DE4226372A1 - Photographic bleach bath with suppressed iron hydroxide pptn. - contg. biodegradable iron complex of amino-, imino- or nitrilo-carboxylic acid and biodegradable free hydroxy-carboxylic acid - Google Patents
Photographic bleach bath with suppressed iron hydroxide pptn. - contg. biodegradable iron complex of amino-, imino- or nitrilo-carboxylic acid and biodegradable free hydroxy-carboxylic acidInfo
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- DE4226372A1 DE4226372A1 DE19924226372 DE4226372A DE4226372A1 DE 4226372 A1 DE4226372 A1 DE 4226372A1 DE 19924226372 DE19924226372 DE 19924226372 DE 4226372 A DE4226372 A DE 4226372A DE 4226372 A1 DE4226372 A1 DE 4226372A1
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- Prior art keywords
- alkyl
- carboxylic acid
- biodegradable
- iii
- acid
- 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.)
- Ceased
Links
- -1 amino- Chemical class 0.000 title claims abstract description 17
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000007844 bleaching agent Substances 0.000 title abstract description 13
- 235000014413 iron hydroxide Nutrition 0.000 title description 5
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 title description 5
- 150000004698 iron complex Chemical class 0.000 title description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011975 tartaric acid Substances 0.000 claims abstract description 3
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 3
- 238000004061 bleaching Methods 0.000 claims description 21
- 239000008139 complexing agent Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 238000005406 washing Methods 0.000 abstract description 3
- 239000002738 chelating agent Substances 0.000 abstract description 2
- 150000004820 halides Chemical class 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract 2
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 abstract 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 abstract 1
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- UMEAURNTRYCPNR-UHFFFAOYSA-N azane;iron(2+) Chemical compound N.[Fe+2] UMEAURNTRYCPNR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- KEAYESYHFKHZAL-OUBTZVSYSA-N sodium-24 Chemical compound [24Na] KEAYESYHFKHZAL-OUBTZVSYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
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
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
Die Erfindung betrifft ein für die Verarbeitung farb fotografischer Silberhalogenidmaterialien geeignetes Bleichbad, das einen Eisenkomplex mit einem biologisch abbaubaren Chelatbildner, ein Rehalogenierungsmittel und eine Hydroxycarbonsäure enthält.The invention relates to a color for processing photographic silver halide materials Bleach that has an iron complex with a biological degradable chelating agent, a rehalogenating agent and contains a hydroxycarboxylic acid.
Zum Bleichen des bei der Entwicklung farbfotografischer Materialien entstandenen Silbers verwendet man üblicher weise Eisenkomplexsalze von Aminopolycarbonsäuren, bei spielsweise das Eisenammoniumkomplexsalz der Ethylen diamintetraessigsäure (Ullmanns Encyklopädie der tech nischen Chemie; 4. Aufl., Bd. 18. S. 463). Dieser und ähnliche, ebenfalls verwendete Komplexbildner sind bio logisch nur sehr langsam abbaubar.To bleach the color photographic in developing Materials resulting silver is used more commonly example iron complex salts of aminopolycarboxylic acids, at For example, the iron ammonium complex salt of ethylene diamintetraacetic acid (Ullmanns Encyklopadie der tech niche chemistry; 4th ed., Bd. 18. p. 463). This and similar, also used complexing agents are bio logically only very slowly degradable.
Es ist aus EP-A-430 000 bekannt, daß mit Eisenkomplex salzen von Nitrilotriessigsäure-Derivaten gut bleichende Bleichbäder für fotografische Materialien hergestellt werden können. Besonders geeignet sind die Eisenkomplex salze der Nitrilotriessigsäure und der Nitrilodiessigmo nopropionsäure.It is known from EP-A-430 000 that with iron complex Salts of nitrilotriacetic acid derivatives bleach well Bleaching baths made for photographic materials can be. Particularly suitable are the iron complex Salts of nitrilotriacetic acid and Nitrilodiessigmo nopropionsäure.
Die erwähnten Komplexbildner sind biologisch leicht ab baubar. Sie haben allerdings den Nachteil, daß ihre Eisenkomplexsalze in der dem Bleichbad nachfolgenden Wässerung infolge der Verdünnung zu einem merklichen Teil hydrolysieren. Es wird eine Abscheidung von Eisenhydroxid beobachtet.The mentioned complexing agents are easily biodegradable building land. However, they have the disadvantage that their Iron complex salts in the bleaching bath subsequent Irrigation due to dilution to a noticeable Partly hydrolyze. It will be a deposition of Iron hydroxide observed.
Diese Reaktion läßt sich vermeiden, wenn man einen Über schuß an freiem Komplexbildner einsetzt, der mehr als die bisher üblichen 5 bis 20 Mol-% beträgt.This reaction can be avoided by using an over shot at free complexing agent that more than the usual 5 to 20 mol%.
Aufgabe der Erfindung war es, Substanzen zu finden, die die Eisenhydroxid-Abscheidung in der dem Bleichbad nachfolgenden Wässerung unterdrücken, geringere Kosten als große Mengen zusätzlicher freier Komplexbildner verursachen und biologisch leicht abbaubar sind.The object of the invention was to find substances that the iron hydroxide deposition in the bleach suppress subsequent watering, lower costs as large amounts of additional free complexing agent cause and are readily biodegradable.
Diese Aufgabe wird mit einem Bleichbad gelöst, das (1) ein Eisen(III)-Komplexsalz, dessen Komplexbildner der Formel IThis object is achieved with a bleaching bath which (1) a ferric complex salt whose complexing agent is the Formula I
R1 = Carboxy-C1-C10-alkyl,
R2 = H, C1-C10-Alkyl, Hydroxy-C1-C10-alkyl, Carboxy-
C1-C10-alkyl, Carboxyhydroxy-C1-C10-alkyl,
R3 = H, C1-C10-Alkyl, Hydroxy-C1-C10-alkyl, Carboxy-
C1-C10-alkyl, Carboxyhydroxy-C1-C10-alkyl
entspricht, und
(2) eine Hydroxycarbonsäure enthält.R 1 = carboxy-C 1 -C 10 -alkyl,
R 2 = H, C 1 -C 10 -alkyl, hydroxy-C 1 -C 10 -alkyl, carboxy-C 1 -C 10 -alkyl, carboxyhydroxy-C 1 -C 10 -alkyl,
R 3 = H, C 1 -C 10 -alkyl, hydroxy-C 1 -C 10 -alkyl, carboxy-C 1 -C 10 -alkyl, carboxyhydroxy-C 1 -C 10 -alkyl
corresponds, and (2) contains a hydroxycarboxylic acid.
In einer bevorzugten Ausführungsform der Erfindung tragen alle Substituenten des Komplexbildners der Formel I einen Carboxy-C1-C10-alkylrest.In a preferred embodiment of the invention, all substituents of the complexing agent of the formula I carry a carboxy-C 1 -C 10 -alkyl radical.
In einer besonders bevorzugten Ausführungsform handelt es sich bei dem Komplexbildner um die Nitrilotriessig säure oder die Nitrilodiessigmonopropionsäure.In a particularly preferred embodiment it is the complexing agent to the Nitrilotriessig acid or Nitrilodiessigmonopropionsäure.
Die erfindungsgemäßen Hydroxycarbonsäuren entsprechen bevorzugt der Formel II:The hydroxycarboxylic acids according to the invention correspond preferably of the formula II:
R1, R2 = Wasserstoff oder Hydroxy
R3, R4 = Wasserstoff, Hydroxy oder Carboxy
l, n, m = 0 oder 1, wobei l, n und m nicht gleichzeitig
0 sind.R 1 , R 2 = hydrogen or hydroxy
R 3 , R 4 = hydrogen, hydroxy or carboxy
l, n, m = 0 or 1, where l, n and m are not 0 at the same time.
Besonders bevorzugte Hydroxycarbonsäuren sind die Citronensäure und die Weinsäure.Particularly preferred hydroxycarboxylic acids are the Citric acid and tartaric acid.
Das Bleichbad enthält üblicherweise 0,005 bis 1 Mol/l an Eisenkomplexsalz.The bleaching bath usually contains 0.005 to 1 mol / l on iron complex salt.
Die Hydroxycarbonsäure wird in einer Konzentration von 0,005 bis 0,5 Mol/l verwendet, wobei die Erfindung in einer bevorzugten Form 0,025 bis 0,15 Mol/l enthält.The hydroxycarboxylic acid is in a concentration of 0.005 to 0.5 mol / l used, the invention in a preferred form 0.025 to 0.15 mol / l.
Außer den erfindungsgemäßen Komponenten enthält das Bleichbad in einer bevorzugten Ausführungsform noch folgende Bestandteile:In addition to the components of the invention contains Bleach in a preferred embodiment yet following components:
- - freien Komplexbildner,- free complexing agent,
- - Bromid- oder Chlorid-Ionen als Rehalogenierungsmittel,Bromide or chloride ions as rehalogenating agents,
- - Nitrat-Ionen als Korrosionsschutzmittel.- Nitrate ions as corrosion inhibitors.
Weiterhin kann das erfindungsgemäße Bleichbad Ammonium-, Lithium-, Natrium- oder Kalium-Ionen enthalten.Furthermore, the bleaching solution according to the invention ammonium, Contain lithium, sodium or potassium ions.
Das Bleichbad hat insbesondere einen pH-Wert zwischen 0 und 7. The bleaching bath in particular has a pH value between 0 and 7.
Vorzugsweise enthält das Bleichbad einen Überschuß von 5 bis 20 Mol-%, bezogen auf den Eisenkomplex, an freiem Komplexbildner.Preferably, the bleach contains an excess of 5 to 20 mol%, based on the iron complex, of free Complexing agent.
Im gebrauchsfertigen Zustand enthält das Bleichbad be vorzugt 0,05 bis 2 Mol/l Halogenid und 0,01 bis 2 Mol/l Nitrat.When ready for use, the bleach contains be preferably 0.05 to 2 mol / l of halide and 0.01 to 2 mol / l Nitrate.
In einem Bleichbad für die Colorpapierverarbeitung wird vorzugsweise als Komplexverbindung das Eisen(III)-salz der Nitrilodiessigmonopropionsäure und als Hydroxycar bonsäure die Citronensäure verwendet.In a bleaching bath for color paper processing is preferably as a complex compound, the iron (III) salt Nitrilodiacs monopropionic acid and Hydroxycar acid which uses citric acid.
Weitere bevorzugte Bestandteile sind Natriumnitrat, Na triumbromid und das Trinatriumsalz der Nitrolodiessig monopropionsäure. In der bevorzugten Ausführungsform hat das Bleichmittel einen pH-Wert zwischen 2 und 5.Other preferred ingredients are sodium nitrate, Na triumbromide and the trisodium salt of Nitrolodiessig monopropionsäure. In the preferred embodiment the bleaching agent has a pH between 2 and 5.
Die Hydroxycarbonsäure können auch direkt dem auf das Bleichbad folgenden Wässerungsbad in einer Konzentra tion von 5·10-5 bis 5·10-3 Mol/l zugegeben werden. Be vorzugt werden in diesen Fall 10-4 bis 10-3 Mol/l ver wendet.The hydroxycarboxylic acid may also be added directly to the washing bath following the bleaching bath at a concentration of 5 x 10 -5 to 5 x 10 -3 mol / l. Be preferred in this case, 10 -4 to 10 -3 mol / l ver used.
Der unerwartete und überraschende Effekt der Erfindung liegt darin, daß bei der Kombination der beanspruchten Komplexbildner mit den verwendeten Hydroxycarbonsäuren ein biologisch leicht abbaubares Bleichbad erhalten wird, ohne daß in dem auf das Bleichbad folgendem Wäs serungsbad ein Eisenhydroxid-Niederschlag entsteht. Die Verhinderung der Eisenhydroxid-Bildung durch Hydroxy carbonsäuren war nicht vorhersehbar, da diese Verbin dungen eine wesentlich niedrigere Komplexbildungskon stante als Aminopolycarbonsäuren besitzen. Bei ver gleichbaren Konzentrationen wird die niederschlagshem mende Wirkung der Aminopolycarbonsäuren durch Hydroxy carbonsäuren deutlich übertroffen.The unexpected and surprising effect of the invention is that in the combination of the claimed Complexing agent with the hydroxycarboxylic acids used obtained a readily biodegradable bleaching bath is, without in the following on the bleach Wäs an iron hydroxide precipitate is formed. The Prevention of iron hydroxide formation by hydroxy Carboxylic acids was unpredictable as these are verbin a much lower complex formation con have constant as aminopolycarboxylic acids. At ver Equivalent concentrations will be the precipitate mende effect of the aminopolycarboxylic acids by hydroxy significantly outperformed carboxylic acids.
Das erfindungsgemäße Bleichbad eignet sich insbesondere für farbfotografische Silberhalogenidaufzeichnungsmate rialien, deren Silberhalogenidemulsion überwiegend aus AgBr, AgBrI, AgBrCl oder AgCl bestehen. Vorzugsweise ent hält das farbfotografische Material auf einem reflektie renden oder transparenten Träger (z. B. beidseitig mit Polyethylen beschichtetes Papier oder Cellulosetri acetatfilm) wenigstens eine blauempfindliche, wenigstens eine grünempfindliche und wenigstens eine rotempfind liche Silberhalogenidemulsionsschicht, denen in der an gegebenen Reihenfolge wenigstens ein Gelbkuppler, wenig stens ein Purpurkuppler und wenigstens ein Blaugrün kuppler zugeordnet sind.The bleaching bath according to the invention is particularly suitable for color photographic silver halide recording mate rialien whose silver halide emulsion predominantly AgBr, AgBrI, AgBrCl or AgCl. Preferably ent Holds the color photographic material on a reflectie or transparent carrier (eg on both sides with Polyethylene coated paper or cellulose tri acetate film) at least one blue-sensitive, at least a green-sensitive and at least one red-sensitive a silver halide emulsion layer to which in given order at least one yellow coupler, little at least one purple coupler and at least one teal are associated with couplers.
Das erfindungsgemäße Bleichbad wird innerhalb des üb lichen Verarbeitungsverfahrens für farbfotografische Silberhalogenidmaterialien eingesetzt und eignet sich zum Bleichen aller bekannten fotografischen Silberhalo genidmaterialien wie Colornegativfilmen, Colornegativ papier, Colorumkehrfilmen und Colorumkehrpapier.The bleaching bath according to the invention is within the üb processing method for color photographic Silver halide materials used and is suitable for bleaching all known photographic silver halo genidmaterialien such as color negative films, color negative paper, color reversal films and color reversal paper.
Das Verarbeitungsverfahren läßt sich unter ständigem Re generieren der einzelnen Verarbeitungsbäder kontinuier lich ausführen.The processing method can be under constant Re generate the individual processing baths continuously execute.
Ein Bleichbad nachfolgender Zusammensetzung wurde herge stellt und mit verschiedenen Komplexbildnern in unter schiedlichen Konzentrationen versetzt (Tabelle 1).A bleaching bath of the following composition was prepared sets and with different complexing agents in offset to different concentrations (Table 1).
Einstellung auf pH 4 mit Natriumcarbonat oder Essig säure. Mit Wasser auf 1 Liter auffüllen.Adjust to pH 4 with sodium carbonate or vinegar acid. Make up to 1 liter with water.
Zur Nachahmung der durch Verschleppung der Chemikalien entstehenden Konzentrationsverhältnisse in dem auf das Bleichbad folgenden Wässerungsbad wurden die Bleichbäder der Beispiele 1 bis 4 stark verdünnt. Zu jeweils 1 l Wasser wurde von jedem Bleichbad 3 ml gegeben. Die re sultierenden Lösungen wurden zwei Tage bei 40°C in of fenen Gefäßen gelagert.To imitate the by delaying the chemicals resulting concentration ratios in the on the Bleaching bath following washing bath were the bleaching baths of Examples 1 to 4 greatly diluted. To each 1 l Water was added 3 ml of each bleach. The re Two solutions were given at 40 ° C in two days stored in containers.
Tabelle 2 zeigt, daß die erfindungsgemäßen Hydroxycar bonsäuren einen Niederschlag verhindern.Table 2 shows that Hydroxycar invention Prevent precipitation of carboxylic acids.
Ein Bleichfixierbad nachfolgender Zusammensetzung wurde hergestellt und zur Herstellung von zwei Proben stark verdünnt. Zu jeweils 1 l Wasser wurde 1,2 ml Bleichfi xierbad gegeben. Eine Probe wurde mit 0,1 g (5·10-4 Mol) Citronensäure versetzt. Die resultierenden Lösungen wur den zwei Tage bei 40°C in offenen Gefäßen gelagert.A bleach-fix bath of the following composition was prepared and heavily diluted to prepare two samples. To 1 liter of water was added 1.2 ml Bleichfi xierbad. To a sample was added 0.1 g (5 x 10 -4 mol) of citric acid. The resulting solutions were stored in open vessels at 40 ° C for two days.
Einstellung auf pH 6 mit Ammoniak oder Essigsäure. Mit Wasser auf 1 Liter auffüllen.Adjust to pH 6 with ammonia or acetic acid. With Fill water to 1 liter.
Tabelle 3 zeigt, daß der Zusatz von Citronensäure einen Niederschlag verhindert.Table 3 shows that the addition of citric acid gives a Precipitation prevents.
Claims (6)
R2 = H, C1-C10-Alkyl, Hydroxy-C1-C10-alkyl, Carboxy-C1-C10-alkyl, Carboxyhydroxy-C1-C10- alkyl,
R3 = H, C1-C10-Alkyl, Hydroxy-C1-C10-alkyl, Carboxy-C1-C10-alkyl, Carboxyhydroxy-C1-C10- alkyl
entspricht, und (2) eine Hydroxycarbonsäure enthält.1. Bleaching bath, the (1) a ferric complex salt, the complexing agent of the formula I. R 1 = carboxy-C 1 -C 10 -alkyl,
R 2 = H, C 1 -C 10 -alkyl, hydroxy-C 1 -C 10 -alkyl, carboxy-C 1 -C 10 -alkyl, carboxyhydroxy-C 1 -C 10 -alkyl,
R 3 = H, C 1 -C 10 -alkyl, hydroxy-C 1 -C 10 -alkyl, carboxy-C 1 -C 10 -alkyl, carboxyhydroxy-C 1 -C 10 -alkyl
corresponds, and (2) contains a hydroxycarboxylic acid.
R3, R4 = Wasserstoff, Hydroxy oder Carboxy
l, n, m = 0 oder 1, wobei l, n und m nicht gleich zeitig 0 sind,
entspricht.4. bleaching bath according to claim 1, characterized in that the hydroxycarboxylic acid of the formula II R 1 , R 2 = hydrogen or hydroxy
R 3 , R 4 = hydrogen, hydroxy or carboxy
l, n, m = 0 or 1, where l, n and m are not 0 at the same time,
equivalent.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19924226372 DE4226372A1 (en) | 1992-08-10 | 1992-08-10 | Photographic bleach bath with suppressed iron hydroxide pptn. - contg. biodegradable iron complex of amino-, imino- or nitrilo-carboxylic acid and biodegradable free hydroxy-carboxylic acid |
| JP5213593A JPH06167788A (en) | 1992-08-10 | 1993-08-06 | Bleaching bath for photographic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19924226372 DE4226372A1 (en) | 1992-08-10 | 1992-08-10 | Photographic bleach bath with suppressed iron hydroxide pptn. - contg. biodegradable iron complex of amino-, imino- or nitrilo-carboxylic acid and biodegradable free hydroxy-carboxylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE4226372A1 true DE4226372A1 (en) | 1994-02-17 |
Family
ID=6465201
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19924226372 Ceased DE4226372A1 (en) | 1992-08-10 | 1992-08-10 | Photographic bleach bath with suppressed iron hydroxide pptn. - contg. biodegradable iron complex of amino-, imino- or nitrilo-carboxylic acid and biodegradable free hydroxy-carboxylic acid |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH06167788A (en) |
| DE (1) | DE4226372A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5434035A (en) * | 1993-12-29 | 1995-07-18 | Eastman Kodak Company | Fixer additives used in combination with iron complex based bleaches to improve desilvering |
| EP0663613A2 (en) * | 1993-12-29 | 1995-07-19 | Eastman Kodak Company | Fixer additives used in combination with iron complex based bleaches to prevent iron retention |
| US5582958A (en) * | 1995-01-10 | 1996-12-10 | Eastman Kodak Company | Photographic bleaching composition and processing method using ternary iron carboxylate complexes as bleaching agents |
| US5693456A (en) * | 1996-02-01 | 1997-12-02 | Eastman Kodak Company | Photographic bleaching compositions and method of photographic processing using mixture of ferric complexes |
| US5928844A (en) * | 1998-05-27 | 1999-07-27 | Eastman Kodak Company | Method of photographic processing using spray wash after bleaching |
| US6197483B1 (en) | 1998-12-18 | 2001-03-06 | Eastman Kodak Company | Photographic processing using biodegradable bleaching agent followed by fixing |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004052072A1 (en) | 2002-12-02 | 2004-06-17 | Matsushita Electric Industrial Co., Ltd. | Parts mounting device and method |
-
1992
- 1992-08-10 DE DE19924226372 patent/DE4226372A1/en not_active Ceased
-
1993
- 1993-08-06 JP JP5213593A patent/JPH06167788A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5434035A (en) * | 1993-12-29 | 1995-07-18 | Eastman Kodak Company | Fixer additives used in combination with iron complex based bleaches to improve desilvering |
| EP0663613A2 (en) * | 1993-12-29 | 1995-07-19 | Eastman Kodak Company | Fixer additives used in combination with iron complex based bleaches to prevent iron retention |
| EP0663613A3 (en) * | 1993-12-29 | 1996-03-27 | Eastman Kodak Co | Fixer additives used in combination with iron complex based bleaches to prevent iron retention. |
| US5508150A (en) * | 1993-12-29 | 1996-04-16 | Eastman Kodak Company | Fixer additives used in combination with iron complex based bleaches to prevent iron retention |
| US5582958A (en) * | 1995-01-10 | 1996-12-10 | Eastman Kodak Company | Photographic bleaching composition and processing method using ternary iron carboxylate complexes as bleaching agents |
| US5693456A (en) * | 1996-02-01 | 1997-12-02 | Eastman Kodak Company | Photographic bleaching compositions and method of photographic processing using mixture of ferric complexes |
| US5928844A (en) * | 1998-05-27 | 1999-07-27 | Eastman Kodak Company | Method of photographic processing using spray wash after bleaching |
| US6197483B1 (en) | 1998-12-18 | 2001-03-06 | Eastman Kodak Company | Photographic processing using biodegradable bleaching agent followed by fixing |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06167788A (en) | 1994-06-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8110 | Request for examination paragraph 44 | ||
| 8120 | Willingness to grant licences paragraph 23 | ||
| 8127 | New person/name/address of the applicant |
Owner name: AGFAPHOTO GMBH, 51373 LEVERKUSEN, DE |
|
| 8127 | New person/name/address of the applicant |
Owner name: A&O IMAGING SOLUTIONS GMBH, 56068 KOBLENZ, DE |
|
| 8127 | New person/name/address of the applicant |
Owner name: A&O IMAGING SOLUTIONS GMBH, 41468 NEUSS, DE |
|
| 8131 | Rejection |