EP0948666A1 - Method for treating metallic surfaces - Google Patents

Method for treating metallic surfaces

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Publication number
EP0948666A1
EP0948666A1 EP97954820A EP97954820A EP0948666A1 EP 0948666 A1 EP0948666 A1 EP 0948666A1 EP 97954820 A EP97954820 A EP 97954820A EP 97954820 A EP97954820 A EP 97954820A EP 0948666 A1 EP0948666 A1 EP 0948666A1
Authority
EP
European Patent Office
Prior art keywords
group
acid
aqueous solution
metallic surfaces
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP97954820A
Other languages
German (de)
French (fr)
Other versions
EP0948666B1 (en
EP0948666B2 (en
Inventor
Hans-Jürgen P. ADLER
Christian Bram
Ralf Feser
Evelin JÄHNE
Christian Jung
Iris MÄGE
Jürgen Rudolph
Lars Sebralla
Martin Stratmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemetall GmbH
Original Assignee
Chemetall GmbH
Metallgesellschaft AG
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Publication date
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Application filed by Chemetall GmbH, Metallgesellschaft AG filed Critical Chemetall GmbH
Publication of EP0948666A1 publication Critical patent/EP0948666A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C22/06—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
    • C23C22/05—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
    • C23C22/78—Pretreatment of the material to be coated

Definitions

  • the invention relates to a method for the treatment of metallic surfaces which consist of zinc, magnesium or aluminum or of the alloys of zinc, magnesium or aluminum and to which lacquers, plastic layers, paints, sealants or adhesives are applied after the treatment .
  • 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 causes the high passivity of the surface against corrosion.
  • the residual content of unused chromate ions deposited in the oxide layer additionally causes one
  • DE-A 31 37 525 discloses a method for inhibiting corrosion in an aqueous system, in which 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 with a concentration of 0.1 to 20 ppm. Corrosion problems in cooling systems in particular are to be avoided with the known aqueous system.
  • hydroxyethylidene diphosphonic acid and its inorganic salts are particularly 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 one another or together with other known corrosion inhibitors.
  • the compounds are generally added to aqueous, aqueous-alcoholic, alcoholic and / or oil-containing media.
  • they can be used as corrosion inhibitors in the heat transfer media of cooling or heating circuits, cooling lubricants, mineral oils or savings.
  • the corrosion of metals, in particular of copper and its alloys is prevented by adding the compounds and / or their salts to the media or circulating liquids mentioned.
  • 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 benzimidazole radical, the straight-chain or branched hydrocarbon radical and the benzimidazole radical being in position 2 of the benzimidazole residue are linked together.
  • aqueous solution for the treatment of zinc, zinc alloys or cadmium which contains nitric acid, an oxidizing agent (H 2 0 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.
  • An aqueous solution containing amines, aminal alcohols, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates or ammonia is used to produce the hydroxide layer.
  • a solution is used to produce the second layer, in which the phosphinic and phosphonic acids are present in a concentration of 0.001 mol / l up to the saturation concentration and which contains water, an alcohol or an organic solvent as solvent.
  • the phosphinic and phosphonic acids contain, 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 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 consisting of zinc, magnesium or aluminum or of the alloys of zinc, magnesium or aluminum are treated in order to give the metallic surfaces in particular good adhesion for Varnishes, plastic layers, paints, sealants and Giving adhesives and protecting the metallic surfaces against corrosion.
  • the effect of the process according to the invention is based on the ability of the compounds XYZ to organize themselves spontaneously and to form very thin, closed films on metallic surfaces, with in particular an orientation of the acidic groups in The direction of the metallic surface takes place and a chemical bond is formed between the hydroxyl groups on the metallic surface and the acidic groups of the compound XYZ.
  • the structure of the compounds XYZ was chosen according to the invention in such a way that there is both a reactive bond of the thin film to the metal surface and to the matrix of lacquers, plastic coatings, paints, sealants and adhesives.
  • 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, since the organic group Y has hydrophobic properties.
  • Group Z gives the coated surface good wettability and reactivity to paints, plastic coatings, paints, sealants and adhesives. If lacquers, 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 paints.
  • 0.1 to 50% of the water in the aqueous solution is replaced by an alcohol having 1 to 4 carbon atoms, by acetone, by dioxane or by tetrahydrofuran.
  • organic solvents result in a higher solubility of the compounds XYZ, which are generally larger molecules, the solubility of which is not very high in pure water.
  • the solution always contains a large amount of water, so that one can still speak of an aqueous system even in the presence of organic solvents.
  • the aqueous solution contains one or more compounds of the type XYZ in a concentration which is in the range of the critical micelle formation concentration.
  • the critical micelle formation concentration cc is a concentration which is characteristic of the respective surfactant and at which the aggregation of the surfactant molecules to micelles starts. The aggregation is reversible. Below the cmc, ie when the solutions are diluted, the micelles break down again into monomeric surfactant molecules.
  • the numerical value of the cmc for each surfactant depends on its constitution and on external parameters such as ionic strength, temperature and concentration of additives. Suitable methods for determining the cmc u. a. Surface tension measurements. With the help of the ring or plate method, the surface tension ⁇ of a surfactant solution is dependent on it
  • the aqueous solution contains a defoamer and / or a solubilizer in each case in an amount of 0.05 to 5% by weight.
  • 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. Amino alcohols, for example, can be used both as defoamers and as solubilizers.
  • the compounds of the type XYZ are present as salts in the aqueous solution.
  • the salts are usually more soluble than the compounds themselves, and also the dissolved salts are very stable, so that the handling of the solution according to the invention is improved by using the salts of the compounds XYZ.
  • the sodium and potassium salts are used in particular.
  • 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 thus 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:
  • 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 which contain the compounds of type XYZ mentioned below have very good adhesion-promoting and corrosion-inhibiting properties: 1-phosphonic acid-12-mercaptododecane, 1-phosphonic acid-12- (N-ethylamino) odecan, 1-phosphonic acid-12-dodecene, p-xylylenediphosphonic acid, 1, 10-decanediphosphonic acid, 1,12-dodecanediphosphonic acid, l-phosphoric acid-12-hydroxvdodecane, l-phosphoric acid-12 (N-ethylamino) dodecane, l-phosphoric acid-12-mercaptododecane,
  • the aqueous solution is applied to the metallic surfaces by dipping, spraying or rolling at 10 to 100 ° C., the dipping time being 5 seconds to 20 minutes, the spraying time 5 seconds to 15 Minutes and the rolling time is 2 to 120 seconds. It has been shown that a thin film is formed on the metallic surfaces when the aqueous solution is immersed, sprayed or rolled is applied, wherein rinsing of the treated metallic surfaces is not absolutely necessary, but can be advantageous.
  • the metallic surfaces are alkali and / or acid pickled before the aqueous solution is applied and then rinsed with water.
  • the water used can be desalinated or not.
  • the metallic surfaces consisting of zinc, magnesium, aluminum and their alloys are always covered by oxide layers and additionally contaminated by the surface adsorption of carbon dioxide, water and / or hydrocarbons. These contaminated top layers are unable to permanently bind paints, plastic coatings, paints, sealants and adhesives and to ensure long-term corrosion protection. Therefore, the metallic surfaces are cleaned in the manner according to the invention before treatment with the aqueous solution.
  • 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 stream of nitrogen or air, the Temperature of the nitrogen or air flow is 15 to 150 ° C. Rinsing and drying do not hinder the formation of the thin film on the metallic surfaces.
  • the water used for rinsing can be desalinated or not.
  • the method according to the invention is used for the treatment of metallic surfaces, to which a cathodic or anodic electro-dip coating, a powder coating, a coil coating coating, a low-solvent high-solid coating or a coating diluted with water is then applied .
  • the pretreatment of the metallic surfaces with the aqueous solution according to the invention has proven particularly useful in all painting processes.
  • Sheets are used as the substrate, which from the
  • the sheets are immersed in an alkaline pickling solution containing 32 g / 1 NaOH and 8 g / 1 Na 2 CO 3 at room temperature for 3 minutes. Then it is rinsed with deionized water. Then the alkaline pickled sheets are immersed for 3 minutes at 40 ° C. in an acid pickling solution which contains 10 g / 1 H 2 SO 4 and 33 g / 1 H 2 0 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 / 1. This is followed by rinsing with demineralized water and drying at room temperature in nitrogen flow.
  • the sheets are first sprayed at 65 ° C. for 10 seconds with an alkaline pickling solution which contains 10 g / 1 Bonder V338M ® . The sheets are then rinsed by spraying them with water. The alkaline pickled sheets are then sprayed at 50 ° C. for 30 seconds with an acid pickling solution containing 16 g / 1 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 about 10 "3 mol / 1. ( ® 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 applied to the sheets. rolled on at room temperature for two seconds, 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 / 1.
  • the metal sheets are dried in a forced air oven at 105.degree.
  • Aqueous solutions containing the following compounds XYZ were used to carry out the process variants: l-phosphonic acid-12- (N-ethylamino) dodecane 1-phosphoric acid-12-hydroxydodecane p-xylylenediphosphonic acid 1, 12-dodecanediphosphonic acid
  • the sheets treated with the aqueous solution according to the invention were painted by various methods. Both a cathodic electrodeposition paint and a powder paint and also a polyester paint were used.
  • the electrocoat material was electrolytically deposited on the metal sheets at a voltage of approximately 250 volts and then dried at 180 ° C. for 22 minutes.
  • the powder coating was applied to the sheets by electrostatic spraying and then dried at 200 ° C. for 10 minutes.
  • the polyester paint system consisted of a primer and a top coat. Both components were applied to the sheets by squeegees.
  • the primer had a layer thickness of 5 ⁇ m, while the top coat had a layer thickness of 25 ⁇ m.
  • the baking temperatures were 216 ° C for the primer and 241 ° C for the top coat.
  • Example 2 Example 2:
  • the following table contains the test results which were measured using different substances according to the invention.
  • the substances were present in the solutions according to the invention in a concentration of approximately 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 comparison sheets; only that of the comparison sheets 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 Results achieved with the invention are surprisingly good, since they are equivalent to the result obtained with chromating in terms of corrosion resistance and clearly superior in terms of paint adhesion.
  • ARXPS X-ray photoelectron spectroscopy
  • FIG. 1 shows the X-ray photoelectron spectrum of the 1-phosphoric acid-12- (N-ethylamino) dodecane on the AlMgl 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 der
  • P2s peak is the phosphoric acid group and is the abbreviation XPS for the term
  • HDLS OH- (CH 2 ) ⁇ l -COOH
  • HDPS (OH) 2 P0 2 - (CH.) 12 -OH

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 DEG C and 100 DEG 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

Verfahren zur Behandlung metallischer Oberflächen Process for treating metallic surfaces
Beschreibungdescription
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 the treatment of metallic surfaces which consist of zinc, magnesium or aluminum or of the alloys of zinc, magnesium or aluminum and to which lacquers, plastic layers, paints, sealants or adhesives are applied after the treatment .
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 Metalloberflächen 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. In many coating processes used in technology, metal surfaces are therefore coated with an inorganic conversion layer (eg zinc phosphate) before applying a lacquer or plastic layer. The metallic surface is passivated and mostly for conversion treatment by means of layer-forming phosphating or chromating subsequent coating with a varnish or with a plastic prepared.
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 unlöslichenThe 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
Aluminium-Chrom- (III) -Mischoxid und bewirkt die hohe Passivität der Oberfläche gegen Korrosion. Der in der Oxidschicht deponierte Restgehalt unverbrauchter Chromationen bewirkt zusätzlich einenAluminum-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 one
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.Self-healing effect with 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 from weathered 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- undAs an alternative to chromating, a process has been developed that works with zirconium salts, fluorides, phosphates and organic polymers (eg polyacrylates and polyvinyl alcohols). With this procedure Layers are formed on aluminum surfaces, which provide the substrate with a certain degree of corrosion protection and a fairly good adhesion for paint and
Kunststoffbeschichtungen verleihen. Allerdings ist der erzielte Korrosionsschutz nicht immer befriedigend.Give plastic coatings. However, the corrosion protection achieved 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 made of zinc, magnesium, aluminum and their alloys by treatment with organic substances for the application of lacquer 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. 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 Phosphonsauregruppe, 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. Aus der US-A 4 351 675 ist eine wäßrige Lösung zur Behandlung von Zink, Zinklegierungen oder Cadmium bekannt, die Salpetersäure, ein Oxidationsmittel (H202, 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.DE-A 31 37 525 discloses a method for inhibiting corrosion in an aqueous system, in which 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 with a concentration of 0.1 to 20 ppm. Corrosion problems in cooling systems in particular are to be avoided with the known aqueous system. In the aqueous system, hydroxyethylidene diphosphonic acid and its inorganic salts are particularly preferred. It is known from EP-A 0 012 909 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, combined with one another or together with other known corrosion inhibitors. For corrosion inhibition, the compounds are generally added to aqueous, aqueous-alcoholic, alcoholic and / or oil-containing media. For example, they can be used as corrosion inhibitors in the heat transfer media of cooling or heating circuits, cooling lubricants, mineral oils or savings. The corrosion of metals, in particular of copper and its alloys, is prevented by adding the compounds and / or their salts to the media or circulating liquids mentioned. 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 benzimidazole radical, the straight-chain or branched hydrocarbon radical and the benzimidazole radical being in position 2 of the benzimidazole residue are linked together. 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 0 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.
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 Lind. Zur Erzeugung der zweiten Schicht wird eine Lösung verwendet, in der die Phosphin- und Phosphonsäuren in einer Konzentration von 0,001 mol/1 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.Finally, from US-A 5 059 258 a method is known in which a layer of aluminum hydroxide is first produced on an aluminum substrate at a pH of 2 to 14 and in which thereafter on the aluminum hydroxide layer by treatment with an organic phosphinic acid or organic phosphonic acid is deposited another layer. The organic residue of phosphine and phosphonic acid contains 1 to 10 organic groups and 1 to 30 C atoms. The molecule of organic phosphinic and phosphonic acids contains 1 to 10 phosphinic and phosphonic acid groups. An aqueous solution containing amines, aminal alcohols, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates or ammonia is used to produce the hydroxide layer. A solution is used to produce the second layer, in which the phosphinic and phosphonic acids are present in a concentration of 0.001 mol / l up to the saturation concentration and which contains water, an alcohol or an organic solvent as solvent. As organic groups, the phosphinic and phosphonic acids contain, 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 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 consisting of zinc, magnesium or aluminum or of the alloys of zinc, magnesium or aluminum are treated in order to give the metallic surfaces in particular good adhesion for Varnishes, plastic layers, paints, sealants and Giving adhesives and protecting 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/1 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-, HS03 -, HS04 -, (OH).PO-, (OH)2P02-, (OH) (OR')PO- oder (OH) (OR')P02 - Gruppe ist, wobei Z eine OH-, SH- , NH2 -, NHR'-, CN-, CH = CH2 - , OCN-, Epoxy-, CH2=CR" -COO- , Acrylsäureamid-, COOH-, (OH)2PO-, (OH)2P02-, (OH) (OR' ) PO- oder (OH) (OR' ) P02 -Gruppe ist und wobei R1 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.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 / 1 of one or more compounds 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, HS0 3 , HS0 4 , (OH) ., (OH) 2 P0 2 PO -, (OH) (oR ') PO or (OH) (oR') P0 2 - group where Z is an OH-, SH-, NH 2 -, NHR ' -, CN, CH = CH 2 -, OCN-, epoxy, CH2 = CR "-COO-, Acrylsäureamid-, COOH-, (OH) 2 PO-, (OH) 2 P0 2 -, (OH) (OR ') PO or (OH) (OR') P0 2 group and where R 1 is an alkyl group with 1 to 4 carbon atoms, where R "is an H atom or an alkyl group with 1 to 4 carbon atoms. Is atoms, and wherein the groups X and Z are each bound to the group Y in its end position.
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. 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.The effect of the process according to the invention is based on the ability of the compounds XYZ to organize themselves spontaneously and to form very thin, closed films on metallic surfaces, with in particular an orientation of the acidic groups in The direction of the metallic surface takes place and a chemical bond is formed between the hydroxyl groups on the metallic surface and the acidic groups of the compound XYZ. The structure of the compounds XYZ was chosen according to the invention in such a way that there is both a reactive bond of the thin film to the metal surface and to the matrix of lacquers, plastic coatings, paints, sealants and adhesives. 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, since the organic group Y has hydrophobic properties. Group Z gives the coated surface good wettability and reactivity to paints, plastic coatings, paints, sealants and adhesives. If lacquers, 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 paints. In a further embodiment of the invention, 0.1 to 50% of the water in the aqueous solution is replaced by an alcohol having 1 to 4 carbon atoms, by acetone, by dioxane or by tetrahydrofuran. These organic solvents result in a higher solubility of the compounds XYZ, which are generally larger molecules, the solubility of which is not very high in pure water. On the other hand, the solution always contains a large amount of water, so that one can still speak of an aqueous system even in the presence of organic solvents.
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 c c ist eine für das jeweilige Tensid charakteristische Konzentration, bei der die Aggregation der Tenεidmoleküle 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 ihrerAccording 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 formation concentration. The critical micelle formation concentration cc is a concentration which is characteristic of the respective surfactant and at which the aggregation of the surfactant molecules to micelles starts. The aggregation is reversible. Below the cmc, ie when the solutions are diluted, the micelles break down again into monomeric surfactant molecules. The numerical value of the cmc for each surfactant depends on its constitution and on external parameters such as ionic strength, temperature and concentration of additives. Suitable methods for determining the cmc u. a. Surface tension measurements. With the help of the ring or plate method, the surface tension δ of a surfactant solution is dependent on it
Konzentration c bei konstanter Temperatur bestimmt. Die cmc erkennt man als Knickpunkt in der Meßkurve δ = f (lg c) . Beispiele zur Bestimmung der cmc verschiedenerConcentration 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
Tenside finden sich in "Die Tenside" Hrsg. v. Kosswig und Stäche, Carl Hanser Verlag, München, Wien, 1993.Surfactants can be found in "Die Tenside" ed. V. Kosswig and Stächen, 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% by weight. 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. Amino alcohols, for example, can be used both as defoamers and as solubilizers.
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 itself in some cases if the compounds of the type XYZ are present as salts in the aqueous solution. The salts are usually more soluble than the compounds themselves, and also the dissolved salts are very stable, so that the handling of the solution according to the invention is improved by using the salts of the compounds XYZ. In practice, the sodium and potassium salts are used in particular.
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: 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 thus 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-(CH2)m -Z; m = 2 bis 20 b) X- (CsH4)n -Z; n = 1 bis 4 c) X-(CH2)0 - (C6H4)P- (CH2)q; o = 0 bis 12, p = 1 bis 4, q = 0 bis 12, o oder q ungleich 0.a) X- (CH 2 ) m -Z; m = 2 to 20 b) X- (C s H 4 ) n -Z; n = 1 to 4 c) X- (CH 2 ) 0 - (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)2P02- oder (OH) (OR1 ) P02-Gruppe ist und wenn Z eine (0H)2P02-, (OH) (OR' )P02-, 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 P0 2 or (OH) (OR 1 ) P0 2 group and if Z is a (0H) 2 P0 2 -, (OH) (OR ') P0 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) odecan, 1-Phosphonsäure-12-Dodecen, p-Xylylendiphosphonsäure, 1 , 10-Decandiphosphonsäure, 1,12-Dodecandiphosphonsäure, l-Phosphorsäure-12-Hydroxvdodecan, l-Phosphorsäure-12 (N-ethylamino) dodecan, l-Phosphorsäure-12-mercaptododecan,Aqueous solutions which contain the compounds of type XYZ mentioned below have very good adhesion-promoting and corrosion-inhibiting properties: 1-phosphonic acid-12-mercaptododecane, 1-phosphonic acid-12- (N-ethylamino) odecan, 1-phosphonic acid-12-dodecene, p-xylylenediphosphonic acid, 1, 10-decanediphosphonic acid, 1,12-dodecanediphosphonic acid, l-phosphoric acid-12-hydroxvdodecane, l-phosphoric acid-12 (N-ethylamino) dodecane, l-phosphoric acid-12-mercaptododecane,
1, 10-Decandiphosphorsäure, 1, 12-Dodecandiphosphorsäure, p, p1 -Biphenyldiphosphorsäure, l-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.1, 10-decanediphosphoric acid, 1, 12-dodecanediphosphoric acid, p, p 1 -biphenyldiphosphoric acid, l-phosphoric acid-12-acryloyldodecane. These compounds enter into a bond with the metallic surfaces via the phosphonic and phosphoric acid groups and, both through their aliphatic or aromatic group and through their functional group Z, act as adhesion promoters with respect to the various organic constituents of the lacquers, the plastic coatings, and the paints , the sealing compounds 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 to the metallic surfaces by dipping, spraying or rolling at 10 to 100 ° C., the dipping time being 5 seconds to 20 minutes, the spraying time 5 seconds to 15 Minutes and the rolling time is 2 to 120 seconds. It has been shown that a thin film is formed on the metallic surfaces when the aqueous solution is immersed, sprayed or rolled is applied, wherein rinsing of the treated metallic surfaces is not absolutely necessary, but can 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 alkali and / or acid pickled before the aqueous solution is applied and then rinsed with water. The water used can be desalinated or not. The metallic surfaces consisting of zinc, magnesium, aluminum and their alloys are always covered by oxide layers and additionally contaminated by the surface adsorption of carbon dioxide, water and / or hydrocarbons. These contaminated top layers are unable to permanently bind paints, plastic coatings, paints, sealants and adhesives and to ensure long-term corrosion protection. Therefore, the metallic surfaces are cleaned in the manner according to the invention before 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- ode 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 to which the aqueous solution has been applied by dipping or spraying are then rinsed with water and optionally dried in a stream of nitrogen or air, the Temperature of the nitrogen or air flow is 15 to 150 ° C. Rinsing and drying do not hinder the formation of the thin film on the metallic surfaces. The water used for rinsing 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 method according to the invention is used for the treatment of metallic surfaces, to which a cathodic or anodic electro-dip coating, a powder coating, a coil coating coating, a low-solvent high-solid coating or a coating diluted with water is then applied . The pretreatment of the metallic surfaces with the aqueous solution according to the invention has proven particularly useful in all painting processes.
Der Gegenstand der Erfindung wird nachfolgend anhand meherer Ausführungsbeispiele näher erläutert :The subject matter of the invention is explained in more detail below using several exemplary embodiments:
Beispiel 1 :Example 1 :
Verfahrenmethod
Als Substrat werden Bleche verwendet, die aus derSheets are used as the substrate, which from the
Legierung AlMgl bestehen. a) TauchverfahrenAlMgl alloy exist. a) Immersion process
Zunächst werden die Bleche bei Raumtemperatur während 3 Minuten in eine alkalische Beizlösung getaucht, die 32 g/1 NaOH und 8 g/1 Na2C03 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/1 H2 S04 und 33 g/1 H202 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/1 enthält. Anschließend erfolgt eine Spülung mit entsalztem Wasser und eine Trocknung bei Raumtemperatur im Stickstoffström.First, the sheets are immersed in an alkaline pickling solution containing 32 g / 1 NaOH and 8 g / 1 Na 2 CO 3 at room temperature for 3 minutes. Then it is rinsed with deionized water. Then the alkaline pickled sheets are immersed for 3 minutes at 40 ° C. in an acid pickling solution which contains 10 g / 1 H 2 SO 4 and 33 g / 1 H 2 0 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 / 1. This is followed by rinsing with demineralized water and drying at room temperature in nitrogen flow.
b) Spritzverfahrenb) spraying process
Die Bleche werden zunächst bei 65 °C während 10 Sekunden mit einer alkalischen Beizlösung besprüht, die 10 g/1 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/1 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/1 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 which contains 10 g / 1 Bonder V338M ® . The sheets are then rinsed by spraying them with water. The alkaline pickled sheets are then sprayed at 50 ° C. for 30 seconds with an acid pickling solution containing 16 g / 1 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 about 10 "3 mol / 1. ( ® 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 wassrige 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"3 mol/1 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. Subsequently, the aqueous solution according to the invention is applied to the sheets. rolled on at room temperature for two seconds, 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 / 1. After the aqueous solution has been rolled on, the metal sheets are dried in a forced air oven at 105.degree.
d) Verbindungen des Typs XYZd) XYZ type compounds
Zur Durchführung der Verfahrensvarianten wurden u. a. wassrige Lösungen verwendet, die folgende Verbindungen XYZ enthielten: l-Phosphonsäure-12- (N-ethylamino) -dodecan 1-Phosphorsäure-12-Hydroxydodecan p-Xylylendiphosphonsäure 1, 12-DodecandiphosphonsäureAqueous solutions containing the following compounds XYZ were used to carry out the process variants: l-phosphonic acid-12- (N-ethylamino) dodecane 1-phosphoric acid-12-hydroxydodecane p-xylylenediphosphonic acid 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. Beispiel 2 :The sheets treated with the aqueous solution according to the invention were painted by various methods. Both a cathodic electrodeposition paint and a powder paint and also a polyester paint were used. The electrocoat material was electrolytically deposited on the metal sheets at a voltage of approximately 250 volts and then dried at 180 ° C. for 22 minutes. The powder coating was applied to the sheets by electrostatic spraying and then dried at 200 ° C. for 10 minutes. The polyester paint system consisted of a primer and a top coat. Both components were applied to the sheets by squeegees. The primer had a layer thickness of 5 μm, while the top coat had a layer thickness of 25 μm. The baking temperatures were 216 ° C for the primer and 241 ° C for the top coat. 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/1 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. Durch winkelabhängigeThe following table contains the test results which were measured using different substances according to the invention. The substances were present in the solutions according to the invention in a concentration of approximately 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 comparison sheets; only that of the comparison sheets 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 Results achieved with the invention are surprisingly good, since they are equivalent to the result obtained with chromating in terms of corrosion resistance and clearly superior in terms of paint adhesion. Through angle-dependent
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 dieX-ray photoelectron spectroscopy (ARXPS) determined the orientation of the molecules of the compounds of the type XYZ. 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. That's the way it is
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 l-Phosphorsäure-12- (N-ethylamino) -dodecans auf der Legierung AlMgl, 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 derInformation depth at small angles in the range of approx. 1 nm and at larger angles in the range up to approx. 10 nm. This allows the orientation of the molecules to be determined. 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 AlMgl 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 der
P2s-Peak der Phosphorsäuregruppe ist und wobei die Abkürzung XPS für den BegriffP2s peak is the phosphoric acid group and is the abbreviation XPS for the term
Röntgenphotoelektronenspektroskopie steht. Das Spektrum beweist, daß die Phosphorsäuregruppe an die Metalloberfläche anbindet und die Aminogruppe von der Metalloberfläche abgewandt ist. TabelleX-ray photoelectron spectroscopy is available. The spectrum shows that the phosphoric acid group binds to the metal surface and the amino group faces away from the metal surface. table
VerbinT-Bend-Test ESS-Test Gitterschnitt mit Filiform -TestVerbinT bend test ESS test Cross-cut with filiform test
(TO) nach DIN nach dung Abgeplatzte 50021 Erichsentiefung DIN 65472(TO) according to DIN according to dung chipped 50021 Erichsen deepening DIN 65472
Fläche ESS nach ISO 1520 [mm] nach LPV 75 Unterwande Surface ESS according to ISO 1520 [mm] according to LPV 75 lower walls
ADPS 1 <1 0ADPS 1 <1 0
AUDS 10 1 0AUDS 10 1 0
HDLS 10 1 0HDLS 10 1 0
XDPS 20 <1 <1XDPS 20 <1 <1
HDPS 10 <1 <1HDPS 10 <1 <1
DDPS 0 <1 <1DDPS 0 <1 <1
Vergleichs blechComparative sheet
O 100 8 0 5O 100 8 0 5
G 85 4 5 4G 85 4 5 4
P 10 3 1 <1P 10 3 1 <1
C 25 <1 2 <1 C 25 <1 2 <1
Erläuterungen zur TabelleExplanations to the table
ADPS C2 Hs NH- (CH2 )12 -PO(OH)2 ADPS C 2 H s NH- (CH 2 ) 12 -PO (OH) 2
AUDS = NH2 - (CH2)10 -COOHAUDS = NH 2 - (CH 2 ) 10 -COOH
HDLS = OH- (CH2 ) λl -COOHHDLS = OH- (CH 2 ) λl -COOH
XDPS = (OH)2 PO-CH2 -C6 H4 -CH2 -PO (OH)2 XDPS = (OH) 2 PO-CH 2 -C 6 H 4 -CH 2 -PO (OH) 2
HDPS = (OH)2 P02 - (CH. ) 12 -OHHDPS = (OH) 2 P0 2 - (CH.) 12 -OH
DDPS = (OH)2 PO- (CH2 )12-PO (OH)2 DDPS = (OH) 2 PO- (CH 2 ) 12 -PO (OH) 2
0 = AlMgl Originalblech0 = AlMgl original sheet
G = AlMgl, alkalisch/sauer gebeiztG = AlMgl, alkaline / acid pickled
P = AlMgl, phosphatiertP = AlMgl, phosphated
C = AlMgl, chromatiertC = AlMgl, chromated
LPV = Labor-Prüf-Vorschriften, betriebsintern LPV = laboratory test regulations, in-house

Claims

Patentansprüche claims
1. 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, dadurch gekennzeichnet, 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"s bis 1 mol/1 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-,HS03 -, HS04-, (OH)2PO-, (OH)2P02-, (OH) (OR') PO- oder (OH) (OR1) P02- Gruppe ist, wobei Z eine OH-, SH- , NH2 -, NHR'-, CN-, CH=CH2 -, OCN-, Epoxy-, CH2 = CR"-COO-, Acrylsäureamid-, COOH-, (OH). PO-, (OH)2P02 -, (OH) (OR') PO- oder (OH) (OR- ) P02- Gruppe ist, 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. 1. A process for the treatment of metallic surfaces which consist of zinc, magnesium or aluminum or of the alloys of zinc, magnesium or aluminum and to which lacquers, plastic layers, paints, sealants or adhesives are applied after the treatment, characterized 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 contains 10 "s to 1 mol / 1 of one or more compounds 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, HS0 3 , HS0 4 , (OH) 2 PO, (OH) 2 P0 2 , (OH) (OR ') PO or (OH) (OR 1 ) P0 2 group, where Z is an OH, SH, NH 2 , NHR', CN, CH = CH 2 , OCN -, epoxy, CH 2 = CR "-COO-, acrylic acid amide, COOH-, (OH). PO-, (OH) 2 P0 2 -, (OH) (OR ') PO- or (OH) (OR-) P0 2 - group, where R' is an alkyl group with 1 to 4 carbon atoms, where R "is an H atom or an alkyl group having 1 to 4 C atoms, and the groups X and Z are each bound to the group Y in its end position.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, 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.2. The method according to claim 1, characterized in 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.
3. Verfahren nach den Ansprüchen 1 bis 2, dadurch gekennzeichnet, daß die wäßrige Lösung eine oder mehrere Verbindungen des Typs XYZ in einer Konzentration enthält, die im Bereich der kritischen Mizellbildungskonzentration liegt .3. Process according to claims 1 to 2, characterized in that the aqueous solution contains one or more compounds of the type XYZ in a concentration which is in the range of the critical micelle formation concentration.
4. Verfahren nach den Ansprüchen 1 bis 3 , dadurch gekennzeichnet, daß die wäßrige Lösung einen Entschäumer und/oder einen Lösungsvermittler jeweils in einer Menge von 0,05 bis 5 Gew.-% enthält.4. Process according to claims 1 to 3, characterized in that the aqueous solution contains a defoamer and / or a solubilizer in each case in an amount of 0.05 to 5 wt .-%.
5. Verfahren nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß die Verbindungen des Typs XYZ in der wäßrigen Lösung als Salze vorliegen. 5. Process according to claims 1 to 4, characterized in that the compounds of the type XYZ are present as salts in the aqueous solution.
6. Verfahren nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß Y eine unverzweigte, geradkettige Alkylgruppe mit 2 bis 20 C-Atomen, oder eine unverzweigte, geradkettige, aus 1 bis 4 aromatischen, in p-Stellung verbundenen C6H4-Kernen bestehende Gruppe oder eine aus 1 oder 2 unverzweigten geradkettigen Alkylresten mit jeweils 1 bis 12 C-Atomen sowie 1 bis 4 aromatischen, in p-Stellung verbundenen C6H4-Kernen bestehende Gruppe ist.6. The method according to claims 1 to 5, characterized in that Y is an unbranched, straight-chain alkyl group having 2 to 20 carbon atoms, or an unbranched, straight-chain, from 1 to 4 aromatic, in the p-position connected C 6 H 4 - Is a group consisting of nuclei 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 C 6 H 4 nuclei connected in the p-position.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß Y eine unverzweigte, geradkettige Alkylgruppe mit 10 bis 12 C-Atomen oder eine p-CH2-C6H4-CH2-Gruppe oder eine p,p' -C6H4-C6H4-Gruppe ist.7. The method according to claim 6, characterized in that Y is an unbranched, straight-chain alkyl group having 10 to 12 carbon atoms or a p-CH 2 -C 6 H 4 -CH 2 group or a p, p '-C 6 H 4 -C 6 H 4 group.
8. Verfahren nach den Ansprüchen 1 bis 7, dadurch gekennzeichnet, daß X eine (OH)2P02- oder8. The method according to claims 1 to 7, characterized in that X is an (OH) 2 P0 2 - or
(OH) (OR' )P02-Gruppe ist.(OH) (OR ') P0 2 group.
9. Verfahren nach den Ansprüchen 1 bis 8, dadurch gekennzeichnet, daß Z eine (OH)2P02-, (OH) (OR1 ) P02- , OH-, SH-, NHR'-, CH=CH2- oder CH2=CR" -COO-Gruppe ist . 9. The method according to claims 1 to 8, characterized in that Z is an (OH) 2 P0 2 -, (OH) (OR 1 ) P0 2 -, OH-, SH-, NHR'-, CH = CH 2 - or CH 2 = CR "-COO group.
10. Verfahren nach den Ansprüchen 1 bis 9, dadurch gekennzeichnet, daß die wäßrige Lösung als Verbindungen des Typs XYZ10. The method according to claims 1 to 9, characterized in that the aqueous solution as compounds of the type XYZ
1-Phosphonsäure-12 -mercaptododecan, l-Phosphonsäure-12 - (N-ethylamino) -dodecan,1-phosphonic acid-12-mercaptododecane, l-phosphonic acid-12 - (N-ethylamino) dodecane,
1- Phosphonsäure-12 -dodecen, p-Xylylendiphosphonsäure ,1- phosphonic acid-12-dodecene, p-xylylenediphosphonic acid,
1, 10-Decandiphosphonsäure,1, 10-decanediphosphonic acid,
1 , 12 -Dodecandiphosphonsäure ,1, 12 -dodecanediphosphonic acid,
1 -Phosphorsäure- 12 -Hydroydodecan, l-Phosphorsäure-12 - (N-ethylamino) dodecan,1-phosphoric acid- 12 -hydroydodecane, l-phosphoric acid-12 - (N-ethylamino) dodecane,
1-Phosphorsäure-12 -dodecen, 1 -Phosphorsäure-1-phosphoric acid-12-dodecene, 1-phosphoric acid-
12-mercaptododecan, 1, 10-Decandiphosphorsäure,12-mercaptododecane, 1, 10-decanediphosphoric acid,
1 , 12 -Dodecandiphosphorsäure , p , p ' -Biphenyldiphosphorsäure , l-Phosphorsäure-12-acrylododecan enthäl .1, 12 -dodecanediphosphoric acid, p, p '-biphenyldiphosphoric acid, l-phosphoric acid-12-acrylododecane contain.
11. Verfahren nach den Ansprüchen 1 bis 10, dadurch gekennzeichnet, daß die Tauchzeit 5 Sekunden bis 20 Minuten, die Spritzzeit 5 Sekunden bis 15 Minuten und die Walzzeit 2 bis 120 Sekunden beträgt. 11. The method according to claims 1 to 10, characterized in that the dipping time is 5 seconds to 20 minutes, the spraying time 5 seconds to 15 minutes and the rolling time is 2 to 120 seconds.
12. Verfahren nach den Ansprüchen 1 bis 11, dadurch gekennzeichnet, daß die metallischen Oberflächen vor dem Aufbringen der wäßrigen Lösung alkalisch und/oder sauer gebeizt sowie danach mit Wasser gespült werden.12. The method according to claims 1 to 11, characterized in that the metallic surfaces are alkali and / or acid pickled before application of the aqueous solution and then rinsed with water.
13. Verfahren nach den Ansprüchen 1 bis 12, dadurch gekennzeichnet, daß die metallischen Oberflächen, auf welche die wäßrige Lösung durch Tauchen oder Spritzen aufgebracht wurde, danach mit Wasser gespült und gegebenenfalls im Stickstoff- oder Luftström getrocknet werden, wobei die Temperatur des Stickstoff- oder Luftstroms 15 bis 150°C beträgt . 13. The method according to claims 1 to 12, characterized in that the metallic surfaces to which the aqueous solution has been applied by dipping or spraying, then rinsed with water and optionally dried in a stream of nitrogen or air, the temperature of the nitrogen or air flow is 15 to 150 ° C.
EP97954820A 1996-12-28 1997-12-18 Method for treating metallic surfaces Expired - Lifetime EP0948666B2 (en)

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DE19654642 1996-12-28
DE19654642A DE19654642C2 (en) 1996-12-28 1996-12-28 Process for treating metallic surfaces with an aqueous solution
PCT/EP1997/007100 WO1998029580A1 (en) 1996-12-28 1997-12-18 Method for treating metallic surfaces

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JP3986092B2 (en) 2007-10-03
NO993118L (en) 1999-06-23
CA2275729C (en) 2007-09-25
KR20000062344A (en) 2000-10-25
AU6205898A (en) 1998-07-31
CA2275729A1 (en) 1998-07-09
ES2195202T3 (en) 2003-12-01
US6436475B1 (en) 2002-08-20
NO993118D0 (en) 1999-06-23
DE19654642C2 (en) 2003-01-16
JP2001508499A (en) 2001-06-26
EP0948666B1 (en) 2003-03-19
AU735281B2 (en) 2001-07-05
BR9713638A (en) 2000-04-11
EP0948666B2 (en) 2007-09-26
WO1998029580A1 (en) 1998-07-09
DK0948666T4 (en) 2008-01-07
ATE234948T1 (en) 2003-04-15
DK0948666T3 (en) 2003-07-07
DE19654642A1 (en) 1998-09-17
NO326333B1 (en) 2008-11-10
DE59709588D1 (en) 2003-04-24
TR199901466T2 (en) 1999-10-21
KR100487855B1 (en) 2005-05-09
ES2195202T5 (en) 2008-04-01

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