EP1102830B1 - Water-miscible cooling lubricant concentrate - Google Patents

Water-miscible cooling lubricant concentrate Download PDF

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Publication number
EP1102830B1
EP1102830B1 EP99927938A EP99927938A EP1102830B1 EP 1102830 B1 EP1102830 B1 EP 1102830B1 EP 99927938 A EP99927938 A EP 99927938A EP 99927938 A EP99927938 A EP 99927938A EP 1102830 B1 EP1102830 B1 EP 1102830B1
Authority
EP
European Patent Office
Prior art keywords
cooling lubricant
weight
lubricant concentrate
water
concentrate according
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.)
Revoked
Application number
EP99927938A
Other languages
German (de)
French (fr)
Other versions
EP1102830A1 (en
Inventor
Heinz Gerhard Theis
Rüdiger SCHWAB
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fuchs SE
Original Assignee
Fuchs Petrolub SE
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Publication date
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Application filed by Fuchs Petrolub SE filed Critical Fuchs Petrolub SE
Publication of EP1102830A1 publication Critical patent/EP1102830A1/en
Application granted granted Critical
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Anticipated expiration legal-status Critical
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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
    • 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
    • C10M129/04—Hydroxy compounds
    • C10M129/06—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
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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
    • C10M129/56—Acids of unknown or incompletely defined constitution
    • C10M129/60—Tall oil acids
    • C—CHEMISTRY; METALLURGY
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    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M133/08—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups
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    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
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    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
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    • 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
    • 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
    • C10M2227/062—Cyclic esters
    • 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
    • C10M2227/063—Complexes of boron halides
    • 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
    • C10M2227/065—Organic compounds derived from inorganic acids or metal salts derived from Ti or Zr
    • 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
    • C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
    • 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
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • the subject matter of the invention is a water-miscible cooling lubricant concentrate which, in the water-mixed state, is characterized both by excellent performance properties in cutting or non-cutting metalworking and by a particularly high level of skin tolerance.
  • cooling lubricants make up almost 40% of the triggering of occupational skin diseases in the commercial sector (Brochure ZH 1/467, Skin Protection in Metal Works, Hämé der Metallconcesartenschaften, 1996).
  • Cooling lubricants are used in metal cutting and metal forming to cool and lubricate workpieces. They are used in machining processes such as milling, turning, drilling and grinding as well as in non-cutting deformations such as rolling, deep drawing or cold extrusion. According to DIN 51385, a distinction is made between water-miscible and water-mixed cooling lubricants.
  • water-mixed means the final state of the finished medium, usually in the form of an oil-in-water emulsion, and "water-miscible” means the cooling lubricant concentrate.
  • Water-mixed cooling lubricants are produced by the user by mixing the concentrate with water. Their main task as an emulsion, solution or in a concentrated form in metalworking is the cooling, lubrication and removal of the material removed from the workpiece and tool by the multitude of manufacturing operations such as turning, drilling, milling, grinding, etc.
  • the water-mixed cooling lubricant fulfills a large number of other secondary tasks, such as keeping the systems clean and protecting machine parts from corrosion.
  • the water-mixed cooling lubricants usually used have a pH value between 8.2 and 9.4, depending on the concentration and type of cooling lubricant, which can only be higher in exceptional cases.
  • the disadvantage here is that a high pH value reduces the skin tolerance of the cooling lubricant, because the protective acid layer of the skin is destroyed and skin problems can arise for the operator of the metal processing machine if the exposure time is longer.
  • a lowering of the pH value of water-mixed cooling lubricants down to the neutral point has so far proven impossible, because then the high requirements on the rust protection effect of water-mixed cooling lubricants can no longer be met.
  • the task was therefore to provide a water-mixed cooling lubricant whose pH value is as close as possible to the neutral point and nevertheless does not lead to rust formation in metal parts that have been processed with an aqueous solution of the cooling lubricant.
  • Such a cooling lubricant concentrate contains paraffinic or paraffinic mineral oils as natural or synthetic mineral oils naphthenic hydrocarbons, which can also be mixed with one another in a ratio of 1: 3 to 5: 1, white oils, esters, polyisobutenes, polyvinylpyrrolidones or polyalkylene glycols. These compounds, also known as base oils, are generally contained in the cooling lubricant concentrate in an amount of 5 to 80 percent by weight, preferably in an amount of 5 to 50 percent by weight.
  • the emulsifiers represent the most important group in the production of the cooling lubricant concentrate according to the invention.
  • anionic emulsifiers such as alkali salts of saturated or unsaturated carboxylic acids, alkali salts of sulphonates and sulphonic acids and salts of phosphoric acid esters have a very special meaning.
  • non-ionic emulsifiers especially fatty alcohol ethoxylates, fatty alcohol propoxylates, sugar esters, neopentyl glycol esters, pentaerythritol esters, 2-ethylhexyl esters and trimethylolpropane esters are successfully used to produce the water-miscible cooling lubricant concentrate according to the invention.
  • boric acid compounds can also increase the cooling lubricant biostasis and the buffer capacity. As a result, longer service lives of the cooling lubricant are achieved in practical use and thus its economic efficiency is improved.
  • the significantly increased biocidal effectiveness of boric acid compounds which is observed above all in the low pH range and can be explained by a blockage of the enzymes of the phosphate metabolism of the microorganisms, also allows the amount of others Adding inhibitors to reduce the growth of microorganisms.
  • the corrosion protection of boron compounds is considerably increased if they are used together with polyalkoxylated fatty acid amides and / or imides, especially with neutral ethoxylated and / or propyxylated fatty acid amides based on vegetable and / or animal origin and / or specifically adjusted fatty acid mixtures and / or alkyl succinic acid imides or with other corrosion protection additives also contained in conventional cooling lubricant formulations, for example phosphoric acid esters, triazoles or thiadiazoles, can be used, the corrosion protection agent being added in an amount of 5 to 25 percent by weight.
  • a water-mixed cooling lubricant equipped with the above-mentioned corrosion protection additives shows a corrosion protection equivalent to DIN 51360-1 and -2 as the cooling lubricants previously used.
  • boric acid-free formulations consisting of ethoxylated and / or propoxylated fatty acid alkanolamides are used, a concentration of 2 to 25 percent by weight is sufficient to achieve corrosion protection that meets the highest requirements previously placed on cooling lubricants.
  • fatty acids, in particular ether carboxylic acids are used as corrosion inhibitors, a degree of ethoxylation of 2 to 12 mol of ethylene oxide per mol of ether carboxylic acid is particularly advantageous.
  • Such ethoxylated ether carboxylic acids are used as anti-corrosion agents in a concentration of 2 to 15 percent by weight.
  • biocidal compounds which are otherwise not provided with sufficient stability have active ingredient stability even after long storage times and at elevated temperatures retained by significantly greater than 95%.
  • These compounds include, in particular, 3-iodo-2-propynyl-butylcarbamate, methylisothiazolinone and other isothiazolinone derivatives.
  • nitrosating substances such as nitrite, which is formed from the nitrate of the batch water by bacterial activity, to form carcinogenic nitrosamines and their formation depends on the pH value, especially in the acidic range takes place
  • inhibitors include free primary amines, which are formed in small amounts in the cooling lubricant according to the invention as a result of a dissociation equilibrium from fatty acid alkanolamides, or, for example, ascorbic acid. This prevents nitrosamine formation.
  • the results of the tests that amides in particular cannot form stable nitrosamines in a pH range of 6-8 also speak against an increased risk of nitrosamine formation in the cooling lubricant formulations according to the invention.
  • the active ingredients contained in the cooling lubricant concentrate according to the invention can only develop their optimal effect if they are homogeneously distributed and the cooling lubricant concentrate does not separate into several phases. Therefore, solubilizers must be added to the concentrate.
  • solubilizers In addition to water, glycols such as ethylene glycol and, above all, butyl triglycol, as well as straight-chain and branched fatty alcohols with 16 to 24 carbon atoms are suitable if they are added in amounts of 5 to 50 percent by weight.
  • the water-mixed cooling lubricant is a good breeding ground for microorganisms. Increased contamination with bacteria, fungi and yeasts leads to chemical changes in the emulsion components and influences the usability of the water-mixed cooling lubricant. If harmful microorganisms are introduced, for example coliform bacteria, this can also have serious effects on the health of employees. For this reason, it is usually essential to equip the cooling lubricant concentrate with the appropriate biocidal or fungicidal compounds.
  • components that are otherwise unusual in the cooling lubricant concentrate such as isothiazolinones or 3-iodo-2-propynyl carbamate, have an interesting and economical spectrum of activity, as was not previously known.
  • Other particularly suitable preservatives taking into account the pH value of ⁇ 7.6, are above all guanidine derivatives, imidazole derivatives and aromatic carboxylic acids such as salicylic or benzoic acid and their derivatives.
  • methylolurea derivatives such as dimethylolurea and / or tri- and tetramethylolacetylenediurea, contrary to previous experience, do not polymerize through to ineffective polyurea derivatives even in higher concentrations and then thus are no longer available as a biocidal active substance or cause problems through precipitation reactions and inhomogeneities.
  • the preservatives are generally added to the cooling lubricant concentrate in amounts of 0.1 to 5 percent by weight.
  • the water-miscible and water-mixed cooling lubricants according to the invention can contain further functional additives contain, for example, castoroil ethoxylates, petroleum sulfonates up to a total base number of less than / equal to 400, solid lubricants, toluyltriazoles, defoamers and / or anti-fog additives.
  • the aqueous solutions or emulsions produced from the water-miscible cooling lubricant concentrate contain these additives generally in amounts of 1 to 10 percent by weight, preferably in amounts of 2 to 5 percent by weight, based on the water-miscible cooling lubricant concentrate.
  • TEWL transepidermal water loss
  • the water-miscible cooling lubricant concentrate according to the invention was produced according to the following recipe examples.
  • Paraffinic solvent raffinate 24% Boric acid-triethanolamine reaction product 25% Fatty acid monoethanolamide (degree of ethoxylation 4) 12% Alkyl succinic imide 4.5% Castoroil ethoxylate (degree of ethoxylation 5) 3% Synthetic sodium petroleum sulfonate 5% Ethylene propylene glycol 4.3% Polypropylene glycol monobutyl ether 2% Ethyl hexyl oleate 16% Hexitidine 3.5% 3-iodo-2-propynyl butyl carbamate (IPBC) 0.5%
  • Triethanolamine salt of a cyclic Tricarboxylic acid (Irgacor® L 190) 50% Rüboelfettklakladolamid (degree of ethoxylation 4) 2.5% Partial phosphoric acid ester, neutralized with a primary alkanolamine 7% C 10 monocarboxylic acid (neodecanoic acid) 3% n-octylisothiazolinone 0.3% Polymeric cationic microbiocide 0.15% water 37.05%
  • Recipe example 1 2 3a 3b 4th Look coarsely dispersed / milky clear solution PH value 7.4 7.5 7.4 7.4 7.5 Corrosion protection after DIN 51 360-2 Rust grade 0 at% 4.5 4th 4th 4th 3.5

Description

Der Gegenstand der Erfindung ist ein wassermischbares Kühlschmierstoff-Konzentrat, das sich in wassergemischtem Zustand sowohl durch hervorragende Gebrauchseigenschaften bei der spanenden oder spanlosen Metallbearbeitung als auch durch eine besonders hohe Hautverträglichkeit auszeichnet.The subject matter of the invention is a water-miscible cooling lubricant concentrate which, in the water-mixed state, is characterized both by excellent performance properties in cutting or non-cutting metalworking and by a particularly high level of skin tolerance.

Kühlschmierstoffe sind gemäß den Informationen der Arbeitsgemeinschaft der Metallberufsgenossenschaften mit fast 40% an der Auslösung von berufsbedingten Hauterkrankungen im gewerblichen Bereich beteiligt (Broschüre ZH 1/467, Hautschutz in Metallbetrieben, Arbeitsgemeinschaft der Metallberufsgenossenschaften, 1996).According to the information provided by the Arbeitsgemeinschaft der Metallberufsgenossenschaften (Arbeitsgemeinschaft der Metallberufsgenossenschaften), cooling lubricants make up almost 40% of the triggering of occupational skin diseases in the commercial sector (Brochure ZH 1/467, Skin Protection in Metal Works, Arbeitsgemeinschaft der Metallberufsgenossenschaften, 1996).

Kühlschmierstoffe werden bei der Metallzerspanung und bei der Metallumformung zum Kühlen und Schmieren von Werkstücken verwendet. Sie werden sowohl bei spanenden Bearbeitungsverfahren wie dem Fräsen, Drehen, Bohren und Schleifen als auch bei spanlosen Verformungen wie dem Walzen, Tiefziehen oder Kaltfließpressen verwendet. Nach der DIN 51385 unterscheidet man zwischen wassermischbaren und wassergemischten Kühlschmierstoffen. Unter dem Begriff "wassergemischt" ist der Endzustand des fertigen Mediums, meist in Form einer Öl-In-Wasser-Emulsion, und unter "wassermischbar" das Kühlschmierstoff-Konzentrat verstanden.Cooling lubricants are used in metal cutting and metal forming to cool and lubricate workpieces. They are used in machining processes such as milling, turning, drilling and grinding as well as in non-cutting deformations such as rolling, deep drawing or cold extrusion. According to DIN 51385, a distinction is made between water-miscible and water-mixed cooling lubricants. The term "water-mixed" means the final state of the finished medium, usually in the form of an oil-in-water emulsion, and "water-miscible" means the cooling lubricant concentrate.

Wassergemischte Kühlschmierstoffe werden beim Verwender durch Mischen des Konzentrats mit Wasser hergestellt. Ihre Hauptaufgabe als Emulsion, Lösung oder auch in konzentrierter Form in der Metallbearbeitung ist das Kühlen, das Schmieren und der Abtransport des durch die Vielzahl von Fertigungsoperationen wie Drehen, Bohren, Fräsen, Schleifen usw. entstandenen Materialabtrags weg von Werkstück und Werkzeug. Daneben erfüllt der wassergemischte Kühlschmierstoff noch eine Vielzahl weiterer sekundärer Aufgaben, wie das Sauberhalten der Systeme und den Korrosionsschutz der Maschinenteile.Water-mixed cooling lubricants are produced by the user by mixing the concentrate with water. Their main task as an emulsion, solution or in a concentrated form in metalworking is the cooling, lubrication and removal of the material removed from the workpiece and tool by the multitude of manufacturing operations such as turning, drilling, milling, grinding, etc. In addition, the water-mixed cooling lubricant fulfills a large number of other secondary tasks, such as keeping the systems clean and protecting machine parts from corrosion.

Die üblicherweise verwendeten wassergemischten Kühlschmierstoffe weisen je nach Einsatzkonzentration und Kühlschmierstofftyp einen pH-Wert zwischen 8,2 und 9,4 auf, der nur ausnahmsweise auch noch höher liegen kann. Nachteilig ist dabei, dass ein hoher pH-Wert die Hautverträglichkeit des Kühlschmierstoffes senkt, weil der Säureschutzmantel der Haut dadurch zerstört und bei längeren Einwirkzeiten Hautprobleme beim Bediener der Metallverarbeitungsmaschine auftreten können. Eine Absenkung des pH-Wertes von wassergemischten Kühlschmierstoffen bis zum Neutralpunkt hin hat sich bisher als unmöglich erwiesen, weil dann den hohen Anforderungen an die Rostschutzwirkung von wassergemischten Kühlschmierstoffen nicht mehr genügt werden kann. Nach der Bearbeitung in Kühlschmierstoffen ist es im allgemeinen aus wirtschaftlichen Gründen oder wegen der Verknüpfung von Fertigungsprozessen unüblich, das bearbeitete Metallteil zu trocknen oder mit einem besonderen Korrosionschutz zu versehen. Die Teile werden normalerweise nass in Kästen gelegt und dürfen dann auch im nassen Zustand nicht rosten. Zur Prüfung der Rostschutzwirkung wird bei der Entwicklung und auch bei der Kontrolle von wassergemischten Kühlschmierstoffen im allgemeinen der Test mit Gussspänen nach DIN 51360-1 und -2 verwendet. Dieser Test zeigt, dass die Gefahr der Rostbildung auf dem bearbeiteten Metallteil umso größer ist, je weiter der pH-Wert des wassergemischten Kühlschmierstoffes vom Alkalischen in Richtung auf den neutralen pH-Bereich verschoben wird.The water-mixed cooling lubricants usually used have a pH value between 8.2 and 9.4, depending on the concentration and type of cooling lubricant, which can only be higher in exceptional cases. The disadvantage here is that a high pH value reduces the skin tolerance of the cooling lubricant, because the protective acid layer of the skin is destroyed and skin problems can arise for the operator of the metal processing machine if the exposure time is longer. A lowering of the pH value of water-mixed cooling lubricants down to the neutral point has so far proven impossible, because then the high requirements on the rust protection effect of water-mixed cooling lubricants can no longer be met. After machining in cooling lubricants, it is generally unusual, for economic reasons or because of the linking of manufacturing processes, to dry the machined metal part or to provide it with special corrosion protection. The parts are usually placed wet in boxes and must not rust even when wet. In order to test the rust protection effect in the development and also in the control of water-mixed cooling lubricants, the test with cast chips according to DIN 51360-1 and -2 is generally used. This test shows that the risk of rust formation on the machined metal part is greater, the higher the pH value of the water-mixed cooling lubricant is shifted from the alkaline in the direction of the neutral pH range.

Es stellte sich deshalb die Aufgabe, einen wassergemischten Kühlschmierstoff zur Verfügung zu stellen, dessen pH-Wert möglichst nahe am Neutralpunkt liegt und trotzdem nicht zur Rostbildung bei Metallteilen führt, die mit einer wässrigen Lösung des Kühlschmierstoffes bearbeitet worden sind.The task was therefore to provide a water-mixed cooling lubricant whose pH value is as close as possible to the neutral point and nevertheless does not lead to rust formation in metal parts that have been processed with an aqueous solution of the cooling lubricant.

Gelöst wird diese Aufgabe durch ein wassermischbares Kühlschmierstoff-Konzentrat gemäß Anspruch 1.This object is achieved by a water-miscible cooling lubricant concentrate according to claim 1.

Ein derartiges Kühlschmierstoff-Konzentrat enthält als natürliche oder synthetische Mineralöle paraffinische oder naphthenische Kohlenwasserstoffe, die auch im Mengenverhältnis 1:3 bis 5:1 miteinander gemischt sein können, Weißöle, Ester, Polyisobutene, Polyvinylpyrrolidone oder Polyalkylenglykole. Diese auch als Grundöle bezeichneten Verbindungen sind im allgemeinen in einer Menge von 5 bis 80 Gewichtsprozent, vorzugsweise in einer Menge von 5 bis 50 Gewichtsprozent im Kühlschmierstoff-Konzentrat enthalten.Such a cooling lubricant concentrate contains paraffinic or paraffinic mineral oils as natural or synthetic mineral oils naphthenic hydrocarbons, which can also be mixed with one another in a ratio of 1: 3 to 5: 1, white oils, esters, polyisobutenes, polyvinylpyrrolidones or polyalkylene glycols. These compounds, also known as base oils, are generally contained in the cooling lubricant concentrate in an amount of 5 to 80 percent by weight, preferably in an amount of 5 to 50 percent by weight.

Unter den Additiven, die in das Grundöl eingearbeitet werden müssen, stellen die Emulgatoren bei der Herstellung des erfindungsgemäßen Kühlschmierstoff-Konzentrats die wichtigste Gruppe dar. Vor allem anionische Emulgatoren wie Alkalisalze von gesättigten oder ungesättigten Carbonsäuren, Alkalisalze von Sulfonaten und Sulfonsäuren sowie Salze von Phosphorsäureestern haben eine ganz besondere Bedeutung. Daneben werden aber auch nicht-ionische Emulgatoren, vor allem Fettalkoholethoxylate, Fettalkoholpropoxylate, Zuckerester, Neopentylglycolester, Pentaerythritester, 2-Ethylhexylester und Trimethylolpropanester zur Herstellung des erfindungsgemäßen wassermischbaren Kühlschmierstoff-Konzentrats mit Erfolg eingesetzt.Among the additives that have to be incorporated into the base oil, the emulsifiers represent the most important group in the production of the cooling lubricant concentrate according to the invention. Above all, anionic emulsifiers such as alkali salts of saturated or unsaturated carboxylic acids, alkali salts of sulphonates and sulphonic acids and salts of phosphoric acid esters have a very special meaning. In addition, however, non-ionic emulsifiers, especially fatty alcohol ethoxylates, fatty alcohol propoxylates, sugar esters, neopentyl glycol esters, pentaerythritol esters, 2-ethylhexyl esters and trimethylolpropane esters are successfully used to produce the water-miscible cooling lubricant concentrate according to the invention.

Ganz besondere Bedeutung hat die Auswahl geeigneter Korrosionsschutzmittel. Besonders bewährt haben sich neutrale Umsetzungsprodukte von Borsäure mit primären oder tertiären Alkanolaminen sowie ethoxylierte oder propoxylierte Säuren oder Fettsäurealkanolamide. Durch den Einsatz von Borsäureverbindungen lässt sich zudem die Kühlschmierstoffbiostase und die Pufferkapazität anheben. Dadurch werden im praktischen Einsatz höhere Standzeiten des Kühlschmierstoffes erreicht und damit dessen Wirtschaftlichkeit verbessert. Die deutlich erhöhte biozide Wirksamkeit von Borsäureverbindungen, die vor allem im niedrigen pH-Bereich beobachtet wird und durch eine Blockade der Enzyme des Phosphatstoffwechsels der Mikroorganismen zu erklären ist, erlaubt es außerdem, die Menge anderer zuzusetzender Hemmstoffe gegen das Wachstum von Mikroorganismen zu reduzieren. Überraschenderweise wird der Korrosionsschutz von Borverbindungen erheblich gesteigert, wenn sie zusammen mit polyalkoxylierten Fettsäureamiden und/oder Imiden, vor allem mit neutralen ethoxylierten und/oder propyxylierten Fettsäureamiden auf Basis pflanzlichen und/oder tierischen Ursprungs und/oder gezielt eingestellten Fettsäuremischungen und/oder Alkylbernsteinsäureimiden oder mit anderen, auch in konventionellen Kühlschmierstoff-Formulierung enthaltenen Korrosionsschutzadditiven, zum Beispiel Phosphorsäureestern, Triazolen oder Thiadiazolen verwendet werden, wobei das Korrosionsschutzmittel in einer Menge von 5 bis 25 Gewichtsprozent zugesetzt werden soll. Ein mit den genannten Korrosionsschutzadditiven ausgerüsteter wassergemischter Kühlschmierstoff zeigt selbst bei einem pH-Wert zwischen 7,0 und 7,5 in wässriger Lösung einen nach DIN 51360-1 und -2 gleichwertigen Korrosionsschutz wie die bisher im Einsatz befindlichen Kühlschmierstoffe. Setzt man borsäurefreie Formulierungen ein, die aus ethoxylierten und/oder propoxylierten Fettsäurealkanolamiden bestehen, reicht eine Konzentration von 2 bis 25 Gewichtsprozent aus, um einen Korrosionsschutz zu erreichen, der den höchsten, bisher an Kühlschmierstoffe gestellten Anforderungen genügt. Werden als Korrosionsschutzmittel Fettsäuren, insbesondere Ethercarbonsäuren, eingesetzt, dann ist ein Ethoxylierungsgrad von 2 bis 12 Mol Ethylenoxid pro Mol Ethercarbonsäure besonders vorteilhaft. Derartige ethoxylierte Ethercarbonsäuren werden als Antikorrosionsmittel in einer Konzentration von 2 bis 15 Gewichtsprozent eingesetzt.The selection of suitable anti-corrosion agents is of particular importance. Neutral reaction products of boric acid with primary or tertiary alkanolamines and ethoxylated or propoxylated acids or fatty acid alkanolamides have proven particularly useful. The use of boric acid compounds can also increase the cooling lubricant biostasis and the buffer capacity. As a result, longer service lives of the cooling lubricant are achieved in practical use and thus its economic efficiency is improved. The significantly increased biocidal effectiveness of boric acid compounds, which is observed above all in the low pH range and can be explained by a blockage of the enzymes of the phosphate metabolism of the microorganisms, also allows the amount of others Adding inhibitors to reduce the growth of microorganisms. Surprisingly, the corrosion protection of boron compounds is considerably increased if they are used together with polyalkoxylated fatty acid amides and / or imides, especially with neutral ethoxylated and / or propyxylated fatty acid amides based on vegetable and / or animal origin and / or specifically adjusted fatty acid mixtures and / or alkyl succinic acid imides or with other corrosion protection additives also contained in conventional cooling lubricant formulations, for example phosphoric acid esters, triazoles or thiadiazoles, can be used, the corrosion protection agent being added in an amount of 5 to 25 percent by weight. Even at a pH value between 7.0 and 7.5 in aqueous solution, a water-mixed cooling lubricant equipped with the above-mentioned corrosion protection additives shows a corrosion protection equivalent to DIN 51360-1 and -2 as the cooling lubricants previously used. If boric acid-free formulations consisting of ethoxylated and / or propoxylated fatty acid alkanolamides are used, a concentration of 2 to 25 percent by weight is sufficient to achieve corrosion protection that meets the highest requirements previously placed on cooling lubricants. If fatty acids, in particular ether carboxylic acids, are used as corrosion inhibitors, a degree of ethoxylation of 2 to 12 mol of ethylene oxide per mol of ether carboxylic acid is particularly advantageous. Such ethoxylated ether carboxylic acids are used as anti-corrosion agents in a concentration of 2 to 15 percent by weight.

Weiterhin hat sich gezeigt, dass durch den niedrigen pH-Wert und die dadurch bedingte gezielte Auswahl der Basisemulgatoren und Korrosionschutzadditive ansonsten nicht mit ausreichender Stabilität versehene biozide Verbindungen auch bei langen Lagerzeiten und erhöhter Temperatur eine Wirkstoffstabilität von deutlich größer 95% behalten. Zu diesen Verbindungen gehören vor allem 3-Jod-2-propinyl-butylcarbamat, Methylisothiazolinon und andere Isothiazolinonderivate.Furthermore, it has been shown that, due to the low pH value and the resulting targeted selection of the base emulsifiers and anti-corrosion additives, biocidal compounds which are otherwise not provided with sufficient stability have active ingredient stability even after long storage times and at elevated temperatures retained by significantly greater than 95%. These compounds include, in particular, 3-iodo-2-propynyl-butylcarbamate, methylisothiazolinone and other isothiazolinone derivatives.

Basierend auf der Problematik, dass insbesondere sekundäre Alkanolamine und ihre Derivate während des praktischen Einsatzes mit nitrosierenden Substanzen wie Nitrit, das durch bakterielle Aktivität aus dem Nitrat des Ansatzwassers gebildet wird, zu cancerogenen Nitrosaminen reagieren und deren Bildung abhängig vom pH-Wert insbesondere im saurem Bereich stattfindet, ist dem pH-Bereich von 7,0 bis 7,5 besondere Aufmerksamkeit zu widmen. Wie Untersuchungen zeigen, kann die Nitrosaminbildung durch die Verwendung von Inhibitoren unterbunden werden. Als derartige Inhibitoren wirken unter anderem freie primäre Amine, die in dem erfindungsgemäßen Kühlschmierstoff infolge eines Dissoziationsgleichgewichtes in geringen Mengen aus Fettsäurealkanolamiden entstehen, oder zum Beispiel Ascorbinsäure. Eine Nitrosaminbildung wird dadurch unterbunden. Gegen ein erhöhtes Risiko der Nitrosaminbildung der erfindungsgemäßen Kühlschmierstoffformulierungen sprechen auch Untersuchungsresultate, dass insbesondere Amide in einem pH-Bereich von 6-8 keine stabilen Nitrosamine bilden können.Based on the problem that in particular secondary alkanolamines and their derivatives react during practical use with nitrosating substances such as nitrite, which is formed from the nitrate of the batch water by bacterial activity, to form carcinogenic nitrosamines and their formation depends on the pH value, especially in the acidic range takes place, special attention should be paid to the pH range from 7.0 to 7.5. As studies show, the formation of nitrosamines can be prevented by using inhibitors. Such inhibitors include free primary amines, which are formed in small amounts in the cooling lubricant according to the invention as a result of a dissociation equilibrium from fatty acid alkanolamides, or, for example, ascorbic acid. This prevents nitrosamine formation. The results of the tests that amides in particular cannot form stable nitrosamines in a pH range of 6-8 also speak against an increased risk of nitrosamine formation in the cooling lubricant formulations according to the invention.

Die in dem erfindungsgemäßen Kühlschmierstoffkonzentrat enthaltenen Wirkstoffe können nur dann ihre optimale Wirkung entfalten, wenn sie homogen verteilt sind und das Kühlschmierstoffkonzentrat sich nicht in mehrere Phasen trennt. Deshalb müssen dem Konzentrat Lösungsvermittler zugesetzt werden. Neben Wasser sind hierfür Glykole wie Ethylenglykol und vor allem Butyltriglykol, außerdem auch geradkettige und verzweigte Fettalkohole mit 16 bis 24 Kohlenstoffatomen geeignet, wenn sie in Mengen von 5 bis 50 Gewichtsprozent zugesetzt werden.The active ingredients contained in the cooling lubricant concentrate according to the invention can only develop their optimal effect if they are homogeneously distributed and the cooling lubricant concentrate does not separate into several phases. Therefore, solubilizers must be added to the concentrate. In addition to water, glycols such as ethylene glycol and, above all, butyl triglycol, as well as straight-chain and branched fatty alcohols with 16 to 24 carbon atoms are suitable if they are added in amounts of 5 to 50 percent by weight.

Im Allgemeinen ist der wassergemischte Kühlschmierstoff ein guter Nährboden für Mikroorganismen. Eine verstärkte Kontamination mit Bakterien, Pilzen und Hefen führt zu chemischen Veränderungen der Emulsionsbestandteile und beeinflusst die Brauchbarkeit des wassergemischten Kühlschmierstoffes. Sind gesundheitsschädliche Mikroorganismen eingebracht, zum Beispiel coliforme Bakterien, so kann dies auch gravierende Auswirkungen auf die Gesundheit der Mitarbeiter haben. Aus diesem Grund ist eine Ausrüstung des Kühlschmierstoff-Konzentrates mit entsprechenden biozid oder fungizid wirkenden verbindungen meist unerlässlich.In general, the water-mixed cooling lubricant is a good breeding ground for microorganisms. Increased contamination with bacteria, fungi and yeasts leads to chemical changes in the emulsion components and influences the usability of the water-mixed cooling lubricant. If harmful microorganisms are introduced, for example coliform bacteria, this can also have serious effects on the health of employees. For this reason, it is usually essential to equip the cooling lubricant concentrate with the appropriate biocidal or fungicidal compounds.

Hier hat es sich nun gezeigt, dass bei den erfindungsgemäßen Formulierungen ansonsten im Kühlschmierstoff-Konzentrat unübliche Komponenten wie Isothiazolinone oder 3-Jod-2-propinyl-carbamat ein interessantes und wirtschaftliches Wirkungsspektrum aufweisen, wie es vorher nicht bekannt war. Als weitere besonders geeignete Konservierungsstoffe sind unter Beachtung des pH-Wertes von < 7,6 vor allem Guanidinderivate, Imidazolderivate und aromatische Carbonsäuren wie die Salicyl- oder Benzoesäure und deren Derivate zu nennen. Durch den Einsatz in den erfindungsgemäßen Formulierungen mit einem pH-Wert von 7 bis 7,5 hat es sich überraschenderweise gezeigt, dass Methylolharnstoffderivate wie Dimethylolurea und/oder Tri- und Tetramethylolacetylendiurea entgegen bisheriger Erfahrung auch in höheren Konzentrationen nicht zu unwirksamen Polyharnstoffderivaten durchpolymerisieren und dann somit nicht mehr als biozider Wirkstoff zur Verfügung stehen bzw. Probleme durch Ausfällreaktionen und Inhomogenitäten verursachen. Die Konservierungsstoffe werden im allgemeinen in Mengen von 0,1 bis 5 Gewichtsprozent dem Kühlschmierstoff-Konzentrat zugesetzt.It has now been shown that in the formulations according to the invention, components that are otherwise unusual in the cooling lubricant concentrate, such as isothiazolinones or 3-iodo-2-propynyl carbamate, have an interesting and economical spectrum of activity, as was not previously known. Other particularly suitable preservatives, taking into account the pH value of <7.6, are above all guanidine derivatives, imidazole derivatives and aromatic carboxylic acids such as salicylic or benzoic acid and their derivatives. By using the formulations according to the invention with a pH of 7 to 7.5, it has surprisingly been shown that methylolurea derivatives such as dimethylolurea and / or tri- and tetramethylolacetylenediurea, contrary to previous experience, do not polymerize through to ineffective polyurea derivatives even in higher concentrations and then thus are no longer available as a biocidal active substance or cause problems through precipitation reactions and inhomogeneities. The preservatives are generally added to the cooling lubricant concentrate in amounts of 0.1 to 5 percent by weight.

Die erfindungsgemäßen wassermischbaren und wassergemischten Kühlschmierstoffe können weitere funktionelle Zusatzstoffe enthalten, zum Beispiel Castoroilethoxylate, Petrolsulfonate bis zu einer Total Base Number von kleiner /gleich 400, Festschmierstoffe, Toluyltriazole, Entschäumer und/oder Antinebelzusätze. Zur Anwendung bei der Metallbearbeitung enthalten die aus dem wassermischbaren Kühlschmierstoffkonzentrat hergestellten wässrigen Lösungen oder Emulsionen diese Additive im allgemeinen in Mengen von 1 bis 10 Gewichtsprozent, vorzugsweise in Mengen von 2 bis 5 Gewichtsprozent, bezogen auf das wassermischbare Kühlschmierstoff-Konzentrat.The water-miscible and water-mixed cooling lubricants according to the invention can contain further functional additives contain, for example, castoroil ethoxylates, petroleum sulfonates up to a total base number of less than / equal to 400, solid lubricants, toluyltriazoles, defoamers and / or anti-fog additives. For use in metalworking, the aqueous solutions or emulsions produced from the water-miscible cooling lubricant concentrate contain these additives generally in amounts of 1 to 10 percent by weight, preferably in amounts of 2 to 5 percent by weight, based on the water-miscible cooling lubricant concentrate.

Die Messung des transepidermalen Wasserverlustes (TEWL, transepidermal water loss) hat sich heute als praxisnahes Prüfkriterium zur Abschätzung des Einflusses eines Kühlschmierstoffes auf die Schädigung der Barrierefunktion der Haut etabliert. Gemessen wird dabei, wieviel Wasser pro Zeiteinheit und Fläche von innen nach außen durch die Haut diffundiert. Hohe TEWL-Werte weisen auf einen hohen Wasserverlust und somit eine Schädigung der Barrierefunktion, niedrige TEWL-Werte auf eine intakte Barrierefunktion hin. Als Referenzmedium wird Wasser und das sehr aggressive Natriumdodecylsulfat (SDS) eingesetzt. Der Kühlschmierstoff wird üblicherweise in seiner Einsatzkonzentration, meist 5 Gewichtsprozent oder 10 Gewichtsprozent, geprüft. Berücksichtigt man, dass der Kühlschmierstoff auf der Haut auch aufkonzentrieren kann und dann deutlich die Einsatz-/Prüfkonzentration überschreitet, sind höhere Prüfkonzentrationen naheliegend, werden aber nicht durchgeführt, da kritische Werte zu erwarten sind.The measurement of the transepidermal water loss (TEWL, transepidermal water loss) has established itself today as a practical test criterion for assessing the influence of a cooling lubricant on the damage to the skin's barrier function. It measures how much water diffuses through the skin from the inside to the outside per unit of time and area. High TEWL values indicate high water loss and thus damage to the barrier function, low TEWL values indicate an intact barrier function. The reference medium used is water and the very aggressive sodium dodecyl sulfate (SDS). The cooling lubricant is usually tested in its use concentration, usually 5 percent by weight or 10 percent by weight. If one takes into account that the cooling lubricant can also concentrate on the skin and then clearly exceeds the use / test concentration, higher test concentrations are obvious, but are not carried out because critical values are to be expected.

Durch Prüfung erfindungsgemäßer Formulierungen mit einem pH Wert von 7 bis 7,5 wurde nun mittels TEWL- Messung der Nachweis erbracht, dass der Kühlschmierstoff in einer Prüfkonzentration von 100 Gewichtsprozent als nicht irritierend eingestuft werden kann.By testing formulations according to the invention with a pH of 7 to 7.5, it was now demonstrated by means of TEWL measurement that the cooling lubricant can be classified as non-irritating in a test concentration of 100 percent by weight.

Das erfindungsgemäße wassermischbare Kühlschmierstoff-Konzentrat wurde gemäß den nachfolgenden Rezepturbeispielen hergestellt.The water-miscible cooling lubricant concentrate according to the invention was produced according to the following recipe examples.

Beispiel 1example 1 Semisynthetisches, borhaltiges Kühlschmierstoff-KonzentratSemi-synthetic, boron-containing cooling lubricant concentrate

Paraffinischer KohlenwasserstoffParaffinic hydrocarbon 30%30% Borsäurealkanolaminester/amid-GemischBoric acid alkanolamine ester / amide mixture 20%20% TalloelfettsäureTallow fatty acid 5%5% C16 / C18 FettsäurealkanolamidC16 / C18 fatty acid alkanolamide 11%11% Oleylethercarbonsäure (Ethoxylierungsgrad 9)Oleyl ether carboxylic acid (degree of ethoxylation 9) 3%3% Trimethylolpropan-TrioleatTrimethylol propane trioleate 16%16% C16-GuebertalkoholC 16 gruber alcohol 5%5% MethylisothiazolinonMethylisothiazolinone 0,5%0.5% 3-Jod-2-propinylbutylcarbamat (IPBC)3-iodo-2-propynyl butyl carbamate (IPBC) 0,5%0.5% Wasserwater 9%9%

Beispiel 2Example 2 Semisynthetischer, borhaltiger KühlschmierstoffSemi-synthetic, boron-containing cooling lubricant

Paraffinisches SolventraffinatParaffinic solvent raffinate 24%24% Borsäure-Triethanolamin-ReaktionsproduktBoric acid-triethanolamine reaction product 25%25% Fettsäuremonoethanolamid (Ethoxylierungsgrad 4)Fatty acid monoethanolamide (degree of ethoxylation 4) 12%12% AlkylbernsteinsäureimidAlkyl succinic imide 4,5%4.5% Castoroilethoxylat (Ethoxylierungsgrad 5)Castoroil ethoxylate (degree of ethoxylation 5) 3%3% Synthetisches NatriumpetrolsulfonatSynthetic sodium petroleum sulfonate 5%5% Ethylen-PropylenglykolEthylene propylene glycol 4,3%4.3% PolypropylenglykolmonobutyletherPolypropylene glycol monobutyl ether 2%2% EthylhexyloleatEthyl hexyl oleate 16%16% HexitidinHexitidine 3,5%3.5% 3-Jod-2-propinylbutylcarbamat (IPBC)3-iodo-2-propynyl butyl carbamate (IPBC) 0,5%0.5%

Beispiele 3a und 3bExamples 3a and 3b Semisynthetisches, borfreies Kühlschmierstoff-KonzentratSemi-synthetic, boron-free cooling lubricant concentrate

3a) Medizinisches Weißoel oder3a) Medical white oil or 42,5%42.5% 3b) Trimethylolpropanadipat3b) trimethylol propane adipate 42,5%42.5% KOH-verseiftes RüboelKOH-saponified Rüboel 25%25% C16 / C18 Fettsäurealkanolamid (Ethoxylierungsgrad 4)C16 / C18 fatty acid alkanolamide (degree of ethoxylation 4) 12%12% AlkylbernsteinsäureimidAlkyl succinic imide 3,5%3.5% PolypropylenglycolmonobutyletherPolypropylene glycol monobutyl ether 5%5% Synthetisches Natriumpetrolsulfonat (Petronate® CR)Synthetic Sodium Petrol Sulphonate (Petronate® CR) 4%4% Cocosalkylguanidiniumderivat (Dodigen®)Coconut alkylguanidinium derivative (Dodigen®) 1%1% n-Octylisothiazolinonn-octylisothiazolinone 0,6%0.6% MethylolharnstoffderivatMethylolurea derivative 2,5%2.5% Wasserwater 3,9%3.9%

Beispiel 4Example 4 Synthetisches, mineralölfreies Kühlschmierstoff-KonzentratSynthetic, mineral oil-free cooling lubricant concentrate

Triethanolaminsalz einer cyclischenTriethanolamine salt of a cyclic Tricarbonsäure (Irgacor® L 190)Tricarboxylic acid (Irgacor® L 190) 50%50% Rüboelfettsäurealkanolamid (Ethoxylierungsgrad 4)Rüboelfettsäurealkanolamid (degree of ethoxylation 4) 2,5%2.5% Phosphorsäureteilester, neutralisiertPartial phosphoric acid ester, neutralized mit einem primären Alkanolaminwith a primary alkanolamine 7%7% C10 Monocarbonsäure (Neodecansäure)C 10 monocarboxylic acid (neodecanoic acid) 3%3% n-Octylisothiazolinonn-octylisothiazolinone 0,3%0.3% Polymeres kationisches MikrobiozidPolymeric cationic microbiocide 0,15%0.15% Wasserwater 37,05%37.05%

Typkennwerte der erfindungsgemäßen Rezepturbeispiele als 5%ige Emulsion/LösungType characteristics of the formulation examples according to the invention as a 5% emulsion / solution

RezepturbeispielRecipe example 11 22 3a3a 3b3b 44th AussehenLook grobdispers/milchig klare Lösungcoarsely dispersed / milky clear solution pH-WertPH value 7,47.4 7,57.5 7,47.4 7,47.4 7,57.5 Korrosionsschutz nachCorrosion protection after DIN 51 360-2DIN 51 360-2 Rostnote 0 bei %Rust grade 0 at% 4,54.5 44th 44th 44th 3,53.5

Claims (14)

  1. Water-miscible cooling lubricant concentrate, which contains natural or synthetic mineral oils, emulsifiers, anti-corrosive agents, solubility promoters, preservatives, metal inhibitors and other standard additives, characterized in that it has a pH value between 7.0 and 7.5 after dilution to an aqueous solution containing between 2 and 25 percent by weight and further contains as a preservative and an anti-corrosive agent a mixture containing
    a) at least one substance selected from the group consisting of ethoxylated fatty acids, propoxylated fatty acids, ethoxylated fatty acid alkanolamides, propoxylated fatty acid alkanolamides and reaction products of boric acid and a primary or tertiary alkanolamine
    as well as
    b) at least one substance selected from the group consisting of carboxylic acid imides, phosphoric acid esters, thiadiazoles, isothiazolinones, imidazoles, guanidines, aromatic carboxylic acids, 3-iod-2-propinyl-carbamate and methylol urea derivatives.
  2. Cooling lubricant concentrate according to claim 1, characterized in that it contains as a preservative and an anti-corrosive agent a mixture containing
    a1) at least one reaction product of boric acid and a primary or tertiary alkanolamine and
    a2) at least one ethoxylated or propoxylated fatty acid or at least one ethoxylated or propoxylated fatty acid alkanolamide
    as well as
    b) at least one further substance selected from the group consisting of carboxylic acid imides, phosphoric acid esters, thiadiazoles, isothiazolinones, imidazoles, guanidines, aromatic carboxylic acids, 3-iod-2-propinyl-carbamate and methylol urea derivatives.
  3. Cooling lubricant concentrate according to claim 1 or 2, characterized in that the preservative and anti-corrosive agent mixture contains beside at least one component of group a)
    b1) at least one further substance selected from the group consisting of carboxylic acid imides, phosphoric acid esters, thiadiazoles, isothiazolinones, imidazoles, guanidines, aromatic carboxylic acids and 3-iod-2-propinyl-carbamate
    as well as
    b2) at least one methylol urea derivative.
  4. Cooling lubricant concentrate according to claim 1 or 3, characterized in that the preservative and anti-corrosive agent mixture is free of a reaction product of boric acid and a primary or tertiary alkanolamine.
  5. Cooling lubricant concentrate according to claim 2, characterized in that the concentration of anti-corrosive agents is 5 to 25 % by weight and the concentration of preservatives is 0,1 to 5 % by weight.
  6. Cooling lubricant concentrate according to claim 4, characterized in that the concentration of anti-corrosive agents is 2 to 25 % by weight and the concentration of preservatives is 0,1 to 5 % by weight.
  7. Cooling lubricant concentrate according to any of claims 1 to 6, characterized in that it contains 2 to 15 % by weight of a ethoxylated or propoxylated fatty acid.
  8. Cooling lubricant concentrate according to any of claims 1 to 7, characterized in that it contains as natural or synthetic mineral oils paraffinic or naphthenic hydrocarbons, esters, polyisobutenes, polyvinyl pyrrolidones or polyalkylene glycols in a proportion of 5 to 80 % by weight, preferably in a proportion of 5 to 50 % by weight.
  9. Cooling lubricant concentrate according to any of claims 1 to 8, characterized in that it contains one or more anionic or non-ionic surface-reactive substances as emulsifiers and, if necessary, as a co-emulsifying agent further one or more mono- or dicarboxylic acids with 16 to 54 carbon atoms or an alkali salt thereof in a proportion of 2 to 20 % by weight.
  10. Cooling lubricant concentrate according to any of claims 1 to 9, characterized in that it contains as solubility promoter water, ethylene glycol, butyltriglycol, straight-chain or branched fatty alcohols with 16 to 24 carbon atoms in a proportion of 5 to 50 % by weight.
  11. Cooling lubricant concentrate according to any of claims 1 to 10, characterized in that it contains as further additives alkyl succinimides, castor oil ethoxylates, petroleum sulfonates, solid lubricants, toluyl triazoles, antifoaming agents and/or antifogging additives.
  12. Cooling lubricant composition, which contains natural or synthetic mineral oils, water, emulsifiers, anti-corrosive agents, solubility promoters, preservatives, metal inhibitors and other standard additives, characterized in that the composition has a water content between 98 and 75 % by weight and a pH value between 7.0 and 7.5 as well as it further contains as a preservative and an anti-corrosive agent a mixture comprising
    a) at least one substance selected from the group consisting of ethoxylated fatty acids, propoxylated fatty acids, ethoxylated fatty acid alkanolamides, propoxylated fatty acid alkanolamides and reaction products of boric acid and a primary or tertiary alkanolamine
    as well as
    b) at least one substance selected from the group consisting of carboxylic acid imides, phosphoric acid esters, thiadiazoles, isothiazolinones, imidazoles, guanidines, aromatic carboxylic acids, 3-iod-2-propinyl-carbamate and methylol urea derivatives.
  13. Use of the water-miscible cooling lubricant concentrate according to any of claims 1 to 11 for the production of a cooling lubricant solution, characterized in that the cooling lubricant concentrate is diluted with water to an aqueous solution containing between 2 and 25 percent by weight and adjusted to a pH value between 7.0 and 7.5.
  14. Use of the cooling lubricant composition according to claim 12 in form of an aqueous solution or an emulsion for the cutting or non-cutting metalworking.
EP99927938A 1998-07-28 1999-06-10 Water-miscible cooling lubricant concentrate Revoked EP1102830B1 (en)

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DE19833894A DE19833894A1 (en) 1998-07-28 1998-07-28 Water-miscible coolant concentrate
PCT/EP1999/003990 WO2000006675A1 (en) 1998-07-28 1999-06-10 Water-miscible cooling lubricant concentrate

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WO2000006675A1 (en) 2000-02-10
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DE19833894A1 (en) 2000-02-03
JP4084927B2 (en) 2008-04-30
US6511946B1 (en) 2003-01-28
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BR9912475A (en) 2001-04-17
KR100451979B1 (en) 2004-10-08

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