DE4229848A1 - Aminfreie Kühlschmierstoffe - Google Patents
Aminfreie KühlschmierstoffeInfo
- Publication number
- DE4229848A1 DE4229848A1 DE4229848A DE4229848A DE4229848A1 DE 4229848 A1 DE4229848 A1 DE 4229848A1 DE 4229848 A DE4229848 A DE 4229848A DE 4229848 A DE4229848 A DE 4229848A DE 4229848 A1 DE4229848 A1 DE 4229848A1
- Authority
- DE
- Germany
- Prior art keywords
- cooling lubricants
- acids
- cooling
- water
- 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.)
- Withdrawn
Links
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- C—CHEMISTRY; METALLURGY
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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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- C10M105/12—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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- C—CHEMISTRY; METALLURGY
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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Description
Gegenstand der Erfindung sind aminfreie Kühlschmierstoffe für die
Metallbearbeitung, enthaltend Grundöle, Emulgatoren, Lösungsver
mittler 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 Metallbearbeitungsver
fahren 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 auftre
tende 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 Tei
len Einfluß auf die Maßhaltigkeit hat. Eine weitere Hauptaufgabe
der Kühlschmierstoffe ist, die Standzeit der Werkzeuge zu
verbessern, die unter dem Einfluß hoher Temperatur schnell ver
schleißen. Durch Verwendung eines Kühlschmierstoffes wird die
Rauhigkeit der Oberflächen vermindert, da der Schmierstoff Ver
schweißungen von Werkzeug und Werkstückoberfläche verhindert und
das Anhaften von Partikeln vermeidet. Darüber hinaus übernimmt der
Kühlschmierstoff die Aufgabe, die gebildeten Späne abzutranspor
tieren. Dies hat besonders bei Massenproduktionen große Bedeutung.
Kühlschmierstoffe werden normalerweise im Umlaufverfahren einge
setzt, d. h. im einfachsten Fall, dem Einsatz von Kühlschmier
stoffen an einer Einzelmaschine, hat die Maschine einen Behälter
für den Kühlschmierstoff.
Mit der Neufassung der DIN 51 385 Nr. 1 wurde eine eindeutige Be
nennung der Kühlschmierstoffe geschaffen, wobei von nichtwasser
mischbaren, wassermischbaren und von wassergemischten Kühlschmier
stoffen die Rede ist. Nach DIN 51 385 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 Kühlschmier
stoffs, 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 Ar
beitsgeschwindigkeiten 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 Kühl
schmierstoffen 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 Nichteisenme
talle nicht angegriffen werden. Die Kühlschmierstoffe müssen gut
hautverträglich sein, da die Bediener der Maschinen häufig in di
rekten Kontakt mit der Flüssigkeit kommen. Es darf bei der Umwäl
zung des Kühlschmierstoffes kein störender Schaum entstehen, und
der Anstrich und die Dichtungen der Maschine dürfen nicht ange
griffen werden. Besondere Bedeutung hat die Emulsionsstabilität,
die Einfluß auf fast alle anderen Eigenschaften des Kühlschmier
stoffes 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 was
sermischbare 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 norma
lerweise 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
51 360/2 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 al
len Dingen aber Chloride und Sulfate, verschlechtern die Rost
schutzwirkung 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, natürliche
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, Korrosionsschutzzusätze, Biozide, EP-Zusätze, polare
Zusätze, Antinebelzusätze, Alterungsschutzstoffe, Festschmierzu
sätze und Entschäumer.
Emulgatoren (z. B. Tenside, Petroleumsulfonate, Alkaliseifen, Al
kanolaminseifen) 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 Korrosionsschutzzusätze (z. B. Alkanolamine und ihre Salze,
Sulfonate, organische Borverbindungen, Fettsäureamide, Aminodicar
bonsäuren, Phosphorsäureester, Thiophosphonsäureester, Dialkyldi
thiophosphate, Mono- und Dialkylarylsulfonate, Benzotriazole,
Polyisobutenbernsteinsäurederivate) sollen das Rosten von Metall
oberflächen 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 Korrosionsschutzzu
sätze 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 Ver
bindungen) 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 wasser
mischbaren 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 hinsicht
lich der Emulsionsstabilität und des Rostschutzes eine besondere
Bedeutung zu. Umsetzungsprodukte von Alkanolaminen mit Borsäure
wirken wachstumshemmend auf Bakterien und Schimmelpilze und ver
bessern 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, reagie
ren 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 Or
ganen (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 Metallbearbei
tungsmaschinen muß deshalb die Bildung von Nitrosaminen vermieden
werden.
Die Aufgabe der vorliegenden Erfindung besteht in der Bereitstel
lung von aminfreien Kühlschmierstoffen, die jedoch in bezug auf die
Rostschutzwirkung in der Stabilität und Verwendungsdauer sowie an
deren Gebrauchseigenschaften den bisher üblichen aminhaltigen
Kühlschmierstoffen nicht nachstehen.
Die vorstehend genannte Aufgabe wird gelöst durch aminfreie Kühl
schmierstoffe enthaltend Grundöle, Emulgatoren, Lösevermittler und
Korrosionsschutzzusätze, dadurch gekennzeichnet, daß als Korro
sionsschutzzusatz 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 Dimer
fettsäure und weiteren Carbonsäuren, ausgewählt aus aliphatischen
und aromatischen Carbonsäuren bzw. deren Alkalimetall-, Magnesium-
und/oder Calciumsalze, geeignet ist, Kühlschmierstoffe zur Verfü
gung zu stellen, die in bezug auf die Korrosionsschutzwirkung ge
genüber handelsüblichen Kühlschmierstoffen auf der Basis von
Alkanolaminen vergleichbare Korrosionsschutzwirkungen aufweisen.
Die Auswahl der erfindungsgemäß enthaltenden Grundöle in den Kühl
schmierstoffen ist praktisch nicht begrenzt. So enthalten Emul
sionen im Sinne der vorliegenden Erfindung häufig Komponenten, die
ausgewählt sind aus paraffinischen, naphthenischen und paraffi
nisch-naphthenischen Mineralölen. In gleicher Weise ist der Einsatz
von Esterölen, z. B. Trimethylolpropanestern, Neopentyl- oder
Pentaerythritestern, von Fettöl-Derivaten, Polyisobutylenen,
hydrierten Polydecenen, Polypropylenglykol, Silicatestern, Kohlen
säureestern, 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 ausge
wählt sind aus a) anionischen Emulgatoren, insbesondere Seifen,
Sulfonaten und Phosphorsäureestern und deren Salze und b) nicht
ionischen Emulgatoren, insbesondere Fettalkoholethoxylaten, Fett
alkoholpropoxylaten und Zuckerestern.
Kühlschmierstoffe im Sinne der vorliegenden Erfindung enthalten
neben Grundölen, Emulgatoren und den erfindungsgemäßen Korrosions
schutzzusätzen auch Lösevermittler. Im Sinne der vorliegenden Er
findung ist auch Wasser als Lösevermittler anzusehen. Dement
sprechend sind in einer bevorzugten Ausführungsform der vorliegen
den 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 aus
gewählt 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 Ben
zoesäure, substituierten Benzoesäuren und besonders Salicylsäure.
Mögliche Substituenten der Benzoesäure können sein eine Hydroxy
gruppe, eine Nitrogruppe, sowie geradkettige oder verzweigte Alkyl-
oder Alkyloxygruppen mit bis zu 4 C-Atomen. Kurzkettige Carbon
säuren sind als Komponenten von wasserlöslichen Korrosionsschutz
mitteln bekannt, z. B. aus DE 32 23 940, nicht jedoch als Kompo
nenten von Emulsionen in der erfindungsgemäßen Kombination mit
Dimerfettsäuren, Emulgatoren, Grundölen usw.
Weiterer wesentlicher Bestandteil der erfindungsgemäßen Kühl
schmierstoffe 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 Tonerde
katalysierte Dimerisierung ungesättigter Fettsäuren gewonnene
Gemische aus acyclischen und cyclischen Dicarbonsäuren mit durch
schnittlich 36 C-Atomen (Literaturhinweis: Dimer Acids, E. C.
Leonard, 1975, Humeo Sheffield). Nebenprodukte der Dimerisierung
sind verzweigte C-18-Fettsäuren und Trimerfettsäuren bzw. poly
hasische 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. Empol®
1022, Fa. Emery, USA oder Pripol® 1040 bzw. Pripol® 1013 von Fa.
Unichema, Emmerich.
Die erfindungsgemäß verwendeten Dicarbonsäuren unterscheiden sich
in der Struktur wesentlich von den in WO 90/15663 genannten Di
carbonsäuren bzw. Dicarbonsäureanhydriden, die durch Reaktion von
Olefinen mit ungesättigten Carbonsäuren bzw. deren Anhydriden her
gestellt werden.
Die erfindungsgemäßen wassermischbaren bzw. wassergemischten Kühl
schmierstoffe können weitere funktionelle Zusatzstoffe wie polare
Zusätze, EP-Zusätze, Anti-Nebel-Zusätze, Alterungsschutzstoffe,
Festschmierstoffe, Pigmente, Entschäumer und/oder Biozide enthal
ten. Zur Anwendung bei der Metallbearbeitung enthalten die wäßrigen
Emulsionen oder wäßrigen Lösungen der erfindungsgemäßen Kühl
schmierstoffe 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 Er
findung ist es darüber hinaus besonders bevorzugt, den alkalischen
pH-Wert mittels Alkalimetallhydroxid einzustellen. Die Verwendung
von Magnesium oder Calciumhydroxid ist weniger bevorzugt, da mög
licherweise schwerlösliche Salze gebildet werden könnten. Dement
sprechend ist der Einsatz von Kalium- und/oder Natriumhydroxid im
Sinne der vorliegenden Erfindung besonders bevorzugt.
1/3 der benötigten Menge Mineralöl, Lösungsvermittler und Tallöl
fettsäure 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 in
nerhalb 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, Capryl säure (nur in den Rezepturbeispielen 1 und 2) und die Fettalkohol ethoxylate wurden danach in o. g. Reihenfolge zudosiert. Es wurde ca. 1 Stunde nachgerührt, bis eine braune klare Lösung vorlag.
Petrolsulfonat (nur im Rezepturbeispiel 1), Dimerfettsäure, Capryl säure (nur in den Rezepturbeispielen 1 und 2) und die Fettalkohol ethoxylate 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.
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 ent
stand.
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 erfindungs
gemäßen Formulierungen mit den nicht erfindungsgemäßen Beispielen
hinsichtlich Korrosionsschutzwirkung (Test nach DIN 51 360/2) wie
der.
Nach DIN 51 360/2 wird die Korrosionsschutzwirkung von wasser
gemischten Kühlschmierstoffen geprüft, indem Gußspäne auf Filter
papier mit dem Kühlschmierstoff benetzt werden. Nach zwei Stunden
werden die Korrosionsabzeichnungen auf dem Filterpapier bewertet
entsprechend einer Vergleichsskala, wobei Korrosionsgrad 0 bedeu
tet, daß keine Korrosion beobachtet wurde.
Zu den Beispielen wurde die Mindestkonzentration angegeben, die
erforderlich ist, um Korrosionsgrad 0 zu erreichen.
Claims (13)
1. Aminfreie Kühlschmierstoffe, enthaltend Grundöl, Emulgatoren
und Lösevermittler, dadurch gekennzeichnet, daß als Korrosions
schutzzusatz ein Gemisch aus
- a) Dimerfettsäuren und
- b) einer oder mehreren Carbonsäuren ausgewählt aus aliphathi schen 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.
2. 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.
3. Kühlschmierstoffe nach Anspruch 1 oder 2, dadurch gekennzeich
net, daß die Emulgatoren ausgewählt sind aus
- a) anionischen Emulgatoren, insbesondere Seifen, Sulfonaten, Phosphorsäureestern und deren Salzen und
- b) nichtionischen Emulgatoren, insbesondere Fettalkoholethoxy laten, Fettalkoholpropoxylaten und Zuckerestern.
4. Kühlschmierstoffe nach einem oder mehreren der Ansprüche 1 bis
3, dadurch gekennzeichnet, daß die Lösevermittler ausgewählt
sind aus Wasser, Alkoholen, Glykolen und/oder Glykolethern.
5. 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.
6. 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.
7. 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.
8. 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.
9. 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.-%, insbeson
dere 3 bis 10 Gew. %, bezogen auf den Kühlschmierstoff, betra
gen.
10. Kühlschmierstoffe nach einem oder mehreren der Ansprüche 1 bis
9, enthaltend weiterhin polare Zusätze, EP-Zusätze, Antinebel
zusätze, Alterungsschutzstoffe, Festschmierstoffe, Pigmente,
Entschäumer und/oder Biozide.
11. Wassermischbare Kühlschmierstoffe nach einem oder mehreren der
Ansprüche 1 bis 10.
12. Wassergemischte Kühlschmierstoffe nach einem oder mehreren der
Ansprüche 1 bis 10.
13. 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
Kühlschmierstoffe.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4229848A DE4229848A1 (de) | 1992-09-07 | 1992-09-07 | Aminfreie Kühlschmierstoffe |
EP93919222A EP0658182B1 (de) | 1992-09-07 | 1993-08-30 | Aminfreie kühlschmierstoffe |
DE59303152T DE59303152D1 (de) | 1992-09-07 | 1993-08-30 | Aminfreie kühlschmierstoffe |
ES93919222T ES2088683T3 (es) | 1992-09-07 | 1993-08-30 | Lubricantes refrigeradores exentos de aminas. |
JP6506862A JPH08501119A (ja) | 1992-09-07 | 1993-08-30 | 無アミン冷却潤滑剤 |
PCT/EP1993/002344 WO1994005746A1 (de) | 1992-09-07 | 1993-08-30 | Aminfreie kühlschmierstoffe |
AT93919222T ATE140023T1 (de) | 1992-09-07 | 1993-08-30 | Aminfreie kühlschmierstoffe |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4229848A DE4229848A1 (de) | 1992-09-07 | 1992-09-07 | Aminfreie Kühlschmierstoffe |
Publications (1)
Publication Number | Publication Date |
---|---|
DE4229848A1 true DE4229848A1 (de) | 1994-03-10 |
Family
ID=6467394
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE4229848A Withdrawn DE4229848A1 (de) | 1992-09-07 | 1992-09-07 | Aminfreie Kühlschmierstoffe |
DE59303152T Expired - Fee Related DE59303152D1 (de) | 1992-09-07 | 1993-08-30 | Aminfreie kühlschmierstoffe |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE59303152T Expired - Fee Related DE59303152D1 (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) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997015645A1 (de) * | 1995-10-26 | 1997-05-01 | Henkel Kommanditgesellschaft Auf Aktien | Öllösliche stickstofffreie korrosionsinhibitoren mit guter pufferwirkung |
US5795372A (en) * | 1994-12-16 | 1998-08-18 | Henkel Kommanditgesellschaft Auf Aktien | Nitrogen-free corrosion inhibitors having a good buffering effect |
EP0958339A1 (de) * | 1996-08-29 | 1999-11-24 | Henkel Corporation | Schmiermittel auf wasserbasis für die plastische kaltbearbeitung von metallen |
WO2000006675A1 (de) * | 1998-07-28 | 2000-02-10 | Fuchs Petrolub Ag | Wassermischbares kühlschmierstoff-konzentrat |
EP1035192A1 (de) * | 1999-01-26 | 2000-09-13 | Stefan Graichen | Additiv für einen Kühlschmierstoff |
US6318139B1 (en) | 1996-08-29 | 2001-11-20 | Henkel Corporation | Waterborne lubricant for the cold plastic working of metals |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 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 EP EP93919222A patent/EP0658182B1/de not_active Expired - Lifetime
- 1993-08-30 WO PCT/EP1993/002344 patent/WO1994005746A1/de active IP Right Grant
- 1993-08-30 DE DE59303152T patent/DE59303152D1/de not_active Expired - Fee Related
- 1993-08-30 JP JP6506862A patent/JPH08501119A/ja active Pending
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5795372A (en) * | 1994-12-16 | 1998-08-18 | Henkel Kommanditgesellschaft Auf Aktien | Nitrogen-free corrosion inhibitors having a good buffering effect |
WO1997015645A1 (de) * | 1995-10-26 | 1997-05-01 | Henkel Kommanditgesellschaft Auf Aktien | Öllösliche stickstofffreie korrosionsinhibitoren mit guter pufferwirkung |
EP0958339A1 (de) * | 1996-08-29 | 1999-11-24 | Henkel Corporation | Schmiermittel auf wasserbasis für die plastische kaltbearbeitung von metallen |
EP0958339A4 (de) * | 1996-08-29 | 2000-09-20 | Henkel Corp | Schmiermittel auf wasserbasis für die plastische kaltbearbeitung von metallen |
US6318139B1 (en) | 1996-08-29 | 2001-11-20 | Henkel Corporation | Waterborne lubricant for the cold plastic working of metals |
WO2000006675A1 (de) * | 1998-07-28 | 2000-02-10 | Fuchs Petrolub Ag | Wassermischbares kühlschmierstoff-konzentrat |
US6511946B1 (en) | 1998-07-28 | 2003-01-28 | Fuchs Petrolub Ag | Water-miscible cooling lubricant concentrate |
EP1035192A1 (de) * | 1999-01-26 | 2000-09-13 | Stefan Graichen | Additiv für einen Kühlschmierstoff |
Also Published As
Publication number | Publication date |
---|---|
EP0658182B1 (de) | 1996-07-03 |
ES2088683T3 (es) | 1996-08-16 |
JPH08501119A (ja) | 1996-02-06 |
DE59303152D1 (de) | 1996-08-08 |
ATE140023T1 (de) | 1996-07-15 |
EP0658182A1 (de) | 1995-06-21 |
WO1994005746A1 (de) | 1994-03-17 |
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