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
  • G03C5/40—Chemically transforming developed images
  • G03C5/44—Bleaching; Bleach-fixing
• • 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
  • G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials

Definitions

• the present invention relates to a method for processing photographic silver color bleaching materials.
• Processes for processing silver color bleaching materials with the process steps silver development, color and silver bleaching and fixation are known for example from DE-A-25 30 469.
• DE-A-27 16 136 describes a method according to which the duration of the color and silver bleaching can be shortened by adding quaternary ammonium salts to the bleaching bath.
• the color and silver bleaching can also be shortened in the presence of water-soluble phosphines. This is known from DE-A-26 51 969.
• the invention therefore relates to a process for processing exposed silver color bleaching materials with the process measures silver development, color and silver bleaching and fixation, characterized in that a preparation is used for the combined color and silver bleaching which (a) has a strong acid, ( b) a water-soluble iodide, (c) a water-soluble organic nitro compound, (d) an antioxidant, (e) a bleaching catalyst and (f) an organic developer and / or a benzotriazole derivative.
• the preparations for carrying out the color and silver bleaching and the pack units of these preparations in the form of liquid, paste or powdered concentrates are further objects of the present invention.
• the strong acids (a) used in the preparation for color and silver bleaching according to the invention are intended to give the latter a pH of at most 2.
• the water-soluble iodide (b) is preferably sodium or potassium iodide.
• Suitable water-soluble organic nitro compounds (c) are e.g. aromatic nitro compounds, for example nitrobenzenesulfonic acids such as o- or m-nitrobenzenesulfonic acid, 2,4- or 3,5-dinitrobenzenesulfonic acid, 2-chloro-5-nitrobenzenesulfonic acid, 4-methyl-3,5-dinitrobenzenesulfonic acid, 3-chloro-2,5- dinitrobenzenesulfonic acid, 2-amino-4-nitrobenzenesulfonic acid and 2-amino-4-nitro-5-methoxybenzenesulfonic acid.
• aromatic nitro compounds for example nitrobenzenesulfonic acids such as o- or m-nitrobenzenesulfonic acid, 2,4- or 3,5-dinitrobenzenesulfonic acid, 2-chloro-5-nitrobenzenesulfonic acid, 4-methyl-3,5-dinitrobenzenesulfonic acid, 3-chlor
• Reductones or mercapto compounds are the main antioxidants (d).
• Suitable reductones are in particular aci-reductones with a 3-carbonyl-endiol (1,2) grouping such as reductone, triose reductone or preferably ascorbic acid.
• Preferred mercapto compounds are mercaptocarboxylic acids, in particular those of the formula HS- (CH 2 ) m -COOH, in which m is 3 or 4.
• the mercapto compounds can also be added in the corresponding thioketo and / or thiolactone form.
• Suitable bleaching catalysts are, in particular, those from the class of diazines.
• pyrazines or, in particular, quinoxalines can be used.
• Particularly suitable are those quinoxalines, e.g. are substituted by methyl, methoxy, (acylated) hydroxymethyl or (acylated) amino groups.
• quinoxalines of the formula correspond in which R 1 and R 2 independently of one another are hydrogen, alkyl having 1 to 5 carbon atoms, a radical of the formula -CH 2 -X, in which X is hydroxyl, halogen, acyloxy or alkoxy having 1 to 4 carbon atoms, or phenyl and R 3 and R 4 independently of one another are hydrogen, alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 4 carbon atoms, hydroxyl, halogen, amino, acylamino or a sulfonic acid group or together form a radical of the formula -O (CH 2 ) p -O-, where p is 1 or 2.
• Quinoxalines of the formula (1) are particularly suitable, those of the formula or in which R 5 and R 6 independently of one another are alkyl having 1 to 5 carbon atoms, -CH 2 OH, -CH 2 Cl or phenyl and R 7 and R 8 are independently hydrogen, alkyl with 1 to 5 carbon atoms, alkoxy with 1 to 4 Are carbon atoms, hydroxyl or amino and R 9 and R 10 are alkyl having 1 to 5 carbon atoms and R 11 and R 12 are independently hydrogen, alkyl having 1 to 5 carbon atoms or hydroxyl.
• Table 1 shows a number of particularly effective bleaching catalysts.
• Component (f) the use of which in bleaching baths is new and essential to the invention, is suitable in photography for organic development substances, such as hydroquinone and pyrazolidinone derivatives.
• the compounds of the formulas are particularly suitable and wherein Q 1 and Q 2 independently of one another are hydrogen, alkyl or alkoxy each having 1 to 4 carbon atoms, preferably methyl, methoxy, ethyl, ethoxy, propyl, butyl, butoxy or tert.
• Q 3 is phenyl optionally substituted with alkyl or alkoxy each having 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl and methoxy or ethoxy
• Q 4 and Q S are independently of one another
• Q 3 is phenyl and Q 4 and Q 5 are independently hydrogen, methyl or hydroxymethyl.
• Particularly suitable pyrazolidinone derivatives are 1-phenylpyrazolidinone, 1-phenyl-4-methyl-4'-hydroxymethylpyrazolidinone and 1-phenyl-4-methylpyrazolidinone.
• hydroquinone particularly suitable developer substances of the hydroquinone type are 2-chlorohydroquinone, 2-methylhydroquinone, 2-bromohydroquinone, 2,3-dichlorohydroquinone, 2,3-dimethylhydroquinone, 2,5-dimethylhydroquinone, 2,5-diethyrhydroquinone, 2,5-dimethoxyhydroquinone , 2,5-dibromo hydroquinone. 2,6-dimethylhydroquinone, 2-methyl-5-tert-butylhydroquinone and 2-methyl-3-chlorohydroquinone.
• Benztriazole derivatives of the formula can also be used as component (f) are used, wherein Q 6 is hydrogen or alkyl having 1 to 4 carbon atoms, Q, hydrogen, alkyl or alkoxy each having 1 to 4 carbon atoms, -S0 3 H or -SO 2 NH 2 and Q 8 hydrogen, alkyl having 1 to 4 carbon atoms or is halogen.
• Q 6 is preferably hydrogen or methyl
• Q 7 is hydrogen, methyl, methoxy or amidosulfone
• Q 8 is hydrogen, methyl or chlorine.
• Benzotriazole itself is particularly well suited, e.g. 4-methyl and 5-methylbenztriazole, 5,6-dimethylbenztriazole, 5-methyl-6-chlorobenzotriazole and 5-sulfobenzotriazole.
• the benzotriazole derivatives and the organic developer substances mentioned can also be used together as component (f).
• the preparation for the combined color and silver bleaching may contain, in addition to the components (a) to (f) mentioned, a quaternary ammonium salt, component (g).
• a quaternary ammonium salt component (g).
• This preferably corresponds to the formulas or wherein A 1 , A 2 and A 3 are independently alkyl with 1 to 4 carbon atoms, for example methyl, ethyl, propyl or butyl, A 4 (hydroxy) methyl or (hydroxy) ethyl, X ⁇ is a halide, preferably chloride or bromide, and r is 2 to 12.
• the pyridinium compounds of the formula (8) are particularly suitable, in particular hydroxyethylpyridinium chloride.
• the preparation according to the invention can contain a mixture of several bleaching catalysts (e), organic developer substances and / or benzotriazole derivatives (f) and optionally quaternary ammonium compounds (g).
• e bleaching catalysts
• organic developer substances organic developer substances and / or benzotriazole derivatives
• f benzotriazole derivatives
• g optionally quaternary ammonium compounds
• Preparations containing 2,3-dimethyl-, 2,3,6-trimethyl- or 2,3,6-trimethyl-7-hydroxyquinoxaline as component (e), hydroquinone as component (f) and additionally as component are particularly suitable (g) Contain N-hydroxyethyl pyridinium chloride.
• the organic developer substances can also e.g. in the form of so-called precursor compounds such as acylated hydroquinones are added to the silver color bleaching bath.
• precursor compounds such as acylated hydroquinones are added to the silver color bleaching bath.
• precursor compounds are e.g. described in EP 84290.
• the pH value of the color and silver bleach bath should be less than 2, which can easily be achieved with the strong acid (a) mentioned above.
• the temperature of the bleach bath can be 20 to 90 ° C. In general it is advantageous not to go higher than 60 ° C and e.g. to work at 30 to 40 ° C. However, it is a further advantage of the method that it can be used at elevated temperature, e.g. at 50 ° C and above still provides good images with normal color balance. Processing can be further shortened by increasing the temperature, although the baths remain stable long enough even under these conditions.
• the preparations required for processing are used in the form of dilute aqueous solutions.
• the preparations can also be produced in the form of a liquid, paste or powdered concentrate and, because of their good stability, can also be stored in this state for a long time.
• a liquid, in particular aqueous concentrates one containing components (a) and (c) and the other the other components (b), (d), (e) and (f) and optionally (g).
• an additional solvent such as ethyl or propyl alcohol, ethylene glycol monomethyl or ethyl ether can be added to improve the solubility, in particular component (d).
• the diluted preparations suitable for processing are obtained by combining and diluting these liquid, paste-like or powdery concentrates, which are the packaging units of the preparations according to the invention, with water and, if appropriate, the organic solvents mentioned.
• Baths of conventional composition can be used for silver development, e.g. those which contain hydroquinone as developer substance and optionally additionally 1-phenyl-3-pyrazolidone. If the silver development is carried out in the presence of compounds which are known as optical brighteners, an acceleration of the color and silver bleaching can also be achieved indirectly.
• Such connections are e.g. Heteroaromatics such as triazines or pyrazoles which are linked to aromatic systems, naphthalic imides, diarylpyrazolines, derivatives of coumarin and carbostyril, stilbenes substituted by heterocycles or heteroaromatics and aromatic systems and in particular 4,4'-diaminostilbene-2,2'-disulfonic acids substituted by cyanuric acid derivatives .
• the fixing bath can be composed in a known and customary manner.
• a fixative e.g. Sodium thiosulfate or preferably ammonium thiosulfate, optionally with additions of sodium bisulfite and / or sodium metabisulfite.
• All baths can also contain additives such as hardening agents, wetting agents, optical brighteners and UV protection agents. Washings are preferably carried out between the processing steps.
• the method according to the invention can e.g. in the production of positive color images in copying or recording machines or in the rapid processing of other silver color bleaching materials, e.g. for scientific records, e.g. colored screen photography, and industrial purposes.
• the residence time of the silver color bleaching material in the developer, bleaching and fixing bath is usually the same, the times for the development and fixing step having to be based on the time for the bleaching step (as the longest process).
• the time required for development and fixation can be reduced relatively easily. With the reduction in time for color and silver bleaching that can now be achieved according to the invention, the total processing time from development to fixation can be significantly reduced. Due to the technically prescribed identical treatment times in the individual treatment stages, the time saved for the overall process can be seen as three times the value achieved in the bleaching time. This is essential for machine processing.
• Transparent, metallic-reflective, or preferably white-opaque material can be used as the silver color bleaching material.
• the carrier can consist, for example, of pigmented cellulose triacetate or polyester. If it is made of paper felt, it must be coated on both sides or coated with polyethylene.
• the photosensitive layers are located on at least one side of this support, preferably in the known arrangement, i.e. at the bottom a red sensitized silver halide emulsion layer containing a blue-green azo dye, above a green sensitized silver halide emulsion layer containing a purple azo dye and at the top a blue sensitive silver halide emulsion layer containing a yellow azo dye.
• the material can also contain sub-layers, intermediate layers, filter layers and protective layers.
• the silver color bleaching materials to be processed according to the invention can also have partially spatially separated arrangements of silver halide and dye, as is the case e.g. in EP-A-39313.
• a silver color bleaching material which has a layer of a red-sensitive silver bromide gelatin emulsion with a cyan dye of the formula on a pigmented cellulose triacetate support an intermediate gelatin layer, a layer of a green-sensitive silver bromide gelatin emulsion with a magenta dye of the formula an intermediate gelatin layer and a layer of a blue-sensitive silver bromide gelatin emulsion with a yellow dye of the formula contains.
• the reflectance density of the incorporated image dyes is 2.0, the image dye layers contain 0.8 g / m 2 of silver, and the total thickness of the photographic material produced is 15 ⁇ m.
• This material is exposed and processed in the immersion process. It goes through the processing stages of development (30 seconds), washing (10 seconds), bleaching (see Table 2 below), washing (10 seconds), fixing (30 seconds) and final washing (60 seconds), with the temperature of the corresponding processing baths Is 35 ° C.
• the bleaching times listed in Table 2 below are those times which are necessary in order to be exposed, i.e. white areas of the image to bleach the material to a reflectance density of at most 0.03 (via veil).
• the bleaching baths No. 3 to 8 according to the invention in Table 2 and the comparative bleaching baths No. 1 and 2 contain 50 g of conc. Per liter of aqueous solution. Sulfuric acid, 2 g, 4-mercaptobutyric acid, 10 g potassium iodide, 7 g m-nitrobenzenesulfonic acid (sodium salt), 2 g bleach catalyst and the additives listed in the table. The bleaching acceleration achieved by these additives is surprising and also exceeds the bleaching acceleration achieved with quaternary ammonium salts described in DE-A-27 16 136.
• a silver color bleaching material is prepared which contains a non-sensitive silver bromide iodide emulsion layer on a white opaque cellulose triacetate support, a red sensitive silver bromide iodide emulsion layer which contains a cyan dye of the formula (100), an intermediate gelatin layer, a green sensitive silver bromide iodide emulsion, which contains a layer of magenta green-sensitive silver bromide iodide emulsion layer, a yellow filter layer (40 mg / m 2 yellow silver hydrosol), a blue-sensitive iodide-free silver bromide emulsion layer containing a 6-yeast dye of the formula (102), a blue-sensitive iodide-free silver bromide emulsion layer, and a gelatin protective layer.
• a gelatin layer is cast on the back of the carrier.
• the iodide-containing emulsion layers contain silver halide crystals with 2.6 mol% silver iodide and 97.4 mol-X silver bromide.
• the image dyes are used in such a concentration that their reflectance density is 2.0; the total silver content of the 22 ⁇ m thick layers is 2.0 g / m 2 .
• This material is exposed and processed in the immersion process. It goes through the processing stages of development (2 minutes), washing (2 minutes), bleaching (see table 3 below), washing (2 minutes), "fixation (5 minutes) and final washing (5 minutes), the temperature being the corresponding Processing baths is 24 ° C.
• the bleaching times listed in Table 3 below are those times which are necessary in order to be exposed, i.e. white areas of the image to bleach the material to a reflectance density of at most 0.03 (via veil).
• the aqueous developer bath contains per liter:
• aqueous bleaching baths 1 to 5 in Table 3 contain per liter: and the additives listed in Table 3.
• Example 3 This example shows the reduction in the total processing time of exposed silver color bleaching materials, which is composed of the time saving achieved according to the invention in the combined color and silver bleaching and the time saving achieved by known measures during development and fixation.
• Exposed silver color bleaching materials are usually processed e.g. in a developer bath according to Example 1, a bleaching bath according to Table 2, No. 1, and a fixing bath according to Example 1 at a processing temperature of 35 ° C.
• the total processing time for this process is 4 minutes 20 seconds (1 minute each in the developer, bleaching and fixing bath, 1 minute for final washing and 20 seconds for intermediate washing).
• a developer which contains 15 g of hydroquinone, 2 g of 1-phenylpyrazolidone, 40 g of sodium sulfite (anhydrous), 25 g of potassium carbonate, 10 g of potassium hydrogen carbonate, 2 g of potassium bromide, 0.1 g of benzotriazole and 3 g of sodium ethylenediaminetetraacetate per liter of aqueous solution contains, a bleaching bath according to Table 2, Nos.
• a fixing bath which contains 250 g ammonium thiosulfate, 50 g potassium metabisulfite and 19 g potassium hydroxide per liter of aqueous solution, and rinses 10 seconds after the bleaching process and finishes with a final rinse 1 minute through, this results in a total processing time of only 2 minutes 40 seconds at a bath temperature of 35 ° C, since development, bleaching and fixation each require only 30 seconds. This means a time saving of 1 minute 40 seconds compared to conventional processing.
• Such processing is particularly important for the production of photographic images in photo booths.

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• 1983
  • 1983-07-20 CH CH3990/83A patent/CH657710A5/de not_active IP Right Cessation
• 1984
  • 1984-07-16 DE DE8484810351T patent/DE3465638D1/de not_active Expired
  • 1984-07-16 EP EP84810351A patent/EP0133163B1/fr not_active Expired
  • 1984-07-18 US US06/632,087 patent/US4546069A/en not_active Expired - Fee Related
  • 1984-07-20 JP JP59149825A patent/JPS6042757A/ja active Pending

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