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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
  • G03C5/266—Supplying of photographic processing chemicals; Preparation or packaging thereof of solutions or concentrates
• • 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
  • G03C7/4136—Developers p-Phenylenediamine or derivatives thereof

Definitions

• Holter ABSTRACT The stability of acidic solutions of phenylenediamine compounds and sulfite is enhanced by controlling the phenylenediaminezsulfitc ratio.
• This invention relates to photographic developers.
• this invention relates to photographic color developers and compositions and processes used in the production thereof, especially wherein the color developer components are prepackaged in solution form for ready mixing and use by the trade.
• the minimum amount of sulfite useful in the acid solutions to retard aerial oxidation will vary somewhat depending inter alia upon the particular color developing agent in use since the p-phenylenediamines are oxidized at different rates, and upon the oxidizing agent such as air present in the solution.
• 4-amino-N)-ethyl-N-[fimethanesulfonamidoethyl]m toluidine especially useful results are obtained using more than about 0.08 mole of sulfite (e.g., about 10.l g.
• sodium sulfite i.e., the sO -containing moiety or moieties that are produced when various metallic (especially alkali metal) sulfites, bisulfites, sulfurous acid, etc. in combination or separately are added to water or water contion of the color developing agent.
• metallic (especially alkali metal) sulfites, bisulfites, sulfurous acid, etc. in combination or separately are added to water or water contion of the color developing agent.
• the maximum amount of sulfite desirable will also depend in part upon the particular color developing agent in use since the various p-phenylenediamines can be expected to be degraded at difierent rates.
• the amine-containing developing agents are referred to aboveas being free bases.
• Such amines are usually unstable in their free base form so theyare commonly sold as salts.
• 4-amino-N-ethyl-N-lfi-methanesulfonamidoethyll-m'toluidine is advantageously handled as a sesquisulfate monohydrate salt.
• the amino-containing moiety is the group which effects development.
• the mole ratios recited refer to the moles of amine as though the amine were in its free base state. 1
• Similar molar ratios of the other p-phenylenediamine color developing agents also give improved stability. Accordingly, in the acid solutions, from about 0.08 to 1.50 moles of sulfite per mole of p-phenylenediamine developing agent is useful to retard aerial oxidation and degradation of the color-developing agent.
• the weight ratio advantageously employed ranges about-from 0.1 -l.8 grams sodium sulfite: 3 grams of this developing agent.
• sodium sulfite is used as the sulfite source and 4-amino-3-methyl-N-ethyl-N-[B-hydroxyethyl]- aniline sulfate
• the silver halide developing agents especially useful in the acidic sulfite-containing solution are the p-phenylenediamine color developing agents well known in the art especially those forming nondiffusing dyes with phenolic and reactive methylene couplers.
• These developing agents include p-phenylenediamine and N,N-dialkyl-p-phenylenediamines wherein the alkyl groups or the aromatic nucleus may be substituted, for example: N,N-diethyl-p-phenylenediaminc monohydrochloride, 2-amino-S-diethylaminotoluene monohydrochloride, 4-amino-N-ethyl-N-[B-methanesulfoamidoethyll-m-toluidine sesquisulfate monohydrate; 4- amino-3-methyl-N-ethyl-N-[B-hydroxyethyl]-aniline sulfate,
• the solution be acidic to assist in the-stabilization of the developing agent and also to keep the developing agent in solution.
• the pH is preferably less than about 4. However, the optimum pH will vary depending upon the particular developing agent in use, for example, when 4- have a pH less than I particularly to keep the developing agent in solution in a concentrate.
• sulfite and color developing agents can be prepackaged in the same compartment with sulfite and color developing agents, for example, other substances useful in the color development reaction may 'be present such as antifoggants, e.g., benzotriazole, development restrainers, e.g., bromide and auxiliary black and white developing agents such as the 3-pyrazolidone silver halide developing agents, e.g., 4,4-dimethyl-l-phenyl-3- pyrazolidone.
• antifoggants e.g., benzotriazole
• development restrainers e.g., bromide and auxiliary black and white developing agents
• 3-pyrazolidone silver halide developing agents e.g., 4,4-dimethyl-l-phenyl-3- pyrazolidone.
• concentration of the sulfite and developing agent combined can vary widely. Since the developer package is designed for shipment and storage, it is usually desirable to utilize the highest concentration of ingredients which will readily stay in acid
• the stabilization effect obtained by controlling the ingredient ratio as indicated above is generally advantageous in any acidic solution which contains both a p-phenylenediamine and sulfite. Maintaining the ratio is especially significant in photographic silver halide developer packages which are to be utilized with well known color products having differently sensitized silver halide emulsion layers containing nondiffusing coupler compounds.
• a color product is used of the type having superposed on a support, blue, green and red sensitized emulsion layers containing yellow, magenta and cyan dye forming couplers, respectively, the mentioned degradation of the color developing agent in the presence of excess sulfite results, for example, in magenta dye appearing of the yellow color scale.
• THe developer compositions when mixed and ready for use can and desirably do contain the usual amounts of developing agent, sulfite and alkali as disclosed generally in the Jelley et al. US Pat. No. 2,322,027.
• packaged developer components must be separated to the extent that in compartments containing developing agents, the s'ulfite concentration and the pH is controlled as previously indicated.
• Other components which may form part of the mixed developer package for example, additional sulfite, accelerators, complexing agents, buffers, e.g., citric acid-citrate, boric acid-borate, etc. are advantageously contained in the compartment containing the alkali, e.g., potassium hydroxide, although placing selected addenda in other or separate compartments may be desirable depending upon the particular ingredient chosen.
• the packaged developed effectively may be a single package, for example, an outside container or cardboard box in which the developer components are compartmentalized.
• the compartments can be an integral part of the exterior packaging material but advantageously are, at least in part, merely bottles of, for example, glass and/or plastic enclosed in the outside container.
• the choice of sizes and shapes of the bottles which form the compartments can vary with the selected ingredients, concentrations desired, etc. Usually it is desirable to choosethe bottle size, shape, etc. which will result in a total package of minimum size and weight to minimize shipping and storage costs. As a result, it may in some instances be desirable to place a single component type in a plurality of compartments, e.g., to conserve space.
• Example 1-Unstable package A developer kit containing separate bottles respectively containing:
• *4-umino-N-ethyl-N-[B-methanesullbnumidoethylj-m-toluidine sesquisulfate monohydrate is stored at room temperature for about 6 months or at elevated temperatures (e.g., 90-120 F.) for shorter periods of time.
• the solutions are then added to sufficient water (about 70 F.) to make one liter.
• the solution is then utilized as the developer for a photographic color print material having respectively superposed on a paper support, blue, green and red sensitized emulsion layers containing yellow. magenta and cyan dye-forming couplers respectively which has been exposed to a test pattern. After general processing otthe photographic clement using the developer mentioned above. the test pattern shows serious magenta contamination of the areas which should have appeared yellow.
• EXAMPLE 2 A developer kit containing separate bottles respectively containing:
• the developer kit of example 2, Part B can further be modified by replacing sodium hexametaphosphate by other calcium sequestering agents, such as amino polyacetic acids, e.g., diaminopropanol tetraacetic acid, ethylenediamine tetraacetic acid, nitrilo triacetic acid, etc., sodium carbonate added as a buffer. 7
• amino polyacetic acids e.g., diaminopropanol tetraacetic acid, ethylenediamine tetraacetic acid, nitrilo triacetic acid, etc.
• EXAMPLE 3 A developer kit containing separate bottles respectively containing:
• EXAMPLE 5 The procedure according to example 3 is followed except that 4-amino-3-(B-methylsulfonamidoethyl)-N,N- diethylaniline hydrochloride is utilized as the color developing agent. No detectable magenta contamination appears in the yellow areas.
• EXAMPLE 6 A developer kit containing separate bottles respectively containing:
• EXAMPLE 7 The process of example 6 is carried out in the identical manner except using 0.6 g. of sodium sulfite in part D and 1.5 g. in part B. As a result, no detectable magenta contamination appears in the yellow areas.
• EXAMPLE 8 The process of example 6 is carried out in the identical manner except using 0.8 g. of sodium sulfite in part D and 1.3 g. in part B. As a result, slight magenta contamination appears in the yellow areas but marked improvement over that of example 1.
• EXAMPLE 9 The process of example 6 is carried out in the identical manner except using 1.0 g. of sodium sulfite in part D and 1.1 g. in part B. As a result, slight detectable magenta contamination appears in the yellow areas but marked improvement over that ofexample 1.
• EXAMPLE 10 The process of example 6 is carried out in the identical manner except using 1.2 g. of sodium sulfite in part D and 0.9 g. in part B. As a result, slight detectable magenta contamination appears in the yellow areas but marked improvement over that of example 1
• EXAMPLE 11 The process of example 6 is carried out in the identical manner except using 1.4 g. of sodium sulfite in part D and 0.7 g. in part B. As a result, magenta contamination appears in the yellow areas but there is improvement over that of example 1.
• EXAMPLE 12 The process of example 6 is carried out in the identical manner except using 1.6 g. of sodium sulfite in part D and 0.5 g. in part B. As a result, magenta contamination appears in the yellow areas but there is improvement over that of example 1.
• EXAMPLE 13 The process of example 6 is carried out in the identical g. in part B. Magenta contamination appears in the yellow areas but there is improvement over that ofexample 1.
• An acidic aqueous solution of pH less than about 4 comprising at least one phenylenediamine silver halide developing agent and an amount of sulfite sufficient to retard aerial oxidation of said developing agent and insufficient to cause significant degradation of said latter developing agent upon aging of said solution, the mole ratio of said developing agent to sulfite being about 1 to 0.08 -1.5.
• aqueous solution contains at least one N,N-dialkyl-p-phenylenediamine silver halide developing agent.
• N,N-dialkylp-phenylenediamine silver halide developing agent contains el k ls eemie w 4.
• the developing agent is at least one developing agent selected from the group consisting of N,N-diethyl-p-phenylenediamine, 2-amino-5- diethylaminotoluene, 4-amino-N-ethyl-N-[B-methane-sulfonamidoethyl]-m-toluidine, 4-amino-3-methyl-N-ethyl-N-[B- hydroxyethyl]-aniline, 4-amino-3-(p-methylsulfonamidoethyl)-N,N-diethylaniline, or 4-amino-N,N-diethyl- 3-(N'-methyl-/3-methy1sulfonamidoethyl)-ani
• a method for the production of a photographic silver halide developer composition comprising combining (1) an acidic aqueous solution pH less than about 4 comprising p-

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=24715266

Family Applications (1)

Country Status (10)

Cited By (6)

• 0
  • IT IT845033D patent/IT845033A/it unknown
• 1967
  • 1967-10-19 US US676623A patent/US3615572A/en not_active Expired - Lifetime
• 1968
  • 1968-10-01 CH CH1466368A patent/CH489834A/fr not_active IP Right Cessation
  • 1968-10-14 BE BE722299D patent/BE722299A/xx not_active IP Right Cessation
  • 1968-10-16 BR BR203182/68A patent/BR6803182D0/pt unknown
  • 1968-10-16 FR FR1588394D patent/FR1588394A/fr not_active Expired
  • 1968-10-17 NL NL6814905.A patent/NL164137C/xx not_active IP Right Cessation
  • 1968-10-18 GB GB49513/68A patent/GB1244623A/en not_active Expired
  • 1968-10-21 SE SE14183/68A patent/SE357631B/xx unknown
• 1973
  • 1973-04-05 CA CA167,984A patent/CA939551B/xx not_active Expired

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