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EP0468325A1 - Bleach bath - Google Patents

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Publication number
EP0468325A1
EP0468325A1 EP91111713A EP91111713A EP0468325A1 EP 0468325 A1 EP0468325 A1 EP 0468325A1 EP 91111713 A EP91111713 A EP 91111713A EP 91111713 A EP91111713 A EP 91111713A EP 0468325 A1 EP0468325 A1 EP 0468325A1
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EP
European Patent Office
Prior art keywords
mol
layer
bleaching
bath
schicht
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP91111713A
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German (de)
French (fr)
Other versions
EP0468325B1 (en
Inventor
Gustav Tappe
Ralf Dr. Wichmann
Heinz Dr. Meckl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert AG
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Agfa Gevaert AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority claimed from DE19904023817 external-priority patent/DE4023817A1/en
Priority claimed from DE19904029805 external-priority patent/DE4029805A1/en
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Publication of EP0468325A1 publication Critical patent/EP0468325A1/en
Application granted granted Critical
Publication of EP0468325B1 publication Critical patent/EP0468325B1/en
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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
    • G03C5/40—Chemically transforming developed images
    • G03C5/44—Bleaching; Bleach-fixing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes

Definitions

  • the invention relates to a bleaching bath which is suitable for processing color photographic silver halide materials and which is particularly environmentally friendly.
  • Iron complex salts of aminopolycarboxylic acids for example the iron ammonium complex salt of ethylenediaminetetraacetic acid, are usually used to bleach the silver formed during the development of color photographic materials. This and similar complexing agents that are also used are only very slowly biodegradable.
  • bleaching baths containing iron complexes of readily biodegradable complexing agents such as nitrilotriacetic acid are used for bleaching color photographic materials under the usual conditions at pH 6 to 8, they lack sufficient bleaching capacity.
  • the object of the invention was to provide a bleaching bath which is suitable for processing color photographic silver halide materials and which contains readily biodegradable constituents and has a sufficient bleaching effect.
  • a bleaching bath which contains (1) an iron (III) complex, the complexing agent of which is at least 20 mol%, preferably at least 80 mol%, of the formula I. corresponds, and
  • the bleaching bath can contain thiosulfate, but at most in an amount which is insufficient to fix the undeveloped silver halide.
  • the amount of thiosulfate is preferably less than 0.03 mol / l; in particular, the bleaching bath is free of thiosulfate.
  • complexing agents can be conventional complexing agents such as ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid or nitrilodipropion monoacetic acid or mixtures of these compounds. Only the complexing agents according to the invention are preferably used.
  • bleaching baths also contain a halide for rehalogenating the silver.
  • the halides of the bleaching baths are in particular the chlorides and bromides of sodium, potassium and ammonium.
  • the bleach bath When ready for use, the bleach bath contains 0.05 to 2.0 mol / l halide.
  • the bleaching bath preferably contains an excess of 1 to 120 mol%, preferably 5 to 20 mol%, based on the iron complex, of free complexing agent.
  • the bleaching bath according to the invention is particularly suitable for color photographic silver halide recording materials whose silver halide emulsions consist predominantly of AgBr, AgBrl, AgBrCI or AgCI.
  • the color photographic material preferably contains on a reflective or transparent support (for example paper coated on both sides with polyethylene or cellulose triacetate film) at least one blue-sensitive, at least one green-sensitive and at least one red-sensitive silver halide emulsion layer, to which at least one yellow coupler, at least one magenta coupler and at least one cyan coupler in the order given assigned.
  • the bleaching bath according to the invention is used within the usual processing method for color photographic silver halide materials and is suitable for bleaching all known color photographic silver halide materials such as color negative films, color negative paper, color reversal films and color reversal paper.
  • the processing method can be carried out continuously with constant regeneration of the individual processing baths.
  • the bleaching baths listed in the examples were examined for their bleaching behavior (residual silver in the processed material).
  • the exposed step wedge of the photographic material which was subsequently processed as described below, was examined for residual silver in the image blackness using an infrared silver detector PM 8030 from Photo-Matic, Denmark.
  • a color photographic recording material was produced by applying the following layers in the order given to a support on paper coated on both sides with polyethylene. The amounts given relate in each case to 1 m 2. The corresponding amounts of AgNO 3 are given for the silver halide application.
  • Example 1 The exposure and processing were carried out as described in Example 1.
  • the developer had the same composition as in Example 1.
  • Example 1 The exposure and processing were carried out as described in Example 1.
  • the developer had the same composition as in Example 1.
  • Table 1 shows the good bleaching action of the bleaching bath A according to the invention, which contains a biodegradable complexing agent.
  • the bleaching effect corresponds to that of the usual bleaching bath C, which contains the biodegradable EDTA.
  • the bleaching bath B which is composed essentially like bleaching bath A, but lies in the pH range prescribed for EDTA bleaching baths, on the other hand only bleaches insufficiently.
  • the amounts given relate in each case to 1 m 2.
  • the equivalent amounts of AgN0 3 are given.
  • a step wedge was exposed on the photographic material described above and processed as follows:
  • the processing baths had the following composition:
  • the result with regard to residual silver is shown in Table 2 below.
  • the color image produced was of the type.
  • the bleaching action of the bleaching bath D according to the invention with a biodegradable complexing agent corresponds to the bleaching action of the customary bleaching bath F with the biodegradable complexing agent EDTA.
  • the bleaching bath E which is composed essentially like bleaching bath D, but has a pH value customary for EDTA bleaching baths, on the other hand only bleaches insufficiently.
  • the bleaching tests carried out showed that the bleaching bath D according to the invention does not lead to the formation of leuco blue-green dye, while in a conventional bleaching bath with EDTA there are significant losses of blue-green dye at the corresponding pH.
  • the samples produced in this way were exposed under a step part and processed as follows:
  • the processing baths had the following composition:
  • Example 7 The exposure and processing were carried out as described in Example 7. With the exception of the bleach bath, all processing baths had the same composition as in Example 7.
  • Example 7 The exposure and processing were carried out as described in Example 7. With the exception of the bleach bath, all processing baths had the same composition as in Example 7.
  • the bleaching action of the bleaching bath G according to the invention with a biodegradable complexing agent corresponds to the bleaching action of the conventional bleaching bath I with the biodegradable complexing agent EDTA.
  • the bleaching bath H which is composed essentially like bleaching bath G, but has a pH value customary for EDTA bleaching baths, on the other hand only bleaches insufficiently.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

An easily biologically degradable bleaching bath having satisfactory bleaching action contains (1) an iron(III) complex whose complex former corresponds to at least 20 mol % to formula I (HOOC-CH2)2-N-CH2-CH2-COOH (I> and is (2) adjusted to a pH x, where 6.0 > x > 4.5. a

Description

Die Erfindung betrifft ein für die Verarbeitung farbfotografischer Silberhalogenidmaterialien geeignetes Bleichbad, das besonders umweltfreundlich ist.The invention relates to a bleaching bath which is suitable for processing color photographic silver halide materials and which is particularly environmentally friendly.

Zum Bleichen des bei der Entwicklung farbfotografischer Materialien entstandenen Silbers verwendet man üblicherweise Eisenkomplexsalze von Aminopolycarbonsäuren, beispielsweise das Eisenammoniumkomplexsalz der Ethylendiamintetraessigsäure. Dieser und ähnliche, ebenfalls verwendete Komplexbildner sind biologisch nur sehr langsam abbaubar.Iron complex salts of aminopolycarboxylic acids, for example the iron ammonium complex salt of ethylenediaminetetraacetic acid, are usually used to bleach the silver formed during the development of color photographic materials. This and similar complexing agents that are also used are only very slowly biodegradable.

Verwendet man unter den üblichen Bedingungen bei pH 6 bis 8 zum Bleichen farbfotografischer Materialien Bleichbäder, die Eisenkomplexe biologisch leicht abbaubarer Komplexbildner wie Nitrilotriessigsäure aufweisen, so fehlt ihnen ein ausreichendes Bleichvermögen.If bleaching baths containing iron complexes of readily biodegradable complexing agents such as nitrilotriacetic acid are used for bleaching color photographic materials under the usual conditions at pH 6 to 8, they lack sufficient bleaching capacity.

Aufgabe der Erfindung war die Bereitstellung eines für die Verarbeitung farbfotografischer Silberhalogenidmaterialien geeigneten Bleichbades, das biologisch gut abbaubare Bestandteile enthält und eine ausreichende Bleichwirkung hat.The object of the invention was to provide a bleaching bath which is suitable for processing color photographic silver halide materials and which contains readily biodegradable constituents and has a sufficient bleaching effect.

Diese Aufgabe wird mit einem Bleichbad gelöst, das (1) einen Eisen (III)-komplex enthält, dessen Komplexbildner zu wenigstens 20 Mol-%, vorzugsweise zu wenigstens 80 Mol-% der Formel I

Figure imgb0001
entspricht, undThis object is achieved with a bleaching bath which contains (1) an iron (III) complex, the complexing agent of which is at least 20 mol%, preferably at least 80 mol%, of the formula I.
Figure imgb0001
 corresponds, and

(2) auf einen pH-Wert x eingestellt ist, wobei 6,0 > x > 4,5 gilt.(2) is adjusted to a pH value x, where 6.0> x> 4.5 applies.

Das Bleichbad kann Thiosulfat enthalten, jedoch höchstens in einer Menge, die zum Fixieren des nicht entwickelten Silberhalogenids nicht ausreicht. Vorzugsweise beträgt die Thiosulfatmenge weniger als 0,03 Mol/I; insbesondere ist das Bleichbad frei von Thiosulfat.The bleaching bath can contain thiosulfate, but at most in an amount which is insufficient to fix the undeveloped silver halide. The amount of thiosulfate is preferably less than 0.03 mol / l; in particular, the bleaching bath is free of thiosulfate.

Die restlichen höchstens 80 Mol-%, bzw. vorzugsweise höchstens 20 Mol-% an Komplexbildner können übliche Komplexbildner wie Ethylendiamintetraessigsäure, Propylendiamintetraessigsäure, Nitrilotriessigsäure oder Nitrilodipropionmonoessigsäure oder Mischungen dieser Verbindungen sein. Bevorzugt werden nur die erfindungsgemäßen Komplexbildner eingesetzt.The remaining at most 80 mol%, or preferably at most 20 mol%, of complexing agents can be conventional complexing agents such as ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid or nitrilodipropion monoacetic acid or mixtures of these compounds. Only the complexing agents according to the invention are preferably used.

An Eisenkomplex werden insbesondere 0,005 bis 1,0 Mol/I eingesetzt.In particular 0.005 to 1.0 mol / l of iron complex are used.

Bleichbäder enthalten außer den erfindungsgemäßen Komponenten noch ein Halogenid zur Rehalogenierung des Silbers.In addition to the components according to the invention, bleaching baths also contain a halide for rehalogenating the silver.

Als Halogenide der Bleichbäder kommen insbesondere die Chloride und Bromide des Natriums, Kaliums und Ammoniums in Betracht.The halides of the bleaching baths are in particular the chlorides and bromides of sodium, potassium and ammonium.

Im gebrauchsfertigen Zustand enthält das Bleichbad 0,05 bis 2,0 Mol/I Halogenid.When ready for use, the bleach bath contains 0.05 to 2.0 mol / l halide.

Vorzugsweise enthält das Bleichbad einen Überschuß von 1 bis 120 Mol-%, vorzugsweise 5 bis 20 Mol- %, bezogen auf den Eisenkomplex, an freiem Komplexbildner.The bleaching bath preferably contains an excess of 1 to 120 mol%, preferably 5 to 20 mol%, based on the iron complex, of free complexing agent.

Das erfindungsgemäße Bleichbad eignet sich insbesonders für farbfotografische Silberhalogenidaufzeichnungsmaterialien, deren Silberhalogenidemulsionen überwiegend aus AgBr, AgBrl, AgBrCI oder AgCI bestehen. Vorzugsweise enthält das farbfotografische Material auf einem reflektierenden oder transparenten Träger (z.B. beidseitig mit Polyethylen beschichtetes Papier oder Cellulosetriacetatfilm) wenigstens eine blauempfindliche, wenigstens eine grünempfindliche und wenigstens eine rotempfindliche Silberhalogenidemulsionsschicht, denen in der angegebenen Reihenfolge wenigstens ein Gelbkuppler, wenigstens ein Purpurkuppler und wenigstens ein Blaugrünkuppler zugeordnet sind.The bleaching bath according to the invention is particularly suitable for color photographic silver halide recording materials whose silver halide emulsions consist predominantly of AgBr, AgBrl, AgBrCI or AgCI. The color photographic material preferably contains on a reflective or transparent support (for example paper coated on both sides with polyethylene or cellulose triacetate film) at least one blue-sensitive, at least one green-sensitive and at least one red-sensitive silver halide emulsion layer, to which at least one yellow coupler, at least one magenta coupler and at least one cyan coupler in the order given assigned.

Das erfindungsgemäße Bleichbad wird innerhalb des üblichen Verarbeitungsverfahrens für farbfotografische Silberhalogenidmaterialien eingesetzt und eignet sich zum Bleichen aller bekannten farbfotografischen Silberhalogenidmaterialien wie Colornegativfilmen, Colornegativpapier, Colorumkehrfilmen und Colorumkehrpapier.The bleaching bath according to the invention is used within the usual processing method for color photographic silver halide materials and is suitable for bleaching all known color photographic silver halide materials such as color negative films, color negative paper, color reversal films and color reversal paper.

Das Verarbeitungsverfahren läßt sich unter ständigem Regenerieren der einzelnen Verarbeitungsbäder kontinuierlich ausführen.The processing method can be carried out continuously with constant regeneration of the individual processing baths.

Die in den Beispielen aufgeführten Bleichbäder wurden auf ihr Bleichverhalten (Restsilber im verarbeiteten Material) untersucht.The bleaching baths listed in the examples were examined for their bleaching behavior (residual silver in the processed material).

Restsilberbestimmung:Residual silver determination:

Der belichtete und anschließend wie unten beschrieben verarbeitete Stufenkeil des fotografischen Materials wurde mit einem Infrarot-Silberdetektor PM 8030 der Firma Photo-Matic, Dänemark auf Restsilber in den Bildschwärzen untersucht.The exposed step wedge of the photographic material, which was subsequently processed as described below, was examined for residual silver in the image blackness using an infrared silver detector PM 8030 from Photo-Matic, Denmark.

Beispiel 1 (erfindungsgemäß)Example 1

Ein farbfotografisches Aufzeichnungsmaterial wurde hergestellt, indem auf einen Schichtträger auf beidseitig mit Polyethylen beschichtetem Papier die folgenden Schichten in der angegebenen Reihenfolge aufgetragen wurden. Die Mengenangaben beziehen sich jeweils auf 1 m2. Für den Silberhalogenidauftrag werden die entsprechenden Mengen AgN03 angegeben.A color photographic recording material was produced by applying the following layers in the order given to a support on paper coated on both sides with polyethylene. The amounts given relate in each case to 1 m 2. The corresponding amounts of AgNO 3 are given for the silver halide application.

SchichtaufbauLayer structure

  • 1. Schicht (Substratschicht):
    • 0,2 g Gelatine
  • 2. Schicht (blauempfindliche Schicht):
    • blauempfindliche Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,8 um) aus 0,63 g AgN03 mit
    • 1,38 g Gelatine
    • 0,95 g Gelbkuppler Y
    • 0,29 g Trikresylphosphat (TKP)
  • 3. Schicht (Schutzschicht)
    • 1,1 g Gelatine
    • 0,06 g 2,5-Dioctylhydrochinon
    • 0,06 g Dibutylphthalat (DBP)
  • 4. Schicht (grünempfindliche Schicht) grünsensibilisierte Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,6 um) aus 0,45 g AgN03 mit
    • 1,08 g Gelatine
    • 0,41 g Purpurkuppler M
    • 0,08 g 2,5-Dioctylhydrochinon
    • 0,34 g DBP
    • 0,04 g TKP
  • 5. Schicht (UV-Schutzschicht)
    • 1,15 g Gelatine
    • 0,6 g UV-Absorber der Formel
      Figure imgb0002
    • 0,045g 2,5-Dioctylhydrochinon
    • 0,04 g TKP
  • 6. Schicht (rotempfindliche Schicht)
    • rotsensibilisierte Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,5 µm) aus 0,3 g AgNO3 mit
    • 0,75 g Gelatine
    • 0,36 g Blaugrünkuppler C
    • 0,36 g TKP
  • 7. Schicht (UV-Schutzschicht)
    • 0,35 g Gelatine
    • 0,15 g UV-Absorber gemäß 5. Schicht
    • 0,2 g TKP
  • 8. Schicht (Schutzschicht)
    • 0,9 g Gelatine
    • 0,3 g Härtungsmittel H der folgenden Formel
      Figure imgb0003
Die verwendeten Komponenten haben folgende Formel:
Figure imgb0004
Figure imgb0005
Figure imgb0006
Ein Stufenkeil wurde auf das oben beschriebene fotografische Aufzeichnungsmaterial aufbelichtet und wie folgt verarbeitet:
Figure imgb0007
  • 1st layer (substrate layer):
    • 0.2 g gelatin
  • 2nd layer (blue-sensitive layer):
    • blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.8 µm) from 0.63 g AgN0 3 with
    • 1.38 g gelatin
    • 0.95 g yellow coupler Y
    • 0.29 g tricresyl phosphate (CPM)
  • 3rd layer (protective layer)
    • 1.1 g gelatin
    • 0.06 g 2,5-dioctylhydroquinone
    • 0.06 g dibutyl phthalate (DBP)
  • 4th layer (green-sensitive layer) green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.6 µm) from 0.45 g AgN0 3 with
    • 1.08 g gelatin
    • 0.41 g purple coupler M
    • 0.08 g 2,5-dioctyl hydroquinone
    • 0.34 g DBP
    • 0.04 g CPM
  • 5th layer (UV protective layer)
    • 1.15 g gelatin
    • 0.6 g UV absorber of the formula
      Figure imgb0002
    • 0.045g 2,5-dioctyl hydroquinone
    • 0.04 g CPM
  • 6th layer (red-sensitive layer)
    • red-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.5 µm) from 0.3 g AgNO 3 with
    • 0.75 g gelatin
    • 0.36 g cyan coupler C
    • 0.36 g CPM
  • 7th layer (UV protective layer)
    • 0.35 g gelatin
    • 0.15 g UV absorber according to the 5th layer
    • 0.2 g CPM
  • 8th layer (protective layer)
    • 0.9 g gelatin
    • 0.3 g of curing agent H of the following formula
      Figure imgb0003
The components used have the following formula:
Figure imgb0004
Figure imgb0005
Figure imgb0006
 A step wedge was exposed on the photographic material described above and processed as follows:
Figure imgb0007

Die einzelnen Verarbeitungsbäder hatten die folgende Zusammensetzung:

  • Entwickler:
    Figure imgb0008
    pH-Wert Einstellung auf 10 mit KOH bzw. H2S04. Mit Wasser auf 1 Liter auffüllen.
  • Bleichbad A
    Figure imgb0009
  • Fixierbad
    Figure imgb0010
    Einstellung auf pH 7 mit Ammoniak oder Essigsäure Mit Wasser auf 1 Liter auffüllen. Ergebnis der Restsilberbestimmung siehe Tab. 1.
The individual processing baths had the following composition:
  • Developer:
    Figure imgb0008
    pH adjustment to 10 with KOH or H 2 S0 4 . Make up to 1 liter with water.
  • Bleach bath A
    Figure imgb0009
  • Fixer
    Figure imgb0010
    Adjust to pH 7 with ammonia or acetic acid. Make up to 1 liter with water. For the result of the residual silver determination, see Tab. 1.

Beispiel 2 (Vergleich)Example 2 (comparison)

Die Belichtung und Verarbeitung erfolgten wie in Beispiel 1 beschrieben. Der Entwickler hatte die gleiche Zusammensetzung wie in Beispiel 1.The exposure and processing were carried out as described in Example 1. The developer had the same composition as in Example 1.

Bleichbad BBleach bath B

Figure imgb0011
Figure imgb0011

Fixierbad wie Beispiel 1Fixing bath as in example 1

Ergebnis der Restsilberbestimmung: siehe Tabelle 1.Result of the residual silver determination: see Table 1.

Beispiel 3 (Vergleich)Example 3 (comparison)

Die Belichtung und Verarbeitung erfolgten wie in Beispiel 1 beschrieben. Der Entwickler hatte die gleiche Zusammensetzung wie in Beispiel 1.The exposure and processing were carried out as described in Example 1. The developer had the same composition as in Example 1.

Bleichbad CBleaching bath C

Figure imgb0012
Einstellung auf pH 6,0 mit Ammoniakwasser oder Essigsäure.
Figure imgb0012
 Adjust to pH 6.0 with ammonia water or acetic acid.

Mit Wasser auf 1 Liter auffüllen.Make up to 1 liter with water. Fixierbad wie Beispiel 1Fixing bath as in example 1

Ergebnis der Restsilberbestimmung: siehe Tabelle 1.

Figure imgb0013
Result of the residual silver determination: see Table 1.
Figure imgb0013

Tabelle 1 zeigt die gute Bleichwirkung des erfindungsgemäßen Bleichbades A, in dem ein biologisch abbaubarer Komplexbildner enthalten ist. Die Bleichwirkung entspricht der des üblichen Bleichbades C, das die biologisch schwer abbaubare EDTA enthält. Das Bleichbad B, das im wesentlichen wie Bleichbad A zusammengesetzt ist, aber in dem für EDTA-Bleichbäder vorgeschriebenen pH-Bereich liegt, bleicht dagegen nur ungenügend.Table 1 shows the good bleaching action of the bleaching bath A according to the invention, which contains a biodegradable complexing agent. The bleaching effect corresponds to that of the usual bleaching bath C, which contains the biodegradable EDTA. The bleaching bath B, which is composed essentially like bleaching bath A, but lies in the pH range prescribed for EDTA bleaching baths, on the other hand only bleaches insufficiently.

Beispiel 4 (erfindungsgemäß)Example 4

Auf einen transparenten Schichtträger aus Cellulosetriacetat wurden jeweils folgende Schichten in der hier angegebenen Reihenfolge aufgetragen.The following layers were each applied to a transparent cellulose triacetate support in the order given here.

Die Mengenangaben beziehen sich jeweils auf 1 m2. Für den Silberhalogenidauftrag werden die äquivalenten Mengen an AgN03 angegeben.The amounts given relate in each case to 1 m 2. For the silver halide application, the equivalent amounts of AgN0 3 are given.

Alle Silberhalogenidemulsionen waren mit 0,1 g 4-Hydroxy-6-methyl-1,3,3a,7-tetraazainden pro 100 g AgN03 stabilisiert.

  • 1. Schicht: (Antihalo-Schicht)
    • 0,2 g schwarzes kolloidales Silber
    • 1,2 g Gelatine
    • 0,1 g UV-Absorber UV 1
    • 0,2 g UV-Absorber UV 2
    • 0,02 g Trikresylphosphat
    • 0,03 g Dibutylphthalat
  • 2. Schicht: (Mikrat-Zwischenschicht)
    • 0,25 g AgN03 einer Mikrat-Ag (Br,J)-Emulsion:
    • mittlerer Korn-∅ = 0,07 µm, 0,5 Mol-% lodid
    • 1,0 g Gelatine
    • 0,05 g farbiger Kuppler RM 1
    • 0,10 g Trikresylphosphat
  • 3. Schicht: (niedrig empfindlich rotsensibilisierte Schicht)
    • 2,2 g AgN03, 4 Mol-% lodid, mittlerer Korndurchmesser 0,45 um, rotsensibilisiert 2,0 g Gelatine
    • 0,6 g farbloser Blaugrünkuppler C 1 emulgiert in 0,5 g Trikresylphosphat (TKP) 50 mg farbiger Blaugrünkuppler RM 1 und
    • 30 mg DIR-Kuppler DIR 1 emulgiert in 20 mg TKP.
  • 4. Schicht: (hochempfindliche rotsensibilisierte Schicht)
    • 2,8 g AgN03, 8,5 Mol-% lodid, mittlerer Korndurchmesser 0,8 um, rotsensibilisiert 1,8 g Gelatine
    • 0,15 g farbloser Blaugrünkuppler C 2 emulgiert mit 0,15 g Dibutylphthalat (DBP)
  • 5. Schicht: (Trennschicht)
    • 0,7 g Gelatine
    • 0,2 g 2,5-Diisooctylhydrochinon
    • emulgiert mit 0,15 g DBP
  • 6. Schicht: (niedrigempfindliche grünsensibilisierte Schicht)
    • 1,8 g AgN03 einer spektral grünsensibilisierten Ag(Br,l)-Emulsion mit 4,5 Mol-% lodid und einem mittleren Korndurchmesser von 0,4 um, grünsensibilisiert,
    • 1,6 g Gelatine
    • 0,6 g Purpurkuppler M 1 (Latexkuppler)
    • 50 mg Maskenkuppler YM 1
    • emulgiert mit 50 mg TKP,
    • 30 mg DIR-Kuppler DIR 2
    • emulgiert in 20 mg DBP
    • 80 mg DIR-Kuppler DIR 3
    • emulgiert in 60 mg TKP
  • 7. Schicht (hochempfindliche grünsensibilisierte Schicht)
    • 2,2 g AgNO3 mit 7 Mol-% lodid und einem mittleren Korndurchmesser von 0,7 um, grünsensibilisiert, 1,4 g Gelatine
    • 0,15 g Purpurkuppler M 2
    • emulgiert mit 0,45 g TKP
    • 30 mg Maskenkuppler gemäß 6. Schicht,
    • emulgiert mit 30 mg TKP
  • 8. Schicht: (Trennschicht)
    • 0,5 g Gelatine
    • 0,1 g 2,5-Diisooctylhydrochinon
    • emulgiert mit 0,08 g DBP
  • 9. Schicht: (Gelbfilterschicht)
    • 0,2 g Ag (gelbes kolloidales Silbersol)
    • 0,9 g Gelatine
    • 0,2 g 2,5-Diisooctylhydrochinon
    • emulgiert mit 0,16 g DBP
  • 10. Schicht: (niedrigempfindliches blauempfindliche Schicht)
    • 0,6 g AgN03, 4,9 Mol-% lodid, mittlerer Korndurchmesser 0,45 um, blausensibilisiert, 0,85 g Gelatine
    • 0,7 g Gelbkuppler Y 1
    • emulgiert mit 0,7 g TKP,
    • 0,5 g DIR-Kuppler DIR 3
    • emulgiert mit 0,5 g TKP
  • 11. Schicht: (hochempfindliche blauempfindliche Schicht
    • 1,0 g AgN03, 9,0 Mol-% lodid, mittlerer Korndurchmesser 0,9 um, blausensibilisiert, 0,85 g Gelatine
    • 0,3 g Gelbkuppler gemäß 10. Schicht
    • emulgiert mit 0,3 g TKP
  • 12. Schicht: (Schutz- und Härtungsschicht)
    • 0,5 g AgNO3 einer Mikrat-Ag(Br,l)-Emulsion, mittlerer Korndurchmesser 0,07 um, 0,5 Mol-% lodid 1,2 g Gelatine
    • 0,4 g Härtungsmittel der Formel
    • (CH2 = CH-SO2-CH2-CONH-CH2-)2-
    • 1,0 g Formaldehydfänger der Formel
      Figure imgb0014
      Figure imgb0015
      Figure imgb0016
      Figure imgb0017
      Figure imgb0018
      Figure imgb0019
      Figure imgb0020
      Figure imgb0021
      Figure imgb0022
      Figure imgb0023
      Figure imgb0024
      Figure imgb0025
      Figure imgb0026
All silver halide emulsions were stabilized with 0.1 g 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per 100 g AgN0 3 .
  • 1st layer: (antihalo layer)
    • 0.2 g black colloidal silver
    • 1.2 g gelatin
    • 0.1 g UV absorber UV 1
    • 0.2 g UV absorber UV 2
    • 0.02 g tricresyl phosphate
    • 0.03 g dibutyl phthalate
  • 2nd layer: (intermediate layer)
    • 0.25 g AgN0 3 of a Mikrat-Ag (Br, J) emulsion:
    • average grain ∅ = 0.07 µm, 0.5 mol% iodide
    • 1.0 g gelatin
    • 0.05 g colored coupler RM 1
    • 0.10 g tricresyl phosphate
  • 3rd layer: (low sensitive red-sensitive layer)
    • 2.2 g AgN0 3 , 4 mol% iodide, average grain diameter 0.45 µm, red-sensitized 2.0 g gelatin
    • 0.6 g colorless cyan coupler C 1 emulsifies in 0.5 g tricresyl phosphate (TKP) 50 mg colored cyan coupler RM 1 and
    • 30 mg DIR coupler DIR 1 emulsifies in 20 mg CPM.
  • 4th layer: (highly sensitive red-sensitized layer)
    • 2.8 g AgN0 3 , 8.5 mol% iodide, average grain diameter 0.8 µm, red-sensitized 1.8 g gelatin
    • 0.15 g colorless cyan coupler C 2 emulsified with 0.15 g dibutyl phthalate (DBP)
  • 5th layer: (separation layer)
    • 0.7 g gelatin
    • 0.2 g of 2,5-diisooctyl hydroquinone
    • emulsified with 0.15 g DBP
  • 6th layer: (low-sensitivity green-sensitized layer)
    • 1.8 g AgN0 3 of a spectrally green-sensitized Ag (Br, l) emulsion with 4.5 mol% iodide and an average grain diameter of 0.4 μm, green-sensitized,
    • 1.6 g gelatin
    • 0.6 g purple coupler M 1 (latex coupler)
    • 50 mg mask coupler YM 1
    • emulsified with 50 mg CPM,
    • 30 mg DIR coupler DIR 2
    • emulsified in 20 mg DBP
    • 80 mg DIR coupler DIR 3
    • emulsified in 60 mg CPM
  • 7th layer (highly sensitive green-sensitized layer)
    • 2.2 g AgNO 3 with 7 mol% iodide and an average grain diameter of 0.7 μm, green-sensitized, 1.4 g gelatin
    • 0.15 g purple coupler M 2
    • emulsified with 0.45 g CPM
    • 30 mg mask coupler according to 6th layer,
    • emulsified with 30 mg CPM
  • 8th layer: (separation layer)
    • 0.5 g gelatin
    • 0.1 g of 2,5-diisooctyl hydroquinone
    • emulsified with 0.08 g DBP
  • 9th layer: (yellow filter layer)
    • 0.2 g Ag (yellow colloidal silver sol)
    • 0.9 g gelatin
    • 0.2 g of 2,5-diisooctyl hydroquinone
    • emulsified with 0.16 g DBP
  • 10th layer: (low-sensitivity blue-sensitive layer)
    • 0.6 g AgN0 3 , 4.9 mol% iodide, average grain diameter 0.45 µm, blue-sensitized, 0.85 g gelatin
    • 0.7 g yellow coupler Y 1
    • emulsified with 0.7 g CPM,
    • 0.5 g DIR coupler DIR 3
    • emulsified with 0.5 g CPM
  • 11th layer: (highly sensitive blue-sensitive layer
    • 1.0 g AgN0 3 , 9.0 mol% iodide, average grain diameter 0.9 µm, blue-sensitized, 0.85 g gelatin
    • 0.3 g yellow coupler according to the 10th shift
    • emulsified with 0.3 g CPM
  • 12th layer: (protective and hardening layer)
    • 0.5 g AgNO 3 of a Mikrat-Ag (Br, I) emulsion, average grain diameter 0.07 µm, 0.5 mol% iodide 1.2 g gelatin
    • 0.4 g hardening agent of the formula
    • (CH 2 = CH-SO 2 -CH 2 -CONH-CH 2 -) 2 -
    • 1.0 g formaldehyde scavenger of the formula
      Figure imgb0014
      Figure imgb0015
      Figure imgb0016
      Figure imgb0017
      Figure imgb0018
      Figure imgb0019
      Figure imgb0020
      Figure imgb0021
      Figure imgb0022
      Figure imgb0023
      Figure imgb0024
      Figure imgb0025
      Figure imgb0026

Ein Stufenkeil wurde auf das oben beschriebene fotografische Aufzeichnungsmaterial aufbelichtet und wie folgt verarbeitet:

Figure imgb0027
Die Verarbeitungsbäder hatten die folgende Zusammensetzung:A step wedge was exposed on the photographic material described above and processed as follows:
Figure imgb0027
 The processing baths had the following composition:

Entwickler:Developer:

Figure imgb0028
Figure imgb0028

Bleichbad DBleach bath D

Figure imgb0029
mit Ammoniak
Figure imgb0029
 with ammonia

auf pH 5,0 einstellenadjust to pH 5.0

mit Wasser auf 1 Liter auffüllenMake up to 1 liter with water

FixierbadFixer

Figure imgb0030
Figure imgb0030

SchlußbadFinal bath

Figure imgb0031
Das Ergebnis bezüglich Restsilber ist der nachfolgenden Tabelle 2 zu entnehmen. Das erzeugte Farbbild war typgemäß.
Figure imgb0031
 The result with regard to residual silver is shown in Table 2 below. The color image produced was of the type.

Beispiel 5 (Vergleich)Example 5 (comparison)

Die Belichtung und Verarbeitung erfolgten wie in Beispiel 4 beschrieben. Entwickler-, Fixier- und Schlußbad hatten die gleiche Zusammensetzung wie in Beispiel 4.The exposure and processing were carried out as described in Example 4. Developer, fixer and final bath had the same composition as in Example 4.

Bleichbad EBleach bath E

Figure imgb0032
mit Ammoniak pH-Wert auf 6,0 einstellen
Figure imgb0032
 adjust pH to 6.0 with ammonia

mit Wasser auf 1 Liter auffüllenMake up to 1 liter with water

Das Ergebnis der Restsilberbestimmung ist der nachfolgenden Tabelle 2 zu entnehmen.The result of the residual silver determination is shown in Table 2 below.

Beispiel 6 (Vergleich)Example 6 (comparison)

Die Belichtung und Verarbeitung erfolgten wie in Beispiel 4 beschrieben. Entwickler-, Fixier- und Schlußbad hatten die gleiche Zusammensetzung wie in Beispiel 4.The exposure and processing were carried out as described in Example 4. Developer, fixer and final bath had the same composition as in Example 4.

Bleichbad FBleach bath F

Figure imgb0033
mit Ammoniak pH-Wert auf 6,0 einstellen
Figure imgb0033
 adjust pH to 6.0 with ammonia

mit Wasser auf 1 Liter auffüllenMake up to 1 liter with water

Das Ergebnis bezüglich Restsilber ist der nachfolgenden Tabelle 2 zu entnehmen.

Figure imgb0034
The result with regard to residual silver is shown in Table 2 below.
Figure imgb0034

Wie aus Tabelle 2 zu ersehen ist, entspricht die Bleichwirkung des erfindungsgemäßen Bleichbades D mit einem biologisch abbaubaren Komplexbildner der Bleichwirkung des üblichen Bleichbades F mit dem biologisch schwer abbaubaren Komplexbildner EDTA. Das Bleichbad E, das im wesentlichen wie Bleichbad D zusammengesetzt ist, aber einen für EDTA-Bleichbäder üblichen pH-Wert besitzt, bleicht dagegen nur ungenügend. Die durchgeführten Bleichversuche zeigten, daß das erfindungsgemäße Bleichbad D nicht zur Bildung von Leuco-Blaugrünfarbstoff führt, während bei einem üblichen Bleichbad mit EDTA bei entsprechendem pH-Wert deutliche Verluste an Blaugrünfarbstoff auftreten.As can be seen from Table 2, the bleaching action of the bleaching bath D according to the invention with a biodegradable complexing agent corresponds to the bleaching action of the customary bleaching bath F with the biodegradable complexing agent EDTA. The bleaching bath E, which is composed essentially like bleaching bath D, but has a pH value customary for EDTA bleaching baths, on the other hand only bleaches insufficiently. The bleaching tests carried out showed that the bleaching bath D according to the invention does not lead to the formation of leuco blue-green dye, while in a conventional bleaching bath with EDTA there are significant losses of blue-green dye at the corresponding pH.

Beispiel 7 (erfindungsgemäß)Example 7

Ein farbfotografisches Aufzeichnungsmaterial für die Umkehrverarbeitung wurde hergestellt, indem auf einen mit einer Haftschicht versehenen Schichtträger aus Cellulosetriacetat nacheinander die folgenden Schichten aufgetragen wurden.

  • 1. (Antihaloschicht)
    • schwarzes kolloidales Silbersol mit
    • 0,2 g Ag
    • 1,2 g Gelatine
    • 0,10 g UV-Absorber UV-1
    • 0,20 g UV-Absorber UV-2
    • 0,02 g Trikresylphosphat (TKP)
    • 0,03 g Dibutylphthalat (DBP)
  • 2. (Mikrat-Zwischenschicht)
    • Mikrat-Silberbromidiodidemulsion
    • (0,5 mol-% lodid;
    • mittlerer Korndurchmesser 0,07 um) aus
    • 0,25 g AgN03, mit
    • 1,0 g Gelatine
    • 0,10 g TKP
  • 3. Eine rotsensibilisierte Silberhalogenidemulsion, mittlerer Korndurchmesser 0,5 um, enthaltend pro kg 70 g Gelatine, 60 g Silber (davon 96 Mol-% in Form des Bromids und 4 Mol-% in Form des lodids) und 55 g des Blaugrünkupplers BG.
    • Der Silberauftrag pro m2 beträgt 2,5 g Silbernitrat.
  • 4. Eine 2 gew.-%ige wäßrige Gelatinelösung mit einem Naßauftrag von 60 g/m2, enthaltend pro kg 4 g des polymeren Weißkupplers W.
  • 5. Eine grünsensibilisierte Silberhalogenidemulsion, mittlerer Korndurchmesser 0,45 um, enthaltend pro kg 70 g Gelatine, 60 g Silber (davon 96 Mol-% in Form des Bromids und 4 Mol-% in Form des lodids) und 60 g des Purpurkupplers PP.
    • Der Silberauftrag pro m2 beträgt 2,8 g Silbernitrat.
  • 6. Eine gelbe Silberdispersion, enthaltend pro kg die 1,8 g Silbernitrat entsprechende Menge Silber und 12 g Gelatine. Die Farbdichte der Gelbfilterschicht, gemessen hinter einem Blaufilter, beträgt 0,6; der Silberauftrag pro m2 beträgt 0,2 g Silber nitrat.
  • 7. Eine unsensibilisierte Silberhalogenidemulsion, mittlerer Korndurchmesser 0,6 um, enthaltend pro kg 70 g Gelatine, 60 g Silber (davon 95 Mol-% in Form des Bromids und 5 Mol-% in Form des lodids) und 140 g des Gelbkupplers GB.
A color photographic recording material for reverse processing was prepared by successively applying the following layers to a cellulose triacetate support provided with an adhesive layer.
  • 1. (antihalation layer)
    • black colloidal silver sol with
    • 0.2 g Ag
    • 1.2 g gelatin
    • 0.10 g UV absorber UV-1
    • 0.20 g UV absorber UV-2
    • 0.02 g tricresyl phosphate (CPM)
    • 0.03 g dibutyl phthalate (DBP)
  • 2. (Mikrat intermediate layer)
    • Mikrat-silver bromide iodide emulsion
    • (0.5 mol% iodide;
    • average grain diameter 0.07 µm)
    • 0.25 g AgN0 3 , with
    • 1.0 g gelatin
    • 0.10 g CPM
  • 3. A red-sensitized silver halide emulsion, average grain diameter 0.5 μm, containing 70 g gelatin, 60 g silver (thereof 96 mol% in the form of the bromide and 4 mol% in the form of the iodide) and 55 g of the cyan coupler BG per kg.
    • The amount of silver applied per m 2 is 2.5 g of silver nitrate.
  • 4. A 2% by weight aqueous gelatin solution with a wet application of 60 g / m 2 , containing 4 g of the polymeric white coupler W per kg.
  • 5. A green-sensitized silver halide emulsion, average grain diameter 0.45 µm, containing 70 g of gelatin, 60 g of silver (thereof 96 mol% in the form of the bromide and 4 mol% in the form of the iodide) and 60 g of the magenta coupler PP per kg.
    • The amount of silver applied per m 2 is 2.8 g of silver nitrate.
  • 6. A yellow silver dispersion containing per kg the amount of silver corresponding to 1.8 g of silver nitrate and 12 g of gelatin. The color density of the yellow filter layer, measured behind a blue filter, is 0.6; the amount of silver applied per m 2 is 0.2 g of silver nitrate.
  • 7. An unsensitized silver halide emulsion, average grain diameter 0.6 µm, containing 70 g of gelatin, 60 g of silver (thereof 95 mol% in the form of the bromide and 5 mol% in the form of the iodide) per kg and 140 g of the yellow coupler GB.

Der Silberauftrag pro m2 beträgt 1,5 g Silbernitrat.

  • 8. Eine 1 gew.-%ige Gelatinelösung mit einem Naßauftrag von 60 g pro m2.
  • 9. Eine 1 gew.-%ige wäßrige Lösung des Härters H mit einem Naßauftrag von 60 g pro m2:
    Figure imgb0035
    Figure imgb0036
    Figure imgb0037
Figure imgb0038
Figure imgb0039
Figure imgb0040
Figure imgb0041
 The amount of silver applied per m 2 is 1.5 g of silver nitrate.
  • 8. A 1% by weight gelatin solution with a wet application of 60 g per m 2 .
  • 9. A 1% strength by weight aqueous solution of hardener H with a wet application of 60 g per m 2 :
    Figure imgb0035
    Figure imgb0036
    Figure imgb0037
Figure imgb0038
Figure imgb0039
Figure imgb0040
Figure imgb0041

Die auf diese Weise hergestellten Proben wurden unter einem Stufenteil belichtet und wie folgt verarbeitet:

Figure imgb0042
Die Verarbeitungsbäder hatten folgende Zusammensetzung:The samples produced in this way were exposed under a step part and processed as follows:
Figure imgb0042
 The processing baths had the following composition:

Erstentwickler:First developer:

Figure imgb0043
Figure imgb0043

UmkehrbadReverse bath

Figure imgb0044
Figure imgb0044

Farbentwickler:Color developer:

Figure imgb0045
Figure imgb0045

Konditionierbad:Conditioning bath:

Figure imgb0046
Figure imgb0046

Bleichbad G:Bleaching bath G:

Figure imgb0047
Figure imgb0047

Fixierbad:Fixing bath:

Figure imgb0048
Figure imgb0048

Stabilisierbad:Stabilizing bath:

Figure imgb0049
Das Ergebnis bezüglich Restsilber ist der nachfolgenden Tabelle 3 zu entnehmen.
Figure imgb0049
 The result with regard to residual silver is shown in Table 3 below.

Beispiel 8 (Vergleich)Example 8 (comparison)

Die Belichtung und Verarbeitung erfolgten wie in Beispiel 7 beschrieben. Mit Ausnahme des Bleichbades hatten alle Verarbeitungsbäder die gleiche Zusammensetzung wie in Beispiel 7.The exposure and processing were carried out as described in Example 7. With the exception of the bleach bath, all processing baths had the same composition as in Example 7.

Bleichbad H:Bleach bath H:

Figure imgb0050
Das Ergebnis der Restsilberbestimmung ist der nachfolgenden Tabelle 3 zu entnehmen.
Figure imgb0050
 The result of the residual silver determination is shown in Table 3 below.

Beispiel 9 (Vergleich)Example 9 (comparison)

Die Belichtung und Verarbeitung erfolgten wie in Beispiel 7 beschrieben. Mit Ausnahme des Bleichbades hatten alle Verarbeitungsbäder die gleiche Zusammensetzung wie in Beispiel 7.The exposure and processing were carried out as described in Example 7. With the exception of the bleach bath, all processing baths had the same composition as in Example 7.

Bleichbad IBleach bath I

Figure imgb0051
Figure imgb0051
Figure imgb0052
Figure imgb0052

Das Ergebnis bezüglich Restsilber ist der nachfolgenden Tabelle 3 zu entnehmen.

Figure imgb0053
The result with regard to residual silver is shown in Table 3 below.
Figure imgb0053

Wie aus Tabelle 3 zu ersehen ist, entspricht die Bleichwirkung des erfindungsgemäßen Bleichbades G mit einem biologisch abbaubaren Komplexbildner der Bleichwirkung des üblichen Bleichbades I mit dem biologisch schwer abbaubaren Komplexbildner EDTA. Das Bleichbad H, das im wesentlichen wie Bleichbad G zusammengesetzt ist, aber einen für EDTA-Bleichbäder üblichen pH-Wert besitzt, bleicht dagegen nur ungenügend.As can be seen from Table 3, the bleaching action of the bleaching bath G according to the invention with a biodegradable complexing agent corresponds to the bleaching action of the conventional bleaching bath I with the biodegradable complexing agent EDTA. The bleaching bath H, which is composed essentially like bleaching bath G, but has a pH value customary for EDTA bleaching baths, on the other hand only bleaches insufficiently.

Claims (5)

1. Bleichbad, das (1) einen Eisen (III)-komplex, dessen Komplexbildner zu wenigstens 20 Mol-% der Formel I
Figure imgb0054
entspricht, enthält, und
(2) auf einen pH-Wert x eingestellt ist, wobei 6,0 > x > 4,5 gilt.1. bleaching bath containing (1) an iron (III) complex, the complexing agent of which is at least 20 mol% of the formula I.
Figure imgb0054
 corresponds, contains, and
(2) is adjusted to a pH value x, where 6.0>x> 4.5 applies. 2. Bleichbad nach Anspruch 1, dessen Komplexbildner zu wenigstens 80 Mol-% der Formel I entspricht,2. bleaching bath according to claim 1, the complexing agent of which corresponds to at least 80 mol% of formula I, 3. Bleichbad nach Anspruch 1 mit einem Überschuß an freiem Komplexbildner von 1 bis 120 Mol-%.3. bleaching bath according to claim 1 with an excess of free complexing agent from 1 to 120 mol%. 4. Bleichbad nach Anspruch 1, das Thiosulfat höchstens in einer Menge enthält, die zum Fixieren des nicht entwickelten Silberhalogenids nicht ausreicht.4. bleaching bath according to claim 1, which contains thiosulfate at most in an amount which is insufficient for fixing the undeveloped silver halide. 5. Bleichbad nach Anspruch 1, das frei von Thiosulfat ist.5. bleaching bath according to claim 1, which is free of thiosulfate.
EP91111713A 1990-07-27 1991-07-13 Bleach bath Expired - Lifetime EP0468325B1 (en)

Applications Claiming Priority (4)

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DE4023817 1990-07-27
DE19904023817 DE4023817A1 (en) 1990-07-27 1990-07-27 Bleach bath contg. nitrilo di:acetic mono:propionic acid as chelant
DE4029805 1990-09-20
DE19904029805 DE4029805A1 (en) 1990-09-20 1990-09-20 Bleach bath contg. nitrilo di:acetic mono:propionic acid as chelant

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0534086A1 (en) * 1991-07-26 1993-03-31 Konica Corporation Bleach solution for colour photographic process
US5627015A (en) * 1993-12-07 1997-05-06 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic material
US6824965B2 (en) 2000-08-04 2004-11-30 Agfa-Gevaert Bleach bath

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1980000624A1 (en) * 1978-09-14 1980-04-03 Eastman Kodak Co Photographic bleach compositions and methods of photographic processing
EP0270217A2 (en) * 1986-10-08 1988-06-08 Konica Corporation Bleach-fixing solution having good processing performance and method for processing light-sensitive material using the same
EP0293729A1 (en) * 1987-05-25 1988-12-07 Konica Corporation Composition containing ferric complex salt
US4914008A (en) * 1985-04-25 1990-04-03 Konishiroku Photo Industry Co., Ltd. Processing method of light-sensitive silver halide color photographic material

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3770437A (en) * 1972-04-06 1973-11-06 D Brugger Photographic bleach compositions
JPS5165939A (en) * 1974-12-05 1976-06-08 Fuji Photo Film Co Ltd KARAASHASHINZAIRYONO SHORIHOHO
JPS60263152A (en) * 1984-06-12 1985-12-26 Konishiroku Photo Ind Co Ltd Solution capable of bleaching for processing silver halide color photographic sensitive material
JPS61248044A (en) * 1985-04-25 1986-11-05 Konishiroku Photo Ind Co Ltd Treatment of silver halide color plhotographic sensitive material
JPH06103383B2 (en) * 1985-05-27 1994-12-14 コニカ株式会社 Method for forming color photographic image

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1980000624A1 (en) * 1978-09-14 1980-04-03 Eastman Kodak Co Photographic bleach compositions and methods of photographic processing
US4914008A (en) * 1985-04-25 1990-04-03 Konishiroku Photo Industry Co., Ltd. Processing method of light-sensitive silver halide color photographic material
EP0270217A2 (en) * 1986-10-08 1988-06-08 Konica Corporation Bleach-fixing solution having good processing performance and method for processing light-sensitive material using the same
EP0293729A1 (en) * 1987-05-25 1988-12-07 Konica Corporation Composition containing ferric complex salt

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0534086A1 (en) * 1991-07-26 1993-03-31 Konica Corporation Bleach solution for colour photographic process
US5627015A (en) * 1993-12-07 1997-05-06 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic material
US6824965B2 (en) 2000-08-04 2004-11-30 Agfa-Gevaert Bleach bath

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