US 3,980,479 AGranted

Positive-working immobile photographic compounds which cleave by intramolecular nucleophilic displacement in alkali unless oxidized

AssigneeEastman Kodak Company

InventorsDonald Lee Fields, Richard Paul Henzel, Philip Thiam Shin Lau, Richard Allan Chasman

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Abstract

Photographic elements, processes for forming images in photographic elements and new compounds are disclosed. Generally, the invention relates to immobile compounds which can be used to provide positive images from negative recording-developing photographic materials such as negative silver halide emulsions. The compounds contain a photographically useful group such as a dye or dye precursor and are capable of releasing said photographically useful group under alkaline conditions, and are also capable of reaction with an oxidized silver halide developing agent before substantial release of said photographically useful group occurs, to provide a reaction product having a substantially lower rate of release of said photographically useful group. In specific embodiments, the compounds of this invention contain an electrophilic cleavage group located in the linkage between a ballast group and a photographically useful moiety wherein said electrophilic cleavage group is a carbamic acid derivative.

Claims44

Dependent claims

In a photographic element comprising a support having thereon at least one alkali-permeable layer comprising an immobile compound which contains an electrophilic cleavage group linking a photographically useful moiety to a ballast moiety, said compound comprising a nucleophilic group which is capable of a) interaction with said electrophilic cleavage group to release a diffusible, photographically useful substance from said compound under alkaline conditions and b) reacting with an oxidized silver halide developing agent before substantial release of said photograhically useful substance occurs to lower substantially the rate of release of said photographically useful group under alkaline conditions, and said compound having the formula:

##SPC5##
wherein Nu is an oxidizable nucleophilic group or a precursor therefor;
E is carbonyl or thiocarbonyl;
Q is a bivalent group providing a mono atom linkage between E and R.sup.1 wherein said mono atom 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 hydroxy group or a precursor therefor, a primary amino group or a precursor therefor, or a substituted amino group;
R.sup.6 is a bivalent alkylene group containing from 1 to 3 atoms in the bivalent linkage;
n is a positive integer of 1 or 2;
R.sup.1 can be an aromatic group containing from 6 to 20 carbon atoms or an alkylene group containing 1 to 12 carbon atoms;
R.sup.2 can be an alkyl group containing from 1 to 40 carbon atoms, an aryl group containing from 6 to 20 carbon atoms, or the substituent X.sup.1 ;
R.sup.3, R.sup.4 and R.sup.5 can each be mono atom 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.3 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.1 is an alkylene group, R.sup.3 and R.sup.4 are polyatomic groups, and when G.sup.1 is a substituent defined for Nu, an adjacent R.sup.3 or R.sup.4 can be the group:
##EQU6## X.sup.1 is a ballasting group of sufficient size to render said compound immobile in an alkali-permeable layer of the photographic element or X.sup.1 is a photographically useful moiety which is an image dye-providing material or a photographic reagent;
X.sub.2 is a group which, together with Q and R.sup.1, 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.1 --X.sub.2) is said ballasting group and one of X.sup.1 and --Q--R.sup.1 --X.sub.2) is said ballasting group and one of X .sup.1 and --Q--R.sup.1 --X.sub.2) is said photographically useful group.

9 more elements

A photographic element comprising a support having thereon at least one layer containing a photographic silver halide emulsion having associated therewith an immobile compound having the formula:

##SPC6##
wherein Nu is an oxidizable nucleophilic group or a precursor therefor;
E is carbonyl or thiocarbonyl;
Q is a bivalent group providing a mono atom linkage between E and R.sup.1 wherein said mono atom 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 hydroxy group or a precursor therefor, a primary amino group or a precursor therefor, or a substituted amino group;
R.sup.6 is a bivalent alkylene group containing from 1 to 3 atoms in the bivalent linkage;
n is a positive integer of 1 or 2;
R.sup.1 can be an aromatic group containing from 6 to 20 carbon atoms or an alkylene group containing 1 to 12 carbon atoms;
R.sup.2 can be an alkyl group containing from 1 to 40 carbon atoms, an aryl group containing from 6 to 20 carbon atoms, or the substituent X.sup.1 ;
R.sup.3, R.sup.4 and R.sup.5 can beach be mono atom 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.3 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 provisions that, when R.sup.1 is an alkylene group, R.sup.3 and R.sup.4 are polyatomic groups, and when G.sup.1 is a substituent defined for Nu, an adjacent R.sup.3 or R.sup.4 can be the group:
##EQU7## X.sup.1 is a ballasting group of sufficient size to render said compound immobile in an alkali-permeable layer of the photographic element or X.sup.1 is a photographically useful moiety which is an image dye-providing material;
X.sub.2 is a group which, together with Q and R.sup.1, 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.1 --X.sub.2) is said ballasting group and one of X.sup.1 and --Q--R.sup.1 --X.sub.2) is said photographically useful group.

9 more elements

A photographic element comprising a support having thereon a layer containing a blue-sensitive silver halide emulsion having associated therewith an intramolecular nucleophilic displacement compound which comprises a yellow image dye-providing moiety, a layer containing a green-sensitive silver halide emulsion having associated therewith an intramolecular nucleophilic displacement compound which comprises a magenta image dye-providing moiety, and a red-sensitive silver halide emulsion having associated therewith an intramolecular nucleophilic displacement compound which comprises a cyan image dye-providing moiety, wherein each of said intramolecular nucleophilic displacement compounds is an immobile compound which contains an electrophilic cleavage group linking a photographically useful moiety to a ballast moiety, said compounds comprising a nucleophilic group which is capable of a) interaction with said electrophilic cleavage group to release a diffusible, photographically useful substance from said compound under alkaline conditions and b) reacting with an oxidized silver halide developing agent before substantial release of said photographically useful substance occurs to lower substantially the rate of release of said photographically useful group under alkaline conditions, and said immobile compound having the formula:

##SPC7##
wherein Nu is an oxidizable nucleophilic group or a precursor therefor;
E is carbonyl or thiocarbonyl;
Q is a bivalent group providing a mono atom linkage between E and R.sup.1 wherein said mono atom 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 hydroxy group or a precursor therefor, a primary amino group or a precursor therefor, or a substituted amino group;
R.sup.6 is a bivalent alkylene group containing from 1 to 3 atoms in the bivalent linkage;
n is a positive integer of 1 or 2;
R.sup.1 can be an aromatic group containing from 6 to 20 carbon atoms or an alkylene group containing 1 to 12 carbon atoms;
R.sup.2 can be an alkyl group containing from 1 to 40 carbon atoms, an aryl group containing from 6 to 20 carbon atoms, or the substituent X.sup.1 ;
R.sup.3, R.sup.4 and R.sup.5 can each be mono atom 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.3 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.1 is an alkylene group, R.sup.3 and R.sup.4 are polyatomic groups, and when G.sup.1 is a substituent defined for Nu, an adjacent R.sup.3 or R.sup.4 can be the group:
##EQU8## X.sup.1 is a ballasting group of sufficient size to render said compond immobile in an alkali-permeable layer of the photographic element or X.sup.1 is an image dye-providing material;
X.sub.2 is a group which, together with Q and R.sup.1, can be a ballasting group or image dye-providing material as defined for X.sup.1, provided one of X.sup.1 and -Q--R.sup.1 --X.sub.2) is said ballasting group and one of X.sup.1 and -Q--R.sup.1 --X.sub.2) is said image dye-providing material.

9 more elements

A process of forming an image record in a photographic element comprising 1) applying an alkaline processing composition to an imagewise-exposed photographic element comprising a support having thereon at least one layer containing a silver halide emulsion having associated therewith an immobile compound which contains an electrophilic cleavage group linking a photographically useful moiety to a ballast moiety, said compound comprising a nucleophilic group which is capable of a) interaction with said electrophilic cleavage group to release a diffusible, photographically useful substance from said compound under alkaline conditions and b) reacting with an imagewise pattern of oxidized silver halide developing agent before substantial release of said photographically useful substance occurs to lower substantially the rate of release of said photographically useful group under alkaline conditions, and said immobile compound having the formula:

##SPC8##
wherein Nu is an oxidizable nucleophilic group or a precursor therefor;
E is carbonyl or thiocarbonyl;
Q is a bivalent group providing a mono atom linkage betwen E and R.sup.1 wherein said mono atom 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 hydroxy group or a precursor therefor, a primary amino group or a precursor therefor, or a substituted amino group;
R.sup.6 is a bivalent alkylene group containing from 1 to 3 atoms in the bivalent linkage;
n is a positive integer of 1 or 2;
R.sup.1 can be an aromatic group containing from 6 to 20 carbon atoms or an alkylene group containing 1 to 12 carbon atoms;
R.sup.2 can be an alkyl group containing from 1 to 40 carbon atoms, an aryl group containing from 6 to 20 carbon atoms, or the substituent X.sup.1 ;
R.sup.3, R.sup.4 and R.sup.5 can each be mono atom 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.3 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.1 is an alkylene group, R.sup.3 and R.sup.4 are polyatomic groups, and when G.sup.1 is a substituent defined for Nu, an adjacent R.sup.3 or R.sup.4 can be the group:
##EQU9## X.sup.1 is a ballasting group of sufficient size to render said compound immobile in an alkali-permeable layer of the photographic element or X.sup.1 is a photographically useful moiety which is an image dye-providing material or a photographic reagent;
X.sub.2 is a group which, together with Q and R.sup.1, 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.1 --X.sub.2) is said ballasting group and one of X.sup.1 and -Q--R.sup.1 --X.sub.2) is said photographically useful group and 2) providing said silver halide developing agent to develop said silver halide during application of said alkaline processing composition.

9 more elements

A film unit adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members comprising:

a. a photographic element comprising a support having thereon at least one layer containing a silver halide emulsion having associated therewith an immobile compound which contains an electrophilic cleavage group linking a photographically useful moiety to a ballast moiety, said compound comprising a nucleophilic group which is capable of (1) interaction with said electrophilic cleavage group to release a diffusible, photographically useful substance from said compound under alkaline conditions and (2) reacting with an oxidized silver halide developing agent before substantial release of said photographically useful substance occurs to lower substantially the rate of release of said photographically useful group under alkaline conditions, and wherein said compound has the formula:
##SPC9##
wherein Nu is an oxidizable nucleophilic group or a precursor therefor;
E is carbonyl or thiocarbonyl;
Q is a bivalent group providing a mono atom linkage between E and R.sup.1 wherein said mono atom 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 hydroxy group or a precursor therefor, a primary amino goup or a precursor therefor, or a substituted amino group;
R.sup.6 is a bivalent alkylene group containing from 1 to 3 atoms in the bivalent linkage;
n is a positive integer of 1 or 2;
R.sup.1 can be an aromatic group containing from 6 to 20 carbon atoms or an alkylene group containing 1 to 12 carbon atoms;
R.sup.2 can be an alkyl group containing from 1 to 40 carbon atoms, an aryl group containing from 6 to 20 carbon atoms, or the substituent X.sup.1 ;
R.sup.3, R.sup.4 and R.sup.5 can each be mono atom 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.3 and R.sup.5 or R.sup.4 and R.sup.5 when on adjacent positions on the ring may be taken together for form a 5- or 6-membered ring with the remainder of the molecule, with the provision that, when R.sup.1 is an alkylene group, R.sup.3 and R.sup.4 are polyatomic groups, and when G.sup.1 is a substituent defined for Nu, an adjacent R.sup.3 or R.sup.4 can be the group:
##EQU10## X.sup.1 is a ballasting group of sufficient size to render said compound immobile in an alkali-permeable layer of the photographic element or X.sup.1 is a photographically useful moiety which is an image dye-providing material or a photographic reagent;
X.sub.2 is a group which, together with Q and R.sup.1, 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.1 --X.sub.2) is said ballasting group and one of X.sup.1 and --Q--R.sup.1 --X.sub.2) is said photographically useful group;
b. an image dye-receiving layer;
c. means containing an alkaline processing solution which is adapted to discharge said solution within said film unit;
and
d. a silver halide developing agent which is soluble in said alkaline processing solution.

14 more elements

A film unit comprising:

a. a photographic element comprising a transparent support having thereon, in sequence, (1) an image-receiving layer, (2) an opaque alkali-permeable layer and (3) at least one layer containing a silver halide emulsion having associated therewith an immobile compound which contains an electrophilic cleavage group linking a photographically useful moiety to a ballast moiety, said compound comprising a nucleophilic group which is capable of (a) interaction with said electrophilic cleavage group to release a diffusible, photographically useful substance from said compound under alkaline conditions and (b) reacting with an oxidized silver halide developing agent before substantial release of said photographically useful substance occurs to lower substantially the rate of release of said photographically useful group under alkaline conditions, and said immobile compound has the formula:
##SPC10##
wherein Nu is an oxidizable nucleophilic group or a precursor therefor;
E is carbonyl or thiocarbonyl;
Q is a bivalent group providing a mono atom linkage between E and R.sup.1 wherein said mono atom 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 hydroxy group or a precursor therefor, a primary amino group or a precursor therefor, or a substituted amino group;
R.sup.6 is a bivalent alkylene group containing from 1 to 3 atoms in the bivalent linkage;
n is a positive integer of 1 or 2;
R.sup.1 can be an aromatic group containing from 6 to 20 carbon atoms or an alkylene group containing 1 to 12 carbon atoms;
R.sup.2 can be an alkyl group containing from 1 to 40 carbon atoms, an aryl group containing from 6 to 20 carbon atoms, or the substituent X.sup.1 ;
R.sup.3, R.sup.4 and R.sup.5 can each be mono atom 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.3 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.1 is an alkylene group, R.sup.3 and R.sup.4 are polyatomic groups, and when G.sup.1 is a substituent defined for Nu, an adjacent R.sup.3 or R.sup.4 can be the group:
##EQU11## X.sup.1 is a ballasting group of sufficient size to render said compound immobile in an alkali-permeable layer of the photographic element or X.sup.1 is a photographically useful moiety which is an image dye-providing material or a photographic reagent;
X.sub.2 is a group which, together with Q and R.sup.1, 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.1 --X.sub.2) is said ballasting group and one of X.sup.1 and -Q--R.sup.1 --X.sub.2) is said photographically useful group;
b. means containing an alkaline processing solution adapted to discharge said solution within said film unit;
and
c. a cover sheet which can be superposed or adapted to be superposed on said photographic element.

13 more elements

An image-transfer film unit comprising:

a. a photographic element comprising a support having thereon at least one layer containing a silver halide emulsion having associated therewith an immobile compound which contains an electrophilic cleavage group linking a diffusible image dye-providing material to a ballast moiety, said compound comprising a nucleophilic group which is capable of (1) interaction with said electrophilic cleavage group to release said diffusible image dye-providing material from said compound under alkaline conditions and (2) reacting with an oxidized silver halide developing agent before substantial release of said photographically useful substance occurs to lower substantially the rate of release of said photographically useful group under alkaline conditions, and wherein said compound has the formula:
##SPC11##
wherein Nu is an hydroxy nucleophilic group or a precursor therefor;
E is carbonyl;
Q is an oxygen atom;
G.sup.1 is an hydroxy group or a precursor therefor, a primary amino group or a precursor therefor, or a substituted amino group;
R.sup.6 is a bivalent alkylene group containing 1 atom in the bivalent linkage;
n is a positive integer of 1 or 2;
R.sup.1 can be an aromatic group containing from 6 to 20 carbon atoms or an alkylene group containing 1 to 12 carbon atoms;
R.sup.2 can be an alkyl group containing from 1 to 40 carbon atoms, an aryl group containing from 6 to 20 carbon atoms;
R.sup.3, R.sup.4 and R.sup.5 can each be mono atom groups which can be hydrogen atoms, halogen atoms, or polyatomic groups which can be alkyl groups, aryl groups, carbonyl groups, sulfamyl groups or sulfonamido groups, and the substituents for R.sup.4 and R.sup.5 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.1 is an alkylene group, R.sup.3 and R.sup.4 are polyatomic groups;
X.sub.2 is a group which, taken together with Q and R.sup.1, is an image dye-providing material and one of R.sup. 5, R.sup.4, R.sup.3 or R.sup.2 is of sufficient size to provide a ballast group and render said compound immobile in said photographic element;
b. an image dye-receiving layer;
c. means containing an alkaline processing solution which is adapted to discharge said solution within said film unit;
and
d. a silver halide developing agent which is soluble in said alkaline processing solution.

13 more elements

Dependencies are inferred from the claim text.