EP0948666B2 - Method for treating metallic surfaces - Google Patents

Method for treating metallic surfaces Download PDF

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Publication number
EP0948666B2
EP0948666B2 EP97954820A EP97954820A EP0948666B2 EP 0948666 B2 EP0948666 B2 EP 0948666B2 EP 97954820 A EP97954820 A EP 97954820A EP 97954820 A EP97954820 A EP 97954820A EP 0948666 B2 EP0948666 B2 EP 0948666B2
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Prior art keywords
aqueous solution
acid
process according
group
atoms
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German (de)
French (fr)
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EP0948666A1 (en
EP0948666B1 (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 process for the treatment of metallic surfaces consisting of zinc, magnesium or aluminum or of the alloys of zinc, magnesium or aluminum and to which after the treatment lacquers, plastic layers, paints, sealants or adhesives are applied ,
  • scale surfaces are coated with an inorganic conversion layer (e.g., zinc phosphate) prior to the application of a lacquer or plastic layer.
  • an inorganic conversion layer e.g., zinc phosphate
  • conversion treatment by means of layer-forming phosphating or chromating the metallic surface is passivated and prepared for the usually subsequent coating with a paint or with a plastic.
  • the conversion treatment of aluminum surfaces is still carried out today by yellow chromating, using an acidic chromate solution with a pH of 1 to 2, which forms a protective layer on the aluminum.
  • the protective layer consists of an insoluble 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 coating of lacquer or plastic.
  • the yellow chromated aluminum surfaces has the disadvantage that it has only insufficient adhesion-promoting properties with respect to a paint and plastic layer.
  • chromate ions are washed out of free-weathered layers disadvantageously.
  • the DE-A 31 37 525 discloses a process for inhibiting corrosion in an aqueous system, wherein the aqueous system contains at least one water-soluble inorganic nitrite and at least one organic diphosphonic acid or at least one salt of the diphosphonic acid.
  • the diphosphonic acid is present in the aqueous system at a concentration of 0.1 to 20 ppm.
  • corrosion problems in cooling systems should be avoided.
  • especially the hydroxyethylidenediphosphonic acid and its inorganic salts are 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, with each other or together with other known corrosion inhibitors.
  • the compounds are added for corrosion inhibition in general aqueous, aqueous-alcoholic, alcoholic and / or oil-containing media.
  • they can be used as corrosion inhibitors in heat carriers of cooling or heating circuits, cooling lubricants, mineral oils or Sparbeizen. the corrosion of metals is prevented by addition of the compounds and / or their salts to the media or circulatory liquids, in particular of copper and its alloys.
  • the benzimidazolyl-2-alkane-phosphonic acids contain a phosphonic acid group, a straight-chain or branched, saturated or unsaturated, bivalent, optionally substituted hydrocarbon radical having 1 to 15 carbon atoms and a substituted benzimidazole radical, where the straight-chain or branched hydrocarbon radical and the benzimidazole radical are in position 2 the benzimidazole radical are linked together.
  • DE-AS 1 013 814 teaches one-component reaction primer solutions (one-component "wash primer") for improving the printability of aluminum foils which contain not only hydroxyl-containing acetalized synthetic resin but also one or two oxygen-containing inorganic acids in hydroxyl-containing solvents and from 0.1 to 5% of an additive of organic hydroxyl group-containing acids or esters such as of oxybutyric acid or tartaric acid.
  • a method in which firstly a layer of aluminum is produced on an aluminum substrate at a pH value of from 2 to 14 and in which then at the Aluminum hydroxide layer is deposited by treatment with an organic phosphinic acid or an organic phosphonic acid another layer.
  • the organic radical of the phosphinic and phosphonic acid contains in each case 1 to 10 organic groups and 1 to 30 C atoms.
  • the molecule of the organic phosphinic and phosphonic acids contains from 1 to 10 phosphine and phosphonic acid groups.
  • an aqueous solution is used in which amines, amine alcohols, alkali hydroxides, alkaline earth hydroxides, alkali metal carbonates. Alkali bicarbonates or ammonia are included.
  • a solution is used in which the phosphinic and phosphonic acids are present in a concentration of 0.001 mol / l up to the saturation concentration and contains as solvent water, an alcohol or an organic 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 should act on the substrate in particular as a good adhesion promoter for paint and plastic coatings and for paints.
  • the invention has for its object to provide a method according to which metallic surfaces, which consist of zinc, magnesium or aluminum or of the alloys of zinc, magnesium or aluminum, treated to the metallic surfaces in particular a good adhesion for Paints, plastic layers, paints, sealants and adhesives and to protect the metallic surfaces against corrosion.
  • the object underlying the invention is achieved in that the metallic surfaces are treated at 10 to 100 ° C by dipping, spraying or rolling with an aqueous solution having a pH of 2 to 13 and 10 -5 to 1 mol / l one or more compounds.
  • Y is a straight-chain alkyl group having 10 to 20 C atoms
  • X is a COOH, HSO 3 , HSO 4 , (OH) 2 PO, (OH) 2 PO 2 - , (OH) (OR ') PO or (OH) (OR') PO 2 - group
  • R ' is an alkyl group having 1 to
  • the effect of the method according to the invention is based on the ability of the compounds XYZ to spontaneously organize and to form very thin, closed films on metallic surfaces, in particular an orientation of the acidic groups in the direction of the metallic surface and between the hydroxyl groups on the metallic surface and the acidic groups of the compound XYZ is a chemical bond is formed.
  • the structure of the compounds XYZ was chosen according to the invention so that both a reactive binding of the thin film to the metal surface and to the matrix of paints, plastic coatings, paints, sealants and adhesives results.
  • the straight-chain organic group Y acts as a "spacer" between the groups X and Z; it virtually gives the compound XYZ the properties of a surfactant, since the organic group Y has hydrophobic properties.
  • the Z group imparts wettability and reactivity to the coated surface to paints, plastic coatings, paints, sealants and adhesives.
  • paints, plastic coatings, paints, sealants and adhesives are applied to the thin films, the advantageous properties of the thin films are retained even under the action of corrosive media, so that the metallic surfaces are protected against corrosion.
  • the reactive group Z should be matched in particular to the individual coatings.
  • aqueous solution 0.1 to 50% of the water is replaced by an alcohol having 1 to 4 carbon atoms, by acetone, by dioxane or by tetrahydrofuran.
  • organic solvents cause a higher solubility of the compounds XYZ, which are usually larger molecules whose solubility in pure water is not very high.
  • the solution always contains a large amount of water, so that even in the presence of organic solvents can still be spoken of an aqueous system.
  • the aqueous solution contains one or more compounds of the type XYZ in a concentration which is in the range of the critical micelle concentration.
  • the critical micelle formation concentration cmc is a characteristic of the particular surfactant concentration, in which the aggregation of the surfactant molecules to micelles begins. The aggregation is reversible. Below the cmc, ie, when the solutions are diluted, the micelles again break down into monomeric surfactant molecules.
  • the numerical value of cmc for each surfactant depends on its constitution as well as external parameters such as ionic strength, temperature and concentration of additives. Surface tension measurements are suitable as methods for determining the cmc.
  • the surface tension is determined ⁇ of a surfactant solution as a function of its concentration c at constant temperature by means of the ring or plate method.
  • the aqueous solution contains a defoamer and / or a solubilizer in each case in an amount of 0.05 to 5 wt .-%.
  • the defoamer facilitates the handling of the solution according to the invention, which tends to foam due to the surfactant properties of the compounds XYZ.
  • the solubilizer advantageously limits the use of organic solvents and favors the use of pure water. Both as defoamers and as solubilizers, for example, amino alcohols can be used.
  • the compounds of the type XYZ are present in the aqueous solution as salts.
  • the salts are generally more soluble than the compounds themselves, and moreover the dissolved salts are very stable, so that the handling of the solution according to the invention is improved by the use of the salts of the compounds XYZ.
  • the sodium and potassium salts are used.
  • Y is a straight-chain, straight-chain alkyl group having 10 to 12 C atoms. These groups Y give the compounds XYZ according to the invention very good adhesion-promoting properties for coatings and other organic coatings.
  • Aqueous solutions containing the following compounds of the type XYZ have very good adhesion-promoting and corrosion-inhibiting properties: 1-phosphonic acid 12-mercaptododecane, 1-phosphonic acid 12- (N-ethylamino) dodecane, 1-phosphonic acid 12-dodecene, 1,10-decanediphosphonic acid, 1,12-dodecanediphosphonic acid, 1-phosphoric acid 12-hydroxvdodecane, 1-phosphoric acid 12 (N-ethylamino) dodecane, 1-phosphoric acid 12-mercaptododecane, 1,10-decanediphosphoric acid, 1,12- Dodecanediphosphoric acid, 1-phosphoric acid 12-acryloyldodecane.
  • These compounds bond to the metallic surfaces via the phosphonic and phosphoric acid groups and act as adhesion promoters to the various organic constituents of the coatings, the plastic coatings, the paints, the sealants, both through their aliphatic group and through their functional group Z. and the adhesives.
  • the aqueous solution is applied by the known dipping, spraying or rolling at 10 to 100 ° C on the metallic surfaces, the dipping time 5 seconds to 20 minutes, the injection time 5 seconds to 15 Minutes and the rolling time is 2 to 120 seconds. It has been found that a thin film is formed on the metallic surfaces when the aqueous solution is applied by dipping, spraying or rolling, wherein rinsing of the treated metallic surfaces is not essential, but may be advantageous.
  • the metallic surfaces are stained alkaline and / or acid before applying the aqueous solution and then rinsed with water.
  • the used water can be desalted or not desalted.
  • the metallic surfaces consisting of zinc, magnesium, aluminum and their alloys are always covered by oxide layers and additionally contaminated by the superficial adsorption of carbon dioxide, water and / or hydrocarbons. These contaminated coatings are unable to permanently bond paints, plastic coatings, paints, sealants and adhesives and provide long term corrosion protection. Therefore, the metallic surfaces are cleaned in the manner according to the invention prior to treatment with the aqueous solution.
  • the metallic surfaces on which the aqueous solution was applied by dipping or spraying, then rinsed with water and optionally dried in a stream of nitrogen or air, wherein the temperature of the nitrogen or air flow is 15 to 150 ° C. Rinsing and drying does not hinder the formation of the thin film on the metallic surfaces.
  • the water used for rinsing may be desalted or not desalted.
  • the method according to the invention is used for the treatment of metallic surfaces, to which a cathodic or anodic electrodeposition paint, a powder coating, a coil coating lacquer, a low-solvent high-solids lacquer or a water-diluted lacquer is subsequently applied ,
  • a cathodic or anodic electrodeposition paint a powder coating, a coil coating lacquer, a low-solvent high-solids lacquer or a water-diluted lacquer is subsequently applied
  • the pretreatment of the metallic surfaces with the aqueous solution according to the invention has proven particularly useful.
  • the substrate sheets consist of the alloy AlMg1.
  • the 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. Thereafter, the alkaline pickled sheets are immersed for 3 minutes at 40 ° C in an acid pickling solution containing 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 in the aqueous solution according to the invention at 40 ° C. for 3 minutes, which contains the compound XYZ according to the invention in a concentration of about 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®. Subsequently, the sheets are rinsed by spraying with water. Thereafter, the alkaline pickled sheets are sprayed at 50 ° C for 30 seconds with an acidic pickling solution containing 16 g / l Bonder V450M®. Subsequently, the pickled sheets are rinsed by spraying with demineralized 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 deionized water and drying in a stream of air at room temperature.
  • the compound XYZ according to the invention is present in the aqueous solution in a concentration of about 10 -3 mol / l (® registered trademark of Metallgesellschaft AG, Frankfurt / Main, DE).
  • the sheets are pickled according to the spraying alkaline and acidic and rinsed. Subsequently, the aqueous solution according to the invention is rolled onto the sheets for two seconds at room temperature, wherein the roller is driven at 25 U / minute.
  • the compound XYZ is present in a concentration of about 10 -3 mol / l. After rolling the aqueous solution, the sheets are dried in a convection oven at 105 ° C.
  • the treated with the inventive aqueous solution panels were painted according to different methods. Both a cathodic electrodeposition paint and a powder coating as well as a polyester paint were used.
  • the electrocoating was electrolytically deposited on the sheets at a voltage of about 250 volts and then dried at 180 ° C for 22 minutes.
  • the powder coating was applied to the panels by electrostatic spraying and then dried at 200 ° C for 10 minutes.
  • the polyester coating system consisted of a primer and a topcoat. Both components were applied to the sheets by knife coating. The primer had a layer thickness of 5 microns, while the topcoat had a layer thickness of 25 microns. The stoving temperatures were 216 ° C for the primer and 241 ° C for the top coat.
  • the following table contains the test results which 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 about 10 -3 mol / l.
  • the acetic acid-enhanced salt spray test ESS shows that the thin films produced according to the invention provide very good undercounter protection over the comparison sheets; Of the comparison sheets only the chromated sheet is sufficiently protected against corrosion.
  • the T-bend test which was carried out under the T 0 condition, as well as the cross-hatching with Erichsentiefung show that the paint adhesion is better on the inventively treated sheets than on the comparison sheets. Overall, therefore, the results obtained with the invention are surprisingly good, since they are equivalent to the result obtained with the chromating equivalent corrosion resistance and with respect to the paint adhesion significantly.
  • angle-dependent X-ray photoelectron spectroscopy By angle-dependent X-ray photoelectron spectroscopy (ARXPS) the orientation of the molecules of the compounds of the type XYZ was determined. Due to the very limited penetration depth of the characteristic photoelectrons, angle-resolved x-ray photoelectrospectroscopy allows a different information depth of the spectral data as a function of the angle ⁇ . Thus, the information depth at small angles in the range of about 1 nm and at larger angles in the range to about 10 nm. This allows to determine the orientation of the molecules. This method is, for example, in the publication of Briggs, Practical Surface Analysis, 1990, Wiley & Sons, Chichester , described. FIG.

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  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
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  • ing And Chemical Polishing (AREA)

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 process for the treatment of metallic surfaces consisting of zinc, magnesium or aluminum or of the alloys of zinc, magnesium or aluminum and to which after the treatment lacquers, plastic layers, paints, sealants or adhesives are applied ,

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 is due to electrochemical reactions at the metal / polymer phase boundary. Thus, in many coating processes used in the art, scale surfaces are coated with an inorganic conversion layer (e.g., zinc phosphate) prior to the application of a lacquer or plastic layer. By conversion treatment by means of layer-forming phosphating or chromating the metallic surface is passivated and prepared for the usually subsequent coating with a paint or with a 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 acidic chromate solution with a pH of 1 to 2, which forms a protective layer on the aluminum. The protective layer consists of an insoluble
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 coating of lacquer or plastic. However, the yellow chromated aluminum surfaces has the disadvantage that it has only insufficient adhesion-promoting properties with respect to a paint and plastic layer. In addition, chromate ions are washed out of free-weathered layers disadvantageously.

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.As an alternative to chromating, a process has been developed which works with zirconium salts, fluorides, phosphates and organic polymers (e.g., polyacrylates and polyvinyl alcohols). With this method, layers are formed on aluminum surfaces, which give the substrate a certain corrosion protection and a fairly good adhesion for paint and 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 also been no lack of attempts to optimally equip metallic surfaces of zinc, magnesium, aluminum and their alloys by treatment with organic substances for the application of paint and 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.So is out of the DE-A 31 37 525 discloses a process for inhibiting corrosion in an aqueous system, wherein the aqueous system contains at least one water-soluble inorganic nitrite and at least one organic diphosphonic acid or at least one salt of the diphosphonic acid. The diphosphonic acid is present in the aqueous system at a concentration of 0.1 to 20 ppm. With the known aqueous system in particular corrosion problems in cooling systems should be avoided. In the aqueous system, especially the hydroxyethylidenediphosphonic acid and its inorganic salts are 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 the 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. For corrosion inhibition they can be used individually, with each other or together with other known corrosion inhibitors. The compounds are added for corrosion inhibition in general aqueous, aqueous-alcoholic, alcoholic and / or oil-containing media. For example, they can be used as corrosion inhibitors in heat carriers of cooling or heating circuits, cooling lubricants, mineral oils or Sparbeizen. the corrosion of metals is prevented by addition of the compounds and / or their salts to the media or circulatory liquids, in particular of copper and its alloys. The benzimidazolyl-2-alkane-phosphonic acids contain a phosphonic acid group, a straight-chain or branched, saturated or unsaturated, bivalent, optionally substituted hydrocarbon radical having 1 to 15 carbon atoms and a substituted benzimidazole radical, where the straight-chain or branched hydrocarbon radical and the benzimidazole radical are in position 2 the benzimidazole radical are linked together.

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 the US Pat. No. 4,351,675 is an 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, wherein the two phosphonic acid groups are linked together via a carbon atom, which also has a 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 contain not only hydroxyl-containing acetalized synthetic resin but also one or two oxygen-containing inorganic acids in hydroxyl-containing solvents and from 0.1 to 5% of an additive of organic hydroxyl group-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, out of the US Pat. No. 5,059,258 A method is known in which firstly a layer of aluminum is produced on an aluminum substrate at a pH value of from 2 to 14 and in which then at the Aluminum hydroxide layer is deposited by treatment with an organic phosphinic acid or an organic phosphonic acid another layer. The organic radical of the phosphinic and phosphonic acid contains in each case 1 to 10 organic groups and 1 to 30 C atoms. The molecule of the organic phosphinic and phosphonic acids contains from 1 to 10 phosphine and phosphonic acid groups. To produce the hydroxide layer, an aqueous solution is used in which amines, amine alcohols, alkali hydroxides, alkaline earth hydroxides, alkali metal carbonates. Alkali bicarbonates 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.To produce the second layer, a solution is used in which the phosphinic and phosphonic acids are present in a concentration of 0.001 mol / l up to the saturation concentration and contains as solvent water, an alcohol or an organic 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 should act on the substrate in particular as a good adhesion promoter for paint and plastic coatings and for paints.

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 to provide a method according to which metallic surfaces, which consist of zinc, magnesium or aluminum or of the alloys of zinc, magnesium or aluminum, treated to the metallic surfaces in particular a good adhesion for Paints, plastic layers, paints, sealants and adhesives and to protect the metallic surfaces 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 unverzweigte geradkettige Alkyl-Gruppe mit 10 bis 20 C-Atomen ist, 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 underlying the invention is achieved in that the metallic surfaces are treated at 10 to 100 ° C by dipping, spraying or rolling with an aqueous solution having a pH of 2 to 13 and 10 -5 to 1 mol / l one or more compounds. of the type XYZ, where Y is a straight-chain alkyl group having 10 to 20 C atoms, 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, wherein 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 And wherein R 'is an alkyl group having 1 to 4 C atoms, wherein R "is an H atom or an alkyl group having 1 to 4 C atoms, and wherein the groups X and Z to the group Y each in the end position of which is bound, 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 the compounds XYZ to spontaneously organize and to form very thin, closed films on metallic surfaces, in particular an orientation of the acidic groups in the direction of the metallic surface and between the hydroxyl groups on the metallic surface and the acidic groups of the compound XYZ is a chemical bond is formed. The structure of the compounds XYZ was chosen according to the invention so that both a reactive binding of the thin film to the metal surface and to the matrix of paints, plastic coatings, paints, sealants and adhesives results. The straight-chain organic group Y acts as a "spacer" between the groups X and Z; it virtually gives the compound XYZ the properties of a surfactant, since the organic group Y has hydrophobic properties. The Z group imparts wettability and reactivity to the coated surface to paints, plastic coatings, paints, sealants and adhesives. When paints, plastic coatings, paints, sealants and adhesives are applied to the thin films, the advantageous properties of the thin films are retained even under the action of corrosive media, so that the metallic surfaces are protected against corrosion. The reactive group Z should be matched in particular to the individual coatings.

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, it is provided that in the aqueous solution 0.1 to 50% of the water is replaced by an alcohol having 1 to 4 carbon atoms, by acetone, by dioxane or by tetrahydrofuran. These organic solvents cause a higher solubility of the compounds XYZ, which are usually larger molecules whose solubility in pure water is not very high. On the other hand, the solution always contains a large amount of water, so that even in the presence of organic solvents can still 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 contains one or more compounds of the type XYZ in a concentration which is in the range of the critical micelle concentration. The critical micelle formation concentration cmc is a characteristic of the particular surfactant concentration, in which the aggregation of the surfactant molecules to micelles begins. The aggregation is reversible. Below the cmc, ie, when the solutions are diluted, the micelles again break down into monomeric surfactant molecules. The numerical value of cmc for each surfactant depends on its constitution as well as external parameters such as ionic strength, temperature and concentration of additives. Surface tension measurements are suitable as methods for determining the cmc. The surface tension is determined δ of a surfactant solution as a function of its concentration c at constant temperature by means of the ring or plate method. The cmc can be seen as a break point in the trace δ = f (log c). Examples for determining the cmc of various surfactants can be found in "The Surfactants" Ed. 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 contains a defoamer and / or a solubilizer in each case in an amount of 0.05 to 5 wt .-%. The defoamer facilitates the handling of the solution according to the invention, which tends to foam due to the surfactant properties of the compounds XYZ. The solubilizer advantageously limits the use of organic solvents and favors the use of pure water. Both as defoamers and as solubilizers, for example, amino alcohols can 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, it has proven useful in some cases when the compounds of the type XYZ are present in the aqueous solution as salts. The salts are generally more soluble than the compounds themselves, and moreover the dissolved salts are very stable, so that the handling of the solution according to the invention is improved by the use of the salts of the compounds XYZ. In practice, especially the sodium and potassium salts are used.

Gemäß der Erfindung ist Y eine unverzweigte, geradkettige Alkylgruppe mit 10 bis 20 C-Atomen. 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:

  1. a) X-(CH2)m -Z; m = 10 bis 20
According to the invention Y is an unbranched, straight-chain alkyl group having 10 to 20 carbon atoms. All groups Y according to the invention are therefore characterized by a straight-chain, unbranched molecular structure which is best suited to act as a "spacer" between the groups X and Z. The groups Y can therefore according to the invention have the following structure:
  1. a) X- (CH 2 ) m -Z; m = 10 to 20

Nach der Erfindung ist es besonders vorteilhaft, wenn Y eine unverzweigte, geradkettige Alkylgruppe mit 10 bis 12 C-Atomen 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 a straight-chain, straight-chain alkyl group having 10 to 12 C atoms. These groups Y give the compounds XYZ according to the invention very good adhesion-promoting properties for coatings 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 provided with the aforementioned groups X and Z, also have good adhesion-promoting properties for paints and plastic coatings and also go with the metallic surfaces a solid chemical bond.

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, 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, 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 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 containing the following compounds of the type XYZ have very good adhesion-promoting and corrosion-inhibiting properties: 1-phosphonic acid 12-mercaptododecane, 1-phosphonic acid 12- (N-ethylamino) dodecane, 1-phosphonic acid 12-dodecene, 1,10-decanediphosphonic acid, 1,12-dodecanediphosphonic acid, 1-phosphoric acid 12-hydroxvdodecane, 1-phosphoric acid 12 (N-ethylamino) dodecane, 1-phosphoric acid 12-mercaptododecane, 1,10-decanediphosphoric acid, 1,12- Dodecanediphosphoric acid, 1-phosphoric acid 12-acryloyldodecane. These compounds bond to the metallic surfaces via the phosphonic and phosphoric acid groups and act as adhesion promoters to the various organic constituents of the coatings, the plastic coatings, the paints, the sealants, both through their aliphatic group and through their functional group Z. and the 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, it is provided that the aqueous solution is applied by the known dipping, spraying or rolling at 10 to 100 ° C on the metallic surfaces, the dipping time 5 seconds to 20 minutes, the injection time 5 seconds to 15 Minutes and the rolling time is 2 to 120 seconds. It has been found that a thin film is formed on the metallic surfaces when the aqueous solution is applied by dipping, spraying or rolling, wherein rinsing of the treated metallic surfaces is not essential, but may be advantageous.

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 are stained alkaline and / or acid before applying the aqueous solution and then rinsed with water. The used water can be desalted or not desalted. The metallic surfaces consisting of zinc, magnesium, aluminum and their alloys are always covered by oxide layers and additionally contaminated by the superficial adsorption of carbon dioxide, water and / or hydrocarbons. These contaminated coatings are unable to permanently bond paints, plastic coatings, paints, sealants and adhesives and provide long term corrosion protection. Therefore, the metallic surfaces are cleaned in the manner according to the invention prior to treatment with 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 it is provided that the metallic surfaces on which the aqueous solution was applied by dipping or spraying, then rinsed with water and optionally dried in a stream of nitrogen or air, wherein the temperature of the nitrogen or air flow is 15 to 150 ° C. Rinsing and drying does not hinder the formation of the thin film on the metallic surfaces. The water used for rinsing may be desalted or not desalted.

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 method according to the invention is used for the treatment of metallic surfaces, to which a cathodic or anodic electrodeposition paint, a powder coating, a coil coating lacquer, a low-solvent high-solids lacquer or a water-diluted lacquer is subsequently applied , In all painting processes, the pretreatment of the metallic surfaces with the aqueous solution according to the invention has proven particularly useful.

Der Gegenstand der Erfindung wird nachfolgend anhand meherer Ausführungsbeispiele näher erläutert:The object of the invention is explained in detail below with reference Handle multiple embodiments:

Beispiel 1:Example 1: Verfahrenmethod

Als Substrat werden Bleche verwendet, die aus der Legierung AlMg1 bestehen.As the substrate sheets are used, which consist of the alloy AlMg1.

a) Tauchverfahrena) Dipping 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 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. Thereafter, the alkaline pickled sheets are immersed for 3 minutes at 40 ° C in an acid pickling solution containing 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 in the aqueous solution according to the invention at 40 ° C. for 3 minutes, which contains the compound XYZ according to the invention in a concentration of about 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 method

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®. Subsequently, the sheets are rinsed by spraying with water. Thereafter, the alkaline pickled sheets are sprayed at 50 ° C for 30 seconds with an acidic pickling solution containing 16 g / l Bonder V450M®. Subsequently, the pickled sheets are rinsed by spraying with demineralized 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 deionized water and drying in a stream of air at room temperature. The compound XYZ according to the invention is present in the aqueous solution in a concentration of about 10 -3 mol / l (® registered trademark of Metallgesellschaft AG, Frankfurt / Main, DE).

c) Walzverfahren (Rollcoating)c) rolling process (rollcoating)

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 pickled according to the spraying alkaline and acidic and rinsed. Subsequently, the aqueous solution according to the invention is rolled onto the sheets for two seconds at room temperature, wherein the roller is driven at 25 U / minute. In the aqueous solution according to the invention, the compound XYZ is present in a concentration of about 10 -3 mol / l. After rolling the aqueous solution, the sheets are dried in a convection oven at 105 ° C.

d) Verbindungen des Typs XYZd) compounds of the type XYZ

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
  • 1,12-Dodecandiphosphonsäure
To carry out the process variants, aqueous solutions were used which contained the following compounds XYZ:
  • 1-phosphonic acid-12- (N-ethylamino) dodecane
  • 1-phosphoric acid-12-hydroxydodecane
  • 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 treated with the inventive aqueous solution panels were painted according to different methods. Both a cathodic electrodeposition paint and a powder coating as well as a polyester paint were used. The electrocoating was electrolytically deposited on the sheets at a voltage of about 250 volts and then dried at 180 ° C for 22 minutes. The powder coating was applied to the panels by electrostatic spraying and then dried at 200 ° C for 10 minutes. The polyester coating system consisted of a primer and a topcoat. Both components were applied to the sheets by knife coating. The primer had a layer thickness of 5 microns, while the topcoat had a layer thickness of 25 microns. The stoving temperatures were 216 ° C for the primer and 241 ° C for the top coat.

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 which 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 about 10 -3 mol / l. The acetic acid-enhanced salt spray test ESS shows that the thin films produced according to the invention provide very good undercounter protection over the comparison sheets; Of the comparison sheets only the chromated sheet is sufficiently protected against corrosion. The T-bend test, which was carried out under the T 0 condition, as well as the cross-hatching with Erichsentiefung show that the paint adhesion is better on the inventively treated sheets than on the comparison sheets. Overall, therefore, the results obtained with the invention are surprisingly good, since they are equivalent to the result obtained with the chromating equivalent corrosion resistance and with respect to the paint adhesion significantly.

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. Tabelle 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 -- 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 HDPS = (OH)2 PO2 - (CH2 ) 12 -OH 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 By angle-dependent X-ray photoelectron spectroscopy (ARXPS) the orientation of the molecules of the compounds of the type XYZ was determined. Due to the very limited penetration depth of the characteristic photoelectrons, angle-resolved x-ray photoelectrospectroscopy allows a different information depth of the spectral data as a function of the angle α. Thus, the information depth at small angles in the range of about 1 nm and at larger angles in the range to about 10 nm. This allows to determine the orientation of the molecules. This method is, for example, in the publication of Briggs, Practical Surface Analysis, 1990, Wiley & Sons, Chichester , described. FIG. 1 shows the X-ray photoelectron spectrum of the 1-phosphoric acid 12- (N-ethylamino) dodecane on the alloy AlMg1, 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 of the Amino group and P is the P2s peak of the phosphoric acid group and wherein the abbreviation XPS stands for the term X-ray photoelectron spectroscopy. The spectrum proves that the phosphoric acid group binds to the metal surface and the amino group faces away from the metal surface. table connection T-Bend Test (TO) Chipped Area to LPV 75 [%] ESS test according to DIN 50021 ESS infiltration Cross-cut with Erichsen indentation to ISO 1520 Filiform test according to DIN 65472 [mm] ADPS 1 <1 0 - AUDS 10 1 0 - HDLS 10 1 0 - 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 HDPS = (OH) 2 PO 2 - (CH 2) 12 -OH DDPS = (OH) 2 PO- (CH 2 ) 12 -PO (OH) 2 O = AlMg1 original sheet G = AlMg1, pickled alkaline / acid P = AlMg1 phosphate, C = AlMg1, chromated LPV = Laboratory Pruf regulations, internal

Claims (12)

  1. A process for the treatment of metallic surfaces which consist of zinc, magnesium or aluminium or of the alloys of zinc, magnesium or aluminium and to which lacquers, plastic coatings, paints, sealants or adhesives are to be applied after the treatment, characterised in that the metallic surfaces are treated at 10 to 100°C by dipping, spraying or roller coating 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 unbranched, straight-chain alkyl group having 10 to 20 C atoms, 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, wherein R' is an alkyl group having 1 to 4 C atoms, wherein R" is an H atom or an alkyl group having 1 to 4 C atoms and wherein the groups X and Z are each bonded to the Y group in their end position, wherein the aqueous solution is not used as a synthetic-resin-containing reactive primer solution (one-component wash primer) on aluminium foils.
  2. A process according to claim 1, characterised in that in the aqueous solution 0.1 to 50 % of the water is replaced by an alcohol having 1 to 4 C atoms, by acetone, by dioxan or by tetrahydrofuran.
  3. A 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. A 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. A process according to claims 1 to 4, characterised in that the compounds of type XYZ are present as salts in the aqueous solution.
  6. A process according to claims 1 to 5, characterised in that Y is an unbranched, straight-chain alkyl group having 10 to 12 C atoms.
  7. A process according to claims 1 to 6, characterised in that X is an (OH)2PO2 or (OH)(OR')PO2 group.
  8. A process according to claims 1 to 7, characterised in that Z is an (OH)2PO2, (OH)(OR')PO2, OH, SH, NHR', CH=CH2 or CH2=CR"-COO group.
  9. A process according to claims 1 to 8, characterised in that as compounds of type XYZ the aqueous solution contains 1-phosphonic acid-12-mercaptododecane, 1-phosphonic acid-12-(N-ethylamino)dodecane, 1-phosphonic acid-12-dodecene, 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, 1-phosphoric acid-12-acrylododecane.
  10. A process according to claims 1 to 9, characterised in that the dipping time is 5 seconds to 20 minutes, the spraying time is 5 seconds to 15 minutes and the roller coating time is 2 to 120 seconds.
  11. A process according to claims 1 to 10, characterised in that the metallic surfaces are pickled with alkali and/or acid and then rinsed with water before application of the aqueous solution.
  12. A process according to claims 1 to 11, 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, wherein the temperature of the nitrogen or air stream is 15 to 150°C.
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EP0948666A1 (en) 1999-10-13
AU6205898A (en) 1998-07-31
EP0948666B1 (en) 2003-03-19
TR199901466T2 (en) 1999-10-21
DK0948666T4 (en) 2008-01-07
BR9713638A (en) 2000-04-11
DE19654642A1 (en) 1998-09-17
JP3986092B2 (en) 2007-10-03
JP2001508499A (en) 2001-06-26
NO326333B1 (en) 2008-11-10
KR100487855B1 (en) 2005-05-09
WO1998029580A1 (en) 1998-07-09
DE59709588D1 (en) 2003-04-24
ES2195202T5 (en) 2008-04-01
CA2275729A1 (en) 1998-07-09
DK0948666T3 (en) 2003-07-07
ES2195202T3 (en) 2003-12-01
AU735281B2 (en) 2001-07-05
NO993118D0 (en) 1999-06-23
ATE234948T1 (en) 2003-04-15
DE19654642C2 (en) 2003-01-16
CA2275729C (en) 2007-09-25
US6436475B1 (en) 2002-08-20
NO993118L (en) 1999-06-23

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