EP0530921B1 - Photographische Farbentwicklerzusammensetzung enthaltend eine Alpha-Aminosäure für verbesserte Stabilität der Lösung - Google Patents

Photographische Farbentwicklerzusammensetzung enthaltend eine Alpha-Aminosäure für verbesserte Stabilität der Lösung Download PDF

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Publication number
EP0530921B1
EP0530921B1 EP19920202662 EP92202662A EP0530921B1 EP 0530921 B1 EP0530921 B1 EP 0530921B1 EP 19920202662 EP19920202662 EP 19920202662 EP 92202662 A EP92202662 A EP 92202662A EP 0530921 B1 EP0530921 B1 EP 0530921B1
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EP
European Patent Office
Prior art keywords
color developing
photographic
silver halide
photographic color
acid
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Expired - Lifetime
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EP19920202662
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English (en)
French (fr)
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EP0530921A1 (de
Inventor
Jean Marie Buongiorne
Janet Marie Huston
Paul Andrew Schwartz
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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
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers

Definitions

  • This invention pertains to novel compositions and methods for processing photographic color elements. More specifically, this invention relates to novel photographic color developing compositions and to a method of processing photographic elements utilizing such developing compositions.
  • the color-forming coupler may be either in the developer solution or incorporated in the light-sensitive photographic emulsion layer, so that during development, it is available in the emulsion layer to react with the color developing agent that is oxidized by silver image development.
  • Diffusible couplers are used in color developer solutions.
  • Nondiffusing couplers are incorporated in photographic emulsion layers.
  • couplers are selected which form non-diffusing dyes.
  • couplers are used which will produce diffusible dyes capable of being mordanted or fixed in the receiving sheet.
  • the amount of sulfite which can be tolerated in the developer solution is limited by the fact that sulfite competes with couplers for oxidized developing agent and thereby adversely affects dye formation.
  • yellow dye-forming couplers react with oxidized developing agent more slowly than cyan or magenta dye-forming couplers so that the competition between coupler and sulfite has the greatest adverse effect on the formation of the yellow dye image.
  • hydroxylamine or a water-soluble acid salt thereof, is disadvantageous since it tends to act as a scavenger which reduces oxidized color developing agent before it can react with a coupler to form a dye. It also acts as a developing agent which competes with the color developing agent unless it is adequately restrained. Some hydroxylamines have a characteristic amine odor and are volatile.
  • U.S. Patent 4,273,863 discloses employing amino acids as building blocks to synthesize larger molecules for use as preservatives in combination with the developing agent, hydroquinone.
  • U.S. Patent 4,189,319 discloses using the amino acid, arginine, as a development accelerator.
  • U.S. Patent 4,124,391 discloses using monosaccharides to protect against aerial oxidation either alone or in combination with an amino acid.
  • U.S. Patent 4,833,068 discloses using the combination of an hydroxylamine and iminodiacetic acid to retard oxidation.
  • U.S. Patent 4,273,863 discloses employing amino acids as building blocks to synthesize larger molecules for use as preservatives in combination with the developing agent, hydroquinone.
  • U.S. Patent 4,189,319 discloses using the amino acid, arginine, as a development accelerator.
  • U.S. Patent 4,124,391 discloses using monosaccharides to protect against aerial oxidation either alone or in
  • Patent 4,170,478 discloses using an unsubstituted or monosubstituted hydroxylamine in combination with an amino acid, alkanolamine, or ortho- or para- aminobenzoic acid in a low- or no-sulfite system to prevent aerial oxidation.
  • a photographic color developing composition comprising a primary aromatic amino color developing agent and an alpha amino acid as sole developer preservative.
  • a method of rapid access processing of a silver halide photographic color element comprising a support and a silver halide emulsion containing an imagewise distribution of developable silver halide grains, which comprises the steps of: contacting said element with a color developing composition as defined above; bleach-fixing the element without washing between the developing and bleach-fixing steps; and stabilizing the element without washing between the bleach-fixing and stabilizing steps.
  • a method of processing a chlorobromide or all-chloride silver halide photographic element comprising a support and a silver halide emulsion containing an imagewise distribution of developable silver halide grains, comprising the steps of contacting the element with a prebath; rinsing the element; contacting the element with a color developing composition as defined above; contacting the element with a stop bath; washing the element; optionally fixing the element followed by washing the element; bleaching the element; washing the element; fixing the element; washing the element; and rinsing the element.
  • photographic color developer compositions containing a primary aromatic amino color developing agent can be protected against aerial oxidation by the use of an alpha amino acid exclusively. It has been determined that glycine and threonine in particular provide superior developer preservative protection to color developing compositions.
  • an alpha amino acid in combination with an alkanolamine or an N,N-dialkylhydroxylamine provides an additional improvement in developer preservative protection to color developing compositions.
  • novel photographic color developing compositions of this invention are especially useful with high-chloride silver halide emulsions. They are free of or at least substantially free of bromide, since bromide in significant quantities can unduly restrain the development reaction. They are free of or contain low concentrations of sulfite to minimize competition with the dye forming reactions.
  • the aforesaid photographic color developing composition is free of benzyl alcohol and is used in a rapid access process for processing silver halide photographic emulsions, for example high-chloride silver halide photographic color elements.
  • Said rapid access process comprises the steps of color developing, bleach-fixing without washing between the color developing and bleach-fixing steps, and stabilizing without washing between the bleach-fixing and stabilizing steps. Elimination of the benzyl alcohol from the developing composition allows the bleach-fix to be utilized at a lower pH than is otherwise permissible, without the risk of producing leuco cyan dye. The low pH increases the rate of bleach-fix reactions, thereby enabling the use of a short bleach-fix time as is needed for a rapid access process.
  • high chloride denotes a silver chloride content of at least about 75%, preferably at least 90%, on a molar basis.
  • process is not limited to such emulsions, but can also be used with emulsions having a lower silver chloride content.
  • the aforesaid photographic color developing composition is used in a method of developing a chlorobromide or all-chloride silver halide photographic element, which comprises the sequential steps of contacting the element with a prebath, a rinse, a color developing composition as defined above, a stop bath, a wash, an optional fixing bath and a second wash, a bleaching bath, another wash, a fixing bath, another wash, and a final rinse.
  • the novel color developer compositions according to the invention comprise an alpha amino acid which functions to retard the aerial oxidation of the developing agent. It is represented by the formula I: wherein R is, for example, H, an alkyl group, an alkaryl group, or another substituent. Examples include glycine, alanine, leucine, serine, threonine, valine and isoleucine. Glycine and threonine are particularly preferred alpha amino acids. Other alpha amino acids are also encompassed within the invention.
  • the primary aromatic amino color developing agents that are utilized in the compositions and methods of this invention are well known and widely used in a variety of color photographic processes. They include aminophenols and p-phenylenediamines. They are usually used in the salt form, such as the hydrochloride or sulfate, as the salt form is more stable than the free amine.
  • the agents are generally employed in concentrations of from 0.1 to 20 grams per liter (g/l) of developing solution and more preferably from 0.5 to 10 g/l of developing solution.
  • amino phenol developing agents examples include o-aminophenol, p-aminophenol, 5-amino-2hydroxytoluene, 2-amino-3-hydroxytoluene, 2-hydroxy-3-amino-1,4-dimethylbenzene, and the like.
  • Particularly useful primary aromatic amino color developing agents are the p-phenylenediamines, and especially the N,N-dialkyl-p-phenylenediamines in which the alkyl groups or the aromatic nucleus can be substituted or unsubstituted.
  • Examples of useful p-phenylenediamine color developing agents include: N,N-diethyl-p-phenylenediamine monohydrochloride; 4-N,N-diethyl-2-methylphenylenediamine monohydrochloride; 4-(N-ethyl-N-2methanesulfonylaminoethyl)-2-methyl-phenylenediamine sesquisulfate monohydrate; 4-(N-ethyl-N-2-hydroxyethyl) -2-methylphenylenediamine sulfate; 4-N,N-diethyl-2,2'-methanesulfonylaminoethylphenylenediamine hydrochloride, and the like.
  • An especially preferred class of p-phenylenediamine developing agents are those containing at least one alkylsulfonamidoalkyl substituent attached to the aromatic nucleus or to an amino nitrogen.
  • Other classes of p-phenylenediamines are the 3-alkyl-N-alkyl-N-alkoxyalkyl-p-phenylenediamines and the 3-alkoxy-N-alkyl-N-alkoxyalkyl-p-phenylenediamines. These developing agents are described in U.S.
  • Patents 3,656,950 and 3,658,525 can be represented by the formula II: wherein n is an integer from 2 to 4, R 1 is an alkyl group of from 1 to 4 carbon atoms, and R 2 is an alkyl group of from 1 to 4 carbon atoms or an alkoxy group of from 1 to 4 carbon atoms.
  • Illustrative examples of these developing agents include the following compounds: N-ethyl-N-methoxybutyl-3-methyl-p-phenylenediamine, N-ethyl-N-ethoxyethyl-3-methyl-p-phenylenediamine, N-ethyl-N-methoxyethyl-3-n-propyl-p-phenylenediamine, N-ethyl-N-methoxyethyl-3-methoxy-p-phenylenediamine, N-ethyl-N-butoxyethyl-3-methyl-p-phenylenediamine, and the like.
  • compositions of this invention are employed in the form of aqueous alkaline working solutions having a pH of 10 and most typically in the range of from 9 to 13.
  • the compositions include one or more of the well-known and widely used pH buffering agents, such as the alkali metal carbonates or phosphates. Potassium carbonate is especially useful as a pH buffering agent.
  • the color developing compositions utilized in the method according to the invention typically contain one or more sequestering agents, for example, an aminopolycarboxylic acid chelating agent or an aminopolyphosphonic acid chelating agent.
  • sequestering agents for example, an aminopolycarboxylic acid chelating agent or an aminopolyphosphonic acid chelating agent.
  • aminopolycarboxylic acid chelating agents include: nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), 1,3-diamino-2-propanol-N,N,N,N-tetraacetic acid (DPTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylethylenediaminetriacetic acid, cyclohexanediaminotetraacetic acid, aminomalonic acid, and the like.
  • NTA nitrilotriacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • DPTA 1,3-diamino-2-propanol-N,N,N,N-tetraacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • hydroxyethylethylenediaminetriacetic acid cyclohexanediaminotetraacetic acid, aminomalonic acid, and the like.
  • aminopolyphosphonic acid chelating agents are the following:
  • aminopolyphosphonic acid chelating agents useful in the novel color developing compositions according to the invention include: 1-aminoethane-1,1-diphosphonic acid, 1-aminopropane-1,1-diphosphonic acid, N-acetyl-1-aminoethane-1,1-diphosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, 1,2-cyclohexanediamine-N,N,N,Ntetramethylenephosphonic acid, o-carboxyanilino-N,N-dimethylenephosphonic acid, propylamino-N,N-dimethylenephosphonic acid, 4-(N-pyrrolidino) butylamine-N,N-bis-methylenephosphonic acid, 1,3-diaminopropanol-N,N,N,N-tetramethylenephosphonic acid, 1,6-
  • Additional ingredients which can optionally be included in the photographic color developing compositions include thickening agents, brightening agents, wetting agents and so forth.
  • the photographic color developing compositions of this invention be free of benzyl alcohol.
  • the photosensitive layers can contain conventional addenda and be coated on any of the photographic supports, such as, for example, cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polycarbonate film, polystyrene film, polyethylene terephthalate film, paper, polymer-coated paper and the like.
  • the photographic color developing solution shown below will be referred to as Developer 1.
  • a photographic color print material of the high chloride type as described in U.S. Patent 4,269,927 (May 26, 1981, to Atwell) was processed in a three-step process consisting of 45 sec. development, 45 sec. bleach-fix and 90 sec. wash steps. Each step was carried out at 35° C. The print material was then dried. Results for Developer 1 + 5.18 g/l glycine in comparison to Developer 1 alone are summarized below as percent change. Quantity % Change Dmin R 0 Dmin G 0 Dmin B 0 Dmax R 1.8% Dmax G 1.8% Dmax B 2.5% Speed R 1.5% Speed G 1.2% Speed B 1.1%
  • compositions were prepared and their decomposition rates were determined.
  • the photographic color developing solution shown below will be referred to as Developer 2.
  • Developer 2 Component Concentration Diethylenetriaminepentaacetic acid, Na salt, 40% in water 7.0 ml/l Potassium chloride 3.1 g/l Potassium bromide 0.1 g/l Diethylamino-ortho-toluidine hydrochloride 2.8 g/l Sodium carbonate 21.0 g/l Water to make 1 liter pH to 10.55 Developer Solution Decomposition Rate (g/l/week) Developer 2 0.39 Developer 2 + 3.9 g/l Glycine 0.12

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

Claims (12)

  1. Photographische Farbentwicklerzusammensetzung mit:
    (a) einer aus einem primären aromatischen Amin bestehenden Farbentwicklerverbindung, dadurch gekennzeichnet, daß die Zusammensetzung weiterhin enthält:
    (b) eine alpha-Aminosäure als einzigem Entwickler-Präservierungsmittel.
  2. Photographische Farbentwicklerzusammensetzung nach Anspruch 1, worin die alpha-Aminosäure Glycin, Alanin, Leucin, Serin, Threonin, Valin oder Isoleucin ist.
  3. Photographische Farbentwicklerzusammensetzung nach Anspruch 1 oder 2, worin die Entwicklerverbindung ein p-Phenylendiamin oder ein Aminophenol ist.
  4. Photographische Farbentwicklerzusammensetzung nach einem der Ansprüche 1 bis 3, weiterhin enthaltend ein Sequestriermittel.
  5. Photographische Farbentwicklerzusammensetzung nach Anspruch 4, worin das Sequestriermittel ein Säure-Chelatmittel ist, ausgewählt aus einem Aminopolycarbonsäure-Chelatbildner, einem Aminopolyphosphonsäure-Chelatbildner oder einer Mischung hiervon.
  6. Photographische Farbentwicklerzusammensetzung nach einem der Ansprüche 1 bis 5, die von Benzylalkohol praktisch frei ist.
  7. Photographische Farbentwicklerzusammensetzung nach einem der Ansprüche 1 bis 6, die von Sulfitionen praktisch frei ist.
  8. Verfahren zur Zurückdrängung einer Luftoxidation einer aus einem primären aromatischen Amin bestehenden Farbentwicklerverbindung in einer photographischen Farbentwicklerlösung mit einer alpha-Aminosäure wie in Anspruch 1 oder 2 definiert, als einzigem Entwickler-Präservierungsmittel.
  9. Verfahren zur Entwicklung eines Farbbildes in einem photographischen Element mit einem Träger sowie einer Silberhalogenidemulsion mit einer bildweisen Verteilung von entwickelbaren Silberhalogenidkörnern, das die Stufe des Kontaktierens des Elementes mit einer Farbentwicklerzusammensetzung nach einem der Ansprüche 1 bis 7 umfaßt.
  10. Verfahren zur Schnellentwicklung eines farbphotographischen Silberhalogenidelementes mit einem Träger sowie einer Silberhalogenidemulsion mit einer bildweisen Verteilung von entwickelbaren Silberhalogenidkörnern, das die Stufen umfaßt:
    (a) Kontaktieren des Elementes mit einer Farbentwicklerzusammensetzung nach einem der Ansprüche 1 bis 7;
    (b) Ausbleichen und Fixieren oder Bleich-Fixieren des Elementes; und
    (c) Stabilisieren des Elementes, wobei gegebenenfalls Waschstufen zwischen jeder Verarbeitungsstufe eingeschaltet sind.
  11. Verfahren zur Entwicklung eines photographischen Elementes nach Anspruch 9 oder 10, bei dem die Silberhalogenidschichten des photographischen Elementes Chlorobromid umfassen oder Chloridschichten sind.
  12. Verfahren nach Anspruch 11, bei dem das Element behandelt wird mit einem Unterbrecherbad nach der Entwicklungsstufe und fixiert und nachfolgend gewaschen wird vor der Bleich- oder Bleich-Fixierstufe.
EP19920202662 1991-09-06 1992-09-03 Photographische Farbentwicklerzusammensetzung enthaltend eine Alpha-Aminosäure für verbesserte Stabilität der Lösung Expired - Lifetime EP0530921B1 (de)

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US75597391A 1991-09-06 1991-09-06
US755973 1991-09-06

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EP0530921A1 EP0530921A1 (de) 1993-03-10
EP0530921B1 true EP0530921B1 (de) 1996-06-19

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JP (1) JPH05197108A (de)
DE (1) DE69211630T2 (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5506092A (en) * 1993-12-06 1996-04-09 Konica Corporation Method of processing black and white silver halide photographic compositions with a developer containing an anti sludgant
US5508155A (en) * 1994-12-22 1996-04-16 Eastman Kodak Company Photographic color developers containing odorless antioxidants formed in situ from reaction of hydroxylamine and epoxide and use of same
JPH09211817A (ja) * 1996-01-23 1997-08-15 Eastman Kodak Co 写真処理方法および発色現像液の安定化方法
US6159670A (en) * 1999-11-10 2000-12-12 Eastman Kodak Company Calcium ion stable photographic color developing concentrate and method of manufacture
US6548235B2 (en) 2000-10-19 2003-04-15 Eastman Chemical Company Stabilized solution of an alkali metal or alkaline earth metal salt of p-phenylenediamine color developer and method of making same
EP1203993A1 (de) 2000-11-03 2002-05-08 Eastman Kodak Company Entwicklerzusammensetzung und Verfahren zur Entwicklung von photographischen Farbnegativfilmen
US6383726B1 (en) 2000-11-03 2002-05-07 Eastman Kodak Company Method for formulating a photographic developer composition and process conditions to optimize developed images for digital scanning
US6492099B1 (en) 2001-06-28 2002-12-10 Eastman Chemical Company Method for purifying free-base p-phenylenediamine-type photographic color developers
US6551767B1 (en) 2001-10-13 2003-04-22 Eastman Chemical Company Process for preparing p-phenylenediamine color developers in a concentrated free-base form
US6520694B1 (en) 2002-01-18 2003-02-18 Eastman Kodak Company System and method for processing photographic film images

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4170478A (en) * 1977-06-06 1979-10-09 Eastman Kodak Company Photographic color developer compositions
EP0285010A3 (en) * 1987-03-25 1989-11-08 Fuji Photo Film Co., Ltd. Method for forming a direct positive color image

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JPH05197108A (ja) 1993-08-06
DE69211630T2 (de) 1997-01-23
DE69211630D1 (de) 1996-07-25
EP0530921A1 (de) 1993-03-10

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