WO2005114326A1 - 2-halonapthol couplers - Google Patents

Abstract

This invention relates to a silver halide photographic element comprising a support and a red sensitive silver halide emulsion layer wherein the grains of the silver halide emulsion are greater than 50 mol percent silver chloride, said layer containing only one cyan image dye forming coupler, wherein said coupler, after wet-chemical processing with a solution comprising p­phenylenediame developer, has a lambda max of 650 to 680 and a half bandwidth of greater than 150nm.

Description

2-HALONAPTHOL COUPLERS

FIELD OF THE INVENTION This invention relates to silver halide photographic elements, particularly high chloride elements, comprising a halonaphfhol coupler. BACKGROUND OF THE INVENTION It is well known that in silver halide color photographic light sensitive materials an aromatic primary amine based color developing agent, oxidized by using an exposed silver as an oxidizer, reacts with a couplers to form dyes such as indophenol, indoaniline, indamine, azomethine, phenoxazine, and phenazine, thereby forming images. This photographic process uses subtraction color processes and forms images by combing yellow, magenta and cyan couplers. The dye hue of images is affected by the absorption properties of the cyan dye. If the cyan dye absorption is too narrow then it is difficult to obtain good black and gray colors and lower density colors such as flesh tones may be oversaturated. If the lambda max of the dye absorption is too hypsochromic, then it is difficult to obtain good cyan deep green colors. Cyan couplers are usually 2,5 diacetamidephenols which often give dyes that are less than 650nm in lamda max or 2-carbamoyl napthols that often give dyes deeper than 690nm in lambda max. It is desirable to have couplers that when processed with p-phenylenediame developers give cyan dyes that are greater than 650nm in lambda max and have halfbandwidths of greater than 150nm. 2-Substituted-5-amino-l-napthol derivatives are well known in the photographic art as cyan couplers. For example, see U.S.4690889, U.S. 4883746, EP 307927B1 and Research Disclosure (1988), 290 367-70. It is also well known to use this type of coupler to release PUGs (photographically useful groups) upon reaction with oxidized developer. For example, see U.S. 5112730. In particular, it is known to use this type of coupler to release inhibitors of silver development. For example, see EP 161,626, EP 572,887 and DE 3,635,391. In general, the nature of the 2-substituent in these 5-amino-l- napthol compounds is widely disclosed and not limited to any particular type. However, it is commonly found that 2-carbamoyl groups are often useful and in particular, N-alkyl-2-carbarnoyl groups, where the N-alkyl contains a sufficient number of atoms to limit diffusion of the coupler and subsequently formed cyan dye within the photographic film, are desirable. JP08320541A2 describes 2-N-arylcarbamoyl-5-amino-l-napthol couplers where the N-aryl contains an ørt/rø-alkyloxy group in addition to other alkyl or alkyloxy groups. JP2001163847A2 describes the preparation of a wide number of 2-N-arylcarbamoyl-5-amino-l-napthol couplers. JP07140606 and JP07036158 describe a 2-N-(4-sulfamoylphenyl)carbamoyl-5-amino-l-napthol that indirectly releases an inhibitor of silver development via a timing group. JP2003075970 and JP2000171933 describe the use of 2-chloro-5- amino-1-napthol derivatives, among others, for use in thermally developable imaging systems. JP07281371 describes the use of various 2-(N-alkyl, aryl and unsubstituted) carbamoyl-5-amino-l-napthols as cyan image couplers. JP07287367 describes the use of similar 2-(N-unsubstituted) carbamoyl couplers for the same purpose. U.S. 6107016, U.S. 6194131, U.S. 6437169 and JP2002006456 all describe the use of 2-substituted-5-amino-l-napthols where the 5-amino group is substituted with an inhibitor of silver developer such that the inhibitor can be released via an intramolecular cyclization upon reaction with oxidized developer. Such materials do not form permanent cyan dyes. The 2-carbamoyl couplers form dyes with p-phenylenediame developers that are too deep for direct viewing. There is still needed a cyan dye image coupler which form dyes that are suitable for direct viewing and combine with magenta a yellow image dyes to form pleasant neutrals and good pastel colors.

SUMMARY OF THE INVENTION This invention provides a silver halide photographic element comprising a support and a red sensitive silver halide emulsion layer wherein the grains of the silver halide emulsion are greater than 50 mol percent silver chloride, said layer containing only one cyan image dye forming coupler, wherein said coupler, after wet-chemical processing with a solution comprising p- phenylenediame developer, has a lambda max of 650 to 680 and a half bandwidth of greater than 150nm. In one embodiment it provides a silver halide element comprising a support and a silver halide emulsion layer wherein the grains of the silver halide emulsion are greater than 50 mol percent silver chloride, said emulsion layer comprising a halonaphtiiol coupler represented by formula (1)

wherein R¹ is a halogen, X is a coupling off group that is not a PUG, R² is independently an alkyl, aryl sulfonyl, carbonyl or phosphonyl group, and R³ is independently H, or an alkyl, aryl, sulfonyl, carbonyl or phosphonyl group, provided that R² and R³ combined comprise 12 or more carbon atoms and that when R² or R³ is a sulfonyl, carbonyl, or phosphonyl group it is additionally substituted by an alkyl group, an aryl group, an alkylamino group, an arylamino group, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an alkenylamino group, an alkynylamino group, a cycloalkylamino group, or a cycloalkenylamino group. This invention further provides a method of developing said silver halide element in a color developer containing p-phenylenediamine as the developing agent. This invention provides a coupler that is low in molecular weight such that desired densities can be reached coating less material. The coupler is low cost to manufacture due to its simple structure and can be incorporated into photographic dispersions in a conventional manner. The coupler forms image dyes which are suitable for viewing and forming pleasing neutrals and pastel colors when combined with magenta and yellow image dyes. DETAILED DESCRIPTION OF THE INVENTION The element of the invention is a silver halide photographic element comprising a support and a red sensitive silver halide emulsion layer wherein the grains of the silver halide emulsion are greater than 50 mol percent silver chloride and more preferably greater than 90 mol percent silver chloride. The red sensitive silver halide emulsion layer contains only one cyan image dye forming coupler, wherein said coupler, after wet-chemical processing with a solution comprising p-phenylenediame developer, has a lambda max of 650 to 680 and a half bandwidth of greater than 150nm. Preferably the silver halide element comprises a cyan dye image-forming unit comprised of at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye- forming coupler, a magenta dye image-forming unit comprising at least one green- sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler, and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler. In a prefeπed embodiment the cyan dye image-forming unit comprises only one red-sensitive silver halide emulsion layer containing only one cyan image dye forming coupler as described above. Preferably the cyan image dye forming coupler utilized in the invention is a halonaphtiiol coupler represented by structure (1) below

R¹ is a halogen, more preferably a chloride. R² is independently an alkyl, aryl, sulfonyl, carbonyl, or phosphonyl group and R³ is independently an H atom or an alkyl, aryl, sulfonyl, carbonyl, or phosphonyl group, provided that R and R³ combined comprise 12 or more carbon atoms. When R² or R³ is an alkyl group it preferably has 6 to 30 carbon atoms. When R² or R³ is an aryl group it preferably has 6 to 30 carbon atoms. When R² or R³ is a sulfonyl, carbonyl, or phosphonyl group it is additionally substituted by an alkyl group, an aryl group, an alkylamino group, an arylamino group, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an alkenylamino group, an alkynylamino group, a cycloalkylamino group, or a cycloalkenylamino group. More specifically, when R² or R³ is a sulfonyl, carbonyl, or phosphonyl group it is additionally substituted by 1 to 32 straight or branched-chain alkyl group, a 7 to 32-carbon aralkyl group, a 2to 32-carbon alkenyl group, a 2 to 32-carbon alkynyl group, a 3 to 32-carbon cycloakyl group, a 3 to 32-carbon cycloalkenyl group, a 1 to 32 straight or branched-chain alkylamino group, a 7 to 32-carbon aralkylamino group, a 2 to 32-carbon alkenylamino group, a 2 to 32-carbon alkynylamino group, a 3-32-carbon cycloalkylamino group, or a 3 to 32-carbon cycloalkenylamino group. Preferably R² is a sulfonyl or carbonyl group. Preferably R³ is a H atom. X is a coupling-off group (COG), a group that is released from the coupler upon reaction with oxidized developer. However, X is not a PUG. Rather X is a photographically inert group, i.e. it has no intended photographic effect on the element. Coupling-off groups are well known in the art. Such groups can determine the chemical equivalency of a coupler, i.e., whether it is a 2-equivalent or a 4-equivalent coupler, or modify the reactivity of the coupler. The presence of hydrogen at the coupling site provides a 4-equivalent coupler, and the presence of another coupling-off group usually provides a 2-equivalent coupler. Representative classes of such coupling-off groups include, for example, chloro, bromo, fluoro, iodo, alkoxy, aryloxy, hetero-oxy, sulfonyloxy, acyloxy, heterocyclyl such as oxazolidinyl or hydantoinyl, sulfonamido, benzothiazole, phosphonyloxy, alkylthio, arylthio, alkoxycarbonyloxy, aryloxycarbonyloxy, carbamoyloxy acyloxy, and cyano. These coupling-off groups are described in the art, for example, in U.S. Pat. Nos. 2,455,169, 3,227,551, 3,432,521, 3,476,563, 3,617,291, 3,880,661, 4,052,212 and 4,134,766; and in U.K. Patents and published application Nos. 1,466,728, 1,531,927, 1,533,039, 2,006,755A and 2,017,704A, the disclosures of which are incorporated herein by reference. Preferably X is a chloride. Unless otherwise specifically stated, use of the term "substituted" or "substituent" means any group or atom other than hydrogen. Additionally, when the term "group" is used, it means that when a substituent group contains a substitutable hydrogen, it is also intended to encompass not only the substituent's unsubstituted form, but also its form further substituted with any substituent group or groups as herein mentioned, so long as the substituent does not destroy properties necessary for photographic utility. Suitably, a substituent group may be halogen or may be bonded to the remainder of the molecule by an atom of carbon, silicon, oxygen, nitrogen, phosphorous, or sulfur. The substituent maybe, for example, halogen, such as chlorine, bromine or fluorine; nitro; hydroxyl; cyano; carboxyl; or groups which may be further substituted, such as alkyl, including straight or branched chain or cyclic alkyl, such as methyl, trifluoromethyl, ethyl, t- butyl, 3-(2,4-di-t-pentylphenoxy) propyl, and tefradecyl; alkenyl, such as ethylene, 2-butene; alkoxy, such as methoxy, ethoxy, propoxy, butoxy, 2-methoxyethoxy, sec-butoxy, hexyloxy, 2-ethylhexyloxy, tetradecyloxy, 2-(2,4-di-t- pentylphenoxy)ethoxy, and 2-dodecyloxyethoxy; aryl such as phenyl, 4-t- butylphenyl, 2,4,6-trimethylphenyl, naphthyl; aryloxy, such as phenoxy, 2- methylphenoxy, alpha- or beta-naphthyloxy, and 4-tolyloxy; carbonamido, such as acetamido, benzamido, butyramido, tetradecanamido, alpha-(2,4-di-t-pentyl- phenoxy)acetamido, alpha-(2,4-di-t-pentylphenoxy)butyramido, alpha-(3- pentadecylphenoxy)-hexanamido, alpha-(4-hydroxy-3-t-butylphenoxy)- tetradecanamido, 2-oxo-pyrrolidin-l-yl, 2-oxo-5-tetradecylρyπolin-l-yl, N- methyltefradecanamido, N-succinimido, N-phthalimido, 2,5-dioxo- 1 -oxazolidinyl, 3-dodecyl-2,5-dioxo-l-imidazolyl, and N-acetyl-N-dodecylamino, ethoxycarbonylamino, phenoxycarbonylamino, benzyloxycarbonylamino, hexadecyloxycarbonylamino, 2,4-di-t-butylphenoxycarbonylamino, phenylcarbonylamino, 2,5-(di-t-pentylphenyl)carbonylamino,^-dodecyl- phenylcarbonylamino, -tolylcarbonylamino, N-methylureido, N,N- dimethylureido, N-methyl-N-dodecylureido, N-hexadecylureido, N,N- dioctadecylureido, N,N-dioctyl-N'-ethylureido, N-phenylureido, N,N- diphenylureido, N-phenyl-N- -tolylureido, N-(m-hexadecylphenyl)ureido, N,N- (2,5-di-t-pentylphenyl)-N'-ethylureido, and t-butylcarbonamido; sulfonamido, such as methylsulfonamido, benzenesulfonamido, ?-tolylsulfonamido, >- dodecylbenzenesulfonamido, N-methyltetradecylsulfonamido, N,N-dipropyl- sulfamoylamino, and hexadecylsulfonamido; sulfamoyl, such as N- methylsulfamoyl, N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N- hexadecylsulfamoyl, N,N-dimethylsulfamoyl; N-[3-(dodecyloxy)propyl]- sulfamoyl, N-[4-(2,4-di-t-pentylphenoxy)butyl]sulfamoyl, N-methyl-N- tetradecylsulfamoyl, and N-dodecylsulfamoyl; carbamoyl, such as N- methylcarbamoyl, N,N-dibutylcarbamoyl, N-octadecylcarbamoyl, N-[4-(2,4-di-t- pentylphenoxy)butyl] carbamoyl, N-methyl-N-tetradecylcarbamoyl, and N,N- dioctylcarbamoyl; acyl, such as acetyl, (2,4-di-t-amylphenoxy)acetyl, phenoxycarbonyl, ?-dodecyloxyphenoxycarbonyl methoxycarbonyl, butoxycarbonyl, tetradecyloxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, 3- pentadecyloxycarbonyl, and dodecyloxycarbonyl; sulfonyl, such as methoxy- sulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl, 2-ethylhexyloxysulfonyl, phenoxysulfonyl, 2,4-di-t-pentylρhenoxysulfonyl, methylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl, hexadecylsulfonyl, phenylsulfonyl, 4- nonylphenylsulfonyl, and >-tolylsulfonyl; sulfonyloxy, such as dodecylsulfonyloxy, and hexadecylsulfonyloxy; sulfinyl, such as methylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, hexadecylsulfinyl, phenylsulfinyl, 4-nonylρhenylsulfinyl, and -tolylsulfinyl; thio, such as ethylthio, octylthio, benzylthio, tetradecylthio, 2-(2,4-di-t-pentylphenoxy)ethylthio, phenylthio, 2-butoxy-5-t-octylphenylthio, and^-tolylthio; acyloxy, such as acetyloxy, benzoyloxy, octadecanoyloxy, -dodecylamidobenzoyloxy, N- phenylcarbamoyloxy, N-ethylcarbamoyloxy, and cyclohexylcarbonyloxy; amine, such as phenylanilino, 2-chloroanilino, diethylamine, dodecylamine; imino, such as 1 (N-phenylimido)ethyl, N-succinimido or 3-benzylhydantoinyl; phosphate, such as dimethylphosphate and ethylbutylphosphate; phosphite, such as diethyl and dihexylphosphite; a heterocyclic group, a heterocyclic oxy group or a heterocyclic thio group, each of which may be substituted and which contain a 3 to 7 membered heterocyclic ring composed of carbon atoms and at least one hetero atom selected from the group consisting of oxygen, nitrogen and sulfur, such as 2-furyl, 2-thienyl, 2-benzimidazolyloxy or 2-benzothiazolyl; quaternary ammonium, such as triethylammonium; and silyloxy, such as trimethylsilyloxy. If desired, the substituents may themselves be further substituted one or more times with the described substituent groups. The particular substituents used may be selected by those skilled in the art to attain the desired photographic properties for a specific application and can include, for example, hydrophobic groups, solubilizing groups, blocking groups, releasing or releasable groups, etc. When a molecule may have two or more substituents, the substituents may be joined together to form a ring such as a fused ring unless otherwise provided. Generally, the above groups and substituents thereof may include those having up to 48 carbon atoms, typically 1 to 36 carbon atoms and usually less than 24 carbon atoms, but greater numbers are possible depending on the particular substituents selected. Specific examples of the 2-halonapthol coupler represented by the formula (1) will be shown below, which, however are not intended to be limiting of the present invention.

Coupler 1 Coupler 2

Coupler 3 Coupler 4

Coupler 5 Coupler 6

Coupler 7 Coupler 8

Coupler 9 Coupler 10

Coupler 11 Coupler 12

Coupler 13 Coupler 14

Coupler 15 Coupler 16

Coupler 17 Coupler 18

Coupler 19 Coupler 20 The materials of the invention can be used in any of the ways and in any of the combinations known in the art. Typically, the invention materials are incorporated in a melt and coated as a layer described herein on a support to form part of a photographic element. To control the migration of various components, it may be desirable to include a high molecular weight hydrophobe or "ballast" group in the component molecule. Representative ballast groups include substituted or unsubstituted alkyl or aryl groups containing 8 to 40 carbon atoms. Representative substituents on such groups include alkyl, aryl, alkoxy, aryloxy, alkylthio, hydroxy, halogen, alkoxycarbonyl, aryloxcarbonyl, carboxy, acyl, acyloxy, amino, anilino, carbonamido, carbamoyl, alkylsulfonyl, arysulfonyl, sulfonamido, and sulfamoyl groups wherein the substituents typically contain 1 to 40 carbon atoms. Such substituents can also be further substituted. The elements of the invention are traditional photographic elements as opposed to photothermographic elements or elements utilizing very low volumes of processing solution. The imaging arts have long recognized that the field of photothermography is clearly distinct from that of photography. Photothermographic materials differ significantly from conventional silver halide photographic materials that require processing with aqueous processing solutions to provide a visible image. In photothermographic imaging materials, a visible image is created solely by heat as a result of the reaction of a developer incorporated within the material. Heating at 50°C or more is essential for this dry development. In contrast, conventional photographic imaging materials require contact with an aqueous processing solution. Heat may be utilized in addition to the processing solution but at more moderate temperatures (generally from 30°C to 50°C) to provide a visible image. In photothermographic materials, all of the "chemistry" for imaging is incorporated within the material itself. For example, such materials include a developer (that is, a reducing agent for the reducible silver ions) while conventional photographic materials usually do not. Even in so-called "instant photography", the developer chemistry is physically separated from the photosensitive silver halide until development is desired. Moreover, in photothermographic materials, the unexposed silver halide generally remains intact after development and the material must be stabilized against further imaging and development. In contrast, silver halide is removed from conventional photographic elements after solution development to prevent further imaging (that is, in the aqueous fixing step). The silver halide photographic elements of the cuπent invention are also not utilized with low volume systems. Low volume systems are those where film processing is initiated by contact to a processing solution, but where the processing solution volume is comparable to the total volume of the imaging layer to be processed. This type of system may include the addition of non solution processing aids, such as the application of heat or of a laminate layer that is applied at the time of processing. Low volume processing is defined as processing where the volume of applied developer solution is between about 0.1 to about 10 times, preferably about 0.5 to about 10 times, the volume of solution required to swell the photographic element. This processing may take place by a combination of solution application, external layer lamination, and heating. The low volume system photographic element may receive some or all of the following treatments: (I) Application of a solution directly to the film by any means, including spray, inkjet, coating, gravure process, and the like. (II) Soaking of the film in a reservoir containing a processing solution. This process may also take the form of dipping or passing an element through a small cartridge. (III) Lamination of an auxiliary processing element to the imaging element. The laminate may have the purpose of providing processing chemistry, removing spent chemistry, or transferring image information from the latent image recording film element. The transfeπed image may result from a dye, dye precursor, or silver containing compound being transfeπed in an image- wise manner to the auxiliary processing element. (IV) Heating of the element by any convenient means, including a simple hot plate, iron, roller, heated drum, microwave heating means, heated air, vapor, or the like. Heating may be accomplished before, during, after, or throughout any of the preceding treatments I - III. Heating may cause processing temperatures ranging from room temperature to 100°C. The halonaphtiiol couplers are used in silver halide photographic elements wherein processing is done by traditional wet-chemical processing. Preferably the elements of the invention do not contain any incorporated developer or any silver source except silver halide. Specifically they do not contain a non-photosensitive source of reducible silver ions. By "traditional wet- chemical processing" or, synonymously, "wet-chemical processing" is herein meant a commercially standardized process in which the imagewise exposed color photographic element is completely immersed in a solution containing a developing agent, preferably p-phenylenediamine or its equivalent, at a temperature of under 60°C, preferably 30 to 45°C, in order to form a color image from a latent image. The developing agent is an unblocked developing agent which (after oxidation) forms dyes by reacting with the image-dye couplers contained in the photographic element. Preferably the aqueous developer is agitated during development. The film element is may or may not then be desilvered, for example bleached and fixed, to remove unwanted silver and silver halide, thereby forming a color negative film capable of use to make a positive image print. One example of such a process is KODAK FLEXICOLOR (C-41) process as described in British Journal of Photo graphy Annual. 1988, pp 191-198. Such processes are also described in Research Disclosure 40145, Sept. 1997, Section XXIII. Conventional photographic elements in accordance with the invention can be processed in any of a number of well-known photographic processes utilizing any of a number of well-known conventional photographic processing solutions, described, for example, in the Research Disclosures referenced hereafter, or in T.H. James, editor, The Theory of the Photo raphic

Process.4th Edition, Macmillan, New York, 1977. The development process may take place for any length of time and any process temperature that is suitable to render an acceptable image In the case of processing a negative working color element, the element is treated with a color developer (that is, one which will form the colored image dyes with the color couplers), and then with an oxidizer and a solvent to remove silver and silver halide. In the case of processing a reversal color element, the element is first treated with a black-and-white developer (that is, a developer which does not form colored dyes with the coupler compounds) followed by a treatment to fog silver halide (usually chemical fogging or light fogging), followed by treatment with a color developer. Prefeπed color developing agents are p-phenylenediamines. Especially prefeπed are: 4-amino-N,N-diethylaniline hydrochloride, 4-amino-3 -methyl-N,N-diethylaniline hydrochloride, 4-amino-3 -methyl-N-ethyl-N-(2-(methanesulfonamido) ethylaniline sesquisulfate hydrate, 4-amino-3 -mefhyl-N-ethyl-N-(2-hydroxyethyl)aniline sulfate, 4-amino-3-α -(methanesulfonamido)ethyl-N,N-diethylaniline hydrochloride and 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluene sulfonic acid. Development is usually followed by the conventional steps of bleaching, fixing, or bleach-fixing to remove silver or silver halide, washing, and drying. With negative-working silver halide, the processing steps provide a negative image. One type of such element, refeπed to as a color negative film, is designed for image capture. Speed (the sensitivity of the element to low light conditions) is usually critical to obtaining sufficient image in such elements. Such elements are typically silver bromoiodide emulsions coated on a transparent support and are sold packaged with instructions to process in known color negative processes such as the Kodak C-41 process as described in The British Journal of Photography Annual of 1988, pages 191-198. If a color negative film element is to be subsequently employed to generate a viewable projection print as for a motion picture, a process such as the Kodak ECN-2 process described in the H-24 Manual available from Eastman Kodak Co. may be employed to provide the color negative image on a transparent support. Color negative development times are typically 3' 15" or less and desirably 90 or even 60 seconds or less. Another type of color negative element is a color print. This is the prefeπed embodiment of the invention. Such an element is designed to receive an image optically printed from an image capture color negative element. A color print element may be provided on a reflective support for reflective viewing (e.g., a snapshot) or on a transparent support for projection viewing as in a motion picture. Elements destined for color reflection prints are provided on a reflective support, typically paper, employ silver chloride emulsions, and may be optically printed using the so-called negative-positive process where the element is exposed to light through a color negative film which has been processed as described above. The element is sold packaged with instructions to process using a color negative optical printing process, for example the Kodak RA-4 process, as generally described in PCT WO 87/04534 or U.S. 4,975,357, to form a positive image. Color projection prints may be processed, for example, in accordance with the Kodak ECP-2 process as described in the H-24 Manual. Color print development times are typically 90 seconds or less and desirably 45 or even 30 seconds or less. A reversal element is capable of forming a positive image without optical printing. To provide a positive (or reversal) image, the color development step is preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form dye, and followed by uniformly fogging the element to render unexposed silver halide developable. Such reversal elements are typically sold packaged with instructions to process using a color reversal process such as the Kodak E-6 process as described in The British Journal of Photography Annual of 1988, page 194. Alternatively, a direct positive emulsion can be employed to obtain a positive image. Other processing methods useful with the cuπent invention include less conventional processors such as those described in U. S. Patent 5,890,028, a drum processor such as the Kodak RS-11 Drum Processor, or a wave processor which processes a photographic material by loading the material into a chamber, introducing a metered amount of processing solution into the chamber, and rotating the chamber in a fashion which forms a wave in the solution through which the material passes. The appropriate solution for each processing stage is added and removed sequentially from the processing space and can be treated for disposal as described in the cuπent invention. The wave processor is described in more detail in U.S. Application 09/920,495, filed August 1, 2001. Another processor and processing method with which the cuπent invention is particularly useful is the merged process described in U.S. Application Serial No. 09/ filed October 30, 2001 of Peter J. Twist titled "Processing

Photographic Material". This processing method for silver halide photographic material comprises loading the material into a chamber, introducing a metered amount of a first processing solution into the chamber, and processing the photographic material with the first processing solution. It then comprises introducing a metered amount of a second processing solution into the chamber without removing the first processing solution so that at least part of the whole volume of the second processing solution is provided by the first processing solution and processing the photographic material with the second processing solution. The merged method further comprises, after processing the photographic material with the second processing solution, introducing a metered amount of a third processing solution into the chamber without removing any processing solution remaining from the preceding processing solution or solutions so that at least part of the total volume of the third processing solution is provided by the preceding processing solution or solutions and processing the photographic material with the third processing solution. Using the merged solution processing method it is possible to add all of the processing solutions except the wash solution on top of one another in the coπect sequence without removing the previous solution. Thus, the whole of the previous solution is mixed with the next solution. The method is preferably carried out in a high agitation single use processor which processes one film at a time with small volumes similar to those used to replenish continuous processors with tanks of several litres. Thus, a developer solution may be added to the tank of the single use processor, and after development is complete, a bleach solution, for example, is added to the developer solution to transform the developer into a bleach solution, then a fix solution is added to the developer plus bleach solution to convert it into a bleach-fix solution. The previous solution acts as a diluent for the next solution which means that the next solution can be more concentrated than it would be if it were used alone. This means that the total volume used in the process can be less than that used if each solution is removed after the particular stage it performs is complete. Photographic silver halide elements utilize more silver halide than do photothermographic materials. In photothermographic materials, only a small amount of silver halide is used to capture light and a non-photosensitive source of reducible silver ions (for example, a silver salt of substituted carboxylic acid or heterocylic thiol or heterocylic amine) is used to generate the visible image using thermal development. Thus imaged, the photosensitive silver halide serves as a catalyst for the physical development process involving the non-photosensitive source of reducible silver ions and the incorporated reducing agent. In contrast, conventional wet-processed photographic materials use only one form of silver (that is, silver halide) that, upon chemical development, is itself converted into the silver image, or that upon physical development requires addition of an external silver source (or other reducible metal ions that form black images upon reduction to the coπesponding metal). Thus, photothermographic materials require an amount of silver halide per unit area that is only a fraction of that used in conventional wet-processed photographic materials. Additionally the silver halide to organic Ag salt ratio is very different for the two types of imaging materials. The two are defined as follows. AgX is all the silver halide in an element either added via ex-situ methods (preformed AgX) or generated in-situ by addition of free halide to the organic silver salt. AgR is the reducible silver ions coming from a non-photosensitive source. In conventional photographic elements AgX / AgR is always greater than 1 on a mass basis or a mass/surface area basis. In photothermographic systems AgX / AgR is always less than 1 on a mass basis or a mass/surface area basis. Therefore, the silver halide photographic elements of the invention generally have, over the multiplicity of element layers, a ratio of AgX / AgR > 1 and photothermographic systems generally have, over the multiplicity of element layers, a ratio of AgX / AgR < 1. These and other distinctions between photothermographic and photographic materials are described in Imaging Processes and Materials (Neblette's Eighth Edition), noted above, Unconventional Imaging Processes,

E. Brinckman et al (Eds.), The Focal Press, London and New York, 1978, pp.

74-75, in Zou et al, J. Imaging Sci. Technol. 1996, 40, 94-103, and in M. R. V.

Sahyun, J. Imaging Sci. Technol. 1998, 42, 23. The photographic emulsions of this invention are generally prepared by precipitating silver halide crystals in a colloidal matrix by methods conventional in the art. The colloid is typically a hydrophilic film formation agent such as gelatin, alginic acid, or derivatives thereof. The crystals formed in the precipitation step are washed and then chemically and spectrally sensitized by adding spectral sensitizing dyes and chemical sensitizers, and by providing a heating step during which the emulsion temperature is raised, typically from 40° C. to 70° C, and maintained for a period of time. The precipitation and spectral and chemical sensitization methods utilized in preparing the emulsions employed in the invention can be those methods known in the art. Chemical sensitization of the emulsion typically employs sensitizers such as: sulfur-containing compounds, e.g., allyl isothiocyanate, sodium thiosulfate and allyl thiourea; reducing agents, e.g., polyamines and stannous salts; noble metal compounds, e.g., gold, platinum; and polymeric agents, e.g., polyalkylene oxides. As described, heat treatment is employed to complete chemical sensitization. Spectral sensitization is effected with a combination of dyes, which are designed for the wavelength range of interest within the visible or infrared spectrum. It is known to add such dyes both before and after heat treatment. After spectral sensitization, the emulsion is mixed with a melt containing dispersions of one or more color forming couplers and is coated on a support. The photographic elements of the invention can be prepared by any of a number of well-know coating techniques, such as dip coating, rod coating, blade coating, air knife coating, gravure coating and reverse roll coating, extrusion coating, slide coating, curtain coating, and the like. Known coating and drying methods are described in further detail in Research Disclosure No. 308119, Published Dec. 1989, pages 1007 to 1008. The couplers used in the invention can be added to a mixture containing silver halide before coating or, more suitably, be mixed with the silver halide just prior to or during coating. In either case, additional components like couplers, doctors, surfactants, hardeners and other materials that are typically present in such solutions may also be present at the same time. The materials are not water-soluble and cannot be added directly to the solution. They may be added directly if dissolved in an organic water miscible solution such as methanol, acetone or the like or more preferably as a dispersion. A dispersion incorporates the material in a stable, finely divided state in a hydrophobic organic solvent (often refeπed to as a coupler solvent or permanent solvent) that is stabilized by suitable surfactants and surface active agents usually in combination with a binder or matrix such as gelatin. The dispersion may contain one or more permanent solvents that dissolve the material and maintain it in a liquid state. Some examples of suitable permanent solvents are tricresylphosphate, N,N- diethyllauramide, N,N-dibutyllauramide, p-dodecylphenol, dibutylphthalate, di-n- butyl sebacate, N-n-butylacetanilide, 9-octadecen-l-ol, ortAo-methylphenyl benzoate, trioctylamine and 2-ethylhexylρhosphate. Permanent solvents can also be described in terms of physical constants such as alpha, beta and pi* as defined by M. J. Kamlet, J-L.M. Abboud, M.H. Abraham and R.W. Taft, J. Org Chem, 48, 2877(1983). Prefeπed classes of solvents are carbonamides, phosphates, alcohols and esters. When a solvent is present, it is prefeπed that the weight ratio of compound to solvent be at least 1 to 0.5, or most preferably, at least 1 to 1. The dispersion may require an auxiliary coupler solvent initially to dissolve the component but this is removed afterwards, usually either by evaporation or by washing with additional water. Some examples of suitable auxiliary coupler solvents are ethyl acetate, cyclohexanone and 2-(2-butoxyethoxy)ethyl acetate. The dispersion may also be stabilized by addition of polymeric materials to form stable latexes. Examples of suitable polymers for this use generally contain water-solubilizing groups or have regions of high hydrophilicity. Some examples of suitable dispersing agents or surfactants are Alkanol XC or saponin. The materials used in the invention may also be dispersed as an admixture with another component of the system such as a coupler or an oxidized developer scavenger so that both are present in the same oil droplet. It is also possible to incorporate the materials of the invention as a solid particle dispersion; that is, a slurry or suspension of finely ground (through mechanical means) compound. These solid particle dispersions may be additionally stabilized with surfactants and/or polymeric materials as known in the art. Also, additional permanent solvent may be added to the solid particle dispersion to help increase activity. The amount of a cyan coupler in the present invention is preferably 0.01 to 2 g m², more preferably 0.05 to 1 g/m². The silver halide emulsions utilized in this invention are predominantly silver chloride emulsions. By predominantly silver chloride, it is meant that the grains of the emulsion are greater than about 50 mole percent silver chloride. Preferably, they are greater than about 90 mole percent silver chloride; and optimally greater than about 95 mole percent silver chloride. These emulsions may contain iodides or bromides or both as the remainder of the total halide composition. The silver halide emulsions can contain grains of any size and morphology. Thus, the grains may take the form of cubes, octahedrons, cubo- octahedrons, or any of the other naturally occurring morphologies of cubic lattice type silver halide grains. Further, the grains may be iπegular such as spherical grains or tabular grains. Grains having a tabular or cubic morphology are prefeπed. Tefradecahedral grains with {111} and {100} crystal faces may also be utilized. The Au(I) compounds may also be used in reversal systems having core shell silver halide emulsions. The multilayer, multicolor photographic elements of this invention typically contain dye image-forming layers sensitive to each of the three primary regions of the visible spectrum. Each layer can comprise a single emulsion layer or of multiple emulsion layers sensitive to a region of the spectrum. The layers of the element can be aπanged in various orders as known in the art. A typical multicolor photographic element comprises a support bearing a yellow dye image- forming layer comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler, a magenta dye image-forming layer comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler, and a red dye image-forming layer comprising at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye- forming coupler. The element typically contains additional layers, such as interlayers and overcoat layers. All of these can be coated on a support which can be transparent or reflective. Preferably the support is reflective. The couplers are preferably used in red light sensitive silver halide emulsion layers. When there are multiple layers with different degrees of red- light sensitivity present, they may be used in any layer or layers in combination. It is prefeπed that the couplers are used in the most red-light sensitive layer when two or more layers of differing red-light sensitivity are present. It is also possible to use the couplers in conjunction with other types of known cyan couplers, either in the same layer or in different layers. The photographic emulsions may be incorporated into color negative (particularly color paper) or reversal photographic elements. The photographic element may also comprise a transparent magnetic recording layer such as a layer containing magnetic particles on the underside of a transparent support, as described in Research Disclosure, November 1992, Item 34390 published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire PO107DQ, ENGLAND. Typically, the element will have a total thickness (excluding the support) of from about 5 to about 30 microns. Further, the photographic elements may have an annealed polyethylene naphthalate film base such as described in Hatsumei Kyoukai Koukai Gihou No. 94-6023, published Mar. 15, 1994 (Patent Office of Japan and Library of Congress of Japan) and may be utilized in a small format system, such as described in Research Disclosure, June 1994, Item 36230 published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire PO107DQ, ENGLAND, and such as the Advanced Photo System, particularly the Kodak ADVANTIX films or cameras. In the following Table, reference will be made to (1) Research Disclosure, December 1978, Item 17643, (2) Research Disclosure, December 1989, Item 308119, (3) Research Disclosure, September 1994, Item 36544, and (4) Research Disclosure, September 1996, Item 38957, all published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire PO107DQ, ENGLAND, the disclosures of which are incorporated herein by reference. The Table and the references cited in the Table are to be read as describing particular components suitable for use in the elements of the invention. The Table and its cited references also describe suitable ways of preparing, exposing, processing and manipulating the elements, and the images contained therein. Photographic elements and methods of processing such elements particularly suitable for use with this invention, particularly those describing high chloride color papers, are described in Research Disclosure, February 1995, Item 37038, published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire PO107DQ, ENGLAND, the disclosure of which is incorporated herein by reference.

The photographic elements can be incorporated into exposure stractures intended for repeated use or exposure structures intended for limited use, variously refeπed to as single use cameras, lens with film, or photosensitive material package units. The photographic elements can be exposed with various forms of energy which encompass the ultraviolet, visible, and infrared regions of the electromagnetic spectrum as well as the electron beam, beta radiation, gamma radiation, X-ray, alpha particle, neutron radiation, and other forms of corpuscular and wave-like radiant energy in either noncoherent (random phase) forms or coherent (in phase) forms, as produced by lasers. When the photographic elements are intended to be exposed by X-rays, they can include features found in conventional radiographic elements. The photographic elements are preferably exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image, and then processed to form a visible dye image. The following examples are intended to illustrate, but not to limit, the invention.

Examples

_A B Coupler 1 Synthesis of Coupler 1 N-(6-chloro-5-hydroxy-l-naphthalenyl)acetamide A was prepared as described in A. Friedman and T. Kissel, EP603953A1 (1994) incorporated herein by reference. 5-amino-2-chloro-l-naphthol hydrochloride salt. B was prepared as follows. N-(6-chloro-5-hydroxy-l-naphthalenyl)acetamide (20g, 84.9 mmol) was mixed with THF (50 mL). To that solution was added an aqueous solution of NaOH (6.0M, 0.4 moles, 70 mL). The mixture was refluxed for 3 h. After cooling, the solution was acidified to pH = 1.0 using 2.0M HCI. Upon cooling, the product (17.6g, 76.4 mmol, 90% yield) precipitated. The solid was collected by filtration, filtered, washed with distilled water, then heptane, and dried under vacuum. Obtained analytical data consistent with structure. Into a separate flask was placed B (9.67g, 50.0 mmol), dimethylaniline (13.38& 110.4 mmol, 14.0 mL), and THF (125 mL). N- hexadecylsulfonylchloride was added dropwise in 50 mL THF. Once addition was complete, the reaction was warmed to room temperature then stiπed for 16 h. The reaction mixture was poured into 250 mL 10% HCI, then extracted with EtOAc (3 x 250 mL). The extracts were combined, washed with brine (50 mL), dried over anhydrous Na₂SO₄, filtered, then evaporated to dryness. Trituration of the reddish solid with CH₂C1₂ produced the product as a white solid. The product was isolated by filtration, then dried under vacuum resulting in white solid (13.95g, 32.3 mmol, 64% yield). Obtained analytical data was consistent with structure.

Photographic Example On a gel- subbed, polyethylene- coated paper support were coated the following layers: First Layer An underlayer containing 3.23 grams gelatin per square meter.

Second Layer A photosensitive layer containing (per square meter) 2.15 grams gelatin, an amount of red- sensitized silver chloride emulsion containing the amount of silver (determined by the equivalency of the coupler) 18 mg/ft² for a 2 equivalency coupler. The dispersion containing δ.όlxlO^"4 mole of the coupler and 0.043 gram surfactant Alkanol XC (trademark of E.I. Dupont Co.) (in addition to the Alkanol XC used to prepare the coupler dispersion). The coupler dispersion contained the coupler, all of the gelatin in the layer except that supplied by the emulsion, an amount of coupler solvent equal to the weight of the coupler, and 0.22 grams Alkanol XC. The ultraviolet light absorber UV-1, was added in an amount equal to 1.5 molar equivalents of the inventive coupler. Third Layer A protective layer containing (per square meter) 1.40 grams gelatin, 0.15 gram bis(vinylsulfonyl)methane, 0.043 gram Alkanol XC, and 4.40x10-6 gram tefraethylammonium perfluorooctanesulfonate. The compounds used are shown below.

Comparison 1 Comparison 2

Comparison 3 Comparison 4

UV-1

Processed samples were prepared by exposing the coatings through a step wedge and processing as follows: Process Step Time (min.) Temp. (° C.)

Developer 0.75 35.0

Bleach-Fix 0.75 35.0

Water wash 1.50 35.0

The processing solutions used in the above process had the following compositions (amounts per liter of solution):

Developer

Triethanolamine 12.41 g

Blankophor REU (trademark of Mobay Corp.) 2.30 g

Lithium polystyrene sulfonate 0.09 g

N,N-Diethylhydroxylamine 4.59 g

Lithium sulfate 2.70 g

4-amino-3- methyl-N-ethyl-N-(2-methansulfonamidoethyl)- 55..0000 gg aniline-sesquisulfate hydrate

1- Hydroxyethyl-l,l-diphosphonic acid 0.49 g

Potassium carbonate, anhydrous 21.16 g

Potassium chloride 1.60 g

Potassium bromide 7.00 mg pH adjusted to 10.4 at 26.7 C.

Bleach-Fix

Solution of ammonium thiosulfate 71.85 g

Ammonium sulfite 5.10 g

Sodium metabisulfite 10.00 g

Acetic acid 10.20 g

Ammonium ferric ethylenediaminetetra acetate 48.58 g

Ethylenediaminetetraacetic acid 3.86 g pH adjusted to 6.7 at 26.7 C. The Data for the Comparison and 2-Chloronapthol Cyan Couplers is shown in Table 1.

The data in Table 1 demonstrates that the couplers of the invention give dyes with dyes greater than 650nm but less than 690 nm in lamda max with a half band width greater 150 nm.

Claims

CLAIMS:

1. A silver halide photographic element comprising a support and a red sensitive silver halide emulsion layer wherein the grains of the silver halide emulsion are greater than 50 mol percent silver chloride, said layer containing only one cyan image dye forming coupler, wherein said coupler, after wet- chemical processing with a solution comprising p-phenylenediame developer, has a lambda max of 650 to 680 and a half bandwidth of greater than 150nm.

2. The silver halide element of claim 1 wherein the grains of the silver halide emulsion are greater than 90 mol percent silver chloride.

3. The silver halide element of claim 1 comprising a cyan dye image-forming unit comprising only one red-sensitive silver halide emulsion layer.

4. A silver halide photographic element comprising a support and a silver halide emulsion layer wherein the grains of the silver halide emulsion are greater than 50 mol percent silver chloride, said emulsion layer comprising a halonaphthol coupler represented by formula (1)

wherein R¹ is a halogen, X is a coupling off group that is not a PUG, R² is independently an alkyl, aryl sulfonyl, carbonyl or phosphonyl group, and R³ is independently H, or an alkyl, aryl, sulfonyl, carbonyl or phosphonyl group, provided that R² and R³ combined comprise 12 or more carbon atoms and that when R² or R³ is a sulfonyl, carbonyl, or phosphonyl group it is additionally substituted by an alkyl group, an aryl group, an alkylamino group, an arylamino group, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an alkenylamino group, an alkynylamino group, a cycloalkylamino group, or a cycloalkenylamino group.

5. The silver halide element of claim 4 wherein when R² or R³ is a sulfonyl, carbonyl, or phosphonyl group it is additionally substituted by 1 to 32- carbon straight or branched-chain alkyl group, a 7 to 32-carbon aralkyl group, a 2 to 32-carbon alkenyl group, a 2 to 32-carbon alkynyl group, a 3 to 32-carbon cycloalkyl group, a 3 to 32-carbon cycloalkenyl group, a 1 to 32 straight or branched-chain alkylamino group, a 7 to 32-carbon aralkylamino group, a 2to 32- carbon alkenylamino group, a 2 to 32-carbon alkynylamino group, a 3 to 32- carbon cycloakylamino group, or a 3 to 32-carbon cycloalkenylamino group.

6. The silver halide element of claim 4 wherein R² is a sulfonyl or carbonyl group.

7. The silver halide element of claim 4 wherein R¹ is chlorine.

The silver halide element of claim 4 wherein R³ is an H atom.

9. The silver halide element of claim 4 wherein X is chlorine.

10. The silver halide element of claim 4 wherein R¹ is chlorine, X is chlorine, R² is a sulfonyl or carbonyl group, and R³ is an H atom.

11. The silver halide element of claim 4 wherein the grains of the silver halide emulsion are greater than 90 mol percent silver chloride.

12. The silver halide element of claim 4 wherein said element comprises a cyan dye image-forming unit comprised of at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye- forming coupler, a magenta dye image-forming unit comprising at least one green- sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler, and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler.

13. The silver halide element of claim 12 wherein the halonapthol coupler is located in a red-sensitive layer.

14. The silver halide element of claim 13 wherein the halonaphtiiol coupler is the only image dye forming coupler in the red sensitive layer.

15. The silver halide element of claim 14 wherein the cyan dye image-forming unit is comprised of only one red-sensitive silver halide emulsion layer.

16. The silver halide element of claim 4 wherein said element is processed using traditional wet processing.

17. A silver halide photographic element comprising a support and on said support further comprising a cyan dye image-forming unit comprised of at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler, and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler, wherein the grains of the red sensitive silver halide emulsion are greater than 50 mol percent silver chloride, and wherein the red sensitive silver halide emulsion layer contains only one cyan dye forming coupler and the coupler is a halonaphthol coupler represented by formula (1)

wherein R¹ is a halogen, X is a chlorine, R³ is an H, and R² is a sulfonyl or carbonyl group additionally substituted by a 12 to 32-carbon straight or branched-chain alkyl group, a 12 to 32-carbon aralkyl group, a 12 to 32-carbon alkenyl group, a 12 to 32-carbon alkynyl group, a 12 to 32-carbon cycloakyl group, a 12 to 32-carbon cycloalkenyl group, a 12 to 32 straight or branched-chain alkylamino group, a 12 to 32-carbon aralkylamino group, a 12 to 32-carbon alkenylamino group, a 12 to 32-carbon alkynylamino group, a 12 to 32-carbon cycloakylamino group, or a 12 to 32-carbon cycloalkenylamino group.

18. A method of processing a silver halide element comprising taking a silver halide element comprising a support and a silver halide emulsion layer wherein the grains of the silver halide emulsion are greater than 50 mol percent silver chloride, said layer comprising a halonaphthol coupler represented by formula (1)

wherein R¹ is a halogen, X is a coupling off group that is not a PUG, R is independently an alkyl, aryl sulfonyl, carbonyl or phosphonyl grou and R³ is independently H, or an alkyl, aryl, sulfonyl, carbonyl or phosphonyl group, provided that R² and R³ combined comprise 12 or more carbon atoms and that when R² or R³ is a sulfonyl, carbonyl, or phosphonyl group it is additionally substituted by an alkyl group, an aryl group, an alkylamino group, an arylamino group, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an alkenylamino group, an alkynylamino group, a cycloalkylamino group, or a cycloalkenylamino group, and developing the silver halide element in a developer comprising p-phenylenediamine, using traditional wet processing.

19. The method of claim 18 wherein when R² or R³ is a sulfonyl, carbonyl, or phosphonyl group it is additionally substituted by 1 to 32-carbon straight or branched-chain alkyl group, a 7 to 32-carbon aralkyl group, a 2 to 32- carbon alkenyl group, a 2 to 32-carbon alkynyl group, a 3 to 32-carbon cycloakyl group, a 3 to 32-carbon cycloalkenyl group, a 1 to 32 straight or branched-chain alkylamino group, a 7 to 32-carbon aralkylamino group, a 2to 32-carbon alkenylamino group, a 2 to 32-carbon alkynylamino group, a 3 to 32-carbon cycloalkylamino group, or a 3 to 32-carbon cycloalkenylamino group.

20. The method of claim 18 wherein R² is a sulfonyl or carbonyl group.

21. The method of claim 18 wherein R¹ is chlorine.

22. The method of claim 18 wherein R is an H atom.

23. The method of claim 18 wherein X is chlorine.

24. The method of claim 18 wherein R¹ is chlorine, X is chlorine, R is a sulfonyl or carbonyl group, and R is an H atom.

25. The method of claim 18 wherein the p-phenylenediamine is Methanesulfonamide, N-(2-((4-amino-3-methylphenyl)ethylamino)ethyl)-, sulfate (2:3).

26. The method of claim 18 wherein the grains of the silver halide emulsion are greater than 90 mol percent silver chloride.

27. The method of claim 18 wherein said element comprises a cyan dye image-forming unit comprised of at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye- forming coupler, and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler.

28. The method of claim 27 wherein the halonapthol coupler is located in a red-sensitive layer.

29. The method of claim 28 wherein the halonaphthol coupler is the only image dye forming coupler in the red sensitive layer. *

30. The method of claim 29 wherein the cyan dye image-forming unit is comprised of only one red-sensitive silver halide emulsion layer.