Color-forming para-sulfonamidodiphenylamine dye precursor and sulfonimide dye in photographic material and process
AssigneeEastman Kodak Company
InventorsRolf S. Gabrielsen, Patricia A. Graham, James E. Klijanowicz, Max H. Stern
Life of this patent
Estimating the term…
Abstract
A color-forming para-sulfonamidodiphenylamine dye precursor in a photographic material and process enables formation of a sulfonimide dye image by means of cross-oxidation without the need for a coupling reaction. The color-forming para-sulfonamidodiphenylamine dye precursor is useful in a photographic silver halide material for producing (i) a dye image, or (ii) a dye image and silver image. The exposed photographic material is processed to produce (a) a positive dye image, (b) a negative dye and negative silver image, (c) a negative dye image or (d) a positive dye image and a positive silver image.
Claims55
In a photographic element comprising a support having thereon, in reactive association, in binder,
- (a) photosensitive silver halide;
- and
- (b) a color-forming dye precursor which is imagewise converted upon exposure and processing of said element to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
- the improvement comprising
- as said dye precursor, a color-forming parasulfonamidodiphenylamine which is free of sulfonamido groups in an ortho position relative to the amino --NH-- separating the two aryl rings and which forms a sulfonimide dye.
In a photographic element comprising a support having thereon, in reactive association, in a gelatino binder,
- (a) photosensitive silver halide;
- and
- (b) a color-forming dye precursor which is imagewise converted upon exposure and processing of said element to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
- the improvement comprising
- as said dye precursor, a para-sulfonamidodiphenylamine consisting essentially of 4-N,N-dihexylamino-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine.
In a photographic element comprising a support having thereon, in reactive association, in a gelatino binder,
- (a) photosensitive silver halide;
- and
- (b) a color-forming dye precursor which is imagewise converted upon exposure and processing of said element to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
- the improvement comprising
- as said dye precursor, a color-forming parasulfonamidodiphenylamine consisting essentially of 4-n-hexyloxy-3'-methyl-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylam ine.
In a photographic element comprising a support having thereon, in reactive association, in a gelatino binder,
- (a) photosensitive silver halide;
- and
- (b) a color-forming dye precursor which is imagewise converted upon exposure and processing of said element to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
- the improvement comprising
- as said dye precursor, a color-forming sulfonamidodiphenylamine consisting essentially of 4-[N-ethyl-N-(.beta.-methanesulfonamidoethyl)amino]-2-methyl-2',5'-dipival amido-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine represented by the formula:
- ##STR106##
In a photographic element comprising a support having thereon, in reactive association, in a gelatino binder,
- (a) photosensitive silver halide;
- and
- (b) a color-forming dye precursor which is imagewise converted upon exposure and processing of said element to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
- the improvement comprising
- as said dye precursor, a color-forming sulfonamidodiphenylamine consisting essentially of 4-n-hexyloxy-2',5'-dipivalamido-4'-(2,4,6-triisopropylbenzenesulfonamido)d iphenylamine represented by the formula:
- ##STR107##
In a photographic composition comprising:
- (a) photosensitive silver halide;
- and
- (b) a color-forming dye precursor which is imagewise converted upon exposure and processing of said composition to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
- the improvement comprising
- as said dye precursor, a color-forming parasulfonamidodiphenylamine which is free of sulfonamido groups in an ortho position relative to the amino --NH-- separating the two aryl rings and which forms a sulfonimide dye.
In a photographic composition comprising, in a gelatino binder,
- (a) photosensitive silver halide;
- and
- (b) a color-forming dye precursor which is imagewise converted upon exposure and processing of said element to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
- the improvement comprising
- as said dye precursor, a para-sulfonamidodiphenylamine consisting essentially of 4-N,N-dihexylamino-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine.
In a photographic composition comprising, in a gelatino binder,
- (a) photosensitive silver halide;
- and
- (b) a color-forming dye precursor which is imagewise converted upon exposure and processing of said element to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
- the improvement comprising
- as said dye precursor, a para-sulfonamidodiphenylamine consisting essentially of 4-n-hexyloxy-3'-methyl-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylam ine.
In a photographic composition comprising:
- (a) photosensitive silver halide;
- and
- (b) a color-forming dye precursor which is imagewise converted upon exposure and processing of said composition to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
- the improvement comprising
- as said dye precursor, a para-sulfonamidodiphenylamine consisting essentially of 4-[N-ethyl-N-(.beta.-methanesulfonamidoethyl)amino]-2-methyl-2',5'-dipival amido-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine represented by the formula:
- ##STR116##
In a photographic composition comprising:
- (a) photosensitive silver halide;
- and
- (b) a color-forming dye precursor which is imagewise converted upon exposure and processing of said composition to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
- the improvement comprising
- as said dye precursor, a para-sulfonamidodiphenylamine consisting essentially of 4-n-hexyloxy-2',5'-dipivalamido-4'-(2,4,6-triisopropylbenzenesulfonamido)d iphenylamine represented by the formula:
- ##STR117##
A process of producing a negative dye image and a negative silver image in an imagewise exposed photographic element comprising a support having thereon, in reactive association, in binder,
- (a) photosensitive silver halide, and
- (b) a color-forming para-sulfonamidodiphenylamine dye precursor which is free of sulfonamido groups in an ortho position relative to the amino --NH-- separating the two aryl rings and which is converted upon processing of said element to a sulfonimide dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
- said process comprising:
- (A) developing said photographic element in an alkaline, cross-oxidizing, photographic silver halide developer composition to produce a negative dye image and silver image.
A process of producing a negative dye image and a silver image in an imagewise exposed photographic element comprising a support having thereon, in reactive association, in a gelatino binder,
- (a) photosensitive silver halide;
- and
- (b) a color-forming para-sulfonamidodiphenylamine dye precursor consisting essentially of 4-N,N-dihexylamino-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine;
- said process comprising:
- (A) developing said photographic element in an aqueous, alkaline, cross-oxidizing, photographic silver halide developer solution comprising a cross-oxidizing photographic silver halide developing agent consisting essentially of 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone.
A process of producing a negative dye image and a silver image in an imagewise exposed photographic element comprising a support having thereon, in reactive association, in a gelatino binder,
- (a) photosensitive silver halide;
- (b) a color-forming para-sulfonamidodiphenylamine dye precursor consisting essentially of 4-n-hexyloxy-3'-methyl-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylam ine;
- said process comprising:
- (A) developing said photographic element in an aqueous, alkaline, cross-oxidizing, photographic silver halide developer solution comprising a cross-oxidizing photographic silver halide developing agent consisting essentially of 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone.
A process of producing a positive dye image in an imagewise exposed photographic element comprising a support having thereon, in reactive association, in binder,
- (a) photosensitive silver halide;
- and
- (b) a color-forming para-sulfonamidodiphenylamine dye precursor which is free of sulfonamido groups in an ortho position in relation to the amine --NH-- separating the two aryl rings and which is converted upon processing of said element to a sulfonimide dye by cross-oxidation by means of a cross-oxidizing photographic silver halide developing agent;
- said process comprising the steps:
- (A) developing a silver image in said photographic element by means of an alkaline, photographic silver halide developer in the absence of a cross-oxidizing, photographic silver halide developing agent;
- (B) fogging the resulting element;
- (C) producing a dye image in the photographic element by means of an alkaline, cross-oxidizing, photographic silver halide developer;
- and
- (D) bleaching and fixing the photographic element by means of a silver halide bleaching and fixing solution;
- to produce a positive sulfonimide dye image in the photographic element.
A process of producing a positive dye image in an imagewise exposed photographic element comprising a support having thereon, in reactive association, in a gelatino binder,
- (a) photosensitive silver halide gelatino emulsion;
- and
- (b) a color-forming sulfonamidodiphenylamine dye precursor consisting essentially of 4-n-hexyloxy-3'-methyl-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylam ine;
- said process comprising the steps:
- (A) developing said photographic element in an alkaline, photographic developer in the absence of a cross-oxidizing, photographic silver halide developing agent;
- (B) treating the photographic element by means of a photographic development stop bath;
- (C) fogging the resulting element;
- (D) producing a dye image in the photographic element by means of an alkaline, cross-oxidizing, photographic silver halide developer comprising an alkaline solution of 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, and then
- (E) bleaching and fixing the photographic element in a silver halide bleaching and fixing solution;
- to produce a positive sulfonimide dye image in the photographic element.
A process of producing a positive dye image in an imagewise exposed photographic element comprising a support having thereon, in reactive association, in a gelatino binder,
- (a) photosensitive silver halide gelatino emulsion;
- and
- (b) a color-forming sulfonamidodiphenylamine dye precursor consisting essentially of 4-N,N-dihexylamino-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine;
- said process comprising the steps:
- (A) developing said photographic element in an alkaline, photographic silver halide developer in the absence of a cross-oxidizing, photographic silver halide developing agent;
- (B) treating the photographic element by means of a photographic development stop bath;
- (C) fogging the resulting element;
- (D) producing a dye image in the photographic element by means of an alkaline, cross-oxidizing, photographic silver halide developer comprising an alkaline solution of 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, and then
- (E) bleaching and fixing the photographic element in a silver halide bleaching and fixing solution;
- to produce a positive sulfonimide dye image in the photographic element.
A process of producing a negative dye image in an imagewise exposed photographic element comprising a support having thereon, in reactive association, in binder,
- (a) photosensitive silver halide, and
- (b) a color-forming para-sulfonamidodiphenylamine dye precursor which is free of sulfonamide groups in an ortho position in relation to the amine --NH-- separating the two aryl rings and which is converted upon processing of said element to a sulfonimide dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
- said process comprising:
- (A) developing said photographic element in an alkaline, cross-oxidizing, photographic silver halide developer composition to produce a negative sulfonimide dye image and silver image;
- then
- (B) removing at least part of the silver image from the photographic element.
A process of producing a negative dye image in an imagewise exposed photographic element comprising a support having thereon, in reactive association, in a gelatino binder,
- (a) photosensitive silver halide, and
- (b) a color-forming para-sulfonamidodiphenylamine dye precursor consisting essentially of 4-N,N-dihexylamino-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine;
- said processing comprising:
- (A) developing said photographic element in an aqueous, alkaline, cross-oxidizing, photographic silver halide developer solution comprising a cross-oxidizing photographic silver halide developing agent consisting essentially of 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone;
- then
- (B) removing at least part of the silver image from the photographic element.
A process of producing a negative sulfonimide dye image in an imagewise exposed photographic element comprising a support having thereon, in reactive association, in a gelatino binder,
- (a) photosensitive silver halide, and
- (b) a color-forming para-sulfonamidodiphenylamine dye precursor consisting essentially of 4-n-hexyloxy-3'-methyl-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylam ine;
- said process comprising:
- (A) developing said photographic element in an aqueous, alkaline, cross-oxidizing photographic silver halide developing solution comprising a cross-oxidizing photographic silver halide developing agent consisting essentially of 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone;
- then
- (B) removing at least part of the silver image from the photographic element.
A process of producing a positive dye image and a positive silver image in an imagewise exposed photographic element comprising a support having thereon, in reactive association, in binder,
- (a) direct-positive photographic silver halide, and
- (b) a color-forming para-sulfonamidodiphenylamine dye precursor which is free of sulfonamido groups in an ortho position in relation to the amine --NH-- separating the two aryl rings which is converted upon processing of said element to a sulfonimide dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
- said process comprising:
- (A) developing said photographic element in an alkaline, cross-oxidizing photographic silver halide developing composition;
- then
- (B) fixing the resulting photographic element to produce a positive sulfonimide dye image and a positive silver image.
A process of producing a positive dye image and a positive silver image in an imagewise exposed photographic element comprising a support having thereon, in reactive association, in a gelatino binder,
- (a) direct-positive photographic silver halide, and
- (b) a color-forming para-sulfonamidodiphenylamine dye precursor consisting essentially of 3-methanesulfonamido-4-methoxy-2'-pivalamido-4'-(2,4,6-triisopropylbenzene sulfonamido)diphenylamine;
- said process comprising:
- (A) developing said photographic element in an alkaline, cross-oxidizing photographic silver halide developing composition comprising a 3-pyrazolidone silver halide developing agent;
- then
- (B) fixing the resulting photographic element to produce a positive sulfonimide dye image and a positive silver image.
In an exposed and processed photographic element comprising a support having thereon a dye image, the improvement comprising:
- as said dye image, a dye consisting essentially of a sulfonimide dye represented by the formula:
- ##STR118## wherein:
- R is in the meta or para position and is an electron donating substituent selected from ##STR119## alkoxy containing 1 to 20 carbon atoms, aryloxy containing 6 to 20 carbon atoms, sulfonamido and carboxamido groups;
- R.sup.1 is in the ortho or meta position and is hydrogen, alkyl containing 1 to 3 carbon atoms, carbamoyl, alkoxy containing 1 to 3 carbon atoms, sulfonylalkyl containing 1 to 3 carbon atoms, sulfonylaryl containing 6 to 12 carbon atoms, chlorine, bromine, iodine or fluorine;
- R.sup.2 is hydrogen, alkyl containing 1 to 3 carbon atoms, carbamoyl, alkoxy containing 1 to 3 carbon atoms, sulfonylalkyl containing 1 to 5 carbon atoms, sulfonylaryl containing 6 to 12 carbon atoms, chlorine, bromine, iodine or fluorine;
- R.sup.3 is hydrogen, alkyl containing 1 to 20 carbon atoms, haloalkyl containing 1 to 3 carbon atoms, alkoxy containing 1 to 20 carbon atoms, an ester containing 1 to 20 carbon atoms, carboxy, carboxamido, chlorine, bromine, iodine, fluorine, carbamoyl, sulfonic acid, sulfamyl, sulfonylalkyl containing 1 to 5 carbon atoms, ureido or a carbocyclic group containing 5 to 12 carbon atoms;
- R.sup.4 is hydrogen, alkyl containing 1 to 3 carbon atoms, alkoxy containing 1 to 20 carbon atoms, an ester represented by the formula ##STR120## carboxy, carboxamido, chlorine, bromine, iodine, fluorine, carbamoyl, sulfonic acid, sulfamyl, sulfonylalkyl containing 1 to 3 carbon atoms, uredio and a carbocyclic group containing 3 to 6 carbon atoms;
- R.sup.5 is alkyl containing 1 to 20 carbon atoms or aryl containing 6 to 20 carbon atoms;
- R.sup.6 is hydrogen, alkyl containing 1 to 20 carbon atoms, ##STR121## or aryl containing 6 to 20 carbon atoms, or represents, with R.sup.7, atoms completing a 5- or 6-member heterocyclic group;
- R.sup.7 is alkyl containing 1 to 20 carbon atoms, carbamoyl, carboxamido, or represents, with R.sup.6, atoms completing a 5- or 6-member heterocyclic group;
- R.sup.8 is alkyl containing 1 to 4 carbon atoms;
- and
- R.sup.6A is alkyl containing 1 to 20 carbon atoms.
An exposed and processed photographic element comprising a support having thereon, in reactive association, in binder, developed silver image enhanced by a sulfonimide dye image wherein said dye image consists essentially of a sulfonimide dye represented by the formula:
- ##STR128##
An exposed and processed photographic element comprising a support having thereon, in binder, a developed silver image enhanced by a sulfonimide dye image wherein said dye image consists essentially of a sulfonimide dye represented by the formula:
- ##STR129##
Dependencies are inferred from the claim text.