

In an image transfer film unit according to claim 27 the further improvement in which said film unit incorporates an antifoggant.

Claim 41

In an image transfer film unit according to claim 27 the further improvement in which said film unit additionally includes hydrazide, hydrazone or quaternary ammonium salt nucleating means.

Claim 42

An image transfer film unit comprising a. a photographic element including 1. a layer containing a blue-sensitive silver halide emulsion having associated therewith an immobile material capable of releasing a mobile yellow image dye,

Claim 43

An image transfer film unit comprising a. a photographic element including 1. a layer containing a blue-sensitive silver halide emulsion having associated therewith an immobile material capable of releasing a mobile yellow image dye,

Claim 44

a layer containing a green-sensitized silver halide emulsion having associated therewith an immobile material capable of releasing a mobile magenta image dye, and 3. a layer containing a red-sensitized silver halide emulsion having associated 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, said grains being substantially unfogged on their surfaces and being chemically sensitized on their surfaces 1. to a level which will provide a maximum density of less than 0.4 when developed in a test surface developer of the composition indicated below for 5 minutes at 27° C after exposure to a light intensity scale for a fixed time of from 1 × 10.sup. -2 to 1 second when said photosensitive composition is coated at a coverage of between about 3 and 4 g of silver per square meter, and 2. to at least a level which would provide a maximum density of at least 0.5 using undoped silver halide grains of the same grain size and halide composition when coated, exposed and developed in like manner, b. an image-receiving layer, c. means containing and adapted to introducing an alkaline processing composition into contact with said silver halide emulsions, d. a silver halide surface developing agent located in said processing composition of said photographic element, and e. from 0.5 to 25 mg per mole of silver of a nucleating agent incorporated within at least one of said silver halide emulsion layers, said nucleating agent having the formula ##STR65## wherein R is hydrogen, phenyl, alkylphenyl, cyanophenyl, halophenyl, alkoxyphenyl, alkyl cycloalkyl, haloalkyl, alkoxyalkyl or a phenylalkyl substituent; R 1 is a para-phenylene or 3-alkyl, 3-halo- or 3-alkoxy-substituted para-phenylene group; R 2 is an alkyl substituent having from 1 to 12 carbon atoms; a cycloalkyl substituent; a haloalkyl, alkoxyalkyl or phenylalkyl substituent; phenyl or naphthyl; or an alkylphenyl, cyanophenyl, halophenyl or alkoxyphenyl substituent; R 3 is hydrogen, benzyl, 4-alkoxybenzyl, 4-halobenzyl or 4-alkylbenzyl; said alkyl moieties of R have from 1 to 4 carbon atoms; said alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms; and said cycloalkyl moieties have from 3 to 10 carbon atoms; the test surface developer consisting essentially of: ______________________________________ water (52° C) 500.0 cc N-methyl-p-aminophenol sulfate 2.5 grams sodium sulfite, desiccated 30.0 grams hydroquinone 2.5 grams sodium metaborate 10.0 grams potassium bromide 10.0 grams water to make 1 liter. ______________________________________

Claim 45

a layer containing a green-sensitized silver halide emulsion having associated therewith an immobile material capable of releasing a mobile magenta image dye, and 3. a layer containing a red-sensitized silver halide emulsion having associated 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, said grains being substantially unfogged on their surfaces and being chemically sensitized on their surfaces 1. to a level which will provide a maximum density of less than 0.4 when developed in a test surface developer of the composition indicated below for 5 minutes at 27° C after exposure to a light intensity scale for a fixed time of from 1 × 10.sup. -2 to 1 second when said photosensitive composition is coated at a coverage of between about 3 and 4 g of silver per square meter, and 2. to at least a level which would provide a maximum density of at least 0.5 using undoped silver halide grains of the same grain size and halide composition when coated, exposed and developed in like manner, b. an image-receiving layer, c. means containing and adapted to introducing an alkaline processing composition into contact with said silver halide emulsions, d. a silver halide surface developing agent located in said processing composition of said photographic element, and e. from 0.5 to 25 mg per mole of silver of a nucleating agent incorporated within at least one of said silver halide emulsion layers, said nucleating agent having the formula ##STR65## wherein R is hydrogen, phenyl, alkylphenyl, cyanophenyl, halophenyl, alkoxyphenyl, alkyl cycloalkyl, haloalkyl, alkoxyalkyl or a phenylalkyl substituent; R 1 is a para-phenylene or 3-alkyl, 3-halo- or 3-alkoxy-substituted para-phenylene group; R 2 is an alkyl substituent having from 1 to 12 carbon atoms; a cycloalkyl substituent; a haloalkyl, alkoxyalkyl or phenylalkyl substituent; phenyl or naphthyl; or an alkylphenyl, cyanophenyl, halophenyl or alkoxyphenyl substituent; R 3 is hydrogen, benzyl, 4-alkoxybenzyl, 4-halobenzyl or 4-alkylbenzyl; said alkyl moieties of R have from 1 to 4 carbon atoms; said alkyl moieties, except as otherwise noted, in each instance include from 1 to 6 carbon atoms; and said cycloalkyl moieties have from 3 to 10 carbon atoms; the test surface developer consisting essentially of: ______________________________________ water (52° C) 500.0 cc N-methyl-p-aminophenol sulfate 2.5 grams sodium sulfite, desiccated 30.0 grams hydroquinone 2.5 grams sodium metaborate 10.0 grams potassium bromide 10.0 grams water to make 1 liter. ______________________________________

Claim 46

An image transfer film unit according to claim 30 wherein said nucleating agent is present in at least said red-sensitive silver halide layer.

Claim 47

An image transfer film unit according to claim 22 wherein said nucleating agent comprises one or a combination of the following nucleating agents: 1,3-bis[4-(2-formylhydrazino)phenyl]thiourea; 1,3-bis[4-(2-acetylhydrazino)phenyl]thiourea; 1,3-bis[4-(2-benzoylhydrazino)phenyl]thiourea; 1-[4-(2-formylhydrazino)phenyl-3-phenylthiourea; 1-[4-(2-acetylhydrazino)phenyl]-3-phenylthiourea; 1 1-[4-(2-benzoylhydrazino)phenyl]-3-phenylthiourea; 1-[4-(2formylhydrazino)phenyl]-3-methylthiourea; 1-[4-(2-acetylhydrazino)phenyl]-3-ethylthiourea; 1-[4-(2-formylhydrazino)phenyl]-3-butylthiourea; 1-[4-(2-formylhydrazino)phenyl]-3-cyclohexylthiourea; 1-[4-(2-formylhydrazino)phenyl]-3-benzylthiourea; 1-[4-(2-formylhydrazino)phenyl-3-hepthylthiourea; 1-[4-(2-formylhydrazino)phenyl-3-decylthiourea; 1-[4-(2-formylhydrazino)phenyl]-3-(4-cyanophenyl)-thiourea; 1-[4-(2-formylhydrazino)phenyl]-3-(4-methoxy-phenyl)thiourea; 1-[4-(2-formylhydrazino)-3-methoxyphenyl]-3-phenylthiourea; 1-[4-(2-formylhydrazino)-3-methoxyphenyl]-3-butylthiourea; 1-[4-(2-formylhydrazino)-3-methoxyphenyl]-3-cyclohexylthiourea; 1-[4-(2-formylhydrazino)-3-methoxyphenyl]-3-(4-methoxyphenyl)thiourea; 1-[4-(2-trifluoroacetylhydrazino)phenyl]-3-phenylthiourea; 1-{4-[2-(4-cyanobenzoyl)hydrazino]phenyl}-3-phenylthiourea; 1-{4-[2-(4-chlorobenzoyl)hydrazino]phenyl}-3-phenylthiourea; 1-{4-[2-(4-fluorobenzoyl)hydrazino]phenyl}-3-phenylthiourea; 1-{4-[2-(4-methylbenzoyl)hydrazino]phenyl}-3-phenylthiourea; 1-{4-[2-(4-methoxybenzoyl)hydrazino]-phenyl}-3-phenylthiourea; 1-{4-[2-(4-chlorobenzoyl)hydrazino[phenyl}-3-benzylthiourea; 1{4-[2-(4-fluorobenzoyl)hydrazino]phenyl}-3-benzylthiourea; 1-[4-(2-acetylhydrazino)phenyl]-1-benzyl-3-phenylthiourea; and 1-[4-(2-acetylhydrazino)phenyl]-1-(4-methoxybenzyl)-3-phenylthiourea.