Hendess, Raymond W. (Webster, NY)
Gilmour, Hugh S. A. (Rochester, NY)

05/052721

03/07/1972

07/06/1970

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Eastman Kodak Company (Rochester, NY)

430/379

430/384, 430/388, 430/389, 430/386, 430/505, 430/385, 430/376, 430/387

G03C5/50; G03C7/30; G03C7/32; G03C1/40; G03C7/00; G03C5/52

96/100,66,9,55,22

Torchin, Norman G.

Suro Pico, Alfonso T.

We claim

1. A light-sensitive photographic element for direct reversal color processing, said element comprising a support coated with at least one light-sensitive hardened hydrophilic colloid silver halide emulsion layer containing at least one nondiffusible dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color developing agent produced in a color developer solution by silver halide development to form a nondiffusible dye image and on the same side of said support at least one hardened hydrophilic colloid layer containing at least one competing coupler that is capable of reacting with said oxidation product of said color developing agent to form a reaction product selected from the class of a diffusible reaction product and a colorless reaction product, said competing coupler, instead of said dye-image-forming coupler, reacts with said oxidation product of said color developing agent, so that when said element is light image exposed to produce a latent image and then contacted with said color developer solution, there is a sufficient amount of said competing coupler present in said element to react with substantially all of said color developing agent oxidized during development of the light exposed areas in said latent image, but not enough of said competing coupler present in said element during subsequent fogging color development of unexposed areas of silver halide to interfere with the reaction of oxidized color developing agent with said dye-image-forming coupler to produce a positive dye image.

2. A light-sensitive photographic element of claim 1 in which said competing coupler is incorporated into at least one light-sensitive layer.

3. A light-sensitive photographic element of claim 1 in which the side of said support opposite the side containing said competing coupler is coated with at least one hydrophilic colloid silver halide emulsion layer containing a nondiffusible dye-image-forming coupler that forms a nondiffusible dye image.

4. A light-sensitive photographic element of claim 1 in which said competing coupler is soluble, diffusible and produces, upon reaction with oxidized aromatic primary amine color-developing agent, a colorless compound.

5. A light-sensitive photographic element of claim 1 in which said competing coupler is soluble, diffusible and produces, upon reaction with oxidized aromatic primary amine color-developing agent, a soluble compound, substantially all of which diffuses out of said element during development into said developer solution.

6. A light-sensitive photographic element for direct reversal color processing, said element comprising a support coated on one side with a hardened hydrophilic colloid red-sensitized silver halide emulsion layer containing a nondiffusible cyan-dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened hydrophilic colloid green-sensitized silver halide emulsion layer containing a nondiffusible magenta-dye-image-forming coupler that is capable of reacting with said oxidation product of said color developing agent to form a nondiffusible magenta dye image, and a hardened hydrophilic colloid blue-sensitive silver halide emulsion layer containing a nondiffusible yellow-dye-image-forming coupler that is capable of reacting with said oxidation product of said color developing agent to form a nondiffusible yellow dye image and on the same side of said support at least one hardened hydrophilic colloid layer containing an incorporated competing coupler that is capable of reacting with said oxidation product of said color developing agent to form a reaction product leaving no perceptible color after processing, said competing coupler, instead of said dye-image-forming couplers reacting with said oxidation product of said color developing agent so that when said element is light image exposed to produce a latent image and then contacted with said color developer solution, there is a sufficient amount of said competing coupler present in said element to react with substantially all of the oxidation product of said color-developing agent produced by development of the light-exposed areas in said latent images, but not enough of said competing coupler present in said element to interfere during subsequent fogging color development of unexposed areas of silver halide with the reaction of said oxidation product of said color-developing agent formed with said color-forming coupler to produce a positive dye image.

7. A light-sensitive photographic element for direct reversal color processing, said element comprising a support coated on one side with a hardened hydrophilic colloid red-sensitized silver halide emulsion layer containing a nondiffusible cyan-dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color-developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened hydrophilic colloid green-sensitized silver halide emulsion layer containing a nondiffusible magenta-dye-image-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible magenta dye image, and a hardened hydrophilic colloid blue-sensitive silver halide emulsion layer containing a nondiffusible yellow-dye-image forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible yellow dye image and on the same side of said support at least one hardened hydrophilic colloid layer containing an incorporated competing coupler that is capable of reacting with said oxidation product of said color developing agent to form a reaction product that is selected from the class consisting of a diffusible reaction product and a colorless reaction product, said competing coupler being selected from the class consisting of (1) any diffusible competing coupler that reacts with said oxidation product of said color developing agent without producing a perceptible image that remains in said element, and (2) any nondiffusible competing coupler that initially reacts with said oxidation product of said color developing agent without producing any perceptible image, but upon contact with said developer solution slowly becomes non-reactive with oxidized color developing agent, said competing coupler, instead of said dye-image-forming couplers reacting with said oxidation product of said developing agent so that when said element is light image exposed to produce a latent image and then contacted with said color developer solution, there is a sufficient amount of said competing coupler present in said element to react with substantially all of said oxidation product of said color developing agent produced during development of the light exposed areas in said latent images, but not enough of said competing coupler present in said element during subsequent fogging development of unexposed areas of silver halide to interfere with the reaction of said oxidation product of said color developing agent formed during said fogging development with said color-forming coupler to produce a positive dye image.

8. A light-sensitive photographic element for direct reversal color processing, said element comprising a support coated on one side with a hardened hydrophilic colloid red-sensitized silver halide emulsion layer containing a nondiffusible cyan-dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color-developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened hydrophilic colloid green-sensitized silver halide emulsion layer containing a nondiffusible magenta-dye-image-forming coupler that is capable of reacting with said oxidation product of said color developing agent to form a nondiffusible magenta dye image, and a hardened hydrophilic colloid blue-sensitive silver halide emulsion layer containing a nondiffusible yellow-dye-image-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible yellow dye image and on the same side of said support at least one hardened hydrophilic colloid layer containing an incorporated competing coupler that is capable of reacting with said oxidation product of said color-developing agent to form a reaction product that is selected from the class consisting of a diffusible reaction product and a colorless reaction product, said competing coupler being selected from the class consisting of those having the formula:

9. A light-sensitive photographic element for direct reversal color processing, said element comprising a support coated on one side with a hardened hydrophilic colloid red-sensitized silver halide emulsion layer containing a nondiffusible cyan-dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color-developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened hydrophilic colloid green-sensitized silver halide emulsion layer containing a nondiffusible magenta-dye-image-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible magenta dye image, and a hardened hydrophilic colloid blue-sensitive silver halide emulsion layer containing a nondiffusible yellow-dye-image-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible yellow dye image and on the same side of said support at least one hardened hydrophilic colloid layer containing an incorporated competing coupler that is capable of reacting with said oxidation product of said color developing agent to form a reaction product that is selected from the class consisting of a diffusible reaction product and a colorless reaction product, said competing coupler being selected from the class consisting of those having the formulas:

10. A light-sensitive photographic element for direct reversal color processing, said element comprising a support coated on one side with a hardened hydrophilic colloid red sensitized silver halide emulsion layer containing a nondiffusible cyan-dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened hydrophilic colloid green-sensitized silver halide emulsion layer containing a nondiffusible magenta-dye-image-forming coupler that is capable of reacting with said oxidation product of said color developing agent to form a nondiffusible magenta dye image and a hardened hydrophilic colloid blue-sensitive silver halide emulsion layer containing a nondiffusible yellow-dye-image-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible yellow dye image and on the same side of said support at least one hardened hydrophilic colloid layer containing an incorporated competing coupler that is capable of reacting with said oxidation product of said color-developing agent to form a reaction product that leaves no perceptible color in said element after processing, said competing coupler being selected from those having the formulas: ##SPC6##

11. A light-sensitive photographic element for direct reversal color processing, said element comprising a support coated on one side with a hardened hydrophilic colloid red-sensitized silver halide emulsion layer containing a nondiffusible cyan-dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color-developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened hydrophilic colloid green-sensitized silver halide emulsion layer containing a nondiffusible magenta-dye-image-forming coupler that is capable of reacting with said oxidation product of said color developing agent to form a nondiffusible magenta dye image, and a hardened hydrophilic colloid blue-sensitive silver halide emulsion layer containing a nondiffusible yellow-dye-image-forming coupler that is capable of reacting with said oxidation product of said color developing agent to form a nondiffusible yellow dye image and on the same side of said support at least one hardened hydrophilic colloid layer containing an incorporated competing coupler that is capable of reacting with said oxidation product of said color-developing agent to form a reaction product that leaves no perceptible color in said element after processing, said competing coupler being selected from those having the formulas:

12. A light-sensitive photographic element for direct reversal color processing, said element comprising a support coated on one side with a hardened hydrophilic colloid red-sensitized silver halide emulsion layer containing a nondiffusible cyan-dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened hydrophilic colloid green-sensitized silver halide emulsion layer containing a nondiffusible magenta-dye-image-forming coupler that is capable of reacting with said oxidation product of said color developing agent to form a nondiffusible magenta dye image, and a hardened hydrophilic colloid blue-sensitive silver halide emulsion layer containing a nondiffusible yellow-dye-image-forming coupler that is capable of reacting with said oxidation product of said color developing agent to form a nondiffusible yellow dye image and on the same side of said support at least one hardened hydrophilic colloid layer containing at least one competing coupler that is capable of reacting with said oxidation product of said color developing agent to form a reaction product that leaves no perceptible color in said element after processing, said competing coupler being selected from the class consisting of:

13. ,4-dimethyl-1-(4-sulfophenyl)-5-pyrazolone

14. -methyl-1-(4-sulfophenyl)-5-pyrazolone

15. -amino-5-naphthol-7-sulfonic acid

16. -amino-1-naphthol-3,6-disulfonic acid

17. ,6-dichloro-5-methyl-2-(4-sulfobenzamido)phenol

18. ,6-dihydroxyisonicotinic acid

19. ,5-dihydroxybenzoic acid

20. -amino-8-naphthol-3,6-disulfonic acid,

21. -amino-8-naphthol-2,4-disulfonic acid,

22. -amino-8-naphthol-6-sulfonic acid,

23. -acetamino-8-naphthol-3,6-disulfonic acid, and

24. -[N-ethyl-N-(3,5-dicarboxyphenyl)carbamyl]-α-naphthol; said competing coupler present in said element in sufficient amount to react with substantially all of said oxidation product of said color-developing agent produced during development of the light exposed areas in said latent images, but not enough of said competing coupler present in said element during subsequent fogging development of unexposed areas of silver halide to interfere with the reaction of said oxidation product of said color-developing agent formed during said fogging development with said color-forming coupler to produce a positive dye image.

25. A photographic element of claim 12 in which the said hydrophilic colloid silver halide emulsions are gelatin silver bromoiodide emulsions and in which said red-sensitized layer, said green-sensitized layer and said blue-sensitive layer are arranged in that order on said support.

26. A photographic element of claim 12 in which the said hydrophilic colloid silver halide emulsions are gelatin silver chlorobromide emulsions and in which said blue-sensitive layer, said green-sensitized layer and said red-sensitized layer are arranged in that order on said support.

27. A light-sensitive photographic element for direct reversal color processing, said element comprising a support coated in succession on one side with a hardened gelatin red-sensitized silver bromoiodide emulsion layer containing a nondiffusible phenolic cyan-dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color-developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened gelatin green-sensitized silver bromoiodide emulsion layer containing a nondiffusible 5-pyrazolone magenta-dye-image-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible magenta dye image, and a hardened gelatin blue-sensitive silver bromoiodide emulsion layer containing a nondiffusible open chain ketomethylene yellow-dye-image-forming coupler that is capable of reacting with said oxidation product of said color developing agent to form a nondiffusible yellow dye image and on the same side of said support at least one hardened gelatin layer containing the competing coupler α-methyl-α-pivalylacet-2,4-dicarboxyanilide so that the total amount of said competing coupler in said element is in the range of from about 0.1 g./ft.² to about 5.0 g./ft.² of said element.

28. A light-sensitive photographic element for direct reversal color processing, said element comprising a support coated in succession on one side with a hardened gelatin red-sensitized silver bromoiodide emulsion layer containing a nondiffusible phenolic cyan-dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color-developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened gelatin green-sensitized silver bromoiodide emulsion layer containing a nondiffusible 5-pyrazolone magenta-dye-image-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible magenta dye image and a hardened gelatin blue-sensitive silver bromoiodide emulsion layer containing a nondiffusible open chain ketomethylene yellow-dye-image-forming coupler that is capable of reacting with said oxidation product of said color developing agent to form a nondiffusible yellow dye image and on the same side of said support at least one hardened gelatin layer containing the competing coupler 8-amino-1naphthol-3,6-disulfonic acid so that the total amount of said competing coupler in said element is in the range of from about 0.1 g./ft.² to about 5.0 g./ft.² of said element.

29. A light-sensitive photographic element for direct reversal color processing, said element comprising a support coated in succession on one side with a hardened gelatin red-sensitized silver bromoiodide emulsion layer containing a nondiffusible phenolic cyan-dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened gelatin green-sensitized silver bromoiodide emulsion layer containing a nondiffusible 5-pyrazolone magenta-dye-image-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible magenta dye image, and a hardened gelatin blue-sensitive silver bromoiodide emulsion layer containing a nondiffusible open chain ketomethylene yellow-dye-image-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible yellow dye image and on the same side of said support at least one hardened gelatin layer containing the competing coupler 2-amino-5-naphthol-7-sulfonic acid so that the total amount of said competing coupler in said element is in the range of from about 0.1 g./ft.² to about 5.0 g./ft.² of said element.

30. A light-sensitive photographic element for direct reversal color processing, said element comprising a support coated in succession on one side with a hardened gelatin red-sensitized silver bromoiodide emulsion layer containing a nondiffusible phenolic cyan-dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened gelatin green-sensitized silver bromoiodide emulsion layer containing a nondiffusible 5-pyrazolone magenta-dye-image-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible magenta dye image, and a hardened gelatin blue-sensitive silver bromoiodide emulsion layer containing a nondiffusible open chain ketomethylene yellow-dye-image-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible yellow dye image and on the same side of said support at least one hardened gelatin layer containing the competing coupler 2,6-dihydroxyisonicotinic acid so that the total amount of said competing coupler in said element is in the range of from about 0.1 g./ft.² to about 5.0 g./ft.² of said element.

31. A light-sensitive photographic element for direct reversal color processing, said element comprising a support coated in succession on one side with a hardened gelatin red-sensitized silver bromoiodide emulsion layer containing a nondiffusible phenolic cyan-dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color-developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened gelatin green-sensitized silver bromoiodide emulsion layer containing a nondiffusible 5-pyrazolone magenta-dye-image-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible magenta dye image and a hardened gelatin blue-sensitive silver bromoiodide emulsion layer containing a nondiffusible open chain ketomethylene yellow-dye-image-forming coupler that is capable of reacting with said oxidation product of said color developing agent to form a nondiffusible yellow dye image and on the same side of said support at least one hardened gelatin layer containing the competing coupler 3,5-dihydroxy benzoic acid so that the total amount of said competing coupler in said element is in the range of from about 0.1 g./ft.² to about 5.0 g./ft.² of said element.

32. A direct reversal color process for a color photographic element containing at least one hydrophilic colloid-silver halide emulsion layer in which is incorporated a nondiffusible dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color developing agent produced in a color developer solution by silver halide development to form a nondiffusible dye image, said silver halide containing a latent image of an original light image, said process comprising the steps:

33. developing substantially all light-exposed areas of said latent image in said silver halide to a corresponding negative silver image reproduction of said original light image and forming a reaction product that is selected from the class consisting of a diffusible reaction product and a colorless reaction product by contacting said silver halide with an aqueous alkaline solution of an aromatic primary amine color-developing agent in the presence of a sufficient amount of at least one competing coupler to react with substantially all of the oxidation product of said color developing agent produced by development of said negative silver image to form a reaction product leaving no perceptible color after processing but not enough of said competing coupler remaining in said element to interfere during subsequent fogging development of unexposed areas of silver halide with the reaction of said oxidation product of said color developing agent formed therefrom with said dye-image-forming coupler and maintaining contact of the negative-developed silver halide emulsion layer with said developer solution until the unexposed silver halide is chemically fogged and developed by said solution to form a positive silver and a positive dye image reproduction of said original light image; and

34. removing silver and any residual silver halide in said photographic element by contacting with a silver bleach-fix bath or a bleach bath followed by a fixing bath, leaving a positive dye image reproduction of said original light image.

35. A direct reversal color process for a color photographic element containing at least one hydrophilic colloid silver halide emulsion layer in which is incorporated a nondiffusible dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color-developing agent produced in a color developer solution by silver halide development to form a nondiffusible dye image, said silver halide containing a latent image of an original light image, said process comprising the steps:

36. imbibing into said emulsion layer a sufficient amount of a solution of a diffusible competing coupler so that there is enough of said competing coupler present during the subsequent development step to react with substantially all of said oxidation product of said color-developing agent formed during development of substantially all light-exposed areas of said latent image in said silver halide without interfering with the reaction of said dye-image forming coupler with said oxidation product of said color-developing agent formed during subsequent fogging development of unexposed silver halide,

37. developing of substantially all light-exposed areas of said latent image in said silver halide to a corresponding negative silver image reproduction of said original light image and forming a reaction product that is selected from the class consisting of a diffusible reaction product and a colorless reaction product by contacting said silver halide emulsion layer in the presence of said competing coupler imbibed in step (1), with an aqueous alkaline developer solution containing an aromatic primary amine color-developing agent and subsequent fogging development of unexposed areas of said silver halide and the reaction of incorporated nondiffusible dye-image-forming coupler with said oxidation product of said color-developing agent to form a positive silver image and a positive dye image reproduction of said original light image, and

38. removing silver and any residual silver halide from said developed element by contacting with a silver bleach-fix bath or a bleach bath followed by a fixing bath, leaving a positive dye image reproduction of said original light image.

39. A direct reversal color process for a color photographic element comprising a support coated on one side with a hydrophilic colloid red-sensitized silver halide emulsion layer containing a nondiffusible cyan-dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color-developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hydrophillic colloid green-sensitized silver halide emulsion layer containing a nondiffusible magenta-dye-image-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible magenta dye image, and a hydrophilic colloid blue-sensitive silver halide emulsion layer containing a nondiffusible yellow-dye-image-forming coupler that is capable of reacting with said oxidation product of said color developing agent to form a nondiffusible yellow dye image, said silver halide containing a latent image of an original light image, said process comprising the steps:

40. developing substantially all light-exposed areas of said latent image in said silver halide to a corresponding negative silver image reproduction of said original light image and forming a reaction product that is selected from the class consisting of a diffusible reaction product and a colorless reaction product by contacting said silver halide with an aqueous alkaline solution of an aromatic primary amine color developing agent in the presence of a sufficient amount of a competing coupler to react with substantially all of the oxidation product of said color developing agent produced by development of said silver negative image to form a reaction product leaving no perceptible color after processing, but not enough of said competing coupler remaining in said element to interfere during subsequent fogging development of unexposed areas of silver halide with the reaction of said oxidation product of said color-developing agent formed therefrom with said dye-image-forming coupler, said competing coupler being selected from the class consisting of those having the formulas:

41. removing silver and any residual silver halide in said photographic element by contacting with a silver bleach-fix bath or a silver bleach bath followed by a fixing bath, leaving a positive dye image reproduction of said original light image.

42. A direct reversal color process for a color photographic element comprising a support coated on one side with a hydrophilic colloid red-sensitized silver halide emulsion layer containing a nondiffusible phenolic cyan-dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color-developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hydrophilic colloid green-sensitized silver halide emulsion layer containing a nondiffusible 5-pyrazolone magenta-dye-image-forming coupler that is capable of reacting with said oxidation product of said color developing agent to form a nondiffusible magenta dye image, and a hydrophilic colloid blue-sensitive silver halide emulsion layer containing a nondiffusible open chain ketomethylene yellow-dye-image-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible yellow dye image, said silver halide containing a latent image of an original light image, said process comprising the steps:

43. contacting the outermost emulsion layer of said element with an aqueous solution containing a soluble, diffusible competing coupler selected from the class consisting of

44. ,4-dimethyl-1-(4-sulfophenyl)-5-pyrazolone

45. -methyl-1-(4-sulfophenyl)-5-pyrazolone

46. -amino-5-naphthol-7-sulfonic acid

47. -amino-1-naphthol-3,6-disulfonic acid

48. ,6-dichloro-5-methyl-2-(4-sulfobenzamido)phenol

49. ,6-dihydroxyisonicotinic acid

50. ,5-dihydroxybenzoic acid

51. -amino-8-naphthol-3,6disulfonic acid

52. -amino-8-naphthol-2,4-disulfonic acid

53. -amino-8-naphthol-6-sulfonic acid

54. -acetamino-8-naphthol-3,6-disulfonic acid and

55. -[N-ethyl-N-(3,5-dicarboxyphenyl)carbamyl]-α -naphthol.

56. contacting said element containing said competing coupler with an aqueous alkaline color developer solution containing in the range of from about 2.0 g./l. to about 100 g./l. of an aromatic primary amine color developing agent while light exposed areas of silver halide in said latent image are developed to a negative silver image and an oxidation product of aromatic primary amine color-developing agent formed by development of said negative silver image, reacts with said competing coupler to produce a compound that leaves no perceptible color in said element after processing, and while the unexposed silver halide in each of said emulsion layers is subsequently developed to a positive silver image by fogging development and the oxidation product of said color developing agent formed by development of said positive silver image thereby reacts with the said nondiffusible dye-image-forming couplers present to form a positive dye image;

57. contacting the developed element from step (2) with an acidic solution containing sulfite ions;

58. contacting the element from step (3) with a silver bleach to convert silver to a silver salt; and

59. contacting the element from step (4) with a fixing bath to remove silver salts from said element leaving a color reversal image formed in step (2).

60. A direct reversal color process for a color photographic element comprising a support coated on one side with a hydrophilic colloid red-sensitized silver halide emulsion layer containing a nondiffusible phenolic cyan-dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color-developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hydrophilic colloid green-sensitized silver halide emulsion layer containing a nondiffusible 5-pyrazolone magenta-dye-image-forming coupler that is capable of reacting with said oxidation product of said color developing agent to form a nondiffusible magenta dye image, and a hydrophilic colloid blue-sensitive silver halide emulsion layer containing a nondiffusible open chain ketomethylene yellow-dye-image-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible yellow dye image, said silver halide containing a latent image of an original light image, said process comprising the steps:

61. contacting the outermost emulsion layer of said element with an aqueous solution containing a soluble, diffusible competing coupler selected from the class consisting of:

62. ,4-dimethyl-1-(4-sulfophenyl)-5-pyrazolone

63. -methyl-1-(4-sulfophenyl)-5-pyrazolone

64. -amino-5-naphthol-7-sulfonic acid

65. -amino-1-naphthol-3,6-disulfonic acid

66. ,6-dichloro-5-methyl-2-(4-sulfobenzamido)phenol

67. ,6-dihydroxyisonicotinic acid

68. ,5-dihydroxybenzoic acid

69. -amino-8-naphthol-3,6-disulfonic acid

70. -amino-8-naphthol-2,4-disulfonic acid

71. -amino-8-naphthol-6-sulfonic acid

72. -acetamino-8-naphthol-3,6-disulfonic acid and

73. -[N-ethyl-N-(3,5-dicarboxyphenyl)carbamyl]-α-naphthol.

74. contacting said element containing said competing coupler with an aqueous alkaline color developer solution containing in the range of from about 2.0 g./l. to about 100 g./l. of an aromatic primary amine color developing agent while light-exposed areas of silver halide in said latent image are developed to a negative silver image and an oxidation product of said aromatic primary amine color developing agent formed by negative development reacts with said competing coupler to produce a compound that leaves no perceptible color in said element after processing, and while the unexposed silver halide in each of said emulsion layers is subsequently developed to a positive silver image by fogging development and an oxidation product of said aromatic primary amine color developing agent produced by said positive silver image formation reacts with the said nondiffusible dye-image-forming coupler present to form a positive dye image reproduction of said original light image;

75. contacting said developed element from (2) with a silver bleach-fix bath to remove silver and silver salts; and

76. A direct reversal color process for a color photographic element containing at least one hydrophilic colloid-silver halide emulsion layer in which is incorporated a nondiffusible dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color developing agent produced in a color developer solution by silver halide development to form a nondiffusible dye image, said silver halide containing a latent image of an original light image, said process comprising the steps:

77. developing substantially all light-exposed areas of said latent image in said silver halide to a corresponding negative silver image reproduction of said original light image and forming a reaction product that is selected from the class consisting of a diffusible reaction product and a colorless reaction product by contacting said silver halide with an aqueous alkaline solution of an aromatic primary amine color-developing agent in the presence of a sufficient amount of at least one competing coupler to react with substantially all of the oxidation product of said color-developing agent produced by development of said negative silver image to form a reaction product leaving no perceptible color after negative development;

78. developing the unexposed areas of silver halide with an aqueous alkaline solution of an aromatic primary amine color-developing agent until substantially all of the unexposed silver halide is converted to silver by fogging action of said solution and allowing the oxidation product of the aromatic primary amine formed thereby to react with said dye-image-forming coupler to form a positive dye image reproduction of said original light image; and

79. removing silver and any residual silver halide in said photographic element by contacting with a silver bleach-fix bath or a bleach bath followed by a fixing bath, leaving a positive dye image reproduction of said original light image.

80. A direct reversal color process of claim 20 that is operated continuously and in which said aqueous alkaline solution of color-developing agent used to develop said photographic element is recirculated through an anion exchange column containing an anion exchange resin to remove unused competing coupler that diffused into said solution from said photographic element during the development step so that said unused competing coupler will not be available in said solution to diffuse back into the said element and interfere with the positive dye image formation during said fogging development.

81. A direct reversal color process of claim 20 in which said solution of color-developing agent contains a compound which renders competing coupler in said solution at least one of unreactive with oxidized aromatic primary amine color developing agent and nondiffusible in hydrophilic colloid layers of a photographic element.

82. A direct reversal color process of claim 20 in which said solution of color developing agent contains a compound selected from the class consisting of an alkali metal salt of boric acid and a quaternary ammonium salt having the formula:

83. A light-sensitive photographic element for direct reversal color processing, said element comprising a support coated on one side with a hardened hydrophilic colloid silver halide emulsion layer containing a mixture of a nondiffusible cyan-dye-image-forming coupler, a nondiffusible magenta-dye-image-forming coupler and a nondiffusible yellow-dye-image-forming coupler, said couplers being capable of reacting with an oxidation product of an aromatic primary amine color developing agent produced in a color developer solution by silver halide development to form a cyan dye image, a magenta dye image and a yellow dye image, respectively, said mixture of said couplers being such that said cyan dye image, said magenta dye image and said yellow dye image formed by reaction with oxidized aromatic primary amine color-developing agent forms an essentially neutral colored dye image, and on the same side of said support at least one hydrophilic colloid layer containing at least one competing coupler that is capable of reacting with said oxidation product of said color-developing agent to form a reaction product selected from the class consisting of a diffusible reaction product and a colorless reaction product, said competing coupler, instead of said dye-image-forming coupler, reacts with said oxidation product of said color developing agent, so that when said element is light image exposed to produce a latent image and then contacted with said color developer solution, there is a sufficient amount of said competing coupler present in said element to react with substantially all of said color-developing agent oxidized during development of the light-exposed areas in said latent image, but not enough of said competing coupler present in said element during subsequent fogging color development of unexposed areas of silver halide to interfere with the reaction of oxidized color developing agent with said dye-image-forming coupler to produce a positive neutral colored dye image.

84. In a color photographic process for processing color photographic elements that contain a support coated with at least one hydrophilic colloid silver halide emulsion layer in which is incorporated a nondiffusible dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color-developing agent produced in a color developer solution by silver halide development to form a nondiffusible dye image, said silver halide containing a latent image of an original light image, said process being either (A) a negative process comprising the steps of:

85. contacting said latent image with said color developer solution to develop the light exposed areas of said latent image to a negative silver and a negative dye image,

86. contacting said developed images with a silver bleaching agent to convert said negative silver image to a silver salt and

87. contacting said silver salt with a fixing bath to remove said silver salt, leaving said negative dye image reproduction of said original light image or (B) a reversal process comprising the steps of:

88. contacting said latent image with a non-color-forming silver halide developer solution to develop the light-exposed areas of said latent image to a negative silver image,

89. contacting said developed silver halide with an acid stop bath,

90. fogging the previously unexposed and undeveloped areas of said latent image to render them developable.

91. contacting said fogged, undeveloped areas of said latent image with an aromatic primary amine color developing solution to develop said undeveloped areas of said latent image to a positive silver image and oxidized color developing agent which reacts with said nondiffusible coupler to form a nondiffusible positive dye image,

92. contacting said developed images with a silver bleaching agent to convert said negative silver image and said positive silver images into a silver salt and

93. contacting said silver salt with a fixing bath to remove said silver salt, leaving said positive dye image reproduction of said original light image, said processes A and B being incompatible, the improvement comprising the use of a single color process for processing a color negative photographic element and/or a direct reversal color photographic element with said color negative element and said direct reversal color element being processed as desired through said process, said color negative element containing a support coated with at least one hydrophilic colloid silver halide emulsion layer in which is incorporated a nondiffusible dye-image-forming coupler that is capable of reacting with an oxidation product of said color-developing agent produced in a color developer solution by silver halide development to form a nondiffusible dye image, said direct reversal color element containing a support coated with at least one hydrophilic colloid silver halide emulsion layer in which is incorporated a nondiffusible-dye-image-forming coupler that is capable of reacting with an oxidation product of said color-developing agent produced in a color developer solution by silver halide development to form a nondiffusible dye image and on the side of said support on which it is desired to have a reversal image, at least one hydrophilic colloid layer containing a competing coupler in the range of from about 0.1 g. to about 5.0 g. per square foot of said element, said competing coupler reacting with said oxidation product of said color-developing agent to produce a compound that leaves no perceptible color in said element after processing, said process comprising the steps:

94. contacting said latent image with an aqueous alkaline color developer solution containing in the range of from about 2.0 g./l. to about 100 g./l. of an aromatic primary amine color-developing agent so that light-exposed areas of said latent image in said color negative element are developed to a negative silver image and an oxidation product of said color developer that reacts with said image-forming coupler to form a negative dye image, and so that light-exposed areas of said latent image in said direct reversal color element are developed to a negative silver image and an oxidation product of said color-developing agent formed by development of said negative silver image which reacts with said competing coupler to produce a compound that leaves no perceptible color in said element after processing and while the unexposed silver halide in said emulsion layer is subsequently developed to a positive silver image by fogging development and the oxidation product of said color-developing agent formed by development of said positive silver image reacts with said nondiffusible dye-image-forming coupler present to form a positive dye image;

95. contacting said elements developed in step (1) with a silver bleach-fix bath or a silver bleach followed by a fixing bath to convert said silver to a silver salt and to remove said silver salt, leaving a negative dye image reproduction of said original image in said negative color element and leaving a reversal dye image reproduction of said original image in said direct reversal color element.

96. An improved process of claim 30 in which said competing coupler is selected from the class consisting of those having the formulas:

97. An improved process of claim 30 in which said competing coupler is selected from the class consisting of those having the formulas: ##SPC11##

98. An improved process of claim 30 in which said competing coupler is selected from the class consisting of those having the formulas:

99. An improved process of claim 30 in which said competing coupler is selected from the class consisting of:

100. ,4-dimethyl-1-(4-sulfophenyl)-5-pyrazolone

101. -methyl-1-(4-sulfophenyl)-5-pyrazolone

102. -amino-5-naphthol-7-sulfonic acid

103. -amino-1-naphthol-3,6-disulfonic acid

104. ,6-dichloro-5-methyl-2-(4-sulfobenzamido)phenol

105. ,6-dihydroxyisonicotinic acid

106. ,5-dihydroxybenzoic acid

107. -amino-8-naphthol-3,6-disulfonic acid

108. -amino-8-naphthol-2,4-disulfonic acid

109. -amino-8-naphthol-6-sulfonic acid

110. -acetamino-8-naphthol-3,6-disulfonic acid, and

111. -[N-ethyl-N-(3,5-dicarboxyphenyl)carbamyl]-α-naphthol.

This invention is related to photography, to novel direct reversal photographic films and papers, to novel direct color reversal processes and to developer compositions.

The usual color reversal photographic process for photographic elements containing incorporated color-forming couplers, involves the use of a negative silver development step in which the negative silver is developed by a conventional hydroquinone-p-methylaminophenol sulfate developer or a conventional hydroquinone-1-phenyl-3-pyrazolidone developer. Negative silver development is usually followed by a stop bath and wash to rapidly stop development and prevent overdevelopment, and to remove residual developing agent. The remaining silver halides are then fogged either physically by a light exposure, or chemically by means of a reducing agent such as t-butylamine borane or stannous chloride, and this positive fogged silver halide is then color developed with a p-phenylenediamine developing agent to give a reversal color image. In a commercial process, this procedure may take as long as 32 minutes at 24° C. up to and including the color development step and the washes required to remove the chemicals at the end of each step. Typical reversal processes are described in line 74, column 11 through line 36, column 12 of Carroll et al., U.S. Pat. No. 2,944,900, line 40, column 3 through line 11, page 4 of Henn et al., U.S. Pat. No. 2,984,567, and line 32, column 9 through line 26, column 10 of Bard et al., U.S. Pat. No. 3,189,452.

Of particular note is that these processes have five critical steps as follows:

First developer (non-color-image-forming)

Hardener or stop

Wash

Reversal exposure

Color developer

The first developer, which forms the negative silver image must be uniformly distributed throughout all layers of a multilayer color element, and negative development must stop at precisely the correct moment. The stop bath must therefore be uniformly applied and effective on all layers so that the cessation of development is uniform. The wash must remove all of the ingredients from both the development and stop bath stages so that the color development step is not interfered with. The reversal exposure step must expose all residual silver halide and, if done chemically, must not interfere with the color development step. Color development must again be uniform in all three layers to give the proper balance of speeds and curve shapes. Color development must go to completion in D-max areas, and yet in D-min areas must not give rise to unwanted color fog or stain.

In continuous processing, such as is done for motion picture films, carryover of one solution into another may become a major problem. Seasoning of solution due to usage and leaching out of photographic reaction products and emulsion addenda from the photographic element into the processing solutions also becomes a problem. Elaborate control systems and replenishment systems have been worked out and excellent results are now obtained using the hereinbefore described system. However, much is to be desired when five complex steps are involved in producing reversal color photographs, and much effort has been expended to obtain direct color reversal systems which replace all five steps with a single process step, namely, the color development step.

Many systems have been proposed for obtaining direct reversal images either in color or black-and-white photographic elements. Solarization with an intense light source was one of the earliest methods of obtaining direct reversal. In Berriman, U.S. Pat. No. 3,367,778; Fallessen, U.S. Pat. Nos. 2,497,875 and 2,497,876; and Illingsworth, Belgian Pat. No. 695,366, elaborate emulsion systems are described whereby the silver halide emulsions themselves are treated to give direct reversal images. Internal latent images or latent image traps are provided for in these inventions which give excellent results in terms of direct reversal; however, direct reversal systems are desired which do not require special silver halide emulsions and which give excellent three-color image reproductions using conventional multicolor photographic elements of camera speed (or a lower speed) with a color process requiring substantially fewer process steps than a conventional color reversal process.

Barr (U.S. Pat. No. 3,243,294) has described a direct color reversal process in which the black-and-white developing agent is incorporated into the coating, and a single color development step completes both the negative silver development and positive dye development step. The developer solution requires a nucleating agent and a silver halide solvent to complete color development. This system has its limits in that the photographic element has less preprocess stability than is many times desired due to the incorporated black-and-white developing agent. Also, with both color and black-and-white developing agents present at the same time, negative image development may occur from both developing agents, and positive image development may occur from both developing agents due to cross-oxidation and competition.

One object of our invention is to provide a novel direct color reversal system replacing the first developer, stop bath, wash, reversal exposure and color developer steps with a single processing step.

It is another object of our invention to provide a novel and less sensitive process-emulsion combination than that described in the prior art.

Another object of our invention is to provide a novel photographic element for producing direct reversal image reproductions.

Another object of our invention is to provide a novel process in which color negative and our novel color reversal films are advantageously interspliced and processed together.

Another object is to provide a novel process system in which an image exposed color photographic film is processed either as a color negative or as a color reversal reproduction as desired.

It is another object of our invention to provide for a novel direct color reversal development process with no upper limit on color development time and therefore with broad tolerance for time variations, temperature variations and chemical seasoning.

It is another object of our invention to provide a novel direct color reversal process that reduces water pollution by reducing the number of processing solutions, the number and/or amounts of processing chemicals, and the quantities of replenishers used, and also by reducing the amount of fresh water consumed for washing.

It is another object of our invention to provide a novel direct color reversal process in which there are no preceding processing steps from which chemicals and/or water are carried over into the color developer, or if there are preceding steps, their nature is such that it has no effect on the developer in our color development step.

It is a further object of this invention to accomplish the above objects using standard emulsion systems in our photographic elements and to obtain thereby a high-speed, high quality material comparable to that commercially available and not possible with other direct color reversal systems hereinabove cited.

These and other objects of our invention are accomplished by the preparation and use of our novel light-sensitive photographic elements for direct color reversal processing and by the use of our novel photographic direct reversal color processes.

Our light-sensitive photographic elements for direct reversal color-processing comprise a support coated with at least one hardened hydrophilic colloid-silver halide emulsion layer containing or associated with at least one nondiffusible (in emulsion layer) dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color-developing agent produced in a color developer solution by silver halide development to form a nondiffusible dye image (i.e., a dye image that does not wander from the site in the hydrophilic colloid layer where it is formed by color development) and on the same side of said support at least one hardened hydrophilic colloid layer containing a sufficient amount of at least one incorporated acceptor, scavenger or competer which reacts with oxidized aromatic primary amine color-developing agent but does not react with light exposed silver halide, e.g., a competing coupler (which chemically reacts with the oxidized color-developing agent and forms a single, nonreactive compound that is different from either of the reactants), so that when the elements are light-image exposed and developed by contacting with an aqueous alkaline solution in the presence of an aromatic primary amine color developing agent, substantially all of said color-developing agent oxidized by development of light-exposed silver halide reacts with said competer but so that there is not enough of said competer present during subsequent fogging development in the color developer to interfere with the reaction of the incorporated dye-forming coupler with the color-developing agent oxidized during the fogging development of previously unexposed silver halide and the formation of a positive dye image and a positive silver image. Any soluble, diffusible, competing coupler (i.e., soluble in water, aqueous alkali or in a polar organic solvent) and diffusible in hydrophilic layers, or any competing coupler which is rendered noninterfering during color development by diffusing out of the photographic element or by reaction to form noncoupling compounds in aqueous, alkaline solution is used to advantage in our invention. Competing couplers used to advantage in our photographic elements include:

1. any soluble, diffusible competing coupler which forms a colorless compound upon reaction with an oxidized color-developing agent, i.e., the oxidation product of an aromatic primary amine color developing agent formed by silver halide development, or

2. any soluble, diffusible competing coupler which forms a soluble, diffusible colored compound upon reacting with an oxidized color developing agent, or

3. any soluble, diffusible or insoluble, nondiffusible competing coupler which becomes noncoupling slowly upon contact with developer solution, and which reacts with oxidized color-developing agent as described in (1) or when soluble, diffusible (2) above. By diffusible, we mean capable of moving freely into, through or out of the hydrophilic colloid layers of the photographic element. By nondiffusible, we mean immobile or fixed in the hydrophilic colloid layer. These terms have these meanings throughout our application as applied to competing couplers, image-forming couplers, dye images, etc.

Competing couplers as in (1), (2) and (3) above are advantageously incorporated in our photographic elements in a range of from about 0.10 g./ft. ² to about 5.0 g./ft. ² with a preferred range being from about 0.50 g./ft. ² to about 2.0 g./ft. ² by addition to one or more of the emulsion layers as a solution or dispersion during the coating operation or applied to the outermost emulsion layer of an already coated photographic element by imbibition of a solution brought into contact with the emulsion layer or by coating a solution in a hydrophilic colloid coating composition on the emulsion layer. Application is made by dipping, rolling extruding, wiping, or any other conventional techniques. Insoluble, nondiffusible competing couplers are incorporated in each light-sensitive emulsion layer of our photographic elements and, is desired, they are also incorporated in interlayers. The amount of competing coupler advantageously incorporated in our photographic elements depends upon a number of factors, including the photographic element and the particular competing coupler. It is important that there be a sufficient amount of competing coupler available in the silver halide emulsion layers to react with substantially all of the oxidation product of aromatic primary amine color-developing agent formed by negative silver image development and thus prevent reaction of dye-image-forming coupler with the oxidized color developer during negative silver image development, but not enough competing coupler left in the emulsion layers to interfere with the reaction of dye-image-forming coupler with oxidation product of the color-developing agent formed by subsequent fogging color development of the unexposed silver halide and the formation of a positive dye image along with the positive silver image. The amount of competing coupler that is incorporated in a photographic element is generally more than the stoichiometric amount for the silver halide present and ranges up to about 30 times the stoichiometric amount, depending upon the rate at which the competing coupler decomposes and/or diffuses out of the silver halide emulsion layers into the developer solution.

Usually, our photographic elements contain a blue-sensitive hydrophilic colloid silver halide emulsion layer containing a nondiffusible yellow-dye-forming coupler that couples with an oxidized aromatic primary amine to form a nondiffusible yellow image, a green-sensitized hydrophilic colloid silver halide emulsion layer containing a magenta-dye-forming coupler that couples with an oxidized aromatic primary amine color developing agent to form a nondiffusible magenta dye and a red-sensitized hydrophilic colloid silver halide emulsion layer containing a cyan-dye-forming coupler that couples with an oxidized aromatic primary amine color developing agent to form a nondiffusible cyan dye or, alternately, dispersions of each of the three differently sensitized hydrophilic colloid silver halide emulsions each containing the appropriate dye-forming coupler are dispersed in one light-sensitive layer. The differently sensitized layers in our multilayer elements are advantageously arranged on the supports in any of the orders conventionally used in color photographic elements and advantageously include any of the interlayers, filter layers, U.V. absorbing layers, antihalation layers, etc., found in color photographic elements. Our competers for oxidized color developers are advantageously added to one or more layers of any of the prior art photographic color elements. Especially advantageous is the embodiment in which any of the prior art color photographic elements (including commercial elements) are given an application (over the outermost light sensitive layer) of a solution or hydrophilic colloid containing one of our water-soluble and diffusible competers for oxidized color-developing agents.

Another embodiment of our invention is a direct reversal color process for a color photographic element containing at least one hydrophilic colloid-silver halide emulsion layer containing a nondiffusible dye-image-forming coupler, the silver halide containing a latent image of an original light image, said process comprising the steps:

1. developing substantially all of the latent image in the silver halide to a corresponding negative silver image reproduction of said original light image without forming any nondiffusible negative dye image by contacting the silver halide with an aqueous alkaline solution of an aromatic primary amine color-developing agent in the presence of a sufficient amount of at least one competer for oxidized aromatic primary amine color developing agent to react with substantially all of the oxidized developing agent produced by development of the negative silver image, to form a reaction product that is colorless (diffusible or not) or colored and diffusible and maintaining contact of the negative-developed silver halide emulsion layer with the developer solution until the unexposed silver halide is chemically fogged and developed by the solution to form a positive silver and a positive dye image reproduction of the original light image; and

2. removing of silver and any residual silver halide in said photographic element by contacting with a silver bleach bath followed by a fixing bath or, alternatively, with a bleach-fix bath, i.e., a blix bath, leaving a positive dye image reproduction of said original light image.

Competers for oxidized color-developing agents for our direct reversal color process are advantageously incorporated in the photographic element when manufactured (any time prior to image exposure) or applied to the element before or after light image exposure and prior to the development step as a prebath or applied to the element during the development step. We have found that an aqueous solution containing 1 mole per liter of sulfite ions is a competer for oxidized color developing agent used to advantage in a prebath in our process. Preferred competers are any soluble diffusible competing couplers which react with oxidized color developing agent to form a colorless compound (diffusible or nondiffusible) or form a soluble diffusible colored compound. Competing couplers are used to advantage in the concentration range of from about 6 grams per liter to about 500 grams per liter in an aqueous prebath having a pH in the range of from about 6 to about 13, in an aqueous prebath comprising an aqueous solution containing all the components of a developing solution except the developing agent and containing our competing coupler in the concentration range from about 6 g./l. about 500 g./l., or the competing coupler is used in the complete developer solution in the concentration range of from about 6 g./l. to about 500 g./l., and at a pH range of from about 8.0 to about 13.0.

The competing coupler is advantageously used in processing solutions as well as in the photographic element, provided sufficient competing coupler is present in our photographic element to prevent the formation of any nondiffusible negative dye image during the development step and is either rendered inactive or is removed by diffusion out of the photographic element during this part of the development, so that positive silver development will now take place with the formation of positive image dye from the reaction of the incorporated coupler. It is advantageous to recirculate our developer solution through an ion exchange column so that residual or excess soluble and diffusible competing coupler of our invention is removed, thus preventing seasoning effects due to this residue or excess. Alternatively, a soluble complexing agent is used in our developer solution to render inactive or nondiffusible any residue or excess of our soluble and diffusible competing couplers (in the developer solution).

Photographic elements for use in our invention are any color photographic element containing a nondiffusible colored or uncolored color-forming coupler that forms a nondiffusible dye on reaction with oxidized aromatic primary amine color-developing agents, such as those described in Froehlich et al., U.S. Pat. No. 2,376,679; Vittum et al., U.S. Pat. No. 2,322,027; Fierke et al., U.S. Pat. No. 2,801,171; Godowsky, U.S. Pat. No. 2,698,794; Barr et al., U.S. Pat. No. 3,227,554; Graham, U.S. Pat. No. 3,046,129; Martinez, U.S. Pat. No. 2,284,877 and Wolf et al., U.S. Pat. application Ser. No. 634,104, filed Apr. 27, 1967 and now U.S. Pat. No. 3,516,831.

Any of the photographic silver halide emulsions, e.g., silver bromide, silver bromoiodide, silver chloride, silver chlorobromide, silver bromochloroiodide, etc., used in photography can be used to advantage in our photographic materials. Coarse grain or fine grain silver halide emulsions prepared by well-known procedures are used. Silver halide grains having concentric shells that vary as to silver halide, such as are described by Porter et al., U.S. Pat. No. 3,206,313, U.S. Pat. No. 3,317,322 and British Pat. No. 1,027,146 are used advantageously.

The emulsions used in the photographic element of our invention can be chemically sensitized by any of the accepted procedures. The emulsions can be digested with naturally active gelatin, or sulfur compounds can be added, such as those described in Sheppard, U.S. Pat. No. 1,574,944, issued Mar. 2, 1926; Sheppard et al., U.S. Pat. No. 1,623,499, issued Apr. 5, 1927; and Sheppard et al., U.S. Pat. No. 2,410,689, issued Nov. 5, 1946.

The emulsions can also be treated with salts of the noble metals, such as ruthenium, rhodium, palladium, iridium and platinum, as described in Smith et al., U.S. Pat. No. 2,448,060, issued Aug. 31, 1948 and as described in Trivelli et al., U.S. Pat. Nos. 2,566,245 and 2,566,263, both issued Aug. 28, 1951.

The emulsions can also be spectrally sensitized with cyanine and merocyanine dyes, such as those described in Brooker U.S. Pat. Nos. 1,846,301 and 1,846,302, both issued Feb. 23, 1932; and 1,942,854, issued Jan. 9, 1934; White U.S. Pat. No. 1,990,507, issued Feb. 12, 1935; Brooker and White U.S. Pat. Nos. 2,112,140, issued Mar. 22, 1938; 2,165,338, issued July 11, 1939; 2,493,747, issued Jan. 10, 1950; and 2,739,964, issued Mar. 27, 1956; Brooker et al. U.S. Pat. No. 2,493,748, issued Jan. 10, 1950; Sprague U.S. Pat. Nos. 2,503,776, issued Apr. 11, 1950, and 2,519,001, issued Aug. 15, 1950; Heseltine et al. U.S. Pat. No. 2,666,761, issued Jan. 19, 1954; Heseltine U.S. Pat. No. 2,734,900, issued Feb. 14, 1956; VanLare U.S. Pat. No. 2,739,149, issued Mar. 20, 1956; and Kodak Limited British Pat. No. 450,958, accepted July 15, 1936.

The emulsions may also contain speed-increasing compounds of the quaternary ammonium type of Carroll U.S. Pat. No. 2,271,623, issued Feb. 3, 1942; Carroll et al. U.S. Pat. No. 2,288,226, issued June 30, 1942; and Carroll et al. U.S. Pat. No. 2,334,864, issued Nov. 23, 1943; and the polyethylene glycol type of Carroll et al. U.S. Pat. No. 2,708,162, issued May 10, 1955.

The emulsions can also be chemically sensitized with gold salts as described in Waller et al. U.S. Pat. No. 2,399,083, issued Apr. 23, 1946, or stabilized with gold salts as described in Damschroder U.S. Pat. No. 2,597,856, issued May 27, 1952; and Yutzy et al. U.S. Pat. No. 2,597,915, issued May 27, 1942. Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and 2-aurosulfobenzo-thiazole methochloride.

Hydrophilic colloids used to advantage include gelatin, colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound. Some colloids which may be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in Lowe, U.S. Pat. No. 2,286,215, issued June 16, 1942; a far hydrolyzed cellulose ester, such as cellulose acetate hydrolyzed to an acetyl content of 19-26 percent as described in Lowe et al. U.S. Pat. No. 2,327,808, issued Aug. 24, 1943; a water-soluble ethanolamine cellulose acetate as described by Yutzy U.S. Pat. No. 2,322,085, issued June 15, 1943; a polyacrylamide having a combined acrylamide content of 30-60 percent and a specific viscosity of 0.25-1.5 or an imidized polyacrylamide of like acrylamide content and viscosity as described in Lowe et al. U.S. Pat. No. 2,541,474, issued Feb. 13, 1951; zein as described in Lowe U.S. Pat. No. 2,563,791, issued Aug. 7, 1951, a vinyl alcohol polymer containing urethane carboxylic acid groups of the type described in Unruh et al. U.S. Pat. No. 2,768,154, issued Oct. 23, 1956, or containing cyano-acetyl groups, such as the vinyl alcohol-vinyl cyano-acetate copolymer as described in Unruh et al. U.S. Pat. No. 2,808,331, issued Oct. 1, 1957; or a polymeric material which results from polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group as described in Illingsworth et al. U.S. Pat. No. 2,852,382, issued Sept. 16, 1958.

The hydrophilic colloids described above are used in various layers of our photographic elements and are advantageously hardened sufficiently to withstand photographic processing temperatures up to about 93° C. without the coated layer reticulating, frilling, blistering, transferring, etc., with hardening agents, such as, aziridine hardeners, isoxazolium salt hardeners, epoxy hardeners, vinyl sulfone hardeners, mucochloric acid, formaldehyde hardeners, etc. The aziridine hardeners used to advantage include 1,3-bis(1-aziridinylsulfonyl)-propane, 1-(1-aziridinyl carbonyl)- 3-(1-aziridinyl-sulfonyl)-benzene and others described in Burness U.S. Pat. No. 2,964,404 issued Dec. 13, 1960; N,N'-trimethylene bis(1-aziridine-carboxamide), N,N'-octamethylene bis-(1-aziridine-carboxamide), toluene-2,4-bis(1-aziridine-carboxamide), N,N'-tetramethylene bis(1-aziridine-carboxamide) and others described in Allen and Webster, U.S. Pat. No. 2,950,197, issued Aug. 23, 1960; and the aziridinyl azine hardener compounds prepared by reacting cyanine chloride with ethylene imine as described by Yudelson U.S. Pat. No. 3,017,280, issued Jan. 16, 1962. The oxazolium hardeners used to advantage include 2,5-dimethylisoxazolium perchlorate, 2-ethyl-5-phenylisoxazolium-3'-sulfonate, 2-methyl-5-p-tolylisoxazolium-3'-sulfonate and others described in VanCampen and Graham U.S. Pat. No. 3,316,095, issued Apr. 25, 1967, 2-methylisoxazolium-p-toluenesulfonate, 3-(2-isoxazolium)propanesulfonate, 2,5-dimethylisoxazolium p-toluenesulfonate, 2-methyl-5-phenylisoxazolium perchlorate, 4-( 3-hydroxypropyl)- 2-methylisoxazolium p-toluenesulfonate, 5-isopropyl-2-methylisoxazolium perchlorate, 2,4-dimethylisoxazolium p-toluenesulfonate, 3-[2-(5-methylisoxazolium)]propanesulfonate described by Burness and Wilson U.S. Pat. No. 3,321,313, issued May 23, 1967. The vinylsulfones used to advantage as hardeners for hydrophilic colloids in our photographic elements include hardening compounds having two vinylsulfonylalkyl groups linked to a single linking heteroatom (e.g., nitrogen atom, or oxygen atom) or radical, including hardeners such as, bis(4-vinylsulfonylbutyl)ether, bis-(2-vinylsulfonylethyl)ether, bis(vinylsulfonylmethyl)ether, N,N-bis(2-vinylsulfonylethyl)-n-propylamine, N,N-bis(2-vinylslfonylethyl)- N-ethyl-N-propylammonium tetrafluoroborate, and bis(1-vinylsulfonylethyl)ether, etc., and other compounds of the formula:

in which m ₂ is an integer of from 1 to 4, Z ^OO is a heteroatom (e.g., nitrogen or oxygen) and R ⁶ is hydrogen, or lower alkyl groups (e.g., methyl, ethyl, isopropyl, etc., which can in turn be further substituted), and hardening compounds having two or more vinylsulfonylalkyl groups (i.e., lower alkyl from one to four carbon atoms) attached to a plurality of tertiary or quaternary nitrogen atoms and/or a plurality of ether oxygen atoms including typical compounds, such as:

1. N,N'-bis(2-vinylsulfonylethyl)piperazine

2. N,N'-bis(2-vinylsulfonylethyl)piperazine-bis(methoperchlorat e)

3. N,N'-bis(2-vinylsulfonylethyl)-N,N'-dimethyl-2-butene-1,4-di amine bis(metho-p-toluenesulfonate) and the corresponding bis(methofluoborate)

4. N,N'-bis(2-vinylsulfonylethyl)-N,N'-dimethylethylene bis(metho-p-toluenesulfonate)

5. 1,2-bis(vinylsulfonylmethoxy)ethane

6. 1,4-bis(2-vinylsulfonylethoxy)ethane

7. bis[2-(2-vinylsulfonylethoxy)ethyl]sulfone

8. N,N'-bis[2-(2-vinylsulfonylethoxy)ethyl]urea

9. 1,14-bis(vinylsulfonyl)-3,6,9,12-tetraoxatetradecane

as are described in Belgian Pat. No. 686,440, granted Nov. 14, 1966. The disclosures of U.S. Pat. Nos. 2,964,404, 2,950,197, 3,017,280, 3,316,095, and 3,321,313 and Belgian Pat. No. 686,440 mentioned above are incorporated herein by reference.

The following synthesis will illustrate the preparation of compounds having Formula IX:

Bis(2-vinylsulfonylethyl)ether

6-Oxa-3,9-dithiaundecane-1,11-diol is prepared by the reaction of two molar proportions of sodium 2-hydroxyethyl-mercaptide with 1 mole of bis(2-chloroethyl)ether in methanol, followed by evaporation of the solvent.

The disulfide is oxidized to the disulfone by hydrogen peroxide according to the method of H. S. Schultz et al., J. Org. Chem., 28, 1140, (1963). The resulting diol is converted to 2,2'-bis(2-chloroethylsulfonyl)ethyl ether by adding two molar proportions of thionyl chloride to a refluxing solution of the diol in acetonitrile containing a catalytic amount of N,N-dimethylformamide. When the reaction is complete, removal of the solvent and recrystallization from ethanol-acetone gives a high yield of a colorless chloride having a melting point of 70°-71° C.

Dehydrohalogenation is effected in tetrahydrofuran solution at about 0°-5° C. with two molar proportions of triethylamine. After 24 hours, the solvent is removed and the product recrystallized from methanol giving colorless crystals having a melting point of 47.5°-48.5° C.

Bis(vinylsulfonylmethyl)ether

Following the procedure of bis(2-vinylsulfonylethyl)ether and starting with bis(chloromethyl)ether, the colorless intermediate chloride is prepared having a melting point of 83°-84° C. A similar process of dehydrohalogenation as in bis(2-vinylsulfonyl-ethyl)ether and subsequent recrystallization from a methanolethanol mixture yields a colorless product with a melting point of 41.5°-42.5° C.

Bis(4-vinylsulfonylbutyl)ether

Following the procedure of bis(2-vinylsulfonylethyl)ether and starting with bis(4-chlorobutyl)ether, a colorless intermediate chloride is prepared having a melting point of 66°-68° C. Dehydrohalogenation, as in bis(2-vinylsulfonylethyl)ether, carbon decolorization in methanol solution and evaporation of the methanol under reduced pressure yields a pale yellow oily product of n _D ²⁵ 1.5023.

The light-sensitive layers of our photographic elements are advantageously coated on a wide variety of photographic emulsion supports. Typical supports used to advantage include cellulose nitrate film, cellulose acetate film, polyacetal film, polystyrene film, poly(ethylene-terephthalate) film, polyethylene film and related films of resinous materials as well as paper, glass and others.

Any of the known nondiffusible dye-image-forming couplers known in the art that form nondiffusible dye images are advantageously used in our elements, including the open-chain active methylene couplers, the 5-pyrazolone couplers, the phenolic couplers and the naphtholic couplers described on pages 7 through 18 in Wolf et al. forementioned, U.S. Pat. Application Ser. No. 634,104, incorporated herein by reference.

Soluble, diffusible competing couplers used to advantage according to our invention are represented by the formula:

wherein Coup. represents a photographic coupling moiety (e.g., an open-chain ketomethylene coupler, a 5-pyrazolone coupler, a pyrazolinobenzimidazole coupler, a 1H-pyrazolo[3,2-c]-s-triazole coupler, a phenolic coupler, a naphtholic coupler, an 8-hydroxyquinoline coupler, a hydroxyisonicotinic acid, an ester of a hydroxyisonicotinic acid, an amide of a hydroxyisonicotinic acid, a hydroxybenzoic acid, an ester of a hydroxybenzoic acid, an amide of a hydroxybenzoic acid, an isoxazolone coupler, an indazolone coupler, etc.); L represents a member, e.g., an alkyl group, an aryl group, a heterocyclic group, an acyloxy group, a heterocycloxy group, an alkoxy group, an alkylthio group, an arylthio group (each of which is advantageously substituted with a solubilizing group is desired), hydrogen, thiocyano, chlorine, bromine, fluorine, sulfo, etc., attached to the carbon at the active site of said coupler; Sol. and Sol. ₁ represent independently selected solubilizing groups (e.g., carboxy, sulfo, hydroxy, mercapto, a cyclopentylidene group, a pyrrolyl group, a carboxyalkyl, a carboxyaryl, a carboxyheterocyclic group, a sulfoalkyl, a sulfoaryl group, a sulfoheterocyclic group, etc.); and p represents an integer of from 1 to 3. These couplers include those described by Formulas I, II, III, IV, V, VI, VII, VIII IX and X.

Soluble, diffusible couplers which form colorless compounds upon coupling with oxidized color developing agents include those described by Formulas I and II.

wherein R represents an alkyl group (substituted or not) (e.g., methyl, ethyl, sulfoethyl, carboxyethyl, aminoethyl, hydroxyethyl, propyl, butyl, sulfobutyl, amyl, sulfoamyl, hexyl, cyclohexyl, etc.), an aromatic group (substituted or not) (such as, a phenyl group, e.g., phenyl, tolyl, chlorophenyl, sulfophenyl, carboxyphenyl, aminophenyl, carbamylphenyl, etc.), a hetero-cyclic group (substituted or not) (e.g., a benzofuranyl group, a furanyl group, a thiazolyl group, an oxazolyl group, an imidazolyl group, a quinolyl group, etc.), etc., an amino group (e.g., amino, dialkylamino, alkylamino, anilino, etc.); R _o represents an alkyl group (substituted or not) or an aromatic group (substituted or not) or a heterocyclic group (substituted or not) each as already defined for R; and X represents a cyano group, a carbamyl group (substituted or not), etc., such that at least one of the groups R, R _o and X is substituted with a solubilizing group, especially a sulfo group or a carboxy group.

Also included among the soluble, diffusible competing couplers that react with oxidized color developing agents to form colorless compounds are any of the substituted 5-pyrazolone solubilized competing couplers of the formula:

wherein R and R _o are as described previously and R ₁ represents a group such as an alkyl group, preferably lower alkyl having one to six carbon atoms, a carbamyl group (substituted or not) (e.g., an alkyl carbamyl group such as ethylcarbamyl, sulfoethylcarbamyl, butylcarbamyl, sulfobutylcarbamyl, etc.), an arylcarbamyl group such as a phenylcarbamyl group (e.g., phenylcarbamyl, sulfophenylcarbamyl, tolylcarbamyl, etc.), an amino group (substituted or not with one or two alkyl groups and/or one or two aryl groups) (e.g., N-methylamino, N,N-dimethylamino, N-methylanilino, N-ethyl sulfoanilino, etc.), a substituted amido group, e.g., a benzamido group (substituted or not) (e.g., benzamido sulfo-benzamido, carboxybenzamido, bromobenzamido, etc.), an alkamido group (substituted or not) (e.g., ethylamido, sulfoethylamido, chloroethylamido, benzylamido, etc.) such that at least one of the groups R, R _o and R ₁ is substituted with a solubilizing group.

Representative competing couplers of formula I include:

1. α-methyl-α-pivalylacet-4-sulfoanilide

2. α-methyl-α-pivalylacet-2-sulfoanilide

3. α-methyl-α-pivalylacet-2,4-dicarboxyanilide

4. α-butyl-α-pivalylacet-4-sulfanilide

5. α-methyl-α-benzoylacet-4-sulfoanilide

6. α-methyl-α-[4-carboxybenzoyl]acetanilide

Representative competing couplers of Formula II include:

1. 3-amino-4-methyl-1-(4-sulfophenyl)-5-pyrazolone

2. 3-(4-sulfoanilino)-4-methyl-1-(4-chlorophenyl)-5-pyrazolone

3. 3-carbamyl-4-ethyl-1-(3-sulfophenyl)-5-pyrazolone

4. 3.-(sulfoethylcarbamyl)-1-(4-sulfophenyl)-4-hexyl-5-pyrazolo ne

5. 3-(sulfobenzamido)-4-methyl-1-(4-carboxyphenyl)-5-pyrazolone

6. 3-[N-ethyl-(4-sulfoanilino)]-4-methyl-1-(2-thiazolyl)-5-pyra zolone

7. 3-methyl-4-(4-carboxycyclohexyl)-1-(4-sulfophenyl)-5-pyrazol one

Other suitable soluble, diffusible competing couplers are derived from the osazones of German Pat. No. 1,083,125 or the hydrazones of U.S. Pat. No. 3,457,077 described in column 7, lines 20 through 44 by preparing unballasted derivatives which also contain appropriate solubilizing groups, e.g., sulfo, carboxy, etc.

Soluble, diffusible competing couplers forming soluble dyes used to advantage according to our invention include those having Formulas III, IV, V and VI described herein below:

wherein R and X are as described previously and where Y is fluoro, hydrogen, the thiocyano group, an acyloxy group [such as an alkoyloxy group (substituted or not) (e.g., acetoxy, butyryloxy, hexanoyloxy, sulfobutyryloxy, chlorobutyryloxy, etc.), an aroyloxy group (substituted or not) (e.g., a benzoyloxy group, such as, benzoyloxy, methylbenzoyloxy, chlorobenzoyloxy, sulfobenzoyloxy, carboxybenzoyloxy, aminobenzoyloxy, carbamylbenzoyloxy, etc.)] and a cycloxy group [e.g., an aryloxy group (e.g., a phenoxy group, such as, phenoxy, 4-sulfophenoxy, 3-methoxyphenoxy, 4-carboxyphenoxy, 2-chlorophenoxy, etc., a naphthoxy group, such as, naphthoxy, 4-sulfonaphthoxy, 4-chloronaphthoxy, etc.), a heterocycloxy group having from five to six atoms in the heterocyclic ring (e.g., a pyridinyloxy group, a tetrahydropyranyloxy group, a tetrahydroquinolyloxy group, etc.)], an alkoxy group (e.g., methoxy, ethoxy, butoxy, sulfobutoxy, hexoxy, etc.), an alkylthio group (e.g., methylthio, propylthio, butylthio, hexylthio, etc.), an arylthio group [e.g., a phenylthio, e.g., phenylthio, tolylthio, chlorophenylthio, sulfophenylthio, etc.] and an arylazo group in which the Y groups are advantageously substituted with a wide variety of groups used on couplers, and in which R and/or X is substituted with a solubilizing group (e.g., a sulfo group, a carboxy group, etc.). Also included are couplers of formula:

wherein R and R ₁ are as described previously and Y' represents halogen (e.g., Cl, F, etc.), hydrogen, the thiocyano group, an acyloxy group and an arylazo group as defined for Y previously, an aryloxy group as defined previously for Y, an alkoxy group as defined previously for Y, an arylthio group as defined previously for Y and an alkylthio group as defined previously for Y, so that R and/or R ₁ is substituted with a solubilizing group and if desired YY' is also substituted with a solubilizing group (e.g., sulfo, carboxy, etc.). Also included are couplers of the following formulas: ##SPC1##

wherein R ₂ represents hydrogen, an alkyl group, preferably a lower alkyl group having from one to six carbon atoms (e.g., methyl, ethyl, sulfoethyl, carboxyethyl, hydroxyethyl, aminoethyl, carbamylethyl, butyl, sulfobutyl, hexyl, sulfohexyl, cyclohexyl, etc.), an aryl group [e.g., a phenyl group, such as, phenyl, 4-sulfophenyl, tolyl, methoxyphenyl, 4-carboxyphenyl, 2-chlorophenyl, aminophenyl, methoxyphenyl, carbamylphenyl, etc.), a naphthyl group (e.g., naphthyl, 4-sulfonaphthyl, 4-carboxynaphthyl, etc.)], a heterocyclic group having from five to six atoms in the heterocyclic ring (e.g., a pyridyl group, a quinolyl group, an imidazolyl group, a thiazolyl group, an oxazolyl group, etc.), an amino group (e.g., amino, alkylamino, acylamino, arylamino, heterocyclicamino, etc.), a substituted carbonamido group [e.g., an alkylcarbonamido group (e.g., methylcarbonamido, ethylcarbonamido, sulfobutylcarbonamido, benzylcarbonamido, etc.), an arylcarbonamido group (e.g., phenylcarbonamido, 4-sulfophenylcarbonamido, tolylcarbonamido, aminophenylcarbonamido, etc.), a heterocycliccarbonamido group (e.g., a pyridylcarbonamido group, a thiazolylcarbonamido group, etc.)], a substituted sulfonamido group [e.g., an alkylsulfonamido group (e.g., methylsulfonamido, butylsulfonamido, hexylsulfonamido, cyclohexylsulfonamido, etc.), an arylsulfonamido group (e.g., phenylsulfonamido, 4-sulfophenylsulfonamido, 4-methoxyphenylsulfonamido, etc.), a heterocyclicsulfonamido group (e.g., pyridysulfonamido, thiazolylsulfonamido, etc.)], a substituted sulfamyl group [e.g., an alkylsulfamyl group (e.g., methylsulfamyl, butylsulfamyl, etc.), an arylsulfamyl group (e.g., a phenylsulfamyl group, phenylsulfamyl, 4-sulfophenylsulfamyl, tolylsulfamyl, 2-methoxyphenylsulfamyl, 4-aminophenylsulfamyl, etc.), a heterocyclic sulfamyl group (e.g., pyridylsulfamyl, thiazolylsulfamyl, etc.)], a substituted carbamyl group [e.g., an alkylcarbamyl group (e.g., methylcarbamyl, ethylcarbamyl, sulfoethylcarbamyl, butylcarbamyl, hexylcarbamyl, etc.), an arylcarbamyl group, such as a phenylcarbamyl (e.g., phenylcarbamyl, tolylcarbamyl, sulfophenylcarbamyl, chlorophenylcarbamyl, methoxyphenylcarbamyl, aminophenylcarbamyl, carboxyphenylcarbamyl, N-ethyl-N-(3,5-dicarboxyphenyl)carbamyl, etc.), a heterocycliccarbamyl group in which the heterocyclic group has from five to six atoms in the ring (e.g., pyridylcarbamyl, thiazolylcarbamyl, oxazolylcarbamyl, etc.), etc.], a sulfo group, a halogen (e.g., chlorine, bromine, fluorine), an alkoxy group (e.g., methoxy, ethoxy, hexoxy, etc.), carboxy, hydroxy, an aryloxy group [e.g., a phenoxy group (e.g., phenoxy, tolyloxy, chlorophenoxy, fluorophenoxy, 4-hydroxyphenoxy, carboxyphenoxy, sulfophenoxy, aminophenoxy, etc.), a naphthoxy group (e.g., α-naphthoxy, sulfo α-naphthoxy, carboxy α-naphthoxy, β-naphthoxy, etc.)], a ureido group (e.g., ureido, phenylureido, alkylureido, etc.), alkoyloxy (e.g., acetoxy, ethylcarbonyloxy, etc.); R ₃ , R ₄ , R ₅ and R ₆ each represent any of the groups represented by R ₂ ; Y ₂ represents hydrogen or those groups previously defined for Y, but does not represent an aryloxy group; Y ₃ represents the groups previously defined for Y ₂ and also includes a cyclic imido group (e.g., a maleimido group, a succinimido group, a 1,2-dicarboximido group, a phthalimido group, etc.); Y ₂ and Y ₃ are also substituted with a solubilizing group; Z ^o represents a member, such as,

etc.; and R ₇ represents any of the groups represented by R ₂ so that at least one of R ₂ , R ₃ , R ₄ and R ₅ in structure V or at least one of R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ in structure VI is substituted with a solubilizing group and, where desired Y ₂ or Y ₃ are also substituted with a solubilizing group.

Another class of soluble and diffusible competing couplers is represented by the formula: ##SPC2##

wherein R ₈ represents a group such as hydroxyl, an alkoxy group (e.g., methoxy, ethoxy, propoxy, dodecyloxy, benzyloxy, etc.), an amino group (e.g., amino, N-methylamino, N-ethylamino, N-methylanilino, N-butylamino, etc.); n represents an integer of from 1 to 2; R ₉ represents hydrogen or a halogen atom (e.g., Cl, Br, I or F); R ₁₀ represents hydroxyl or an acyloxy group (e.g., acetyloxy, butyryloxy, lauroyloxy, etc.); Z represents nitrogen or CR ₁₁ --; R ₁₁ represents hydrogen or a halogen atom (e.g., Cl, Br, I or F); R ₁₂ represents hydroxyl or an acyloxy group (e.g., acetyloxy, butyryloxy, lauroyloxy, etc.); and R ₁₃ represents hydrogen or halogen (e.g., Cl, Br, I or F).

Representative competing couplers of Formula III include the following:

1. α-pivaloylacet-4-sulfoanilide

2. α-pivaloylacet-2-sulfoanilide

3. α-pivaloylacet-2,4-dicarboxyanilide

4. α-benzoyl-α-thiocyanoacet-4-sulfoanilide

5. α-acetoxy-α-(4 -sulfobenzoyl)acet-4-sulfoanilide

6. α-benzoyloxy-α-(4-sulfobenzoyl)acet-4-sulfoanilide

7. α-phenoxyacetoacet-4-sulfoanilide

8. α-methoxyacetoacet-4-sulfoanilide

9. 4-(ω-benzoylacetamino)benzene sulfonic acid

Representative competing couplers of Formula IV include the following:

1. 3-amino-1-(4-sulfophenyl)-5-pyrazolone

2. 3-(4-sulfoanilino)-1-(chlorophenyl)-5-pyrazolone

3. 3-amino-1-(4-sulfophenyl)-4-thiocyano-5-pyrazolone

4. 4-acetoxy-3-amino-1-(4-sulfophenyl)-5-pyrazolone

5. 3-amino-4-benzoyloxy-1-(4-sulfophenyl)-5-pyrazolone

6. 3-dimethylamino-4-methoxy-1-(4-sulfophenyl)-5-pyrazolone

7. 3-(4-sulfoanilino)-4-(sulfophenoxy)-1-(4-sulfophenyl)-5-pyra zolone

8. 3-methyl-1-(4-sulfophenyl)-5-pyrazolone

9. 1-phenyl-3-(3-sulfobenzamido)-5-pyrazolone

Representative competing couplers of Formulas V and VI include the following:

1. 1-amino-8-naphthol-3,6-disulfonic acid

2. 2-amino-5-naphthol-7-sulfonic acid

3. 1,8-dihydroxynaphthalene-3,6-disulfonic acid

4. 1-naphthol -3,6,8-trisulfonic acid

5. 1-naphthol-2-sulfonic acid

6. 1-amino-8-naphthol-2,4-disulfonic acid

7. 1-naphthol-4,8-disulfonic acid

8. 1-naphthol-5-sulfonic acid

9. 1-phenol-3,5-disulfonic acid

10. 1-phenol- 3-sulfonic acid

11. 3-amino-1-phenol-5-sulfonic acid

12. 2-methyl-1-phenol-5-sulfonic acid

13. 2-methoxy-1-phenol-5-sulfonic acid

14. 2-chloro-1-phenol-5-sulfonic acid

15. 3-(4-sulfophenyl)-1-phenol

16. 2-[N-ethyl-N-(3,5-dicarboxyphenol)carbamyl]-α-naphthol

17. 1-acetamino-8-naphthol-3,6-disulfonic acid

18. 2-amino-8-naphthol-3,6-disulfonic acid

19. 1-amino-8-naphthol-6-sulfonic acid

Representative competing couplers of Formula VII include the following:

1. 2,6-dihydroxyisonicotinic acid

2. 3,5-dihydroxybenzoic acid

3. methyl 2,6-dihydroxyisonicotinate

4. ethyl 2,6-dihydroxyisonicotinate

5. propyl 2,6-dihydroxyisonicotinate

6. butyl 2,6-dihydroxyisonicotinate

7. benzyl 2,6-dihydroxyisonicotinate

8. dodecyl 2,6-dihydroxyisonicotinate

9. 2,6-dihydroxyisonicotinamide

10. 2,6-dihydroxy-N-(2-hydroxyethyl)-isonicotinamide

11. 2,6-dilauroyloxyisonicotinic acid

12. 2-lauryloxy- 6-hydroxyisonicotinic acid

13. 2,6-dihydroxy-3-chloroisonicotinic acid

14. methyl 3,5-dihydroxybenzoate

15. ethyl 3,5-dihydroxybenzoate

16. n-butyl 3,5-dihydroxybenzoate

17. n-dodecyl 3,5-dihydroxybenzoate

18. 3,5-dihydroxybenzamide

19. 2-chloro-3,5-dihydroxybenzoic acid

Sulfonated- or carboxylated-unballasted isoxazolone couplers or indazolone couplers are used to advantage as soluble, diffusible competing couplers that form soluble, diffusible colored compounds. Similar, but nondiffusible, ballasted isoxazolone couplers are described in British Pat. No. 778,089 and indazolone couplers are described by J. Jennen, Ind. Chim. Belg. 16, 472 (1951), 67 (2), 356 (1952) and by Vittum et al. J. Photo Science 6, 158 (1958).

Decomposable competing couplers which are advantageously incorporated in a photographic element, and which decompose or are rendered inactive slowly, upon contact with developing solution, include those having the following formula:

wherein R ₁₄ is as defined for R and R substituted with a solubilizing group or any well-known ballast group, X ₁ is as defined for X and X substituted with any well-known ballast group, Y ₄ is chlorine or bromine, provided that when R ₁₄ and/or X ₁ contain ballasting substitutes that make the coupler nondiffusible, the reaction product of this coupler and oxidized color developing agent is colorless or does not have any perceptible color or, alternatively, is colored and remains behind as a negative mask. Couplers of Formula VIII, when contacted with strongly alkaline solutions, slowly decompose into R ₁₄ COOH and Y ₄ CH ₂ X ₁ . Preferred compounds of Formula VIII include:

aceto-αbromo-ω-sulfoacetanilide

α-(4-sulfobenzoyl)-α-chloroacetanilide

α-(4-carboxybenzoyl)-α-chloro-ω-carboxyacetanilide

α-(4-hydroxybenzoyl)-α-chloro-ω-sulfoacetanilide

Formulas for other completing couplers are: ##SPC3##

wherein R ₁₅ and R ₁₇ each represent the same or a different member, e.g., hydrogen, an alkyl group (e.g., methyl, ethyl, propyl, butyl, sulfoethyl, carboxyethyl, hydroxyethyl, sulfobutyl, amyl, sulfoamyl, hexyl, etc.), an aryl group [e.g., a phenyl group (e.g., phenyl, tolyl, chlorophenyl, sulfophenyl, carboxyphenyl, aminophenyl, carbamylphenyl, etc.), a napthyl group (e.g., α-naphthyl, β-naphthyl, etc.), a heterocyclic group having from five to six atoms in the ring (e.g., a pyridyl group, a thienyl group, a quinolyl group, etc.), an amino group (e.g., amino, methylamino, diethylamino, anilino, tolylamino, etc.), an acylamido group (e.g., ethylcarbonamido, butylcarbonamido, phenylcarbonamido, tolylcarbonamido, etc.), etc.: R ₁₆ represents a member such as hydrogen, a halogen atom (e.g., Cl, Br, I or F.), the sulfo group (including an alkali metal or ammonium salt), the carboxy group (including an alkali metal or ammonium salt), an acyloxy group [an alkoyloxy group (e.g., acetoxy, butyryloxy, sulfobutyryloxy, chlorobutyryloxy, etc.), an aroyloxy group (e.g., benzoyloxy, methylbenzoyloxy, chlorobenzoyloxy, sulfobenzoyloxy, carboxybenzoyloxy, etc.)], a substituted sulfonyloxy group (e.g., methylsulfonyloxy, butylsulfonyloxy, phenylsulfonyloxy, carboxyphenylsulfonyloxy, sulfophenylsulfonyloxy, tolylsulfonyloxy, etc.), thiocyano, a benzotriazolyl group, an R ₁₈ O-- group, an R ₁₈ S-- group, an R ₁₉ NN-- group, an R ₂₀ OOC-- group, etc.; R ₁₈ represents an alkyl group (e.g., methyl, ethyl, butyl, hexyl, etc.), an aryl group [e.g., a phenyl group (e.g., phenyl, tolyl, chlorophenyl, sulfophenyl, aminophenyl, carboxyphenyl, etc.), a naphthyl group (e.g., α-naphthyl, β-naphthyl, etc.)], a heterocyclic group in which the heterocyclic group has from five to six atoms in the heterocyclic ring, e.g., pyridyl, quinolyl, triazolyl, benzotriazolyl, etc.); R ₁₉ represents a radical of a diazotizable amine, such as, an aryl amine [(e.g., a phenyl amine in which the phenyl moiety is phenyl, tolyl, ethylphenyl, 4-carboxyphenyl, sulfophenyl, methoxyphenyl, etc.), a naphthyl amine (in which the naphthyl moiety is α-naphthyl, β-naphthyl, etc.)], a heterocyclic amine having from five to six atoms in the ring (in which the heterocyclic moiety is 2-benzothiazolyl, 2-thiazolyl, 2-quinolyl, 4-quinolyl, a pyrazolyl group; etc.; R ₂₀ represents an alkyl group (e.g., methyl, ethyl, phenethyl, 2-chloroethyl, 2-methoxyethyl, butyl, etc.), an aryl group, such as, a phenyl group (e.g., phenyl, tolyl, methoxyphenyl, chlorophenyl, etc.); R ₂₁ represents an alkyl group (e.g., methyl, ethyl, butyl, phenethyl, etc.) and an aryl group, such as, a phenyl group (e.g., phenyl, tolyl, ethylphenyl methoxyphenyl, dimethylaminophenyl, etc.), such that at least one of R ₁₅ and R ₁₇ contains a solubilizing group, preferably a sulfo group or a carboxy group and, if desired, R ₁₆ and R ₂₁ also contain a solubilizing group.

Competing couplers of Formula IX are advantageously prepared by ring closure of a compound having the formula:

wherein R ₁₅ , R ₁₇ and R ₂₀ are as defined previously, in the presence of POCl ₃ in an inert solvent, e.g., benzene, toluene, xylene, etc., or, alternatively, by ring closure of a compound of the formula:

in the presence of bromine and sodium acetate in acetic acid. When the product of the ring closure reaction is treated with sulfuric acid, the R ₂₀ group is hydrolyzed, leaving a free carboxy group on the carbon in the 7-position of the ring (i.e., R ₁₆ ) and if the treatment is continued, the carboxy group is split off, leaving the free base (i.e., R ₁₆ =hydrogen). Various R ₁₆ groups are advantageously substituted for the hydrogen on the free base by reacting the free base with the appropriate reagent; for example, a halogen atom is introduced by treating with the desired halogen in acetic acid; a sulfo group is introduced by treating with oleum; a phenylthio group is advantageously introduced by condensing with the appropriate RSCl where R is as defined previously in the presence of a base and an inert solvent; a substituted sulfonyloxy group is advantageously introduced by reaction of the 7-bromo derivative with the silver salt of the alkyl or aryl sulfonic acid; an acyloxy group is advantageously introduced at the 7 -position by reacting the 7-bromo derivative with the appropriate organic acid (or alkali metal salt thereof); a phenoxy group is advantageously introduced by reaction of the 7-bromo derivative with sodium phenolate; the thiocyano group is advantageously introduced by treating the free base with the product of the reaction of an alkali metal or ammonium thiocyanate with bromine.

A benzotriazol-2-yl group is advantageously substituted on the 7-position of the coupler by preparing the 7-(2-nitrophenylazo) derivative and heating this in aqueous ethanol containing sodium hydroxide while zinc dust is added. Refluxing is continued until the solution turns colorless, after which the excess zinc is removed by filtration and the reaction mixture is advantageously acidified with hydrochloric acid to form the coupler. Still other substitutents are advantageously introduced by known methods.

The couplers of Formula X are made from the free base of couplers of Formula IX by heating with the appropriate aldehyde in dry benzene. Belgian Pat. No. 724,427, issued May 27, 1969 describes couplers of Formulas IX and X.

The compounds of Formula XI are advantageously made by reacting the appropriate heterocyclic substituted hydrazine with

in the presence of a base, e.g., pyridine, and compounds of Formula XII are advantageously made by reacting the appropriate heterocyclic substituted hydrazine with

in an inert solvent.

Typical soluble, diffusible competing couplers of Formulas IX and X are as follows:

6-methyl-3-sulfobutyl-1H-pyrazolo [3,2-c]-s-triazole

3,6-dicarboxyethyl-1H-pyrazolo [3,2-c]-s-triazole

3-methyl-6-sulfobutyl- 1H-pyrazolo [3,2-c]-s-triazole

7-benzylidene-3-methyl-6-sulfoethyl-1H-pyrazolo-[3,2-c]- s-triazole

Our aqueous alkaline aromatic primary amino color develop solutions typically have the following general formulation:

Development Accelerator 0-50 g./l. Color Developing Agent 2-100 g./l. Alkali Metal Bromide 0-100 g./l. Antifoggant 0-1.0 g./l. Alkali Metal Iodide 0-1.0 g./l. Alkali Metal Chloride 0-25 g./l. Soluble Diffusible Competing Coupler 0-500 g./l. Buffer 0-100 g./l. Silver Halide Solvent 0-50 g./l. Antioxidant 0-50 g./l. pH Range 8.0 to 14.0

The pH is adjusted with an alkali metal or ammonium hydroxide.

Useful development accelerators are those common in commercial processes and well known in the prior art and include:

benzyl alcohol

p-cresol

phenyl ethyl alcohol

p-n-amyl phenol

n-octyl alcohol

p-sec.-butyl phenol, etc.

Useful developing agents are of the p-phenylene-diamine type well known in the prior art and include:

1. p-amino-N,N-diethylaniline HCl

2. 4-amino-3-methyl-N,N-diethylaniline HCl

3. 4-amino-N-ethyl-N-β-hydroxyethylaniline H ₂ SO ₄

4. 4-amino-N-butyl-N-ω-sulfobutylaniline

5. 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline H ₂ SO ₄

6. 4-amino-3-methyl-N-ethyl-N-β-(methane sulfonamido) ethylaniline 3/2 H ₂ SO ₄ --H ₂ O

7. 4-amino-3-β-(methanesulfonamido)ethyl-N,N-diethylaniline HCl

8. 4-amino-3-methoxy-N-ethyl-N-β-hydroxyethylaniline 2HCl

9. N,N-diethyl-3-(2-hydroxyethyl)-p-phenylenediamine 2HCl

Useful antifoggants are selected from those well known in the prior art and representative compounds are:

1. benzotriazole

2. 5-nitrobenzimidazol nitrate

3. 5-nitroindazole

4. 1-phenyl-5-mercaptotetrazole

5. 5-methylbenzotriazole

6. N-methylbenzothiazolium-p-toluene sulfonate

Useful buffers are those commonly used alkali metal salts such as:

K ₃ PO ₄ , K ₂ HPO ₄ , KH ₂ Po ₄ , Na ₂ CO ₃ , NaHCO ₃ , an alkali metal salt of boric acid, etc., or organic buffers, such as described in Bard et al., U.S. Pat. No. 3,305,364 and etc.

Useful silver halide solvents include:

1. Na ₂ S ₂ O ₃

2. naCNS

3. nh ₄ oh

4. ethylenediamine

5. dithiooctanediol

6. thiourea

7. isopropylamine

8. n-butylamine, etc.

Useful antioxidants include:

1. hydroxylamine sulfate

2. diethylhydroxyylamine

3. sodium sulfite

4. dextrose

5. p-hydroxyphenyl glycine

6. ascorbic acid

7. oxytetronic acids

8. dihydroxyacetone

Other useful compounds which are advantageously added to our developer include thallium nitrate and tetramethylammonium chloride.

Solutions containing our soluble and diffusible competing couplers and all the components of a color developer solution, excepting the developing agent, are used advantageously as a prebath from which is imbibed our soluble and diffusible competing couplers. Solutions having this composition and containing both color developing agent and soluble diffusible competing couplers are used advantageously to apply said competing coupler to the photographic element and also carry out negative silver development as described hereinunder. Solutions having the above composition, but lacking our soluble, diffusible competing coupler are used advantageously to carry out negative silver and positive image dye development using photographic elements in which said competing couplers have been imbibed or precoated.

The remainder of the process after color development is advantageously carried out as described in the patent references such as U.S. Pat. No. 3,046,129 (columns 27 and 28), U.S. Pat. No. 2,956,879 (columns 5 and 6), etc. This includes removal of the silver image by bleaching and then fixing or by blixing with a combined bleach-fix bath, appropriate washing, and stabilization of the dyes if desired. Suitable bleach-fixes (blixes) are described in Jacobson, British Pat. No. 991,412.

During continuous processing, or extended use of our developing solution, our competing coupler which does not decompose tends to build up and thereby reduce the quality of the processed image. If desired, these compounds are removed by passing the developer solution through an anion exchange column containing any known anion exchange resin. Useful anion exchange resins include those sold under the trademarks, e.g.:

1. AMBERLITE IRA 400, 401 or 410 (Rohm & Haas Co. trademark for insoluble, cross-linked polymers used as anionic exchange resins)

2. IONAC A-550 (permutit Co. trademark for quaternary amine polystyrenes used as anionic exchange resins)

3. PERMUTIT ES S-1, A (Permutit Co. trademark for anionic exchange resins)

4. DUOLITE A-40, A-42, A-101, A-102 (Diamond Alkali Co. trademark for insoluble, infusible cross-linked polystyrene or a phenol-formaldehyde condensate as an anionic exchange resin)

or by including in the developing solution, compounds which render the excess coupler either unreactive or nondiffusible in hydrophilic colloid layers of a photographic element, e.g., an alkali metal salt of boric acid in range up to 100 g./l. or a compound having the formula:

wherein R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are the same or different alkyl groups having from one to 20 carbon atoms with at least one of those alkyl groups having from 12 to 20 carbon atoms and x 2 ^- is an anion, e.g., Cl ^- , Br ^- , H ₂ PO ₄ ^- , p-toluene sulfonate, etc., in a concentration at or near the solubility limit. Typical examples include N,N-dimethyl-N-B-hydroxyethyl-N-γ-stearamidopropylammonium bromide, methyl-tri-N-dodecylammonium-p-toluene sulfonate, etc.

From the preceding description of our invention, it can be seen that many of out components are described in the prior art as competing couplers or white (i.e., colorless) couplers. They were used in the prior art to reduce fog or to enhance image sharpness as in for example Weller et al., U.S. Pat. No. 2,689,793; Salminen, U.S. Pat. No. 2,742,832; or Pueschel, U.S. Pat. No. 2,998,314; however, we have found that by selecting the proper activity and solubility of such compounds, they will react with all of the p-phenylenediamine developing agent oxidized during negative silver development and then allow subsequent positive image dye formation to go on unhindered. In all of the prior art, the negative silver development had been carried out in a separate step before being brought into contact with a p-phenylenediamine color developing agent, and the positive image was produced in the presence of a relatively low concentration of a competing coupler. Alternatively, the prior art discloses the production of a negative color image in the presence of a color developer and a competing coupler. In our invention, negative development is carried out by a p-phenylenediamine color developing agent in the presence of a sufficient amount of our competing coupler such that the oxidized color developer produces no image dyes, but rather, reacts with our competing coupler. It is then necessary for most of the competing coupler to be removed by diffusion or inactivation as described hereinabove, and that all traces of the reaction products be unapparent due to their lack of color, or also to diffusion from the photographic element. The positive dye image is then produced normally in the same solution.

Our invention is preferably used for the production of a direct positive image in any incorporated coupler (i.e., that form nondiffusible dyes on color development) color photographic elements by processing the element in a single color development step by the use of our competing couplers. Typical process cycles include the following:

1. Develop, stop, wash, bleach, wash, fix, wash, stabilize

2. Develop, bleach-fix, wash, stabilize

3. Prebath*, develop, bleach-fix, wash, stabilize

4. Develop*, develop, bleach-fix, wash, stabilize

5. Prebath*, develop, stop, wash, bleach, wash, fix, wash, stabilize, etc.

(*Denoting solutions containing our soluble, diffusible competing couplers)

All of these processes are advantageously used for our photographic elements which contain our competing couplers and will give a direct positive image, while process cycles 3, 4 and 5 will process conventional color photographic elements and give a direct positive image.

In process cycle 4 above, there is described an alternate embodiment of our invention in which the negative silver and positive dye development take place in separate solutions. Process Cycle 4 is not strictly a direct reversal process, and the element being processes is removed from the negative developer when the negative image is developed, but it does use our invention and, therefore, does offer obvious advantages over reversal processes of the prior art.

In addition, we may also process incorporated coupler color photographic elements in process cycles 1 and 2 and obtain a negative image, but in processes 3 4 and 5, they will give a positive dye image.

In all of our process cycles, a photographic element developed to a direct positive color image is left in the developer solution as long as is desired with no image degradation because all reactions go to completion. There is a minimum inhibition and development time, but no maximum practical time in these solutions. This shows the insensitivity of our process to variations in process time, and demonstrates the noncritical nature of our single development step. Also, our invention can be utilized over a broad temperature range such as from about 20° C. to about 93° C. We have found, however, that additional forehardening of the coating during manufacture or prehardening of the coating in the process is advantageous when the elements are processed at temperatures above 29° C. Prehardening can be used only with process cycles 3, 4 and 5 while forehardening can be used for all process cycles. Advantageous prehardener solutions have been described in Baden et al., U.S. Pat. No. 3,294,536; Allen et al., U.S. Pat. No. 3,232,761; Re. No. 26,601 and Bard et al., U.S. Pat. No. 3,451,817. These are common dialdehyde (e.g., succinaldehyde) formaldehyde hardeners. The hardener is advantageously followed by a common scavenger or a neutralizer bath, such as described in Blackmer et al., U.S. Pat. No. 3,168,400 and which describes agents that react with the excess aldehyde before development. A useful agent, for example, is hydroxylamine.

The following examples are included for a further understanding of our invention:

EXAMPLE 1

Six samples of a camera speed incorporated coupler reversal color film comprising a film support coated in succession with a red-sensitized gelatinosilver bromoiodide emulsion layer containing a nondiffusible phenolic cyan-dye-forming coupler of the type shown in columns 15, 16 and 17 of Graham et al., U.S. Pat. No. 3,046,129, a green-sensitized gelatinosilver bromoiodide emulsion layer containing a nondiffusible 5-pyrazolone magenta-dye-forming coupler of the type shown in column 17 of U.S. Pat. No. 3,046,129, a blue light-absorbing filter layer, such as Carey-Lea, colloidal silver dispersed in gelatin and a blue-sensitive gelatinosilver bromoiodide emulsion layer containing a nondiffusible open-chain ketomethylene yellow-dye-forming coupler of the type shown in columns 17 and 18 of U.S. Pat. No. 3,046,129 are light-exposed to a test object and processed at 51.6° C. as follows:

Prehardener 45" Neutralizer 15" Prebath 2' Developer 10", 30", 1', 2', 3'or 4' Stop 30" Wash 30" Bleach 1' Fix 1' Wash 2' Stabilizer 30"

The prehardener is a conventional aqueous succinaldehyde-formaldehyde prehardener solution and the neutralizer is an aqueous solution of hydroxylamine. The prebath is an aqueous solution consisting of 320 g./l. of H-Acid, i.e., 8-amino-1-naphthol-3,6-disulfonic acid and 114 g./l. of Na ₂ CO ₃ adjusted to a pH of 8.0 at 26.7° C. The developer is an aqueous solution as follows:

diaminopropanol tetraacetic acid (water softener) 5.0 g./l. Na ₂ SO ₃ 7.5 g./l. Na ₃ PO ₄ ^. 12H ₂ O 36.0 g./l. KI (0.1 percent solution) 24.0 ml./l. 4-amino-3-methyl-N-ethyl-N-β-hydroxy- ethylaniline sulfate 29.2 g./l. pH at 26.7° C. 11.0

the stop bath is an acidic aqueous solution which advantageously contains sulfite ions, the bleach a conventional potassium ferricyanide-postassium bromide aqueous solution, the fix a conventional sodium thiosulfate aqueous fixing solution and the stabilizer an aqueous formalin solution. A good direct reversal image is produced at the 2-, 3- and 4-minute development times, each development time giving substantially identical results. Color reversal images are obtained with one minute of development, however the dye densities and contrast are lower then desired. Colors from the test object and a neutral scale are properly reproduced at the intended speed for this product. The results are comparable to a similar sample of this film exposed as above and reversal processed by conventional techniques using a negative developing step, stop bath, wash, flash to light or treatment with a chemical fogging agent, color development, etc., as described in Henn et al., U.S. Pat. No. 2,984,567, Example 2.

EXAMPLE 2

Example 1 is repeated at 30° C. and 82,2° C. and gives good direct reversal image reproductions with development times of 8 minutes and 60 seconds, respectively.

EXAMPLE 3

Examples 1 and 2 are repeated, but with extended development times. Good direct reversal image reproductions are obtained that are substantially identical with those obtained at the minimum satisfactory development time. There is no image degradation. This demonstrates that there is a minimum development time, but no maximum development time.

EXAMPLE 4

Examples 1, 2, and 3 are repeated, but with a developer pH of 10.0. Useful direct reversal image reproductions obtained using the appropriate development times (i.e. 8 min, at 30° C., 2 min. at 51.6° C. and 60 sec. at 82.2° C.) indicated in the previous examples.

EXAMPLE 5

Examples 1, 2 and 3 are repeated, but with a developer pH of 13.0. Useful direct reversal image reproductions are obtained using the appropriate development times, indicated in the previous examples.

EXAMPLE 6

Examples 1, 2 and 3 are repeated, but with 10 g./l. of developing agent. Good direct reversal image reproductions are obtained using the appropriate development times indicated in the previous examples.

EXAMPLE 7

Examples 1, 2 and 3 are repeated but with 100 g./l. of developing agent. Good direct reversal image reproductions are obtained using the appropriate development times indicated in the previous examples.

Examples 6 and 7 demonstrate that our system has low sensitivity to developing agent concentration once the minimum threshold development time and developing agent concentration are established

EXAMPLE 8

Examples 1, 2, 3, 6 and 7 are repeated, but using in one prebath 115 g./l. of 2,6-dihydroxyisonicotinic acid and in another prebath 155 g./l. of 3,5-dihydroxybenzoic acid in place of H-Acid. Useful reversal image reproductions are obtained using the appropriate development times indicated in the previous examples.

EXAMPLE 9

Examples 1, 2, 3, 6 and 7 are repeated, but using as developing agent an equimolar amount of N,N'-diethylparaphenylenediamine and again good direct reversal image reproductions are obtained by using the appropriate development times indicated in the previous examples.

When other color developing agents are substituted on an equal molar basis to either Example 1 or Example 9, substantially the same results are obtained.

EXAMPLE 10

Samples of 8 different 3-color coupler incorporated reversal color films having the general layer arrangements described for the film in Example 1 and using cyan-dye-image-forming couplers of the type shown in columns 15, 16 and 17 of U.S. Pat. No. 3,046,129 or of the type shown in column 3 of U.S. Pat. No. 2,895,826 using 5-pyrazalone magenta-dye-image-forming couplers of the type shown in column 17 of U.S. Pat. No. 3,046,129 and column 4 of U.S. Pat. No. 3,342,597, and using open-chain ketomethylene yellow-dye-image-forming couplers of the type shown in columns 17 and 18 of U.S. Pat. No. 3,046,129 or in columns 4, 5, 6 and 7 of U.S. Pat. No. 3,408,194, are treated as described in Examples 1, 2, 3, 6, 7, 8 and 9 using the appropriate development times and high-quality direct color reversal images are obtained. The results in all cases are comparable to the results obtained when the exposed materials are processed by the much longer but conventional techniques.

EXAMPLE 11

Nine color photographic reversal materials are processed as described in Example 1 using 2 or 4 minutes development time and Examples 2, 3, 6, 7, 9 and 10, but after development in each instance the samples are treated in a conventional bleach-fix (blix) solution containing sodium ferric ethylenediamine tetraacetate and ammonium thiosulfate until all silver and silver salts are removed. Good direct reversal color image reproductions are obtained.

EXAMPLE 12

Examples 1, 2, 3, 6, 7 and 9 through 11 are repeated, but substituting in place of the prebath, a solution having the composition:

Diaminopropanol tetraacetic acid 5.0 g. Na ₂ SO ₃ 7.5 g. Na ₃ PO ₄ ^. 12H ₂ O 36.0 g. KI (0.1 percent solution) 24.0 cc. 8-amino-1-naphthol-3,6-disulfonic acid 320.0 g. Water to 1.0 l.

Good direct reversal color image reproductions are obtained using the appropriate development times in the previous examples.

EXAMPLE 13

Two samples of developer as described in Example 1 are prepared, but one contains in addition 100 g./l. of 8-amino-1-naphthol-3,6-disulfonic acid. The following process is carried out with all solutions at a temperature of 51.6° C., except the developer solutions which are at 82.2° C.:

prehardener 45' Neutralizer 15" Wash 1' Negative development 30" Reversal development 30" Stop 30" Wash 30" Bleach 1' Fix 1' Wash 2' Stabilizer 30"

The developer containing the soluble coupler is used for negative development. Good direct reversal color images are obtained with 30 seconds color development at 82.2° C. This process has the advantage of using almost identical solutions for negative and reversal development, and having fewer stops than conventional reversal processes. It also uses our invention to achieve reversal, but because there is not only a minimum but a maximum limit on negative development time, it is a less preferred embodiment of our invention.

EXAMPLE 14

A three-color photographic element having a transparent poly(ethylene terephthalate) film support coated on one side in succession a gelatin red-sensitized silver bromoiodide emulsion layer containing an incorporated nondiffusible phenolic cyan-dye-image-forming coupler of the type shown in columns 15, 16 and 17 of Graham et al., U.S. Pat. No. 3,046,129, a gelatin green-sensitized silver bromoiodide emulsion layer containing an incorporated nondiffusible 5-pyrazolone magenta-dye-image-forming coupler of the type shown in column 17 of U.S. Pat. No. 3,046,129, a gelatin layer containing a bleachable blue light-absorbing filter and a gelatin blue-sensitive silver bromoiodide emulsion layer containing an incorporated nondiffusible open-chain ketomethylene yellow-dye-image-forming coupler of the type shown in columns 17 and 18 of U.S. Pat. No. 3,046,129 is prepared. The gelatin in each of the coupler-containing layers is forehardened with a vinyl sulfone hardener, such as those described in Belgian Pat. No. 686,440 on page 2, line 1 through page 9, using an amount of hardener that is about 1.5 percent by weight of gelatin. To the coated side of this support is then applied a solution of the soluble, diffusible competing coupler 8-amino-1-naphthol-3,6-disulfonic acid such that 2 grams of our competing coupler are found to be present in every square foot of the element. The photographic film is then slit and treated as described in Examples 1, and 2, 3, 6, 7 and 9 using the appropriate development times; however, no prehardener, no neutralizer, no neutralizer and no prebath is used in any of the processes, since the gelatin is forehardened and all of the competing coupler necessary is supplied from that coated over the photographic element. Excellent direct reversal color reproductions are made.

EXAMPLE 15

Example 14 is repeated, but instead of applying to the outermost light-sensitive layer of the commercial photographic element 2 g./ft. ² of 8-amino-1-naphthol-3,6-disulfonic acid (in solution), application is made to other pieces of the commercial photographic element solutions of the following competing couplers:

α-methyl-α-pivalylacet-2,4-dicarboxyanilide

α-methyl-α-pivalylacet-4-sulfoanilide

benzoyl-α-methylacet-4-sulfoanilide

3,4-dimethyl-1-(4-sulfophenyl)-5-pyrazolone

benzolyacet-4-sulfoanilide

3-methyl-1-(4-sulfophenyl)-5-pyrazolone

2-amino-5-naphthol-7-sulfonic acid

8-amino-1-naphthol-3,6-disulfonic acid

4,6-dichloro-5-methyl-2-(4-sulfobenazmido)phenol

2,6-dihydroxyisonicotinic acid

3,5-dihydroxybenzoic acid

α-chloro-α-pivalylacet-4-sulfoanilide

benozyl-α-chloroacet-4-sulfonanilide

each competing coupler being applied to separate pieces of the commercial element so that each coupler is applied at the rates of 0.5 g./ft. ² , 1.0 g./ft. ² and 3.0 g./ft. ² . The coatings are then slit and treated as described in Examples 1, 2, 3, 6, 7, and 9; however, no prehardener, no neutralizer and no prebath is used in any of these processes since all of the soluble, diffusing competing coupler necessary is supplied by the overcoating described above. Useful reversal dye images are obtained when the appropriate development times are used. Useful results are obtained when this example is repeated for each of the competing couplers coated at 0.1 g./ft. ² and 5.0 g./ft. ² .

EXAMPLE 16

A photographic element is made by coating on one side of a transparent film support a hardened gelatin red-sensitized silver bromoiodide emulsion layer containing a solution of our competing coupler 8-amino-1-naphthol-3,6-disulfonic acid and an incorporated nondiffusible phenolic cyan-dye-image-forming coupler of the type shown in columns 15, 16 and 17 of U.S. Pat. No. 3,046,129, a hardened gelatin green-sensitized silver bromoiodide emulsion layer containing a solution of 8-amino-1-naphthol-3,6-disulfonic acid and an incorporated nondiffusible 5-pyrazolone magenta-dye-image-forming coupler of the type shown in column 17 of U.S. Pat. No. 3,046,129, a hardened gelatin layer containing a bleachable blue light-absorbing filter and a hardened gelatin blue-sensitive silver bromoiodide emulsion layer containing a solution of 8-amino-1-naphthol-3,6-disulfonic acid and an incorporated nondiffusible open-chain ketomethylene yellow-dye-image-forming coupler of the type shown in columns 17 and 18 of U.S. Pat. No. 3,046,129 so that there is a total of 1.5 g. of 8-amino-1-naphthol-3,6-disulfonic acid per square foot of the coated element. The gelatin in each of the layers of this element is forehardened as describe in Example 14. Samples of this coating are treated as in Examples 1, 2, 3, 6, 7 and 9 using the appropriate development times; however, no prehardener, no neutralizer and no prebath is used in any of these processes since all of the competing coupler necessary is already incorporated in the photographic element. Good direct reversal color reproductions are obtained.

EXAMPLE 17

Example 16 is repeated for each of the competing couplers used in Example 15. The results are similar to those obtained in Example 16.

EXAMPLE 18

To the outermost coating of a three-color photographic element having a paper support coated on one side in succession with a hardened gelatin blue sensitive silver chlorobromide emulsion layer containing an incorporated nondiffusible open chain ketomethylene yellow-dye-image-forming coupler, a hardened gelatin green-sensitized silver chlorobromide emulsion layer containing an incorporated nondiffusible 5-pyrazolone magenta-dye-forming coupler, and a hardened gelatin red-sensitized silver chlorobromide emulsion layer containing an incorporated nondiffusible phenolic cyan-dye-image-forming coupler [i.e., a photographic element of the type described in Example 2 (column 7, line 55 through line 28 in column 8) of Van Campen, U.S. Pat. No. 2,956,879], is applied a solution of competing coupler 8-amino-1-naphthol-3,6disulfonic acid so that 2 g. of our competing coupler are imbibed in each square foot of the coated element. The forehardened gelatin layers are forehardened as described in Example 14. This element is exposed to a light image, developed in the developer solution described in Example 1, for 2 or 4, given an acid stop bath, wash, bleach in a sodium ferricyanide bleach bath, fix in a sodium thiosulfate fix bath, wash and dried. The results from this process are similar to the results obtained by the conventional and substantially longer process used for processing conventional photographic element (not containing the competing coupler solution overcoat) which require the steps first developer, harden or stop, wash, reversal exposing, color developer, stop bath, wash, bleach, fix, wash and dry.

Similar results are obtained when Example 18 is repeated using applications of other soluble, diffusible competing couplers of our invention (including those specific competing couplers used in Example 15) over the color photographic element. Coating rates in the range of from about 0.1 g./ft. ² to about 5.0 g./ft. ² are advantageously used.

EXAMPLE 19

A photographic element is made like the three-color element described in Example 18, excepting that a solution of 8-amino-1-naphthol-3,6-disulfonic acid is added to each of the coating compositions before they are coated on the paper support so that each square foot of the resulting photographic element contains a total of 2.0 g. of our competing coupler. A piece of this element and the overcoated element of our invention prepared in Example 18 are light image exposed and then developed in the developer solution described in Example 1 for 2 or 4 minutes, given an acid stop, wash, bleach, fix, wash, and dry. Good direct reversal color reproductions are obtained in each of our processed elements.

EXAMPLE 20

Photographic elements are made in which the differently sensitized silver halide emulsion layers containing the appropriate incorporated nondiffusible dye-image-forming couplers described in Example 14 are coated on a film support with different layer arrangements then used in Example 14 an in Example 18. In element A, the support is coated in succession with the blue-sensitive layer, the red-sensitized layer and the green-sensitized layer. In element B, the support is coated in succession with the red-sensitized layer, the blue-sensitive layer and the green-sensitized layer. In element C, the support is coated in succession with the green-sensitized layer, the red-sensitized layer and the blue-sensitive layer. Elements element D, the support is coated in succession with the green-sensitized layer, the blue-sensitive layer and the red-sensitized layer. Elements A', B', C' and D' of our invention are made by applying to the outermost light sensitive layer of elements A, B, C and D, respectively, a solution of 8-amino-1-naphthol-3,6-disulfonic acid. Each of the elements are given identical light image exposures. Elements A', B', C' and D' processed using four minutes of the developer of Example 1, acid stop, wash, bleach, fix, wash and dry. elements A, B, C and D are processed by the longer, conventional process using negative developer, stop, wash, re-exposure flash, color developer, acid stop, wash, bleach, fix, wash and dry. A comparison of the processed elements shows that A' is similar to A; B' is similar to B; C' is similar to C, and D' is similar to D. The preferred arrangement of the light-sensitive layers are those of the elements described in Examples 14 and 18; however, elements like A', B', C' and D' are advantageously used for special purposes. Elements A', B', C' and D' have 2 g. of competing coupler/ft. ² .

EXAMPLE 21

Example 14 is repeated, by using a photographic element in which instead of having a single layer of each of the differently sensitized emulsion layers, there are two red-sensitized emulsion layers, two green-sensitized emulsion layers and two blue-sensitive emulsion layers. To one piece of this element is applied a solution of 8-amino-1-naphthol-3,6-disulfonic acid as described in Example 14. Good direct reversal color image reproductions are obtained in this example, just as in Example 14.

EXAMPLE 22

An incorporated coupler masked color negative film such as is described in U.S. Pat. No. 3,046,129, column 25, line 67 through line 16, column 26, is treated as in Example 1, using a 4-minute development time and a useful masked direct positive image is obtained. This shows the wide versatility of our invention. This film is now useful as a masked reversal intermediate film for printing purposes.

EXAMPLE 23

Examples 1 and 14 are repeated, using the appropriate development times (as indicated in Examples, 1, 2, 3, 6, 7, 9 and 14), but using a continuous processing machines and a continuous strand of 35 mm. film. The developer solutions are continuously recirculated through a column containing an anionic exchange resin. Good direct reversal images are obtained and there is no degradation in image quality produced during this example. After completion of the example, the unused soluble competing coupler is recovered from the resin by using standard recovery procedures well known in the chemical industry.

EXAMPLE 24

Example 23 is repeated, but instead of recirculating the developer, a suitable complexing agent such as N,N-dimethyl-N-β-hydroxyethyl-Nγ-stearamidopropyl-ammonium dihydrogen phosphate is added to the developer solution in a a concentration of 5 g./l. Again, good direct color reversals are obtained and no image degradation is observed because our competing coupler is mutually complexed and rendered inactive in our system.

EXAMPLE 25

A processing machine is charged with chemicals for the processing of a three-color negative film as described in Example 22. Negatives are processed using the conventional developing systems. Intercut with the film are samples of a color reversal film as described in Example 14 above. Direct reversal images are produced from this film. During the processing, the developer solution is continually circulated through an ion exchange column to remove out soluble competing coupler that leaches from the film into the developer solution. This shows the versatility of our process.

EXAMPLE 26

Example 25 is repeated with another film coating containing a diffusible competing coupler which decomposes slowly upon contact with the developer. It is added as a dispersion to the coating composition used to coat the light-sensitive images. Since the decomposition products from the decomposition of the competing coupler are photographically nonreacting, direct color reversal is obtained and other films may be intercut during continuous processing with no need for an ion exchange treatment of the developer.

EXAMPLE 27

The previous examples are rerun, varying the developer components as hereinabove described, and the well-known addenda, such as antifoggants, accelerators, inhibitors, buffers and etc., are found to be beneficial in processes wherein our invention is also used. This indicates that substitutents in commercial color developers are suitable so long as a sufficient quantity of one of our competing couplers is present to prevent dye formation during negative development, but not enough to interfere with reversal image dye formation.

EXAMPLE 28

A continuous drum processing machine is built using the principles described in Burner et al., U.S. Pat. No. 3,093,052 and Edens et al. British Pat. Nos. 1,057,585 and 1,064,914 in which a continuous fresh supply of each processing solution in sequence is applied to the moving photographic element as a film by a series of rotating drums, so that each processing solution is applied to the element by a different drum. A continuous stand of 35 mm. film (described in Example 14) is processed on this machine to direct color reversal image reproductions and no seasoning effect due to a buildup of our soluble and diffusible completing coupler is observed. There is no need for the ion exchange resin or the complexing agent due to the high turnover of developer solution in this processing machine.

EXAMPLE 29

The preceding examples are repeated, using the appropriate development times (indicated in the previous examples) and in the developer formula of Example 1, 20 ml./l. of benzyl alcohol. The benzyl alcohol performs as a development accelerator as described in the prior art, giving good direct color reversal image reproductions with increased contrast, speed and D-max.

EXAMPLE 30

The preceding examples are repeated, adding to the developer 10 mg./l. of 1-phenyl-5-mercaptotetrazole. It acts as an antifoggant, lowering speed and fog.

Examples 29 and 30 are repeated with a variety of addenda used in color photographic processes for both black-and-white and color developer solutions. The results are predictable and similar to the prior art. This shows that our system responds well to well-known photographic processing solution constituents.

EXAMPLE 31

A multilayer three-color photographic element containing incorporated color-forming couplers of the type described in Example 1 is exposed to an original light image and then given direct color reversal processing of our invention at 23.9° C. as follows:

Prebath from Example 1 8' Color developer from Example 1 12' Blix until silver and silver halide is removed Wash 10' Stabilizer 2'

to produce a good color positive reproduction of the original light image. The blix (a bleach-fix bath) is a conventional, aqueous sodium ferric ethylenediamine tetraacetate, sodium thiosulfate blix. The stabilizer is an aqueous formalin solution.

EXAMPLE 32

A piece of the multilayer color photographic element used in Example 1 is contacted with a solution containing our competing coupler 8-amino-1-naphthol-3,6-disulfonic acid so that each square foot of the element imbibes a total of 2 g. of our competing coupler. This element is exposed to an original light images and then given direct reversal color processing according to our invention at 23.9° C. as follows:

Color developer from Example 1 12' Blix from Example 31 until silver and silver halide are removed Wash 10' Stabilizer from example 31 2'

to produce a good color positive reproduction of the original light image

EXAMPLE 33

A multilayer color photographic element of the type described in Example 1 containing incorporated color-forming couplers in which the gelatin emulsion layers are hardened with mucochloric acid and formaldehyde sufficiently to withstand 51.6° C. processing is given light image exposure and direct color reversal processed as described in Example 31, but using the solutions at 51.6° C. to give good direct color reversal image reproductions similar to those obtained in Example 31.

In addition to, or in place of, mucochloric acid and formaldehyde hardening of the gelatin emulsions of Example 33, aziridin hardeners such as those described in Burness, U.S. pat. No. 2,964,404 (in column 1, line 57 through column 3, line 26); in Allen et al., U.S. Pat. No. 2,950,197 (in column 1, line 50 through column 6, line 25) etc.; isoxazolium hardeners such as those described in Van Campen et al., U.S Pat. No. 3,316,095 (in column 1, line 31 through column 3, line 64); in Burness et al., U.S. Pat. No. 3,321,313 (in column 1, line 32 through column 6, line 13); vinyl sulfone hardeners such as those described in Belgian Pat. No. 686,440 (in page 2, line 1 through page 9), are used to advantage as described in the immediate references in hardening the emulsions used to coat elements for our examples, such as 33 and 34 where elevated processing solution temperatures are used.

EXAMPLE 34

A piece of the multilayer color photographic element containing our competing coupler prepared in Example 32 is prepared with gelatin hardened as described in Example 33, exposed to an original light image, then given direct reversal color-processing according to our invention at 51.7° C. as follows:

Color developer from Example 1 4' blix from Example 31 until silver and silver halide is removed Wash 2' Stabilizer from Example 31 30"

to produce a good color positive reproduction of the original light image.

Similar good direct color reversal image reproductions are obtained when Examples 31, 32, 33 and 34 are repeated using other competing couplers of our invention, including the specific illustrative competing couplers used in Example 15.

The following examples illustrate another embodiment of our invention in which at least one direct color reversal emulsion layer, containing an incorporated nondiffusible color-image-forming coupler and a soluble, diffusible competing coupler is coated on one side of a film support and on the other side of the support is coated at least one conventional emulsion layer containing an incorporated nondiffusible color-image-forming coupler.

EXAMPLE 35

On a transport support is coated on side A, a gelatin green-sensitized silver bromoiodide camera speed emulsion layer containing an incorporated nondiffusible magenta-image-forming coupler of the type shown in column 17 of U.S. Pat. No. 3,046,129 and about 1 g. of our competer 8-amino-1-naphthol-3,6-disulfonic acid per square feet and coated on side B, an identical gelatin green-sensitized silver bromoiodide camera speed emulsion, but containing an incorporated nondiffusible yellow- image-forming coupler of the type shown in columns 17 and 18 of U.S. Pat. No. 3,046,129 and containing no competing coupler. The gelatin in the element is hardened as in Example 14. The element is exposed to a light image and processed as described in Example 34 to produce on side A a good positive magenta dye image and on side B a good negative yellow image mask.

EXAMPLE 36

A photographic element is made like the element described in Example 35, excepting that the competing coupler in side A of Example 35 element is placed in side B, and side A contains no competing coupler. After image exposure and processing as described in Example 35, side A contains a good negative magenta dye reproduction and side B contains a good positive yellow-colored mask.

EXAMPLE 37

A color photographic element comprising a cellulose acetate film support coated with a gelatin layer containing a dispersion of blue-sensitized packets, green-sensitized packets and red-sensitized packets is made. The blue-sensitive packets include gelatin, a resin, a blue-sensitive silver bromoiodide emulsion and a nondiffusible yellow-dye-forming open chain ketomethylene coupler; the green-sensitized packets include gelatin, a resin, a green-sensitized silver bromoiodide emulsion and a nondiffusible magenta-dye-forming 5-pyrazolone coupler, and the red-sensitized packets include gelatin, a resin, a red-sensitized silver bromoiodide emulsion and a nondiffusible cyan-dye-forming phenolic coupler prepared as described by Martinez, U.S. Pat. No. 2,284,877. This photographic element is exposed to a test object and processed as described in Example 1. A useful direct color reversal image is obtained.

EXAMPLE 38

The light-sensitive layer of the photographic element made in Example 37 is contacted with an aqueous solution of our competing coupler 8-amino-1-naphthol-3,6-disulfonic acid so that about 2 g. of our competing coupler are imbibed per square foot. This element is exposed to a light image and processed as described in Example 31, but without the prebath. Useful direct color reversal image reproductions are obtained of the light image.

Mixtures of two or more of our competing couplers are advantageously used in place of a single competing coupler in our photographic elements and/or in a prebath according to our invention.

EXAMPLE 39

Example 14 is repeated but instead of applying to the multilayer color photographic element a solution of the single competing coupler 8-amino-1-naphthol- 3,6-disulfonic acid, a solution of 8-amino-1-naphthol-3,6-disulfonic acid and 2,6-dihydroxyisonicotinic acid is applied so that each square foot of the element imbibes 1 g. of each competing coupler. Good direct color reversal image reproductions are obtained.

EXAMPLE 40

Example 1 is repeated but with a prebath that contains instead of 320 g./l. of 8-amino-1-naphthol-3,6-disulfonic acid, 160 g./l. of 8-amino-1-naphthol-3,6-disulfonic acid and 160 g./l. of 2,6-dihydroxyisonicotinic acid. A development time of 4 minutes is used. Good direct color reversal image reproductions are obtained.

EXAMPLE 41

Example 1 is repeated at 93° C., using N,N-diethyl-3-(β-hydroxyethyl)-p-phenylenediamine 2HCl as the developing agent instead of 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate. Good direct reversal image reproductions are obtained with a development time of 60 seconds.

EXAMPLE 42

Photographic elements are made as described in Examples 14, 15 and 18 and solutions of competing couplers are applied as described in Examples 14, 15 and 18, respectively. The elements are then slit, light exposed to a test object and processed according to our invention as described in Example 1, but using no prehardener step, no neutralizer step and no prebath step, and using N,N-diethyl-3-(B-hydroxyethyl)-p-phenylenediamine 2HCl as the developing agent, instead of 4-amino-3-methyl-N-ethyl-N-B-hydroxyethylaniline sulfate in the developer solution (of Example 1) and processing at 93° C., instead of 51.6° C. Good direct reversal color image reproductions are obtained with 60 seconds development.

EXAMPLE 43

A panchromatically sensitized hardened gelatin silver bromoiodide emulsion is prepared and intimately blended with a dispersion of a mixture of (1) a nondiffusible phenolic cyan-dye-image-forming coupler (of the type shown in columns 15, 16 and 17 of Graham et al., U.S. Pat. No. 3,046,129), (2) a nondiffusible 5-pyrazolone magenta-dye-image-forming coupler (of the type shown in column 17 of U.S. Pat. No. 3,046,129), and (3) a nondiffusible open-chain ketomethylene yellow-dye-image-forming coupler (of the type shown in columns 17 and 18 of U.S. Pat. No. 3,046,129) in a hardened gelatin. The weight ratio of the three couplers is adjusted to give upon direct reversal processing approximately a neutral image. The resulting emulsion is coated on a poly(ethylene-terephthalate) film support. After drying, the emulsion coating is overcoated with a solution of the competing coupler 8-amino-1-naphthol-3,6-disulfonic acid such that two grams of our competing coupler are present in every square foot of the coatings. The resulting element is sensitometrically exposed to a light image and processed as described in Example 1, except that no prehardener, no neutralizer and no prebath are used. Useful direct reversal neutral image reproductions are obtained of the original light image.

EXAMPLE 44

Examples 1 and 14 are repeated seven times, once each for each of seven different developing agents in the developing solution, i.e., using in place of 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate in the developer solution an equimolar amount of p-amino-N,N-di-ethylaniline HCl, 4-amino-3-methyl-N,N-diethylaniline HCl 4-amino-N-ethyl-N-β-hydroxyethylaniline H ₂ SO ₄ , 4-amino-N-butyl-N-ω-sulfobutylaniline, 4-amino-3-methyl-N-β-(methane sulfonamido)ethylaniline 3/2 H ₂ SO ₄ H ₂ O, 4-amino-3-β-(methane sulfonamido)ethyl-N,N-diethylaniline HCl and 4-amino-3-methoxy-N-ethyl-N-β-hydroxyethylaniline 2HCl. Good direct reversal color image reproductions are obtained when each of these developing agents are used in our process.

Similarly, it can be shown that still other para phenylenediamine color developing agents are used to advantage in our direct reversal color process.

EXAMPLE 45

Example 24 is repeated twice, using in the developing solution in place of N,N-dimethyl-N-β-hydroxyethyl-N-γ-stearamidopropyl ammonium dihydrogen phosphate, an equimolar amount of N-n-octadecyl-N,N,N-tributyl ammonium bromide in one repeat, and methyl-tri-N-dodecylammonium-p-toluene sulfonate in the second repeat. In each repeat, the results are essentially the same as obtained in Example 24.

Our direct reversal color photographic elements and process provide a shorter and simpler process that is less sensitive to process variations than any of the prior art elements and processes and yet gives reversal color reproductions that are as good as, or better than, the prior art. This represents a valuable technical advance in color photography. For example, in one embodiment of our invention, a single-process step, i.e., development is used to replace the conventional process steps of (1) first development (2) stop bath (3) wash and (4) reversal color development. In another embodiment, we use (1) a prebath (containing a diffusible competing coupler) and (2) a development step in place of the four process steps used by the prior art. Our process advantageously uses a single developing agent while conventional processes use from two to three different developing agents. Our development step goes to completion, so there is no upper limit on the development time, while the prior art has an upper limit, as well as a lower limit, on not only one development step but two development steps that must be controlled precisely. Our process is less sensitive to temperature variations that the prior art because our development step goes to completion and the process does not depend upon stopping a first development step at the proper stage of development as well as stopping the reversal development step at the proper stage of development.

Our process is distinguished from prior art processes by using an aromatic primary amine color developer to develop a negative silver image as well as a positive silver image and a positive dye image in our photographic element. Substantially all of the oxidized aromatic primary amine color developing agent that is formed during development of light-exposed areas of a latent image in our element reacts with a competing coupler that is present in the emulsion layers so there is no nondiffusible negative dye image formed in the element, while during the subsequent fogging development of the unexposed areas of the silver halide (advantageously in the same developer solution), there is not enough competing coupler present to interfere with the formation of a positive dye image along with the positive silver image. The competing coupler is advantageously incorporated in the appropriate hydrophilic colloid layer or layers during manufacture of the color photographic element that contains nondiffusible color-forming couplers that form the nondiffusible image dyes, or the photographic element is advantageously made without the competing coupler which is then imbibed into the element as the last stage of manufacture or at any subsequent time desired (before or after light image exposure), as long as it is present in the element just prior to the development step. The appropriate amount of a diffusible, competing coupler is advantageously imbibed into the emulsion layers of any commercial or other prior art color photographic element (containing incorporated couplers that form nondiffusible dye images) as indicated and then advantageously processed by our process to give good, direct reversal color reproductions.

Our process cycles 3, 4 and 5 described herein previously (on page 36 of our application) for processing our direct reversal color elements are also used to advantage for processing color negative elements by omitting the first step of each of these process cycles in which a competing coupler is imbibed into the color element.

Our process Cycle 1, i.e., develop, stop, wash, bleach, wash, fix, wash stabilize and our process Cycle 2, i.e., develop, bleach-fix, wash, stabilize are used to advantage to process our novel direct reversal color elements to form direct reversal images as we have described herein previously and also to process color negative elements to color negative images. These two different color elements are advantageously processed concurrently (i.e., side by side or direct color reversal on one side of the support and color negative on the other side of the same support in a single element) or sequentially (i.e., one after the other) through the same, identical processing steps under the same conditions of time and temperature. Thus, our direct reversal color elements and color negative elements are advantageously interspliced and passed continuously through our process in a processing machine. This is an important technical advance over the prior art which requires the use of two different incompatible processes to process color reversal images and color negative images.

The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.