DE1183373B - Photographic bleach bath containing no fixatives - Google Patents
Photographic bleach bath containing no fixativesInfo
- Publication number
- DE1183373B DE1183373B DEA42171A DEA0042171A DE1183373B DE 1183373 B DE1183373 B DE 1183373B DE A42171 A DEA42171 A DE A42171A DE A0042171 A DEA0042171 A DE A0042171A DE 1183373 B DE1183373 B DE 1183373B
- Authority
- DE
- Germany
- Prior art keywords
- acid
- photographic
- bleaching
- bleach
- alkali
- 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.)
- Pending
Links
- 239000007844 bleaching agent Substances 0.000 title claims description 21
- 239000000834 fixative Substances 0.000 title description 3
- 239000003513 alkali Substances 0.000 claims description 12
- 238000004061 bleaching Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 8
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 6
- -1 Dihydroxyethyl Chemical group 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000000337 buffer salt Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000276 potassium ferrocyanide Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 2
- TYFSYONDMQEGJK-UHFFFAOYSA-N 2-(2,2-dihydroxyethylamino)acetic acid Chemical compound OC(O)CNCC(O)=O TYFSYONDMQEGJK-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- FOUZISDNESEYLX-UHFFFAOYSA-N 2-(2-hydroxyethylazaniumyl)acetate Chemical compound OCCNCC(O)=O FOUZISDNESEYLX-UHFFFAOYSA-N 0.000 description 1
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241001479434 Agfa Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- PZZHMLOHNYWKIK-UHFFFAOYSA-N eddha Chemical compound C=1C=CC=C(O)C=1C(C(=O)O)NCCNC(C(O)=O)C1=CC=CC=C1O PZZHMLOHNYWKIK-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-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
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Internat. Kl.: G 03 cBoarding school Class: G 03 c
Deutsche Kl.: 57 b -18/13 German class: 57 b - 18/13
Nummer:
Aktenzeichen:
Anmeldetag:
Auslegetag:Number:
File number:
Registration date:
Display day:
1183 373:
A 42171IX a/57 b
25. Januar 1963
10. Dezember 19641183 373:
A 42171IX a / 57 b
January 25, 1963
December 10, 1964
Die Erfindung betrifft nichtkorrodierende Bäder zur Bleichung photographischer Silberbilder im Rahmen farbphotographischer Verfahren, die als Bleichmittel Ferricyanid enthalten.The invention relates to non-corrosive baths for bleaching photographic silver images in frames color photographic processes which contain ferricyanide as bleaching agent.
Alkaliferricyanide sind als Bleichmittel für den genannten Zweck seit langem bekannt. Die Lösungen dieser Substanzen besitzen jedoch den Nachteil, daß sie selbst bei Aufbewahrung in Gefäßen aus rostfreiem Stahl das Gefäß korrodieren. Mit der: Korrosion geht eine Zersetzung der Bleichlösungen konform. Zur Beseitigung dieses Nachteils wurde bereits vorgeschlagen, derartigen Bädern Korrosionsinhibitoren, wie beispielsweise Phosphate, Nitrate oder Bichromate, zuzusetzen. Neben der Tatsache, daß die bekannten Inhibitoren nur bei hohen pH-Werten wirken, stören sie außerdem die photographischen Eigenschaften der Materialien, beispielsweise beeinflussen sie die Härte der Emulsionsschichten und verursachen in vielen Fällen Fleckenbildung oder Verfärbung der photographischen Schichten.Alkali ferricyanides have long been known as bleaching agents for the stated purpose. However, the solutions of these substances have the disadvantage that they corrode the vessel even when stored in stainless steel vessels. With the : Corrosion a decomposition of the bleaching solutions is compliant. To eliminate this disadvantage, it has already been proposed to add corrosion inhibitors such as phosphates, nitrates or bichromates to such baths. In addition to the fact that the known inhibitors only act at high pH values, they also interfere with the photographic properties of the materials, for example they affect the hardness of the emulsion layers and in many cases cause staining or discoloration of the photographic layers.
Es ist bekannt, in Bleichfixierbädern als Bleichmittel Komplexe des dreiwertigen Eisens mit Aminopolycarbonsäuren zu verwenden. In diesem Fall sind die Aminopolycarbonsäuren als Liganden in den Eisenkomplexen vorhanden. Sie können daher nicht als Korrosionsschutzmittel wirken.'It is known to use trivalent iron with aminopolycarboxylic acids as bleaching agents in bleach-fix baths to use. In this case the aminopolycarboxylic acids are present as ligands in the iron complexes. So you can't act as a corrosion protection agent. '
Es wurde nun gefunden, daß als Korrosionsinhibitoren für Alkaliferricyanid-Bleichbäder, die keine Fixiermittel enthalten, aliphatische Aminopolycarbonsäuren oder ihre Alkalisalze geeignet sind. Es handelt sich dabei beispielsweise um die folgenden Verbindungen:It has now been found that as corrosion inhibitors for alkali ferricyanide bleach baths, the contain no fixing agents, aliphatic aminopolycarboxylic acids or their alkali salts are suitable. These are, for example, the following connections:
Nitrilotriessigsäure,Nitrilotriacetic acid,
Diäthyltriaminpentaessigsäure, Äthylendiamintetraessigsäure, 1,2-Diamincyclohexantetraessigsäure, Hydroxyäthylaminoessigsäure, Dihydroxyäthylaminoessigsäure, Hydroxyäthyl-äthylendiaminotriessigsäure, Dihydroxyäthyldiaminessigsäure,Diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, 1,2-diaminecyclohexanetetraacetic acid, Hydroxyethylaminoacetic acid, dihydroxyethylaminoacetic acid, hydroxyethyl-ethylenediaminotriacetic acid, Dihydroxyethyl diamine acetic acid,
Äthylendiamin-di-(o-hydroxyphenylessigsäure).Ethylenediamine di (o-hydroxyphenylacetic acid).
Andere brauchbare Verbindungen der genannten Art sind beispielsweise in dem Buch von Robert L. Smith, »The Sequestration of Metals«, erschienen 1959 bei Chapman & Hall Ltd., London. Es sei besonders auf die Seiten 88 bis 98 verwiesen.Other useful compounds of the type mentioned are, for example, in the book by Robert L. Smith, "The Sequestration of Metals", published in 1959 by Chapman & Hall Ltd., London. Be it especially refer to pages 88 to 98.
Die erfindungsgemäßen Verbindungen sind als Komplexbildner oder zur Enthärtung von Wasser zur Verhinderung von Niederschlägen bei Verwendung von hartem Wasser bekannt.The compounds according to the invention are used as complexing agents or for softening water known for preventing precipitation when using hard water.
Photographisches, kerne Fixiermittel enthaltendes BleichbadPhotographic bleach bath containing core fixatives
Anmelder: ■"-„...'......Applicant: ■ "-" ...'......
Agfa Aktiengesellschaft,; ■ ■Agfa Public Company; ■ ■
Leverkusen, Kaiser-Wilhelm-AUee 24Leverkusen, Kaiser-Wilhelm-AUee 24
Als Erfinder benannt; .' 'Named as inventor; . ' '
Paul Barringer Means jun., Binghamton, Ν.Ϋ., .V Vicent Joseph Miceli, Conklin, N.Y. (V. St. A.)Paul Barringer Means Jr., Binghamton, Ν.Ϋ., .V Vicent Joseph Miceli, Conklin, N.Y. (V. St. A.)
Beanspruchte Priorität:Claimed priority:
V. St. v. Amerika vom 5. März 1962 (177 240) - -V. St. v. America March 5, 1962 (177 240) - -
In der photographischen Praxis werden jedoch stets Bäder aus destilliertem Wasser oder zumindest aus Wasser verwendet, das beispielsweise durch Behandlung mit Ionenaustauschern enthärtet wurde. Diese Maßnahmen sind erforderlich, da bei photographischen Verfahren bereits Härtegrade, die einem Gehalt von 43 oder 13 ppm rCalciumcarbonat entsprechen, zu Störungen Anlaß geben können. Die erfindungsgemäße Wirkung von Aminopolycarbonsäuren zur Verhinderung der Korrosion von Ferricyanidlösungen, die einen relativ niedrigen pH-Wert haben und zu deren Herstellung destilliertes oder zumindest sehr weiches Wasser benutzt wurde, war daher nicht zu erwarten.In photographic practice, however, baths of distilled water or at least are always used from water that has been softened, for example, by treatment with ion exchangers. These measures are necessary, since in photographic processes already degrees of hardness that one Content of 43 or 13 ppm calcium carbonate can give rise to malfunctions. the inventive effect of aminopolycarboxylic acids to prevent the corrosion of ferricyanide solutions, which have a relatively low pH and for their production distilled or at least very soft water was used was therefore not to be expected.
Die Zusatzmengen der erfihdungsgemäßen Korrosionsinhibitoren können in weiten Grenzen schwanken. Zusätze von mehr als 5 g/l Bleächlösungsmittel bringen jedoch keine weitere Verbesserung. Im allgemeinen genügen Mengen von 1 bis 8 g/l. Der bevorzugte Bereich liegt zwischen 2 und 5 g/l.The added amounts of the corrosion inhibitors according to the invention can vary within wide limits. Additions of more than 5 g / l sheet metal solvent however, do not bring any further improvement. In general amounts of 1 to 8 g / l are sufficient. The preferred range is between 2 and 5 g / l.
Die weitere Zusammensetzung der Ferricyanid-Bleichbäder, denen die erfindungsgemäßen Verbindungen zugesetzt werden, ist an sich bekannt. Diese Bleichbäder bestehen aus wäßrigem Lösungen, aus Alkaliferricyanid, 'beispielsweise KaMumferricyanid, und anderen Zusätzen, wie Alkaliferrocyardd, Bromid oder Acetat. Die erfindungsgemäßen Inhibitoren sind in allen Ferricyanid-Bleichbädern wirksam. Ihre Brauchbarkeit ist unabhängig von sonstigen Zusätzen.The further composition of the ferricyanide bleach baths to which the compounds according to the invention are added is known per se. These bleach baths are made up of aqueous solutions Alkali ferricyanide, for example KaMumferricyanid, and other additives such as alkali ferrocyide, bromide or acetate. The inhibitors according to the invention are effective in all ferricyanide bleach baths. Their usefulness is independent of others Additives.
Alkaliferricyanide, wobei als Kationen Lithium, Natrium oder Kalium brauchbar sind, führen das metallische Silberbild, das bei der Entwicklung entstanden ist, durch Oxydation in ein SilbersalzbildAlkali ferricyanides, lithium, sodium or potassium being useful as cations, do this metallic silver image, which was created during development, through oxidation into a silver salt image
409 757/313409 757/313
über, das in Fixiermitteln, wie beispielsweise Natriumthiosulfat, löslich ist. Die in derartigen Bleichbädern meistens noch enthaltenen Alkalihalogenide dienen dazu, die zunächst gebildeten Silberferricyanide in weniger lösliches Silberchlorid oder SiI-berbromid überzuführen und dadurch den vollständigen Ablauf der Bleichreaktion zu gewährleisten. Es ist wesentlich, daß die Bleichreaktion bei einem festgesetzten pH-Wert abläuft. Aus diesem Grund enthalten die Bleichbäder Puffersalze, die die Konstanthaltung des pH-Wertes ermöglichen. Der bevorzugte pH-Bereich liegt bei Werten zwischen 4 und 5. Als Puffersystem können beispielsweise verwendet werden: Alkaliphosphate, wie Mono- oder Diphosphat, Natriumeitrate, Natriumbisulfat bzw. Zitronensäure oder Phthalsäure.over that is soluble in fixatives such as sodium thiosulfate. The ones in such bleach baths mostly still contained alkali halides serve to the initially formed silver ferricyanides to be converted into less soluble silver chloride or SiI berbromid and thereby the complete Ensure the bleaching reaction proceeds. It is essential that the bleaching reaction in one established pH runs out. For this reason, the bleach baths contain buffer salts to keep them constant of the pH value. The preferred pH range is between 4 and 5. The following can be used as a buffer system, for example: alkali metal phosphates, such as mono- or diphosphate, Sodium citrate, sodium bisulfate or citric acid or phthalic acid.
: In den meisten Fällen werden dem Bleichbad außerdem Metallferrocyanide zugesetzt, um zur Erreichung einer konstanten Bleichwirkung ein bestimmtes Redoxpotential einzustellen. Es ist außer- «o dem vorgeschlagen worden, den Bleichbädern Alkalipersulfat zuzusetzen, beispielsweise Natriumsulfat, um das verbrauchte Bleichmittel wieder aufzuoxydieren. : In most cases, metal ferrocyanides are also added to the bleaching bath in order to set a certain redox potential to achieve a constant bleaching effect. It has also been proposed to add alkali persulphate, for example sodium sulphate, to the bleaching baths in order to reoxidize the used bleach.
Zu den erfindungsgemäßen Bleichbädern mit ausgezeichneter Lagerstabilität gehört die folgende Richtrezeptur:The bleach baths of the present invention having excellent storage stability include the following Guide formulation:
Alkaliferricyanid 30 bis 120 TeileAlkali ferricyanide 30 to 120 parts
Alkalihalogenide 2 bis 20 TeileAlkali halides 2 to 20 parts
Puffersalze 5 bis 30 TeileBuffer salts 5 to 30 parts
Alkaüferrocyanid 2 bis 12 TeileAlkaüferrocyanid 2 to 12 parts
Alkalipersulfat 2 bis 12 TeileAlkali persulfate 2 to 12 parts
Aminopolycarbonsäure .. 2 bis 5 Teile
mit Wasser aufgefüllt auf 11Aminopolycarboxylic acid .. 2 to 5 parts
topped up with water to 11
3535
Bei der Herstellung derartiger Bleichbäder können zunächst die Alkaliferricyanide aufgelöst werden und anschließend die anderen Zusätze hinzugefügt werden. Selbstverständlich können die Bestandteile auch zusammen gelöst werden. Der besondere Vorteil der erfindungsgemäßen Korrosionsinhibitoren besteht darin, daß in dem bevorzugten pH-Bereich von 4,0 bis 5,0 ihre korrosionsverhindernde Wirkung besonders ausgeprägt ist.In the preparation of such bleaching baths, the alkali ferricyanides can first be dissolved and then the other additives are added. Of course, the components can also be solved together. The particular advantage of the corrosion inhibitors according to the invention is that in the preferred pH range of 4.0 to 5.0 their corrosion-preventing effect is particularly pronounced.
Eine Bleichlösung der folgenden Zusammensetzung: A bleach solution of the following composition:
Kaliumferricyanid 50,0 gPotassium ferricyanide 50.0 g
Kaliumferrocyanid (3 H2O) 5,0 gPotassium ferrocyanide (3 H 2 O) 5.0 g
Natriumbromid 15,0 gSodium bromide 15.0 g
Natriumsulfat 20,0 gSodium sulfate 20.0 g
Natriumacetat 7,5 gSodium acetate 7.5 g
Äthylendiamintetraessigsäure ..... 5,0 gEthylenediaminetetraacetic acid ..... 5.0 g
mit Wasser aufgefüllt auf 11topped up with water to 11
Die obige Lösung hat bei 20° C einen pH-Wert von 4,7 und korrodiert auch nach längerer Lagerung in einem Gefäß aus rostfreiem Stahl das Gefäßmetall nicht. The above solution has a pH of 4.7 at 20 ° C and corrodes even after prolonged storage in a stainless steel vessel, the vessel metal does not.
Ein Vergleichsbad der gleichen Zusammensetzung, jedoch ohne einen Gehalt an Äthylendiamintetraessigsäure, zeigt bereils nach kurzer Lagerung in einem derartigen Gefäß eine erhebliche Verfärbung. Ein ähnliches Ergebnis wird erhalten, wenn bei dem obengenannten Bleichbad die Äthylendiamintetraessigsäure durch Nitrilotriessigsäure ersetzt wird. A comparison bath of the same composition, but without a content of ethylenediaminetetraacetic acid, shows considerable discoloration after a short storage period in such a vessel. A similar result is obtained when the ethylenediaminetetraacetic acid is replaced by nitrilotriacetic acid in the above-mentioned bleaching bath.
Beispiel 2
Ein Bleichbad der folgenden Zusammensetzung:Example 2
A bleach bath of the following composition:
Kaliumferricyanid 50,0 gPotassium ferricyanide 50.0 g
Kaliumferrocyanid 5,0 gPotassium ferrocyanide 5.0 g
Natriumbromid 15,0 gSodium bromide 15.0 g
Natriumphosphat 11,0 gSodium phosphate 11.0 g
Zitronensäure 8,0 gCitric acid 8.0 g
Äthylendiamintetraessigsäure 4,0 gEthylenediaminetetraacetic acid 4.0 g
mit Wasser aufgefüllt auf 11topped up with water to 11
ist nach 3tägiger Lagerung in einem Gefäß aus rostfreiem Stahl unverändert. In der gleichen Zeit nimmt ein Bleichbad entsprechender Zusammensetzung, jedoch ohne Äthylendiamintetraessigsäure bereits eine tiefblaue Farbe an.is unchanged after 3 days of storage in a stainless steel vessel. At the same time it takes a bleach bath of the same composition, but already without ethylenediaminetetraacetic acid a deep blue color.
Beispiel3
Ein Bleichbad der folgenden Zusammensetzung:Example3
A bleach bath of the following composition:
Kaliumferricyanid 30,0 gPotassium ferricyanide 30.0 g
Nitrilotriessigsäure 5,0 gNitrilotriacetic acid 5.0 g
Natriumpersulfat ....... 4,0 gSodium persulfate ....... 4.0 g
Natriumbromid 10,0 gSodium bromide 10.0 g
Natriumacetat 8,0 gSodium acetate 8.0 g
Zitronensäure 9,0 gCitric acid 9.0 g
Dinatriumphosphat 12,0 gDisodium phosphate 12.0 g
mit Wasser aufgefüllt auf 11topped up with water to 11
ist nach 3tägiger Lagerung in einem Gefäß aus rostfreiem Stahl unverändert. In der gleichen Zeit nimmt ein Bleichbad entsprechender Zusammensetzung, jedoch ohne Nitrilotriessigsäure, bereits eine tiefblaue Farbe an.is unchanged after 3 days of storage in a stainless steel vessel. At the same time it takes a bleach bath of the same composition, but without nitrilotriacetic acid, already a deep blue one Color on.
Claims (4)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US177240A US3256092A (en) | 1962-03-05 | 1962-03-05 | Corrosion inhibitors in bleach solutions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1183373B true DE1183373B (en) | 1964-12-10 |
Family
ID=22647785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEA42171A Pending DE1183373B (en) | 1962-03-05 | 1963-01-25 | Photographic bleach bath containing no fixatives |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US3256092A (en) |
| DE (1) | DE1183373B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1209050A (en) * | 1967-12-27 | 1970-10-14 | Agfa Gevaert Nv | Photographic silver halide processing liquids |
| US3645736A (en) * | 1968-07-11 | 1972-02-29 | Itek Corp | Physical development systems, processes and related materials |
| US3960565A (en) * | 1973-11-12 | 1976-06-01 | Minnesota Mining And Manufacturing Company | Silver bleaching solutions |
| US4277556A (en) * | 1976-08-18 | 1981-07-07 | Konishiroku Photo Industry Co., Ltd. | Process for treating light-sensitive silver halide color photographic materials |
| JPS5633646A (en) * | 1979-08-29 | 1981-04-04 | Fuji Photo Film Co Ltd | Processing method for color photographic material |
| EP0664481B1 (en) * | 1994-01-19 | 2000-03-15 | Eastman Kodak Company | Color photographic processes comprising a bleach starter |
| DE19549103A1 (en) * | 1995-12-29 | 1997-07-03 | Agfa Gevaert Ag | Bleach bath for black and white photographic material |
| EP3110982A4 (en) * | 2014-02-25 | 2017-11-22 | Entegris, Inc. | Wet based formulations for the selective removal of noble metals |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE866605C (en) * | 1944-11-27 | 1953-02-12 | Bayer Ag | Process for making photographic attenuator and bleach-fix baths |
| DE966410C (en) * | 1953-05-13 | 1957-08-01 | Agfa Ag | Process for bleach-fixing silver photographic images |
| DE1051117B (en) * | 1957-09-03 | 1959-02-19 | Agfa Ag | Process for simultaneously bleaching and fixing a color photographic image |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE500365A (en) * | 1949-12-30 | |||
| BE536212A (en) * | 1954-03-11 | |||
| GB774194A (en) * | 1954-06-19 | 1957-05-08 | Photo Chemical Company Ltd | Improvements in photographic bleach-fix baths |
-
1962
- 1962-03-05 US US177240A patent/US3256092A/en not_active Expired - Lifetime
-
1963
- 1963-01-25 DE DEA42171A patent/DE1183373B/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE866605C (en) * | 1944-11-27 | 1953-02-12 | Bayer Ag | Process for making photographic attenuator and bleach-fix baths |
| DE966410C (en) * | 1953-05-13 | 1957-08-01 | Agfa Ag | Process for bleach-fixing silver photographic images |
| DE1051117B (en) * | 1957-09-03 | 1959-02-19 | Agfa Ag | Process for simultaneously bleaching and fixing a color photographic image |
Also Published As
| Publication number | Publication date |
|---|---|
| US3256092A (en) | 1966-06-14 |
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