Peroxide redox amplification imaging using manganese catalyst images

Claim 1

A method of forming a dye image comprising: imagewise reducing a cobalt(III) complex to cobalt(II) to form an immobile cobalt complex image in an imaging layer of a photographic element, forming in the imaging layer an immobile catalytic manganese complex image which is a reversal of the cobalt complex image, said manganese complex image exhibiting a substantially higher degree of catalytic activity than said reversal immobile cobalt complex image, and employing the imaging layer containing the immobile catalytic manganese complex image and the reversal cobalt complex image as a catalyst in a peroxide redox amplification reaction occurring at the site of said manganese complex image to form a dye image.

Claim 2

A method of forming a dye image comprising: imagewise reducing a cobalt(III) complex to cobalt(II) to form an immobile cobalt complex image in an imaging layer of a photographic element, forming in the imaging layer an immobile catalytic manganese complex image which is a reversal of the cobalt complex image, said manganese complex image exhibiting a substantially higher degree of catalytic activity than said reversal immobile cobalt complex image, and employing the imaging layer containing the immobile catalytic manganese complex image and the reversal cobalt complex image as a catalyst in a peroxide redox amplification reaction occurring at the site of said manganese complex image to form a dye image.

Claim 11

A method of forming a dye image comprising: imagewise reducing a cobalt(III) complex to cobalt(II) to form an immobile cobalt complex image in an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of an agent capable of complexing with manganese ions and, preferentially, cobalt(II) ions and radiation-responsive means capable of permitting an imagewise distribution of cobalt(II) ions to be formed, defining a catalytic image which is a reversal of the immobile cobalt comlex image by providing manganese ions in association with the complexing agent before or after the immobile cobalt complex image is formed and removing manganese ions from the element layer not associated with the complexing agent after the cobalt and manganese complex images are formed to leave in immobile catalytic manganese image and a complementary immobile cobalt complex image, said manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, contacting the layer containing the immobile catalytic manganese complex image and the complementary immobile cobalt complex image with a peroxide oxidizing agent and a reducing agnet which upon oxidation provides a dye-image-generating reaction product, wherein the peroxide oxidizing agent and the reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, and selectively reacting the peroxide oxidizing agent and the reducing agent at the site of the immobile catalytic manganese complex to permit a dye image to be formed which is a reversal of the image pattern of the immobile cobalt complex.

Claim 12

A method of forming a dye image comprising: imagewise reducing a cobalt(III) complex to cobalt(II) to form an immobile cobalt complex image in an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of an agent capable of complexing with manganese ions and, preferentially, cobalt(II) ions and radiation-responsive means capable of permitting an imagewise distribution of cobalt(II) ions to be formed, defining a catalytic image which is a reversal of the immobile cobalt comlex image by providing manganese ions in association with the complexing agent before or after the immobile cobalt complex image is formed and removing manganese ions from the element layer not associated with the complexing agent after the cobalt and manganese complex images are formed to leave in immobile catalytic manganese image and a complementary immobile cobalt complex image, said manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, contacting the layer containing the immobile catalytic manganese complex image and the complementary immobile cobalt complex image with a peroxide oxidizing agent and a reducing agnet which upon oxidation provides a dye-image-generating reaction product, wherein the peroxide oxidizing agent and the reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, and selectively reacting the peroxide oxidizing agent and the reducing agent at the site of the immobile catalytic manganese complex to permit a dye image to be formed which is a reversal of the image pattern of the immobile cobalt complex.

Claim 17

A method of forming a dye image comprising: providing an element comprised of a support and, as a coating thereon, at least one layer containing a substantially uniform distribution of a complexing agent, an imagewise distribution of cobalt ions associated with the complexing agent to form an immobile cobalt complex image and a complementary imagewise distribution of manganese ions associated with the complexing agent to form an immobile, catalytic manganese complex reversal image, said manganese complex image exhibiting a substantially higher degree of catalytic activity than said reversal immobile cobalt complex image, contacting the layer containing the immobile catalytic manganese complex reversal image and the immobile cobalt complex image with a peroxide oxidizing agent and a reducing agent which upon oxidation provides a dye-image-generating reaction product, wherein the peroxide oxidizing agent and the reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, and selectively reacting the peroxide oxidizing agent and the reducing agent at the site of the immobile catalytic manganese complex reversal image to permit a dye image to be formed which is a reversal of the image pattern of the cobalt complex.

Claim 18

A method of forming a dye image comprising: providing an element comprised of a support and, as a coating thereon, at least one layer containing a substantially uniform distribution of a complexing agent, an imagewise distribution of cobalt ions associated with the complexing agent to form an immobile cobalt complex image and a complementary imagewise distribution of manganese ions associated with the complexing agent to form an immobile, catalytic manganese complex reversal image, said manganese complex image exhibiting a substantially higher degree of catalytic activity than said reversal immobile cobalt complex image, contacting the layer containing the immobile catalytic manganese complex reversal image and the immobile cobalt complex image with a peroxide oxidizing agent and a reducing agent which upon oxidation provides a dye-image-generating reaction product, wherein the peroxide oxidizing agent and the reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, and selectively reacting the peroxide oxidizing agent and the reducing agent at the site of the immobile catalytic manganese complex reversal image to permit a dye image to be formed which is a reversal of the image pattern of the cobalt complex.

Claim 19

A method of forming a dye image comprising: imagewise reducing a cobalt(III) complex to cobalt(II) to form an image pattern of an immobile catalytic manganese complex comprised of manganese ions in coordination with a complexing agent capable of complexing with cobalt(II) ions in preference to manganese ions and a complementary immobile cobalt complex image, said manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, by imagewise displacement of manganese ions from an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of the immobile catalytic manganese complex and a radiation-responsive means capable of permitting an imagewise distribution of cobalt(II) ions to be formed, selectively removing from the element the imagewise-displaced manganese ions, contacting the layer containing the immobile catalytic manganese complex image and the immobile cobalt complex image with a peroxide oxidizing agent and a reducing agent which upon oxidation provides a dye-image-generating reaction product, wherein the peroxide oxidizing agent and the reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, and selectively reacting the peroxide oxidizing agent and the reducing agent at the site of the immobile catalytic manganese complex image to permit a corresponding dye image to be formed.

Claim 20

A method of forming a dye image comprising: imagewise reducing a cobalt(III) complex to cobalt(II) to form an image pattern of an immobile catalytic manganese complex comprised of manganese ions in coordination with a complexing agent capable of complexing with cobalt(II) ions in preference to manganese ions and a complementary immobile cobalt complex image, said manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, by imagewise displacement of manganese ions from an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of the immobile catalytic manganese complex and a radiation-responsive means capable of permitting an imagewise distribution of cobalt(II) ions to be formed, selectively removing from the element the imagewise-displaced manganese ions, contacting the layer containing the immobile catalytic manganese complex image and the immobile cobalt complex image with a peroxide oxidizing agent and a reducing agent which upon oxidation provides a dye-image-generating reaction product, wherein the peroxide oxidizing agent and the reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, and selectively reacting the peroxide oxidizing agent and the reducing agent at the site of the immobile catalytic manganese complex image to permit a corresponding dye image to be formed.

Claim 21

A method of forming a dye image comprising: forming an immobile catalytic manganese complex image in an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of an immobile catalytic manganese complex and a radiation-sensitive silver halide, comprising: imagewise-exposing the element layer to actinic radiation, developing the element to produce a silver image, bleaching the silver image with a cobalt(III) complex bleaching agent to form cobalt(II) ions as one reaction product, and displacing manganese from the manganese complex with the cobalt(II) ions form the immobile catalytic manganese complex image and a complementary immobile cobalt complex image, said manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, selectively removing from the element the manganese displaced from the manganese complex, contacting the layer containing the immobile catalytic manganese complex image and immobile cobalt complex image with a peroxide oxidizing agent and a reducing agent which upon oxidation provides a dye-image-generating reaction product, wherein the peroxide oxidizing agent and the reducing agent are chosen so that they are essentially inert to oxidiation-reduction in the absence of a catalyst, and selectively reacting the peroxide oxidizing agent and the reducing agent at the site of the immobile catalytic manganese complex image to permit a dye image to be formed.

Claim 22

A method of forming a dye image comprising: forming an immobile catalytic manganese complex image in an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of an immobile catalytic manganese complex and a radiation-sensitive silver halide, comprising: imagewise-exposing the element layer to actinic radiation, developing the element to produce a silver image, bleaching the silver image with a cobalt(III) complex bleaching agent to form cobalt(II) ions as one reaction product, and displacing manganese from the manganese complex with the cobalt(II) ions form the immobile catalytic manganese complex image and a complementary immobile cobalt complex image, said manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, selectively removing from the element the manganese displaced from the manganese complex, contacting the layer containing the immobile catalytic manganese complex image and immobile cobalt complex image with a peroxide oxidizing agent and a reducing agent which upon oxidation provides a dye-image-generating reaction product, wherein the peroxide oxidizing agent and the reducing agent are chosen so that they are essentially inert to oxidiation-reduction in the absence of a catalyst, and selectively reacting the peroxide oxidizing agent and the reducing agent at the site of the immobile catalytic manganese complex image to permit a dye image to be formed.

Claim 31

A method of forming a dye image comprising: providing an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of a radiation-sensitive silver halide and an immobile catalytic manganese complex comprised of manganese and at least one compound forming an immobilizing bidentate or tridentate complex therewith, the manganese being present in a concentration of from 1 × 10 -7 to 1 × 10 -4 mole per 0.093 square meter, imagewise-exposing the element layer to actinic radiation, immersing the exposed element in a silver halide developer solution to achieve development of silver in an imagewise manner, immersing the element in a photographic bleaching solution having a pH in the range of from 5 to 9, at least one of the element and the bleach solution containing a cobalt(III) complex bleaching agent, thereby in an imagewise manner forming cobalt(II) ions as a reaction product which in turn displace manganese from the immobile catalytic manganese complex so that an immobile catalytic manganese image is defined and a complementary immobile cobalt complex image is formed, said manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, and immersing the element in a redox amplification solution containing a peroxide oxidizing agent and a silver halide color-developing agent, at least one of the element and the amplification solution containing a color coupler and the peroxide oxidizing agent and the silver halide color-developing agent being chosen to be substantially inert to oxidation-reduction in the absence of a catalyst, so that the peroxide oxidizing agent selectively oxidizes the silver halide color-developing agent at the site of the immobile catalytic manganese image to form a dye image.

Claim 32

A method of forming a dye image comprising: providing an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of a radiation-sensitive silver halide and an immobile catalytic manganese complex comprised of manganese and at least one compound forming an immobilizing bidentate or tridentate complex therewith, the manganese being present in a concentration of from 1 × 10 -7 to 1 × 10 -4 mole per 0.093 square meter, imagewise-exposing the element layer to actinic radiation, immersing the exposed element in a silver halide developer solution to achieve development of silver in an imagewise manner, immersing the element in a photographic bleaching solution having a pH in the range of from 5 to 9, at least one of the element and the bleach solution containing a cobalt(III) complex bleaching agent, thereby in an imagewise manner forming cobalt(II) ions as a reaction product which in turn displace manganese from the immobile catalytic manganese complex so that an immobile catalytic manganese image is defined and a complementary immobile cobalt complex image is formed, said manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, and immersing the element in a redox amplification solution containing a peroxide oxidizing agent and a silver halide color-developing agent, at least one of the element and the amplification solution containing a color coupler and the peroxide oxidizing agent and the silver halide color-developing agent being chosen to be substantially inert to oxidation-reduction in the absence of a catalyst, so that the peroxide oxidizing agent selectively oxidizes the silver halide color-developing agent at the site of the immobile catalytic manganese image to form a dye image.

Claim 41

A method of forming a dye image comprising: providing an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of a radiation-sensitive silver halide, an incorporated color coupler, and an immobile catalytic complex of manganese and a complexing agent chosen from the group consisting of nitroresorcinol, 5-bromo-o-salicylaldehyde and pyridylazoresorcinol, imagewise-exposing the element layer to actinic radiation, immersing the exposed element in a silver halide developer solution to achieve development of silver in an imagewise manner, immersing the element in a photographic bleaching solution having a pH in the range of from 5 to 9, at least one of the element and the bleaching solution containing cobalt hexammine, thereby in an imagewise manner forming cobalt(II) ions as a reaction product which in turn displace manganese from the immobile catalytic manganese complex so that an immobile catalytic manganese image is defined and a complementary immobile cobalt complex image is formed, said manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, and immersing the element in a redox amplification solution containing a peroxide oxidizing agent and a silver halide color-developing agent, so that the hydrogen peroxide selectively oxidizes the silver halide color-developing agent at the site of the immobile catalytic manganese image to form a corresponding dye image.

Claim 42

A method of forming a dye image comprising: providing an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of a radiation-sensitive silver halide, an incorporated color coupler, and an immobile catalytic complex of manganese and a complexing agent chosen from the group consisting of nitroresorcinol, 5-bromo-o-salicylaldehyde and pyridylazoresorcinol, imagewise-exposing the element layer to actinic radiation, immersing the exposed element in a silver halide developer solution to achieve development of silver in an imagewise manner, immersing the element in a photographic bleaching solution having a pH in the range of from 5 to 9, at least one of the element and the bleaching solution containing cobalt hexammine, thereby in an imagewise manner forming cobalt(II) ions as a reaction product which in turn displace manganese from the immobile catalytic manganese complex so that an immobile catalytic manganese image is defined and a complementary immobile cobalt complex image is formed, said manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, and immersing the element in a redox amplification solution containing a peroxide oxidizing agent and a silver halide color-developing agent, so that the hydrogen peroxide selectively oxidizes the silver halide color-developing agent at the site of the immobile catalytic manganese image to form a corresponding dye image.

Claim 43

A method of forming a dye image comprising: forming an immobile catalytic manganese complex image in an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of an immobile catalytic manganese complex and a cobalt(III) complex, comprising: imagewise-reducing the cobalt(III) complex in the element layer to form cobalt(II) ions as a reaction product and displacing manganese from the manganese complex with the cobalt(II) ions, so that the immobile catalytic manganese image and a complementary immobile cobalt complex image are formed, said manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary cobalt complex image, selectively removing from the element the manganese displaced from the manganese complex, contacting the layer containing the immobile catalytic manganese complex image and the immobile cobalt complex image with a peroxide oxidizing agent and a reducing agent which upon oxidation provides a dye-image-generating product, wherein the peroxide oxidizing agent and the reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, and selectively reacting the peroxide oxidizing agent and the reducing agent at the site of the immobile catalytic manganese complex image to permit a dye image to be formed.

Claim 44

A method of forming a dye image comprising: forming an immobile catalytic manganese complex image in an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of an immobile catalytic manganese complex and a cobalt(III) complex, comprising: imagewise-reducing the cobalt(III) complex in the element layer to form cobalt(II) ions as a reaction product and displacing manganese from the manganese complex with the cobalt(II) ions, so that the immobile catalytic manganese image and a complementary immobile cobalt complex image are formed, said manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary cobalt complex image, selectively removing from the element the manganese displaced from the manganese complex, contacting the layer containing the immobile catalytic manganese complex image and the immobile cobalt complex image with a peroxide oxidizing agent and a reducing agent which upon oxidation provides a dye-image-generating product, wherein the peroxide oxidizing agent and the reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, and selectively reacting the peroxide oxidizing agent and the reducing agent at the site of the immobile catalytic manganese complex image to permit a dye image to be formed.

Claim 52

A method comprising: imagewise reducing a cobalt(III) complex to cobalt(II) to form an immobile catalytic manganese complex image and a complementary immobile cobalt complex image, said manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, in an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of (a) an immobile catalytic manganese complex comprised of manganese and at least one bidentate or tridentate chelate ligand-forming complexing agent chosen from the group consisting of ortho-salicylaldehydes, nitrosoarols, dithiooxamides, formazans, aromatic azo compounds, hydrazones and Schiff bases, (b) a cationic cobalt(III) ammine or amine complex and (c) a photoreductant, by imagewise-exposing to visible radiation and heating the coating, and forming a dye image defined by said immobile catalytic manganese complex image by immersing the element in a redox amplification bath comprising a peroxide oxidizing agent and a color-developing agent, wherein the peroxide oxidizing agent and the color-developing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, but enter into a redox amplification reaction at the site of said manganese complex image, at least one of the element and the amplification bath containing a color coupler.

Claim 53

A method comprising: imagewise reducing a cobalt(III) complex to cobalt(II) to form an immobile catalytic manganese complex image and a complementary immobile cobalt complex image, said manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, in an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of (a) an immobile catalytic manganese complex comprised of manganese and at least one bidentate or tridentate chelate ligand-forming complexing agent chosen from the group consisting of ortho-salicylaldehydes, nitrosoarols, dithiooxamides, formazans, aromatic azo compounds, hydrazones and Schiff bases, (b) a cationic cobalt(III) ammine or amine complex and (c) a photoreductant, by imagewise-exposing to visible radiation and heating the coating, and forming a dye image defined by said immobile catalytic manganese complex image by immersing the element in a redox amplification bath comprising a peroxide oxidizing agent and a color-developing agent, wherein the peroxide oxidizing agent and the color-developing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, but enter into a redox amplification reaction at the site of said manganese complex image, at least one of the element and the amplification bath containing a color coupler.

Claim 59

A method comprising: imagewise reducing a cobalt(III) complex to cobalt(II) to form an immobile catalytic manganese complex image and a complementary immobile cobalt complex image, said manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, in an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of (a) an immobile catalytic complex manganese and a complexing agent chosen from the group consisting of nitrosoresorcinol, 5-bromo-o-salicylaldehyde and pyridylazoresorcinol, (b) a cobalt hexammine, (c) an incorporated color coupler and (d) an internal hydrogen source quinone photoreductant, by imagewise-exposing to visible radiation and heating the coating, and forming a dye image defined by said immobile catalytic manganese image by immersing the element in a redox amplification solution containing hydrogen peroxide and a colordeveloping agent so that a redox amplification reaction occurs at the site of the immobile catalytic manganese image.

Claim 60

A method comprising: imagewise reducing a cobalt(III) complex to cobalt(II) to form an immobile catalytic manganese complex image and a complementary immobile cobalt complex image, said manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, in an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of (a) an immobile catalytic complex manganese and a complexing agent chosen from the group consisting of nitrosoresorcinol, 5-bromo-o-salicylaldehyde and pyridylazoresorcinol, (b) a cobalt hexammine, (c) an incorporated color coupler and (d) an internal hydrogen source quinone photoreductant, by imagewise-exposing to visible radiation and heating the coating, and forming a dye image defined by said immobile catalytic manganese image by immersing the element in a redox amplification solution containing hydrogen peroxide and a colordeveloping agent so that a redox amplification reaction occurs at the site of the immobile catalytic manganese image.

Claim 61

A method of forming a dye image comprising: imagewise reducing a cobalt(III) complex to cobalt(II) to form an immobile cobalt complex image in an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of an agent capable of complexing and immobilizing manganese or cobalt ions and a radiation-responsive means capable of permitting an imagewise distribution of cobalt ions to be formed, forming an imagewise distribution of an immobile catalytic manganese complex by introducing manganese ions into the element to form a catalytic manganese complex with residual complexing agnet not complexed with cobalt, so that an immobile catalytic manganese complex image and a complementary immobile cobalt complex image are formed, the manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, contacting the layer containing the immobile catalytic manganese complex image and the complementary immobile cobalt complex image with a peroxide oxidizing agent and a reducing agent which upon oxidation provides a dye-image-generating reaction product, wherein the peroxide oxidizing agent and the reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, and selectively reacting the peroxide oxidizing agent and the reducing agent at the site of the immobile catalytic manganese complex image to permit a dye image to be formed which is a reversal of the cobalt complex image generated.

Claim 62

A method of forming a dye image comprising: imagewise reducing a cobalt(III) complex to cobalt(II) to form an immobile cobalt complex image in an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of an agent capable of complexing and immobilizing manganese or cobalt ions and a radiation-responsive means capable of permitting an imagewise distribution of cobalt ions to be formed, forming an imagewise distribution of an immobile catalytic manganese complex by introducing manganese ions into the element to form a catalytic manganese complex with residual complexing agnet not complexed with cobalt, so that an immobile catalytic manganese complex image and a complementary immobile cobalt complex image are formed, the manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, contacting the layer containing the immobile catalytic manganese complex image and the complementary immobile cobalt complex image with a peroxide oxidizing agent and a reducing agent which upon oxidation provides a dye-image-generating reaction product, wherein the peroxide oxidizing agent and the reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, and selectively reacting the peroxide oxidizing agent and the reducing agent at the site of the immobile catalytic manganese complex image to permit a dye image to be formed which is a reversal of the cobalt complex image generated.

Claim 63

A method of forming a dye image comprising: forming an immobile cobalt complex image in an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of an agent capable of complexing and immobilizing manganese and cobalt ions and a radiation-sensitive silver halide, comprising: imagewise-exposing the element layer to actinic radiation, developing the exposed element to produce a silver image, bleaching the silver image with a cobalt(III) complex-containing bleaching agent to form cobalt(II) ions as one reaction product, and reacting the cobalt(II) ions and the complexing agent to form an immobile cobalt complex image, forming an imagewise distribution of an immobile catalytic manganese complex by introducing manganese ions into the element to form a catalytic manganese complex with residual complexing agent not complexed with cobalt, so that an immobile catalytic manganese complex image and a complementary immobile cobalt complex image are formed, the manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, contacting the layer containing the immobile catalytic manganese complex image and the complementary immobile cobalt complex image with a peroxide oxidizing agent and a reducing agent which upon oxidation provides a dye-image-generating reaction product, wherein the peroxide oxidizing agent and the reducting agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, and selectively reacting the peroxide oxidizing agent and the reducing agent at the site of the immobile catalytic manganese complex image to permit a dye image to be formed which is a reversal of the cobalt complex image generated.

Claim 64

A method of forming a dye image comprising: forming an immobile cobalt complex image in an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of an agent capable of complexing and immobilizing manganese and cobalt ions and a radiation-sensitive silver halide, comprising: imagewise-exposing the element layer to actinic radiation, developing the exposed element to produce a silver image, bleaching the silver image with a cobalt(III) complex-containing bleaching agent to form cobalt(II) ions as one reaction product, and reacting the cobalt(II) ions and the complexing agent to form an immobile cobalt complex image, forming an imagewise distribution of an immobile catalytic manganese complex by introducing manganese ions into the element to form a catalytic manganese complex with residual complexing agent not complexed with cobalt, so that an immobile catalytic manganese complex image and a complementary immobile cobalt complex image are formed, the manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, contacting the layer containing the immobile catalytic manganese complex image and the complementary immobile cobalt complex image with a peroxide oxidizing agent and a reducing agent which upon oxidation provides a dye-image-generating reaction product, wherein the peroxide oxidizing agent and the reducting agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, and selectively reacting the peroxide oxidizing agent and the reducing agent at the site of the immobile catalytic manganese complex image to permit a dye image to be formed which is a reversal of the cobalt complex image generated.

Claim 73

A method comprising: providing an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of a radiation-sensitive silver halide and at least one compound capable of forming an immobilizing bidentate or tridentate complex with either manganese or cobalt, the complex-forming compound being present in a concentration of from 1 × 10 -7 to 1 × 10 -4 mole per 0.093 square meter. imagewise-exposing the element layer to actinic radiation, immersing the exposed element in a silver halide developer solution to achieve development of silver in an imagewise manner, immersing the element in a photographic bleaching solution having a pH in the range of from 5 to 9, at least one of the element and the bleach solution containing a cobalt(III) complex bleaching agent, thereby in an imagewise manner forming cobalt(II) ions which in turn react with the complex-forming compound to form an immobile cobalt complex image, immersing the element in a solution containing from 1 × 10 -5 to 1 × 10 -2 mole per liter of mobile manganese ions to form a catalytic manganese complex with residual complexforming compound not complexed with cobalt, so that an immobile catalytic manganese complex image and a complementary immobile cobalt complex image are formed, the manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, immersing the element in a redox amplification bath containing a peroxide oxidizing agent and a silver halide color-developing agent, at least one of the element and the amplification bath containing a color coupler and the peroxide oxidizing agent and the silver halide color-developing agent being chosen to be substantially inert to oxidation-reduction in the absence of a catalyst, so that the peroxide oxidizing agent oxidizes the silver halide color-developing agent at the site of the immobile catalytic manganese complex image to form a dye image.

Claim 74

A method comprising: providing an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of a radiation-sensitive silver halide and at least one compound capable of forming an immobilizing bidentate or tridentate complex with either manganese or cobalt, the complex-forming compound being present in a concentration of from 1 × 10 -7 to 1 × 10 -4 mole per 0.093 square meter. imagewise-exposing the element layer to actinic radiation, immersing the exposed element in a silver halide developer solution to achieve development of silver in an imagewise manner, immersing the element in a photographic bleaching solution having a pH in the range of from 5 to 9, at least one of the element and the bleach solution containing a cobalt(III) complex bleaching agent, thereby in an imagewise manner forming cobalt(II) ions which in turn react with the complex-forming compound to form an immobile cobalt complex image, immersing the element in a solution containing from 1 × 10 -5 to 1 × 10 -2 mole per liter of mobile manganese ions to form a catalytic manganese complex with residual complexforming compound not complexed with cobalt, so that an immobile catalytic manganese complex image and a complementary immobile cobalt complex image are formed, the manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, immersing the element in a redox amplification bath containing a peroxide oxidizing agent and a silver halide color-developing agent, at least one of the element and the amplification bath containing a color coupler and the peroxide oxidizing agent and the silver halide color-developing agent being chosen to be substantially inert to oxidation-reduction in the absence of a catalyst, so that the peroxide oxidizing agent oxidizes the silver halide color-developing agent at the site of the immobile catalytic manganese complex image to form a dye image.

Claim 84

A method comprising: providing an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of a radiation-sensitive silver halide and from 1 × 10 -7 to 1 × 10 31 4 mole per 0.093 square meter of a complexing agent chosen from the group consisting of nitrosoresorcinol, 5-bromo-o-salicylaldehyde and pyridlyazoresorcinol, and a color coupler, imagewise-exposing the element layer to actinic radiation, immersing the exposed element in a black-and-white silver halide developer to achieve development of silver in an imagewise manner, immersing the element in a photographic bleaching solution having a pH in the range of from 6 to 8, at least one of the element and the bleaching solution containing cobalt hexammine, thereby in an imagewise manner forming cobalt(II) ions which in turn react with the complex-forming compound to form an immobile cobalt complex image, immersing the element in a solution containing from 1 × 10 -5 to 1 × 10 -2 mole per liter of mobile manganese ions so that an immobile catalytic manganese complex image and a complementary immobile cobalt complex image are formed, the manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, immersing the element in a redox amplification bath containing hydrogen peroxide and a phenylenediamine silver halide color-developing agent, so that the hydrogen peroxide selectively oxidizes the silver halide color-developing agent at the site of the immobile catalytic manganese image to form a corresponding dye image.

Claim 85

A method comprising: providing an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of a radiation-sensitive silver halide and from 1 × 10 -7 to 1 × 10 31 4 mole per 0.093 square meter of a complexing agent chosen from the group consisting of nitrosoresorcinol, 5-bromo-o-salicylaldehyde and pyridlyazoresorcinol, and a color coupler, imagewise-exposing the element layer to actinic radiation, immersing the exposed element in a black-and-white silver halide developer to achieve development of silver in an imagewise manner, immersing the element in a photographic bleaching solution having a pH in the range of from 6 to 8, at least one of the element and the bleaching solution containing cobalt hexammine, thereby in an imagewise manner forming cobalt(II) ions which in turn react with the complex-forming compound to form an immobile cobalt complex image, immersing the element in a solution containing from 1 × 10 -5 to 1 × 10 -2 mole per liter of mobile manganese ions so that an immobile catalytic manganese complex image and a complementary immobile cobalt complex image are formed, the manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, immersing the element in a redox amplification bath containing hydrogen peroxide and a phenylenediamine silver halide color-developing agent, so that the hydrogen peroxide selectively oxidizes the silver halide color-developing agent at the site of the immobile catalytic manganese image to form a corresponding dye image.

Claim 86

A method of forming a dye image comprising: forming an immobile cobalt image in an element comprised of a support and, as a coating thereon, at least one layer comprised of a cobalt(III) complex and a substantially uniform distribution of an agent capable of complexing manganese of cobalt ions, comprising: imagewise-reducing the cobalt(III) complex in the element layer to form cobalt(II) ions as a reaction product and reacting the cobalt(II) ions and the complexing agent to form an immobile cobalt(II) complex image, forming an imagewise distribution of an immobile catalytic manganese complex by introducing manganese ions into the element to form a catalytic manganese complex with residual complexing agent not complexed with cobalt, so that an immobile catalytic manganese complex image and a complementary immobile cobalt complex image are formed, the manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, contacting the layer containing the immobile catalytic manganese complex image and the complementary immobile cobalt complex image with a peroxide oxidizing agent and a reducing agent which upon oxidation provides a dye-image-generating reaction product, wherein the peroxide oxidizing agent and the reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, and selectively reacting the peroxide oxidizing agent and the reducing agent at the site of the immobile catalytic manganese complex image to permit a dye image to be formed which is a reversal of the cobalt complex image generated.

Claim 87

A method of forming a dye image comprising: forming an immobile cobalt image in an element comprised of a support and, as a coating thereon, at least one layer comprised of a cobalt(III) complex and a substantially uniform distribution of an agent capable of complexing manganese of cobalt ions, comprising: imagewise-reducing the cobalt(III) complex in the element layer to form cobalt(II) ions as a reaction product and reacting the cobalt(II) ions and the complexing agent to form an immobile cobalt(II) complex image, forming an imagewise distribution of an immobile catalytic manganese complex by introducing manganese ions into the element to form a catalytic manganese complex with residual complexing agent not complexed with cobalt, so that an immobile catalytic manganese complex image and a complementary immobile cobalt complex image are formed, the manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, contacting the layer containing the immobile catalytic manganese complex image and the complementary immobile cobalt complex image with a peroxide oxidizing agent and a reducing agent which upon oxidation provides a dye-image-generating reaction product, wherein the peroxide oxidizing agent and the reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, and selectively reacting the peroxide oxidizing agent and the reducing agent at the site of the immobile catalytic manganese complex image to permit a dye image to be formed which is a reversal of the cobalt complex image generated.

Claim 95

A method comprising providing an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of (a) at least one compound capable of forming an immobile complex with manganese and cobalt chosen from the group consisting of ortho-salicylaldehydes, nitroso-arols, dithiooxamides, formazans, aromatic azo compounds, hydrazones and Schiff bases, (b) a cationic cobalt(III) ammine or amine complex and (c) a photoactivator, the complex-forming compound being present in a concentration of from 1 × 10 -7 to 1 × 10 -4 mole per 0.093 square meter, imagewise-exposing to actinic radiation and heating the coating, thereby in an imagewise manner forming cobalt(II) ions which in turn react with the complex-forming compound to form an immobile cobalt complex image, immersing the element in a solution containing from 1 × 10 -5 to 1 × 10 -2 mole per liter of mobile manganese ions so that an immobile catalytic manganese complex image and a complementary immobile cobalt complex image are formed, the manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, immersing the element in a redox amplification bath containing a peroxide oxidizing agent, at least one of the element and the amplification bath containing a color coupler and a silver halide color-developing agent and the peroxide oxidizing agent and the silver halide color-developing agent being chosen to be substantially inert to oxidation-reduction in the absence of a catalyst, so that the peroxide oxidizing agent selectively oxidizes the silver halide color-developing agent at the site of the immobile catalytic manganese complex image to form a dye image.

Claim 96

A method comprising providing an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of (a) at least one compound capable of forming an immobile complex with manganese and cobalt chosen from the group consisting of ortho-salicylaldehydes, nitroso-arols, dithiooxamides, formazans, aromatic azo compounds, hydrazones and Schiff bases, (b) a cationic cobalt(III) ammine or amine complex and (c) a photoactivator, the complex-forming compound being present in a concentration of from 1 × 10 -7 to 1 × 10 -4 mole per 0.093 square meter, imagewise-exposing to actinic radiation and heating the coating, thereby in an imagewise manner forming cobalt(II) ions which in turn react with the complex-forming compound to form an immobile cobalt complex image, immersing the element in a solution containing from 1 × 10 -5 to 1 × 10 -2 mole per liter of mobile manganese ions so that an immobile catalytic manganese complex image and a complementary immobile cobalt complex image are formed, the manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, immersing the element in a redox amplification bath containing a peroxide oxidizing agent, at least one of the element and the amplification bath containing a color coupler and a silver halide color-developing agent and the peroxide oxidizing agent and the silver halide color-developing agent being chosen to be substantially inert to oxidation-reduction in the absence of a catalyst, so that the peroxide oxidizing agent selectively oxidizes the silver halide color-developing agent at the site of the immobile catalytic manganese complex image to form a dye image.

Claim 101

A method comprising: providing an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of (a) from 1 × 10 -7 to 1 × 10 -4 mole per 0.093 square meter of a complexing agent chosen from the class consisting of nitrosoresorcinol, 5-bromo-o-salicylaldehyde and pyridylazoresorcinol, (b) a cobalt hexammine, (c) an incorporated color coupler and (d) an internal hydrogen source quinone photoreductant, imagewise-exposing to actinic radiation and heating the coating, thereby in an imagewise manner forming cobalt(II) ions which in turn react with the complex-forming compound to form an immobile cobalt complex image, immersing the element in a solution containing from 1 × 10 -5 to 1 × 10 -2 mole per liter of mobile manganese ions so that an immobile catalytic manganese complex image and a complementary immobile cobalt complex image are formed, the manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, immersing the element in a redox amplification bath containing hydrogen peroxide and a silver halide color-developing agent, so that the hydrogen peroxide selectively oxidizes the silver halide color-developing agent at the site of the immobile catalytic manganese image to form a corresponding dye image.

Claim 102

A method comprising: providing an element comprised of a support and, as a coating thereon, at least one layer comprised of a substantially uniform distribution of (a) from 1 × 10 -7 to 1 × 10 -4 mole per 0.093 square meter of a complexing agent chosen from the class consisting of nitrosoresorcinol, 5-bromo-o-salicylaldehyde and pyridylazoresorcinol, (b) a cobalt hexammine, (c) an incorporated color coupler and (d) an internal hydrogen source quinone photoreductant, imagewise-exposing to actinic radiation and heating the coating, thereby in an imagewise manner forming cobalt(II) ions which in turn react with the complex-forming compound to form an immobile cobalt complex image, immersing the element in a solution containing from 1 × 10 -5 to 1 × 10 -2 mole per liter of mobile manganese ions so that an immobile catalytic manganese complex image and a complementary immobile cobalt complex image are formed, the manganese complex image exhibiting a substantially higher degree of catalytic activity than said complementary immobile cobalt complex image, immersing the element in a redox amplification bath containing hydrogen peroxide and a silver halide color-developing agent, so that the hydrogen peroxide selectively oxidizes the silver halide color-developing agent at the site of the immobile catalytic manganese image to form a corresponding dye image.