EP0124851A2 - Composition et procédé pour le nettoyage et la passivation de métaux par pulvérisation - Google Patents

Composition et procédé pour le nettoyage et la passivation de métaux par pulvérisation Download PDF

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Publication number
EP0124851A2
EP0124851A2 EP84104860A EP84104860A EP0124851A2 EP 0124851 A2 EP0124851 A2 EP 0124851A2 EP 84104860 A EP84104860 A EP 84104860A EP 84104860 A EP84104860 A EP 84104860A EP 0124851 A2 EP0124851 A2 EP 0124851A2
Authority
EP
European Patent Office
Prior art keywords
cleaning
phosphoric acid
mono
atoms
vew
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
EP84104860A
Other languages
German (de)
English (en)
Other versions
EP0124851A3 (en
EP0124851B1 (fr
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/fr
Publication of EP0124851A3 publication Critical patent/EP0124851A3/de
Application granted granted Critical
Publication of EP0124851B1 publication Critical patent/EP0124851B1/fr
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, for example combinations of alkanolamines and fatty acids, surfactants, anti-foaming agents and / or Ph q sponates, 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.
  • non-ferrous and light metals and their alloys are increasingly coming into contact with cleaning and passivating agents.
  • B untmetalle stand as inhibitors eg mercaptobenzothiazole and benzotriazole are available.
  • these passivation components have the disadvantage that they do not prevent discoloration of the surfaces 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.
  • 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 cleaning agents according to the invention are characterized in that those phosphoric acid esters are used which ensure a trouble-free process flow 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.
  • the agents according to the invention do not contain phosphates, there is also no disadvantageous precipitation of phosphate salts.
  • 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 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.
  • Suitable alkanolamines for the purposes of the invention are, for example, the following compounds: mono-, di- and triisopropanolamine, n-propanolamine, N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine and preferably mono-, Di- and 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-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.
  • such combinations is achieved that separates from eenfines g, little self-emulsifying oil on the surface of the storage baths, and, for example, can be separated by Ringwaitentöler or separators, in mechanical form by the use. 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 Detergent 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 which is appropriate to practice by using the phosphoric acid esters mentioned in combination with alkanolamines and / or alkanölamine salts of linear and / or branched mono- or dicarboxylic acids and / or sulfonic acid derivatives. In particular, mixtures of monoethanolamine, if necessary, 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.
  • compositions of the invention have the desired conductivity is carried within the framework of the total combination in amounts of a total of 0.5 - 5 wt -.%.
  • 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 metering and control. At the same time, the mixtures must not lead to precipitation.
  • no biocides, cleaning agents according to the invention for example, derivatives of hexahydrotriazine, such as the reaction product of monoethanolamine with formaldehyde, can be added without this the essential characteristics such as cleaning and passivating ungs- g, conductivity or foaming affected.
  • non-ferrous metal inhibitors e.g. 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 acidic and alkaline components, the surfactants, the non-ferrous and light metal additives were gradually added to the amount of water at room temperature while stirring and if necessary. added the biocides.
  • 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.
  • the inhibitory properties of the agents according to the invention on zinc, aluminum and aluminum alloys were determined according to the arrangement described under B.
  • the degree of inhibition k is calculated using the formula:
  • 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 / 1 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 / 1 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 g / 1 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)
  • ing And Chemical Polishing (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Manufacture Of Electron Tubes, Discharge Lamp Vessels, Lead-In Wires, And The Like (AREA)
  • Paints Or Removers (AREA)
EP84104860A 1983-05-07 1984-04-30 Composition et procédé pour le nettoyage et la passivation de métaux par pulvérisation Expired EP0124851B1 (fr)

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 true EP0124851A2 (fr) 1984-11-14
EP0124851A3 EP0124851A3 (en) 1986-07-30
EP0124851B1 EP0124851B1 (fr) 1988-10-05

Family

ID=6198404

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84104860A Expired EP0124851B1 (fr) 1983-05-07 1984-04-30 Composition et procédé pour le nettoyage et la passivation de métaux par pulvérisation

Country Status (9)

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

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992003595A1 (fr) * 1990-08-24 1992-03-05 Man-Gill Chemical Company Produit nettoyant alcalin et procede servant a reduire l'oxydation de surfaces en aluminium
EP0683246A1 (fr) * 1994-05-20 1995-11-22 Betz Europe, Inc. Traitement de nettoyage et de passivation de métaux
US5668096A (en) * 1994-05-20 1997-09-16 Betzdearborn Inc. Cleaning and passivating treatment for metals
WO2002064642A1 (fr) * 2001-02-10 2002-08-22 Creavis Gesellschaft Für Technologie Und Innovation Mbh Procede de production de surfaces microbicides par immobilisation d'amino-alcools
WO2003080895A1 (fr) * 2002-03-18 2003-10-02 The Lubrizol Corporation Sels inhibiteurs de la corrosion, concentres et fluides de travail de metaux en contenant

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
WO1994003571A1 (fr) * 1992-07-31 1994-02-17 Henkel Corporation Procede et composition aqueuse pour degraisser les surfaces metalliques
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
US5705472A (en) * 1995-07-18 1998-01-06 Petroferm Inc. Neutral aqueous cleaning composition
CA2227577A1 (fr) * 1995-07-25 1997-02-13 Henkel Corporation Composition et procede de degraissage de surfaces metalliques
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
DE10154105A1 (de) 2001-11-02 2003-05-15 Henkel Kgaa Emulgatorsystem, Korrosionsschutz- und Kühlschmierstoffemulsion
US20040256595A1 (en) * 2003-06-16 2004-12-23 Seagate Technology Llc Formulation of grinding coolant
EP1580302A1 (fr) * 2004-03-23 2005-09-28 JohnsonDiversey Inc. Composition et procédé de nettoyage et d'inhibition de la corrosion pour des surfaces d'aluminium ou pour des métaux colorés et leurs alliages dans des conditions alcalines
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 (fr) * 2015-11-11 2017-05-18 Basf Se Formulations aqueuses présentant de bonnes capacités de stockage

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2921908A (en) * 1956-07-02 1960-01-19 Procter & Gamble Sequestering composition containing a corrosion inhibitor
FR2015278A1 (fr) * 1968-08-08 1970-04-24 Mo Och Domsjoe Ab
FR2118472A5 (fr) * 1970-12-18 1972-07-28 Marles Kuhlmann Wyandotte
GB1293440A (en) * 1970-09-08 1972-10-18 Frank Joseph Quattrini Improvements in or relating to scale removal solvents and processes
FR2384860A1 (fr) * 1977-03-24 1978-10-20 Henkel Kgaa Procede de nettoyage de metaux par pulverisation

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AT235149B (de) * 1961-01-11 1964-08-10 B O S A Prodotti Chimici Botta Schaumbildendes Produkt, insbesondere Schaumlöschmittel
BE612534A (fr) * 1961-01-11
US3715324A (en) * 1971-10-18 1973-02-06 G Krall Insoluble polymeric diazonium salt chromogen
FR2193871B1 (fr) * 1972-07-25 1977-07-22 Colgate Palmolive Co
US4247424A (en) * 1979-10-11 1981-01-27 The Procter & Gamble Company Stable liquid detergent compositions
US4539134A (en) * 1982-12-02 1985-09-03 Halliburton Company Methods and cleaning compositions for removing organic materials from metallic surfaces

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2921908A (en) * 1956-07-02 1960-01-19 Procter & Gamble Sequestering composition containing a corrosion inhibitor
FR2015278A1 (fr) * 1968-08-08 1970-04-24 Mo Och Domsjoe Ab
GB1293440A (en) * 1970-09-08 1972-10-18 Frank Joseph Quattrini Improvements in or relating to scale removal solvents and processes
FR2118472A5 (fr) * 1970-12-18 1972-07-28 Marles Kuhlmann Wyandotte
FR2384860A1 (fr) * 1977-03-24 1978-10-20 Henkel Kgaa Procede de nettoyage de metaux par pulverisation

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992003595A1 (fr) * 1990-08-24 1992-03-05 Man-Gill Chemical Company Produit nettoyant alcalin et procede servant a reduire l'oxydation de surfaces en aluminium
EP0683246A1 (fr) * 1994-05-20 1995-11-22 Betz Europe, Inc. Traitement de nettoyage et de passivation de métaux
US5668096A (en) * 1994-05-20 1997-09-16 Betzdearborn Inc. Cleaning and passivating treatment for metals
WO2002064642A1 (fr) * 2001-02-10 2002-08-22 Creavis Gesellschaft Für Technologie Und Innovation Mbh Procede de production de surfaces microbicides par immobilisation d'amino-alcools
WO2003080895A1 (fr) * 2002-03-18 2003-10-02 The Lubrizol Corporation Sels inhibiteurs de la corrosion, concentres et fluides de travail de metaux en contenant

Also Published As

Publication number Publication date
ES532260A0 (es) 1985-01-01
US4578208A (en) 1986-03-25
CA1231294A (fr) 1988-01-12
EP0124851A3 (en) 1986-07-30
ES8502484A1 (es) 1985-01-01
DE3316724A1 (de) 1984-11-08
MX166996B (es) 1993-02-19
EP0124851B1 (fr) 1988-10-05
ATE37728T1 (de) 1988-10-15
JPH059519B2 (fr) 1993-02-05
BR8402107A (pt) 1984-12-11
JPS59211581A (ja) 1984-11-30
DE3474463D1 (en) 1988-11-10

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