EP0948666B1 - Method for treating metallic surfaces - Google Patents

Method for treating metallic surfaces Download PDF

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Publication number
EP0948666B1
EP0948666B1 EP97954820A EP97954820A EP0948666B1 EP 0948666 B1 EP0948666 B1 EP 0948666B1 EP 97954820 A EP97954820 A EP 97954820A EP 97954820 A EP97954820 A EP 97954820A EP 0948666 B1 EP0948666 B1 EP 0948666B1
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group
acid
process according
aqueous solution
atoms
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German (de)
French (fr)
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EP0948666A1 (en
EP0948666B2 (en
Inventor
Hans-Jürgen P. ADLER
Christian Bram
Ralf Feser
Evelin JÄHNE
Christian Jung
Iris MÄGE
Jürgen Rudolph
Lars Sebralla
Martin Stratmann
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Chemetall GmbH
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Chemetall GmbH
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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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • 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
    • C23C22/68—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 solutions with pH between 6 and 8
    • 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
    • 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
    • C23C22/58—Treatment of other metallic material
    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • C23C22/66—Treatment of aluminium or alloys based thereon
    • 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
    • C23C22/78—Pretreatment of the material to be coated

Definitions

  • the invention relates to a method for Treatment of metallic surfaces made of zinc, Magnesium or aluminum or from the alloys Zinc, magnesium or aluminum are made up and on the paints, plastic layers after the treatment, Coatings, sealants or adhesives applied become.
  • the conversion treatment of aluminum surfaces is still carried out today by yellow chromating, using an acid chromate solution with a pH of 1 to 2, which forms a protective layer on the aluminum.
  • the protective layer consists of an insoluble one Aluminum-chromium (III) mixed oxide and causes the high passivity of the surface against corrosion.
  • the residual content of unused chromate ions deposited in the oxide layer additionally causes a self-healing effect in the case of a damaged paint or plastic coating.
  • the yellow chromating of aluminum surfaces has the disadvantage that it has only insufficient adhesion-promoting properties compared to a lacquer and plastic layer.
  • chromate ions are washed out of exposed weather layers in a disadvantageous manner.
  • a process has been developed as an alternative to chromating developed that with zirconium salts, fluorides, phosphates and organic polymers (e.g. polyacrylates and Polyvinyl alcohols) works. With this procedure layers formed on aluminum surfaces to match the Some corrosion protection and a right good adhesion for paint and Give plastic coatings. However, the achieved corrosion protection is not always satisfactory.
  • DE-A 31 37 525 describes a method for Corrosion inhibition known in an aqueous system which the aqueous system has at least one water-soluble inorganic nitrite and at least one organic Diphosphonic acid or at least one salt of Contains diphosphonic acid.
  • the diphosphonic acid is in the aqueous system with a concentration of 0.1 to 20 ppm before.
  • those are particularly Hydroxyethylidenediphosphonic acid and its inorganic Salts preferred.
  • Benzimidazolyl-2-alkane-phosphonic acids and their salts have a pronounced corrosion-inhibiting effect and can be used as corrosion inhibitors.
  • they can be used individually, combined with each other or together with others known corrosion inhibitors are used.
  • the Compounds are used to inhibit corrosion in the general aqueous, aqueous-alcoholic, alcoholic and / or oil-containing media added.
  • they can be used as corrosion inhibitors in Heat transfer media from cooling or heating circuits, Cooling lubricants, mineral oils or savings be used.
  • By adding the connections and / or their salts to the media mentioned or Circulatory fluids becomes the corrosion of metals, especially of copper and its alloys, prevented.
  • the benzimidazolyl-2-alkane-phosphonic acids contain a phosphonic acid group, a straight chain or branched, saturated or unsaturated, bivalent, optionally substituted hydrocarbon radical with 1 to 15 carbon atoms and a substituted one Benzimidazolerest, the straight-chain or branched Hydrocarbon residue and the benzimidazole residue on the Position 2 of the benzimidazole residue linked together are.
  • aqueous solution for the treatment of zinc, zinc alloys or cadmium which contains nitric acid, an oxidizing agent (H 2 O 2 , nitrate, nitrite, chlorate) and a diphosphonic acid, the two phosphonic acid groups via one Carbon atom are connected to each other, which also has an OH group and an alkyl radical having 1 to 4 carbon atoms.
  • DE-AS 1 013 814 teaches one-component reaction primer solutions (one-component "wash primer") for improving the printability of aluminum foils, which in addition to hydroxyl-containing acetalized synthetic resin as a binder or two oxygen-containing inorganic acids in hydroxyl-containing solvents and 0.1 to 5% of an addition of organic hydroxyl-containing Acids or esters such as of oxybutyric acid or tartaric acid.
  • wash primer one-component reaction primer solutions for improving the printability of aluminum foils, which in addition to hydroxyl-containing acetalized synthetic resin as a binder or two oxygen-containing inorganic acids in hydroxyl-containing solvents and 0.1 to 5% of an addition of organic hydroxyl-containing Acids or esters such as of oxybutyric acid or tartaric acid.
  • a solution is used to create the second layer used in which the phosphinic and phosphonic acids in a concentration of 0.001 mol / l up to Saturation concentration are present and as Solvent water, an alcohol or an organic Contains solvent.
  • the phosphinic and phosphonic acids contain as organic groups for example aliphatic hydrocarbons, aromatic Hydrocarbons, organic acids, aldehydes, ketones, Amines, amides, thioamides, imides, lactams, anilines, Piperidines, pyridines, carbohydrates, esters, lactones, Ethers, alkenes, alcohols, nitriles, oximes, silicones, Ureas, thioureas, perfluorinated organic Groups, silanes and combinations of these groups.
  • the second layer is said to be in particular on the substrate good adhesion promoter for paint and Plastic coatings as well as for paints work.
  • the invention has for its object a method to create, according to the metallic surfaces that from Zinc, magnesium or aluminum or from the alloys zinc, magnesium or aluminum, be treated to the metallic surfaces especially good adhesion for paints, Plastic layers, paints, sealants and Giving adhesives and the metallic surfaces protect against corrosion.
  • the object on which the invention is based is achieved in that the metallic surfaces are treated at 10 to 100 ° C. by dipping, spraying or rolling with an aqueous solution which has a pH of 2 to 13 and 10 -5 to 1 mol / l of one or more connections.
  • Y is an organic group which contains 2 to 50 C atoms and has a straight-chain structure
  • X is a COOH, HSO 3 , HSO 4 , (OH) 2 PO, (OH) 2 PO 2 -, (OH) (OR ') PO or (OH) (OR') PO 2 - group
  • the effect of the method according to the invention is based on the ability of compounds XYZ to spontaneously organize and very on metallic surfaces to form thin, closed films, whereby in particular an orientation of the acidic groups in Direction of the metallic surface occurs and between those on the metallic surface located hydroxyl groups and the acidic groups the compound XYZ forms a chemical bond.
  • the structure of the compounds XYZ was according to the invention chosen that both a reactive connection of the thin film on the metal surface as well as on the Matrix of varnishes, plastic coatings, paints, Sealing compounds and adhesives results.
  • the straight chain organic group Y acts as a "spacer" between the groups X and Z; it gives the compound XYZ quasi the properties of a surfactant, because the organic Group Y has hydrophobic properties.
  • the group Z gives the coated surface a good one Wettability and reactivity to paints, Plastic coatings, paints, sealants and adhesives. If varnishes on the thin films, Plastic coatings, paints, sealants and Adhesives are applied, remain the most beneficial Properties of the thin films also under the influence Corrosive media obtained, so that the metallic Surfaces are protected against corrosion.
  • the reactive Group Z should pay particular attention to the individual paints be coordinated.
  • the aqueous solution one or more compounds of Type XYZ contains in a concentration that is in the range the critical micelle concentration.
  • the critical micelle concentration cmc is one for the respective surfactant characteristic concentration, in which the aggregation of the surfactant molecules into micelles starts. The aggregation is reversible. Below the cmc, d. H. when the solutions are diluted, they disintegrate Micelles back into monomeric surfactant molecules.
  • the numerical value of the cmc depends on its for each surfactant Constitution as well as external parameters, such as Ionic strength, temperature and concentration of additives, from. Suitable methods for determining the cmc u. a. Surface tension measurements.
  • the aqueous solution is a defoamer and / or Solubilizers in each case in an amount of 0.05 to 5 Contains% by weight.
  • the defoamer makes it easier Handling the solution according to the invention based on the surfactant properties of the compounds XYZ for Foaming tends.
  • the mediator limits in advantageously the use of organic Solvent and favors the use of pure Water.
  • Both as a defoamer and as Solubilizers can, for example, amino alcohols be used.
  • the XYZ connections in the aqueous solution as salts are in usually more soluble than the compounds themselves, and besides, the dissolved salts are very stable, so that the handling of the solution according to the invention by the Use of the salts of the compounds XYZ improved becomes.
  • the sodium and Potassium salts used are used.
  • Y is an unbranched, straight-chain alkyl group having 10 to 12 carbon atoms or a p-CH 2 -C 4 H 6 -CH 2 group or a p, p'- C 6 H 4 - C 6 H 4 group.
  • These groups Y give the compounds XYZ according to the invention very good adhesion-promoting properties for lacquers and other organic coatings.
  • Compounds of the type XYZ, which are equipped with the aforementioned groups X and Z, also have good adhesion-promoting properties for paints and plastic coatings and also form a firm chemical bond with the metallic surfaces.
  • Aqueous solutions the following XYZ type compounds have very good adhesion-promoting and corrosion-inhibiting properties: 1-phosphonic acid-12-mercaptododecan, 1-phosphonic acid-12- (N-ethylamino) dodecane, 1-phosphonic acid-12-dodecene, p-xylylenediphosphonic acid, 1,10-decanediphosphonic acid, 1,12-dodecanediphosphonic acid, 1-phosphoric acid-12-Hydroxvdodecan, 1-phosphoric acid-12 (N-ethylamino) dodecane, 1-phosphoric acid-12-mercaptododecan, 1,10-decanediphosphoric acid, 1,12-dodecanediphosphoric acid, p, p'-biphenyldiphosphoric acid, 1-phosphoric acid-12-Acryloyldodecan.
  • aqueous solution by what is known per se Dip, spray or roll at 10 to 100 ° C on the metallic surfaces is applied, the Diving time 5 seconds to 20 minutes, the spraying time 5 Seconds to 15 minutes and the rolling time 2 to 120 Seconds. It has been shown that on the metallic surfaces a thin film arises when the aqueous solution by dipping, spraying or rolling is applied, with a rinse of the treated metallic surfaces not absolutely necessary is, but can be beneficial.
  • the metallic Surfaces before applying the aqueous solution alkaline and / or acid pickled and then with water be rinsed.
  • the water used can be desalinated or not be desalinated.
  • the zinc, magnesium, aluminum and their alloys existing metallic Surfaces are always covered by oxide layers and additionally by the superficial adsorption of Carbon dioxide, water and / or hydrocarbons contaminated. These are contaminated cover layers unable to paint, plastic coatings, Coatings, sealants and adhesives permanently bind and long-term corrosion protection guarantee. Therefore, the metallic surfaces in the manner according to the invention before treatment with cleaned the aqueous solution.
  • Sheets are used as the substrate, which from the Alloy AlMg1 exist.
  • the metal sheets are immersed in an alkaline pickling solution containing 32 g / l NaOH and 8 g / l Na 2 CO 3 at room temperature for 3 minutes. Then it is rinsed with deionized water.
  • the alkaline pickled sheets are then immersed for 3 minutes at 40 ° C. in an acid pickling solution which contains 10 g / l H 2 SO 4 and 33 g / l H 2 O 2 . Then it is rinsed with deionized water.
  • the pickled sheets are immersed at 40 ° C. for 3 minutes in the aqueous solution according to the invention which contains the compound XYZ according to the invention in a concentration of approximately 10 -3 mol / l. This is followed by rinsing with demineralized water and drying at room temperature in a stream of nitrogen.
  • the sheets are first sprayed at 65 ° C for 10 seconds with an alkaline pickling solution containing 10 g / l Bonder V338M®. The sheets are then rinsed by spraying with water. Then the alkaline pickled sheets are sprayed at 50 ° C for 30 seconds with an acid pickling solution containing 16 g / l Bonder V450M®. The pickled sheets are then rinsed by spraying them with deionized water. Finally, the sheets are sprayed with the aqueous solution according to the invention at 40 ° C. for 30 seconds. This is followed by rinsing with demineralized water and drying in an air stream at room temperature.
  • the compound XYZ according to the invention is present in the aqueous solution in a concentration of approximately 10 -3 mol / l. (® registered trademark of Metallgesellschaft AG, Frankfurt / Main, DE)
  • the sheets are alkali and acid pickled and rinsed according to the spray process.
  • the aqueous solution according to the invention is then rolled onto the metal sheets for two seconds at room temperature, the roll being driven at 25 rpm.
  • the compound XYZ is present in the aqueous solution according to the invention in a concentration of approximately 10 -3 mol / l.
  • the sheets are dried in a forced air oven at 105 ° C.
  • Treated sheets were made using various methods painted. It became both a cathodic Electrocoat as well as a powder paint as well Polyester paint used. The electrocoat was used for a voltage of approx. 250 volts on the sheets electrodeposited and then during 22 Dried minutes at 180 ° C. The powder coating was on the sheets are applied by electrostatic spraying and then at 200 ° C for 10 minutes dried.
  • the polyester paint system consisted of one Primer and a top coat. Both components were on the sheets are applied by squeegees. The primer had a layer thickness of 5 microns, while the topcoat Has layer thickness of 25 microns. The baking temperatures were 216 ° C for the primer and for the topcoat 241 ° C.
  • the following table contains the test results that were measured when using different substances according to the invention.
  • the substances were present in the solutions according to the invention in a concentration of approx. 10 -3 mol / l.
  • the salt spray test ESS reinforced with acetic acid shows that the thin films produced according to the invention ensure very good protection against infiltration compared to the comparative sheets; of the comparison sheets, only the chromated sheet is adequately protected against corrosion.
  • the T-bend test which was carried out under the T 0 condition, and the cross-cut with Erichsen indentation show that the paint adhesion on the sheets treated according to the invention is better than on the comparison sheets. Overall, the results achieved with the invention are surprisingly good, since they are equivalent to the results achieved with chromating in terms of corrosion resistance and clearly superior in terms of paint adhesion.
  • the orientation of the molecules of the compounds of the type XYZ was determined by angle-dependent X-ray photoelectron spectroscopy (ARXPS). Due to the very limited penetration depth of the characteristic photoelectrons, the angle-resolved X-ray photoelectrospectroscopy enables a different information depth of the spectral data depending on the angle ⁇ . For example, the depth of information is at small angles in the range of approximately 1 nm and at larger angles in the range up to approximately 10 nm. This makes it possible to determine the orientation of the molecules. This method is described, for example, in the publication by Briggs, Practical Surface Analysis, 1990, Wiley & Sons, Chichester. FIG.
  • XPS X-ray photoelectron spectrum of the 1-phosphoric acid-12- (N-ethylamino) dodecane on the AlMg1 alloy, in which the XPS intensity ratio N / P is shown as a function of the angle ⁇ , where N is the intensity of the Nls peak Amino group and P is the P2s peak of the phosphoric acid group and the abbreviation XPS stands for the term X-ray photoelectron spectroscopy.
  • the spectrum shows that the phosphoric acid group binds to the metal surface and the amino group faces away from the metal surface.
  • connection T-bend test (TO) chipped area according to LPV 75 [%] ESS test according to DIN 50021 ESS infiltration Cross-cut with Erichsen indentation according to ISO 1520 Filiform test according to DIN 65472 [mm]

Abstract

The invention relates to a method for treating metallic surfaces consisting of zinc, magnesium or aluminium or of the alloys of zinc, magnesium or aluminium, to which lacquer, coatings of plastic material, paint, sealants or adhesives are applied after treatment. The treatment of the metallic surfaces takes place at between 10° C. and 100° C. by immersion, spraying or rolling with an aqueous solution. The solution has a pH of between 2 and 13 and contains one or more compounds of the type XYZ at a concentration of between 10-5 and 1 mol/l. Y is an organic group containing between 2 and 50 C atoms and has a straight-chain structure. X is a COOH, HSO3, HSO4, (OH)2PO, (OH)2PO2, (OH)(OR')PO or (OH)(OR')PO2 group. Z is a OH, SH, NH2, NHR', CN, CH=CH2, OCN, epoxy, CH2=CR''-COO, acrylamide, COOH, (OH)2PO, (OH)2PO2, (OH)(OR')PO or (OH)(OR')PO2 group. R' is an alkyl group with between 1 and 4 C atoms. R'' is an H atom or an alkyl group with between 1 and 4 C atoms. Groups X. and Z are each bonded to group Y in their final positions.

Description

Die Erfindung bezieht sich auf ein Verfahren zur Behandlung metallischer Oberflächen, die aus Zink, Magnesium oder Aluminium oder aus den Legierungen- des Zinks, des Magnesiums oder des Aluminiums bestehen und auf die nach der Behandlung Lacke, Kunststoffschichten, Anstriche, Dichtungsmassen oder Klebstoffe aufgebracht werden.The invention relates to a method for Treatment of metallic surfaces made of zinc, Magnesium or aluminum or from the alloys Zinc, magnesium or aluminum are made up and on the paints, plastic layers after the treatment, Coatings, sealants or adhesives applied become.

Es ist bekannt, daß die Korrosion von polymerbeschichteten, metallischen Oberflächen auf elektrochemische Reaktionen an der Phasengrenze Metall /Polymer zurückzuführen ist. Bei vielen in der Technik angewendeten Beschichtungsverfahren werden daher Mecalloberflächen vor dem Auftragen einer Lack- oder Kunststoffschicht mit einer anorganischen Konversionsschicht (z.B. Zinkphosphat) überzogen. Durch Konversionsbehandlung mittels schichtbildender Phosphatierung oder Chromatierung wird die metallische Oberfläche passiviert und für die sich meist anschließende Beschichtung mit einem Lack oder mit einem Kunststoff vorbereitet.It is known that the corrosion of polymer-coated, metallic surfaces electrochemical reactions at the metal / polymer phase boundary is due. With many in technology applied coating processes are therefore Mecall surfaces before applying a varnish or Plastic layer with an inorganic Conversion layer (e.g. zinc phosphate) coated. By Conversion treatment using layer-forming Phosphating or chromating becomes the metallic Passivated surface and for which mostly subsequent coating with a varnish or with a Prepared plastic.

Die Konversionsbehandlung von Aluminiumoberflächen erfolgt auch heute noch durch Gelbchromatierung, wobei eine saure Chromatlösung mit einem pH-Wert von 1 bis 2 verwendet wird, durch die sich auf dem Aluminium eine Schutzschicht ausbildet. Die Schutzschicht besteht aus einem unlöslichen
Aluminium-Chrom-(III)-Mischoxid und bewirkt die hohe Passivität der Oberfläche gegen Korrosion. Der in der Oxidschicht deponierte Restgehalt unverbrauchter Chromationen bewirkt zusätzlich einen Selbstheilungseffekt bei einer beschädigten Lack- oder Kunststoffbeschichtung. Die Gelbchromatierung von Aluminiumoberflächen hat allerdings den Nachteil, daß sie gegenüber einer Lack- und Kunststoffschicht nur unzureichende haftungsvermittelnde Eigenschaften aufweist. Es kommt hinzu, daß Chromationen aus freibewitterten Schichten in nachteiliger Weise ausgewaschen werden.The conversion treatment of aluminum surfaces is still carried out today by yellow chromating, using an acid chromate solution with a pH of 1 to 2, which forms a protective layer on the aluminum. The protective layer consists of an insoluble one
Aluminum-chromium (III) mixed oxide and causes the high passivity of the surface against corrosion. The residual content of unused chromate ions deposited in the oxide layer additionally causes a self-healing effect in the case of a damaged paint or plastic coating. However, the yellow chromating of aluminum surfaces has the disadvantage that it has only insufficient adhesion-promoting properties compared to a lacquer and plastic layer. In addition, chromate ions are washed out of exposed weather layers in a disadvantageous manner.

Als Alternative zur Chromatierung wurde ein Verfahren entwickelt, daß mit Zirkonsalzen, Fluoriden, Phosphaten und organischen Polymeren (z.B. Polyacrylate und Polyvinylalkohole) arbeitet. Mit diesem Verfahren werden auf Aluminiumoberflächen Schichten gebildet, die dem Substrat einen gewissen Korrosionsschutz und ein recht gutes Haftungsvermögen für Lack- und Kunststoffbeschichtungen verleihen. Allerdings ist der erzielte Korrosionsschutz nicht immer befriedigend.A process has been developed as an alternative to chromating developed that with zirconium salts, fluorides, phosphates and organic polymers (e.g. polyacrylates and Polyvinyl alcohols) works. With this procedure layers formed on aluminum surfaces to match the Some corrosion protection and a right good adhesion for paint and Give plastic coatings. However, the achieved corrosion protection is not always satisfactory.

Es hat auch nicht an Versuchen gefehlt, metallische Oberflächen aus Zink, Magnesium, Aluminium und deren Legierungen durch Behandlung mit organischen Substanzen für das Aufbringen von Lack- und Kunststoffbeschichtungen optimal auszurüsten.There has been no lack of attempts, metallic Surfaces made of zinc, magnesium, aluminum and their Alloys by treatment with organic substances for the application of paint and Optimally equip plastic coatings.

So ist aus der DE-A 31 37 525 ein Verfahren zur Korrosionshemmung in einem wässrigen System bekannt, bei dem das wässrige System wenigstens ein wasserlösliches anorganisches Nitrit und wenigstens eine organische Diphosphonsäure oder wenigstens ein Salz der Diphosphonsäure enthält. Die Diphosphonsäure liegt im wässrigen System mit einer Konzentration von 0,1 bis 20 ppm vor. Mit dem bekannten wässrigen System sollen insbesondere Korrosionsprobleme in Kühlsystemen vermieden werden. Im wässrigen System sind besonders die Hydroxyethylidendiphosphonsäure und deren anorganische Salze bevorzugt. DE-A 31 37 525 describes a method for Corrosion inhibition known in an aqueous system which the aqueous system has at least one water-soluble inorganic nitrite and at least one organic Diphosphonic acid or at least one salt of Contains diphosphonic acid. The diphosphonic acid is in the aqueous system with a concentration of 0.1 to 20 ppm before. With the known aqueous system especially corrosion problems in cooling systems be avoided. In the aqueous system, those are particularly Hydroxyethylidenediphosphonic acid and its inorganic Salts preferred.

Aus der EP-A 0 012 909 ist bekannt, daß Benzimidazolyl-2-alkan-phosphonsäuren und deren Salze eine ausgeprägte korrosionsinhibierende Wirkung haben und als Korrosionsinhibitoren verwendet werden können. Zur Korrosionsinhibition können sie einzeln, untereinander kombiniert oder zusammen mit anderen bekannten Korrosionsinhibitoren eingesetzt werden. Die Verbindungen werden zur Korrosionsinhibition im allgemeinen wässrigen, wässrig-alkoholischen, alkoholischen und/oder ölhaltigen Medien zugesetzt. Beispielsweise können sie als Korrosionsinhibitoren in Wärmeträgern von Kühl- oder Heizkreisläufen, Kühlschmierstoffen, Mineralölen oder Sparbeizen eingesetzt werden. Durch Zusatz der Verbindungen und/oder deren Salzen zu den genannten Medien oder Kreislaufflüssigkeiten wird die Korrosion von Metallen, insbesondere von Kupfer und dessen Legierungen, verhindert. Die Benzimidazolyl-2-alkan-phosphonsäuren enthalten eine Phosphonsäuregruppe, einen geradkettigen oder verzweigten, gesättigten oder ungesättigten, bivalenten, ggf. substituierten Kohlenwasserstoffrest mit 1 bis 15 Kohlenstoffatomen und einen substituierten Benzimidazolrest, wobei der geradkettige oder verzweigte Kohlenwasserstoffrest und der Benzimidazolrest über die Position 2 des Benzimidazolrestes miteinander verknüpft sind. From EP-A 0 012 909 it is known that Benzimidazolyl-2-alkane-phosphonic acids and their salts have a pronounced corrosion-inhibiting effect and can be used as corrosion inhibitors. To inhibit corrosion, they can be used individually, combined with each other or together with others known corrosion inhibitors are used. The Compounds are used to inhibit corrosion in the general aqueous, aqueous-alcoholic, alcoholic and / or oil-containing media added. For example, they can be used as corrosion inhibitors in Heat transfer media from cooling or heating circuits, Cooling lubricants, mineral oils or savings be used. By adding the connections and / or their salts to the media mentioned or Circulatory fluids becomes the corrosion of metals, especially of copper and its alloys, prevented. The benzimidazolyl-2-alkane-phosphonic acids contain a phosphonic acid group, a straight chain or branched, saturated or unsaturated, bivalent, optionally substituted hydrocarbon radical with 1 to 15 carbon atoms and a substituted one Benzimidazolerest, the straight-chain or branched Hydrocarbon residue and the benzimidazole residue on the Position 2 of the benzimidazole residue linked together are.

Aus der US-A 4 351 675 ist eine wäßrige Lösung zur Behandlung von Zink, Zinklegierungen oder Cadmium bekannt, die Salpetersäure, ein Oxidationsmittel (H2O2, Nitrat, Nitrit, Chlorat) und eine Diphosphonsäure enthält, wobei die beiden Phosphonsäuregruppen über ein Kohlenstoffatom miteinander verbunden sind, das außerdem eine OH-Gruppe und einen Alkylyrest mit 1 bis 4 Kohlenstoffatomen aufweist.From US-A 4 351 675 an aqueous solution for the treatment of zinc, zinc alloys or cadmium is known, which contains nitric acid, an oxidizing agent (H 2 O 2 , nitrate, nitrite, chlorate) and a diphosphonic acid, the two phosphonic acid groups via one Carbon atom are connected to each other, which also has an OH group and an alkyl radical having 1 to 4 carbon atoms.

DE-AS 1 013 814 lehrt Einkomponenten-Reaktionsgrundierlösungen (Einkomponenten-"Wash-Primer") für die Verbesserung der Bedruckbarkeit von Aluminiumfolien, die neben hydroxylgruppenhaltigem acetalisierten Kunstharz als Bindemittel eine oder zwei sauerstoffhaltige anorganische Säuren in hydroxylgruppenhaltigen Lösungsmitteln und 0,1 bis 5 % eines Zusatzes von organischen hydroxylgruppenhaitigen Säuren oder Estem wie z.B. von Oxybuttersäure oder Weinsäure enthalten.DE-AS 1 013 814 teaches one-component reaction primer solutions (one-component "wash primer") for improving the printability of aluminum foils, which in addition to hydroxyl-containing acetalized synthetic resin as a binder or two oxygen-containing inorganic acids in hydroxyl-containing solvents and 0.1 to 5% of an addition of organic hydroxyl-containing Acids or esters such as of oxybutyric acid or tartaric acid.

Schließlich ist aus der US-A 5 059 258 ein Verfahren bekannt, bei dem zunächst auf einem Aluminiumsubstrat bei einem pH-Wert von 2 bis 14 eine Schicht aus Aluminiumhydroxid erzeugt wird und bei dem danach auf der Aluminiumhydroxidschicht durch Behandlung mit einer organischen Phosphinsäure oder einer organischen Phosphonsäure eine weitere Schicht abgeschieden wird. Der organische Rest der Phosphin- und Phosphonsäure enthält jeweils 1 bis 10 organische Gruppen und 1 bis 30 C-Atome. Im Molekül der organischen Phosphin- und Phosphonsäuren sind 1 bis 10 Phosphin- und Phosphonsäure-Gruppen enthalten. Zur Erzeugung der Hydroxidschicht wird eine wäßrige Lösung verwendet, in der Amine, Aminalkohole, Alkalihydroxide, Erdalkalihydroxide, Alkalicarbonate. Alkalihydrogencarbonate oder Ammoniak enthalten sind. Finally, a method is known from US Pat. No. 5,059,258 known, in which first on an aluminum substrate at a pH of 2 to 14 one layer Aluminum hydroxide is generated and then on the aluminum hydroxide layer by treatment with a organic phosphinic acid or an organic Another layer of phosphonic acid is deposited. The organic residue of phosphinic and phosphonic acid contains 1 to 10 organic groups and 1 to 30 each C-atoms. In the molecule of organic phosphine and Phosphonic acids are 1 to 10 phosphinic and Contain phosphonic acid groups. To generate the Hydroxide layer, an aqueous solution is used in the amines, aminal alcohols, alkali hydroxides, Alkaline earth hydroxides, alkali carbonates. Alkali hydrogen carbonates or ammonia are included.

Zur Erzeugung der zweiten Schicht wird eine Lösung verwendet, in der die Phosphin- und Phosphonsäuren in einer Konzentration von 0,001 mol/l bis zur Sättigungskonzentration vorliegen und die als Lösungsmittel Wasser, einen Alkohol oder ein organisches Lösungsmittel enthält. Die Phosphin- und Phosphonsäuren enthalten als organische Gruppen beispielsweise aliphatische Kohlenwasserstoffe, aromatische Kohlenwasserstoffe, organische Säuren, Aldehyde, Ketone, Amine, Amide, Thioamide, Imide, Lactame, Aniline, Piperidine, Pyridine, Kohlehydrate, Ester, Lactone, Ether, Alkene, Alkohole, Nitrile, Oxime, Silikone, Harnstoffe, Thioharnstoffe, perfluorierte organische Gruppen, Silane und Kombinationen dieser Gruppen. Die zweite Schicht soll auf dem Substrat insbesondere als guter Haftvermittler für Lack- und Kunststoffbeschichtungen sowie für Anstriche wirken.A solution is used to create the second layer used in which the phosphinic and phosphonic acids in a concentration of 0.001 mol / l up to Saturation concentration are present and as Solvent water, an alcohol or an organic Contains solvent. The phosphinic and phosphonic acids contain as organic groups for example aliphatic hydrocarbons, aromatic Hydrocarbons, organic acids, aldehydes, ketones, Amines, amides, thioamides, imides, lactams, anilines, Piperidines, pyridines, carbohydrates, esters, lactones, Ethers, alkenes, alcohols, nitriles, oximes, silicones, Ureas, thioureas, perfluorinated organic Groups, silanes and combinations of these groups. The second layer is said to be in particular on the substrate good adhesion promoter for paint and Plastic coatings as well as for paints work.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zu schaffen, gemäß dem metallische Oberflächen, die aus Zink, Magnesium oder Aluminium oder aus den Legierungen des Zinks, des Magnesiums oder des Aluminiums bestehen, behandelt werden, um den metallischen Oberflächen insbesondere ein gutes Haftungsvermögen für Lacke, Kunststoffschichten, Anstriche, Dichtungsmassen und Klebstoffe zu verleihen und die metallischen Oberflächen gegen Korrosion zu schützen.The invention has for its object a method to create, according to the metallic surfaces that from Zinc, magnesium or aluminum or from the alloys zinc, magnesium or aluminum, be treated to the metallic surfaces especially good adhesion for paints, Plastic layers, paints, sealants and Giving adhesives and the metallic surfaces protect against corrosion.

Die der Erfindung zugrunde liegende Aufgabe wird dadurch gelöst, daß die metallischen Oberflächen bei 10 bis 100°C durch Tauchen, Spritzen oder Walzen mit einer wäßrigen Lösung behandelt werden, die einen pH-Wert von 2 bis 13 hat und 10-5 bis 1 mol/l einer oder mehrerer Verbindungen. des Typs XYZ enthält, wobei Y eine organische Gruppe ist, die 2 bis 50 C-Atome enthält sowie eine geradkettige Struktur hat, wobei X eine COOH-, HSO3-, HSO4-, (OH)2 PO-, (OH)2PO2-, (OH) (OR')POoder (OH) (OR')PO2- Gruppe ist, wobei Z eine OH-, SH-, NH2-, NHR'-, CN-, CH = CH2-, OCN-, Epoxy-, CH2=CR"-COO-, Acrylsäureamid-, (OH)2 PO-, (OH)2 PO2-, (OH) (OR') PO- oder (OH) (OR') PO2 -Gruppe ist und wobei R' eine Alkylgruppe mit 1 bis 4 C-Atomen ist, wobei R" ein H-Atom oder eine Alkylgruppe mit 1 bis 4 C-Atomen ist, und wobei die Gruppen X und Z an die Gruppe Y jeweils in deren Endstellung gebunden sind, wobei die wäßrige Lösung nicht als Kunstharz enthaltende Reaktionsgrundierlösung (Einkomponenten-"Wash-Primer") auf Aluminiumfolien verwendet wird.The object on which the invention is based is achieved in that the metallic surfaces are treated at 10 to 100 ° C. by dipping, spraying or rolling with an aqueous solution which has a pH of 2 to 13 and 10 -5 to 1 mol / l of one or more connections. of the type XYZ, where Y is an organic group which contains 2 to 50 C atoms and has a straight-chain structure, where X is a COOH, HSO 3 , HSO 4 , (OH) 2 PO, (OH) 2 PO 2 -, (OH) (OR ') PO or (OH) (OR') PO 2 - group, where Z is an OH, SH, NH 2 , NHR', CN, CH = CH 2 -, OCN-, epoxy-, CH 2 = CR "-COO-, acrylic acid amide-, (OH) 2 PO-, (OH) 2 PO 2 -, (OH) (OR ') PO- or (OH) (OR ') PO 2 group and where R' is an alkyl group having 1 to 4 carbon atoms, where R "is an H atom or an alkyl group having 1 to 4 carbon atoms, and wherein the groups X and Z are attached to the Group Y are bound in their final position, the aqueous solution not being used as a synthetic resin-containing reaction primer solution (one-component "wash primer") on aluminum foils.

Die Wirkung des erfindungsgemäßen Verfahrens beruht auf der Fähigkeit der Verbindungen XYZ, sich spontan zu organisieren und auf metallischen Oberflächen sehr dünne, geschlossene Filme auszubilden, wobei insbesondere eine Orientierung der sauren Gruppen in Richtung der metallischen Oberfläche erfolgt und zwischen den auf der metallischen Oberfläche befindlichen Hydroxylgruppen sowie den sauren Gruppen der Verbindung XYZ eine chemische Bindung entsteht. Die Struktur der Verbindungen XYZ wurde erfindungsgemäß so gewählt, daß sich sowohl eine reaktive Anbindung des dünnen Films an die Metalloberfläche als auch an die Matrix von Lacken, Kunststoffbeschichtungen, Anstrichen, Dichtungsmassen und Klebstoffen ergibt. Die geradkettige organische Gruppe Y wirkt als "Abstandhalter" zwischen den Gruppen X und Z; sie verleiht der Verbindung XYZ quasi die Eigenschaften eines Tensids, da die organische Gruppe Y hydrophobe Eigenschaften aufweist. Die Gruppe Z verleiht der beschichteten Oberfläche eine gute Benetzbarkeit und Reaktivität gegenüber Lacken, Kunststoffbeschichtungen, Anstrichen, Dichtungsmassen und Klebstoffen. Wenn auf die dünnen Filme Lacke, Kunststoffbeschichtungen, Anstriche, Dichtungsmassen und Klebstoffe aufgebracht werden, bleiben die vorteilhaften Eigenschaften der dünnen Filme auch unter der Einwirkung korrosiver Medien erhalten, so daß die metallischen Oberflächen gegen Korrosion geschützt sind. Die reaktive Gruppe Z sollte insbesondere auf die einzelnen Lacke abgestimmt sein. The effect of the method according to the invention is based on the ability of compounds XYZ to spontaneously organize and very on metallic surfaces to form thin, closed films, whereby in particular an orientation of the acidic groups in Direction of the metallic surface occurs and between those on the metallic surface located hydroxyl groups and the acidic groups the compound XYZ forms a chemical bond. The The structure of the compounds XYZ was according to the invention chosen that both a reactive connection of the thin film on the metal surface as well as on the Matrix of varnishes, plastic coatings, paints, Sealing compounds and adhesives results. The straight chain organic group Y acts as a "spacer" between the groups X and Z; it gives the compound XYZ quasi the properties of a surfactant, because the organic Group Y has hydrophobic properties. The group Z gives the coated surface a good one Wettability and reactivity to paints, Plastic coatings, paints, sealants and adhesives. If varnishes on the thin films, Plastic coatings, paints, sealants and Adhesives are applied, remain the most beneficial Properties of the thin films also under the influence Corrosive media obtained, so that the metallic Surfaces are protected against corrosion. The reactive Group Z should pay particular attention to the individual paints be coordinated.

In weiterer Ausgestaltung der Erfindung ist vorgesehen, daß in der wäßrigen Lösung 0,1 bis 50 % des Wassers durch einen Alkohol mit 1 bis 4 C-Atomen, durch Aceton, durch Dioxan oder durch Tetrahydrofuran ersetzt sind. Diese organischen Lösungsmittel bewirken eine höhere Löslichkeit der Verbindungen XYZ, bei denen es sich in der Regel um größere Moleküle handelt, deren Löslichkeit in reinem Wasser nicht sehr hoch ist. Andererseits enthält die Lösung immer eine große Menge an Wasser, so daß auch bei Anwesenheit organischer Lösungsmittel noch von einem wäßrigen System gesprochen werden kann.In a further embodiment of the invention, that in the aqueous solution 0.1 to 50% of the water by an alcohol with 1 to 4 carbon atoms, by acetone, are replaced by dioxane or by tetrahydrofuran. These organic solvents have a higher effect Solubility of the compounds XYZ, which are in usually larger molecules whose solubility is not very high in pure water. on the other hand the solution always contains a large amount of water, so that even in the presence of organic solvents can be spoken of an aqueous system.

Nach der Erfindung ist es besonders vorteilhaft, wenn die wäßrige Lösung eine oder mehrere Verbindungen des Typs XYZ in einer Konzentration enthält, die im Bereich der kritischen Mizellbildungskonzentration liegt. Die kritische Mizellbildungskonzentration cmc ist eine für das jeweilige Tensid charakteristische Konzentration, bei der die Aggregation der Tensidmoleküle zu Mizellen einsetzt. Die Aggregation ist reversibel. Unterhalb der cmc, d. h. beim Verdünnen der Lösungen, zerfallen die Mizellen wieder in monomere Tensidmoleküle. Der Zahlenwert der cmc hängt für jedes Tensid von seiner Konstitution sowie von äußeren Parametern, wie Ionenstärke, Temperatur und Konzentration von Additiven, ab. Als Methoden zur Bestimmung der cmc eignen sich u. a. Oberflächenspannungsmessungen. Dabei wird mit Hilfe der Ring- oder Plattenmethode die Oberflächenspannung δ einer Tensidlösung in Abhängigkeit von ihrer Konzentration c bei konstanter Temperatur bestimmt. Die cmc erkennt man als Knickpunkt in der Meßkurve δ = f (lg c). Beispiele zur Bestimmung der cmc verschiedener Tenside finden sich in "Die Tenside" Hrsg. v. Kosswig und Stache, Carl Hanser Verlag, München, Wien, 1993.According to the invention it is particularly advantageous if the aqueous solution one or more compounds of Type XYZ contains in a concentration that is in the range the critical micelle concentration. The critical micelle concentration cmc is one for the respective surfactant characteristic concentration, in which the aggregation of the surfactant molecules into micelles starts. The aggregation is reversible. Below the cmc, d. H. when the solutions are diluted, they disintegrate Micelles back into monomeric surfactant molecules. The The numerical value of the cmc depends on its for each surfactant Constitution as well as external parameters, such as Ionic strength, temperature and concentration of additives, from. Suitable methods for determining the cmc u. a. Surface tension measurements. With help the ring or plate method the surface tension δ a surfactant solution depending on your Concentration c determined at constant temperature. The cmc can be seen as a kink in the measurement curve δ = f (lg c). Examples for determining the cmc different Surfactants can be found in "Die Tenside" ed. V. Kosswig and Stache, Carl Hanser Verlag, Munich, Vienna, 1993.

Nach der Erfindung hat es sich besonders bewährt, wenn die wäßrige Lösung einen Entschäumer und/oder einen Lösungsvermittler jeweils in einer Menge von 0,05 bis 5 Gew.-% enthält. Der Entschäumer erleichtert die Handhabung der erfindungsgemäßen Lösung, die aufgrund der Tensideigenschaften der Verbindungen XYZ zur Schaumbildung neigt. Der Lösungsvermittler begrenzt in vorteilhafter Weise die Verwendung organischer Lösungsmittel und begünstigt die Verwendung von reinem Wasser. Sowohl als Entschäumer als auch als Lösungsvermittler können beispielsweise Aminoalkohole verwendet werden.According to the invention, it has proven particularly useful if the aqueous solution is a defoamer and / or Solubilizers in each case in an amount of 0.05 to 5 Contains% by weight. The defoamer makes it easier Handling the solution according to the invention based on the surfactant properties of the compounds XYZ for Foaming tends. The mediator limits in advantageously the use of organic Solvent and favors the use of pure Water. Both as a defoamer and as Solubilizers can, for example, amino alcohols be used.

Nach der Erfindung hat es sich in einigen Fällen bewährt, wenn die Verbindungen des Typs XYZ in der wäßrigen Lösung als Salze vorliegen. Die Salze sind in der Regel besser löslich als die Verbindungen selbst, und außerdem sind die gelösten Salze sehr stabil, so daß die Handhabung der erfindungsgemäßen Lösung durch die Verwendung der Salze der Verbindungen XYZ verbessert wird. In der Praxis werden insbesondere die Natrium- und Kaliumsalze eingesetzt.According to the invention, in some cases proven when the XYZ connections in the aqueous solution as salts. The salts are in usually more soluble than the compounds themselves, and besides, the dissolved salts are very stable, so that the handling of the solution according to the invention by the Use of the salts of the compounds XYZ improved becomes. In practice, the sodium and Potassium salts used.

Gemäß der Erfindung ist Y eine unverzweigte, geradkettige Alkylgruppe mit 2 bis 20 C-Atomen, oder eine unverzweigte, geradkettige Gruppe, die aus 1 bis 4 aromatischen, in p-Stellung verbundenen C6H4-Kernen besteht, oder eine Gruppe, die aus einem oder zwei unverzweigten, geradkettigen Alkylresten mit jeweils 1 bis 12 C-Atomen sowie aus 1 bis 4 aromatischen, in p-Stellung verbundenen C6H4-Kernen besteht. Alle erfindungsgemäßen Gruppen Y sind also durch eine geradkettige, unverzweigte Molekülstruktur gekennzeichnet, die bestens geeignet ist, als "Abstandhalter" zwischen den Gruppen X und Z zu wirken. Die Gruppen Y können also erfindungsgemäß folgende Struktur haben:

  • a) X-(CH2)m -Z; m = 2 bis 20
  • b) X-(C6H4)n -Z; n = 1 bis 4
  • c) X-(CH2)o -(C6H4)p-(CH2)q; o = 0 bis 12, p = 1 bis 4; q = 0 bis 12, o oder q ungleich 0.
    • According to the invention, Y is an unbranched, straight-chain alkyl group having 2 to 20 C atoms, or an unbranched, straight-chain group consisting of 1 to 4 aromatic C 6 H 4 nuclei connected in the p-position, or a group which consists of one or two unbranched, straight-chain alkyl radicals each having 1 to 12 carbon atoms and 1 to 4 aromatic C 6 H 4 nuclei connected in the p-position. All groups Y according to the invention are therefore characterized by a straight-chain, unbranched molecular structure which is ideally suited to act as a "spacer" between the groups X and Z. The groups Y can therefore have the following structure according to the invention:
  • a) X- (CH 2 ) m -Z; m = 2 to 20
  • b) X- (C 6 H 4 ) n -Z; n = 1 to 4
  • c) X- (CH 2 ) o - (C 6 H 4 ) p - (CH 2 ) q ; o = 0 to 12, p = 1 to 4; q = 0 to 12, o or q not equal to 0.

    • Nach der Erfindung ist es besonders vorteilhaft, wenn Y eine unverzweigte, geradkettige Alkylgruppe mit 10 bis 12 C-Atomen oder eine p-CH2-C4H6-CH2-Gruppe oder eine p, p'- C6H4-C6H4-Gruppe ist. Diese Gruppen Y verleihen den erfindungsgemäßen Verbindungen XYZ sehr gute haftvermittelnde Eigenschaften für Lacke und andere organische Beschichtungen. Ferner ist es besonders vorteilhaft, wenn X eine (OH)2PO2- oder (OH)(OR')PO2-Gruppe ist und wenn Z eine (OH)2PO2-, (OH)(OR')PO2-, OH-, SH-, NHR'-, CH=CH2- oder CH2=CR"-COO-Gruppe ist. Verbindungen des Typs XYZ, die mit den vorgenannten Gruppen X und Z ausgestattet sind, haben ebenfalls gute haftvermittelnde Eigenschaften für Lacke und Kunststoffbeschichtungen und gehen darüber hinaus mit den metallischen Oberflächen eine feste chemische Bindung ein.According to the invention, it is particularly advantageous if Y is an unbranched, straight-chain alkyl group having 10 to 12 carbon atoms or a p-CH 2 -C 4 H 6 -CH 2 group or a p, p'- C 6 H 4 - C 6 H 4 group. These groups Y give the compounds XYZ according to the invention very good adhesion-promoting properties for lacquers and other organic coatings. Furthermore, it is particularly advantageous if X is an (OH) 2 PO 2 - or (OH) (OR ') PO 2 group and if Z is an (OH) 2 PO 2 -, (OH) (OR') PO 2 -, OH-, SH-, NHR'-, CH = CH 2 - or CH 2 = CR "-COO group. Compounds of the type XYZ, which are equipped with the aforementioned groups X and Z, also have good adhesion-promoting properties for paints and plastic coatings and also form a firm chemical bond with the metallic surfaces.

    Wäßrige Lösungen, welche die nachfolgend genannten Verbindungen des Typs XYZ enthalten, haben sehr gute haftvermittelnde und korrosionshemmende Eigenschaften: 1-Phosphonsäure-12-mercaptododecan, 1-Phosphonsäure-12-(N-ethylamino)dodecan, 1-Phosphonsäure-12-Dodecen, p-Xylylendiphosphonsäure, 1,10-Decandiphosphonsäure, 1,12-Dodecandiphosphonsäure, 1-Phosphorsäure-12-Hydroxvdodecan, 1-Phosphorsäure-12(N-ethylamino)dodecan, 1-Phosphorsäure-12-mercaptododecan, 1,10-Decandiphosphorsäure, 1,12-Dodecandiphosphorsäure, p, p'-Biphenyldiphosphorsäure, 1-Phosphorsäure-12-Acryloyldodecan. Diese Verbindungen gehen mit den metallischen Oberflächen über die Phosphon- und Phosphorsäure-Gruppe eine Bindung ein und wirken sowohl durch ihre aliphatische bzw. aromatische Gruppe als auch durch ihre funktionelle Gruppe Z als Haftvermittler gegenüber den verschiedenen organischen Bestandteilen der Lacke, der Kunststoffbeschichtungen, der Anstriche, der Dichtungsmassen und der Klebstoffe.Aqueous solutions, the following XYZ type compounds have very good adhesion-promoting and corrosion-inhibiting properties: 1-phosphonic acid-12-mercaptododecan, 1-phosphonic acid-12- (N-ethylamino) dodecane, 1-phosphonic acid-12-dodecene, p-xylylenediphosphonic acid, 1,10-decanediphosphonic acid, 1,12-dodecanediphosphonic acid, 1-phosphoric acid-12-Hydroxvdodecan, 1-phosphoric acid-12 (N-ethylamino) dodecane, 1-phosphoric acid-12-mercaptododecan, 1,10-decanediphosphoric acid, 1,12-dodecanediphosphoric acid, p, p'-biphenyldiphosphoric acid, 1-phosphoric acid-12-Acryloyldodecan. These connections go over with the metallic surfaces Phosphonic and phosphoric acid group a bond and act both through their aliphatic or aromatic Group as well as by their functional group Z as Adhesion promoter towards the various organic Constituents of paints, plastic coatings, of paints, sealants and adhesives.

    In weiterer Ausgestaltung der Erfindung ist vorgesehen, daß die wäßrige Lösung durch das an sich bekannte Tauchen, Spritzen oder Walzen bei 10 bis 100°C auf die metallischen Oberflächen aufgebracht wird, wobei die Tauchzeit 5 Sekunden bis 20 Minuten, die Spritzzeit 5 Sekunden bis 15 Minuten und die Walzzeit 2 bis 120 Sekunden beträgt. Es hat sich gezeigt, daß auf den metallischen Oberflächen ein dünner Film entsteht, wenn die wäßrige Lösung durch Tauchen, Spritzen oder Walzen aufgebracht wird, wobei eine Spülung der behandelten metallischen Oberflächen nicht unbedingt erforderlich ist, aber vorteilhaft sein kann.In a further embodiment of the invention, that the aqueous solution by what is known per se Dip, spray or roll at 10 to 100 ° C on the metallic surfaces is applied, the Diving time 5 seconds to 20 minutes, the spraying time 5 Seconds to 15 minutes and the rolling time 2 to 120 Seconds. It has been shown that on the metallic surfaces a thin film arises when the aqueous solution by dipping, spraying or rolling is applied, with a rinse of the treated metallic surfaces not absolutely necessary is, but can be beneficial.

    Nach der Erfindung ist vorgesehen, daß die metallischen Oberflächen vor dem Aufbringen der wäßrigen Lösung alkalisch und/oder sauer gebeizt sowie danach mit Wasser gespült werden. Das verwendete Wasser kann entsalzt oder nicht entsalzt sein. Die aus Zink, Magnesium, Aluminium und deren Legierungen bestehenden metallischen Oberflächen sind stets von oxidischen Schichten bedeckt und zusätzlich durch die oberflächliche Adsorption von Kohlendioxid, Wasser und/oder Kohlenwasserstoffen kontaminiert. Diese kontaminierten Deckschichten sind nicht in der Lage, Lacke, Kunststoffbeschichtungen, Anstriche, Dichtungsmassen und Klebstoffe dauerhaft zu binden und einen langfristigen Korrosionsschutz zu gewährleisten. Daher werden die metallischen Oberflächen in der erfindungsgemäßen Weise vor der Behandlung mit der wäßrigen Lösung gereinigt.According to the invention it is provided that the metallic Surfaces before applying the aqueous solution alkaline and / or acid pickled and then with water be rinsed. The water used can be desalinated or not be desalinated. The zinc, magnesium, aluminum and their alloys existing metallic Surfaces are always covered by oxide layers and additionally by the superficial adsorption of Carbon dioxide, water and / or hydrocarbons contaminated. These are contaminated cover layers unable to paint, plastic coatings, Coatings, sealants and adhesives permanently bind and long-term corrosion protection guarantee. Therefore, the metallic surfaces in the manner according to the invention before treatment with cleaned the aqueous solution.

    In weiterer Ausgestaltung der Erfindung ist vorgesehen, daß die metallischen Oberflächen, auf welche die wäßrige Lösung durch Tauchen oder Spritzen aufgebracht wurde, danach mit Wasser gespült und gegebenenfalls im Stickstoff- oder Luftstrom getrocknet werden, wobei die Temperatur des Stickstoff- oder Luftstroms 15 bis 150°C beträgt. Durch das Spülen und Trocknen wird die Ausbildung des dünnen Films auf den metallischen Oberflächen nicht behindert. Das zum Spülen verwendete Wasser kann entsalzt oder nicht entsalzt sein.In a further embodiment of the invention, that the metallic surfaces on which the aqueous Solution was applied by dipping or spraying, then rinsed with water and if necessary in Nitrogen or air stream are dried, the Temperature of the nitrogen or air flow 15 to 150 ° C is. By rinsing and drying the Formation of the thin film on the metallic Surfaces not obstructed. The one used for rinsing Water can be desalinated or not.

    Es ist besonders vorteilhaft, wenn das erfindungsgemäße Verfahren zur Behandlung metallischer Oberflächen eingesetzt wird, auf die anschließend ein kathodischer oder anodischer Elektrotauchlack, ein Pulverlack, ein Coil-Coating-Lack, ein lösungsmittelarmer High-Solid-Lack oder ein mit Wasser verdünnter Lack aufgebracht wird. Bei allen Lackierverfahren hat sich die Vorbehandlung der metallischen Oberflächen mit der erfindungsgemäßen wäßrigen Lösung besonders bewährt.It is particularly advantageous if the invention Process for the treatment of metallic surfaces is used, then a cathodic or anodic electrodeposition paint, a powder paint Coil coating varnish, a low solvent High solid paint or a paint thinned with water is applied. With all painting processes has the pretreatment of the metallic surfaces with the aqueous solution according to the invention particularly proven.

    Der Gegenstand der Erfindung wird nachfolgend anhand meherer Ausführungsbeispiele näher erläutert:The object of the invention is described below Several exemplary embodiments explained in more detail:

    Beispiel 1:Example 1: Verfahrenmethod

    Als Substrat werden Bleche verwendet, die aus der Legierung AlMg1 bestehen. Sheets are used as the substrate, which from the Alloy AlMg1 exist.

    a) Tauchverfahrena) Immersion process

    Zunächst werden die Bleche bei Raumtemperatur während 3 Minuten in eine alkalische Beizlösung getaucht, die 32 g/l NaOH und 8 g/l Na2CO3 enthält. Anschließend wird mit entsalztem Wasser gespült. Danach werden die alkalisch gebeizten Bleche während 3 Minuten bei 40°C in eine saure Beizlösung getaucht, die 10 g/l H2 SO4 und 33 g/l H2 O2 enthält. Anschließend wird mit entsalztem Wasser gespült. Schließlich werden die gebeizten Bleche bei 40°C während 3 Minuten in die erfindungsgemäße wässrige Lösung getaucht, welche die erfindungsgemäße Verbindung XYZ in einer Konzentration von ca. 10-3 mol/l enthält. Anschließend erfolgt eine Spülung mit entsalztem Wasser und eine Trocknung bei Raumtemperatur im Stickstoffstrom.First, the metal sheets are immersed in an alkaline pickling solution containing 32 g / l NaOH and 8 g / l Na 2 CO 3 at room temperature for 3 minutes. Then it is rinsed with deionized water. The alkaline pickled sheets are then immersed for 3 minutes at 40 ° C. in an acid pickling solution which contains 10 g / l H 2 SO 4 and 33 g / l H 2 O 2 . Then it is rinsed with deionized water. Finally, the pickled sheets are immersed at 40 ° C. for 3 minutes in the aqueous solution according to the invention which contains the compound XYZ according to the invention in a concentration of approximately 10 -3 mol / l. This is followed by rinsing with demineralized water and drying at room temperature in a stream of nitrogen.

    b) Spritzverfahrenb) spraying process

    Die Bleche werden zunächst bei 65°C während 10 Sekunden mit einer alkalischen Beizlösung besprüht, die 10 g/l Bonder V338M® enthält. Anschließend werden die Bleche durch Besprühen mit Wasser gespült. Danach werden die alkalisch gebeizten Bleche bei 50°C während 30 Sekunden mit einer sauren Beizlösung besprüht, die 16 g/l Bonder V450M® enthält. Anschließend werden die gebeizten Bleche durch Besprühen mit entsalztem Wasser gespült. Schließlich werden die Bleche mit der erfindungsgemäßen wässrigen Lösung bei 40°C während 30 Sekunden besprüht. Es folgt eine Spülung mit entsalztem Wasser und eine Trocknung im Luftstrom bei Raumtemperatur. Die erfindungsgemäße Verbindung XYZ liegt in der wässrigen Lösung in einer Konzentration von ca. 10-3 mol/l vor.(® eingetragene Marke der Metallgesellschaft AG, Frankfurt/Main, DE)The sheets are first sprayed at 65 ° C for 10 seconds with an alkaline pickling solution containing 10 g / l Bonder V338M®. The sheets are then rinsed by spraying with water. Then the alkaline pickled sheets are sprayed at 50 ° C for 30 seconds with an acid pickling solution containing 16 g / l Bonder V450M®. The pickled sheets are then rinsed by spraying them with deionized water. Finally, the sheets are sprayed with the aqueous solution according to the invention at 40 ° C. for 30 seconds. This is followed by rinsing with demineralized water and drying in an air stream at room temperature. The compound XYZ according to the invention is present in the aqueous solution in a concentration of approximately 10 -3 mol / l. (® registered trademark of Metallgesellschaft AG, Frankfurt / Main, DE)

    c) Walzverfahren (Rollcoating)c) Rolling process

    Zunächst werden die Bleche entsprechend dem Spritzverfahren alkalisch und sauer gebeizt sowie gespült. Anschließend wird die erfindungsgemäße wässrige Lösung auf die Bleche während zwei Sekunden bei Raumtemperatur aufgewalzt, wobei die Walze mit 25 U/Minute gefahren wird. In der erfindungsgemäßen wässrigen Lösung liegt die Verbindung XYZ in einer Konzentration von ca. 10-3mol/l vor. Nach dem Aufwalzen der wässrigen Lösung werden die Bleche im Umluftofen bei 105°C getrocknet.First, the sheets are alkali and acid pickled and rinsed according to the spray process. The aqueous solution according to the invention is then rolled onto the metal sheets for two seconds at room temperature, the roll being driven at 25 rpm. The compound XYZ is present in the aqueous solution according to the invention in a concentration of approximately 10 -3 mol / l. After the aqueous solution has been rolled on, the sheets are dried in a forced air oven at 105 ° C.

    d) Verbindungen des Typs XYZd) XYZ type compounds

    Zur Durchführung der Verfahrensvarianten wurden u. a. wässrige Lösungen verwendet, die folgende Verbindungen XYZ enthielten:

  • 1-Phosphonsäure-12-(N-ethylamino)-dodecan
  • 1-Phosphorsäure-12-Hydroxydodecan
  • p-Xylylendiphosphonsäure
  • 1,12-Dodecandiphosphonsäure
    • Aqueous solutions containing the following compounds XYZ were used to carry out the process variants:
  • 1-phosphonic acid-12- (N-ethylamino) dodecane
  • 1-phosphoric acid-12-hydroxydodecane
  • p-Xylylendiphosphonsäure
  • 1,12-dodecanediphosphonic acid

    • e) Lackierverfahrene) painting process

    Die mit der erfindungsgemäßen wässrigen Lösung behandelten Bleche wurden nach verschiedenen Verfahren lackiert. Es wurde sowohl ein kathodischer Elektrotauchlack als auch ein Pulverlack als auch ein Polyesterlack verwendet. Der Elektrotauchlack wurde bei einer Spannung von ca. 250 Volt auf den Blechen elektrolytisch abgeschieden und anschließend während 22 Minuten bei 180°C getrocknet. Der Pulverlack wurde auf die Bleche durch elektrostatisches Sprühen aufgebracht und anschließend bei 200°C während 10 Minuten getrocknet. Das Polyesterlack-System bestand aus einem Primer und einem Decklack. Beide Komponenten wurden auf die Bleche durch Rakeln aufgebracht. Der Primer hatte eine Schichtdicke von 5 µm, während der Decklack eine Schichtdicke von 25 µm aufwies. Die Einbrenntemperaturen betrugen für den Primer 216°C und für den Decklack 241°C. The with the aqueous solution according to the invention Treated sheets were made using various methods painted. It became both a cathodic Electrocoat as well as a powder paint as well Polyester paint used. The electrocoat was used for a voltage of approx. 250 volts on the sheets electrodeposited and then during 22 Dried minutes at 180 ° C. The powder coating was on the sheets are applied by electrostatic spraying and then at 200 ° C for 10 minutes dried. The polyester paint system consisted of one Primer and a top coat. Both components were on the sheets are applied by squeegees. The primer had a layer thickness of 5 microns, while the topcoat Has layer thickness of 25 microns. The baking temperatures were 216 ° C for the primer and for the topcoat 241 ° C.

    Beispiel 2:Example 2: Prüfungsergebnisseexam results

    In der nachfolgenden Tabelle sind die Prüfungsergebnisse enthalten, die bei Verwendung unterschiedlicher erfindungsgemäßer Substanzen gemessen wurden. Die Substanzen lagen in den erfindungsgemäßen Lösungen in einer Konzentration von ca. 10-3 mol/l vor. Der mit Essigsäure verstärkte Salzsprühtest ESS zeigt, daß die erfindungsgemäß hergestellten dünnen Filme einen sehr guten Unterwanderungsschutz gegenüber den Vergleichsblechen gewährleisten; von den Vergleichsblechen ist nur das chromatierte Blech ausreichend gegen Korrosion geschützt. Der T-Bend-Test, der unter der T0 -Bedingung durchgeführt wurde, sowie der Gitterschnitt mit Erichsentiefung zeigen, daß die Lackhaftung auf den erfindungsgemäß behandelten Blechen besser ist als auf den Vergleichsblechen. Insgesamt sind also die mit der Erfindung erzielten Ergebnisse überraschend gut, da sie dem mit der Chromatierung erzielten Ergebnis bezüglich der Korrosionsbeständigkeit gleichwertig und bezüglich der Lackhaftung deutlich überlegen sind. The following table contains the test results that were measured when using different substances according to the invention. The substances were present in the solutions according to the invention in a concentration of approx. 10 -3 mol / l. The salt spray test ESS reinforced with acetic acid shows that the thin films produced according to the invention ensure very good protection against infiltration compared to the comparative sheets; of the comparison sheets, only the chromated sheet is adequately protected against corrosion. The T-bend test, which was carried out under the T 0 condition, and the cross-cut with Erichsen indentation show that the paint adhesion on the sheets treated according to the invention is better than on the comparison sheets. Overall, the results achieved with the invention are surprisingly good, since they are equivalent to the results achieved with chromating in terms of corrosion resistance and clearly superior in terms of paint adhesion.

    Durch winkelabhängige Röntgenphotoelektronenspektroskopie (ARXPS) wurde die Orientierung der Moleküle der Verbindungen des Typs XYZ bestimmt. Durch die sehr begrenzte Ausdringtiefe der charakteristischen Photoelektronen ermöglicht die winkelaufgelöste Röntgenphotoelektrospektroskopie in Abhängigkeit vom Winkel α eine unterschiedliche Informationstiefe der Spektraldaten. So liegt die Informationstiefe bei kleinen Winkeln im Bereich von ca. 1 nm und bei größeren Winkeln im Bereich bis ca. 10 nm. Dies erlaubt es, die Orientierung der Moleküle zu bestimmen. Diese Methode ist zum Beispiel in der Veröffentlichung von Briggs, Practical Surface Analysis, 1990, Wiley & Sons, Chichester, beschrieben. Figur 1 zeigt das Röntgenphotoelektronenspektrum des 1-Phosphorsäure-12-(N-ethylamino)-dodecans auf der Legierung AlMg1, in dem das XPS-Intensitätsverhältnis N/P in Abhängigkeit vom Winkel α dargestellt ist, wobei N die Intensität des Nls-Peaks der Aminogruppe und P der P2s-Peak der Phosphorsäuregruppe ist und wobei die Abkürzung XPS für den Begriff Röntgenphotoelektronenspektroskopie steht. Das Spektrum beweist, daß die Phosphorsäuregruppe an die Metalloberfläche anbindet und die Aminogruppe von der Metalloberfläche abgewandt ist. Verbindung T-Bend-Test (TO) Abgeplatzte Fläche nach LPV 75 [%] ESS-Test nach DIN 50021 ESS Unterwanderung Gitterschnitt mit Erichsentiefung nach ISO 1520 Filiform-TestnachDIN 65472 [mm] ADPS 1 < 1 0 -- AUDS 10 1 0 -- HDLS 10 1 0 -- XDPS 20 < 1 -- < 1 HDPS 10 < 1 -- < 1 DDPS 0 < 1 0 < 1 Vergleichs blech O 100 8 0 5 G 85 4 5 4 P 10 3 1 < 1 C 25 < 1 2 < 1 ADPS C2 H5 NH- (CH2 )12 -PO(OH)2 AUDS = NH2 - (CH2)10 -COOH HDLS = OH-(CH2)11-COOH XDPS = (OH)2 PO-CH2 -C6H4 -CH2 -PO (OH)2 HDPS = (OH)2 PO2 - (CH2 ) 12 -OHs DDPS= (OH)2 PO- (CH2)12-PO (OH)2 O = AlMg1 Originalblech G = AlMg1, alkalisch/sauer gebeizt P = AlMg1, phosphatiert C = AlMg1, chromatiert LPV = Labor-Pruf-Vorschriften, betriebsintern The orientation of the molecules of the compounds of the type XYZ was determined by angle-dependent X-ray photoelectron spectroscopy (ARXPS). Due to the very limited penetration depth of the characteristic photoelectrons, the angle-resolved X-ray photoelectrospectroscopy enables a different information depth of the spectral data depending on the angle α. For example, the depth of information is at small angles in the range of approximately 1 nm and at larger angles in the range up to approximately 10 nm. This makes it possible to determine the orientation of the molecules. This method is described, for example, in the publication by Briggs, Practical Surface Analysis, 1990, Wiley & Sons, Chichester. FIG. 1 shows the X-ray photoelectron spectrum of the 1-phosphoric acid-12- (N-ethylamino) dodecane on the AlMg1 alloy, in which the XPS intensity ratio N / P is shown as a function of the angle α, where N is the intensity of the Nls peak Amino group and P is the P2s peak of the phosphoric acid group and the abbreviation XPS stands for the term X-ray photoelectron spectroscopy. The spectrum shows that the phosphoric acid group binds to the metal surface and the amino group faces away from the metal surface. connection T-bend test (TO) chipped area according to LPV 75 [%] ESS test according to DIN 50021 ESS infiltration Cross-cut with Erichsen indentation according to ISO 1520 Filiform test according to DIN 65472 [mm] ADPS 1 <1 0 - AUDS 10 1 0 - HDLS 10 1 0 - XDPS 20 <1 - <1 HDPS 10 <1 - <1 DDPS 0 <1 0 <1 Comparative sheet O 100 8th 0 5 G 85 4 5 4 P 10 3 1 <1 C 25 <1 2 <1 ADPS C 2 H 5 NH- (CH 2 ) 12 -PO (OH) 2 AUDS = NH 2 - (CH 2 ) 10 -COOH HDLS = OH- (CH 2 ) 11 -COOH XDPS = (OH) 2 PO-CH 2 -C 6 H 4 -CH 2 -PO (OH) 2 HDPS = (OH) 2 PO 2 - (CH 2 ) 12 -OHs DDPS = (OH) 2 PO- (CH 2 ) 12 -PO (OH) 2 O = AlMg1 original sheet G = AlMg1, alkaline / acid pickled P = AlMg1, phosphated C = AlMg1, chromated LPV = laboratory test regulations, in-house

    Claims (13)

    1. Process for the treatment of metallic surfaces consisting of zinc, magnesium or aluminium or of alloys of zinc, magnesium or aluminium and to which lacquers, plastic coatings, paints, sealants or adhesives are applied after the treatment, characterised in that the metallic surfaces are treated at 10 to 100°C by dipping, spraying or roller with an aqueous solution having a pH of 2 to 13 and containing 10-5 to 1 mol/l of one or more compounds of the type XYZ, wherein Y is an organic group containing 2 to 50 C atoms and having a straight-chain structure, wherein X is a -COOH, -HSO3, -HSO4, (OH)2PO-, (OH)2PO2-, (OH)(OR')PO- or (OH)(OR')PO2- group, wherein Z is an -OH, -SH, -NH2, -NHR', -CN, -CH=CH2, -OCN, epoxy, CH2=CR"-COO-, acrylic acid amide, (OH)2PO-, (OH)2PO2-, (OH)(OR')PO- or (OH)(OR')PO2- group, with R' being an alkyl group having 1 to 4 C atoms, R" being an H atom or an alkyl group having 1 to 4 C atoms and with the groups X and Z each being bonded to the Y group in their end position.
    2. Process according to claim 1, characterised in that in the aqueous solution 0.1 to 50 % of the water in the aqueous solution is replaced by an alcohol having 1 to 4 C atoms, by acetone, by dioxan or by tetrahydrofuran.
    3. Process according to claims 1 to 2, characterised in that the aqueous solution contains one or more compounds of the type XYZ in a concentration lying in the range of critical micelle concentration.
    4. Process according to claims 1 to 3, characterised in that the aqueous solution contains a defoaming agent and/or a solution aid, each in a quantity of 0.05 to 5 wt.%.
    5. Process according to claims 1 to 4, characterised in that the compounds of type XYZ are present as salts in the aqueous solution.
    6. Process according to claims 1 to 5, characterised in that Y is an unbranched, straight-chain alkyl group having 2 to 20 C atoms, or an unbranched, straight-chain group consisting of 1 to 4 aromatic C6H4 nuclei bonded in the para position or a group consisting of 1 or 2 unbranched straight-chain alkyl radicals each having 1 to 12 C atoms and 1 to 4 aromatic C6H4 nuclei bonded in the para position.
    7. Process according to claim 6, characterised in that Y is an unbranched, straight-chain alkyl group having 10 to 12 C atoms or a p-CH2-C6H4-CH2 group or a p,p'-C6H4-C6H4 group.
    8. Process according to claims 1 to 7, characterised in that X is an (OH)2PO2 or (OH)(OR')PO2 group.
    9. Process according to claims 1 to 8, characterised in that Z is an (OH)2PO2-, (OH) (OR')PO2-, OH, -SH, -NHR', -CH=CH2 or CH2=CR"-COO- group.
    10. Process according to claims 1 to 9, characterised in that the aqueous solution contains as compounds of type XYZ 1-phosphonic acid-12-mercaptododecane, 1-phosphonic acid-12-(N-ethylamino)dodecane, 1-phosphonic acid-12-dodecene, p-xylylene diphosphonic acid, 1,10-decanediphosphonic acid, 1,12-dodecanediphosphonic acid, 1-phosphoric acid-12-hydroxydodecane, 1-phosphoric acid-12-(N-ethylamino)dodecane, 1-phosphoric acid-12-dodecene, 1-phosphoric acid-12-mercaptododecane, 1,10-decanediphosphoric acid, 1,12-dodecanediphosphoric acid, p,p'-biphenyl diphosphoric acid, 1-phosphoric acid-12-acrylododecane.
    11. Process according to claims 1 to 10, characterised in that the dipping time is 5 seconds to 20 minutes, the spraying time is 5 seconds to 15 minutes and the roller application time is 2 to 120 seconds.
    12. Process according to claims 1 to 11, characterised in that the metallic surfaces are pickled with alkali and/or acid and then rinsed with water before application of the aqueous solution.
    13. Process according to claims 1 to 12, characterised in that the metallic surfaces to which the aqueous solution has been applied by dipping or spraying are then rinsed with water and optionally dried in a nitrogen or air stream, with the temperature of the nitrogen or air stream being 15 to 150°C.
    EP97954820A 1996-12-28 1997-12-18 Method for treating metallic surfaces Expired - Lifetime EP0948666B2 (en)

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    US7815963B2 (en) * 1996-10-17 2010-10-19 The Trustees Of Princeton University Enhanced bonding layers on titanium materials
    US6299983B1 (en) 1997-06-27 2001-10-09 E. I. Du Pont De Nemours And Company Derivatized metallic surfaces, composites of functionalized polymers with such metallic surfaces and processes for formation thereof
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    EP0948666A1 (en) 1999-10-13
    ATE234948T1 (en) 2003-04-15
    ES2195202T3 (en) 2003-12-01
    ES2195202T5 (en) 2008-04-01
    TR199901466T2 (en) 1999-10-21
    BR9713638A (en) 2000-04-11
    DK0948666T3 (en) 2003-07-07
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    DK0948666T4 (en) 2008-01-07
    NO993118L (en) 1999-06-23
    CA2275729A1 (en) 1998-07-09
    NO993118D0 (en) 1999-06-23
    WO1998029580A1 (en) 1998-07-09
    DE59709588D1 (en) 2003-04-24
    AU6205898A (en) 1998-07-31
    DE19654642C2 (en) 2003-01-16
    CA2275729C (en) 2007-09-25
    JP3986092B2 (en) 2007-10-03
    EP0948666B2 (en) 2007-09-26
    KR100487855B1 (en) 2005-05-09
    NO326333B1 (en) 2008-11-10

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