PHOTOGRAPHIC MATERIAL

Abstract: A photographic material is described having a silver halide emulsion layer that includes a wandering magenta dye-forming coupler compound, and a silver halide emulsion layer that includes a low-reactivity yellow dye-forming coupler, wherein either the yellow coupler layer or a layer between the magenta coupler layer and the yellow coupler layer comprises an oxidized developer competitor compound having a high reactivity.

Description: PHOTOGRAPHIC MATERIAL Field of the Invention TJiis invention relates to photography and to radiation—sensitive silver halide photographic materials. Background of the Invention Color silver halide photographic materials rely on coupler compounds to form dyes that make up the image recorded in such materials. Usually a yellow dye—forming coupler will be associated with a blue-sensitive silver halide emulsion layer, a magenta dye-forming coupler will be associated with a green—sensitive silver halide emulsion layer, and a cyan dye-forming coupler will be associated with a red—sensitive silver halide emulsion layer. These couplers will be referred to below simply as yellow couplers, magenta couplers, and cyan couplers. With color negative materials, the material is exposed to light and processed with a color developer that imagewise forms a silver image and a dye image. The silver image is formed by the color developer reducing the exposed silver halide to form silver and oxidized color developer. The dye image is formed by the reaction of oxidized color developer with dye—forming coupler. The silver image is bleached and solubilized for removal, leaving only a negative color dye image. This image is then used to expose another color negative material to form a positive color dye image. With reversal materials, the material is generally exposed and processed with a black-and- white developer to form a negative silver image in each layer. The remaining undeveloped silver halide thus forms a positive imagewise pattern. The remaining silver halide is then fogged and processed in a color developer to form a dye image along with the silver. All the silver is then bleached and solubilized for removal, leaving only the positive color dye .image. There are many known classes of compounds that are useful as couplers in photographic materials. 5-Pyrazolone compounds and pyrazoloazole (e.g., pyrazolotriazole) compounds are well—known as magenta couplers. Such couplers are described in, for example, James, The Theory of the Photographic Process. MacMillan, 1977. Couplers may be of the 2-equivalent or the 4—equivalent type. With 4—equivalent couplers, a hydrogen atom is cleaved from the coupler compound at the coupling position when the compound couples with the oxidized color developer. This type of coupler requires the reduction of four moles of silver halide to silver in order to form one mole of dye. With 2—equivalent couplers, a coupling—off group, such as halogen, is cleaved from the coupler compound at the coupling position during coupling with oxidized color developer. This type of coupler requires the reduction of two moles of silver halide to silver to form one mole of dye. Certain magenta couplers can wander out of the layer in which they are coated. It has now been discovered that when such magenta couplers are used in a photographic material containing a yellow coupler having a low enough relative reactivity with oxidized developer compared to the reactivity of the magenta coupler with oxidized developer, unwanted dye can be formed as a result of reaction between magenta coupler that has wandered out of its layer and developer that has been oxidized by reaction with silver halide from the yellow coupler layer. This results in undesirable magenta contamination of the yellow record of the photographic material. Summarv of the Invention This problem is addressed by the present invention., According to the invention, there is provided a photographic material comprising a support having thereon: a first silver halide emulsion layer that includes a magenta coupler compound, and a second silver halide emulsion layer that includes a yellow coupler, wherein the yellow coupler layer or a layer between the first silver halide emulsion layer and the second silver halide emulsion layer comprises an oxidized developer competitor compound having a relative reaction rate, as defined herein, of at at least 1.6, the yellow coupler having a relative reactivity with oxidized color developer such that, in the absence of the oxidized developer competitor, dye is formed outside the first silver halide emulsion layer as a result of reaction between the magenta coupler and developer that has been oxidized by reaction with silver halide from the second silver halide emulsion layer. The material of the invention provides photographic images while the problem of magenta dye contamination of the yellow record is substantially alleviated. Description of the Preferred Embodiments The magenta couplers useful in the practice of the invention can be a member of any of the known classes of couplers that are well-known in the art, as described for example in the above—referenced James. These include both 5-pyrazolone couplers and pyrazoloazole couplers such as pyrazolotriazole couplers. In order to achieve the benefit of the invention, the magenta coupler should be one that is susceptible to wandering out of the layer in which it is coated. The degree of susceptibility to wandering that it should have, however, will vary with factors such as th.e reactivity of the magenta coupler with oxidized developer, the choice of yellow coupler and its reactivity with oxidized developer, the processing conditions, the concentration of the magenta coupler, and the concentration of the yellow coupler. High concentrations of the magenta coupler, low concentrations of the yellow coupler, high reactivity and/or extinction of the magenta coupler, low reactivity and/or extinction of the yellow coupler, and combinations thereof are all factors that would allow the invention to be practiced with a magenta coupler having a relatively low susceptibility to wandering compared to the situation where those factors reversed (e.g., low concentrations of the magenta coupler, etc.). As discussed above, the magenta coupler used in the practice of the invention can be from any class. One such class of couplers is the 5-pyrazolone class, which can be represented by the formula: N- -^ (I) ΛΛ wherein R, represents a carbonamido group, an arylamino (preferably anilino) group, a ureido group, a sulfonamido group, an alkylamino group, or a heterocyclic amino group, R-2 represent a substituted or unsubstituted aryl group, and X represents hydrogen, or a group capable of being released by a coupling reaction with an oxidized aromatic primary amine developing agent. This group is hereinafter referred to as a coupling—off group. Coupling—off groups are known in the art and may include a group containing an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic, aromatic, or heterocyclic sulfonyl group, or an aliphatic, aromatic, or heterocyclic carbonyl group that is bonded to the coupling active carbon via an oxygen atom, a nitrogen atom, a sulfur atom, or a carbon atom, a halogen atom, an aromatic azo group, and the like. The aliphatic, aromatic, or heterocyclic group contained in such coupling-off groups may have one or more substituents, as described below. Examples of coupling-off groups include a halogen atom (e.g., fluorine, chlorine, bromine), an alkoxy group (e.g., ethoxy, dodecyloxy, carboxypropyloxy), an aryloxy group (e.g., 4-chlorophenoxy group, a 4-methoxyphenoxy group), an acyloxy group (e.g., an acetoxy group, a tetradecanoyloxy group), an aliphatic or aromatic sulfonyloxy group (e.g., a methanesulfonyloxy group, a toluenesulfonyloxy group), an acylamino group (e.g., a dichloroacetylamino group, a trifluoroacetylamino group), an aliphatic or aromatic sulfonamido group (e.g., a methanesulfonamido group, a p—toluenesulfonamide group), an alkoxycarbonyloxy group (e.g., an ethoxycarbonyloxy group, a benzyloxycarbonyloxy group), an aryloxycarbonyloxy group (e.g., a phenoxycarbonyloxy group), an aliphatic, aromatic or heterocyclic thio group (e.g., an ethylthio group, a phenylthio group), a carbamoylamino group (e.g., an N—methylcarbamoylamino group, an N-phenylcarbamoylamino group), a 5-membered or 6—membered nitrogen—containing heterocyclic group (e.g., an imidazolyl group, a pyrazolyl group), an imido group (e.g., a succinimido group, a hydantoinyl group), an aromatic azo group (e.g., a phenylazo group), and the like. The aliphatic, aromatic, or heterocyclic groups included in X and the groups shown by R-, and R 2 may be substituted by a substituent such as, for example, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group (e.g., a methyl group, a t—octyl group, a dodecyl group, a trifluoromethyl group, etc.), an alkenyl group (e.g., an allyl group, an octadecenyl group, etc.), an aryl group (e.g., a phenyl group, a p-tolyl group, a naphthyl group, etc.), an alkoxy group (e.g., a methoxy group, a benzyloxy group, a methoxyethoxy group, etc.), an aryloxy group (e.g., a phenoxy group, a 2,4—di—tert—amylphenoxy group, a 3—tert—butyl—4—hydroxyphenoxy group, etc.), an acyl group (e.g., an acetyl group, a benzoyl group, etc.), a sulfonyl group (e.g., a methanesulfonyl group, a toluenesulfonyl group, etc.), a carboxy group, a sulfo group, a cyano group, a hydroxy group, an amino group (e.g., a primary amino group, a dimethylamino group, etc.), a carbonamido group (e.g., an acetamido group, a trifluoroacetamido group, a tetradecanamido group, a benzamido group, etc.), a sulfonamido group (e.g., a methanesulfonamido group, a hexadecanesulfonamido group, a p—toluenesulfonamido group, etc.), an acyloxy group (e.g., an acetoxy group, etc.), a sulfonyloxy group (e.g., a methanesulfonyloxy group, etc.), an alkoxycarbonyl group (e.g., a dodecyloxycarbonyl group, etc.), an aryloxycarbonyl group (e.g., phenoxycarbonyl group, etc.), a carbamoyl group (e.g., a dimethylcarbamcyl group, a tetradecylcarbamoyl group, etc.), a sulfamoyl group (e.g., a methylsulfamoyl group, a hexadecylsulfamoyl group, etc.), an imido group (e.g., a succini ido group, a phthali ido group, an octadecenylsuccinimido group, etc.), a heterocyclic group (e.g., a 2-pyridyl group, a 2-furyl group, a 2—thienyl group, etc.), an alkylthio group (e.g., a methylthio group, etc.), and an arylthio group (e.g., a phenylthio group, etc.). Another useful class of magenta couplers are pyrazoloazole couplers. Pyrazoloazole couplers useful in the practice of the invention include those according to the formula: (II) Z , wherein R represents hydrogen or a substituent, X is as defined above for formula (I), and Z represents the non—metallic atoms necessary to complete a heterocyclic ring. A more specific expression of compounds according to formula (II) is made by reference to formula (III): , wherein R-. represents hydrogen or a substituent, X is as described above for formula (I), Z , Z, , and Z each represents a substituted or unsubstituted methine group, =N-, or -NH-, one of either the Za-Z,b bond or the Z,b-Z„e bond is a double bond with the other being a single bond, when the Z,b—Ze„ bond iβ a carbon—carbon double bond, it may form part of an aromatic ring, and when any one of R-,, X, and a substituted methine group represented by Z , Z, , or Z is a divalent or polyvalent group, it may form a dimer or a polymer... As the magenta coupler used in the practice of the invention is preferably susceptible to wandering, it will include nόn—polymeric couplers according to formulas (I) or (II); however, it may also be a polymer, oligomer, or dimer coupler. Such couplers are included in the description of formula (II) above. In the case of formula (I), any of R.,, R 2 , or X may also be a divalent or a more polyvalent group to form an oligomer such as a dimer, etc., or may connect a polymeric main chain and a coupler skeleton to form a polymeric coupler. If the magenta coupler is a polymeric coupler, low molecular weight polymer chains or polymer compositions containing unreacted coupler monomer that would exhibit a tendency to wander are preferred. A typical amount of polymeric coupler that would be used in a photographic material will generally represent a number of polymer molecule chains having a distribution of varying molecular weights. The molecular weight of the polymer is usually described as having a single molecular weight, which is actually a mean or average molecular weight around which the actual molecular weights of the molecules are distributed. Thus, some so-called high molecular weight polymeric couplers may contain a sufficient number of low molecular weight molecules so as to make wandering a problem. Such polymeric couplers are intended to be included within the scope of the present invention. Examples of magenta couplers useful in the practice of the invention are presented below. M-l The yellow coupler useful in the practice of the invention can be essentially any type of yellow coupler, as is well—known in the art. The reactivity of the yellow coupler with oxidized color developer must be low enough so that, in the absence of the oxidized developer competitor, magenta dye would be formed as a result of reaction between magenta coupler that has wandered out of its layer and developer that has been oxidized by reaction with silver halide from the yellow coupler layer. The selection of a yellow coupler that will benefit from practice of the present invention depends on a number of factors, including the specific magenta coupler involved and its reactivity with oxidized color developer, the choice of oxidized color developer, the concentrations of the yellow and magenta couplers, and other factors affecting the reaction kinetics of oxidized developer and couplers (e.g., pH) . One skilled in the art would know the relative reactivities of yellow couplers in various photographic systems. For example, U.S. Patents, 4,710,453, 4,738,917, and 4,820,614, the disclosures of which are incorporated herein by reference, describe relative reactivities of couplers in color negative systems, such as color paper. The present invention is particularly applicable to color reversal systems, which, unlike color negative systems, do not offer the option of compensating for unwanted magenta dye stain during the printing process. In a preferred embodiment of the invention, the photographic material is a reversal material, such as Kodak Ektachrome or Fuji Fujichrome . For a reversal material, the yellow coupler preferably has a relative reactivity, as defined below, of not greater than 0.9. In this embodiment, the relative reactivity of the yellow coupler is determined as follows. A photographic element is prepared by coating a cellulose acetate—butyrate film support with a photosensitive layer containing 3.77 gm/m 2 gelatin, 0.76 gm/m2 silver 2 bromoiodide emulsion, and 2.7 mmole/m of the yellow coupler which had been dispersed in half its weight of dibutylphthalate. The photosensitive layer is overcoated 2 with a layer containing gelatin at at 1.08 gm/m and bis—vinyl sulfonyl methyl ether at 1.75 weight percent based upon total gelatin.. The sample is imagewise exposed and processed ® © using Kodak E—6 processing (E—6 processing is described in British Journal of Photography Annual. 1977, pp. 194—197). The relative reactivities represent the status A blue D—max obtained for the sample compared to that obtained for an identical coating, but containing a coupler having the structure: Examples of yellow couplers useful in the practice of the invention along with their relative reactivity values are presented below. The oxidized developer competitor compound useful in the practice of the invention has a relative rjsaction rate of at least 1.6. Such competitor compounds are described as "quencher" compounds in European patent application publication no. 326,406, the disclosure of which is incorporated herein by reference. The relative reaction rate herein considered is what can be determined as a relative value obtainable by measuring the dye density of the color image that coupler N forms after the competitor has been mixed with said coupler, incorporated with a silver halide emulsion, and subjected to color development. Coupler N The ratio of reaction activity of a competitor compound with coupler N, represented as R, can be TN r defined in a formula as R = , wherein DM represents DM « density of a color image of coupler N when a competitor compound is not used; DM 1 represents the density of the color image of the coupler N when a competitor compound is added in a quantity of 1/10 mol against coupler N. The reaction rate of a competitor with the oxidation product of a color developing agent can be determined as a relative value by finding R for the competitor against coupler N in the above formula. The oxidized developer competitor compound may be incorporated in any layer between the magenta coupler layer and the yellow coupler layer, or within the yellow coupler layer. This layer can be a yellow filter layer, such as a Carey Lea silver layer or a yellow filter dye-containing layer, or it can be a separate interlayer. The effectiveness of the oxidized developer competitor will be felt to a greater extent when the yellow coupler layer and the magenta coupler layer are closer in physical proximity. Thus, preferred embodiments are contemplated when there are no additional silver halide layers between the magenta coupler layer and the competitor layer, between the yellow coupler layer and the competitor layer, or both. The competitor is preferably incorporated in the material 2 at levels of from about 0.03 g/ to about 0.22 2 g/m , although other levels may be useful. An especially preferred class of oxidized developer compounds is described in U.S. Patent 4,923,787, the disclosure of which is incorporated herein by reference. Such compounds have the formula: (IV) (R1 ) »V• -S / —NHNHC0R2, wherein R represents an electron donating group, 2 R represents hydrogen, alkyl, alkoxy, aryl, aryloxy, aralkyl or amino of the formula -NHR 3, where R3 is phenyl or benzyl, with the proviso that at least one of the substituents R ,1 2 and R (a) represents (1) a ballast group of sufficient size as to render the hydrazide compound non-diffusible in the photographic element prior to development in alkaline processing solution and (b) comprises a polar group, and n is 0, 1 or 2. According to f- rmula (IV), R substituents, which are electron donating groups, include alkyl, which can be substituted or unsubstituted, straight or branched chain, having fro 1 to about 20 carbon atoms, preferably from about 8 to about 16 carbon atoms; alkoxy, which can be substituted or an unsubstituted, straight or branched chain, having from 1 to about 20 carbon atoms, preferably from about 8 to about 16 carbon atoms; carboxy; carbonamido naving the formula -NR 4 C0R 5 ; sulfonamido having the -NR 4 S0 7 R 5 ; or amino having the formula —NR 4R5 where R4 is hydrogen or alkyl having from 1 to about 8 carbon atoms and R 5 is as defined for R4 or is a benzyl or a phenyl group which may be substituted. 2 R substituents that are alkyl or alkoxy can be as defined for these same substituents in R 1, or R2 can be substituted or unsubstituted aryl or substituted or unsubstituted aryloxy having from 6 to about 30 carbon atoms, such as phenyl, phenoxy, naphthyl or naphthoxy. 2 When R represents phenyl or phenoxy it is preferred that the aryl ring have a hydrogen bonding substituent in a position ortho to the point of attachment of the carbonyl group to a hydrazide nitrogen atom. Preferred hydrogen bonding groups include hydroxy, primary or secondary amino groups of the formula —NR 4R5, sulfonamido of the formula 4 — HS0 9 R , carbonamido of the formula 4 ~ 4 -NR COR , and ureido of the formula -NHCONHR where R 4 and 5 can be hydrogen or alkyl of from 5 1 to about 8 carbon atoms and R is as defined for R or a benzyl or phenyl group. These groups can also be present as 2 substituents on R alkyl groups or on other 2 positions of R aryl groups. A polar group which can represent R or 2 R can be a single group or a combination of groups which have a tr constant which is more negative than —1.0. The ir constant is defined by C. Hansch, A. Leo, S. Unger, K. Hwan Kim, D. Nikaitani and E. T. Lien, in JOURNAL OF ORGANIC CHEMISTRY. 11, 1973 (pp. 1 2 1207-1216),. The R or R polar group or groups include, but are not limited to, /* —# \ -NHS0 2 CH 3 , -NHS0 2 aryl, — ζ - —OH, -CH 2 0H, -NH 2 , -C00H, -C0NH 2 , -NHC0NH 2> -NHCSNH 2 , -N + (R°) 3 , -SO -S0 2 and -•. J. These groups tend to increase the surfactant nature of the hydrazine during alkaline processing. The alkyl, alkoxy, aryl, aryloxy, aralkyl and benzyl groups which are represented by one or 1 2 3 4 5 more of R , R , R , R and R can be substituted with halogen atoms, for example chlorine, or with haloalkyl groups, for example trifluoromethyl, or with -N0 - and - -NH Examples of oxidized developer competitor compounds useful in the practice of the invention are disclosed in the above-referenced EP 326,406 and U.S. 4,923,787, and include: CO O to to O Cπ O Cπ Cπ to CO to to Cπ O π O Cπ <-π The support of the element of the invention can be any, of a number of well—known supports for photographic elements. These include polymeric films such as cellulose esters (e.g., cellulose triacetate and diacetate) and polyesters of dibasic aromatic carboxylic acids with divalent alcohols (e.g., poly(ethylene terephthalate)), paper, and polymer- coated paper. Such supports are described in further detail in Research Disclosure. December, 1989, Item 308119 [hereinafter referred to as Research Disclosure II τ Section XVII. The silver halide emulsion used in the practice of the invention can contain, for example, silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, or mixtures thereof. The emulsions can include coarse, medium, or fine silver halide grains bounded by 100, 111, or 110 crystal planes. Silver halide emulsions and their preparation are further described in Research Disclosure I t Section I. Also useful are tabular grain silver halide emulsions, as described in Research Disclosure, January, 1983, Item 22534 and U.S. Patent 4,425,426. The couplers and competitor compound described above used in the practice of the invention (and other couplers and compounds contained in the photographic material) can be incorporated in hydrophilic layers of photographic materials by techniques well—known in the art. One common technique involves the use of high—boiling water—immiscible organic solvents and/or surfactants . Useful organic solvents include tricresyl phosphates, di—n—butyl phthalate, and others described in Research Disclosure I. Section XIV. Surfactants are well—known to one skilled in the art, and are described in Research Disclosure I. Section XI. Mixtures of solvents and surfactants may also be used. The silver halide described above can be sensitized to a particular wavelength range of radiation, such as the red, blue, or green portions of the visible spectrum, or to other wavelength ranges, such as ultraviolet, infrared, and the like. In a preferred embodiment, the silver halide emulsion associated with the magenta coupler is spectrally sensitized to green light so as to complement the magenta color of the dye formed by the coupler during processing. The silver halide emulsion associated with the yellow coupler is preferably spectrally sensitized to blue light so as to complement the yellow color of the dye formed by the coupler. Chemical sensitization of silver halide can be accomplished with chemical sensitizers such as gold compounds, iridium compounds, or other group VIII metal compounds. Spectral sensitization is accomplished with spectral sensitizing dyes such as cyanine dyes, merocyanine dyes, styryls, or other known spectral sensitizers. Additional information on sensitization of silver halide is described in Research Disclosure I. Sections I-IV. Although only a yellow coupler layer and a magenta coupler layer are required for the practice of the invention, multicolor photographic elements generally comprise a blue—sensitive silver halide layer having a yellow color—forming coupler associated therewith, a green—sensitive layer having a magenta color—forming coupler associated therewith, and a red—sensitive silver halide layer having a cyan color-forming coupler associated therewith. The oxidized developer competitor compound can be incorporated in the yellow coupler layer or, more preferably, in an interlayer between the yellow coupler layer and the magenta coupler layer. This interlayer. can be the yellow filter layer typically used in color photographic materials between the yellow and magenta layers, or it can be a separate layer. Color photographic elements and color—forming couplers are well—known in the art and are further described in Research Disclosure I. Section VII. The element of the invention can also include any of a number of other well—known additives and layers, as described in Research Disclosure I. These include, for example, optical brighteners, antifoggants, oxidized developer scavengers (which can be the same as or different than the competitor according to formula (I)), development accelerators, image stabilizers, light—absorbing materials such as filter layers or intergrain absorbers, light—scattering materials, gelatin hardeners, coating aids and various surfactants, overcoat layers, interlayers and barrier layers, antistatic layers, plasticizers and lubricants, matting agents, development inhibitor—releasing couplers, bleach accelerator—releasing couplers, and other additives and layers known in the art. The photographic elements of the invention, when exposed, are processed to yield an image. Processing can be by any type of known photographic processing, as described in Research Disclosure I. Sections XIX—XXIV. A negative image can be developed by color development with a chromogenic developing agent followed by bleaching and fixing. A positive image can be developed by first developing with a non—chromogenic developer, then uniformly fogging the element, and then developing with a chromogenic developer. Bleaching and fixing can be performed with any of the materials known to be used for that purpose. Bleach baths generally comprise an aqueous solution of an oxidizing agent such as water soluble salts and complexes of iron (III) (e.g., potassium ferricyanide, ferric chloride, ammonium or potassium salts of ferric ethylenediaminetetraacetic acid), water—soluble persulfates (e.g., potassium, sodium, or ammonium persulfate), water—soluble dichromates (e.g., potassium, sodium, and lithium dichromate), and the like. Fixing baths generally comprise an aqueous solution of compounds that form soluble salts with silver ions, such as sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, thiourea, and the like. The invention is further illustrated by the following Example. On a cellulose triacetate film film support provided with a subbing layer was coated each layer having the composition set forth below to prepare a multilayer color photographic light—sensitive material, which was designated sample 101. In the composition of the layers, the 2 coating amounts are shown as g/m except for sensitizing dyes, which are shown as the molar amount per mole of silver halide present in the same layer. First Layer: Antihalation Layer Black Colloidal Silver 0.54 (as silver) Gelatin 2.44 Second Layer: Intermediate Layer Fine Grain Silver Bromide 0.05 (as silver) (0.07μ equivalent spherical diameter) Competitor A 0.05 Gelatin 1.22 Third Layer: Slow Red Sensitive Layer Fourth Layer: Fast Red Sensitive Layer Fifth Layer: Intermediate Layer Competitor A 0.22 Dye-1 0.05 Gelatin 0.61 Sixth Layer: Slow Green Sensitive Layer Silver lodobromide Emulsion 0.43 (as silver) Sensitizing Dye-1 0.46xl0 3 Sensitizing Dye-2 0.21xl0 3 Coupler M-7 0.28 Coupler M-l 0.12 Solvent-2 0.20 Gelatin 1.83 Seventh Layer: Fast Green Sensitive Layer Silver lodobromide Emulsion 0.75 (as silver) Sensitizing Dye-1 1.02xl0 3 Sensitizing Dye-2 0.38xl0 3 Coupler M-7 0.49 Coupler M-l 0.21 Solvent-2 0.35 Gelatin 1.72 Tenth Layer: First Protective Layer Competitor A 0.06 Gelatin 1.40 Eleventh Layer: Second Protective Layer Fine Grain Silver Bromide 0.12 (as silver) (0.07 μ equivalent spherical diameter) Matte 0.02 (3.3 μ spherical diameter) Bis(vinylsulfonylmethane) 0.28 Gelatin 0.98 Samples 102 to 106 were prepared in the same manner as described above for Sample 101 except for the addition of the competitors listed in Table I to the Eighth Layer. The added competitors were coated at the levels (in g/m 2) shown in Table I. Each of the samples thus prepared was cut into a 35mm width strip. The samples were exposed to a step exposure using green and red light followed by a series of blue flash exposures and processed using ® standard Kodak E—6 processing solutions and methods. The Status A green density was measured (or interpolated) for an area in the reversal D—min region of the step exposure of each sample with a Status A blue density of 3.0. These values are tabulated in Table I; higher values indicate an increased amount of magenta dye formed by magenta coupler which has migrated out of its layer. The degree of coupler wandering was confirmed by photomicrography. SAMPLE NO. 101 (Comparison) 102 (Comparison) 103 (Invention) 104 (Invention) From the results shown in Table I above, it is clear that the samples using the competitors of the present invention effectively suppress the unwanted formation of dye from magenta coupler which has migrated out of its layer. The competitors selected according to the invention offered an advantage over the comparison competitor even when the comparison competitor was coated at twice the level of the competitor selected according to the invention. The components employed for the preparation of the light—sensitive materials not already identified above are shown below. Sensitizing Dye-1 Sensitizing Dye—2 Sensitizing Dye—3 Solvent 1 - tritolyl phosphates Solvent—2 — dibutyl phthalate Competitor A The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims: WHAT IS CLAIMED IS: 1. A photographic material comprising a support having thereon: a first silver halide emulsion layer that includes a magenta coupler compound, a second silver halide emulsion layer that includes a yellow coupler, wherein the yellow coupler layer or a layer between the first silver halide emulsion layer and the second silver halide emulsion layer comprises an oxidized developer competitor compound having a relative reaction rate, as defined herein, of at at least 1.6, the yellow coupler having a relative reactivity with oxidized color developer such that, in the absence of the oxidized developer competitor, dye is formed outside the first silver halide emulsion layer as a result of reaction between the magenta coupler and developer that has been oxidized by reaction with silver halide from the second silver halide emulsion layer. 2. A photographic material according to claim 1 wherein the yellow coupler layer is nearer to the magenta coupler layer than any other yellow coupler layer in the material. 3. A photographic material according to claim 1 wherein the magenta coupler layer is nearer • to the yellow coupler layer than any other magenta coupler layer in the material. 4. A photographic material according to claim 1 wherein the oxidized developer competitor—containing layer is also a yellow filter layer. 5. A photographic material according to claim 1 wherein the oxidized developer competitorτ-containing layer is other than a yellow filter layer. 6. A photographic material according to claim 1 wherein the oxidized developer competitor-containing layer is the yellow coupler layer. 7. A photographic material according to claim 1 wherein the photographic material is a reversal photographic material. 8. A photographic material according to claim 1 wherein the magenta coupler is a 5—pyrazolone coupler. 9. A photographic material according to claim 1 wherein the magenta coupler has the formula: wherein R-. represents a carbonamido group, an arylamino group, a ureido group, a sulfonamido group, an alkylamino group, or a heterocyclic amino group, and R 2 represent a substituted or unsubstituted aryl group. X represents hydrogen or a group capable of being released by a coupling reaction with an oxidized aromatic primary amine developing agent. 10. A photographic material according to claim 1 wherein the oxidized developer competitor compound has the structure: wherein R represents an electron donating group, 2 R represents hydrogen, alkyl, alkoxy, 10 aryl, aryloxy, aralkyl or amino of the formula -NHR 3, where R3 is phenyl or benzyl, with the proviso that at least one of the substituents R J 2 and R (a) represents (1) a ballast group of sufficient size as to render the hydrazide compound -. ,. non-diffusible in the photographic element prior to development in alkaline processing solution and (b) comprises a polar group, and n is 0, 1 or 2. 11. A photographic element according to 20 claim 10 wherein n is either 0 or, if n is 1 or 2, then R 1 is carbonamido of the formula —NR4COR5 4 where R is hydrogen or alkyl of 1 to 8 carbon atoms and R 5 is as defined for R4 or a benzyl or phenyl group. 5 12. A color reversal photographic material comprising a support having thereon: a first silver halide emulsion layer that includes a magenta coupler compound, and 0 a second silver halide emulsion layer that includes a yellow coupler having a relative reactivity, as defined herein, of not greater than 0.9, wherein the yellow coupler layer or a layer between 5 the first silver halide emulsion layer and the second silver halide emulsion comprises an oxidized developer competitor compound having a relative reaction rate, as defined herein, of at at least 1.6. 13. A photographic material according to claim 12 wherein the yellow coupler layer is nearer to the magenta coupler layer than any other yellow coupler layer in the material. 14. A photographic 1 material according to claim 13 wherein the magenta coupler layer is nearer to the yellow coupler layer than any other magenta coupler layer in the material. 15. A photographic material according to claim 12 wherein the oxidized developer competitor—containing layer is also a yellow filter layer. 16. A photographic material according to claim 12 wherein the oxidized developer competitor—containing layer is other than a yellow filter layer. 17. A photographic material according to claim 12 wherein the oxidized developer competitor—containing layer is the yellow coupler layer. 18. A photographic material according to claim 12 wherein the magenta coupler is a 5-pyrazolone coupler. 19. A photographic material according to claim 12 wherein the magenta coupler has the formula: wherein R., represents a carbonamido group, an arylamino group, a ureido group, a sulfonamido group, an alkylamino group, or a heterocyclic amino group, and R 2 represent a substituted or unsubstituted aryl group,. X represents hydrogen or a group capable of being 5 released by a coupling reaction with an oxidized aromatic primary amine developing agent. 20. A photographic material according to claim 12 wherein the oxidized developer competitor 10 compound has the structure: , wherein • j c R represents an electron donating group, R represents hydrogen, alkyl, alkoxy, aryl, aryloxy, aralkyl or amino of the formula -NHR 3, where R3 is phenyl or benzyl, with the proviso that at least one of the substituents R ,1 2 20 and R (a) represents (1) a ballast group of sufficient size as to render the hydrazide compound non-diffusible in the photographic element prior to development in alkaline processing solution and (b) comprises a polar group, and 5 n is 0, 1 or 2. 21. A photographic material according to claim 20 wherein n is either 0 or, if n is 1 or 2, then R 1 i.s carbonami.do of the formula -NR4COR5 4 0 where R is hydrogen or alkyl of 1 to 8 carbon atoms and R 5 is as defined for R4 or a benzyl or phenyl group 22. A photographic material according to 5 claim 12 wherein the yellow coupler has a relative reaction rate of not greater than 0.8. 23. A photographic material according to claim 12 wherein the oxidized developer compound has a relative reaction rate, as defined herein, of at at least 1.7.

Inventors: BOWNE ARLYCE TOLMAN, NELSON JOHN VICTOR, BOWNE, ARLYCE, TOLMAN, NELSON, JOHN, VICTOR
Applicants: EASTMAN KODAK CO, EASTMAN KODAK COMPANY
Application year: 1991
Main classification: G03C7
IPC codes: G03C7