Redox amplification process employing a combination of oxidizing agents

• US 4,097,278 A
• Filed: 10/08/1976
• Issued: 06/27/1978
• Est. Priority Date: 09/02/1975
• Status: Expired due to Term

• Current Assignee: Eastman Kodak Company
• Original Assignee: Eastman Kodak Company
• Inventors: Bissonette, Vernon L.
• Primary Examiner(s): Brown, J. Travis
• Assistant Examiner(s): Schilling, Richard L.
• Application Number:
  US05/730,914
• Time in Patent Office: 627 Days
• Field of Search: 96/3, 96/29 D, 96/54, 96/55, 96/51, 96/60 R, 96/48 R, 96/49, 96/56.5, 96/22, 96/48 PD, 96/61 R
• US Class Current: 430/223
• CPC Class Codes: G03C 7/3017 with intensification of the image by oxido-reduction

Abstract

My invention is directed to a process of forming dye images. I accomplish this through a first redox amplification reaction in which a cobalt (III) complex oxidizing agent enters into a redox reaction with a reducing agent at the site of a catalyst image. A second redox amplification reaction follows in which a peroxide oxidizing agent is employed along with dye-image-generating reducing agent to form a dye image corresponding to the pattern of the catalyst.

Claims

1. A method of forming an image comprising:

in a first aqueous alkaline solution performing a first redox reaction by

bringing a cobalt(III) complex, which permanently releases ligands upon reduction, and a reducing agent together and into contact with an element containing an image pattern of a heterogeneous catalyst, wherein the cobalt(III) complex and the reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of the heterogeneous catalyst, and

permitting the selective reaction of the cobalt(III) complex and the reducing agent at the site of the heterogeneous catalyst to produce cobalt(II) as an immobile reaction product in a pattern conforming to the heterogeneous catalyst image pattern; and

in a second aqueous alkaline solution performing a second redox reaction by

bringing into material contact a peroxide oxidizing agent, the immobile cobalt(II) reaction product and a dye-image-generating reducing agent capable of producing a dye-image-generating reaction product, wherein the peroxide oxidizing agent and the dye-image-generating reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, and

permitting the selective reaction of the peroxide oxidizing agent and the dye-image-generating reducing agent in a pattern conforming to the heterogeneous catalyst image pattern to permit a corresponding dye image to be formed,

wherein each of the first and second redox reactions is performed in an aqueous alkaline solution.

2. A method according to claim 1 wherein the reducing agent employed in the first redox reaction is a dye-image-generating reducing agent.

3. A method according to claim 2 wherein the aqueous alkaline solution employed in performing each of the redox reactions is sufficiently alkaline to immobilize substantially completely the cobalt(II) reaction product.

4. A method according to claim 2 wherein the aqueous alkaline solution employed in performing each of the redox reactions exhibits a pH of at least 10.

5. A method according to claim 1 wherein the cobalt(III) complex contains only monodentate and/or bidentate ligands.

6. A method according to claim 5 wherein the cobalt(III) complex is incorporated in an aqueous alkaline solution used in performing the first redox reaction.

7. A method according to claim 1 wherein the dye-image-generating reducing agent is comprised of a color-developing agent which, in its oxidized form, is capable of reacting with a color coupler to form a dye.

8. A method according to claim 7 wherein the color-developing agent is incorporated in an aqueous alkaline solution employed in the second redox reaction and the color coupler is incorporated in the photographic element being processed.

9. A method according to claim 1 wherein the reducing agent employed in the first redox reaction is a silver halide developing agent.

10. A method according to claim 9 wherein the silver halide developing agent employed in the first redox reaction is a color-developing agent.

11. A method according to claim 1 wherein the dye-image-generating reducing agent is a redox dye-releaser.

12. A method of forming an image comprising:

developing in the presence of a developing agent to produce a silver image pattern, an imagewise-exposed photographic element comprised of a support and at least one radiation-sensitive silver halide layer containing a developable latent image therein;

performing a first redox reaction by

bringing a cobalt(III) complex, which permanently releases ligands upon reduction, and a reducing agent together and into contact with the element containing the silver image pattern, and

permitting the selective reaction of the cobalt(III) complex and the reducing agent at the site of the silver image pattern to produce cobalt(II) as an immobile reaction product in a pattern conforming to the silver image pattern; and

performing a second redox reaction by

bringing into material contact a peroxide oxidizing agent, the immobile cobalt(II) reaction product and a dye-image-generating reducing agent capable of producing a dye-image generating reaction product, and

permitting the selective reaction of the peroxide oxidizing agent and the dye-image-generating reducing agent in a pattern conforming to the silver image pattern to permit a corresponding dye image to be formed, wherein each of the developing, first redox reaction and second redox reaction steps is performed using a common aqueous alkaline processing solution and the cobalt(III) complex, peroxide oxidizing agent, reducing agent and dye-image-generating reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst.

13. A method according to claim 12 wherein a black-and-white developing agent is employed to produce a silver image.

14. A method according to claim 12 wherein the silver halide within the photographic element is fixed after the second redox reaction step is completed.

15. A method according to claim 12 wherein the dye-image-generating reducing agent is incorporated in the photographic element and is a redox dye-releaser.

16. A method of forming an image comprising:

in a first aqueous alkaline solution bringing a photographic element bearing a silver image pattern into contact with an aqueous alkaline first amplification solution containing less than a 0.5 molar concentration of any compound which will form a tridentate or higher dentate ligand with cobalt, at least one of the photographic element and the first amplification solution additionally containing a cobalt(III) complex which permanently releases ligands upon reduction and a reducing agent wherein the cobalt(III) complex and the reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of the image silver, and

in a second aqueous alkaline solution bringing the photographic element into contact with an aqueous alkaline second amplification solution comprising a peroxide oxidizing agent and at least one of the photographic element and the second amplification solution containing a dye-image-generating reducing agent, wherein the peroxide oxidizing agent and the dye-image-generating reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst so that a dye image can be formed conforming to the silver image pattern originally present.

17. A method according to claim 16 wherein the cobalt(III) complex has a coordination number of 6 and contains at least 4 ammine ligands.

18. A method according to claim 17 wherein the cobalt(III) complex is a cobalt hexammine complex.

19. A method according to claim 16 wherein the peroxide oxidizing agent is water-soluble.

20. A method according to claim 19 wherein the peroxide oxidizing agent is hydrogen peroxide.

21. A method according to claim 16 wherein the dye-image-generating reducing agent is comprised of a primary aromatic amine developing agent and the photographic element includes incorporated therein at least one photographic color coupler.

22. 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 contains 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 pattern into contact with an aqueous alkaline first amplification 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 reducing agent and at least one of the photographic element and the first amplification solution additionally containing a cobalt(III) complex which permanently releases ligands upon reduction, wherein the cobalt(III) complex and the reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of the image silver, and

thereafter bringing the photographic element into contact with an aqueous alkaline second amplification solution, separate from said first amplification 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 and at least one of the photographic element and the second amplification solution containing a dye-image-generating reducing agent capable of entering into a redox reaction with the cationic cobalt(III) oxidizing agent, wherein the peroxide oxidizing agent and the dye-image-generating reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of the cobalt(II) reaction product, so that a dye image can be formed.

23. A method according to claim 22 wherein the developing agent is a black-and-white developing agent.

24. A method according to claim 22 wherein the dye-image-generating reducing agent is a color-developing agent contained within the aqueous alkaline second amplification solution and the photographic element contains at least one color coupler.

25. A method according to claim 22 wherein the steps of developing and first amplification are performed using a single aqueous alkaline processing solution having a pH of at least 10 and the cobalt(III) complex, the silver halide developing agent and the reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst.

26. A method according to claim 22 wherein the reducing agent employed in the aqueous alkaline first amplification solution is a dye-image-generating reducing agent.

27. A method according to claim 26 wherein the dye-image-generating reducing agent employed in the first amplification solution is a color-developing agent.

28. A method according to claim 22 wherein the developer solution is a color developer.

29. A method of forming an image comprising:

bringing a photographic element bearing a silver image pattern into contact with an aqueous alkaline first amplification 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 ligands with cobalt and comprising a silver halide developing agent as a reducing agent, at least one of the photographic element and the aqueous alkaline first amplification solution comprising a cobalt(III) complex having a coordination number of 6 and only monodentate or bidentate ligands, at least 4 of the ligands being ammine ligands,

thereafter bringing the photographic element into contact with an aqueous alkaline second 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 second amplification solution containing a color-developing agent and a photographic color coupler, and

bleaching at least a portion of the silver halide image to leave an amplified image comprised of image dye,

wherein the cobalt(III) complex and the silver halide developing agent are essentially inert to oxidation-reduction in the absence of a catalyst and the peroxide oxidizing agent and the color-developing agent are essentially inert to oxidation-reduction in the absence of a catalyst.

30. A method according to claim 29 wherein the cobalt(III) complex is cobalt hexammine.

31. A method according to claim 29 wherein the peroxide oxidizing agent is hydrogen peroxide present in a concentration of from about 0.001 to 0.5 mole per liter.

32. 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 first amplification 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 containing a developing agent as a reducing agent, at least one of the photographic element and the aqueous alkaline first amplification solution comprising a cobalt(III) complex having a coordination number of 6 and only monodentate or bidentate ligands, at least 4 of the ligands being ammine ligands,

thereafter 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 and a primary aromatic amine, at least one of the photographic element and the amplification solution containing a photographic color coupler, and

bleaching at least a portion of the silver image to leave an amplified image comprised of image dye, wherein the cobalt(III) complex and the silver halide developing agent are essentially inert to oxidation-reduction in the absence of a catalyst.

33. A method according to claim 32 wherein the aqueous alkaline first amplification solution initially contains less than a 0.01 molar concentration of any compound which will form a tridentate or higher dentate ligand with cobalt.

34. A method according to claim 32 wherein the developer solution and the first amplification solution are formed by a common aqueous alkaline solution and the second amplification solution is formed by a separate aqueous alkaline solution.

35. A method according to claim 32 wherein the developer solution, the first amplification solution and the second amplification solution are each formed by separate aqueous alkaline processing solutions.

36. 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 containing a developable latent image pattern, each of said layer units being primarily responsible 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, comprising:

developing a silver image in each of the three layer units corresponding to the latent image pattern thereof;

with a first aqueous alkaline processing solution performing a first redox reaction in each of the layer units by

bringing a cobalt(III) complex, which permanently releases ligands upon reduction, and a reducing agent together and into contact with the element containing the silver image pattern in each layer unit, wherein the cobalt(III) complex and the reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of the silver image, and

permitting the selective reaction of the cobalt(III) complex and the reducing agent at the site of the silver image pattern within each layer unit to produce cobalt(II) as an immobile reaction product in a pattern conforming to the silver image pattern in each layer unit; and

thereafter, with a second aqueous alkaline processing solution performing a second redox reaction by

bringing into mutual contact a peroxide oxidizing agent, the immobile cobalt(II) reaction product and a dye-image-generating reducing agent capable of producing a dye-image-generating reaction, wherein the peroxide oxidizing agent and the dye-image-generating reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, and

permitting the selective reaction of the peroxide oxidizing agent and the dye-image-generating reducing agent in a pattern conforming to the silver image pattern in each of the layer units to permit a corresponding dye image to be formed therein.

37. A method according to claim 36 wherein the first aqueous alkaline amplification solution contains less than a 0.05 molar concentration of any compound which will form a tridentate or higher dentate chelate with cobalt.

38. A method according to claim 36 wherein each layer unit contains from about 1.0 to 325 milligrams per square meter of silver halide.

39. A method according to claim 38 wherein each layer unit contains at least a 40% stoichiometric exess of the color coupler based on the weight of silver halide present.

40. A method according to claim 36 wherein the silver halide is fixed and the silver image is bleached.

41. 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 the 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 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 first amplification 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 developing agent as a reducing agent, at least one of the photographic element and the aqueous alkaline first amplification solution comprising a cobalt(III) complex having a coordination number of 6 and only monodentate or bidentate ligands, at least 4 of the ligands being ammine ligands, wherein the cobalt(III) complex and the silver halide developing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst,

thereafter bringing the photographic element into contact with a separate aqueous aklaline second 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, and

bleaching at least a portion of the silver image in each of the three layer units to leave an amplified image comprised of image dye.

42. A method according to claim 41 wherein the cobalt(III) complex is present as cobalt hexammine acetate or chloride in a concentration of from about 0.2 to 20 grams per liter of the bleach-fix solution.

43. The method according to claim 41 wherein the hydrogen peroxide is present in a concentration of from 0.001 to 0.5 mole per liter of the second amplification solution.

44. 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 first amplification solution having a pH in the range of from 10 to 13 which is substantially free from any compound which will form a tridentate or higher dentate ligand with cobalt and comprising from 1 to 20 grams per liter of a silver halide developing agent and from 0.2 to 20 grams per liter of cobalt hexammine acetate or chloride, and

thereafter bringing the photographic element into contact with an aqueous alkaline second amplification solution separate from the first 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-phenylenediamine color-developing agent, thereby forming the silver image in each layer unit with a dye image corresponding to the silver image pattern therein.

45. A color diffusion transfer method comprising

developing a silver image in at least one silver halide emulsion layer coated on a photographic support and containing a developable latent image pattern,

performing a first redox reaction by

bringing a cobalt(III) complex, which permanently releases ligands upon reduction, and a reducing agent together and into contact with the silver image, wherein the cobalt(III) complex and the reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of the silver image, and

permitting the selective reaction of the cobalt(III) complex and the reducing agent at the site of the silver image within the emulsion layer to produce cobalt(II) as an immobile reaction product in a pattern conforming to the silver image;

performing a second redox reaction by

bringing into mutual contact a peroxide oxidizing agent, the immobile cobalt(II) reaction product and a dye-image-generating reducing agent capable of producing a dye-image-generating reaction, wherein the peroxide oxidizing agent and the dye-image-generating reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, and

permitting the selective reaction of the peroxide oxidizing agent and the dye-image-generating reducing agent in a pattern conforming to the silver image pattern to permit a corresponding dye image to be formed in the emulsion layer; and

selectively transferring one of the dye image and the residual dye-image-generating reducing agent to a receiver for viewing,

wherein each of the first and second redox reactions is performed in an aqueous alkaline processing solution.

46. A color diffusion transfer method comprising

developing a silver image in at least one silver halide emulsion layer coated on a photographic support and containing a developable latent image pattern,

performing a first redox reaction by

bringing a cobalt(III) complex, which permanently releases ligands upon reduction, and a reducing agent together and into contact with the silver image, wherein the cobalt(III) complex and the reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of the silver image, and

permitting the selective reaction of the cobalt(III) complex and the reducing agent at the site of the silver image within the emulsion layer to produce cobalt(II) as an immobile reaction product in a pattern conforming to the silver image;

performing a second redox reaction by

bringing into mutual contact a peroxide oxidizing agent, the immobile cobalt(II) reaction product and a dye-image-generating reducing agent capable of producing a dye-image-generating reaction, wherein the peroxide oxidizing agent and the dye-image-generating reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, and

permitting the selective reaction of the peroxide oxidizing agent and the dye-image-generating reducing agent in a pattern conforming to the silver image pattern to permit a corresponding dye image to be formed in the emulsion layer; and

selectively transferring one of the dye image and the residual dye-image-generating reducing agent to a receiver for viewing,

wherein development of the silver image, the first redox reaction and the second redox reaction are performed by bringing an aqueous alkaline processing solution into contact with the silver halide emulsion layer and the cobalt(III) complex, the peroxide oxidizing agent, the reducing agent and the dye-image-generating reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst.

47. A color diffusion transfer method according to claim 46 wherein the aqueous alkaline processing solution initially upon contact with the emulsion layer exhibits a pH in the range of from 10 to 13.

48. A color diffusion transfer method according to claim 46 wherein the emulsion layer of a processing solution permeable layer adjacent thereto contains a redox dye-releaser as the dye-image-generating reducing agent and the peroxide oxidizing agent is present in the aqueous alkaline processing solution.

49. A color diffusion transfer method according to claim 48 wherein the peroxide oxidizing agent is hydrogen peroxide.

50. A color diffusion transfer method comprising

bringing into contact with a photographic element comprised of a support, at least one radiation-sensitive silver halide emulsion layer containing a developable latent image pattern and the emulsion layer or an aqueous alkaline processing solution permeable layer adjacent thereto containing a uniformly distributed redox dye-releaser, an aqueous alkaline processing 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 chelate with cobalt, a cobalt(III) complex oxidizing agent which permanently releases ligands upon reduction, a peroxide oxidizing agent and a crossoxidizing silver halide developing agent, wherein the redox dye-releaser, the developing agent and the oxidizing agents are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, and

selectively transferring a mobile dye image from the emulsion layer or the layer adjacent thereto to a receiver for viewing.

51. A method of forming an image comprising

in a first aqueous alkaline processing solution,

developing in the presence of a developing agent to produce a silver image pattern, an imagewise-exposed photographic element comprised of a support and at least one radiation-sensitive silver halide layer containing a developable latent image therein and

performing a first redox reaction by

bringing a cobalt(III) complex, which permanently releases ligands upon reduction, and a reducing agent together and into contact with the element containing the silver image pattern, wherein the developing agent, cobalt(III) complex and reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of the silver image, and

permitting the selective reaction of the cobalt(III) complex and the reducing agent at the site of the silver image pattern to produce cobalt(II) as an immobile reaction product in a pattern conforming to the silver image pattern;

and

in a second aqueous alkaline processing solution, performing a second redox reaction by

bringing into material contact with a peroxide oxidizing agent, the immobile cobalt(II) reaction product and a dye-image-generating reducing agent capable of producing a dye-image-generating reaction product, wherein the peroxide oxidizing agent and the dye-image-generating reducing agent are chosen so that they are essentially inert to oxidation-reduction in the absence of a catalyst, and

permitting the selective reaction of the peroxide oxidizing agent and the dye-image-generating reducing agent in a pattern conforming to the silver image pattern to permit a corresponding dye image to be formed.

52. A method according to claim 51 wherein the developing agent is also the reducing agent.

53. 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 processing solution having a pH in the range of from 10 to 13, at least one of the photographic element and the processing solution contains a photographic color coupler and a cobalt(III) complex having a coordination number of 6 and only monodentate or bidentate ligands, at least 4 of the ligands being ammine ligands, the aqueous alkaline processing solution contains a dye-image-generating primary aromatic amine silver halide developing agent, a peroxide oxidizing agent and less than a 0.5 molar concentration of any compound which will form a tridentate or higher dentate ligand with cobalt, wherein the cobalt(III) complex, the dye-image-generating developing agent and the peroxide oxidizing agent are essentially inert to oxidation-reduction in the absence of a catalyst, so that a silver image is formed in the photographic element corresponding to the developable latent image and an amplified dye image is formed which corresponds to the silver image and

thereafter bleaching at least a protion of the silver image to leave the amplified dye image.