EP0133163A2 - Method of processing photographic silver dye-bleaching materials - Google Patents
Method of processing photographic silver dye-bleaching materials Download PDFInfo
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- EP0133163A2 EP0133163A2 EP84810351A EP84810351A EP0133163A2 EP 0133163 A2 EP0133163 A2 EP 0133163A2 EP 84810351 A EP84810351 A EP 84810351A EP 84810351 A EP84810351 A EP 84810351A EP 0133163 A2 EP0133163 A2 EP 0133163A2
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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
- 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
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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
- G03C7/28—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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Abstract
Verkürzung der Verarbeitungszeit belichteter photographischer Silberfarbbleichmaterialien durch Verwendung einer Bleichzubereitung, die eine starke Säure, ein wasserlösliches Jodid, eine wasserlösliche organische Nitroverbindung, ein Oxidationsschutzmittel, einen Bleichkatalysator, eine organische Entwicklersubstanz und/oder ein Benztriazolderivat enthält.Shortening the processing time of exposed silver color photographic bleaching materials by using a bleaching preparation containing a strong acid, a water-soluble iodide, a water-soluble organic nitro compound, an antioxidant, a bleaching catalyst, an organic developer and / or a benzotriazole derivative.
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Verarbeitung photographischer Silberfarbbleichmaterialien.The present invention relates to a method for processing photographic silver color bleaching materials.
Verfahren zur Verarbeitung von Silberfarbbleichmaterialien mit den Verfahrensstufen Silberentwicklung, Farb- und Silberbleichung und Fixierung sind beispielsweise aus DE-A-25 30 469 bekannt. Ferner beschreibt DE-A-27 16 136 ein Verfahren, gemäss dem die Dauer der Farb- und Silberbleichung durch Zugabe quaternärer Ammoniumsalze zum Bleichbad verkürzt werden kann. Auch in Gegenwart von wasserlöslichen Phosphinen kann die Farb- und Silberbleichung verkürzt werden. Dies ist aus DE-A-26 51 969 bekannt.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. Furthermore, 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.
Diese Verfahren eignen sich bereits für die Verarbeitung von Silberfarbbleichmaterialien. Es hat sich jedoch gezeigt, dass eine weitere Verkürzung der Verarbeitungszeit, insbesondere der kombinier- ten Farb- und Silberbleichung, beispielsweise in Kopier- und Aufnahmeautomaten, wünschenswert ist.These processes are already suitable for processing silver color bleaching materials. It has, however, shown that a further shortening the processing time, particularly combinable - th dye and silver bleaching, for example in photocopying and recording machines, is desirable.
Aufgabe der vorliegenden Erfindung ist es daher, ein Verfahren zur Verarbeitung von belichteten Silberfarbbleichmaterialien bereitzustellen, welches die Herstellung photographischer Bilder innerhalb kürzerer Zeit ermöglicht.It is therefore an object of the present invention to provide a process for processing exposed silver color bleaching materials which enables photographic images to be produced in a shorter time.
Ueberraschenderweise wurde nun gefunden, dass die Anwesenheit gewisser organischer Entwicklersubstanzen in Bleichbädern zu einer Erhöhung der Farb- und Silberbleichung führen kann. Dies steht im Gegensatz zu dem sonst in der Photographie üblichen Grundsatz, Bleichbäder von Entwicklersubstanzen frei zu halten.Surprisingly, it has now been found that the presence of certain organic developer substances in bleaching baths can lead to an increase in color and silver bleaching. This is in Contrary to the principle usually used in photography to keep bleach baths free of developer substances.
Ein Gegenstand der Erfindung ist daher ein Verfahren zur Verarbeitung von belichteten Silberfarbbleichmaterialien mit den Verfahrensmassnahmen Silberentwicklung, Farb- und Silberbleichung und Fixierung, dadurch gekennzeichnet, dass man für die kombinierte Farb-und Silberbleichung eine Zubereitung verwendet, die (a) eine starke Säure, (b) ein wasserlösliches Jodid, (c) eine wasserlösliche organische Nitroverbindung, (d) ein Oxidationsschutzmittel, (e) einen Bleichkatalysator und (f) eine organische Entwicklersubstanz und/oder ein Benztriazolderivat enthält.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.
Die Zubereitungen zur Durchführung der Farb- und Silberbleichung sowie die Packungseinheiten dieser Zubereitungen in Form von flüssigen, pasten- oder pulverförmigen Konzentraten sind weitere Gegenstände der vorliegenden Erfindung.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.
Die in der erfindungsgemässen Zubereitung für die Farb- und Silberbleichung verwendeten starken Säuren (a) sollen dieser einen pH-Wert von höchstens 2 verleihen. Vorzugsweise kommen Schwefelsäure oder Sulfaminsäure, ferner aber auch andere starke Säuren wie z.B. Phosphorsäure, in Frage.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. Preferably come sulfuric acid or sulfamic acid, but also other strong acids such as e.g. Phosphoric acid, in question.
Das wasserlösliche Jodid (b) ist vorzugsweise Natrium- oder Kaliumjodid.The water-soluble iodide (b) is preferably sodium or potassium iodide.
Geeignete wasserlösliche organische Nitroverbindungen (c) sind z.B. aromatische Nitroverbindungen, beispielsweise Nitrobenzolsulfonsäuren wie o- oder m-Nitrobenzolsulfonsäure, 2,4- oder 3,5-Dinitrobenzolsulfonsäure, 2-Chlor-5-Nitrobenzolsulfonsäure, 4-Methyl-3,5-dinitrobenzolsulfonsäure, 3-Chlor-2,5-dinitrobenzolsulfonsäure, 2-Amino-4-nitrobenzolsulfonsäure und 2-Amino-4-nitro-5-methoxybenzolsulfonsäure.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.
Als Oxidationsschutzmittel (d) kommen hauptsächlich Reduktone oder Mercaptoverbindungen in Frage. Geeignete Reduktone sind insbesondere Aci-Reduktone mit einer 3-Carbonyl-endiol(1,2)-Gruppierung wie Redukton, Trioseredukton oder vorzugsweise Ascorbinsäure. Bevorzugte Mercaptoverbindungen sind Mercaptocarbonsäuren, insbesondere solche der Formel HS-(CH2)m-COOH, worin m 3 oder 4 ist. Die Mercaptoverbindungen können auch in der entsprechenden Thioketo- und/oder Thiolactonform zugegeben werden.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.
Als Bleichkatalysatoren (e) kommen insbesondere solche aus der Verbindungsklasse der Diazine in Frage. Beispielsweise können Pyrazine oder insbesondere Chinoxaline verwendet werden. Geeignet sind vor allem solche Chinoxaline, die z.B. durch Methyl-, Methoxy-, (acylierte) Hydroxymethyl- oder (acylierte) Aminogruppen substituiert sind.Suitable bleaching catalysts (e) are, in particular, those from the class of diazines. For example, 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.
Vorzugsweise verwendet man also Chinoxaline, die der Formel
Besonders geeignet sind solche Chinoxaline der Formel (1), die der Formel
Die folgende Tabelle 1 gibt eine Anzahl besonders wirksamer Bleichkatalysatoren wieder.
Besonders gut geeignete Pyrazolidinonderivate sind 1-Phenylpyrazolidinon, 1-Phenyl-4-methyl-4'-hydroxymethylpyrazolidinon und 1-Phenyl-4-methylpyrazolidinon.Particularly suitable pyrazolidinone derivatives are 1-phenylpyrazolidinone, 1-phenyl-4-methyl-4'-hydroxymethylpyrazolidinone and 1-phenyl-4-methylpyrazolidinone.
Besonders gut geeignete Entwicklersubstanzen vom Hydrochinontyp sind neben Hydrochinon 2-Chlorhydrochinon, 2-Methylhydrochinon, 2-Bromhydrochinon, 2,3-Dichlorhydrochinon, 2,3-Dimethylhydrochinon, 2,5-Dimethylhydrochinon, 2,5-Diäthyrhydrochinon, 2,5-Dimethoxyhydrochinon, 2,5-Dibromhydrochinon. 2,6-Dimethylhydrochinon, 2-Methyl-5-tert.butylhydrochinon und 2-Methyl-3-chlorhydrochinon.In addition to 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.
Als Komponente (f) können auch Benztriazolderivate der Formel
Vorzugsweise ist in den Verbindungen der Formel (6) Q6 Wasserstoff oder Methyl, Q7 Wasserstoff, Methyl, Methoxy oder Amidosulfon und Q8 Wasserstoff, Methyl oder Chlor.In the compounds of the formula (6), Q 6 is preferably hydrogen or methyl, Q 7 is hydrogen, methyl, methoxy or amidosulfone and Q 8 is hydrogen, methyl or chlorine.
Benztriazol selbst ist besonders gut geeignet wie auch z.B. 4-Methyl-und 5-Methylbenztriazol, 5,6-Dimethylbenztriazol, 5-Methyl-6-Chlor- benztriazol und 5-Sulfobenztriazol.Benzotriazole itself is particularly well suited, e.g. 4-methyl and 5-methylbenztriazole, 5,6-dimethylbenztriazole, 5-methyl-6-chlorobenzotriazole and 5-sulfobenzotriazole.
Die Benztriazolderivate und die genannten organischen Entwicklersubstanzen können auch zusammen als Komponente (f) eingesetzt werden.The benzotriazole derivatives and the organic developer substances mentioned can also be used together as component (f).
Die Zubereitung für die kombinierte Farb- und Silberbleichung kann zusätzlich zu den genannten Komponenten (a) bis (f) ein quaternäres Ammoniumsalz, Komponente (g), enthalten. Vorzugsweise entspricht dieses den Formeln
Die erfindungsgemässe Zubereitung kann ein Gemisch mehrerer Bleichkatalysatoren (e), organischer Entwicklersubstanzen und/oder Benztriazolderivate (f) und gegebenenfalls quaternärer Ammoniumverbindungen (g) enthalten. Besonders geeignet sind solche Zubereitungen, die als Komponente (e) 2,3-Dimethyl-, 2,3,6-Trimethyl- oder 2,3,6-Trimethyl-7-hydroxychinoxalin, als Komponente (f) Hydrochinon und zusätzlich als Komponente (g) N-Hydroxyäthylpyridiniumchlorid enthalten.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). 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.
Die organischen Entwicklersubstanzen können auch z.B. in Form von sogenannten Vorläuferverbindungen wie acylierten Hydrochinonen dem Silberfarbbleichbad zugefügt werden. Solche Vorläuferverbindungen sind z.B. in EP 84290 beschrieben.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. Such precursor compounds are e.g. described in EP 84290.
Die Mengenverhältnisse der im Bleichbad vorhandenen Komponenten (a),
- (b), (c), (d), (e), (f) und gegegenenfalls (g) können in ziemlich weiten Grenzen schwanken. Vorteilhaft ist es, wenn die Bleichbäder zur Durchführung des erfindungsgemässen Verfahrens (a) soviel einer starken Säure, um den pH-Wert der Zubereitung unter 2 zu halten,
- (b) 2 bis 50 g/1 eines wasserlöslichen Jodids, (c) gegebenenfalls 1 bis 30 g/1 einer wasserlöslichen organischen Nitroverbindung, (d) 0,5 bis 10 g/1 eines Oxydationsschutzmittels, und (e) 0,2 bis 5 g/l eines Bleichkatalysators, (f) 0,1 bis 10 g/1 einer organischen Entwicklersubstanz und/oder eines Benztriazolderivates und gegebenenfalls (g) 0,1 bis 5 g/1 eines quaternären Ammoniumsalzes, enthalten.
- (b), (c), (d), (e), (f) and optionally (g) can vary within fairly wide limits. It is advantageous if the bleaching baths for carrying out process (a) according to the invention have sufficient acid to keep the pH of the preparation below 2,
- (b) 2 to 50 g / 1 of a water-soluble iodide, (c) optionally 1 to 30 g / 1 of a water-soluble organic nitro compound, (d) 0.5 to 10 g / 1 of an antioxidant, and (e) 0.2 to 5 g / l a bleaching catalyst, (f) 0.1 to 10 g / 1 of an organic developer and / or a benzotriazole derivative and optionally (g) 0.1 to 5 g / 1 of a quaternary ammonium salt.
Der pH-Wert des Farb- und Silberbleichbades soll kleiner als 2 sein, was durch die bereits erwähnte starke Säure (a) ohne weiteres zu erreichen ist. Die Temperatur des Bleichbades, wie auch der anderen Behandlungsbäder, kann 20 bis 90° C betragen. Im allgemeinen ist es vorteilhaft, nicht höher als 60° C zu gehen, und z.B. bei 30 bis 40° C zu arbeiten. Es ist aber ein weiterer Vorteil des Verfahrens, dass es bei erhöhter Temperatur, z.B. bei 50° C und darüber noch gute Bilder mit normalem Farbgleichgewicht liefert. Durch die Temperaturerhöhung lässt sich die Verarbeitung weiter verkürzen, wobei auch unter diesen Bedingungen die Bäder immer noch lange genug stabil bleiben.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, like the other treatment baths, 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.
Im allgemeinen werden die für die Verarbeitung benötigten Zubereitungen in Form von verdünnten wässrigen Lösungen verwendet. Die Zubereitungen können aber auch in Form eines flüssigen, pasten- oder pulverförmigen Konzentrates hergestellt und wegen ihrer guten Stabilität auch längere Zeit in diesem Zustand gelagert werden. Vorzugsweise verwendet man z.B. zwei flüssige, insbesondere wässrige Konzentrate, wobei eines die Komponenten (a) und (c) und das andere die übrigen Komponenten (b), (d), (e) und (f) sowie gegebenenfalls (g) enthält. Im letzteren Konzentrat kann zur Verbesserung der Löslichkeit, insbesondere der Komponente (d), ein zusätzliches Lösungsmittel wie Aethyl- oder Propylalkohol, Aethylenglykolmonomethyl- oder -äthyläther zugesetzt werden.In general, the preparations required for processing are used in the form of dilute aqueous solutions. However, 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. Preferably, e.g. two 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). In the latter concentrate, 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).
Durch Zusammengeben und Verdünnen dieser flüssigen, pasten- oder pulverförmigen Konzentrate, welche die Packungseinheiten der erfindungsgemässen Zubereitungen darstellen, mit Wasser und gegebenenfalls den genannten organischen Lösungsmitteln erhält man die für die Verarbeitung geeigneten verdünnten Zubereitungen.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.
Zur Silberentwicklung können Bäder üblicher Zusammensetzung verwendet werden, z.B. solche, die als Entwicklersubstanz Hydrochinon und gegebenenfalls zusätzlich noch 1-Phenyl-3-pyrazolidon enthalten. Führt man die Silberentwicklung in Gegenwart von Verbindungen, die als optische Aufheller bekannt sind, durch, so kann indirekt auch eine Beschleunigung der Farb- und Silberbleichung erreicht werden. Solche Verbindungen sind z.B. Heteroaromaten wie Triazine oder Pyrazole, die mit aromatischen Systemen verknüpft sind, Naphthalsäureimide, Diarylpyrazoline, Derivate des Cumarins und Carbostyrils, durch Heterocyclen oder Heteroaromaten und aromatische Systeme substituierte Stilbene und insbesondere durch Cyanursäurederivate substituierte 4,4'-Diaminostilben-2,2'-disulfonsäuren.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 .
Das Fixierbad kann in bekannter und üblicher Weise zusammengesetzt sein. Als Fixiermittel ist z.B. Natriumthiosulfat oder vorzugsweise Ammoniumthiosulfat, gegebenenfalls mit Zusätzen von Natriumbisulfit und/oder Natriummetabisulfit geeignet.The fixing bath can be composed in a known and customary manner. As a fixative e.g. Sodium thiosulfate or preferably ammonium thiosulfate, optionally with additions of sodium bisulfite and / or sodium metabisulfite.
Alle Bäder können noch Zusätze wie Härtungsmittel, Netzmittel, optische Aufheller und UV-Schutzmittel enthalten. Zwischen den Verarbeitungsschritten werden vorzugsweise Wässerungen vorgenommen.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.
Die Wiederholung einzelner Behandlungen (jeweils in einem weiteren Tank mit einem Bad gleicher Zusammensetzung wie das vorangehende) ist möglich, wodurch in manchen Fällen eine bessere Badausnützung erreicht werden kann.The repetition of individual treatments (in each case in a further tank with a bath of the same composition as the previous one) is possible, whereby in some cases better use of the bath can be achieved.
Auch hier ist es vorteilhaft, zwischen Bädern verschiedener Wirkung Wasserbäder einzusetzen.It is also advantageous to use water baths between baths with different effects.
Die Vorteile des erfindungsgemässen Verfahrens liegen darin, dass sowohl die Silber- als auch die Farbbleichung beschleunigt werden, wobei das Verhältnis der Geschwindigkeiten der beiden Reaktionen erhalten bleibt.The advantages of the method according to the invention are that both the silver and the color bleaching are accelerated, the ratio of the rates of the two reactions being retained.
Das erfindungsgemässe Verfahren kann z.B. bei der Herstellung positiver Farbbilder in Kopier- oder Aufnahmeautomaten oder bei der Schnellverarbeitung anderer Silberfarbbleichmaterialien, wie z.B. für wissenschaftliche Aufzeichnungen, z.B. farbige Schirmbildphotographie, und Industriezwecke, verwendet werden.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.
Bei der Automatenverarbeitung belichteter Silberfarbbleichmaterialien ist die Verweilzeit des Silberfarbbleichmaterials im Entwickler-, Bleich-und Fixierbad üblicherweise gleich gross, wobei sich die Zeiten für den Entwicklungs- und Fixierschritt nach der Zeit für den Bleichschritt (als dem längsten Vorgang) zu richten haben. Der Zeitaufwand für die Entwicklung und Fixierung kann relativ problemlos verkürzt werden. Mit der nun erfindungsgemäss erzielbaren Reduktion der Zeit für die Farb- und Silberbleichung kann die Gesamtverarbeitungszeit von der Entwicklung bis zur Fixierung deutlich herabgesetzt werden. Aufgrund der technisch vorgegebenen gleichen Behandlungszeiten in den einzelnen Behandlungsstufen kann man die Zeitersparnis für den Gesamtprozess als dreifachen Wert der bei der Bleichzeit erzielten Reduktion ansehen. Dies ist für die Automatenverarbeitung von wesentlicher Bedeutung.In automated processing of exposed silver color bleaching materials, 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.
Als Silberfarbbleichmaterial kann transparentes, metallisch-refelktierendes, oder vorzugsweise weiss-opakes Material verwendet werden.Transparent, metallic-reflective, or preferably white-opaque material can be used as the silver color bleaching material.
Der Träger kann beispielsweise aus gegebenenfalls pigmentiertem Cellulosetriacetat oder Polyester bestehen. Wenn er aus Papierfilz besteht, muss dieser beidseitig lackiert oder mit Polyäthylen beschichtet sein. Auf mindestens einer Seite dieses Trägers befinden sich die lichtempfindlichen Schichten, vorzugsweise in der bekannten Anordnung, d.h. zu unterst eine rot sensibilisierte Silberhalogenidemulsionsschicht, die einen blaugrünen Azofarbstoff enthält, darüber eine grün sensbilisierte Silberhalogenidemulsionsschicht, die einen purpurnen Azofarbstoff enthält und zu oberst eine blauempfindliche Silberhalogenidemulsionsschicht, die einen gelben Azofarbstoff enthält. Das Material kann auch Unterschichten, Zwischenschichten, Filterschichten und Schutzschichten enthalten.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.
Die erfindungsgemäss zu verarbeitenden Silberfarbbleichmaterialien können auch teilweise räumlich getrennte Anordnungen von Silberhalogenid und Farbstoff aufweisen, wie dies z.B. in EP-A-39313 beschrieben ist.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.
Die nachfolgenden Beispiele erläutern die Erfindung, ohne sie darauf zu beschränken.The following examples illustrate the invention without restricting it.
Beispiel 1: Man stellt ein Silberfarbbleichmaterial her, das auf einem pigmentierten Cellulosetriacetatträger eine Schicht aus einer rotempfindlichen Silberbromidgelatineemulsion mit einem Cyanfarbstoff der Formel
Die Remissionsdichte der eingearbeiteten Bildfarbstoffe beträgt 2,0, die Bildfarbstoffschichten enthalten 0,8 g/m2 Silber, und die Gesamtdicke des hergestellten photographischen Materials beträgt 15 µm.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 μm.
Dieses Material wird belichtet und im Tauchverfahren verarbeitet. Es durchläuft dabei die Verarbeitungsstufen Entwicklung (30 Sekunden), Wässerung (10 Sekunden), Bleichung (vgl. nachfolgende Tabelle 2), Wässerung (10 Sekunden), Fixierung (30 Sekunden) und Schlusswässerung (60 Sekunden), wobei die Temperatur der entsprechenden Verarbeitungsbäder 35°C beträgt.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.
Die in der nachfolgenden Tabelle 2 aufgeführten Bleichzeiten sind jene Zeiten, die notwendig sind, um an belichteten, d.h. weissen Bildstellen, das Material bis zu einer Remissionsdichte von höchstens 0,03 (über Schleier) auszubleichen.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).
Das wässrige Entwicklerbad enthält pro Liter 10 g Hydrochinon, 2 g 1-Phenylpyrazolidinon, 40 g Natriumsulfit (wasserfrei), 25 g Kaliumcarbonat, 10 g Kaliumhydrogencarbonat, 2,5 g Kaliumbromid und 0,6 g Benztriazol. Das Fixierbad enthält pro Liter wässriger Lösung:
- 220 g Ammoniumthiosulfat, 10 g Natriummetabisulfit und 40 g Natriumsulfit.
- 220 g ammonium thiosulfate, 10 g sodium metabisulfite and 40 g sodium sulfite.
Die erfindungsgemässen Bleichbäder Nr. 3 bis 8 in Tabelle 2 sowie die Vergleichsbleichbäder Nr. 1 und 2 enthalten pro Liter wässriger Lösung 50 g konz. Schwefelsäure, 2 g,4-Mercaptobuttersäure, 10 g Kaliumjodid, 7 g m-Nitrobenzolsulfonsäure (Natriumsalz), 2 g Bleichkatalysator sowie die in der Tabelle angegebenen Zusätze.
Aehnliche Effekte werden z.B. auch mit anderen Bleichkatalysatoren gemäss Formel I und Zusätzen der Formeln (4) bis (9) erhalten.Similar effects are e.g. also obtained with other bleaching catalysts according to formula I and additions of formulas (4) to (9).
Beispiel 2: Es wird ein Silberfarbbleichmaterial hergestellt, das auf einem weissopaken Cellulosetriacetatträger einerotempfindliche Silberbromidjodidemulsions schicht, eine rotempfindliche Silberbromidjodidemulsionsschicht,die einen Cyanfarbstoff der Formel (100) enthält, eine Gelatinezwischenschicht, eine grünempfindliche Silberbromidjodidemulsionsschicht, die einen Magentafarbstoff der Formel (100) enthält, eine grünempflindliche Silberbromidjodidemulsionsschicht, eine Gelbfilterschicht (40 mg/m2 gelbes Silberhydrosol), eine blauempfindliche jodidfreie Silberbromidemulsionsschicht, die einen 6elbfarbstoff der Formel (102) enthält, eine blauempfindliche jodidfreie Silberbromidemulsionsschicht, und eine Gelatineschutzschicht enthält. Auf die Trägerrückseite ist eine Gelatineschicht gegossen.Example 2: 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.
Die jodidhaltigen Emulsionsschichten enthalten Silberhalogenidkristalle mit 2,6 Mol-% Silberjodid und 97,4 Mol-X Silberbromid. Die Bildfarbstoffe werden in einer solchen Konzentration verwendet, dass ihre Remissionsdichte je 2,0 beträgt; der Gesamt-Silbergehalt der 22 µm dicken Schichten beträgt 2,0 g/m2.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 µm thick layers is 2.0 g / m 2 .
Dieses Material wird belichtet und im Tauchverfahren verarbeitet. Es durchläuft dabei die Verarbeitungsstufen Entwicklung (2 Minuten), Wässerung (2 Minuten), Bleichung (vgl. nachfolgende Tabelle 3), Wässerung (2 Minuten),"Fixierung (5 Minuten) und Schlusswässerung (5 Minuten), wobei die Temperatur der entsprechenden Verarbeitungsbäder 24°C beträgt.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.
Die in der nachfolgenden Tabelle 3 aufgeführten Bleichzeiten sind jene Zeiten, die notwendig sind, um an belichteten, d.h. weissen Bildstellen, das Material bis zu einer Remissionsdichte von höchstens 0,03 (über Schleier) auszubleichen.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).
Das wässrige Entwicklerbad enthält pro Liter :
Die wässrigen Bleichbäder 1 bis 5 in Tabelle 3 enthalten pro Liter:
Die Ergebnisse in Tabelle 3 zeigen, dass die erfindungsgemässen Zusätze zum Bleichbad eine deutliche Verkürzung der Bleichzeit bewirken.The results in Table 3 show that the additives to the bleaching bath according to the invention bring about a significant reduction in the bleaching time.
Aehnliche Ergebnisse werden auch mit anderen Katalysatoren der Formel (1) und Zusätzen der Formeln (4) bis (9) erhalten.Similar results are also obtained with other catalysts of the formula (1) and additions of the formulas (4) to (9).
Beispiel 3: Dieses Beispiel zeigt die Verkürzung der Gesamtverarbeitungszeit belichteter Silberfarbbleichmaterialien, die sich aus der erfindungsgemäss erreichten Zeitersparnis bei der kombinierten Farb- und Silberbleichung sowie der durch bekannte Massnahmen erreichbaren Zeitersparnis bei der Entwicklung und Fixierung zusammensetzt.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.
Die Verarbeitung belichteter Silberfarbbleichmaterialien erfolgt üblicherweise z.B. in einem Entwicklerbad gemäss Beispiel 1, einem Bleichbad gemäss Tabelle 2, Nr. 1, und einem Fixierbad gemäss Beispiel 1 bei einer Verarbeitungstemperatur von 35°C. Die Gesamtdauer der Verarbeitung beträgt bei diesem Verfahren 4 Minuten 20 Sekunden(je 1 Minute in Entwickler-, Bleich- und Fixierbad, 1 Minute für Schlusswässerung und 20 Sekunden für Zwischenwässerung).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).
Verwendet man nun jedoch einen Entwickler, der pro Liter wässriger Lösung 15 g Hydrochinon, 2 g 1-Phenylpyrazolidon, 40 g Natriumsulfit (wasserfrei ), 25 g Kaliumcarbonat, 10 g Kaliumhydrogencarbonat, 2 g Kaliumbromid, 0,1 g Benztriazol und 3 g Natriumäthylendiamintetraacetat enthält, ein Bleichbad gemäss Tabelle 2, Nr. 5 bis 8, und ein Fixierbad, das 250 g Ammoniumthiosulfat, 50 g Kaliummetabisulfit und 19 g Kaliumhydroxid pro Liter wässriger Lösung enthält, und führt eine Zwischenwässerung von 10 Sekunden nach dem Bleichvorgang und eine Schlusswässerung von 1 Minute durch, so ergibt sich bei einer Badtemperatur von 35°C eine Gesamtverarbeitungszeit von nur 2 Minuten 40 Sekunden, da für Entwicklung, Bleichung und Fixierung jeweils nur 30 Sekunden benötigt werden. Dies bedeutet eine Zeitersparnis gegenüber herkömmlichen Verarbeitungen von 1 Minute 40 Sekunden.However, if a developer is used 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. 5 to 8, and 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.
Solche Verarbeitungen sind vor allem für die Herstellung photographischer Bilder in Photoautomaten von Bedeutung.Such processing is particularly important for the production of photographic images in photo booths.
Claims (22)
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CH3990/83A CH657710A5 (en) | 1983-07-20 | 1983-07-20 | METHOD FOR PROCESSING PHOTOGRAPHIC SILVER COLOR MATERIALS. |
CH3990/83 | 1983-07-20 |
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EP0133163A2 true EP0133163A2 (en) | 1985-02-13 |
EP0133163A3 EP0133163A3 (en) | 1985-08-14 |
EP0133163B1 EP0133163B1 (en) | 1987-08-26 |
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US (1) | US4546069A (en) |
EP (1) | EP0133163B1 (en) |
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US5552264A (en) * | 1995-04-05 | 1996-09-03 | Eastman Kodak Company | Photographic conditioning solution concentrate containing bleach accelerator and formaldehyde precursor and method of use |
US5945265A (en) * | 1998-03-26 | 1999-08-31 | Eastman Kodak Company | Uniformly mixed dry photographic developing composition containing antioxidant and method of preparation |
US5900355A (en) * | 1998-03-26 | 1999-05-04 | Eastman Kodak Company | Method of making uniformly mixed dry photographic processing composition using hot melt binder |
US5922521A (en) * | 1998-03-26 | 1999-07-13 | Eastman Kodak Company | Uniformly mixed dry photographic processing composition and method of preparation |
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EP0014688A2 (en) * | 1979-02-09 | 1980-08-20 | Ciba-Geigy Ag | Process for the treatment of silver dye-bleaching materials, aqueous preparation therefor, concentrate and process for making the preparation |
JPS5876838A (en) * | 1981-10-30 | 1983-05-10 | Fuji Photo Film Co Ltd | Treatment of silver halide color photosensitive material |
DE3234467A1 (en) * | 1981-10-29 | 1983-05-11 | DEFA Zentralstelle für Filmtechnik, Wissenschaftlich-technisches Zentrum, DDR 1197 Berlin | Quinone-containing solution, in particular photographic bleach bath |
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US2507183A (en) * | 1945-03-23 | 1950-05-09 | Eastman Kodak Co | Silver bleach for color materials |
CH594912A5 (en) * | 1974-07-10 | 1978-01-31 | Ciba Geigy Ag | |
CH597627A5 (en) * | 1975-11-17 | 1978-04-14 | Ciba Geigy Ag | |
GB1563380A (en) * | 1976-08-19 | 1980-03-26 | Ciba Geigy Ag | Method of processing silver dye bleaching materials and compositions suitable for the dye bleaching thereof |
DE2938803A1 (en) * | 1978-09-26 | 1980-04-03 | Fuji Photo Film Co Ltd | REVERSE DEVELOPMENT METHOD FOR BLACK AND WHITE PHOTOGRAPHIC LIGHT SENSITIVE MATERIALS |
-
1983
- 1983-07-20 CH CH3990/83A patent/CH657710A5/en not_active IP Right Cessation
-
1984
- 1984-07-16 EP EP84810351A patent/EP0133163B1/en not_active Expired
- 1984-07-16 DE DE8484810351T patent/DE3465638D1/en 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/en active Pending
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US2564238A (en) * | 1946-12-14 | 1951-08-14 | Gen Aniline & Film Corp | Silver azo dye bleach-out process and bleaching baths for use therein |
US3259497A (en) * | 1961-09-06 | 1966-07-05 | Ciba Ltd | Photographic color reversal process |
FR1504238A (en) * | 1965-12-10 | 1967-12-01 | Eastman Kodak Co | New photographic materials for use in the discoloration process |
FR1541483A (en) * | 1966-10-20 | 1968-10-04 | Fuji Photo Film Co Ltd | Photographic process of silver dye bleaching |
FR2169779A1 (en) * | 1971-11-29 | 1973-09-14 | Ciba Geigy Ag | |
US3963492A (en) * | 1973-10-12 | 1976-06-15 | Ciba-Geigy Ag | Method for processing silver dye bleach materials |
DE2616638A1 (en) * | 1975-04-16 | 1976-10-28 | Fuji Photo Film Co Ltd | Processing silver dye bleach material - using black and white developer with low hydroquinone content, for soft gradation |
US4186008A (en) * | 1977-03-23 | 1980-01-29 | Ciba-Geigy Aktiengesellschaft | Method for processing silver dye-bleach materials |
EP0014688A2 (en) * | 1979-02-09 | 1980-08-20 | Ciba-Geigy Ag | Process for the treatment of silver dye-bleaching materials, aqueous preparation therefor, concentrate and process for making the preparation |
DE3234467A1 (en) * | 1981-10-29 | 1983-05-11 | DEFA Zentralstelle für Filmtechnik, Wissenschaftlich-technisches Zentrum, DDR 1197 Berlin | Quinone-containing solution, in particular photographic bleach bath |
JPS5876838A (en) * | 1981-10-30 | 1983-05-10 | Fuji Photo Film Co Ltd | Treatment of silver halide color photosensitive material |
Non-Patent Citations (1)
Title |
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PATENTS ABSTRACTS OF JAPAN, Band 7, Nr. 172(P-213)[1317], 29. Juli 1983; & JP - A - 58 76838 (FUJI SHASIN FILM K.K.) 10.05.1983 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0274357A2 (en) * | 1987-01-06 | 1988-07-13 | Ilford Ag | Process for treating exposed photographic silver dyebleaching materials |
EP0274357A3 (en) * | 1987-01-06 | 1989-09-20 | Ciba-Geigy Ag | Process for treating exposed photographic silver dyebleaching materials |
US8270271B2 (en) * | 2003-03-25 | 2012-09-18 | Ricoh Company, Ltd. | Optical recording medium and information recording method |
Also Published As
Publication number | Publication date |
---|---|
DE3465638D1 (en) | 1987-10-01 |
US4546069A (en) | 1985-10-08 |
EP0133163A3 (en) | 1985-08-14 |
EP0133163B1 (en) | 1987-08-26 |
JPS6042757A (en) | 1985-03-07 |
CH657710A5 (en) | 1986-09-15 |
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