EP2671972B1 - Utilisation d'une solution contenant de l'acide phosphonique et/ou un dérivé d'acide phosphonique au dégraissage de surfaces métalliques, solution dégraissante et procédé de dégraissage d'une surface métallique - Google Patents

Utilisation d'une solution contenant de l'acide phosphonique et/ou un dérivé d'acide phosphonique au dégraissage de surfaces métalliques, solution dégraissante et procédé de dégraissage d'une surface métallique Download PDF

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Publication number
EP2671972B1
EP2671972B1 EP13168021.7A EP13168021A EP2671972B1 EP 2671972 B1 EP2671972 B1 EP 2671972B1 EP 13168021 A EP13168021 A EP 13168021A EP 2671972 B1 EP2671972 B1 EP 2671972B1
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EP
European Patent Office
Prior art keywords
degreasing
solution
phosphonic acid
surfactant
metal surface
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.)
Active
Application number
EP13168021.7A
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German (de)
English (en)
Other versions
EP2671972A1 (fr
Inventor
Sascha ROTHFELD
Gunter Neuhaus
Jürgen Kader
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.)
Stockmeier Chemie & Co KG GmbH
Original Assignee
Stockmeier Chemie & Co KG GmbH
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Publication date
Application filed by Stockmeier Chemie & Co KG GmbH filed Critical Stockmeier Chemie & Co KG GmbH
Priority to PL13168021T priority Critical patent/PL2671972T3/pl
Publication of EP2671972A1 publication Critical patent/EP2671972A1/fr
Application granted granted Critical
Publication of EP2671972B1 publication Critical patent/EP2671972B1/fr
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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
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/088—Iron or steel solutions containing organic acids

Definitions

  • the present invention relates to the use of a degreasing solution and a method for degreasing an iron or steel surface during hot-dip galvanizing or galvanic treatment of the metal surface.
  • the EP 1 310 306 A1 discloses a cleaning process that is assisted by sound waves.
  • the cleaning agent used is intended, on the one hand, to reduce hydrogen embrittlement and has a pH value greater than 4.0, in particular greater than 5.0.
  • a degreasing solution is used according to claim 1.
  • Degreasing in this case means the removal of oils or fats from the metal surface.
  • the use according to the invention can also surprisingly increase the service life of baths.
  • the solution itself can be used as a bath can be used or added to a solution in the bath during or after a degreasing process in order to adjust the salt concentration of the bath, which changes due to degreasing.
  • a particularly favorable proportion of phosphonic acid or the phosphonic acid derivative is 0.0001 to 50% by weight, based on the total amount of free acid in a solution used for degreasing or pickling, in particular the bath solution.
  • the solution containing phosphonic acid or phosphonic acid derivative has a pH of less than 4.0.
  • a degreasing solution for use in degreasing iron or steel surfaces contains a phosphonic acid and / or a phosphonic acid derivative and a surfactant.
  • the salt concentration of the solution can be adjusted by the phosphonic acid and / or the phosphonic acid derivative in such a way that the degreasing effect of the surfactant is maintained over a long period of time.
  • Such a degreasing solution can be used for a bath for degreasing a metal surface during hot-dip galvanizing, whereby a long service life of the bath is achieved.
  • the degreasing solution can also only be provided after a few degreasing passes by adding phosphonic acid or phosphonic acid derivatives to a surfactant-containing solution.
  • the degreasing solution also has one or more other acids, the solution having a pH of less than 4.0. This also helps reduce the salt concentration of the degreasing solution through precipitation.
  • the degreasing solution has a phosphonic acid content of 0.0001 to 50%, based on the amount of free acid in the degreasing solution.
  • a particularly good degreasing of a metal surface takes place with a surfactant content of 0.01 to 10% by weight.
  • the degreasing solution can additionally contain at least one solvent, an inhibitor, a solubilizer, an adjusting agent and / or a fragrance in a concentration of 0.001 to 10% by weight.
  • the degreasing solution can be used as a bath for degreasing iron steel surfaces in hot-dip galvanizing or electroplating.
  • the surfactant-containing solution can be adjusted depending on the salt content after each degreasing or after several degreasing operations, so that the service life of the surfactant-containing solution can be increased.
  • a proportion of the phosphonic acid or the phosphonic acid derivative in the solution in step c) of 0.0001 to 10% is sufficient.
  • an iron or steel surface is provided with a zinc layer, which is partially diffused into the surface. At the same time, some of the iron molecules diffuse from the iron or steel surface into the zinc layer. This is done before the actual zinc layer is applied various known preparatory steps are used, which among other things depend on the quality of the surface to be coated.
  • an abrasive surface treatment in the form of sandblasting or the like can take place in order to remove rust or paint residues from the surface.
  • a pickling treatment is carried out to remove impurities that can be traced back to the metal itself. These are, for example, oxidation products such as rust or scale.
  • the duration of the pickling process and the concentration of the pickling bath depend on the extent of the oxidation products occurring on the metal surface.
  • degreasing is also carried out in the pickling area, in which case it is called pickling degreasing.
  • fluxing can also be carried out using a layer of salt that floats on the zinc bath (so-called wet galvanizing).
  • wet galvanizing a layer of salt that floats on the zinc bath
  • the surfaces to be treated should not be dried before galvanizing.
  • the metal surface can be dried, for example in drying ovens at 80-90 ° C.
  • post-processing steps such as deburring, plastering, polishing, painting or powder coating can take place.
  • hot-dip galvanizing plants usually do not have a sewage system, but only so-called standing sinks. The substances used in hot-dip galvanizing are thus carried over into the subsequent baths. These baths are gradually used up and have to be disposed of externally. In order to minimize environmental pollution and achieve a corresponding reduction in costs, a longer service life for bathrooms should be aimed for.
  • a bath is generally considered exhausted when the iron concentration and thus the salt concentration of the degreasing solution exceeds a certain level, so that the degreasing surfactants contained in the bath and the impurities kept in solution by the surfactants are no longer stable or soluble in the degreasing solution are present.
  • the salt concentration is usually increased automatically in acidic solutions, since iron ions are inevitably dissolved in the degreasing solution with every degreasing process.
  • a known way of increasing the service life is the use of phosphoric acid.
  • iron phosphates are precipitated, as a result of which the iron concentration and thus also the salt concentration of the solution - based on the ions in solution - are reduced overall.
  • the subject matter of the present invention takes an alternative route by adding a cleaning agent or a solution containing a phosphonic acid or a phosphonic acid derivative to the degreasing solution.
  • the addition of the cleaning agent containing phosphonic acid derivatives surprisingly forms a precipitate which, on the one hand, binds the excess iron.
  • organic contaminants are removed from the bath.
  • Such a phosphonic acid derivative is preferably HEDP (1-hydroxyethane (1,1-diphosphonic acid), HEMPA (hexamethylene diamine tetra (methylene phosphonic acid)), HDTMP (hexaethylene diamine tetramethylene phosphonic acid), ATMP (aminotrimethylene phosphonic acid), methylene diamine phosphonic acid, EDTMP (ethylene diamine phosphonic acid), EDTMP (ethylene diamine phosphonic acid) (Diethylenetriaminepenta (methylenephosphonic acid)) and / or PBTC (2-phosphonobutane-1,2,4-tricarboxylic acid).
  • HEMPA hexamethylene diamine tetra (methylene phosphonic acid)
  • HDTMP hexaethylene diamine tetramethylene phosphonic acid
  • ATMP aminotrimethylene phosphonic acid
  • EDTMP ethylene diamine phosphonic acid
  • EDTMP ethylene diamine phosphonic acid
  • a preferred dosage of a phosphonic acid derivative can adjust the iron content in the solution of the bath, which practically leads to an almost unlimited service life of the bath.
  • the phosphonic acid derivative can be a derivative of a simple or complex phosphonic acid.
  • the detergent added has a pH value of less than 4.0.
  • the degreasing solution made from the cleaning agent is used for degreasing an iron or steel surface during hot-dip galvanizing or during the galvanic treatment of metal surfaces.
  • the concentration of phosphonic acid or a phosphonic acid derivative in the degreasing solution is preferably 0.0001 to 50%, in particular 0.1 to 10%, based on the amount of free acid present in the degreasing solution.
  • the degreasing solution always contains at least one acid.
  • a phosphonic acid can also be added separately to an existing cleaning solution for metal precipitation.
  • phosphonic acid or a phosphonic acid derivative of preferably 0.0001 to 10%, in particular 0.01 to 1%, based on the amount of free acid present, can be added in added to the degreasing solution.
  • a mineral acid and / or an organic acid can also be added in order to achieve increased cleaning or precipitation.
  • Preferred mineral acids are hydrochloric acid, sulfuric acid, phosphoric acid and / or nitric acid.
  • Preferred organic acids are oxalic acid, tartaric acid, citric acid and / or acetic acid.
  • the concentration of the mineral acid and / or organic acid in the degreasing solution is preferably 0.1 to 90% by weight, based on the total weight of the solution.
  • the degreasing solution contains surfactants, in particular nonionic, anionic and / or cationic surfactants, a proportion of phosphonic acid or phosphonic acid derivative having a particularly positive effect on the solubility of nonionic surfactants, in particular in a particularly preferred concentration of 0.01 to 10 wt. %, in particular 0.1-1% by weight based on the total weight of the degreasing solution.
  • surfactants in particular nonionic, anionic and / or cationic surfactants
  • a proportion of phosphonic acid or phosphonic acid derivative having a particularly positive effect on the solubility of nonionic surfactants in particular in a particularly preferred concentration of 0.01 to 10 wt. %, in particular 0.1-1% by weight based on the total weight of the degreasing solution.
  • the degreasing solution can also contain inhibitors in order to minimize the absorption of iron ions from the treated metal surfaces.
  • Inhibitors on the one hand, reduce the uptake of metal and, on the other hand, reduce the formation of hydrogen and, in some cases, are also intended to reduce the diffusion of hydrogen into the metal structure.
  • the service life of pickling is increased because the metal content then increases more slowly. That is why the inhibitor-containing pickling solutions are sometimes also referred to as economy pickling.
  • the inhibitors are usually substances which cover the metal surface with a coating, sometimes a monomolecular film.
  • inhibitors are unsaturated diols such as butynediol or its derivatives, organic sulfur compounds such as thiourea or its derivatives or nitrogen-containing compounds such as hexamethylenetetramine or quaternary nitrogen compounds or other inhibitors. These are present in a concentration of 0.01-1% by weight, based on the total weight of the solution.
  • Further preferred additives to the degreasing solution are solvents, solubilizers, adjusting agents and / or fragrances, each in a preferred concentration of 0.001 to 10% by weight, in particular in a concentration of 0.01 to 5% by weight.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Claims (7)

  1. Application d'une solution dégraissante pour dégraisser des surfaces de fer ou d'acier, galvanisées à chaud ou un traitement galvanique,
    caractérisée en ce que
    la solution dégraissante contient de l'acide phosphonique et/ou un dérivé d'acide phosphonique et un agent tensio-actif dégraissant,
    la solution dégraissante contient un autre acide et elle a un pH inférieur à 4,0.
  2. Application selon la revendication 1,
    caractérisée en ce que
    la solution dégraissante a une teneur en acide phosphonique comprise entre 0,0001-50% rapportée à la quantité d'acide libre dans la solution dégraissante.
  3. Application selon l'une des revendications précédentes,
    caractérisée en ce que
    la solution dégraissante a une teneur en agent tensio-actif comprise en 0,01-10% pondéraux.
  4. Application selon l'une des revendications précédentes,
    caractérisée en ce que
    la solution dégraissante contient en plus au moins un solvant, un inhibiteur, un détachant, un agent de fixation et/ou un parfum avec une concentration de 0,001-10% pondéraux.
  5. Application selon l'une des revendications précédentes,
    caractérisée en ce que
    la concentration d'inhibiteur, de la solution dégraissante contenant un inhibiteur pour minimiser la prise d'ions de fer de la surface métallique traitée, se situe entre 0,01 et 1% pondéraux par rapport au poids total de la solution.
  6. Procédé de dégraissage d'une surface de fer ou d'acier galvanisée à chaud ou ayant subi un traitement galvanique de la surface métallique, procédé caractérisé par les étapes suivantes consistant à :
    a) disposer d'une solution contenant un agent tensio-actif, ayant un pH inférieur à 4,0 pour dégraisser la surface du métal,
    b) dégraisser la surface du métal en appliquant la solution contenant un agent tensio-actif, et
    c) ajouter une solution d'acide phosphonique et/ou contenant des dérivés d'acide phosphonique ayant un pH inférieur à 4,0 pendant ou après le dégraissage de la surface du métal, à la solution d'agent tensio-actif pour réduire la teneur en ions métal de la solution,
    la solution formée ayant en plus de l'acide phosphonique ou du dérivé d'acide phosphonique, un ou plusieurs autres acides.
  7. Procédé selon la revendication 6,
    caractérisé en ce que
    la teneur en acide phosphonique ou en dérivés d'acide phosphonique dans la solution selon l'étape c) est comprise entre 0,0001-50% pondéraux par rapport à la quantité totale d'acide libre dans la solution utilisée pour le dégraissage ou l'enlèvement de décapant.
EP13168021.7A 2012-06-08 2013-05-16 Utilisation d'une solution contenant de l'acide phosphonique et/ou un dérivé d'acide phosphonique au dégraissage de surfaces métalliques, solution dégraissante et procédé de dégraissage d'une surface métallique Active EP2671972B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL13168021T PL2671972T3 (pl) 2012-06-08 2013-05-16 Zastosowanie roztworu zawierającego kwas fosfonowy i/lub pochodną kwasu fosfonowego przy odtłuszczaniu powierzchni metalu, roztwór odtłuszczający i sposób odtłuszczania powierzchni metalu

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102012104951A DE102012104951A1 (de) 2012-06-08 2012-06-08 Verwendung einer phosphonsäure- und/oder phosphonsäurederivathaltigen Lösung bei der Entfettung von Metalloberflächen, entfettende Lösung und Verfahren zur Entfettung einer Metalloberfläche

Publications (2)

Publication Number Publication Date
EP2671972A1 EP2671972A1 (fr) 2013-12-11
EP2671972B1 true EP2671972B1 (fr) 2021-05-05

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EP13168021.7A Active EP2671972B1 (fr) 2012-06-08 2013-05-16 Utilisation d'une solution contenant de l'acide phosphonique et/ou un dérivé d'acide phosphonique au dégraissage de surfaces métalliques, solution dégraissante et procédé de dégraissage d'une surface métallique

Country Status (4)

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EP (1) EP2671972B1 (fr)
DE (1) DE102012104951A1 (fr)
ES (1) ES2871404T3 (fr)
PL (1) PL2671972T3 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104862719A (zh) * 2015-03-12 2015-08-26 浏阳市三鹰新材料有限责任公司 一种环保型多功能高效酸洗抑雾缓蚀剂

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0789094A1 (fr) * 1994-10-21 1997-08-13 Nippon Paint Co., Ltd. Solution aqueuse et acide servant a nettoyer de l'aluminium et methode de nettoyage afferente

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1216066B (de) * 1963-01-29 1966-05-05 Henkel & Cie Gmbh Verfahren zur Behandlung von entfetteten und mit einer sauren Loesung gebeizten Metallober-flaechen vor dem Emaillieren
DE10154922B4 (de) * 2001-11-08 2004-04-01 Benteler Automobiltechnik Gmbh Verfahren zur Reinigung von metallischen Bauteilen
ES2393813T3 (es) * 2007-04-04 2012-12-28 Henkel Ag & Co. Kgaa Detergente o agente de lavado que contiene un medio de blanqueo
DE102007042859A1 (de) * 2007-09-10 2009-03-12 Henkel Ag & Co. Kgaa Reinigungsverfahren

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0789094A1 (fr) * 1994-10-21 1997-08-13 Nippon Paint Co., Ltd. Solution aqueuse et acide servant a nettoyer de l'aluminium et methode de nettoyage afferente

Also Published As

Publication number Publication date
DE102012104951A1 (de) 2013-12-12
ES2871404T3 (es) 2021-10-28
PL2671972T3 (pl) 2021-11-02
EP2671972A1 (fr) 2013-12-11

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