Photographic elements containing ballasted electron-accepting nucleophilic displacement compounds

A photographic element comprising a support and at least one layer thereon containing a photographic, light-sensitive silver halide having associated therewith a BEND compound having the formula:

• ##STR35## where ENuP is an electron-accepting precursor for an hydroxylamine nucleophilic group;
• A represents a group containing the atoms necessary to form an aromatic ring with the remainder of said formula;
• W is an electron-withdrawing group;
• R.sup.12 is a hydrogen atom, an alkyl group or an aryl group;
• R.sup.3 is a bivalent organic group containing from 1-3 atoms in the bivalent linkage;
• m and q are positive integers of 1 or 2;
• p and r are positive integers of 1 or greater with [(R.sup.12).sub.q-1 W] being a substituent on any portion of the aromatic-ring structure of A;
• E and Q provide an electrophilic cleavage group where E is an electrophilic center and Q is a bivalent group providing a monoatom linkage between E and X.sup.2 wherein said bivalent group can be an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom which provides an amino group;
• n is an integer of 1-3;
• X.sup.2, together with Q, is either an image dye-providing material or a photographic reagent;
• X.sup.1 is a ballasting group;
• and at least one of X.sup.1 and R.sup.12 is present in said compound and is of a size sufficient to render said compound immobile.

A photographic element comprising a support having thereon at least one layer containing a photographic, light-sensitive silver halide having associated therewith a BEND compound having the formula:

• ##STR36## wherein ENuP is an electron-accepting nucleophilic precursor for an hydroxy nucleophilic group;
• E is carbonyl or thiocarbonyl;
• Q is a bivalent group providing a monoatom linkage between E and R.sup.9 wherein said monoatom is a nonmetallic atom of Group VA or VIA of the periodic table in its minus 2 or minus 3 valence state;
• G.sup.1 is an imido group or any of the groups specified for ENuP;
• R.sup.7 is a bivalent alkylene group containing from 1-3 atoms in the bivalent linkage;
• n is a positive integer of 1 or 2;
• R.sup.9 can be an aromatic group containing from 6-20 carbon atoms or an alkylene group containing 1-12 carbon atoms;
• R.sup.8 can be an alkyl group containing from 1-40 carbon atoms, an aryl group containing from 6-20 carbon atoms, or the substituent X.sup.1 ;
• R.sup.6, R.sup.4 and R.sup.5 can each be monoatom groups which can be hydrogen atoms, halogen atoms or polyatomic groups which can be alkyl groups, aryl groups, carbonyl groups, sulfamyl groups, sulfonamido groups or the sbustituent X.sup.1, and the substituents for R.sup.6 and R.sup.5 or R.sup.4 and R.sup.5 when on adjacent positions on the ring may be taken together to form a 5- or 6-membered ring with the remainder of the molecule with the provision that, when R.sup.9 is an alkylene group, R.sup.6 and R.sup.4 are polyatomic groups, and when G.sup.1 is a substituent defined for ENuP, an adjacent R.sup.6 or R.sup.4 can be the group:
• ##STR37## X.sup.1 is provided in at least one of the substituent positions and is a ballasting group of sufficient size to render said compound immobile in an alkali-permeable layer of the photographic element, or is a photographically useful moiety which is an image dye-providing material or a photographic reagent;
• X.sup.3 is a group which, together with Q and R.sup.9, can be a ballasting group or photographically useful group as defined for X.sup.1, provided one of X.sup.1 and --Q--R.sup.9 --X.sup.3) is said ballasting group and one of X.sup.1 and --Q--R.sup.9 --X.sup.3) is said photographically useful group.

An image-transfer film unit comprising:

• (a) a photographic element comprising a support having at least one alkali-permeable layer thereon containing a photographic, light-sensitive, silver halide composition which has associated therewith a BEND compound having the formula:
• ##STR39## where w, x, y, z, n and m are positive integers of 1 or 2;
• ENuP is an electron-accepting nucleophilic precursor group;
• R.sup.1 is an organic group providing a cyclic group to which ENuP and E are attached optionally through R.sup.2 and R.sup.3 ;
• R.sup.2 and R.sup.3 are bivalent organic groups containing from 1-3 atoms in the bivalent linkage;
• E and Q provide an electrophilic cleavage group where E is an electrophilic group and Q is a bivalent group providing a monoatom linkage between E and X.sup.2 and which can be displaced from E by the nucleophilic group provided by ENuP, and Q is an amino group, an oxygen atom or a sulfur atom;
• X.sup.1 is a substituent on at least one of R.sup.1, R.sup.2 and R.sup.3, and one of X.sup.1 or Q--X.sup.2 is a ballasting group of sufficient size to render said compound immobile in an alkali-permeable layer of a photographic element, and one of X.sup.1 and Q--X.sup.2 is an image dye-providing material or a photographic reagent;
• (b) an image-receiving layer;
• (c) a container means containing an alkaline processing composition;
• and
• (d) either (i) an electron donor which is a silver halide developer or (ii) an electron donor in combination with an electron transfer agent which is a silver halide developer.

An image-transfer film unit comprising:

• (a) A photographic element comprising a support having at least one alkali-permeable layer thereon containing a photographic, light-sensitive silver halide emulsion which has associated therewith a BEND compound having the formula:
• ##STR40## wherein ENuP is an electron-accepting precursor for an hydroxylamine nucleophilic group;
• A represents a group containing the atoms necessary to form an aromatic ring with the remainder of said formula;
• W is an electron-withdrawing gorup;
• R.sup.12 is a hydrogen atom, an alkyl group or an aryl group;
• R.sup.3 is a bivalent organic group containing from 1-3 atoms in the bivalent linkage;
• m and q are positive integers of 1 or 2;
• p and r are positive integers of 1 or greater, with [(R.sup.12).sub.q-1 W] being a substituent on any portion of the aromatic-ring structure of A;
• E and Q provide an electrophilic cleavage group where E is an electrophilic center and Q is a bivalent group providing a monoatom linkage between E and X.sup.2 wherein said bivalent group can be an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom which provides an amino group;
• n is an integer of 1-3;
• X.sup.2, together with Q, is either an image dye-providing material or a photographic reagent;
• X.sup.1 is a ballasting group;
• and at least one of X.sup.1 and R.sup.12 is present in said compound and is of a size sufficient to render said compound immobile;
• (b) an image-receiving layer;
• (c) a container means containing an alkaline processing composition;
• and
• (d) an electron donor in combination with an electron-transfer agent which is a silver halide developer.

An image-transfer film unit comprising:

• (a) a photographic element comprising a support having at least one alkali-permeable layer thereon containing a photographic, light-sensitive silver halide composition which has associated therewith a BEND compound having the formula:
• ##STR42## wherein ENuP is an electron-accepting nucleophilic precursor for an hydroxy nucleophilic group;
• E is carbonyl or thiocarbonyl;
• Q is a bivalent group providing a monoatom linkage between E and R.sup.9 wherein said monoatom is a nonmetallic atom of Group VA or VIA of the periodic table in its minus 2 or minus 3 valence state;
• G.sup.1 is an imino group or any of the groups specified for ENuP;
• R.sup.7 is a bivalent alkylene group containing from 1-3 atoms in the bivalent linkage;
• n is a positive integer of 1 or 2;
• R.sup.9 can be an aromatic group containing from 6-20 carbon atoms or an alkylene group containing 1-12 carbon atoms;
• R.sup.8 can be an alkyl group containing from 1-40 carbon atoms, an aryl group containing from 6-20 carbon atoms, or the substituent X.sup.1 ;
• R.sup.6, R.sup.4 and R.sup.5 can each be monoatom groups which can be hydrogen atoms, halogen atoms or polyatomic groups which can be alkyl groups, aryl groups, carbonyl groups, sulfamyl groups, sulfonamido groups or the substituent X.sup.1, and the substituents for R.sup.6 and R.sup.5 or R.sup.4 and R.sup.5 when on adjacent positions on the ring may be taken together to form a 5- or 6-membered ring with the remainder of the molecule with the provision that, when R.sup.9 is an alkylene group, R.sup.6 and R.sup.4 are polyatomic groups, and when G.sup.1 is a substituent defined for ENuP, an adjacent R.sup.6 or R.sup.4 can be the group:
• ##STR43## X.sup.1 is provided in at least one of the substituent positions and is a ballasting group of sufficient size to render said compound immobile in an alkali-permeable layer of the photographic element, or is a photographically useful moiety which is an image dye-providing material or a photographic reagent;
• X.sup.3 is a group which, together with Q and R.sup.9, can be a ballasting group or a photographically useful group as defined for X.sup.1, provided one of X.sup.1 and --Q--R.sup.9 --X.sup.3) is said ballasting group and one of X.sup.1 and --Q--R.sup.9 --X.sup.3) is said photographically useful group;
• (b) an image-receiving layer;
• (c) a container means containing an alkaline processing composition;
• and
• (d) either (i) an electron donor which is a silver halide developer or (ii) an electron donor in combination with an electron-transfer agent which is a silver halide developer.

An image-transfer film unit comprising:

• (a) a photographic element containing a support having coated thereon, in order:
• (i) an image dye-receiving layer;
• (ii) a white reflective layer;
• (iii) an opaque layer having sufficient opacity, together with said reflective layer, to preclude adverse exposure through said layers during normal roomlight processing of the film unit;
• and
• (iv) a layer containing a silver halide emulsion having associated therewith a BEND compound having the formula:
• ##STR45## where w, x, y, z, n and m are positive integers of 1 or 2;
• ENuP is an electron-accepting nucleophilic precursor group;
• R.sup.1 is an organic group providing a cyclic group to which ENuP and E are attached optionally through R.sup.2 and R.sup.3 ;
• R.sup.2 and R.sup.3 are bivalent organic groups containing from 1-3 atoms in the bivalent linkage;
• E and Q provide an electrophilic cleavage group where E is an electrophilic group and Q is a bivalent group providing a monoatom linkage between E and X.sup.2 and which can be displaced from E by the nucleophilic group provided by ENuP, and Q is an amino group, an oxygen atom or a sulfur atom;
• X.sup.1 is a substituent on at least one of R.sup.1, R.sup.2 and R.sup.3, and one of X.sup.1 or Q--X.sup.2 is a ballasting group of sufficient size to render said compound immobile in an alkali-permeable layer of a photographic element, and one of X.sup.1 and Q--X.sup.2 is an image dye-providing material;
• (b) an image dye-receiving layer;
• (c) a container means containing an alkaline processing composition;
• and
• (d) either (i) an electron donor which is a silver halide developer or (ii) an electron donor in combination with an electron-transfer agent which is a silver halide developer.

A process of forming an image record in an photographic element which comprises at least one layer containing a silver halide emulsion which has been imagewise-exposed, having associated therewith a BEND compound having the formula:

• ##STR54## wherein w, x, y, z, n and m are positive integers of 1 or 2;
• ENuP is an electron-accepting nucleophilic precursor group;
• R.sup.1 is an organic group providing a cyclic group to which ENuP and E are attached optionally through R.sup.2 and R.sup.3 ;
• R.sup.2 and R.sup.3 are bivalent organic groups containing from 1-3 atoms in the bivalent linkage;
• E and Q provide an electrophilic cleavage group where E is an electrophilic group and Q is a group providing a monoatom linkage between E and X.sup.2 and which can be displaced from E by the nucleophilic group provided by ENuP, wherein said monoatom is a nitrogen atom, an oxygen atom or a sulfur atom;
• X.sup.1 is a substituent on at least one of R.sup.1, R.sup.2 and R.sup.3, and one of X.sup.1 or --Q--X.sup.2) is a ballasting group of sufficient size to render said compound immobile in an alkali-permeable layer of a photographic element, and one of X.sup.1 and --Q--X.sup.2) is a diffusible image dye-providing material;
• said process comprising contacting said photographic element with an alkaline processing composition in the presence of an electron donor which is a silver halide developing agent under conditions where the silver halide is developed as a function of exposure and said BEND compound is reduced as an inverse function of silver halide development, and said reduced BEND compound undergoes intramolecular nucleophilic displacement of said diffusible image dye-providing material with diffusion of said dye image-providing moiety away from its original location.

An image-transfer process comprising contacting an imagewise-exposed photographic element with an alkaline processing composition in the presence of an electron-transfer agent which is a silver halide developer, wherein said photographic element comprises at least one layer containing a silver halide emulsion having associated therewith an electron donor and a BEND compound having the formula:

• ##STR57## where w, x, y, z, n and m are positive integers of 1 or 2;
• ENuP is an electron-accepting nucleophilic precursor group;
• R.sup.1 is an organic group providing a cyclic group to which ENuP and E are attached optionally through R.sup.2 and R.sup.3 ;
• R.sup.2 and R.sup.3 are bivalent organic groups containing from 1-3 atoms in the bivalent linkage;
• E and Q provide an electrophilic cleavage group where E is an electrophilic group and Q is a group providing a monoatom linkage between E and X.sup.2 and which can be displaced from E by the nucleophilic group provided by ENuP, wherein said monoatom is a nitrogen atom, an oxygen atom or a sulfur atom;
• X.sup.1 is a substituent on at least one of R.sup.1, R.sup.2 and R.sup.3, and one of X.sup.1 or Q--X.sup.2 is a ballasting group of sufficient size to render said compound immobile in an alkali-permeable layer of a photographic element and one of X.sup.1 and Q--X.sup.2 is an image dye-providing material;
• said process being carried out under conditions where (a) said electron-transfer agent develops said silver halide as a function of exposure to provide oxidized electron-transfer agent, (b) said oxidized electron-transfer agent reacts with said electron donor to destroy an imagewise pattern of electron donor, (c) the inverse pattern of electron donor remaining transfers electrons to the BEND compound, reducing it to provide a nucleophilic group on said BEND compound, (d) said reduced BEND compound undergoes intramolecular nucleophilic displacement of the diffusible image dye-providing moiety, and (e) said diffusible image dye-providing moiety is transferred away from its original location.

An image-transfer film unit comprising:

• (a) a photographic element comprising a support having at least one alkali-permeable layer thereon containing a photographic, light-sensitive, silver halide composition which has associated therewith a BEND compound having the formula:
• ##STR62## wherein w, x, y, z, n and m are positive integers of 1 or 2;
• ENuP is an electron-accepting nucleophilic precursor group;
• R.sup.1 is an organic group providing a cyclic group to which ENuP and E are attached optionally through R.sup.2 and R.sup.3 ;
• R.sup.2 and R.sup.3 are bivalent organic groups containing from 1-3 atoms in the bivalent linkage;
• E and Q provide an electrophilic cleavage group where E is an electrophilic group and Q is a group providing a mono atom linkage between E and X.sup.2 and which can be displaced from E by the nucleophilic group provided by ENuP, wherein said monoatom is a nitrogen atom, an oxygen atom or a sulfur atom;
• X.sup.1 is a substituent on at least one of R.sup.1, R.sup.2 and R.sup.3, and one of X.sup.1 or Q--X.sup.2 is a ballasting group of sufficient size to render said compound immobile in an alkali-permeable layer of a photographic element, and one of X.sup.1 and Q--X.sup.2 is an image dye-providing material or a photographic reagent;
• (b) an image dye-receiving layer;
• (c) a container means containing an alkaline processing composition;
• (d) an electron-transfer agent which is a silver halide developer;
• and
• (e) a hydrolyzable electron donor associated with said BEND compound.

A photographic element comprising at least one alkali-permeable layer containing a photographic light-sensitive silver halide having associated therewith a BEND compound having the formula:

• ##STR65## wherein w, x, y, z, n and m are positive integers of 1 or 2;
• ENuP is an electron-accepting nucleophilic precursor group;
• R.sup.1 is an organic group providing a cyclic group to which ENuP and E are attached optionally through R.sup.2 and R.sup.3 ;
• R.sup.2 and R.sup.3 are bivalent organic groups containing from 1-3 atoms in the bivalent linkage;
• E and Q provide an electrophilic cleavage group wherein E is an electrophilic group and Q is a group providing a monoatom linkage between E and X.sup.2 and which can be displaced from E by the nucleophilic group provided by ENuP, wherein said monoatom is a nitrogen atom, an oxygen atom, a selenium atom or a sulfur atom;
• X.sup.1 is a substituent on at least one of R.sup.1, R.sup.2 and R.sup.3, and one of X.sup.1 or Q--X.sup.2 is a ballasting group of sufficient size to render said compound immobile in an alkali-permeable layer of a photographic element, and one of X.sup.1 and Q--X.sup.2 is a photographic reagent.

A photographic element comprising a support having thereon at least one layer containing a photographic, light-sensitive silver halide having associated therewith a BEND compound having the formula:

• ##STR66## wherein ENuP is an electron-accepting nucleophilic precursor for an hydroxy nucleophilic group;
• E is carbonyl or thiocarbonyl;
• Q is a group providing a monoatom linkage between E and R.sup.9 wherein said monoatom is a nonmetallic atom of Group VA or VIA of the periodic table in its minus 2 or minus 3 valence state;
• G.sup.1 is an imido group or any of the groups specified for ENuP;
• R.sup.7 is a bivalent alkylene group containing from 1-3 atoms in the bivalent linkage;
• n is a positive integer of 1 or 2;
• R.sup.9 can be an aromatic group or an alkylene group;
• R.sup.8 can be an alkyl group containing from 1 to 40 carbon atoms, an aryl group containing from 6-20 carbon atoms, or the substituent X.sup.1 ;
• R.sup.6, R.sup.4 and R.sup.5 can each be monoatom groups which can be hydrogen atoms, halogen atoms or polyatomic groups which can be alkyl groups, aryl groups, carbonyl groups, sulfamyl groups, sulfonamido groups or the substituent X.sup.1 , and the substituents for R.sup.6 and R.sup.5 or R.sup.4 and R.sup.5 when on adjacent positions on the ring may be taken together to form a 5- or 6-membered ring with the remainder of the molecule with the provision that, when R.sup.9 is an alkylene group, R.sup.6 and R.sup.4 are polyatomic groups, and when G.sup.1 is a substituent defined for ENuP, an adjacent R.sup.6 or R.sup.4 can be the group:
• ##STR67## X.sup.1 is provided in at least one of the substituent positions and is a ballasting group of sufficient size to render said compound immobile in an alkali-permeable layer of the photographic element, or is a photographic reagent;
• X.sup.3 is a group which, together with Q and R.sup.9, can be a ballasting group or photographic reagent as defined for X.sup.1, provided one of X.sup.1 and --Q--R.sup.9 --X.sup.3) is said ballasting group and one of X.sup.1 and --Q--R.sup.9 --X.sup.3) is said photographic reagent.