Dry heat-activated bleaching of silver images

Claim 2

A silver dye-bleach process of thermally dye bleaching a photographic element comprising a silver image in association with a dye that is bleachable in a silver dye-bleach process comprising contacting said image with a dry, activator sheet comprising a support having thereon a layer or layers comprising (a) a non-volatile, diffusible acid selected from the group consisting of non-volatile, diffusible mineral acids and organic acids containing up to 10 carbon atoms, (b) a 3-substituted thiazoline, oxazoline, imidazoline or imidazolidine-2-thione silver halide complexing agent; and (c) a non-hydrolyzable polymeric vehicle wherein said sheet has an effective pH of up to 6.0 and is solid up to at least 50° C. with a melting point lower than 200° C.; and heating to a temperature within the range of about 50° C. to about 150° C. to laminate the sheet to the element and produce a dye image.

Claim 3

The process of claim 1 wherein the activator sheet also contains a non-hydrolyzable thermal solvent containing up to 10 carbon atoms.

Claim 4

The process of claim 1 wherein the bleachable dye is an azo dye.

Claim 5

The process of claim 1 wherein the activator sheet also contains a dye-bleach catalyst.

Claim 6

The process of claim 1 wherein the complexing agent has the structure ##STR20## wherein Z is S, O or NR 1 and wherein R and R 1 are independently selected from the group consisting of an aliphatic organic radical and an aromatic organic radical; wherein neither R nor R 1 contains a terminal alcoholic OH group; X represents the atoms necessary to close a 5-membered unsaturated or saturated heterocyclic ring and wherein X can be aryl-substituted or fused to an aryl group; and, wherein said complexing agent contains a total of 20 carbon atoms or less.

Claim 7

The process of claim 1 wherein the mineral or organic acid is selected from the group consisting of sulfuric acid, acetic acid, citric acid, phenylphosphoric acid, phenylphosphonic acid, phenylphosphinic acid, para-toluenesulfonic acid, benzenesulfonic acid, and carboxylic acids containing up to 10 carbon atoms.

Claim 8

The process of claim 1 wherein the activator sheet also contains a non-hydrolyzable thermal solvent which is selected from the group consisting of poly(ethylene glycol), poly(ethylene oxide), decanediol and hexanediol.

Claim 9

The process of claim 1 wherein the activator sheet comprises from about 1.0 g/m 2 to about 50 g/m 2 of a mineral or organic acid, from about 1.0 g/m 2 to about 50 g/m 2 of a substituted heterocyclic thiazoline, oxazoline, imidazoline or imidazolidine silver halide complexing agent, and from about 1.0 g/m 2 to about 50 g/m 2 of a non-hydrolyzable polymeric vehicle.

Claim 10

A silver dye-bleach process of thermally dye bleaching a photographic element comprising a silver image in association with a dye that is bleachable in a silver dye-bleach process comprising contacting said image with a dry, activator sheet comprising a support having thereon a layer or layers comprising (a) a non-volatile, diffusible acid consisting essentially of para-toluenesulfonic acid, (b) a silver halide complexing agent consisting essentially of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione, and (c) a non-hydrolyzable, polymeric vehicle consisting essentially of poly(vinylpyrrolidone), wherein said layer or layers has an effective pH of up to 6.0 and is solid up to 50° C. with a melting point lower than 200° C.; and heating the resulting laminate to a temperature within the range of about 50° C. to about 150° C. to laminate the sheet to the element and produce a dye image.

Claim 11

A silver dye-bleach process of thermally dye bleaching a photographic element comprising a silver image in association with a dye that is bleachable in a silver dye-bleach process comprising contacting said image with a dry, activator sheet comprising a support having thereon a layer or layers comprising (a) a non-volatile, diffusible acid consisting essentially of para-toluenesulfonic acid, (b) a silver halide complexing agent consisting essentially of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione, and (c) a non-hydrolyzable, polymeric vehicle consisting essentially of poly(vinylpyrrolidone), wherein said layer or layers has an effective pH of up to 6.0 and is solid up to 50° C. with a melting point lower than 200° C.; and heating the resulting laminate to a temperature within the range of about 50° C. to about 150° C. to laminate the sheet to the element and produce a dye image.

Claim 12

A silver dye-bleach process of thermally dye bleaching a photographic element comprising a silver image in association with a dye that is bleachable in a silver dye-bleach process comprising contacting said image, in the absence of a silver dye-bleach catalyst, with a dry, activator sheet comprising a support having thereon a layer or layers comprising (a) a non-volatile, diffusible acid selected from the group consisting of non-volatile, diffusible mineral acids and organic acids containing up to 10 carbon atoms, (b) a 3-substituted thiazoline, oxazoline, imidazoline or imidazolidine-2-thione silver halide complexing agent; and (c) a non-hydrolyzable polymeric vehicle wherein said sheet has an effective ph of up to 6.0 and is solid up to at least 50° C. with a melting point lower than 200° C.; and heating to a temperature within the range of about 50° C. to about 150° C. to laminate the sheet to the element and produce a dye image.

Claim 13

A silver dye-bleach process of thermally dye bleaching a photographic element comprising a silver image in association with a dye that is bleachable in a silver dye-bleach process comprising contacting said image, in the absence of a silver dye-bleach catalyst, with a dry, activator sheet comprising a support having thereon a layer or layers comprising (a) a non-volatile, diffusible acid selected from the group consisting of non-volatile, diffusible mineral acids and organic acids containing up to 10 carbon atoms, (b) a 3-substituted thiazoline, oxazoline, imidazoline or imidazolidine-2-thione silver halide complexing agent; and (c) a non-hydrolyzable polymeric vehicle wherein said sheet has an effective ph of up to 6.0 and is solid up to at least 50° C. with a melting point lower than 200° C.; and heating to a temperature within the range of about 50° C. to about 150° C. to laminate the sheet to the element and produce a dye image.

Claim 14

The process of claim 10 wherein the activator sheet also contains a non-hydrolyzable thermal solvent containing up to 10 carbon atoms.

Claim 15

The process of claim 10 wherein the activator sheet also contains a non-hydrolyzable thermal solvent which is selected from the group consisting of poly(ethylene glycol), poly(ethylene oxide), decanediol and hexanediol.

Claim 16

The process of claim 10 wherein the complexing agent has the structure ##STR21## wherein Z is S, O or NR 1 and wherein R and R 1 are independently selected from the group consisting of an aliphatic organic radical and an aromatic organic radical; wherein neither R nor R 1 contains a terminal alcoholic OH group; X represents the atoms necessary to close a 5-membered unsaturated or saturated heterocyclic ring and wherein X can be aryl-substituted or fused to an aryl group; and, wherein said complexing agent contains a total of 20 carbon atoms or less.

Claim 17

The process as in claim 10 wherein the complexing agent consists essentially of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione.

Claim 18

The process as in claim 10 wherein the mineral or organic acid is selected from the group consisting of sulfuric acid, acetic acid, citric acid, phenylphosphoric acid, phenylphosphonic acid, phenylphosphinic acid, para-toluenesulfonic acid, benzenesulfonic acid, and carboxylic acids containing up to 10 carbon atoms.

Claim 19

A silver dye-bleach process of thermally dye bleaching a photographic element comprising a silver image in association with a dye that is bleachable in a silver dye-bleach process comprising contacting said image, in the absence of a silver dye-bleach catalyst, with a dry, activator sheet comprising a support having thereon a layer or layers comprising (a) a non-volatile, diffusible acid consisting essentially of para-toluenesulfonic acid, (b) a silver halide complexing agent consisting essentially of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione, and (c) a non-hydrolyzable, polymeric vehicle consisting essentially of poly(vinylpyrrolidone), wherein said layer or layers has an effective pH of up to 4.0 and is solid up to 50° C. with a melting point lower than 200° C.; and heating the resulting laminate to a temperature within the range of about 50° C. to about 150° C. to laminate the sheet to the element and produce a dye image.

Claim 20

A silver dye-bleach process of thermally dye bleaching a photographic element comprising a silver image in association with a dye that is bleachable in a silver dye-bleach process comprising contacting said image, in the absence of a silver dye-bleach catalyst, with a dry, activator sheet comprising a support having thereon a layer or layers comprising (a) a non-volatile, diffusible acid consisting essentially of para-toluenesulfonic acid, (b) a silver halide complexing agent consisting essentially of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione, and (c) a non-hydrolyzable, polymeric vehicle consisting essentially of poly(vinylpyrrolidone), wherein said layer or layers has an effective pH of up to 4.0 and is solid up to 50° C. with a melting point lower than 200° C.; and heating the resulting laminate to a temperature within the range of about 50° C. to about 150° C. to laminate the sheet to the element and produce a dye image.

Claim 21

A silver dye-bleach process of thermally dye bleaching a photographic element comprising a silver image in association with a dye that is bleachable in a silver dye-bleach process comprising contacting said image with a dry, activator sheet comprising a support having thereon a layer comprising (a) a non-volatile, diffusible acid selected from the group consisting of phenylphosphonic acid, phenylphosphoric acid, phenylphosphinic acid, sulfuric acid, acetic acid, citric acid, para-toluenesulfonic acid, benzene sulfonic acid and carboxylic acids containing up to 10 carbon atoms, (b) a 3-substituted thiazoline, oxazoline, imidazoline or imidazolidine-2-thione silver halide complexing agent and (c) a non-hydrolyzable polymeric vehicle selected from the group consisting of poly(styrene sulfonic acid), poly(ethylene oxide), poly(acrylamide), poly(acrylic acid), poly(vinylpyrrolidone) and poly(vinyl alcohol) vehicles, wherein said sheet has an effective pH up to 6.0 and is solid up to at least 50° C. with a melting point lower than 200° C.; and heating to a temperature within the range of about 50° C. to about 150° C. to laminate the sheet to the element and produce a dye image.

Claim 22

A silver dye-bleach process of thermally dye bleaching a photographic element comprising a silver image in association with a dye that is bleachable in a silver dye-bleach process comprising contacting said image with a dry, activator sheet comprising a support having thereon a layer comprising (a) a non-volatile, diffusible acid selected from the group consisting of phenylphosphonic acid, phenylphosphoric acid, phenylphosphinic acid, sulfuric acid, acetic acid, citric acid, para-toluenesulfonic acid, benzene sulfonic acid and carboxylic acids containing up to 10 carbon atoms, (b) a 3-substituted thiazoline, oxazoline, imidazoline or imidazolidine-2-thione silver halide complexing agent and (c) a non-hydrolyzable polymeric vehicle selected from the group consisting of poly(styrene sulfonic acid), poly(ethylene oxide), poly(acrylamide), poly(acrylic acid), poly(vinylpyrrolidone) and poly(vinyl alcohol) vehicles, wherein said sheet has an effective pH up to 6.0 and is solid up to at least 50° C. with a melting point lower than 200° C.; and heating to a temperature within the range of about 50° C. to about 150° C. to laminate the sheet to the element and produce a dye image.

Claim 23

The process of claim 17 wherein the activator sheet also comprises a silver dye-bleach catalyst.

Claim 24

A silver dye-bleach process of thermally dye bleaching a photographic element comprising a silver image in association with a dye that is bleachable in a silver dye-bleach process comprising contacting said image, in the absence of a silver dye-bleach catalyst, with a dry, activator sheet comprising a support having thereon a layer comprising (a) a non-volatile, diffusible acid selected from the group consisting of phenylphosphonic acid, phenylphosphoric acid, phenylphosphinic acid, sulfuric acid, acetic acid, citric acid, para-toluenesulfonic acid, benzene sulfonic acid and carboxylic acids containing up to 10 carbon atoms, (b) a 3-substituted thiazoline, oxazoline, imidazoline or imidazolidine-2-thione silver halide complexing agent and (c) a non-hydrolyzable polymeric vehicle selected from the group consisting of poly(styrene sulfonic acid), poly(ethylene oxide), poly(acrylamide), poly(acrylic acid), poly(vinylpyrrolidone) and poly(vinyl alcohol) vehicles, wherein said sheet has an effective pH of up to 6.0 and is solid up to at least 50° C. with a melting point lower than 200° C.; and heating to a temperature within the range of about 50° C. to about 150° C. to laminate the sheet to the element and produce a dye image.

Claim 25

A silver dye-bleach process of thermally dye bleaching a photographic element comprising a silver image in association with a dye that is bleachable in a silver dye-bleach process comprising contacting said image, in the absence of a silver dye-bleach catalyst, with a dry, activator sheet comprising a support having thereon a layer comprising (a) a non-volatile, diffusible acid selected from the group consisting of phenylphosphonic acid, phenylphosphoric acid, phenylphosphinic acid, sulfuric acid, acetic acid, citric acid, para-toluenesulfonic acid, benzene sulfonic acid and carboxylic acids containing up to 10 carbon atoms, (b) a 3-substituted thiazoline, oxazoline, imidazoline or imidazolidine-2-thione silver halide complexing agent and (c) a non-hydrolyzable polymeric vehicle selected from the group consisting of poly(styrene sulfonic acid), poly(ethylene oxide), poly(acrylamide), poly(acrylic acid), poly(vinylpyrrolidone) and poly(vinyl alcohol) vehicles, wherein said sheet has an effective pH of up to 6.0 and is solid up to at least 50° C. with a melting point lower than 200° C.; and heating to a temperature within the range of about 50° C. to about 150° C. to laminate the sheet to the element and produce a dye image.

Claim 26

A heat developable, photographic element for a dry, thermal silver dye-bleach process comprising a support having thereon (A) a first layer comprising (1) photosensitive silver halide, (2) an image-forming combination comprising (i) an organic, silver salt oxidizing agent with (ii) a reducing agent, (3) a polymeric binder and (4) a dye that is bleachable in a silver dye-bleach process, and, contiguous to (A), a second layer comprising (a) a non-volatile, diffusible acid selected from the group consisting of phenylphosphonic acid, phenylphosphoric acid, phenylphosphinic acid, sulfuric acid, acetic acid, citric acid, para-toluenesulfonic acid, benzene sulfonic acid and carboxylic acids containing up to 10 carbon atoms, (b) a 3-substituted thiazoline, oxazoline, imidazoline or imidazolidine-2-thione silver halide complexing agent and (c) a non-hydrolyzable polymeric vehicle selected from the group consisting of poly(styrene sulfonic acid), poly(ethylene oxide), poly(acrylamide), poly(acrylic acid), poly(vinylpyrrolidone) and poly(vinyl alcohol) vehicles, wherein said second layer has an effective pH of up to 4.0 and is solid up to at least 50° C. with a melting point lower than 200° C.

Claim 27

A heat developable, photographic element for a dry, thermal silver dye-bleach process comprising a support having thereon (A) a first layer comprising (1) photosensitive silver halide, (2) an image-forming combination comprising (i) an organic, silver salt oxidizing agent with (ii) a reducing agent, (3) a polymeric binder and (4) a dye that is bleachable in a silver dye-bleach process, and, contiguous to (A), a second layer comprising (a) a non-volatile, diffusible acid selected from the group consisting of phenylphosphonic acid, phenylphosphoric acid, phenylphosphinic acid, sulfuric acid, acetic acid, citric acid, para-toluenesulfonic acid, benzene sulfonic acid and carboxylic acids containing up to 10 carbon atoms, (b) a 3-substituted thiazoline, oxazoline, imidazoline or imidazolidine-2-thione silver halide complexing agent and (c) a non-hydrolyzable polymeric vehicle selected from the group consisting of poly(styrene sulfonic acid), poly(ethylene oxide), poly(acrylamide), poly(acrylic acid), poly(vinylpyrrolidone) and poly(vinyl alcohol) vehicles, wherein said second layer has an effective pH of up to 4.0 and is solid up to at least 50° C. with a melting point lower than 200° C.

Claim 28

A heat developable, photographic element for a dry, thermal silver dye-bleach process comprising, respectively, a support having thereon (A) a first layer comprising (1) photosensitive silver halide, (2) an image-forming combination comprising (i) an organic, silver salt oxidizing agent with (ii) a reducing agent, (3) a polymeric binder, and (4) a dye that is bleachable in a silver dye-bleach process, and, contiguous to (A), a second layer comprising (a) a non-volatile, diffusible acid selected from the group consisting of non-volatile, diffusible mineral acids and organic acids containing up to 10 carbon atoms; (b) a 3-substituted thiazoline, oxazoline, imidazoline or imidazolidine-2-thione silver halide complexing agent; and (c) a non-hydrolyzable polymeric vehicle, wherein said second layer has an effective pH of up to 4.0 and is solid up to at least 50° C. with a melting point lower than 200° C.

Claim 29

A heat developable, photographic element for a dry, thermal silver dye-bleach process comprising, respectively, a support having thereon (A) a first layer comprising (1) photosensitive silver halide, (2) an image-forming combination comprising (i) an organic, silver salt oxidizing agent with (ii) a reducing agent, (3) a polymeric binder, and (4) a dye that is bleachable in a silver dye-bleach process, and, contiguous to (A), a second layer comprising (a) a non-volatile, diffusible acid selected from the group consisting of non-volatile, diffusible mineral acids and organic acids containing up to 10 carbon atoms; (b) a 3-substituted thiazoline, oxazoline, imidazoline or imidazolidine-2-thione silver halide complexing agent; and (c) a non-hydrolyzable polymeric vehicle, wherein said second layer has an effective pH of up to 4.0 and is solid up to at least 50° C. with a melting point lower than 200° C.

Claim 30

A heat developable, photographic element as in claim 21 wherein the non-hydrolyzable polymeric vehicle is a member selected from the group consisting of poly(styrene sulfonic acid), poly(ethylene oxide), poly(acrylamide), poly(acrylic acid), poly(vinylpyrrolidone), and poly(vinyl alcohol).

Claim 31

A heat developable, photographic element for a dry, thermal silver dye-bleach process comprising, respectively, a support having thereon (A) a first layer comprising (1) photosensitive silver halide, (2) an image-forming combination comprising (i) an organic, silver salt oxidizing agent, (3) a polymeric binder, and (4) a dye that is bleachable in a silver dye-bleach process, and, contiguous to (A), a second layer comprising (a) a non-volatile, diffusible acid selected from the group consisting of non-volatile, diffusible mineral acids and organic acids containing up to 10 carbon atoms; (b) a silver halide complexing agent having the structure ##STR22## wherein R is an aliphatic radical containing from 1 to 12 carbon atoms which has a terminal acidic hydrogen atom bonded to an oxygen atom and salts thereof; R 2 and R 3 are independently selected from the group consisting of hydrogen, aliphatic radicals and phenyl; or, R 2 and R 3 taken together form a 6 to 12 carbon atom containing aromatic ring or a 5 to 7 member alicyclic ring, and (c) a non-hydrolyzable polymeric vehicle, wherein said second layer has an effective pH up to 4.0 and is solid up to at least 50° C. with a melting point lower than 200° C.

Claim 32

A heat developable, photographic element for a dry, thermal silver dye-bleach process comprising, respectively, a support having thereon (A) a first layer comprising (1) photosensitive silver halide, (2) an image-forming combination comprising (i) an organic, silver salt oxidizing agent, (3) a polymeric binder, and (4) a dye that is bleachable in a silver dye-bleach process, and, contiguous to (A), a second layer comprising (a) a non-volatile, diffusible acid selected from the group consisting of non-volatile, diffusible mineral acids and organic acids containing up to 10 carbon atoms; (b) a silver halide complexing agent having the structure ##STR22## wherein R is an aliphatic radical containing from 1 to 12 carbon atoms which has a terminal acidic hydrogen atom bonded to an oxygen atom and salts thereof; R 2 and R 3 are independently selected from the group consisting of hydrogen, aliphatic radicals and phenyl; or, R 2 and R 3 taken together form a 6 to 12 carbon atom containing aromatic ring or a 5 to 7 member alicyclic ring, and (c) a non-hydrolyzable polymeric vehicle, wherein said second layer has an effective pH up to 4.0 and is solid up to at least 50° C. with a melting point lower than 200° C.

Claim 33

A heat developable, photographic element as in claim 23 wherein said complexing agent consists essentially of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione.