EP0124851B1 - Mittel und Verfahren zur Reinigung und Passivierung von Metallen im Spritzverfahren - Google Patents

Mittel und Verfahren zur Reinigung und Passivierung von Metallen im Spritzverfahren Download PDF

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Publication number
EP0124851B1
EP0124851B1 EP84104860A EP84104860A EP0124851B1 EP 0124851 B1 EP0124851 B1 EP 0124851B1 EP 84104860 A EP84104860 A EP 84104860A EP 84104860 A EP84104860 A EP 84104860A EP 0124851 B1 EP0124851 B1 EP 0124851B1
Authority
EP
European Patent Office
Prior art keywords
cleaning
phosphoric acid
range
passivation
preparations
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP84104860A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0124851A2 (de
EP0124851A3 (en
Inventor
Jürgen Dr. Geke
Bernd Stedry
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
Priority to AT84104860T priority Critical patent/ATE37728T1/de
Publication of EP0124851A2 publication Critical patent/EP0124851A2/de
Publication of EP0124851A3 publication Critical patent/EP0124851A3/de
Application granted granted Critical
Publication of EP0124851B1 publication Critical patent/EP0124851B1/de
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
    • C23G1/26—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions using inhibitors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/16—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions using inhibitors

Definitions

  • the invention relates to agents and a method for cleaning and / or passivating metals by spraying, as an additive to grinding and pressure water and as a passivating agent in cooling circuits.
  • aqueous cleaners based on organic rust inhibitors, e.g. B. combinations of alkanolamines and fatty acids, surfactants, anti-foaming agents and / or phosphonates and if necessary.
  • Biocides and builder substances, the cleaners mentioned being used in aqueous liquids at a pH of 7.5 to 10.5; usually called “neutral cleaner”.
  • neutral cleaners and corrosion protection agents that have been customary up to now are only suitable for the treatment of iron and steel without further additives.
  • cleaning and passivating agents which inhibit the corrosion of iron and steel surfaces contain, for example, alkali metal nitrites, alkanolamines, soaps and benzoates.
  • ferrous metals are increasingly being also non-ferrous and light metals and their alloys, particularly zinc, aluminum and its alloys, cleaning or passive i réellesstoffn in contact.
  • nonferrous metals are available as inhibitors such.
  • these passivation components have the disadvantage that they do not prevent discoloration of the surface of light metals (fountain water blackness).
  • Zinc, aluminum and their alloys are also attacked by the cleaning agents. A correspondingly high metal removal is found, which can sometimes no longer be tolerated with precision parts. This applies in particular to the new types of motors and transmissions made of light metal alloys in the automotive sector.
  • the cleaning agents that have been common until now contain polyphosphates, which break down to pyro- or orthophosphates, especially at higher temperatures.
  • polyphosphates which break down to pyro- or orthophosphates, especially at higher temperatures.
  • the use of such inorganic ions very often leads to precipitation with the hardness constituents of the water, that is to say to calcium or magnesium phosphate precipitates, and in the presence of corresponding alloys also to aluminum phosphate precipitation. The result is not only annoying drying on the parts to be machined, but also gluing, stoning or even clogging of storage parts and pumps.
  • precipitated phosphates especially aluminum phosphates
  • electrolyte-containing products usually result in increased metal removal and very rapid discoloration of the light or non-ferrous metal.
  • the solutions contain these components in total in a concentration of 0.1 to 4 percent by weight, the weight ratio of b) to c) 20: 1 to 1: 1 and the weight ratio of a) to the sum of b) and c) 20: 1 to 1:20.
  • Other possible additives for such solutions are: alkanolamines, phosphates, borates, nitrites, inhibitors and / or biocides.
  • the invention accordingly relates to means and methods for cleaning and passivation of metals in the spray process, which by the Merk Male of claim 1 and 4 are marked.
  • the cleaning agents according to the invention are distinguished by the fact that they use phosphoric acid esters which ensure a trouble-free process sequence without foaming. This is all the more surprising since the OE-PS 235 149 describes phosphoric acid esters as foam stabilizers.
  • the preferred phosphoric acid esters of ethoxylated fatty alcohols are also insensitive to calcium and magnesium ions. The effect of inhibiting the surfaces of various light metals is therefore guaranteed even in hard water.
  • All alcohols can be straight-chain, branched, saturated or unsaturated.
  • Straight-chain fatty alcohols alkanols with 10-20 C atoms are preferably used.
  • the monoesters of phosphoric acid with ethoxylated, straight-chain alkanols having 10-20 C atoms and their sodium, potassium, ammonium or alkanolamine salts are preferably used in the agents according to the invention.
  • This class of compounds is particularly characterized in that when they are used in the combination according to the invention in aqueous solution, especially in spray systems, no disruptive foam is generated and thus a smooth process flow in automatic cleaning machines is ensured.
  • hydrophilic monoesters do not cause calcium or magnesium salts to precipitate even in hard water, drying on the cleaned parts is avoided, which could give rise to corrosion. Such precipitates would also cause unnecessary, non-effect-related consumption of the inhibitor, which would make practical use impossible. The inhibition effect is therefore also unrestricted in hard water.
  • the use of zinc salts can be dispensed with when using the cleaners according to the invention.
  • Suitable alkanolamines for the purposes of the invention are, for example, the following compounds: mono-, di- or triisopropanolamine, n-propanolamine, N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine and preferably mono-, Di- or triethanolamine, individually or in a mixture.
  • Suitable alkanolamine salts are, for example, salts of the abovementioned compounds with linear and / or branched mono- and / or dicarboxylic acids and / or sulfonic acid derivatives.
  • Suitable mono- and / or dicarboxylic acids are, in particular, 2-ethylhexyl acid, caprylic acid, isononanoic acid, capric acid and sebacic acid.
  • a suitable sulfonic acid derivative is, for example, benzenesulfonyl-N-methyl-s-aminocaproic acid.
  • the cleaning liquids contain such sprayable nonionic surfactants that the agents can be used and sprayed in all temperature ranges without disturbing foaming.
  • the surfactants of such combinations remain dispersed in the cleaning liquid above the cloud point and do not separate. This results in a very good, constant cleaning effect.
  • the use of such combinations ensures that washed-off, little self-emulsifying oil is deposited on the surface of the storage baths and in mechanical form, e.g. can be separated by ring chamber deoiler or separators. Emulsification is practically prevented, which significantly extends the service life of the baths. If necessary, however, the emulsifying effect can be increased by appropriate emulsifier additives if this should be necessary or desired in special cases.
  • a major advantage that the agents according to the invention have is that they enable automatic control of the cleaning process and metering of the cleaning solution.
  • the control and metering are carried out via the conductivity of the cleaning solution, but without the need to use phosphates to generate conductivity.
  • electrolytes generally greatly increase the removal of light metals, it is possible to achieve a conductivity that is suitable for practice by using the above-mentioned phosphoric acid esters in combination with alkanolamines and / or alkanolamine salts of linear and / or branched mono- or dicarboxylic acids and / or sulfonic acid uses rederivaten.
  • mixtures of monoethanolamine, if necessary, are used for the conductivity combination.
  • builder substances such as borates, gluconates, potassium hydroxide and / or aminopolycarboxylic acids or their salts, preferably ethylenediaminetetraacetate or nitrilotriacetate, are added.
  • the combination on the basis of which the agents according to the invention have the desired conductivity, is used in the total combination in amounts of 0.5-5% by weight in total.
  • the aqueous solutions whose pH is between 7.5 and 10.5, contain the following components:
  • the respective application concentration of these components must be selected so that the conductivity in the corresponding process water is sufficiently large to enable automatic dosing and control. At the same time, the mixtures must not lead to precipitation.
  • the cleaning agents according to the invention can also contain biocides, e.g. B. derivatives of hexahydrotriazine, such as the reaction product of monoethanolamine with formaldehyde, are added without this affecting the essential properties such as cleaning and passivation effect, conductivity or low foam.
  • biocides e.g. B. derivatives of hexahydrotriazine, such as the reaction product of monoethanolamine with formaldehyde, are added without this affecting the essential properties such as cleaning and passivation effect, conductivity or low foam.
  • the cleaning agents are additionally non-ferrous metal corrosion inhibitors, for. B. mercaptobenzothiazole or benzotriazole added.
  • the use concentrations of the phosphoric acid esters in the application solutions are 10 to 1000 ppm, but preferably 10 to 300 ppm when the agent is used as a neutral cleaner.
  • the amounts can be above 300 ppm.
  • the process according to the invention is therefore carried out using the agents mentioned, the pH of which is in the range from 7.5 to 10.5.
  • the aluminum concentration in the clear solution could be determined either with the aid of atomic absorption or photometrically (filter 535 nm) with eriochrome cyanine in ammonium acetate buffered solution, the zinc concentration only with atomic absorption.
  • composition of the inhibitors used for the production of the cleaning agents according to the invention can be seen from the following list:
  • This mixture was used in a concentration of 30 g / l in LW or VEW at a pH of 9.7.
  • Examples 12, 17, 19 and 21 are control examples in which the cleaning mixture did not contain an inhibitor according to the invention.
  • Examples 23 and 27 are control examples in which the cleaning agents did not contain an inhibitor.
  • This mixture was used in a concentration of 10 g / l in VEW at a pH of 8.6.
  • Example 30 is a control example in which the cleaning agent contained no inhibitor.
  • This mixture was used in a concentration of 20 gll in VEW or LW at a pH of 9.2.
  • Examples 33, 36 and 39 are control examples in which the cleaning agents contained no inhibitor.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Coating By Spraying Or Casting (AREA)
  • ing And Chemical Polishing (AREA)
  • Paints Or Removers (AREA)
  • Manufacture Of Electron Tubes, Discharge Lamp Vessels, Lead-In Wires, And The Like (AREA)
EP84104860A 1983-05-07 1984-04-30 Mittel und Verfahren zur Reinigung und Passivierung von Metallen im Spritzverfahren Expired EP0124851B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84104860T ATE37728T1 (de) 1983-05-07 1984-04-30 Mittel und verfahren zur reinigung und passivierung von metallen im spritzverfahren.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19833316724 DE3316724A1 (de) 1983-05-07 1983-05-07 Mittel und verfahren zur reinigung und passivierung von metallen im spritzverfahren
DE3316724 1983-05-07

Publications (3)

Publication Number Publication Date
EP0124851A2 EP0124851A2 (de) 1984-11-14
EP0124851A3 EP0124851A3 (en) 1986-07-30
EP0124851B1 true EP0124851B1 (de) 1988-10-05

Family

ID=6198404

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84104860A Expired EP0124851B1 (de) 1983-05-07 1984-04-30 Mittel und Verfahren zur Reinigung und Passivierung von Metallen im Spritzverfahren

Country Status (9)

Country Link
US (1) US4578208A (enrdf_load_stackoverflow)
EP (1) EP0124851B1 (enrdf_load_stackoverflow)
JP (1) JPS59211581A (enrdf_load_stackoverflow)
AT (1) ATE37728T1 (enrdf_load_stackoverflow)
BR (1) BR8402107A (enrdf_load_stackoverflow)
CA (1) CA1231294A (enrdf_load_stackoverflow)
DE (2) DE3316724A1 (enrdf_load_stackoverflow)
ES (1) ES8502484A1 (enrdf_load_stackoverflow)
MX (1) MX166996B (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6780824B2 (en) 2001-11-02 2004-08-24 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Emulsifier system, anti-corrosive and low-temperature lubricant emulsion

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GB8711534D0 (en) * 1987-05-15 1987-06-17 Ciba Geigy Ag Corrosion inhibiting composition
US4992212A (en) * 1988-10-18 1991-02-12 Lever Brothers Company, Division Of Conopco, Inc. Alkaline light duty liquid detergents that are non-staining to aluminum
US5480860A (en) * 1988-12-23 1996-01-02 Petrolite Corporation Methods for reducing sulfides in sewage gas
US5200114A (en) * 1990-08-24 1993-04-06 Man-Gill Chemical Company Alkaline cleaner for reducing stain on aluminum surfaces
US5110494A (en) * 1990-08-24 1992-05-05 Man-Gill Chemical Company Alkaline cleaner and process for reducing stain on aluminum surfaces
US5192461A (en) * 1991-08-23 1993-03-09 Enthone-Omi, Inc. Aqueous degreasing solution having high free alkalinity
US5372741A (en) * 1991-11-27 1994-12-13 Ethone-Omi, Inc. Aqueous degreasing composition and process
AU4676893A (en) * 1992-07-31 1994-03-03 Henkel Corporation Process and aqueous composition for degreasing metal surface
US5296042A (en) * 1992-11-06 1994-03-22 C. L. R. Resources, Inc. Composition and process for treating sheet steel
US5468412A (en) * 1993-08-16 1995-11-21 Betz Laboratories, Inc. Low foaming aqueous cleaning and passivating treatment for metals
CA2143471A1 (en) * 1994-05-20 1995-11-21 Edward A. Rodzewich Cleaning and passivating treatment for metals
US5668096A (en) * 1994-05-20 1997-09-16 Betzdearborn Inc. Cleaning and passivating treatment for metals
US5705472A (en) * 1995-07-18 1998-01-06 Petroferm Inc. Neutral aqueous cleaning composition
US6328816B1 (en) 1995-07-25 2001-12-11 Henkel Corporation Composition and method for degreasing metal surfaces
US5746973A (en) * 1996-07-10 1998-05-05 Naraghi; Ali Method for reducing odorant depletion
US5968370A (en) * 1998-01-14 1999-10-19 Prowler Environmental Technology, Inc. Method of removing hydrocarbons from contaminated sludge
DE10106230A1 (de) * 2001-02-10 2002-08-14 Creavis Tech & Innovation Gmbh Verfahren zur Herstellung mikrobizider Oberflächen durch Immobilisierung von Aminoalkoholen
WO2003080895A1 (en) * 2002-03-18 2003-10-02 The Lubrizol Corporation Corrosion inhibiting salts, concentrates and metal working fluids containing same
US20040256595A1 (en) * 2003-06-16 2004-12-23 Seagate Technology Llc Formulation of grinding coolant
EP1580302A1 (en) * 2004-03-23 2005-09-28 JohnsonDiversey Inc. Composition and process for cleaning and corrosion inhibition of surfaces of aluminum or colored metals and alloys thereof under alkaline conditions
US20060225605A1 (en) * 2005-04-11 2006-10-12 Kloeckener James R Aqueous coating compositions and process for treating metal plated substrates
US20100256034A1 (en) * 2005-09-22 2010-10-07 Pantheon Chemical, Inc. Copper chelating agent, composition including the agent, and methods of forming and using the agent and composition
DE102007029837A1 (de) * 2007-06-28 2009-01-02 Siemens Ag Zusatz für ein Reinigungs- und/oder Pflegemittel zur Verwendung in Haushaltsgeräten sowie derartiges Reinigungs- und/oder Pflegemittel
JP2013133458A (ja) * 2011-12-27 2013-07-08 Idemitsu Kosan Co Ltd 水性洗浄剤
FR3005964B1 (fr) * 2013-05-27 2016-06-24 Ceca Sa Formulations anti-corrosion stables au stockage
WO2017080880A1 (en) * 2015-11-11 2017-05-18 Basf Se Aqueous formulations with good storage capabilities

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DK130747A (enrdf_load_stackoverflow) * 1968-08-08
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FR2193871B1 (enrdf_load_stackoverflow) * 1972-07-25 1977-07-22 Colgate Palmolive Co
DE2712900C2 (de) * 1977-03-24 1986-04-10 Henkel KGaA, 4000 Düsseldorf Verfahren zur Reinigung von Metallen im Spritzverfahren
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6780824B2 (en) 2001-11-02 2004-08-24 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Emulsifier system, anti-corrosive and low-temperature lubricant emulsion

Also Published As

Publication number Publication date
DE3474463D1 (en) 1988-11-10
JPH059519B2 (enrdf_load_stackoverflow) 1993-02-05
DE3316724A1 (de) 1984-11-08
JPS59211581A (ja) 1984-11-30
MX166996B (es) 1993-02-19
EP0124851A2 (de) 1984-11-14
ES532260A0 (es) 1985-01-01
US4578208A (en) 1986-03-25
BR8402107A (pt) 1984-12-11
ATE37728T1 (de) 1988-10-15
CA1231294A (en) 1988-01-12
ES8502484A1 (es) 1985-01-01
EP0124851A3 (en) 1986-07-30

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