EP1102830A1 - Water-miscible cooling lubricant concentrate - Google Patents

Water-miscible cooling lubricant concentrate

Info

Publication number
EP1102830A1
EP1102830A1 EP99927938A EP99927938A EP1102830A1 EP 1102830 A1 EP1102830 A1 EP 1102830A1 EP 99927938 A EP99927938 A EP 99927938A EP 99927938 A EP99927938 A EP 99927938A EP 1102830 A1 EP1102830 A1 EP 1102830A1
Authority
EP
European Patent Office
Prior art keywords
cooling lubricant
percent
water
weight
lubricant concentrate
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.)
Granted
Application number
EP99927938A
Other languages
German (de)
French (fr)
Other versions
EP1102830B1 (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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=7875546&utm_source=***_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1102830(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Fuchs Petrolub SE filed Critical Fuchs Petrolub SE
Publication of EP1102830A1 publication Critical patent/EP1102830A1/en
Application granted granted Critical
Publication of EP1102830B1 publication Critical patent/EP1102830B1/en
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/56—Acids of unknown or incompletely defined constitution
    • C10M129/60—Tall oil acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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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
    • 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
    • C10M133/16—Amides; Imides
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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
    • C10M133/38—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
    • C10M135/10—Sulfonic acids or derivatives thereof
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    • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/24—Polyethers
    • C10M145/26—Polyoxyalkylenes
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
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    • C10M2201/087—Boron oxides, acids or salts
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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 object of the invention is a water-miscible cooling lubricant concentrate which, in the water-mixed state, is distinguished both by excellent performance properties in cutting or non-cutting metalworking and by a particularly high skin tolerance.
  • cooling lubricants account for almost 40% of the triggering of occupational skin diseases in the commercial sector (brochure ZH 1/467, Skin Protection in Metalworkers, Working Group of Metalworking Cooperatives, 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.
  • Your main task as an emulsion, solution or in a concentrated form in metalworking is cooling, lubricating and removing the material removal caused by the multitude of manufacturing operations such as turning, drilling, milling, grinding etc. away from the workpiece and tool.
  • the water-mixed cooling lubricant fulfills a number of other secondary tasks, such as keeping the systems clean and protecting the machine parts against corrosion.
  • the commonly used water-mixed cooling lubricants have a pH value between 8.2 and 9.4, depending on the concentration and type of cooling lubricant, which can only exceptionally be higher.
  • the disadvantage here is that a high pH value lowers the skin compatibility of the cooling lubricant, because the protective acid mantle of the skin is thereby destroyed and skin problems can occur for the operator of the metal processing machine with prolonged exposure times.
  • a lowering of the pH value of water-mixed cooling lubricants up to the neutral point has so far proven to be impossible, because then the high demands on the rust protection effect of water-mixed cooling lubricants can no longer be met.
  • a water-miscible cooling lubricant concentrate which contains natural or synthetic mineral oils, emulsifiers, corrosion protection additives, solubilizers, preservatives, metal inhibitors and other common additives and, after dilution to a 2 to 25 percent by weight aqueous solution, a pH between 7.0 and 7.5, and additionally as a preservative and / or corrosion protection additive, a mixture of
  • a carboximide a phosphoric acid ester, a triazole, a thiadiazole, an isothiazolinone, an imidazole, a guanidine, an aromatic carboxylic acid and the 3-iodo-2-propynylcarbamate and / or
  • Such a cooling lubricant concentrate contains paraffinic or as natural or synthetic mineral oils naphthenic hydrocarbons, which can also be mixed in a ratio of 1: 3 to 5: 1, white oils, esters, polyisobutenes, polyvinylpyrrolidones or polyalkylene glycols. These compounds, also referred to as base oils, are generally present 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 are the most important 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 sulfonates and sulfonic acids and salts of phosphoric acid esters have a very special meaning.
  • nonionic emulsifiers especially fatty alcohol ethoxylates, fatty alcohol propoxylates, sugar esters, neopentyl glycol esters, pentaerythritol esters, 2-ethylhexyl esters and
  • Trimethylolpropane ester used for the preparation of the water-miscible coolant concentrate according to the invention with success.
  • 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, thus improving its economy.
  • the significantly increased biocidal activity of boric acid compounds which is observed especially in the low pH range and can be explained by a blockade of the enzymes of the phosphate metabolism of the microorganisms, also allows the amount of others to reduce added inhibitors against the growth of microorganisms.
  • the corrosion protection of boron compounds is significantly 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 selected fatty acid mixtures and / or alkyl succinimides other corrosion protection additives, for example phosphoric acid esters, triazoles or thiadiazoles, which are also contained in conventional cooling lubricant formulation, the corrosion protection agent being added in an amount of 5 to 25 percent by weight.
  • a water-mixed cooling lubricant equipped with the corrosion protection additives mentioned shows corrosion protection equivalent to DIN 51360-1 and -2 in aqueous solution, even at a pH value between 7.0 and 7.5, as the cooling lubricants previously used.
  • boric acid-free formulations which consist of ethoxylated and / or propoxylated fatty acid alkanolamides, 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 moles of ethylene oxide per mole 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 also have an active ingredient stability even after long storage times and at elevated temperatures of significantly larger than 95%.
  • These compounds include above all 3-iodo-2-propynyl butyl carbamate, methyl isothiazolinone and other isothiazolinone derivatives.
  • inhibitors can prevent nitrosamine formation.
  • Such inhibitors include, inter alia, free primary amines which arise in small amounts from fatty acid alkanolamides in the cooling lubricant according to the invention as a result of a dissociation equilibrium, or, for example, ascorbic acid. This prevents nitrosamine formation.
  • Test results also speak against an increased risk of nitrosamine formation of the cooling lubricant formulations according to the invention, in particular that amides in a pH range of 6-8 cannot form stable nitrosamines.
  • the active substances 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, butyltriglycol, and also 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.
  • methylolurea derivatives such as dimethylolurea and / or tri- and tetramethylolacetylene diurea, contrary to previous experience, do not polymerize to ineffective polyurea derivatives even in higher concentrations and then thus are no longer available as a biocidal active ingredient or cause problems due to 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 400 or less, solid lubricants, toluyltriazoles, defoamers and / or anti-fog additives.
  • the aqueous solutions or emulsions prepared from the water-miscible cooling lubricant concentrate generally contain these additives 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
  • Trimethylolpropane trioleate 16% C 16 excess alcohol 5%
  • IPBC 3-iodo-2-propynyl butyl carbamate
  • IPBC 3-iodo-2-propynyl butyl carbamate
  • Cocosalkylguanidinium derivative (Dodigen®) 1% n-octylisothiazolinone 0.6%
  • Triethanolamine salt of a cyclic compound Triethanolamine salt of a cyclic compound
  • Tricarboxylic acid (Irgacor® L 190) 50%

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

The invention relates to a 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 and after dilution to an aqueous solution containing between 2 and 25 percent by weight has a pH between 7.0 and 7.5. As preservative and/or anti-corrosive agent said concentrate further contains a mixture of a) a reaction product of boric acid and a primary or tertiary alkanolamine and/or, b) an ethoxylated and/or propoxylated fatty acid or a fatty acid alkanolamide and at least one other compound selected from the group consisting of c) a carboxylic acid imide, a phosphoric acid ester, a triazole, a thiadiazole, an isothiazolinone, an imidazole, a guanidine, an aromatic carboxylic acid and 3-iod-2-propinyl-carbamate, and/or d) a methylol urea derivative.

Description

Wassermischbares Kühlschmierstoff-KonzentratWater-miscible coolant concentrate
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 object of the invention is a water-miscible cooling lubricant concentrate which, in the water-mixed state, is distinguished both by excellent performance properties in cutting or non-cutting metalworking and by a particularly high 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 Working Group of Metalworking Associations, cooling lubricants account for almost 40% of the triggering of occupational skin diseases in the commercial sector (brochure ZH 1/467, Skin Protection in Metalworkers, Working Group of Metalworking Cooperatives, 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-InWasser-Emulsion, und unter "wassermischbar" das Kühlschmierstoff-Konzentrat verstanden. 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.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. Water-mixed cooling lubricants are produced by the user by mixing the concentrate with water. Your main task as an emulsion, solution or in a concentrated form in metalworking is cooling, lubricating and removing the material removal caused by the multitude of manufacturing operations such as turning, drilling, milling, grinding etc. away from the workpiece and tool. In addition, the water-mixed cooling lubricant fulfills a number of other secondary tasks, such as keeping the systems clean and protecting the machine parts against 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 commonly used water-mixed cooling lubricants have a pH value between 8.2 and 9.4, depending on the concentration and type of cooling lubricant, which can only exceptionally be higher. The disadvantage here is that a high pH value lowers the skin compatibility of the cooling lubricant, because the protective acid mantle of the skin is thereby destroyed and skin problems can occur for the operator of the metal processing machine with prolonged exposure times. A lowering of the pH value of water-mixed cooling lubricants up to the neutral point has so far proven to be impossible, because then the high demands 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 connection 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. To test the rust protection effect, the test with cast chips according to DIN 51360-1 and -2 is generally used in the development and also in the control of water-mixed cooling lubricants. This test shows that the risk of rust formation on the machined metal part, the greater the pH of the water-mixed cooling lubricant is shifted from the alkaline towards 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.It was therefore the task to provide a water-mixed cooling lubricant, the pH value of which is as close as possible to the neutral point and yet does not lead to rust formation in metal parts which have been processed with an aqueous solution of the cooling lubricant.
Gelöst wird diese Aufgabe durch ein wassermischbares Kühlschmierstoff-Konzentrat, das natürliche oder synthetische Mineralöle, Emulgatoren, Korrosionsschutzadditive, Lösungsvermittler, Konservierungsstoffe, Metallinhibitoren und andere übliche Additive enthält und nach Verdünnung zu einer 2 bis 25 gewichtsprozentigen wässrigen Lösung einen pH-Wert zwischen 7,0 und 7,5 aufweist sowie zusätzlich als Konservierungsstofff und/oder Korrosionsschutzadditiv eine Mischung vonThis task is solved by a water-miscible cooling lubricant concentrate, which contains natural or synthetic mineral oils, emulsifiers, corrosion protection additives, solubilizers, preservatives, metal inhibitors and other common additives and, after dilution to a 2 to 25 percent by weight aqueous solution, a pH between 7.0 and 7.5, and additionally as a preservative and / or corrosion protection additive, a mixture of
a) einem Umsetzungsprodukt von Borsäure und einem primären oder tertiären Alkanolamin und/odera) a reaction product of boric acid and a primary or tertiary alkanolamine and / or
b) einer ethoxylierten und/oder propoxylierten Fettsäure oder einem Fettsäurealkanolamid sowie wenigstens eine weitere Verbindung ausgewählt aus der Gruppe bestehend ausb) an ethoxylated and / or propoxylated fatty acid or a fatty acid alkanolamide and at least one further compound selected from the group consisting of
c) einem Carbonsäureimid, einem Phosphorsäureester, einem Triazol, einem Thiadiazol, einem Isothiazolinon, einem Imidazol, einem Guanidin, einer aromatischen Carbonsäure und dem 3-Jod-2-propinyl-carbamat und/oderc) a carboximide, a phosphoric acid ester, a triazole, a thiadiazole, an isothiazolinone, an imidazole, a guanidine, an aromatic carboxylic acid and the 3-iodo-2-propynylcarbamate and / or
d) einem Methylolharnstoffderivat enthält.d) contains a methylol urea derivative.
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 as natural or synthetic mineral oils naphthenic hydrocarbons, which can also be mixed in a ratio of 1: 3 to 5: 1, white oils, esters, polyisobutenes, polyvinylpyrrolidones or polyalkylene glycols. These compounds, also referred to as base oils, are generally present 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 wichtigsteAmong the additives that have to be incorporated into the base oil, the emulsifiers are the most important in the production of the cooling lubricant concentrate according to the invention
Gruppe dar. Vor allem anionische Emulgatoren wie Alkalisalze von gesättigten oder ungesättigten Carbonsäuren, Alkalisalze von Sulfonaten und Sulfonsäuren sowie Salze von Phosphorsäu- reestern haben eine ganz besondere Bedeutung. Daneben werden aber auch nicht-ionische Emulgatoren, vor allem Fettalko- holethoxylate, Fettalkoholpropoxylate, Zuckerester, Neopentyl- glycolester, Pentaerythritester, 2-Ethylhexylester undGroup. Above all, anionic emulsifiers such as alkali salts of saturated or unsaturated carboxylic acids, alkali salts of sulfonates and sulfonic acids and salts of phosphoric acid esters have a very special meaning. In addition, nonionic emulsifiers, especially fatty alcohol ethoxylates, fatty alcohol propoxylates, sugar esters, neopentyl glycol esters, pentaerythritol esters, 2-ethylhexyl esters and
Trimethylolpropanester zur Herstellung des erfindungsgemäßen wassermischbaren Kühlschmierstoff-Konzentrats mit Erfolg eingesetzt.Trimethylolpropane ester used for the preparation of the water-miscible coolant concentrate according to the invention with success.
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 Mikroorga- nismen 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 pro- poxylierten 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 Ethercarbon- säuren, 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 as well as 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, thus improving its economy. The significantly increased biocidal activity of boric acid compounds, which is observed especially in the low pH range and can be explained by a blockade of the enzymes of the phosphate metabolism of the microorganisms, also allows the amount of others to reduce added inhibitors against the growth of microorganisms. Surprisingly, the corrosion protection of boron compounds is significantly 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 selected fatty acid mixtures and / or alkyl succinimides other corrosion protection additives, for example phosphoric acid esters, triazoles or thiadiazoles, which are also contained in conventional cooling lubricant formulation, the corrosion protection agent being added in an amount of 5 to 25 percent by weight. A water-mixed cooling lubricant equipped with the corrosion protection additives mentioned shows corrosion protection equivalent to DIN 51360-1 and -2 in aqueous solution, even at a pH value between 7.0 and 7.5, as the cooling lubricants previously used. If boric acid-free formulations are used, which consist of ethoxylated and / or propoxylated fatty acid alkanolamides, 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 moles of ethylene oxide per mole 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, Methyliso- thiazolinon und andere Isothiazolinonderivate.Furthermore, it has been shown that due to the low pH value and the consequent targeted selection of the base emulsifiers and corrosion protection additives, biocidal compounds which are otherwise not provided with sufficient stability also have an active ingredient stability even after long storage times and at elevated temperatures of significantly larger than 95%. These compounds include above all 3-iodo-2-propynyl butyl carbamate, methyl isothiazolinone 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 Nitrosamin- bildung 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 to carcinogenic nitrosamines during practical use with nitrosating substances such as nitrite, which is formed from the nitrate of the preparation water by bacterial activity, and their formation depending on the pH value, especially in the acidic range special attention should be paid to the pH range from 7.0 to 7.5. As studies show, the use of inhibitors can prevent nitrosamine formation. Such inhibitors include, inter alia, free primary amines which arise in small amounts from fatty acid alkanolamides in the cooling lubricant according to the invention as a result of a dissociation equilibrium, or, for example, ascorbic acid. This prevents nitrosamine formation. Test results also speak against an increased risk of nitrosamine formation of the cooling lubricant formulations according to the invention, in particular that amides in a pH range of 6-8 cannot form stable nitrosamines.
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 . 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 Kühlschmiersto fes. 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.The active substances 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, butyltriglycol, and also 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. 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 the employees. For this reason, equipping the cooling lubricant concentrate with appropriate biocidal or fungicidal compounds is usually essential.
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 Guanidinde- rivate, 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 ver- Ursachen. Die Konservierungsstoffe werden im allgemeinen in Mengen von 0,1 bis 5 Gewichtsprozent dem Kuhlschmierstoff- Konzentrat zugesetzt.It has now been shown here that, in the formulations according to the invention, components which are otherwise unusual in the cooling lubricant concentrate, such as isothiazolinones or 3-iodo-2-propynylcarbamate, have an interesting and economical spectrum of action, as was not previously known. Guanidine derivatives, imidazole derivatives and aromatic carboxylic acids such as salicylic or benzoic acid and their derivatives are to be mentioned as further particularly suitable preservatives, taking into account the pH value of <7.6. Through use in the formulations according to the invention with a pH of 7 to 7.5, it has surprisingly been found that methylolurea derivatives such as dimethylolurea and / or tri- and tetramethylolacetylene diurea, contrary to previous experience, do not polymerize to ineffective polyurea derivatives even in higher concentrations and then thus are no longer available as a biocidal active ingredient or cause problems due to 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 funktioneile 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 Kuhlschmierstoffkonzen- trat 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 Kuhlschmierstoff-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 400 or less, solid lubricants, toluyltriazoles, defoamers and / or anti-fog additives. For use in metalworking, the aqueous solutions or emulsions prepared from the water-miscible cooling lubricant concentrate generally contain these additives 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 Natriumdo- decylsulfat (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-/Prüfkon- zentration überschreitet, sind höhere Prüfkonzentrationen naheliegend, werden aber nicht durchgeführt, da kritische Werte zu erwarten sind.The measurement of 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 barrier function of the skin. It measures how much water diffuses through the skin per unit of time and area from the inside to the outside. High TEWL values indicate high water loss and thus damage to the barrier function, low TEWL values indicate an intact barrier function. Water and the very aggressive sodium decyl sulfate (SDS) are used as the reference medium. 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 exceed the application / test concentration, higher test concentrations are obvious, but are not carried out, since 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. Das erfindungsgemäße wassermischbare Kühlschmierstoff- Konzentrat wurde gemäß den nachfolgenden Rezepturbeispielen hergestellt.By testing formulations according to the invention with a pH value of 7 to 7.5, the TEWL measurement has now been used to prove that the cooling lubricant can be classified as non-irritating in a test concentration of 100 percent by weight. The water-miscible cooling lubricant concentrate according to the invention was produced in accordance with the following recipe examples.
Beispiel 1example 1
Semisynthetisches, borhaltiges Kühlschmierstoff-KonzentratSemisynthetic, boron-containing coolant concentrate
Paraffinischer Kohlenwasserstoff 30% Borsäurealkanolaminester/amid-Gemisch 20%Paraffinic hydrocarbon 30% boric acid alkanolamine ester / amide mixture 20%
Talloelfettsäure 5%Tall oil fatty acid 5%
C16 / C18 Fettsäurealkanolamid 11%C16 / C18 fatty acid alkanolamide 11%
Oleylethercarbonsäure (Ethoxylierungsgrad 9) 3%Oleyl ether carboxylic acid (degree of ethoxylation 9) 3%
Trimethylolpropan-Trioleat 16% C16-Guebertalkohol 5%Trimethylolpropane trioleate 16% C 16 excess alcohol 5%
Methylisothiazolinon 0,5%Methylisothiazolinone 0.5%
3-Jod-2-propinylbutylcarbamat (IPBC) 0,5%3-iodo-2-propynyl butyl carbamate (IPBC) 0.5%
Wasser 9%Water 9%
Beispiel 2Example 2
Semisynthetischer, borhaltiger KühlschmierstoffSemisynthetic, boron-containing coolant
Paraffinisches Solventraffinat 24% Borsäure-Triethanolamin-Reaktionsprodukt 25%Paraffinic solvent raffinate 24% boric acid-triethanolamine reaction product 25%
Fettsäuremonoethanolamid (Ethoxylierungsgrad 4) 12%Fatty acid monoethanolamide (degree of ethoxylation 4) 12%
Alkylbernsteinsäureimid 4,5%Alkyl succinimide 4.5%
Castoroilethoxylat (Ethoxylierungsgrad 5) 3%Castoroil ethoxylate (degree of ethoxylation 5) 3%
Synthetisches Natriumpetrolsulfonat 5% Ethylen-Propylenglykol 4,3%Synthetic sodium petrol sulfonate 5% ethylene propylene glycol 4.3%
Polypropylenglykolmonobutylether 2%Polypropylene glycol monobutyl ether 2%
Ethylhexyloleat 16%Ethyl hexyl oleate 16%
Hexitidin 3,5%Hexitidine 3.5%
3-Jod-2-propinylbutylcarbamat (IPBC) 0,5% Beispiele 3a und 3b3-iodo-2-propynyl butyl carbamate (IPBC) 0.5% Examples 3a and 3b
Semisynthetisches, borfreies Kühlschmierstoff-KonzentratSemisynthetic, boron-free coolant concentrate
3a) Medizinisches Weißoel oder 42,5%3a) Medical white oil or 42.5%
3b) Trimethylolpropanadipat 42,5%3b) trimethylolpropane adipate 42.5%
KOH-verseiftes Rüboel 25% C16 / C18 Fettsäurealkanolamid (Ethoxylierungsgrad 4) 12%KOH-saponified sugar beet 25% C16 / C18 fatty acid alkanolamide (degree of ethoxylation 4) 12%
Alkylbernsteinsäureimid 3,5% Polypropylenglycolmonobutylether 5%Alkyl succinimide 3.5% polypropylene glycol monobutyl ether 5%
Synthetisches Natriumpetrolsulfonat (Petronate® CR) 4%Synthetic sodium petrol sulfonate (Petronate® CR) 4%
Cocosalkylguanidiniumderivat (Dodigen®) 1% n-Octylisothiazolinon 0,6%Cocosalkylguanidinium derivative (Dodigen®) 1% n-octylisothiazolinone 0.6%
Methylolharnstoffderivat 2,5% Wasser 3,9% Beispiel 4Methylol urea derivative 2.5% water 3.9% Example 4
Synthetisches, mineralölfreies Kühlschmierstoff-KonzentratSynthetic, mineral oil-free coolant concentrate
Triethanolaminsalz einer cyclischenTriethanolamine salt of a cyclic
Tricarbonsäure (Irgacor® L 190) 50%Tricarboxylic acid (Irgacor® L 190) 50%
Rüboelfettsäurealkanolamid (Ethoxylierungsgrad 4) 2,5% Phosphorsäureteilester, neutralisiert mit einem primären Alkanolamin 7% C10 Monocarbonsäure (Neodecansäure) 3% n-Octylisothiazolinon 0,3%Rubo fatty acid alkanolamide (degree of ethoxylation 4) 2.5% phosphoric acid partial ester, neutralized with a primary alkanolamine 7% C 10 monocarboxylic acid (neodecanoic acid) 3% n-octylisothiazolinone 0.3%
Polymeres kationisches Mikrobiozid 0,15%Polymeric cationic microbicide 0.15%
Wasser 37,05% Typkennwerte der erfindungsgemäßen Rezepturbeispiele als 5%ige Emulsion/LösungWater 37.05% Characteristic values of the formulation examples according to the invention as a 5% emulsion / solution
Rezepturbeispiel 1 2 3a 3b 4Recipe example 1 2 3a 3b 4
Aussehen grobdispers/milchig klare Lösung pH-Wert 7,4 7,5 7,4 7,4 7,5Appearance of coarsely dispersed / milky clear solution pH 7.4 7.5 7.4 7.4 7.5
Korrosionsschutz nach DIN 51 360-2 Rostnote 0 bei % 4,5 4 4 4 3,5 Corrosion protection according to DIN 51 360-2 rust grade 0 at% 4.5 4 4 4 3.5

Claims

Patentansprüche: Claims:
1. Wassermischbares Kuhlschmierstoff-Konzentrat, das natürliche oder synthetische Mineralöle, Emulgatoren, Korrosionsschutzadditive, LösungsVermittler, Konservierungsstoffe, Metallinhibitoren und andere übliche Additive enthält, dadurch gekennze'ichnet, dass es nach Verdünnung zu einer 2 bis 25 Gewichtsprozentigen wässrigen Lösung einen pH-Wert zwischen 7,0 und 7,5 aufweist und zusätzlich als Konservierungsstoff und/oder Korrosionssschutzadditiv eine Mischung vonContains 1. Water-miscible cooling lubricant concentrate, the natural or synthetic mineral oils, emulsifiers, corrosion protection additives, solubilisers, preservatives, metal inhibitors and other conventional additives, characterized ichnet gekennze 'that there between after dilution aqueous to a 2 to 25 percent by weight solution has a pH 7.0 and 7.5 and, in addition, as a preservative and / or anti-corrosion additive, a mixture of
a) einem Umsetzungsprodukt von Borsäure und einem primären oder tertiären Alkanolamin und/odera) a reaction product of boric acid and a primary or tertiary alkanolamine and / or
b) einer ethoxylierten und/oder propoxylierten Fettsäure oder einem Fettsäurealkanolamid sowie wenigstens eine weitere Verbindung ausgewählt aus der Gruppe bestehend ausb) an ethoxylated and / or propoxylated fatty acid or a fatty acid alkanolamide and at least one further compound selected from the group consisting of
c) einem Carbonsäureimid, einem Phosphorsäureester, einem Triazol, einem Thiadiazol, einem Isothiazolinon, einem Imidazol, einem Guanidin, einer aromatischen Carbonsäure und dem 3-Jod-2-propinyl-carbamat und/oderc) a carboximide, a phosphoric acid ester, a triazole, a thiadiazole, an isothiazolinone, an imidazole, a guanidine, an aromatic carboxylic acid and the 3-iodo-2-propynylcarbamate and / or
d) einem Methylolharnstoffderivat enthält.d) contains a methylol urea derivative.
2. Kühlschmierstoff-Konzentrat nach Anspruch 1, dadurch gekennzeichnet, dass es als natürliche oder synthetische Mineralöle paraffinische oder naphthenische Kohlenwasserstoffe, Ester, Polyisobutene, Polyvinylpyrrolidone oder Polyalkylenglykole in einer Menge von 5 bis 80 Gewichtsprozent, vorzugsweise in einer Menge von 5 bis 50 Gewichts- prozent enthält. 2. Cooling lubricant concentrate according to claim 1, characterized in that it is natural or synthetic mineral oils paraffinic or naphthenic hydrocarbons, esters, polyisobutenes, polyvinylpyrrolidones or polyalkylene glycols in an amount of 5 to 80 percent by weight, preferably in an amount of 5 to 50 percent by weight. percent contains.
3. Kühlschmierstoff-Konzentrat nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass es einen oder mehrere anionische oder nicht-ionische oberflächenaktive Verbindungen als Emulgatoren und gegebenenfalls als Coemulgator zusätzlich eine oder mehrere Mono- oder Dicarbonsäuren mit 16 bis 54 Kohlenstoffatomen oder deren Alkalisalze in einer Menge von 2 bis 20 Gewichtsprozent enthält.3. Cooling lubricant concentrate according to claim 1 or 2, characterized in that there are one or more anionic or non-ionic surface-active compounds as emulsifiers and optionally as co-emulsifiers additionally one or more mono- or dicarboxylic acids with 16 to 54 carbon atoms or their alkali metal salts in one Contains amount from 2 to 20 weight percent.
4. Kühlschmierstoff-Konzentrat nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, dass es als Lösungsvermittler Wasser,4. Cooling lubricant concentrate according to claims 1 to 4, characterized in that it is water as a solubilizer,
Ethylenglykol, Butyltriglykol, geradkettige oder verzweigte Fettalkohole mit 16 bis 24 Kohlenstoffatomen in Mengen von 5 bis 50 Gewichtsprozent enthält.Contains ethylene glycol, butyl triglycol, straight-chain or branched fatty alcohols with 16 to 24 carbon atoms in amounts of 5 to 50 percent by weight.
5. Kühlschmierstoff-Konzentrat nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, dass es als Konvervierungsstoffe bakterizide und fungizide Wirkstoffe in Mengen von 0,1 bis 5 Gewichtsprozent enthält.5. Cooling lubricant concentrate according to claims 1 to 4, characterized in that it contains bactericidal and fungicidal active ingredients in amounts of 0.1 to 5 percent by weight as converters.
6. Kühlschmierstoff-Konzentrat nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, dass es als weitere Additive Alkylbernsteinsäureimide, Castoroilethoxylate, Petrolsulfonate, Festschmierstoffe, Toluyltriazole, Entschäumer und/oder Antinebelzjusätze enthält.6. Cooling lubricant concentrate according to claims 1 to 5, characterized in that it contains as further additives alkyl succinimides, castoroil ethoxylates, petroleum sulfonates, solid lubricants, toluyl triazoles, defoamers and / or antifog additives.
7. Wassergemischter Kuhlschmierstoff, dadurch gekennzeichnet, dass er das Kuhlschmierstoff-Konzentrat der Ansprüche 1 bis 6 in einer Menge von 2 bis 25 Gewichtsprozent enthält und einen pH-Wert zwischen 7,0 und 7,5 aufweist.7. Water-mixed cooling lubricant, characterized in that it contains the cooling lubricant concentrate of claims 1 to 6 in an amount of 2 to 25 percent by weight and has a pH between 7.0 and 7.5.
8. Verwendung des wassergemischten Kühlschmierstoffes von Anspruch 7 in Form einer wässrigen Lösung oder als Emulsion für die spanende und spanlose Metallbearbeitung. 8. Use of the water-mixed cooling lubricant of claim 7 in the form of an aqueous solution or as an emulsion for cutting and non-cutting metalworking.
EP99927938A 1998-07-28 1999-06-10 Water-miscible cooling lubricant concentrate Revoked EP1102830B1 (en)

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

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