EP1137748A1 - Procede d'usinage et de nettoyage de metal - Google Patents

Procede d'usinage et de nettoyage de metal

Info

Publication number
EP1137748A1
EP1137748A1 EP99956005A EP99956005A EP1137748A1 EP 1137748 A1 EP1137748 A1 EP 1137748A1 EP 99956005 A EP99956005 A EP 99956005A EP 99956005 A EP99956005 A EP 99956005A EP 1137748 A1 EP1137748 A1 EP 1137748A1
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
cleaning solution
cleaning
polyglycol
aqueous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99956005A
Other languages
German (de)
English (en)
Inventor
Jürgen Geke
Bernd Stedry
Wiltrud Klose
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1137748A1 publication Critical patent/EP1137748A1/fr
Withdrawn legal-status Critical Current

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    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0084—Antioxidants; Free-radical scavengers
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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
    • C10M129/04—Hydroxy compounds
    • C10M129/06—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/08—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least 2 hydroxy groups
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    • 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
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/30—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms
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    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
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    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C10M2215/226—Morpholines
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/30—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
    • 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
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/16—Metals

Definitions

  • metal cutting is understood to mean machining operations in which the shape of a piece of metal is changed by removing material from the workpiece to be machined with a machining tool. Examples of such metal machining processes are drilling, turning, milling and grinding. For such machining operations it is necessary to rinse the tool and workpiece with a liquid cooling lubricant, which has the following functions: lubricating the tool to avoid welding and overheating, dissipating the heat generated and removing the chips or other metal particles that are formed. that it prevents corrosion of the workpiece.
  • oils, oil-in-water emulsions or water-soluble cooling lubricants which consist only of an aqueous solution are known as cooling lubricants.
  • the present invention is concerned with such water-soluble Lubricants, i.e. cooling lubricants that do not contain water-insoluble components such as oils.
  • the cleaner Depending on the load with cooling lubricant, the cleaner must either be replenished with new cleaning-active components, regenerated by bath care measures or discarded and re-prepared leads to a high consumption of detergent active ingredients, which must be disposed of at the end of the service life of the detergent, which has an environmental impact and is also economically disadvantageous due to the required use of materials.
  • the invention has for its object to provide a Nerfahrkombination for metal cutting using an aqueous cooling lubricant and subsequent cleaning of the processed metal parts with an aqueous cleaning solution, in which the ingredients of the cooling lubricant and the aqueous cleaning solution are matched so that the ingredients of the Cooling lubricant supplement the cleaning solution or at least not negatively influence it.
  • the cooling lubricant does not represent a "dirt load" for the cleaner, but rather complements it. This enables the cleaning solution itself to use less active ingredients.
  • the service life of the cleaning solution is extended even without bathroom care measures Lower disposal costs relieve the environment and make the entire process cheaper.
  • the invention is based on aqueous ("water-soluble") cooling lubricants which contain polyglycol monoether and / or polyglycol diether as the lubricating component.
  • aqueous cooling lubricants contain corrosion inhibitors.
  • German patent application DE 197 23 990.0 discloses cleaning agents for metal cleaning. the glycol monoethers of the general formula as cleaning-active components
  • glycol monoethers are used in combination with cationic surfactants in a weight ratio of glycol monoether to cationic surfactant between 8: 1 and 100: 1.
  • This cleaner preferably contains corrosion inhibitors as further active ingredients.
  • the object of the invention is achieved by a method for metal cutting using an aqueous cooling lubricant and subsequent cleaning of the machined metal parts with an aqueous cleaning solution, characterized in that
  • a) uses an aqueous solution as cooling lubricant for metal cutting, which contains corrosion inhibitors and polyglycol monoether and / or polyglycol diether, and
  • an aqueous solution is used as the cleaning solution which contains cleaning-active substances and the same corrosion inhibitors as the cooling lubricant.
  • the lubricating polyglycol monoethers or polyglycol diethers are selected so that they are compatible with the components of the cleaning solution. They therefore do not cause any loss of the cleaning action, nor do they impair the effectiveness of the corrosion inhibitors of the cleaning solution. So they do not represent contamination for the cleaning solution and therefore do not require any bath care measures to remove them. Rather, a steady content of these components occurs in the cleaning solution during operation, since the same amounts of lubricants are carried into the cleaning solution in equilibrium as are discharged through the cleaned metal parts.
  • polyglycol monoethers or polyglycol diethers to be used as lubricating components in the cooling lubricant are known as such for this use and are commercially available.
  • the polyglycol monoethers are also frequently shortened, but incorrectly, referred to as “polyglycols”. They are obtained by reacting suitable starting molecules, for example monohydric or polyhydric alcohols having 1 to 5 carbon atoms, with ethylene oxide and / or propylene oxide become. This creates a polyethylene glycol, polypropylene glycol or a mixed chain in which the alkylene oxide units are linked to form polyethers after the ring has been opened. In the term "polyglycols", however, these ether bonds are generally disregarded.
  • glycol monoethers or polyglycol monoethers are oligomeric or polymeric polyalkylene glycol chains which are at one end
  • glycol diether or polyglycol diether mean oligomeric or polymeric alkylene glycol chains which are etherified with alcohols at both ends, and it is not necessary for the molecules to carry the same alcohol groups at both ends.
  • glycol diether or “polyglycol diether” chosen here corresponds to This means that the term “end group-closed glycol or polyglycol ether” can also be found in technology.
  • the aqueous cooling lubricant to be used according to the invention preferably contains those polyglycol monoethers and / or polyglycol diethers which can be obtained by ethoxylation and / or propoxylation of mono- or polyhydric alcohols having 1 to 5 carbon atoms.
  • the polyalkylene glycol chains are closed at the other end with alcohols with 1 to 6 carbon atoms.
  • the polyglycol monoethers or diethers preferably have an average molecular weight in the range from 500 to 25,000.
  • the corrosion inhibitors which are used according to the invention both in the aqueous cooling lubricant and in the aqueous cleaning solution are preferably selected from alkanolamines and / or from salts of branched or unbranched, saturated or unsaturated aliphatic mono- or dicarboxylic acids with 6 to 10 carbon atoms and / or from aromatic carboxylic acids with 7 to 10 carbon atoms. If this refers to alkanolamines and salts of carboxylic acids, this can mean, on the one hand, that the alkanolamine salts of the carboxylic acids are used directly. This is equivalent to a mixture of alkanolamines and carboxylic acids that react with one another to form salts.
  • the alkanolamines can be used as such, the carboxylic acids as alkali metal salts. Mixtures of carboxylic acids and alkali metal hydroxides are equivalent to alkali metal salts of carboxylic acids.
  • the alkanolamines and / or the carboxylic acids will be present as an equilibrium mixture of the neutral molecules and the cations in the case of the alkanolamines or the anions in the case of the carboxylic acids.
  • the ready-to-use aqueous cooling lubricant preferably contains 2 to 15 g / 1 polyglycol monoether and / or polyglycol diether and 8 to 40 g / 1 corrosion inhibitors.
  • the aqueous cooling lubricant can additionally contain emulsifiers, buffer substances, surfactants and / or biocides as further components. Its pH is preferably in the range between about 6 and about 9.5.
  • the aqueous cooling lubricant can be mixed together on site by dissolving the individual components in water at the desired concentrations.
  • aqueous cooling lubricants in the form of an aqueous concentrate which contains the individual active ingredients in the correct proportions, but in concentrated form.
  • this concentrate must be diluted with water to the application concentration on site become.
  • the concentrate can be one component. ie contain all active ingredients of the cooling lubricant.
  • the concentrate can also be sold in the form of two or more separate containers, each of which contains certain components or combinations of components.
  • the cooling lubricant can be marketed as a concentrate which contains both about 50 to about 300 g / 1 of polyglycol monoether and or polyglycol diether and also about 50 to about 600 g / 1 of the corrosion inhibitors mentioned and, if appropriate, further active ingredients and auxiliaries .
  • separate concentrates of the polyglycol monoethers and / or polyglycol diethers on the one hand and the corrosion inhibitors on the other hand can also be used to prepare or supplement the ready-to-use aqueous cooling lubricant.
  • additional active ingredients and auxiliaries to be used optionally are preferably added to the concentrate component which contains the polyglycol monoethers and / or polyglycol diethers.
  • the second concentrate then merely represents an aqueous solution of the corrosion inhibitors. This concept has the advantage that the concentrate of the corrosion inhibitors can be used both to supplement the cooling lubricant and to supplement the aqueous cleaning solution.
  • the aqueous cleaning solution can also be prepared by dissolving the individual active ingredients in water in the required concentrations on site.
  • the preferred procedure is to bring concentrates of the cleaning solution to the market in the same way as to dilute with water on site in the required ratio.
  • the concentrate can contain all active and auxiliary substances in the correct relative proportions to each other.
  • the same concentrate can then be used which is also used to prepare or to supplement the ready-to-use aqueous cooling lubricant.
  • This concept of providing a total of three product concentrates for the cooling lubricant and the cleaning solution increases the flexibility of the subsequent dosing of the individual components and leads to a particularly economical use of materials.
  • the cleaning-active substances in the cleaning solution are preferably selected from anionic surfactants, nonionic surfactants, cationic surfactants and from glycol monoethers of the general formula
  • R is an alkyl radical having 1 to 5 carbon atoms or a phenyl radical and n is a number in the range from 1 to 5, preferably in the range from 1 to 3.
  • Preferred glycol monoethers are: tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether and propylene glycol phenyl ether. Tripropylene glycol monomethyl ether and tripropylene glycol n-butyl ether are particularly preferred.
  • the cleaning solution a) preferably contains glycol monoether of the general formula RO- (CH 2 -CH (CH 3 ) -O) n -H, where R is an alkyl radical with 1 to 5 carbon atoms or a phenyl radical and n is a number in the range from 1 to 5, preferably in the range from 1 to 3, and b) cationic surfactants in the weight ratio a) to b) between 5: 1 and 100 : 1. This is preferably
  • the cationic surfactants to be used optionally in the cleaning solution are preferably selected from quaternary ammonium compounds of the general formula
  • R is a linear or branched alkyl radical having 1 to 22 carbon atoms
  • R and R independently of one another are methyl, ethyl, 2-hydroxyethyl or hydroxypropyl,
  • R represents alkyl radicals having 1 to 12 atoms, a benzyl radical or alkylphenyl radicals having 1 to 3 carbon atoms in the alkyl radical and the total number of carbon atoms in the quaternary ammonium cation is at least 9 and at least one of the radicals R and R 5 has more than 4 carbon atoms has, and
  • X stands for halide, methyl sulfate or an anion of an aliphatic or aromatic organic acid with up to 15 carbon atoms.
  • cationic surfactants are preferred in which R 3 and R 4 is methyl and R ⁇ is benzyl.
  • cationic surfactants examples include lauryl-dimethyl-benzyl-ammonium salts or 2-hydroxydodecyl-dimethyl-benzyl-ammonium salts.
  • Anions X "in these salts are, for example, halides, in particular chloride, or anions of organic acids, such as, for example, acetate, propionate, lactate or benzoate ions.
  • the ready-to-use cleaning solution preferably contains 1 to 15 g / 1 of the corrosion inhibitors mentioned.
  • the content of cleaning-active substances in the ready-to-use cleaning solution is preferably 0.1 to 5.0 g / l.
  • the cleaning solution preferably contains 0.1 to 4.0 g / 1 of the glycol monoethers mentioned and 0.001 to 0.5 g / 1 of the cationic surfactants mentioned.
  • the cleaning solution can additionally contain builder substances, biocides and / or complexing agents.
  • builder substances are alkali metal orthophosphates, polyphosphates, silicates, borates, carbonates, polyacrylates and gluconates. Some of these builder substances have complexing properties and therefore have a water-softening effect.
  • stronger complexing agents such as 1-hydroxyethane-1, 1-diphosphonic acid or 2-phosphonobutane-1, 2,4-tricarboxylic acid can be used. Ethylene diamine tetraacetates or nitrilotriacetates are also suitable.
  • the cleaning solution is preferably formulated as a so-called neutral cleaner.
  • the temperature of the cleaning solution is preferably in the range from 15 to 80 ° C.
  • the cleaning can be done in a dipping system or in a spraying system. Spray cleaning is particularly effective, so cleaning is preferably carried out in a spray system.
  • the glycol monoethers described above are preferably selected as cleaning-active substances for the cleaning solution, in particular in combination with the cationic surfactants mentioned. These are particularly low-foaming and can therefore be used for spray cleaning in the entire temperature range mentioned.
  • an aqueous cooling lubricant with the following composition can be used:
  • An aqueous cleaning solution which can be used in the process according to the invention can have, for example, the following composition:
  • Example for the cleaner 0.60 g monoethanolamine 2.70 g triethanolamine 1.79 g sebacic acid
  • the cleaning solution is also preferably prepared on site by diluting a concentrate with water.
  • the dilution factor of the concentrate is preferably in the range from about 1: 200 to about 1: 20.
  • a concentrate containing all components of the detergent solution in the appropriate weight ratio can be used to prepare a detergent bath.
  • the use of a concentrate that contains fewer or no corrosion inhibitors is recommended, since these are introduced into the cleaning solution by the cooling lubricant and thereby supplemented.
  • the cleaning effect of unloaded and coolant-loaded cleaners is determined in the following test: Steel sheets of quality St 1405 are manually pre-cleaned with surfactant solution and soiled with a test dirt consisting of soot, graphite, fatty acid triglyceride and hydrocarbon fractions. After 30 minutes of storage in an oven at 60 ° C, they are sprayed with cleaning solution in a laboratory spraying system at 60 ° C for 2 min at 3 bar. To simulate additional foreign oils, 10 g / 1 Gerolub ⁇ 3005/7 (registered trademark of Henkel KGaA, Düsseldorf), a metastable O / W emulsion, was added to the cleaning solution. After rinsing with water, the residual contamination is quantified by oxidation of the carbon remaining on the surface.
  • cleaning efficiency is the quotient from the cleaned contamination to the contamination before the cleaning attempt, likewise measured by oxidation of the carbon on the surface, multiplied by 100 for representation as a% value.
  • Example 4 Cleaner without cooling lubricant Composition of the cleaning liquid 10.00 g Gerolub 3005/7 0.80 g monoethanolamine 3.60 g triethanolamine 2.38 g sebacic acid
  • Example 6 Cleaner loaded with aqueous cooling lubricant Composition of the cleaning liquid 10.00 g Gerolub 3005/7 1.00 g monoethanolamine 4.10 g triethanolamine 2.38 g sebacic acid
  • tripropylene glycol monomethyl ether 0.01 g 2-hydroxododyl-dimethyl-benzyl-ammonium-benzoate 1.25 g polyethylene / propylene glycol ether (starting molecule: pentaerythritol),

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Biochemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un procédé d'usinage de métal avec enlèvement de copeaux, impliquant l'utilisation d'un lubrifiant de refroidissement aqueux, et de nettoyages consécutifs des pièces métalliques usinées à l'aide d'une solution de nettoyage aqueux. Ce procédé se caractérise en ce que l'on utilise: (a) comme lubrifiant de refroidissement pour l'usinage de métal avec enlèvement de copeaux, une solution aqueuse qui contient des inhibiteurs de corrosion ainsi que des monoéthers de polyglycol et/ou des diéthers de polyglycol; et (b) comme solution de nettoyage, une solution aqueuse qui contient les substances nettoyantes et les mêmes inhibiteurs de corrosion que ceux contenus dans le lubrifiant de refroidissement.
EP99956005A 1998-11-26 1999-11-17 Procede d'usinage et de nettoyage de metal Withdrawn EP1137748A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19854592A DE19854592A1 (de) 1998-11-26 1998-11-26 Metallbearbeitungs- und Reinigungsverfahren
DE19854592 1998-11-26
PCT/EP1999/008827 WO2000031218A1 (fr) 1998-11-26 1999-11-17 Procede d'usinage et de nettoyage de metal

Publications (1)

Publication Number Publication Date
EP1137748A1 true EP1137748A1 (fr) 2001-10-04

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EP (1) EP1137748A1 (fr)
CZ (1) CZ294158B6 (fr)
DE (1) DE19854592A1 (fr)
WO (1) WO2000031218A1 (fr)

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WO2010040860A2 (fr) 2008-10-10 2010-04-15 Magna Steyr Fahrzeugtechnik Ag & Co Kg Procédé de fabrication et première mise en service d'une boîte avec un lubrifiant à base aqueuse et lubrifiant de ce type
DE102008051264A1 (de) * 2008-10-10 2010-04-15 Magna Steyr Fahrzeugtechnik Ag & Co. Kg Korrosionsschutzmittel
CZ303547B6 (cs) * 2009-03-10 2012-11-28 Wetter@Antonín Prostredek pro odstranování korozních zplodin z kovových povrchu
US9617502B2 (en) 2014-09-15 2017-04-11 The Procter & Gamble Company Detergent compositions containing salts of polyetheramines and polymeric acid
EP3197988B1 (fr) 2014-09-25 2018-08-01 The Procter & Gamble Company Compositions de nettoyage contenant une polyétheramine
US9631163B2 (en) 2014-09-25 2017-04-25 The Procter & Gamble Company Liquid laundry detergent composition
US9752101B2 (en) 2014-09-25 2017-09-05 The Procter & Gamble Company Liquid laundry detergent composition
US9388368B2 (en) * 2014-09-26 2016-07-12 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
CN108467772B (zh) * 2018-03-30 2021-06-25 广州杜朗介质科技有限公司 全合成铝合金磨削液及其制备方法
CN113667552A (zh) * 2020-05-15 2021-11-19 安集微电子科技（上海）股份有限公司 一种用于铜大马士革工艺的清洗液
CN111909770A (zh) * 2020-08-13 2020-11-10 华阳-恩赛有限公司 全合成高润滑金属加工液、其制备方法及用途

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DE1446388A1 (de) * 1962-06-22 1968-11-28 Dea Mineraloel Verkauf Gmbh Reinigungsoel
DE4323909A1 (de) * 1993-07-16 1995-01-19 Henkel Kgaa Mittel zum Reinigen und Passivieren von Metalloberflächen
US5795400A (en) * 1994-05-16 1998-08-18 Berger; Mitchell H. Method for recycling coolant for a cutting machine
DE19703083A1 (de) * 1997-01-29 1998-07-30 Henkel Kgaa Schaumarmes Emulgatorsystem und dieses enthaltendes Emulsionskonzentrat
DE19723990A1 (de) * 1997-06-06 1998-12-10 Henkel Kgaa Schaumarmes Reinigungsmittel
DE19835328A1 (de) * 1998-08-05 2000-02-10 Henkel Kgaa Mittel und Verfahren für die Metallbearbeitung und für Metallreinigung oder Korrosionsschutz

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See references of WO0031218A1 *

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WO2000031218A1 (fr) 2000-06-02
CZ294158B6 (cs) 2004-10-13
CZ20011852A3 (cs) 2001-09-12
DE19854592A1 (de) 2000-05-31

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