US3703375A

US3703375A - Photographic processes and materials

Info

Publication number: US3703375A
Application number: US86609A
Authority: US
Inventors: Nicholas H Groet; Wilho M Salminen
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1968-04-01
Filing date: 1970-11-03
Publication date: 1972-11-21
Anticipated expiration: 1989-11-21

Abstract

PHOTOGRAPHIC SILVER HALIDE EMULSIONS HAVE INCORPORATED THEREIN A FIRST COLORLESS, NON-DIFFUSIBLE PHOTOGRAPHIC SECOND COUPLER, UPON REACTION WITH OXIDIZED COLOR DEVELOPER, FORMS A NON-DIFFUSIBLE DYE IMAGE; A SECOND COLORED, NON-DIFFUSIBLE PHOTOGRAPHIC COUPLER HAVING AN AZO CHROMOPHORIC GROUP IN ITS COUPLING POSITION, WHICH SECOND COUPLER, UPON REACTION WITH OXIDIZED COLOR DEVELOPING AGENT, FORMS DYE AND RELEASES THE AZO GROUP; AND, A THIRD COLORLESS, NON-DIFFUSICBLE PHOTOGRAPHIC COUPLER HAVING A MONOTHIO GROUP IN ITS COUPLING POSITION, WHICH THIRD COUPLER, UPON REACTION WITH OXIDIZED COLOR DEVELOPER, FORMS A DYE AND A DIFFUSCIBLE MERCAPTAN DEVELOPMENT INHIBITOR. THE EMULSIONS MAY HAVE INCORPORATED THEREIN FINELY DIVIDED LIQUID PARTICLES OF WATER INSOLUBLE COUPLER SOLVENT, WHICH PARTICLES CONTAIN THE INDICATED COMBINATION OF COUPLERS. THE EMULSIONS MAY BE PREPARED BY DISPERSING THE COLORLESS, COLORED AND DIR COUPLERS IN PHOTOGRAPHIC COUPLER SOLVENT, AND DISPERSING THE SOLUTIO OF COUPLER SOLVENT INTO THE EMULSIONS.

Description

nited States Patent Ofice.

Int. Cl. G03c I/40 U.S. Cl. 96100 34 Claims ABSTRACT OF THE DISCLOSURE Photographic silver halide emulsions have incorporated therein a first colorless, non-dilfusible photographic second coupler, upon reaction with oxidized color developer, forms a non-diifusible dye image; a second colored, non-ditfusible photographic coupler having an azo chromophoric group in its coupling position, which second coupler, upon reaction with oxidized color develpoing agent, forms dye and releases the azo group; and, a third colorless, non-diifusible photographic coupler having a monothio group in its coupling position, which third coupler, upon reaction with oxidized color developer, forms a dye and a difl usible mercaptan development inhibitor.

The emulsions may have incorporated therein finely divided liquid particles of water insoluble coupler solvent, which particles contain the indicated combination of conplers. The emulsions may be prepared by dispersing the colorless, colored and DIR couplers in photographic coupler solvent, and dispersing the solution of coupler solvent into the emulsion.

This invention is a combined continuation application of pending U.S. Ser. Nos. 717,912, 717,921 and 717,925 tiled on Apr. 1, 1968, all now abandoned and relates to photographic materials, and more particularly to photographic materials useful in forming dye images.

It is well known that in various photographic color processes, photographic elements can be employed which feature a photographic silver halide emulsion layer containing colored coupler which functions as a mask. The colored coupler absorbs or masks undesired absorptions of the final dye image. The dye image is produced primarily by a colorless coupler. In operation, upon reaction with oxidized primary aromatic amine color developing agent, dye image is formed by the color coupler (and by colorless coupler) in areas of exposure. The colored coupler remains in the unexposed areas after development. When color reproductions are made from such elements, an adjustment is made in the color of the printing light to correct the unwanted absorption of the image dye with the absorption of the colored coupler remaining in the element. The absorption of the colored coupler remaining in the film and the unwanted absorption of the image dye should be as nearly equal as possible. Processes and elements of this type are described by Glafkides, Photographic Chemistry, pages 580 and 5-81, vol. 2 (published in 1962 by the Fountain Press, London) and by Baines, The Science of Photography, pages 264 and 265 (published in 1968 by the Fountain Press, London).

It is known, for instance, that the unwanted absorpr tions of magenta dye images produced by 5-pyrazolone couplers can be corrected by employing a yellow-colored coupler which forms magenta dye upon reaction with oxidized color developing agent. As noted by Beavers in U.S. Pat. 2,983,608, many yellow-colored magenta-form- 3,703,375 Patented Nov. 21, 1972 ing (5-pyrazolone) couplers are insufficiently reactive to give the desired color correction. Typical of such insufficiently reactive couplers are the 3-benzamido-4-arylazo- S-pyrazolone couplers. Beavers discloses the highly useful yellow-colored 3-anilino-4-arylazo-S-pyrazolone masking couplers. While that class of yellow-colored couplers exhibits the desired reactivity, emulsions containing such couplers have a high level of fog. It therefore appears highly desirable to provide good color correction masking of magenta dye images in the absence of excessive fog.

A wide variety of photographic colored couplers have been suggested for masking. One particularly useful class of colored masking couplers are those couplers which have in the coupling position an azo group, such as an arylazo group or an heterocyclic azo group. These couplers, upon reaction with oxidized primary aromatic amine color developing agent, form a dye image with the oxidized color developer and release the azo group. It appears highly desirable to improve the sharpness of the image obtained with such elements, and to provide photographic elements of this type which exhibit reduced fog as well as desirable interimage effects.

One object of this invention is to provide novel photographic materials and elements.

Another object of this invention is to provide novel photographic materials and elements which exhibit good sharpness and novel photographic processes.

Still another object of this invention is to provide novel photographic materials and elements which exhibit good interimage characteristics.

Another object of this invention is to provide novel photographic materials and elements which produce low fog and to provide good color correction of magenta dye images in the absence of excessive fog.

A further object of this invention is to provide novel photographic materials and elements which contain colored masking coupler.

Still another object of this invention is to provide photographic materials which havem good sharpness and exhibit desirable interimage efiects.

Still other objects of this invention will be apparent from this disclosure and the appended claims.

In accordance with one embodiment of this invention, photographic silver halide emulsions are provided which have incorporated therein a first colorless, nondiffusible photographic coupler such as 5 pyrazolone photographic coupler which reacts with oxidized primary aromatic amino color developing agent to form a dye image such as a magenta image; a second nondiifusible colored photographic coupler such as yellowcolored 3-analino 4 arylazo 5 pyrazolone which contains an azo substituent in the coupling position which second coupler, upon reaction with oxidized primary aromatic amine color developing agent, releases said azo group; and, a third non-diffusible photographic coupler exemplified by 5-pyrazolone DIR coupler which contains a monothio group in the coupling position, which third coupler, upon reaction with oxidized primary aromatic color developing agent, forms a difrusible mercaptan which inhibits development and, as exemplified above, a magenta dye.

In accordance with another embodiment of this invention, photographic emulsions are provided which have incorporated therein a first colorless, non-ditfusible photographic coupler which, upon reaction with oxidized primary aromatic amine color developing agent, forms nondifi'usible image dye; a colored photographic coupler having an azo group in the coupling position, which second coupler, upon reaction with oxidized primary aromatic amine color developing agent, forms a dye of essentially the same color ass aid image dye, and releases the azo group; and a third non-difiusible photographic coupler which has a monothio group in its coupling position, which third coupler, upon reaction with oxidized primary aromatic amine developing agent, forms a difiusible mercaptan development inhibitor and a dye of essentially the same color as the image dye.

In still another embodiment of this invention, photographic elements are provided comprising a support having coated thereon at least one photographic silver halide emulsion as described herein.

In another embodiment of this invention, a photographic element is provided which comprises a support having coated thereon red, green and blue-sensitive silver halide emulsion layers which contain, respectively, colorless non-diffusible photographic couplers which form, upon reaction with oxidized primary aromatic amine color developing agent, non-ditfusible cyan, magenta and yellow image dyes, said photographic element having incorporated in said green sensitive silver halide emulsion layer a non-diffusible yellow colored photographic coupler (such as 3-anilino-4-arylazo-S-pyrazolone) having an azo group in its coupling position, which photographic coupler, upon reaction with oxidized primary aromatic amine color developing agent, releases the azo group and forms magenta dye of essentially the same color as the magenta image dye and said red sensitive layer has incorporated therein a red colored (blue-green absorbing) photographic color former which has an azo group in its coupling position, which color former, upon reaction with oxidized primary aromatic amine color developing agent, forms a cyan dye of essentially the same color as said cyan image dye and releases the azo group; each of said green and red sensitive layers having incorporated therein a non-ditfusible development inhibitor-releasing photographic color former having a monothio group in its coupling osition, which development inhibitor-releasing coupler, upon reaction with oxidized primary aromatic amine color developing agent, releases a ditfusible mercaptan development inhibitor and forms a dye of essentially the same color as the image dye of the layer in which it is incorporated.

The colorless coupler employed herein functions as the primary image forming dye. The deficiencies in the absorption characteristics of the dye image formed by the colorless coupler are corrected by employing a colored coupler having an azo chromophoric group in its coupling position. The development inhibitor-releasing coupler improves sharpness; promotes desirable interirnage effects and reduces fog caused by release of the azo groupfrom the colored coupler.

In another embodiment of this invention, photographic emulsions comprising light sensitive silver halide grains dispersed in a hydrophilic colloid are provided which have incorporated therein finely divided liquid particles of a water insoluble photographic coupler solvent, which particles contain the combination of a first colorless, nondilfusible photographic coupler which reacts with oxidized primary aromatic amine color developing agent to form a dye; a second non-diffusible colored photographic coupler which contains an azo substituent in the coupling position which second coupler upon reaction with oxidized color developing agent, releases said azo group; and, a third non-dilfusible photographic coupler which contains a monothio group in the coupling position, which third coupler, upon reaction with oxidized primary aromatic color developing agent, forms a difiusible mercaptan which inhibits development. Such photographic emulsions exhibit a synergistic reduction in contrast due to the incorporation of each of the couplers in the same coupler solvent dispersion.

In accordance with a still further embodiment of this invention, photographic emulsions are provided which have incorporated therein finely divided liquid particles of a water-insoluble photographic coupler solvent, which particles contain the combination of: a first colorless, nonditfusible photographic coupler which, upon reaction with oxidized primary aromatic amine color developing agent, forms non-ditfusible image dye; a colored photographic coupler having an azo group in the coupling position, which second coupler, upon reaction with oxidized primary aromatic amine color developing agent, forms a dye of essentially the same color as said image dye, and releases the azo group; and, a third non-diflusible photographic coupler which has a monothio group in its coupling position, which third coupler, upon reaction with oxidized primary aromatic amine developing agent, forms a difiusible mercaptan development inhibitor and a dye of essentially the same color as the image dye.

In an additional embodiment of this invention, a photographic element is provided which comprises a support having coated thereon red, green and blue sensitive silver halide emulsion layers which contain, respectively, colorless non-ditfusible photographic couplers which form, upon reaction with oxidized primary aromatic amine color developing agent, cyan, magenta and yellow image dyes, said photographic element having incorporated in said green sensitive layer a non-ditfusible yellow colored photographic coupler having an azo group in its coupling position, which photographic coupler, upon reaction with oxidized primary aromatic amine color developing agent, releases the azo group and forms magenta dye of essentially the same color as the magenta image dye; and, said red sensitive layer has incorporated therein a red colored (blue-green absorbing) photographic coupler which has an azo group in its coupling position, which coupler, upon reaction with oxidized primary aromatic amine color developing agent, forms cyan dye of essentially the same color as said cyan image dye and releases the azo group; each of said green and red sensitive layers having incorporated therein a non-difiusible development inhibitorreleasing photographic coupler having a monothio group in its coupling position, which development inhibitor-releasing coupler, upon reaction with oxidized primary aromatic amine color developing agent, release a diffusible mercaptan development inhibitor and forms a dye of essentially the same color as the image dye of the layer in which it is incorporated; the colorless, colored and development inhibitor-releasing couplers in the red and green sensitive layers being combined in particles of finely divided water-insoluble photographic coupler solvent.

In still another embodiment of this invention, the combination of colorless coupler, colored masking coupler and development inhibitor-releasing coupler are dissolved in photographic coupler solvent, and the coupler solvent solution containing all three couplers is dispersed in a hydrophilic colloid, which can contain light sensitive silver halide, or which may be combined subsequently with a dispersion of light sensitive silver halide in hydrophilic colloid. The combined addition of all three classes of couplers to the photographic coupler solvent facilitates dissolving the coupler in the coupler solvent.

Any of the water-insoluble photographic coupler solvents can be employed in the practice of this invention. The term water-insoluble photographic coupler solvent is used herein as a word of art. As is known (see Jelley et al. US. Pat. 2,322,027, issued June 15, 1943, which disclosure is incorporated herein by reference) photographic coupler solvents are crystalloidal materials (i.e., non-colloidal materials; substances which pass through a semipermeable membrane). They are organic materials of low molecular weight (non-polymeric). Photographic coupler solvents typically are high boiling; they may have boiling points above or C. They generally are liquid at room temperatures (20 C.) or melt at relatively low temperatures (below 100 C.). These materials are frequently referred to as oil-formers because they produce an oily or liquid solution when mixed with the coupler even though the coupler is a solid. The most useful compounds contain one or more polar groups such as halogen, hydroxyl, carboxylic acid, amide, ketone, etc., although this is not a limiting factor. They should have a high solvent action for the coupler and for the dye produced by coupling and should, of course, be inert toward the silver halide emulsion in which they are incorporated. They should also be substantially colorless and stable to ward light, heat and moisture, in addition to being inert to the various processing baths which may be encountered such as developers, oxidized developers, silver removal baths and fixing baths. They should be of low volatility. They should be permeable to photographic processing solutions since this affects the ease of dye formation and the removal of excess developer, the latter in turn affecting the formation of stain. They should have a sufliciently low refractive index so that the solutions of couplers in them have approximately the same refractive index as gelatin, thereby minimizing the opacity or light scattering of the coating. Most couplers themselves have high refractive indices and for this reason it is desirable that the oil formers have low refractive indices. They should be easily dispersible in emulsions and should be chemically inert toward the couplers. They preferably do not form peroxides.

It is sometimes advantageous to employ a mixture of two or more individual crystalloidal materials or oil formers in the same dispersion in order to obtain the desired combination of properties. Thus one might use a mixture of one compound having exceptionally good solvent action, with another compound added in the correct proportions to give the final dispersion the desired refractive index.

It might be of advantage also to use oil formers which could be removed from the coated emulsion layer or layers at any desired stage of the process. This could be accomplished, for example, with some of the acidic oil formers which would be removed from the coating in an alkaline bath. An oil former might also be chosen which was incapable of diffusing through gelatin but which could be changed chemically before, during or after the processing steps into a substance or substances which would be removable.

It is also possible, in accordance with the present invention, to dissolve the coupler and the high boiling solvent in low boiling solvent and disperse the mixture in an aqueous solution after which the lower boiling solvent is removed. Although this is not necessary in our process, in many cases it is desirable to proceed in this way using a solvent which can be removed before coating the emulsion. Low boiling solvents suitable for our purposes include nitromethane, nitroethane, methyl, ethyl, propyl and butyl acetates and ethyl and butyl formate.

The couplers can be dissolved in photographic coupler solvent, and added to a light sensitive silver halide emulsion, in any convenient manner. Suitable processes are described by Jelley et al. in US. Pat. 2,322,027, referred to above, or by the procedure described by Fierke et al. in US. Pat. 2,801,171, issued July 30, 1957, which disclosure is incorporated herein by reference. Particularly good results are obtained when ultrasonics are utilized in dissolving the photographic couplers in coupler solvent, as described by Salminen in US. patent application Ser. No. 544,818, filed Apr. 25, 1966, now abandoned, and entitled Ultrasonics for Dissolving Color Coupler, which disclosure is incorporated herein by reference.

The colorless couplers which form the primary dye image, the colored couplers and the development inhibitorreleasing couplers which are utilized in the practice of this invention may embody any photographic coupler radical. Typical useful photographic coupler radicals include the S-pyrazolone coupler radicals, the phenolic (including u-naphthol) coupler radicals, and the open-chain ketomethylene coupler radicals. As is well known in the art, S-pyrazolone coupler radicals are customarily utilized for the formation of magenta dyes; phenolic coupler radicals are generally utilized for the formation of cyan colored dyes; and, open-chain ketomethylene coupler radicals are generally utilized in the formation of yellow dyes. The coupling position of such coupler radicals is also well known in the art. The 5-pyrazolone coupler radicals couple at the carbon atom in the 4-position thereof; the phenolic coupler radicals couple at the carbon atom in the 4-position (relative to the hydroxyl group); and, the open-chain ketomethylene coupler radicals couple at the carbon atom forming the methylene moiety (e.g.

wherein denotes the coupling position).

An especially useful class of open-chain ketomethylene coupler radicals are described in Formula I below:

Formula I 0 H RHLLY.

wherein R X and Y represent substituents of the type used in open-chain ketomethylene couplers. For example, R can represent an alkyl group (which can be substituted and preferably has from about 6 to 22 carbon atoms); an aryl group (preferably a phenyl or naphthyl group); or a heterocyclic group (preferably a carbon containing heterocyclic radical which contains from 5 to 6 atoms in the heterocyclic ring, which ring contains at least one hetero oxygen, sulfur or nitrogen atom); X can represent a member selected from the group consisting of cyano and carbamyl (which can be substituted); and, Y can have a meaning given below for the colorless, colored or development inhibitor-releasing couplers utilized herein.

The colorless, colored and development inhibitor-releasing couplers utilized in this invention can feature a 5- pyrazolone coupler radical having the following general formula:

Formula II wherein R R and Y represent substituents of the type used in S-pyrazolone couplers. For example, R can represent a value given for R R can represent a member selected from the group consisting of an alkyl group, a carbamyl group (which can be substituted), an amino group (which can be substituted with various groups such as one or two alkyl or aryl groups), an amido group e.g., a benzamido group (which can be substituted) or an alkylamido group (which can be substituted); and, Y can represent a value given below for the colorless, colored or development inhibitor-releasing couplers utilized herein.

Yellow-colored magenta dye-forming masking couplers including, for instance, 3-anilino-4-arylazo-S-pyrazolone couplers may be utilized in this invention. Such couplers are described in Beavers, US. Pat. 2,983,608, issued May 9, 1961, the disclosure of which is incorporated herein by reference. Particularly useful 3-anilino-4-arylazo-5- pyrazolones which can he used in the practice of this invention are selected from those having the following formula:

wherein R" is an aryl group such as a phenyl radical or a phenyl radical substituted at the 2,4, and 6 carbons with halogen atoms, such as a 2,4,6-ditrichlorophenyl, a 2,4,6- tribromophenyl, a 2,4,6-triiodophenyl or a 2,4,6-trifiuorophenyl group; R is a hydrogen atom or an alkyl group having from 1-8 carbon atoms but preferably from 1-4 carbon atoms; X, Y and Z are hydrogen atoms and alkyl radicals usually having from 1-20 carbon atoms but preferably 1-15 with at least one of the substituents X, Y and Z being an alkyl radical; R" is a hydrogen atom, an alkyl or an alkoxy radical usually having from l-lO carbon atoms but preferably from 1-16 carbon atoms.

In addition to the preferred embodiments defined above, this invention also includes compounds of the above formula wherein R' is a phenyl group substituted at the 2,4, and 6 carbons with alkyl or alkoxy radicals usually having from 1-6 carbon atoms, aryl groups, aryloxy groups, cyano groups, carbalkoxy groups, or nitro groups; and where R" is an acylamido group, a carbalkoxy group, a dialkylamino group, an arylether group or other electron-donating substituent.

Some typical useful 3-anilino-4-arylazo-5-pyrazolones which can be used in this invention are listed below:

1- (2',4',6-trichlorophenyl -3-{4"- a (2"',4"'-di-tertiaryamylphenoxy) -butyramido] anilino}-4(4"-rne thoxyphenyl azo-S-pyrazolone 1- 2.,4, '-trichlorophenyl -3-{4"- a-2",4'-di-tertiaryamylphenoxy butyramido] anilino}-4- 4"- ethoxyphenyl azo-S-pyrazolone 1-(2,4',6-trichloropheny1)-3-{4" [oc-(2"',4"'-di-t6rfiaryamylphenoxy) butyramido] anilino}-4- (2""-ethoxyphenyl azo-5-pyrazolone 1- (2',4,6'-trichlorophenyl -3-{4"- oc- (2",4"'-di-tertiaryamylphenoxy -butyramido] anilino}-4- (4""-butoxyphenyl azo-5-pyrazolone 1- 2',4,6-trichlorophenyl -3-{4"- [a- 2",4"'-di-tertiaryamylphenoxy) butyramido] anilino}-4- (4""-dodecyloxyphenyl) azo-S-pyrazolone 1-phenyl-3-{4" [a- 2",4"'-di-tertiaryamylphenoxy) butyramido] anilino}-4-( 4"-methoxyphenyl azo-5- pyrazolone l- 2',4,6'-trichlorophenyl -3-{4"- [oc- (2",4'-di-tertiaryarylamylphenoxy butyramido] anilino}-4- (4""- secondary amylphenyl azo-S-pyrazolone The photographic colorless, colored and development inhibitor-releasing couplers employed in the practice of this invention can utilize any suitable phenolic (including a-naphtholic), coupler radicals, including those described in the structural formula below:

Formula III rs- R wherein R R R R and Y; can represent a substituent of the type used in phenolic couplers. For example, R and R each can represent a value given for R and in addition can represent a member selected from the group consisting of hydrogen, amino, carbonamido, sulfonamido, sulfamyl, carbamyl, halogen and alkoxy; R and R when taken together, can represent the carbon atoms necessary to complete a benzo group, which benzo group can be substituted with any of the groups given for R and R and, when taken separately, R and R can each, independently, represent a value given for R and R and, Y represents a value given below for the colorless, colored, or development inhibitor-releasing couplers utilized herein.

The colorless couplers which can be utilized in the practice of this invention include the non-dilfusible, colorless open-chain, S-pyrazolone and phenolic couplers referred to above, such as those couplers represented by Formulas I, II and III above wherein Y and Y each represents a non-chromophoric group of the type used in colorless image forming couplers, such as hydrogen or a coupling off group, e.g., halogen, such as a chlorine or a fluorine atom; a thiocyano group; an acyloxy group, for example an alkoyloxy group which can be substituted, or an aryloxy group which can be substituted, or a heterocycloyloxy group which can be substituted; a cyclooxy group including an aryloxy group e.g., phenoxy, naphthoxy, or a. heterocyclooxy group, such as pyridinyloxy group, a tetrahydropyranyloxy group, a tetrahydroquinolyloxy group, etc. and, an alkoxy group; and, Y can represent any value given for Y and Y except an aryloxy group, and in addition Y can also represent a cycloimido group (e.g., a maleimido group, a succinimido group, a 1,2-dicarboximido group, a phthalimido group etc.) when R and R are taken together to form a benzo group.

The useful colorless couplers include both the fourequivalent and two-equivalent non-dilfusing couplers. Typical useful four-equivalent yellow forming couplers which can be utilized in this invention include the following:

( l) N-amyl-p-benzoylacetaminobenzenesulfonate (2) N- (4-anisoylacetaminobenzenesulfonyl) -N-benzyl-mtoluidine (3) N-(4-benzoylacetaminobenzenesulfonyl)-N-benzylaniline (4) w- (p-benzoylbenzoyl acetanilide (5 w-benzoyl-p-sec.-amylacetanilide (6) N,N'-di(w-benzoylacetyl)-p-phenylenediamine (7) oc-{3- [a- (2,4-di-tert-amylphenoxy)butyramido] benzoyl}-2-methoxyacetanilide (8) 4,4-di-(acetoacetamino -3,3 '-dimethyldiphenyl (9) p,p'-di-(acetoacetamino diphenylmethane l0) nonyl-p-benzoylacetaminobenzenesulfonate (11) N-phenyl-N'- (p-acetoacetaminophenyl urea l2) n-propyl-p-benzoylacetaminobenzenesulfonate acetoacetpiperidide (13) N(w-benzoylacetyl) 1,2,3,5-tetrahydroquinoline 14) N (w-b enzoylacetyl) morpholine The two-equivalent yellow-forming couplers can be derived from corresponding parent four-equivalent couplers by replacing one of the two hydrogens on the alpha-carbon (i.e., methylene) with any nonchromophoric coupling off group, including coupling olf groups such as the fluorine atom, the chlorine atom, an acyloxy group, a cyclooxy group and a thiocyano group. Typical useful 2-equivalent couplers include the alpha-fiuoro couplers of U.S. Pat. 3,277,155, the a-chloro couplers of U.S. Pat. 2,778,- 658, the u-thiocyano couplers of U.S. Pat. 3,253,924, the a-acyloxy couplers of Loria U.S. patent application 477,- 353, Pat. No. 3,447,928 filed July 26, 1965, the Ot-CYCIO- oxy couplers of Loria U.S. patent application 469,887, Pat. No. 3,908,194 filed July 6, 1965, and the a-alkoxy couplers of the type shown in Whitmore et a1. U.S. Pat. 3,227,550.

(6) S-diphenylethersulfonamido-l-naphthol (7) l-hydroxy-Z- (N-isoamyl-N-phenyl naphthamide (8) 8-hydroxyl-a-naphthoyl-1,2,3,4-tetrahydroquinoline (9) 1-naphthol-S-octyl-cyclohexylamide (10) 5-phenoxyacetaminol-naphthol 1 1 Monochlor-S- (N- -phenylpropyl-N-p-sec.-

amylbenzoylamino -1-naphthol (12) 2-benzoylamino-3 ,5 -dimethylphenol (13) 2-u- (p-tert-amylphenoxy -n-butyrylamino-5- methylphenol 14) l-hydroxy-N-[a-(2,4-di-tert.-amylphenoxy) butyl] -2-naphthamide (15) 2- 4-tert.-amyl-3-phenoxybenzoylamino -3 ,5-

dimethylphenol (16) 2-(4-tert.-amyl-3-phenoxybenzoylamino)phenol (17) 2- [oz- (4'-tert.-butylphenoxy propionylamino] phenol 18) 2- [N-methyl-N- (4-tert.-amyl-3-phenoxybenzoy1- amino) phenol 19) Z-oc- (4-tert.-amylphenoxy)butyrylamino-l-phenol (20) 2- (4-tert.-amyl-3-phenoxybenzoylamino -3,5-

dimethylphenol (21) 2-[a-(-tert.-amylphenoxy)-n-butyrylamino]-5- methylphenol (22) 3-(4-tert.-amyl-3-phenoxybenzoylamino) phenol (23) 2-[a-(4-tert.-amylphenoxy)-n-butyrylamino]-6- chlorophenol (24) 3- [a-(4-tert.-amylphenoxy)-n-butyrylamin0]-5- chlorophenol (25 5-benzene sulfonamidol-naphthol (26) 2-chloro-S-benzenesulfonamido-l-napthol (27) 5- 1,2,3,4-tetrahydronaphthalene-fi-sulfonamido)- l-naphthol (28) 2-chloro-5-(4-bromodiphenyl-4-sulfonamido)-1- naphthol An of the colorless two-equivalent cyan-forming phenolic couplers can be used in the practice of this invention. The two-equivalent couplers can be derived from the corresponding four-equivalent phenolic couplers by substituting a non-chromophoric coupling off group on the carbon in the 4-position of the phenolic or naphthoic ring. Included among the coupling off groups are the acyloxy group illustrated by the 4-acyloxyphenols and 4-acyloxynaphthols of Loria US. Pat. 3,311,476, issued Mar. 28, 1967, the cyclooxy group illustrated by the 4-cyclooxy naphthols of Loria US. Pat. application 483,807, Pat. No. 3,476,563, filed Aug. 30, 1965, the thiocyano group illustrated by the 4-thiophenols and 4-thionaphthols of Loria U.S. Pat. 3,253,294, the cyclic imido groups as illustrated by the 4-cyclic imido derivatives of l-hydrogen-Z-naphthamides of Loria US. patent application 504,994, Pat. No. 3,458,315, the chlorine atom as illustrated in the 4-chlorophenols of Weissberger US. Pat. 2,423,730, the alkoxy group as illustrated by the 4-alkoxynaphthols (and naphthols) of Whitmore et al. US. Pat. 3,227,550, the sulfo group as in 4-sulfophenols and 4-sulfonaphthols, etc.

Typical colorless Z-equivalent cyan-forming couplers which can be used in this invention include the follow- 1) 1-hydroxy-4-decyloxy-2-naphthamide (2) 1-hydroxy-4-acetoxy-N- oc- (2,4-di-tert-amylphenoxy) butyl] -2-naphthamide (3) 1-hydroXy-4-methoxy-N-octadecyl-3',5'-dicarboxy- Z-naphthanilide (4) 1-hydroxy-4-thiocyano-N- [OL- 2,4-di-tert-amylphenoxy butyl] -2-naphthamide (5) 1-hydroxy-4- (pentafiuorophenoxy -N-{{3-{4- [oc- 2,4-

di-tert-amylphenoxy acetamido] phenyl}ethyl}- Z-naphthamide (6) 1-hydroxy-4- 4-nitrophenoxy -N- [a- 2,4-di-tertamylphenoxy butyl] -2-naphthamide 7) 1-hydroxy-4- (4-chlorophenoxy) -2'-tetradecyloxy-2- naphthanilide The colorless coupler is used at a sufiicient concentration to give a dye image of suitable density. The concentration employed will depend on the characteristics of the dye formed by the coupler, and on the nature of the photographic emulsion in which it is incorporated.

Colored couplers which contain an azo group in the coupling position are well known in the photographic art. See, for example, Galfkides, supra, pp. 580-581 and 613- 615, which disclosure is incorporated herein by reference. Any suitable azo chromophoric group which splits off when the coupler is contacted with oxidized primary aromatic amine developing agent, can be utilized in the practice of this invention. Numerous photographic couplers having various azo chromophoric groups substituted in their coupling position are described in the literature. Representative useful azo substituted couplers are described in the following US. patents: 2,428,054; 2,449,966; 2,453,- 661 (open-chain ketomethylene couplers having an arylazo group in the coupling position; corresponding couplers in which the arylazo group is replaced with an alkylazo or a heterocyclicazo group in the coupling position are also useful); 2,455,169 (phenolic couplers having an arylazo group in the coupling position; couplers in which a heterocyclicazo group replaces the arylazo group are also useful); 2,455,170, 2,521,908; 2,569,418 (5-pyrazolones having an arylazo or heterocyclicazo group in the coupling position); 2,706,684; 2,725,292; 3,005,712; 3,034,892; and, in British Pats. 800,262 and 1,043,044. Specific useful photographic couplers can be selected from the disclosure of the foregoing reference which are incorporated herein by reference.

The particular colored coupler utilized will depend on the nature of the color correction required for the dye image formed by the primary coupler, i.e., the colorless coupler. As is well known, the most serious deficiencies appear in the cyan and magenta dye images. It is frequently desirable to employ a yellowed colored magenta dye-forming coupler in the green sensitive layer to compensate for the inadequate transmission of blue light by the primary magenta dye image. An especially useful class of yellow colored magenta dye-forming couplers is described in Loria et al. US. Pat. 2,600,788, issued June 7, 1949. A red-colored (blue-green absorbing) coupler which forms cyan dye is advantageously utilized in the red sensitive layer to compensate for the undesirable absorption of green and blue radiation by the primary cyan dye image formed by the commonly used cyan dye-forming couplers. Particularly useful red colored cyan dye forming couplers are described in British Pats. 586,211 and 627,814. The yellow dye images produced by available primary colorless open-chain ketomethylene couplers do not require correction. However, when it is desirable to correct the yellow dye image for undesirable absorption, a suitable colored coupler can be used which selectively absorbs radiation corresponding to the undesired absorption of the yellow dye image.

The colored coupler is utilized at a concentration sulficient to compensate for unwanted absorptions in the primary dye image. The useful concentration of colored coupler will vary, therefor, depending on the nature of the dye formed by the colorless coupler, as well as the nature of the colored coupler.

The development inhibitor-releasing (DIR) couplers which can be utilized in the practice of this invention can be represented by the following general formula:

Coup-S-R wherein Coup represents a photographic coupler radical, S is a monothio radical attached to the coupling position of the photographic coupler, and R is colorless (chromophore-free) organic radical that does not inhibit photographic development as long as it is attached to Coup. which photographic coupler forms, on reaction with oxidized primary aromatic amine color developing agent, a colorless, dilfusible mercaptan which inhibits photographic development. Some typical DI R couplers useful in this invention can be represented by Formulas I, II and III above wherein Y Y and Y each represents a monothio group, such as an ortho nitro or ortho amino substituted-arylmonothio group, such as 2-nitrophenyl and 3-aminophenyl; a carbon-containing heterocyclic monothio group (generally having a to 6 membered ring containing at least one heteronitrogen, oxygen or sulfur atom and preferably 1 to 4 heteronitrogen atoms) including heterocyclic radicals, such as, tetrazolyls, triazinyls, triazolyls, oxazolyls, oxadiazolyls, diazolyls, thiazyls, thiadiazolyls, benzoxazolyls, benzothiazolyls, pyrimidyls, pyridinyls, quinolinyls, etc., and in which the heterocyclic moieties of the monothio group are either unsubstituted or substituted with various groups, such as, nitro, halogen (chlorine, bromine, iodine, fluorine), lower alkyl, lower alkylamido, lower alkoxy, lower alkylsulfonamido, oz-ChlO- roacetylthio, lower alkylcarbamyl, amino, etc., typical monothio groups representing the above include an arylthio group (e.g., Z-aminophenylthio and 2-nitrophenylthio); and,'a heterocyclicthio group (e.g., 2-benzothiazol ylthio, l-phenyl-S-tetrazolylthio, 1-(4-carbomethoxyphenyl)-5-tetrazolylthio, s-phenyl-1,3,4-oxadiazolyl-2-thio, 2- phenyl 5 (1,3,4) oxadiazolylthio, 2 benzoxazolylthio, etc.).

Representative DIR couplers that can be used herein include the following:

( l a-B enzoyla- (2-nitrophenylthio) -4- [N- -phenylpropyl) -N- (p-tolyl -sulfamyl] acetanilide (2) a-BCHZOyI-a- (2-benzothiazolylthio )-4- [N- ('yphenylpropyl -N- (p-tolyl sulfamyl] acetanilide (3) u-{3- [oc- (2,4-di-tert-amylphenoxy) butyramido] benzoyl}-a- (Z-nitrophenylthio) -2-methoxyacetanilide (4) a-{ 3- ['y- 2,4-di-tert-amylphenoxy) butyramido] benzoyl}-a-'(2-benzoxazolylthio -2-methoxyacetanilide 5 a-Benzoyla-[ 1- (3-phenyl) -5-tetrazolylthio] stearamido acetanilide (6) 1-phenyl-3-octadecylarnino-4- [2-phenyl-5-( 1,3,4)

oxadiazoylythio] -5-pyrazolone (7) l-{4- ['y- (2,4-di-tert-arnylphenoxy) butyramido] phenyl}-3ethoxy-4- 1-phenyl-5-tetrazolylthio -5- pyrazolone (8) 1-{4- [oc- 3-pentadecylphenoxy)butyramido] phenyl}- 3-ethoxy-4-( 1-phenyl-5-tetrazo1ylthio)-5-pyrazolone (9) 1- (2,4, 6-trichlorophenyl -3-{ 4- [a- 2,4-di-tert-amylphenoxy) butyramido] anilino}-4- l-phenyl-S- tetrazolylthio) -5-pyrazolone 10) 1-phenyl-3-octadecylamir1o-4- l-phenyl-S-tetrazolylthio -5-pyrazolone 1 1 1- [4- (4-tert-butylphenoxy) phenyl] -3-pheny1-4-( lphenyl-S-tetrazolylthio) -5-pyrazolone 12) 1- [4- (4-tert-butylphenoxy) phenyl]-3- [a- (4-tertbutylphenoxy) propionamido] -4- 5-phenyl-1,3,4- oxadiazolyl-Z-thio )-5-pyrazolone 13) 1- [4- (4-tert-butylphenoxy) phenyl]-3- rx- (4-tertbutylphenoxy) propionamido] -4- (2-nitrophenylthio) -5-pyrazolone (14) 1- [4- (4 -tert-butylphenoxy) phenyl] -3- [oc- (4-tertbutylphenoxy) propionamido] -4- l- (4-methoxyph'enyl) -5-tetrazolylthio] -5-pyrazolone l 5 1- [4-(4-tert-butylphenoxy)phenyl] -3- [oc- (4 tertbutylphenoxy) propionamido] -4- (Z-benzothiazolylthio)5 pyrazolone (1'6) 1- [4-'( 4-tert-butylphenoxy) phenyl] -3- [a- (4-tertbutylphenoxy) propionamido] -4- (Z-nitrophenylthio -5-pyrazolone 17) 1- [4- (4-tert-butylphenoxy) phenyl]-3- [a- (tertbutylphenoxy) propionamido]-4-( 2-benzoxazolylthio) -5-pyrazolone 18) 1- (2,4-dichloro-6-methoxyphenyl) -3- [a- 3-pentadecylphenoxy) acetamido] -4- I-phenyl-S -tetrazoly1- thio)-5-pyrazolone 19) 1-phenyl-3-benzamido-4- l-phenyl-S-tetrazolylthio) -5-pyrazolone (20) 1-phenyl-3- [a- (2,4-di-tert-amylphenoxy) acetamido] -4-( 1-phenyl-5-tetrazolylthio5-pyrazolone (21 l-phenyl-3- ['y 2,4-di-tert-amylphenoxy)butyramido] -4-( l-phenyl-S-tetrazolylthio -5pyrazolone (22) 1-phenyl-3- 3,5-dicarbethoxybenzamido) -4- (2- nitrophenylthio) -5-pyrazolone (23 1-phenyl-3-octadecyl-4-( 1-phenyl-5-tetrazolylthio) S-pyrazolone 24) 1-phenyl-3- [a (2,4-di-tert-amylphenoxy)acetamid01- 4- l-phenyl-S-tetrazolylthio) -5-pyrazolone (25 1-phenyl-3- [7- 2,4-di-tert-amylphenoxy) butyramido] -4- 1-phenyl-5-tetrazolylthio) -5-pyrazolone (26) 1-phenyl-3- 3,S-didodecyloxybenzamido 4 (2- nitrophenylthio )-5-pyrazolone (27 1-hydroxy-4- (Z-nitrophenylthio) -N- [(x- (2,4 di-tertamylphenoxy butyl] -2-naphthamide (28) l-hydroXy-4-(2-benzothiazolylthio )-N- [a- (2,4-ditert-amylphenoxy) butyl] -2-naphthamide (29) l-hydroxy-4- l-phenyl-S-tetrazolylthio -N- oc- (2,4-

di-tert-amylphenoxy) butyl] -2-naphthamide (3 0) 1-hydroxy-4- (Z-benzothiazolylthio)-N-octadecyl- 3,5'-dicarboxyl-Z-naphthanilide (3 1 1-hydroxy-4-( l-phenyl-S-tetrazolylthio -2'-tetradecyloxy-2-naphthanilide (32 1-hydroxy-4- 1- (4-methoxyphenyl)-S-tetrazolylthio] -N- [oz- (2,4-di-tert-amylphenoxy)butyl-2- naphthamide (3 3) 1-hydroxy-4- S-phenyl-1,3,4-oxadiazolyl-2-thio) -N- [u- (2,4-di-tert-amylphenoxy) butyl] -2-naphthamide (34) S-methoxy-Z- [ac- (3-n-pentadecylphenoxy) butyramido] -4-( l-phenyl-5-tetrazolylthio )phenol The above DIRs can be prepared by the method described in Barr et al. U.S. Pat. 3,227,554. The development inhibitor-releasing coupler is utilized at a concentration sufiicient to provide the desired, effective improvement in sharpness, the desired, effective interimage effects and the desired, eflective reduction in fog introduced by the azo group released from the reaction of colored coupler with oxidized color developer.

The colorless coupler, colored coupler and development inhibitor-releasing coupler utilized in the photographic emulsions and elements of this invention are nondiifusable. The term non-dilfusible as used herein has the meaning commonly applied to that term in color photography, and denotes materials which for all practical purposes do not migrate or wander through photographic hydrophilic colloid layers, such as gelatin, particularly during processing in aqueous alkaline solutions. The term dillusible has the converse meaning.

Preferably, the colorless, the colored and the development inhibitor-releasing couplers utilized herein are ballasted. That is, the coupler contains an organic radical of such molecular size and configuration as to render the coupler non-difi'usible in the element and when the element is processed in alkaline developing solutions. The organic ballasting radical is chosen so that it does not exercise any detrimental effects on the photographic material.

The colorless, colored and development inhibitorreleasing couplers utilized in this invention can be incorporated into the silver halide emulsion in any convenient manner. For example, the coupler can contain a solubilizing group, such as a sulfonic acid group or a carboxylic acid group, which render the couplers soluble in alkaline solution. This enables incorporation of the coupler into the silver halide emulsion by preparing an aqueous alkaline solution of coupler and mixing that solution directly into the photographic silver halide emulsion. Preferably, the couplers are incorporated into the emulsion by dissolving them in a suitable coupler solvent, for example, one of the color coupler solvent (and utilizing one of the processes) described in U.S. Pat. 2,322,027 or 2,801,171. The colorless coupler, the colored coupler and the development inhibitor-releasing coupler can be incorporated in the same coupler solvent, and dispersed in the silver halide emulsion in accordance with the process described by Salminen in U.S. patent application Ser. No. 717,912 and 717,921, filed concurrently with U.S. Ser. No. 717,925.

The following high boiling crystalloidal photographic coupler solvent materials or oil formers have been found suitable for use within the scope of this invention, this list being illustrative only.

ACIDS p-Sec. amylbenzoic acid 8-phenylpropionic acid Dibenzyl acetic acid Phenyl ethyl acetic acid Mono-n-amylphthalate (acid ester) Undecylenic acid Benzyl hydrogen succinate (acid ester) ALCOHOL n-Hexylphenylcarbinol AMIDES Acetyl n-butyl aniline Acetyl methyl p-toluidine Benzoyl piperidine AMIDE DERIVATIVES N-n-amylphthalimide N-n-amyl succinimide N-2-cyanobutylphthalimide CARBAMATES Ethyl N,N-di-n-butyl carbamate Ethyl N-phenyl carbamate ESTERS KETONE DERIVATIVES Benzophenone 2,4-dichlorobenzophenone a-Methoxy acetophenone Acetophenone Cyclohexanone 2,4-dihydroxy valerophenone p-Sec.-amylbenzophenone Methyl isobutyl ketone PHOSPHATE ESTERS T riphenyl phosphate Tricresyl phosphate Diphenyl mono-p-tert. 'butyl phenyl phosphate Monophenyl di-p-tert. butyl phenyl phosphate Diphenyl mono-o-chlorophenyl phosphate Monophenyl di-o-chlorophenyl phosphate Tri-p-tert. butyl phenyl phosphate 1 6 PHOSPHATE ESTERS Tri-o-phenylphenyl phosphate Di-p-tert. butyl phenyl mono (S-tert. butyl-Z-phenylphenyl) phosphate SULFONAMIDES p-Toluenesulfonyl methyl o-toluidine p-Toluenesulfonyl dimethylamide SULFONAMIDES DERIVATIVES p,p'-Di-n-amylbenzenesulfonanilide p-Toluenesulfonyl di-n-butyl amide UREAS N,N'-diethyl-N,N-diphenyl urea N,N-di-n-butyl urea Especially useful classes of coupler solvents are the triaryl esters of phosphoric acid (i.e., triaryl phosphates) and the dialkyl esters of phthalic acid, (i.e., dialkyl phthalates).

The colorless coupler employed herein functions as the primary image forming dye. The deficiencies in the adsorption characteristics of the dye image formed by the colorless coupler are corrected by employing the colored coupler having an azo chromophoric group in its coupling position. The development inhibitor-releasing coupler improves sharpness; promotes desirable interimage etfects; and reduces fog caused by release of the azo group from the colored coupler.

The coupler combination of this invention provides elfective color correction of the magenta dye image. Effective color correction, as used herein, means that there is not more than an increase of plus .03 in the blue density for every .5 increase in the magenta dye density formed in the green sensitive layer. Larger increases than that indicated can be seen visually in multi-layer coatings.

In addition to colorless coupler, colored masking coupler and development inhibitor-releasing coupler, the photographic emulsions of this invention can contain a competing coupler, which can 'be introduced prior to coating the emulsion or during development thereof. The competing coupler can be one which forms a leuco dye or a diffusible dye. Typical useful competing couplers are described by Loria, Williams and Barr in British Pat. 1,038,331; Weller and Groet in U.S. Pat. 2,689,793; and U.S. Pat. 2,998,314.

The coupler combination featured in this invention is advantageously employed in a silver halide emulsion spectrally sensitized to green radiation. The emulsions of this invention are especially useful in multi-layer photographic elements which include (in addition to a layer prepared from an emulsion in accordance with this invention) silver halide emulsion layers which are sensitive to red and blue radiation, and which produce, respectively, cyan and yellow dye. The unwanted adsorption of the cyan and yellow dye images can be corrected using colored masking couplers in the manner known in the art.

The useful ratio of the three couplers utilized herein will vary considerably depending on the dye image formed by the colorless dye, the color of the colored coupler, and the nature of the development inhibitor releasing coupler. As a general guide, a weight ratio of about 1:2 up to about 1: of development inhibitor-releasing coupler to the combined Weight of colorless and colored couplers can be used. The optimum ratio must be separately determined for each colorless coupler and colored ooupler utilized, as well as silver grain size and composition. In preparing silver halide emulsions or dispersions used in the photographic elements of the invention a wide variety of organic hydrophilic dispersing agents or substrates for the silver halide can be utilized. Gelatin is preferred although other colloidal materials such as colloidal albumin, cellulose derivatives or synthetic resins such as polyvinyl alcohol can also be utilized.

In preparing the photographic elements of the invention, silver halide emulsions can be coated on a wide variety of photographic supports. Typical supports include 17 cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyterephthalate film, polyethylene film, polypropylene film, polyethylene-coated paper, paper, glass and others.

The photographic silver halide emulsions and other layers on the present photographic elements can contain the addenda generally utilized in such elements including optical sensitizers, speed-increasing materials, antifoggants, coating aids, gelatin hardeners, plasticizers, ultraviolet absorbers and the like.

The photographic elements of the invention are developed with photographic alkaline color developing solutions containing aromatic primary amino color developing agents. Such developing agents are well known in the art and typically are p-phenylenediamines. Suitable color developing agents include 3-acetamido-4-amino-N,Ndiethylaniline, p-amino-N-ethyl-'N-/8-hydroxyethylaniline sulfate, p-aminoethyl p hydroxyaniline, N,N diethyl-pphenylenediamine, Z-amino 5 diethylaminotoluene, N- ethyl-fi-methanesulfonamidoethyl 3 methyI-4-aminoaniline, 4-amino N ethyl-3-methyl-N-(fl-sulfoethyl) aniline and the like. Reference is also made to Bent et al., JACS 73, 3100-3125 (1951) for additional typical suitable color developing agents.

As used herein, blue radiation refers to radiation of from about 400 to 500 nm.; green refers to radiation of from about 500 to 600 nm.; and red refers to radiation of from about 600 to 7 nm. Preferably, the cyan dyes formed by the colorless coupler has its major adsorption between about 600 and 680 nm.; the magenta dye between about 500 and 580 nm.; and the yellow dye between about 400 and 480 nm.

The following examples are included for a further understanding of this invention.

Example 1 A photographic element is prepared comprising a cellulose acetate film support having coated thereon in the order given, red sensitive gelatin silver bromoiodide emulsion coated at a coverage of 441 mg. per square foot gelatin, 174 mg. per square foot silver and a coupler combina tion consisting of 26.3 mg. per square foot 1-hydroxy-4'- (4-tert butylphenoxy)-4-phenylazo 2 naphthanilide; 31.7 mg. per square foot 1-hydroxy-N-[ot-(2,4-di-tertamylphenoxy)butyl] -2 naphthamide; and 6 mg. per square foot 1-hydroxy-4-(l-phenyl-S-tetrazolylthio)-N-['y- (2,4-di-tert-amylphenoxy)butyl]-2-naphthamide, the couplers being separately dispersed in 39.8 mg. per square foot of di-t-amylphenol; a gelatin interlayer containing 83 mg. per square foot gelatin and mg. per square foot dioctyl hydroquinone (as anti-stain agent) dispersed in tricresyl phosphate; green sensitive gelatin silver bromoiodide emulsion coated at 400 mg. per square foot gelatin; 242.5 mg. per square foot silver; a coupler combination consisting of 24.3 mg. per square foot 1-(2,4,6-trichlorophenyl-3-{ 3-[m-(2,4-di tert amylphenoxy)acetamido] benzamido} 4 (4 methoxyphenylazo)-5-pyrazolone; 24.3 mg. per square foot 1-(2,4,6-trichlorophenyl)-3-{ 3- [a-2,4-di tert amylphenoxy)acetamido]benzamido}-5- pyrazolone and, 6.0 mg. per square foot 1-[4-(4-tertbutylphenoxy)phenyl]-3 a (4-tert-butylphenoxy)propionamido1-4-(1-phenyl 5 tetrazolylthio)-5-pyrazolone, the couplers all being separately dispersed in tri-cresyl phosphate; and, 8.7 mg. per square foot di-octyl hydroquinone dispersed in tri-cresyl phosphate; a gelatin interlayer coated at 83 mg. per square foot containing 5 mg. per square foot di-octyl hydroquinone in tri-cresyl phosphate; and, a blue sensitive gelatin silver bromoiodide emulsion coated at 200 mg. gelatin per square foot, 62 mg. silver per square foot; 102.5 mg. per square foot N-(p-benzoylacetamidobenzenesulfonyl N ('y-phenylpropyl)-p-toluidine dispersed in di-butyl phthalate, and 2.3 mg. per square foot di-octyl hydroquinone dispersed in di-butyl phthalate. The element obtained is sensitometrically exposed and processed in the Eastman Color Print Process, described in Production of Motion Picture Film and Motion Pictures in Color Using 'Eastman Color Films III-15 et seq., published by the Eastman Kodak Company, 1963, using development time of 10 minutes at 75 F. Images of excellent sharpness are produced. The film exhibits low fog, and has excellent interimage characteristics. Unwanted adsorption by the primary dye images are corrected by the colored coupler remaining in the unexposed areas.

Results generally similar to those in Example 1 are obtained when other combinations of colorless coupler, colored coupler and development inhibitor-releasing coupler are substituted for the couplers in Example 1. A highly useful development inhibitor-releasing coupler which can be used in the red sensitive layer is 1-hydroxy-4-(1- phenyl-S-tetrazolylthio)-2-tetradecyloxy-2-naphthanilide.

Example 2 A photographic element is prepared as described in Example 1 except that 5 mg. per square foot of DI'R coupler number 5 is added to the blue sensitive emulsion layer. Results generally similar to those of Example 1 are obtained. The element has excellent interimage characteristics.

Example 3 The procedure of Example 2 is repeated except that the DIR couplers in the red, green and blue sensitive layers are replaced with equivalent amounts of, respectively, DIR compound 7 above; DIR compound 25 above; and a-(1-phenyl-5-tetrazolylthio) a pivalyl-Z-chloro-S- (2,4-di-tert-amylphenoxy)butyramido]acetanilide. Generally similar results are obtained.

Example 4 A gelatin silver bromoiodide emulsion is spectrally sensitized to green radiation. l-(2,4,6-trichlorophenyl)-3-3- [Ct-(2,4-dl tert amylphenoxy)acetamido]benzamido-S- pyrazolone magenta coupler (U.S. Pat. 2,600,788 Compd. 7; the development inhibitor-releasing coupler 1-[4-{ lX-(3" pentadecyl-phenoxy) butylamido}phenyl] 3 ethoxy- 4-(1-phenyl 5 tetrazolyl-thio)-5-pyrazolone) Compound 37 of U.S. Pat. 3,277,554); and the yellow color-eorrecting coupler 1-(2,4,6-trichlorophenyl-3-p-methoxyphenazo- 4-[a-(2,4-di tert amylphenoxy)butyramido]anilino-S- pyrazolone (Coupler I of U.S. Pat. 2,983,608) are dissolved together in tricresyl phosphate and dispersed in the emulsion. The emulsion obtained is coated on a cellulose acetate film support at a coverage of 200 mg. Ag, 40 mg. of the magenta coupler, 20 mg. of the DIR coupler and 20 mg. of the color-correcting coupler per square foot. It is referred to in Table I below as Coating 1. Coating 2 is prepared in the same way except that the DIR coupler is omitted. Coating 3 is prepared the same as Coating 1, except that the color-correcting coupler is omitted. Coating 4 is prepared the same as Coating 1 except that both the DIR coupler and the color correcting couplers are omitted. Each coating is sensitometrically exposed and processed in the Eastman Color Print Process described in Production of Motion Picture Film and Motion Pictures in Color Using Eastman Color iFilms III-15 et seq., published by the Eastman Kodak Company, 1963, using a development time of 10 minutes at 75 F. Results in the following Table I show that the DIR coupler added to the magentaforming coupler does not affect fog, that the color-correcting coupler causes fog, and that the DIR coupler controls the fog caused by the color-correcting coupler.

The fog level of Coating 1 is acceptable. Color-correction is efiective. In addition, the image of Coating 1 shows excellent sharpness. Generally similar results are obtained when the other primary magenta dye forming couplers, color-correcting couplers and development inhibitor-releasing couplers described and referred to herein are substituted for the couplers used in the above example. Thus, generally similar results are obtained when the pri mary image forming coupler 1(2',4',6'-trichlorophenyl)- 3-[3"-(2"',4" diamylphenoxyacetamido)benzamido]-- pyrazolone; the colored coupler 1-(2',4,6 trichlorophenyl 3 {4"[zx(2"',4"'-Cli tertiaryamylphenoxy)- butyramido] anilino} 4 (2""-ethoxyphenyl) azo-S-pyrazolone; or, the DIR coupler 1-(2,4,6-trichlorophenyl)-3- {4-[a-(2,4-di tert amylphenoxy)butyramido]ani'lino}- 4-(il-phenyl 5 tetrazolylthio)-5-pyrazolone, are substituted for the corresponding couplers in the above example.

Example 5 To a gelatin silver bromoiodide emulsion spectrally red-sensitized is added a gelatin dispersion of the cyanforming coupler, l-hydroxy-Z-[(2,4-di-tert-amylphenoxy)- N-butyl]-naphthamide described in US. Pat. 2,474,293 disolved in tricresyl phosphate.

Example 6 To a gelatin silver bromoiodide emulsion spectrally red-sensitized is added a gelatin disp-rsion of the cyanforming coupler of Example 1 plus the color-correcting coupler (magenta colored), 1-hydr0xy-4-(2-acetylphenylazo)-N-[(2,4-di-tert-amylphenoxy)butyl] 2 naphthamide described in US. Pat. 3,034,892 (Compound 11) dissolved in tricresyl phosphate.

Example 7 To a gelatin silver bromoiodide emulsion spectrally red-sensitized is added separate gelatin dispersions of the cyan-forming coupler of Example 1 and the DIR (development inhibitor-releasing) coupler number 25, l-hydroxy- 4(l-phenyl 5 tetrazolylthio)-2-[-(2,4 di tert-amylphenoxy)-n butyl]naphthamide (Compound II of US. Pat. 3,227,554) dissolved in tricresyl phosphate.

Example 8 To a gelatin silver bromoiodide emulsion spectrally red-sensitized is added to a gelatin dispersion of the cyan-forming coupler of Example 5 plus the DIR coupler of Example 7 dissolved together in tricresyl phosphate.

Example 9 To a gelatin silver bromoiodide emulsion spectrally redsensitized is added a separate gelatin dispersion of the cyan-forming coupler of Example 5 and the color-correcting coupler of Example 6 dissolved in tricresyl phosphate and a separate gelatin dispersion of the DIR coupler of Example 7 dissolved in tricresyl phosphate.

Example 10 To a gelatin silver bromoiodide emulsion spectral-1y red-sensitized is added a gelatin dispersion containing the combination of the cyan-forming coupler of Example 5, the color-correcting coupler of Example 6 and the DIR coupler of Example 7, are dissolved together in tricresyl phosphate.

The emulsions are then coated on separate cellulose acetate film support at a coverage of 200 mg. Ag, 54.7 mg. of the cyan-forming coupler, mg. of the colorcorrecting coupler and 10 mg. of the DIR coupler per square foot. The elements are sensitometrically exposed and processed in the Eastman Color Print Process described in Production of Motion Picture Film and Mo- 20 tion Pictures in Color Using Eastman Color Films III- 15 et seq., published by Eastman Kodak Company 1963, using a development time of 10 minutes at a temperature of F. The following results were obtained:

Example Number Cou lers (in dispersion) trust 1 Cyn-forming 1.00 Cyan-forming plus color-correcting (combined) 0. Cyan-forming plus DIR (separate) 0. 66 Cyan-forming plus DIR (combined) 0.55 Cyan-forming plus color-correcting, DIR (separate)- 0. 69

6 Cyan-forming plus color-correcting plus DIR (combined) 0.33

The above examples demonstrate the synergistic reduction in contrast obtained when photographic emulsions are provided containing colorless coupler, colored coupler and development inhibitor-releasing coupler are combined in coupler solvent in accordance with this invention. In addition, the combined addition of colorless, colored and development inhibitor-releasing couplers to coupler solvent results in faster and more efiicient dissolving of the couplers to coupler solvent results in faster and more efficient dissolving of the couplers than when each coupler is added separately to coupler solvent, dispersed in gelatin (or other hydroph'ilic colloid), and then separate gelatin dispersions are added to the emulsion.

Results similar to those of Examples 5-10 are obtained when the gelatin silver bromoiodide emulsion is green-sensitized; the colorless coupler is a magenta-forming coupler such as l-(2,4,6-trichlorophenyl)-3{'3-[a(2,4- di-tert-amylphenoxy)acetamidoJbenzamido} 5 pyrazolone described in US. Patent 2,600,788 Compound 7; the color correcting coupler is yellow colored 1-(2,4,6- trichlorophenyl 3 {3-[a-(2, 4-di-tert-amylphenoxy)acetamido]-benzamido} 4 (4-methoxyphenylazo)-5-pyrazolone; and the DIR coupler is l [4{a (3 pentadecylphenoxy)-butyl-amido}phenyl]-3-ethoxy 4 (l-phenyl-S- tetrazolyl-thio) 5 pyrazolone) (Compound 37 of US. Pat. 3,227,554).

When Examples 5-10 are repeated but using dibutyl phthalate in place of tricresyl phosphate, similar results are achieved.

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

We claim:

1. A photographic silver halide emulsion having incorporated therein:

a first non-diifusible, colorless photographic coupler consisting of an open-chain ketomethylene coupler, a S-pyrazolone coupler, or a phenolic coupler which reacts with oxidized primary aromatic amine color developing agent to form non-diffusible image dye;

a second colored photographic masking coupler consisting of an open-chain ketomethylene coupler, a 5- pyrazolone coupler, or a phenolic coupler having an azo group in coupling position, Which second coupler, upon reaction with oxidized primary aromatic amine color developing agent, releases said azo group and forms a dye of essentially the same color as the dye formed by said first coupler; and

a third photographic coupler consisting of an openchain ketomethylene coupler, a S-pyrazolone coupler, or a phenolic coupler having a monothio group in its coupling position, which third coupler, upon reaction with oxidized primary aromatic amine color developing agent, forms (1) a ditfusible mercaptan which inhibits development and (2) a dye of essentially the same color as the dye formed by said first coupler.

2. A photographic silver halide emulsion as defined in claim 1 wherein each of said couplers has one of the following structural formulae:

wherein R1, X1, R5, R6, R10, R11, R12 and R13 each represents a group of the type employed in, respectively, openchain ketomethylene couplers, -pyrazolone couplers, and phenolic couplers; and Y Y and Y each represents: (a) a member selected from the group consisting of hydrogen and a colorless coupling off group to complete said first colorless coupler; (b) an azo chromophoric group to complete said second colored coupler; and (c) a colorless monothio group to complete said third coupler. 3. The emulsion of claim 1 wherein said first non-diifusible, colorless photographic coupler is a S-pyrazolone coupler which, upon reaction with oxidized primary aromatic amine color developing agent, forms a non-difiusible magenta image dye;

said second colored photographic coupler is a yellowcolored 3-anilino-4-arylazo-5-pyrazolone which, upon reaction with oxidized primary aromatic amine color developing agent, forms magenta dye and releases the arylazo gimp; and said third non-diffusible photographic coupler is a 5- pyrazolone photographic development inhibitor-releasing coupler which, upon reaction with oxidized primary aromatic amine color developing agent, forms magenta dye and a diffusible mercaptan. 4. A photographic silver halide emulsion as defined in claim 1 wherein each of said couplers has one of the following structural formulae:

wherein R and R each represents a member selected from the group consisting of alkyl, aryl and a heterocyclic group containing at least one hetero atom selected from oxygen, sulfur and nitrogen; X; represents a member selected from the group consisting of cyano and carbamyl; R represents a member selected from the group consisting of alkyl, carbamyl, amino, amido, benzamido, and alkamido; R and R each represents a member selected from the group consisting of hydrogen, alkyl, aryl, a heterocyclic group containing at least one hetero atom selected from oxygen, sulfur and nitrogen; amino, carbonamido, sulfonamido, sulfamyl, carbamyl, halogen and alkoxy; R and R when taken together, represent the atoms required to complete a benzo group, and when taken separately, each represents a value selected from those given for R and R and, said Y Y and Y each represents:

(a) a member selected from the group consisting of hydrogen, halogen, a thiocyano group, an acyloxy group, an aryloxy group, a cyclooxy group, and, when said R and R represent the atoms to complete a benzo group, Y represents any of the foregoing groups given for Y and Y except aryloxy, and can in addition represent a a cycloimido group, to complete said first colorless photographic coupler;

(b) an azo chromophoric group to complete said second colored coupler; and

(c) a monothio group selected from an ortho nitrosubstituted arylmonothio group; an ortho amino-substituted arylmonothio group; and, a heterocyclic radical containing at least one hetero atom selected from oxygen, sulfur and nitrogen, to complete said third coupler. 5. A photographic silver halide emulsion as defined in claim 4 wherein said Y Y and Y each represents a heterocyclic monothio radical containing from 1 to 4 hetero nitrogen atoms, to complete said third coupler.

6. A photographic silver halide emulsion as defined in claim 4 wherein said Y Y and Y each represents a member selected from the group consisting of: a 3-octadecylcarbamylphenylthio group; a nitrophenylthio group; an aminophenylthio group; a l-phenyl-5-tetrazoly1thio group; a 2 benzothiazolylthio group; and, a 5-phenyl-1,3,4-oxadiazolylthio group to complete said third coupler.

7. A photographic silver halide emulsion as defined in claim 3 wherein said first colorless coupler has the following formula:

wherein R represents a member selected from the group consisting of alkyl, aryl and a heterocyclic group containing at least one hetero atom selected from oxygen, sulfur and nitrogen; R represents a member selected from the group consisting of alkyl, carbamyl, amino, amido, benzamido, and alkamido; and, Y, represents a member selected from the group consisting of hydrogen, halogen, a thiocyano group, an acyloxy group, an aryloxy group, and a cyclooxy group; and, said third development inhibitor releasing coupler has the folowing formula:

wherein Y represents a monothio group selected from an ortho-nitro substituted arylmonothio group; and orthoamino substituted arylmonothio group; and, a heterocyclic radical containing at least one hetero atom selected from oxygen, sulfur and nitrogen.

8. A photographic silver halide emulsion as defined in claim 7 wherein said second coupler is selected from those having the following formula:

wherein R' is a member selected from the group consisting of a phenyl radical and halo substituted phenyl radicals; R is a member selected from the group consisting of hydrogen atoms and alkyl radicals having 1 to 4 carbon atoms; X, Y, and Z are selected from the group consisting of hydrogen atoms and alkyl radicals having 1 to 20 carbon atoms, at least one of X, Y, and Z being an alkyl radical; R" is selected from the group consisting of alkyl radicals having from 1 to carbon atoms and alkoxy radicals having 1 to 10 carbon atoms; and, said first colorless coupler is selected from those having the formula:

as above defined, where at least one of the substituents X. Y, and Z is an alkyl radical and R is a phenyl or halo-substituted phenyl radical.

9. A photographic silver halide emulsion as defined in claim 8 wherein the monothio group of said third development inhibitor-releasing coupler is a heterocyclic monothio radical containing from 1 to 4 hetero nitrogen atoms.

10. A photographic silver halide emulsion as defined in claim 8 wherein the monothio group of said third development inhibitor-releasing coupler is selected from the group consisting of: a 3-octadecylcarbamylphenylthio group; a nitrophenylthio group; an aminophenylthio group; a 1-phenyl-5-tetrazolylthio group; a 2-benzothiazolylthio group, and a S-phenyl-1,3,4-oxadiazolylthio group, to complete said third coupler.

11. A photographic silver halide emulsion as defined in claim 8 wherein the monothio group of said third development inhibitor-releasing coupler is a S-tetrazolylthio group.

12. The photographic emulsion of claim 1 wherein said first, second and third photographic couplers are dissolved in a low-molecular weight, water-insoluble organic crystalloidal coupler solvent having a boiling point above about 175 C., the coupler solution being present as finely divided liquid particles in said emulsion.

13. The photographic emulsion as defined in claim 12 wherein said coupler solvent is a triaryl ester of phosphoric acid.

14. The photographic emulsion as defined in claim 12 wherein said coupler solvent is a dialkyl ester of phthalic acid.

15. The photographic emulsion of claim 1 wherein said first, second and third photographic couplers are dissolved in a low-molecular weight, water insoluble organic crystalloid coupler solvent having a boiling point above about 175 C., the coupler solution being present as finely divided liquid particles in said emulsion.

16. The photographic emulsion as defined in claim 1 wherein said photographic coupler solvent is a member 24 selected from the group consisting of a diaryl phosphoric acid ester and dialkyl phthalic acid ester.

17. A photographic element comprising a support having coated thereon at least one photographic emulsion as defined in claim 12.

18. A photographic element comprising a support having coated thereon a photographic emulsion as defined in claim 15.

19. A photographic element comprising a support having coated thereon a photographic emulsion as defined in claim 16.

20. A photographic element comprising a support having coated thereon at least one photographic silver halide emulsion layer containing a first non-ditfusible colorless photographic image dye-forming coupler consisting of an open-chain ketomethylene coupler, a S-pyrazolone coupler, or a phenolic coupler; a second non-dilfusible, colored masking photographic coupler consisting of an open-chain ketomethylene coupler, a S-pyrazolone coupler, or a phenolic coupler having a releasable azo group in its coupling position and reactable with oxidized primary aromatic amine developing agent to form a dye of essentially the same color as said image dye; and, a third non-difiusible photographic coupler consisting of an openchain ketomethylene coupler, a 5-pyrazolone coupler, or a phenolic coupler having a monothio group in its coupling position, which third coupler, upon reaction with oxidized primary aromatic amine color developing agent, forms a dye of essentially the same color as said image dye and releases a diffusible mercaptan which inhibits development.

21. The photographic element of claim 20 wherein said third coupler is a compound of the formulae:

wherein R X 11 R R R11, R and R each represents a group of the type employed in, respectively, open-chain ketomethylene couplers, 5-pyrazolone couplers, and phenolic couplers; and Y Y and Y each represents a colorless monothio group to complete said third coupler.

22. A photographic element as defined in claim 21 wherein said Y Y and Y each represents a heterocyclic monothio radical containing from 1 to 4 hetero nitrogen atoms, to complete said third coupler.

23. A photographic element as defined in claim 21 wherein said Y Y and Y each represents a member selected from the group consisting of: a 3-octadecylcarbamylphenylthio group; a nitrophenylthio group; an aminophenylthio group; a l-phenyl-S-tetrazolylthio group; a 2-benzothiazolylthio group; and a 5-phenyl-1,3,4-oxadiazolylthio group, to complete said third coupler.

24. The photographic element of claim 20 wherein separate red, green and blue sensitive silver halide emulsion layers are coated onto the support, said green sensitive silver halide emulsion layer containing (A) a nondilfusible yellow-colored 3-anilino-4-phenylazo-5-pyrazolone photographic masking coupler which releases the phenyl azo group and forms magenta dye upon reaction with oxidized primary aromatic amine color developing agent; and (B) a third non-difiusible S-pyrazolone photographic development inhibitor-releasing coupler having a monothio group in its coupling position, which third coupler, upon reaction with oxidized primary aromatic amine color developing agent, forms magenta dye and a dilfusible mercaptan which inhibits development.

25. A photographic element as defined in claim wherein said colorless image dye forming coupler forms magenta dye and has the following formula:

wherein Y represents a monothio group selected from an ortho-nitro substituted arylmonothio group; an orthoamino substituted arylmonothio group; and, a heterocyclic radical containing at least one hetero atom selected from oxygen, sulfur and nitrogen.

26. A photographic element of claim 20 wherein said colored masking coupler is a yellow dye having the formula:

N=CNH R R NHatH Z wherein R is a member selected from the group con sisting of a phenyl and halo substituted phenyl radical; R is a member selected from the group consisting of hydrogen atom and alkyl radical having 1 to 4 carbon atoms; X, Y, and Z are individually selected from the group consisting of hydrogen atom and alkyl radical having 1 to 20 carbon atoms, at least one of the substituents X, Y, and Z being an alkyl radical; R" is selected from the group consisting of alkyl radical having from 1 to 10 carbon atoms and alkoxy radical having 1 to 10 carbon atoms; and said first colorless non-difiusible photographic coupler forms magenta dye and has the formula 26 nitrophenylthio group; an aminophenylthio group; a l-phenyl-S tetrazolylthio group; a 2-benzothiazolylthio group; and, a 5-phenyl-1,3,4-oxadiazolylthio group; to complete said third coupler.

28. A photographic element as defined in claim 24 wherein the monothio group of said third development inhibitor releasing coupler is a S-tetrazolylthio group.

29. In a photographic silver halide emulsion spectrally sensitized to green radiation and containing a first nondiffusi-ble, colorless S-pyrazolone photographic coupler which, upon reaction with oxidized primary aromatic color developing agent, forms non-diffusible magenta image dye, and a second non-difiusible yellow-colored 3-anilino-4-phenylazo-5-pyrazolone photographic masking coupler which, upon reaction with oxidized primary aromatic amine color developing agent, forms magenta dye and releases said arylazo group, the improvement which comprises: incorporating in said emulsion a third nonditfusible, S-pyrazolone photographic development ininhibitor-releasing coupler having a monothio group in its coupling position, which third coupler, upon reaction with oxidized primary aromatic amine color developing agent, forms magenta dye and a difiusible mercaptan with inhibits development.

30. A photographic element comprising a support having coated thereon:

a silver halide emulsion layer sensitive to red radiation and having incorporated therein:

a first non-ditfusible, colorless phenolic photographic coupler which, upon reaction with oxidized primary aromatic amine color develop ing agent, forms non-diifusible cyan image dye;

a second non-difiusible blue-green colored, phenolic photographic coupler having an azo group in its coupling position, which second non-diffusible coupler, upon reaction with oxidized primary aromatic amine color developing agent, releases the azo group and forms cyan dye of substantially the same color as said cyan image dye; and,

a third non-diifusible, phenolic photographic coupler having a monothio group in its coupling position, which third coupler, upon reaction with oxidized primary aromatic amine color developer, forms cyan dye of essentially the same color as said cyan image dye and releases a diifusible mercaptan which inhibits development;

a silver halide emulsion layer sensitive to green radiation and having incorporated therein;

a first non-ditfusible, colorless S-pyrazolone phographic coupler which forms magenta image dye upon reaction with oxidized primary aromatic amine color developing agent;

a second non-diffusible yellow colored S-pyrazolone photographic coupler having an azo group in its coupling position, which second coupler, upon reaction with oxidized primary aromatic amine color developing agent, forms magenta dye of essentially the same color as said magenta image dye, and releases the azo group; and,

a third non-dilfusible S-pyrazolone photographic coupler having a monothio group in its coupling position, which third coupler, upon reaction with oxidized primary aromatic amine color developing agent, forms magenta dye of essentially the same color as said magenta image dye and a diifusible mercaptan which inhibits development; and,

a silver halide emulsion sensitive to blue radiation and having incorporated therein a non-diffusible, colorless photographic coupler which, upon reaction with oxidized primary aromatic amine color developing agent, forms a non-difiusible yellow image dye 31. A photographic element as defined in claim 30 wherein each coupler in said layer sensitive to red radiation has the following general formula:

and each coupler in said layer sensitive to green radiation has the following general formula:

RsN H wherein R represents a member selected from the group consisting of alkyl, aryl and a heterocyclic group containing at least one hetero atom selected from oxygen, sulfur and nitrogen; R represents a member selected from the group consisting of alkyl, carbamyl, amino, amido, benzamido, and alkamido; R and R each represents a member selected from the group consisting of hydrogen, alkyl, aryl, a heterocyclic group containing at least one hetero atom selected from oxygen, sulfur and nitrogen; amino, carbonamido, sulfonamido, sulfamyl, carbamyl, halogen and alkoxy; R and R when taken together, represent the atoms required to complete a benzo group, and when taken separately, each represents a value selected from those given for R and R and,

said Y and Y each represents:

(a) a member selected from the group consisting of hydrogen, halogen, a thiocyano group, an acyloxy group, an aryloxy group, a cyclooxy group, and, when said R and R represent the atoms to complete a benzo group, Y represents any of the foregoing groups except aryloxy, and can in addition represent a cycloimido group, to complete said first colorless photographic coupler;

(b) an azo chromophoric group to complete said second colored coupler; and

(c) a monothio group selected from an ortho nitrosubstituted arylmonothio group; an ortho amino-substituted arylmonothio group; and, a heterocyclic radical containing at least one hetero atom selected from oxygen, sulfur and nitrogen, to complete said third coupler.

32. A photographic silver halide emulsion as defined in claim 31 wherein said Y and Y each represents a member selected from the group consisting of: a 3-octadecylcarbamylphenylthio group; a nitrophenylthio group; an aminophenylthio group; a 1-phenyl-5tetrazolylthio group; a 2benzothiazolylthio group; and, a 5-phenyl-1,3, 4-oxadiazolylthio group; to complete said third coupler.

33. A photographic emulsion having incorporated therein 1- 2,4,6-trichlorophenyl -3-{ 3- 6- (2,4-di-tert-amylphenoxy)acetamido]-benzamido} 5 pyrazolone, 1-[4- {a-(3-pentadecyl-phenoxy)-butylarnido}-phenyl] 3 ethoxy-4-(1-phenyl 5 tetrazolyl-thio)-5-pyrazolone) and 1 (2,4,6-trichlorophenyl-3-p-methoxyphenazo-4-[or-(2,4- di-tert-amylphenoxy) butyramido] -anilino-5-pyrazolone.

34. A photographic element comprising a support having coated thereon:

a silver halide emulsion layer sensitive to red radiation and having incorporated therein finely divided particles of a water insoluble coupler solvent which is a low molecular weight, organic, crystalloidal material having a boiling point above about C., and having good solvent action for photographic couplers, which particles have dissolved therein:

a first non-diifusible, colorless phenolic photographic coupler which, upon reaction with oxidized primary aromatic amine color developing agent, forms non-diffusible cyan image dye;

a third non-ditfusible, phenolic photographic coupler having a monothio group in its coupling position, which third coupler, upon reaction with oxidized primary aromatic amine color developer, forms cyan dye of essentially the same color as said cyan image dye and releases a diifusible mercaptan which inhibits development;

a silver halide emulsion layer sensitive to green radiation and having incorporated therein finely divided particles of a water insoluble coupler solvent which is a low molecular weight, organic, crystalloidal material having a boiling point above about 175 C., and having good solvent action for photographic couplers, which particles have dissolved therein:

a first non-diffusible, colorless 5-pyrazolone photographic coupler which forms magenta image dye upon reaction with oxidized primary aromatic amine color developing agent;

a third non-diffusible S-pyrazolone photographic coupler having a monothio group in its coupling position, which third coupler, upon reaction with oxidized primary aromatic amine color developing agent, forms magenta dye of essentially the same color as said magenta image dye and a dilfusible mercaptan which inhibits development; and

a silver halide emulsion sensitive to blue radiation and having incorporated therein a non-diffusible, colorless open-chain kctomethylene photographic coupler which, upon reaction with oxidized primary aromatic amine color developing agent, forms a non-diifusible yellow image dye.

References Cited UNITED STATES PATENTS 3,148,062 9/1964 Whitmore et al. 969 3,227,554- l/1966 Barr et al. 9674- 3,481,741 12/ 1969 Yoshida et al. 96100 5 NORMAN G. TORCHIN, Primary Examiner E. C. KIMLIN, Assistant Examiner U.S. Cl. X.R. 9674, 9

. W050 UNITED STATES PATENT omcr all/$9) m d @E'HFECTE @F QQEQ'HQN Patent No. 7 3,375 Dated November 21. 1972 mw Nlcholas H. Groet and Wilho M. Salmine Hill- It is certified, that error appears in the above-identified patent and that said'Lett ers Patent are hereby corrected as shown below:

gm "Ea I w "Column 1., line 17, delete "second";

5011mm line 40, "havem" should read -have-;'

@o l umn 2, line C 72,' "ass aid" should read as said Column 7, line 28, "16" should' read ---6---;

wherein R and R have a meaning given for R and X and X each have a maning given for X Column 8, line 73, "3, 968,194" should read ---3,40s,19 4---;

Column 9, line 12, "3-f2,4di should read -{3-[y- Column 9, line 14, "-berlzoyl" should read -a-benzoyl- Column 10, line 24, "l(2,4',6'-" should read Column 12., line 30, "reference" should read --references---;

Column 16, line 21, "adsorp should read -'--abs0 rp- UNITED STATES PA'l'EN'l' Ulrlut.

" n-H w Y 4- CERTlFlCA'lE GP CQECUQN Patent No. 3, 703, 3.7.5 Dated November 21; 1972 lmfinytofls) Nicholas H. Groet and Wilho M. Salmin en a 5 Z nag-sag It is certified that error appears in the above-identified patent and that saidv Letters Patent are hereby corrected as shown below:

' Column 16, line 53 "adsorption" should read =--absorption--;

Column 16, line'60, "1:2" should read --Z:1+--; 1*? j3za r Cdlumn 16, line 61, "1:100" should read --l00:l--;

Column l7, line 29, "adsorption" should read. --absorption- Column 18, line 8, "adsorption" should read 7 --absorption--;

Column 18, line 44, "3,277,554" should read ---3,227,ss4-.--;

Column 20, line 6, "Bon should read '--Con Column 20, line 7-, "C013 lers" should read --Couplers'-- Column 21, line 10, insert after the second formula Column 26, line 24, "with" should read --which----.

mg UNITED sr Es PATENT oEErcE CE TlFlCA'liE 9F CQRREQHN Pggeni; 3, 703, 375 I Dated November 21, 1972 Inventor) Nicholas Groet and W-ilho M. Salminen Page 3 p- 1'. filo-W,

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 20, lines 25 and Z6, cancel "to coupler solvent results in faster and more efficient dissolving of the couplers"; In?! fi'olumn 26, 11T18 33, replace "colored" with ---absorb1ng--;

Column 28, line 9, replace "colored" with ---absorbing--.

Signed and sealed this 5th day of February 1974.-

(SEAL) I Attest:

EDWARD M.FLET'CHE'R,JR. RENE D. TEGTMEYER Attesting Officer Acting Commissioner of Pa'lten