Photographic sulfonamido compounds and elements and processes using them

Abstract

A novel class of redox releasing compounds contains an N,N-disubstituted carbamoyl ballast group. These compounds can be used in photographic elements and processes to release a dye or other photographically useful group as a function of silver halide development.

We claim: 
     
       1. A photographic element comprising a support, at least one photosensitive silver halide emulsion layer and a redox releasing compound having the structure: ##STR39## where: R 1  and R 2  independently represent an aliphatic, alicyclic or aromatic group; G represents an --OR 5  group or an --NHR 6  group, where R 5  is hydrogen or a hydrolyzable moiety and R 6  is hydrogen, an alkyl group of 1 to 22 carbon atoms or an --SO 2  PUG moiety;   Z represents the atoms necessary to complete a one-, two- or three-ringed carbocyclic or heterocyclic group containing 5 to 7 nuclear atoms in each ring, the sulfonamido group, --NHSO 2  --PUG, being joined to a position on Z so as to be linked to G through a conjugated carbon chain and is ortho or para to G; and PUG represents a photographically useful group.   
     
     
       2. In a photographic element comprising a support, at least one photosensitive silver halide emulsion layer and a ballasted non-diffusible p-sulfonamidophenol or p-sulfonamidoaniline having attached thereto through the sulfonamido group, a photographically useful group which is alkali-cleavable upon oxidation, the improvement wherein the p-sulfonamidophenol or p-sulfonamidoaniline contains, meta to the sulfonamido group, an N,N-disubstituted carbamoyl ballast group containing substituents selected from the group consisting of aliphatic, alicyclic and aromatic groups. 
     
     
       3. A photographic element comprising a support and at least one photosensitive silver halide emulsion layer having associated therewith a non-diffusible p-sulfonamidophenol or p-sulfonamidoaniline which is alkalicleavable upon oxidation to release a photographically useful group and which has the structure: ##STR40## where: X represents the atoms required to complete a benzene or naphthalene ring; R 1  and R 2  independently represent an aliphatic, alicyclic or aromatic group of such size and configuration as to render the compound non-diffusible in an alkaline processing composition; G represents an --OR 5  group or an --NHR 6  group, where R 5  is hydrogen or a hydrolyzable moiety and R 6  is hydrogen, an alkyl group of 1 to 22 carbon atoms or an --SO 2  PUG group; and PUG is a photographically useful group.   
     
     
       4. A photographic element of claim 3 wherein the p-sulfonamidophenol or p-sulfonamidoaniline is in the silver halide emulsion layer. 
     
     
       5. A photographic element of claim 3 wherein the p-sulfonamidophenol or p-sulfonamidoaniline is in a layer contiguous to the silver halide emulsion layer. 
     
     
       6. A photographic element of claim 5 wherein: R 1  and R 2  are straight chain alkyl groups of 1 to 30 carbon atoms and together they contain a total of 8 to 50 carbon atoms; G is -OR 5  and R 5  is hydrogen; and PUG is a dye or dye precursor moiety. 
     
     
       7. A photographic element of claim 3 wherein: PUG is a dye or dye precursor moiety. 
     
     
       8. A photographic element comprising a support and at least one photosensitive silver halide emulsion layer having associated therewith a non-diffusible p-sulfonamidophenol which is alkali-cleavable upon oxidation to release a dye or dye precursor and which has the structure: ##STR41## where: X represents the atoms required to complete a benzene or naphthalene ring; R 1  and R 2  are straight chain alkyl groups of 1 to 30 carbon atoms and together they contain a total of 8 to 50 carbon atoms; and Dye is a dye or dye precursor.   
     
     
       9. A photographic element of claim 8 wherein R 1  and R 2  each represent the same alkyl group of 10 to 22 carbon atoms. 
     
     
       10. A photographic element of claim 9 wherein X represents the atoms required to complete a naphthalene ring. 
     
     
       11. A photographic element of claim 10 wherein the p-sulfonamidophenol is in at least one of the silver halide emulsion layers. 
     
     
       12. A photographic element of claim 10 wherein the p-sulfonamidophenol is in a layer contiguous to at least one of the silver halide emulsion layers. 
     
     
       13. A photographic element of claim 8 wherein the support is a transparent support. 
     
     
       14. A photographic element comprising a transparent support, at least one photosensitive silver halide emulsion layer and, in a layer contiguous thereto, a non-diffusible p-sulfonamidophenol which is alkali-cleavable upon oxidation to release a dye or dye precursor and which has the structure: ##STR42## where: X represents the atoms to complete a naphthalene ring; R 1  and R 2  each represent the same alkyl group of 10 to 22 carbon atoms; and   Dye represents a dye or dye precursor.   
     
     
       15. A photographic element comprising a support having thereon a red-sensitive silver halide emulsion layer having associated therewith a cyan-dye-image-providing material, a green-sensitive silver halide emulsion layer having associated therewith a magenta-dye-image-providing material, and a blue-sensitive silver halide emulsion layer having associated therewith a yellow-dye-image-providing material, at least one of said dye-image-providing materials being a dye redox releasing compound which is a non-diffusible p-sulfonamidoaniline or p-sulfonamidophenol having attached thereto through the sulfonamido group, a dye or dye precursor which is alkali-cleavable upon oxidation, said sulfonamido compound containing, meta to the sulfonamido group, an N,N-disubstituted carbamoyl ballast group containing substituents selected from the group consisting of aliphatic, alicyclic and aromatic groups. 
     
     
       16. A photographic element of claim 15 wherein the p-sulfonamidophenol or p-sulfonamidoaniline has the structure: ##STR43## where: X represents the atoms required to complete a benzene or naphthalene ring; R 1  and R 2  independently represent an aliphatic, alicyclic or aromatic group of such size and configuration as to render the compound nondiffusible in an alkaline processing composition; G represents an --OR 5  group or an--NHR 6  group, where R 5  is hydrogen or a hydrolyzable moiety and R 6  is hydrogen, an alkyl group of 1 to 22 carbon atoms or an --SO 2  PUG group; and   Pug is a dye or dye precursor.   
     
     
       17. A photographic film unit comprising: (a) a photographic element comprising a support having thereon at least one photosensitive silver halide emulsion layer having associated therewith a dye redox releasing compound which is a non-diffusible p-sulfonamidophenol or p-sulfonamidoaniline having attached thereto through the sulfonamido group, a dye or dye precursor which is alkali-cleavable upon oxidation, said sulfonamido compound containing, meta to the sulfonamido group, an N,N-disubstituted carbamoyl ballast group containing substituents selected from the group consisting of aliphatic, alicyclic and aromatic groups;   (b) an alkaline processing composition; and   (c) means for discharging the alkaline processing composition within the film unit; said film unit containing a silver halide developing agent.   
     
     
       18. A film unit of claim 17 wherein the p-sulfonamidophenol or p-sulfonamidoaniline has the structure ##STR44## where: X represents the atoms required to complete a benzene or naphthalene ring; R 1  and R 2  independently represent an aliphatic, alicyclic or aromatic group of such size and configuration as to render the compound non-diffusible in an alkaline processing composition; G represents an --OR 5  group or an --NHR 6  group, where R 5  is hydrogen or a hydrolyzable moiety and R 6  is hydrogen, an alkyl group of 1 to 22 carbon atoms or an --SO 2  PUG group; and   Pug is a dye or dye precursor.   
     
     
       19. A process for producing a photographic image comprising: (a) imagewise exposing a photographic element comprising a support having thereon at least one photosensitive silver halide emulsion layer having associated therewith a dye redox releasing compound which is a non-diffusible p-sulfonamidoaniline or p-sulfonamidophenol having attached thereto through the sulfonamido group, a dye or dye precursor which is alkali cleavable upon oxidation, said sulfonamido compound containing, meta to the sulfonamido group, an N,N-disubstituted carbamoyl ballast group containing substituents selected from the group consisting of aliphatic, alicyclic and aromatic groups;   (b) treating the exposed photographic element with an alkaline processing composition in the presence of a silver halide developing agent to effect development of the silver halide emulsion layer as a function of exposure, thereby oxidizing the developing agent;   (c) the oxidized developing agent cross-oxidizing the dye redox releasing compound; and   (d) the oxidized dye redox releasing compound then cleaving, thus forming an imagewise distribution of diffusible dye or dye precursor as a function of development of the silver halide emulsion layer and   (e) at least a portion of the imagewise distribution of diffusible dye or dye precursor diffusing out of the layer in which it is coated.   
     
     
       20. In a photographic element comprising a support, at least one photosensitive silver halide emulsion layer and a ballasted non-diffusible p-sulfonamidophenol having attached thereto through the sulfonamido group, a photographically useful group which is alkali-cleavable upon oxidation, the improvement wherein the p-sulfonamidophenol contains, meta to the sulfonamido group, an N,N-disubstituted carbamoyl ballast group containing substituents selected from the group consisting of alkyl, cycloalkyl and aryl groups. 
     
     
       21. A photographic element comprising a support having thereon a red-sensitive silver halide emulsion layer having associated therewith a cyan-dye-image-providing material, a green-sensitive silver halide emulsion layer having associated therewith a magenta-dye-image-providing material, and a blue-sensitive silver halide emulsion layer having associated therewith a yellow-dye-image-providing material, at least one of said dye-image-providing materials being a non-diffusible p-sulfonamidophenol dye redox releasing compound having attached thereto through the sulfonamido group a dye or dye precursor which is alkali-cleavable upon oxidation, said sulfonamido compound containing, meta to the sulfonamido group, an N,N-disubstituted carbamoyl ballast group containing substituents selected from the group consisting of alkyl, cycloalkyl and aryl group. 
     
     
       22. A photographic element of claim 21 wherein each silver halide emulsion is a direct-positive silver halide emulsion. 
     
     
       23. A photographic element of claim 22 wherein the p-sulfonamidophenol has the structure: ##STR45## where: X represents the atoms required to complete a benzene or napththalene ring; R 1  and R 2  each represent the same alkyl group of 10 to 22 carbon atoms; and   Dye is a dye or dye precursor.   
     
     
       24. A photographic film unit comprising: (a) a photographic element comprising a support having thereon at least one photosensitive silver halide emulsion layer having associated therewith a non-diffusible p-sulfonamidophenol dye redox releasing compound having attached thereto through the sulfonamido group, a dye or dye precursor which is alkali-cleavable upon oxidation, said sulfonamido compound containing, meta to the sulfonamido group, an N,N-disubstituted carbamoyl ballast group containing substituents selected from the group consisting of alkyl, cycloalkyl and aryl groups,   (b) an alkaline processing composition; and   (c) means for discharging the alkaline processing composition within the film unit; said film unit containing a silver halide developing agent.     
     
     
       25. A photographic film unit of claim 24, further comprising a dye-image-receiving layer. 
     
     
       26. A film unit of claim 25 wherein said dye-image-receiving layer is located in the photographic element between the support and the lowermost photosensitive silver halide emulsion layer. 
     
     
       27. A film unit of claim 26 wherein the support is a transparent support. 
     
     
       28. A film unit of claim 25 wherein the dye-image-receiving layer is coated on a separate support and is adapted to be superposed on the photographic element after exposure thereof. 
     
     
       29. A film unit of claim 25 wherein the discharging means is a rupturable container and is positioned for processing the film unit so that a compressive force applied to the container by pressure-applying members will effect a discharge of the container's contents for diffusion into the photosensitive silver halide emulsion layers. 
     
     
       30. A film unit of claim 24 wherein each silver halide emulsion is a direct-positive silver halide emulsion. 
     
     
       31. A film unit of claim 24 wherein the p-sulfonamidophenol has the structure: ##STR46## where: X represents the atoms required to complete a benzene or napththalene ring; R 1  and R 2  are straight chain alkyl groups of 1 to 30 carbon atoms and together they contain a total of 8 to 50 carbon atoms; and   Dye is a dye or dye precursor.   
     
     
       32. A film unit of claim 24 wherein the p-sulfonamidophenol has the structure: ##STR47## where: X represents the atoms to complete a napththalene ring; R 1  and R 2  each represent the same alkyl group of 10 to 22 carbon atoms; and   Dye represents a dye or dye precursor.   
     
     
       33. A process for producing a photographic image comprising: (a) imagewise exposing a photographic element comprising a support having thereon at least one photosensitive silver halide emulsion layer having associated therewith a non-diffusible p-sulfonamidophenol dye redox releasing compound having attached thereto through the sulfonamido group, a dye or dye precursor which is alkali cleavable upon oxidation, said sulfonamido compound containing, meta to the sulfonamido group, an N,N-disubstituted carbamoyl ballast group containing substituents selected from the group consisting of alkyl, cycloalkyl and aryl groups;   (b) treating the exposed photographic element with an alkaline processing composition in the presence of a silver halide developing agent to effect development of the silver halide emulsion layer as a function of exposure, thereby oxidizing the developing agent;   (c) the oxidized developing agent cross-oxidizing the dye redox releasing compound; and   (d) the oxidized dye redox releasing compound then cleaving, thus forming an imagewise distribution of diffusible dye or dye precursor as a function of development of the silver halide emulsion layer and   (e) at least a portion of the imagewise distribution of diffusible dye or dye precursor diffusing out of the layer in which it is coated.   
     
     
       34. A process of claim 33 wherein after cleaving from the dye redox releasing compound the diffusible dye or dye precusor diffuses to a dye-image-receiving layer to provide a transfer image. 
     
     
       35. A process of claim 33 wherein after cleaving from the dye redox releasing compound the diffusible dye or dye precursor is removed from the element retaining in the element an imagewise distribution of dye redox releasing compound to provide a retained image. 
     
     
       36. A process of claim 35 wherein dye redox releasing compound retained in the element contains a dye precursor and the dye precursor is converted to a dye. 
     
     
       37. A process of claim 35 wherein silver and residual silver halide are removed from the element by bleaching and fixing.