GB2329720A - Silver halide light sensitive element - Google Patents

Abstract

A silver halide light sensitive photographic element is disclosed comprising a support bearing at least one yellow image forming hydrophilic colloid layer comprising yellow image dye forming coupler of Formula I: wherein R represents a substituent, Y represents an aryl group or a heterocyclic group, and Z represents a non-metallic atomic group necessary to complete with the indicated nitrogen atom a nitrogen-containing heterocyclic coupling-off group, wherein the yellow image forming layer is substantially free of high boiling permanent solvents and nonionic polymeric stabilizers. Such photographic elements exhibit high coupler reactivity and excellent sensitometric curve shape, and yellow dyes formed from couplers of Formula I exhibit markedly improved stability to light fading when the couplers are dispersed without any high boiling solvent or nonionic polymeric stabilizer compared to coupler solvent-containing dispersions of these couplers. Additionally, the absence of nonionic polymeric stabilizers enables photographic elements having relatively thinner yellow image forming layers to be obtained.

Description

SILVER HALIDE LIGHT-SENSITIVE ELEMENT TECHNICAL FIELD This invention relates generally to the field of silver halide light sensitive elements, and in particular to photographic elements having at least one yellow imaging layer which is essentially free of permanent high boiling coupler solvents and nonionic polymeric stabilizers. In a particular aspect it relates to motion picture print films.

BACKGROUND OF THE INVENTION Various techniques are known for dispersing hydrophobic photographically useful compounds such as photographic couplers into photographic element layer coating compositions comprising hydrophilic colloids.

Photographic dye forming couplers, as well as other hydrophobic photographically useful compounds, are typically incorporated into a hydrophilic colloid layer of a photographic element by first forming an aqueous dispersion of the couplers and then mixing such dispersion with the layer coating solution. An organic solvent is typically used to dissolve the coupler, and the resulting organic solution is then dispersed in an aqueous medium to form the aqueous dispersion.

The organic phase of these dispersions frequently includes high boiling or permanent organic solvents, either alone or with low boiling or water miscible solvents which are removed after dispersion formation. Permanent high boiling solvents have a boiling point sufficiently high, generally above 1500C at atmospheric pressure, such that they are not evaporated under normal dispersion making and photographic layer coating procedures. Permanent high boiling coupler solvents are primarily used in the conventional "oil-protection" dispersion method whereby the organic solvent remains in the dispersion, and thereby is incorporated into the emulsion layer coating solution and ultimately into the photographic element.

The conventional "oil in water" dispersion method for incorporating hydrophobic couplers is described, e.g., in U.S. Patent 2,322,027 by Jelly and Vittum. In such conventional process, the coupler is dissolved in a high boiling water immiscible solvent, mixed with aqueous gelatin, and dispersed using a colloid mill or homogenizer. The presence of the high boiling solvent provides a stable environment for the hydrophobic coupler, as well as generally increasing the reactivity of the coupler upon photographic processing.

U.S. Patent 2,801,170 of Vittum et al. discloses preparing separate dispersions of a coupler and a high boiling point solvent and mixing the two dispersions with a silver halide emulsion. U.S. Patent 2,787,544 of Godowsky et al. discloses a method of making mixed packet photographic systems. A dispersion of high boiling point solvent is mixed with a dispersion of coupler.

Both these processes help prevent crystallization of the coupler prior to layer coating by keeping the solvent and the coupler separate until just prior to coating, while providing solvent in the coated layer to enhance coupler reactivity in the photographic element.

While the presence of high boiling solvents in certain coupler dispersions in photographic elements is frequently desirable to provide, e.g., adequate coupler reactivity upon photographic processing, lower thermal yellowing, modified dye hues, enhanced dye dark stability, and reduced crystallization, there are also certain advantages which may result from the substantial elimination of high boiling permanent solvent from a photographic element imaging layer.

Minimizing the amount of permanent coupler solvent coated in a photographic element is useful, e.g., for reducing the coated thickness of photographic layers.

Reductions in coupler solvent level also afford concomitant reductions in gelatin level which leads to further reductions in coated dry thickness. Layer thinning is advantageous for reasons such as improved image sharpness due to reduced light scattering during exposure and increased developability due to shorter diffilsion paths through the multilayer structure. This increase in developability can lead to lower silver and/or coupler coated levels, hence lower materials cost.

One method of preparing solvent-free coupler dispersions which may be used to provide photographic elements having reduced solvent levels is by precipitation such as described, e.g., in EP 374,837, in which the coupler is dissolved in a mixture of water miscible organic solvent and an alkali, and adding the resulting solution to water that contains an anionic surfactant and a nonionic polymer to form a dispersion. The combination of surfactant and nonionic polymer is disclosed as a requirement to obtain a stable precipitated dispersion, as the use of only surfactants without the nonionic polymer resulted in unstable dispersions. One serious drawback to this approach is that use of the nonionic polymer stabilizer increases the dry thickness of the coated layer, which counteracts one of the major benefits of coupler solvent reduction. Another disadvantage of using this method is that the small precipitated dispersion particles interact with gelatin resulting in coating solutions with very high viscosities, as described, e.g., in US 5,358,831. The prior art also teaches that dispersions of hydrophobic couplers formed by the precipitation technique can lead to extremely unreactive dispersions even though they have very small particles. These dispersions may require the addition of high boiling coupler solvent to achieve adequate coupler reactivity. Low coupler reactivity in the absence of high boiling coupler solvent may also be a problem with conventional coupler dispersions.

In color photographic materials, it is also desirable to form dye images which are stable to light fading. It would accordingly be desirable to provide a silver halide color photographic material with reduced dry thickness capable of forming dye images of high maximum density with improved stability to light fading through use of an imaging layer which is substantially free of high boiling permanent solvents and nonionic polymeric dispersants.

SUMMARY OF THE INVENTION One embodiment of the invention comprises a silver halide light sensitive photographic element comprising a support bearing at least one yellow image forming hydrophilic colloid layer comprising yellow image dye forming coupler of Formula I:

Formula I wherein R represents a substituent, Y represents an aryl group or a heterocyclic group, and Z represents a non-metallic atomic group necessary to complete with the indicated nitrogen atom a nitrogen-containing heterocyclic coupling-off group, wherein the yellow image forming layer is substantially free of high boiling permanent solvents and nonionic polymeric stabilizers.

In a preferred embodiment, a silver halide light sensitive photographic element is described comprising a support bearing in sequential order on one side thereof at least one yellow image forming hydrophilic colloid layer comprising a blue-sensitive silver halide emulsion and yellow image dye forming coupler, at least one cyan image forming hydrophilic colloid layer comprising red-sensitive silver halide emulsion and cyan image dye forming coupler, and at least one magenta image forming hydrophilic colloid layer comprising green-sensitive silver halide emulsion and magenta image dye forming coupler; wherein the yellow image forming coupler is of Formula I above, and the yellow image forming layer is substantially free of high boiling permanent solvent and nonionic polymeric stabilizers.

ADVANTAGES The photographic elements of the invention employing substantially solvent-free yellow imaging layers comprising yellow dye forming couplers of Formula I exhibit high coupler reactivity and excellent sensitometric curve shape in the absence of high boiling coupler solvent compared to other yellow couplers. Furthermore, we have also found that the yellow dyes formed from couplers of Formula I exhibit markedly improved stability to light fading when the couplers are dispersed without any high boiling solvent or nonionic polymeric stabilizer compared to coupler solvent-containing dispersions of these couplers. Additionally, the absence of nonionic polymeric stabilizers enables photographic elements having relatively thinner yellow image forming layers to be obtained.

DETAILED DESCRIPTION The photographic elements of the invention comprise at least one yellow image forming hydrophilic colloid layer comprising yellow image dye forming couplers, which layer is substantially free of high boiling permanent solvent and nonionic polymeric stabilizers. The term "high boiling permanent solvent" as used herein refers to those coupler solvents which have conventionally been employed in the photographic industry, such solvents typically being water imtiscible and having a boiling point of above 1 50 C. The term "nonionic polymeric stabilizers" refers to compounds such as disclosed in EP 374 837 used to stabilize precipitated coupler dispersions, such as poly(vinylpyrrolidone). For the purposes of this invention, "substantially free of high boiling permanent solvent", "no-solvent", "solvent-free" and like terms are intended to denote the absence of permanent organic solvents beyond trace or impurity levels. Similarly, reference to the absence of nonionic polymeric stabilizers is intended to denote such absence beyond trace or impurity levels. Yellow image forming layers in accordance with the invention which are substantially free of high boiling permanent solvents and nonionic polymeric stabilizers preferably contain 1.0 wt % or less of such components relative to the total amount of yellow coupler in the layer, more preferably less than 0.5 wt %, and most preferably less than 0.1 wt % of such components relative to the amount of yellow coupler. Such no-solvent dispersions of yellow image forming couplers of Formula I have been found to provide improved performance with respect to yellow image dye fading problems in exposed and processed photographic elements in comparison to use of yellow coupler dispersions having significant permanent solvent levels, and to enable thinner coated layers in comparison to use of yellow coupler dispersions employing nonionic polymeric stabilizers.

Couplers of Formula I which form yellow dyes upon reaction with oxidized color developing agent and which comprise nitrogen-containing heterocyclic coupling off groups are well known in the art, such as disclosed in representative patents US 3,973,968, 4,057,432, 4,221,860, 4,269,936, 4,314,023, 4,327,175, 4,404,274, 4,456,681, 4,581,324, 4,748,107, 4,770,985. The nonmetallic atomic group represented by Z in Formula I may comprise, e.g., carbon atoms, oxygen atoms, nitrogen atoms, or sulfur atoms. Preferably Z represents the atoms necessary to complete a 5- or 6-membered heterocyclic ring. Examples of 5and 6-membered hetero rings formed by such non-metallic atomic group together with the nitrogen atom include 2,5-dioxoimadazolidine, 2,3,5-trioxoimidazolidme, 2,5-dioxotriazolidine, 3,5-dioxotriazolidine, 2,4-oxozolidinediontriazolidine, 2,4thiazolidinediontriazolidine, pyridone, pyrimidone, pyrazone, tetrazolone, tetrazole, imidazole, triazole, imidazolone, triazolone, pyrazolone, isothioazolone, quinaoxazolone, benzoxazolone, isoxazolone, and fluorone. Preferably, the coupling-off group comprises a diacylamino group connected by the nitrogen atom contained therein to the coupling active position of the yellow coupler. Such groups include, e.g., a succinimido group, a maleinimido group, a phthalimido group, a 1methylimidazolidine-2,4-dion-3-yl group, a 1 -benzylimidoazolidine-2,4-dion-3 -yl group, a 5,5-dimethyloxazolidine-2,4-dion-3-yl group, a 5-methyl-5 propyloxazolidine-2,4-dion-3 -yl group, ,5-dimethylthiazolidine-2,4-dion-3 -yl group, a 5,5-dimethylimidazolidine-2,4-dion-3-yl group, a 3 methylimidazolidinetrion-l-yl group, a 1,2,4-triazolidine-3,5-dion-4-yl group, a 1 methyl-2-phenyl- 1 ,2,4-triazolidine-3 ,5-dion-t-yl group, a 1 -benzyl-2-phenyl- 1,2,4- triazolidine-3,5-dion4-yl group, a 5 -hexyloxy- 1 -methylimidazolidine-2,4-dion-3 -yl group, a 5 -methoxy- 1 -methylimidazolidine-2,4-dion- 3 -yl group, a 1 -benzyl-5 ethoxyimidazolidine-2,4-dion-3-yl group, and a l-benzyl-5dodecyloxyimidazolidine-2,4-dion-3-yl group.

Preferred yellow couplers for use in accordance with the invention are represented by the following formulas:

YELLOW- 1 YELLOW-2 YELLOW-3 YELLOW-4 wherein R1, R2, Q1 and Q2 each represent a substituent; Z represents an atomic group necessary to complete a nitrogen containing heterocyclic coupling-off group; Y represents an aryl group or a heterocyclic group; Q3 represents an organic residue required to form a nitrogen-containing heterocyclic group together with the illustrated nitrogen atom; and Q4 represents nonmetallic atoms necessary to form a 3- to 5-membered hydrocarbon ring or a 3- to 5-membered heterocyclic ring which contains at least one hetero atom selected from N, O, S, and P in the ring. Preferred couplers are of YELLOW-1 and YELLOW-4 wherein Q1 and Q2 each represent an alkyl group, an aryl group, or a heterocyclic group, and R2 represents an aryl or alkyl group, including cycloalkyl and bridged cycloalkyl groups, and more preferably a tertiary alkyl group. Particularly preferred yellow couplers for use in elements of the invention are represented by YELLOW-4, wherein R2 represents a tertiary alkyl group and Y represents an aryl group.

Examples of preferred yellow couplers of formula I include the following:

Dispersions of yellow image forming couplers which are substantially free of high boiling permanent solvents and nonionic polymeric stabilizers for use in the invention can be prepared by dissolving the couplers in a low boiling or partially water soluble auxiliary organic solvent, or by melting the couplers. The resulting liquid organic phase may then be mixed with an aqueous gelatin solution, and the mixture is then passed through a mechanical mixing device suitable for high shear or turbulent mixing generally suitable for preparing photographic emulsified dispersions, such as a colloid mill, homogenizer, microfluidizer, high speed mixer, ultrasonic dispersing apparatus, blade mixer, device in which a liquid stream is pumped at high pressure through an orifice or interaction chamber, Gaulin mill, blender, etc., to form small particles of the organic phase suspended in the aqueous phase. More than one type of device may be used to prepare the dispersions. The auxiliary organic solvent, if present, may then be removed by evaporation, noodle washing, or membrane dialysis. If not removed prior to coating in a photographic element layer, partially water soluble auxiliary organic solvents may diffuse throughout the hydrophilic colloid layers of the element, and be removed during photographic processing. The dispersion particles preferably have an average particle size of less than 2 microns, generally from about 0.02 to 2 microns, more preferably from about 0.02 to 0.5 micron.

These methods are described in detail in U.S. Patents 2,322,027, 2,787,544, 2,801,170, 2,801,171, 2,949,360, and 3,396,027.

Examples of suitable auxiliary solvents which can be used include: ethyl acetate, isopropyl acetate, butyl acetate, ethyl propionate, 2 ethoxyethylacetate, 2-(2-butoxyethoxy) ethyl acetate, triethylcitrate, dimethylformamide, 2-methyl tetrahydrofuran, triethyiphosphate, cyclohexanone, butoxyethyl acetate, methyl isobutyl ketone, methyl acetate, 4-methyl-2-pentanol, diethyl carbitol, 1,1,2-trichloroethane, 1 ,2-dichloropropane, and the like. Preferred auxiliary solvents include ethyl acetate and 2-(2-butoxyethyoxy) ethyl acetate.

The aqueous phase of the coupler dispersions preferably comprise gelatin as a hydrophilic colloid. This may be gelatin or a modified gelatin such as acetylated gelatin, phthalated gelatin, oxidized gelatin, etc. Gelatin may be baseprocessed, such as lime-processed gelatin, or may be acid-processed, such as acid processed ossein gelatin. Other hydrophilic colloids and ionic polymeric thickeners may also be used in combination with gelatin, such as a water soluble ionic polymer or copolymer including, but not limited to poly(acrylic acid), poly(sodium styrene sulfonate), and poly(2-acrylamido-2-methylpropane sulfonic acid). Copolymers of these polymers with hydrophobic monomers may also be used.

The solvent-free yellow image forming layers of the photographic elements of the invention may advantageously be used in combination with adjacent image forming hydrophilic colloid layers comprising cyan or magenta image dye forming couplers which are substantially free of high boiling solvents having a logP value of less than about 5.5. The log P parameter is a well-known measurement of the solubility of a compound in aqueous liquids compared to its solubility in a nonpolar organic solvent (octanol). The solvent-free yellow image forming layers may also be advantageously used in combination with solid substituted bisphenol light stabilizers.

Multicolor photographic elements in accordance with preferred embodiments of the invention preferably comprise a support bearing light sensitive image dye forming layers sensitized to the blue (approx. 380-500 nm), green (approx. 500-600 nm), and red (approx. 600-760 nm) regions of the electromagnetic spectrum. In accordance with a preferred embodiment of the invention, the element comprises cyan, magenta and yellow dye forming silver halide emulsion hydrophilic colloid layer units sensitized to the red, green and blue regions of the spectrum. Each unit can comprise a single emulsion layer or multiple emulsion layers sensitive to a given region of the spectrum. The layers of the element, including the layers of the image forming units, can be arranged in various orders as known in the art. It is within the scope of this invention, however, for the light sensitive material to alternatively or additionally be sensitive to one or more regions of the electromagnetic spectrum outside the visible, such as the infrared region of the spectrum. In most color photographic systems, color-forming couplers are incorporated in the light-sensitive photographic emulsion layers so that during development, they are available in the emulsion layer to react with the color developing agent that is oxidized by silver halide image development. Non-diffusing couplers are incorporated in photographic emulsion layers. When the dye image formed is to be used in situ, couplers are selected which form non-diffusing dyes. Color photographic systems can also be used to produce black-and-white images from non-diffusing couplers as described, e.g., by Edwards et al. in International Publication No. WO 93/012465.

The invention is particularly useful with color photographic print elements, and especially to photographic print elements designed for exposure though a negative film and projection display, such as motion picture print and intermediate films. In color photographic element printing, there are usually three records to record in the image area frame region of a print film, i.e., red, green and blue. The original record to be reproduced is preferably an image composed of sub-records having radiation patterns in different regions of the spectrum.

Typically it will be a multicolor record composed of sub-records formed from cyan, magenta and yellow dyes. The principles by which such materials form a color image are described in James, The Theory of the Photographic Process, Chapter 12, Principles and Chemistry of Color Photography, pp 335-372, 1977, Macmillan Publishing Co. New York, and suitable materials useful to form original records are described in Research Disclosure, December, 1987, Item 17643, published by Industrial Opportunities Ltd., Homewell Havant, Hampshire, P09 1EF, United Kingdom, and Research Disclosure, September 1994, Item 36544, published by Kenneth Mason Publications, Ltd., Emsworth, Hampshire P010 7DQ, England. Materials in which such images are formed can be exposed to an original scene in a camera, or can be duplicates formed from such camera origination materials, e.g., records formed in color negative intermediate films such as those identified by the tradenames Eastman Color Intermediate Films 2244, 5244 and 7244. Alternatively, the original record may be in the form of electronic image data, which may be used to control a printer apparatus, such as a laser printer, for selective imagewise exposure of a print film in accordance with the invention.

Image dyes formed in photographic print elements designed for direct or projection viewing generally have been found to be far more susceptible to degradation due to light exposures than dyes formed in camera negative films, which are typically stored in dark conditions. Accordingly, the photographic elements of the invention in accordance with particular embodiments of the invention preferably comprise photographic print elements. Relatively small grain, high chloride emulsions (e.g., emulsions having average grain size equivalent circular diameters of less than about 1 micron and halide contents of greater than 50 mole % chloride) are typically used in photographic print films and papers in order to optimize print image quality and enable rapid processing. Such emulsions typically result in relatively low speed photographic elements in comparison to camera negative films. Low speed is compensated for by the use of relatively high intensity print lamps or lasers for exposing such print elements. For comparison purposes, it is noted that print films and papers, such as motion picture color print films, e.g., when rated using the same international standards criteria used for rating camera negative films, would typically have an ISO speed rating of less than 10, which is several stops slower than the slowest camera negative films in current use.

In the following discussion of suitable materials for use in the emulsions and elements that can be used in conjunction with the invention, reference will be made to Research Disclosure, September 1994, Item 36544, available as described above, which will be identified hereafter by the term "Research Disclosure." The contents of the Research Disclosure, including the patents and publications referenced therein, are incorporated herein by reference, and the Sections hereafter referred to are Sections of the Research Disclosure, Item 36544.

Suitable silver halide emulsions and their preparation as well as methods of chemical and spectral sensitization are described in Sections I, and III IV. Vehicles and vehicle related addenda are described in Section II. Dye image formers and modifiers are described in Section X. Various additives such as UV dyes, brighteners, luminescent dyes, antifoggants, stabilizers, light absorbing and scattering materials, coating aids, plasticizers, lubricants, antistats and matting agents are described, for example, in Sections VI-IX. Layers and layer arrangements, color negative and color positive features, scan facilitating features, supports, exposure and processing conditions can be found in Sections XI-XX.

It is also contemplated that the materials and processes described in an article titled "Typical and Preferred Color Paper, Color Negative, and Color Reversal Photographic Elements and Processing," published in Research Disclosure, February 1995, Item 37038 also may be advantageously used with elements of the invention.

Photographic light-sensitive print elements of the invention may utilize silver halide emulsion image forming layers wherein chloride, bromide and/or iodide are present alone or as mixtures or combinations of at least two halides. The combinations significantly influence the performance characteristics of the silver halide emulsion. Print elements are typically distinguished from camera negative elements by the use of high chloride (e.g., greater than 50 mole% chloride) silver halide emulsions containing no or only a minor amount of bromide (typically less than 40 mole %), which are also typically substantially free of iodide. As explained in Atwell, U.S. Patent 4,269,927, silver halide with a high chloride content possesses a number of highly advantageous characteristics.

For example, high chloride silver halides are more soluble than high bromide silver halide, thereby permitting development to be achieved in shorter times.

Furthermore, the release of chloride into the developing solution has less restraining action on development compared to bromide and iodide and this allows developing solutions to be utilized in a manner that reduces the amount of waste developing solution. Since print films are intended to be exposed by a controlled light source, the imaging speed gain which would be associated with high bromide emulsions and/or iodide incorporation offers little benefit for such print films.

Photographic print elements are also distinguished from camera negative elements in that print elements typically comprise only fine silver halide emulsions comprising grains having an average equivalent circular diameter (ECD) of less than about 1 micron, where the ECD of a grain is the diameter of a circle having the area equal to the projected area of a grain. The ECDs of silver halide emulsion grains are usually less than 0.60 micron in red and green sensitized layers and less than 0.90 micron in blue sensitized layers of a color photographic print element. Such fine grain emulsions used in print elements generally have an aspect ratio of less than 1.3, where the aspect ratio is the ratio of a grain's ECD to its thickness. Such grains may take any regular shapes, such as cubic, octahedral or cubo-octahedral (i.e., tetradecahedral) grains, or the grains can take other shapes attributable to ripening, twinning, screw dislocations, etc. Typically, print element emulsions grains are bounded primarily by {100} crystal faces, since (100) grain faces are exceptionally stable. Specific examples of high chloride emulsions used for preparing photographic prints are provided in U.S. Patents 4,865,962; 5,252,454; and 5,252,456, the disclosures of which are here incorporated by reference.

The cyan and magenta dye forming couplers that may be used in the elements of the invention can be defined as being 4-equivalent or 2-equivalent depending on the number of atoms of Ag+ required to form one molecule of dye.

A 4-equivalent coupler can generally be converted into a 2-equivalent coupler by replacing a hydrogen at the coupling site with a different coupling-off group. The yellow couplers of Formula I are 2-equivalent couplers, as they comprise a heterocyclic coupling-off group. Various other coupling-off groups are well known in the art. Such groups can modify the reactivity of the coupler. Such groups can advantageously affect the layer in which the coupler is coated, or other layers in the photographic recording material, by performing, after release from the coupler, functions such as dye formation, dye hue adjustment, development acceleration or inhibition, bleach acceleration or inhibition, electron transfer facilitation, color correction and the like. Representative classes of such couplingoff groups include, for example, chloro, alkoxy, aryloxy, hetero-oxy, sulfonyloxy, acyloxy, acyl, heterocyclyl, sulfonamido, mercaptotetrazole, benzothiazole, alkylthio (such as mercaptopropionic acid), arylthio, phosphonyloxy and arylazo.

These coupling-off groups are described in the art, for example, in U.S. Patents 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.

Image dye forming couplers may be included in elements of the invention such as couplers that form cyan dyes upon reaction with oxidized color developing agents which are described in such representative patents and publications as: U.S. Patents 2,367,531; 2,423,730; 2,474,293; 2,772,162; 2,895,826; 3,002,836; 3,034,892; 3,041,236; 4,883,746 and "Farbkuppler- Eine Literature Ubersicht," published in Agfa Mitteilungen, Band III, pp. 156-175 (1961). Preferably such couplers are phenols and naphthols that form cyan dyes on reaction with oxidized color developing agent. Also preferable are the cyan couplers described in, for instance, European Patent Application Nos. 544,322; 556,700; 556,777; 565,096; 570,006; and 574,948.

Typical cyan couplers are represented by the following formulas:

CYAN-1

CYAN-2 CYAN-3 CYAN4 CYAN-5 CYAN-6 wherein R1 and Rs each represent a hydrogen or a substituent; R2 represents a substituent; R3 and R4 each represent an electron attractive group having a Hammett's substituent constant spara of 0.2 or more and the sum of the spara values of R3 and R4 is 0.65 or more; R6 represents an electron attractive group having a Hammett's substituent constant spara of 0.35 or more; X represents a hydrogen or a coupling-off group; Z1 represents nonmetallic atoms necessary for forming a nitrogen-containing, six-membered, heterocyclic ring which has at least one dissociative group. A dissociative group has an acidic proton, e.g. -NH-, -CH(R)-, etc., that preferably has a pKa value of from 3 to 12 in water. The values for Hammett's substituent constants can be found or measured as is described in the literature. For example, see C. Hansch and A.J. Leo, J. Med. Chem., 16, 1207 (1973); J. Med Chem., 20, 304 (1977); and J.A. Dean, Lange's Handbook of Chemistry, 12th Ed. (1979) (McGraw-Hill).

More preferable are cyan couplers of the following formulas:

CYAN-7 CYAN-8 wherein R7 represents a substituent (preferably a carbamoyl, ureido, or carbonamido group); R8 represents a substituent (preferably individually selected from halogen, alkyl, and carbonamido groups); Rg represents a ballast substituent; R10 represents a hydrogen or a substituent (preferably a carbonamido or sulphonamido group); X represents a hydrogen or a coupling-off group; and m is from 1-3. Couplers of the structure CYAN-7 are most preferable for use in elements of the invention.

Couplers that form magenta dyes upon reaction with oxidized color developing agent which can be incorporated in elements of the invention are described in such representative patents and publications as: U.S. Patents 2,600,788; 2,369,489; 2,343,703; 2,311,082; 2,908,573; 3,062,653; 3,152,896; 3,519,429 and "Farbkuppler - Eine Literature Ubersicht," published in Agfa Mitteilungen, Band III, pp. 126-156 (1961). Preferably such couplers are pyrazolones, pyrazolotriazoles, or pyrazolobenzimidazoles that form magenta dyes upon reaction with oxidized color developing agents. Especially preferred couplers are lH-pyrazolo [5,1-c]-1,2,4-triazole and lH-pyrazolo [1,5-b]-1,2,4- triazole. Examples of lH-pyrazolo [5,1-c]-1,2,4-triazole couplers are described in U.K. Patent Nos. 1,247,493; 1,252,418; 1,398,979; U.S. Patents 4,443,536; 4,514,490; 4,540,654; 4,590,153; 4,665,015; 4,822,730; 4,945,034; 5,017,465; and 5,023,170. Examples of lH-pyrazolo [1,5-b]-1,2,4-triazoles can be found in European Patent Applications 176,804; 177,765; U.S Patents 4,659,652; 5,066,575; and 5,250,400.

Typical pyrazoloazole and pyrazolone couplers are represented by the following formulas:

MAGENTA-1 MAGENTA-2 wherein Ra and Rb independently represent H or a substituent; Re is a substituent (preferably an aryl group); Rd is a substituent (preferably an anilino, carbonamido, ureido, carbamoyl, alkoxy, aryloxycarbonyl, alkoxycarbonyl, or N-heterocyclic group); X is hydrogen or a coupling-off group; and Za, Zb, and Zc are independently a substituted methine group, =N-, =C-, or -NH-, provided that one of either the Za-Zb bond or the Zb-Zc bond is a double bond and the other is a single bond, and when the Zb-Zc bond is a carbon-carbon double bond, it may form part of an aromatic ring, and at least one of Za, Zb, and Zc represents a methine group connected to the group Rb. Use of yellow image forming layers in accordance with the invention may be particularly useful in combination with magenta image forming layers comprising pyrazoloazole dye forming couplers of formula MAGENTA-1 to provide improved color reproduction performance.

Typical examples of photographic substituents which may be included in the yellow, cyan and magenta couplers which may be used in the elements of the invention include alkyl, aryl, anilino, carbonamido, sulfonamido, alkylthio, arylthio, alkenyl, cycloalkyl, and further to these exemplified are halogen, cycloalkenyl, alkynyl, heterocyclyl, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclyloxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imido, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclylthio, spiro compound residues and bridged hydrocarbon compound residues. Usually the substituent will have less than 30 carbon atoms and typically less than 20 carbon atoms. It is understood throughout this specification that any reference to a substituent by the identification of a group containing a substitutable hydrogen (e.g. alkyl, amine, aryl, alkoxy, heterocyclic, etc.), unless otherwise specifically stated, shall encompass not only the substituent's unsubstituted form, but also its form substituted with any other photographically useful substituents.

To control the migration of various components coated in a photographic layer, including couplers, 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 (also known as acylamino), carbamoyl, allcylsulfonyl, arysulfonyl, sulfonamido, and sulfamoyl groups wherein the substituents typically contain 1 to 40 carbon atoms. Such substituents can also be further substituted. Alternatively, the molecule can be made immobile by attachment to a polymeric backbone.

It may be useful to use a combination of couplers any of which may contain known ballasts or coupling-off groups such as those described in U.S.

Patents 4,301,235; 4,853,319 and 4,351,897.

If desired, the photographic element can be used in conjunction with an applied magnetic layer as described in Research Disclosure, November 1992, Item 34390. It is also specifically contemplated to use photographic elements according to the invention in combination with technology useful in small format film as described in Research Disclosure, June 1994, Item 36230.

Research Disclosure is published by Kenneth Mason Publications, Ltd., Dudley House, 12 North Street, Emsworth, Hampshire P010.7DQ, ENGLAND.

Photographic elements in accordance with the invention may comprise any conventional support materials, which may be reflective or transparent. Preferred supports for elements in accordance with the invention comprise transparent polymeric films, such as cellulose nitrate and cellulose esters (such as cellulose triacetate and diacetate), polycarbonate, and polyesters of dibasic aromatic carboxylic acids with divalent alcohols such as poly(ethylene terephthalate). In addition to the light sensitive image forming layers described above, the photographic elements of the invention may include further features and layers as are known in the art, including, e.g., antistatic, antihalation, subbing, interlayer, backing, and overcoat layers. Polyester supports, e.g., typically employ undercoat or primer layers to improve adhesion of other layers thereto. Such undercoat layers are well known in the art and comprise, e.g., a vinylidene chloride/methyl acrylate/itaconic acid terpolymer or vinyldene chloride/acrylonitrile/acrylic acid terpolymer as described in U.S. Patents 2,627,088; 2,698,235; 2,698,240; 2,943,937; 3,143,421; 3,201,249; 3,271,178; 3,501,301.

Photographic elements of the invention preferably comprise an antihalation layer comprising process removable filter dyes or silver. The antihalation layer may be located between the light sensitive layers and the support, or may be positioned on the back side of the support opposite to the light sensitive layers. The filter dyes and/or silver used in antihalation layers are preferably designed to be solubilized and removed or decolorized during photographic processing. Conventional processing of photographic print elements include the Kodak ECP-2B Process for motion picture print films, described in Kodak Publication No. H-24, Manual For Processing Eastman Color Films, the disclosure of which is hereby incorporated by reference.

The following examples illustrate the preparation of photographic elements in accordance with this invention.

Example 1 27.0g of yellow coupler Y-l and 13.5g of di-n-butyl phthalate (DBP) were dissolved in 54.0g of ethyl acetate at 650C. This oil phase solution was then combined with an aqueous phase solution consisting of 18.0g gelatin, 18.0g of a 10% solution of Alkanol-XC (Dupont), and 169.5g of distilled water.

This mixture was then passed through a Gaulin colloid mill five times followed by removal of ethyl acetate by rotary evaporation. Distilled water was then added back to form Dispersion A which consisted of 9.0% coupler and 6.0% gel.

Dispersions B through I were similarly prepared using yellow couplers Y-2 through Y-6 and comparison yellow couplers CY-1 through CY-3, respectively, in place of Y-l as described in Table I. Dispersions J through R were also similarly prepared using yellow couplers Y-1 through Y-6 and comparison yellow couplers CY-1 through CY-3, respectively, except that no di-n-butylphthalate was included in the oil phase and 183.0g of distilled water was employed in the aqueous phase.

Dispersion A was incorporated in a bi-layer monochrome photographic element (element 1) by coating the following layers on a gelatin subbed polyethylene terephthalate support with a rem-jet carbon black containing backing layer.

Layer 1: Blue Light Sensitive Layer AgCl cubic grain emulsion, 0.58 micron, spectrally sensitized with SD-1, 0.3336 mmole /Ag mole, 645.6 mg / sq. m.

AgCl cubic grain emulsion, 0.76 micron, spectrally sensitized with SD-1, 0.2669 mmole /Ag mole, 215.2 mg / sq. m.

Gelatin, 2797.6 mg / sq. m.

Yellow dye forming coupler (Y- 1) from Dispersion A, 1291.2 mg / sq. m.

Sequestrant cpd (SQ-1), 305.8 mg / sq. m.

Sequestrant cpd (SQ-2), 100.0 mg / sq. m.

Layer 2: Protective Overcoat Layer Gelatin, 977.0 mg / sq. m.

Poly (dimethyl siloxane) 200-CS, 65.9 mg / sq. m.

Poly (methyl methacrylate) beads, 5.03 mg /sq. m.

Soluble blue absorber dye (AD-3), 16.1 mg / sq. m.

Spreading aids.

Dispersions B through R were similarly incorporated into the described photographic element format in place of Dispersion A to form elements 2-9 and 1 '-9', respectively, as summarized in Table I. In these elements, the molar lay down of yellow image coupler was maintained constant.

The elements were exposed for 1/500 second by means of a 3000K Tungsten light source through a 0-3 neutral density step tablet, a heat-absorbing filter, and a filter designed to represent a motion picture color negative film. After exposure, the elements were processed through Process ECP-2B with the exception that those steps specific to sound track development were omitted. The process consisted of a prebath (10"), water rinse (20"), color developer (3'), stop bath (40"), first wash (40"), first fix (40"), second wash (40"), bleach (1'), third wash (40"), second fix (40"), fourth wash (1'), final rinse (10"), and then drying with hot air.

The ECP-2B Prebath consists of: Water 800 mL Borax (decahydrate) 20.0 g Sodium sulfate (anhydrous) 100.0 g Sodium hydroxide 1.0 g Water to make 1 liter pH @ 26.7"C is 9.25+1- 0.10 The ECP-2B Color Developer consists of: Water 900 mL Kodak Anti-Calcium, No. 4 (40% solution of a pentasodium 1.00 mL salt of nitrilo-tri(methylene phosphonic acid) Sodium sulfite (anhydrous) 4.35 g Sodium bromide (anhydrous) 1.72 g Sodium carbonate (anhydrous) 17.1 g Kodak Color Developing Agent, CD-2 2.95 g Sulfuric acid (7.0N) 0.62 mL Water to make 1 liter pH @ 26.7"C is 10.53+1-0.05 The ECP-2B Stop Bath consists of: Water 900 mL Sulfuric acid (7.0N) 50 mL Water to make 1 liter pH @ 26.70C is 0.90 The ECP-2B Fixer consists of: Water 800 mL Ammonium thiosulfate (58.0% solution) 100.0 mL Sodium bisulfate (anhydrous) 13.0 g Water to make 1 liter pH @ 26.7"C is 5.00 +/- 0.15 The ECP-2B Ferricyanide Bleach consists of: Water 900 mL Potassium ferricyanide 30.0 g Sodium bromide (anhydrous) 17.0 g Water to make 1 liter pH @ 26.70C is 6.50+1- 0.05 The Final Rinse solution consists of: Water 900 rnL Kodak Photo-Flo 200 (TM) Solution 3.0 mL Water to make 1 liter Processing of the exposed elements was done with the color developing solution adjusted to 36.70C. The stopping, fixing, bleaching, washing, and final rinsing solution temperatures were adjusted to 26.7"C.

The optical density due to dye formation was then measured on a densitometer using filters in the densitometer appropriate to the intended use of the photographic element. Dye density was then graphed versus log(exposure) to form the Red, Green, and Blue D-logE characteristic curves of the photographic elements. The maximum blue density (Dmax) for each element, and the percentage of blue Dmax lost in the element employing a solvent-free yellow imaging layer relative to the comparable element containing coupler solvent in the yellow imaging layer is reported in Table I. In some cases, elements containing solvent-free dispersions of the comparative yellow couplers exhibited decreased blue density with increased exposure beyond Dmax. This is reported in Table I as the amount of blue density formed at the highest level of exposure (Emax) for each element. The percentage of blue density lost at Emax in the element employing a solvent-free yellow imaging layer relative to the comparable element containing coupler solvent in the yellow imaging layer is also reported in Table I.

Table I - Coupler Dispersion Reactivity Data Element No. Disp Yellow Solvent Dma % Dmax Blue % Decreased Coupler x Loss Density @ Blue Density Upon Emax i), Emax Upon Solvent Solvent Removal Removal 1 (Comparison) A Y-1 DBP 3.64 3.59 1' (Invention) J Y-1 None 3.28 9.9 3.25 9.5 2 (Comparison) B Y-2 DBP 3.29 3.25 2' (Invention) K Y-2 None 3.04 7.7 3.00 7.7 3 (Comparison) C Y-3 DBP 3.57 3.56 3' (Invention) L Y-3 None 3.40 5.9 3.35 5.9 4 (Comparison) D Y-4 DBP 3.33 3.31 4' (Invention) M Y-4 None 3.07 7.8 3.03 8.5 5 (Comparison) E Y-5 DBP 3.08 3.04 5' (Invention) N Y-5 None 3.07 0.3 2.98 2.0 6 (Comparison) F Y-6 DBP 3.64 3.61 6' (Invention) O Y None 3.38 6.4 3.32 8.0 7 (Comparison) G CY-1 DBP 3.47 3.44 7' (Comparison) P CY-1 None 3.06 11.8 2.80 18.6 8 (Comparison) H CY-2 DBP 3.41 3.40 8' (Comparison) Q CY-2 None 3.04 10.9 2.14 37.1 9 (Comparison) I CY-3 DBP 2.23 2.23 9' (Comparison) R CY-3 None 1.73 22.4 1.73 22.4 These data clearly show that the yellow couplers of the present invention exhibited substantially less blue Dmax loss upon removal of coupler solvent from the yellow imaging layer than comparison yellow couplers. The data also show that the yellow couplers of the present invention exhibited higher blue density at Emax and showed much less blue density loss at Emax upon removal of coupler solvent from the yellow imaging layer.

The processed elements were then irradiated with light from a high intensity 50 Klux Xenon light source for 6 days. After irradiation, the dye density was measured again as described above. The amount of blue density lost due to light fading from an initial blue density of 2.5 for each element is reported in Table II.

Table II - 6 Day 50 Klux Light Fade Data Element No. Dispersion Yellow Solvent Delta Blue % Increased Coupler Density Stability Upon Solvent Removal 1(Comparison) A V-1 DBP -1.43 1' (Invention) J Y-1 None -0.93 35 2 (Comparison) B V-2 DBP -1.25 2' (Invention) K V-2 None -0.37 70 3 (Comparison) C V-3 DBP -1.52 3' (Invention) L V-3 None -0.59 61 4 (Comparison) D VA DBP -0.41 4' (Invention) M Y-4 None -0.19 54 5 (Comparison) E Y-5 DBP -0.21 5' (Invention) N Y-5 None -0.13 38 6 (Comparison) F V-6 DBP -1.50 6' (Invention) O Y None -0.82 45 7 (Comparison) G CY-1 DBP -0.44 7' (Comparison) P CY-1 None -0.39 11 8 (Comparison) H CY-2 DBP -0.35 8' (Comparison) Q CY-2 None -0.34 3 9 (Comparison) I CY-3 DBP * 9' (Comparison) R CY-3 None * * initial maximum blue density less than 2.5 These data clearly show that the removal of coupler solvent from the yellow imaging layer resulted in a greater improvement in yellow dye light stability with the couplers of the present invention.

The following structures represent compounds utilized in the above described photographic elements not previously illustrated.

SD-1 soluble blue filter dye AD-3 sequestrant SQ-1 sequestrant SQ-2

Example 2 A multilayer photographic element in accordance with the invention may be prepared by coating the following layers on a gelatin subbed polyethylene terephthalate support: Layer 1: Blue Light Sensitive Layer AgCl cubic grain emulsion, 0.58 micron, spectrally sensitized with SD-1, 0.3336 mmole / Ag mole, 645.6 mg t sq. m.

AgCl cubic grain emulsion, 0.76 micron, spectrally sensitized with SD-1, 0.2669 mmole I Ag mole, 215.2 mg / sq. m.

Yellow dye forming coupler (Y-1), 1291.2 mg / sq. m.

Stabilizer (ST-1), 322.8 mg / sq. m.

Sequestrant cpd (SQ-1), 305.8 mg / sq. m.

Sequestrant cpd (SQ-2), 100.0 mg / sq. m.

Gelatin, 2797.6 mg / sq. m.

Spreading aids.

Layer 2: Interlayer Oxidized developer scavenger (SC-1), 75.3 mg / sq. m.

Gelatin, 645.6 mg / sq. m.

Spreading aids.

Layer 3: Red Light Sensitive Layer AgClBr cubic grain emulsion, 25% Br, 0.15 micron, spectrally sensitized with SD-2, 0.1808 mmole / Ag mole, supersensitizer compound (SS-1), 0.6327 mmole / Ag mole, 397.0 mg I sq. m.

AgClBr cubic grain emulsion, 25% Br, 0.24 micron, spectrally sensitized with SD-2, 0.1356 mmole / Ag mole, supersensitizer compound (SS-1), 0.7444 mmole / Ag mole, 44.1 mg / sq. m.

Cyan dye forming coupler (C-l), 914.6 mg / sq. m.

Coupler Solvent (S-l), 548.8 mg / sq. m.

Coupler Solvent (S-2), 548.8 mg / sq. m.

Oxidized developer scavenger (SC-1), 12.9 mg / sq. m.

Gelatin, 3410.9 mg / sq. m.

Spreading aids.

Layer 4: Interlayer Oxidized developer scavenger (SC-1), 75.3 mg / sq. m.

Gelatin, 645.6 mg / sq. m.

Spreading aids.

Layer 5: Green Light Sensitive Layer AgClBr cubic grain emulsion, 25% Br, 0.15 micron, spectrally sensitized with SD-3, 0.5273 mmole / Ag mole, supersensitizer compound (SS-1), 1.1212 mmole / Ag mole, 419.6 mg / sq. m.

AgC1Br cubic grain emulsion, 25% Br, 0.24 micron, spectrally sensitized with SD-3, 0.4785 mmole / Ag mole, supersensitizer compound (SS-l), 1.3902 mmole / Ag mole, 32.3 mg / sq. m.

Magenta dye forming coupler (M-1), 645.6 mg / sq. m.

Coupler Solvent (S-1), 193.7 mg / sq. m.

Oxidized developer scavenger (SC-1), 53.8 mg / sq. m.

Gelatin, 1915.3 mg I sq. m.

Spreading aids Layer 6: Protective Overcoat Layer Poly (dimethyl siloxane) 200-CS, 65.9 mg / sq. m.

Poly (methyl methacrylate) beads, 5.0 mg / sq. m.

Gelatin, 977.0 mg / sq. m.

Soluble green absorber dye (AD-1), 32.3 mg / sq. m.

Soluble green absorber dye (AD-2), 32.3 mg / sq. m.

Soluble blue absorber dye (AD-3), 16.1 mg / sq. m.

Soluble red absorber dye (AD4), 110.8 mg / sq. m.

Gelatin hardener.

Spreading aids.

The following structures represent additional compounds in the above described photographic element.

solvent S-l solvent S-2

0 stabilizer Jl oH o' Me ST-i t-Bu Bu-t Me Me C1 OO 1111 YD-1 (CR3) 3CCCCNH N t"CH3 NHS02C16H33 CH3CH2-N CH2CH3 803 OH OH N=N 4Na+ AD-i -OgS' co2 02C CH=CH-CH AD-2 NWOH / 2 2 (HNEt3)+ 2Na 43 ' 03 3 AD4 green sensitizing dye SD-3 supersensitizer SS-1 magenta coupler M-l scavenger SC-1

red sensitizing dye SD-2 cyan coupler C-i

This invention has been described in detail with particular reference to preferred embodiments thereof. It will be understood that variations and modifications can be made within the spirit and scope of the invention.

Claims (14)

We claim:

1. A silver halide light sensitive photographic element comprising a support bearing at least one yellow image forming hydrophilic colloid layer comprising yellow image dye forming coupler of Formula I:

Formula I wherein R represents a substituent, Y represents an aryl group or a heterocyclic group, and Z represents a non-metallic atomic group necessary to complete with the indicated nitrogen atom a nitrogen-containing heterocyclic coupling-off group, wherein the yellow image forming layer is substantially free of high boiling permanent solvents and nonionic polymeric stabilizers.

2. The element of claim 1, wherein R represents an aryl or alkyl group.

3. The element of claim 1, wherein R represents a tertiary alkyl group.

4. The element of any one of claims 1-3, wherein Y represents an aryl group.

5. The element of any one of claims 14, wherein Z represents the atoms necessary to complete a 5- or 6-membered heterocyclic ring.

6. The element of any one of claims 1-4, wherein Z represents the atoms necessary to complete a 2,5-dioxoimadazolidine, 2,3,5-trioxoimidazolidine, 2,5-dioxotriazolidine, 3,5-dioxotriazolidine, 2,4-oxozolidinediontriazolidine, 2,4thiazolidinediontriazolidine, pyridone, pyrimidone, pyrazone, tetrazolone, tetrazole, imidazole, triazole, imidazolone, triazolone, pyrazolone, isothioazolone, quinaoxazolone, benzoxazolone, isoxazolone, or fluorone heteroring.

7. The element of any one of claims 14, wherein Z represents the atoms necessary to complete diacylamino group connected by the nitrogen atom contained therein to the coupling active position of the yellow coupler.

8. The element of any one of claims 1-4, wherein Z represents the atoms necessary to complete a succinimido group, a maleinimido group, a phthalimido group, a l-methylimidazolidine-2,4-dion-3-yl group, a 1benzylimidoazolidine-2,4-dion-3-yl group, a 5,5-dimethyloxazolidine-2,4-dion-3-yl group, a 5-methyl-5-propyloxazolidine-2,4-dion-3-yl group, a 5,5dimethylthiazolidine-2,4-dion-3-yl group, a 5,5-dimethylimidazolidine-2,4-dion-3yl group, a 3-methylimidazolidinetrion-1-yl group, a 1,2,4-triazolidine-3,5-dionX yl group, a 1-methyl-2-phenyl-l,2,4-triazolidine-3,5-dion4-yl group, a 1-benzy1-2- phenyl-1,2,4-triazolidine-3,5-dion-4-yl group, a 5 -hexyloxy- 1 -methylimidazolidine- 2,4-dion-3-yl group, a 5- methoxy-1-methylimidazolidine-2,4-dion-3-yl group, a 1 benzyl-5-ethoxyimidazolidine-2,4-dion-3-yl group, or a 1-benzyl-5 dodecyloxyimidazolidine-2,4-dion-3 -yl group.

9. The element of any one of claims 1-8, having an effective ISO speed rating of less than about 10.

10. The element of any one of claims 1-9, wherein the yellow image forming layer comprises silver chloride or bromochloride emulsion grains comprising greater than 50 mole% chloride.

11. The element of claim 10, wherein the yellow image forming layer emulsion grains have an average equivalent circular diameter of less than 1 micron and an aspect ratio of less than 1.3.

12. The element of any one of claims 1-11, comprising a support bearing in sequential order on one side thereof at least one yellow image forming hydrophilic colloid layer substantially free of high boiling permanent solvent and nonionic polymeric stabilizers comprising a blue-sensitive silver halide emulsion and yellow image dye forming coupler of Formula I, at least one cyan image forming hydrophilic colloid layer comprising red-sensitive silver halide emulsion and cyan image dye forming coupler, and at least one magenta image forming hydrophilic colloid layer comprising green-sensitive silver halide emulsion and magenta image dye forming coupler.

13. The element of claim 12, wherein each of the blue-sensitive, red-sensitive, and green-sensitive silver halide emulsions comprise silver chloride or silver bromochloride emulsion grains comprising greater than 50 mole% chloride.

14. The element of claim 13, wherein each ofthe red-sensitive and green-sensitive silver halide emulsions comprise emulsion grains having an average equivalent circular diameter of less than 0.60 micron, and the bluesensitive silver halide emulsion comprises emulsion grains having an average equivalent circular diameter of less than 0.90 micron.