US3868252A - Photographic elements containing polymeric oxidants - Google Patents

Photographic elements containing polymeric oxidants Download PDF

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US3868252A
US3868252A US412081A US41208173A US3868252A US 3868252 A US3868252 A US 3868252A US 412081 A US412081 A US 412081A US 41208173 A US41208173 A US 41208173A US 3868252 A US3868252 A US 3868252A
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film unit
formula
group
polymer
photographic
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Gerald A Campbell
Hyman L Cohen
Hans G Ling
Ignazio S Ponticello
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to CA210663A priority patent/CA1035898A/fr
Priority to DE2451628A priority patent/DE2451628C3/de
Priority to FR7436210A priority patent/FR2249908B1/fr
Priority to BE150108A priority patent/BE821740A/fr
Priority to GB47395/74A priority patent/GB1481570A/en
Priority to JP49126127A priority patent/JPS5845696B2/ja
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/42—Structural details
    • G03C8/52—Bases or auxiliary layers; Substances therefor

Definitions

  • 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.
  • the dye-providing material can be initially immobile or initially mobile in the processing solution.
  • 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.
  • the dye-providing material 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.
  • 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.
  • 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.
  • 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.
  • D is a group which is a silver halide developer such as a hydroquinone moiety
  • 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.
  • 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.
  • 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:
  • 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.
  • 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.
  • 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.
  • a color diffusion transfer element of a class of nitroxylcontaining polymeric oxidants.
  • 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.
  • 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:
  • oxidants of this invention are water soluble polymers comprising at least 40 mole percent of a recurring unit having the formula:
  • n an integer having a value of O or I;
  • Q represents a bivalent linking group having the formula:
  • R has the same definition as R and in which the carbonyl moiety is attached directly to the polymeric backbone;
  • n and p each represent an integer having a value of Oor l;
  • 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,
  • 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.
  • 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
  • Suitable nitroxyl radicals useful in this invention include those of the formula:
  • 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.
  • 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;
  • substituted imino e.g., -NR wherein R is an alkyl group having 1 to about 25 carbon atoms
  • R is an alkyl group having 1 to about 25 carbon atoms
  • 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
  • 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.
  • binitroxyls and conjugated biradicals are also known. See, for example, Organic Chemistry of Stable Free Radicals, Forrester et al., 1968.
  • 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.
  • 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.
  • 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.
  • 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:
  • Starting polymer is a tertiary amine o II 1IIHCCH Cl Polltymer O V II (NIOX) R1 ⁇ lICH CNH-(NIOX)
  • Starting polymer is an alkylating agent II NHCCH N(R) V Polymer (NIOX) :69 CIl l ⁇ l-CH Cl:IH
  • 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:
  • 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:
  • 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.
  • sulfonated monomers e.g., B-acryloyloxypropanc-lsulfonic acid, sodium salt or 3 methacryloyloxypropane-l-sulfonic acid, sodium salt
  • sulfonated monomers e.g., B-acryloyloxypropanc-lsulfonic acid, sodium salt or 3 methacryloyloxypropane-l-sulfonic acid, sodium salt
  • 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.
  • nitroxyl-containing polymers described herein can be used in a wide variety of photographic elements or in photographic film units.
  • 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.
  • 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)
  • 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.
  • 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.
  • 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.
  • the nitroxyl radical can be used to stabilize a preformed image dye.
  • the nitroxyls produce a beneficial increase in the stability of azo dyes which are transferred to an image-receiving layer.
  • 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.
  • 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.
  • 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.
  • the present nitroxyl radical oxidants are incorporated into photographic elements containing oxichromic compounds of the formula:
  • (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:
  • 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:
  • 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
  • a silver halide developing agent the resultant compound preferably is initially mobile.
  • 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.
  • the nitroxyl oxidant 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.
  • a binder such as gelatin, poly( vinyl alcohol), etc.
  • the nitroxyl-containing polymers described herein can also be one of several ingredients in a given layer.
  • the nitroxyl polymers 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.
  • nitroxyl-containing polymer 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.
  • 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:
  • 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;
  • 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;
  • the support is preferably a transparent support
  • an opaque layer is preferably positioned between the imagereceiving layer and the photosensitive silver halide layer
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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,
  • 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.
  • 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.
  • 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.
  • 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.
  • 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):
  • layer containing gelatin at 50 mglft A transparent cover sheet for the above element is prepared as follows:
  • 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 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?
  • n is an integer having a value of 0 or 1;
  • 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,
  • R can in which R and R each represent an alkylene group, also represent a group of the formula:
  • 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;
  • n 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;
  • R ' represents a hydrogen atom, an alkyl group or,
  • L represents an onium salt group
  • R represents a hydrogen atom of an alkyl group
  • 40 (NIOX) represents a stable free nitroxyl radical
  • 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.
  • solubilizing P- 5 (NIOX) represents a heterocyclic nitroxyl radical hav- 2.
  • a photographic m unit comprising; wherein R R R and R", when taken separately,
  • a photosensitive element comprising a support each represent a lower alkyl group
  • 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;
  • 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
  • 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;
  • Z represents the carbon atoms necessary to complete a 5- or 6-membered heterocyclic nucleus.
  • (NIOX) represents a heterocyclic nitroxyl radical having the formula:
  • R R", R and R each represent a lower alkyl group.
  • a photographic film unit comprising:
  • 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,
  • 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:
  • n is an integer having a value of 0 or 1;
  • Q represents a bivalent linking group of the formula:
  • R and R each represent an alkylene group
  • R can also represent a group of the formula:
  • n and p each represent an integer having a value of 0 or 1;
  • R 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;
  • 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;
  • 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.
  • 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:
  • R is an alkyl or aryl group
  • R is a hydrogen atom or a group having the formula:
  • T is a silver halide developing agent or an oxidizable releasing group.
  • 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:
  • 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.
  • said water-soluble polymer comprises at least 40 mole percent of a recurring unit having the following formula:
  • 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.
  • said water-soluble polymer comprises at least 40 mole percent of a recurring unit having the following formula:
  • 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
  • X is an anion
  • 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
  • R when taken together with R, R represents a carbonyl group
  • NEOX 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.

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  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US412081A 1973-11-02 1973-11-02 Photographic elements containing polymeric oxidants Expired - Lifetime US3868252A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US412081A US3868252A (en) 1973-11-02 1973-11-02 Photographic elements containing polymeric oxidants
CA210663A CA1035898A (fr) 1973-11-02 1974-10-03 Produits photographiques renfermant des oxydants polymeriques
DE2451628A DE2451628C3 (de) 1973-11-02 1974-10-30 Photographisches Aufzeichnungsmaterial für das Farbdiffusionsiibertragungsverfahren
FR7436210A FR2249908B1 (fr) 1973-11-02 1974-10-30
BE150108A BE821740A (fr) 1973-11-02 1974-10-31 Produit photographique contenant un nouvel oxydant polymere
GB47395/74A GB1481570A (en) 1973-11-02 1974-11-01 Photographic process and polymeric oxidants useful therei
JP49126127A JPS5845696B2 (ja) 1973-11-02 1974-11-02 カラ−拡散転写法用写真フィルム単位

Applications Claiming Priority (1)

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US412081A US3868252A (en) 1973-11-02 1973-11-02 Photographic elements containing polymeric oxidants

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US (1) US3868252A (fr)
JP (1) JPS5845696B2 (fr)
BE (1) BE821740A (fr)
CA (1) CA1035898A (fr)
DE (1) DE2451628C3 (fr)
FR (1) FR2249908B1 (fr)
GB (1) GB1481570A (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4030929A (en) * 1975-09-19 1977-06-21 Agfa-Gevaert, A.G. Photographic silver halide emulsion
US4323644A (en) * 1979-11-05 1982-04-06 Fuji Photo Film Co., Ltd. Photographic material containing polymers with active ester groups
US4407928A (en) * 1982-06-28 1983-10-04 Eastman Kodak Company Use of ketal blocked quinones to reduce post-process Dmin increase in positive redox dye-releasing image transfer systems
US4435502A (en) 1982-06-28 1984-03-06 Eastman Kodak Company Use of ketal blocked quinones to reduce post-process D-min increase in positive redox dye-releasing image transfer systems
US4672088A (en) * 1983-09-30 1987-06-09 Gerald Scott Stabilized thermoplastic polymer compositions comprising a C-nitroso compound
US5620941A (en) * 1996-04-16 1997-04-15 Eastman Kodak Company Stabilizers for dye-donor element used in thermal dye transfer

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2698798A (en) * 1949-05-21 1955-01-04 Polaroid Corp Color photographic process and product
US3065074A (en) * 1958-08-20 1962-11-20 Polaroid Corp 1,4-benzoquinone oxidizing agents for color transfer processes
US3384484A (en) * 1963-04-11 1968-05-21 Agfa Ag Silver halide photographic materials containing organic hydrazone compounds
US3698897A (en) * 1971-07-06 1972-10-17 Eastman Kodak Co Diffusion transfer processes and film units comprising compounds which are cleavable upon oxidation in alkali media to produce diffusible dyes or dye precursors
US3709690A (en) * 1968-03-01 1973-01-09 Eastman Kodak Co Novel polymers and photographic elements containing same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2698798A (en) * 1949-05-21 1955-01-04 Polaroid Corp Color photographic process and product
US3065074A (en) * 1958-08-20 1962-11-20 Polaroid Corp 1,4-benzoquinone oxidizing agents for color transfer processes
US3384484A (en) * 1963-04-11 1968-05-21 Agfa Ag Silver halide photographic materials containing organic hydrazone compounds
US3709690A (en) * 1968-03-01 1973-01-09 Eastman Kodak Co Novel polymers and photographic elements containing same
US3698897A (en) * 1971-07-06 1972-10-17 Eastman Kodak Co Diffusion transfer processes and film units comprising compounds which are cleavable upon oxidation in alkali media to produce diffusible dyes or dye precursors

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4030929A (en) * 1975-09-19 1977-06-21 Agfa-Gevaert, A.G. Photographic silver halide emulsion
US4323644A (en) * 1979-11-05 1982-04-06 Fuji Photo Film Co., Ltd. Photographic material containing polymers with active ester groups
US4407928A (en) * 1982-06-28 1983-10-04 Eastman Kodak Company Use of ketal blocked quinones to reduce post-process Dmin increase in positive redox dye-releasing image transfer systems
US4435502A (en) 1982-06-28 1984-03-06 Eastman Kodak Company Use of ketal blocked quinones to reduce post-process D-min increase in positive redox dye-releasing image transfer systems
US4672088A (en) * 1983-09-30 1987-06-09 Gerald Scott Stabilized thermoplastic polymer compositions comprising a C-nitroso compound
US5620941A (en) * 1996-04-16 1997-04-15 Eastman Kodak Company Stabilizers for dye-donor element used in thermal dye transfer

Also Published As

Publication number Publication date
JPS5080131A (fr) 1975-06-30
FR2249908A1 (fr) 1975-05-30
DE2451628A1 (de) 1975-05-07
JPS5845696B2 (ja) 1983-10-12
FR2249908B1 (fr) 1976-10-22
DE2451628B2 (de) 1979-09-27
GB1481570A (en) 1977-08-03
BE821740A (fr) 1975-04-30
DE2451628C3 (de) 1980-08-21
CA1035898A (fr) 1978-08-01

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