Radiation-sensitive compositions and photographic elements containing N-(acylhydrazinophenyl) thioamide nucleating agents

A radiation-sensitive silver halide emulsion comprising silver halide grains capable of forming an internal latent image when coated on a photographic element and exposed to actinic radiation and, adsorbed to the surface of said silver halide grains, a nucleating amount of a heterocyclic N-(acylhydrazinophenyl)thioamide nucleating agent having the formula ##STR24## wherein:

• A is .dbd.N--R.sup.2, --S-- or --O--;
• Q.sup.3 is represented by the formula ##STR25## X is .dbd.S or .dbd.O;
• T.sup.1 is ##STR26## R.sup.3 is an alkyl substituent;
• R.sup.4 is an alkyl, ##STR27## or alkoxy substituent;
• Z represents the nonmetallic atoms necessary to complete a basic heterocyclic nucleus of the type found in cyanine dyes having ring-forming atoms chosen from the class consisting of carbon, nitrogen, oxygen, sulfur and selenium;
• n and d are independently chosen from the integers 1 and 2;
• R.sup.8 is hydrogen, phenyl, methyl, ethyl, propyl or butyl;
• R.sup.9 is a meta- or para-phenylene group;
• R.sup.2, r.sup.5 and R.sup.6 are independently chosen from hydrogen, phenyl, alkyl, alkylphenyl and phenylalkyl;
• and
• said alkyl moieties in each instance include from 1 to 6 carbon atoms.

A radiation-sensitive silver halide emulsion comprising

• (1) monodispersed silver halide grains having 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.degree. 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;
• and
• (2) adsorbed to the surface of said silver halide grains, 0.5 to 25 mg per mole of silver of a heterocyclic N-(acylhydrazinophenyl)thioamide nucleating agent having the formula ##STR28## wherein:
• A is .dbd.N--R.sup.2, --S-- or --O--;
• Q.sup.3 is represented by the formula ##STR29## X is .dbd.S or .dbd.O;
• T.sup.1 is ##STR30## R.sup.3 is an alkyl substituent;
• R.sup.4 is an alkyl ##STR31## or alkoxy substituent;
• Z represents the nonmetallic atoms necessary to complete a basic heterocyclic nucleus of the type found in cyanine dyes having ring-forming atoms chosen from the class consisting of carbon, nitrogen, oxygen, sulfur and selenium;
• n and d are independently chosen from the integers 1 and 2;
• R.sup.8 is hydrogen, phenyl, methyl, ethyl, propyl or butyl;
• R.sup.2, r.sup.5 and R.sup.6 are independently chosen from hydrogen, phenyl, akyl, alkylphenyl and phenylalkyl;
• said alkyl moieties in each instance include from 1 to 6 carbon atoms;
• and
• wherein the surface developer composition consists essentially of
• ______________________________________ water (52.degree. 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 liter. ______________________________________

A photographic element comprising a support and, as a coating thereon, at last one radiation-sensitive silver halide emulsion layer comprised of silver halide grains capable of forming an internal latent image when coated in a photographic element and exposed to actinic radiation and, adsorbed to the surface of said silver halide grains, a nucleating amount of a heterocyclic N-(acylhydrazinophenyl)thioamide nucleating agent having the formula ##STR32## wherein:

• R.sup.1 is a phenylene group;
• A is a .dbd.N--R.sup.2, --S-- or --O--;
• Q.sup.1 represents the atoms necessary to complete a five-membered heterocyclic nucleus;
• R.sup.2 and R.sup.7 are independently chosen from hydrogen, phenyl, alkyl, alkylphenyl and phenylalkyl;
• and
• said alkyl moieties in each instance include from 1 to 6 carbon atoms.

A photographic element comprising a support and, as a coating thereon, at least one radiation-sensitive silver halide emulsion layer comprised of

• silver halide grains containing a metal dopant therein which 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 1 .times. 10.sup.-2 to 1 second and developed for 5 minutes at 25.degree. C in a surface developer of the composition indicated below and which provide a maximum optical density at least five times greater than the above maximum optical density when the above procedure is repeatedly additionally including in the surface developer 0.5 gram per liter of potassium iodide to form an internal developer and,
• adsorbed to the surface of said silver halide grains, from 0.5 to 25 mg per mole of silver of a heterocyclic N-(acylhydrazinophenyl)thioamide nucleating agent of the formula ##STR37## wherein:
• A is .dbd.N--R.sup.2, --S-- or --O--;
• Q.sup.3 is represented by the formula ##STR38## X is .dbd.S or .dbd.O;
• T.sup.1 is:
• ##STR39## R.sup.3 is an alkyl substituent;
• R.sup.4 is an alkyl, ##STR40## or alkoxy substituent;
• Z represents the nonmetallic atoms necessary to complete a basic heterocyclic nucleus of the type found in cyanine dyes having ring-forming atoms chosen from the class consisting of carbon, nitrogen, oxygen, sulfur and selenium;
• n and d are independently chosen from the integers 1 and 2;
• R.sup.8 is hydrogen, phenyl, methyl, ethyl, propyl or butyl;
• R.sup.9 is a meta- or para-phenylene group;
• R.sup.2, r.sup.5 and R.sup.6 are independently chosen from hydrogen, phenyl, alkyl, alkylphenyl and phenylalkyl;
• said alkyl moieties in each instance include from 1 to 6 carbon atoms;
• and
• wherein the surface developer composition consists essentially of
• ______________________________________ water (52.degree. 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 liter. ______________________________________

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 a heterocyclic N-(acylhydrazinophenyl)thioamide nucleating agent incorporated within said photographic emulsion layer having the formula ##STR41## wherein:
• R.sup.1 is a phenylene group;
• A is .dbd.N--R.sup.2, --S-- or --O--;
• Q.sup.1 represents the atoms necessary to complete a five-membered heterocyclic nucleus;
• R.sup.2 and R.sup.7 are independently chosen from hydrogen, phenyl, alkyl, alkylphenyl and phenylalkyl;
• and
• said alkyl moieties in each instance include from 1 to 6 carbon atoms.

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,
• (2) a layer containing a green-sensitized silver halid 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
• (i) 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.degree. C after exposure to a light intensity scale for a fixed time of from 1 .times. 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
• (ii) 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 for introducing an alkaline processing composition into contact with said silver halide emulsions,
• (d) a silver halide surface developing agent located in said processing composition or 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 ##STR42## wherein:
• A is .dbd.N--R.sup.2, --S-- or --O--;
• Q.sup.3 is represented by the formula ##STR43## X is .dbd.S or .dbd.O;
• T.sup.1 is ##STR44## R.sup.3 is an alkyl substituent;
• R.sup.4 is an alkyl, ##STR45## or alkoxy substituent;
• Z represents the nonmetallic atoms necessary to complete a basis heterocyclic nucleus of the type found in cyanine dyes having ring-forming atoms chosen from the class consisting of carbon, nitrogen, oxygen, sulfur and selenium;
• n and d are independently chosen from the integers 1 and 2;
• R.sup.8 is hydrogen, phenyl, methyl, ethyl, propyl or butyl;
• R.sup.9 is a meta- or para-phenylene group;
• R.sup.2, r.sub.5 and R.sup.6 are independently chosen from hydrogen, phenyl, alkyl, alkylphenyl and phenylalkyl;
• said alkyl moieties in each instance include from 1 to 6 carbon atoms;
• the test surface developer consisting essentially of:
• ______________________________________ Water (53.degree. 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 liter. ______________________________________