EP1097255B1 - Process of pre-treating a metallic workpiece before painting - Google Patents
Process of pre-treating a metallic workpiece before painting Download PDFInfo
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- EP1097255B1 EP1097255B1 EP99931072A EP99931072A EP1097255B1 EP 1097255 B1 EP1097255 B1 EP 1097255B1 EP 99931072 A EP99931072 A EP 99931072A EP 99931072 A EP99931072 A EP 99931072A EP 1097255 B1 EP1097255 B1 EP 1097255B1
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- European Patent Office
- Prior art keywords
- workpiece
- solution
- polyaspartic acid
- acid
- painted
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- 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.)
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- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/50—Treatment of iron or alloys based thereon
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/56—Treatment of aluminium or alloys based thereon
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- 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
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- 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
Definitions
- the invention relates to a method for pretreating a metallic Workpiece for painting, the surface to be painted using a Solution containing degreasing agent cleaned and with a corrosion-resistant layer is coated.
- the surfaces of metallic workpieces to be painted are before painting to clean and degrease the necessary for permanent painting Requirements for good paint adhesion on the workpiece surface create.
- the surfaces of the Workpiece with an appropriate degreasing solution treated which is either sprayed onto the surfaces to be painted or which serves as an immersion bath for the workpiece.
- the workpieces after rinsing to improve corrosion resistance phosphated Following this degreasing the workpieces after rinsing to improve corrosion resistance phosphated.
- the workpiece surface becomes oxidative due to the phosphating attacked, causing a slight removal of a surface covering layer comes The associated roughening of the surface improves the adhesion of the varnish applied later.
- To the oxidative surface reaction too finish the workpiece surface in a further treatment step passivated, so that there is an overall laborious pretreatment of the workpiece results
- the amino acid group can contain aspartic acid among others. If a comparatively low pH of at most 7, those with a such solution treated metallic surface cleaned of corrosion , but this does not result in any corrosion protection required for subsequent painting reached.
- the invention is therefore based on the object of a method for pretreatment a metallic workpiece for painting the type described above to design that the procedural effort can be significantly reduced, without affecting paint adhesion or endangering corrosion protection.
- the invention relates to a method for pretreating a metallic Workpiece for painting, the surface to be painted using a Solution containing degreasing agent cleaned and with a Corrosion-resistant layer is coated, characterized in that the varnishing surface of the workpiece to apply a corrosion-inhibiting Layer is treated with a solution of polyaspartic acid.
- the solution containing a degreasing agent is preferably an aqueous solution of a so-called neutral cleaner or an alkaline Cleaner.
- Neutral cleaners usually have a pH in the range between about 7 and about 9 and contain nonionic surfactants as degreasing agents.
- Alkaline cleaners are made by adding alkalis or alkaline Builder substances adjusted to pH values above 8.5.
- As a degreasing agent preferably contain anionic surfactants.
- polyaspartic acid or one Aspartic acid-containing copolymer it is meant that the Solution containing free acid and / or acid anions. As is known, it is one Question of the pH of the solution, what ratio of free acid to Acid anions appear.
- the aspartic acid units in polyaspartic acid can by so-called ⁇ or so-called ⁇ linkage with each other be connected. as a rule, both lie within one polymer strand Link types next to each other. For the present invention that is Ratio of ⁇ - to ⁇ -linkages insignificant.
- An aspartic acid containing Copolymer is a copolymer in addition to aspartic acid units contains further monomeric assemblies. These can have other amino acids, however also represent polymerizable other carboxylic acids. Preferably you bet Copolymers containing at least 50 mol%, preferably at least 80 mol% consist of aspartic acid.
- the metal surface coated with a layer of polyaspartic acid can be painted immediately. This means that between treatment with the Solution containing aspartic acid and the painting, if necessary rinsing steps, however, no other processes such as transporting the workpieces another processing facility, forming or joining processes.
- the treatment described with the solution containing polyaspartic acid can also be used as a temporary corrosion protection measure. This means that they unite the metal surface even without immediate painting gives adequate corrosion protection to the metal workpieces in front of the Transporting, storing, reshaping or joining paint. Find such Processes takes place, is a post-treatment immediately before the final painting with a further solution to reinforce or extend the in step b) corrosion protection effect achieved.
- This can be, for example are phosphating, treatment with a solution of chromium compounds, a solution of complex fluorides of boron, silicon, titanium and / or Zircon and / or a solution or dispersion of other organic polymers.
- a solution of chromium compounds a solution of complex fluorides of boron, silicon, titanium and / or Zircon and / or a solution or dispersion of other organic polymers.
- the surface of the workpiece to be painted for simultaneous degreasing and coating with a solution of polyaspartic acid or an aspartic acid-containing polymer and a degreasing agent is treated.
- the solution preferably contains a degreasing agent on the basis of iminodisuccinic acid sodium salt.
- the polyaspartic acid works for the detach the sodium iminosuccinic acid salt from the workpiece surface Fat particles as a dispersant, so that the detached fat particles through this Dispersant kept in dispersion and prevented from re-entering the To set down the workpiece surface.
- polyaspartic acid does not bring only one Dispersion effect for the fat particles with it, but also requires one Particularly advantageous in terms of the imparting of adhesion, corrosion-inhibiting Surface layer, which are advantageous conditions for a creates permanent paint, especially since the iminodisuccinic acid sodium salt for one appropriate roughening of the workpiece surface ensures.
- the weight ratio of polyaspartic acid to iminodisuccinic acid sodium salt should be between 10: 1 and 1:10, with a minimum concentration of polyaspartic acid of 2% in the solution to adjust the to achieve the desired effects.
- the iminodisuccinic acid sodium salt Corresponding additives can of course be added, e.g. B. wetting agents or the like
- the corrosion protection achieved when degreasing with iminodisuccinic acid sodium salt can be reinforced if necessary, that the surface to be painted of the workpiece after degreasing another treatment in a 10 to 40 percent solution of the polyaspartic acid is subjected to the coating with the organic polymer caused by the polyaspartic acid.
- the solution obtained from this aftertreatment also be subjected to membrane filtration to the polyaspartic acid after removal of unwanted loads again for the workpiece treatment to be able to use.
- the system has pretreatment a metallic workpiece, in particular made of sheet metal, a plunge pool 1 for the Workpiece treatment on with an aqueous solution of a degreasing agent based on iminodisuccinic acid sodium salt and a polyaspartic acid is filled.
- the workpieces to be treated are immersed in this basin 1, to clean and degrease them on the one hand and with a corrosion-inhibiting, to coat organic polymer layer.
- the through the use of Iminodisuccinic acid sodium salt dissolved fats and impurities are in the Bad kept in dispersion by the polyaspartic acid because the Polyaspartic acid acts as a dispersant.
- Dip tank 1 connected to a membrane filter device 2, via the in particular the fat particles can be separated from the solution.
- the Retentate is discharged from the membrane filter device 2 via a drain 3, while the permeate, the organic degreasing agent and Polyaspartic acid contains the via a return line 4 in the circuit again Plunge pool 1 is supplied.
- the ongoing bath losses are over a Supply line 5 replaced, about the fresh solution of the degreasing agent and Polyaspartic acid can be refilled.
- the invention is not is limited to the illustrated embodiment.
- a conventional spray treatment the only decisive factor is that for corrosion protection and the improvement of Adhesion of the paint a polyaspartic acid is used, namely advantageous in combination with a degreasing agent based on Iminodisuccinic sodium salt.
- the treatment the metal surface with polyaspartic acid or containing an aspartic acid Copolymer as a measure for temporary corrosion protection used.
- Processing processes such as forming or joining (welding, Flanging). Forming processes through the polymer layer relieved on the metal surface After such processes the Metal surface usually dirty, so that it is before the final Corrosion protection treatment must be cleaned again.
- the previous one Coating with polyaspartic acid or a containing polyaspartic acid Polymer has the advantage that in such a subsequent cleaning step the impurities can be removed more easily.
- the surface to be painted is then coated with another one before painting Treated solution that creates a conversion layer on the surface.
- this can be a layer-forming phosphating, such as in particular in the automotive industry and in the household appliance industry is common.
- phosphating instead of phosphating, one can Chromating, treatment with a solution of complex fluorides, in particular the elements boron, silicon, titanium and / or zirconium, and / or one Other organic polymers are used.
- Polymers can be, for example, polymers or copolymers of Acrylic acid or methacrylic acid or around polyvinylphenols.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Chemical Treatment Of Metals (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
Die Erfindung bezieht sich auf ein Verfahren zur Vorbehandlung eines metallischen Werkstücks für eine Lackierung, dessen zu lackierende Oberfläche mit Hilfe einer Entfettungsmittel enthaltenden Lösung gereinigt und mit einer korrosionshemmenden Schicht überzogen wird.The invention relates to a method for pretreating a metallic Workpiece for painting, the surface to be painted using a Solution containing degreasing agent cleaned and with a corrosion-resistant layer is coated.
Die zu lackierenden Oberflächen metallischer Werkstücke sind vor einer Lackierung zu reinigen und zu entfetten, um die für eine dauerhafte Lackierung notwendigen Voraussetzungen für eine gute Lackhaftung auf der Werkstückoberfläche zu schaffen. Zu diesem Zweck werden die zu lackierenden Oberflächen des Werkstücks mit einer entsprechende Entfettungsmittel enthaltenden Lösung behandelt, die entweder auf die zu lackierenden Oberflächen aufgespritzt wird oder die als Tauchbad für das Werkstück dient. Im Anschluß an diese Entfettung werden die Werkstücke nach einer Spülung zur Verbesserung der Korrosionsbeständigkeit phosphatiert. Durch die Phosphatierung wird die Werkstückoberfläche oxidativ angegriffen, wobei es zu einem geringfügigen Abtrag einer Oberflächendeckschicht kommt Die damit verbundene Aufrauhung der Oberfläche verbessert die Haftung des später aufgebrachten Lackes. Um die oxidative Oberflächenreaktion zu beenden, wird die Werkstückoberfläche in einem weiteren Behandlungsschritt passiviert, so daß sich eine insgesamt autwendige Vorbehandlung des Werkstücks ergibtThe surfaces of metallic workpieces to be painted are before painting to clean and degrease the necessary for permanent painting Requirements for good paint adhesion on the workpiece surface create. For this purpose, the surfaces of the Workpiece with an appropriate degreasing solution treated, which is either sprayed onto the surfaces to be painted or which serves as an immersion bath for the workpiece. Following this degreasing the workpieces after rinsing to improve corrosion resistance phosphated. The workpiece surface becomes oxidative due to the phosphating attacked, causing a slight removal of a surface covering layer comes The associated roughening of the surface improves the adhesion of the varnish applied later. To the oxidative surface reaction too finish the workpiece surface in a further treatment step passivated, so that there is an overall laborious pretreatment of the workpiece results
Um Weicheisenoberflächen vor einem Korrosionsangriff durch Salzwasser zu schützen, ist es bekannt (WO 96127696), dem Salzwasser vergleichsweise geringe Mengen an Polyasparaginsäure zuzumischen. Die korrosionshemmende Wirkung von Polyasparaginsäure und Polyasparaginpolymeren aus Polyasparaginsäure sowie deren Salz oder Amid wird auch bei Kühl- und Schmiermitteln für die spanabhebende Bearbeitung von Werkstücken ausgenützt (WO 95/10583, WO 95/24456). Solche korrosionshemmenden Zusätze zu Flüssigkeiten, die metallische Oberflächen korrosiv angreifen, können jedoch keine Lehre dafür geben, wie Oberflächen metallischer Werkstücke für eine dauerhafte Lackierung behandelt werden müssen.To protect soft iron surfaces from corrosion by salt water, it is known (WO 96127696) that the salt water is comparatively low Mix amounts of polyaspartic acid. The corrosion-inhibiting effect of polyaspartic acid and polyaspartic polymers from polyaspartic acid as well as their salt or amide is also used in coolants and lubricants for the machining of workpieces used (WO 95/10583, WO 95/24456). Such corrosion-inhibiting additives to liquids, the metallic Attacking surfaces corrosively, however, cannot teach how Surfaces of metallic workpieces treated for permanent painting Need to become.
Schließlich ist es bekannt (WO 95/24456), zur Reinigung einer metallischen Oberfläche eine wäßrige Lösung einer Polyaminosäure vorzusehen, deren Aminosäure-Gruppe unter anderem Asparaginsäure enthalten kann. Bei Einhaltung eines vergleichsweise niedrigen pH-Wertes von höchstens 7 können zwar die mit einer solchen Lösung behandelten metallischen Oberfläche von Korrosionen gereinigt werden, doch wird dadurch kein für eine spätere Lackierung erforderlicher Korrosionsschutz erreicht.Finally, it is known (WO 95/24456) for cleaning a metallic Surface to provide an aqueous solution of a polyamino acid, the amino acid group can contain aspartic acid among others. If a comparatively low pH of at most 7, those with a such solution treated metallic surface cleaned of corrosion , but this does not result in any corrosion protection required for subsequent painting reached.
Der Erfindung liegt somit die Aufgabe zugrunde, ein Verfahren zur Vorbehandlung eines metallischen Werkstücks für eine Lackierung der eingangs geschilderten Art so auszugestalten, daß der Verfahrensaufwand erheblich herabgesetzt werden kann, ohne die Lackhaftung zu beeinträchtigen oder den Korrosionsschutz zu gefährden.The invention is therefore based on the object of a method for pretreatment a metallic workpiece for painting the type described above to design that the procedural effort can be significantly reduced, without affecting paint adhesion or endangering corrosion protection.
Die Erfindung betrifft ein Verfahren zur Vorbehandlung eines metallischen Werkstücks für eine Lackierung, dessen zu lackierende Oberfläche mit Hilfe einer Entfettungsmittel enthaltenden Lösung gereinigt und mit einer korrosionshemmenden Schicht überzogen wird, dadurch gekennzeichnet, daß die zu lackierende Oberfläche des Werkstücks zum Auftragen einer korrosionshemmenden Schicht mit einer Lösung von Polyasparaginsäure behandelt wird.The invention relates to a method for pretreating a metallic Workpiece for painting, the surface to be painted using a Solution containing degreasing agent cleaned and with a Corrosion-resistant layer is coated, characterized in that the varnishing surface of the workpiece to apply a corrosion-inhibiting Layer is treated with a solution of polyaspartic acid.
Bei der ein Enffettungsmittel enthaltenden Lösung handelt es sich vorzugsweise um eine wäßrige Lösung eines sogenannten Neutralreinigers oder eines alkalischen Reinigers. Neutralreiniger weisen in der Regel einen pH-Wert im Bereich zwischen etwa 7 und etwa 9 auf und enthalten als Enffettungsmittel nichtionische Tenside. Alkalische Reiniger sind durch Zugabe von Alkalien oder alkalisch wirkenden Buildersubstanzen auf pH-Werte oberhalb von 8,5 eingestellt. Als Entfettungsmittel enthalten Sie vorzugsweise anionische Tenside. The solution containing a degreasing agent is preferably an aqueous solution of a so-called neutral cleaner or an alkaline Cleaner. Neutral cleaners usually have a pH in the range between about 7 and about 9 and contain nonionic surfactants as degreasing agents. Alkaline cleaners are made by adding alkalis or alkaline Builder substances adjusted to pH values above 8.5. As a degreasing agent preferably contain anionic surfactants.
Wenn hier und im folgenden von einer Lösung von Polyasparaginsäure oder eines Asparaginsäure-enthaltenden Copolymers die Rede ist, so ist damit gemeint, daß die Lösung die freie Säure und/oder Säureanionen enthält. Bekanntermaßen ist es eine Frage des pH-Wertes der Lösung, welches Verhältnis von freier Säure zu Säureanionen sich einstellt. Die Asparaginsäure-Einheiten in Polyasparaginsäure können durch sogenannte α- oder sogenannte β-Verknüpfung miteinander verbunden sein. in der Regel liegen innerhalb eines Polymerstrangs beide Verknüpfungstypen nebeneinander vor. Für die vorliegende Erfindung ist das Verhältnis von α- zu β-Verknüpfungen unwesentlich. Ein Asparaginsäure-enthaltendes Copolymer ist ein Copolymer, das neben Asparaginsäure-Einheiten weitere monomere Baugruppen enthält. Diese können andere Aminosäuren, jedoch auch polymerisierbare andere Carbonsäuren darstellen. Vorzugsweise setzt man Copolymere ein, die zu mindestens 50 Mol.-%, vorzugsweise zu mindestens 80 Mol-% aus Asparaginsäure bestehen.If here and below from a solution of polyaspartic acid or one Aspartic acid-containing copolymer is mentioned, it is meant that the Solution containing free acid and / or acid anions. As is known, it is one Question of the pH of the solution, what ratio of free acid to Acid anions appear. The aspartic acid units in polyaspartic acid can by so-called α or so-called β linkage with each other be connected. as a rule, both lie within one polymer strand Link types next to each other. For the present invention that is Ratio of α- to β-linkages insignificant. An aspartic acid containing Copolymer is a copolymer in addition to aspartic acid units contains further monomeric assemblies. These can have other amino acids, however also represent polymerizable other carboxylic acids. Preferably you bet Copolymers containing at least 50 mol%, preferably at least 80 mol% consist of aspartic acid.
Wenn in der folgenden Beschreibung kurz von Polyasparaginsäure die Rede ist, so ist damit sowohl Polyasparaginsäure als auch ein Asparaginsäure-enthaltendes Copolymer gemeint.If the following description briefly speaks of polyaspartic acid, then is both polyaspartic acid and an aspartic acid-containing Copolymer meant.
Durch die Behandlung der zu lackierenden Oberfläche des Werkstücks mit einer Lösung von Polyasparaginsäure kann die Werkstückoberfläche mit einem dünnen organischen Film aus einem organischen Polymer belegt werden, dessen verzweigte Struktur nicht nur eine gute Verbindung zum Untergrund, sondern auch eine gute Haftvermittlung zum Lack sicherstellt. Der Einsatz einer Polyasparaginsäure für die Vorbehandlung eines zu lackierenden, metallischen Werkstücks, das in üblicher Weise in einem Tauch- bzw. Spritzverfahren mit der Polyasparaginsäurelösung behandelt werden kann, bringt somit den Vorteil mit sich, daß im Vergleich zu einer Phosphatierung ein der Passivierung entsprechender Behandlungsschritt entfällt, so daß die durch eine unzureichende Passivierung gegebene Korrosionsgefährdung ausgeschlossen werden kann. By treating the surface of the workpiece to be painted with a Solution of polyaspartic acid can thin the workpiece surface organic film can be covered from an organic polymer, the branched Structure not only a good connection to the underground, but also a good one Guarantees adhesion to the paint. The use of a polyaspartic acid for the Pretreatment of a metallic workpiece to be painted, which is in the usual Way in a dipping or spraying process with the polyaspartic acid solution can be treated, therefore has the advantage that compared to a Phosphating does not apply to a treatment step corresponding to the passivation that the corrosion hazard posed by inadequate passivation can be excluded.
Die mit einer Schicht von Polyasparaginsäure überzogene Metalloberfläche kann unmittelbar lackiert werden. Damit ist gemeint, daß zwischen der Behandlung mit der Asparaginsäure-enthaltenden Lösung und der Lackierung allenfalls Spülschritte, jedoch keine weiteren Vorgänge wie beispielsweise Transport der Werkstücke zu einer weiteren Verarbeitungsstätte, Umformungs- oder Fügeprozesse stattfinden. Die beschriebene Behandlung mit der Polyasparaginsäure-enthaltenden Lösung kann jedoch auch als temporäre Korrosionsschutzmaßnahme eingesetzt werden. Dies heißt, daß sie der Metalloberfläche auch ohne unmittelbare Lackierung einen hinreichenden Korrossionsschutz verleiht, um die metallischen Werkstücke vor der Lackierung zu transportieren, zu lagern, umzuformen oder zu fügen. Finden solche Prozesse statt, ist unmittelbar vor der endgültigen Lackierung eine Nachbehandlung mit einer weiteren Lösung zur Verstärkung oder Verlängerung der im Teilschritt b) erzielten Korrosionsschutzwirkung vorzuziehen. Hierbei kann es sich beispielsweise handeln um eine Phosphatierung, eine Behandlung mit einer Lösung von Chromverbindungen, einer Lösung von komplexen Fluoriden von Bor, Silizium, Titan und/oder Zirkon und/oder einer Lösung oder Dispersion weiterer organischer Polymere. Dabei kann das Werkstück vor dieser Nachbehandlung nochmals gereinigt werden.The metal surface coated with a layer of polyaspartic acid can be painted immediately. This means that between treatment with the Solution containing aspartic acid and the painting, if necessary rinsing steps, however, no other processes such as transporting the workpieces another processing facility, forming or joining processes. The treatment described with the solution containing polyaspartic acid can also be used as a temporary corrosion protection measure. This means that they unite the metal surface even without immediate painting gives adequate corrosion protection to the metal workpieces in front of the Transporting, storing, reshaping or joining paint. Find such Processes takes place, is a post-treatment immediately before the final painting with a further solution to reinforce or extend the in step b) corrosion protection effect achieved. This can be, for example are phosphating, treatment with a solution of chromium compounds, a solution of complex fluorides of boron, silicon, titanium and / or Zircon and / or a solution or dispersion of other organic polymers. there the workpiece can be cleaned again before this post-treatment.
Besonders vorteilhafte Verhältnisse ergeben sich in diesem Zusammenhang, wenn in weiterer Ausbildung der Erfindung die zu lackierende Oberfläche des Werkstücks zum gleichzeitigen Entfetten und Beschichten mit einer Lösung von Polyasparaginsäure oder einem Asparaginsäure-enthaltenden Polymer und einem Entfettungsmittel behandelt wird. In diesem Fall kann nämlich in einem einzigen Behandlungsschritt sowohl für die Entfettung als auch für einen entsprechenden Korrosionsschutz gesorgt werden. Vorzugsweise enthält die Lösung ein Enffettungsmittel auf der Basis von Iminodibernsteinsäure-Natriumsalz. Die Polyasparaginsäure wirkt für die durch das lminodibemsteinsäure-Natriumsalz von der Werkstückoberfläche abgelösten Fetteilchen als Dispergiermittel, so daß die abgelösten Fetteilchen durch diesen Dispergator in Dispersion gehalten und daran gehindert werden, sich erneut auf der Werkstückoberfläche abzusetzen. Die Polyasparaginsäure bringt aber nicht nur eine Dispergierwirkung für die Fetteilchen mit sich, sondern bedingt auch eine insbesondere hinsichtlich der Haftvermittlung besonders vorteilhafte, korrosionshemmende Oberflächenschicht, was vorteilhafte Voraussetzungen für eine dauerhafte Lackierung schafft, zumal das Iminodibernsteinsäure-Natriumsalz für eine entsprechende Aufrauhung der Werkstückoberfläche sorgt.In this context, particularly advantageous conditions arise if in a further embodiment of the invention, the surface of the workpiece to be painted for simultaneous degreasing and coating with a solution of polyaspartic acid or an aspartic acid-containing polymer and a degreasing agent is treated. In this case, namely, in a single treatment step both for degreasing and for appropriate corrosion protection be taken care of. The solution preferably contains a degreasing agent on the basis of iminodisuccinic acid sodium salt. The polyaspartic acid works for the detach the sodium iminosuccinic acid salt from the workpiece surface Fat particles as a dispersant, so that the detached fat particles through this Dispersant kept in dispersion and prevented from re-entering the To set down the workpiece surface. But polyaspartic acid does not bring only one Dispersion effect for the fat particles with it, but also requires one Particularly advantageous in terms of the imparting of adhesion, corrosion-inhibiting Surface layer, which are advantageous conditions for a creates permanent paint, especially since the iminodisuccinic acid sodium salt for one appropriate roughening of the workpiece surface ensures.
Das Gewichtsverhältnis von Polyasparaginsäure zu Iminodibernsteinsäure-Natriumsalz soll dabei zwischen 10 : 1 und 1 : 10 betragen, wobei eine Mindestkonzentration an Polyasparaginsäure von 2 % in der Lösung einzustellen ist, um die angestrebten Wirkungen zu erzielen. Dem Iminodibernsteinsäure-Natriumsalz können selbstverständlich entsprechende Zusätze beigemischt werden, z. B. Benetzungsmittel od. dgl.The weight ratio of polyaspartic acid to iminodisuccinic acid sodium salt should be between 10: 1 and 1:10, with a minimum concentration of polyaspartic acid of 2% in the solution to adjust the to achieve the desired effects. The iminodisuccinic acid sodium salt Corresponding additives can of course be added, e.g. B. wetting agents or the like
Wird die mit den von der Werkstückoberfläche abgelösten Fetten belastete Lösung des Iminodibernsteinsäure-Natriumsalzes und der Polyasparaginsäure einer Membranfiltration unterworfen, so können die abgelösten Fette und Verunreinigungen abgeschieden und die Lösung des Iminodibernsteinsäure-Natriumsalzes und der Polyasparaginsäure zur Werkstückbehandlung rückgeführt werden. Die Lösung des organischen Enffettungsmittels und der Polyasparaginsäure durchsetzen nämlich die Membranfilter als Permeat, während die Fette und Verunreinigungen als Retentat abgeschieden und entsorgt werden können. Die vom Iminodibernsteinsäure-Natriumsalz aus der Werkstückoberfläche gelösten Metallionen können dann aus dem Permeat abgeschieden werden, um eine Aufkonzentrierung dieser Metallionen zu vermeiden.Becomes the solution loaded with the greases detached from the workpiece surface of iminodisuccinic acid sodium salt and polyaspartic acid of a membrane filtration subject to detached fats and contaminants deposited and the solution of the iminodisuccinic acid sodium salt and Polyaspartic acid can be recycled for workpiece treatment. The solution of the organic degreasing agent and polyaspartic acid namely enforce the Membrane filters as permeate, while fats and contaminants as retentate can be separated and disposed of. The iminodisuccinic acid sodium salt Metal ions released from the workpiece surface can then escape the permeate are deposited to concentrate these metal ions to avoid.
Der bei der Entfettung mit Iminodibemsteinsäure-Natriumsalz erreichte Korrosionsschutz kann bei Bedarf dadurch verstärkt werden, daß die zu lackierende Oberfläche des Werkstücks nach dem Enffetten einer weiteren Behandlung in einer 10 bis 40 prozentigen Lösung der Polyasparaginsäure unterworfen wird, um die Beschichtung mit dem durch die Polyasparaginsäure bedingten organischen Polymer zu verbessern. Selbstverständlich kann die aus dieser Nachbehandlung anfallende Lösung ebenfalls einer Membranfiltration unterworfen werden, um die Polyasparaginsäure nach einem Abscheiden von unerwünschten Belastungen wieder für die Werkstückbehandlung einsetzen zu können. The corrosion protection achieved when degreasing with iminodisuccinic acid sodium salt can be reinforced if necessary, that the surface to be painted of the workpiece after degreasing another treatment in a 10 to 40 percent solution of the polyaspartic acid is subjected to the coating with the organic polymer caused by the polyaspartic acid. Of course, the solution obtained from this aftertreatment also be subjected to membrane filtration to the polyaspartic acid after removal of unwanted loads again for the workpiece treatment to be able to use.
Anhand der Zeichnung wird das erfindungsgemäße Verfahren näher erläutert, und zwar wird eine Anlage zur Durchführung des Verfahrens in einem schematischen Blockschaltbild gezeigt.The method according to the invention is explained in more detail with reference to the drawing, and although a plant for performing the method is shown in a schematic Block diagram shown.
Gemäß dem dargestellten Ausführungsbeispiel weist die Anlage zur Vorbehandlung
eines metallischen Werkstückes, insbesondere aus Blech, ein Tauchbecken 1 für die
Werkstückbehandlung auf, das mit einer wäßrigen Lösung eines Entfettungsmittels
auf der Basis von Iminodibernsteinsäure-Natriumsalz und einer Polyasparaginsäure
gefüllt ist. In dieses Becken 1 werden die zu behandelnden Werkstücke eingetaucht,
um sie einerseits zu reinigen und zu entfetten und anderseits mit einer korrosionshemmenden,
organischen Polymerschicht zu überziehen. Die durch den Einsatz von
Iminodibernsteinsäure-Natriumsalz gelösten Fette und Verunreinigungen werden im
Bad durch die Polyasparaginsäure in Dispersion gehalten, weil die
Polyasparaginsäure als Dispergiermittel wirkt. Damit wird ein neuerliches Absetzen
dieser Teilchen auf der Werkstückoberfläche verhindert, die nach der Entnahme des
Werkstücks aus dem Tauchbad 1 und einer anschließenden Spülung lackiert werden
kann, falls nicht in einem weiteren Behandlungsschritt die korrosionshemmende
Schicht durch ein weiteres Bad in einer Polyasparaginsäure-Lösung verstärkt wird.According to the illustrated embodiment, the system has pretreatment
a metallic workpiece, in particular made of sheet metal, a
Um die Wirkung des Tauchbades nicht durch die Zunahme der Konzentration der
von der Werkstückoberfläche abgelösten Teilchen zu beeinträchtigen, ist an das
Tauchbecken 1 eine Membranfiltereinrichtung 2 angeschlossen, über die
insbesondere die Fetteilchen aus der Lösung abgeschieden werden können. Das
Retentat wird aus der Membranfiltereinrichtung 2 über eine Ableitung 3 abgeführt,
während das Permeat, das das organische Enffettungsmittel und die
Polyasparaginsäure enthält über eine Rückleitung 4 im Kreislauf wieder dem
Tauchbecken 1 zugeführt wird. Die laufenden Badverluste werden über eine
Zuleitung 5 ersetzt, über die frische Lösung des Entfettungsmittels und der
Polyasparaginsäure nachgefüllt werden können.In order to avoid the effects of the immersion bath by increasing the concentration of
Affecting particles detached from the workpiece surface is therefore
Da der Einsatz von Iminodibernsteinsäure-Natriumsalz auch das Ablösen von Metallionen
von der Werkstückoberfläche bewirkt, ist auch für ein entsprechendes
Abscheiden dieser Metallionen zu sorgen. Dies ist in dem Blockschaltbild der
Zeichnung durch einen lonentauscher 6 angedeutet, der an die
Membranfiltereinrichtung 2 angeschlossen ist. Die im lonentauscher 6
abgebundenen Metalle können über die Leitung 7 entsorgt werden.Since the use of iminodisuccinic acid sodium salt also removes metal ions
caused by the workpiece surface is also appropriate for one
To deposit these metal ions. This is in the block diagram of the
Drawing indicated by an
Es braucht wohl nicht besonders hervorgehoben zu werden, daß die Erfindung nicht auf das dargestellte Ausführungsbeispiel beschränkt ist. Anstelle einer Tauchbehandlung kann beispielsweise eine übliche Spritzbehandlung treten, entscheidend ist ja lediglich, daß für den Korrosionsschutz und die Verbesserung der Haftfähigkeit des Lackes eine Polyasparaginsäure eingesetzt wird, und zwar vorteilhaft im Zusammenwirken mit einem Entfettungsmittel auf der Basis von Iminodibernsteinsäure-Natriumsalz.Needless to say that the invention is not is limited to the illustrated embodiment. Instead of one Immersion treatment can be followed, for example, by a conventional spray treatment, the only decisive factor is that for corrosion protection and the improvement of Adhesion of the paint a polyaspartic acid is used, namely advantageous in combination with a degreasing agent based on Iminodisuccinic sodium salt.
In einer speziellen Ausführungsform der vorliegenden Erfindung wird die Behandlung der Metalloberfläche mit Polyasparaginsäure oder einem Asparaginsäureenthaltendem Copolymer als Maßnahme für einen temporären Korrosionsschutz eingesetzt. Dies heißt, daß das Werkstück vor der endgültigen Korrosionsschutzbehandlung für einen längeren Zeitraum (Tage bis Wochen) gelagert und/oder transportiert wird. Weiterhin können vor der endgültigen Korrosionsschutzbehandlung Verarbeitungsprozesse wie beispielsweise Umformen oder Fügen (Schweißen, Bördeln) durchgeführt werden. Dabei werden Umformprozesse durch die Polymerschicht auf der Metalloberfläche erleichtert Nach derartigen Prozessen ist die Metalloberfläche in der Regel verschmutzt, so daß sie vor der endgültigen Korrosionsschutzbehandlung nochmals gereinigt werden muß. Dabei hat die vorausgegangene Beschichtung mit Polyasparaginsäure oder einem Polyasparaginsäureenthaltendem Polymer den Vorteil, daß in einem solchen nachfolgenden Reinigungsschritt die Verunreinigungen leichter entfernt werden können.In a special embodiment of the present invention, the treatment the metal surface with polyaspartic acid or containing an aspartic acid Copolymer as a measure for temporary corrosion protection used. This means that the workpiece before the final anti-corrosion treatment stored for a longer period (days to weeks) and / or is transported. Furthermore, before the final anti-corrosion treatment Processing processes such as forming or joining (welding, Flanging). Forming processes through the polymer layer relieved on the metal surface After such processes the Metal surface usually dirty, so that it is before the final Corrosion protection treatment must be cleaned again. The previous one Coating with polyaspartic acid or a containing polyaspartic acid Polymer has the advantage that in such a subsequent cleaning step the impurities can be removed more easily.
Die zu lackierende Oberfläche wird dann vor dem Lackieren mit einer weiteren Lösung behandelt, die auf der Oberfläche eine Konversionsschicht erzeugt. Insbesondere kann es sich hierbei um eine schichtbildende Phosphatierung handeln, wie sie insbesondere im Automobilbau und in der Haushaltsgeräteindustrie gebräuchlich ist. Statt einer Phosphatierung können jedoch auch eine Chromatierung, eine Behandlung mit einer Lösung komplexer Fluoride, insbesondere der Elemente Bor, Silizium, Titan und/oder Zirkon, und/oder einer Lösung anderer organischer Polymere erfolgen. Bei diesen anderen organischen Polymeren kann es sich beispielsweise handeln um Polymere oder Copolymere von Acrylsäure oder Methacrylsäure oder um Polyvinylphenole.The surface to be painted is then coated with another one before painting Treated solution that creates a conversion layer on the surface. In particular, this can be a layer-forming phosphating, such as in particular in the automotive industry and in the household appliance industry is common. However, instead of phosphating, one can Chromating, treatment with a solution of complex fluorides, in particular the elements boron, silicon, titanium and / or zirconium, and / or one Other organic polymers are used. With these other organic ones Polymers can be, for example, polymers or copolymers of Acrylic acid or methacrylic acid or around polyvinylphenols.
Wenn im vorstehenden allgemein von metallischen Werkstücken die Rede war, so sind hiermit insbesondere Werkstücke aus Metallen gemeint, wie sie in der Fahrzeug-, Möbel- oder Haushaltsgeräteindustrie gebräuchlich sind. Insbesondere handelt es sich um Werkstücke aus Stahl, verzinktem oder legierungsverzinktem Stahl oder aus Aluminium oder dessen Legierungen. Weiterhin kommen Werkstücke aus Magnesium oder Magnesiumlegierungen in Frage.If in the foregoing there was general talk of metallic workpieces, then are meant in particular workpieces made of metals, as in the Vehicle, furniture or household appliance industry are common. In particular are workpieces made of steel, galvanized or alloy galvanized Steel or aluminum or its alloys. Workpieces also come made of magnesium or magnesium alloys in question.
Claims (6)
- A process for pretreating a metal workpiece for painting, the surface of the workpiece to be painted being cleaned with a solution containing degreasing agents and being coated with a corrosion-inhibiting layer, characterized in that the surface of the workpiece to be painted is treated with a solution of polyaspartic acid for application of a corrosion-inhibiting layer.
- A process as claimed in claim 1, characterized in that, for simultaneous degreasing and coating, the surface of the workpiece to be painted is treated with a solution of polyaspartic acid and a degreasing agent based on the sodium salt of iminodisuccinic acid.
- A process as claimed in claim 2, characterized in that the ratio by weight of polyaspartic acid to the sodium salt of iminodisuccinic acid is between 10:1 and 1:10, a minimum polyaspartic acid concentration of 2% being established in the solution.
- A process as claimed in claim 2 or 3, characterized in that the solution laden with the fats detached from the workpiece surface is subjected to membrane filtration, the permeate being recirculated for surface treatment of the workpiece and the retentate being disposed of.
- A process as claimed in claim 4, characterized in that free metal ions are removed from the permeate before it is recirculated for treatment of the workpiece.
- A process as claimed in any of claims 2 to 5, characterized in that, after degreasing, the surface of the workpiece to be painted is subjected to another treatment in a 10 to 40 % solution of polyaspartic acid.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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AT0109198A AT408103B (en) | 1998-06-24 | 1998-06-24 | METHOD FOR PRE-TREATING A METAL WORKPIECE FOR A PAINTING |
AT109198 | 1998-06-24 | ||
PCT/EP1999/004125 WO1999067442A1 (en) | 1998-06-24 | 1999-06-15 | Process for the preliminary treatment of a metallic workpiece before coating |
Publications (2)
Publication Number | Publication Date |
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EP1097255A1 EP1097255A1 (en) | 2001-05-09 |
EP1097255B1 true EP1097255B1 (en) | 2002-09-04 |
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Application Number | Title | Priority Date | Filing Date |
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EP99931072A Expired - Lifetime EP1097255B1 (en) | 1998-06-24 | 1999-06-15 | Process of pre-treating a metallic workpiece before painting |
Country Status (10)
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US (1) | US6432220B1 (en) |
EP (1) | EP1097255B1 (en) |
JP (1) | JP2002518602A (en) |
AT (1) | AT408103B (en) |
AU (1) | AU4772499A (en) |
BR (1) | BR9912205A (en) |
CA (1) | CA2335987A1 (en) |
DE (1) | DE59902585D1 (en) |
ES (1) | ES2183578T3 (en) |
WO (1) | WO1999067442A1 (en) |
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AT407227B (en) * | 1998-06-26 | 2001-01-25 | Aware Chemicals Llc | METHOD FOR CLEANING LACQUERING PARTS OF A LACQUERING PLANT, IN PARTICULAR LACQUERING LINES |
EP1293589A3 (en) * | 2001-09-17 | 2004-10-13 | Nissan Motor Company, Limited | Apparatus for pretreatment prior to painting |
DE102004053015A1 (en) * | 2004-11-03 | 2006-05-04 | Lanxess Deutschland Gmbh | Use of water-soluble polymer polycarboxylate as dispersing agent for the cleaning of sooted surfaces e.g. tunnel linings, street signs, signaling devices, heating systems, engines, soot particle filters and window panes |
US8377207B2 (en) | 2007-05-09 | 2013-02-19 | Ulvac, Inc. | Purge gas assembly |
WO2009130248A1 (en) * | 2008-04-23 | 2009-10-29 | Martin-Nikolaus Meyn | Method for chemical deburring |
AT508612B1 (en) * | 2009-08-14 | 2011-05-15 | Bohnes Alfred | PROCESS FOR PREPARING THE CIRCULATORY WATER OF A PAINT LINE |
US9290850B2 (en) | 2013-10-31 | 2016-03-22 | U.S. Water Services Inc. | Corrosion inhibiting methods |
WO2016120669A1 (en) | 2015-01-30 | 2016-08-04 | Arcelormittal | Method for the production of a coated metal sheet, comprising the application of an aqueous solution containing an amino acid, and associated use in order to improve corrosion resistance |
WO2016120671A1 (en) | 2015-01-30 | 2016-08-04 | Arcelormittal | Method for the production of a coated metal sheet, comprising the application of an aqueous solution containing an amino acid, and associated use in order to improve tribological properties |
WO2016120670A1 (en) * | 2015-01-30 | 2016-08-04 | Arcelormittal | Method for the production of a coated metal sheet, comprising the application of an aqueous solution containing an amino acid, and associated use in order to improve compatibility with an adhesive |
CA2982739C (en) | 2015-04-15 | 2023-06-27 | Henkel Ag & Co. Kgaa | Thin corrosion protective coatings incorporating polyamidoamine polymers |
CN104845522A (en) * | 2015-04-22 | 2015-08-19 | 重庆长安汽车股份有限公司 | Automobile brake disc anti-corrosion treatment method |
CN109778211B (en) * | 2019-03-01 | 2021-04-20 | 统崴精密涂装(上海)有限公司 | Workpiece degreasing process before electrophoresis and degreasing device |
CN110253306B (en) * | 2019-07-09 | 2024-05-31 | 江苏金陵体育器材股份有限公司 | Basketball stand production line |
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US3578508A (en) * | 1967-04-12 | 1971-05-11 | Martin B Pearlman | Treatment of ferrous metal surfaces to prevent corrosion |
US4299640A (en) * | 1980-07-25 | 1981-11-10 | The General Tire & Rubber Company | Rubber-brass adhesion improved through treatment of the metal with amino carboxylic acid or salt thereof |
US5443651A (en) * | 1990-02-06 | 1995-08-22 | Monsanto Company | Process for metal cleaning |
DE4239076A1 (en) * | 1992-11-20 | 1994-05-26 | Basf Ag | Mixtures of polymers of monoethylenically unsaturated dicarboxylic acids and polymers of ethylenically unsaturated monocarboxylic acids and / or polyaminocarboxylic acids and their use |
DE4244031A1 (en) * | 1992-12-24 | 1994-06-30 | Bayer Ag | Process for the preparation and use of polyaspartic acid and its salts |
US5401428A (en) * | 1993-10-08 | 1995-03-28 | Monsanto Company | Water soluble metal working fluids |
US5531934A (en) * | 1994-09-12 | 1996-07-02 | Rohm & Haas Company | Method of inhibiting corrosion in aqueous systems using poly(amino acids) |
DE4439193A1 (en) * | 1994-11-03 | 1996-05-09 | Bayer Ag | Mixture for corrosion inhibition of metals |
US5607623A (en) * | 1995-03-08 | 1997-03-04 | Donlar Corporation | Inhibition of carbon dioxide corrosion of metals |
CN1196079A (en) * | 1995-07-20 | 1998-10-14 | 孟山都公司 | Improved water soluble metal working fluids |
DE19528059A1 (en) * | 1995-07-31 | 1997-02-06 | Bayer Ag | Detergent and cleaning agent with imino disuccinates |
DE19842053A1 (en) * | 1998-09-15 | 2000-03-23 | Bayer Ag | Use of polyaspartic acids in cleaning formulations with an abrasive effect |
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1998
- 1998-06-24 AT AT0109198A patent/AT408103B/en not_active IP Right Cessation
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1999
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ES2183578T3 (en) | 2003-03-16 |
AU4772499A (en) | 2000-01-10 |
ATA109198A (en) | 2001-01-15 |
AT408103B (en) | 2001-09-25 |
WO1999067442A1 (en) | 1999-12-29 |
BR9912205A (en) | 2001-04-10 |
JP2002518602A (en) | 2002-06-25 |
EP1097255A1 (en) | 2001-05-09 |
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