EP0321839A2 - Bleaching bath with bleach accelerating substances - Google Patents

Bleaching bath with bleach accelerating substances Download PDF

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Publication number
EP0321839A2
EP0321839A2 EP88120873A EP88120873A EP0321839A2 EP 0321839 A2 EP0321839 A2 EP 0321839A2 EP 88120873 A EP88120873 A EP 88120873A EP 88120873 A EP88120873 A EP 88120873A EP 0321839 A2 EP0321839 A2 EP 0321839A2
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Prior art keywords
bleaching
bleach
alkyl
cycloalkyl
aryl
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German (de)
French (fr)
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EP0321839A3 (en
EP0321839B1 (en
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Peter Dr. Bergthaller
Helmut Häseler
Heinz Dr. Meckl
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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
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
    • G03C7/421—Additives other than bleaching or fixing agents

Definitions

  • the invention relates to bleaching baths for processing an exposed color photographic light-sensitive silver halide material in which the bleaching function is accelerated, as a result of which the processing time is shortened and also difficult to bleach image silver can be completely bleached.
  • the minimum densities are reduced for reversible materials.
  • the basic stages of processing color photosensitive materials generally include a color development stage and a silver removal stage. In the case of reversal materials, there is also an upstream black / white development and a second exposure. In the last stage, the silver produced during development is oxidized with a bleaching agent and dissolved with a fixing agent.
  • the removal of the silver can be carried out in two stages with a bleaching bath and a fixing bath or in one stage with a bleach-fixing bath.
  • the bleaching process is predominantly carried out using an iron (III) ion complex salt (for example aminopolycarboxylic acid iron (III) complex salt, in particular iron (III) ethylenediaminetetraacetate complex salt).
  • iron (III) ion complex salt for example aminopolycarboxylic acid iron (III) complex salt, in particular iron (III) ethylenediaminetetraacetate complex salt.
  • Iodoso compounds, persulfates, cobalt (III) ion complex salts and cerium IV ion complex salts are also suitable.
  • iron (III) ion complex salts have a comparatively low oxidizing power. There has been a need, therefore, to increase the bleaching power of a bleaching solution or bleach-fixing solution containing a bleaching agent with a low bleaching power, in particular an iron (III) ion complex salt.
  • bleach accelerators examples include thiourea derivatives (JP-OS 8506/70, US Pat. No. 3,706,561), selenourea derivatives (JP-OS 280/71), mercapto compounds with a five-membered ring (GB-PS 1 138 842), thiazole derivatives and thiadiazole derivatives ( CH-PS 336 257).
  • 5-Mercaptotetrazole has also been used as an accelerating agent for the removal of silver in a bleaching Fixing solution used (GB-PS 1 138 842). However, these compounds have weak accelerating power, poor solubility, or poor stability in the processing solution.
  • DE-OS 3 518 257 describes the bleaching accelerating effect of compounds of the formulas where R19 to R20 are hydrogen, alkyl, acyl or together the remaining members of a ring, m and l are an integer 1 to 3.
  • bleach-fixing baths based on iron-III-EDTA are usually used after the first development, the second exposure and the color development to remove silver from the paper.
  • bleach accelerators are added to the Bleach-fix bath required to effect bleaching sufficiently quickly and completely.
  • compounds such as 3-mercapto-1,2,4-triazole or 5-amino-2-mercapto-1,3,4-triadiazole are used successfully.
  • bleach accelerators in the bleach-fixer has also proven to be useful for color negative paper. If the bleaching is inadequate, residual amounts of silver remain in the materials, which in the case of the mostly IR-controlled cutting device can lead to incorrect information, by which the image strip is not cut between the images but in the middle of the images.
  • bleach-fixing bath namely bleaching bath and fixing bath
  • bleach accelerators cannot be used because they no longer have a sufficient, accelerating effect in the bleaching bath, and because some of them do not are sufficiently soluble or cause sediments.
  • bleach accelerator Without bleach accelerator, the insufficiently bleached photo papers show considerable residual silver content in the dark areas of the image, which cannot be significantly reduced even by a longer bath time.
  • the object of the present invention is to provide bleaching or bleach-fixing baths, preferably bleaching baths, which are stable and have an excellent bleaching rate and do not form any sediment. They are intended to ensure low minimum densities in the case of reversal materials during the usual processing times and to completely bleach the residual silver in the blacks in the case of color negative papers. Other photographic properties should not be deteriorated.
  • bleaching or bleach-fixing baths which contain an iron (III) ion complex salt as bleaching agent are a 5- to 7-membered heterocyclic, at least one N- and at least one further heteroatom from the series O, N, S containing compound, which is substituted by -S ⁇ and carries a positive charge on a quaternary ring nitrogen atom, arranged in such a way that tautomeric charge balance to a neutral thione form is not possible.
  • R2 is hydrogen, C1-C8-alkyl, C2-C8-alkenyl, heteroaryl, C5-C10-cycloalkyl and C6-C12-aryl, C1-C8-dialkylamino, optionally containing a hydrophilizing group
  • R4 C1-C8-alkyl, heteroaryl, C5-C10-cycloalkyl and C6-C12-aryl, optionally containing a hydrophilizing group
  • R5 is hydrogen, di-C1-C8-alkylamino, C1-C8-alkyl, C2-C8-alkenyl, heteroaryl, C5-C10-cycloalkyl and C6-C12-aryl, optionally containing a hydrophilizing group, mean, where R4 and R5 together can be the groups required to complete a heterocyclic ring; and Formula IV in the R6 C1-C8-alkyl, heteroaryl, C5-C10-cycloalkyl and C6-C12-aryl, optionally containing a hydrophilizing group, R7 is hydrogen, di-C1-C8-alkylamino, C1-C8-alkyl, C2-C8-alkenyl
  • Sulfonamido stands for compounds of the general formula R15-SO2-NH-, where R15 is hydrogen, C1-C8-alkyl, C5-C7-cycloalkyl, C6-C12-aryl or heteroaryl.
  • Sulfamoylamino stands for compounds of the general formula R16R17N-SO2-NH-, where R16 and R17 are the same or different and are hydrogen, C1-C8-alkyl, C5-C6-cycloalkyl, C6-C12-aryl or heteroaryl.
  • Acylamino stands for compounds of the general formula R18-CO-NH-, where R18 is hydrogen, C1-C8-alkyl, C5-C7-cycloalkyl, C6-C12-aryl or heteroaryl.
  • Heteroaryl in general represents a five- or six-membered optionally benzo-fused heteroaromatic ring containing 1 to 3 heteroatoms from the series N, O and S.
  • Hydrophilizing group is understood to mean the following structures: COOH, SO3H, PO (OH) 2, CH2OH, - (O-CH2-CH2) 2 ⁇ 20-OH.
  • Triazolium thiolates according to formula I are known from US 4,631,253 and the common preparation methods are described there.
  • Examples of thiadiazolium thiolates according to formulas II and III and their representation are from Grashey, Baumann and Lubos, Tetrahedron Letters 1968, 5881 and Kier, Scott, J. Heterocycl. Chem. 5, 277, (1968).
  • the oxadiazolium thiolates according to formulas IV are described by McCarthy, Ollis and Ramsden in J. Chem. Soc., Perkin Trans. I 1974, 627.
  • Thiazolium thiolates of the formula V and imidozolium thiolates of the formula VI are published by Huisgen et al in THL 1967, 1809-14.
  • the amount of the compound of the present invention in the bleaching and bleach-fixing baths varies depending on the kind of the processing solution, the kind of the photographic material to be processed, the processing temperature, the time required to perform the desired processing, etc. However, an amount is 1 x 10 ⁇ 5 to 1 mole per liter of bleaching or bleach-fixing bath is suitable, 1 x 10 ⁇ 3 to 1 x 10 Mol1 mol being preferred. In general, the best range is determined by simple preliminary tests.
  • the compound to be used according to the invention can be added directly to the bleaching or bleach-fixing bath or introduced through an upstream conditioning bath.
  • the bleaching baths according to the invention can also be used in rapid processing processes with development times of less than 60 seconds, the color photographic recording materials used there having chloride-rich silver halide emulsion layers (at least 80 mol% AgCl).
  • Suitable iron (III) ion complex salts are complexes of iron (III) ions and a chelating agent such as an aminopolycarboxylic acid, an aminopolyphosphonic acid or a salt thereof, in particular an alkali metal salt or ammonium salt.
  • Typical examples of chelating agents are ethylenediaminetetraacetic acid; Disodium ethylenediaminetetraacetate; Diammonium ethylenediaminetetraacetate; Tetra (trimethylammonium) ethylenediaminetetraacetate; Tetrapotassium ethylenediaminetetraacetate; Tetrasodium ethylenediaminetetraacetate; Trisodium ethylenediaminetetraacetate; Diethylenetriaminepentaacetic acid; Pentasodium diethylenetriaminepentaacetate; Ethylenediamine-N- ( ⁇ -hydroxyethyl) -N, N ′, N′-triacetic acid; Trisodium ethylenediamine-N- ( ⁇ -hydroxyethyl) -N, N ′, N′-triacetate; Triammonium ethylenediamine-N- ( ⁇ -hydroxyethyl) -N, N ′, N′-triacetate; Propyl
  • the iron (III) ion complex salt can be used in the form of the complex salt or prepared in situ in the bleach or bleach-fix bath. Suitable cations are alkali cations and ammonium; the latter is preferred.
  • the bleaching solution of the present invention may contain rehalogenating agents such as bromides (e.g. potassium bromide, sodium bromide, ammonium bromide, etc.), chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride, etc.) and the like in addition to the bleaching agents.
  • rehalogenating agents such as bromides (e.g. potassium bromide, sodium bromide, ammonium bromide, etc.), chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride, etc.) and the like in addition to the bleaching agents.
  • additives which have a pH buffering action such as inorganic acids, organic acids or the salts thereof, which are known for use in conventional bleaching solutions (for example boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid , Phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid,
  • the pH of the bleaching solution is preferably 3.0 to 8.0, in particular 4.0 to 7.0.
  • conventional fixing agents ie water-soluble, silver halide dissolving agents, such as thiosulfate (eg sodium thiosulfate, ammonium thiosulfate, ammonium sodium thiosulfate, potassium thiosulfate, etc.); Thiocyanates (eg sodium thiocyanate; Ammonium thiocyanate; Potassium thiocyanate, etc.); Thioether compounds (e.g. ethylene bisthioglycolic acid, 3,6-dithia-1,8-octanediol, etc.); and thioureas can be used alone or in a combination of two or more.
  • special bleach-fixing agents containing a combination of a fixing agent and a large amount of a halide compound such as potassium iodide can also be used.
  • the ferric ion complex salt is usually present in an amount of 0.1 to 1 mol / l.
  • the amount of the fixing agent is generally 0.2 to 4 mol per liter of the bleach-fixing solution.
  • Bleach-fix solutions can also contain preservatives such as sulfites (e.g. sodium sulfite, potassium sulfite, ammonium sulfite, etc.), hydroxylamine, hydrazine, aldehyde-bisulfite adducts (e.g. acetaldehyde sodium bisulfite adduct), etc.
  • sulfites e.g. sodium sulfite, potassium sulfite, ammonium sulfite, etc.
  • hydroxylamine e.g. sodium sulfite, potassium sulfite, ammonium sulfite, etc.
  • hydroxylamine e.g. sodium sulfite, potassium sulfite, ammonium sulfite, etc.
  • hydroxylamine e.g. sodium sulfite, potassium sulfite, ammonium sulfite, etc.
  • hydroxylamine e.
  • the pH of the bleach-fix solution when used is usually 4.0 to 9.0, particularly preferably 5.0 to 8.0.
  • a color negative paper with a silver chloride bromide emulsion (80% AgBr and 20% AgCl) is exposed behind a step wedge and processed as follows: Color developer 210 sec. 33 ° C Watering 20 sec. 20 ° C Wiping the water off the surface of the pictures Bleach bath 50 sec. 20 ° C Watering 60 sec. 20 ° C Fixer 60 sec. 20 ° C Watering 120 sec. 20 ° C dry
  • the step wedges shown are examined with a PM 8030 infrared silver detector from Photo-Matic, Denmark.
  • the table below shows whether residual silver is still present in the blackening after using the freshly prepared bleaching bath.
  • the resistance of the bleaching bath was tested after 4 and 15 days of standing at 33 ° C.
  • sediment formation was assessed after 15 days of inactivity, which can occur especially when a bleach bath containing silver ions is in use.
  • Example 1 is repeated, 2.2 g of thioglycerol / l being added to the bleaching bath as the reference substance.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

Bleaching baths and bleach-fixing baths, which contain an iron(III) ion complex salt as bleaching agent and additionally a 5- to 7-membered heterocyclic compound which contains at least one N atom and at least one further hetero atom from the series O, N, S and which is substituted by -S<(-)> and carries a positive charge on the quaternary ring nitrogen atom, arranged in such a way that no tautomeric charge compensation to give a neutral thione form is possible, ensure, due to an excellent bleaching rate and simultaneously good stability, good bleaching in colour materials within the usual processing times, that is to say they ensure blackening without residual silver in colour negative materials and low minimum densities in colour reversal materials.

Description

Die Erfindung betrifft Bleichbäder zur Verarbeitung eines belichteten farbfotografischen lichtempfindlichen Silberhalogenidmaterials, bei dem die Bleichfunktion be­schleunigt ist, wodurch die Verarbeitungszeit abgekürzt wird und auch schwerbleichbares Bildsilber vollständig gebleicht werden kann. Bei Umkehrmaterialien werden die Minimaldichten verringert.The invention relates to bleaching baths for processing an exposed color photographic light-sensitive silver halide material in which the bleaching function is accelerated, as a result of which the processing time is shortened and also difficult to bleach image silver can be completely bleached. The minimum densities are reduced for reversible materials.

Die grundlegenden Stufen der Verarbeitung von lichtemp­findlichen Farbmaterialien umfassen allgemein eine Farb­entwicklungsstufe und eine Silber-Entfernungsstufe. Bei Umkehrmaterialien kommen noch eine vorgeschaltete Schwarz/Weiß-Entwicklung und eine Zweitbelichtung hin­zu.
In der letzten Stufe wird das bei der Entwicklung er­zeugte Silber mit einem Bleichmittel oxidiert und mit einem Fixiermittel gelöst.The basic stages of processing color photosensitive materials generally include a color development stage and a silver removal stage. In the case of reversal materials, there is also an upstream black / white development and a second exposure.
In the last stage, the silver produced during development is oxidized with a bleaching agent and dissolved with a fixing agent.

Die Entfernung des Silbers kann zweistufig mit einem Bleichbad und einem Fixierbad oder einstufig mit einem Bleich-Fixier-Bad durchgeführt werden.The removal of the silver can be carried out in two stages with a bleaching bath and a fixing bath or in one stage with a bleach-fixing bath.

Die Bleichverarbeitung wird überwiegend unter Verwendung eines Eisen(III)-ionenkomplexsalzes (zum Beispiel Amino­polycarbonsäure-Eisen(III)-komplexsalz, insbesondere Eisen(III)-ethylendiamintetraacetat-komplexsalz) durch­geführt. Auch Iodosoverbindungen, Persulfate, Kobalt­(III)ionenkomplexsalze sowie Cer-IV-ionenkomplexsalze sind geeignet.The bleaching process is predominantly carried out using an iron (III) ion complex salt (for example aminopolycarboxylic acid iron (III) complex salt, in particular iron (III) ethylenediaminetetraacetate complex salt). Iodoso compounds, persulfates, cobalt (III) ion complex salts and cerium IV ion complex salts are also suitable.

Jedoch weisen Eisen(III)-ionenkomplexsalze eine ver­gleichsweise geringe Oxidationskraft auf. Es bestand daher ein Bedürfnis, die Bleichkraft einer Bleichlösung oder Bleich-Fixier-Lösung, die ein Bleichmittel mit ge­ringer Bleichkraft, insbesondere ein Eisen(III)-ionen­komplexsalz enthält, zu erhöhen.However, iron (III) ion complex salts have a comparatively low oxidizing power. There has been a need, therefore, to increase the bleaching power of a bleaching solution or bleach-fixing solution containing a bleaching agent with a low bleaching power, in particular an iron (III) ion complex salt.

Um die Bleichkraft einer Bleichlösung oder Bleich-­Fixier-Lösung, die ein Eisen(III)-ionkomplexsalz wie Eisen(III)-ethylendiamintetraacetat als Bleichmittel enthält, zu erhöhen wurde vorgeschlagen, verschiedene Bleichbeschleuniger dem Verarbeitungsbad zuzusetzen.In order to increase the bleaching power of a bleaching solution or bleach-fixing solution which contains an iron (III) ion complex salt such as iron (III) ethylenediaminetetraacetate as a bleaching agent, it has been proposed to add various bleaching accelerators to the processing bath.

Beispiele für solche Bleichbeschleuniger umfassen Thio­harnstoffderivate, (JP-OS 8506/70, US-PS 3 706 561), Selenoharnstoffderivate (JP-OS 280/71), Mercaptover­bindungen mit fünfgliedrigem Ring (GB-PS 1 138 842), Thiazolderivate und Thiadiazolderivate (CH-PS 336 257). Außerdem worden 5-Mercaptotetrazole als beschleunigende Mittel für die Entfernung von Silber in einer Bleich-­ Fixier-Lösung verwendet (GB- PS 1 138 842). Jedoch wei­sen diese Verbindungen eine schwache beschleunigende Kraft, geringe Löslichkeit oder mangelnde Stabilität in der Verarbeitungslösung auf.Examples of such bleach accelerators include thiourea derivatives (JP-OS 8506/70, US Pat. No. 3,706,561), selenourea derivatives (JP-OS 280/71), mercapto compounds with a five-membered ring (GB-PS 1 138 842), thiazole derivatives and thiadiazole derivatives ( CH-PS 336 257). 5-Mercaptotetrazole has also been used as an accelerating agent for the removal of silver in a bleaching Fixing solution used (GB-PS 1 138 842). However, these compounds have weak accelerating power, poor solubility, or poor stability in the processing solution.

DE-OS 3 518 257 beschreibt die bleichbeschleunigende Wirkung von Verbindungen der Formeln

Figure imgb0001
wobei R¹⁹ bis R²⁰ Wasserstoff, Alkyl, Acyl oder gemein­sam die restlichen Glieder eines Ringes, m und l eine ganze Zahl 1 bis 3 bedeuten.DE-OS 3 518 257 describes the bleaching accelerating effect of compounds of the formulas
Figure imgb0001
 where R¹⁹ to R²⁰ are hydrogen, alkyl, acyl or together the remaining members of a ring, m and l are an integer 1 to 3.

Auch diese Verbindungen zeigen nur eine mäßige bleichbe­schleunigende Wirkung und sind für Color-Umkehrmateri­alien, insbesondere für Color-Umkehrpapier wenig ge­eignet.These compounds also show only a moderate bleaching accelerating effect and are not very suitable for color reversal materials, in particular for color reversal paper.

Bei der Colorumkehrpapier-Verarbeitung werden nach der Erstentwicklung, der Zweitbelichtung und der Farbent­wicklung zur Silberentfernung aus dem Papier üblicher­weise Bleichfixierbäder auf Basis Eisen-III-EDTA be­nutzt. Im Gegensatz zur Colornegativpapier-Verarbeitung sind hierbei Zusätze von Bleichbeschleunigern zum Bleichfixierbad erforderlich, um das Bleichen aus­reichend schnell und vollständig zu bewirken. Dazu werden Verbindungen wie 3-Mercapto-1,2,4-triazol oder 5-Amino-2-mercapto-1,3,4-triadiazol mit Erfolg benutzt.In color reversal paper processing, bleach-fixing baths based on iron-III-EDTA are usually used after the first development, the second exposure and the color development to remove silver from the paper. In contrast to color negative paper processing, bleach accelerators are added to the Bleach-fix bath required to effect bleaching sufficiently quickly and completely. For this, compounds such as 3-mercapto-1,2,4-triazole or 5-amino-2-mercapto-1,3,4-triadiazole are used successfully.

Aber auch bei Colornegativpapier hat sich der Einsatz von Bleichbeschleunigern im Bleichfixierbad als zweck­mäßig erwiesen. Bei unzureichendem Bleichen verbleiben Restsilbermengen in den Materialien, was bei dem meist IR-gesteuerten Schneidegerät zu Fehlinformationen führen kann, durch die der Bildstreifen nicht zwischen den Bildern sondern mitten durch die Bilder geschnitten wird.However, the use of bleach accelerators in the bleach-fixer has also proven to be useful for color negative paper. If the bleaching is inadequate, residual amounts of silver remain in the materials, which in the case of the mostly IR-controlled cutting device can lead to incorrect information, by which the image strip is not cut between the images but in the middle of the images.

Benutzt man statt eines Bleichfixierbades zwei getrennte Bäder, nämlich Bleichbad und Fixierbad, was wegen der leichteren Rückgewinnungsmöglichkeit des gelösten Sil­bers vorteilhaft sein kann, lassen sich diese Bleich­beschleuniger nicht benutzen, weil sie im Bleichbad keine ausreichende, beschleunigende Wirkung mehr haben, und weil sie teilweise nicht ausreichend löslich sind oder Sedimente verursachen. Ohne Bleichbeschleuniger zeigen die unzureichend gebleichten Photopapiere in den dunklen Bildpartien erhebliche Restsilbergehalte, die auch durch eine längere Badverweilzeit nicht wesentlich verringert werden können.If you use two separate baths instead of a bleach-fixing bath, namely bleaching bath and fixing bath, which can be advantageous because of the easier way of recovering the dissolved silver, these bleach accelerators cannot be used because they no longer have a sufficient, accelerating effect in the bleaching bath, and because some of them do not are sufficiently soluble or cause sediments. Without bleach accelerator, the insufficiently bleached photo papers show considerable residual silver content in the dark areas of the image, which cannot be significantly reduced even by a longer bath time.

Bei der Colorumkehrpapier-Verarbeitung ist üblicherweise in den Verarbeitungsmaschinen die Zahl der Chemikalien- und Wassertanks begrenzt. Bei getrenntem Bleichen und Fixieren erhöht sich die erforderliche Tankzahl ohnehin um 2, ein zusätzliches Conditionierbad, wie es beim Um­kehrfilm gebräuchlich ist, weil sich das üblicherweise verwendetet Conditioniermittel Thioglyzerin im Bleichbad sehr schnell zersetzt, würde sie um 3 Tanks erhöhen. Das ist in vielen Fällen ohne kostpielige Maschinenumbauten nicht möglich. Um die Zahl der Tanks möglichst gering zu halten, ist man deshalb bestrebt, ein zusätzliches Conditionierbad zu vermeiden.In color reversal paper processing, the number of chemical and water tanks is usually limited in the processing machines. With separate bleaching and fixing, the required number of tanks increases anyway by 2, an additional conditioning bath, as is customary with the reversal film, because the commonly used conditioning agent thioglycerin decomposes very quickly in the bleaching bath, it would increase by 3 tanks. In many cases, this is not possible without expensive machine conversions. In order to keep the number of tanks as low as possible, efforts are therefore made to avoid an additional conditioning bath.

Es besteht deshalb Interesse an Zusätzen zu Bleich­bädern, die so stark bleichbeschleunigend wirken, daß innerhalb der üblichen Bleichzeiten (1 bis 5 min) auf den Colorumkehrpapieren reine Weißen entstehen, und die zudem ausreichend beständig in den üblichen Eisen-III-­EDTA-Bleichbädern sind.There is therefore interest in additives for bleaching baths which act so strongly to accelerate the bleaching that pure whites are formed on the color reversal papers within the usual bleaching times (1 to 5 minutes) and which are also sufficiently stable in the conventional iron III-EDTA bleaching baths.

Aufgabe der vorliegenden Erfindung ist die Bereitstel­lung von Bleich- bzw. Bleichfixierbädern, vorzugsweise Bleichbädern, die stabil sind und eine ausgezeichnete Bleichgeschwindigkeit aufweisen und kein Sediment bil­den. Sie sollen bei Umkehrmaterialien bei den üblichen Verarbeitungszeiten für niedrige Minimaldichten und bei Colornegativpapieren für vollständige Bleichung des Restsilbers in den Schwärzen sorgen. Dabei sollen andere photographische Eigenschaften nicht verschlechtert werden.The object of the present invention is to provide bleaching or bleach-fixing baths, preferably bleaching baths, which are stable and have an excellent bleaching rate and do not form any sediment. They are intended to ensure low minimum densities in the case of reversal materials during the usual processing times and to completely bleach the residual silver in the blacks in the case of color negative papers. Other photographic properties should not be deteriorated.

Die Aufgabe wird dadurch gelöst, daß man Bleich- oder Bleichfixierbädern, die ein Eisen(III)-ionenkomplexsalz als Bleichmittel enthalten, eine 5- bis 7-gliedrige heterocyclische, wenigstens ein N- und wenigstens ein weiteres Heteroatom aus der Reihe O, N, S enthaltende Verbindung, die durch -S⊖ substituiert ist und an einem quartären Ringstickstoffatom eine positive Ladung trägt, derart angeordnet, daß ein tautomerer Ladungsausgleich zu einer neutralen Thionform nicht möglich ist, zu­setzt.The object is achieved in that bleaching or bleach-fixing baths which contain an iron (III) ion complex salt as bleaching agent are a 5- to 7-membered heterocyclic, at least one N- and at least one further heteroatom from the series O, N, S containing compound, which is substituted by -S ⊖ and carries a positive charge on a quaternary ring nitrogen atom, arranged in such a way that tautomeric charge balance to a neutral thione form is not possible.

Besonders bevorzugt sind Verbindungen der Formel I

Figure imgb0002
in der
R¹      C₁-C₈-Alkyl, Heteroaryl, C₅-C₁₀-Cycloalkyl und C₆-­C₁₂-Aryl, gegebenenfalls eine hydrophilierende Gruppe enthaltend,
R²      Wasserstoff, C₁-C₈-Alkyl, C₂-C₈-Alkenyl, Hetero­aryl, C₅-C₁₀-Cycloalkyl und C₆-C₁₂-Aryl, C₁-C₈-­Dialkylamino, gegebenenfalls eine hydrophilierende Gruppe enthaltend,
R³      Amino, Acylamino, C₁-C₈-Dialkylamino, Sulfonamido, Sulfamoylamino, C₁-C₈-Alkyl, C₂-C₈-Alkenyl, C₁-C₃-­Alkoxy-C₁-C₅-alkyl, C₅-C₁₀-Cycloalkyl und C₆-C₁₂-­Aryl, gegebenenfalls eine hydrophilierende Gruppe enthaltend,
bedeuten, wobei R¹ und R² bzw. R² und R³ gemeinsam die zur Vervollständigung eines heterocyclischen Rings er­forderlichen Gruppen sein können.Compounds of the formula I are particularly preferred
Figure imgb0002
 in the
R¹ C₁-C₈-alkyl, heteroaryl, C₅-C₁₀-cycloalkyl and C₆-C₁₂-aryl, optionally containing a hydrophilizing group,
R² is hydrogen, C₁-C₈-alkyl, C₂-C₈-alkenyl, heteroaryl, C₅-C₁₀-cycloalkyl and C₆-C₁₂-aryl, C₁-C₈-dialkylamino, optionally containing a hydrophilizing group,
R³ amino, acylamino, C₁-C₈-dialkylamino, sulfonamido, sulfamoylamino, C₁-C₈-alkyl, C₂-C₈-alkenyl, C₁-C₃-alkoxy-C₁-C₅-alkyl, C₅-C₁₀-cycloalkyl and C₆-C₁₂-aryl , optionally containing a hydrophilizing group,
mean, where R¹ and R² or R² and R³ together can be the groups required to complete a heterocyclic ring.

Weiterhin bevorzugt sind Verbindungen der Formeln II und III,

Figure imgb0003
in denen
R⁴      C₁-C₈-Alkyl, Heteroaryl, C₅-C₁₀-Cycloalkyl und C₆-­C₁₂-Aryl, gegebenenfalls eine hydrophilierende Gruppe enthaltend,
R⁵      Wasserstoff, Di-C₁-C₈-alkylamino, C₁-C₈-Alkyl, C₂-­C₈-Alkenyl, Heteroaryl, C₅-C₁₀-Cycloalkyl und C₆-C₁₂-Aryl, gegebenenfalls eine hydrophilierende Gruppe enthaltend,
bedeuten, wobei R⁴ und R⁵ gemeinsam die zur Vervoll­ständigung eines heterocyclischen Rings erforderlichen Gruppen sein können;
sowie der Formel IV
Figure imgb0004
 in der
R⁶      C₁-C₈-Alkyl, Heteroaryl, C₅-C₁₀-Cycloalkyl und C₆-­C₁₂-Aryl, gegebenenfalls eine hydrophilierende Gruppe enthaltend,
R⁷      Wasserstoff, Di-C₁-C₈-alkylamino, C₁-C₈-Alkyl, C₂-­C₈-Alkenyl, Heteroaryl, C₅-C₁₀-Cycloalkyl und C₆-C₁₂-Aryl, gegebenenfalls eine hydrophilierende Gruppe enthaltend,
bedeuten, wobei R⁶ und R⁷ gemeinsam die zur Vervoll­ständigung eines heterocyclischen Rings erforderlichen Gruppen sein können;
der Formel V
Figure imgb0005
 in der
R⁸      C₁-C₈ Alkyl, Heteroaryl, C₅-C₁₀ Cycloalkyl und C₆-C₁₂ Aryl, gegebenenfalls eine hydrophilierende Gruppe enthaltend,
R⁹ und R¹⁰      Wasserstoff, C₁-C₈ Alkyl, C₂-C₈ Alkenyl, Heteroaryl, C₅-C₁₀ Cycloalkyl und C₆-C₁₂-Aryl, gegebenenfalls eine hydrophilierende Gruppe enthaltend,
bedeuten, wobei R⁸ und R⁹ bzw. R⁸ und R¹⁰ gemeinsam die zur Vervollständigung eines heterocyclischen Rings er­forderlichen Gruppen sein können,
der Formel VI
Figure imgb0006
 in der
R¹¹ und R¹³ C₁-C₈ Alkyl, Heteroaryl, C₅-C₁₀ Cyclo­alkyl und C₆-C₁₂ Aryl, gegebenenfalls eine hydrophilierende Gruppe enthaltend
R¹² und R¹⁴ Wasserstoff, C₁-C₈-Alkyl, C₂-C₈ Alkenyl, Heteroaryl, C₅-C₁₀ Cycloalkyl und C₆-C₁₂ Aryl, gegebenenfalls eine hydrophilierende Gruppe enthaltend,
bedeuten, wobei R¹¹ und R¹⁴ bzw. R¹¹ und R¹² bzw. R¹² und R¹³ gemeinsam die zur Vervollständigung eines heterocyclischen Rings erforderlichen Gruppen sein können,
und der Formel
Figure imgb0007
 in der
R¹⁹ und R²⁰ C₁-C₃-Alkyl,
R²¹ Waserstoff und Methyl bedeuten.Compounds of the formulas II and III are furthermore preferred,
Figure imgb0003
 in which
R⁴ C₁-C₈-alkyl, heteroaryl, C₅-C₁₀-cycloalkyl and C₆-C₁₂-aryl, optionally containing a hydrophilizing group,
R⁵ is hydrogen, di-C₁-C₈-alkylamino, C₁-C₈-alkyl, C₂-C₈-alkenyl, heteroaryl, C₅-C₁₀-cycloalkyl and C₆-C₁₂-aryl, optionally containing a hydrophilizing group,
mean, where R⁴ and R⁵ together can be the groups required to complete a heterocyclic ring;
and Formula IV
Figure imgb0004
 in the
R⁶ C₁-C₈-alkyl, heteroaryl, C₅-C₁₀-cycloalkyl and C₆-C₁₂-aryl, optionally containing a hydrophilizing group,
R⁷ is hydrogen, di-C₁-C₈-alkylamino, C₁-C₈-alkyl, C₂-C₈-alkenyl, heteroaryl, C₅-C₁₀-cycloalkyl and C₆-C₁₂-aryl, optionally containing a hydrophilizing group,
mean, where R⁶ and R⁷ together can be the groups required to complete a heterocyclic ring;
Formula V
Figure imgb0005
 in the
R⁸ C₁-C₈ alkyl, heteroaryl, C₅-C₁₀ cycloalkyl and C₆-C₁₂ aryl, optionally containing a hydrophilizing group,
R⁹ and R¹⁰ are hydrogen, C₁-C₈ alkyl, C₂-C₈ alkenyl, heteroaryl, C₅-C₁₀ cycloalkyl and C₆-C₁₂ aryl, optionally containing a hydrophilizing group,
mean, where R⁸ and R⁹ or R⁸ and R¹⁰ together can be the groups required to complete a heterocyclic ring,
of formula VI
Figure imgb0006
 in the
R¹¹ and R¹³ C₁-C₈ alkyl, heteroaryl, C₅-C₁₀ cycloalkyl and C₆-C₁₂ aryl, optionally containing a hydrophilizing group
R¹² and R¹⁴ are hydrogen, C₁-C₈-alkyl, C₂-C₈ alkenyl, heteroaryl, C₅-C₁₀ cycloalkyl and C₆-C₁₂ aryl, optionally containing a hydrophilizing group,
mean, where R¹¹ and R¹⁴ or R¹¹ and R¹² or R¹² and R¹³ together can be the groups required to complete a heterocyclic ring,
and the formula
Figure imgb0007
 in the
R¹⁹ and R²⁰ C₁-C₃-alkyl,
R²¹ is hydrogen and methyl.

Sulfonamido steht für Verbindungen der allgemeinen Formel R¹⁵-SO₂-NH-, wobei R¹⁵ Wasserstoff, C₁-C₈-Alkyl, C₅-C₇-Cycloalkyl, C₆-C₁₂-Aryl oder Heteroaryl bedeutet. Sulfonamido stands for compounds of the general formula R¹⁵-SO₂-NH-, where R¹⁵ is hydrogen, C₁-C₈-alkyl, C₅-C₇-cycloalkyl, C₆-C₁₂-aryl or heteroaryl.

Sulfamoylamino steht für Verbindungen der allgemeinen Formel R¹⁶R¹⁷N-SO₂-NH-, wobei R¹⁶ und R¹⁷ gleich oder verschieden sind und Wasserstoff, C₁-C₈-Alkyl, C₅-C₆-­Cycloalkyl, C₆-C₁₂-Aryl oder Heteroaryl bedeuten. Sulfamoylamino stands for compounds of the general formula R¹⁶R¹⁷N-SO₂-NH-, where R¹⁶ and R¹⁷ are the same or different and are hydrogen, C₁-C₈-alkyl, C₅-C₆-cycloalkyl, C₆-C₁₂-aryl or heteroaryl.

Acylamino steht für Verbindungen der allgemeinen Formel R¹⁸-CO-NH-, wobei R¹⁸ Wasserstoff, C₁-C₈-Alkyl, C₅-C₇-­Cycloalkyl, C₆-C₁₂-Aryl oder Heteroaryl bedeutet. Acylamino stands for compounds of the general formula R¹⁸-CO-NH-, where R¹⁸ is hydrogen, C₁-C₈-alkyl, C₅-C₇-cycloalkyl, C₆-C₁₂-aryl or heteroaryl.

Heteroaryl steht im allgemeinen für einen fünf- oder sechsgliedrigen gegebenenfalls benzokondensierten heteroaromatischen Ring, der 1 bis 3 Heteroatome aus der Reihe N, O und S enthält. Heteroaryl in general represents a five- or six-membered optionally benzo-fused heteroaromatic ring containing 1 to 3 heteroatoms from the series N, O and S.

Unter hydrophilierender Gruppe werden folgende Strukturen verstanden: COOH, SO₃H, PO(OH)₂, CH₂OH, -(O-CH₂-CH₂)₂₋₂₀-OH. Hydrophilizing group is understood to mean the following structures: COOH, SO₃H, PO (OH) ₂, CH₂OH, - (O-CH₂-CH₂) ₂₋₂₀-OH.

Im folgenden sind geeignete Verbindungen dargestellt.

Figure imgb0008
Figure imgb0009
Figure imgb0010
 Suitable connections are shown below.
Figure imgb0008
Figure imgb0009
Figure imgb0010

Triazoliumthiolate gemäß Formel I sind aus US 4 631 253 bekannt und die gängigen Darstellungs­methoden sind dort beschrieben. Beispiele für Thiadia­zoliumthiolate gemäß den Formeln II und III und deren Darstellung sind aus Grashey, Baumann und Lubos, Tetra­hedron Letters 1968, 5881 und Kier, Scott, J. Hetero­cycl. Chem. 5, 277, (1968) zu entnehmen. Die Oxadiazol­iumthiolate gemäß der Formeln IV sind von McCarthy, Ollis und Ramsden in J. Chem. Soc., Perkin Trans. I 1974, 627 beschrieben. Thiazoliumthiolate der Formel V und Imidozoliumthiolate der Formel VI sind durch Huisgen et al in THL 1967, 1809 - 14 veröffentlicht.Triazolium thiolates according to formula I are known from US 4,631,253 and the common preparation methods are described there. Examples of thiadiazolium thiolates according to formulas II and III and their representation are from Grashey, Baumann and Lubos, Tetrahedron Letters 1968, 5881 and Kier, Scott, J. Heterocycl. Chem. 5, 277, (1968). The oxadiazolium thiolates according to formulas IV are described by McCarthy, Ollis and Ramsden in J. Chem. Soc., Perkin Trans. I 1974, 627. Thiazolium thiolates of the formula V and imidozolium thiolates of the formula VI are published by Huisgen et al in THL 1967, 1809-14.

Beispiele für Triazoliumthiolate gemäß Formel VII sind in Begtrup, Tetrahedron Letters 19, S. 1578 (1971) zu finden.Examples of triazolium thiolates according to formula VII can be found in Begtrup, Tetrahedron Letters 19, p. 1578 (1971).

Die Menge der erfindungsgemäßen Verbindung in den Bleich- und Bleichfixierbädern variiert je nach der Art der Verarbeitungslösung, der Art des zu verarbeitenden photographischen Materials, der Verarbeitungstemperatur, der zur Durchführung der gewünschten Verarbeitung be­nötigten Zeit, usw. Jedoch ist eine Menge von 1 x 10⁻⁵ bis 1 Mol pro Liter Bleich- bzw. Bleichfixierbad geeig­net, wobei 1 x 10⁻³ bis 1 x 10⁻¹ Mol bevorzugt sind. Im allgemeinen wird der jeweils beste Bereich durch ein­fache Vorversuche bestimmt. Die erfindungsgemäß zu ver­wendende Verbindung kann dem Bleich- oder Bleichfixier­bad direkt zugesetzt oder durch ein vorgeschaltetes Con­ditionierbad eingebracht werden.The amount of the compound of the present invention in the bleaching and bleach-fixing baths varies depending on the kind of the processing solution, the kind of the photographic material to be processed, the processing temperature, the time required to perform the desired processing, etc. However, an amount is 1 x 10⁻ ⁵ to 1 mole per liter of bleaching or bleach-fixing bath is suitable, 1 x 10⁻³ to 1 x 10 Mol¹ mol being preferred. In general, the best range is determined by simple preliminary tests. The compound to be used according to the invention can be added directly to the bleaching or bleach-fixing bath or introduced through an upstream conditioning bath.

Die erfindungsgemäßen Bleichbäder können auch bei Schnellverarbeitungsprozeßen mit Entwicklungszeiten unter 60 Sekunden verwendet werden, wobei die dort eingesetzten farbfotografischen Aufzeichnungsmaterialien chloridreiche Silberhalogenidemulsionsschichten auf­weisen (mindestens 80 Mol% AgCl).The bleaching baths according to the invention can also be used in rapid processing processes with development times of less than 60 seconds, the color photographic recording materials used there having chloride-rich silver halide emulsion layers (at least 80 mol% AgCl).

Als Eisen(III)-ionenkomplexsalze eignen sich Komplexe von Eisen(III)-ionen und einem chelatbildenden Mittel wie einer Aminopolycarbonsäure, einer Aminopolyphosphon­säure oder einem Salz davon, insbesondere einem Alkali­metallsalz oder Ammoniumsalz.Suitable iron (III) ion complex salts are complexes of iron (III) ions and a chelating agent such as an aminopolycarboxylic acid, an aminopolyphosphonic acid or a salt thereof, in particular an alkali metal salt or ammonium salt.

Typische Beispiele chelatbildender Mittel sind Ethylen­diamintetraessigsäure; Dinatriumethylendiamintetraace­tat; Diammoniumethylendiamintetraacetat; Tetra(tri­methylammonium)-ethylendiamintetraacetat; Tetrakalium­ethylendiamintetraacetat; Tetranatriumethylendiamin­tetraacetat; Trinatriumethylendiamintetraacetat; Di­ethylentriaminpentaessigsäure; Pentanatriumdiethylen­triaminpentaacetat; Ethylendiamin-N-(β-hydroxyethyl)-­N,N′,N′-triessigsäure; Trinatrium ethylendiamin-N-(β-­hydroxyethyl)-N,N′,N′-triacetat; Triammoniumethylen­diamin-N-(β-hydroxyethyl)-N,N′,N′-triacetat; Propylen­diamintetraessigsäure; Dinatriumpropylendiamintetra­acetat; Nitrilotriessigsäure; Trinatriumnitrilotri­acetat; Cyclohexandiamintetraessigsäure; Dinatrium­cyclohexandiamintetraacetat; Nitrilotriessigsäure; Trinatriumnitrilotriacetat; Cyclohexandiamintetra­essigsäure; Dinatriumcyclohexandiamintetraacetat; Imino­diessigsäure; Dihydroxyethylglycin; Ethylether-diamin­tetraessigsäure; Glykoletherdiamintetraessigsäure; Ethylendiamintetrapropionsäure; Phenylendiamintetra­essigsäure; 1,3-Diaminopropanol-N,N,N′,N′-tetramethylen­phosphonsäure; Ethylendiamin-N,N,N′,N′-tetramethylen­phosphonsäure; 1,3-Propylendiamin-N,N,N′,N′-tetra­methylenphosphonsäure, usw.Typical examples of chelating agents are ethylenediaminetetraacetic acid; Disodium ethylenediaminetetraacetate; Diammonium ethylenediaminetetraacetate; Tetra (trimethylammonium) ethylenediaminetetraacetate; Tetrapotassium ethylenediaminetetraacetate; Tetrasodium ethylenediaminetetraacetate; Trisodium ethylenediaminetetraacetate; Diethylenetriaminepentaacetic acid; Pentasodium diethylenetriaminepentaacetate; Ethylenediamine-N- (β-hydroxyethyl) -N, N ′, N′-triacetic acid; Trisodium ethylenediamine-N- (β-hydroxyethyl) -N, N ′, N′-triacetate; Triammonium ethylenediamine-N- (β-hydroxyethyl) -N, N ′, N′-triacetate; Propylenediaminetetraacetic acid; Disodium propylene diamine tetraacetate; Nitrilotriacetic acid; Trisodium nitrilotriacetate; Cyclohexanediamine tetraacetic acid; Disodium cyclohexanediamine tetraacetate; Nitrilotriacetic acid; Trisodium nitrilotriacetate; Cyclohexanediamine tetraacetic acid; Disodium cyclohexanediamine tetraacetate; Iminodiacetic acid; Dihydroxyethylglycine; Ethyl ether diamine tetraacetic acid; Glycol ether diamine tetraacetic acid; Ethylenediaminetetrapropionic acid; Phenylenediaminetetraacetic acid; 1,3-diaminopropanol-N, N, N ′, N′-tetramethylenephosphonic acid; Ethylenediamine-N, N, N ′, N′-tetramethylenephosphonic acid; 1,3-propylenediamine-N, N, N ′, N′-tetramethylenephosphonic acid, etc.

Das Eisen(III)-ionenkomplexsalz kann in der Form des Komplexsalzes verwendet oder in situ in dem Bleich- oder Bleichfixierbad hergestellt werden. Geeignete Kationen sind Alkalikationen und Ammonium; letzteres ist bevor­zugt.The iron (III) ion complex salt can be used in the form of the complex salt or prepared in situ in the bleach or bleach-fix bath. Suitable cations are alkali cations and ammonium; the latter is preferred.

Die erfindungsgemäße Bleichlösung kann rehalogenierende Mittel wie Bromide (z.B. Kaliumbromid, Natriumbromid, Ammoniumbromid, usw.), Chloride (z.B. Kaliumchlorid, Natriumchlorid, Ammoniumchlorid, usw.) und dergleichen zusätzlich zu den Bleichmitteln enthalten. Darüber hinaus können Zusätze, die eine pH-Pufferwirkung haben, wie anorganische Säuren, organische Säuren oder die Salze davon, die zur Verwendung in üblichen Bleich­lösungen bekannt sind(z.B. Borsäure, Borax, Natrium­metaborat, Essigsäure, Natriumacetat, Natriumcarbonat, Kaliumcarbonat, Phosphorige-Säure, Phosphorsäure, Na­triumphosphat, Zitronensäure, Natriumzitrat, Weinsäure, usw.) zugesetzt werden.The bleaching solution of the present invention may contain rehalogenating agents such as bromides (e.g. potassium bromide, sodium bromide, ammonium bromide, etc.), chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride, etc.) and the like in addition to the bleaching agents. In addition, additives which have a pH buffering action, such as inorganic acids, organic acids or the salts thereof, which are known for use in conventional bleaching solutions (for example boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid , Phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc.) can be added.

Der pH-Wert der Bleichlösung beträgt vorzugsweise 3,0 bis 8,0, insbesondere 4,0 bis 7,0.The pH of the bleaching solution is preferably 3.0 to 8.0, in particular 4.0 to 7.0.

Bei Verwendung in einem Bleich-Fixier-Bad können übliche Fixiermittel, d.h. wasserlösliche, Silberhalogenid auf­lösende Mittel, wie Thiosulfat (z.B. Natriumthiosulfat, Ammoniumthiosulfat, Ammoniumnatriumthiosulfat, Kalium­thiosulfat, usw.); Thiocyanate (z.B. Natriumthiocyanat; Ammoniumthiocyanat; Kaliumthiocyanat, usw.); Thioether­verbindungen (z.B. Ethylenbisthioglykolsäure, 3,6-Di­thia-1,8-octandiol, usw.); und Thioharnstoffe allein oder in einer Kombination von zwei oder mehreren ver­wendet werden. Zusätzlich können spezielle Bleich-­Fixier-Mittel, die eine Kombination eines Fixiermittels und eine große Menge einer Halogenidverbindung wie Kaliumjodid enthalten, ebenfalls verwendet werden.When used in a bleach-fix bath, conventional fixing agents, ie water-soluble, silver halide dissolving agents, such as thiosulfate (eg sodium thiosulfate, ammonium thiosulfate, ammonium sodium thiosulfate, potassium thiosulfate, etc.); Thiocyanates (eg sodium thiocyanate; Ammonium thiocyanate; Potassium thiocyanate, etc.); Thioether compounds (e.g. ethylene bisthioglycolic acid, 3,6-dithia-1,8-octanediol, etc.); and thioureas can be used alone or in a combination of two or more. In addition, special bleach-fixing agents containing a combination of a fixing agent and a large amount of a halide compound such as potassium iodide can also be used.

In der Bleich-Fixier-Zusammensetzung ist das Eisen(III)-­ionenkomplexsalz üblicherweise in einer Menge von 0,1 bis 1 Mol/l vorhanden. Die Menge des Fixiermittels be­trägt im allgemeinen 0,2 bis 4 Mol pro Liter der Bleich-­Fixier-Lösung.In the bleach-fix composition, the ferric ion complex salt is usually present in an amount of 0.1 to 1 mol / l. The amount of the fixing agent is generally 0.2 to 4 mol per liter of the bleach-fixing solution.

Bleich-Fixier-Lösungen können darüber hinaus konservier­ende Mittel wie Sulfite (z.B. Natriumsulfit, Kaliumsul­fit, Ammoniumsulfit, usw.), Hydroxylamin, Hydrazin, Al­dehyd-Bisulfit-Addukte (z.B. Acetaldehydnatriumbisul­fitaddukt), usw. enthalten. Darüber hinaus können ver­schiedene optische Aufheller, Entschäumungsmittel, oberflächenaktive Mittel, organische Lösungsmittel (z.B. Methanol) und bekannte Bleich-Fixier-Beschleunigungs­mittel, z.B. Polyaminverbindungen. (US-PS 3 578 457), Thioharnstoffe (US-PS 3 617 283), Iodide (DE-PS 1 127 715), Polyethylenoxide (DE-PS 966 410), Stickstoff enthaltende heterocyclische Verbindungen (DE-PS 1 290 812) und andere Thioharnstoffe verwendet werden. Der pH-Wert der Bleich-Fixier-Lösung liegt bei der Ver­wendung gewöhnlich bei 4,0 bis 9,0, besonders bevorzugt bei 5,0 bis 8,0.Bleach-fix solutions can also contain preservatives such as sulfites (e.g. sodium sulfite, potassium sulfite, ammonium sulfite, etc.), hydroxylamine, hydrazine, aldehyde-bisulfite adducts (e.g. acetaldehyde sodium bisulfite adduct), etc. In addition, various optical brighteners, defoamers, surfactants, organic solvents (e.g. methanol) and known bleach-fix accelerating agents, e.g. polyamine compounds. (US-PS 3 578 457), thioureas (US-PS 3 617 283), iodides (DE-PS 1 127 715), polyethylene oxides (DE-PS 966 410), nitrogen-containing heterocyclic compounds (DE-PS 1 290 812) and other thioureas can be used. The pH of the bleach-fix solution when used is usually 4.0 to 9.0, particularly preferably 5.0 to 8.0.

Beispielexample Versuch 1Trial 1

Ein Colornegativpapier mit einer Silberchloridbromid­emulsion (80% AgBr und 20% AgCl) wird hinter einem Stufenkeil belichtet und wie folgt verarbeitet: Farbentwickler 210 sec. 33°C Wässerung 20 sec. 20°C Abstreifen des Wassers von der Oberfläche der Bilder Bleichbad 50 sec. 20°C Wässerung 60 sec. 20°C Fixierbad 60 sec. 20°C Wässerung 120 sec. 20°C Trocknen A color negative paper with a silver chloride bromide emulsion (80% AgBr and 20% AgCl) is exposed behind a step wedge and processed as follows: Color developer 210 sec. 33 ° C Watering 20 sec. 20 ° C Wiping the water off the surface of the pictures Bleach bath 50 sec. 20 ° C Watering 60 sec. 20 ° C Fixer 60 sec. 20 ° C Watering 120 sec. 20 ° C dry

RestsilberbestimmungResidual silver determination

Die abgebildeten Stufenkeile werden mit einem Infrarot-­Silberdetector PM 8030 der Fa. Photo-Matic, Denmark untersucht. In der nachfolgenden Tabelle ist angegeben, ob nach Verwendung des frisch angesetzten Bleichbades noch Restsilber in den Bildschwärzen vorhanden ist. Eine Prüfung der Beständigkeit des Bleichbades erfolgte nach 4 und 15 Tagen Standzeit bei 33°C. Außerdem wurde nach 15 Tagen Standzeit die Sedimentbildung begutachtet, die vor allem im Gebrauchszustand eines Bleichbades, welches Silberionen enthält, auftreten kann.The step wedges shown are examined with a PM 8030 infrared silver detector from Photo-Matic, Denmark. The table below shows whether residual silver is still present in the blackening after using the freshly prepared bleaching bath. The resistance of the bleaching bath was tested after 4 and 15 days of standing at 33 ° C. In addition, sediment formation was assessed after 15 days of inactivity, which can occur especially when a bleach bath containing silver ions is in use.

Versuch 2Trial 2

Beispiel 1 wird wiederholt, wobei dem Bleichbad als Ver­gleichssubstanz 2,2 g Thioglyzerin/l zugesetzt werden.

Figure imgb0011
Example 1 is repeated, 2.2 g of thioglycerol / l being added to the bleaching bath as the reference substance.
Figure imgb0011

Versuch 3Trial 3

Versuch 1 wird wiederholt, wobei dem Bleichbad als Ver­gleichssubstanz 2,3 g/l der Verbindung V 2 zugesetzt werden.
H₂N-CH₂CH₂-SH·HCl      V 2.Experiment 1 is repeated, with 2.3 g / l of compound V 2 being added to the bleaching bath as the reference substance.
H₂N-CH₂CH₂-SH · HCl V 2.

Versuch 4Trial 4

Versuch 1 wird wiederholt, wobei dem Bleichbad als Ver­gleichssubstanz 3,7 g/l der Verbindung V 3 zugesetzt werden.

Figure imgb0012
Experiment 1 is repeated, 3.7 g / l of compound V 3 being added to the bleaching bath as a reference substance.
Figure imgb0012

Versuch 5Trial 5

Versuch 1 wird wiederholt, wobei dem Bleichbad als Vergleichssubstanz 3,0 g/l der Verbindung V 4 zugesetzt werden.

Figure imgb0013
Experiment 1 is repeated, 3.0 g / l of compound V 4 being added to the bleaching bath as a reference substance.
Figure imgb0013

Versuch 6Trial 6

Versuch 1 wird wiederholt, wobei dem Bleichbad 2,9 g/l der erfindungsgemäßen Verbindung B 2 zugesetzt werden.

Figure imgb0014
Tabelle Versuch Zusatz zum Bleichbad Restsilber nach Anwendung eines frischangesetzten Bleichbades Restsilber nach Anwendung eines Bleichbades nach 4 Tagen Standzeit bei 33°C Restsilber nach Anwendung eines Bleichbades nach 15 Tagen Standzeit bei 33°C Sedimentbildung im Bleichbad nach 15 Tagen Standzeit bei 33°C 1 Vergleich ja ja ja nein 2 Vergleich nein ja ja ja 3 Vergleich ja ja ja ja 4 Vergleich ja ja ja ja 5 Vergleich ja ja ja nein 6 erfindungsgemäß nein nein nein nein Experiment 1 is repeated, 2.9 g / l of the compound B 2 according to the invention being added to the bleaching bath.
Figure imgb0014
 table attempt Additive to the bleach bath Residual silver after using a freshly prepared bleach bath Residual silver after using a bleaching bath after 4 days standing at 33 ° C Residual silver after using a bleaching bath after 15 days standing at 33 ° C Sediment formation in the bleaching bath after 15 days standing at 33 ° C 1 comparison Yes Yes Yes No 2nd comparison No Yes Yes Yes 3rd comparison Yes Yes Yes Yes 4th comparison Yes Yes Yes Yes 5 comparison Yes Yes Yes No 6 according to the invention No No No No

Aus der Tabelle ist zu ersehen, daß nur die erfindungs­gemäße Verbindung B 2 eine gute Beständigkeit im Bleich­bad aufweist und außerdem keine Sedimentbildung verur­sacht.It can be seen from the table that only the compound B 2 according to the invention has good resistance in the bleaching bath and also does not cause sediment formation.

Claims (9)

1. Bleich- und Bleichfixierbäder, die ein Eisen III-­ionenkomplexsalz als Bleichmittel enthalten, dadurch gekennzeichnet, daß sie zusätzlich eine 5- bis 7-gliedrige heterocyclische, wenigstens ein N- und wenigstens ein weiteres Heteroatom aus der Reihe O, N, S enthaltende Verbindung, die durch -S⊖ substituiert ist und an einem quartären Ringstick­stoffatom eine positive Ladung trägt, derart ange­ordnet, daß ein tautomerer Ladungsausgleich zu einer neutralen Thionform nicht möglich ist, ent­halten.1. bleaching and bleach-fixing baths containing an iron III-ion complex salt as bleaching agent, characterized in that they additionally contain a 5- to 7-membered heterocyclic, at least one N and at least one further heteroatom from the series O, N, S containing Compound, which is substituted by -S ⊖ and carries a positive charge on a quaternary ring nitrogen atom, arranged such that tautomeric charge balance to a neutral thione form is not possible. 2. Bleich- und Bleichfixierbäder gemäß Anspruch 1, dadurch gekennzeichnet, daß die heterocyclische Verbindung der allgemeinen Formel I
Figure imgb0015
 entspricht, in der
R¹      C₁-C₈-Alkyl, Heteroaryl, C₅-C₁₀-Cycloalkyl und C₆-C₁₂-Aryl, gegebenenfalls eine hydrophi­lierende Gruppe enthaltend,
R²      Wasserstoff, C₁-C₈-Alkyl, C₂-C₈-Alkenyl, Heteroaryl, C₅-C₁₀-Cycloalkyl und C₁₆-C₁₂-­Aryl, C₁-C₈-Dialkylamino, gegebenenfalls eine hydrophilierende Gruppe enthaltend,
R³      Amino, Acylamino, C₁-C₈-Dialkylamino, Sulfon­amido, Sulfamoylamino, C₁-C₈-Alkyl, C₂-C₈-­Alkenyl, C₁-C₃-Alkoxy-C₁-C₅-alkyl, C₅-C₁₀-­Cycloalkyl und C₆-C₁₂-Aryl, gegebenenfalls eine hydrophilierende Gruppe enthaltend,
bedeuten, wobei R¹ und R² bzw. R² und R³ gemeinsam die zur Vervollständigung eines heterocyclischen Rings erforderlichen Gruppen sein können.2. bleaching and bleach-fixing baths according to claim 1, characterized in that the heterocyclic compound of the general formula I.
Figure imgb0015
 corresponds in which
R¹ C₁-C₈-alkyl, heteroaryl, C₅-C₁₀-cycloalkyl and C₆-C₁₂-aryl, optionally containing a hydrophilizing group,
R² is hydrogen, C₁-C₈-alkyl, C₂-C₈-alkenyl, heteroaryl, C₅-C₁₀-cycloalkyl and C₁₆-C₁₂-aryl, C₁-C₈-dialkylamino, optionally containing a hydrophilizing group,
R³ amino, acylamino, C₁-C₈-dialkylamino, sulfonamido, sulfamoylamino, C₁-C₈-alkyl, C₂-C₈-alkenyl, C₁-C₃-alkoxy-C₁-C₅-alkyl, C₅-C₁₀-cycloalkyl and C₆-C₁₂-aryl , optionally containing a hydrophilizing group,
mean, where R¹ and R² or R² and R³ together can be the groups required to complete a heterocyclic ring. 3. Bleich- und Bleichfixierbäder gemäß Anspruch 1, dadurch gekennzeichnet, daß die heterocyclische Verbindung der Formeln II
und/oder III
Figure imgb0016
 entspricht, in der
R⁴      C₁-C₈-Alkyl, Heteroaryl, C₅-C₁₀-Cycloalkyl und C₆-C₁₂-Aryl, gegebenenfalls eine hydrophi­lierende Gruppe enthaltend,
R⁵      Wasserstoff, Di-C₁-C₈-alkylamino, C₁-C₈-Alkyl, C₂-C₈-Alkenyl, Heteroaryl, C₅-C₁₀-Cycloalkyl und C₆-C₁₂-Aryl, gegebenenfalls eine hydro­philierende Gruppe enthaltend,
bedeuten, wobei R⁴ und R⁵ gemeinsam die zur Ver­vollständigung eines heterocyclischen Rings er­forderlichen Gruppen sein können.3. bleaching and bleach-fixing baths according to claim 1, characterized in that the heterocyclic compound of the formulas II
and / or III
Figure imgb0016
 corresponds in which
R⁴ C₁-C₈-alkyl, heteroaryl, C₅-C₁₀-cycloalkyl and C₆-C₁₂-aryl, optionally containing a hydrophilizing group,
R⁵ is hydrogen, di-C₁-C₈-alkylamino, C₁-C₈-alkyl, C₂-C₈-alkenyl, heteroaryl, C₅-C₁₀-cycloalkyl and C₆-C₁₂-aryl, optionally containing a hydrophilizing group,
mean, where R⁴ and R⁵ together can be the groups required to complete a heterocyclic ring. 4. Bleich- und Bleichfixierbäder gemäß Anspruch 1, dadurch gekennzeichnet, daß die heterocyclische Verbindung der Formel IV
Figure imgb0017
 entspricht, in der
R⁶      C₁-C₈-Alkyl, Heteroaryl, C₅-C₁₀-Cycloalkyl und C₆-C₁₂-Aryl, gegebenenfalls eine hydrophi­lierende Gruppe enthaltend,
R⁷      Wasserstoff, Di-C₁-C₈-alkylamino, C₁-C₈-Alkyl, C₂-C₈-Alkenyl, C₅-C₆-Heteroaryl, C₅-C₁₀-Cyclo­alkyl und C₆-C₁₂-Aryl, gegebenenfalls eine hydrophilierende Gruppe enthaltend,
bedeuten, wobei R⁶ und R⁷ gemeinsam die zur Ver­vollständigung eines heterocyclischen Rings er­forderlichen Gruppen sein können.4. bleaching and bleach-fixing baths according to claim 1, characterized in that the heterocyclic compound of formula IV
Figure imgb0017
 corresponds in which
R⁶ C₁-C₈-alkyl, heteroaryl, C₅-C₁₀-cycloalkyl and C₆-C₁₂-aryl, optionally containing a hydrophilizing group,
R⁷ is hydrogen, di-C₁-C₈-alkylamino, C₁-C₈-alkyl, C₂-C₈-alkenyl, C₅-C₆-heteroaryl, C₅-C₁₀-cycloalkyl and C₆-C₁₂-aryl, optionally containing a hydrophilizing group,
mean, where R⁶ and R⁷ together can be the groups required to complete a heterocyclic ring. 5. Bleich- und Bleichfixierbäder gemäß Anspruch 1, dadurch gekennzeichnet, daß die heterocylische Verbindung der Formel V
Figure imgb0018
 entspricht, in der
R⁸      C₁-C₈-Alkyl, Heteroaryl, C₅-C₁₀-Cycloalkyl und C₆-C₁₂-Aryl, gegebenenfalls eine hydrophi­lierende Gruppe enthaltend,
R⁹ und R¹⁰      Wasserstoff, C₁-C₈-Alkyl, C₂-C₈-Alkenyl, Heteroaryl, C₅-C₁₀ Cycloalkyl und C₆-C₁-Aryl, gegebenenfalls eine hydrophilierende Gruppe enthaltend
bedeuten, wobei R⁸ und R⁹ bzw. R⁸ und R¹⁰ gemeinsam die zur Vervollständigung eines heterocyclischen Rings erforderlichen Gruppen sein können.5. bleaching and bleach-fixing baths according to claim 1, characterized in that the heterocyclic compound of formula V
Figure imgb0018
 corresponds in which
R⁸ C₁-C₈-alkyl, heteroaryl, C₅-C₁₀-cycloalkyl and C₆-C₁₂-aryl, optionally containing a hydrophilizing group,
R⁹ and R¹⁰ are hydrogen, C₁-C₈-alkyl, C₂-C₈-alkenyl, heteroaryl, C₅-C₁₀ cycloalkyl and C₆-C₁-aryl, optionally containing a hydrophilizing group
mean, where R⁸ and R⁹ or R⁸ and R¹⁰ together can be the groups required to complete a heterocyclic ring. 6. Bleich- und Bleichfixierbäder gemäß Anspruch 1, dadurch gekennzeichnet, daß die heterocyclische Verbindung der Formel VI
Figure imgb0019
 entspricht, in der
R¹¹ und R¹³      C₁-C₈-Alkyl, C₅-C₆ Heteroaryl, C₅-C₁₀ Cycloalkyl und C₆-C₁₂ Aryl, gegebenenfalls eine hydrophilierende Gruppe enthaltend,
R¹² und R¹⁴      Wasserstoff, C₁-C₈-Alkyl, C₂-C₈-Alkenyl, Heteroaryl, C₅-C₁₀ Cycloalkyl und C₆-C₁₂-Aryl, gegebenenfalls eine hydrophilierende Gruppe enthaltend,
bedeuten, wobei R¹¹ und R¹⁴ bzw. R¹¹ und R¹² bzw. R¹² und R¹³ gemeinsam die zur Vervollständigung eines heterocyclischen Ringes erforderlichen Gruppen sein können.6. bleaching and bleach-fixing baths according to claim 1, characterized in that the heterocyclic compound of formula VI
Figure imgb0019
 corresponds in which
R¹¹ and R¹³ are C₁-C₈-alkyl, C₅-C₆ heteroaryl, C₅-C₁₀ cycloalkyl and C₆-C₁₂ aryl, optionally containing a hydrophilizing group,
R¹² and R¹⁴ are hydrogen, C₁-C₈-alkyl, C₂-C₈-alkenyl, heteroaryl, C₅-C₁₀ cycloalkyl and C₆-C₁₂-aryl, optionally containing a hydrophilizing group,
mean, where R¹¹ and R¹⁴ or R¹¹ and R¹² or R¹² and R¹³ together can be the groups required to complete a heterocyclic ring. 7. Bleich- und Bleichfixierbäder gemäß Anspruch 1, dadurch gekennzeichnet, daß die heterocyclische Verbindung der Formel VII
Figure imgb0020
 entspricht, in der
R¹⁹ und R²⁰      C₁-C₃-Alkyl
R²¹      Wasserstoff und Methyl
bedeuten.7. bleaching and bleach-fixing baths according to claim 1, characterized in that the heterocyclic compound of formula VII
Figure imgb0020
 corresponds in which
R¹⁹ and R²⁰ C₁-C₃-alkyl
R²¹ is hydrogen and methyl
mean. 8. Bleich- und Bleichfixierbäder gemäß Anspruch 1, wobei die zusätzliche Verbindung in einer Menge von 10⁻⁵ bis 1 Mol pro Liter Bleich- bzw. Bleichfixier­bad eingesetzt wird.8. bleaching and bleach-fixing baths according to claim 1, wherein the additional compound is used in an amount of 10⁻⁵ to 1 mol per liter of bleaching or bleach-fixing bath. 9. Bleich- und Bleichfixierbäder gemäß Anspruch 1, wobei das Eisen III-ionenkomplexsalz der Ethylen­diamintetraessig-Säure als Bleichmittel verwendet wird.9. bleaching and bleach-fixing baths according to claim 1, wherein the iron III-ion complex salt of ethylenediaminetetraacetic acid is used as a bleaching agent.
EP88120873A 1987-12-23 1988-12-14 Bleaching bath with bleach accelerating substances Expired - Lifetime EP0321839B1 (en)

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DE3743783 1987-12-23

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Cited By (3)

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EP0431568A1 (en) * 1989-12-04 1991-06-12 Fuji Photo Film Co., Ltd. Method for processing a silver halide photographic material
EP0496887A4 (en) * 1989-12-04 1992-01-17 Fuji Photo Film Co Ltd Process for treating silver halide photographic meterial and composition therefor.
EP0533182A1 (en) * 1991-09-20 1993-03-24 Eastman Kodak Company Triazolium thiolate baths for silver halide development acceleration

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JP2775518B2 (en) * 1989-12-04 1998-07-16 富士写真フイルム株式会社 Processing method of silver halide photographic material
JP2640984B2 (en) * 1989-12-21 1997-08-13 富士写真フイルム株式会社 Processing method of silver halide color photographic light-sensitive material
JPH04229860A (en) * 1990-12-06 1992-08-19 Fuji Photo Film Co Ltd Processing method for silver halide photosensitive material
JPH04243252A (en) * 1991-01-18 1992-08-31 Fuji Photo Film Co Ltd Development processing method for sliver halide photosensitive material
JP2893101B2 (en) * 1991-02-19 1999-05-17 富士写真フイルム株式会社 Processing method of silver halide photographic light-sensitive material and photographic fixing function composition
JP2772875B2 (en) * 1991-05-14 1998-07-09 富士写真フイルム株式会社 Processing method of silver halide color photographic light-sensitive material and photographic bleach-fixing composition
JPH04365036A (en) * 1991-06-11 1992-12-17 Fuji Photo Film Co Ltd Processing for silver halogenide color photosensitive material
JPH04365038A (en) * 1991-06-11 1992-12-17 Fuji Photo Film Co Ltd Processing for silver halogenide color photosensitive material
JP2867350B2 (en) * 1991-09-19 1999-03-08 富士写真フイルム株式会社 Silver halide photographic material
DE69424983T2 (en) 1993-11-24 2000-10-19 Fuji Photo Film Co., Ltd. Photographic processing composition and processing method
JP3773278B2 (en) 1994-11-10 2006-05-10 富士写真フイルム株式会社 Processing method of silver halide color photographic light-sensitive material
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DE10038018A1 (en) 2000-08-04 2002-02-21 Agfa Gevaert Ag Bleaching solution for processing photographic silver halide materials, especially color reversal films, comprises an iron propylenediaminetetraacetic acid and beta-alaninediacetic acid complex
US20050123865A1 (en) * 2003-12-03 2005-06-09 Eastman Kodak Company Single-part bleach-fixing composition and method of processing

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EP0496887A4 (en) * 1989-12-04 1992-01-17 Fuji Photo Film Co Ltd Process for treating silver halide photographic meterial and composition therefor.
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DE3743783A1 (en) 1989-07-13
EP0321839B1 (en) 1992-11-11

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