EP0512311B1 - Developer solution for process with reduced chemical overflow - Google Patents

Developer solution for process with reduced chemical overflow Download PDF

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Publication number
EP0512311B1
EP0512311B1 EP92106781A EP92106781A EP0512311B1 EP 0512311 B1 EP0512311 B1 EP 0512311B1 EP 92106781 A EP92106781 A EP 92106781A EP 92106781 A EP92106781 A EP 92106781A EP 0512311 B1 EP0512311 B1 EP 0512311B1
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EP
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Prior art keywords
developer
developer solution
phenylenediamine
processing method
kcl
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German (de)
French (fr)
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EP0512311A2 (en
EP0512311A3 (en
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Ubbo Dr. Wernicke
Peter Dr. Buttner
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers

Definitions

  • the silver halide emulsion layers Halide ions released, which hinder development when they accumulate in the developer.
  • the released halide ions have been washed out by high developer regeneration rates with a halide-free regenerator.
  • the regeneration rates were approximately 1.8 liters per m 2 of film; approx. 350 ml / m 2 paper.
  • the halide-laden overflow had to be disposed of and, in accordance with the high regeneration rates, has a low halide content of 0.6 to 3 g / l.
  • the exchange resin is used only once, as long and as far as there are halide ions can absorb, then the resin must be disposed of.
  • the object of the invention was to provide a development process which with regard to the disposal of the used developer further ecological advantages offers without the sensitometric properties of the processed Material deteriorate.
  • the processing method according to the invention is suitable for processing photographic silver halide materials, their silver halides too more than 95 mol%, preferably more than 98 mol%, of silver chloride consist. The remaining amount is up to 5 mol%, preferably up to 2 mol% especially silver bromide.
  • the invention thus relates to a processing method for photographic Silver halide materials whose silver halides consist of at least 95 mol% Silver chloride exist, with the process steps (a) developing, (b) bleaching, (c) fixing, (d) stabilizing or washing and (e) drying, taking the steps (b) and (c) combined into one step, between the individual steps Washing steps can be provided and the developer solution Contains color developer of the p-phenylenediamine series, characterized in that the developer solution additionally 10 to 150 g potassium chloride / l, preferably 15 to Contains 100 g / l, in particular 20 to 80 g / l and the pH of the developer solution ⁇ 10.2, preferably ⁇ 10.7.
  • the desired pH is set in particular by means of buffer mixtures and kept constant.
  • the buffer is preferably 0.1 to per liter of developer solution 0.3 mol of phosphate buffer, borate buffer, carbonate buffer, glycine buffer or others Buffer substances suitable. Mixtures of different buffers can also be used Consideration.
  • a color developer of the p-phenylenediamine series preferably salts of 1- [N-ethyl-N- (2-methylsulfonylaminoethyl)] - 3-methyl-p-phenylenediamine (CD3) or des 1- [N-ethyl-N- (2-hydroxyethyl)] - 3-methyl-p-phenylenediamine (CD4) or mixtures of CD3 and CD4 used.
  • Homologous CD-4 developers such as 1- [N-ethyl-N- (2-hydroxy-n-propyl) - and - (2-hydroxy-n-butyl)] - 3-methyl-p-phenylenediamine, are suitable.
  • CD3 is preferably used in a quantity from 4.5 to 9 g / l, in particular 6 to 8 g / l.
  • One opposite the standard RA-4 developer is increased amount mostly beneficial.
  • the developer solution can also have small proportions Contain bromide ions, for example from 0.005 up to 1.5 g KBr / l.
  • the phosphate ions are preferably introduced as K 3 PO 4 or K 2 HPO 4 .
  • the borate ions are preferably introduced as NaBO 2 .
  • Optical brighteners are further components, Lubricants, e.g. Polyalkylene glycols, surfactants, sodium and potassium sulfite, anti-limescale, anti-oxidant and means for adjusting the desired pH in question.
  • Lubricants e.g. Polyalkylene glycols
  • surfactants e.g. Polyalkylene glycols
  • sodium and potassium sulfite e.g. sodium and potassium sulfite
  • anti-limescale e.g. anti-limescale
  • anti-oxidant e.g., sodium and potassium sulfite, anti-limescale, anti-oxidant and means for adjusting the desired pH in question.
  • the ready-to-use solution can consist of the individual components or made from so-called concentrates in the concentrates, the individual Components dissolved in a much higher concentration will.
  • the concentrates are composed in such a way that they are either added directly to the ready-to-use solution in order to regenerate them or that they arise from them can produce a so-called regenerator, i.e.
  • the resulting overflow amount can be collected inexpensive, for example by evaporation and dumping to dispose.
  • the ecological advantage is calculated as follows: Instead of 160 ml overflow per m 2 of paper with 5 g CD 3 / l and 1 g KCl / l, for example 1.6 ml overflow with 100 g KCl / l but the same CD 3 content is obtained, ie with regard to the CD 3 load an improvement by a factor of 10 2 , with respect to the amount of solution to be disposed of also an improvement by a factor of 10 2 .
  • the invention Procedure with a subsequent treatment step combined in which by the photographic Substances carried over as far as possible recovered and the developer, if necessary after Concentration, fed again.
  • Another object of the invention is a ready-to-use Developer solution for a color photographic Processing method using a color developer of the p-phenylenediamine series, thereby characterized in that they additionally 10 to 150 g KCl / l contains and is adjusted to a pH> 10.7.
  • Photographic color papers from various manufacturers based on silver chloride were developed in the standard process RA 4 / AP 94.
  • Material Kodak 2001 (a), Konika QA (b), Agfa type 9 (c).
  • Process Times temperature Color developer 45 sec 35 ° C
  • Bleach-fixer 45 sec 35 ° C
  • the color developer is identical to that of Example 2.
  • the bleach-fix bath contains 50 g of ammonium thiosulfate per liter, 10 g sodium sulfite and 50 g ammonium iron EDTA and is adjusted to pH 5.5.
  • sensitometric results are marked through veil (D-Min) Gamma 1, Gamma 2 (foot and Shoulder gradation) and maximum density (D-Max).
  • Example 2 reference, finisher process with separate bleaching and fixing bath
  • Example 2 The procedure was as in Example 2, but that was Developer added 100 g of potassium chloride / l to the enrichment the one normally released from the photographic material Anticipate inhibitors.
  • Example 6c now also achieves good Gamme 2-yellow values.
  • Example 6 The procedure was as in Example 6, except that Developer added 50 mg of potassium bromide per liter, though this addition by the developers of Examples 1 and 2 on similarly poor sensitometric results as in example 3 leads. In the developer according to the invention however, this addition has a positive effect and lowers it Effective level of minimum densities.
  • the sensitometric influence of Na 2 SO 4 is not disadvantageous.
  • the sensitometric values are still approximately according to type.

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

Description

Beim fotografischen Entwicklungsprozess werden aus den Silberhalogenidemulsionsschichten Halogenidionen freigesetzt, die die Entwicklung behindern, wenn sie sich im Entwickler anreichern.In the photographic development process, the silver halide emulsion layers Halide ions released, which hinder development when they accumulate in the developer.

Bisher wurden die freigesetzten Halogenidionen durch hohe Regenerierquoten des Entwicklers mit halogenidfreiem Regenerator ausgeschwemmt. Die Regenerierquoten betrugen ca. 1,8 Liter pro m2 Film; ca. 350 ml/m2 Papier. Der halogenidbeladene Überlauf mußte entsorgt werden und weist entsprechend den hohen Regenierquoten einen geringen Halogenidgehalt von 0,6 bis 3 g/l auf.So far, the released halide ions have been washed out by high developer regeneration rates with a halide-free regenerator. The regeneration rates were approximately 1.8 liters per m 2 of film; approx. 350 ml / m 2 paper. The halide-laden overflow had to be disposed of and, in accordance with the high regeneration rates, has a low halide content of 0.6 to 3 g / l.

In den letzten Jahren haben sich Rejuvenierverfahren durchgesetzt, bei denen der halogenidhaltige Entwickler-Überlauf mit Ionenaustauscher-Harzen behandelt wird, an denen das Halogenid gebunden und so aus der Lösung entfernt wird. Der Entwickler konnte dadurch teilweise zurückgewonnen werden.In recent years, rejuvenation procedures have become established in which the developer overflow containing halide is treated with ion exchange resins, to which the halide is bound and thus removed from the solution. The developer could be partially recovered.

Dieses Recycling-System verminderte zwar die Menge des ins Abwasser gelangenden Entwicklers deutlich, führt aber dennoch zu ökologischen Folgeproblemen:This recycling system did reduce the amount of waste that went into the wastewater Developer, but still leads to ecological problems:

Wird das Austauscherharz nur einmal verwendet, so lange und so weit es Halogenidionen aufnehmen kann, dann muß das Harz entsorgt werden.If the exchange resin is used only once, as long and as far as there are halide ions can absorb, then the resin must be disposed of.

Wird andererseits das Harz erneut aufbereitet, so fällt ein Eluat an, das nunmehr die vorher vom Harz aufgenommenen Substanzen enthält. Außerdem muß das Harz gespült werden, ehe es erneut zur Aufbereitung von Entwicklerlösungen eingesetzt werden kann. Damit fallen belastete Spülwässer an.On the other hand, if the resin is reprocessed, an eluate is obtained, which is now contains the substances previously absorbed by the resin. Besides that Rinsing resin before using it again for processing developer solutions can be. This results in contaminated rinsing water.

Bekannt ist, Silberhalogenidmaterialien mit Silberhalogenidkörnern mit ≥ 70 Mol-% AgCl mit einem Entwickler zu entwickeln, der ≥ 3 · 10-2 Mol KCl/l enthält, entsprechend 2,2 g/l um die Bildeigenschaften zu stabilisieren (JP-A 11 89 652) oder Silberhalogenidmaterialien mit Silberhalogenidkörnern mit ≥ 95 Mol-% AgCl mit einem Entwickler zu entwickeln, wobei kein Überlauf entsteht, der Entwickler im frischen Zustand aber chloridfrei ist (EP-A 0 173 203) bzw. Silberhalogenidmaterialien mit Silberhalogenidkörnern mit ≥ 95 Mol-% AgCl mit einem Entwickler zu entwickeln, der 0,5 bis 5,0 KCl/l enthält und auf einen pH-Wert zwischen 10,4 und 12,9 eingestellt ist, um die Entwicklungszeit auf höchstens 40 Sekunden zu verkürzen (EP-A 0 330 035).It is known to develop silver halide materials with silver halide grains containing ≥ 70 mol% AgCl with a developer containing ≥ 3 · 10 -2 mol KCl / l, corresponding to 2.2 g / l, in order to stabilize the image properties (JP-A 11 89 652) or silver halide materials with silver halide grains with ≥ 95 mol% AgCl with a developer, whereby there is no overflow, but the developer is chloride-free in the fresh state (EP-A 0 173 203) or silver halide materials with silver halide grains with ≥ 95 mol% % AgCl develop with a developer that contains 0.5 to 5.0 KCl / l and is adjusted to a pH between 10.4 and 12.9 in order to shorten the development time to a maximum of 40 seconds (EP-A 0 330 035).

Aufgabe der Erfindung war die Bereitstellung eines Entwicklungsverfahrens, das hinsichtlich der Entsorgung des gebrauchten Entwicklers weitere ökologische Vorteile bietet, ohne daß die sensitometrischen Eigenschaften des verarbeiteten Materials verschlechtert werden.The object of the invention was to provide a development process which with regard to the disposal of the used developer further ecological advantages offers without the sensitometric properties of the processed Material deteriorate.

Überraschenderweise wurde gefunden, daß die Entwicklerlösung eines Farbentwicklers der p-Phenylendiaminreihe große Mengen an Chlorid toleriert, wenn der pH-Wert gegenüber dem Standard-RA 4-Verfahren erhöht wird. Dadurch ist es möglich, daß im Dauerbetrieb nur geringe Volumina, die hohe Chloridkonzentrationen aufweisen, ausgeschleust werden müssen, was ihre Entsorgung erleichtert. Das erfindungsgemäße Verarbeitungsverfahren eignet sich für die Verarbeitung fotografischer Silberhalogenidmaterialien, deren Silberhalogenide zu mehr als 95 Mol-%, vorzugsweise zu mehr als 98 Mol-%, aus Silberchlorid bestehen. Die verbleibende Menge bis 5 Mol-%, vorzugsweise bis zu 2 Mol-%, ist insbesondere Silberbromid.Surprisingly, it was found that the developer solution was one Color developer of the p-phenylenediamine series tolerates large amounts of chloride, if the pH is increased compared to the standard RA 4 method. Thereby it is possible that in continuous operation only small volumes, the high chloride concentrations have to be removed, what their disposal facilitated. The processing method according to the invention is suitable for processing photographic silver halide materials, their silver halides too more than 95 mol%, preferably more than 98 mol%, of silver chloride consist. The remaining amount is up to 5 mol%, preferably up to 2 mol% especially silver bromide.

Gegenstand der Erfindung ist somit ein Verarbeitungsverfahren für fotografische Silberhalogenidmaterialien, deren Silberhalogenide zu wenigstens 95 Mol-% aus Silberchlorid bestehen, mit den Verfahrensschritten (a) Entwickeln, (b) Bleichen, (c) Fixieren, (d) Stabilisieren oder Wässern und (e) Trocknen, wobei die Schritte (b) und (c) zu einem Schritt zusammengefaßt, zwischen den einzelnen Schritten Wässerungsschritte vorgesehen werden können und die Entwicklerlösung einen Farbentwickler der p-Phenylendiaminreihe enthält, dadurch gekennzeichnet, daß die Entwicklerlösung zusätzlich 10 bis 150 g Kaliumchlorid/l, vorzugsweise 15 bis 100 g/l, insbesondere 20 bis 80 g/l enthält und der pH-Wert der Entwicklerlösung ≥10,2, vorzugsweise ≥10,7 ist.The invention thus relates to a processing method for photographic Silver halide materials whose silver halides consist of at least 95 mol% Silver chloride exist, with the process steps (a) developing, (b) bleaching, (c) fixing, (d) stabilizing or washing and (e) drying, taking the steps (b) and (c) combined into one step, between the individual steps Washing steps can be provided and the developer solution Contains color developer of the p-phenylenediamine series, characterized in that the developer solution additionally 10 to 150 g potassium chloride / l, preferably 15 to Contains 100 g / l, in particular 20 to 80 g / l and the pH of the developer solution ≥10.2, preferably ≥10.7.

Der gewünschte pH-Wert wird insbesondere durch Puffergemische eingestellt und konstant gehalten. Als Puffer sind pro Liter Entwicklerlösung vorzugsweise 0,1 bis 0,3 Mol Phosphatpuffer, Boratpuffer, Carbonatpuffer, Glycinpuffer oder andere Puffersubstanzen geeignet. Auch Mischungen unterschiedlicher Puffer kommen in Betracht. The desired pH is set in particular by means of buffer mixtures and kept constant. The buffer is preferably 0.1 to per liter of developer solution 0.3 mol of phosphate buffer, borate buffer, carbonate buffer, glycine buffer or others Buffer substances suitable. Mixtures of different buffers can also be used Consideration.

Als Farbentwickler der p-Phenylendiaminreihe werden bevorzugt Salze des 1-[N-Ethyl-N-(2-methylsulfonylaminoethyl)]-3-methyl-p-phenylendiamins (CD3) oder des 1-[N-Ethyl-N-(2-hydroxyethyl)]-3-methyl-p-phenylendiamins (CD4) oder Mischungen aus CD3 und CD4 verwendet. Auch homologe CD-4-Entwickler, wie 1-[N-Ethyl-N-(2-hydroxy-n-propyl)- und -(2-hydroxy-n-butyl)]-3-methyl-p-phenylendiamin, sind geeignet.As a color developer of the p-phenylenediamine series preferably salts of 1- [N-ethyl-N- (2-methylsulfonylaminoethyl)] - 3-methyl-p-phenylenediamine (CD3) or des 1- [N-ethyl-N- (2-hydroxyethyl)] - 3-methyl-p-phenylenediamine (CD4) or mixtures of CD3 and CD4 used. Homologous CD-4 developers, such as 1- [N-ethyl-N- (2-hydroxy-n-propyl) - and - (2-hydroxy-n-butyl)] - 3-methyl-p-phenylenediamine, are suitable.

Vorzugsweise wird CD3 eingesetzt und zwar in einer Menge von 4,5 bis 9 g/l, insbesondere 6 bis 8 g/l. Eine gegenüber dem Standard-RA-4-Entwickler erhöhte Menge ist meist vorteilhaft.CD3 is preferably used in a quantity from 4.5 to 9 g / l, in particular 6 to 8 g / l. One opposite the standard RA-4 developer is increased amount mostly beneficial.

Die Entwicklerlösung kann darüber hinaus geringe Anteile Bromidionen enthalten, beispielsweise von 0,005 bis zu 1,5 g KBr/l.The developer solution can also have small proportions Contain bromide ions, for example from 0.005 up to 1.5 g KBr / l.

Die Phosphat-Ionen werden vorzugsweise als K3PO4 oder K2HPO4 eingebracht. Die Borationen werden vorzugsweise als NaBO2 eingebracht.The phosphate ions are preferably introduced as K 3 PO 4 or K 2 HPO 4 . The borate ions are preferably introduced as NaBO 2 .

Als weitere Bestandteile kommen optische Aufheller, Gleitmittel, z.B. Polyalkylenglykole, Tenside, Natrium- und Kaliumsulfit, Kalkschutzmittel, Oxidationsschutzmittel und Mittel zur Einstellung des gewünschten pH-Wertes in Frage.Optical brighteners are further components, Lubricants, e.g. Polyalkylene glycols, surfactants, sodium and potassium sulfite, anti-limescale, anti-oxidant and means for adjusting the desired pH in question.

Die gebrauchsfertige Lösung kann aus den einzelnen Bestandteilen oder aus sogenannten Konzentraten hergestellt werden, wobei in den Konzentraten die einzelnen Bestandteile wesentlich höher konzentriert gelöst werden. Die Konzentrate sind so zusammengesetzt, daß sie entweder direkt zur gebrauchsfertigen Lösung gegeben werden, um diese zu regenerieren oder daß sich aus ihnen ein sogenannter Regenerator herstellen läßt, d.h. eine Lösung, die etwas höhere Konzentrationen an den einzelnen Bestandteilen als die gebrauchsfertige Lösung aufweist, einerseits durch weiteres Verdünnen und Zusatz des Starters eine gebrauchsfertige Lösung ergibt und andererseits ständig einer in Gebrauch befindlichen Entwicklerlösung zugesetzt wird, um die beim Entwickeln verbrauchten oder aus der Entwicklerlösung ausgeschleppten Chemikalien zu ersetzen, wobei für den KCl-Gehalt besondere Maßnahmen, wie nachfolgend dargestellt, zu beachten sind.The ready-to-use solution can consist of the individual components or made from so-called concentrates in the concentrates, the individual Components dissolved in a much higher concentration will. The concentrates are composed in such a way that they are either added directly to the ready-to-use solution in order to regenerate them or that they arise from them can produce a so-called regenerator, i.e. a Solution that slightly higher concentrations at the individual Components as the ready-to-use solution, on the one hand by further dilution and addition the starter gives a ready-to-use solution and on the other hand, a developer solution in use all the time is added to the while developing used or dragged out of the developer solution Substitute chemicals, taking care of the KCl content special measures, as shown below, are to be observed.

Da das Verfahren eine große Chloridkonzentration im Entwickler toleriert, können die Regenerierquoten erniedrigt werden, und es fällt eine geringe Menge an Überlauf an, die eine hohe Chloridkonzentration aufweist. Dieser Überlauf enthält auch Entwicklersubstanz, jedoch, verglichen mit der Menge bereits entwickelten Materials, in so geringer Menge, daß man auf eine Wiedergewinnung verzichtet.Since the process has a large chloride concentration in the Developers tolerated, the regeneration rates be lowered and a small amount is produced Overflow that has a high chloride concentration. This overflow also contains developer substance, however, compared to the amount already developed Material, in such a small amount that you can on a No recovery.

Die so entstehende Uberlaufmenge läßt sich nach Sammlung kostengünstig beispielsweise durch Eindampfen und Deponieren entsorgen.The resulting overflow amount can be collected inexpensive, for example by evaporation and dumping to dispose.

Im Einzelfall berechnet sich der ökologische Vorteil wie folgt:
Statt 160 ml Überlauf pro m2 Papier mit 5 g CD 3/l und 1 g KCl/l fallen z.B. 1,6 ml Überlauf mit 100 g KCl/l aber gleichem CD 3-Gehalt an, d.h. hinsichtlich der CD 3-Belastung wird eine Verbesserung um den Faktor 102, hinsichtlich der zu entsorgenden Lösungsmenge ebenfalls eine Verbesserung um den Faktor 102 erreicht.In individual cases, the ecological advantage is calculated as follows:
Instead of 160 ml overflow per m 2 of paper with 5 g CD 3 / l and 1 g KCl / l, for example 1.6 ml overflow with 100 g KCl / l but the same CD 3 content is obtained, ie with regard to the CD 3 load an improvement by a factor of 10 2 , with respect to the amount of solution to be disposed of also an improvement by a factor of 10 2 .

In einer bevorzugten Ausführungsform wird das erfindungsgemäße Verfahren mit einer nachfolgenden Behandlungsstufe kombiniert, in der die durch das fotografische Material verschleppten Substanzen weitestgehend zurückgewonnen und dem Entwickler, gegebenenfalls nach Aufkonzentrierung, wieder zugeführt werden.In a preferred embodiment, the invention Procedure with a subsequent treatment step combined in which by the photographic Substances carried over as far as possible recovered and the developer, if necessary after Concentration, fed again.

Ein weiterer Gegenstand der Erfindung ist eine gebrauchsfertige Entwicklerlösung für ein farbfotografisches Verarbeitungsverfahren, die einen Farbentwickler der p-Phenylendiaminreihe enthält, dadurch gekennzeichnet, daß sie zusätzlich 10 bis 150 g KCl/l enthält und auf einen pH-Wert >10,7 eingestellt ist. Another object of the invention is a ready-to-use Developer solution for a color photographic Processing method using a color developer of the p-phenylenediamine series, thereby characterized in that they additionally 10 to 150 g KCl / l contains and is adjusted to a pH> 10.7.

Beispiel 1example 1 (Referenz, Minilab-Prozeß mit Bleichfixierbad)(Reference, minilab process with bleach-fix bath)

Fotografische Colorpapiere verschiedener Hersteller auf Basis von Silberchlorid wurden im Standardprozeß RA 4/AP 94 entwickelt. Material Kodak 2001 (a), Konika QA (b), Agfa Typ 9 (c). Prozeß Zeiten Temperatur Farbentwickler 45 sek 35°C Bleichfixierbad 45 sek 35°C Wässerung 4 x 22,5 sek 25-35°C Photographic color papers from various manufacturers based on silver chloride were developed in the standard process RA 4 / AP 94. Material Kodak 2001 (a), Konika QA (b), Agfa type 9 (c). Process Times temperature Color developer 45 sec 35 ° C Bleach-fixer 45 sec 35 ° C Watering 4 x 22.5 sec 25-35 ° C

Der Farbentwickler ist mit dem von Beispiel 2 identisch. Das Bleichfixierbad enthält pro Liter 50 g Ammoniumthiosulfat, 10 g Natriumsulfit und 50 g Ammoniumeisen-EDTA und ist auf pH 5,5 eingestellt.The color developer is identical to that of Example 2. The bleach-fix bath contains 50 g of ammonium thiosulfate per liter, 10 g sodium sulfite and 50 g ammonium iron EDTA and is adjusted to pH 5.5.

Die sensitometrischen Ergebnisse sind gekennzeichnet durch Schleier (D-Min) Gamma 1, Gamma 2 (Fuß- und Schultergradation) und Maximaldichte (D-Max).The sensitometric results are marked through veil (D-Min) Gamma 1, Gamma 2 (foot and Shoulder gradation) and maximum density (D-Max).

Beispiel 2 (Referenz, Finisher-Prozeß mit getrenntem Bleich- und Fixierbad) Example 2 (reference, finisher process with separate bleaching and fixing bath)

Zeittime Temperaturtemperature FarbentwicklerColor developer 45 sek45 sec 35°C35 ° C WässerungWatering 45 sek45 sec 20°C20 ° C BleichbadBleach bath 90 sek90 sec 35°C35 ° C WässerungWatering 45 sek45 sec 20°C20 ° C FixierbadFixer 45 sek45 sec 35°C35 ° C WässerungWatering 45 sek45 sec 20°C20 ° C FarbentwicklerColor developer CD 3CD 3 5 g5 g Polyglykol 400Polyglycol 400 15 ml15 ml EthylenglykolEthylene glycol 5 ml5 ml DiethylhydroxylaminDiethylhydroxylamine 4 g4 g PottaschePotash 20 g20 g NitrilotriessigsäureNitrilotriacetic acid 2 g2 g pH-WertPH value 10,2 mit KOH10.2 with KOH KClKCl 1,5 g1.5 g BleichbadBleach bath AmmoniumbromidAmmonium bromide 100 g100 g Ammonium Eisen EDTAAmmonium iron EDTA 50 g50 g NatriumsulfitSodium sulfite 5 g5 g pHpH 5,55.5 FixierbadFixer Ammonium-thiosulfatAmmonium thiosulfate 100 g100 g NatriumsulfitSodium sulfite 15 g15 g pH-WertPH value 7,57.5

Alle Mengenangaben beziehen sich auf 1 l gebrauchsfertige wäßrige Lösung. All quantities refer to 1 l ready-to-use aqueous solution.

Diskussion der Ergebnisse der Referenzentwicklungen an den Beispielen 1 und 2:

  • 1. Die Minimaldichten variieren bei den drei Papieren zwischen 0,100 und 0,139.
  • 2. Die Gamma 1-Werte unterscheiden sich nur geringfügig bei 1,65 bis 1,89.
  • 3. Die Gamma 2-Werte differieren zwischen 2,75 und 4,08.
  • 4. Die Maximaldichten differieren zwischen 2,33 und 2,68.
    • Discussion of the results of the reference developments using examples 1 and 2:
  • 1. The minimum densities for the three papers vary between 0.100 and 0.139.
  • 2. The gamma 1 values differ only slightly at 1.65 to 1.89.
  • 3. The gamma 2 values differ between 2.75 and 4.08.
  • 4. The maximum densities differ between 2.33 and 2.68.

    • Trotz abweichender sensitometrischer Werte führen alle Papiere zu verkäuflichen Bildkopien von den derzeitig erhältlichen Color-Negativ-Filmen.Despite differing sensitometric values, everyone leads Papers for sale of copies of the images currently available available color negative films.

    Beispiel 3Example 3

    Es wurde wie im Beispiel 2 verfahren, jedoch wurde dem Entwickler 100 g Kalium-Chlorid/l zugesetzt, um die Anreicherung der normalerweise aus dem Fotomaterial freigesetzten Hemmstoffe vorwegzunehmen.The procedure was as in Example 2, but that was Developer added 100 g of potassium chloride / l to the enrichment the one normally released from the photographic material Anticipate inhibitors.

    Bei allen 3 Materialien ist die Entwicklung so stark gehemmt, daß die Maximaldichten Werte zwischen 0,3 und 1,35 annehmen. The development is so strong for all 3 materials inhibited that the maximum densities values between 0.3 and Assume 1.35.

    Beispiel 4 (Vergleich) Example 4 (comparison)

    Es wurde wie im Beispiel 3 verfahren, jedoch wurde Carbonat durch eine äquivalente Menge Phosphat ersetzt und der pH-Wert auf 11,5 eingestellt.The procedure was as in Example 3, but was Carbonate replaced by an equivalent amount of phosphate and the pH adjusted to 11.5.

    Die Maximaldichten Purpur und Blaugrün erreichen bereits annähernd typgemäße Werte. Gelb ist noch viel zu niedrig.The maximum densities of purple and teal have already been reached approximate values. Yellow is still too much low.

    Beispiel 5 (erfindungswesentlich) Example 5 (essential to the invention)

    Es wurde wie im Beispiel 4 verfahren, jedoch wurde die CD 3-Konzentration um 1 g/l angehoben. Dadurch steigt die Maximaldichte Gelb auf annähernd typgemäße Werte und auch die Gamma 2-Werte sind im Fall 5a und 6b bereits ausreichend.The procedure was as in Example 4, but the CD 3 concentration increased by 1 g / l. This increases the maximum density yellow to approximately standard values and the gamma 2 values are already in cases 5a and 6b sufficient.

    Beispiel 6 (erfindungswesentlich) Example 6 (essential to the invention)

    Es wurde wie im Beispiel 4 verfahren, jedoch wurde die CD 3-Konzentration um 2 g/l angehoben.The procedure was as in Example 4, but the CD 3 concentration increased by 2 g / l.

    Jetzt erreicht auch das Beispiel 6c gute Gamme 2-Gelb-Werte.Example 6c now also achieves good Gamme 2-yellow values.

    Beispiel 7 (erfindungswesentlich) Example 7 (essential to the invention)

    Es wurde wie im Beispiel 6 verfahren, jedoch wurde dem Entwickler 50 mg Kalium-Bromid pro Liter zugefügt, obwohl dieser Zusatz bei den Entwicklern der Beispiele 1 und 2 zu ähnlich schlechten sensitometrischen Resultaten wie im Beispiel 3 führt. Im erfindungsgemäßen Entwickler ist dieser Zusatz jedoch positiv wirksam und senkt das Niveau der Minimaldichten wirksam ab.The procedure was as in Example 6, except that Developer added 50 mg of potassium bromide per liter, though this addition by the developers of Examples 1 and 2 on similarly poor sensitometric results as in example 3 leads. In the developer according to the invention however, this addition has a positive effect and lowers it Effective level of minimum densities.

    Beispiel 8 (erfindungswesentlich) Example 8 (essential to the invention)

    Es wird wie im Beispiel 7 verfahren, jedoch wird 50 g KCl durch 50 g Na2SO4 ersetzt, das sich im Dauerbetrieb aus Sulfitzusatz bildet und sich ebenfalls anreichern kann.The procedure is as in Example 7, but 50 g of KCl is replaced by 50 g of Na 2 SO 4 , which is formed from the addition of sulfite in continuous operation and can likewise accumulate.

    Der sensitometrische Einfluß des Na2SO4 ist nicht nachteilig. Die sensitometrischen Werte sind nach wie vor annähernd typgemäß.The sensitometric influence of Na 2 SO 4 is not disadvantageous. The sensitometric values are still approximately according to type.

    Die Ergebnisse sind in der nachfolgenden Tabelle dargestellt; gb bedeutet Gelb, pp Purpur und bg Blaugrün.

    Figure 00110001
    The results are shown in the table below; gb means yellow, pp purple and bg blue-green.
    Figure 00110001

    Claims (8)

    1. A processing method for photographic silver halide materials, at least 95 mole % of the silver halides of which consist of silver chloride, comprising the processing steps of (a) developing, (b) bleaching, (c) fixing, (d) stabilising or washing, and (e) drying, wherein steps (b) and (c) are combined to form one step, washing steps can be provided between the individual steps, and the developer solution contains a colour developer of the p-phenylenediamine series and is adjusted to a pH ≥ 10.2, characterised in that the developer solution additionally contains 10 to 150 g potassium chloride/l.
    2. A method according to claim 1, characterised in that the developer solution contains 15 to 100 g KCl/l.
    3. A method according to claim 1, characterised in that the developer solution contains 20 to 80 g KCl/l.
    4. A processing method according to claim 1, characterised in that the pH of the developer solution is ≥ 10.7.
    5. A processing method according to claim 1, characterised in that the colour developer of the p-phenylenediamine series is a salt of 1-[N-ethyl-N-(2-methylsulphonylaminoethyl)]-3-methyl-p-phenylenediamine (CD3) or of 1-[N-ethyl-N-(2-hydroxyethyl)]-3-methyl-p-phenylenediamine (CD4) or a mixture of CD3 and CD4.
    6. A processing method according to claim 1, characterised in that CD3 is used as the colour developer in an amount of 4.5 to 9 g/l, preferably 6 to 8 g/l.
    7. A ready-for-use developer solution for a colour photographic processing method, which contains a colour developer of the p-phenylenediamine series and is adjusted to a pH ≥ 10.7, characterised in that it additionally contains 10 to 150 g KCl/l.
    8. A ready-for-use developer solution according to claim 7, characterised in that the pH is adjusted with a buffer mixture.
    EP92106781A 1991-05-03 1992-04-21 Developer solution for process with reduced chemical overflow Expired - Lifetime EP0512311B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE4114481A DE4114481A1 (en) 1991-05-03 1991-05-03 ENVIRONMENTALLY IMPROVED DEVELOPMENT PROCESS FOR PHOTO MATERIALS AND SUITABLE DEVELOPER SOLUTION
    DE4114481 1991-05-03

    Publications (3)

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    EP0512311A2 EP0512311A2 (en) 1992-11-11
    EP0512311A3 EP0512311A3 (en) 1994-02-02
    EP0512311B1 true EP0512311B1 (en) 1998-02-04

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    DE (2) DE4114481A1 (en)

    Family Cites Families (6)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE3431860A1 (en) * 1984-08-30 1986-03-06 Agfa-Gevaert Ag, 5090 Leverkusen METHOD FOR PRODUCING COLOR PHOTOGRAPHIC IMAGES
    CA1314424C (en) * 1986-01-24 1993-03-16 Sheridan E. Vincent Photographic color developing compositions which are especially useful with high chloride photographic elements
    DE3800385A1 (en) * 1988-01-09 1989-07-20 Agfa Gevaert Ag OVERFLOW-FREE COLOR PHOTOGRAPHIC DEVELOPMENT SYSTEM
    JPH01189652A (en) * 1988-01-25 1989-07-28 Konica Corp Color developer for silver halide color photographic sensitive material and method for processing said material using same
    DE3805699A1 (en) * 1988-02-24 1989-09-07 Agfa Gevaert Ag PHOTOGRAPHIC COLOR DEVELOPER SOLUTION AND METHOD FOR DEVELOPING A COLOR PHOTOGRAPHIC MATERIAL
    JP2811117B2 (en) * 1990-07-24 1998-10-15 コニカ株式会社 Color developer for silver halide color photographic materials

    Also Published As

    Publication number Publication date
    EP0512311A2 (en) 1992-11-11
    DE59209177D1 (en) 1998-03-12
    JPH05142731A (en) 1993-06-11
    EP0512311A3 (en) 1994-02-02
    DE4114481A1 (en) 1992-11-05

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