EP0520498B1 - Verfahren zur Herstellung photographischer Kuppler - Google Patents

Verfahren zur Herstellung photographischer Kuppler Download PDF

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Publication number
EP0520498B1
EP0520498B1 EP92110838A EP92110838A EP0520498B1 EP 0520498 B1 EP0520498 B1 EP 0520498B1 EP 92110838 A EP92110838 A EP 92110838A EP 92110838 A EP92110838 A EP 92110838A EP 0520498 B1 EP0520498 B1 EP 0520498B1
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Prior art keywords
photographic
compound
coupler
group
product
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English (en)
French (fr)
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EP0520498A1 (de
Inventor
William James C/O Eastman Kodak Company Begley
Teh-Hsuan C/O Eastman Kodak Company Chen
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Eastman Kodak Co
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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
    • G03C7/30576—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the linking group between the releasing and the released groups, e.g. time-groups

Definitions

  • This invention relates to a method of preparing a photographic coupler that comprises a parent coupler moiety (COUP) containing a phenoxy coupling-off group having an aminoalkyl group linking a photographically useful group to the 2-position of the phenoxy coupling-off group.
  • COUP parent coupler moiety
  • a method of preparing a photographic coupler that comprises a parent coupler moiety (COUP) containing a phenoxy coupling-off group having an aminoalkyl group linking a photographically useful group to the 2-position of the phenoxy coupling-off group, comprising:
  • the coupler moiety (COUP) as described can be any coupler moiety known in the photographic art, preferably a naphtholic coupler moiety or acetanilide coupler moiety.
  • a highly preferred coupler moiety is a naphtholic coupler moiety containing a water solubilizing group, such as -CONH 2 or -CONHCH 3 , in the 2-position of the naphtholic nucleus.
  • Such coupler moieties typically react with oxidized color developing agent in photographic processing to yield colorless compounds or colored compounds.
  • the coupler moiety can be ballasted or unballasted. It can be monomeric, or it can be a dimeric, oligomeric or polymeric coupler.
  • the coupler moiety is typically a dye-forming coupler such as a colored or colorless dye-forming coupler and can be diffusible or non-diffusible.
  • the coupler moiety is preferably a 2-equivalent coupler of the open-chain ketomethylene, pyrazolone, pyrazolotriazole, pyrazolobenzimidazole, phenol or naphthol type know in the photographic art.
  • the phenoxy coupling-off group can be any such coupling-off group known in the photographic art provided that the phenoxy group contains a substituted or unsubstituted hydroxyalkyl as described, in the 2-position of the phenoxy group.
  • the phenoxy coupling-off group can be unsubstituted except for the substituted or unsubstituted hydroxyalkyl group.
  • the phenoxy coupling-off group can be substituted with groups that do not adversely affect the coupler or the photographic material in which the coupler is used or the reaction as described.
  • substituent groups include, for example, groups known to be useful on phenoxy coupling-off groups in the photographic art, such as ballast groups, alkyl, aryl, nitro, sulfonamide, sulfamyl, carbamoyl, ethers, esters, carbonamide, and the like groups.
  • the described hydroxyalkyl group preferably containing 1 to 40 carbon atoms, has the hydroxy group on the alpha carbon atom of the alkyl.
  • This hydroxyalkyl group is represented by the formula: wherein R 1 and R 2 are individually hydrogen or substituents that do not adversely affect the described synthesis, such as alkyl or phenyl, but preferably hydrogen.
  • the hydroxyalkyl group is preferably hydroxymethyl.
  • the described unsubstituted or substituted hydroxyalkyl group preferably containing 1 to 40 carbon atoms, also has the hydroxy group on the alpha carbon atom.
  • Substituents in the described hydroxyalkyl groups that can adversely affect the described synthesis include other hydroxyl and amine groups.
  • the halogening agent as described can be any halogenating agent known in the organic compound synthesis art. Such halogenating agents are preferably brominating agents but can be chlorinating agents. Illustrative examples of such halogenating agents include, HBr, phosphorous tribromide, SOCl 2 , PCl2, and PCl 5 which do not affect the remainder of the molecule.
  • the halogenating reaction is carried out under conditions of pressure and temperature that are dependent upon the halogenating agent used.
  • the pressure and temperature are typical normal atmospheric conditions.
  • elevated temperatures such as 60°C. It is not necessary to carry out this reaction above or below normal atmospheric pressure.
  • the reaction is carried out at a temperature within the range of 0 to 100°C.
  • the halogenating reaction is carried out to completion. Typically an excess of halogenating agent is used in the reaction.
  • the step (B) as described is carried out with any amine compound that reacts with the product of step (A).
  • the amine compound is preferably an alkylamine or arylamine.
  • the alkylamine is typically an alkylamine comprising 1 to 40 carbon atoms, such as methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, t-butylamine, ethanolamine, chloroethylamine, or other substituted alkylamines.
  • the arylamine is typically an unsubstituted or substituted phenylamine containing 6 to 40 carbon atoms.
  • arylamines include aniline, methoxyaniline, chloroaniline or nitroaniline.
  • Illustrative phenylamine compounds are represented by the formula: R 3 is -NHSO 2 R 4 , -SO 2 NHR 5 , -NHCOR 6 , -CONHR 7 , -CO 2 R 8 , -OR 9 or hydrogen: wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 individually are substituents that do not adversely affect the described synthesis, such as alkyl, for instance alkyl containing 1 to 40 carbon atoms, or aryl, for instance phenyl.
  • the arylamine is preferably
  • the reaction of the product of step (A) as described with the amine compound is carried out under conditions of pressure and temperature that are dependent upon the amine compound used, 0° to 100°C being preferred. Typically the reaction is carried out under normal atmospheric conditions of temperature and pressure. Elevated temperatures and pressures above or below may be required depending on the amine. The described reaction is typically carried out at a temperature within the range of 0 to 100°C. Less nucleophilic amines such as nitroanilines may require elevated temperatures. The more nucleophilic amines may require reaction at room temperature (20°C) or below.)
  • reaction of the product of step (A) as described with the amine compound is typically carried to completion.
  • concentrations of reactants can be mixed in stoichiometric ratios; however, typically the amine compound is typically added in excess of that required.
  • step (B) is typically reacted with phosgene under normal atmospheric conditions and the product of this reaction then reacted with a photographically useful compound. This enables formation of a coupler that is capable of releasing a photographically useful group (PUG) in a photographic material upon processing.
  • PAG photographically useful group
  • the product from the reaction in step (B) can be reacted with a bis-mercaptotetrazole compound known in the photographic art, such as bis-phenylmercaptotetrazole or benzotriazole carbonyl chloride.
  • a bis-mercaptotetrazole compound known in the photographic art such as bis-phenylmercaptotetrazole or benzotriazole carbonyl chloride.
  • This reaction can also be carried out under normal atmospheric pressure and temperatures preferably within the range of 0 to 100°C. This enables formation of a coupler that is capable of releasing a mercaptotetrazole development inhibitor moiety in a photographic material upon processing.
  • the described bis-mercaptotetrazole moiety can be any such compound known in the organic compound synthesis art, preferably those compounds known in the photographic art that enable formation of a development inhibitor releasing compound that is useful in a photographic silver halide material.
  • a preferred method as described is a method of forming a photographic coupler represented by the formula: wherein PUG is a photographically useful group; R 10 is a hydrogen or a photographic ballast group known in the photographic art; R 11 is unsubstituted or substituted aryl or alkyl; R 12 and R 13 individually are hydrogen or substituents that do not adversely affect the coupler, preferably hydrogen; one of R 10 , R 11 , R 12 or R 13 is a photographic ballast group preferably R 11 ; comprising
  • the PUG can be any group that is typically made available in a photographic element in an imagewise fashion.
  • the PUG can be a photographic reagent or a photographic dye.
  • a photographic reagent herein is a moiety that upon release further reacts with components in the photographic element, such as a development inhibitor, a development accelerator, a coupler (for example, a competing coupler, a dye-forming coupler, or a development inhibitor releasing coupler [DIR coupler]), a dye precursor, a dye, a developing agent (for example, a competing developing agent, a dye-forming developing agent, or a silver halide developing agent), a silver complexing agent, a fixing agent, an image toner, a stabilizer, a hardener, a tanning agent, a fogging agent, an ultraviolet radiation absorber, an antifoggant, a nucleator, a chemical or spectral sensitizer, or a desensitizer.
  • a development inhibitor for example, a competing coupler,
  • the PUG can be present in the coupling-off group as a preformed species or it can be in a blocked form or as a precursor.
  • the PUG can be, for example, a preformed development inhibitor or the development inhibiting function can be blocked by being the point of attachment to the carbonyl group bonded to the PUG.
  • Other examples are a preformed dye, a dye that is blocked to shift its absorption, and a leuco dye.
  • Preferred naphtholic compounds are prepared according to the following methods that are illustrative of the described process: These compounds are photographic couplers that can be used in photographic materials and are compounds that can be used for preparation of other photographic couplers, as described, such as DIR and DIAR couplers.
  • the image dye-forming couplers can be incorporated in photographic elements and/or in photographic processing solutions, such as developer solutions, so that upon development of an exposed photographic element they will be in reactive association with oxidized color developing agent.
  • Coupler compounds incorporated in photographic processing solutions should be of such molecular size and configuration that they will diffuse through photographic layers with the processing solution.
  • the coupler compounds should be non-diffusible, that is they should be of such molecular size and configuration that they will not significantly diffuse or wander from the layer in which they are coated.
  • Photographic elements can be processed by conventional techniques in which color forming couplers and color developing agents are incorporated in separate processing solutions or compositions or in the element.
  • Photographic elements in which the compounds are incorporated can be a simple element comprising a support and a single silver halide emulsion layer or they can be multilayer, multicolor elements.
  • the compounds can be incorporated in at least one of the silver halide emulsion layers and/or in at least one other 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, other photographic compounds, such as dye-forming couplers, colored masking couplers, and/or competing couplers. These other photographic couplers can form dyes of the same or different color and hue as the photographic couplers of this invention. Additionally, the silver halide emulsion layers and other layers of the photographic element can contain addenda conventionally contained in such layers.
  • a typical multilayer, multicolor photographic element 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 photographic coupler.
  • 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.
  • the couplers can be incorporated in or associated with one or more layers or units of the photographic element.
  • a layer or unit affected by PUG can be controlled by incorporating in appropriate locations in the element a scavenger layer which will confine the action of PUG to the desired layer or unit.
  • At least one of the layers of the photographic element can be, for example, a mordant layer or a barrier layer.
  • 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 silver halide grains.
  • the emulsion can be of the type used in reversal color photographic materials, color negative photographic materials, such as motion picture films and the like. They can be chemically and spectrally sensitized.
  • the emulsions typically will be gelatin emulsions although other hydrophilic colloids are useful.
  • Tabular grain light sensitive silver halides are particularly useful such as described in Research Disclosure, January 1983, Item No. 22534 and US-A-4,434,226.
  • the support can be any support used with photographic elements. Typical supports include cellulose nitrate film, cellulose acetate film, polyvinylacetal film, polyethylene terephthalate film, polycarbonate film and related films or resinous materials as well as glass, paper, metal and the like. Typically, a flexible support is employed, such as a polymeric film or paper support. Paper supports can be acetylated or coated with baryta and/or an ⁇ -olefin containing 2 to 10 carbon atoms such as polyethylene, polypropylene, ethylene-butene copolymers and the like.
  • the coupling-off group contain a releasable PUG.
  • the couplers can be incorporated in a photographic element for different purposes and in different locations.
  • the photographic elements can be coated on a variety of supports as described in Research Disclosure Section XVII and the references described therein.
  • Photographic elements 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 the processed to form a visible dye image as described in Research Disclosure Section XIX.
  • Processing to form a visible dye image includes the step of contacting the element with a color developing agent to reduce developable silver halide and oxidize the color developing agent. Oxidized color developing agent in turn reacts with the coupler to yield a dye.
  • Preferred color developing agents useful in the method according to the invention are p-phenylene diamines.
  • Preferred color developing agents useful in the method according to the invention are 4-amino-N,N-diethylaniline hydrochloride; 4-amino-3-methyl-N,N-diethylaniline hydrochloride; 4-amino-3-methyl-N-ethyl-ethyl- ⁇ -(methanesulfonamido)-ethylaniline sulfate hydrate; 4-amino-3-methyl-N-ethyl-N- ⁇ -hydroxyethylaniline sulfate; 4-amino-3- ⁇ -(methanesulfonamido)-ethyl-N,N-diethyl-aniline hydrochloride; and 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluenesulfonic acid.
  • the processing step described above gives a negative image.
  • this step can be preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form a dye, and then uniformly fogging the element to render unexposed silver halide developable.
  • a direct positive emulsion can be employed to obtain a positive image.
  • Compound I-4 (15) was prepared as described in Example 1.
  • Compounds I-1, I-2 and I-3 were also prepared by similar procedures.
  • Photographic elements were prepared by coating the following layers on a cellulose ester film support (amounts of each component are indicated in mg/m 2 ):
  • Emulsion layer 1 Gelatin - 2420 red sensitized silver bromoiodide (as Ag)-1615; yellow image coupler dispersed in dibutyl phthalate (RECEIVER LAYER) Interlayer Gelatin - 860; didodecylhydroquinone - 113 Emulsion layer 2 Gelatin - 2690; green sensitized silver bromoiodide (as Ag)-1615; magenta image coupler dispersed in tritolyl phosphate; DIR compound of Table 1 dispersed in N,N-diethyl-dodecanamide and coated at levels of 5, 10, 15 and 20 ⁇ m/ft 2 .
  • CAUSER LAYER Protective Gelatin
  • Color Developer Distilled water 800 mL Sodium Metabisulfite 2.18 g Sodium Sulfite, anhydrous 0.38 g CD-4 (color developer)* 4.52 g Potassium Carbonate, anhyd.
  • Interimage effect (the degree of color correction) was evaluated after a daylight exposure. Interimage effect, as reported in Table I, was quantified as the ratio of the gamma of the green-sensitive layer (causer) to that of the red-sensitive layer (receiver). Table I Compound Gamma Reduction 1 Gamma Causer Gamma Receiver Acutance(AMT) I-1 0.40 2.52 92 I-2 0.71 2.87 94 I-3 1.15 3.01 94 I-4 1.84 1.94 92

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  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (6)

  1. Verfahren zur Herstellung eines photographischen Kupplers, der einen Stammkupplerrest (COUP) mit einer abkuppelnden Phenoxygruppe aufweist, die eine Aminoalkylgruppe, welche eine photographisch nützliche Gruppe an die 2-Position der abkuppelnden Phenoxygruppe bindet, aufweist, bei dem man:
    (a) einen Kupplerrest mit einer abkuppelnden Phenoxygruppe mit einer Hydroxyalkylgruppe in der 2-Position, wobei die Hydroxygruppe sich an dem Alpha-Kohlenstoff der Alkylgruppe befindet, mit einer halogenierenden Verbindung unter Erzeugung eines ersten Produktes umsetzt; bei dem man
    (b) das erste Produkt von Stufe (a) mit einer Aminoverbindung unter Erzeugung eines zweiten Produktes umsetzt; und bei dem man
    (c) das zweite Produkt umsetzt mit Phosgen und dann mit einer photographisch nützlichen Verbindung, unter Erzeugung eines photographischen Kupplers für die Freisetzung der photographisch nützlichen Verbindung in einem photographischen Material durch Exponierung und Entwicklung des photographischen Materials.
  2. Verfahren nach Anspruch 1, bei dem das Halogenierungsmittel ein Bromierungs- oder Chlorierungsmittel ist.
  3. Verfahren nach Anspruch 1, bei dem die Aminoverbindung eine aromatische oder aliphatische Aminoverbindung ist.
  4. Verfahren nach Anspruch 1, bei dem das Produkt von Stufe (b) mit Phosgen umgesetzt wird und dann mit einer Entwicklungsinhibitorverbindung (PUG) unter Erzeugung eines Kupplers, der eine Entwicklungsinhibitorverbindung in einem photographischen Material nach Exponierung und Entwicklung des photographischen Materials freizusetzen vermag.
  5. Verfahren nach Anspruch 1, bei dem der Kupplerrest in einem photographischen Material nach Exponierung und Entwicklung einen Farbstoff zu erzeugen vermag, der aus dem photographischen Material ausgewaschen werden kann.
  6. Verfahren nach Anspruch 1 zur Herstellung eines photographischen Kupplers, der durch die Formel wiedergegeben wird:
    Figure imgb0025
     worin PUG eine photographisch nützliche Gruppe ist; R10 steht für Wasserstoff oder einen photographischen Ballast; und R11 eine unsubstituierte oder substituierte Aryl- oder Alkylgruppe ist; R12 und R13 einzeln stehen für Wasserstoff oder Substituenten; wobei einer der Reste R10, R11, R12 und R13 eine photographische Ballastgruppe ist, bei dem man (A) umsetzt,
    (a) einen Kupplerrest gemäß der Formel
    Figure imgb0026
     mit
    (b) einem Bromieruns- oder Chlorierungsmittel unter Umgebungsbedingungen;
    wobei man daraufhin
       (B) das Produkt von Stufe (A) mit einer unsubstituierten oder substituierten Aryl- oder Alkylaminoverbindung umsetzt;
    bei dem man dann
       (c) das Produkt von Stufe (B) mit Phosgen umsetzt;
    und bei dem man
       (d) das Produkt von Stufe (c) mit einer photographisch nützlichen Verbindung umsetzt.
EP92110838A 1991-06-28 1992-06-26 Verfahren zur Herstellung photographischer Kuppler Expired - Lifetime EP0520498B1 (de)

Applications Claiming Priority (2)

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US722807 1985-04-12
US72280791A 1991-06-28 1991-06-28

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Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0594256A1 (de) * 1992-10-20 1994-04-27 Eastman Kodak Company Photographisches Element und Verfahren zur dessen Herstellung

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4248962A (en) * 1977-12-23 1981-02-03 Eastman Kodak Company Photographic emulsions, elements and processes utilizing release compounds

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2036041A1 (en) * 1990-02-22 1991-08-23 William James Begley Photographic material and process comprising wash-out naphtholic coupler

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4248962A (en) * 1977-12-23 1981-02-03 Eastman Kodak Company Photographic emulsions, elements and processes utilizing release compounds

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EP0520498A1 (de) 1992-12-30
DE69223551D1 (de) 1998-01-29
JPH05188540A (ja) 1993-07-30
DE69223551T2 (de) 1998-06-25

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