US3904413A

US3904413A - Multicolor photographic elements containing coarse-grain silver halide emulsions

Info

Publication number: US3904413A
Application number: US307890A
Authority: US
Inventors: Rowland George Mowrey
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1972-11-20
Filing date: 1972-11-20
Publication date: 1975-09-09
Anticipated expiration: 1992-09-09
Also published as: GB1446210A; BE807566A; CA1008292A; FR2207297A1; FR2207297B1

Abstract

Photographic elements are disclosed which comprise a support having thereon at least two image dye-providing layer units which each contain a silver halide emulsion and a color coupler. The silver halide emulsion of one of the image dye-providing layer units has a substantially larger mean grain size than the silver halide emulsion of at least one other image dye-providing layer unit and has associated therewith at least 10 mg./ft.2 of a nondiffusing anionic organic compound. The image dye-providing layer units containing a coarse-grain emulsion and the nondiffusible anionic organic compound exhibit high rates of silver formation when developed with a color-developing agent such as a p-phenylenediamine.

Description

United States Patent Mowrey Sept. 9, 1975 [75] Inventor: Rowland George Mowrey,

Rochester, N.Y.

[73] Assignee: Eastman Kodak Company,

Rochester, NY.

22 Filed: Nov. 20, 1972 211 Appl. No.: 307,890

[52] U.S. C1 96/74; 96/68 [51] Int. Cl. G03C 1/76 [58] Field of Search 96/74, 68

[56] References Cited UNITED STATES PATENTS 3,022,172 2/1962 Ohba ct a1. 96/114 3,251,689 5/1966 96/74 3,402,046 9/1968 96/74 3,411,904 11/1968 96/74 3,411,911 11/1968 .96/114 3,411,912 11/1968 Dykstra 96/114 Millikan 96/74 Hara et a1. 96/74 Primary Examiner-Norman G. Torchin Assistant Examiner-J. P. Brammer Attorney, Agent, or FirmM. R. Chipaloski [5 7 ABSTRACT Photographic elements are disclosed which comprise a support having thereon at least two image dyeproviding layer units which each contain a silver halide emulsion and a color coupler. The silver halide emulsion of one of the image dye-providing layer units has a substantially larger mean grain size than the silver halide emulsion of at least one other image dyeproviding layer unit and has associated therewith at least 10 mg./ft. of a nondiffusing anionic organic compound. The image dye-providing layer units containing a coarse-grain emulsion and the nondiffusible anionic organic compound exhibit high rates of silver formation when developed with a color-developing agent such as a p-phenylenediamine.

18 Claims, No Drawings MULTICOLOR PHOTOGRAPHIC ELEMENTS CONTAINING COARSE-GRAIN SILVER HALIDE EMULSIONS This invention relates to photographic elements designed for producing a color image record therein and improved processes for producing image records in photographic elements where development is effected with an aromatic primary amino silver halide developing agent. In one aspect, this invention relates to the use of certain high-molecular-weight, nondiffusing, ani onic organic acids to increase the rate of development of a silver halide emulsion when developed with'a color-developing agent. In another aspect, this invention relates to photographic silver halide elements comprising at least two image dye-providing layer units wherein at least one of said image dyeproviding layer units contains a silver halide emulsion having an average grain size which is at least 50 percent larger than the silver halide emulsion of the other image dye-providing layer unit.

It is known in the prior art that color-developing agents such as aromatic primary amino compounds develop exposed silver halide at a much slower rate than black-and-white developing agents such as hydroquinones, pyrazolidones, etc. While it may be possible to develop the same amount of silver in an exposed silver halide element with either type of developing agent, it would be desirable to increase the rate of development with a color silver halide developing agent.

It is also known in the art that certain photographic elements contain layers having fine-grain emulsions and layers containing coarse-grain emulsions, such as in color papers where the blue-sensitive emulsion is a coarse-grain emulsion and the spectrally sensitized greenand red-sensitive emulsions are fine-grain emulsions to obtain speed differential to blue light. Generally, the coarse-grain emulsion develops very slowly compared with the fine-grain emulsion when developed with a eolordeveloping agent. In many instances it would be desirable to develop all layers at a uniform rate, or at least to increase the rate of development of the coarse-grain emulsion to provide high silver formation at short development times.

I have now found that nondiffusible anionic organic acids can be incorporated in a photographic element in association with a silver halide emulsion to increase the rate of development with a color developer, especially to increase the rate of development of a slowdeveloping emulsion such as a coarse-grain emulsion.

Generally, the photographic elements in accordance with this invention contain immobile or nondiffusible, anionic organic compounds having acid groups thereon and having an equivalent weight of at least 70 and preferably between 100 and 300 based on said acid groups. The acid groups can generally be sulfmic acid groups, sulfonic acid groups, carboxylic acid groups, phosphonic acid groups, phosphate groups. sulfate groups, and the like or salts thereof, and preferably the alkali metal or alkaline earth salts thereof. In certain highly preferred embodiments, the anionic organic compounds are organic sulfonic acids such polymers containing sulfonic acid groups thereon.

In a highly preferred embodiment of this invention, multicolor photographic elements can be made which comprise at least two image dye-providing layer units which each contain a silver halide emulsion and a color coupler, said silver halide emulsion of at least one image dye-providing layer unit having a mean grain size which is 0.5 micron larger or 50 percent larger than the mean grain size of the silver halide emulsion of another of said image dye-providing layer units, wherein said image dye-providing layer unit containing the silver halide emulsion of larger grain size has associated therewith a compound different from said color coupler which is a nondiffusible anionic organic acid. Preferably, the nondiffusible, anionic organic acid compound is in association only with the coarse-grain silver halide emulsion and the remaining image dye-providing layer units containing fine-grain emulsions are substantially free of the nondiffusible anionic organic acid compounds, and preferably are'substantially free of the nondiffusible, anionic organic acid compound.

In another highly preferred embodiment, the photographic elements of this invention comprises a support having thereon l a yellow image dye-providing layer unit comprising a silver halide emulsion having a mean grain size of at'least 0.8 micron and a yellow image dyeproviding color coupler, (2) a magenta image dyeproviding layer unitcomprising a silver halide emulsion having a mean grain size of less than about 0.4 micron and a magenta image dye-providing coupler, and (3 a cyan image dye-providing layer unit comprising a silver halide emulsion having a mean grain size of less than about 0.4 micron and a cyan image dye-providing coupler, wherein a nondiffusible anionic organic com pound having acid groups thereon and having an equivalent weight of at least 70, and preferably 100, based on acid groups is present in said yellow image dyeproviding layer unit; preferably, said cyan and magenta dye image-providing layer units are substantially free of said anionic organic compound or at least contain less than 5 mg./ft. of said anionic organic compound.

In another preferred embodiment, this invention relates to photographic elements comprising at least two and preferably three image dye-providing layer units comprising silver halide emulsions, wherein at least one and preferably two of said image dye-providing layer units comprise at least a 40 percent stoichiometric excess of an image dye-providing color coupler bas'ed on effective or developable silver, and preferably these layers also each contain less than 30 mg/ft? of silver halide based on silver.

Generally, the organic acids useful according to this invention are water-soluble compounds which are nondiffusing or immobile as incorporated in the photographic element, and have an equivalent weight of at least and preferably between about 100 and 300 based on acid groups. They can be incorporated in either their salt or free-acid form, but are preferably incorporated in the salt form such as with an alkali metal salt. Whereas mobile compounds will generally migrate from layer to layer during the development process, the immobile organic sulfonie acids remain in the proximity of the coarse-grain silver halide during the entire development process.

In one embodiment, l have found that water-soluble polymeric compounds containing acid groups thereon and having a molecular weight of at least 3000 and preferably at least 5000 can be used with coarse-grain silver halide emulsions to provide improvements in accordance with this invention. Typical polymers of this type include the acrylic polymers having acid groups thereon and comprise units of 3- methacryloyloxypropane-l-sulfonic acid. sodium salt; 3-acryloyloxypropane-l-sulfonie acid, sodium salt; sodium methacryloyloxyethyl sulfate; sodium methacrylate; and the like. The polymers can also be polystyrenes such as sulfonated polystyrene and the like.

In another embodiment, the water-soluble polymers of this invention can comprise units having acid groups thereon and units having hardenable or crosslinking groups thereon, wherein the polymer can be crosslinked in situ after coating to provide a polymeric compound which is nondiffusing or immobile. Typical hardening groups which can be incorporated into polymers of this type include 2-acetoacetoxyethyl methacrylate, 2-12-(methacryloyloxy)ethyllisothiouronium methane sulfonate, N-cyanoacetyl-N'-methacryloyl hydrazine. N-methacryloyl-N-glycyl hydrazine hydrochloride, 2- aminoethyl methacrylate hydrochloride and the like. Typical useful polymers of this type include poly(N- isopropylaerylamide-- -3-methacryloyloxypropanel-sulfonic acid, sodium salt--2-acetoacetoxyethyl methacrylate poly( N- isopropylacrylamide-- -3-methacryloyloxypropanel -sulfonic acid, sodium salt--Z-acetoacetoxyethyl methacrylate; and the like, including polymers containing acid groups disclosed in U.S. Pats. No. 3,459,790 by Smith issued Aug. 5, 1969,

etc.

The concentration of the organic acid compound will depend upon the concentration of the silver halide emulsion in the image dye-providing layer unit. Generally, the organic acid is incorporated in an image dyeproviding layer unit in concentrations of at least mg./ft. and preferably at least mg./ft. and generally the anionic organic compound is utilized in the image dye-providing layer in concentrations of at least 50 per cent by weight of any other compound which is a by drophilic colloid and which is generally used as a binder or peptizing agent for the silver halide, i.e., such as gelatin, polymeric peptizers or polymeric vehicles. In certain embodiments, the anionic organic compound is a polymeric compound which is the sole binder or carrier vehicle for the ingredients of the image dyeproviding layer unit. However, when the anionic organic acid compound constitutes over 75 percent of the binder or carrier vehicle, it preferably contains hardening or crosslinking groups to permit hardening to take place.

The anionic organic acid compound is located in the photographic element in association with the image dye-providing layer units containing a coarse-grain silver halide emulsion. Generally, the anionic organic compound is mixed with the silver halide emulsion prior to coating; however, it can also be coated in adjacent and preferably contiguous layers. In most embodiments, it is desirable to locate the anionic acid material within the image dye-providing layer unit whereby it will not have a substantial effect on adjacent image dye-providing layer units which contain smaller-grain silver halide emulsions.

The photographic elements of this invention containing the anionic organic compounds in association with the coarse-grain emulsion layers can generally be processed by any of the color-development processes used for processing silver halide-containing photographic elements. The rate of image dye production in image dye-providing layer units containing coarse-grain silver halide emulsion will be enhanced since color development occurs at a faster rate in coarse-grain emulsions with a color developer such as an aromatic primary amino color-developing agent.

In certain highly preferred embodiments, the photographic elements of this invention are especially useful to obtain uniform image dye produetionin development and amplification processes. such as those described in U.S. Ser. Nos. 189,289 by Bissonette filed Oct. 14, 1971, and 256,071 by Travis filed May 23, 1972, now U.S. Pat. 3,765,891, both applications being incorporated herein by reference. In one aspect of these processes, image dye is formed by contacting an imagewise distribution of metallic silver with a cobalt- (lll) complex and a primary aromatic amino silver halide developing agent wherein the metallic silver acts as a catalyst to generate oxidized color developer, which in turn reacts with a coupler to form the image dye. In processes of this type, it is very desirable to obtain substantial amounts of metallic silver in slowly developing, coarse-grain, silver halide emulsions before overdevelopment of the fine-grain silver halide emulsions occurs, so that catalytic production of oxidized developer will occur only in the exposed areas of each respective layer. The anionic organic acid compounds used in accordance with this invention are water-soluble compounds as coated in the photographic element. The water-soluble polymers are to be distinguished from latexes and hydrophobic polymers and generally have a solubility in water at room temperature of at least 3 percent and preferably at least 5 percent by weight of water. The term water-soluble as used herein thus refers to the property of the compound as coated regardless of whether it has been crosslinked or hardened in the photographic element after coating.

The term anionic organic compound as used herein refers to those compounds which are anionic under the conditions of general use in photography and preferably does not include amphoteric compounds. Preferably, the compounds exhibit anionic properties in the pH range of from about 3 to about 1 1. Moreover, the anionic organic compounds are nonproteinaceous compounds; for example, the term does not include substances such as gelatin which is amphoteric and pro teinaceous. In still one other aspect, the anionic compounds preferably have the equivalent weight as mentioned elsewhere herein, but can be further defined as those compounds having an equivalent weight of less than 800 and preferably less than 600 based on acid groups.

The silver halide emulsions used in accordance with this invention can comprise. for example, silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide, silver chlorobromoiodide crystals or mixtures thereof. The coarseand fine-grain emulsions can be prepared by any of the well-known techniques, e.g., single-jet emulsions such as those described in Trivelli and Smith, The Photographic Jlll rnul, Vol. LXXlX, May, 1939 (pp- 330338), double-jet emulsions such as Lippmann emulsions, ammoniacal emulsions, thiocyanate or thioethcr ripened emulsions such as those described in U.S. Pats. Nos. 2,222,264 by Neitz et al. issued Nov. 19, 1940, 3,320,069 by lllingsworth issued May 16, 1967, and 3,271,157 by McBride issued Sept. 6, 1966. Surface-image emulsions may be used or internal-image emulsions may be used such as those described in U.S. Pats. Nos. 2,592,250 by Davey et al. issued May 8, 1952, 3,206,313 by Porter et al. is-

l 1939. 2.541.472 by Kendall et a1. issued Feb/13. 1951.

3,367,778 by Berriman issued Feb. 6. 1968. 3.501.307 by lllingsworth issued Mar. 17. 1970. 2.563.785 by 'lvcs issued Aug. 7. 1951. 2.456953 by Knott et a1. issued Dec. 21. 1948. and 2.861.885 by Land'issuedNov. 25. 1958. British Patent 723.019 by Schouwenaars issued Feb. 2. 1955. and French Patent 1.520.821 by lllirlgsworth issued Mar. 4. 1968. Preferably. the emulsions are negative. developing-out-type. silver halide emu lsions. I I

Generally. each of the color-providing layer units of the photographic elements contains a lightfsensitive silver salt which is preferably a silver halide. In one preferred embodiment. at least two of the color-providinglayer units each comprise a silver salt at a concentration of up to 30 mg. of silver/ftF. Howeven whilethe developable silver halide is preferably present at conccntrations based on silver of less than 3() mg./ft. it is possible to coat blended emulsions at higher coverages within this embodiment. as long as no more than3'0 mg./ft. of silver develops; for example. such emulsions may contain silver halide grains which are relatiyely light-insensitive or may contain development restrainers. such as with development inhibitor-releasing couplers. and still provide a photographic element which is advantageously used in the various'processes as described herein to produce improved image records. In some instances. emulsions containing relatively lightinsensitive grains or development inhibitors are desirable to enable one to obtain more uniform coating coverage with less precise coating equipmcnt. as well as for other reasons. Thus. highly preferred photegraphic'elcments of this invention Contain at least two colorproviding layer units.'each containing a silver halide emulsion. defined in terms ofeffective coverage and developability. as one which. when it is fully exposed and processed for about 1 minuteat 100 F. in Developer A as follows: I

- -Color' Developer A water to 1 liter pH 10.1 at 24 (1 will provide less than 30 mg. of metallicsilver/ftf and preferably less than 15 mg./ft. It is understoddthat the term effective silver" refers to that amount of silver which is developed in this test and. that ratios of coupler to silver are based on effective silver which is produced by this type of development when so specified herein.

6 In most instances. the quantity of effective silver as silver halide in the undeveloped. unexposed photographic element will be quite similar .to quantity of total silver present as silver halide. The fully exposed layer containing silver halide emulsion is one which is exposed to Dmax as is well-known in the art. for example. by exposure to a SQO-watt. 30OQ K lamp for about 10 seconds (total exposure at the film plane 11.3 X 10" ln certain embodiments. the emulsions of at least one image dye-providing layer unit are coarse-grain silver halide emulsions and generally have a mean grain size of at least 0.8 micron. and preferably at least 1.0 micron. Grain sizes can be measured by methods commonly used in the art for this purpose. A typical procedurc is set forth .by 'Loveland. Methods of Particle- Size Analysis". ASTM Symposimh on Light Microscopy.

19 53. ppf94-122. or in chapter 2 of The Theory Qf the PhotographicPnicess. Mees and James. 3rd Ed. 1966).

published by MaicMillan Co. The grain size can be measured using the projected areas of the grains or approximate diameter. When the grains are substantially uni- :form in shape. the size distribution can be expressed quite accurately as either diameter or projected area. The size-frequency relationshipcan be determined as disclosed in article by Trivelli and Smith entitled Empirical Relations betwcen Sensitometric and Size Frequency in Photographic Emulsion Series. The Film tographic Journal, Vol. LXXIX, 1949, pp. 330338.

The light scnsitive silver salts are generally coated in the color-providing layer units in the same layer with photographic color coupler. However. they can be coated in separate adjacent layers as long as the couinto adjacent color-providing layer units.

As used herein the terrn sphotographic color coupler. and image dye-providing color coupler include any compound which reacts (or couples) with the oxidation products of. primary aromatic amino developing agent on photographic development to form animage dye. and are nondiffusible in a hydrophilic colloid binder (e.g.. gelatin) useful for photographic silver halidesand also those couplers which provide useful image dyes when reacted with oxidized primary aromatic amino developing agents such as by a coupler-release mechanism. The couplers can form diffusible or nondiffusible dyes]. Typical preferred color couplers include phenolic. '5-py razolone and open-chain ketomethylene couplers S pecific cyan. magenta and yellow color couplerswhich can. be employed in the practice of this invention are described in'Graham et a1. U.S. Pat. l\lo. 3.046.129 issued Jan. 24. 1962. column 15. line 45. through column 18. line 51. which disclosure is incorporated herein by reference. Such color couplers can be dispersed in convenient manner. such by using the solvents andthe techniques described in U.S. Pats. Nos. 2,322,027 byJelley et a1. issued June 15, .1943, or 2.894.171, by Fierke et a1. issued July 30. 1957. When coupler solvents are employed. the most useful weight ratios of color coupler to coupler solvent range. from about] :3 to 1:0.1. The useful couplers include Fischer-type incorporated couplers such as those described in Fiescher. US. Pat. No. 1.055.155 issued Mar. .4. l9l3.-and particularly nondiffusible Fieschertype couplers containing branched carbon chains, e.g., those referred to in the references cited in Frohlich et al. U.S. Pat. No. 2.376.679 issued May 22. I945. column 2, lines 50-60. Particularly useful in the practice of this invention are the nondiffusible color couplers which form nondiffusible dyes.

In certainpreferred embodiments, the incorporated couplers in the layer units of this invention are waterinsoluble color couplers which are incorporated in a coupler solvent which is preferably a moderately polar solvent. Typical useful solvents include tri-o-cresyl phosphate, di-n-butyl phthalate. diethyl lauramide. 2.4- diarylphenol. liquid dye stabilizers as described in an article entitled Improved Photographic Dye Image Stabilizer-Solvent Product Licensing [Ill/0X, Vol. 83. pp. 2629. March, l97l, and the like. The elements containing coupler solvents appear also to aid in imbibing color developer in those processes where it is carried from a developer bath into an amplifier bath.

The term nondiffusible" used herein as applied to the anionic acids, the couplers. and the products derived from couplers has the meaning commonly applied to the term in color photography and denotes materials which for all practical purposes do not migrate or wander through photographic hydrophilic Colloid layers. such as gelatin. particularly during processing in aqueous alkaline solutions. The same meaning is attached to the term immobilc. The terms diffusible" and mobile have the converse meaning. I I

The photographic elements of this invention, as defined above. comprise a support having thereon image dye-providing layer units. A multicolor photographic element comprises at least two of said image dyeproviding layer units which each records light primarily in different regions of the light spectrum. The layer unit comprises a light-sensitive silver salt. which is generally spectrally sensitized to a specific region of the light spectrum, and has associated therewith a photographic color coupler. In certain preferredembodiments. the color-providing layer units are continuous layers which are effectively isolated from other layer units by barrier layers. spacer layers. layers containing scavengers for oxidized developer and the like to prevent any substantial color contamination between the image dyeproviding layer units. The effective isolation of the layer units is known in the art and is utilized to prevent contamination in many commercial color products.

In certain preferred embodiments. the photographic elements of this invention comprise a support having thereon at least one image dye-providing layer unit containing a light-sensitive silver salt. preferably silver halide. having associated therewith a stoichiometric excess of coupler of at least 40 percent and at least preferably 70 percent. The equivalency of color couplers is known in the art; for example, a 4-equivalent coupler requires 4 moles of oxidized color developer. which in turn requires development of 4 moles of silver, 'to produce 1 mole of dye. Thus, for a stoichiometric reaction with silver halide, l-equivalent weight of this coupler will be 0.25 mole. Image-providing units of this embodiment comprise at least a 40 percent excess of the equivalent weight of image dye-providing color coupler required to react on a stoichiometric basis with the de velopable silver and preferably a 70 percent excess of said coupler. In one highly preferred embodimenuat least a 1 10 percent excess of the coupler is present in said dye image-providing layers based on silver. Preferably, the coupler-to-silverratio is based on effective silver as defined herein. The ratio can also be defined as an equivalent excess with a coupler-to-silver ratio of at least l.4:l. and preferably at least 1.7:l (i.e., 2:1 being a l00'per cent excess). In certain preferred embodiments. the photographic color couplers are employed in the image dye-providing layer units at a concentration of at least 3 times. such as from 3 to 20 times, the weight of the silver in the silver halide emulsion. Weight ratios 'of coupler-'to-silver coverage which are particularly useful are from 4 to 15 parts by weight coupler to 1 part by weight silver. Advantageously, the coupl er is present in an amount sufficient to give a density of at least L7 and preferably at least 2.0. Preferably. the difference between the maximum density and the minimum density (which can comprise unbleached silver) is at least 0.6 and preferably at least 1.0.

It is realized that the density of the dye may vary with the developing agent combined with the respective coupler. and accordingly the quantity of coupler can be adjusted to provide the desired density. Preferably, each layer unit contains least I X 10 moles/ft. of color coupler.

Advantageously, the photographic color couplers utilized arc sclected so that they will give a good neutral dye image. Preferably, the cyan dye formed has its major visible light absorption between about 600 and 700 nm., the magenta dye has its major absorption between about 500 and 600 nm., and the yellow dye has its major absorption between about 400 and 500 nm.

The photographic elements of this invention are particularly useful in the processes disclosed in Bissonette, U.S. Ser. No. l89, 289, entitled Image-Forming Processes and Compositions, filed Oct. 14, I971, and incorporated herein by reference. Generally, in this process a redox reaction between an oxidizing agent and a reducing agent is utilized to produce a change in light value. This change in light value can come about directly by a change in the light value of either the oxidizing agent or reducing agent. Alternatively, the redox reaction can result in one or more reaction products which can react with each other or with another component, such as a reactive species, to produce a change in light value. In another variation. the reactivity of the reactive species can be reduced imagewise by one of the reaction products of the redox reaction. The redox reaction which takes place when the elements are processed by this procedure occurs at a catalytic surface. The catalyst is metallic silver which, of course, can be produced by development of silver halide which contains a latent image. The catalyst appears to promote redox reaction in true catalytic fashion The amount of redox reaction products is not limited by the amount of catalyst present. since the catalyzed redox reaction .of this invention does not proceed on a stoichiornetric basis with respect to the catalyst.

Oxidants preferred in the practice of this process are the metal complexes, such as a transition metal complex. e.g., a Group VIII metal complex. or a complex of a metal of Series 4 of the periodic table appearing on pp. 54 and 55 of Langes Handbook of Chemistry, 8th Edition, published by HandbookPublisher', Inc.. Sandusky. Ohio. I952. Such complexes feature a molecule having a metallic atom or ion. This metallic atom or ion issurrounded by a group of'atoms. ions or other molecules which are generically referred to as ligands. The metallic atom or ion in the center of these complexes is a Lewis acid; the ligands are Lewis bases. Werner complexes are well-known examples of such complexes. The useful metal salts are typically capable of existing in at least two valent states.

Preferred metal complexes in accordance with this process have coordination numbers of 6. and are known octahedral complexes. Cobalt complexes are especially useful in the practice of this invention. Most square planar complexes (which have a coordination number of 4) are rather labile, although some Group VIII metal square planar complexes, particularly platinum and palladium square planar complexes, exhibit inertness to rapid ligand exchange.

A wide variety of ligands can be used with a metal ion to form suitable metal complexes. Nearly all Lewis bases (i.e.. substances having an unsharedpair of electrons) can be ligands in metal complexes. Some typical useful ligands include the halides, e.g., chloride. bromide, fluoride, nitrite, water, amino, etc., as we] as such common ligands as those referred to-by Basolo and Pearson in Mechanisms of Inorganic- Reactions, a Study Qf A1010! Comp/Laws and Solutions, 2nd Edition, 1967, published by John Wiley and Sons, p. 44. The lability of a complex is influenced by the nature of the ligands selected in forming said complex.

Particularly useful cobalt complexes have a coordination number of 6 and have a ligand selected from the group consisting of ethylenediamine(en), diethylenetriaminc( dien triethylenetctraamine(trien amine(NH;;). nitrate. nitrite, azide, chloride, thiocyanate, isothioeyanate, water, carbonate, and propylenediam i ne(tn). The preferred cobalt complexes comprise l at least 2 ethylenediamine ligands or (2) at least 5 ammine ligands or (3) l triethylenetetraamine ligand. Es-

pecially useful are the cobalt hexammine salts (e.g.. the

chloride, bromide, sulfite, sulfate, perchlorate, nitrite and acetate salts)v Some other specific highly useful eobalt complexes include those having one of the following formulas: [Co( NH;,) -,H O]X; lCo(NH ).-,C ;;]X; l zi )s IX; l NH3)4CO3]X; [CO( en )3]X;

[Co(tn) en) 1X; wherein X represents one or more anions determined by the charge neutralization rule. Complexes containing oxidized noble metals or ferromagnetic metals, such as complexes of Cr', Fe', Rh', Pt. Pd and Ir', which have reactivities similar to the complexes listed above, could be used in the practice of this invention. The redox equilibra published in Stability Constants of Metal-Ion Comp/ates, Sillen and Martcll, published by The Chemical Society, Burlington House, London, Eng. (1964), indicate that other complexes have reactivities generally similar to the cobalt complexes mentioned above.

Numerous reducing agents can be utilized in carrying out the same process. The reducing agents utilized herein undergo redox reaction with the oxidizing agent at a catalytic surface. Especially preferred reducing agents are those which reduce silver halide to metallic silver, such as those which are capable of developing imagewise-exposed light-sensitive photographic silver halidev In certain embodiments, the reducing agent used in this process is an aromatic primary amino color-developing agent such as p-phenylenediamine. Color-developing agents which can be used include 3- acetamido-4-amino- N,N-diethylaniline, 4-amino-N- ethyl-N-B-hydroxyethylaniline sulfate, N,N-diethyl-pphenylencdiamine, Z-amino-5-diethylamiriotoluene, N-ethyl-N-B-methanesulfonamidoethyl3-methyl-4- aminoaniline, 4-amino-N-ethyl-3-methyl-N-(,B-sulfoethyl )aniline, and the like. see Bent et al., JACS, Vol. 73

pp. 3100-3l25 1951 and Mees and James, The Theory oft/1e Photographic Process, 3rd Edition, 1966, published by MacMillan Co., New York, pp. 27831 1, for further typical, useful developing agents.

In one highly preferred embodiment, aromatic primary amino colordeveloping agents which provide good results in this process are 4-amino-N,N- diethylaniline hydrochloride, 4-amino-3-methyl-N,N- diethylaniline hydrochloride, 4-amino-3-methyl-N- ethylN-,8( methanesulfonamido)ethylaniline sulfate hydrate, 4-amino-3.-methyl-,N-ethyl-N-,B hydroxyethylaniline sulfate, 4-amino-3-methylamino- N,N-diethylaniline sulfate hydrate, 4-amino-3- methoxy-l I-ethyl-l l-,l5-hydroxyethylaniline hydrochloride, 4-amino-3-B-( methanesulfonamido )ethyl-N,N diethylaniline' dihydrochloride and 4-amino-N-ethyl-N- (Z-methoxyethyl )-m-toludine di-p-toluenesulfonate.

In certain embodiments, developers other than pphenylenediamines and specifically black-and-white developing-agents can be either.used in the developer composition or incorporated in the photographic elements of this invention to provide further improvements in photographic developmentproperties. In some instances, the rate of development of a coarsegrain silver'halide emulsion is further'increas ed by the combination of the anionic organic'compounds and black-and-white developing agents. T

The invention can be further illustrated by the following examples. The inherent viscosities referred to in the examples are measured ata concentration of 0.25 g. of polymer/deciliter of solution at 25 C. using a 0. l N sodium chloride solution as a solvent.

EXAMPLE 1,

Two photographic elements are prepared as follows:

Element A: a

l. papersupport: I

2. layer containing a silver chlorobromide e'mulsion 1.2 micron mean grain size) at mg. of 'Ag/ftl l-()() mg./ft. of the coupler oz-pivalyl-4-( 4- benzyloxyphenylsulfonyl )phenoxy-Z-chloro-S-'[ 'y- 2,4-di-tert-amylphenoxy )butyramido lacetanilidc dispersed in mg./ft." and di-n-butyl phthalate and 200 mg./ft. 'of gelatin.

Element B:

Same as Element A wherein 100 'm'g./ft. of gelatin is replaced in layer 2 with 100 mg./ft. of'copoly(N- isopropylacrylamide-- '-3methacrylo'yloxypropanel -sulfonic acid, sodium salt--2-acetoacetoxyethyl methacrylate) (7:2:0.25'molar) ('inh'erent'viscosity of 0.48

'Elements A and B are exposed to a test object and processed for 3%, 7 and 14 minutes in a developer of the composition:

water benyyl alcohol hydroxylamine sulfate NaBr 4-amin o-Nethyl-N-( 2methoxyethyl m toluidine di-paraioluenesultbnate I -Continued Na Co water to l liter; pH 10.]

Following development. the elements are bleachfixed, washed and stabilized. Element B has developed almost twice as rapidly as Element A.

EXAMPLE 2 Two photographic elements are prepared as follows: Element A:

1. paper support;

2. layer containing a silver chlorobromide emulsion 1.2 microns mean grain size) at 20 mg. of Ag/ftF, 100 mg./ft. of the coupler a-pivalyl-4-(4- benzyloxyphenylsulfonyl )phenoxy-IZ-chloro-S-l y- (2,4-di-tert-amylphenoxy )butyramido laeetanilide dispersed in 25 mg./ft. of di-n-butyl phthalate and 200 mg./ft. of gelatin.

Element B:

Same as Element A except 200 mgjft. of sulfonated polystyrene (prepared by sulfonation of polystyrene having a MW of 60,0()()l00,()) is added to layer 2.

Each coating is exposed on a test object and processed for l, 2 and 3 /2 minutes in a developer as mentioned in Example 1 which additionally contains L6 g./l. of lCo(NH -,);;]Cl;,. Following development. the coatings are bleach-fixed, washed and stabilized. Element B has developed nearly twice as rapidly as Element A despite its greater thickness. but at the longer development time both coatings have essentially identical curve shapes and speed.

The development acceleration effect is tested with light-sensitive elements where the concentration of sulfonated polystyrene is lowered. Development acceleration is observed at concentrations as low as 10 mg./ft. but preferably the concentration is at least 25 mg/ftf to observe appreciable development acceleration effects.

The use of the sulfonated polystyrene is also tested in other layers and it is found that best results are obtained when the sulfonic acid compound is incorporated in the emulsion layer.

Similar results are obtained when 200 mg. of the following polymers are added to layer 2 of Element A and hardened with formaldehyde; poly( N- isopropylacrylamidc--3-acryloyloxypropanel -sulfonic acid, sodium salt--Z-acetoacetoxyethyl methacrylate) (7:4:0.25 by molar ratio); poly( N- isopropylacrylamidc-- -3-methacryloyloxypropane-l-sulfonic acid, sodium salt--2-acctoacetoxyethyl methacrylate) (7:2:0.25 by molar ratio); poly( Nisopropylacrylamide-- -3-methacryloyloxypropane-l-sulfonic acid, sodium salt--2-acetoacetoxyethyl methacrylate) (2:l2:l by

molar ratio); polymethacrylic acid, sodium salt; and polysodium mcthacryloyloxyethyl sulfate.

EXAMPLE 3 Photographic multilayer elements are made as follows:

Element A:

l. polyethylene-coated paper support; 2. layer containing a blue-sensitive silver halide emulsion 1.2 microns mean grain size) at 16 mg. of sil- 12 ver/ft.'-. gelatin at l22 mg /ft. and a yellow coupler. ae-pivalyl-4-(4- bcnzyloxyphenylsulfonyl )phenoxy-Z-chloro-S-ly- (2'.4-di-tert-amylphenoxy )butyramido laeetanilide, at 60 mg./ft. dispersed in di-nbutyl phthalate at 15 mg./ft.'

3. layer containing lOO mg./ft.' of gelatin;

4. layer containing a green-sensitive silver halide emulsion (0.3 micron mean grain size) at 10 mg. of silver/ft. gelatin at 132 mg./ft. and a magenta coupler, l-( 2,4,6-trichlorophenyl )-3- {5-[ a-( 3-tertbutyl-4-hydroxyphenoxy )tetradeeanamido -2- chloroanilino} -4-pyrazolone, at 25 mg/ft. dispersed in tricresyl phosphate at 12.5 mg./ft.

5. a layer containing 160 mg/t't. of gelatin;

6. a layer containing a red-sensitive silver halide emulsion (0.3 micron mean grain size) at 6 mg. of silver/ftF, gelatin at 90 mg./ft. and a cyan coupler, 2-[ a-( 2,4-di-tert-amylphenoxy )butyramido ]-4,6- dichloro-5-methylphenol, at mg./ft. dispersed in di-n-butyl phthalate at 17.5 mg./ft.

7. a layer containing gelatin at 100 mg./ft. Element B:

This element is prepared exactly as Element A except the layer containing the coarse-grain, bluesensitive, silver halide emulsion also contains 122 mg/ft. of poly( 3-methaeryloxyloxypropanel sulfonic acid, sodium salt), having an inherent viscosity of 0.15.

Elements A and B are exposed through a multicolor,

graduated-density test object and processed in the following sequence:

Process l Process 2 Process 3 (seconds) (seconds) (seconds) color-develop 3U amplify 9U 9U 9U bleach-fix 60 (10 60 Wash 90 90 The processing baths have the following compositions'.

water to 1 liter: pH 4.5

The samples are then sensitometrically evaluated by recording the H and D curves of the yellow. magenta and cyan dye images. In Process 1, Element B contains substantially more yellow dye than Element A. In Process 2, Element B contains more yellow dye than Element A and also exhibits a distinct plateau region on the H and D curve at the same density and has substantially the same contrast as the cyan and magenta curve. In Process 3, there is slightly more yellow dye in Element B than Element A. In all of the processes the dye yield in the cyan and magenta dye layers does not vary substantially in the Dmax areas, but the Dmin areas exhibit more dye at the longer process time. Thus, it is apparent that the incorporated anionic polymer has enabled one to obtain high dye production in the coarsegrain layer without substantial dye production in the Dmin areas of finegrain emulsions which may be caused by overdevelopment of those layers.

Although the invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, variations and modifications can be effected within the spirit and scope of the invention.

I claim:

1. A photographic element comprising a support having an image dye-providing layer unit comprising a finegrain silver halide emulsion having associated therewith a color coupler and another dye imageproviding layer unit containing a coarse-grain silver halide emulsion which has a mean silver halide grain size at least 50 percent larger than the mean grain size of said fine-grain emulsion, and associated therewith a color coupler and at least mg/ft. of a compound different from said color coupler which is a nondiffusible anionic organic polymeric acid having an equivalent weight of at least 100 and less than 800 based on acid groups; and wherein said fine grain emulsion is substantially free of said non-diffusible anionic organic polymer acid compound.

2. A photographic element according to claim 1 wherein said nondiffusible organic acid is a polymer compound containing sulfonic acid groups thereon.

3. A photographic element according to claim 1 wherein said coarse-grain silver halide emulsion has a mean grain size of at least 0.8 micron and said anionic organic compound has an equivalent weight of less than 300.

4. A photographic element according to claim 1 wherein said fine-grain emulsion has a mean grain size of less than 0.4 micron and said coarse-grain emulsion has a mean grain size of at least 1.0 micron.

5. A photographic element according to claim 1 wherein said image dye-providing layer unit containing said fine-grain emulsion comprises at least a 40 percent stoichiometrie excess of said color coupler based on silver.

6. A photographic element according to claim 1 which comprises at least two of said image dyeproviding layer units which each contain fine-grain silver halide emulsion at a coverage of less than mg./ft. based on silver.

7. A photographic element according to claim 1 wherein said anionic organic compound is an anionic sulfonic acid and is present in a concentration of at least l0 mg./ft.

8. A photographic element according to claim 1 wherein said anionic organic acid is a polymeric compound having a molecular weight of at least 3000.

9. A photographic element according to claim 1 wherein said anionic compound is a polymeric compound comprising units having sulfonic acid groups thereon and units having crosslinking groups thereon.

10. A photographic element comprising a support and having thereon (l) a yellow image dye-providing layer unit comprising a silver halide emulsion having a mean grain size of at least 0.8 micron and a yellow image dye-providing color coupler, (2) a magenta image dye-producing layer unit comprising a silver halide emulsion having a mean grain size of less than 0.4 micron and a magenta image dye-providing coupler, and (3) a cyan image dye-providing layer unit comprising a silver halide emulsion having a mean grain size of less than 0.4 micron and a cyan image dye-providing coupler, wherein a nondiffus ible anionic organic polymer compound having sulfonic acid groups thereon and having an equivalent weight of at least based on sulfonic acid groups is present in said yellow image dye-providing layer unit in a concentration of at least 10 mg./ft. and wherein said magenta and cyan image dye providing units are substantially free of said nondiffusible anionic organic polymeric acid compounds.

11. A photographic element according to claim 10 wherein said anionic organic compound is an acrylic polymer.

12. A photographic element according to claim 10 wherein said anionic organic compound is present in said yellow image dye-providing layer unit in a concentration of at least 25 mg./ft. and said cyan and magenta dye image-providing layer units contain less than 5 mg./ft. of said anionic organic compound.

13. A photographic element-according to claim 10 wherein said anionic organic compound has an equivalent weight of less than 800 and is present in said yellow image dye-providing layer unit in a concentration of at least 25 mg./ft.

14. A photographic element according to claim 10 wherein said magenta and cyan image dye-providing layer units contain at least 2140 percent stoichiometric excess based on effective silver.

15. A photographic element according to claim 10 wherein said anionic organic compound is a poly(3- methacryloyloxypropanel-sulfonic acid).

16. A photographic element according to claim 10 wherein said anionic compound is poly(N- isopropylacrylamide--3-acryloyloxypropanel-sulfonie acid, sodium salt--2-acetoacetoxyethyl methacrylate).

17. A photographic element according to claim 10 wherein said anionic compound is poly(N- isopropylacrylamide-- -3-methacryloyloxypropane 1 -sulfonic acid, sodium salt-Z-acetoacetoxyethyl methacrylate 18. A photographic element according to claim 10 wherein said anionic organic compound in said yellow image dye-providing layer unit in a compound different from said image dye-providing color coupler.

' age UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,9 B 3 Dated September 9, 1975 lnven m-( Rowland George Mowrey It is certified that: error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3, line 62, after "organic", -acidshould be added.

Column 6, line 67, 'Flescher", should read --Fischer.

Q Column 6, line 68, "Fiescher", should read --Fischer--.

Column 9, line 19, "we l" should read --well-.

Column l L, line 15, "producing" should read -providing--.

' Column l I, line 60, "organic" should be deleted.

Column l I, line 61, "in", should read --is-.

' Engned and Ewalcd this sixth D y of January 1976 [SEAL] Attest: O

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner of Patents and Trademarks

Claims

1. A PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT HAVING AN IMAGE DYE-PROVIDING LAYER UNIT COMPRISING A FINE-GRAIN SILVER HALIDE EMULSION HAVING ASSOCIATED THEREWITH A COLOR COUPLER AND ANOTHER DYE IMAGE-PROVIDING LAYER UNIT CONTAINING A COARSE-GRAIN SILVER HALIDE EMULSION WHICH HAS A MEAN SILVER HALIDE GRAIN SIZE AT LEAST 50 PERCENT LARGER THAN THE MEAN GRAIN SIZED OF SAID FINE-GRAIN EMULSION, AND ASSOCIATED THEREWITH A COLOR COUPLER AND AT LEAST 10 MG./FT.2 OF A COMPOUND DIFFERENT FROM SAID COLOR COUPLER WHICH IS A NONDIFFUSIBLE ANIONIC ORGANIC POLYMERIC ACID HAVING AN EQUIVALENT WEIGHT OF AT LAST 100 AND LESS THAN 800 BASED ON ACID GROUPS: AND WHEREN SAID FINE GRAIN EMULSION IS SUBSTANTIALLY FREE OF SAID NON-DIFFUSIBLE ANIONIC ARGANIC POLYMER ACID COMPOUND.

5. A photographic element according to claim 1 wherein said image dye-providing layer unit containing said fine-grain emulsion comprises at least a 40 percent stoichiometric excess of said color coupler based on silver.

6. A photographic element according to claim 1 which comprises at least two of said image dye-providing layer units which each contain fine-grain silver halide emulsion at a coverage of less than 30 mg./ft.2 based on silver.

7. A photographic element according to claim 1 wherein said anionic organic compound is an anionic sulfonic acid and is present in a concentration of at least 10 mg./ft.2.

10. A photographic element comprising a support and having thereon (1) a yellow image dye-providing layer unit comprising a silver halide emulsion having a mean grain size of at least 0.8 micron and a yellow image dye-providing color coupler, (2) a magenta image dye-producing layer unit comprising a silver halide emulsion having a mean grain size of less than 0.4 micron and a magenta image dye-providing coupler, and (3) a cyan image dye-providing layer unit comprising a silver halide emulsion having a mean grain size of less than 0.4 micron and a cyan image dye-providing coupler, wherein a nondiffusible anionic organic polymer compound having sulfonic acid groups thereon and having an equivalent weight of at least 100 based on sulfonic acid groups is present in said yellow image dye-providing layer unit in a concentration of at least 10 mg./ft.2 and wherein said magenta and cyan image dye providing units are substantially free of said non-diffusible anionic organic polymeric acid compounds.

12. A photographic element according to claim 10 wherein said anionic organic compound is present in said yellow image dye-providing layer unit in a concentration of at least 25 mg./ft.2 and said cyan and magenta dye image-providing layer units contain less than 5 mg./ft.2 of said anionic organic compound.

13. A photographic element according to claim 10 wherein said anionic organic compound has an equivalent weight of less than 800 and is present in said yellow image dye-providing layer unit in a concentration of at least 25 mg./ft.2.

14. A photographic element according to claim 10 wherein said magenta and cyan image dye-providing layer units contain at least a 40 percent stoichiometric excess based on effective silver.

15. A photographic element according to claim 10 wherein said anionic organic compound is a poly(3-methacryloyloxypropane-1-sulfonic acid).

16. A photographic element according to claim 10 wherein said anionic compound is poly(N-isopropylacrylamide--3-acryloyloxypropane-1-sulfonic acid, sodium salt--2-acetoacetoxyethyl methacrylate).

17. A photographic element according to claim 10 wherein said anionic compound is poly(N-isopropylacrylamide--3-methacryloyloxypropane-1-sulfonic acid, sodium salt--2-acetoacetoxyethyl methacrylate).

18. A photographic element according to claim 10 wherein said anionic organic compound in said yellow image dye-providing layer unit in a compound different from said image dye-providing color coupler.