EP0186868A2 - Photographisches Element und Verfahren zur Lieferung von Metallkomplexfarbbildern - Google Patents

Photographisches Element und Verfahren zur Lieferung von Metallkomplexfarbbildern Download PDF

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Publication number
EP0186868A2
EP0186868A2 EP85116272A EP85116272A EP0186868A2 EP 0186868 A2 EP0186868 A2 EP 0186868A2 EP 85116272 A EP85116272 A EP 85116272A EP 85116272 A EP85116272 A EP 85116272A EP 0186868 A2 EP0186868 A2 EP 0186868A2
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EP
European Patent Office
Prior art keywords
lig
dye
silver halide
compound
moiety
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP85116272A
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English (en)
French (fr)
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EP0186868A3 (en
Inventor
James A. Reczek
Janice M. Madigan-Palumbo
William N. Washburn
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Eastman Kodak Co
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Eastman Kodak Co
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Publication date
Priority claimed from US06/688,478 external-priority patent/US4555478A/en
Priority claimed from US06/688,479 external-priority patent/US4555477A/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of EP0186868A2 publication Critical patent/EP0186868A2/de
Publication of EP0186868A3 publication Critical patent/EP0186868A3/en
Withdrawn legal-status Critical Current

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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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/333—Coloured coupling substances, e.g. for the correction of the coloured image

Definitions

  • This invention relates to color photography.
  • it relates to photographic elements containing essentially colorless, immobile, ligand-releasing compounds, and to processes of using such elements to provide color images.
  • One way to eliminate the unwanted filtering effect is to have the silver halide and the dye in separate layers while maintaining them in reactive association. While this is a useful and practical solution, it increases the number of layers in the element, making it thicker and presenting manufacturing and imaging inefficiencies.
  • the present invention overcomes the problems noted above with a photographic element which comprises a support having thereon at least one silver halide emulsion layer.
  • This element is characterized by having associated with the silver halide emulsion layer an essentially colorless, immobile, ligand-releasing compound of the structure LIG-X.
  • LIG is a ligand which is capable of complexing with metal ions to form a metal complex dye
  • X is a group which, as a function of silver halide development, is cleaved from LIG.
  • This invention also provides a process of forming a dye image in the element described above which has been imagewise exposed.
  • This process comprises the steps of a) developing the element to imagewise cleave the bond between LIG and X as a function of development, and b) treating the element with metal ions to form a metal complex dye with LIG and the metal ions.
  • the photographic elements of this invention of this invention can be used to obtain color images of exceptional stability. Further, these elements and the process of using same provide desirable versatility in the placement of the dye-providing materials described herein because they are essentially colorless until development with development compositions after imagewise exposure and until treatment with metal ions. Hence, the problems of placement often encountered with known metallized or metallizable dyes can be avoided.
  • the dye-providing materials can also be used to provide color masking dyes.
  • the LIG-X compounds are essentially colorless, meaning that prior to complexation of the LIG moiety with metal ions to form a visible dye, LIG-X exhibits essentially no observable color. That is, LIG-X exhibits a low optical density (i.e. less than 0.05), although it may emit or reflect electromagnetic radiation in the non-visible portions of the electromagnetic spectrum. Therefore, the LIG moiety and the metal ions form a colored dye from a colorless precursor, as opposed to compounds which are merely shifted in their absorption X upon complexation with a metal ion to provide a dye of a different color.
  • LIG is a moiety, which when complexed with one or more metal ions, forms a visible dye. Depending on the way LIG and X are joined, this complexation can occur either while LIG and X are joined or after LIG is cleaved from X. In certain embodiments, LIG and X are joined such that LIG is incapable of complexing with metal ions until LIG and X are cleaved. In other words, the metal chelating site on LIG is blocked with X. In other embodiments, LIG and X are joined such that metal-LIG complexation can occur without LIG-X cleavage. Imagewise release and removal of LIG then allows metal complexation with the remaining LIG moiety still attached to X. In either case, complexation of metal ions with the LIG moiety provides a dye image as a function, either directly or inversely, of silver halide development.
  • the dyes formed upon complexation of the LIG moiety and metal ions are visibly colored dyes. That is, they absorb electromagnetic radiation in the visible portion of the electromagnetic spectrum, i.e. between 400 and 700 nm. More than one molecule of a LIG moiety can be complexed with one metal ion. For example, there may be two or three LIG molecules complexed with a single metal ion.
  • Representative dyes which can be formed are cyan, yellow and magenta dyes.
  • Useful LIG moieties can be obtained from ferroin type compounds such as hydrazones, tetrazolylpyridines, pyridylquinazolines, bis-isoquinolines, imines, phenanthrolines, bipyridines, terpyridines, bidiazines, pyridyldiazines, pyridylbenzimidazoles, diazyltriazines, o-nitrosoanilines and phenols, tetrazines, triazines described by Schilt et al in the journal Talanta, 15, pp.
  • ferroin type compounds such as hydrazones, tetrazolylpyridines, pyridylquinazolines, bis-isoquinolines, imines, phenanthrolines, bipyridines, terpyridines, bidiazines, pyridyldiazines, pyridylbenzimidazoles, diazyl
  • LIG can have a ballast group which renders LIG nondiffusible in the photographic element during processing.
  • This type of ligand-releasing compound can be illustrated as BALL-LIG-X wherein LIG and X are as defined above, and BALL is an organic nonpolymeric or polymeric group of such molecular size and configuration as to render the compound nondiffusible in a photographic element during development in an alkaline processing composition.
  • Particularly useful ballast groups include long chain alkyl groups (e.g. 6 to 30 carbon atoms), as well as aromatic groups (phenyl, naphthyl) along with alkyl groups.
  • Representative ballast groups include
  • BALL-LIG-X compounds include: and a polymer having recurring units represented by the structure: wherein x is from 10 to 100 weight percent, and y is from 0 to 90 weight percent.
  • LIG moieties are those derived from compounds represented by the structure: wherein m is 0 or a positive integer of 1 to 3, n and p are independently 0 or 1, and -represents a single or double bond.
  • R 6 is a group defined above, p is 1 and is a single bond.
  • R 1 and R 2 , R 2 and R 3 , and R 3 and R 4 taken together, can independently represent the carbon and heteroatoms (e.g. nitrogen, oxygen, sulfur, selenium, etc.) necessary to complete a substituted or unsubstituted 5 to 20 membered mono- or polycyclic carbocyclic or heterocyclic group (e.g. pyridine, quinolyl, triazinyl, phenanthrolinyl, pyrimidyl, etc.).
  • the heterocyclic nucleus so formed can be substituted with one or more oxo, alkyl, amino, imino, aryl, phosphino (e.g.
  • diphenylphosphino diphenylphosphino
  • alkoxy amide, sulfonamide, thio or sulfo groups as defined above, or a heterocyclic group (e.g. pyridyl, pyrimidyl, thiazolyl, imidazolyl, thienyl, etc.).
  • heterocyclic group e.g. pyridyl, pyrimidyl, thiazolyl, imidazolyl, thienyl, etc.
  • R 1 and R 2 , R 5 and R 6 , and R and R * taken together, can independently represent the carbon and heteroatoms (e.g. nitrogen, oxygen, sulfur, selenium, etc.) necessary to complete a substituted or unsubstituted 5 to 20 membered mono- or polycyclic heterocyclic nucleus as defined above where m is 0.
  • heteroatoms e.g. nitrogen, oxygen, sulfur, selenium, etc.
  • LIG or a ballast group attached to it can contain one or more solubilizing groups, e.g. sulfate, sulfonate, carboxylate, hydroxy or phosphate groups.
  • LIG moieties which form color dye complexes with ferrous ions are shown below.
  • the point of attachment to X is represented by an unsatisfied bond.
  • the approximate ⁇ max of each resulting ferrous ion complex dye is also noted, however, the ⁇ max can be shifted slightly (e.g. 10-15 nm) depending upon the moiety to which LIG is attached.
  • X is any moiety which will react with oxidized developing agent (e.g. oxidized color developing agent).
  • oxidized developing agent e.g. oxidized color developing agent
  • it is a coupler moiety employed in known color-forming couplers which yields a colored product on reaction with oxidized color developing agents or which yields a colorless product on reaction with oxidized color developing agents.
  • coupler moieties are well known to those skilled in the photographic art and described, for example, in Research Disclosure, publication 17643, paragraph VII, December, 1978, and references noted therein.
  • X is another moiety known in the art to release dyes, or other photographically useful fragments as a result of silver halide development.
  • moieties include redox dye releasers and similar compounds as described, for example, in U. S. Patents 4,053,312, 4,055,429, 4,076,529, 4,139,379, 4,139,389, 4,199,354, 4,199,355, and 4,232,107.
  • X can be unballasted or ballasted with an organic ballasting group as described above for LIG.
  • X can be monomeric, or it can form part of a dimeric, oligomeric or polymeric coupler.
  • the LIG moiety is joined to X at any of the positions from which groups cleaved from couplers by reaction with oxidized developing agent can be attached.
  • LIG is attached to X in a coupling position so that upon reaction of the coupler with oxidized developing agent, LIG will be cleaved from X.
  • LIG can be in a non-coupling position of X, from which position it will be cleaved as a result of reaction of X with oxidized developing agent.
  • other groups can be in the coupling position, including the known coupling off groups or the same or a different LIG moiety.
  • the LIG-X compounds useful in this invention can provide more than one mole of LIG per mole of compound.
  • the LIG moieties can be the same or different and can be cleaved at the same or different times or rates.
  • LIG-X there is no linking group between X and LIG.
  • the LIG moiety is blocked by X preventing complexation with metal ions, and cleavage by oxidized developer produces only the coupled product resulting from the coupling reaction with the oxidized developer and LIG.
  • Examples of such preferred LIG-X compounds are: and
  • Z' is an electron withdrawing group
  • Z" is an electron withdrawing group
  • BALL is a suitable ballasting group as defined above
  • Anion- is a suitable anion.
  • release of LIG and X moieties linked with an organic blocking group can occur in several steps wherein the BL-LIG fragment is coupled off from the X moiety upon reaction with oxidized developer.
  • the BL-LIG fragment is then capable of releasing the LIG moiety by an intramolecular reaction.
  • the compounds are resistant to unblocking under storage conditions and in the absence of oxidized developer, but are unblocked upon release from the coupler during the coupling reaction.
  • the intramolecular reaction which results in release of the LIG moiety can be an elimination reaction such as occurs with wherein COUP is any suitable coupler moiety. This concept is described in U.S. Patent 4,409,323.
  • the intramolecular release can occur by a nucleophilic displacement reaction, as occurs with
  • LIG and X are connected with a single bond or with an organic linking moiety which generally remains with LIG when it is cleaved and is protonated or ionized depending upon the pKa of the group.
  • organic linking moieties include -COO-, -CONH-, -0-, -S-, -S0 2 -, -SO 2 NH- , -CH 2 CO-, -SO 2 N(Alkyl)- and the like as well as the timing groups described in U.S. Patent 4,248,962.
  • a particularly useful linking group is a single bond or -0-.
  • X moieties examples useful in the practice of this embodiment of the invention as X moieties are the following color coupler moieties: wherein r is 0 or 1, wherein q is an integer of 1 to 20, wherein R 7 is substituted or unsubstituted alkyl (preferably of 1 to 20 carbon atoms) or substituted or unsubstituted aryl (preferably of 6 to 14 carbon atoms), and
  • BALL is any suitable ballast group as described above (e.g. -NHSO 2 C 16 H 33 , -NHCO-alkylene-oxy-aryl, alkyl of 1 to 20 carbon atoms, aryl of 6 to 14 carbon atoms in the nucleus, etc.), and LINK is a suitable linking moiety, as described above, which links X and LIG prior to reaction with oxidized developing agent.
  • BALL can also be a suitable polymer backbone.
  • LIG-X compounds useful in the practice of this invention include the following:
  • LIG-X compounds useful in the practice of this invention can be readily prepared using chemical reactions known to one skilled in photographic chemistry. Generally, a compound from which the LIG moiety is derived is reacted with a compound (e.g. a color coupler) from which X can be derived. Detailed syntheses of exemplary LIG-X compounds are provided below.
  • LIG-X compounds useful in this invention can be prepared by condensation of a LIG-containing carboxylic acid halide or sulfonic acid halide with a color coupler containing a hydroxy, mercapto or amino group in the coupling position to produce LIG-X compounds having LIG and X moieties joined by an ester, amide, sulfonamide or thioester linkage.
  • the LIG-X compounds preferred for use in this invention can be prepared, in general, by the reaction of a ballasted and optionally solubilized LIG moiety with a coupler moiety containing a leaving group in the coupling-off position. This results in quaternization of LIG by the coupler to form LIG-X where the chelation site of LIG is blocked.
  • the LIG moiety can contain an ethylenically unsaturated polymerizable monomer group (such as acrylamide, acrylate, etc.).
  • the LIG-X compound resulting from reaction with a coupler moiety can be polymerized to yield a polymeric LIG-X compound.
  • LIG is a moiety capable of complexing with metal ions to provide desired dyes in one or more layers of photographic elements.
  • metal ions can be so used as long as the complex of the LIG moiety with the metal ion is stable, or in other words, the complex is likely to remain in complexed form for a substantial period of time.
  • the log of the formation constant of such complexes should be in the range of from 10 to 30, and preferably from 15 to 25.
  • Useful metal ions include Fe ++ , Co ++ , C u , Cu ++ , Ru ++ and Os ++ . Ferrous ions are preferred in the practice of this invention.
  • cleavage of LIG from X results from reaction of oxidized developing agent with the LIG-X compound.
  • Any suitable developing agent can be used in the practice of this invention, which when oxidized from silver halide development, can react with LIG-X.
  • Particularly useful developing agents are color developing agents, including aminophenols, phenylenediamines, tetrahydroquinolines and the like as described, for example, in Research Disclosure, publication 17643, paragraph XX, noted above.
  • Other useful developing agents include hydroquinones, catechols and pyrazolidones.
  • a negative image can be generated in an element.
  • a LIG-X compound wherein X is a moiety which yields a colorless or diffusible reaction product with oxidized developer, and X is attached to LIG in such a manner that it is incapable of complexation with metal ions prior to the reaction with oxidized developer.
  • LIG is appropriately ballasted as outlined above to prevent diffusion.
  • the LIG-X bond is cleaved in exposed areas, and the coupled product may be washed out of the element if desired.
  • Subsequent treatment of the element with metal ions e.g. ferrous ions
  • metal ions e.g. ferrous ions
  • LIG and X are joined such that LIG is capable of complexing with metal ions without cleavage of the LIG-X bond.
  • the metal chelating site in LIG is not blocked by X.
  • a suitable color dye image is formed with a known color coupler and the LIG-X bond is cleaved as a function of silver halide development to yield a soluble ligand which diffuses out of the element during processing so that it is unavailable to form a metal complex dye.
  • the reaction product of X and the oxidized developing agent can be colorless or diffusable, in which case it will not contribute to image density, or colored in which case it can augment or modify the principal dye image (e.g. in color correction).
  • the unreacted LIG-X compound is treated with metal ions (e.g. ferrous ions) to provide a visually colored dye which acts as a masking dye in those areas.
  • the present invention can also be used to generate a reversal image in an element using what are known in the art as universal couplers.
  • This can be done by incorporating a LIG-X compound in the element wherein X is a moiety which yields a colorless or diffusible reaction product with oxidized developing agent and LIG is a moiety capable of complexing with metal ions to provide a dye while still linked to X.
  • X is a moiety which yields a colorless or diffusible reaction product with oxidized developing agent
  • LIG is a moiety capable of complexing with metal ions to provide a dye while still linked to X.
  • Upon imagewise development with a developing agent the LIG-X bond in exposed areas is cleaved and fragments washed out of the element.
  • Subsequent treatment of the element with metal ions e.g. ferrous
  • the photographic element of this invention can provide a diffusion transfer image.
  • This element comprises a support and a plurality of layers including one or more image-recording layers and an image-receiving layer.
  • a LIG-X compound is incorporated in or adjacent an image-recording layer, and the LIG-X bond is cleaved as a function of development either via coupling off chemistry or redox release chemistry.
  • Redox release chemistry is described, e.g. in U.S. Patents 4,108,850 and 4,139,379, whereupon reduction of a hydroquinone compound releases a dye fragment.
  • the released LIG moiety diffuses to the image-receiving layer which contains mordanted metal ions. These ions complex with the LIG moiety to provide the desired dye image.
  • the photographic elements and film units of this invention can be processed by known techniques in which the processing solutions or compositions are incorporated in the element or film unit or are separately applied in a solution or process sheet. These solutions or compositions contain developing agents (e.g. color developing agents) and other suitable processing addenda, as well as metal ions to complex with LIG, if desired. Alternatively, the metal ions can be incorporated within the element in the same or different layer as the LIG-X compound. More specifically, processing of the elements of this invention can be accomplished by suitable silver development, either color or black and white, for example, by treatment with a phenylenediamine or hydroquinone developer, followed by bleaching with an Fe salt bleach, or simply by treatment of the imagewise distribution of LIG with ferrous ions. Electron transfer agents can be used in redox release processes. The ferrous or other ions can be included in the bleach solution for complexation with the LIG moiety.
  • Photographic elements of this invention in which the described LIG-X compounds are incorporated can comprise a support and one or more silver halide emulsion layers and associated dye-forming layers.
  • the LIG-X compounds can be incorporated in the silver halide emulsion layer or in another layer, such as an adjacent layer, where they will come into reactive association with oxidized color developing agent which has developed silver halide in the emulsion layer.
  • the silver halide emulsion layer can contain, or have associated with it, photographic coupler compounds, such as color forming couplers, colored masking couplers, etc. These coupler compounds can form dyes of the same or different color or hue as the dyes formed by complexation of LIG and metal ions. Additionally, the silver halide emulsion layer can contain other addenda generally contained in such layers.
  • a multilayer, multicolor photographic element of this invention can comprise a support having thereon a red-sensitive silver halide emulsion unit having associated therewith a cyan dye image providing material, a green-sensitive silver halide emulsion unit having associated therewith a magenta dye image providing material and a blue-sensitive silver halide emulsion unit having associated therewith a yellow dye image-providing material, at least one of the silver halide emulsion units having associated therewith a LIG-X compound.
  • Each silver halide emulsion unit can be composed of one or more layers and the various units and layers can be arranged in different locations with respect to one another as is known in the art.
  • the LIG-X compounds described herein can be incorporated into or associated with one or more units or layers of the element.
  • the LIG-X compound is in or associated with the green-sensitive silver halide emulsion unit.
  • the light sensitive silver halide emulsions can include coarse, regular or fine grain silver halide crystals or mixtures thereof and can be comprised of such silver halides as silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide, silver chlorobromoiodide and mixtures thereof.
  • the emulsions can be negative-working or direct-positive emulsions. They can form latent images predominantly on the surface of the silver halide grains or predominantly on the interior of the grains. They can be chemically and spectrally sensitized.
  • the emulsions generally are gelatin-containing emulsions although other natural or synthetic hydrophilic colloids, soluble polymers or mixtures thereof can be used if desired.
  • the element support can be any suitable substrate used in photographic elements. Generally, a flexible paper or resinous film support is used, and a paper support is particularly useful. Paper supports can be acetylated or coated with baryta and/or an a-olefin polymer such as polyethylene, polypropylene, ethylene-butene copolymer and the like.
  • a useful magenta dye-forming LIG-X compound is l-hydroxy-N-[4-(2,4-di-t-pentylphenoxy)butyl]-4-[4'-(2,2':6',2"-terpyridyl)oxy]-2-naphthamide which was prepared in the following manner.
  • the reaction mixture was poured into 2 1 of dilute KH 2 PO 4 buffer, and the product solidified upon stirring. After removal of the solvent, the crude product was t.riturated several times with cyclohexane to remove unreacted naphthamide. The resulting purified LIG-X compound was isolated by filtration as a tan solid (9 g). Analysis by mass spectroscopy ahowed the compound to be consistent with the assigned structure.
  • the monomer 1-benzoylmethyl-2-[4-(2-acrylamidoethoxy)-6-(2,2'-bipyridyl)]pyridinium bromide was prepared in the following manner.
  • a useful magenta dye-forming polymeric LIG-X compound is poly ⁇ acrylamide-co-1-benzoylmethyl-2-[4-(2-acrylamidoethoxy)-6-(2,2'-bipyridyl)]-pyridinium bromide ⁇ which is prepared in the following manner.
  • a useful magenta dye-forming LIG-X compound is N- ⁇ 4-chloro-3- ⁇ 4,4-dimethyl-3-oxo-2-[4'-(2,2':6',2"-terpyridyl)oxy]pentanamido ⁇ - phenyl ⁇ hexadecanesulfonamide which was prepared in the following manner:
  • a useful magenta dye-fcrming LIG-X compound is 4- ⁇ 4,4-dimethyl-3-oxo-2- ⁇ 3-[4'-(2,2':6',2"- terpyridyl]phenoxy ⁇ pentanamido ⁇ -N-methyl-N-octadecylbenzenesulfonamide which was prepared in the following manner.
  • Another useful magenta dye-forming LIG-X compound is 1-hydroxy-4- ⁇ 4-nitro-2- ⁇ N-isopropyl-N- ⁇ 4-[6-phenyl-3-(2-pyridyl)-1,2,4-triazin-5-yl]phenoxycarbonyl ⁇ aminomethyl ⁇ - phenoxy ⁇ -N-(2-tetradecyloxyphenyl)-2-naphthamide which was prepared in the following manner.
  • Another useful magenta dye-forming LIG-X compound is 1-hydroxy-N-[4-(2,4-di-t-pentyl- phenoxy)butyl]-4- ⁇ 4- ⁇ N- ⁇ 2-[4'-(2,2':6',2"- terpyridyl)oxy]ethyl ⁇ sulfamoyl ⁇ pirenoxy ⁇ -2-naphthamide which was prepared in the following manner.
  • Example 1 Photographic Element Containing Polymeric LIG-X Compound which Provides a Magenta Dye Complex with Ferrous Ions
  • the emulsion was then coated on a cellulose acetate support at about 129 ml/m 2 laydown.
  • An overcoat solution containing 1.07 g gelatin/m 2 and 85 mg of 2% bis(vinylsulfonylmethyl) ether hardener solution/m 2 was coated over the emulsion at about 54 ml/m 2 laydown.
  • the resulting photographic element was imagewise exposed, developed with pH 11 phenylenediamine color developing solution to cleave LIG from X (polymeric backbone), bleached with ferric ethylenediaminetetraacetic acid bleach solution, and fixed. The element was then placed into a dilute ferrous ammonium sulfate solution (0.1 molar) which provided ferrous ions which complexed with the free LIG moiety to form a magenta dye image in imagewise exposed areas.
  • This example illustrates the use of LIG-X compounds to provide masking dyes in a photographic element.
  • the coating levels were 0.48 g/m 2 of magenta dye-providing LIG-X compound, 0.58 g/m 2 of the cyan dye-providing color coupler, 0.9 g/m 2 of Ag aid 3.8 g/m 2 of gelatin.
  • the resulting element was imagewise exposed, developed with a phenylenediamine color developing solution (pH 10) and bleached using a ferricyanide-based bleach solution.
  • Tais process provided a cyan dye image in the exposed areas and cleaved the terpyridyl LIG moiety from the X moiety in those areas.
  • the free LIG :noiety was washed out of the element in the processing solutions.
  • the element was then placed into a dilute ammonium ferrous sulfate solution (10- 3 molar), providing ferrous ions which complexed with the LIG moiety of the uncoupled LIG-X compound, generating a magenta color correcting dye image in the unexposed areas of the element.
  • This example illustrates the use of a LIG-X compound to correct for undesired green absorption of a yellow dye in a photographic element.
  • the coating levels were 1.8 g/m 2 of magenta dye-providing LIG-X compound, 5.9 g/m 2 of the yellow dye-providing color coupler, 2.5 g/m 2 of Ag and 12.4 g/m 2 of gelatin.
  • the resulting element was imagewise exposed, developed and bleached as described in Example 2 to provide a cyan dye image. Uncoupled LIG moiety was washed out of the exposed areas. The element was then treated with ferrous ions as in Example 2. The ferrous ions complexed with the LIG moiety of the uncoupled LIG-X compound, generating a magenta color correcting dye in the unexposed areas of the element.

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  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP85116272A 1985-01-02 1985-12-19 Photographic element and process for providing metal complex color images Withdrawn EP0186868A3 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US688479 1985-01-02
US06/688,478 US4555478A (en) 1985-01-02 1985-01-02 Photographic element and process for providing metal complex color images
US06/688,479 US4555477A (en) 1985-01-02 1985-01-02 Photographic element and process utilizing metal complex color masking dyes
US688478 1985-01-02

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EP0186868A2 true EP0186868A2 (de) 1986-07-09
EP0186868A3 EP0186868A3 (en) 1988-09-21

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EP0326160A3 (en) * 1988-01-29 1990-05-09 Fuji Photo Film Co., Ltd. Silver halide photographic material
WO2007103694A3 (en) * 2006-03-01 2007-11-01 Bristol Myers Squibb Co Triazine 11-beta hydroxysteroid dehydrogenase type i inhibitors

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JPS5931062B2 (ja) * 1976-03-03 1984-07-31 富士写真フイルム株式会社 拡散転写法用感光要素
CA1247916A (en) * 1981-09-02 1989-01-03 Jasbir Sidhu Method of forming a photographic image dye
US4407931A (en) * 1982-06-28 1983-10-04 Eastman Kodak Company Photographic products and processes employing nondiffusible yellow azo metal complexed dye-releasing compounds and precursors thereof
DE3322058A1 (de) * 1983-06-18 1984-12-20 Agfa-Gevaert Ag, 5090 Leverkusen Mit metallionen chelatisierbare oder chelatisierte monoazofarbstoffe, deren verwendung zur bilderzeugung, ein farbfotografisches aufzeichnungsmaterial mit farbabspaltern, die die farbstoffe freisetzen, und ein farbbild mit einer bildmaessigen verteilung von nickelkomplexen der farbstoffe
GB8333830D0 (en) * 1983-12-20 1984-02-01 Kodak Ltd Photographic dye image compounds
US4555477A (en) * 1985-01-02 1985-11-26 Eastman Kodak Company Photographic element and process utilizing metal complex color masking dyes
US4555478A (en) * 1985-01-02 1985-11-26 Eastman Kodak Company Photographic element and process for providing metal complex color images

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0326160A3 (en) * 1988-01-29 1990-05-09 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5021329A (en) * 1988-01-29 1991-06-04 Fuji Photo Film Co., Ltd. Silver halide photographic material containing a dye precursor residue
WO2007103694A3 (en) * 2006-03-01 2007-11-01 Bristol Myers Squibb Co Triazine 11-beta hydroxysteroid dehydrogenase type i inhibitors
US7834178B2 (en) 2006-03-01 2010-11-16 Bristol-Myers Squibb Company Triazine 11-beta hydroxysteroid dehydrogenase type 1 inhibitors

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