Process of bleaching silver images to form dye images using cobalt complexes and peroxides

Claim 1

A method of forming an image comprising fixing silver halide and concurrently bleaching at least a portion of a silver image contained within a silver halide photographic element by reacting therewith, in the presence of a silver salt-forming compound which is incapable of oxidizing image silver, a cobalt(III) complex which permanently releases ligands upon reduction, while concurrently producing cobalt(II) as an immobile reaction product in a pattern conforming to the silver image pattern and forming a dye image by (1) reacting a peroxide oxidizing agent with the cobalt(II) reaction product to form a cationic cobalt(III) oxidizing agent as a reaction product in a pattern conforming to the silver image pattern and (2) reacting with the cationic cobalt(III) oxidizing agent a dye-image-generating reducing agent, wherein the peroxide oxidizing agent and the dye-image-generating reducing agent are essentially inert to oxidation-reduction in the absence of the cobalt(II) reaction product and the fixing-bleaching and dye image forming steps are each performed using an aqueous alkaline processing solution.

Claim 2

A method of forming an image comprising fixing silver halide and concurrently bleaching at least a portion of a silver image contained within a silver halide photographic element by reacting therewith, in the presence of a silver salt-forming compound which is incapable of oxidizing image silver, a cobalt(III) complex which permanently releases ligands upon reduction, while concurrently producing cobalt(II) as an immobile reaction product in a pattern conforming to the silver image pattern and forming a dye image by (1) reacting a peroxide oxidizing agent with the cobalt(II) reaction product to form a cationic cobalt(III) oxidizing agent as a reaction product in a pattern conforming to the silver image pattern and (2) reacting with the cationic cobalt(III) oxidizing agent a dye-image-generating reducing agent, wherein the peroxide oxidizing agent and the dye-image-generating reducing agent are essentially inert to oxidation-reduction in the absence of the cobalt(II) reaction product and the fixing-bleaching and dye image forming steps are each performed using an aqueous alkaline processing solution.

Claim 6

A method of forming an image comprising in a first aqueous alkaline processing solution, bleaching at least a portion of a silver image contained within a photographic element by reacting therewith, in the presence of a silver salt-forming compound which is incapable of oxidizing image silver, a cobalt(III) complex which permanently releases ligands upon reduction, while concurrently producing cobalt(II) as an immobile reaction product in a pattern conforming to the silver image pattern and in a second aqueous alkaline processing solution, forming a dye image by (1) reacting a peroxide oxidizing agent with the cobalt(II) reaction product to form a cationic cobalt(III) oxidizing agnet as a reaction product in a pattern conforming to the silver image pattern and (2) reacting with the cationic cobalt(III) oxidizing agent a dye-image-generating reducing agent, wherein the peroxide oxidizing agent and the dye-image-generating reducing agent are essentially inert to oxidation-reduction in the absence of the cobalt(II) reaction product and the bleaching and dye image forming steps are each performed using an aqueous alkaline processing solution.

Claim 7

A method of forming an image comprising in a first aqueous alkaline processing solution, bleaching at least a portion of a silver image contained within a photographic element by reacting therewith, in the presence of a silver salt-forming compound which is incapable of oxidizing image silver, a cobalt(III) complex which permanently releases ligands upon reduction, while concurrently producing cobalt(II) as an immobile reaction product in a pattern conforming to the silver image pattern and in a second aqueous alkaline processing solution, forming a dye image by (1) reacting a peroxide oxidizing agent with the cobalt(II) reaction product to form a cationic cobalt(III) oxidizing agnet as a reaction product in a pattern conforming to the silver image pattern and (2) reacting with the cationic cobalt(III) oxidizing agent a dye-image-generating reducing agent, wherein the peroxide oxidizing agent and the dye-image-generating reducing agent are essentially inert to oxidation-reduction in the absence of the cobalt(II) reaction product and the bleaching and dye image forming steps are each performed using an aqueous alkaline processing solution.

Claim 16

A method of forming an image comprising, in a common aqueous alkaline processing solution, developing to produce a silver image, an imagewise-exposed photographic element comprised of a support and at least one radiation-sensitive silver halide layer containing a developable latent image therein, bleaching at least a portion of a silver image contained within the photographic element by reacting therewith, in the presence of a silver salt-forming compound which is incapable of oxidizing image silver, a cobalt(III) complex which permanently releases ligands upon reduction, while concurrently producing cobalt(II) as an immobile reaction product in a pattern conforming to the silver image pattern and forming a dye image by (1) reacting a peroxide oxidizing agent with the cobalt(II) reaction product to form a cationic cobalt(III) oxidizing agent as a reaction product in a pattern conforming to the silver image pattern and (2) reacting with the cationic cobalt(III) oxidizing agent a dye-image-generating reducing agent, wherein, the peroxide oxidizing agent and the dye-image-generating reducing agent are essentially inert to oxidation-reduction in the absence of the cobalt(II) reaction product and the cobalt(III) complex and the dye-image-generating reducing agent are essentially inert to oxidation-reduction in the absence of a redox catalyst.

Claim 17

A method of forming an image comprising, in a common aqueous alkaline processing solution, developing to produce a silver image, an imagewise-exposed photographic element comprised of a support and at least one radiation-sensitive silver halide layer containing a developable latent image therein, bleaching at least a portion of a silver image contained within the photographic element by reacting therewith, in the presence of a silver salt-forming compound which is incapable of oxidizing image silver, a cobalt(III) complex which permanently releases ligands upon reduction, while concurrently producing cobalt(II) as an immobile reaction product in a pattern conforming to the silver image pattern and forming a dye image by (1) reacting a peroxide oxidizing agent with the cobalt(II) reaction product to form a cationic cobalt(III) oxidizing agent as a reaction product in a pattern conforming to the silver image pattern and (2) reacting with the cationic cobalt(III) oxidizing agent a dye-image-generating reducing agent, wherein, the peroxide oxidizing agent and the dye-image-generating reducing agent are essentially inert to oxidation-reduction in the absence of the cobalt(II) reaction product and the cobalt(III) complex and the dye-image-generating reducing agent are essentially inert to oxidation-reduction in the absence of a redox catalyst.

Claim 24

A method of forming a image comprising bringing a photographic element comprised of a support and at least one radiation-sensitive silver halide layer bearing a latent image into contact with an aqueous alkaline solution containing less than a 0.05 molar concentration of any compound which will form a tridentate or higher dentate ligand with cobalt, comprising a silver salt-forming compound which is incapable of oxidizing image silver and a peroxide oxidizing agent, at least one of the photographic element and the solution containing a coablt(III) complex which permanently releases ligands upon reduction, a silver halide developing agent and a dye-image-generating reducing agent, so that a dye image can be formed conforming to the latent image pattern originally present, wherein the peroxide oxidizing agent, the cobalt(III) complex, the silver halide developing agent and the dye-image-generating reducing agent are essentially inert to oxidation-reduction in the absence of a catalyst.

Claim 25

A method of forming a image comprising bringing a photographic element comprised of a support and at least one radiation-sensitive silver halide layer bearing a latent image into contact with an aqueous alkaline solution containing less than a 0.05 molar concentration of any compound which will form a tridentate or higher dentate ligand with cobalt, comprising a silver salt-forming compound which is incapable of oxidizing image silver and a peroxide oxidizing agent, at least one of the photographic element and the solution containing a coablt(III) complex which permanently releases ligands upon reduction, a silver halide developing agent and a dye-image-generating reducing agent, so that a dye image can be formed conforming to the latent image pattern originally present, wherein the peroxide oxidizing agent, the cobalt(III) complex, the silver halide developing agent and the dye-image-generating reducing agent are essentially inert to oxidation-reduction in the absence of a catalyst.

Claim 34

A method of forming an image comprising bringing a photographic element comprised of a support and at least one radiation-sensitive silver halide layer containing a developable latent image into contact with an aqueous alkaline developer solution, wherein at least one of the photographic element and the developer solution contain a silver halide developing agent, so that a silver image is formed in the photographic element corresponding to the developable latent image, poisoning the silver image as a redox amplification catalyst for a peroxide oxidizing agent, bringing the photographic element bearing the silver image into contact with an aqueous alkaline bleaching solution containing less than a 0.05 molar concentration of any compound which will form a tridentate or higher dentate ligand with cobalt and comprising a silver salt former which is incapable of oxidizing image silver, at least one of the photographic element and the bleaching solution containing a cobalt(III) complex which permanently releases ligands upon reduction, thereby converting at least a portion of the silver image to a silver salt and producing cobalt(II) as an immobile reaction product within the silver image pattern, and thereafter bringing the photographic element into contact with an aqueous alkaline amplification solution, separate from the aqueous alkaline bleaching solution, comprising a peroxide oxidizing agent capable of reacting with the cobalt(II) reaction product to form a cationic cobalt(III) oxidizing agent as a reaction product in a pattern conforming to the silver image pattern, at least one of the photographic element and the amplification solution containing a dye-image-generating reducing agent capable of entering into a redox reaction with the cobalt(III) oxidizing agent so that a dye image can be formed, wherein the peroxide oxidizing agent and the dye-image-generating reducing agent are essentially inert to oxidation-reduction in the absence of the cobalt(II) reaction product formed by bringing the photographic element into contact with the aqueous alkaline bleaching solution and formation of the dye image employs the cobalt(II) reaction product as a catalyst for the reaction of the peroxide oxidizing agent and the dye-image-generating reducing agent.

Claim 35

A method of forming an image comprising bringing a photographic element comprised of a support and at least one radiation-sensitive silver halide layer containing a developable latent image into contact with an aqueous alkaline developer solution, wherein at least one of the photographic element and the developer solution contain a silver halide developing agent, so that a silver image is formed in the photographic element corresponding to the developable latent image, poisoning the silver image as a redox amplification catalyst for a peroxide oxidizing agent, bringing the photographic element bearing the silver image into contact with an aqueous alkaline bleaching solution containing less than a 0.05 molar concentration of any compound which will form a tridentate or higher dentate ligand with cobalt and comprising a silver salt former which is incapable of oxidizing image silver, at least one of the photographic element and the bleaching solution containing a cobalt(III) complex which permanently releases ligands upon reduction, thereby converting at least a portion of the silver image to a silver salt and producing cobalt(II) as an immobile reaction product within the silver image pattern, and thereafter bringing the photographic element into contact with an aqueous alkaline amplification solution, separate from the aqueous alkaline bleaching solution, comprising a peroxide oxidizing agent capable of reacting with the cobalt(II) reaction product to form a cationic cobalt(III) oxidizing agent as a reaction product in a pattern conforming to the silver image pattern, at least one of the photographic element and the amplification solution containing a dye-image-generating reducing agent capable of entering into a redox reaction with the cobalt(III) oxidizing agent so that a dye image can be formed, wherein the peroxide oxidizing agent and the dye-image-generating reducing agent are essentially inert to oxidation-reduction in the absence of the cobalt(II) reaction product formed by bringing the photographic element into contact with the aqueous alkaline bleaching solution and formation of the dye image employs the cobalt(II) reaction product as a catalyst for the reaction of the peroxide oxidizing agent and the dye-image-generating reducing agent.

Claim 40

A method of forming an image comprising bringing a photographic element comprised of a support bearing a silver image thereon into contact with an aqueous alkaline bleaching and fixing solution having a pH in the range of from 10 to 30 containing less than a 0.05 molar concentration of any compound which will form a tridentate or higher dentate ligand with cobalt, and comprising a silver halide fixing concentration of at least one of an alkali or ammonium bromide, chloride or thiosulfate, at least one of the photographic element and the aqueous alkaline bleaching and fixing solution comprising a cobalt(III) complex bleaching agent having a coordination number of 6 and monodentate or bidentate ligands, at least four of the ligands being ammine ligands, so that silver halide is fixed and at least a portion of the silver image is bleached, and bringing the photographic element into contact with an aqueous alkaline amplification solution having a pH in the range of from 10 to 13 and containing a peroxide oxidizing agent, at least one of the photographic element and the amplification solution containing a color-developing agent and a photographic color coupler, wherein the peroxide oxidizing agent and the color-developing agent are essentially inert to oxidation-reduction in the absence of a catalyst, bleaching the silver image generates the catalyst and formation of a dye image occurs bringing the photographic element into contact with the amplification solution by employing the catalyst generated by bleaching.

Claim 41

A method of forming an image comprising bringing a photographic element comprised of a support bearing a silver image thereon into contact with an aqueous alkaline bleaching and fixing solution having a pH in the range of from 10 to 30 containing less than a 0.05 molar concentration of any compound which will form a tridentate or higher dentate ligand with cobalt, and comprising a silver halide fixing concentration of at least one of an alkali or ammonium bromide, chloride or thiosulfate, at least one of the photographic element and the aqueous alkaline bleaching and fixing solution comprising a cobalt(III) complex bleaching agent having a coordination number of 6 and monodentate or bidentate ligands, at least four of the ligands being ammine ligands, so that silver halide is fixed and at least a portion of the silver image is bleached, and bringing the photographic element into contact with an aqueous alkaline amplification solution having a pH in the range of from 10 to 13 and containing a peroxide oxidizing agent, at least one of the photographic element and the amplification solution containing a color-developing agent and a photographic color coupler, wherein the peroxide oxidizing agent and the color-developing agent are essentially inert to oxidation-reduction in the absence of a catalyst, bleaching the silver image generates the catalyst and formation of a dye image occurs bringing the photographic element into contact with the amplification solution by employing the catalyst generated by bleaching.

Claim 51

A method of forming an image comprising bringing a photographic element comprised of a support and at least one radiation-sensitive silver halide emulsion layer containing a developable latent image into contact with an aqueous alkaline developer solution having a pH in the range of from 10 to 13, wherein at least one of the photographic element and the developer solution contains a silver halide developing agent, so that a silver image is formed in the photographic element corresponding to the developable latent image, bringing the photographic element into contact with an aqueous alkaline bleaching and fixing solution having a pH in the range of from 10 to 13 containing less than a 0.05 molar concentration of any compound which will form a tridentate or higher dentate ligand with cobalt and comprising a silver halide fixing concentration of at least one of an alkali or ammonium bromide, chloride or thiosulfate, at least one of the photographic element and the aqueous alkaline bleaching and fixing solution comprising a cobalt(III) complex bleaching agent having a coordination number of 6 and monodentate or bidentate ligands, at least four of the ligands being ammine ligands, so that silver halide is fixed and at least a portion of the silver image is bleached, and bringing the photographic element into contact with an aqueous alkaline amplification solution having a pH in the range of from 10 to 13 and containing a peroxide oxidizing agent, at least one of the photographic element and the amplification solution containing a peroxide oxidizing agent, at least one of the photographic element and the amplification solution containing a primary aromatic amine and a photographic color coupler, wherein the peroxide oxidizing agent and the primary aromatic amine are essentially inert to oxidation-reduction in the absence of a catalyst, bleaching the silver image generates the catalyst and formation of a dye image occurs upon bringing the photographic element into contact with the amplification solution by employing the catalyst generated by bleaching.

Claim 52

A method of forming an image comprising bringing a photographic element comprised of a support and at least one radiation-sensitive silver halide emulsion layer containing a developable latent image into contact with an aqueous alkaline developer solution having a pH in the range of from 10 to 13, wherein at least one of the photographic element and the developer solution contains a silver halide developing agent, so that a silver image is formed in the photographic element corresponding to the developable latent image, bringing the photographic element into contact with an aqueous alkaline bleaching and fixing solution having a pH in the range of from 10 to 13 containing less than a 0.05 molar concentration of any compound which will form a tridentate or higher dentate ligand with cobalt and comprising a silver halide fixing concentration of at least one of an alkali or ammonium bromide, chloride or thiosulfate, at least one of the photographic element and the aqueous alkaline bleaching and fixing solution comprising a cobalt(III) complex bleaching agent having a coordination number of 6 and monodentate or bidentate ligands, at least four of the ligands being ammine ligands, so that silver halide is fixed and at least a portion of the silver image is bleached, and bringing the photographic element into contact with an aqueous alkaline amplification solution having a pH in the range of from 10 to 13 and containing a peroxide oxidizing agent, at least one of the photographic element and the amplification solution containing a peroxide oxidizing agent, at least one of the photographic element and the amplification solution containing a primary aromatic amine and a photographic color coupler, wherein the peroxide oxidizing agent and the primary aromatic amine are essentially inert to oxidation-reduction in the absence of a catalyst, bleaching the silver image generates the catalyst and formation of a dye image occurs upon bringing the photographic element into contact with the amplification solution by employing the catalyst generated by bleaching.

Claim 57

A method of forming a multicolor dye image in a photographic element comprised of a support and, coated thereon, at least three layer units each comprised of at least one silver halide emulsion layer, each of said layer units being primarily responsive to a different one of the blue, green and red portions of the visible spectrum, the blue-sensitive layer unit containing a yellow-dye-forming color coupler, the green-sensitive layer unit containing a magenta-dye-forming color coupler and the red-sensitive layer unit containing a cyan-dye-forming color coupler, the silver halide emulsion layers each containing a latent image pattern therein resulting from imagewise exposure of the photographic element, comprising developing a silver image in each of the three layer units corresponding to the latent image pattern thereof, fixing silver halide and concurrently bleaching at least a portion of the silver image in each of the layer units with a cobalt(III) complex which permanently releases ligands upon reduction and a silver salt-forming compound which is incapable of oxidizing image silver, which produces cobalt(II) as an immobile reaction product in a pattern conforming to the silver image pattern, and forming a dye image in each of the three layer units by (1) reacting a peroxide oxidizing agent with the cobalt(II) reaction product to form a cationic cobalt(III) oxidizing agent as a reaction product in a pattern conforming to the silver image pattern and (2) reacting with the cationic cobalt(III) oxidizing agent a primary aromatic amine developing agent, wherein the peroxide oxidizing agent and the primary aromatic amine developing agent are essentially inert to oxidation-reduction in the absence of the cobalt(II) reaction product and developing, bleaching and dye image forming steps are each performed using an aqueous alkaline solution.

Claim 58

A method of forming a multicolor dye image in a photographic element comprised of a support and, coated thereon, at least three layer units each comprised of at least one silver halide emulsion layer, each of said layer units being primarily responsive to a different one of the blue, green and red portions of the visible spectrum, the blue-sensitive layer unit containing a yellow-dye-forming color coupler, the green-sensitive layer unit containing a magenta-dye-forming color coupler and the red-sensitive layer unit containing a cyan-dye-forming color coupler, the silver halide emulsion layers each containing a latent image pattern therein resulting from imagewise exposure of the photographic element, comprising developing a silver image in each of the three layer units corresponding to the latent image pattern thereof, fixing silver halide and concurrently bleaching at least a portion of the silver image in each of the layer units with a cobalt(III) complex which permanently releases ligands upon reduction and a silver salt-forming compound which is incapable of oxidizing image silver, which produces cobalt(II) as an immobile reaction product in a pattern conforming to the silver image pattern, and forming a dye image in each of the three layer units by (1) reacting a peroxide oxidizing agent with the cobalt(II) reaction product to form a cationic cobalt(III) oxidizing agent as a reaction product in a pattern conforming to the silver image pattern and (2) reacting with the cationic cobalt(III) oxidizing agent a primary aromatic amine developing agent, wherein the peroxide oxidizing agent and the primary aromatic amine developing agent are essentially inert to oxidation-reduction in the absence of the cobalt(II) reaction product and developing, bleaching and dye image forming steps are each performed using an aqueous alkaline solution.

Claim 63

A method of forming a multicolor dye image in a photographic element comprised of a support and, coated thereon, at least three layer units each comprised of at least one gelatino-silver halide emulsion layer, each of said layer units being primarily responsive to a different one of the blue, green and red portions of the visible spectrum, the blue-sensitive layer unit containing an open-chain ketomethylene yellow-dye-forming color coupler, the green-sensitive layer unit containing a 5-pyrazolone magenta-dye-forming color coupler and the red-sensitive layer unit containing a phenolic cyan-dye-forming color coupler, and at least one of the layer units containing a developable latent image, comprising sequentially bringing th photographic element into contact with an aqueous alkaline developer solution having a pH in the range of from 10 to 13 wherein at least one of the photographic element and the developer solution contains at least one black-and-white silver halide developing agent, so that a silver image is formed in the photographic element corresponding to the developable latent image, bringing the photographic element into contact with a separate aqueous alkaline bleach-fix solution having a pH in the range of from 10 to 13 which is substantially free of any compound which will form a tridentate or higher dentate ligand with cobalt and comprising an alkali or ammonium bromide or thiosulfate, and at least one of the photographic element and the aqueous alkaline bleach-fix solution comprising cobalt hexammine, so that at least a portion of the silver image is bleached, and bringing the photographic element into contact with a separate aqueous alkaline amplification solution having a pH in the range of from 10 to 13 and containing hydrogen peroxide and a primary para-phenylenediamine color-developing agent, wherein the hydrogen peroxide and the primary para-phenylenediamine color developing agent are essentially inert to oxidation-reduction in the absence of a catalyst, to form a dye image in at least one of the three layer units with a dye image.

Claim 64

A method of forming a multicolor dye image in a photographic element comprised of a support and, coated thereon, at least three layer units each comprised of at least one gelatino-silver halide emulsion layer, each of said layer units being primarily responsive to a different one of the blue, green and red portions of the visible spectrum, the blue-sensitive layer unit containing an open-chain ketomethylene yellow-dye-forming color coupler, the green-sensitive layer unit containing a 5-pyrazolone magenta-dye-forming color coupler and the red-sensitive layer unit containing a phenolic cyan-dye-forming color coupler, and at least one of the layer units containing a developable latent image, comprising sequentially bringing th photographic element into contact with an aqueous alkaline developer solution having a pH in the range of from 10 to 13 wherein at least one of the photographic element and the developer solution contains at least one black-and-white silver halide developing agent, so that a silver image is formed in the photographic element corresponding to the developable latent image, bringing the photographic element into contact with a separate aqueous alkaline bleach-fix solution having a pH in the range of from 10 to 13 which is substantially free of any compound which will form a tridentate or higher dentate ligand with cobalt and comprising an alkali or ammonium bromide or thiosulfate, and at least one of the photographic element and the aqueous alkaline bleach-fix solution comprising cobalt hexammine, so that at least a portion of the silver image is bleached, and bringing the photographic element into contact with a separate aqueous alkaline amplification solution having a pH in the range of from 10 to 13 and containing hydrogen peroxide and a primary para-phenylenediamine color-developing agent, wherein the hydrogen peroxide and the primary para-phenylenediamine color developing agent are essentially inert to oxidation-reduction in the absence of a catalyst, to form a dye image in at least one of the three layer units with a dye image.

Claim 72

A method of forming a multicolor dye image in a photographic element comprised of a support and, coated thereon, at least three layer units each comprised of at least one gelatino-silver halide emulsion layer, each of the layer units incorporating therein a silver image formed by exposure to a separate one of the blue, green and red thirds of the visible spectrum, the layer unit containing the silver image formed by exposure to the blue third of the visible spectrum containing an open-chain ketomethylene yellow-dye-forming color coupler, the layer unit containing the silver image formed by exposure to the green third of the visible spectrum containing a 5-pyrazolone magenta-dye-forming color coupler and the layer unit containing the silver image formed by exposure to the red third of the visible spectrum containing a phenolic cyan-dye-forming color coupler, comprising bringing the photographic element into contact with an aqueous alkaline bleach-fix solution having a pH in the range of from 10 to 13 which is substantially free of any compound which will form a tridentate or higher dentate ligand with cobalt and comprising at least about 2 grams per liter of an alkali thiosulfate and from 0.2 to 20 grams per liter of cobalt hexammine acetate or chloride to bleach the silver image and to fix the silver halide while concurrently forming a redox amplification catalyst in each layer unit conforming to the silver image and bringing the photographic element into contact with an aqueous alkaline amplification solution having a pH in the range of from 10 to 13 containing 0.001 to 0.5 mole per liter of hydrogen peroxide and 1 to 20 grams per liter of a primary para-phenylenedimaine color-developing agent, thereby forming a dye image in each layer unit.

Claim 73

A method of forming a multicolor dye image in a photographic element comprised of a support and, coated thereon, at least three layer units each comprised of at least one gelatino-silver halide emulsion layer, each of the layer units incorporating therein a silver image formed by exposure to a separate one of the blue, green and red thirds of the visible spectrum, the layer unit containing the silver image formed by exposure to the blue third of the visible spectrum containing an open-chain ketomethylene yellow-dye-forming color coupler, the layer unit containing the silver image formed by exposure to the green third of the visible spectrum containing a 5-pyrazolone magenta-dye-forming color coupler and the layer unit containing the silver image formed by exposure to the red third of the visible spectrum containing a phenolic cyan-dye-forming color coupler, comprising bringing the photographic element into contact with an aqueous alkaline bleach-fix solution having a pH in the range of from 10 to 13 which is substantially free of any compound which will form a tridentate or higher dentate ligand with cobalt and comprising at least about 2 grams per liter of an alkali thiosulfate and from 0.2 to 20 grams per liter of cobalt hexammine acetate or chloride to bleach the silver image and to fix the silver halide while concurrently forming a redox amplification catalyst in each layer unit conforming to the silver image and bringing the photographic element into contact with an aqueous alkaline amplification solution having a pH in the range of from 10 to 13 containing 0.001 to 0.5 mole per liter of hydrogen peroxide and 1 to 20 grams per liter of a primary para-phenylenedimaine color-developing agent, thereby forming a dye image in each layer unit.

Claim 75

A method of forming a multicolor dye image in a photograhic element comprised of a support and, coated thereon, at least three layer units each comprised of at least one gelatino-silver halide emulsion layer, each of said layer units being primarily responsive to a different one of the blue, green and red portions of the visible spectrum, the blue-sensitive layer unit containing an open-chain ketomethylene yellow-dye-forming color coupler, the green-sensitive layer unit containing a 5-pyrazolone magenta-dye-forming color coupler and the red-sensitive layer unit containing a phenolic cyan-dye-forming color coupler, and each of said layer units containing a developable latent image, comprising developing the latent image to form a corresponding silver image, bleaching the silver image siver image, concurrently forming a catalyst image corresponding to the silverimage, fixing the silver halide, and forming a dye image corresponding to the original latent image in each layer unit, the improvement wherein each of the developing, bleaching and dye image forming steps are performed by bringing the photographic element into contact with a monobath comprising an aqueous alkaline developer solution having a pH in the range of from 10 to 13 containing at least about 2 grams per liter of an alkali thiosulfate, 0.2 to 2 grams per liter of cobalt hexammine acetate or chloride, 0.001 to 0.5 mole per liter of hydrogen peroxide, and 1 to 20 grams per liter of a primary para-phenylenediamine color-developing agent.

Claim 76

A method of forming a multicolor dye image in a photograhic element comprised of a support and, coated thereon, at least three layer units each comprised of at least one gelatino-silver halide emulsion layer, each of said layer units being primarily responsive to a different one of the blue, green and red portions of the visible spectrum, the blue-sensitive layer unit containing an open-chain ketomethylene yellow-dye-forming color coupler, the green-sensitive layer unit containing a 5-pyrazolone magenta-dye-forming color coupler and the red-sensitive layer unit containing a phenolic cyan-dye-forming color coupler, and each of said layer units containing a developable latent image, comprising developing the latent image to form a corresponding silver image, bleaching the silver image siver image, concurrently forming a catalyst image corresponding to the silverimage, fixing the silver halide, and forming a dye image corresponding to the original latent image in each layer unit, the improvement wherein each of the developing, bleaching and dye image forming steps are performed by bringing the photographic element into contact with a monobath comprising an aqueous alkaline developer solution having a pH in the range of from 10 to 13 containing at least about 2 grams per liter of an alkali thiosulfate, 0.2 to 2 grams per liter of cobalt hexammine acetate or chloride, 0.001 to 0.5 mole per liter of hydrogen peroxide, and 1 to 20 grams per liter of a primary para-phenylenediamine color-developing agent.

Claim 86

A method of forming an image comprising in a first aqueous alkaline processing solution, developing to produce a silver image, an imagewise-exposed photographic element comprised of a support and at least one radiation-sensitive silver halide layer containing a developable latent image therein, in a second aqueous alkaline processing solution, bleaching at least a portion of a silver image contained within the photographic element by reacting therewith, in the presence of a silver salt-forming compound which is incapable of oxidizing image silver, a cobalt(III) complex which permanently released ligands upon reduction, while concurrently producing cobalt(II) ligands upon reduction, while concurrently producing cobalt(II) as an immobile reaction product in a pattern conforming to the silver image pattern and in a third aqueous alkaline processing solution, forming a dye image by (1) reacting a peroxide oxidizing agent with the cobalt(II) reaction product to form a cationic cobalt(III) oxidizing agent as a reaction product in a pattern conforming to the silver image pattern and (2) reacting with the cationic cobalt(III) oxidizing agent a dye-image-generating reducing agent, wherein, the peroxide oxidizing agent and the dye-image-generating reducing agent are essentially inert to oxidation-reduction in the absence of the cobalt(II) reaction product.

Claim 87

A method of forming an image comprising in a first aqueous alkaline processing solution, developing to produce a silver image, an imagewise-exposed photographic element comprised of a support and at least one radiation-sensitive silver halide layer containing a developable latent image therein, in a second aqueous alkaline processing solution, bleaching at least a portion of a silver image contained within the photographic element by reacting therewith, in the presence of a silver salt-forming compound which is incapable of oxidizing image silver, a cobalt(III) complex which permanently released ligands upon reduction, while concurrently producing cobalt(II) ligands upon reduction, while concurrently producing cobalt(II) as an immobile reaction product in a pattern conforming to the silver image pattern and in a third aqueous alkaline processing solution, forming a dye image by (1) reacting a peroxide oxidizing agent with the cobalt(II) reaction product to form a cationic cobalt(III) oxidizing agent as a reaction product in a pattern conforming to the silver image pattern and (2) reacting with the cationic cobalt(III) oxidizing agent a dye-image-generating reducing agent, wherein, the peroxide oxidizing agent and the dye-image-generating reducing agent are essentially inert to oxidation-reduction in the absence of the cobalt(II) reaction product.