EP0178020A1 - Process for the treatment of aluminium surfaces - Google Patents
Process for the treatment of aluminium surfaces Download PDFInfo
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- EP0178020A1 EP0178020A1 EP85201600A EP85201600A EP0178020A1 EP 0178020 A1 EP0178020 A1 EP 0178020A1 EP 85201600 A EP85201600 A EP 85201600A EP 85201600 A EP85201600 A EP 85201600A EP 0178020 A1 EP0178020 A1 EP 0178020A1
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Classifications
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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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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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
- C23C22/34—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 containing fluorides or complex fluorides
- C23C22/36—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 containing fluorides or complex fluorides containing also phosphates
- C23C22/361—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 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
Definitions
- the invention relates to a method for the treatment of aluminum surfaces in two successive stages and the use of this method for pretreatment before the subsequent painting.
- the object of the invention is to provide a method for the treatment of aluminum surfaces, with the aid of which coatings with excellent corrosion protection and adhesion for paint, varnish and the like are obtained, which moreover also largely meet the other aforementioned requirements.
- the zirconium ions can be introduced into the bath in the form of any zirconium compound which is soluble in an aqueous acidic solution and does not introduce any disadvantageous components into the bath.
- suitable soluble zirconium compounds are fluozirconic acid, ammonium or alkali salts thereof, zirconium fluoride, zirconium nitrate, zirconium sulfate and the like.
- alkali metal fluorozirconate for example of potassium fluorozirconate (K2ZrF 6 )
- K2ZrF 6 potassium fluorozirconate
- the concentration of the zirconium ions can vary in a wide range from about 1 ppm to about 5000 ppm and more, with amounts between 4 ppm and 100 ppm being preferred. A particularly satisfactory concentration is around 50 ppm.
- the source of hafnium can also be any hafnium compound which is soluble in the aqueous acidic medium and does not introduce any constituents which adversely affect the solution.
- hafnium compounds are described in H andbook of Chemistry and Physics, 55th edition, CRC Press, Inc., Cleveland, Ohio (1974).
- Preferred hafnium compounds are hafnium oxide and acids or salts, such as hafnium or hafnyl nitrate or fluoride or chloride.
- the hafnium compound should be incorporated in an amount such that the concentration of hafnium ions is between about 1 ppm and about 5000 ppm. A concentration of ions in the range from 4 to 100 ppm, in particular around 50 ppm, is preferred.
- Any compound which is soluble in aqueous, acidic medium and does not introduce any disadvantageously influencing constituents can also be used as a source of titanium.
- suitable titanium compounds are hexafluorotitanic acid, titanium or titanyl sulfate and ammonium or alkali salts of halogenotitanates, such as potassium fluorotitanate. Salts containing both titanium and fluoride are usually preferred because they introduce two of the required bath components into the bath at the same time.
- the concentration of titanium ions can also vary in the range from 1 to 5000 ppm, concentrations in the range from 4 to 100 ppm being preferred, in particular around 50 ppm.
- the treatment solution can contain only hafnium ions or only zirconium ions or only titanium ions, but also mixtures thereof.
- concentration of the mixture should be within the above range, i.e. are within the range of 1 to 5000 ppm, preferably in the range of 4 to 100 ppm.
- the treatment solution contains zirconium ions or predominantly zirconium ions.
- the fluoride ions can be in the solution in the form of simple or complex fluoride compounds, such as in the form of hydrofluoric acid, or in the form of simple or bifluoride salts of alkali metal or ammonium, or as complex fluoride acid or salts with boron, silicon, titanium, zirconium and the like as a central ion be introduced.
- the fluoride concentration can be from about 1 ppm to about 6000 ppm or more, with amounts in the range from 4 to about 100 ppm being preferred. A particularly outstanding fluoride concentration is around 60 ppm.
- the fluoride concentration is preferably related to the amount of hafnium, zirconium and / or fluoride ions.
- the weight ratio of fluoride to zircon is preferably at least 1.25: 1, from fluoride to hafnium at least 0.64: 1.
- the maximum fluoride concentration is limited by a concentration at which there is already considerable etching of the aluminum surface. The maximum fluoride concentration also depends on the type of aluminum surface to be treated, but also on the temperature of the treatment bath and the duration of the treatment.
- the fluoride concentration in the treatment bath is controlled in relation to the concentration of hafnium and / or zirconium and / or titanium, so that a stoichiometric ratio of at least 6 moles of fluoride is present per mole of the metal ions.
- the concentration of free fluoride in the bath is usually measured in millivolt units using a specific fluoride ion electrode. It generally varies depending on the specific bath composition and the concentration of the bath inventory parts and the pH of the bath. For each special bath at an essentially constant pH value, there is a relationship between the millivolt display and the free fluoride content, which is responsible for the satisfactory functioning of the bath.
- the millivolt display therefore represents a simple control system for the functioning of the bath. The millivolt display required in each case can be determined for any bath by simple examinations with regard to the desired result.
- fluoroboric acid in the phosphating bath in cases in which a reservoir for free fluoride ions is desired, so that the fluoride ions which are used for the complex formation of aluminum can be continuously simulated.
- tannins are a group of soluble, complex organic compounds that are widely distributed across the plant kingdom. All tannin extracts contain mixtures of polyphenolic substances and are normally bound to certain sugars (for tannins see Encyclopedia of Chemical Technology, 2nd Edition, Kirk-Othmer; XII (1976), pages 303-341 and The Chemistry and Technology of Leather, Reinhold Publishing Corporation , New York, pp. 98-220 (1958).
- Tannins are typically characterized as polyphenolic compounds that have molecular weights from about 400 to about 3000. They can be so-called hydrolyzable or condensed tannins, depending on whether the product of the hydrolysis is soluble or insoluble in boiling mineral acid. Tannin extracts are often mixed and contained both hydrolyzable and condensed forms. There are not two tannin extracts that are completely the same. The main sources of tannin extracts are bark from lichen, mangrove, oak, eucalyptus, hamloctane, spruce, larch and willow. Certain woods, such as those of quebracho, chestnut and oak, as well as fruits, leaves and roots also contain tannin.
- vegetable tannin used above is used to distinguish organic tannins as mentioned above from mineral tannin materials, e.g. those that chrome, zircon, etc. contain. Both hydrolyzable and condensed and mixed types of vegetable tannin can be used within the present invention.
- the vegetable tannin is usually present in an amount of at least 1 ppm, preferably in an amount of at least 25 ppm, up to the solubility limit in the phosphating bath.
- the upper concentration is preferably 500 ppm. Concentrations in the range of about 70 ppm are particularly advantageous.
- the treatment solution used in the process according to the invention must be adjusted to a pH in the acidic range.
- the best results are obtained when the pH is less than 5 and preferably at least 2.
- the pH is preferably between 2 and 3.5.
- the metal is zircon or predominantly zircon, the pH should be between about 3 and 4.5, but especially between 3.5 and 4.
- titanium or predominantly titanium is used as the metal, the pH should preferably be between about 2.5 and about 4.0.
- the pH can already be in the aforementioned range without further adjustments being necessary.
- the commonly used inorganic or organic compounds can be used for adjustment. These are in particular mineral acids, for example hydrofluoric acid, sulfuric acid, nitric acid and phosphoric acid, or alkali and ammonium hydroxides, carbonates, bicarbonates, oxides or silicate.
- the phosphate ions contained in the treatment bath should be present in an amount of 10 to about 200 ppm, but in particular in an amount of 25 to 75 ppm. The range of 45 to 55 ppm phosphate is particularly preferred.
- Suitable sources of phosphate ions are e.g. Phosphoric acid and the numerous sodium, potassium or ammonium phosphates.
- the treatment solution may also contain polyphosphoric acid such as pyrophosphoric acid, tripolyphosphoric acid, hexametaphosphoric acid, or sodium and potassium salts thereof.
- organophosphate content e.g.
- Phytic acid on nitrodiethanolethylene sulfonic acid, on phosphonates, such as of 2-hydroxyethyl methacrylic acid, of phosphonic acid, of 2-ethylhexyl acid and of ethane-1-hydroxy-1,1-diphosphonic acid.
- the complexing agent of the treatment bath can be of a conventional type, provided that it is compatible with the other bath components.
- suitable complexing agents are ethylenediaminetetraacetic acid, alkali metal gluconates, alkali tartrate and the like.
- the complexing agent is used in an amount such that harmful precipitation of aluminum in the treatment bath is suppressed.
- a particularly preferred bath composition contains zircon at a concentration of about 50 ppm, total fluoride at about 180 ppm, tannin at about 70 ppm (calculated as weight equivalent to tannic acid), phosphate ions at about 50 ppm and an effective amount of complexing agent.
- aids can be incorporated into the treatment bath to influence the layer quality.
- These other aids include nitrate compounds and compounds containing titanium and lithium. The content of such aids is usually low.
- the solutions used in carrying out the process according to the invention are usually used at a temperature from room temperature to the boiling point of the solution, preferably at temperatures in the range from 37.8 ° C. to approximately 71 ° C.
- the treatment time can range from 0.1 sec to 10 min, with 2 sec to about 1 min being the most common.
- the coating formation is a function of the concentration of the solution, its temperature and the contact time. For example, the contact time can be reduced if the temperature and / or concentration of the treatment solution is increased.
- Any customary procedure for applying the solution to the metal surfaces can be used, for example spraying, roller application, dipping or flooding.
- the different types of contact of the solution with the metal surface in combination with the variable concentration of the solution, treatment temperature and duration of treatment make it possible to create coating weights of 0.0215 to 0.538 g / m 2 .
- water is usually carried out rinsing and then post-treatment with a solution as described in US-A-4,457,790.
- the solution for aftertreatment preferably contains a polymer with Z groups, the Z groups in a particularly advantageous manner making up a proportion of 10 to 200% per monomer unit of the polymer. This ensures water solubility or water dispersibility in the aftertreatment solution.
- the aftertreatment solution can contain polymeric compounds with different monomer units each of the above formula.
- a polymer compound can have the following formulation:
- Y has the definition given above - except hydrogen - and A), B), C) and D) can each go from 0 to a number at which the polymer is no longer soluble or dispersible under the conditions of use.
- the sum of A), B), C) and D) must be at least 2.
- the Z group should also be present in such an amount that, after neutralization with an acid, the polymer is water-soluble or water-dispersible.
- the specific amount of Z groups required for water solubility or dispersibility depends on the molecular weight of the polymer, but also on the nature of the R 4 to R 10 groups. In general it can be said that the proportion of the Z group should be 10 to 200%, in particular 50 to 150%, per monomer unit. The same applies to the proportion of amino groups which may be present and which differ from Z.
- the polymer in the aftertreatment solution is based on derivatives of polyalkenylphenol polymers.
- polyalkenylphenols or substituted alkenylphenols are isopropenylphenol, isobutenylphenol, dimethylvinylphenol and the like.
- Suitable derivatives with the above general formula can be prepared, for example, by the Mannich reaction.
- poly-4-vinylphenol can be reacted with formaldehyde and a secondary amine to form a product which can be neutralized with organic or inorganic acids and is water-soluble or dispersible.
- the molecular weight of the polymer compounds can correspond to that of the dimer, but in particular an oligomer of 360 monomer units up to a high polymer of 30,000 units.
- the upper limit is determined by the lack of water solubility or water dispersibility.
- the molecular weight of the polymer ranges from about 200,000, molecular weights in the range from 700 to about 70,000 are preferred.
- the upper value is for n generally 850.
- the preferred value is in the range of 10 to 300.
- the carbon chain length of the substituents R 4 to R 10 is generally between 1 and 18.
- a chain length of 1 to 12 is particularly advantageous.
- the values for " n", for the chain length and for the " Z" group influence each other and must therefore be selected in a suitable manner so that water solubility and / or dispersibility are given.
- the polymer of the aftertreatment solution is in organic solvents, e.g. in ethanol, soluble and can be used as an organic solution.
- the aftertreatment solution is preferably used in the form of an aqueous solution or dispersion.
- the Z content of the polymer can be neutralized by means of an organic or inorganic acid.
- Suitable acids for this purpose are acetic acid, citric acid, oxalic acid, ascorbic acid, phenylphosphonic acid, chloromethylphosphonic acid, mono-, di- and trichloroacetic acid, trifluoroacetic acid, nitric acid, phosphoric acid, hydrofluoric acid, sulfuric acid, boric acid, hydrochloric acid, hexafluorosilicic acid, hexafluorotitanic acid, hexafluorozirconic acid, and the like. These acids can be used individually or used in combination with each other. After dilution of the neutralized or partially neutralized or also with excess acid, the solution is ready for use.
- the pH of the aqueous aftertreatment solution can be in the range from 0.5 to 12.
- the pH is expediently adjusted to a value in the range from 2.0 to 8.0.
- the aftertreatment solution can be used at room temperature and concentrations of about 0.001 to about 5% by weight. In practice, a concentration of 0.005 to about 0.015% by weight is recommended. In addition to the polymer, the aftertreatment solution can contain pigments similar to conventional paints and varnishes.
- the aftertreatment solution can contain further constituents, for example in amounts of 0.01 to 4.0% by weight.
- these are, for example, thiourea, alkyl or arylthiourea compounds, tannic acid, vegetable tannin, gallic acid or mixtures thereof.
- Specific examples of such further contents are methyl, ethyl or butylthiourea, tannin extracts from mangroves, chestnuts or oaks and the like.
- the aftertreatment solution can be applied in a conventional manner.
- the solution may be applied by a spray treatment i roller application or dipping treatment.
- the temperature of the solution applied can vary over a wide range. A temperature in the range from 21.1 to 71 ° C. is preferred.
- the contact time can vary between 1 sec and 1 h.
- rinsing can be carried out if necessary, although good results are obtained even without rinsing. Rinsing is preferred for certain consumption purposes, for example for subsequent electrocoating.
- the final drying is usually done by circulating air. Although room temperature air can be used, it is preferred to use elevated temperature air to reduce the drying time.
- the treated aluminum surfaces are available for painting and the like.
- Suitable standard paint or other coating application methods can be used, for example brush application, spray painting, electrostatic coating formation, dipping or roller application, and electrocoating.
- brushes application for example brush application, spray painting, electrostatic coating formation, dipping or roller application, and electrocoating.
- a treatment solution was prepared which contained the following components:
- the aforesaid concentrate was diluted to 3.75 by adding tap water and adjusting the pH with ammonium bicarbonate to a treatment solution of the following nature.
- the aforementioned solution was then diluted with deionized water and adjusted to a pH of 4.25 by adding 25% phosphoric acid.
- the nature of the diluted solution was:
- Extruded aluminum workpieces were cleaned with an alkaline cleaner, rinsed with tap water and brought into contact with the aforementioned treatment solution by spraying at a temperature of 52 ° C. for 30 minutes, then rinsed with tap water and then also sprayed with the aforementioned aftertreatment solution .
- the aftertreatment solution also had a temperature of 52 ° C. and was applied over a period of 30 seconds.
- the sheets were dried with hot air and provided with a varnish (Duracron 100 from Pitsburgh Plate and Glass Co.). The sheets were then subjected to various tests and judged to be excellent in terms of paint adhesion and corrosion protection.
- a treatment solution for process stage 1 was prepared, which contained the following constituents in demineralized water:
- Example 1 were rinsed, treated with the aforementioned solution, rinsed and aftertreated as indicated in Example 1. These sheets were also characterized by excellent paint adhesion and corrosion resistance.
- Example 2 The procedure of Example 2 was repeated with similar results. However, a solution for process step 1 was used which contained 0.85 g / 1 H 2 HfF 6 instead of the fluorotitanic acid. The pH of the treatment solution was set to 3 instead of 3.75.
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur Behandlung von Aluminiumoberflächen in zwei aufeinanderfolgenden Stufen sowie die Anwendung dieses Verfahrens zur Vorbehandlung vor der anschließenden Lackierung.The invention relates to a method for the treatment of aluminum surfaces in two successive stages and the use of this method for pretreatment before the subsequent painting.
Umweltbestimmungen, die mit Mindestbegrenzungen der zulässigen Richtwerte von umweltschädigenden Substanzen bei der Zuführung zu Abfallsystemen verbunden sind, geben zu einem Austausch der herkömmlichen, Chrom und Phosphat enthaltenden Mittel zur Behandlung von Metalloberflächen durch chromfreie Überzugsmittel Veranlassung. Ein derartiges Überzugsmittel ist in der US - A - 4 338 140 beschrieben. Zur Verbesserung des Korrosionswiderstandes von Metallen, insbesondere von Eisen, Zink und Aluminium, sind dort Lösungen offenbart, die gelöstes Hafnium und/oder Zirkon sowie Fluorid, vorzugsweise auch Tannin, und gegebenenfalls auch Phosphat enthalten. Andere Mittel zur Behandlung von Metalloberflächen, die verdünnte Lösungen von Poly-Alkenylphenol, Salze oder Derivate hiervon darstellen, sind in der US - A - 4 457 790 genannt.Environmental regulations, which are associated with minimum limits on the permissible guide values for environmentally harmful substances when they are fed into waste systems, prompt the chromium and phosphate-containing agents for treating metal surfaces to be replaced by chrome-free coating agents. Such a coating agent is described in US Pat. No. 4,338,140. To improve the corrosion resistance of metals, in particular iron, zinc and aluminum, solutions are disclosed therein which contain dissolved hafnium and / or zirconium and fluoride, preferably also tannin, and optionally also phosphate. Other agents for treating metal surfaces which are dilute solutions of poly-alkenylphenol, salts or derivatives thereof are mentioned in US Pat. No. 4,457,790.
Die an derartige Überzüge gestellten Qualitätsanforderungen sind vielfältig und variieren in ihrer Rangfolge mit dem Endverbrauch, dem das mit der Schutzschicht versehene Werkstück zugeführt wird. Von besonderer Bedeutung sind:
- 1.) Haftung des Überzuges auf der Metalloberfläche
- 2.) Haftung der nachfolgend aufgebrachten Endbeschichtung, z.B. von Farbe, Lack und dergl.
- 3.) Korrosionswiderstand des überzogenen, aber nicht endbeschichteten Werkstückes
- 4.) Korrosionswiderstand des endbeschichteten Werkstückes
- 5.) Farbe bzw. Farblosigkeit des erzeugten Überzuges
- 6.) Gleichmäßigkeit des Überzuges
- 7.) Schichtdicke des Überzuges im Hinblick auf die gestellten Mindestanforderungen
- 8.) Verformbarkeit des mit dem Überzug versehenen Werkstückes
- 9.) Veränderung des Aussehens der metallischen Oberfläche
- 1.) Adhesion of the coating to the metal surface
- 2.) Liability of the subsequently applied final coating, eg paint, varnish and the like.
- 3.) Corrosion resistance of the coated but not finally coated workpiece
- 4.) Corrosion resistance of the finished coated workpiece
- 5.) Color or colorlessness of the coating produced
- 6.) Uniformity of the coating
- 7.) Layer thickness of the coating with regard to the minimum requirements
- 8.) deformability of the workpiece provided with the coating
- 9.) Change in the appearance of the metallic surface
Mit den bisher bekannten Verfahren gelingt es zwar, einzelne der geforderten Qualitätsansprüche zu erfüllen, jedoch sind dafür die Ergebnisse hinsichtlich der anderen Qualitätsanforderungen häufig unzufriedenstellend.With the previously known methods, it is possible to meet some of the required quality requirements, but the results are often unsatisfactory with regard to the other quality requirements.
Aufgabe der Erfindung ist es, ein Verfahren zur Behandlung von Aluminiumoberflächen bereitzustellen, mit dessen Hilfe Überzüge mit hervorragendem Korrosionsschutz und Haftvermögen für Farbe, Lack und dergl. erhalten werden, die zudem auch die weiteren vorgenannten Anforderungen weitestgehend erfüllen.The object of the invention is to provide a method for the treatment of aluminum surfaces, with the aid of which coatings with excellent corrosion protection and adhesion for paint, varnish and the like are obtained, which moreover also largely meet the other aforementioned requirements.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Aluminiumoberfläche zunächst mit einer wäßrigen, sauren Lösung in Berührung bringt, die wirksame Mengen von
- a) gelösten Metallen mindestens eines der Elemente Hafnium, Zirkon oder Titan,
- b) Phosphationen
- c) Fluoridionen
- d) löslicher Tanninverbindung
- e) Komplexverbindung
enthält,
und anschließend mit einer Lösung nachbehandelt, die eine wirksame Menge einer löslichen oder dispergierbaren Verbindung der allgemeinen Formel
- R1 bis R3 Wasserstoff oder eine Alkylgruppe mit 1 bis 5 Kohlenstoffatomen
- Y Wasserstoff, Z, CR4R5OR6, CH2Cl, oder eine Alkyl- oder Arylgruppe mit 1 bis 18 Kohlenstoffatomen
- R4 bis R10 Wasserstoff, Alkyl-, Aryl-, Hydroxyalkyl-, Aminoalkyl-, Mercaptoalkyl-oder Phosphoalkyl-Gruppen mit Kohlenwasserstoffketten bis zu einer Länge, bei der die Verbindung nicht mehr löslich oder dispergierbar ist, und
- n 2 bis zu einer Zahl, bei der die Verbindung nicht mehr löslich oder dispergierbar ist.
- a) dissolved metals of at least one of the elements hafnium, zirconium or titanium,
- b) phosphate ions
- c) fluoride ions
- d) soluble tannin compound
- e) complex compound
contains
and then post-treated with a solution containing an effective amount of a soluble or dispersible compound of the general formula
- R 1 to R 3 are hydrogen or an alkyl group having 1 to 5 carbon atoms
- Y is hydrogen, Z, CR 4 R 5 OR 6 , CH 2 Cl, or an alkyl or aryl group having 1 to 18 carbon atoms
- R 4 to R 10 are hydrogen, alkyl, aryl, hydroxyalkyl, aminoalkyl, mercaptoalkyl or phosphoalkyl groups with hydrocarbon chains up to a length at which the compound is no longer soluble or dispersible, and
- n 2 up to a number at which the compound is no longer soluble or dispersible.
Die Zirkonionen können in das Bad in Form jeder Zirkonverbindung, die in wäßriger, saurer Lösung löslich ist und keine nachteiligen Komponenten in das Bad einbringt, eingeführt werden. Beispiele für geeignete lösliche Zirkonverbindungen sind Fluozirkonsäure, Ammonium oder Alkalisalze hiervon, Zirkonfluorid, Zirkonnitrat, Zirkonsulfat und dergl. Die Verwendung von Alkalifluozirkonat beispielsweise von Kaliumfluorozirkonat (K2ZrF6) wird üblicherweise bevorzugt, da hierdurch gleichzeitig Zirkonionen und Fluoridionen in das B 1 eingebracht werden. Die Konzentration der Zirkonionen kann in einem breiten Bereich von etwa 1 ppm bis etwa 5000 ppm und mehr schwanken, wobei Mengen, die zwischen 4 ppm und 100 ppm liegen, bevorzugt sind. Eine besonders zufriedenstellende Konzentration liegt bei ca. 50 ppm.The zirconium ions can be introduced into the bath in the form of any zirconium compound which is soluble in an aqueous acidic solution and does not introduce any disadvantageous components into the bath. Examples of suitable soluble zirconium compounds are fluozirconic acid, ammonium or alkali salts thereof, zirconium fluoride, zirconium nitrate, zirconium sulfate and the like. The use of alkali metal fluorozirconate, for example of potassium fluorozirconate (K2ZrF 6 ), is usually preferred since zirconium ions and fluoride ions are introduced into the B1 at the same time. The concentration of the zirconium ions can vary in a wide range from about 1 ppm to about 5000 ppm and more, with amounts between 4 ppm and 100 ppm being preferred. A particularly satisfactory concentration is around 50 ppm.
Die Quelle für Hafnium kann ebenfalls jede Hafniumverbindung sein, die im wäßrigen, sauren Medium löslich ist und keine die Lösung nachteilig beeinträchtigenden Bestandteile einbringt. Beispiele für erhältliche Hafniumverbindungen sind im Handbook of Chemistry and Physics, 55. Ausgabe, CRC Press, Inc., Cleveland, Ohio (1974) beschrieben. Bevorzugte Hafniumverbindungen sind Hafniumoxid und Säuren oder Salze, wie Hafnium- oder Hafnylnitrat, bzw. -fluorid oder -chlorid. Die Hafniumverbindung sollte in einer solchen Menge eingebracht werden, daß die Konzentration an Hafniumionen zwischen etwa 1 ppm und etwa 5000 ppm beträgt. Bevorzugt ist eine Konzentration an Hat iumionen im Bereich von 4 bis 100 ppm, insbesondere um etwa 50 ppm.The source of hafnium can also be any hafnium compound which is soluble in the aqueous acidic medium and does not introduce any constituents which adversely affect the solution. Examples of commercially available hafnium compounds are described in H andbook of Chemistry and Physics, 55th edition, CRC Press, Inc., Cleveland, Ohio (1974). Preferred hafnium compounds are hafnium oxide and acids or salts, such as hafnium or hafnyl nitrate or fluoride or chloride. The hafnium compound should be incorporated in an amount such that the concentration of hafnium ions is between about 1 ppm and about 5000 ppm. A concentration of ions in the range from 4 to 100 ppm, in particular around 50 ppm, is preferred.
Auch als Quelle für Titan kann jede Verbindung, die in wäßrigem, saurem Medium löslich ist und keine nachteilig beeinflussenden Bestandteile einbringt, verwendet werden. Beispiele für geeignete Titanverbindungen sind Hexafluorotitansäure, Titan- oder Titanylsulfat und Ammonium- oder Alkalisalze von Halogenotitanaten, wie Kaliumfluorotitanat. Salze, die sowohl Titan und Fluorid enthalten, sind üblicherweise bevorzugt, da sie gleichzeitig zwei der erforderlichen Badkomponenten in das Bad einbringen. Die Konzentration an Titanionen kann ebenfalls im Bereich von 1 bis 5000 ppm schwanken, wobei Konzentrationen im Bereich von 4 bis 100 ppm insbesondere um ca. 50 ppm bevorzugt sind.Any compound which is soluble in aqueous, acidic medium and does not introduce any disadvantageously influencing constituents can also be used as a source of titanium. Examples of suitable titanium compounds are hexafluorotitanic acid, titanium or titanyl sulfate and ammonium or alkali salts of halogenotitanates, such as potassium fluorotitanate. Salts containing both titanium and fluoride are usually preferred because they introduce two of the required bath components into the bath at the same time. The concentration of titanium ions can also vary in the range from 1 to 5000 ppm, concentrations in the range from 4 to 100 ppm being preferred, in particular around 50 ppm.
Die Behandlungslösung kann nur Hafniumionen oder nur Zirkonionen oder nur Titanionen, aber auch Mischungen hiervon enthalten. Wenn Mischungen der genannten Metallionen verwendet werden, sollte die Konzentration der Mischung innerhalb des vorstehend genannten Bereiches, d.h. innerhalb des Bereichs von 1 bis 5000 ppm, vorzugsweise im Bereich von 4 bis 100 ppm liegen.The treatment solution can contain only hafnium ions or only zirconium ions or only titanium ions, but also mixtures thereof. When using mixtures of said metal ions, the concentration of the mixture should be within the above range, i.e. are within the range of 1 to 5000 ppm, preferably in the range of 4 to 100 ppm.
Gemäß einer bevorzugten Ausgestaltung der Erfindung enthält die Behandlungslösung Zirkonionen oder überwiegend Zirkonionen.According to a preferred embodiment of the invention, the treatment solution contains zirconium ions or predominantly zirconium ions.
Die Fluoridionen können in die Lösung in Form einfacher oder komplexer Fluoridverbindungen, wie in Form von Fluorwasserstoffsäure, oder in Form von einfachen oder Bifluoridsalzen von Alkalimetall oder Ammonium oder als komplexe Fluoridsäure bzw. Salze mit Bor, Silizium, Titan, Zirkon und dergl. als Zentralion eingebracht werden. Die Fluoridkonzentration kann etwa 1 ppm bis etwa 6000 ppm oder mehr betragen, wobei Mengen im Bereich von 4 bis etwa 100 ppm bevorzugt sind. Eine besonders herausragende Fluoridkonzentration liegt bei etwa 60 ppm. Die Fluoridkonzentration wird vorzugsweise in Beziehung zur Menge der Hafnium-, Zirkonium- und/oder Fluoridionen gesetzt. Vorzugsweise beträgt das Gewichtsverhältnis von Fluorid zu Zirkon wenigstens 1,25 : 1, von Fluorid zu Hafnium wenigstens 0,64 : 1. Die maximale Fluoridkonzentration ist von einer derartigen Konzentration begrenzt, bei der ein bereits erhebliches Ätzen der Aluminiumoberfläche auftritt. Die maximale Fluoridkonzentration ist darüber hinaus von der Art der zu behandelnden Aluminiumoberflächen, aber auch von der Temperatur des Behandlungsbades und der Dauer der Behandlung abhängig.The fluoride ions can be in the solution in the form of simple or complex fluoride compounds, such as in the form of hydrofluoric acid, or in the form of simple or bifluoride salts of alkali metal or ammonium, or as complex fluoride acid or salts with boron, silicon, titanium, zirconium and the like as a central ion be introduced. The fluoride concentration can be from about 1 ppm to about 6000 ppm or more, with amounts in the range from 4 to about 100 ppm being preferred. A particularly outstanding fluoride concentration is around 60 ppm. The fluoride concentration is preferably related to the amount of hafnium, zirconium and / or fluoride ions. The weight ratio of fluoride to zircon is preferably at least 1.25: 1, from fluoride to hafnium at least 0.64: 1. The maximum fluoride concentration is limited by a concentration at which there is already considerable etching of the aluminum surface. The maximum fluoride concentration also depends on the type of aluminum surface to be treated, but also on the temperature of the treatment bath and the duration of the treatment.
Wie bereits vorstehend ausgeführt, wird die Fluoridkonzentration im Behandlungsbad im Verhältnis zur Konzentration von Hafnium und/oder Zirkon und/oder Titan kontrolliert, so daß ein stöchiometrisches Verhältnis von wenigstens 6 Mol Fluorid pro Mol der Metallionen vorhanden ist. Die Konzentration an freiem Fluorid im Bad wird üblicherweise durch eine spezifische Fluoridionenelektrode in Millivolt-Einheiten gemessen. Sie schwankt im allgemeinen in Abhängigkeit von der speziellen Badzusammensetzung und der Konzentration der Badbestandteile sowie vom pH-Wert des Bades. Für jedes spezielle Bad bei im wesentlichen konstantem pH-Wert besteht eine Relation zwischen der Millivolt-Anzeige und dem Gehalt an freiem Fluorid, die für eine zufriedenstellende Arbeitsweise des Bades verantwortlich ist. Die Millivolt-Anzeige stellt mithin ein einfaches Kontrollsystem für die Arbeitsweise des Bades dar. Die jeweils erforderliche Millivolt-Anzeige kann für jedes beliebige Bad durch einfache Untersuchungen hinsichtlich des gewünschten Ergebnisses festgestellt werden.As already stated above, the fluoride concentration in the treatment bath is controlled in relation to the concentration of hafnium and / or zirconium and / or titanium, so that a stoichiometric ratio of at least 6 moles of fluoride is present per mole of the metal ions. The concentration of free fluoride in the bath is usually measured in millivolt units using a specific fluoride ion electrode. It generally varies depending on the specific bath composition and the concentration of the bath inventory parts and the pH of the bath. For each special bath at an essentially constant pH value, there is a relationship between the millivolt display and the free fluoride content, which is responsible for the satisfactory functioning of the bath. The millivolt display therefore represents a simple control system for the functioning of the bath. The millivolt display required in each case can be determined for any bath by simple examinations with regard to the desired result.
Es ist zweckmäßig, im Phosphatierbad Fluoborsäure in den Fällen einzusetzen, in denen ein Reservoir für freie Fluoridionen erwünscht ist, so daß die Fluoridionen, die zur Komplexbildung von Aluminium gebraucht werden, ständig nachgebildet werden können.It is expedient to use fluoroboric acid in the phosphating bath in cases in which a reservoir for free fluoride ions is desired, so that the fluoride ions which are used for the complex formation of aluminum can be continuously simulated.
Zusätzlich zu Hafnium und/oder Zirkon und/oder Titan sowie Fluoridionen enthält das Bad lösliches, pflanzliches Tannin. Bei Tanninen handelt es sich um eine Gruppe von löslichen, kompliziert aufgebauten organischen Verbindungen, die weit über das Pflanzenreich verteilt sind. Alle Tanninextrakte enthalten Mischungen von polyphenolischen Substanzen und sind normalerweise an bestimmte Zucker gebunden (über Tannine siehe Encyclopedia of Chemical Technology, 2nd Edition, Kirk-Othmer; XII (1976), Seiten 303-341 und The Chemistry and Technology of Leather, Reinhold Publishing Corporation, New York, Seiten 98-220 (1958).In addition to hafnium and / or zircon and / or titanium and fluoride ions, the bath contains soluble, vegetable tannin. Tannins are a group of soluble, complex organic compounds that are widely distributed across the plant kingdom. All tannin extracts contain mixtures of polyphenolic substances and are normally bound to certain sugars (for tannins see Encyclopedia of Chemical Technology, 2nd Edition, Kirk-Othmer; XII (1976), pages 303-341 and The Chemistry and Technology of Leather, Reinhold Publishing Corporation , New York, pp. 98-220 (1958).
Tannine werden üblicherweise als polyphenolische Verbindungen charakterisiert, die Molekulargewichte von etwa 400 bis etwa 3000 aufweisen. Sie können sogenannte hydrolysierbare oder kondensierte Tannine sein, je nach dem, ob das Produkt der Hydrolyse in siedender Mineralsäure löslich oder unlöslich ist. Häufig werden Tanninextrakte gemischt und enthalten sowohl hydrolysierbare als auch kondensierte Formen. Es gibt nicht zwei Tanninextrakte, die vollkommen gleich sind. Die Hauptquellen für Tanninextrakte sind Rinde bzw. Borke von Flechten, Mangroven, Eichen, Eukalyptus, Hamloktannen, Fichten, Lärchen und Weiden. Auch bestimmte Hölzer, wie die von Quebracho, Kastanie und Eiche, sowie Früchte, Blätter und Wurzeln enthalten Tannin.Tannins are typically characterized as polyphenolic compounds that have molecular weights from about 400 to about 3000. They can be so-called hydrolyzable or condensed tannins, depending on whether the product of the hydrolysis is soluble or insoluble in boiling mineral acid. Tannin extracts are often mixed and contained both hydrolyzable and condensed forms. There are not two tannin extracts that are completely the same. The main sources of tannin extracts are bark from lichen, mangrove, oak, eucalyptus, hamloctane, spruce, larch and willow. Certain woods, such as those of quebracho, chestnut and oak, as well as fruits, leaves and roots also contain tannin.
Der vorstehend verwendete Begriff pflanzliches Tannin ist angewendet, um einen Unterschied zu organischen Tanninen, wie vorstehend erwähnt, zu schaffen gegenüber mineralischen Tanninmaterialien, z.B. solchen, die Chrom, Zirkon u.ä. enthalten. Sowohl hydrolysierbare als auch kondensierte und gemischte Arten von pflanzlichem Tannin können innerhalb der vorliegenden Erfindung angewendet werden.The term vegetable tannin used above is used to distinguish organic tannins as mentioned above from mineral tannin materials, e.g. those that chrome, zircon, etc. contain. Both hydrolyzable and condensed and mixed types of vegetable tannin can be used within the present invention.
Das pflanzliche Tannin ist üblicherweise in einer Menge von wenigstens 1 ppm, vorzugsweise in einer Menge von wenigstens 25 ppm, bis hinauf zur Löslichkeitsgrenze im Phosphatierbad enthalten. Die obere Konzentration liegt vorzugsweise bei 500 ppm. Konzentrationen im Bereich von etwa 70 ppm sind insbesondere vorteilhaft.The vegetable tannin is usually present in an amount of at least 1 ppm, preferably in an amount of at least 25 ppm, up to the solubility limit in the phosphating bath. The upper concentration is preferably 500 ppm. Concentrations in the range of about 70 ppm are particularly advantageous.
Die innerhalb des erfindungsgemäßen Verfahrens zum Einsatz kommende Behandlungslösung muß auf einen pH-Wert im sauren Bereich eingestellt werden. Die besten Ergebnisse werden erhalten, wenn der pH-Wert kleiner als 5 und vorzugsweise wenigstens 2 ist. Sofern das Metall der Komponente a) Hafnium oder überwiegend Hafnium ist, liegt der pH-Wert vorzugsweise zwischen 2 und 3,5. Ist das Metall Zirkon oder überwiegend Zirkon, so sollte der pH-Wert zwischen etwa 3 und 4,5, insbesondere aber zwischen 3,5 und 4 liegen. Sofern als Metall Titan oder überwiegend Titan eingesetzt wird, sollte der pH-Wert vorzugsweise zwischen etwa 2,5 und etwa 4,0 liegen.The treatment solution used in the process according to the invention must be adjusted to a pH in the acidic range. The best results are obtained when the pH is less than 5 and preferably at least 2. If the metal of component a) is hafnium or predominantly hafnium, the pH is preferably between 2 and 3.5. If the metal is zircon or predominantly zircon, the pH should be between about 3 and 4.5, but especially between 3.5 and 4. If titanium or predominantly titanium is used as the metal, the pH should preferably be between about 2.5 and about 4.0.
In Abhängigkeit von den eingesetzten Ausgangsstoffen hinsichtlich der Komponenten Hafnium und/oder Zirkon und/oder Titan sowie Fluorid kann der pH-Wert bereits im vorgenannten Bereich liegen, ohne daß es weiterer Anpassungen bedarf. Wenn jedoch eine Einstellung des pH-Wertes erforderlich ist, können die üblicherweise verwendeten anorganischen oder organischen Verbindungen zur Einstellung verwendet werden. Hierbei handelt es sich insbesondere um Mineralsäuren, beispielsweise Fluorwasserstoffsäure, Schwefelsäure, Salpetersäure und Phosphorsäure, bzw. um Alkali- und Ammonhydroxide, -carbonate, -bicarbonate, -oxide oder -silikat.Depending on the starting materials used with regard to the components hafnium and / or zircon and / or titanium and fluoride, the pH can already be in the aforementioned range without further adjustments being necessary. However, if pH adjustment is required, the commonly used inorganic or organic compounds can be used for adjustment. These are in particular mineral acids, for example hydrofluoric acid, sulfuric acid, nitric acid and phosphoric acid, or alkali and ammonium hydroxides, carbonates, bicarbonates, oxides or silicate.
Die im Behandlungsbad enthaltenen Phosphationen sollten in einer Menge von 10 bis etwa 200 ppm, insbesondere aber in einer Menge von 25 bis 75 ppm vorliegen. Der Bereich von 45 bis 55 ppm Phosphat ist besonders bevorzugt. Geeignete Quellen für Phosphationen sind z.B. Phosphorsäure und die zahlreichen Natrium-, Kalium- oder Ammonphosphate. Die Behandlungslösung kann gegebenenfalls auch Polyphosphorsäure, wie Pyrophosphorsäure, Tripolyphosphorsäure, Hexametaphosphorsäure, oder Natrium- und Kaliumsalze hiervon enthalten. Auch ist ein Gehalt an Organophosphaten, wie z.B. Phytinsäure, an Nitrodiäthanolethylensulfonsäure, an Phosphonaten, wie von 2-Hydroxyethylmethacryl-l-säure, von Phosphonsäure, von 2-Ethylhexylsäure und von Ethan-1-hydroxy-1,1-diphosphonsäure, möglich.The phosphate ions contained in the treatment bath should be present in an amount of 10 to about 200 ppm, but in particular in an amount of 25 to 75 ppm. The range of 45 to 55 ppm phosphate is particularly preferred. Suitable sources of phosphate ions are e.g. Phosphoric acid and the numerous sodium, potassium or ammonium phosphates. The treatment solution may also contain polyphosphoric acid such as pyrophosphoric acid, tripolyphosphoric acid, hexametaphosphoric acid, or sodium and potassium salts thereof. There is also an organophosphate content, e.g. Phytic acid, on nitrodiethanolethylene sulfonic acid, on phosphonates, such as of 2-hydroxyethyl methacrylic acid, of phosphonic acid, of 2-ethylhexyl acid and of ethane-1-hydroxy-1,1-diphosphonic acid.
Der Komplexbildner des Behandlungsbades kann konventioneller Art sein, sofern er mit den anderen Badbestandteilen verträglich ist. Beispiele geeigneter Komplexbildner sind Ethylendiamintetraessigsäure, Alkaliglukonate, Alkalitartrat und dergl. Der Komplexbildner wird in einer derartigen Menge angewendet, daß eine schädliche Ausfällung von Aluminium im Behandlungsbad unterdrückt wird.The complexing agent of the treatment bath can be of a conventional type, provided that it is compatible with the other bath components. Examples of suitable complexing agents are ethylenediaminetetraacetic acid, alkali metal gluconates, alkali tartrate and the like. The complexing agent is used in an amount such that harmful precipitation of aluminum in the treatment bath is suppressed.
Eine besonders bevorzugte Badzusammensetzung enthält Zirkon in einer Konzentration von etwa 50 ppm, Gesamtfluorid von etwa 180 ppm, Tannin von etwa 70 ppm (berechnet als Gewichts- äquivalent zu Tanninsäure), Phosphationen von etwa 50 ppm und eine wirksame Menge Komplexbildner.A particularly preferred bath composition contains zircon at a concentration of about 50 ppm, total fluoride at about 180 ppm, tannin at about 70 ppm (calculated as weight equivalent to tannic acid), phosphate ions at about 50 ppm and an effective amount of complexing agent.
Andere üblicherweise verwendete Hilfsmittel können in das Behandlungsbad eingearbeitet werden, um die Schichtqualität zu beeinflussen. Unter diesen weiteren Hilfsmitteln befinden sich Nitratverbindungen und Verbindungen, die Titan und Lithium enthalten. Der Gehalt derartiger Hilfsmittel ist üblicherweise gering.Other commonly used aids can be incorporated into the treatment bath to influence the layer quality. These other aids include nitrate compounds and compounds containing titanium and lithium. The content of such aids is usually low.
Die bei Durchführung des erfindungsgemäßen Verfahrens zum Einsatz kommenden Lösungen werden üblicherweise bei einer Temperatur von Raumtemperatur bis zum Siedepunkt der Lösung, vorzugsweise bei Temperaturen im Bereich von 37,8°C bis ca. 71°C eingesetzt. Die Behandlungszeit kann von 0,1 sec bis zu 10 min betragen, wobei 2 sec bis etwa 1 min am häufigsten sind. Die Überzugsbildung ist eine Funktion der Konzentration der Lösung, deren Temperatur und der Kontaktzeit. Beispielsweise kann die Kontaktzeit reduziert werden, wenn die Temperatur und/oder Konzentration der Behandlungslösung erhöht ist. Jede übliche Verfahrensweise zur Aufbringung der Lösung auf die Metallflächen ist anwendbar, beispielsweise Spritzen, Rollenauftrag, Tauchen oder Fluten. Die unterschiedlichen Arten des Kontaktes der Lösung mit der Metalloberfläche in Kombination mit den Variablen Konzentration der Lösung, Behandlungstemperatur und Behandlungsdauer schaffen die Möglichkeit, Überzugsgewichte von 0,0215 bis 0,538 g/m2 entstehen zu lassen.The solutions used in carrying out the process according to the invention are usually used at a temperature from room temperature to the boiling point of the solution, preferably at temperatures in the range from 37.8 ° C. to approximately 71 ° C. The treatment time can range from 0.1 sec to 10 min, with 2 sec to about 1 min being the most common. The coating formation is a function of the concentration of the solution, its temperature and the contact time. For example, the contact time can be reduced if the temperature and / or concentration of the treatment solution is increased. Any customary procedure for applying the solution to the metal surfaces can be used, for example spraying, roller application, dipping or flooding. The different types of contact of the solution with the metal surface in combination with the variable concentration of the solution, treatment temperature and duration of treatment make it possible to create coating weights of 0.0215 to 0.538 g / m 2 .
Nach der Behandlung der Aluminiumoberfläche in der vorstehend beschriebenen ersten Stufe erfolgt üblicherweise eine Wasserspülung und dann die Nachbehandlung mit einer Lösung, wie in US - A - 4 457 790 beschrieben.After the treatment of the aluminum surface in the first step described above, water is usually carried out rinsing and then post-treatment with a solution as described in US-A-4,457,790.
Vorzugsweise enthält die Lösung zur Nachbehandlung ein Polymer mit Z-Gruppen, wobei die Z-Gruppen in insbesondere vorteilhafter Weise einen Anteil von 10 bis 200 % pro Monomereinheit des Polymers ausmachen. Hierdurch ist Wasserlöslichkeit oder Wasserdispergierbarkeit in der Nachbehandlungslösung gewährleistet.The solution for aftertreatment preferably contains a polymer with Z groups, the Z groups in a particularly advantageous manner making up a proportion of 10 to 200% per monomer unit of the polymer. This ensures water solubility or water dispersibility in the aftertreatment solution.
Während in der Polymerkette der oben genannten Formel die Alkylgruppen in ortho-, meta- oder para-Stellung zur Hydroxylgruppe im aromatischen Ring angeordnet sind, werden bei den Monomereinheiten der oben genannten Formel vorzugsweise solche mit der Alkylgruppe in der para- und/oder ortho-Stellung verwendet.While in the polymer chain of the above formula the alkyl groups are arranged in the ortho, meta or para position to the hydroxyl group in the aromatic ring, in the monomer units of the above formula those with the alkyl group in the para and / or ortho Position used.
Die Nachbehandlungslösung kann polymere Verbindungen mit unterschiedlichen Monomereinheiten jeweils der oben genannten Formel enthalten. Beispielsweise kann eine Polymerverbindung folgende Formulierung besitzen:
Dabei hat Y die oben angegebene Definition - ausgenommen Wasserstoff - und A), B), C) und D) können jeweils 0 bis zu einer Zahl gehen, bei der das Polymer unter den Benutzungsbedingungen nicht mehr löslich oder dispergierbar ist.Y has the definition given above - except hydrogen - and A), B), C) and D) can each go from 0 to a number at which the polymer is no longer soluble or dispersible under the conditions of use.
Die Summe von A), B), C) und D) muß wenigstens 2 betragen. Sofern als Lösungsmittel Wasser verwendet wird, sollte zudem die Z-Gruppe in einer solchen Menge vorhanden sein, daß nach Neutralisation mit einer Säure das Polymer wasserlöslich oder -dispergierbar ist. Die konkrete Menge von Z-Gruppen, die zur Wasserlöslichkeit bzw. -dispergierbarkeit erforderlich ist, hängt vom Molekulargewicht des Polymers, aber auch von der Beschaffenheit der R4- bis RlO-Gruppen ab. Im allgemeinen läßt sich sagen, daß der Anteil der Z-Gruppe 10 bis 200 %, insbesondere 50 bis 150 %, pro Monomereinheit betragen sollte. Gleiches gilt für den Anteil gegebenenfalls vorhandener, von Z verschiedener Aminogruppen.The sum of A), B), C) and D) must be at least 2. If water is used as the solvent, the Z group should also be present in such an amount that, after neutralization with an acid, the polymer is water-soluble or water-dispersible. The specific amount of Z groups required for water solubility or dispersibility depends on the molecular weight of the polymer, but also on the nature of the R 4 to R 10 groups. In general it can be said that the proportion of the Z group should be 10 to 200%, in particular 50 to 150%, per monomer unit. The same applies to the proportion of amino groups which may be present and which differ from Z.
Das Polymer in der Nachbehandlungslösung basiert auf Derivaten von Polyalkenylphenolpolymeren. Beispiele von Polyalkenylphenolen oder substituierten Alkenylphenolen sind Isopropenylphenol, Isobutenylphenol, Dimethylvinylphenol und dergl. Geeignete Derivate mit der oben genannten allgemeinen Formel können beispielsweise durch die Mannichreaktion hergestellt werden. Beispielsweise kann Poly-4-vinylphenol mit Formaldehyd und einem sekundären Amin zur Reaktion gebracht werden, so daß ein mit organischen oder anorganischen Säuren neutralisierbares Produkt entsteht, das wasserlöslich oder dispergierbar ist.The polymer in the aftertreatment solution is based on derivatives of polyalkenylphenol polymers. Examples of polyalkenylphenols or substituted alkenylphenols are isopropenylphenol, isobutenylphenol, dimethylvinylphenol and the like. Suitable derivatives with the above general formula can be prepared, for example, by the Mannich reaction. For example, poly-4-vinylphenol can be reacted with formaldehyde and a secondary amine to form a product which can be neutralized with organic or inorganic acids and is water-soluble or dispersible.
Das Molekulargewicht der Polymerverbindungen kann dem des Dimers, insbesondere aber eines Oligomers von 360 Monomereinheiten bis zu einem Hochpolymer von 30 000 Einheiten entsprechen. Die obere Grenze ist durch die mangelnde Wasserlöslichkeit oder Wasserdispergierbarkeit vorgegeben.The molecular weight of the polymer compounds can correspond to that of the dimer, but in particular an oligomer of 360 monomer units up to a high polymer of 30,000 units. The upper limit is determined by the lack of water solubility or water dispersibility.
Das Molekulargewicht des Polymers reicht etwa bis 200 000, Molekulargewichte im Bereich von 700 bis etwa 70 000 sind bevorzugt. In der allgemeinen Formel ist der obere Wert für n im allgemeinen 850. Der bevorzugte Wert liegt im Bereich von 10 bis 300. Die Kohlenstoffkettenlänge der Substituenten R4 bis R10 liegt im allgemeinen zwischen 1 und 18. Eine Kettenlänge von 1 bis 12 ist besonders vorteilhaft. Die Werte für "n", für die Kettenlänge und für die "Z"-Gruppe beeinflussen sich gegenseitig und sind daher in geeigneter Weise auszuwählen, damit Wasserlöslichkeit und/oder Dispergierbarkeit gegeben sind.The molecular weight of the polymer ranges from about 200,000, molecular weights in the range from 700 to about 70,000 are preferred. In the general formula, the upper value is for n generally 850. The preferred value is in the range of 10 to 300. The carbon chain length of the substituents R 4 to R 10 is generally between 1 and 18. A chain length of 1 to 12 is particularly advantageous. The values for " n", for the chain length and for the " Z" group influence each other and must therefore be selected in a suitable manner so that water solubility and / or dispersibility are given.
Das Polymer der Nachbehandlungslösung ist in organischen Lösungsmitteln, z.B. in Äthanol, löslich und kann als organische Lösung eingesetzt werden. Vorzugsweise erfolgt jedoch die Anwendung der Nachbehandlungslösung in Form einer wäßrigen Lösung oder Dispersion. Um Wasserlöslichkeit oder -dispergierbarkeit des Polymers zu bewirken, kann mittels einer organischen oder anorganischen Säure der Z-Anteil des Polymers neutralisiert werden. Geeignete Säuren hierfür sind Essigsäure, Zitronensäure, Oxalsäure, Ascorbinsäure, Phenylphosphonsäure, Chlormethylphosphonsäure, Mono-, Di- und Trichloressigsäure, Trifluoressigsäure, Salpetersäure, Phosphorsäure, Fluorwasserstoffsäure, Schwefelsäure, Borsäure, Chlorwasserstoffsäure, Hexafluorokieselsäure, Hexafluorotitansäure, Hexafluorozirkonsäure und dergl. Diese Säuren können einzeln oder in Kombination miteinander eingesetzt werden. Nach Verdünnung des neutralisierten oder teilweise neutralisierten oder aber auch mit überschüssiger Säure versetzten Monomers ist die Lösung einsatzfähig.The polymer of the aftertreatment solution is in organic solvents, e.g. in ethanol, soluble and can be used as an organic solution. However, the aftertreatment solution is preferably used in the form of an aqueous solution or dispersion. In order to bring about the water solubility or dispersibility of the polymer, the Z content of the polymer can be neutralized by means of an organic or inorganic acid. Suitable acids for this purpose are acetic acid, citric acid, oxalic acid, ascorbic acid, phenylphosphonic acid, chloromethylphosphonic acid, mono-, di- and trichloroacetic acid, trifluoroacetic acid, nitric acid, phosphoric acid, hydrofluoric acid, sulfuric acid, boric acid, hydrochloric acid, hexafluorosilicic acid, hexafluorotitanic acid, hexafluorozirconic acid, and the like. These acids can be used individually or used in combination with each other. After dilution of the neutralized or partially neutralized or also with excess acid, the solution is ready for use.
Der pH-Wert der wäßrigen Nachbehandlungslösung kann im Bereich von 0,5 bis 12 liegen. Mit Rücksicht auf die Stabilität der Lösung und optimale erzielbare Ergebnisse wird jedoch der pH-Wert zweckmäßigerweise auf einen Wert im Bereich von 2,0 bis 8,0 eingestellt.The pH of the aqueous aftertreatment solution can be in the range from 0.5 to 12. In view of the stability of the solution and optimal results that can be achieved, the pH is expediently adjusted to a value in the range from 2.0 to 8.0.
Die Nachbehandlungslösung kann bei Raumtemperatur und Konzentrationen von etwa 0,001 bis etwa 5 Gew.-% eingesetzt werden. In der Praxis empfiehlt sich eine Konzentration von 0,005 bis etwa 0,015 Gew.-%. Die Nachbehandlungslösung kann außer dem Polymer Pigmente ähnlich herkömmlichen Farben und Lacken enthalten.The aftertreatment solution can be used at room temperature and concentrations of about 0.001 to about 5% by weight. In practice, a concentration of 0.005 to about 0.015% by weight is recommended. In addition to the polymer, the aftertreatment solution can contain pigments similar to conventional paints and varnishes.
Schließlich kann die Nachbehandlungslösung weitere Bestandteile, etwa in Mengen von 0,01 bis 4,0 Gew.-%, enthalten. Hierbei handelt es sich beispielsweise um Thioharnstoff, Alkyl- oder Arylthioharnstoffverbindungen, Tanninsäure, pflanzliches Tannin, Gallussäure oder Mischungen hiervon. Konkrete Beispiele derartiger weiterer Gehalte sind Methyl-, Ethyl- oder Butylthioharnstoff, Tanninextrakte von Mangroven, Kastanien oder Eichen und dergl.Finally, the aftertreatment solution can contain further constituents, for example in amounts of 0.01 to 4.0% by weight. These are, for example, thiourea, alkyl or arylthiourea compounds, tannic acid, vegetable tannin, gallic acid or mixtures thereof. Specific examples of such further contents are methyl, ethyl or butylthiourea, tannin extracts from mangroves, chestnuts or oaks and the like.
Die Applikation der Nachbehandlungslösung kann auf herkömmliche Weise erfolgen. Beispielsweise kann die Lösung durch Spritzbehandlungi Rollenauftrag oder Tauchbehandlung aufgebracht werden. Die Temperatur der aufgebrachten Lösung kann über einen weiten Bereich schwanken. Bevorzugt ist eine Temperatur im Bereich von 21,1 bis 71°C. Die Kontaktdauer kann zwischen 1 sec und 1 h schwanken. Nach Applikation der Nachbehandlungslösung kann gegebenenfalls gespült werden, obgleich gute Ergebnisse auch ohne Nachspülung erhalten werden. Für gewisse Verbrauchszwecke, beispielsweise für eine nachfolgende Elektrotauchlackierung, ist eine Spülung bevorzugt.The aftertreatment solution can be applied in a conventional manner. For example, the solution may be applied by a spray treatment i roller application or dipping treatment. The temperature of the solution applied can vary over a wide range. A temperature in the range from 21.1 to 71 ° C. is preferred. The contact time can vary between 1 sec and 1 h. After application of the after-treatment solution, rinsing can be carried out if necessary, although good results are obtained even without rinsing. Rinsing is preferred for certain consumption purposes, for example for subsequent electrocoating.
Das erfindungsgemäße Verfahren wird üblicherweise wie folgt angewendet:
- 1. Reinigung der Metalloberfläche, vorzugsweise mit einem alkalischen Reiniger
- 2. Spülen der gereinigten Oberfläche mit Wasser
- 3. In-Kontakt-Bringen der Metalloberfläche mit einer wäßrigen, sauren Behandlungslösung entsprechend Stufe 1 des erfindungsgemäßen Verfahrens
- 4. Spülen der mit einem Überzug versehenen Oberfläche mit Wasser
- 5. In-Kontakt-Bringen der gespülten Oberfläche mit der Nachbehandlungslösung entsprechend Stufe 2 des erfindungsgemäßen Verfahrens
- 6. Trocknung der Metalloberfläche
- 1. Cleaning the metal surface, preferably with an alkaline cleaner
- 2. Rinse the cleaned surface with water
- 3. Contacting the metal surface with an aqueous, acidic treatment solution corresponding to stage 1 of the process according to the invention
- 4. Rinse the coated surface with water
- 5. bringing the rinsed surface into contact with the aftertreatment solution in accordance with stage 2 of the method according to the invention
- 6. Drying the metal surface
Die abschließende Trocknung erfolgt üblicherweise durch Umluft. Obgleich Luft von Raumtemperatur eingesetzt werden kann, wird vorzugsweise mit Luft erhöhter Temperatur gearbeitet, um die Trockendauer zu verkürzen.The final drying is usually done by circulating air. Although room temperature air can be used, it is preferred to use elevated temperature air to reduce the drying time.
Nach der Trocknung stehen die behandelten Aluminiumflächen zur Lackierung und dergl. zur Verfügung. Es können geeignete Standard-Farb- oder sonstige Überzugs-Applikationsverfahren angewendet werden, beispielsweise Pinselauftrag, Spritzlackierung, elektrostatische Überzugsbildung, Tauchen oder Rollenauftrag, sowie Elektrotauchlackierung. Als Ergebnis des erfindungsgemäßen Verfahrens werden Oberflächen mit vorzüglicher Lackhaftung und vorzüglichem Korrosionswiderstand erhalten.After drying, the treated aluminum surfaces are available for painting and the like. Suitable standard paint or other coating application methods can be used, for example brush application, spray painting, electrostatic coating formation, dipping or roller application, and electrocoating. As a result of the method according to the invention, surfaces with excellent paint adhesion and excellent corrosion resistance are obtained.
Die Erfindung wird anhand der folgenden Beispiele näher und beispielsweise erläutert.The invention is explained in more detail and, for example, using the following examples.
Es wurde eine Behandlungslösung hergestellt, die folgende Bestandteile enthielt:
Das vorgenannte Konzentrat wurde durch Zugabe von Leitungswasser und durch pH-Wert-Einstellung mittels Ammoniumbicarbonat auf 3,75 zu einer Behandlungslösung der folgenden Beschaffenheit verdünnt.
Zur Herstellung der Nachbehandlungslösung wurden 45,4 kg l-Propoxy-2-propanol in einen Edelstahlreaktor, der mit einem Rührwerk, einer Stickstoffzuführung und einem Rückflußkühler versehen war, eingetragen. Danach wurde vorsichtig auf 50°C erwärmt und Poly-4-vinylphenolpolymer mit einem Molekulargewicht von 5000 in einer Menge von 36,3 kg langsam unter gutem Rühren zugegeben. Nachdem das gesamte Polymer zugegeben war, wurde der Reaktor geschlossen und auf 80°C erwärmt, um die Auflösung des Polymers herbeizuführen. Dann wurde der Reaktor auf 60°C gekühlt und sein Inhalt mit 22,7 kg N-Methylaminoäthanol und 45,4 kg entsalztem Wasser versetzt. Im Anschluß wurden 24,5 kg Formaldehydlösung (37 Gew.-%) während eines Zeitraumes von 1 h zugegeben, wobei die Temperatur auf 60 + 2°C konstantgehalten wurde. Danach wurde der Reaktor 3 h auf der Temperatur von 60°C gehalten. Im Anschluß wurden 9,9 kg Phosphorsäure (75 Gew.-%) zugesetzt und die Mischung mit entsalztem Wasser auf einen Feststoffgehalt von 10 Gew.-% verdünnt. Es resultierte eine stabile Lösung.To prepare the aftertreatment solution, 45.4 kg of l-propoxy-2-propanol were introduced into a stainless steel reactor which was provided with a stirrer, a nitrogen feed and a reflux condenser. The mixture was then carefully warmed to 50 ° C. and poly-4-vinylphenol polymer with a molecular weight of 5000 in an amount of 36.3 kg was slowly added with good stirring. After all of the polymer is added the reactor was closed and heated to 80 ° C to bring about the dissolution of the polymer. The reactor was then cooled to 60 ° C. and its contents were mixed with 22.7 kg of N-methylaminoethanol and 45.4 kg of deionized water. 24.5 kg of formaldehyde solution (37% by weight) were then added over a period of 1 h, the temperature being kept constant at 60 + 2 ° C. The reactor was then kept at 60 ° C. for 3 hours. 9.9 kg of phosphoric acid (75% by weight) were then added and the mixture was diluted to a solids content of 10% by weight with demineralized water. The result was a stable solution.
Die vorgenannte Lösung wurde dann mit entsalztem Wasser verdünnt und durch Zugabe von 25%iger Phosphorsäure auf einen pH-Wert von 4,25 eingestellt. Die Beschaffenheit der verdünnten Lösung war:
Schließlich erfolgte eine Verdünnung im Verhältnis von 1 : 100, so daß eine Nachbehandlungslösung entstand, die
Extrudierte Werkstücke aus Aluminium wurden mit einem alkalischen Reiniger gereinigt, mit Leitungswasser gespült und mit der zunächst erwähnten Behandlungslösung im Sprühen bei einer Temperatur von 52°C während 30 min in Kontakt gebracht, dann mit Leitungswasser gespült und danach mit der vorerwähnten Nachbehandlungslösung ebenfalls im Sprühen behandelt. Die Nachbehandlungslösung hatte eine Temperatur von ebenfalls 52°C und wurde während einer Zeit von 30 sec appliziert. Schließlich wurden die Bleche mit Heißluft getrocknet und mit einem Lack (Duracron 100 der Pitsburgh Plate and Glass Co.) versehen. Die Bleche wurden anschließend verschiedenen Tests unterworfen und hinsichtlich Lackhaftung und Korrosionsschutz für hervorragend beurteilt.Extruded aluminum workpieces were cleaned with an alkaline cleaner, rinsed with tap water and brought into contact with the aforementioned treatment solution by spraying at a temperature of 52 ° C. for 30 minutes, then rinsed with tap water and then also sprayed with the aforementioned aftertreatment solution . The aftertreatment solution also had a temperature of 52 ° C. and was applied over a period of 30 seconds. Finally, the sheets were dried with hot air and provided with a varnish (Duracron 100 from Pitsburgh Plate and Glass Co.). The sheets were then subjected to various tests and judged to be excellent in terms of paint adhesion and corrosion protection.
Es wurde eine Behandlungslösung für die Verfahrensstufe 1 hergestellt, die in entsalztem Wasser folgende Bestandteile enthielt:
Extrudierte Werkstücke aus Aluminium, die gereinigt undExtruded aluminum workpieces that are cleaned and
gespült waren, wurden mit der vorgenannten Lösung behandelt, gespült und nachbehandelt, wie in Beispiel 1 angegeben. Auch diese Bleche zeichneten sich durch eine hervorragende Lackhaftung und Korrosionsbeständigkeit aus.were rinsed, treated with the aforementioned solution, rinsed and aftertreated as indicated in Example 1. These sheets were also characterized by excellent paint adhesion and corrosion resistance.
Das Verfahren von Beispiel 2 wurde wiederholt mit ähnlichen Ergebnissen. Es kam jedoch eine Lösung für die Verfahrensstufe 1 zum Einsatz, die anstelle der Fluorotitansäure 0,85 g/1 H2HfF6 enthielt. Dabei war der pH-Wert der Behandlungslösung auf 3 anstelle von auf 3,75 eingestellt.The procedure of Example 2 was repeated with similar results. However, a solution for process step 1 was used which contained 0.85 g / 1 H 2 HfF 6 instead of the fluorotitanic acid. The pH of the treatment solution was set to 3 instead of 3.75.
Claims (11)
enthält,
und anschließend mit einer Lösung nachbehandelt, die eine wirksame Menge einer löslichen oder dispergierbaren Verbindung der allgemeinen Formel
contains
and then post-treated with a solution containing an effective amount of a soluble or dispersible compound of the general formula
enthält und der Gehalt an Komponente e) ausreicht, eine schädliche Ausfällung von Aluminium zu verhindern.2. The method according to claim 1, characterized in that the aluminum surfaces are first brought into contact with a solution which has a pH of 2.0 to 5.0 and the components
contains and the content of component e) is sufficient to prevent harmful precipitation of aluminum.
enthält.6. The method according to one or more of claims 1 to 5, characterized in that the aluminum surfaces are first brought into contact with an aqueous, acidic solution which the components
contains.
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US65869784A | 1984-10-09 | 1984-10-09 | |
US658697 | 1984-10-09 |
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EP (1) | EP0178020B1 (en) |
JP (1) | JPS6191369A (en) |
AU (1) | AU4751885A (en) |
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ES (1) | ES8607424A1 (en) |
GB (1) | GB2165165A (en) |
PT (1) | PT81269B (en) |
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EP0356855A2 (en) * | 1988-08-27 | 1990-03-07 | Gerhard Collardin Gmbh | Pretreatment of aluminium or aluminium alloy surfaces to be coated with organic materials without using chromium |
WO1990012902A1 (en) * | 1989-04-21 | 1990-11-01 | Henkel Corporation | A method and composition for coating aluminum |
EP0726968A4 (en) * | 1993-07-05 | 1996-05-24 | Henkel Corp | Composition and process for treating tinplate and aluminum |
EP0837954A1 (en) * | 1995-06-30 | 1998-04-29 | Henkel Corporation | Composition and process for treating the surface of aluminiferous metals |
EP0911427A1 (en) * | 1997-10-24 | 1999-04-28 | Nihon Parkerizing Co., Ltd. | Process for surface-treating an aluminium-containing metal |
US6193815B1 (en) | 1995-06-30 | 2001-02-27 | Henkel Corporation | Composition and process for treating the surface of aluminiferous metals |
US6365234B1 (en) | 1997-11-19 | 2002-04-02 | Henkel Kommanditgesellschaft Auf Aktien | Polymerizable, chromium-free, organic coatings for metal |
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WO2016130288A1 (en) * | 2015-02-09 | 2016-08-18 | The Procter & Gamble Company | Cleaning and/or treatment compositions |
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US5370909A (en) * | 1990-06-19 | 1994-12-06 | Henkel Corporation | Liquid composition and process for treating aluminum or tin cans to impart corrosion resistance and mobility thereto |
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ES2175778T3 (en) * | 1997-09-17 | 2002-11-16 | Chemetall Plc | PROCEDURE AND COMPOSTIONS TO PREVENT CORROSION OF METAL SUBSTRATES. |
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- 1985-09-17 AU AU47518/85A patent/AU4751885A/en not_active Abandoned
- 1985-10-02 DE DE19853535135 patent/DE3535135A1/en not_active Withdrawn
- 1985-10-03 DE DE8585201600T patent/DE3565695D1/en not_active Expired
- 1985-10-03 EP EP85201600A patent/EP0178020B1/en not_active Expired
- 1985-10-07 GB GB08524667A patent/GB2165165A/en not_active Withdrawn
- 1985-10-08 PT PT8126985A patent/PT81269B/en not_active IP Right Cessation
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- 1985-10-08 ES ES548344A patent/ES8607424A1/en not_active Expired
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Cited By (16)
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EP0356855A2 (en) * | 1988-08-27 | 1990-03-07 | Gerhard Collardin Gmbh | Pretreatment of aluminium or aluminium alloy surfaces to be coated with organic materials without using chromium |
EP0356855A3 (en) * | 1988-08-27 | 1990-11-14 | Gerhard Collardin Gmbh | Pretreatment of metallic surfaces to be coated with organic materials without using chromium |
WO1990012902A1 (en) * | 1989-04-21 | 1990-11-01 | Henkel Corporation | A method and composition for coating aluminum |
EP0726968A4 (en) * | 1993-07-05 | 1996-05-24 | Henkel Corp | Composition and process for treating tinplate and aluminum |
EP0726968A1 (en) * | 1993-07-05 | 1996-08-21 | Henkel Corporation | Composition and process for treating tinplate and aluminum |
US6193815B1 (en) | 1995-06-30 | 2001-02-27 | Henkel Corporation | Composition and process for treating the surface of aluminiferous metals |
EP0837954A4 (en) * | 1995-06-30 | 1998-10-28 | Henkel Corp | Composition and process for treating the surface of aluminiferous metals |
EP0837954A1 (en) * | 1995-06-30 | 1998-04-29 | Henkel Corporation | Composition and process for treating the surface of aluminiferous metals |
EP0911427A1 (en) * | 1997-10-24 | 1999-04-28 | Nihon Parkerizing Co., Ltd. | Process for surface-treating an aluminium-containing metal |
US6306226B1 (en) | 1997-10-24 | 2001-10-23 | Nihon Papkerizing Co., Ltd. | Process for surface-treating an aluminum-containing metal |
US6365234B1 (en) | 1997-11-19 | 2002-04-02 | Henkel Kommanditgesellschaft Auf Aktien | Polymerizable, chromium-free, organic coatings for metal |
WO2007121898A1 (en) * | 2006-04-19 | 2007-11-01 | Ropal Ag | Process for producing a corrosion-protected and high-gloss substrate |
EP1870489A1 (en) * | 2006-04-19 | 2007-12-26 | Ropal AG | Method to obtain a corrosion-resistant and shiny substrate |
RU2487190C2 (en) * | 2006-04-19 | 2013-07-10 | Ропаль Аг | Method to manufacture substrate protected against corrosion and having mirror shine |
US8993119B2 (en) | 2006-04-19 | 2015-03-31 | Ropal Europe Ag | Process for producing a corrosion-protected and high-gloss substrate |
WO2016130288A1 (en) * | 2015-02-09 | 2016-08-18 | The Procter & Gamble Company | Cleaning and/or treatment compositions |
Also Published As
Publication number | Publication date |
---|---|
DE3565695D1 (en) | 1988-11-24 |
DE3535135A1 (en) | 1986-04-17 |
ES8607424A1 (en) | 1986-06-01 |
GB8524667D0 (en) | 1985-11-13 |
EP0178020B1 (en) | 1988-10-19 |
ES548344A0 (en) | 1986-06-01 |
PT81269A (en) | 1985-11-01 |
PT81269B (en) | 1987-10-20 |
JPS6191369A (en) | 1986-05-09 |
GB2165165A (en) | 1986-04-09 |
AU4751885A (en) | 1986-04-17 |
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