EP0658182B1 - Aminfreie kühlschmierstoffe - Google Patents
Aminfreie kühlschmierstoffe Download PDFInfo
- Publication number
- EP0658182B1 EP0658182B1 EP93919222A EP93919222A EP0658182B1 EP 0658182 B1 EP0658182 B1 EP 0658182B1 EP 93919222 A EP93919222 A EP 93919222A EP 93919222 A EP93919222 A EP 93919222A EP 0658182 B1 EP0658182 B1 EP 0658182B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cooling lubricants
- water
- acids
- acid
- cooling
- 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.)
- Expired - Lifetime
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
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- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
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- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/04—Fatty oil fractions
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- C10M105/10—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
- C10M105/12—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms monohydroxy
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- C10M105/14—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms polyhydroxy
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- C10M105/18—Ethers, e.g. epoxides
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- C10M125/10—Metal oxides, hydroxides, carbonates or bicarbonates
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- C10M129/32—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms monocarboxylic
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
- C10N2040/247—Stainless steel
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/01—Emulsions, colloids, or micelles
Description
- Gegenstand der Erfindung sind aminfreie Kühlschmierstoffe für die Metallbearbeitung, enthaltend Grundöle, Emulgatoren, Lösungsvermittler und Korrosionsschutzzusätze.
- Kühlschmierstoffe sind Zubereitungen/Gemische, die bei der Metall-zerspanung und bei der Metallumformung zum Kühlen und Schmieren der Werkstücke verwendet werden. Die wichtigsten Bearbeitungsverfahren, die sich durch die Art der Bewegungen, die das bearbeitete Teil und Werkzeug ausführen, und durch die Geometrie der herzustellenden Teile unterscheiden bezeichnet man als Fräsen, Drehen, Bohren und Schleifen als spangebende Bearbeitungen sowie Walzen, Tiefziehen und Kaltfließpressen als spanlose Verformungen.
- Das gemeinsame Prinzip der spanabhebenden Metallbearbeitungsverfahren ist, daß die Werkzeugschneide in das Material eingreift und dabei einen Span von der Oberfläche abhebt und eine neue Oberfläche entsteht. Für die Zerteilung des Materials sind sehr hohe Drücke erforderlich. Durch die Verformung des Spans und durch die auftretende Reibung unter dem Druck entsteht Wärme, die das Werkstück, das Werkzeug und vor allem die Späne aufheizt.
- Die erwünschte Wirkung des Einsatzes von Kühlschmierstoffen ist daher die Senkung der Temperatur, die ansonsten in den Spänen z. B. bis auf 1000° C steigen könnte, und die bei den hergestellten Teilen Einfluß auf die Maßhaltigkeit hat. Eine weitere Hauptaufgabe der Kühlschmierstoffe ist, die Standzeit der Werkzeuge zu verbessern, die unter dem Einfluß hoher Temperatur schnell verschleißen. Durch Verwendung eines Kühischmierstoffes wird die Rauhigkeit der Oberflächen vermindert, da der Schmierstoff Verschweißungen von Werkzeug und Werkstückoberfläche verhindert und das Anhaften von Partikeln vermeidet. Darüber hinaus übernimmt der Kühlschmierstoff die Aufgabe, die gebildeten Späne abzutransportieren. Dies hat besonders bei Massenproduktionen große Bedeutung.
- Kühlschmierstoffe werden normalerweise im Umlaufverfahren eingesetzt, d. h. im einfachsten Fall, dem Einsatz von Kühlschmierstoffen an einer Einzelmaschine, hat die Maschine einen Behälter für den Kühlschmierstoff.
- Mit der Neufassung der DIN 51385 Nr. 1 wurde eine eindeutige Benennung der Kühlschmierstoffe geschaffen, wobei von nichtwassermischbaren, wassermischbaren und von wassergemischten Kühlschmierstoffen die Rede ist. Nach DIN 51385 wird unter den Begriffen "wassergemischt" der Endzustand des fertigen Mediums (meistens als Öl-in-Wasser-Emulsionen), unter "wassermischbar" jedoch der Zustand des Konzentrates verstanden.
- Wassergemischte Kühlschmierstoffe werden beim Verwender hergestellt durch Mischen eines Konzentrates, des wassermischbaren Kühlschmierstoffs, mit Betriebswasser. In der Regel werden ca. 5 %ige wäßrige Emulsionen hergestellt. Vorteil dieses Kühlschmierstofftyps ist die gute Kühlwirkung, die auf den thermischen Eigenschaften des Wassers beruht. Durch die gute Kühlwirkung ist es möglich, sehr hohe Arbeitsgeschwindigkeiten zu erreichen und damit die Produktivität von Maschinen zu steigern. Die Schmierwirkung der wassergemischten Kühlschmierstoffe reicht für die meisten Bearbeitungsverfahren in der spangebenden Fertigung aus. Ein weiterer Vorteil sind die niedrigen Kosten, die durch die mögliche Mischung des Konzentrates mit Wasser erreicht werden. Nachteil von wassergemischten Kühlschmierstoffen ist, daß sie gegen den Befall durch Mikroorganismen empfindlich sind und daher mehr Kontrolle und Pflege erfordern. Die Anwesenheit von Wasser kann zur Rostbildung führen und kann empfindliche Metalle angreifen. Wassergemischte Kühlschmierstoffe werden heute für fast alle Zerspanungsarten eingesetzt. Neben der Forderung nach Rostschutz für die Maschinen und für bearbeitete Teile aus Eisenlegierungen wird gefordert, daß auch Nichteisenmetalle nicht angegriffen werden. Die Kühlschmierstoffe müssen gut hautverträglich sein, da die Bediener der Maschinen häufig in direkten Kontakt mit der Flüssigkeit kommen. Es darf bei der Umwälzung des Kühlschmierstoffes kein störender Schaum entstehen, und der Anstrich und die Dichtungen der Maschine dürfen nicht angegriffen werden. Besondere Bedeutung hat die Emulsionsstabilität, die Einfluß auf fast alle anderen Eigenschaften des Kühlschmierstoffes hat, zumindest nach einer längeren Gebrauchszeit. Weiter wird gefordert, daß Rückstände vom Kühlschmierstoff auf der Maschine nicht kleben, daß sich die Kühlschmierstoffe leicht mit Wasser mischen lassen, daß Geruch und Aussehen angenehm sind und daß die üblichen Filtereinrichtungen durch den Kühlschmierstoff nicht beeinträchtigt werden.
- Die Tabelle zeigt eine Zusammenfassung der Anforderungen für wassermischbare und wassergemischte Kühlschmierstoffe:
- Kühl- und Schmierwirkung
- Rostschutz
- kein Angriff auf NE-Metalle
- toxikologische Unbedenklichkeit insbesondere Hautverträglichkeit
- keine Schaumbildung
- kein Angriff auf Lacke und Dichtungen
- Emulsionsstabilität
- keine Verklebung oder Verharzung
- gute Mischbarkeit
- angenehmer Geruch
- sauberes Aussehen
- gute Filtrierbarkeit
- problemlose Entsorgung.
- Die Anforderungen an die Rostschutzwirkung von Kühlschmierstoffen sind besonders hoch, da nach der Bearbeitung mit Kühlschmierstoffen im allgemeinen kein Trocknen möglich ist. Die Teile werden normalerweise naß in Kästen gelegt und dürften auch in nassem Zustand nicht rosten. Zur Prüfung der Rostschutzwirkung werden bei der Entwicklung und auch bei der Kontrolle von im praktischen Einsatz befindlichen Lösungen häufig der Test mit Gußspänen nach DIN 51360/2 verwendet.
- Die Rostschutzwirkung der Kühlschmierstoffe wird beeinflußt von einer Reihe von Faktoren. So hat die Qualität des für die Mischung verwendeten Wassers einen großen Einfluß. Die Wasserhärte, vor allen Dingen aber Chloride und Sulfate, verschlechtern die Rostschutzwirkung der Lösung. Erschwerend kommt bei längerem Einsatz von Kühlschmierstoffen hinzu, daß die Konzentration der Salze ständig ansteigt, da Teile der Emulsion verdampfen und die Verluste mit salzhaltigem Wasser nachgefüllt werden.
- Nichtwassermischbare und wassermischbare Kühlschmierstoffe, soweit sie im Anwendungszustand Emulsionen sind, sind häufig auf Mineralöl aufgebaut. Die verwendeten Mineralölqualitäten sind überwiegend Kombinationen von paraffinischen, naphthenischen und aromatischen Kohlenwasserstoffverbindungen. Neben den Mineralölen haben auch sog. synthetische Schmiermittel ("synthetische Öle") wie Polyolefine, Polyalkylenglykole und -glycolether, nätürliche Esteröle sowie synthetische Ester und ihre Derivate Bedeutung.
- Um die Anforderungen der Praxis erfüllen zu können, müssen die wassermischbaren Kühlschmierstoffe neben dem Grundöl verschiedene Komponenten enthalten. Die wichtigsten Substanzgruppen sind die Emulgatoren, Korrosionschutzzusätze, Biozide, EP-Zusätze, polare Zusätze, Antinebelzusätze, Alterungsschutzstoffe, Festschmierzusätze und Entschäumer.
- Emulgatoren (z. B. Tenside, Petroleumsulfonate, Alkaliseifen, Alkanolaminseifen) stabilisieren die feine Verteilung von Öltröpfchen in der wäßrigen Arbeitsflüssigkeit, die eine Öl-in-Wasser-Emulsion darstellt. Die Emulgatoren stellen mengenmäßig eine wichtige Gruppe an Zusatzstoffen bei den wassermischbaren Kühlschmierstoffen dar.
- Übliche Korosionsschutzzusätze (z. B. Alkanolamine und ihre Salze, Sulfonate, organische Borverbindungen, Fettsäureamide, Aminodicarbonsäuren, Phosphorsäureester, Thiophosphonsäureester, Dialkyldithiophosphate, Mono- und Dialkylarylsulfonate, Benzotriazole, Polyisobutenbernsteinsäurederivate) sollen das Rosten von Metalloberflächen verhindern. Früher wurde als Korrosionsschutzmittel häufig Nitrit verwendet, das jedoch heute wegen der Toxizität und Umweltschädlichkeit, besonders auch wegen der Gefahr der Bildung carcinogener Nitrosamine verpönt ist. Einige Korrosionsschutzzusätze haben gleichzeitig emulgierende Eigenschaften und finden deshalb auch als Emulgator ihre Anwendung. Biozide (z. B. Phenol-Derivate, Formaldehydabkömmlinge, Kathon MW) sollen das Wachstum von Bakterien und Pilzen verhindern. EP-Zusätze (z. B. geschwefelte Fette und Öle, phosphorhaltige Verbindungen, chlororganische Verbindungen) sollen Mikroverschweißungen zwischen Metalloberflächen bei hohen Drücken und Temperaturen verhindern. Polare Zusätze (z. B. natürliche Fette und Öle, synthetische Ester) erhöhen die Schmierungseigenschaften. Alterungsschutzstoffe (z. B. organische Sulfide, Zinkdithiophosphate, aromatische Amine) gewährleisten eine lange Gebrauchsdauer der Kühlschmierstoffe.
- Eine zentrale Stellung unter den Additiven nehmen die Alkanolamine und Alkanolaminderivate ein, die in einer großen Zahl von wassermischbaren Kühlschmierstoffen als Korrosionsschutzzusätze verwendet werden. Außerdem garantieren sie in Verbindung mit Carbonsäuren durch ihre gute Pufferkapazität eine gewisse pH-Wert-Konstanz der wäßrigen Gebrauchsemulsionen. Der pH-Wert Konstanz kommt hinsichtlich der Emulsionsstabilität und des Rostschutzes eine besondere Bedeutung zu. Umsetzungsprodukte von Alkanolaminen mit Borsäure wirken wachstumshemmend auf Bakterien und Schimmelpilze und verbessern deshalb die Gebrauchsdauer von Kühlschmierstoffen.
- Ein Nachteil der Alkanolamine und Alkanolaminderivate ist, daß sie während des Praxiseinsatzes mit nitrosierenden Substanzen, z. B. bakteriell gebildetem Nitrit oder Stickoxiden in der Luft, reagieren können und dabei in Nitrosamine umgewandelt werden. Z. B. kann in wassergemischten Kühlschmierstoffen, die Ethanolamine enthalten, Nitrosodiethanolamin (NDELA) gebildet werden.
- Nitrosamine können nach Tierversuchen Krebs an verschiedenen Organen (z. B. Magen, Lunge, Blase, Leber, Speiseröhre) auslösen. Deshalb sind einige Nitrosamine, z. B. auch NDELA, in der deutschen Gefahrstoffverordnung als krebserzeugend eingestuft. Zur Vermeidung von gesundheitlichen Gefahren für die Bediener von Metallbearbeitungsmaschinen muß deshalb die Bildung von Nitrosaminen vermieden werden.
- Die Aufgabe der vorliegenden Erfindung besteht in der Bereitstellung von aminfreien Kühlschmierstoffen, die jedoch in Bezug auf die Rostschutzwirkung in der Stabilität und Verwendungsdauer sowie anderen Gebrauchseigenschaften den bisher üblichen aminhaltigen Kühlschmierstoffen nicht nachstehen.
- Die vorstehend genannte Aufgabe wird gelöst durch aminfreie Kühlschmierstoffe enthaltend Grundöle, Emulgatoren, Lösevermittler und Korrosionsschutzzusätze, dadurch gekennzeichnet, daß als Korrosionsschutzzusatz ein Gemisch aus
- a) Dimerfettsäuren und
- b) einer oder mehreren Carbonsäuren ausgewählt aus aliphatischen Carbonsäuren mit 6 bis 14 C-Atomen und aromatischen Monocarbonsäuren oder den Alkalimetall-, Magnesium- und/oder Calciumsalzen der unter
- a) und/oder b) genannten Säuren enthalten ist.
- Überraschenderweise wurde gefunden, daß die Kombination aus Dimerfettsäure und weiteren Carbonsäuren, ausgewählt aus aliphatischen und aromatischen Carbonsäuren bzw. deren Alkalimetall-, Magnesium- und/oder Calciumsalze, geeignet ist, Kühlschmierstoffe zur Verfügung zu stellen, die in Bezug auf die Korrosionsschutzwirkung gegenüber handelsüblichen Kühlschmierstoffen auf der Basis von Alkanolaminen vergleichbare Korrosionsschutzwirkungen aufweisen.
- Die Auswahl der erfindungsgemäß enthaltenden Grundöle in den Kühlschmierstoffen ist praktisch nicht begrenzt. So enthalten Emulsionen im Sinne der vorliegenden Erfindung häufig Komponenten, die ausgewählt sind aus paraffinischen, naphthenischen und paraffinisch-naphthenischen Mineralölen. In gleicher Weise ist der Einsatz von Esterölen, z. B. Trimethylolpropanestern, Neopentyl- oder Pentaerythritestern, von Fettöl-Derivaten, Polyisobutylenen, hydrierten Polydecenen, Polypropylenglykol, Silicatestern, Kohlensäureestern, Estern von Phosphor enthaltenden Säuren, kettenartigen Diphenylethern und Phenoxyphenylethern bevorzugt.
- Die erfindungsgemäßen Kühlschmierstoffe enthalten an sich im Stand der Technik bekannte Emulgatoren, insbesondere solche, die ausgewählt sind aus a) anionischen Emulgatoren, insbesondere Seifen, Sulfonaten und Phosphorsäureestern und deren Salze und b) nichtionischen Emulgatoren, insbesondere Fettalkoholethoxylaten, Fettalkoholpropoxylaten und Zuckerestern.
- Kühlschmierstoffe im Sinne der vorliegenden Erfindung enthalten neben Grundölen, Emulgatoren und den erfindungsgemäßen Korrosionsschutzzusätzen auch Lösevermittler. Im Sinne der vorliegenden Erfindung ist auch Wasser als Lösevermittler anzusehen. Dementsprechend sind in einer bevorzugten Ausführungsform der vorliegenden Erfindung die Lösevermittler ausgewählt aus Wasser, Alkoholen, Glykolen und Glykolethern. In besonders bevorzugter Weise werden die Lösevermittler in einer Menge von 1 bis 30 Gew.%, insbesondere 2 bis 10 Gew.%, bezogen auf den wassermischbaren Kühlschmierstoff eingesetzt.
- Kühlschmierstoffe im Sinne der vorliegenden Erfindung enthalten als essentiellen Bestandteil eine oder mehrere Carbonsäuren, die ausgewählt sind aus aliphatischen Carbonsäuren und aromatischen Carbonsäuren. Besonders bevorzugte aliphatische Carbonsäuren sind ausgewählt aus Adipinsäure, Caprylsäure, Sebacinsäure, 2,2,4-Trimethylhexansäure und Ethylhexansäure. In gleicher Weise sind besonders bevorzugte aromatische Carbonsäuren ausgewählt aus Benzoesäure, substituierten Benzoesäuren und besonders Salicylsäure. Mögliche Substituenten der Benzoesäure können sein eine Hydroxygruppe, eine Nitrogruppe, sowie geradkettige oder verzweigte Alkyloder Alkyloxygruppen mit bis zu 4 C-Atomen. Kurzkettige Carbonsäuren sind als Komponenten von wasserlöslichen Korrosionsschutzmitteln bekannt, z. B. aus DE 32 23 940, nicht jedoch als Komponenten von Emulsionen in der erfindungsgemäßen Kombination mit Dimerfettsäuren, Emulgatoren, Grundölen usw.
- Weiterer wesentlicher Bestandteil der erfindungsgemäßen Kühlschmierstoffe sind Dimerfettsäuren, die bevorzugterweise in einer Menge von 2 bis 20 Gew.%, insbesondere 5 bis 15 Gew.%, bezogen auf die wassermischbaren Kühlschmierstoffe enthalten sein können. Üblicherweise versteht man unter Dimerfettsäuren durch Tonerdekatalysierte Dimerisierung ungesättigter Fettsäuren gewonnene Gemische aus acyclischen und cyclischen Dicarbonsäuren mit durchschnittlich 36 C-Atomen (Literaturhinweis: Dimer Acids, E.C. Leonard, 1975, Humeo Sheffield). Nebenprodukte der Dimerisierung sind verzweigte C-18-Fettsäuren und Trimerfettsäuren bzw. polyhasische Fettsäuren, die häufig destillativ abgetrennt werden. Im Sinne der vorliegenden Erfindung sind jedoch auch Dimerfettsäuren einsetzbar, die als Nebenbestandteile Monomersäure, Trimerfettsäure und polymere Fettsäure enthalten. Gut einsetzbar sind z. B. EmpolR 1022, Fa. Emery, USA oder PripolR 1040 bzw. PripolR 1013 von Fa. Unichema, Emmerich.
- Die erfindungsgemäß verwendeten Dicarbonsäuren unterscheiden sich in der Struktur wesentlich von den in WO 90/15663 genannten Dicarbonsäuren bzw. Dicarbonsäureanhydriden, die durch Reaktion von Olefinen mit ungesättigten Carbonsäuren bzw. deren Anhydriden hergestellt werden.
- Die erfindungsgemäßen wassermischbaren bzw. wassergemischten Kühlschmierstoffe können weitere funktionelle Zusatzstoffe wie polare Zusätze, EP-Zusätze, Anti-Nebel-Zusätze, Alterungsschutzstoffe, Festschmierstoffe, Pigmente, Entschäumer und/oder Biozide enthalten. Zur Anwendung bei der Metallbearbeitung enthalten die wäßrigen Emulsionen oder wäßrigen Lösungen der erfindungsgemäßen Kühlschmierstoffe vorzugsweise 1 bis 10 Gew.%, insbesondere 2 bis 5 Gew.% des wassermischbaren Konzentrates.
- Üblicherweise wird der pH-Wert der Kühlschmierstoffe im Bereich von etwa 7 bis 10 eingestellt. Besonders bevorzugt ist eine Einstellung des pH-Wertbereiches von 8 bis 9,5. Im Sinne der vorliegenden Erfindung ist es darüber hinaus besonders bevorzugt, den alkalischen pH-Wert mittels Alkalimetallhydroxid einzustellen. Die Verwendung von Magnesium oder Calciumhydroxid ist weniger bevorzugt, da möglicherweise schwerlösliche Salze gebildet werden könnten. Dementsprechend ist der Einsatz von Kalium- und/oder Natriumhydroxid im Sinne der vorliegenden Erfindung besonders bevorzugt.
- 1/3 der benötigten Menge Mineralöl, Lösungsvermittler und Tallölfettsäure wurden im Reaktor vorgelegt und gerührt. Anschließend wurde die aromatische Carbonsäure (nur in den Beispielen 1 und 3) zugegeben und ca. 15 Minuten nachgerührt.
Unter ständigem Rühren wurde die wäßrige Kaliumhydroxidlösung innerhalb von 30 Minuten vorsichtig zudosiert (exotherme Reaktion). Die Temperatur der Lösung wurde zwischen 50 - 70° C gehalten. Der Ansatz wurde 1 Stunde kräftig gerührt, bis eine klare braune Lösung vorlag. Danach wurde die restliche Menge (2/3) Mineralöl zugegeben.
Die restlichen Komponenten:
Petrolsulfonat (nur im Rezepturbeispiel 1), Dimerfettsäure, Caprylsäure (nur in den Rezepturbeispielen 1 und 2) und die Fettalkoholethoxylate wurden danach in o. g. Reihenfolge zudosiert. Es wurde ca. 1 Stunde nachgerührt, bis eine braune klare Lösung vorlag. - Die nachfolgenden Tabellen 1 und 2 geben erfindungsgemäße (Tabelle 1) und nicht erfindungsgemäße (Tabelle 2) Rezepturbeispiele von Kühlschmierstoffen wieder.
Tabelle 1 Beispiel 1 Beispiel 2 Beispiel 3 Mineralöl (naphthenisches Solventraffinat) 33,3 % 44,0 % 35,5 % Lösungsvermittler (Glykolbasis) 11,7 % 5,2 % 10,0 % langkettige Fettsäure (Tallölfettsäure) 12,5 % 9,0 % 14,0 % Petrolsulfonat 4,2 % - - kurzkettige Fettsäure (Caprylsäure) 4,2 % 4,0 % - Fettalkoholethoxylate (Oleylalkohol + 5 EO) 7,2 % 15,5 % 9,2 % Dimerfettsäure (EmpolR 1022) 8,3 % 13,2 % 16,0 % aromatische Carbonsäure (Salicylsäure*, Benzoesäure**) 4,2 %* - 4,3 %** wäßrige Kaliumhydroxidlösung (45 Gew.%) 14,4 % 9,1 % 11,0 % 100,0 % 100,0 % 100,0 % Tabelle 2 Vergleichsbeispiel 1 Vergleichsbeispiel 2 Mineralöl (naphthenisches Solventraffinat) 40,0 % 60,0 % Lösungsvermittler (Glykolbasis) 3,0 % 5,0 % langkettige Fettsäure (Tallölfettsäure) 6,0 % 12,5 % Petrolsulfonat - 4,0 % kurzkettige Fettsäure (Capryl* - oder Isononansäure) - 3,0 % Fettalkoholethoxylat (Oleylalkohol+5 EO) 8,0 % - Fettsäureester (Ethylhexyloleat) - 4,5 % Fettsäureamid (Tallölfettsäurediethanolamid) 7,0 % 6,0 % wäßrige Kaliumhydroxidlösung (45 Gew.%) 3,0 % 5,0 % Diethanolamin 17,0 % - Borsäure 5,0 % - Kondenswasser 11,0 % - 100,0 % 100,0 % - Kondenswasser und Diethanolamin wurde vorgelegt und Borsäure unter Rühren eingelöst. Danach wurde das Mineralöl und alle weiteren Komponenten in der durch die Tabelle 2 vorgegebenen Reihenfolge zugegeben und gerührt, bis ein klares homogenes Konzentrat entstand.
- In der durch die Tabelle 2 vorgegebenen Reihenfolge wurde gemischt und gerührt, bis ein klares homogenes Konzentrat entstand.
- Die nachfolgende Tabelle 3 gibt einen Vergleich der erfindungsgemäßen Formulierungen mit den nicht erfindungsgemäßen Beispielen hinsichtlich Korrosionsschutzwirkung (Test nach DIN 51360/2) wieder.
Tabelle 3 Beispiel 1 2 3 Vgl.1 Vgl.2 AussehenBeschaffenheit der 5 %igen Emulsion fein dispers, fest transparent fein dispers halb-transparent grob dispers milchig fein dispers, halb-transparent grob dispers, milchig Korrosionsgrad 0 ab.... 4,0 % 4,0 % 5,0 % 3,0 % 7,0 % bei pH.. 8,9 9,4 9,6 9,4 9,2 - Zu den Beispielen wurde die Mindestkonzentration angegeben, die erforderlich ist, um Korrosionsgrad 0 zu erreichen.
Claims (13)
- Aminfreie Kühlschmierstoffe, enthaltend Grundöl, Emulgatoren und Lösevermittler, dadurch gekennzeichnet, daß als Korrosionsschutzzusatz ein Gemisch ausa) Dimerfettsäuren undb) einer oder mehreren Carbonsäuren ausgewählt aus aliphathischen Carbonsäuren mit 6 bis 14 C-Atomen und aromatischen Monocarbonsäuren oder den Alkalimetall-, Magnesium- und/oder Calciumsalzen der unter a) und/ oder b) genannten Säuren enthalten ist.
- Kühlschmierstoffe nach Anspruch 1, dadurch gekennzeichnet, daß das Grundöl ausgewählt ist aus paraffinischen, naphthenischen oder paraffinisch-naphthenischen Mineralölen, Esterölen, z. B. Trimethylolpropanestern, Neopentyl- oder Pentaerythritester, aus Fettöl-Derivaten, Polyisobutylenen, hydrierten Polydecenen, Polypropylenglykol, Silikatestern, Kohlensäureestern, Estern Phospor enthaltender Säuren, kettenartigen Diphenylethern und Phenoxyphenylethern.
- Kühlschmierstoffe nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Emulgatoren ausgewählt sind ausa) anionischen Emulgatoren, insbesondere Seifen, Sulfonaten, Phosphorsäureestern und deren Salzen undb) nichtionischen Emulgatoren, insbesondere Fettalkoholethoxylaten, Fettalkoholpropoxylaten und Zuckerestern.
- Kühlschmierstoffe nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Lösevermittler ausgewählt sind aus Wasser, Alkoholen, Glykolen und/oder Glykolethern.
- Kühlschmierstoffe nach Anspruch 4, dadurch gekennzeichnet, daß die Mengen an Lösevermittler 1 bis 30 Gew. %, insbesondere 2 bis 10 Gew. % bezogen auf den wassermischbaren Kühlschmierstoff betragen.
- Kühlschmierstoffe nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Menge an Dimerfettsäuren 2 bis 20 Gew. %, insbesondere 5 bis 15 Gew. %, bezogen auf die wassermischbaren Kühlschmierstoffe beträgt.
- Kühlschmierstoffe nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die aliphatischen Carbonsäuren ausgewählt sind aus Adipinsäure, Caprylsäure, Sebacinsäure, 2,2,4-Trimethylhexansäure und Ethylhexansäure.
- Kühlschmierstoffe nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die aromatischen Carbonsäuren ausgewählt sind aus Benzoesäure, substituierten Benzoesäuren, wobei die Substituenten sein können eine Hydroxygruppe, eine Nitrogruppe oder geradkettige oder verzweigte Alkyl- oder Alkyloxygruppen, und insbesondere Salicylsäure.
- Kühlschmierstoffe nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die Menge an aliphatischen und/oder aromatischen Carbonsäuren 1 bis 20 Gew. %, insbesondere 3 bis 10 Gew. %, bezogen auf den Kühlschmierstoff betragen.
- Kühlschmierstoffe nach einem oder mehreren der Ansprüche 1 bis 9, enthaltend weiterhin polare Zusätze, EP-Zusätze, Antinebelzusätze, Alterungsschutzstoffe, Festschmierstoffe, Pigmente, Entschäumer und/oder Biozide.
- Wassermischbare Kühlschmierstoffe nach einem oder mehreren der Ansprüche 1 bis 10 in Form von Konzentraten.
- Wassergemischte Kühlschmierstoffe nach einem oder mehreren der Ansprüche 1 bis 10 in Form von wäßrigen Emulsionen oder Lösungen.
- Verwendung der Kühlschmierstoffe nach einem oder mehreren der Ansprüche 1 bis 12 in Form wäßriger Lösungen oder Emulsionen, enthaltend 1 bis 10 Gew. %, insbesondere 2 bis 5 Gew. % der wassermischbaren Kühlschmierstoff-Konzentrate zur Metallbearbeitung.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4229848A DE4229848A1 (de) | 1992-09-07 | 1992-09-07 | Aminfreie Kühlschmierstoffe |
DE4229848 | 1992-09-07 | ||
PCT/EP1993/002344 WO1994005746A1 (de) | 1992-09-07 | 1993-08-30 | Aminfreie kühlschmierstoffe |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0658182A1 EP0658182A1 (de) | 1995-06-21 |
EP0658182B1 true EP0658182B1 (de) | 1996-07-03 |
Family
ID=6467394
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93919222A Expired - Lifetime EP0658182B1 (de) | 1992-09-07 | 1993-08-30 | Aminfreie kühlschmierstoffe |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0658182B1 (de) |
JP (1) | JPH08501119A (de) |
AT (1) | ATE140023T1 (de) |
DE (2) | DE4229848A1 (de) |
ES (1) | ES2088683T3 (de) |
WO (1) | WO1994005746A1 (de) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4444878A1 (de) * | 1994-12-16 | 1996-06-20 | Henkel Kgaa | Stickstofffreie Korrosionsinhibitoren mit guter Pufferwirkung |
DE19539854A1 (de) * | 1995-10-26 | 1997-04-30 | Henkel Kgaa | Öllösliche stickstofffreie Korrosionsinhibitoren mit guter Pufferwirkung |
US6318139B1 (en) | 1996-08-29 | 2001-11-20 | Henkel Corporation | Waterborne lubricant for the cold plastic working of metals |
JP3935230B2 (ja) * | 1996-08-29 | 2007-06-20 | 日本パーカライジング株式会社 | 金属材料の冷間塑性加工用水系潤滑剤 |
DE19833894A1 (de) * | 1998-07-28 | 2000-02-03 | Fuchs Dea Schmierstoffe Gmbh & | Wassermischbares Kühlschmierstoff-Konzentrat |
EP1035192A1 (de) * | 1999-01-26 | 2000-09-13 | Stefan Graichen | Additiv für einen Kühlschmierstoff |
EP1652909B2 (de) † | 2004-10-19 | 2011-04-27 | Helmut Theunissen | Korrosionsschutzmittel für funktionelle Flüssigkeiten, wassermischbares Konzentrat und dessen Verwendung |
CN114133917A (zh) * | 2020-09-04 | 2022-03-04 | 中国石油化工股份有限公司 | 一种具有可生物降解性的导热油组合物及其制备方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR781570A (fr) * | 1934-03-26 | 1935-05-18 | Bataafsche Petroleum | Procédé pour la préparation de lubrifiants |
NL7411032A (nl) * | 1974-08-16 | 1976-02-18 | Beverolfabrieken | Werkwijze ter bereiding van een watervrij dieptrekmiddel. |
GB8713549D0 (en) * | 1987-06-10 | 1987-07-15 | Exxon Chemical Patents Inc | Corrosion inhibiting composition |
US4946616A (en) * | 1988-11-14 | 1990-08-07 | The Dow Chemical Company | Heat transfer fluids containing dicarboxylic acid mixtures as corrosion inhibitors |
US4927550A (en) * | 1989-01-27 | 1990-05-22 | Castrol Industrial Inc. | Corrosion preventive composition |
-
1992
- 1992-09-07 DE DE4229848A patent/DE4229848A1/de not_active Withdrawn
-
1993
- 1993-08-30 JP JP6506862A patent/JPH08501119A/ja active Pending
- 1993-08-30 DE DE59303152T patent/DE59303152D1/de not_active Expired - Fee Related
- 1993-08-30 ES ES93919222T patent/ES2088683T3/es not_active Expired - Lifetime
- 1993-08-30 AT AT93919222T patent/ATE140023T1/de not_active IP Right Cessation
- 1993-08-30 WO PCT/EP1993/002344 patent/WO1994005746A1/de active IP Right Grant
- 1993-08-30 EP EP93919222A patent/EP0658182B1/de not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
ATE140023T1 (de) | 1996-07-15 |
JPH08501119A (ja) | 1996-02-06 |
WO1994005746A1 (de) | 1994-03-17 |
EP0658182A1 (de) | 1995-06-21 |
DE4229848A1 (de) | 1994-03-10 |
ES2088683T3 (es) | 1996-08-16 |
DE59303152D1 (de) | 1996-08-08 |
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