US3868252A - Photographic elements containing polymeric oxidants - Google Patents

Abstract

Nitroxyl-containing polymers are useful as oxidants in photographic elements or film units.

Description

United States Patent Campbell et al.

[4 1 Feb. 25, 1975 PHOTOGRAPHIC ELEMENTS CONTAINING POLYMERIC OXIDANTS Inventors: Gerald A. Campbell; Hyman L.

Cohen; Hans G. Ling; lgnazio S. Ponticello, all of Rochester, NY.

Assignee: Eastman Kodak Company, Rochester, N.Y.

Filed: Nov. 2, 1973 Appl. No.: 412,081

References Cited UNITED STATES PATENTS Land 96/76 R Rogers 96/29 D Schranz et al. 96/77 Gompf et al 96/77 Cohen et a1. 96/67 Primary Examiner-Norman G. Torchin Assistant Examiner-Edward C. Kimlin Attorney, Agent, or FirmD. M. DeLeo ABSTRACT Nitroxyl-containing polymers are useful as oxidants in photographic elements or film units.

19 Claims, No Drawings PIIOTOGRAPI-IIC ELEMENTS. CONTAINING POLYMERIC OXIDANTS FIELD OF THE INVENTION This invention relates to the art of photography and particularly to photographic elements, such as color diffusion transfer elements, employing oxidizing agents.

BACKGROUND OF THE INVENTION Color diffusion transfer processes generally involve the use of a photographic element comprising a support, at least one silver halide emulsion and an image dye-providing material which is contained in or contiguous said layer. After exposure, such a photographic element is treated with an alkaline processing solution to effect imagewise discrimination in the element. As is well known in the art, the dye-providing material can be initially immobile or initially mobile in the processing solution. Upon alkaline processing of an initially immobile dye-providing material, a mobile dye or dye precursor can be released imagewise or the material can be imagewise rendered soluble and thus mobile. If the material is initially mobile, the processing solution typically renders the material insoluble (and thus immobile) in an imagewise fashion. Whether initially mobile or immobile, upon treatment with a processing solution, the dye-providing material typicallyis oxidized under alkaline conditions thereby producing imagewise discrimination in the element.

Exemplary of such color diffusion transfer processes are those using developing agents as disclosed in U.S. Pat. Nos. 2,698,798 and 2,559,643 wherein alatent silver halide image is developed with a color developing agent. As development proceeds, the color developing agent reduces the exposed silver halide to metallic silver and the color developing agent which is oxidized as a function of development forms an immobile species while the unoxidized color developing agent is free to migrate to a receiving element. After migration, the color developing agent in the receiver is oxidized. The oxidized developing agent then self-couples or couples with a color coupler to form apositive dye image.

A more recent example of a photographic process in which oxidation causes formation of an image dye is described in copending Lestina and Bush US. application Ser. No. 308,869, filed Nov. 22, I97 2. and entitled PHOTOGRAPHIC ELEMENTS CONTAINING OX- ICHROMIC COMPOUNDS. Those oxichromic compounds are ones which undergo chromogenic oxidation to form a new chromophore. Useful materials of that type are oxichromic compounds which contain a developing moiety and an oxichromic moiety and have the general formula D-(OC) wherein D is a group which is a silver halide developer such as a hydroquinone moiety and C is a moiety which undergoes chromogenic oxidation to form an image dye. These oxichromic compounds are particularly useful in an image transfer unit format in which the respective initially diffusible oxichromic compounds or the initially nondiffusible compounds are used in combination with the appropriate silver halide emulsions.

In order to achieve optimum results when using such oxichromic compounds, it is desirable to have an oxidant which can be easily incorporated in a photographic element with good stability and which will readily oxidize the oxichromic moiety without adversely affecting other ingredients of a given photographic element or film unit. The oxidative conversion of oxichromic compounds or of other color-providing materials is necessary in order to achieve color image formation. Accordingly, there is a continuing need in the art for materials which exhibit suitable oxidation capability. Copending Chang et al. U.S. application Ser. No. 367,304, filed June 5, 1973 and entitled PHO- TOGRAPl-IIC ELEMENTS CONTAINING OXI- DANTS I, incorporated herein by reference describes the use of a simple nitroxyl free radicals as photographic oxidants. It would be desirable to provide even less mobile nitroxyl compounds than most of those described by Chang et al. in order to prevent wandering of the oxidant throughout the photographic element.

Some polymeric nitroxyl group-containing polymers are known in the art. Those having a high nitroxyl radical content are typically water insoluble, of low molecular weight, unstable, or a combination of these undesirable properties. For example, O. H. Griffith, J. F. W. Keana, S. Rottschaefer, and T. A. Warlick, JACS, 89, 5072 (I967) describe the synthesis and anionic polymerization of monomer I and the reaction of:

copoly(maleic anhydride-methyl vinyl ether) (mole ratio 1:1) with the nitroxyl alcohol II.

3 CH3 3 CH The polymers prepared from monomer I must be polymerized by anionic polymerization techniques which give low molecular weight materials. Further, the polymers derived from monomer l are water insoluble. The desired polymers prepared from the nitroxyl II may be water soluble, but they are described as highly colored materials which suggests instability. Nitroxyl groupcontaining polymers should show only the light red color typical of the nitroxyl radical. The polymers described have nitroxyl groups appended via ester linkages which are typically less stable than, for example, amide linkages.

V. A. Golubev, Dissertation, University of Moscow (1966) describesthe reaction of poly(acryloyl chloride) and nitroxyl II to give insoluble crosslinked polymers which would not be coatable and, therefore, would be unsuitable for photographic purposes.

E. g. Rozantsev and G. F. Pavelko, Vysokomol, Svedin. [B] 9, 866 1967), report the reaction of dialkylbis( l-oxyl-2,2,6,6-tetramethylpiperidine-4-oxyl)silane with sulfur dichloride to give a polymeric product. The polymer is believed to be a highly branched, water insoluble material.

Nitroxyl groups have been incorporated into various polymers, especially biopolymers and proteins, as a label to facilitate analysis by spin-labeling" techniques. In such studies, a-small amount of nitroxyl compound is covalently bonded to the polymer to be studied. The N-O. linkage of the nitroxide possesses an unpaired electron which has a characteristic ESR spectrum. This spectrum is very sensitive to the environment around the N-O. bond and much information can be attained regarding the conformation of the polymer from changes in the ESR spectrum of the nitroxide. These polymers are designed to have very low nitroxyl group concentrations and the methods used for preparing them require tedious handling of hazardous chemicals such as Grignard reagents, nitrosyl chloride, free iodine, lithium metal, and the like. For example, G. Drefahl, H. H. Horhold, and K. D. Hofmann, J. Prdkt. Chem, 37, 137 (1968) describe the treatment of mercurated polystyrene with nitrosyl chloride, conversion of the resulting nitroso derivative to the hydroxylamine with a Grignard reagent, and oxidation with silver oxide to produce a nitroxyl polymer containing about one nitroxyi radical per seven repeating styrene units. Likewise, A. T. Bullock, G. G. Cameron, and P. Smith,

Polymer, 89 (1972) labled polystyrene with a t butylnitroxyl group in 4 to 6% yield. Similarly, US. Pat. No. 3,453,288 of McConnell relates to the use of nitroxyls such as III and IV for ESR labeling:

CH3 CH3 N 3 2 CMQCHB CH 3 6' CH3 III Iv None of these prior art polymers appear to be suitable for photographic use because of instability, waterinsolubility, etc, or because of the difficulty in preparing them on a commercial scale. Thus, there is a need in the art for polymeric nitroxyl-containing compounds for use in photographic elements.

SUMMARY OF THE INVENTION We have found a class of polymeric nitroxylcontaining compounds for use in color diffusion transfer elements and in any other photographic element or system which a stable non-wandering oxidant is a necessary or desirable ingredient.

DESCRIPTION OF PREFERRED EMBODIMENTS The objects of the present invention are achieved through the use in photographic elements, e.g., a color diffusion transfer element, of a class of nitroxylcontaining polymeric oxidants. Typically, these compounds are used in a photosensitive element comprising a support having thereon at least one photographic image recording layer, and at least one layer containing a stable free nitroxyl radical of this invention.

As is well knonw in the literature, nitroxyl radicals are compounds containing the group which has one unpaired electron. The structure of this fragment can be conceived as a superposition of two resonance structures:

e -b t... 'N' O The contribution of either structure (1) or (2) to the ground state may be different, depending on the effects of conjugation and polarity of the medium. Hereinafter, the nitroxyl radicals will be represented simply by resonance structure (2) without designating the electron pair associated with the nitrogen atom in accordance with accepted practice.

The oxidants of this invention are water soluble polymers comprising at least 40 mole percent of a recurring unit having the formula:

I l R1 n C=O (iuox) wherein:

nis an integer having a value of O or I;

Q represents a bivalent linking group having the formula:

II or -c-1 I-R in which R has the same definition as R and in which the carbonyl moiety is attached directly to the polymeric backbone;

m and p each represent an integer having a value of Oor l;and

L represents an onium salt group as a phosphonium where R is alkyl of about 1 to 10 carbon atoms and X- is an anion), an ammonium salt group where R and X are as defined for phosphonium), including a cyclic ammonium salt group (for example,

wherein R is as described above and J represents the atoms necessary to complete a 5- or 6-membered heterocyclic ring such as a piperidinium or piperizinium group), or a sulfonium salt group least 5 mole percent of recurring units having appended therefrom a water solubilizing group such as an onium salt group (c.g., ammonium, sulfonium and phosphonium salts as described above for L), an acid group including acid salt groups (e.g., -COOH, -COONa, COONH,,, -SO H, SO Na), and the like.

Suitable nitroxyl radicals useful in this invention include those of the formula:

'-R it- R wherein:

R represents l an alkylene group including substituted alkylene having about 1 to l2 carbon atoms, preferably about 3 to 8 carbon atoms, and having no hydrogen on the carbon in the ovposition relative to (i.e., immediatcly adjacent) the nitrogen atom of the formula above or (2) an arylenc group having about 6 to 20 carbon atoms including substituted arylene having such substituents as alkyl of up to about 10 carbon atoms, alkoxy of up to about 10 carbon atoms, etc; and

R represents 1 an alkyl group including substituted alkyl having about 1 to 5 carbon atoms, preferably about 3 to 5 carbon atoms, and having no hydrogen on the carbon atom in the a-position relative to the nitrogen atom or (2) a substituted aryl group having about 6 to carbon atoms having such substituents as alkyl of up to about 10 carbon atoms, alkoxy of up to about l0 carbon atoms, nitro, etc.

Preferred nitroxyls are those heterocyclic radicals having the formula:

R R", R and R", when taken separately, can each represent a lower alkyl group having about 1 to 5 carbon atoms;

R and R or R and R can represent an imino group (=NH) including substituted imino (e.g., -NR wherein R is an alkyl group having 1 to about 25 carbon atoms) or together with the carbon atom to which they are attached, can represent the carbon atoms necessary to form a 5- or 6-membered cycloalkyl or cycloalkenyl nucleus including corresponding substituted 5- or 6-membered cyclic nuclei having from about 5 to 25 carbon atoms.

One of R and R, when taken with Z, can represent a double bond in the cyclic nucleus formed by Z, in which case R and R respectively, represents (1) an aryl group having about 6 to 25 carbon atoms, including substituted aryl (e.g., tolyl, aminophenyl, diethylaminophenyl, chlorophenyl, diphenylaminophenyl) or (2) an amino radical including substituted amino (e.g., dimethylamino, methylethylamino, methylphenylamino); and

Z represents the nonmetallic atoms necessary to complete a 5-, 6- or 7-membcred heterocyclic nucleus having up to two nitrogen hetero atoms and including substituted 5-, 6- or 7'membered heterocyclic nuclei having such substituents as alkyl having 1 to about 25 carbon atoms, aryl having 1 to about 25 carbon atoms including substituted aryl, amino including alkyl and aryl substituted amino, substituted carbonamido, substituted sulfonamido, substituted carbonyloxy, oxo (=0), imino (=NH) including substituted imino (e.g., =NR, where R is alkyl as above), hydroxy, an oxygen atom, and the like.

Various synthetic techniques for preparing nitroxyl radicals useful in forming the nitroxyl substituents on the polymers of this invention are described in Free Nitroxyl Radicals, E. G. Rozantsev, Plenum Press, New York, 1970. A large number of stable radicals can be prepared from heterocyclic amines which have no hydrogen on the carbon atoms ato the nitrogen atoms such as di-t-alkylamines, t-alkylarylamines, etc. Those amines are oxidized with hydrogen peroxide in the presence of (l) phosphotungstic acid or (2) a salt of vanadium, molybdenum or tungsten. Diarylamines are oxidized to the corresponding diarylnitroxyl with perbenzoic acid at 0C. Heterocyclic nitroxyls having more than one heteroatom (e.g., porphyrexide are also known in the art as are methods for their preparation. Similarly, binitroxyls and conjugated biradicals are also known. See, for example, Organic Chemistry of Stable Free Radicals, Forrester et al., 1968.

The term stable as used in connection with the nitroxyl radicals pendent from the present polymeric oxidants has reference to the fact that these compounds exist as free radicals without self-decomposing for a period of time extending at least until the imaging process is substantially complete. 7

The nitroxyl-containing polymers of this invention can be colored, provided the coloration of the oxidant does not adversely effect image quality. In a format wherein the oxidant remains behind an opaque layer where it cannot be viewed, the coloration of the oxidant will not interfere with image quality. Of course,

valent bond (linking the nitroxyl radical to the remainder-of the polymer) is located in the 4- r para-position relative to the nitrogen atom of Formula (7).

The nitroxyl-containing polymers of this invention colorless or low color nitroxyl-containing polymers, 5 can be prepared by several methods. In one embodiwhich at most give rise to only a very low Dmin., are particularly preferred in that such materials are more versatile. A colorless or low color oxidant can be positioned in a film unit in any place that a colored oxidant ment, a method is employed similar to that described by Cohen et al. in US. application Ser. No. 400,778, filed Sept. 26, 1973 and entitled POLYMERS AND PHOTOGRAPl-IIC ELEMENTS CONTAINING could be located. In addition, a low color oxidant can l0 SAME, which application is incorporated herein by refbe positioned, for example, in an image-receiving element where it is not hidden from view. Because of their greater versatility, polymers containing nitroxyl radicals having formula (7) above are particularly preferred wherein:

R R R and R", when taken separately, represent a lower alkyl group having 1 to about 5 carbon atoms;

R and R or R and R together with the carbon atom to which they are attached, represent the carbon atoms necessary to form a 5- or 6-membered cycloalkyl Polymer l Polymer 2 represents the carbon atoms necessary to complete 2 Polymer erence. This method involves the alkylation of a tertiary amine with an alkylating agent. According or this method a polymer having recurring tertiary amine or alkylating functional groups is reacted with a monofunctional alkylating agent r tertiary amine, respectively, to form an ammonium salt. The present method differs from that of Cohen et al in that the monofunctional reactant contains a nitroxyl radical as a substituent. This method can be illustrated as follows:

A. Starting polymer is a tertiary amine o II 1IIHCCH Cl Polltymer O V II (NIOX) R1\lICH CNH-(NIOX) B. Starting polymer is an alkylating agent II NHCCH N(R) V Polymer (NIOX) :69 CIl l\ l-CH Cl:IH

R (NIOX) O NHC N NR -9 Polymer (NIOX) ll cH N NC.II\IH C16 (NIOX) a 5- or 6-membered heterocyclic nucleus including a wherein R is an alkyl group of about 1 to 10 carbon substituted 5- or 6-membered heterocyclic nucleus having such substituents as alkyl having 1 to about 25 carbon atoms, acyl having 1 to about 25 carbon atoms, amino, substituted carbonamido, substituted sulfonamatoms, for example, in both A and B.

Another suitable method for preparing polymers of this invention involves the reaction of a nitroxylido, substituted carbonyloxy, oxo (=0), hydroxy and containing primary amine with a copolymer of maleic the like. Typically, when the heterocyclic nucleus formed by Z is a substituted 6-membered ring, the coanhydride to produce an N-substituted polyimide in which the substituent is a nitroxyl radical as follows:

(NIOX) In this latter reaction, a sufficient amount of earboxyl groups remain unreacted so as to impart water solubility to the polymer.

Polymeric oxidants having the recurring units of formula 3 in which n is l and Q is a simple alkylene or arylene can be made from the corresponding polymeric acid chloride or ester with a nitroxyl-containing amine as follows:

Polymer or Polymer IIIH l I an CH CH5 CH (NIOX) C=O 'C=O Cl R Similarly, polymeric oxidants in which Q is a simple carbonyloxyalkyl, carbonyloxyaryl, etc, can be made from the corresponding polymeric acid chloride or acid ester and a nitroxyl-containing amine.

The polymers of the present invention can be homopolymers or copolymers. Suitable copolymers can be comprised of recurring units as described above together with recurring units derived from another addition polymerizable monomer. Representative comonomers include ethylene, styrene, acrylics including acrylic and methacrylic esters (as well as acrylic acids and amides), maleic acid, maleimide, methylvinyl ether, acrylonitrile, phenylacrylate, isopropylacrylate, N-vinyI-Z-pyrrolidone, Z-acetoacetoxyethyl methacrylate, active methylene-containing monomers which are hardenable by conventional photographic hardeners (as described, for example, in U.S. Pat. Nos. 3,459,290 and 3,488,708 incorporated herein by reference), sulfonated monomers (e.g., B-acryloyloxypropanc-lsulfonic acid, sodium salt or 3 methacryloyloxypropane-l-sulfonic acid, sodium salt), and the like.

Whether a homopolymer or a copolymer is used, the nitroxyl-containing polymers of this invention should have a relatively high molecular weight, preferably greater than about 5,000. Also, as mentioned above, the nitroxyl-containing recurring units of the polymer should comprise at least 40 mole percent of the total polymer in order to provide good oxidizing properties. Preferred embodiments of this invention use a polymer of the type described which contains greater than 50 mole percent of the nitroxyl-containing recurring unit. As also mentioned above, the polymer should contain at least mole percent of recurring units which have appended a water solubilizing group. The water solubilizing recurring unit can be the same or different from the nitroxyl-containing recurring unit. Particularly advantageous from the standpoint of preparation are those polymers in which the water-solubilizing group is contained in the same recurring unit as the nitroxyl radical.

The nitroxyl-containing polymers described herein can be used in a wide variety of photographic elements or in photographic film units. In certain embodiments, these polymers can be used in photographic elements or film units to provide an oxidant for the synthesis of image dyes. The nitroxyl radicals ofthese polymers can be used to generate oxidized color developing agent which then reacts with a color coupler to form the image dye. Additionally, these radicals can be used to oxidize a compound directly to an image dye as in the case ofleuco indoanilines, leuco indophenols, leuco triarylmethanes and other dye precursors.

In one embodiment, the present nitroxyl-containing polymers are useful in color diffusion transfer processes such as those in which unreacted color formers in undeveloped or partially developed areas of a photographic element diffuse im agewise, after color development of the exposed layers, to a receiving layer in which the color formers react with oxidized color developer to produce an imagewise distribution of dye.

Polymer CH2 CH2 C=O NH (NIOX) By including a polymeric oxidant of this invention in the receiving layer or having it in association therewith, dyes are formed imagewise in that element as a result of the interreaction of the oxidant, color developer and diffused color former. Processes of this type are described further in British Pat. No. 926,462, dated May 15, I963, incorporated herein by reference.

Examples of processes in which an image is formed upon oxidation of transferred color developer and color coupler are described in U.S. Pat. Nos. 2,559,293 and 2,698,798, incorporated herein by reference. Similarly, the present oxidants can be used in imaging processes based on leuco anthraquinones and other dye precursors which produce dyes when oxidized or processes based on developers which self-couple upon oxidation, thereby producing dyes. Processes of these latter types are described further in U.S. Pat. Nos. 2,892,710 and 2,698,798, respectively, both incorporated herein by reference. Likewise, the described oxidants have utility in color diffusion transfer processes using a leuco developing agent, as discussed in U.S. Pat. Nos. 2,992,105 and 2,909,430, incorporated herein by reference.

In another embodiment, the nitroxyl'containing polymers can be used to oxidize the developer portion of a dye developer (Le, a compound which contains a silver halide developing moiety and a separate moiety which contains the chromophore of an image dye). The nitroxyl radical selected must have an oxidation potential sufficient to oxidize the developer portion of the molecule, such as the hydroquinone portion. In this embodiment, the nitroxyl radicals on the polymeric oxidant can function to immobilize the dye developer, such as when it diffuses to the receiver layer, by forming the quinone, quinonimide, etc, of the developer moiety which is generally quite insoluble in an alkaline processing solution.

In other embodiments, the nitroxyl radical can be used to stabilize a preformed image dye. In some embodiments, the nitroxyls produce a beneficial increase in the stability of azo dyes which are transferred to an image-receiving layer.

In still other embodiments, a photographic element containing the present oxidants can be treated to form an image-wise distribution of oxidant. The photographic element can then be contacted with a material which will undergo oxidation to produce an image record in the photographic element. In one example of this embodiment, a photographic element bearing a silver halide emulsion and an adjacent layer containing the present nondiffusible nitroxyl oxidant can be developed with a silver halide developer. Where silver halide is not developed, the oxidant will be reduced. The element can then be contacted with a solution of color coupler and color developer to react with the remaining imagewise distribution of nitroxyl compound and produce an image dye.

The nitroxyl-containing polymers of this invention are particularly well suited for use as oxidants in photographic elements or film units which contain an oxichromic compound of the type described in copending Lestina and Bush U.S. application Ser. No. 308,869, mentioned above and incorporated herein by reference. Preferred oxichromic compounds are those which undergo chromogenic oxidation to form a photographic image dye. In one embodiment, the present nitroxyl radical oxidants are incorporated into photographic elements containing oxichromic compounds of the formula:

wherein (COUP) is a photographic color coupler linked to the nitrogen atom through a carbon atom at the coupling position, such as a phenolic coupler, a pyrazolone coupler, a pyrazolotriazole coupler, couplers having open-chain ketomethylene groups and the like; Ar is an arylene group containing from 6 to 20 carbon atoms, including substituted and unsubstituted arylene groups, fused-ring arylene groups and the like; J can be an amino group, including substituted amines, a hydroxyl group or the group:

ll -O-CR in which R is a group containing from 1 to 12 carbon atoms, which can be alkyl group, an aryl group, including a substituted alkyl group, a substituted aryl group and the like; R" is a hydrogen atom or the group:

0 ll -C-R in which R" is as defined above and is preferably a polyhalogenated alkyl group; and T is a group which is (l) a silver halide developing agent which is preferably an aromatic group polysubstituted with hydroxy, amino or substituted amino groups or (2) an oxidizable releasing group (i.e., a group which can be oxidized to facilitate subsequent release of a group or a group which can be oxidized to prevent the normal release of a group under the processing conditions When T is a silver halide developing agent, the resultant compound preferably is initially mobile. When T is an oxidizable releasing group, the resultant compound preferably is initially immobile.

The present nitroxyl oxidants can be used in the processing fluid if oxidation is desired at this location in a diffusion transfer film unit. More commonly, the present oxidants are located near or in the image receiving layer of a diffusion transfer film unit employing other image dye-providing materials mentioned above. The image-transfer film units can be any of those described in the following patents, all incorporated herein by reference: U.S. Pat. Nos. 2,543,181, 2,983,606, 3,227,550, 3,227,552, 3,415,644, 3,415,645, 3,415,646 and 3,635,707, Canadian Pat. No. 674,082, and Belgian Pat. Nos. 757,959 and 757,960, both issued Apr. 23, 1971.

When used in the processing fluid of various diffusion transfer film units, the nitroxyl oxidant is typically present in a concentration of about 0.01 to about 0.1 molar. When not contained in the processing fluid, the present oxidants are coated in at least one layer which typically contains a binder such as gelatin, poly( vinyl alcohol), etc. Of course, the nitroxyl-containing polymers described herein can also be one of several ingredients in a given layer. For example, when used in color diffusion transfer units, the nitroxyl polymers can be contained in a mordant layer. In general, these polymers are coated at a coverage of about 40 to 500 mg/ft depending upon the milliequivalents of nitroxyl radical in the polymer of choice. There should, however, be sufficient nitroxyl-containing polymer present to give substantially complete oxidation. The amount necessary to accomplish complete oxidation is, of course, dependent upon the amount and type of oxichromic compound used. In preferred embodiments, the nitroxyl polymers are used in image-transfer film units which are designed to be processed with a single processing solution, and the resulting positive image is viewed through a transparent support against an opaque background, preferably where all of the silver halide recording layers and the image-receiving layer remain laminated between two dimensionally stable supports after processing.

A suitable image transfer film unit in which the present oxidants are useful typically comprises:

1. a photosensitive element comprising a support having thereon at least one layer containing a silver halide emulsion having associated therewith an image dyeproviding material and preferably at least three of said layers wherein one layer contains a blue-sensitive silver halide emulsion, one layer contains a green-sensitive silver halide emulsion, and one layer contains a redsensitive silver halide emulsion;

2. an image-receiving layer which can be located on a separate support superposed or adapted to be superposed on said photosensitive element or, preferably. it can be positioned in the photosensitive element on the same support adjacent to the photosensitive silver halide emulsion layers; and

3. means containing an alkaline processing composition adapted to discharge its contents within said film unit. Where the receiver layer is coated on the same support with the photosensitive silver halide layers, the support is preferably a transparent support, an opaque layer is preferably positioned between the imagereceiving layer and the photosensitive silver halide layer, and the alkaline processing composition preferably contains an opacifying substance such as carbon or pH-indicator dye which is discharged into the film unit between a dimensionally stable support or cover sheet and the photosensitive element. In certain embodiments, the cover sheet can be superposed or adapted to be superposed on the photosensitive element. The image-receiving layer can be coated on the cover sheet. In certain preferred embodiments where the imagereceiving layer is located in the photosensitive element, a neutralizing layer is located on the cover sheet.

The means containing the alkaline processing solution can be any means known in the art for this purpose, including rupturable containers positioned at the point of desired discharge of its contents into the film unit and adapted to be passed between a pair ofjuxtaposed rollers to effect discharge of the contents into the film unit, frangible containers positioned over within the photosensitive element, hypodermic syringes, and the like.

The silver halide emulsions useful in our invention are well known to those skilled in the art and are described in Product Licensing Index, Volume 92, December, 1971, publication 9232, p. 107, paragraph I,

Emulsion types, they may be chemically and spectrally sensitized as described on page 107, paragraph III, Chemical sensitization, and pp. 108-109, paragraph XV, Spectral sensitization, of the above article; they can be protected against the production of fog and can be stabilized against loss of sensitivity during keeping by employing the materials described on p. 107, paragraph V, Antifoggants and stabilizers of the above article; they can contain development modifiers, hardeners, and coating aids asdescribed on pp. 107-108, paragraph IV, Development modifiers, paragraph VII, Hardeners; and paragraph XII, Coating aids of the above article; they and other layers in the photographic elements used in this invention can contain plasticizers, vehicles and filter dyes described on p. 108, paragraph XI, Plasticizers and lubricants, and paragraph VIII, Vehicles, and p. 109, paragraph XVI, Absorbing and filter dyes, of the above article; they and other layers in the photographic elements used in this invention may contain addenda which are incorporated by using the procedures described on p. 109, paragraph XVII, Methods of addition", of the above article; and they can be coated by using the various techniques described on p. 109, paragraph XVIII, Coating procedures, of the above article, the disclosures of which are hereby incorporated by reference.

Any material can be employed as the image-receiving layer in this invention as long as the desired function of mordanting or otherwise fixing the dye images will be obtained. The particular material chosen will, of course, depend upon the dye to be mordanted. If acid dyes are to be mordanted, the image-receiving layer can contain basic polymeric mordants such as polymers of amino guanidine derivatives of vinyl methyl ketone such as described in Minsk U.S. Pat. No. 2,882,156, issued Apr. 14, 1959, and basic polymeric mordants such as described in Cohen et al. U.S. Pat. No. 3,709,690, issued Jan. 9, 1973.

Additional mordants include cationic mordants such as polymeric compounds composed of a polymer having quaternary nitrogen groups and at least two aromatic nuclei for each quaternary nitrogen in the polymer cation (i.e., having at least two aromatic nuclei for each positively charged nitrogen atom), such polymeric compounds being substantially free of carboxy groups. Useful mordants of this type are comprised of units of the following formula in copolymerized relationship with units of at least one other ethylenically unsaturated monomer.

I R X wherein R and R each represent a hydrogen atom or a lower alkyl radical (of 1 to about 6 carbon atoms) and R can additionally be a group containing at least one aromatic nucleus (e.g., phenyl, na'phthyl, tolyl); Q' can be a divalent alkylene radical (of l to about 6 carbon atoms), a divalent arylene radical, a divalent aralkylene radical, a divalent arylenealkylene radical,

wherein R is an alkylene radical, or R can be taken together with Q to form a group; R, R and R can be lower alkyl or aryl, or R and R and the nitrogen atom to which they are attached can together with Q represent the atoms and bonds necessary to form a quaternized nitrogencontaining heterocyclic ring, and X is a monovalent negative salt forming radical or atom in ionic relationship with the positive salt forming radical; wherein said polymer is substantially free of carboxy groups and wherein the positive salt forming radical of said polymer comprises at least two aryl groups for each quaternary nitrogen atom in said polymer. These preferred polymeric cationic mordants are described further in the above-mentioned U.S. Pat. No. 3,709,690, incorporated herein by reference.

Other mordants useful in our invention include poly- 4-vinylpyridine, the 2-vinylpyridine polymer metho-ptoluene sulfonate and similar compounds described in Sprague et al. U.S. Pat. No. 2,484,430, issued Oct. 11, 1949, and cetyl trimethylammonium bromide, etc. Effective mordanting compositions are also described in Whitmore U.S. Pat. No. 3,271,148 and Bush U.S. Pat. No. 3,271,147, both issued Sept. 6, 1966. Additionally, the present nitroxyl-containing polymers which contain a quaternary amine center can be used as mordants for acid dyes without the need for any other mordants. Thus, many of the polymeric compounds of this invention can serve both as an oxidant and as a mordant for image dyes.

The following preparations and examples are included for a further understanding of the present invention.

PREPARATION l A solution of 3.18 g. (0.0202 mole) of poly(2- dimethylaminoethyl methacrylate [n] benzene 0.40* and 5.0 g. (0.0202 mole) of 4-(a-chloroacetamido)-2,2.6,6-tetramethylpiperidine-l-oxyl in 30 mLof N,N-dimethylformamide was heated under nitrogen on the steam bath for 3 hours. The polymer was isolated by precipitation in ether, collected by filtration, and dissolved in 30 ml. of methanol. The polymer was reprecipitated in ether, collected by filtration, and dissolved in 30 ml. of water while still clamp. The solution was then placed on the rotary evaporator for a short time to remove traces of ether, leaving an aqueous solution of polymeric oxidant l (18% solids). The theoretical values calculated for C H N O Cl and the values actually found are as follows:

Calculated: C,56.4;H,8.7;N,10.4;C1,8.8

Found: C,56.4;H,8.6;N,10.4;C1,8.2

*All inherent viscosities were measured at 25C. at a concentration of 0.25 g/deciliter of solution in the solvent specified.

PREPARATION 2 Preparation 1 was repeated using 3.72 g. (0.0202 mole) of poly[N-(3-dimethylamino-l,l-dimethylpropyl)acrylamide] and 5.0-g. (0.0202 mole) of 4-(achloroacetamido )-2 ,2 ,6 ,6-tetramethylpipe ridinel oxyl except that the product was isolated by precipitation' from acetone. The polymer was dissolved in ml. of water to give a clear solution containing 9.9% solids.

Calculated: Found:

C, 58.4; H C, 54.9; H,

bio

PREPARATION 3 A reaction was carried out with 3.15 g. (0.0202 mole) of poly[N-(3-dimethylaminopropyl)acrylamide] [n] 0.28 and 5.0 g. (0.0202 mole) of 4-(achloroacetamido)-2,2,6,6-tetramethylpiperidine-1- oxyl in the same manner as in Preparation 1 except that the product was isolated first by precipitation in acetone, followed by dissolution in 30 ml. of methanol and reprecipitation in ether. The polymer was then dissolved in 35 ml. of water to give a clear solution containing 19.9% solids. The theoretical values calculated for C H ClN O and the values actually found are as follows:

"DMF N,N-Dimethylformamide Calculated: C, 56.4; H, 8.9; N, 13.9; C1, 8.8 Found: C, 56.5; H, 9.6; N, 13.8; CI, 8.2

PREPARATION 4 A reaction was run in the same manner as in Preparation 1 using 2.62 g. (0.0101 mole) of poly[styrene-co- N-(3-dimethylaminopropy1)acrylamide] (1:1) and 5.0 g. (0.0202 mole) of 4-(a-chloroacetamido)-2,2,6,6- tetramethylpiperidine-l-oxyl except that the solution was heated on the steam bath for 5 hours. The final product was dissolved in 30 ml. of water to give a clear solution containing 9.9% solids. The theoretical values calculated for C l-l C1N O and the values actually found are as follows:

Calculated: C.63.8; H.8.7 Cl,7.0; N, 11.0 Found: C.66.8; H.8.2 Cl,5.3; N, 10.0

*DMF N,N-Dimethylformamide PREPARATION 5 A solution of3.l0 g. (0.0203 mole) of poly(vinylbenzyl chloride) ]'q],, 0.42 and 3.0 g. (0.0102 mole) of N-(2-dimethylaminoethyl)-N"(2,2,6,6-tetramethyl- 4-piperidine-l-oxyl)urea in 30 ml. of methoxyethanol was heated at 100C for 3 hours. The polymer was precipitated in acetone, collected by filtration, and dissolved in 30 ml. of methanol. The polymer was reisolated by precipitation in ether, collected by filtration, and dissolved while still damp in 50 ml. of water. The aqueous solution was placed on the rotary evaporator for a short time to remove traces of ether leaving an aqueous solution containing 10.8% solids. The theoretical values calculated for C H C1 N O and the values actually found are as follows:

Calculated:

Cl. 12.0 Found: C,

PREPARATION 6 for C I-I N O Cl and the values actually found are as follows:

Calculated: 8.6; N, Found: 8.9; N,

PREPARATION 7 A solution of 6.4 g. (0.025 mole) of copoly(styrenevinylbenzylchloride) (1:1) [1 0.75 and 7.0 g. (0.0273 mole) of 4-(a-dimethylaminoacetamido)- 2,2,6,6-tetramethylpiperidine-l-oxyl in ml. of benzyl alcohol was heated at 100C under nitrogen for 3 hours. The polymer was isolated by precipitation in acetone, collected by filtration, and dissolved in 50 ml. of methanol. The product was reprecipitated in ether, collected by filtration, and dissolved while still damp in ml. of water. The solution was placed on the rotary evaporator for a short time to remove traces of ether leaving an aqueous solution containing 9.4% solids. The theoretical values calculated for C H N O Cl and the values actually found are as follows:

Calculated:

PREPARATION 8 A solution of 3.55 g. (0.029 mole) of copoly[ethylenemaleic anhydride] (1:1) and 5.0 g. (0.029 mole) of 3-amino-2,2,5,5-tetramethylpyrrolidine-loxyl in 30 ml. of N,N-dimethylformamide was heated at C for 30 minutes. The polymer was precipitated in ether, collected by filtration, and dissolved in 50 ml. of water while still damp. The solution was placed on the rotary evaporator for a short time to remove traces of ether leaving an aqueous solution having a 10% solids content. The theoretical values calculated for C H N O and the values actually found are as follows:

H, 8.2; N, 9.9 H, 8.8; N, 10.4

PREPARATION 9 A solution of 3.55 g. (0.029 mole) of copoly[ethylenemaleic anhydride] (1:1) and 7.0 g. (0.041 mole) of 4-amino-2,2,6,6-tetramethylpiperidine-l-oxyl in 35 ml. of N,N-dimethylformamide was heated at C for 30 minutes. The polymer was precipitated in ether, dissolved in 50 ml. of methanol and reprecipitated in ether. The polymer was collected by filtration and dissolved in 80 ml. of water while still damp. The solution was placed on the rotary evaporator for a short time to remove traces of ether leaving an aqueous solution having an 8.6% solids content. The theoretical values calculated for C I-1 N 0 and the values actually found are-as follows:

Calculated: C, 60.7; H, 8.4 N, 9 8 Found: C, 58.7; H, 9.2 N, 9 3

EXAMPLE 1 The oxidants listed in Table 1 below were tested as follows: A matrix element comprised of a transparent film base support having a layer of 125 mg/ft gelatin and 50 mg/ft of oxichromic compound dissolved in 75 mg/ft of diethyl lauramide is placed in face-to-face contact with a receiver in the presence of an alkaline processing composition between the matrix and the receiver. The receiver was comprised of a transparent film base support having on it a first layer of 200 mg/ft of oxidant (prepared according to the Preparation number given) in 100 mg/ft of gelatin and a second layer (over the first layer) comprising 2000 mg/ft of titanium dioxide in 200 mg/ft of gelatin. The processing composition comprised a 7.5% potassium hydroxide solution containing 2.5% hydroxyethyl cellulose thickener. Upon contact of the two elements, the oxichrome migrated from the matrix through the processing composition and the titanium dioxide layer into the oxidant layer (which was also the mordant layer) of the receiver. The oxichrome was oxidized by the nitroxylcontaining polymeric oxidant to the corresponding dye which was visible through the transparent support and against the white background of the titanium dioxide layer. The oxichromic compounds, the oxidants and the color and density of the dye in the receiver are shown in Table 1 below. The structures ofthe oxichromic compounds are shown after the examples.

Table 1 Time of Oxidant of Contact Dye ln Prep. No. Oxichrome (Seconds) Receiver "max l A 60 Yellow 1.3 l B 60 Magenta 1.7 1 C 60 Cyan 1.7 2 D 60 Cyan 1.5 2 C 60 Cyan 1.2 2 B 60 Magenta 2.1 2 A 60 Yellow 1.7 3 A 60 Yellow 1.4 3 B 60 Magenta 2.2 3 D 60 Cyan 1.5 4 A 60 Yellow 1.5 4 B 60 Magenta 2.3 4 D 60 Cyan 1.8 5 A 60 Yellow 1.3 5 B 60 Magenta 2.4 5 D 60 Cyan 1.6 6 A 60 Yellow 1.2 6 B 60 Magenta 1.3 6 D 60 Cyan 1.3 7 A 60 Yellow 1.5 7 B 60 Magenta 2.1 7 D 60 Cyan 1.5

EXAMPLE 2 The procedure of Example 1 was repeated using the oxidant of Preparation No. 8. This oxidant does not contain a quaternary amine center and thus, between the oxidant layer and the support, there was interposed a mordant layer comprised of 200 mg/ft of copoly[styrene:N,N-dimethyl-N-benzyl-N(3-maleiimidopropyl- )ammonium chloride] in 100 mg/ft of gelatin. After contacting the matrix and the receiver for 60 seconds in the presence of the developing composition, oxichrome A produced a yellow dye having a density of 0.7 and oxichrome B produced a magenta dye having a density of 2.4.

EXAMPLE 3 An integral, color transfer, photographic element is prepared as follows (the full identification of certain components follows the examples):

1. transparent polyethylene terephthalate support;

2. dye mordant/oxidant layer containing gelatin at 100 mg/ft and the nitroxyl-containing oxidant of Preparation No. 4 at 200 mg/ft 3. layer containing titanium dioxide at 2000 mg/ft and gelatin at 200 mg/ft;

4. layer containing carbon opacifying agent at 20 mg/ft and gelatin at 156 mg/ft 5. layer containing gelatin at mg/ft 2,5-disecdodecylhydroquinone at 70 mg/ft and tricresyl phosphate at 23 mglft 6. layer containing a red-sensitive silver bromoiodide emulsion at 70 mg/ft based on silver, gelatin at 230 mg/ft Compound E at 42 mg/ft dispersed in diethyl lauramide at 73 mg/ft 5-(2-cyanoethylthio)- l-phenyltetrazole at 5 mg/ft dispersed in tricresyl phosphate at 15 mg/ft and 5,6,7,8-tetrahydro-5,8- methano-l,4-naphthalenediol at 10 mg/ft 7. layer containing gelatin at 300 mglft 2,5-disecdodecylhydroquinone at 70 mg/ft and a magenta filte'r dye at 30 mg/ft dissolved in diethyl lauramide at 50 mg/ft 8. layer containing green-sensitive silver bromoiodide emulsion at 70 mg/ft based on silver, gelatin at 230 mglft oxichromic compound B at 54 mg/ft dispersed in diethyl lauramide at 64 mg/ft 5-(2- cyanoethylthio)-l-phenyltetrazole at 5 mg/ft dispersed in tricresyl phosphate and 5,6,7,8-tetrahydro-5,8-methano, 1,4-naphthalenediol at 10 mg/ft 9. layer containing gelatin at 300 mglft 2,5-disecdodecylhydroquinone at 70 mg/ft and a yellow filter dye at mg/ft dispersed in diethyl lauramide at 28 mg/ft 10. layer containing a blue-sensitive silver bromoiodide emulsion at 70 mg/ft based on silver, gelatin at 210 mg/ft oxichromic compound A at 64 mg/ft dispersed in diethyl lauramide at 106 mglft 5-(2- cyanoethylthio)-1-phenyltetrazole at 5 mg/ft dispersed in tricresyl phosphate at 15 mg/ft and 5,6,- 7,8-tetrahydro-5 ,S-methano-l ,4-naphthalenediol at 10 mg/ft 11. layer containing gelatin at 50 mglft A transparent cover sheet for the above element is prepared as follows:

1. transparent polyethylene terephthalate support;

2. layer containing gelatin at 900 mg/ft, polyacrylic acid at 900 mg/ft and imidazole at 760 mglft 3. layer containing cellulose acetate at 1140 mg/ft and copoly(styrene-maleic anhydride) at 60 mg/ft The photographic element is exposed through a multicolor, graduated-density test object, the transparent cover sheet superposed on the element, and a pod containing an opaque processing composition is ruptured to discharge between the cover sheet and the photosensitive element by passing the film unit through juxtaposed rollers having a gap of about 8 mils. The processing composition is as follows:

a-benzylpicolinium bromide The invention has been described in detail with par- 5,6,7,8-tetrahydro-f ,8-methano- 'ticular reference to certain preferred embodiments ifl p 3 7 thereof, but it will be understood that variations and wateno I met modlficatlons can be effected within the spirit and 5 scope of the invention.

-Continued After about 1 to 2 minutes, a well-defined color image with good color reproduction is viewed through the We claim:

transparent support of the integral element. 1. A photographic element comprising a support hav- Table 2 below gives the structures of Compounds A ing thereon at least one photosensitive silver salt emulthrough E referred to in the preceding examples. 10 sion layer and at least one layer containing a water- Table 2 Compound Formula 2 I? OC H A (CH C-C-CH-CNH l NH OH E QA OC-CH OH OH mil 2) NHCO (cH h fg B g OH NH Cl Cl 'OQOCH OH I C CO F O F F o (CHQMC NcocF OH X? D Y ?,(CH2MCONH NCOCF3 H c:[ t 01 OH 9 E OH la C.@Y OC5H11 r (cn mcoun or C1 CH Cl 21 22 soluble polymer comprising at least 40 mole percent of prising at least 40 mole percent of a recurring unit hava recurring unit having the formula: i the formula:

R I i CH c CH -cl l l l R R (o I (3:0 C=O 2 l 2 R-N R N l I (NIOX) (NIOX) l5 wherein:

n is an integer having a value of 0 or 1;

wherein: 0 represents a bivalent llnkmg group of the formula:

n is an integer having a value of 0 or 1; )m )p Q represents a bivalent linking group of the formula: in which a and 4 each represent an alkylene group,

a 4 an arylene group or an alkarylene group, and R can in which R and R each represent an alkylene group, also represent a group of the formula:

an arylene group or an alkarylene group, and R 'can v 2 also represent a group of the formula: o O R O 0 2 in which R has the same definition as R and in which 5 or 5 the carbonyl moiety is attached directly to the polymeric backbone;

m and p each represent an integer having a value of 0 or 1; and in which R has the same definition as R and in which L represents an Onium l group; the carbonyl moiety is attached directly to the poly- R represents h d n atom, a carboxy group or mel'ie backbone? when taken together with R represents a linking m and p each represent an integer having a value of carbonyl group;

0 0r and R 'represents a hydrogen atom, an alkyl group or,

L represents an onium salt group; when taken together i h R a bonyl group; and

R represents a hydrogen atom of an alkyl group; 40 (NIOX) represents a stable free nitroxyl radical;

represents a hydrogen atom a earbexy group or said polymer further comprising at least 5 mole percent when taken together with R2 represents a linking of a recurring unit having appended therefrom a water carbonyl group; solubilizing group.

R2 represents a hydrogerl atom, an alkyl group, or 6. The film unit as described in claim 5 wherein said when taken together wlth R2 represents a polymer is associated with said image-receiving layer. hohyl group; and 7. The film unit as described in claim 5 wherein said represents a Stable free nitroxyl radical; polymer is contained in said alkaline processing comsaid polymer further comprising at least 5 mole percent i i Ofa recurring having appended therefrom a water 8. The film unit as described in claim 5 wherein solubilizing P- 5 (NIOX) represents a heterocyclic nitroxyl radical hav- 2. A photographic element as described in claim 1 i the f l wherein (NIOX) represents a heterocyclic nitroxyl radical. ,Z,

3. A photographic element as described in claim 1 lCR 11 wherein n and m are both 1 and L represents an ammo- I R nium salt group.

4. A photographic element as described in claim 1 R E R wherein said polymer has a molecular weight greater than about 5000. l

5. A photographic m unit comprising; wherein R R R and R", when taken separately,

a. a photosensitive element comprising a support each represent a lower alkyl group;

having thereon a photosensitive silver halide emul- R8 ahd Ru R9 and R10 represent an hhhle group or, sion having associated therewith an image dyetogether with the carbon atom to which y are providing compound; attached, represent the carbon atoms necessary to b. an image dye-receiving layer; and complete a 5- or 6-membered cycloalkyl or cyc. means for discharging an alkaline processing comeloalkehyl nucleus;

i i i hi id fil i oneof R and R, when taken with Z, represents a said film unit containing a water-soluble polymer comdouble bond in the cyclic nucleus formed by Z, in

which case R or R respectively, represents 1) an aryl group or (2) an amino radical; and Z represents the nonmetallic atoms necessary to complete a 5-, 6- or 7-membered heterocyclic nucleus. 9. The film unit as described in claim 5 wherein (NIOX) represents a heterocyclic nitroxyl radical having the formula:

wherein:

R R, R and R, when taken separately, represent a lower alkyl group;

R and R or R and R together with the carbon atom to which they are attached, represent the carbon atoms necessary to form a 5- or 6-membered cycloalkyl or cycloalkenyl nucleus; and

Z represents the carbon atoms necessary to complete a 5- or 6-membered heterocyclic nucleus.

10. The film unit as described in claim 5 wherein (NIOX) represents a heterocyclic nitroxyl radical having the formula:

wherein:

R R", R and R each represent a lower alkyl group.

11. A photographic film unit comprising:

a. a photosensitive element comprising a support having thereon a layer containing a red-sensitive silver halide emulsion having associated therewith a cyan image dye-providing material, a layer containing a green-sensitive silver halide emulsion having associated therewith a magenta image dyeproviding material, and a layer containing a bluesensitive silver halide emulsion having associated therewith a yellow image dye-providing material,

b. an image dye-receiving layer; and

c. means for discharging an alkaline processing composition within said tilm unit;

said film unit containing a water-soluble polymer comprising at least 40 mole percent of a recurring unit having the formula:

wherein:

n is an integer having a value of 0 or 1; Q represents a bivalent linking group of the formula:

in which R and R each represent an alkylene group,

an arylene group or an alkarylene group, and R can also represent a group of the formula:

I! I i 5 ..c0R or -C-NR in which R has the same definition as R and in which the carbonyl moiety is attached directly to the polymeric backbone;

m and p each represent an integer having a value of 0 or 1; and

represents an onium salt group;

wherein R R", R and R", when taken separately, each represent a lower alkyl group;

R and R or R and R represent an imino group or, together with the carbon atom to which they are attached, represent the carbon atoms necessary to complete a 5- or 6-membered cycloalkyl or cycloalkenyl nucleus;

one of R and R, when taken with Z, represents a double bond in the cyclic nucleus formed by Z, in which case R or R respectively, represents I) an aryl group or (2) an amino radical; and

Z represents the nonmetallic atoms necessary to complete a 5-, 6- or 7-membered heterocyclic nucleus;

said polymer further comprising at least 5 mole percent of a recurring unit having appended therefrom a water 5 solubilizing group.

12. A film unit as described in claim 11 wherein at least one of said image dye-providing materials is an oxichromic compound.

13. A film unit as described in claim 11 wherein at 60 least one of said image dye-providing materials is an oxichromic compound having the formula:

T (COUP) 1i 7 Ar s wherein:

(COUP) is a photographic color coupler linked to 25 the nitrogen atom through a carbon atom at the coupling position; Ar is an arylene group; J is selected from an amino group, a hydroxyl group or a group having the formula:

H -o-c-R wherein R is an alkyl or aryl group;

R is a hydrogen atom or a group having the formula:

0 ll -0-c-R wherein R" is as defined above; and

T is a silver halide developing agent or an oxidizable releasing group.

14. A film unit as described in claim ll wherein n and m are both 1 and L represents an iminium salt group.

15. A film unit as described in claim 11 wherein said polymer has a molecular weight greater than about 5000.

16. A film unit as described in claim 1 wherein said water-soluble polymer comprises at least 40 mole percent of a recurring unit having the following formula:

wherein:

R and R each represent a hydrogen atom or an alkyl group of about 1 to 6 carbon atoms; R represents a hydrogen atom or a carboxy group; R and R each represent an alkylene group having about 1 to 6 carbon atoms; each R represents an alkyl group of about 1 to 10 carbon atoms; and X is an anion. 17. A film unit as described in claim 1 wherein said water-soluble polymer comprises at least 40 mole percent of a recurring unit having the following formula:

wherein:

R and R each represent a hydrogen atom or an alkyl group of about 1 to 6 carbon atoms; R represents a hydrogen atom or a carboxy group; 5 R" and R each represent an alkylene group having about I to 6 carbon atoms; each R represents an alkyl group carbon atoms; and X is an anion. 18. A film unit as described in claim 1 wherein said water-soluble polymer comprises at least 40 mole percent of a recurring unit having the following formula:

of about I to l0 l 3 set wherein:

R and R each represent a hydrogen atom or an alkyl group of about 1 to 6 carbon atoms;

R represents a hydrogen atom or a carboxy group;

R is an alkarylene group having about 7 to 12 carbon atoms;

R represents an alkyl group of about 1 to 10 carbon atoms; and

X is an anion.

19. A receiving element comprising a support having therein at least one photographic image-receiving layer and at least one layer containing a water soluble polymeric oxidant comprising at least 40 mole percent of a recurring unit having the formula:

eC-I I-R 28 R represents a hydrogen atom, an alkyl group, or

when taken together with R, R represents a carbonyl group; and

(NIOX) represent a stable free nitroxyl radical; said polymer further comprising at least 5 mole percent of a recurring unit having appended therefrom a water solubilizing group.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,868,252 DATED February 5, 1975 |NVENTOR(5) Gerald A. Campbell; Hyman L. Cohen; Hans G. Ling |t H Ignazio S. Ponticello IS cer i ied that error appears in the above-identified atent t are hereby corrected as shown below: and hat Said Letters Patent In the claims:

Column 21, line 35, please omit colon following "backbone" and replace therefor with a semicolon.

Column 2, line 20,

please insert L before the word "represents".

Column 26, beginning with line H2 in the formula, please delete the three hyphens preceding and following the formula.

Signed and sealed this 15th day of July 1975.

(SEAL) Attest:

c. MARSHALL DANN RUTH c MASON. Commissioner of Patents Attesting Officer 1 and Trademarks

Claims (19)

1. A PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT HAVING THEREON AT LEAST ONE PHOTOSENSITIVE SILVER SALT EMULSION LAYER AND AT LEAST ONE LAYER CONTAINING A WATER-SOLUBLE POLYMER COMPRISING AT LEAST 40 MOLE PERCENT OF A RECURRING UNIT HAVING THE FORMULA:

2. A photographic element as described in claim 1 wherein (NIOX) represents a heterocyclic nitroxyl radical.

3. A photographic element as described in claim 1 wherein n and m are both 1 and L represents an ammonium salt group.

4. A photographic element as described in claim 1 wherein said polymer has a molecular weight greater than about 5000.

5. A photographic film unit comprising: a. a photosensitive element comprising a support having thereon a photosensitive silver halide emulsion having associated therewith an image dye-providing compound; b. an image dye-receiving layer; and c. means for discharging an alkaline processing composition within said film unit; said film unit containing a water-soluble polymer comprising at least 40 mole percent of a recurring unit having the formula:

6. The film unit as described in claim 5 wherein said polymer is associated with said image-receiving layer.

7. The film unit as described in claim 5 wherein said polymer is contained in said alkaline processing composition.

8. The film unit as described in claim 5 wherein (NIOX) represents a heterocyclic nitroxyl radical having the formula:

9. The film unit as described in claim 5 wherein (NIOX) represents a heterocyclic nitroxyl radical having the formula:

10. The film unit as described in claim 5 wherein (NIOX) represents a heterocyclic nitroxyl radical having the formula:

11. A photographic film unit comprising: a. a photosensitive element comprising a support having thereon a layer containing a red-sensitive silver halide emulsion having associated therewith a cyan image dye-providing material, a layer containing a green-sensitive silver halide emulsion having associated therewith a magenta image dye-providing material, and a layer containing a blue-sensitive silver halide emulsion having associated therewith a yellow image dye-providing material, b. an image dye-receiving layer; and c. means for discharging an alkaline processing composition within said film unit; said film unit containing a water-soluble polymer comprising at least 40 mole percent of a recurring unit having the formula:

12. A film unit as described in claim 11 wherein at least one of said image dye-providing materials is an oxichromic compound.

13. A film unit as described in claim 11 wherein at least one of said image dye-providing materials is an oxichromic compound having the formula:

14. A film unit as described in claim 11 wherein n and m are both 1 and L represents an iminium salt group.

15. A film unit as described in claim 11 wherein said polymer has a molecular weight greater than about 5000.

16. A film unit as described in claim 1 wherein said water-soluble polymer comprises at least 40 mole percent of a recurring unit having the following formula:

17. A film unit as described in claim 1 wherein said water-soluble polymer comprises at least 40 mole percent of a recurring unit having the following formula:

18. A film unit as described in claim 1 wherein said water-soluble polymer comprises at least 40 mole percent of a recurring unit having the following formula:

19. A receiving element comprising a support having therein at least one photographic image-receiving layer and at least one layer containing a water soluble polymeric oxidant comprising at least 40 mole percent of a recurring unit having the formula: