EP0600561B1 - Gelbkuppler mit ionisierbare und/oder auflösbare Aryloxy freisetzbare Gruppen - Google Patents

Gelbkuppler mit ionisierbare und/oder auflösbare Aryloxy freisetzbare Gruppen Download PDF

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Publication number
EP0600561B1
EP0600561B1 EP19930203352 EP93203352A EP0600561B1 EP 0600561 B1 EP0600561 B1 EP 0600561B1 EP 19930203352 EP19930203352 EP 19930203352 EP 93203352 A EP93203352 A EP 93203352A EP 0600561 B1 EP0600561 B1 EP 0600561B1
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group
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coupling
silver halide
photographic element
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EP0600561A1 (de
Inventor
Phillip T.S. c/o Eastman Kodak Company Lau
Ping Wah C/O Eastman Kodak Company Tang
Stanley W. C/O Eastman Kodak Company Cowan
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Eastman Kodak Co
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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
    • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
    • G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
    • G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
    • G03C7/30535—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution having the coupling site not in rings of cyclic compounds

Definitions

  • This invention pertains to a new class of yellow dye- forming couplers and to silver halide color photographic light-sensitive elements, emulsions and processes comprising such couplers. More specifically, the invention pertains to a new class of yellow couplers having a multicyclic carbon center attached to the 2- position of a substituted phenyl carbamoyl acetyl group and a coupling-off group having a hydrophilic functional group.
  • yellow dye-forming couplers are open chain ketomethylene compounds which yield azomethine dyes upon coupling with an oxidized developer.
  • the most common yellow couplers are acylacetanilides, such as pivaloylacetanilides and benzoylacetanilides.
  • Pivaloylacetanilide yellow couplers which are frequently used in the art have, in general, low coupling efficiencies due to their high pK a values.
  • benzoylacetanilide couplers have been proposed and employed in the art.
  • benzoylacetanilide yellow couplers yield image dyes with very poor light stability.
  • the disclosed couplers were characterized by improved light fastness over the corresponding pivaloylacetanilides. Nevertheless, the adamantoylacetanalide yellow couplers are characterized by unsatisfactory coupling efficiency.
  • 2-equivalent yellow couplers containing a substituent in the coupling position are disclosed and employed in the art.
  • a coupling-off group COG
  • 2- equivalent adamantoylacetanilide yellow couplers are known, for example from U.S. Patent No. 4,336,327, the coupling activity of such couplers is still unsatisfactory.
  • a yellow dye-forming coupler comprising an acyl acetanilide in which the acyl group includes an adamantyl group attached to the carbonyl moiety, and an aryloxy coupling- off group at the coupling position of the acyl acetanilide, the coupling-off group having at least one substituent which is an ionizable group or a solubilizing group.
  • an aryloxy coupling- off group having at least one ionizable or solubilizing substituent significantly enhances the coupling efficiency and image-dye light stability of this class of yellow couplers.
  • the invention in another embodiment, relates to a photographic element comprising a support and a silver halide emulsion layer having associated therewith a yellow dye-forming coupler as described above.
  • this invention relates to a process for developing an image in a photographic element by developing it in the presence of a yellow dye- forming coupler as described above.
  • this invention relates to a photographic silver halide emulsion comprising a yellow dye-forming coupler as described above.
  • the yellow dye-forming coupler comprises an acyl acetanilide in which the acyl group includes an adamantyl group attached to the carbonyl moiety, and an aryloxy coupling-off group at the coupling position of the acyl acetanilide.
  • the aryloxy coupling-off group has at least one substituent which is an ionizable group or a solubilizing group.
  • ionizable substituent denotes a substituent which contains at least one acidic hydrogen that ionizes substantially at the processing pH of the color developer.
  • solubilizing substituent denotes a substituent which has a hydrophilic character and ionizes completely at the processing pH of the color developer.
  • Preferred yellow dye-forming couplers according to the invention can be represented by the formula wherein
  • Each substituent Y is independently the same or different.
  • the adamantyl group can be unsubstituted or substituted.
  • alkyl and aryl portions of the foregoing groups contain 1 to 20 carbon atoms (alkyl) and 6 to 20 carbon atoms (aryl). They can be substituted with halogen, hydroxy, cyano, carboxy, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, amido (-NR 2 COR 3 ), carbamoyl (CONR 2 R 3 ), alkylsulfinyl, alkylsulfonyl, hydroxyalkylsulfonyl, sulfonamido (NR 2 SO 2 R 3 ), and sulfamoyl (SO 2 NR 2 R 3 ).
  • Preferred coupling-off groups include the following:
  • the couplers according to the invention are incorporated in silver halide emulsions and the emulsions are coated on a support to form a photographic element.
  • the inventive couplers can be incorporated in photographic elements adjacent the silver halide emulsion where, during development, the coupler will be in reactive association with development products such as oxidized color developing agent.
  • the term "associated therewith” signifies that the coupler is in a silver halide emulsion layer or in an adjacent location where, during processing, it will come into reactive association with silver halide development products.
  • the amount of coupler to be incorporated in an emulsion is generally between about 5 x 10 -4 and 5 x 10 -3 mol/m 2 .
  • the inventive coupler can be ballasted.
  • Ballast groups if employed, comprise groups of such molecular size and configuration as to render the inventive coupler nondiffusible as described, for example, in U.S. Patent Nos. 4,420,556 and 4,923,789.
  • Advantageous ballast groups include alkyl and aryl groups having from about 8 to 32 carbon atoms.
  • Unballasted couplers can be used in a Kodachrome-type process.
  • the support of the element of the invention can be any of a number of well known supports for photographic elements. These include polymeric films, such as cellulose esters (for example, cellulose triacetate and diacetate) and polyesters of dibasic aromatic carboxylic acids with divalent alcohols (such as polyethylene terephthalate), paper, and polymer-coated paper.
  • polymeric films such as cellulose esters (for example, cellulose triacetate and diacetate) and polyesters of dibasic aromatic carboxylic acids with divalent alcohols (such as polyethylene terephthalate), paper, and polymer-coated paper.
  • the photographic elements according to the invention can be coated on the selected supports as described in Research Disclosure Section XVII and the references cited therein.
  • the radiation-sensitive layer of a photographic element according to the invention can contain any of the known radiation-sensitive materials, such as silver halide, or other light sensitive silver salts.
  • Silver halide is preferred as a radiation-sensitive material.
  • Silver halide emulsions can contain for example, silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, or mixtures thereof.
  • the emulsions can include coarse, medium, or fine silver halide grains bounded by 100, 111, or 110 crystal planes.
  • the silver halide emulsions employed in the elements according to the invention can be either negative-working or positive-working. Suitable emulsions and their preparation are described in Research Disclosure Sections I and II and the publications cited therein.
  • tabular grain silver halide emulsions are those in which greater than 50 percent of the total grain projected area comprises tabular grain silver halide crystals having a grain diameter and thickness selected so that the diameter divided by the mathematical square of the thickness is greater than 25, wherein the diameter and thickness are both measured in microns.
  • An example of tabular grain emulsions is described in U.S. Patent No. 4,439,520.
  • Suitable vehicles for the emulsion layers and other layers of elements according to the invention are described in Research Disclosure Section IX and the publications cited therein.
  • the radiation-sensitive materials described above can be sensitized to a particular wavelength range of radiation, such as the red, blue, or green portions of the visible spectrum, or to other wavelength ranges, such as ultraviolet, infrared, X-ray, and the like.
  • Sensitization of silver halide can be accomplished with chemical sensitizers such as gold compounds, iridium compounds, or other group VIII metal compounds, or with spectral sensitizing dyes such as cyanine dyes, merocyanine dyes, or other known spectral sensitizers.
  • chemical sensitizers such as gold compounds, iridium compounds, or other group VIII metal compounds
  • spectral sensitizing dyes such as cyanine dyes, merocyanine dyes, or other known spectral sensitizers.
  • Exemplary sensitizers are described in Research Disclosure Section IV and the publications cited therein.
  • Multicolor photographic elements generally comprise a blue-sensitive silver halide layer having a yellow color-forming coupler associated therewith, a green-sensitive layer having a magenta color-forming coupler associated therewith, and a red-sensitive silver halide layer having a cyan color- forming coupler associated therewith.
  • Color photographic elements and color-forming couplers are well-known in the art. in Research Disclosure Section VII, paragraphs D, E, F and G and the publications cited therein. These couplers can be incorporated in the elements and emulsions as described in Research Disclosure Section VII, paragraph C and the publications cited therein.
  • a photographic element according to the invention, or individual layers thereof, can also include any of a number of other well-known additives and layers. These include, for example, optical brighteners (see Research Disclosure Section V), antifoggants and image stabilizers (see Research Disclosure Section VI), light-absorbing materials such as filter layers of intergrain absorbers, and light-scattering materials (see Research Disclosure Section VIII), gelatin hardeners (see Research Disclosure Section X), oxidized developer scavengers, coating aids and various surfactants, overcoat layers, interlayers, barrier layers and antihalation layers (see Research Disclosure Section VII, paragraph K), antistatic agents (see Research Disclosure Section XIII), plasticizers and lubricants (see Research Disclosure Section XII), matting agents (see Research Disclosure Section XVI), antistain agents and image dye stabilizers (see Research Disclosure Section VII, paragraphs I and J), development-inhibitor releasing couplers and bleach accelerator-releasing couplers (see Research Disclosure Section VII, paragraph F), development modifiers (see Research Disclosure
  • Photographic elements according to the invention can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image as described in Research Disclosure Section XVIII, and then processed to form a visible dye image as described in Research Disclosure Section XIX.
  • Processing can be any type of known photographic processing, although it is preferably carried out at a pH of 9 to 14 and includes a nucleophile such as hydrogen peroxide, hydroxylamine, perborate, an alkyl peroxide, an aryl peroxide, or a compound releasing such nucleophiles.
  • a negative image can be developed by color development using one or more of the aforementioned nucleophiles.
  • a positive image can be developed by first developing with a nonchromogenic developer, then uniformly fogging the element, and then developing by a process employing one or more of the aforementioned nucleophiles. If the material does not contain a color- forming coupler compound, dye images can be produced by incorporating a coupler in the developer solutions.
  • Bleaching and fixing can be performed with any of the materials known to be used for that purpose.
  • Bleach baths generally comprise an aqueous solution of an oxidizing agent such as water soluble salts and complexes of iron (III) (such as potassium ferricyanide, ferric chloride, ammonium or potassium salts of ferric ethylenediaminetetraacetic acid), water-soluble dichromates (such as potassium, sodium, and lithium dichromate), and the like.
  • an oxidizing agent such as water soluble salts and complexes of iron (III) (such as potassium ferricyanide, ferric chloride, ammonium or potassium salts of ferric ethylenediaminetetraacetic acid), water-soluble dichromates (such as potassium, sodium, and lithium dichromate), and the like.
  • Fixing baths generally comprise an aqueous solution of compounds that form soluble salts with silver ions, such as sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, thioureas, and the like.
  • the coupler is prepared according to the following reaction scheme:
  • Yellow couplers Y-1 and Y-2 can be prepared by the procedure described for Y-3.
  • Couplers C-1, C-2 and C-3 were used for comparison:
  • Dispersions of the couplers were prepared in the following manner. The quantities of each component are found in Table I.
  • the coupler, stabilizer (2,2 , -methylenebis-(3-t-butyl-5-methylphenol) monoacetate), coupler solvent (dibutyl phthalate), and ethyl acetate were combined and warmed to dissolve.
  • the gelatin, Alkanol XCTM (E.I. DuPont Co.) and water were combined and warmed to about 40° C. The two mixtures were mixed together and passed three times through a Gaulin colloid mill. The ethyl acetate was removed by evaporation and water was added to restore the original weight after milling.
  • the photographic elements were prepared by coating the following layers on a resin-coated paper support: DOC Gelatin (1.40 g/m 2 ) bis(vinylsulfonylmethyl) ether (0.14 g/m 2 ) OVERLAYER Gelatin (1.33 g/m 2 ) 2-(2H-benzotriazol-2-yl)-4,6-bis-(1,1-dimethylpropyl)phenol (0.73 g/m 2 ) Tinuvin 326TM (Ciba-Geigy) (0.13 g/m 2 ) EMULSION LAYER Gelatin (1.61 g/m 2 ) Coupler dispersion from Table II (7.0 x 10 -4 mole coupler/m 2 )Blue-sensitized AgCl emulsion (0.24 g Ag/m 2 ) UNDERLAYER Gelatin (3.23 g/m 2 ) FILMBASE Resin-coated paper support
  • the photographic elements were given stepwise exposures to green light and processed as follows at 35° C: Developer 45 sec Bleach-Fix 45 sec Wash (running water) 1 min 30 sec
  • the developer and bleach-fix were of the following compositions: Developer Water 700.00 ml Triethanolamine 12.41 g Anhydrous potassium carbonate 21.16 g Potassium chloride 1.60 g Potassium bromide 7.00 mg Lithium sulfate 2.70 g Lithium polystyrene sulfonate (30%) 0.30 g N- ⁇ 2-[(4-amino-3-methylphenyl)ethylamino]ethyl ⁇ -methanesulfonamide, sesquisulfate 5.00 g N,N-Diethylhydroxylamine (85%) 5.40 g 1-Hydorxyethyl-1,1-diphosphonic acid (60%) 0.81 g Blankophor REUTM (Mobay Corp.) 2.30 g Water to make 1 liter, pH 10.4 ⁇ 0.05 @ 26.7°C Bleach-Fix Water 700.00 ml Solution of ammonium thiosulfate (56.4%) + ammonium sulfit
  • Coupler T-30 Printout (4 weeks) Y-1 1.76 0 C-1 1.70 -1 Y-2 3.44 -1 C-2 2.39 -5 Y-3 2.39 0 C-3 2.12 0
  • the yellow couplers according to the present invention provide not only improved coupling efficiency (as expressed by Dmax and contrast), but, unexpectedly, also superior image dye stability and printout.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (9)

  1. Photographisches Element mit einem Träger und einer Silberhalogenidemulsionsschicht, der ein einen gelben Farbstoff erzeugender Kuppler zugeordnet ist mit (a) einem Acylacetanilid, in dem die Acylgruppe eine Adamantylgruppe einschließt, die an den Carbonylrest gebunden ist, und mit (b) einer abkuppelnden Aryloxygruppe in der Kupplungsposition des Acylacetanilides, wobei die abkuppelnde Gruppe mindestens einen Substituenten aufweist, der eine ionisierbare Gruppe oder eine löslichmachende Gruppe ist.
  2. Photographisches Element nach Anspruch 1, in dem der einen gelben Farbstoff erzeugende Kuppler durch die Formel dargestellt wird:
    Figure 00360001
    worin
    R0 steht für
    Figure 00370001
    R1 steht für eine ionisierbare oder löslichmachende Gruppe;
    v steht für eine ganze Zahl von 1 bis 3;
    X steht für die Atome, die zur Vervollständigung eines Phenyl- oder Naphthylringsystems erforderlich sind;
    Y steht für Wasserstoff, Halogen, CN, CF3, C(O)nR2, CR2R3C(O)nR2, CR2R3CONR2R3, COO(CH2CH2O)pR2, CONR2R3, CONR2(CH2CH2O)pR3, NO2, NR2S(O)nR3, NR2S(O)nNR2R3, NR2COR3, NR2COCH(R2)(OR3), NR2CONR2R3, OR2, O(CH2)qR2, O(CH2CH2O)pR2, O(CH2CH2O)pCOOR2, O(CH2CH2O)pCONR2R3, S(O)nR2, S(O)nNR2 R3 oder S(O)nNR2(CH2CH2-O)pR3;
    R2, R3 stehen unabhängig voneinander für Wasserstoff oder unsubstituiertes oder substituiertes Alkyl, Aryl oder Heterocyclyl, oder sie vervollständigen zusammen einen heterocyclischen Ring mit den Stickstoff- oder Sauerstoffatomen, an die sie gebunden sind;
    n steht für 1 oder 2;
    p, q stehen unabhängig voneinander für eine ganze Zahl von 1 bis 3; und
    r steht für eine ganze Zahl von 1 bis 4.
  3. Photographisches Element nach Anspruch 2, in dem R1 eine Gruppe ist, die ausgewählt ist aus:
       -OH -NH-C2H4OH -N(C2H4-OH)2 -COOH -NH-C3H6-COOH -N(C2H4-COOH)2 2 -N(SO2-C2H4-OH)2 -NHSO2-C2H4-OH -SO2NH-C2H4-OH -SO2N(C2H4OH)2 -N (SO2-C2H4-COOH)2 -NHSO2-C2H4-COOH
    Figure 00380001
    worin p = 1 oder 2 ist.
  4. Photographisches Element nach einem der Ansprüche 1 bis 3, in dem der einen gelben Farbstoff erzeugende Kuppler eine Ballastgruppe aufweist.
  5. Photographisches Element nach einem der vorstehenden Ansprüche, in dem die abkuppelnde Gruppe ausgewählt ist aus:
    Figure 00380002
    Figure 00380003
    Figure 00380004
    Figure 00380005
  6. Photographisches Element nach Anspruch 2, in dem der Gelbkuppler ausgewählt ist aus:
    Figure 00390001
    Figure 00390002
    Figure 00400001
    Figure 00400002
    Figure 00400003
    Figure 00410001
    Figure 00410002
    Figure 00420001
    Figure 00420002
    und
    Figure 00430001
  7. Ein einen gelben Farbstoff erzeugender Kuppler nach einem der Ansprüche 1 bis 6.
  8. Verfahren zur Entwicklung eines Bildes in einem photographischen Element mit einem Träger und einer Silberhalogenidemulsion, die eine bildweise Verteilung von entwickelbaren Silberhalogenidkörnern enthält, wobei das Verfahren umfaßt die Stufe der Entwicklung des Elementes mit einer Silberhalogenid-Farbentwicklerverbindung in Gegenwart eines einen gelben Farbstoff erzeugenden Kupplers nach Anspruch 7.
  9. Photographische Silberhalogenidemulsion, die einen einen gelben Farbstoff erzeugenden Kuppler nach Anspruch 7 enthält.
EP19930203352 1992-12-04 1993-12-01 Gelbkuppler mit ionisierbare und/oder auflösbare Aryloxy freisetzbare Gruppen Expired - Lifetime EP0600561B1 (de)

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US98538492A 1992-12-04 1992-12-04
US985384 1992-12-04

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EP0600561B1 true EP0600561B1 (de) 1999-03-24

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Publication number Priority date Publication date Assignee Title
US6077658A (en) * 1998-12-18 2000-06-20 Eastman Kodak Company Silver halide elements containing yellow couplers with improved dye stability

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5927895B2 (ja) * 1979-12-17 1984-07-09 富士写真フイルム株式会社 黄色カプラ−
EP0447969B1 (de) * 1990-03-15 1997-01-15 Fuji Photo Film Co., Ltd. Gelbkuppler und farbenphotographisches Silberhalogenidmaterial, diesen enthaltend
JP2672205B2 (ja) * 1991-05-21 1997-11-05 富士写真フイルム株式会社 イエロー色素形成カプラー及びこれを含有するハロゲン化銀カラー写真感光材料

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DE69324109D1 (de) 1999-04-29
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JPH06208208A (ja) 1994-07-26

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