EP1862852B1 - Developer concentrate - Google Patents

Developer concentrate Download PDF

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Publication number
EP1862852B1
EP1862852B1 EP07010793A EP07010793A EP1862852B1 EP 1862852 B1 EP1862852 B1 EP 1862852B1 EP 07010793 A EP07010793 A EP 07010793A EP 07010793 A EP07010793 A EP 07010793A EP 1862852 B1 EP1862852 B1 EP 1862852B1
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EP
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Prior art keywords
potassium
developer
ascorbic acid
water
working solution
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EP07010793A
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German (de)
French (fr)
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EP1862852A1 (en
Inventor
Wolfgang Zehner
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Orochemie GmbH and Co KG
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Orochemie GmbH and Co KG
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
    • G03C5/266—Supplying of photographic processing chemicals; Preparation or packaging thereof of solutions or concentrates
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • 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
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • G03C2005/3007—Ascorbic acid
    • 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
    • G03C2200/00—Details
    • G03C2200/44—Details pH value
    • 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
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • G03C5/3028—Heterocyclic compounds
    • G03C5/3035—Heterocyclic compounds containing a diazole ring

Definitions

  • the invention relates to a developer for photosensitive film material according to the preamble of claim 1.
  • a developing solution for use with silver halide film material comprising as a developer ascorbic acid or a salt of ascorbic acid.
  • the pH of the developing solution may be 9.8.
  • JP-A-9-197630 of the WO-A-93-11456 , of the JP-A-10-171076 , of the JP-A-8-211572 , of the JP-A-9-265162 , of the JP-A-9-265161 and the JP-A-9-197628 refer to.
  • Such developers are in a variety of forms on the market. They generally serve to convert, by a reducing agent (developing agent), silver ions or other suitable metal ions contained in the photosensitive layer and sensitized by exposure to light into metallic silver.
  • a reducing agent developer agent
  • silver ions or other suitable metal ions contained in the photosensitive layer and sensitized by exposure to light into metallic silver.
  • the present invention is intended to provide a developer concentrate for photosensitive film material, which is distinguished by particularly good long-term stability under use conditions.
  • the developer according to the invention has as further advantages that it is free of hydroquinone and of GDA (glutaraldehyde adduct). It is also characterized by a very high development activity. It also has excellent yield, especially in roll developing machines.
  • the most important component in terms of quantity is the solvent. This is generally chosen so that it is compatible with the film layer to be developed, so it wets and allows an exchange of solutes with the film layer.
  • a water-based solvent is suggested, which means that this solvent comprises predominantly or completely water.
  • adjuvants may be added to the water which promote wetting of the film layer, optionally swelling of the film layer and later drying of the film layer.
  • the developing agent serves to convert the metal ions of the photosensitive layer, insofar as they have been activated by light, into elemental metal.
  • known developing agents include hydroquinone and other substances that are undesirable for environmental or potential health reasons.
  • One class of reducing agent used in the developer of the present invention includes ascorbic acid and derivatives of ascorbic acid, especially salts thereof. These are particularly advantageous in terms of environmental protection.
  • Development enhancers used in the invention include pyrazolidinone derivatives containing two nitrogen atoms in a five-membered ring.
  • the five-membered ring may carry further aliphatic or aromatic groups.
  • Preferred examples of such pyrazolidinone derivative developing agents are 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone, 1-phenylpyrazolidin-3-one and 1-phenyl-4-methyl-3-pyrazolidinone. These substances are also known under the trade names Dimezone S, Phenidone A and Phenidone B.
  • a development inhibitor is added to the developer.
  • These are preferably alkali halides, in particular those with heavier anions, preferably potassium bromide or sodium bromide.
  • the pH of the use solution be maintained within a given window of from about 8.5 to about 12, preferably from about 9.7 to about 11.2.
  • alkalis preferably potassium hydroxide or sodium hydroxide.
  • the pH can also be stabilized by salts of a weak acid in the desired alkaline range, in particular salts of weak organic or inorganic acids, preferably potassium carbonate, sodium tetraborate, sodium metaborate. You can also use mixtures of alkalis and salts.
  • the development result is advantageously influenced if the developer is additionally added a complexing agent.
  • complexing agents are preferably organic acids with small chain length, which contain nitrogen groups, more preferably additionally short aliphatic groups.
  • Preferred complexing agents are diethyltriamine pentaethanoic acid (DTPA), ethylenediaminetetraethanoic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA) and nitrilotriethanoic acid (NTA) and salts of the aforementioned acids.
  • a ready-to-use developer solution is adversely affected by oxidation in its properties.
  • an antioxidant to the developer.
  • Suitable for this purpose are generally not completely oxidized acids and salts thereof, in particular sulfites such as potassium sulfite, potassium hydrogen sulfite, potassium metabisulfite and sodium bisulfite.
  • a solubilizer can be used.
  • These may be polyhydric alcohols, in particular diols or glycols. Diethylene glycol and triethylene glycol are preferably used here.
  • agents belonging to the group of azoles in particular of the benzotriazole, indazole, mercaptotetrazole and imidazole type), in particular 5-mercapto-1-phenyl-1,2,3,4-tetrazole (PMT ), 1-H-benzotriazole, 5-methylbenzotriazole, 6-nitrobenzimidazole, 5-nitroindazole.
  • compositions of embodiments give an overview of the concentration in which the various components in a Use solution in grams per liter of working solution may be present.
  • the concentrations are recommended, which are recommended if a considered component alone forms the corresponding agent. It is understood that it is also possible to use mixtures of substances that are equally suitable for the same component of the developer, in which case the amounts used are selected such that the corresponding overall effect is obtained. Thus, for example, according to the following table for the different complexing agents in each case the same amount used. In this case, one can then simply replace the omitted portion of a complexing agent with an appropriate amount of another complexing agent.
  • Example 1 Developer for X-ray film processor
  • concentration data in the above description and claims refer, as indicated, to one liter of working solution and not to the concentrate.
  • concentrations in the concentrate are greater according to the prescribed dilution ratio for the concentrate. This dilution ratio is about 1.5 to 5 for a practical developer for roll-fed development machines, and about 0.5 to 1 for roll-free processors (film is moved around the edges by the tanks).

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

Abstract

Developer concentrate (A), for photosensitive film material, comprises a solvent based on water, an adjusting agent, which adjusts the alkali pH-value of the solvent and a formulating agent such as ascorbic acid or its salt, where the pH of the obtained solution is diluted to 8.5-12.

Description

Die Erfindung betrifft einen Entwickler für lichtempfindliches Filmmaterial gemäß dem Oberbegriff des Anspruches 1.The invention relates to a developer for photosensitive film material according to the preamble of claim 1.

In der US-A-5 587 276 ist eine Entwicklerlösung zur Verwendung mit Silberhalogenid-Filmmaterial beschrieben, welches als Entwicklungsmittel Ascorbinsäure oder ein Salz der Ascorbinsäure umfasst. Der pH-Wert der Entwicklungslösung kann bei 9,8 liegen.In the US-A-5 587 276 For example, there is described a developing solution for use with silver halide film material comprising as a developer ascorbic acid or a salt of ascorbic acid. The pH of the developing solution may be 9.8.

Weitere Entwicklerlösungen mit einem pH im Bereich bei 9,7 und 9,8 sind der JP-A-9-197630 , der WO-A-93-11456 , der JP-A-10-171076 , der JP-A-8-211572 , der JP-A-9-265162 , der JP-A-9-265161 und der JP-A-9-197628 zu entnehmen.Other developer solutions with a pH in the range of 9.7 and 9.8 are the JP-A-9-197630 , of the WO-A-93-11456 , of the JP-A-10-171076 , of the JP-A-8-211572 , of the JP-A-9-265162 , of the JP-A-9-265161 and the JP-A-9-197628 refer to.

Derartige Entwickler sind in vielfältiger Form auf dem Markt. Sie dienen generell dazu, durch ein Reduktionsmittel (Entwicklungsmittel) Silberionen oder andere geeignete Metallionen, die in der lichtempfindlichen Schicht enthalten sind und durch Lichteinwirkung sensibilisiert sind, in metallisches Silber umwandelt.Such developers are in a variety of forms on the market. They generally serve to convert, by a reducing agent (developing agent), silver ions or other suitable metal ions contained in the photosensitive layer and sensitized by exposure to light into metallic silver.

Bei Entwicklern, die in Entwicklungsautomaten verwendet werden, die große Volumina an Entwicklern enthalten, stellt sich das Problem der Langzeitstabilität des gebrauchsfertigen Entwicklers ohne Regenerierung. Nach Standzeiten von einigen Tagen oder Wochen lässt die Entwicklungsqualität deutlich nach und der gesamte Entwickler muss durch neuen Entwickler ersetzt werden.For developers used in development machines that contain large volumes of developers, the problem of the long-term stability of the ready-to-use developer without regeneration arises. After a service life of a few days or weeks, the development quality decreases significantly and the entire developer must be replaced by new developers.

Durch die vorliegende Erfindung soll ein Entwicklerkonzentrat für lichtempfindliches Filmmaterial geschaffen werden, welches sich durch besonders gute Langzeitstabilität unter Einsatzbedingungen auszeichnet.The present invention is intended to provide a developer concentrate for photosensitive film material, which is distinguished by particularly good long-term stability under use conditions.

Diese Aufgabe ist erfindungsgemäß gelöst durch einen Entwickler mit den in Anspruch 1 angegebenen Merkmalen.This object is achieved by a developer having the features specified in claim 1.

Der erfindungemäße Entwickler hat als weitere Vorteile, dass er frei von Hydrochinon und von GDA (Glutardialdehydaddukt) ist. Er zeichnet sich auch durch eine sehr hohe Entwicklungsaktivität aus. Er hat auch eine ausgezeichnete Ergiebigkeit, insbesondere in Rollen-Entwicklungsmaschinen.The developer according to the invention has as further advantages that it is free of hydroquinone and of GDA (glutaraldehyde adduct). It is also characterized by a very high development activity. It also has excellent yield, especially in roll developing machines.

Vorteilhafte Weiterbildungen der Erfindung sind Gegenstand der Unteransprüche.Advantageous developments of the invention are the subject of the dependent claims.

Nachstehend werden zu einzelnen Komponenten eines erfindungsgemäßen Entwicklerkonzentrates, welche in diesem enthalten sein können, allgemeine Anmerkungen gegeben.Hereinbelow, general comments will be made on individual components of a developer concentrate of the invention which may be included therein.

Mengenmäßig die wichtigste Komponente ist das Lösungsmittel. Dieses ist generell so gewählt, dass es mit der zu entwickelnden Filmschicht kompatibel ist, also diese benetzt und einen Austausch gelöster Stoffe mit der Filmschicht ermöglicht. Es wird ein Lösungsmittel auf Wasserbasis vorgeschlagen, was bedeutet, dass dieses Lösungsmittel überwiegend oder ganz Wasser umfasst. Dem Wasser können jedoch Hilfsstoffe zugefügt sein, welche die Benetzung der Filmschicht, gegebenenfalls ein Quellen der Filmschicht und später ein Trocknen der Filmschicht begünstigen.The most important component in terms of quantity is the solvent. This is generally chosen so that it is compatible with the film layer to be developed, so it wets and allows an exchange of solutes with the film layer. A water-based solvent is suggested, which means that this solvent comprises predominantly or completely water. However, adjuvants may be added to the water which promote wetting of the film layer, optionally swelling of the film layer and later drying of the film layer.

Das Entwicklungsmittel dient, wie üblich, dazu, die Metallionen der lichtempfindlichen Schicht, soweit sie durch Licht aktiviert wurden, in elementares Metall umzuwandeln. Bekannte Entwicklungsmittel umfassen zum Beispiel Hydrochinon und andere Substanzen, die aus Gründen des Umweltschutzes oder potentieller gesundheitlicher Gefährdung nicht erwünscht sind.The developing agent, as usual, serves to convert the metal ions of the photosensitive layer, insofar as they have been activated by light, into elemental metal. For example, known developing agents include hydroquinone and other substances that are undesirable for environmental or potential health reasons.

Eine Klasse beim erfindungsgemäßen Entwickler verwendeter Reduktionsmittel umfasst Ascorbinsäure und Derivate der Ascorbinsäure, insbesondere Salze derselben. Diese sind im Hinblick auf den Umweltschutz besonders vorteilhaft.One class of reducing agent used in the developer of the present invention includes ascorbic acid and derivatives of ascorbic acid, especially salts thereof. These are particularly advantageous in terms of environmental protection.

Bei der Erfindung verwendete Entwicklungsverstärker umfassen Pyrazolidinon-Derivate, die in einem Fünfring zwei Stickstoffatome enthalten. Der Fünferring kann weitere aliphatische oder aromatische Gruppen tragen.Development enhancers used in the invention include pyrazolidinone derivatives containing two nitrogen atoms in a five-membered ring. The five-membered ring may carry further aliphatic or aromatic groups.

Bevorzugte Beispiele für derartige Pyrazolidinonderivat-Entwicklungsmittel sind 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinon, 1-Phenylpyrazolidin-3-on und 1-Phenyl-4-methyl-3-pyrazolidinon. Diese Substanzen sind auch unter den Handelsnamen Dimezone S, Phenidon A und Phenidon B bekannt.Preferred examples of such pyrazolidinone derivative developing agents are 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone, 1-phenylpyrazolidin-3-one and 1-phenyl-4-methyl-3-pyrazolidinone. These substances are also known under the trade names Dimezone S, Phenidone A and Phenidone B.

Die Vorteile dieser Substanzen liegen in einer intensiveren Schwärzung der belichteten Filmbereiche (Superadditivität).The advantages of these substances lie in a more intense blackening of the exposed film areas (superadditivity).

Legt man größeren Wert auf die Qualität und die Gleichförmigkeit des Entwicklungsergebnisses als auf die Kürze des Entwicklungsprozesses, so wird dem Entwickler ein Entwicklungsverzögerer zugesetzt. Es handelt sich hierbei bevorzugt um Alkalihalogenide, insbesondere solche mit schwereren Anionen, bevorzugt Kaliumbromid oder Natriumbromid.If more emphasis is placed on the quality and uniformity of the development result than on the brevity of the development process, a development inhibitor is added to the developer. These are preferably alkali halides, in particular those with heavier anions, preferably potassium bromide or sodium bromide.

Für die Langzeitstabilität des Entwicklers ist es von großer Bedeutung, dass der pH-Wert der Gebrauchslösung innerhalb eines vorgegebenen Fensters von etwa 8.5 bis etwa 12 gehalten wird, vorzugsweise von etwa 9,7 bis etwa 11,2.For the long-term stability of the developer, it is of great importance that the pH of the use solution be maintained within a given window of from about 8.5 to about 12, preferably from about 9.7 to about 11.2.

Man kann hierzu zum einen einfach Laugen verwenden, bevorzugt Kaliumhydroxid oder Natriumhydroxid. Man kann den pH-Wert aber auch durch Salze einer schwachen Säure im gewünschten alkalischen Bereich stabilisieren, insbesondere Salze von schwachen organischen oder anorganischen Säuren, bevorzugt Kaliumcarbonat, Natriumtetraborat, Natriummetaborat. Auch kann man Mischungen aus Laugen und Salzen verwenden.For this purpose, one can simply use alkalis, preferably potassium hydroxide or sodium hydroxide. However, the pH can also be stabilized by salts of a weak acid in the desired alkaline range, in particular salts of weak organic or inorganic acids, preferably potassium carbonate, sodium tetraborate, sodium metaborate. You can also use mixtures of alkalis and salts.

Das Entwicklungsergebnis wird vorteilhaft beeinflusst, wenn man dem Entwickler zusätzlich ein Komplexierungsmittel zugibt. Es handelt sich hierbei bevorzugt um organische Säuren mit kleiner Kettenlänge, welche Stickstoffgruppen enthalten, nochmals bevorzugt zusätzlich kurze aliphatische Gruppen. Bevorzugte Komplexierungsmittel sind Diethyltriaminpentaethansäure (DTPA), Ethylendiamintetraethansäure (EDTA), Hydroxyethylethylendiamintriessigsäure (HEDTA) und Nitrilotriethansäure (NTA) sowie Salze der vorgenannten Säuren.The development result is advantageously influenced if the developer is additionally added a complexing agent. These are preferably organic acids with small chain length, which contain nitrogen groups, more preferably additionally short aliphatic groups. Preferred complexing agents are diethyltriamine pentaethanoic acid (DTPA), ethylenediaminetetraethanoic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA) and nitrilotriethanoic acid (NTA) and salts of the aforementioned acids.

Eine gebrauchsfertige Entwicklerlösung wird durch Oxidation in ihren Eigenschaften negativ beeinflusst. Zur Verbesserung der Langzeitstabilität eines gebrauchsfertigen Entwicklers gegen Oxidation kann man daher dem Entwickler ein Oxidationsschutzmittel zusetzen. Hierfür sind generell geeignet die nicht voll aufoxidierten Säuren und Salze derselben, insbesondere Sulfite wie Kaliumsulfit, Kaliumhydrogensulfit, Kaliummetabisulfit und Natriumhydrogensulfit.A ready-to-use developer solution is adversely affected by oxidation in its properties. To improve the long-term stability of a ready-to-use developer against oxidation, it is therefore possible to add an antioxidant to the developer. Suitable for this purpose are generally not completely oxidized acids and salts thereof, in particular sulfites such as potassium sulfite, potassium hydrogen sulfite, potassium metabisulfite and sodium bisulfite.

Zur besseren und gleichmäßigen Lösung des Entwicklungsmittels in dem Lösungsmittel kann ein Lösungsvermittler verwendet werden. Hierbei kann es sich um mehrwertige Alkohole, insbesondere Diole bzw. Glycole, handeln. Bevorzugt werden hier Diethylenglycol und Triethylenglycol verwendet.For a better and uniform solution of the developing agent in the solvent, a solubilizer can be used. These may be polyhydric alcohols, in particular diols or glycols. Diethylene glycol and triethylene glycol are preferably used here.

Schließlich wird die Qualität des Entwicklungsergebnisses auch durch ein Antischleiermittel verbessert. Besonders eignen sich Mittel, die zur Gruppe der Azole (insbesondere vom Typ Benzotriazol, vom Typ Indazol, vom Typ Mercaptotetrazol und vom Typ Imidazol) gehören, insbesondere 5-Mercapto-1-phenyl-1,2,3,4-tetrazol (PMT), 1-H-Benzotriazol, 5-Methylbenzotriazol, 6-Nitrobenzimidazol, 5-Nitroindazol.Finally, the quality of the development result is also improved by an antifoggant. Particularly suitable are agents belonging to the group of azoles (in particular of the benzotriazole, indazole, mercaptotetrazole and imidazole type), in particular 5-mercapto-1-phenyl-1,2,3,4-tetrazole (PMT ), 1-H-benzotriazole, 5-methylbenzotriazole, 6-nitrobenzimidazole, 5-nitroindazole.

Die nachstehenden Tabellen der Zusammensetzungen von Ausführungsbeispielen geben einen Überblick über die Konzentration, in welcher die verschiedenen Komponenten in einer Gebrauchslösung in Gramm pro Liter Gebrauchslösung vorliegen können.The tables below of the compositions of embodiments give an overview of the concentration in which the various components in a Use solution in grams per liter of working solution may be present.

Dabei sind jeweils die Konzentrationen angegeben, die empfohlen werden, wenn eine betrachtete Komponente allein das entsprechende Mittel bildet. Es versteht sich, dass man von Substanzen, die gleichermaßen für die gleiche Komponente des Entwicklers in Frage kommen, auch Mischungen verwenden kann, wobei dann die Einsatzmengen so gewählt werden, dass die entsprechende Gesamtwirkung erhalten wird. So ist zum Beispiel gemäß der folgenden Tabelle für die verschiedenen Komplexierungsmittel jeweils die selbe Einsatzmenge angegeben. In diesem Falle kann man dann einfach den weggelassenen Anteil eines Komplexierungsmittels durch eine entsprechende Menge eines anderen Komplexierungsmittels ersetzen.In each case, the concentrations are recommended, which are recommended if a considered component alone forms the corresponding agent. It is understood that it is also possible to use mixtures of substances that are equally suitable for the same component of the developer, in which case the amounts used are selected such that the corresponding overall effect is obtained. Thus, for example, according to the following table for the different complexing agents in each case the same amount used. In this case, one can then simply replace the omitted portion of a complexing agent with an appropriate amount of another complexing agent.

Für das pH-Einstellmittel sind dagegen die Einsatzmengen für die verschiedenen genannten Substanzen sehr unterschiedlich. Man erkennt, dass man zum Ersetzen einer vorgegebenen Menge an Natriumtretraborat eine Menge an Kaliumcarbonat verwenden muss, die etwas das sieben- bis neunfache der zu ersetzenden Menge Natriumtretraborat beträgt.For the pH adjusting agent, however, the amounts used for the various substances mentioned are very different. It will be appreciated that to replace a given amount of sodium tetraborate, one must use an amount of potassium carbonate that is about seven to nine times the amount of sodium tetraborate to be replaced.

Nachstehend werden bevorzugte praktische Ausführungsbeispiele für erfindungsgemäße Entwickler beschrieben.Hereinafter, preferred practical embodiments for developers according to the present invention will be described.

Beispiel 1: Entwickler für Röntgenfilm-Entwicklungsaufautomaten Example 1: Developer for X-ray film processor

Bestandteilcomponent Mengeamount [g/Liter Gebrauchslösung][g / liter working solution] Wasserwater ad 1000 mlad 1000 ml Dissolvine D 88 Art.Nr. 848534 (*)Dissolvine D 88 Art.No. 848534 (*) 6,6606,660 Kaliumsulfit (45%)Potassium sulfite (45%) 109,840109.840 Kaliumcarbonatpotassium carbonate 283,340283.340 Diethylenglycoldiethylene glycol 73,34073.340 Dimezone SDimezone S 5,6605,660 1-Phenyl-5-mercapto-tetrazol1-phenyl-5-mercapto-tetrazole 0,0330.033 Ascorbinsäureascorbic acid 93,34093.340 Kaliumbromidpotassium 6,6606,660 Kalilauge 45%-ig, technischPotassium hydroxide 45%, technical 6,6606,660 (*) Diethylendiaminpentaessigsäure-Na(*) Diethylenediamine pentaacetic acid Na 55 -Salz-Salt

Beispiel 2: Entwickler für Röntgenfilm-Entwicklungsautomaten Example 2 Developer for X-ray Film Developers

Bestandteilcomponent Mengeamount [g/Liter Gebrauchslösung][g / liter working solution] Wasserwater ad 1000 mlad 1000 ml NaEDTANaEDTA 2,02.0 Kaliumhydrogensulfitpotassium hydrogen 15,315.3 Kaliumcarbonatpotassium carbonate 60,060.0 NatriumtetraboratSodium tetraborate 8,08.0 Triethylenglycoltriethylene 20,020.0 Ascorbinsäureascorbic acid 25,025.0 Natrium-IsoascorbatSodium isoascorbate 20,020.0 Natriumbromidsodium 4,54.5 5-Methylbenzotriazol5-methylbenzotriazole 0,30.3

Beispiel 3: Entwickler für Röntgenfilm-Entwicklungsautomaten Example 3 Developer for X-ray Film Developers

Bestandteilcomponent Mengeamount [g/Liter Gebrauchslösung][g / liter working solution] Wasserwater ad 1000 mlad 1000 ml Diethylentriaminpentaethansäurediethylenetriamine pentaacetic 1,761.76 Kaliumhydrogensulfitpotassium hydrogen 14,8314.83 Kaliumcarbonat (Pottasche)Potassium carbonate (potash) 75,0075.00 Kaliumhydroxidpotassium hydroxide 1,901.90 Diethylenglycoldiethylene glycol 22,022.0 Ascorbinsäure (BP2000/USP25)Ascorbic acid (BP2000 / USP25) 38,0038,00 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinon4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone 1,701.70 Kaliumbromidpotassium 2,002.00 5-Mercapto-1-phenyl-1,2,3,4-tetrazol5-mercapto-1-phenyl-1,2,3,4-tetrazole 0,10.1

Beispiel 4: Entwicklerfamilie für Röntgenfilm-Entwicklungsautomaten Example 4 Developer Family for X-Ray Film Developers

Bestandteilcomponent Mengenbereichquantity range [g/Liter Gebrauchslösung][g / liter working solution] Wasserwater ad 1000 mlad 1000 ml Na5DTPANa 5 DTPA 1,00 bis 3,001.00 to 3.00 Kaliumsulfitpotassium 8,00 bis 19,008.00 to 19.00 Kaliumcarbonatpotassium carbonate 65,00 bis 95,0065.00 to 95.00 Diethylenglycoldiethylene glycol 20,00 bis 25,0020.00 to 25.00 Dimezone SDimezone S 1,00 bis 2,301.00 to 2.30 Ascorbinsäureascorbic acid 20,00 bis 35,0020.00 to 35.00 Kaliumbromidpotassium 1,00 bis 4,001.00 to 4.00 Kaliumhydroxidpotassium hydroxide 2,00 bis 4,002.00 to 4.00

Die nachstehende Tabelle gibt unterschiedlich bevorzugte Bereiche für Komponenten eines erfindungsgemäßen Entwicklers an. Unterschiedliche Komponenten, die die gleiche Funktion haben können auch in Kombination verwendet werden, wobei die Mengen so angepaßt werden, das der gewünschte Gesamteffekt erhalten wird. Funktionsbeschreibung Komponenten Einsatzmenge Einsatzmenge bevorzugt Einsatzmenge besonders bevorzugt Handelsname in g/L Gebrauchslösung in g/L Gebrauchslösung in g/L Gebrauchslösung Lösungsmittel Wasser Komplexierungsmittel DTPA 0,8-3,0 0,8-2,5 0,8-2,5 EDTA-Salze 0,8-3,0 0,8-2,5 0,8-2,5 HEDTA 0,8-3,0 0,8-2,5 0,8-2,5 NTA 0,8-3,0 0,8-0,5 0,8-2,5 Oxidationsschutzmittel Kaliumhydrogensulfit 7,0-22,0 7,0-22,0 11,0-17,0 Kaliumdisulfit 4,0-12,0 8,0-12,0 8,0-12,0 Natriumbisulfit 7,0-22,0 7,0-22,0 11,0-17,0 Alkali / pH-Regulator Kaliumcarbonat 35,0-95,0 50,0-95,0 60,0-95,0 Borax 5,0-10,0 5,0-10,0 5,0-10,0 Natriummetaborat 5,0-13,0 5,0-13,0 8,0-13,0 Kaliumhydroxid 0,0-25,0 0,0-25,0 0,0-25,0 Natriumhydroxid 0,0-25,0 0,0-25,0 0,0-25,0 Lösungsvermittler Diethylenglycol 5,0-25,0 5,0-25,0 10,0-25,0 Triethylenglycol 5,0-25,0 5,0-25,0 10,0-25,0 Entwicklersubstanz Ascorbinsäure 15,0-45,0 15,0-45,0 22,0-40,0 Isoascorbinsäure 20,0-40,0 15,0-45,0 22,0-40,0 Dimezone S 1,0-4,0 1,0-4,0 1,0-3,0 Phenidon A 1,0-4,0 1,0-4,0 1,0-3,0 Phenidon B 1,0-4,0 1,0-4,0 1,0-3,0 Entwicklungsverzögerer Kaliumbromid 1,0-4,5 1,0-4,5 1,0-4,5 Natriumbromid 1,0-4,5 1,0-4,5 1,0-4,5 Antischleiermittel PMT 0,05 - 0,40 0,05 - 0,40 0,05 - 0,40 1 H-Benzotriazol 0,08 - 0,30 0,08 - 0,30 0,08 - 0,30 5-Methyl-1H-benzotriazol 0,08 - 0,30 0,08 - 0,30 0,08 - 0,30 6-Nitrobenzimidazol 0,20 - 0,45 0,20 - 0,45 0,20 - 0,45 5-Nitroindazol 0,20 - 0,45 0,20 - 0,45 0,20 - 0,45 The table below indicates differently preferred ranges for components of a developer according to the invention. Different components having the same function may also be used in combination, with the amounts adjusted to give the desired overall effect. function Description components amount used Use amount preferred Use amount particularly preferred trade name in g / L working solution in g / L working solution in g / L working solution solvent water complexing DTPA 0.8-3.0 0.8-2.5 0.8-2.5 EDTA salts 0.8-3.0 0.8-2.5 0.8-2.5 HEDTA 0.8-3.0 0.8-2.5 0.8-2.5 NTA 0.8-3.0 from 0.8 to 0.5 0.8-2.5 Antioxidants potassium hydrogen 7.0 to 22.0 7.0 to 22.0 11.0 to 17.0 called potassium 4.0 to 12.0 8.0-12.0 8.0-12.0 sodium bisulfite 7.0 to 22.0 7.0 to 22.0 11.0 to 17.0 Alkali / pH regulator potassium carbonate 35.0 to 95.0 50.0 to 95.0 60.0 to 95.0 borax 5.0-10.0 5.0-10.0 5.0-10.0 sodium metaborate 5.0 to 13.0 5.0 to 13.0 8.0-13.0 potassium hydroxide 0.0 to 25.0 0.0 to 25.0 0.0 to 25.0 sodium hydroxide 0.0 to 25.0 0.0 to 25.0 0.0 to 25.0 solubilizers diethylene glycol 5.0 to 25.0 5.0 to 25.0 10.0-25.0 triethylene 5.0 to 25.0 5.0 to 25.0 10.0-25.0 developing substance ascorbic acid 15.0 to 45.0 15.0 to 45.0 22.0 to 40.0 isoascorbic 20.0 to 40.0 15.0 to 45.0 22.0 to 40.0 Dimezone S 1.0-4.0 1.0-4.0 1.0-3.0 Phenidone A 1.0-4.0 1.0-4.0 1.0-3.0 Phenidone B 1.0-4.0 1.0-4.0 1.0-3.0 development restrainer potassium 1.0-4.5 1.0-4.5 1.0-4.5 sodium 1.0-4.5 1.0-4.5 1.0-4.5 Antifoggants PMT 0.05-0.40 0.05-0.40 0.05-0.40 1 H-benzotriazole 0.08 - 0.30 0.08 - 0.30 0.08 - 0.30 5-methyl-1H-benzotriazole 0.08 - 0.30 0.08 - 0.30 0.08 - 0.30 6-nitrobenzimidazole 0.20 - 0.45 0.20 - 0.45 0.20 - 0.45 5-nitroindazole 0.20 - 0.45 0.20 - 0.45 0.20 - 0.45

Die oben beschriebenen Entwickler der Beispiele 1 bis 4 wurden in einem Entwicklungsautomaten für Röntgenfilme getestet, der unter der Bezeichnung 'Dürr-Automat 24PRO' vermarktet wird. Es handelt sich hierbei um eine Rollenmaschine, in welcher die Röntgenfilme durch zusammenarbeitende Rollenpaare nacheinander durch einen Tank mit Entwicklerflüssigkeit, einen Fixiertank und einen Wässerungstank bewegt werden. Der Automat ist im wesentlichen allseitig geschlossen, steht jedoch über einen Filmeinlass-Schlitz und einen Filmauslass-Schlitz mit der Umgebungsatmosphäre in Verbindung.The above-described developers of Examples 1 to 4 were tested in an X-ray film developing machine marketed under the name 'Dürr Automat 24PRO'. This is a roller machine in which the X-ray films are moved through cooperating pairs of rollers successively through a tank with developer liquid, a fixing tank and a watering tank. The machine is substantially closed on all sides but communicates with the ambient atmosphere via a film inlet slot and a film outlet slot.

Im Dauerbetrieb wurden mit den oben beschriebenen Entwicklern Standzeiten von bis zu sechs Wochen erzielt.In continuous operation, the developers described above achieved service lives of up to six weeks.

Die Konzentrationsangaben in der obigen Beschreibung und den Ansprüchen beziehen sich, wie angegeben, auf einen Liter Gebrauchslösung und nicht auf das Konzentrat. Die Konzentrationen im Konzentrat sind gemäß dem vorgeschriebenen Verdünnungsverhältnis für das Konzentrat größer. Dieses Verdünnungverhältnis liegt für einen praktischen Entwickler für Rollen-Entwicklungsmaschinen bei etwa 1,5 zu 5, für rollenfreie Entwicklungsmaschinen (Film wird an den Rändern geführt durch die Tanks bewegt) bei etwa 0,5 zu 1.The concentration data in the above description and claims refer, as indicated, to one liter of working solution and not to the concentrate. The concentrations in the concentrate are greater according to the prescribed dilution ratio for the concentrate. This dilution ratio is about 1.5 to 5 for a practical developer for roll-fed development machines, and about 0.5 to 1 for roll-free processors (film is moved around the edges by the tanks).

Claims (1)

  1. A developer solution for photosensitive film material, having a water-based solvent, having an adjusting agent, which adjusts the pH value of the solvent into the alkaline range, and having a developer, the developer comprising ascorbic acid or a salt of ascorbic acid and the pH value being adjusted such that the pH value of the working solution obtained by dilution is between approximately 8.5 and approximately 12, characterised in that its composition corresponds to one of the four tables below: Example 1: Developer for automatic X-ray film developing units Constituent Quantity (g/litre of working solution) Water to make up to 1000 ml Dissolvine D 88, item no. 848534 (*) 6.660 Potassium sulfite (45%) 109.840 Potassium carbonate 283.340 Diethylene glycol 73.340 Dimezone-S 5.660 1-phenyl-5-mercapto-tetrazole 0.033 Ascorbic acid 93.340 Potassium bromide 6.660 Potassium hydroxide solution, 45%, technical grade 6.660 (*) Diethylenediamine pentaacetic acid Na 5 salt
    Example 2: Developer for automatic X-ray film developing units Constituent Quantity (g/litre of working solution) Water to make up to 1000 ml NaEDTA 2.0 Potassium hydrogen sulfite 15.3 Potassium carbonate 60.0 Sodium tetraborate 8.0 Triethylene glycol 20.0 Ascorbic acid 25.0 Sodium isoascorbate 20.0 Sodium bromide 4.5 5-Methylbenzotriazole 0.3
    Example 3: Developer for automatic X-ray film developing units Constituent Quantity (g/litre of working solution) Water to make up to 1000 ml Diethylenetriamine pentaethanoic acid 1.76 Potassium hydrogen sulfite 14.83 Potassium carbonate (potash) 75.00 Potassium hydroxide 1.90 Diethylene glycol 22.0 Ascorbic acid (BP2000/USP25) 38.00 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone 1.70 Potassium bromide 2.00 5-mercapto-1-phenyl-1,2,3,4-tetrazole 0.1
    Example 4: Developer family for automatic X-ray film developing units Constituent Quantity range (g/litre of working solution) Water to make up to 1000 ml Na5DTPA 1.00 to 3.00 Potassium sulfite 8.00 to 19.00 Potassium carbonate 65.00 to 95.00 Diethylene glycol 20.00 to 25.00 Dimezone-S 1.00 to 2.30 Ascorbic acid 20.00 to 35.00 Potassium bromide 1.00 to 4.00 Potassium hydroxide 2.00 to 4.00
EP07010793A 2006-06-04 2007-05-31 Developer concentrate Not-in-force EP1862852B1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU669142B2 (en) 1991-12-02 1996-05-30 E.I. Du Pont De Nemours And Company Improved developer systems for hydrazine containing films
US5858611A (en) * 1994-10-14 1999-01-12 Fuji Photo Film Co., Ltd. Development processing method of silver halide black-and-white photographic material
JPH08201991A (en) 1995-01-23 1996-08-09 Fuji Photo Film Co Ltd Image forming method
JP3406108B2 (en) 1995-02-03 2003-05-12 富士写真フイルム株式会社 Image forming method
JPH09197630A (en) 1996-01-24 1997-07-31 Fuji Photo Film Co Ltd Developer for halogenated silver photographic material and developing method using this developer
JPH09197628A (en) 1996-01-24 1997-07-31 Fuji Photo Film Co Ltd Image forming method
JPH09265161A (en) 1996-01-24 1997-10-07 Fuji Photo Film Co Ltd Image forming method
JPH09265162A (en) 1996-01-24 1997-10-07 Fuji Photo Film Co Ltd Image forming method
JPH10171076A (en) 1996-02-07 1998-06-26 Fuji Photo Film Co Ltd Image forming method
DE69804402D1 (en) * 1997-10-06 2002-05-02 Agfa Gevaert Nv Process for processing a black and white silver halide photographic material
GB9814304D0 (en) * 1998-07-01 1998-09-02 Eastman Kodak Co Method of processing a photographic high contrast silver halide material
DE19834357A1 (en) * 1998-07-30 2000-02-17 Agfa Gevaert Ag Photographic black-and-white processing with ascorbic acid or derivative in developer, useful for film and paper, uses oligophosphate in stop or stop-fix bath

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DK1862852T3 (en) 2010-03-22
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ATE447727T1 (en) 2009-11-15
DE102006026422A1 (en) 2007-12-06

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