DE3534226C1 - Water-miscible coolant - Google Patents
Water-miscible coolantInfo
- Publication number
- DE3534226C1 DE3534226C1 DE3534226A DE3534226A DE3534226C1 DE 3534226 C1 DE3534226 C1 DE 3534226C1 DE 3534226 A DE3534226 A DE 3534226A DE 3534226 A DE3534226 A DE 3534226A DE 3534226 C1 DE3534226 C1 DE 3534226C1
- Authority
- DE
- Germany
- Prior art keywords
- water
- phosphoric acid
- biocide
- organic phosphoric
- cooling lubricant
- 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
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M129/24—Aldehydes; Ketones
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/02—Water
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/046—Hydroxy ethers
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/08—Aldehydes; Ketones
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/286—Esters of polymerised unsaturated acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2211/08—Halogenated waxes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/041—Triaryl phosphates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/042—Metal salts thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/02—Macromolecular compounds from phosphorus-containg monomers, obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
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- 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
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- 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
Abstract
Description
Die Erfindung bezieht sich auf einen wassermischbaren bzw. wassergemischten Kühlschmierstoff gemäß Oberbegriff des Patentanspruches, enthaltend Mineralöl, Emulgatoren, Lösungsvermittler, Korrosionsinhibitoren und ggf. weitere Komponenten sowie ein Biozid, einen sauren organischen Phosphorsäureester, jedoch keine oder nur geringe Mengen Carbonsäuren, insbesondere keine oder nur sehr geringe Mengen konventioneller Fettsäuren.The invention relates to a water-miscible or water-mixed cooling lubricant according to the generic term of the patent claim, containing mineral oil, emulsifiers, Solubilizers, corrosion inhibitors and possibly others Components as well as a biocide, an acidic organic Phosphoric acid esters, but no or only small amounts Carboxylic acids, especially no or very little Amounts of conventional fatty acids.
Wassergemischte Kühlschmierstoffe sind ein ausgezeichnetes Nährmedium für Mikroorganismen, Emulsionen und Lösungen müssen daher gegen mikrobiellen Befall geschützt werden, da sie sonst ihre Gebrauchsfähigkeit verlieren und toxikologische Probleme infolge von Infektionen des wassergemischten Kühlschmierstoffes auftreten können. Zum Schutz gegen mikrobiellen Befall werden normalerweise Biozide eingesetzt, die Bestandteil der Kühlschmierstoff-Konzentrate sind.Water-mixed cooling lubricants are an excellent one Culture medium for microorganisms, emulsions and Solutions must therefore be protected against microbial infestation otherwise they will lose their usability and toxicological problems due to infections of the water-mixed Coolant can occur. For protection biocides are usually used against microbial attack, which are part of the cooling lubricant concentrates.
Die sogenannten Formaldehyddepot-Biozide sind in diesem Anwendungsbereich weit verbreitet, da sie hinsichtlich des Verhältnisses zwischen Kosten und Wirksamkeit (breite antimikrobielle Aktivität bei möglichst niedriger Biozid-Konzentration) sehr günstig sind. Sie haben jedoch den Nachteil, daß ihre Stabilität bei Lagerung des Kühlschmier stoff-Konzentrats nicht ausreichend ist, so daß bei späterer Bereitung der Emulsionen bzw. Lösungen nur noch ein Bruchteil der ursprünglich eingesetzten Biozidmenge verfügbar ist. The so-called formaldehyde depot biocides are in widely used in this field of application as it regards the relationship between cost and effectiveness (broad antimicrobial activity with the lowest possible biocide concentration) are very cheap. However, they have the disadvantage that their stability when storing the cooling lubricant Substance concentrate is not sufficient, so that later Preparation of the emulsions or solutions only a fraction the amount of biocide originally used is available.
Die resultierende Unterdosierung des Biozids führt zu einer nicht mehr ausreichenden Biostabilität der Emulsionen und Lösungen. Die Stabilität der Emulsionen und Lösungen gegenüber Mikroorganismen ist jedoch das entscheidende Kriterium für deren Gebrauchsfähigkeit und Gebrauchsdauer. Ein mikrobieller Befall einer Emulsion kann erhebliche toxikologische Probleme verursachen (starke Vermehrung der Mikroorganismen, Auftreten von coliformen Keimen mit dem Risiko humanpathologischer Infektionen), er führt zu einem Abfall des pH-Wertes (erhöhte Korrosivität des wassergemischten Kühlschmierstoffs) und schließlich zur völligen Spaltung und damit zum völligen Verlust der Emulsionsfüllung (was wiederum Kosten nicht nur für die Neubefüllung, sondern auch für die Beseitigung der alten Füllung verursacht, darüber hinaus können zusätzliche wirtschaftliche Verluste durch mangelnde Zerspanungsleistungen und verkürzte Werkzeugstandzeiten entstehen).The resulting underdosing of the biocide leads insufficient biostability of the emulsions and solutions. The stability of the emulsions and However, solutions to microorganisms is the key Criterion for their usability and Service life. A microbial infestation of an emulsion can cause significant toxicological problems (proliferation of microorganisms, occurrence of coliform germs with the risk of human pathological Infections), it leads to a drop in pH (increased corrosiveness of the water-mixed cooling lubricant) and finally to complete division and thus to the complete loss of the emulsion filling (which in turn Costs not only for refilling, but also for the removal of the old filling caused about it It can also result in additional economic losses lack of cutting performance and reduced tool life arise).
Die Zersetzungsgeschwindigkeit des Biozids ist abhängig von der jeweiligen Zusammensetzung des Kühlschmierstoffs.The rate of decomposition of the biocide depends on the respective composition of the cooling lubricant.
Die Erfindung befaßt sich mit dem Problem, einen Kühlschmierstoff der eingangs genannten Art hinsichtlich seiner mikrobiellen Stabilität zu verbessern, d. h. den Biozidzerfall während der Lagerung des Kühlschmierstoff-Konzentrats zu verhindern oder zu hemmen. Erreicht wird dies durch einen Kühlschmierstoff nach den Ansprüchen.The invention addresses the problem of a cooling lubricant of the type mentioned above with regard to its improve microbial stability, d. H. the biocide decay during storage of the coolant concentrate to prevent or inhibit. This is achieved through a cooling lubricant according to the claims.
Dabei wurde insbesondere gefunden, daß eine nachhaltige Hemmung des Biozidzerfalls gemäß der Erfindung dann erreicht wird, wenn als saure Komponenten nicht die üblicherweise verwendeten Carbonsäuren (insbesondere Fettsäuren), sondern saure organische Phosphorsäureester eingesetzt werden. Der deutlich verlangsamte Biozidzerfall führt zu einer erheblich besseren mikrobiellen Resistenz der erfindungsgemäßen Kühlschmierstoffe nach Lagerung, verglichen mit konventionellen Formulierungen. It was found in particular that a sustainable Inhibition of biocide decay according to the invention is then achieved if the acidic components are not the commonly used ones Carboxylic acids (especially fatty acids), but acidic organic phosphoric acid esters are used. The significantly slower biocide decay leads to one considerably better microbial resistance of the invention Cooling lubricants after storage compared to conventional formulations.
Im Rahmen von Untersuchungen konnte auch gezeigt werden, daß eine solche Zusammensetzung der Kühlschmierstoffe zu einem wesentlich verbesserten Schaumverhalten der Emulsionen und Lösungen führt. Hierfür ist ebenfalls entscheidend, daß der Kühlschmierstoff keine oder nur geringe Mengen an Carbonsäuren (insbesondere Fettsäuren) und stattdessen saure organische Phosphorsäureester enthält.Studies have also shown that that such a composition of cooling lubricants to a significantly improved foam behavior Emulsions and solutions leads. For this is also crucial that the cooling lubricant little or no Amounts of carboxylic acids (especially fatty acids) and instead contains acidic organic phosphoric acid esters.
Stand der betrieblichen Technik sind wassermischbare Kühlschmierstoffe für die Metallzerspanung, die Biozide überwiegend formaldehydabspaltende Biozide, sogenannte "Formaldehyd-Depotprodukte" im Konzentrat zum Schutz gegen mikrobiellen Befall der Gebrauchsemulsionen und -lösungen enthalten. Diese wassermischbaren Kühlschmierstoffe enthalten darüberhinaus u. a. alkalische Komponenten (z. B. Alkanolamine) sowie Carbonsäuren (vorwiegend Fettsäuren), die eine neutralisierende, schmierende und teilweise auch emulgierende und korrosionsinhibierende Funktion ausüben.State of the art are water miscible Cooling lubricants for metal cutting, biocides predominantly formaldehyde-releasing biocides, so-called "Formaldehyde depot products" in the concentrate for protection against microbial infestation of use emulsions and solutions included. These water-miscible coolants also contain u. a. alkaline components (e.g. alkanolamines) and carboxylic acids (predominantly fatty acids), which is a neutralizing, lubricating and sometimes also perform emulsifying and corrosion-inhibiting function.
Die eingesetzten Biozide, die in den meisten Fällen durch gezielte mikrobiologische Untersuchungen ausgewählt worden sind, verleihen den Gebrauchsemulsionen und -lösungen eine gute oder zumindest voll ausreichende Resistenz gegenüber Mikroorganismen, sofern die Emulsionen bzw. Lösungen aus Konzentraten bereitet werden, die frisch hergestellt oder nur kurze Zeit gelagert wurden.The biocides used, in most cases selected by targeted microbiological tests have been given to use emulsions and -solutions have good or at least fully sufficient resistance against microorganisms, provided the emulsions or solutions are prepared from concentrates that are freshly made or were only stored for a short time.
Wegen der beschriebenen Zersetzung der Biozide bei längerer Lagerung des Konzentrats ist jedoch die Biostabilität der Gebrauchsemulsionen und -lösungen häufig unbefriedigend oder zumindest nicht mehr voll ausreichend, da wegen des Biozidzerfalls während der Lagerung die für den mikrobiellen Schutz in der Gebrauchsemulsion oder -lösung notwendige Biozidkonzentration (die sogenannte "minimale Hemmkonzentration") nicht mehr zur Verfügung steht.Because of the described decomposition of the biocides longer storage of the concentrate is the biostability the use emulsions and solutions are often unsatisfactory or at least not fully sufficient, because of the Biocide decay during storage for the microbial Protection in the use emulsion or solution necessary Biocide concentration (the so-called "minimal Inhibitory concentration ") is no longer available.
Die resultierende Unterdosierung des Biozids führt zu den bereits beschriebenen erheblichen Nachteilen und Problemen.The resulting underdosing of the biocide leads to the considerable disadvantages already described and Problems.
Hinsichtlich der Schaumneigung konventioneller Formulierungen (die Carbonsäuren enthalten) wurde versucht, diese durch Verwendung von Entschäumern (häufig silikonhaltig) zu dämpfen. Solche Entschäumer werden jedoch meist bereits nach kurzem Einsatz unwirksam (da sie adsorbiert und ausgetragen oder in ihrer Teilchenstruktur verändert werden). Anzustreben sind daher Kühlschmierstoff-Formulierungen, die als solche nicht schäumen und daher der Verwendung von Entschäumern nicht bedürfen.With regard to the tendency of conventional formulations to foam (containing carboxylic acids) was tried by using defoamers (often containing silicone) to dampen. However, such defoamers are mostly ineffective after only a short use (because it adsorbs and carried out or changed in their particle structure will). Cooling lubricant formulations should therefore be aimed at, which do not foam as such and therefore do not require the use of defoamers.
Es wurden auch Biozide geprüft, deren Wirkungsmechanismus nicht auf der Freisetzung von antimikrobiell wirkendem Formaldehyd beruht. Es zeigte sich jedoch, daß diese sogenannten formaldehydfreien Biozide entweder nicht über das notwendige breite Wirkungsspektrum (gegen alle üblicherweise in Metallbearbeitungsemulsionen auftretenden Bakterien, Pilze und Hefen) verfügen oder aber toxikologisch oder ökologisch bedenklich sind. Darüber hinaus lassen sich diese formaldehydfreien Biozide oft nicht in Konzentrate einbauen.Biocides, their mechanism of action, were also examined not on the release of antimicrobial Formaldehyde is based. However, it turned out that these so-called formaldehyde-free biocides either don't have the necessary broad spectrum of action (against all usual occurring in metalworking emulsions Bacteria, fungi and yeasts) or toxicologically or are ecologically questionable. Beyond that these formaldehyde-free biocides are often not in concentrates install.
Es wurde daher versucht, durch systematische Variation der Zusammensetzung der Konzentrate herauszufinden, ob die An- bzw. Abwesenheit bestimmter Komponenten die Zersetzungsgeschwindigkeit der betroffenen Biozide beeinflußt.It was therefore tried through systematic variation the composition of the concentrates to find out whether the presence or absence of certain components the rate of decomposition of the biocides affected.
Durch systematische Variation der Zusammensetzung der Konzentrate konnte gezeigt werden, daß die Zersetzungsgeschwindigkeit der Biozide während der Lagerung der Konzentrate in bestimmtem Maße durch die chemische Zusammensetzung der Konzentrate beeinflußt werden kann. Die An- bzw. Abwesenheit bestimmter Komponenten kann sich günstig oder ungünstig auf die Zersetzungsgeschwindigkeit auswirken.By systematically varying the composition the concentrates could be shown to show the rate of decomposition the biocides during the storage of the concentrates to a certain extent by the chemical composition the concentrates can be influenced. The arrival or the absence of certain components can be beneficial or adversely affect the rate of decomposition.
Dabei wurde insbesondere gefunden, daß der Einbau von sauren organischen Phosphorsäureestern in Kühlschmierstoff- Formulierungen bei gleichzeitiger Abwesenheit von Carbonsäuren gemäß der Erfindung zu einer deutlichen Hemmung des Biozidzerfalls führt.It was found in particular that the installation of acidic organic phosphoric acid esters in cooling lubricant Formulations in the absence of carboxylic acids according to the invention to a significant inhibition of Biocide decay leads.
Außerdem konnte, wie oben beschrieben, nachgewiesen werden, daß der völlige oder zumindest weitgehende Austausch von Carbonsäuren (insbesondere Fettsäuren) durch bestimmte saure organische Phosphorsäureester zu einem erheblich verbesserten Schaumverhalten der Emulsionen und Lösungen führt.In addition, as described above, that the complete or at least extensive exchange of Carboxylic acids (especially fatty acids) due to certain acidic ones organic phosphoric acid esters to a vastly improved Foaming behavior of the emulsions and solutions leads.
Kühlschmierstoff-Formulierungen dieser Art neigen (als Emulsion bzw. Lösung) sowohl in Laborversuchen als auch unter Praxisbedingungen (auch in schwierigen Fällen, z. B. bei hoher Emulsionskonzentration und ungünstigen Einsatzbedingungen wie beim Tieflochbohren) nicht oder in wesentlich geringerem Maße als konventionelle Produkte zur Schaumbildung.Cooling lubricant formulations of this type tend (as an emulsion or solution) both in laboratory tests and even under practical conditions (even in difficult cases, e.g. B. at high emulsion concentration and unfavorable operating conditions as with deep hole drilling) not or in much less than conventional products for Foaming.
Saure organische Phosphorsäureester werden gelegentlich als verschleißmindernde Komponenten (sogenannte "extreme pressure" Wirkstoffe) in Kühlschmierstoffen eingesetzt, eine stabilisierende Wirkung von sauren organischen Phosphorsäureestern auf formaldehydabspaltende Biozide (Hemmung des Biozidzerfalls während der Lagerung des Konzentrats) war jedoch bisher nicht bekannt. Die Anwesenheit von Phosphorverbindungen wurde im Gegenteil eher als günstig für das Wachstum von Mikroorganismen (und damit nachteilig für die Biostabilität von Kühlschmierstoffen) angesehen, da Phosphor zu den Elementen gehört, die für den Stoffwechsel der Mikroorganismen unentbehrlich sind.Acidic organic phosphoric acid esters are uncommon as wear-reducing components (so-called "extreme pressure" active ingredients) used in cooling lubricants, a stabilizing effect of acidic organic Phosphoric acid esters on formaldehyde-releasing biocides (Inhibition of biocide decay during storage of the Concentrate) was however not yet known. The presence on the contrary, rather than favorable for the growth of microorganisms (and thus disadvantageous for the biostability of cooling lubricants) viewed because phosphorus is one of the elements for the Metabolism of the microorganisms are essential.
Überraschend ist auch die erhebliche Verbesserung des Schaumverhaltens wassergemischter Kühlschmierstoffe der hier beschriebenen ZusammensetzungThe considerable improvement in the Foaming behavior of water-mixed cooling lubricants composition described here
Für das verbesserte Schaumverhalten der hier beschriebenen Produkte ist entscheidend, daß die in konventionellen Formulierungen üblicherweise anwesenden Carbonsäuren (insbesondere Fettsäuren) ganz oder weitgehend durch saure organische Phosphorsäureester ausgetauscht worden sind.For the improved foam behavior of those described here It is crucial that those in conventional Formulations usually present carboxylic acids (especially fatty acids) entirely or largely by acid organic phosphoric acid esters have been replaced.
Zur Erzielung der in der Erfindung beschriebenen Verbesserungen (Biostabilität/Hemmung des Biozidzerfalls während der Lagerung, Schaumverhalten) genügt es nicht, eine gewisse Menge eines sauren organischen Phosphorsäureesters zu einer konventionellen Formulierung hinzuzufügen.To achieve those described in the invention Improvements (biostability / inhibition of biocide decay during storage, foaming behavior) it is not sufficient to certain amount of an acidic organic phosphoric acid ester to add to a conventional wording.
Bevorzugte Zusammensetzungen erfindungsgemäßer Kühlschmierstoffe sind in den Ansprüchen beschrieben.Preferred compositions of cooling lubricants according to the invention are described in the claims.
Im Sinne der Erfindung besonders geeignete saure Phosphorsäureester sind Monoalkyl-phosphorsäureester, Dialkyl-phosphorsäureester, Monoisoalkyl-phosphorsäureester, Diisoalkyl-phosphorsäureester, Monoalkenyl- phosphorsäureester, Dialkenyl-phosphorsäureester, Mono(alkylphenyl)-phosphorsäureester, Di(alkylphenyl)- phosphorsäureester, Mono(isoalkylphenyl)-phosphorsäureester, Di(isoalkylphenyl)-phosphorsäureester, sowie Mono- und Dipolyether-phosphorsäureester, wobei die Polyethergruppierung Alkyl-, Isoalkyl-, Phenyl-, Alkylphenyl- und Isoalkylphenyl- und Wasserstoff als endständige Gruppe enthalten kann.Acid particularly suitable for the purposes of the invention Phosphoric acid esters are monoalkyl phosphoric acid esters, Dialkyl phosphoric acid esters, monoisoalkyl phosphoric acid esters, Diisoalkyl phosphoric acid esters, monoalkenyl phosphoric acid esters, dialkenyl phosphoric acid esters, Mono (alkylphenyl) phosphoric acid ester, di (alkylphenyl) - phosphoric acid esters, mono (isoalkylphenyl) phosphoric acid esters, Di (isoalkylphenyl) phosphoric acid esters, and Mono- and dipolyether phosphoric acid esters, the Polyether grouping alkyl, isoalkyl, phenyl, alkylphenyl and isoalkylphenyl and hydrogen as terminal Group can contain.
Claims (5)
- Mineralöl 50-55
Petroleumsulfonat 16-20
Glykolether 12-16
Borsäureaminester 7-10
saurer organischer Phosphorsäureester 3-7
Biozid 2-3.
- Mineral oil 50-55
Petroleum sulfonate 16-20
Glycol ether 12-16
Boric acid amine ester 7-10
acidic organic phosphoric acid ester 3-7
Biocide 2-3.
- Mineralöl 30-35
Petroleumsulfonat 18-22
Glykolether 12-16
Borsäureaminester 5-8
Fettsäureester 5-8
Chlorparaffin 8-12
saurer organischer Phosphorsäureester 6-9
Biozid 2-3.
- Mineral oil 30-35
Petroleum sulfonate 18-22
Glycol ether 12-16
Boric acid amine ester 5-8
Fatty acid esters 5-8
Chlorine paraffin 8-12
acidic organic phosphoric acid ester 6-9
Biocide 2-3.
- Mineralöl 20-30
Nichtionogene Emulgatoren 10-15
Borsäureaminester 9-18
Alkanolamine 0-7
Glykolether 6-12
Chlorparaffin 16-20
Wasser 5-15
saurer organischer Phosphorsäureester 7-12
Biozid 2-5
- Mineral oil 20-30
Nonionic emulsifiers 10-15
Boric acid amine 9-18
Alkanolamines 0-7
Glycol ether 6-12
Chlorine paraffin 16-20
Water 5-15
acidic organic phosphoric acid ester 7-12
Biocide 2-5
- Mineralöl 5-25
Nichtionogene Emulgatoren 10-15
Borsäureaminester 12-18
Alkanolamine 0-7
Glykolether 6-20
Korrosionsinhibitoren 10-15
Wasser 5-20
saurer organischer Phosphorsäureester 5-10
Biozid 2-5
- Mineral oil 5-25
Nonionic emulsifiers 10-15
Boric acid amine ester 12-18
Alkanolamines 0-7
Glycol ether 6-20
Corrosion inhibitors 10-15
Water 5-20
acidic organic phosphoric acid ester 5-10
Biocide 2-5
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3534226A DE3534226C1 (en) | 1985-09-26 | 1985-09-26 | Water-miscible coolant |
JP61219089A JPS62104898A (en) | 1985-09-26 | 1986-09-17 | Water miscible lubricant for metal working |
AT86307185T ATE56745T1 (en) | 1985-09-26 | 1986-09-18 | WATER-MISCIBLE METALWORKING LUBRICANTS. |
EP86307185A EP0217597B1 (en) | 1985-09-26 | 1986-09-18 | Water-miscible metalworking lubricants |
DE8686307185T DE3674315D1 (en) | 1985-09-26 | 1986-09-18 | WATER MIXABLE METAL WORKING LUBRICANTS. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3534226A DE3534226C1 (en) | 1985-09-26 | 1985-09-26 | Water-miscible coolant |
Publications (1)
Publication Number | Publication Date |
---|---|
DE3534226C1 true DE3534226C1 (en) | 1987-04-23 |
Family
ID=6281922
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE3534226A Expired DE3534226C1 (en) | 1985-09-26 | 1985-09-26 | Water-miscible coolant |
DE8686307185T Expired - Fee Related DE3674315D1 (en) | 1985-09-26 | 1986-09-18 | WATER MIXABLE METAL WORKING LUBRICANTS. |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE8686307185T Expired - Fee Related DE3674315D1 (en) | 1985-09-26 | 1986-09-18 | WATER MIXABLE METAL WORKING LUBRICANTS. |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0217597B1 (en) |
JP (1) | JPS62104898A (en) |
AT (1) | ATE56745T1 (en) |
DE (2) | DE3534226C1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0753916B2 (en) * | 1990-03-19 | 1995-06-07 | 住友金属工業株式会社 | Oily scale inhibitor for hot rolling and hot rolling method |
DE19620084A1 (en) * | 1996-05-20 | 1997-11-27 | Schenk Filterbau Gmbh | Use of depth filters for the treatment of cooling lubricants |
US5716917A (en) * | 1996-09-24 | 1998-02-10 | Cincinnati Milacron Inc. | Machining fluid composition and method of machining |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4371447A (en) * | 1981-07-06 | 1983-02-01 | Standard Oil Company | Low viscosity water-in-oil microemulsions |
EP0147760B1 (en) * | 1983-12-19 | 1991-04-03 | Hitachi, Ltd. | Emulsion type liquid lubricant for metal forming, process for preparing the lubricant and process for metal forming with the lubricant |
-
1985
- 1985-09-26 DE DE3534226A patent/DE3534226C1/en not_active Expired
-
1986
- 1986-09-17 JP JP61219089A patent/JPS62104898A/en active Pending
- 1986-09-18 EP EP86307185A patent/EP0217597B1/en not_active Expired - Lifetime
- 1986-09-18 DE DE8686307185T patent/DE3674315D1/en not_active Expired - Fee Related
- 1986-09-18 AT AT86307185T patent/ATE56745T1/en not_active IP Right Cessation
Non-Patent Citations (1)
Title |
---|
NICHTS-ERMITTELT * |
Also Published As
Publication number | Publication date |
---|---|
DE3674315D1 (en) | 1990-10-25 |
EP0217597B1 (en) | 1990-09-19 |
EP0217597A3 (en) | 1988-06-08 |
ATE56745T1 (en) | 1990-10-15 |
EP0217597A2 (en) | 1987-04-08 |
JPS62104898A (en) | 1987-05-15 |
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Owner name: MOBIL OIL CORP., NEW YORK, N.Y., US |
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Free format text: DIEHL, H., DIPL.-PHYS. DR.RER.NAT., 8000 MUENCHEN GLAESER, J., DIPL.-ING., 2000 HAMBURG HILTL, E., DIPL.-CHEM. DR.RER.NAT. BURGER, E., DIPL.-ING., PAT.-ANW., 8000 MUENCHEN |
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