Classifications

• • 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.
• the inventive photographic color developing composition can further include an alkanolamine and an N,N-dialkylhydroxylamine as a second 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.
• 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.
• a further ingredient that optionally can be added is an N,N-dialkylhydroxylamine.
• the N,N-dialkylhydroxylamine can be used in the color developing composition in the form of the free amine, but can also be employed in the form of a water-soluble acid salt. Examples of such salts are sulfates, oxalates, chlorides, phosphates, carbonates, acetates, and the like.
• N,N-dialkylhydroxylamine is preferable of the formula III: wherein R3 and R4 represent the same or different alkyl groups of 1 to 4 carbon atoms.
• Exemplary N,N-dialkylhydroxylamines include: N,N-diethylhydroxylamine, N-ethyl-N-methylhydroxylamine, N-ethyl-N-propylhydroxylamine, N,N-dipropylhydroxylamine, N-methyl-N-butylhydroxylamine, and the like.
• a further ingredient which optionally can be included in the color developing composition is an alkanolamine.
• the alkanolamines are primarily useful in providing additional protection against oxidation.
• U.S. Patent 4,170,478 preferred alkanolamines for use in photographic color developing compositions are compounds of the formula IV: wherein R5 is an hydroxyalkyl group of 2 to 6 carbon atoms, and R6 and R7 individually are a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an hydroxyalkyl group of 2 to 6 carbon atoms, a benzyl radical, or a group according to the formula V: wherein n is an integer from 1 to 6, and R8 and R9 individually are a hydrogen atom, an alkyl group of 1 to 6 carbon atoms or an hydroxylalkyl group of 2 to 6 carbon atoms.
• Alkanolamines which are especially preferred are compounds of the formula VI: wherein R10 is an hydroxylalkyl group of 2 to 4 carbon atoms, and R11 and R12 are individually an alkyl group to 1 to 4 carbon atoms or an hydroxyalkyl group of 2 to 4 carbon atoms.
• alkanolamines which can be used in the color developing compositions according to the invention include: ethanolamine, diethanolamine, triethanolamine, di-isopropanolamine, 2-methylaminoethanol, 2-ethylaminoethanol, 2-dimethylaminoethanol, 2-diethylaminoethanol, 1diethylamino-2-propanol, 3-diethylamino-1-propanol, 3-dimethylamino-1-propanol, isopropylaminoethanol, 3-amino-1-propanol, 2-amino-3-methyl-1,3-propanediol, ethylenediamine tetraisopropanol, benzyldiethanolamine, 2-amino-2-(hydroxymethyl)-1,3-propanediol, and the like.
• 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: amino-N,N-dimethylenephosphonic acids of the formula VII: R13-N(CH2PO3X2)2 VII wherein X is a hydrogen atom or a monovalent cation and R13 is an alkyl group, an aryl group, an aralkyl group, an alkaryl group, an alicyclic group or a heterocyclic radical, all of which can be further substituted with substituents such as hydroxyl, halogen, an alkoxy group, a PO3X2 group, a CH2PO3X2 group, or an N(CH2PO3X2)2 group; aminodiphosphonic acids of the formula VIII: in which R14 is an alkyl group, preferably of one to five carbon atoms; and N-acylaminodiphosphonic acids of the formula IX: where R15, R16 and R17 are hydrogen or an alkyl group, preferably alkyl of one to five carbon atoms.
• 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.
• Component Concentration Lithium salt of sulfonated polystrene (30% by weight aqueous solution) 0.25 mL/L Triethanolamine 11.0 g/L KODAK EKTRAPRINT 2 Stain-Reducing agent (a substituted triazinylstilbene) 2.3 g/L Lithium sulfate 2.7 g/L KODAK ANTI-CALCIUM #5(1- hydroxyethylidene-1-diphosphonic acid) 0.8 ml/L Potassium chloride 1.8 g/L Potassium bromide 0.2 g/L 4-(N-ethyl-N-2-methanesulfonylamidoethyl)-2-methylphenylenediamine sesquisulfate monohydrate 4.85 g/L Potassium carbonate 25.0 g/L Water to one liter pH 10.12
• 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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• 1992
  • 1992-09-03 EP EP19920202662 patent/EP0530921B1/de not_active Expired - Lifetime
  • 1992-09-03 DE DE1992611630 patent/DE69211630T2/de not_active Expired - Fee Related
  • 1992-09-04 JP JP23725792A patent/JPH05197108A/ja active Pending

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