EP0563637A1 - Developping bath - Google Patents

Developping bath Download PDF

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Publication number
EP0563637A1
EP0563637A1 EP93103857A EP93103857A EP0563637A1 EP 0563637 A1 EP0563637 A1 EP 0563637A1 EP 93103857 A EP93103857 A EP 93103857A EP 93103857 A EP93103857 A EP 93103857A EP 0563637 A1 EP0563637 A1 EP 0563637A1
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EP
European Patent Office
Prior art keywords
alkyl
hydroxy
developer
carboxy
bath
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.)
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Application number
EP93103857A
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German (de)
French (fr)
Inventor
Paul Dr. Marx
Gustav Ing.-Grad. Tappe
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Agfa Gevaert AG
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Agfa Gevaert AG
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Publication of EP0563637A1 publication Critical patent/EP0563637A1/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
    • G03C5/29—Development processes or agents therefor
    • G03C5/305—Additives other than developers

Definitions

  • the invention relates to a developer bath which is suitable for processing photographic silver halide materials and which contains a biodegradable limescale inhibitor.
  • EDTA ethylenediaminetetraacetic acid
  • EDTA is classified as dangerous in environmental behavior. It accumulates in waste water because it is hardly biodegradable. If EDTA is now replaced by nitrilotriacetic acid (NTA), the good biodegradability of which is known, a precipitate forms in a developer bath together with the calcium and magnesium ions of the preparation water.
  • NTA nitrilotriacetic acid
  • the object of the invention is to develop an environmentally friendly developer bath which is free of EDTA but does not cause any deposits during the processing process.
  • the complexing agents are usually used in a concentration of 0.5 to 100 mmol / l, the invention in a preferred form containing 2 to 30 mmol / l of complexing agents.
  • the unexpected and surprising effect of the invention lies in the fact that the group of degradable complexing agents according to the invention does not form any precipitate with the calcium and magnesium ions in the preparation water.
  • Other degradable complexing agents such as NTA, produce solid precipitations after just a few days of standing.
  • the developer bath according to the invention is suitable for photographic silver halide recording materials, in particular for black and white photographic materials.
  • the developer bath preferably has a pH of 8.5 to 12.
  • the developer bath according to the invention is used within the usual processing method for photographic silver halide materials.
  • the processing method can be carried out continuously with constant regeneration of the individual processing baths.
  • the developer baths listed in the examples are comparable in their developer behavior to a conventional EDTA-containing developer bath.
  • a developer bath of the following composition with a precisely defined calcium ion concentration was produced and mixed with different complexing agents in different concentrations (Table 1). All developer baths according to the invention showed no precipitation during the observation period of 45 days.
  • the developer baths were stored in open vessels at room temperature. A decrease in volume due to evaporation was compensated for by periodically filling the baths with deionized water.

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

Abstract

The invention relates to a developing bath which is readily biodegradable and contains a complexing agent of the formula <IMAGE> in which R and M are as defined in the description.b

Description

Die Erfindung betrifft ein für die Verarbeitung fotografischer Silberhalogenidmaterialien geeignetes Entwicklerbad, das ein biologisch abbaubares Kalkschutzmittel enthält.The invention relates to a developer bath which is suitable for processing photographic silver halide materials and which contains a biodegradable limescale inhibitor.

Üblicherweise werden diese Bäder mit Ethylendiamintetraessigsäure (EDTA) als Kalkschutzmittel versehen.These baths are usually provided with ethylenediaminetetraacetic acid (EDTA) as a limescale protection agent.

EDTA wird im Umweltverhalten als bedenklich eingestuft. Es reichert sich in Abwässern an, da es biologisch kaum abgebaut wird. Ersetzt man nun EDTA durch Nitrilotriessigsäure (NTA), deren gute biologische Abbaubarkeit bekannt ist, so bildet sich in einem Entwicklerbad zusammen mit den Calcium- und Magnesiumionen des Ansatzwassers ein Niederschlag.EDTA is classified as dangerous in environmental behavior. It accumulates in waste water because it is hardly biodegradable. If EDTA is now replaced by nitrilotriacetic acid (NTA), the good biodegradability of which is known, a precipitate forms in a developer bath together with the calcium and magnesium ions of the preparation water.

Der Erfindung liegt die Aufgabe zugrunde, ein umweltfreundliches Entwicklerbad zu entwickeln, das frei von EDTA ist, aber während des Verarbeitungsprozesses keine Ablagerungen verursacht.The object of the invention is to develop an environmentally friendly developer bath which is free of EDTA but does not cause any deposits during the processing process.

Es wurde nun gefunden, daß Komplexbildner der allgemeinen Formel I in Entwicklerbädern keine Ablagerungen verursachen, biologisch abbaubar sind und keine sensitometrischen Nachteile aufweisen.

Figure imgb0001

worin

R
Wasserstoff, C₁-C₁₀-Alkyl, Hydroxy-C₁-C₁₀-alkyl, C₁-C₁₀-Alkoxy-C₁-C₁₀-alkyl, Carboxy-C₂-C₁₀-alkyl, Dicarboxy-C₁-C₁₀-alkyl, Carboxy-hydroxy-C₁-C₁₀-alkyl, Hydroxy-C₁-C₅-alkyl-(oxy-C₁-C₅-alkyl)n, C₁-C₅-Alkoxy-C₁-C₅-alkyl-(oxy-C₁-C₅-alkyl)n,
M
Wasserstoff, Lithium, Natrium, Kalium und
n
1, 2, 3 oder 4 bedeuten.
Vorzugsweise werden in dem erfindungsgemäßen Entwicklerbad Komplexbildner der Formel I eingesetzt, in denen
R
1-Carboxy-ethyl oder 1-Hydroxy-ethyl und
M
Natrium bedeuten.
It has now been found that complexing agents of the general formula I do not cause deposits in developer baths, are biodegradable and have no sensitometric disadvantages.
Figure imgb0001
wherein
R
Hydrogen, C₁-C₁₀-alkyl, hydroxy-C₁-C₁₀-alkyl, C₁-C₁₀-alkoxy-C₁-C₁₀-alkyl, carboxy-C₂-C₁₀-alkyl, dicarboxy-C₁-C₁₀-alkyl, carboxy-hydroxy-C₁- C₁₀-alkyl, hydroxy-C₁-C₅-alkyl- (oxy-C₁-C₅-alkyl) n , C₁-C₅-alkoxy-C₁-C₅-alkyl- (oxy-C₁-C₅-alkyl) n ,
M
Hydrogen, lithium, sodium, potassium and
n
1, 2, 3 or 4 mean.
Complexing agents of the formula I are preferably used in the developer bath according to the invention, in which
R
1-carboxy-ethyl or 1-hydroxy-ethyl and
M
Mean sodium.

Üblicherweise werden die Komplexbildner in einer Konzentration von 0,5 bis 100 mmol/l verwendet, wobei die Erfindung in einer bevorzugten Form 2 bis 30 mmol/l an Komplexbildner enthält.The complexing agents are usually used in a concentration of 0.5 to 100 mmol / l, the invention in a preferred form containing 2 to 30 mmol / l of complexing agents.

Der unerwartete und überraschende Effekt der Erfindung liegt darin, daß die erfindungsgemäße Gruppe von abbaubaren Komplexbildnern mit den Calcium- und Magnesiumionen des Ansatzwassers keinen Niederschlag bildet. Andere abbaubare Komplexbildner, wie z.B. NTA, ergeben schon nach wenigen Tagen Stehzeit feste Ausfällungen.The unexpected and surprising effect of the invention lies in the fact that the group of degradable complexing agents according to the invention does not form any precipitate with the calcium and magnesium ions in the preparation water. Other degradable complexing agents, such as NTA, produce solid precipitations after just a few days of standing.

Das erfindungsgemäße Entwicklerbad eignet sich für fotografische Silberhalogenidaufzeichnungsmaterialien, insbesondere für schwarzweißfotografische Materialien.The developer bath according to the invention is suitable for photographic silver halide recording materials, in particular for black and white photographic materials.

Neben dem erfindungsgemäßen Komplexbildner und mindestens einer Entwicklersubstanz, z.B. einem Phenol, einem Phenolamin oder einem Pyrazolinon, kann das Entwicklerbad noch weitere Hilfsstoffe enthalten. Hierzu gehören u.a. Antischleiermittel, z.B. Benzotriazole oder Bromide, Oxidationsschutzmittel, z.B. Sulfite und Puffersubstanzen, z.B. Borate oder Carbonate.In addition to the complexing agent according to the invention and at least one developer substance, e.g. a phenol, a phenolamine or a pyrazolinone, the developer bath can also contain further auxiliaries. These include Antifoggants, e.g. Benzotriazoles or bromides, antioxidants, e.g. Sulfites and buffer substances, e.g. Borates or carbonates.

Das Entwicklerbad hat bevorzugt einen pH-Wert von 8,5 bis 12.The developer bath preferably has a pH of 8.5 to 12.

Das erfindungsgemäße Entwicklerbad wird innerhalb des üblichen Verarbeitungsverfahrens für fotografische Silberhalogenidmaterialien eingesetzt.The developer bath according to the invention is used within the usual processing method for photographic silver halide materials.

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 Entwicklerbäder sind in ihrem Entwicklerverhalten einem herkömmlichen EDTA-haltigen Entwicklerbad vergleichbar.The developer baths listed in the examples are comparable in their developer behavior to a conventional EDTA-containing developer bath.

BeispieleExamples

Ein Entwicklerbad nachfolgender Zusammensetzung mit genau definierter Calciumionerkonzentration wurde hergestellt und mit verschiedenen Komplexbildnern in unterschiedlichen Konzentrationen versetzt (Tabelle 1). Alle erfindungsgemäßen Entwicklerbäder zeigten während des Beobachtungszeitraums von 45 Tagen keinen Niederschlag. Die Entwicklerbäder wurden in offenen Gefäßen bei Raumtemperatur gelagert. Eine Volumenabnahme durch Verdunsten wurde durch periodisches Auffüllen der Bäder mit entionisiertem Wasser ausgeglichen. Entwickler 1: Wasser (entionisiert) 800 ml Hydrochinon 5 g Phenidon 0,5 g Natriumsulfit 60 g Kaliumbromid 3 g Natriumtetraborat x 5 H₂O 11,5 g Calciumchloridlösung (80 g/l) 15 ml Komplexbildner siehe Tabelle 1 pH-Wert mit KOH-Lösung auf 8,9 einstellen und mit entionisiertem Wasser auf 1 Liter auffüllen. Entwickler 2: Wasser (entionisiert) 800 ml Hydrochinon 6 g Phenidon 0,8 g Natriumsulfit 25 g Kaliumbromid 1 g Kaliumcarbonat 13 g Natriumtetraborat x 5 H₂O 15 g Calciumchloridlösung (80 g/l) 15 ml Komplexbildner siehe Tabelle 1 pH-Wert mit KOH-Lösung auf 9,5 einstellen und mit entionisiertem Wasser auf 1 Liter auffüllen. Tabelle 1 Beispiel Entwickler Komplexbildner Konzentration [mmol/l][g/l] Niederschlag nach Tagen 1 1 NTA 22 4,2 5 2 1 ADA 22 4,5 - 3 2 NTA 22 4,2 5 4 2 ADA 22 4,5 - 1 und 3 Vergleichsbeispiele
2 und 4 erfindungsgemäße Beispiele
NTA = Nitrilotriessigsäure
ADA = Nitrilodiessigmonopropionsäure A developer bath of the following composition with a precisely defined calcium ion concentration was produced and mixed with different complexing agents in different concentrations (Table 1). All developer baths according to the invention showed no precipitation during the observation period of 45 days. The developer baths were stored in open vessels at room temperature. A decrease in volume due to evaporation was compensated for by periodically filling the baths with deionized water. Developer 1: Water (deionized) 800 ml Hydroquinone 5 g Phenidone 0.5 g Sodium sulfite 60 g Potassium bromide 3 g Sodium tetraborate x 5 H₂O 11.5 g Calcium chloride solution (80 g / l) 15 ml Complexing agent see table 1 Adjust pH to 8.9 with KOH solution and make up to 1 liter with deionized water. Developer 2: Water (deionized) 800 ml Hydroquinone 6 g Phenidone 0.8 g Sodium sulfite 25 g Potassium bromide 1 g Potassium carbonate 13 g Sodium tetraborate x 5 H₂O 15 g Calcium chloride solution (80 g / l) 15 ml Complexing agent see table 1 Adjust pH to 9.5 with KOH solution and make up to 1 liter with deionized water. Table 1 example developer Complexing agent Concentration [mmol / l] [g / l] Rainfall after days 1 1 NTA 22 4.2 5 2nd 1 ADA 22 4.5 - 3rd 2nd NTA 22 4.2 5 4th 2nd ADA 22 4.5 - 1 and 3 comparative examples
2 and 4 examples according to the invention
NTA = nitrilotriacetic acid
ADA = nitrilodysigmonopropionic acid

Claims (4)

Entwicklerbäder, in denen die für die Entwicklung erforderlichen Wirk- und Hilfsstoffe enthalten sind, dadurch gekennzeichnet, daß sie zusätzlich einen Komplexbildner der Formel I
Figure imgb0002
 worin R   Wasserstoff, C₁-C₁₀-Alkyl, Hydroxy-C₁-C₁₀-alkyl, C₁-C₁₀-Alkoxy-C₁-C₁₀-alkyl, Carboxy-C₂-C₁₀-alkyl, Dicarboxy-C₁-C₁₀-alkyl, Carboxy-hydroxy-C₁-C₁₀-alkyl, Hydroxy-C₁-C₅-alkyl-(oxy-C₁-C₅-alkyl)n, C₁-C₅-Alkoxy-C₁-C₅-alkyl-(oxy-C₁-C₅-alkyl)n, M   Wasserstoff, Lithium, Natrium, Kalium und n   1, 2, 3 oder 4 bedeuten, enthalten. Developer baths containing the active ingredients and auxiliaries required for development, characterized in that they additionally contain a complexing agent of the formula I.
Figure imgb0002
 wherein R is hydrogen, C₁-C₁₀-alkyl, hydroxy-C₁-C₁ alkyl-alkyl, C₁-C₁₀-alkoxy-C₁-C₁₀-alkyl, carboxy-C₂-C₁₀-alkyl, dicarboxy-C₁-C₁₀-alkyl, carboxy-hydroxy-C₁ -C₁₀-alkyl, hydroxy-C₁-C₅-alkyl- (oxy-C₁-C₅-alkyl) n , C₁-C₅-alkoxy-C₁-C₅-alkyl- (oxy-C₁-C₅-alkyl) n , M hydrogen, lithium, sodium, potassium and n is 1, 2, 3 or 4. Entwicklerbäder nach Anspruch 1, dadurch gekennzeichnet, daß als zusätzlicher Komplexbildner Verbindungen der Formel I eingesetzt werden, in denen R 1-Carboxy-ethyl oder 1-Hydroxy-ethyl oder M Natrium bedeuten.Developer baths according to Claim 1, characterized in that compounds of the formula I in which R is 1-carboxy-ethyl or 1-hydroxy-ethyl or M are sodium are used as additional complexing agents. Entwicklerbäder nach Anspruch 1, dadurch gekennzeichnet, daß sie den zusätzlichen Komplexbildner in einer Konzentration von 0,5 bis 100 mmol/l enthalten.Developer baths according to claim 1, characterized in that they contain the additional complexing agent in a concentration of 0.5 to 100 mmol / l. Entwicklerbäder nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß sie zur Verarbeitung schwarzweißfotografischer Materialien geeignet sind.Developer baths according to one of Claims 1 to 3, characterized in that they are suitable for processing black and white photographic materials.
EP93103857A 1992-03-23 1993-03-10 Developping bath Withdrawn EP0563637A1 (en)

Applications Claiming Priority (2)

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DE19924209347 DE4209347A1 (en) 1992-03-23 1992-03-23 developer
DE4209347 1992-03-23

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0732620A1 (en) * 1995-03-02 1996-09-18 Kodak-Pathe Composition for developing an exposed photographic product having improved biodegradability

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6474039B2 (en) * 2015-03-27 2019-02-27 日本エクスラン工業株式会社 Discoloration-resistant fiber and fiber structure containing the fiber

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4486339A (en) * 1982-08-04 1984-12-04 The Dow Chemical Company Sequestering agent
JPS60118837A (en) * 1983-11-30 1985-06-26 Konishiroku Photo Ind Co Ltd Photographic color developing composition
EP0429973A1 (en) * 1989-11-21 1991-06-05 Du Pont De Nemours (Deutschland) Gmbh Method for developing photographic silver halide recording materials
JPH0462545A (en) * 1990-07-02 1992-02-27 Konica Corp Photographic processing agent composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4486339A (en) * 1982-08-04 1984-12-04 The Dow Chemical Company Sequestering agent
JPS60118837A (en) * 1983-11-30 1985-06-26 Konishiroku Photo Ind Co Ltd Photographic color developing composition
EP0429973A1 (en) * 1989-11-21 1991-06-05 Du Pont De Nemours (Deutschland) Gmbh Method for developing photographic silver halide recording materials
JPH0462545A (en) * 1990-07-02 1992-02-27 Konica Corp Photographic processing agent composition

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BELGISCHE CHEMISCHE INDUSTRIE Bd. 23, Nr. 10, 1958, Seiten 1105 - 1116 J. WILLEMS 'Nieuwe sekwestrerende verbindingen' *
DATABASE WPIL Week 9215, Derwent Publications Ltd., London, GB; AN 92-119488 (15) & JP-A-4 062 545 (KONICA CORP.) 27. Februar 1992 *
PATENT ABSTRACTS OF JAPAN vol. 9, no. 273 (P-401)(1996) 30. Oktober 1985 & JP-A-60 118 837 ( KONISHIROKU SHASHIN KOGYO K.K. ) 26. Juni 1985 *
PHOTOGRAPHIC SCIENCE AND ENGINEERING Bd. 3, Nr. 3, 1959, Seiten 140 - 144 R. W. HENN 'The calcium-sequestering properties of organic compounds in photographic developers' *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0732620A1 (en) * 1995-03-02 1996-09-18 Kodak-Pathe Composition for developing an exposed photographic product having improved biodegradability

Also Published As

Publication number Publication date
DE4209347A1 (en) 1993-09-30
JPH0619070A (en) 1994-01-28

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