EP0672467A1 - Process for modification of metallic surfaces - Google Patents
Process for modification of metallic surfaces Download PDFInfo
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- EP0672467A1 EP0672467A1 EP95103462A EP95103462A EP0672467A1 EP 0672467 A1 EP0672467 A1 EP 0672467A1 EP 95103462 A EP95103462 A EP 95103462A EP 95103462 A EP95103462 A EP 95103462A EP 0672467 A1 EP0672467 A1 EP 0672467A1
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- metal surfaces
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- 0 CC(C)N(C)C(*)=O Chemical compound CC(C)N(C)C(*)=O 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
- B05D3/102—Pretreatment of metallic substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
Definitions
- the present invention relates to a method for modifying cleaned or chemically pretreated metal surfaces with aqueous solutions of organic polymers and the use of the modified metal surfaces for painting, in particular for cathodic electrocoating.
- the phosphating of iron and iron alloys is a commonly used method to increase the corrosion resistance of the metal and to improve the adhesion to a paint.
- Electrodeposition coating is generally carried out on a phosphated surface. Improved paint adhesion, particularly with regard to electrocoating paints, is often achieved by modifying the phosphating baths (cf. e.g. DE-A 22 32 067, Japanese patent application No. 58 144 477 (Chemical Abstracts 99/216843) and DE-A 34 08 577).
- the paint adhesion and in particular the corrosion resistance on the conversion layers used do not always meet the requirements.
- this object can be achieved particularly advantageously by coating the cleaned or chemically pretreated metal surface with a thin layer of a polymer containing amino groups.
- the present invention relates to a method for modifying cleaned or chemically pretreated metal surfaces with aqueous solutions of organic polymers, which is characterized in that the cleaned or chemically pretreated metal surfaces are treated with an aqueous solution of organic polymers containing amino groups.
- Treatment with aqueous solution of the organic polymer containing amino groups can be carried out by pouring, spraying or dipping.
- the metal surfaces are, in particular, those of iron, iron alloys, zinc, aluminum, copper, cobalt, nickel or manganese, whereby preferably chemically pretreated metal surfaces, in particular metal surfaces with phosphate conversion layers, optionally rinsed with water or chromate solution, can also be used.
- Organic polymers containing amino groups for the process according to the invention are preferably hydrolysis products of polymers which have units of the general formula (I) contain or consist of, wherein R1 and R2 are the same or different and are H or alkyl having 1 to 6 carbon atoms.
- the present invention also relates to the use of the modified metal surfaces produced by the process according to the invention for painting, in particular for cathodic electrocoating.
- the metal surfaces modified by the process according to the invention are distinguished by significantly improved corrosion protection, which is particularly evident after an electro-dip coating, in particular a cathodic electro-dip coating.
- Suitable metal surfaces to be modified for the process according to the invention are those made of iron, iron alloys, steel, zinc, aluminum, copper, cobalt, nickel and manganese, which are either cleaned (degreased) or chemically pretreated, e.g. can be phosphated and / or chromated.
- the organic polymer containing amino groups is generally applied from an aqueous solution, for example by pouring, spraying, dipping and then drying the metal surfaces modified in this way.
- Suitable organic polymers containing amino groups are preferably amino group-containing hydrolysis products of polymers which have structural units of the general formula (I) contain or consist of, wherein R1 and R2 are the same or different and are hydrogen or alkyl having 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amyl, n -Hexyl, isohexyl or cyclohexyl can stand.
- R1 and R2 are the same or different and are hydrogen or alkyl having 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amyl, n -Hexyl, isohexyl or cyclohexyl can stand.
- hydrolysis products examples include hydrolysis products of homo- and copolymers of N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide and N- Vinyl-N-methylpropionamide, N-vinylformamide being preferred as being very easily hydrolyzable.
- Suitable comonomers are monoethylenically unsaturated carboxylic acids with 3 to 8 carbon atoms and the water-soluble salts of these monomers.
- This group of comonomers includes, for example, acrylic acid, methacrylic acid, dimethylacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylene malonic acid, allylacetic acid, vinyl acetic acid, crotonic acid, fumaric acid, mesaconic acid and itaconic acid. From this group of monomers, preference is given to acrylic acid, methacrylic acid, maleic acid or else mixtures of the carboxylic acids mentioned, in particular mixtures of acrylic acid and maleic acid or mixtures of acrylic acid and methacrylic acid.
- the comonomers can be used either in the form of the free carboxylic acids or in partially or completely neutralized form in the copolymerization.
- alkali metal for example alkali metal, alkaline earth metal bases, ammonia or amines, e.g. Sodium hydroxide solution, potassium hydroxide solution, soda, potash, sodium hydrogen carbonate, magnesium oxide, calcium hydroxide, calcium oxide, ammonia, triethylamine, ethanolamine, diethanolamine, triethanolamine, morpholine, diethylene triamine or tetraethylene pentamine.
- alkali metal alkaline earth metal bases
- ammonia or amines e.g. Sodium hydroxide solution, potassium hydroxide solution, soda, potash, sodium hydrogen carbonate, magnesium oxide, calcium hydroxide, calcium oxide, ammonia, triethylamine, ethanolamine, diethanolamine, triethanolamine, morpholine, diethylene triamine or tetraethylene pentamine.
- Suitable comonomers are, for example, the esters, amides and nitriles of the above-mentioned carboxylic acids, for example methyl acrylate, ethyl acrylate, n- and isopropyl acrylate, n- and isobutyl acrylate, hexyl acrylate, methyl methacrylate, methyl methacrylate, methyl acrylate, hydroxylethyl, hydroxyethyl, hydroxyl , Hydroxyisobutylacrylat, hydroxyethyl methacrylate, hydroxypropyl methacrylate, Hydroxyisobutylmethacrylat, monomethyl maleate, dimethyl maleate, monoethyl maleate, diethyl maleate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylamide, methacrylamide, N-dimethylacrylamide, N-tert-butylacrylamide, acryl
- acrylamidoglycolic acid vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, acrylic acid (3-sulfopropyl) ester, methacrylic acid (3-sulfopropyl) ester and acrylamidomethylpropanesulfonic acid as well as monomers containing phosphonic acid groups, such as vinyl phosphate, allyomophosphate phosphate and acrylamide phosphate phosphate.
- the copolymers should contain at least 20% by weight, preferably at least 50% by weight, of copolymerized N-vinylamides.
- the copolymers can be prepared by known processes, e.g. solution, precipitation, suspension or emulsion polymerization using compounds which form free radicals under the polymerization conditions.
- the polymerization temperatures are usually in the range from 30 to 200, preferably 40 to 110 ° C.
- Suitable initiators are, for example, azo and peroxy compounds and the customary redox initiator systems, such as combinations of hydrogen peroxide and reducing compounds, e.g. Sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate and hydrazine. These systems can optionally also contain small amounts of a heavy metal salt.
- the homo- and copolymers to be used according to the invention generally have K values of 7 to 300, preferably 10 to 250.
- the K values can be in aqueous solution at 25 ° C., at concentrations which, depending on the K value, between 0.1% and 5% are measured.
- the above-described homopolymers or copolymers of the general formula (I) are modified by the action of acids or bases in such a way that, as a result of this treatment, the formyl group is split off from the polymerized N-vinylformamide to form amine or ammonium groups.
- the solvolysis temperatures are usually in the range from 20 to 100 ° C., preferably 70 to 90 ° C.
- Suitable acids are, for example, carboxylic acids such as formic acid, acetic acid or propionic acid, a sulfonic acid such as benzenesulfonic acid or toluenesulfonic acid or an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid.
- Suitable bases are sodium hydroxide solution or potassium hydroxide solution as well as ammonia, amines and alkaline earth metal bases such as calcium hydroxide.
- the usual methods such as ion exchangers, electrodialysis or ultrafiltration are used to desalinate the polymers.
- the process according to the invention is particularly suitable for the treatment of iron, iron alloys and chemically pretreated substrates, such as phosphated metal surfaces which may have been rinsed with water or chromate solution. However, it is also suitable for the surface modification of zinc, aluminum, copper, cobalt, nickel and manganese.
- the aqueous polymer solution is advantageously applied by dipping, pouring or spraying.
- Polymer solutions with solids contents between 0.01 and 5, preferably between 0.1 and 1% by weight in the temperature range between 20 and 80 ° C. can be used for the process according to the invention.
- the metal or chemically pretreated metal surfaces modified with the method according to the invention are in principle suitable for all purposes for which chemically pretreated metal surfaces are suitable.
- the polymer layers bring about an unusually strong improvement in the resistance of the paint film to rust penetration under corrosive stress. This advantage is particularly evident in cathodic electrocoating, which is why the method is used particularly advantageously for this type of painting.
- the method according to the invention finds practical application e.g. for modification of phosphated car bodies.
- Test sheets measuring 190 ⁇ 105 ⁇ 0.75 mm were immersed in aqueous polyvinylamine solutions (K value 30) for 1 minute each.
- the concentrations of the polymer solutions were 0.01; 0.1; 1 and 2 %.
- the bath temperature was 23 ° and 50 ° C, see. Table. After drying in air, the sheets were immersed in deionized water for a further 5 seconds and dried again in air.
- the pretreated test panels were coated with an electrocoat.
- An immersion bath solution as specified in DE-A-42 08 056 as a comparative example, was used as the electrodeposition paint.
- the lacquer was deposited on the test sheets connected as cathode in the usual way at room temperature and baked at 175 ° C. for 25 minutes. With deposition voltages of 320 to 380 V, layer thicknesses of 23 ⁇ m were achieved.
- the rusting on the scratch was determined as a measure of the adhesion of the paints.
- a 0.1 mm wide longitudinal cut was carved into the coating on the steel sheets, and a 0.1 mm wide cross cut was cut into the sheets with a phosphate conversion layer, which reached down to the sheet metal substrate.
- the painted steel sheets were then tested for 15 days in the salt spray test (40 ° C., 5% NaCl solution: DIN 50 021) for corrosion resistance.
- the painted steel sheets with a phosphate conversion layer were tested in the salt water soak test.
- the test sheet was immersed in a 5% NaCl solution heated to 55 ° C. for 10 days.
- the table shows the maximum and average amount of rusting (in millimeters) at the interface on both sides.
- the reference samples were electrocoated analogously using the methods described above and then subjected to corrosion tests with the only difference that no adhesion-promoting layer was applied.
- Degreased body steel sheet e.g. St 1405
- aqueous polyvinylamine solutions of various concentrations, aftertreated and electrocoated.
- the overall appearance of the paint surface also shows a significant improvement over the prior art as a result of the method according to the invention. While the paint surfaces of the reference samples show strong blistering, the paint surface on the metal surface modified with aqueous polyvinylamine solution is perfect.
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- Chemical Kinetics & Catalysis (AREA)
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- Application Of Or Painting With Fluid Materials (AREA)
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Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Modifizierung von gereinigten oder chemisch vorbehandelten Metalloberflächen mit wäßrigen Lösungen organischer Polymerer und die Verwendung der modifizierten Metalloberflächen zur Lackierung, insbesondere für die kathodische Elektrotauchlackierung.The present invention relates to a method for modifying cleaned or chemically pretreated metal surfaces with aqueous solutions of organic polymers and the use of the modified metal surfaces for painting, in particular for cathodic electrocoating.
Die Verbesserung der Naßhaftfestigkeit organischer Beschichtungen auf Stahloberflächen, die mit stark verdünnten Lösungen von Polysäuren, wie Polyacryl- und Polymethylenacrylsäure behandelt werden und eine verbesserte Haftung zu Alkyd/Melamin-, Epoxid- und Polyurethanharzen aufweisen, wird von Z. Gao, H. Yamabe, B. Marold und W. Funke in farbe + lack, 98 (1992), Nr. 12, S. 917 beschrieben.The improvement in the wet adhesive strength of organic coatings on steel surfaces which are treated with highly dilute solutions of polyacids such as polyacrylic and polymethylene acrylic acid and have improved adhesion to alkyd / melamine, epoxy and polyurethane resins is described by Z. Gao, H. Yamabe, B. Marold and W. Funke in color + lacquer, 98 (1992), No. 12, p. 917.
Die Phosphatierung von Eisen und Eisenlegierungen ist eine allgemein gebräuchliche Methode, um die Korrosionsbeständigkeit des Metalls zu erhöhen und die Haftung zu einer Lackierung zu verbessern.The phosphating of iron and iron alloys is a commonly used method to increase the corrosion resistance of the metal and to improve the adhesion to a paint.
Aus der Publikation J. of Coatings Technol. 65 (1993), Nr. 819, S. 59-64 sind auch Phosphatierlösungen mit Polyethylenimin als Additiv bekannt, die Phosphatschichten mit einer niedrigen Permeabilität gegenüber Feuchtigkeit aufweisen.From the publication J. of Coatings Technol. 65 (1993), No. 819, pp. 59-64, phosphating solutions with polyethyleneimine as an additive are also known which have phosphate layers with a low permeability to moisture.
Die Elektrotauchlack-Beschichtung erfolgt generell auf phosphatiertem Untergrund. Eine verbesserte Lackhaftung, insbesondere zu den Elektrotauchlacken wird häufig durch eine Modifizierung der Phosphatierungsbäder erreicht (vgl. z.B. DE-A 22 32 067, japanische Patentanmeldung Nr. 58 144 477 (Chemical Abstracts 99/216843) und DE-A 34 08 577).Electrodeposition coating is generally carried out on a phosphated surface. Improved paint adhesion, particularly with regard to electrocoating paints, is often achieved by modifying the phosphating baths (cf. e.g. DE-A 22 32 067, Japanese patent application No. 58 144 477 (Chemical Abstracts 99/216843) and DE-A 34 08 577).
Um die Lackhaftung noch weiter zu erhöhen, werden spezielle passivierende Nachspülungen, beispielsweise Chromatlösungen verwendet (vgl. hierzu auch Dr. Josef Ruf, Organischer Metallschutz: Entwicklung und Anwendung von Beschichtungsstoffen / Josef Ruf - Hannover: Vincentz, 1993, S. 646f).To further increase paint adhesion, special passivating rinses, e.g. chromate solutions, are used (see also Dr. Josef Ruf, Organic Metal Protection: Development and Application of Coating Materials / Josef Ruf - Hanover: Vincentz, 1993, pp. 646f).
Die Lackhaftung und insbesondere die Korrosionsfestigkeit auf den verwendeten Konversionsschichten genügen jedoch nicht immer den gestellten Anforderungen.The paint adhesion and in particular the corrosion resistance on the conversion layers used do not always meet the requirements.
Aufgabe der vorliegenden Erfindung ist es, durch eine auf gereinigte Metalloberflächen oder auf industriell eingesetzte Konversionsschichten zusätzlich aufgebrachte dünne Polymerschicht die Lackhaftung wesentlich zu verbessern und auf diese Weise eine verbesserte Schutzwirkung, insbesondere eine verringerte Rostunterwanderung der Beschichtung zu erhalten.It is an object of the present invention to substantially improve the paint adhesion by means of a thin polymer layer additionally applied to cleaned metal surfaces or on conversion layers used in industry and in this way to obtain an improved protective effect, in particular a reduced rust penetration of the coating.
Überraschenderweise läßt sich diese Aufgabe besonders vorteilhaft dadurch lösen, daß die gereinigte oder chemisch vorbehandelte Metalloberfläche mit einer dünnen Schicht eines Aminogruppen enthaltenden Polymeren überzogen wird.Surprisingly, this object can be achieved particularly advantageously by coating the cleaned or chemically pretreated metal surface with a thin layer of a polymer containing amino groups.
Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Modifizieren von gereinigten oder chemisch vorbehandelten Metalloberflächen mit wäßrigen Lösungen organischer Polymerer, das dadurch gekennzeichnet ist, daß die gereinigten oder chemisch vorbehandelten Metalloberflächen mit einer wäßrigen Lösung von Aminogruppen enthaltenden organischen Polymeren behandelt werden.The present invention relates to a method for modifying cleaned or chemically pretreated metal surfaces with aqueous solutions of organic polymers, which is characterized in that the cleaned or chemically pretreated metal surfaces are treated with an aqueous solution of organic polymers containing amino groups.
Die Behandlung mit wäßriger Lösung des Aminogruppen enthaltenden organischen Polymeren kann dabei durch Gießen, Sprühen oder Tauchen erfolgen.Treatment with aqueous solution of the organic polymer containing amino groups can be carried out by pouring, spraying or dipping.
Bei den Metalloberflächen handelt es sich insbesondere um solche von Eisen, Eisenlegierungen, Zink, Aluminium, Kupfer, Kobalt, Nickel oder Mangan, wobei vorzugsweise auch chemisch vorbehandelte Metalloberflächen, insbesondere Metalloberflächen mit Phosphatkonversionsschichten, gegebenenfalls mit Wasser oder Chromatlösung nachgespült, eingesetzt werden können.The metal surfaces are, in particular, those of iron, iron alloys, zinc, aluminum, copper, cobalt, nickel or manganese, whereby preferably chemically pretreated metal surfaces, in particular metal surfaces with phosphate conversion layers, optionally rinsed with water or chromate solution, can also be used.
Als Aminogruppen enthaltende organische Polymere werden für das erfindungsgemäße Verfahren vorzugsweise Hydrolyseprodukte von Polymeren, die Einheiten der allgemeinen Formel (I)
enthalten oder daraus bestehen, wobei R¹ und R² untereinander gleich oder verschieden sind und für H oder Alkyl mit 1 bis 6 Kohlenstoffatomen stehen, eingesetzt.Organic polymers containing amino groups for the process according to the invention are preferably hydrolysis products of polymers which have units of the general formula (I)
contain or consist of, wherein R¹ and R² are the same or different and are H or alkyl having 1 to 6 carbon atoms.
Gegenstand der vorliegenden Erfindung ist außerdem die Verwendung der nach dem erfindungsgemäßen Verfahren hergestellten modifizierten Metalloberflächen zur Lackierung, insbesondere für die kathodische Elektrotauchlackierung.The present invention also relates to the use of the modified metal surfaces produced by the process according to the invention for painting, in particular for cathodic electrocoating.
Die nach dem erfindungsgemäßen Verfahren modifizierten Metalloberflächen zeichnen sich durch deutlich verbesserten Korrosionsschutz aus, der sich insbesondere nach einer Elektrotauchlackierung, insbesondere einer kathodischen Elektrotauchlackierung ausweist.The metal surfaces modified by the process according to the invention are distinguished by significantly improved corrosion protection, which is particularly evident after an electro-dip coating, in particular a cathodic electro-dip coating.
Im einzelnen ist zum erfindungsgemäßen Verfahren folgendes aus zuführen.In detail, the following is to be performed for the method according to the invention.
Als zu modifizierende Metalloberflächen kommen für das erfindungsgemäße Verfahren solche aus Eisen, Eisenlegierungen, Stahl, Zink, Aluminium, Kupfer, Kobalt, Nickel und Mangan in Frage, die entweder gereinigt (entfettet) oder chemisch vorbehandelt, z.B. phosphatiert und/oder chromatiert sein können.Suitable metal surfaces to be modified for the process according to the invention are those made of iron, iron alloys, steel, zinc, aluminum, copper, cobalt, nickel and manganese, which are either cleaned (degreased) or chemically pretreated, e.g. can be phosphated and / or chromated.
Der Auftrag des Aminogruppen enthaltenden organischen Polymeren erfolgt im allgemeinen aus wäßriger Lösung, beispielsweise durch Gießen, Sprühen, Tauchen und anschließendes Trocknen der so modifizierten Metalloberflächen.The organic polymer containing amino groups is generally applied from an aqueous solution, for example by pouring, spraying, dipping and then drying the metal surfaces modified in this way.
Als Aminogruppen enthaltende organische Polymere eignen sich vorzugsweise Aminogruppen enthaltende Hydrolyseprodukte von Polymeren die Struktureinheiten der allgemeinen Formel (I)
enthalten oder daraus bestehen, wobei R¹ und R² untereinander gleich oder verschieden sind und für Wasserstoff oder Alkyl mit 1 bis 6 Kohlenstoffatomen, z.B. Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, tert.-Butyl, Amyl, n-Hexyl, Isohexyl oder Cyclohexyl stehen können.Suitable organic polymers containing amino groups are preferably amino group-containing hydrolysis products of polymers which have structural units of the general formula (I)
contain or consist of, wherein R¹ and R² are the same or different and are hydrogen or alkyl having 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amyl, n -Hexyl, isohexyl or cyclohexyl can stand.
Beispiele für derartige Hydrolyseprodukte sind Hydrolyseprodukte von Homo- und Copolymeren des N-Vinylformamid, N-Vinyl-N-methylformamid, N-Vinylacetamid, N-Vinyl-N-methylacetamid, N-Vinyl-N-ethylacetamid, N-Vinylpropionamid und N-Vinyl-N-Methylpropionamid, wobei N-Vinylformamid als sehr leicht hydrolisierbar bevorzugt ist. Als Comonomere kommen monoethylenisch ungesättigte Carbonsäuren mit 3 bis 8 C-Atome sowie die wasserlöslichen Salze dieser Monomere in Betracht.Examples of such hydrolysis products are hydrolysis products of homo- and copolymers of N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide and N- Vinyl-N-methylpropionamide, N-vinylformamide being preferred as being very easily hydrolyzable. Suitable comonomers are monoethylenically unsaturated carboxylic acids with 3 to 8 carbon atoms and the water-soluble salts of these monomers.
Zu dieser Gruppe von Comonomeren gehören beispielsweise Acrylsäure, Methacrylsäure, Dimethylacrylsäure, Ethacrylsäure, Maleinsäure, Citraconsäure, Methylenmalonsäure, Allylessigsäure, Vinylessigsäure, Crotonsäure, Fumarsäure, Mesaconsäure und Itaconsäure. Aus dieser Gruppe von Monomeren bevorzugt sind Acrylsäure, Methacrylsäure, Maleinsäure oder auch Mischungen der genannten Carbonsäuren, insbesondere Mischungen aus Acrylsäure und Maleinsäure oder Mischungen aus Acrylsäure und Methacrylsäure. Die Comonomeren können entweder in Form der freien Carbonsäuren oder in partiell oder vollständig neutralisierter Form bei der Copolymerisation eingesetzt werden. Zur Neutralisation der monoethylenisch ungesättigten Carbonsäuren können beispielsweise Alkalimetall-, Erdalkalimetallbasen, Ammoniak oder Amine, z.B. Natronlauge, Kalilauge, Soda, Pottasche, Natriumhydrogencarbonat, Magnesiumoxid, Calciumhydroxyd, Calciumoxid, Ammoniak, Triethylamin, Ethanolamin, Diethanolamin, Triethanolamin, Morpholin, Diethylentriamin oder Tetraethylenpentamin verwendet werden.This group of comonomers includes, for example, acrylic acid, methacrylic acid, dimethylacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylene malonic acid, allylacetic acid, vinyl acetic acid, crotonic acid, fumaric acid, mesaconic acid and itaconic acid. From this group of monomers, preference is given to acrylic acid, methacrylic acid, maleic acid or else mixtures of the carboxylic acids mentioned, in particular mixtures of acrylic acid and maleic acid or mixtures of acrylic acid and methacrylic acid. The comonomers can be used either in the form of the free carboxylic acids or in partially or completely neutralized form in the copolymerization. To neutralize the monoethylenically unsaturated carboxylic acids, for example alkali metal, alkaline earth metal bases, ammonia or amines, e.g. Sodium hydroxide solution, potassium hydroxide solution, soda, potash, sodium hydrogen carbonate, magnesium oxide, calcium hydroxide, calcium oxide, ammonia, triethylamine, ethanolamine, diethanolamine, triethanolamine, morpholine, diethylene triamine or tetraethylene pentamine.
Weitere geeignete Comonomere sind beispielsweise die Ester, Amide und Nitrile der oben angegebenen Carbonsäuren, z.B. Acrylsäuremethylestern, Acrylsäureethylester, Acrylsäure-n- und -isopropylester, Acrylsäure-n- und -isobutylester, Acrylsäurehexylester, Methacrylsäuremethylester, Methacrylsäureethylester, Methacrylsäurebutylester, Hydroxyethylacrylat, Hydroxypropylacrylat, Hydroxybutylacrylat, Hydroxyisobutylacrylat, Hydroxyethylmethacrylat, Hydroxypropylmethacrylat, Hydroxyisobutylmethacrylat, Maleinsäuremonomethylester, Maleinsäuredimethylester, Maleinsäuremonoethylester, Maleinsäurediethylester, 2-Ethylhexylacrylat, 2-Ethylhexylmethacrylat, Acrylamid, Methacrylamid, N-Dimethylacrylamid, N-tert.-Butylacrylamid, Acrylnitril, Methacrylnitril, Dimethylaminoethylacrylat, Dimethylaminoethylmethacrylat, Diethylaminoethylacrylat, Diethylaminoethylmethacrylat, die Salze der zuletzt genannten Monomeren mit Carbonsäuren oder Mineralsäuren sowie die quaternierten Produkte. Außerdem eignen sich als Monomere Acrylamidoglykolsäure, Vinylsulfonsäure, Allylsulfonsäure, Methallylsulfonsäure, Styrolsulfonsäure, Acrylsäure-(3-sulfopropyl)ester, Methacrylsäure-(3-sulfopropyl)ester und Acrylamidomethylpropansulfonsäure sowie Phosphonsäuregruppen enthaltende Monomere, wie Vinylphosphat, Allylphosphat und Acrylamidomethylpropanphosphonsäure.Further suitable comonomers are, for example, the esters, amides and nitriles of the above-mentioned carboxylic acids, for example methyl acrylate, ethyl acrylate, n- and isopropyl acrylate, n- and isobutyl acrylate, hexyl acrylate, methyl methacrylate, methyl methacrylate, methyl acrylate, hydroxylethyl, hydroxyethyl, hydroxyl , Hydroxyisobutylacrylat, hydroxyethyl methacrylate, hydroxypropyl methacrylate, Hydroxyisobutylmethacrylat, monomethyl maleate, dimethyl maleate, monoethyl maleate, diethyl maleate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylamide, methacrylamide, N-dimethylacrylamide, N-tert-butylacrylamide, acrylonitrile, methacrylonitrile, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, Diethylaminoethyl methacrylate, the salts of the latter monomers with carboxylic acids or mineral acids and the quaternized products. Also suitable as monomers are acrylamidoglycolic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, acrylic acid (3-sulfopropyl) ester, methacrylic acid (3-sulfopropyl) ester and acrylamidomethylpropanesulfonic acid as well as monomers containing phosphonic acid groups, such as vinyl phosphate, allyomophosphate phosphate and acrylamide phosphate phosphate.
Weitere geeignete Verbindungen dieser Gruppe sind N-Vinylpyrrolidon, N-Vinylcaprolactam, N-Vinylimidazol, N-Vinyl-2-methylimidazolin, Diallylammoniumchlorid, Vinylacetat und Vinylpropionat. Es ist selbstverständlich auch möglich, Mischungen der genannten Monomere einzusetzen, beispielsweise zur Verbesserung der Haftung.Other suitable compounds of this group are N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinyl-2-methylimidazoline, diallylammonium chloride, vinyl acetate and vinyl propionate. It is of course also possible to use mixtures of the monomers mentioned, for example to improve the adhesion.
Die Copolymeren sollten mindestens 20 Gew.-%, bevorzugt mindestens 50 Gew.-% N-Vinylamide einpolymerisiert, enthalten.The copolymers should contain at least 20% by weight, preferably at least 50% by weight, of copolymerized N-vinylamides.
Die Herstellung der Copolymerisate kann nach bekannten Verfahren, z.B. der Lösungs-, Fällungs-, Suspensions- oder Emulsionspolymerisation unter Verwendung von Verbindungen, die unter den Polymerisationsbedingungen Radikale bilden, erfolgen. Die Polymerisationstemperaturen liegen dabei üblicherweise in dem Bereich von 30 bis 200, vorzugsweise 40 bis 110°C. Geeignete Initiatoren sind beispielsweise Azo-, und Peroxyverbindungen sowie die üblichen Redoxinitiatorsysteme, wie Kombinationen aus Wasserstoffperoxyd und reduzierend wirkenden Verbindungen, z.B. Natriumsulfit, Natriumbisulfit, Natriumformaldehydsulfoxilat und Hydrazin. Diese Systeme können gegebenenfalls zusätzlich noch geringe Mengen eines Schwermetallsalzes enthalten.The copolymers can be prepared by known processes, e.g. solution, precipitation, suspension or emulsion polymerization using compounds which form free radicals under the polymerization conditions. The polymerization temperatures are usually in the range from 30 to 200, preferably 40 to 110 ° C. Suitable initiators are, for example, azo and peroxy compounds and the customary redox initiator systems, such as combinations of hydrogen peroxide and reducing compounds, e.g. Sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate and hydrazine. These systems can optionally also contain small amounts of a heavy metal salt.
Die erfindungsgemäß einzusetzenden Homo- und Copolymeren besitzen im allgemeinen K-Werte von 7 bis 300, bevorzugt 10 bis 250. Die K-Werte können nach H. Fikentscher in wäßriger Lösung bei 25°C, bei Konzentrationen, die je nach K-Wert zwischen 0,1 % und 5 % liegen, gemessen werden.The homo- and copolymers to be used according to the invention generally have K values of 7 to 300, preferably 10 to 250. According to H. Fikentscher, the K values can be in aqueous solution at 25 ° C., at concentrations which, depending on the K value, between 0.1% and 5% are measured.
Die oben beschriebenen Homo- bzw. Copolymerisate der allgemeinen Formel (I) werden durch Einwirkung von Säuren oder Basen dahingehend modifiziert, daß infolge dieser Behandlung die Formylgruppe aus dem einpolymerisierten N-Vinylformamid unter Bildung von Amin- bzw. Ammoniumgruppen abgespalten wird. Die Solvolysetemperaturen liegen üblicherweise im Bereich von 20 bis 100°C, vorzugsweise 70 bis 90°C. Geeignete Säuren sind beispielsweise Carbonsäuren wie Ameisensäure, Essigsäure oder Propionsäure, eine Sulfonsäure wie Benzolsulfonsäure oder Toluolsulfonsäure oder eine anorganische Säure wie Salzsäure, Schwefelsäure, Phosphorsäure oder Bromwasserstoffsäure.The above-described homopolymers or copolymers of the general formula (I) are modified by the action of acids or bases in such a way that, as a result of this treatment, the formyl group is split off from the polymerized N-vinylformamide to form amine or ammonium groups. The solvolysis temperatures are usually in the range from 20 to 100 ° C., preferably 70 to 90 ° C. Suitable acids are, for example, carboxylic acids such as formic acid, acetic acid or propionic acid, a sulfonic acid such as benzenesulfonic acid or toluenesulfonic acid or an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid.
Als Basen eignen sich Natronlauge oder Kalilauge sowie Ammoniak, Amine und Erdalkalimetallbasen wie Kalziumhydroxid.Suitable bases are sodium hydroxide solution or potassium hydroxide solution as well as ammonia, amines and alkaline earth metal bases such as calcium hydroxide.
Beispiele für die Herstellung der Homo- und Copolymerisate und die anschließende Solvolyse sind in DE-A-32 13 873 und DE-A-35 34 273 beschrieben.Examples of the preparation of the homopolymers and copolymers and the subsequent solvolysis are described in DE-A-32 13 873 and DE-A-35 34 273.
Zur Entsalzung der Polymerisate verwendet man die üblichen Methoden wie Ionenaustauscher, Elektrodialyse oder Ultrafiltration.The usual methods such as ion exchangers, electrodialysis or ultrafiltration are used to desalinate the polymers.
Das erfindungsgemäße Verfahren ist insbesondere für die Behandlung von Eisen, Eisenlegierungen und chemisch vorbehandelten Untergrund, wie phosphatierten und ggf. mit Wasser bzw. Chromatlösung nachgespülten Metalloberflächen geeignet. Es eignet sich jedoch auch für die Oberflächenmodifizierung von Zink, Aluminium, Kupfer, Kobalt, Nickel und Mangan.The process according to the invention is particularly suitable for the treatment of iron, iron alloys and chemically pretreated substrates, such as phosphated metal surfaces which may have been rinsed with water or chromate solution. However, it is also suitable for the surface modification of zinc, aluminum, copper, cobalt, nickel and manganese.
Die Aufbringung der wäßrigen Polymerlösung erfolgt, wie bereits oben erwähnt, zweckmäßigerweise durch Tauchen, Gießen oder Sprühen.As already mentioned above, the aqueous polymer solution is advantageously applied by dipping, pouring or spraying.
Für das erfindungsgemäße Verfahren können Polymerlösungen mit Feststoffgehalten zwischen 0,01 und 5, vorzugsweise zwischen 0,1 und 1 Gew.-% im Temperaturbereich zwischen 20 und 80°C eingesetzt werden.Polymer solutions with solids contents between 0.01 and 5, preferably between 0.1 and 1% by weight in the temperature range between 20 and 80 ° C. can be used for the process according to the invention.
Die Modifizierung der Metalloberfläche durch das Aminogruppen enthaltende organische Polymer ließ sich durch Sekundärionen-Massenspektrometrie (TOF-SIMS) und Raster-Kraft-mikroskopie (RKM) nachweisen.The modification of the metal surface by the organic polymer containing amino groups was demonstrated by secondary ion mass spectrometry (TOF-SIMS) and atomic force microscopy (RKM).
Die mit dem erfindungsgemäßen Verfahren modifizierten Metall- oder chemisch vorbehandelten Metalloberflächen eignen sich prinzipiell für alle Zwecke, für die chemisch vorbehandelte Metalloberflächen geeignet sind. In Verbindung mit einer Lackierung, bewirken die Polymerschichten eine ungewöhnlich starke Verbesserung der Beständigkeit des Lackfilmes gegen Rostunterwanderung bei korrosiver Beanspruchung. Dieser Vorteil wird besonders bei der kathodischen Elektrotauchlackierung deutlich, weshalb das Verfahren für diese Lackierart besonders vorteilhaft angewendet wird. Praktische Anwendung findet das erfindungsgemäße Verfahren z.B. für Modifizierung von phosphatierten Autokarosserien.The metal or chemically pretreated metal surfaces modified with the method according to the invention are in principle suitable for all purposes for which chemically pretreated metal surfaces are suitable. In combination with painting, the polymer layers bring about an unusually strong improvement in the resistance of the paint film to rust penetration under corrosive stress. This advantage is particularly evident in cathodic electrocoating, which is why the method is used particularly advantageously for this type of painting. The method according to the invention finds practical application e.g. for modification of phosphated car bodies.
Die in den Beispielen genannten Teile und Prozente sind, soweit nicht anders angegeben, Gewichtsteile und Gewichtsprozente.Unless stated otherwise, the parts and percentages mentioned in the examples are parts by weight and percentages by weight.
Allgemeines Prüfverfahren:
190 x 105 x 0,75 mm große Prüfbleche wurden jeweils 1 Minute in wäßrige Polyvinylaminlösungen (K-Wert 30) getaucht. Die Konzentrationen der Polymerlösungen waren 0,01; 0,1; 1 und 2 %. Die Badtemperatur betrug jeweils 23° und 50°C, s. Tabelle. Nach dem Trocknen an Luft wurden die Bleche noch 5 Sekunden in vollentsalztes Wasser getaucht und erneut an Luft getrocknet.General test procedure:
Test sheets measuring 190 × 105 × 0.75 mm were immersed in aqueous polyvinylamine solutions (K value 30) for 1 minute each. The concentrations of the polymer solutions were 0.01; 0.1; 1 and 2 %. The bath temperature was 23 ° and 50 ° C, see. Table. After drying in air, the sheets were immersed in deionized water for a further 5 seconds and dried again in air.
Zur weiteren Prüfung der Wirkung wurden die vorbehandelten Prüfbleche mit einem Elektrotauchlack beschichtet.To further test the effect, the pretreated test panels were coated with an electrocoat.
Als Elektrotauchlack wurde eine Tauchbadlösung verwendet, wie sie in der DE-A-42 08 056 als Vergleichsbeispiel angegeben ist. An den als Kathode geschalteten Prüfblechen wurde bei Raumtemperatur in üblicher Weise der Lack abgeschieden und 25 Minuten bei 175°C eingebrannt. Bei Abscheidespannungen von 320 bis 380 V wurden Schichtdicken von 23 µm erzielt.An immersion bath solution, as specified in DE-A-42 08 056 as a comparative example, was used as the electrodeposition paint. The lacquer was deposited on the test sheets connected as cathode in the usual way at room temperature and baked at 175 ° C. for 25 minutes. With deposition voltages of 320 to 380 V, layer thicknesses of 23 µm were achieved.
Als Maß für die Haftung der Lacke wurde die Unterrostung am Ritz bestimmt. Hierzu wurde auf den Stahlblechen ein 0,1 mm breiter Längsschnitt, auf den Blechen mit einer Phosphat-Konversionsschicht ein 0,1 mm breiter Kreuzschnitt in die Lackierung eingeritzt, der bis zum Blechuntergrund reichte.The rusting on the scratch was determined as a measure of the adhesion of the paints. For this purpose, a 0.1 mm wide longitudinal cut was carved into the coating on the steel sheets, and a 0.1 mm wide cross cut was cut into the sheets with a phosphate conversion layer, which reached down to the sheet metal substrate.
Die lackierten Stahlbleche wurde sodann 15 Tage im Salzsprühnebeltest (40°C, 5 %ige NaCl-Lösung: DIN 50 021) auf Korrosionsbeständigkeit geprüft. Die lackierten Stahlbleche mit Phosphat-Konversionsschicht wurden im salt-water-soak-test geprüft. Hierzu wurde das Prüfblech 10 Tage in eine auf 55°C aufgeheizte 5 %ige NaCl-Lösung eingetaucht.The painted steel sheets were then tested for 15 days in the salt spray test (40 ° C., 5% NaCl solution: DIN 50 021) for corrosion resistance. The painted steel sheets with a phosphate conversion layer were tested in the salt water soak test. For this purpose, the test sheet was immersed in a 5% NaCl solution heated to 55 ° C. for 10 days.
In der Tabelle ist das maximale und durchschnittliche Ausmaß der Unterrostung (in Millimeter) an der Schnittstelle nach beiden Seiten hin angegeben.The table shows the maximum and average amount of rusting (in millimeters) at the interface on both sides.
Die Referenzproben wurden analog nach den oben beschriebenen Verfahren elektrotauchlackiert und anschließend Korrosionstests unterzogen nur mit dem Unterschied, daß keine haftvermittelnde Schicht aufgebracht war.The reference samples were electrocoated analogously using the methods described above and then subjected to corrosion tests with the only difference that no adhesion-promoting layer was applied.
Entfettetes Karosseriestahlblech (z.B. St 1405) wurde wie oben angegeben in wäßrige Polyvinylaminlösungen verschiedener Konzentration eingetaucht, nachbehandelt und elektrotauchlackiert.Degreased body steel sheet (e.g. St 1405) was immersed, as indicated above, in aqueous polyvinylamine solutions of various concentrations, aftertreated and electrocoated.
Beidseitig Manganmodifiziert-niedrigzink-phosphatiertes (Spritzverfahren) und anschließend mit Cr(VI)/Cr(III)-Lösung nachgespültes Stahlblech (BONDER® 26 60 OC) wurde wie oben angegeben in wäßrige Polyvinylaminlösungen verschiedener Konzentration eingetaucht und weiterverarbeitet.On both sides, manganese-modified, low-zinc-phosphated (spray process) and then rinsed with Cr (VI) / Cr (III) solution, steel sheet (BONDER® 26 60 OC) was immersed in aqueous polyvinylamine solutions of various concentrations and processed as described above.
Ein auf einer Seite verzinktes und auf der anderen Seite Manganmodifiziert-niedrigzink-phosphatiertes (Spritzverfahren) und anschließend mit Cr(VI)/Cr(III)-Lösung nachgespültes Stahlblech (BONDER® 26 W OM) wurde wie oben angegeben in wäßrige Polyvinylaminlösungen verschiedener Konzentration eingetaucht und weiterverarbeitet.A steel sheet galvanized on one side and manganese-modified-low-zinc-phosphated (spray process) on the other side and then rinsed with Cr (VI) / Cr (III) solution (BONDER® 26 W OM) was, as stated above, in aqueous polyvinylamine solutions of various concentrations immersed and processed.
Ein beidseitig Manganmodifiziert-niedrigzink-phosphatiertes (Spritzverfahren) und anschließend mit Wasser nachgespültes Stahlblech (BONDER® 26 W OC) wurde wie oben angegeben in wäßrige Polyvinylaminlösungen verschiedener Konzentration eintaucht und weiterverarbeitet.A steel sheet modified on both sides with low manganese phosphate (spraying) and then rinsed with water (BONDER® 26 W OC) was immersed in aqueous polyvinylamine solutions of various concentrations and processed as described above.
Die Prüfergebnisse sind in der Tabelle zusammengestellt.The test results are summarized in the table.
Bewertung der in den Beispielen erhaltenen Ergebnisse:
Der Korrosionstest zeigt an den Beispielen 1 bis 4 deutlich die Vorteile des erfindungsgemäßen Verfahrens im Vergleich zu den Referenzproben nach dem Stand der Technik.Evaluation of the results obtained in the examples:
The corrosion test clearly shows in Examples 1 to 4 the advantages of the method according to the invention compared to the reference samples according to the prior art.
Das Ausmaß der Unterrostung verringert sich durch die haftvermittelnde Polymerschicht bei den Proben mit Phosphat-Konversionsschicht um das zwei- bis dreifache. Bei dem beidseitig Manganmodifiziert-niedrigzink-phosphatierten (Spritzverfahren) und anschließend mit Cr(VI)/Cr(III)-Lösung nachgespülten Stahlblech verhindert das erfindungsgemäße Verfahren die Unterrostung vollständig. Auch beim entfetteten Karosseriestahlblech ist eine verringerte Unterrostung (Beispiel 1) festzustellen.The extent of under-rusting is reduced by two to three times due to the adhesion-promoting polymer layer in the samples with a phosphate conversion layer. In the case of the steel sheet modified on both sides with manganese-modified low-zinc phosphate (spraying process) and subsequently rinsed with a Cr (VI) / Cr (III) solution, the process according to the invention completely prevents rusting. Reduced rust formation (example 1) can also be seen with degreased body steel sheet.
Auch das gesamte Erscheinungsbild der Lackoberfläche zeigt durch das erfindungsgemäße Verfahren eine deutliche Verbesserung gegenüber dem Stand der Technik. Während die Lackflächen der Referenzproben starke Blasenbildung zeigen, ist die Lackoberfläche auf der mit wäßriger Polyvinylamin-Lösung modifizierten Metalloberfläche einwandfrei.The overall appearance of the paint surface also shows a significant improvement over the prior art as a result of the method according to the invention. While the paint surfaces of the reference samples show strong blistering, the paint surface on the metal surface modified with aqueous polyvinylamine solution is perfect.
Die besten Resultate wurden bei den Blechen mit Phosphat-Konversionsschichten mit einer 0,1 %igen Polyvinylaminlösung bei 50°C erhalten. Die geringste Unterwanderung auf blankem Stahl wurden bei Behandlung mit einer 1 %igen Polyvinylaminlösung (50°C Badtemperatur) erhalten.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4409306A DE4409306A1 (en) | 1994-03-18 | 1994-03-18 | Process for modifying metal surfaces |
| DE4409306 | 1994-03-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0672467A1 true EP0672467A1 (en) | 1995-09-20 |
| EP0672467B1 EP0672467B1 (en) | 1999-01-07 |
Family
ID=6513182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95103462A Expired - Lifetime EP0672467B1 (en) | 1994-03-18 | 1995-03-10 | Process for modification of metallic surfaces |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5494535A (en) |
| EP (1) | EP0672467B1 (en) |
| JP (1) | JPH0847666A (en) |
| AT (1) | ATE175365T1 (en) |
| DE (2) | DE4409306A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008053517A1 (en) | 2008-10-28 | 2010-04-29 | Henkel Ag & Co. Kgaa | Paint adhesion by polyvinylamines in acidic aqueous polymer-containing corrosion protection agents |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4043551B2 (en) * | 1997-05-23 | 2008-02-06 | 栗田工業株式会社 | Scale inhibitor and scale prevention method |
| DE10013828A1 (en) * | 1999-04-01 | 2000-10-05 | Basf Ag | Metal process equipment or container for use in contact with vinyl monomers, e.g. distillation apparatus, has at least part of metal surface treated with polymeric complex former to prevent deposition of polymer |
| DE19961411A1 (en) * | 1999-12-17 | 2001-06-21 | Chemetall Gmbh | Process for the production of coated metal surfaces and their use |
| US6743302B2 (en) | 2000-01-28 | 2004-06-01 | Henkel Corporation | Dry-in-place zinc phosphating compositions including adhesion-promoting polymers |
| DE10164671A1 (en) * | 2001-12-27 | 2003-07-10 | Basf Ag | Derivatives of polymers for metal treatment |
| DE10163892A1 (en) * | 2001-12-27 | 2003-07-17 | Basf Ag | Derivatives of polymers for metal treatment |
| DE10310972A1 (en) | 2003-03-13 | 2004-09-23 | Basf Ag | Passivating layer on a metallic surface, prepared by precipitation of water-soluble, nitrogen-containing polymer at the metal surface upon addition of metal salt(s) at a pH of less than 7 |
| DE102005023728A1 (en) * | 2005-05-23 | 2006-11-30 | Basf Coatings Ag | Lacquer-layer-forming corrosion inhibitor and method for its current-free application |
| DE102006053291A1 (en) * | 2006-11-13 | 2008-05-15 | Basf Coatings Ag | Lacquer-layer-forming corrosion protection agent with good adhesion and method for its current-free application |
| DE102007012406A1 (en) * | 2007-03-15 | 2008-09-18 | Basf Coatings Ag | Process for corrosion protection equipment of metallic substrates |
| DE102009007632A1 (en) | 2009-02-05 | 2010-08-12 | Basf Coatings Ag | Coating agent for corrosion-resistant coatings |
| WO2014162875A1 (en) * | 2013-04-02 | 2014-10-09 | 株式会社Adeka | Additive for copper electroplating bath, copper electroplating bath containing said additive, and copper electroplating method using said copper electroplating bath |
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| EP0274738A1 (en) * | 1986-12-29 | 1988-07-20 | Nihon Parkerizing Co., Ltd. | Method for forming coatings on aluminium surfaces |
| US5373076A (en) * | 1992-07-14 | 1994-12-13 | Air Products And Chemicals, Inc. | Functional oligomeric vinylformamides and vinylamines |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE2907094A1 (en) * | 1979-02-23 | 1980-09-04 | Metallgesellschaft Ag | PHOSPHATION SOLUTIONS |
| DE3213873A1 (en) * | 1982-04-15 | 1983-10-27 | Basf Ag, 6700 Ludwigshafen | Flocculant for sludge |
| US4466840A (en) * | 1981-09-21 | 1984-08-21 | Akzona Incorporated | Hydroxybenzyl amines as corrosion inhibitors and paint adhesion promoters |
| US4433015A (en) * | 1982-04-07 | 1984-02-21 | Parker Chemical Company | Treatment of metal with derivative of poly-4-vinylphenol |
| DE3408577A1 (en) * | 1984-03-09 | 1985-09-12 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR PHOSPHATING METALS |
| DE3534273A1 (en) * | 1985-09-26 | 1987-04-02 | Basf Ag | METHOD FOR PRODUCING VINYLAMINE UNITS CONTAINING WATER-SOLUBLE COPOLYMERISATS AND THE USE THEREOF AS WET AND DRY-FASTENING AGENTS FOR PAPER |
| US4978399A (en) * | 1988-01-04 | 1990-12-18 | Kao Corporation | Metal surface treatment with an aqueous solution |
| US5112413A (en) * | 1990-06-26 | 1992-05-12 | Betz Laboratories, Inc. | Method for treating metal surfaces with a polymer solution |
| US5209788A (en) * | 1990-11-21 | 1993-05-11 | Ppg Industries, Inc. | Non-chrome final rinse for phosphated metal |
| US5226976A (en) * | 1991-04-15 | 1993-07-13 | Henkel Corporation | Metal treatment |
| DE4208056A1 (en) * | 1992-03-13 | 1993-09-16 | Basf Lacke & Farben | BINDING AGENT FOR ELECTRO DIP PAINTING |
-
1994
- 1994-03-18 DE DE4409306A patent/DE4409306A1/en not_active Withdrawn
-
1995
- 1995-03-10 EP EP95103462A patent/EP0672467B1/en not_active Expired - Lifetime
- 1995-03-10 DE DE59504710T patent/DE59504710D1/en not_active Expired - Lifetime
- 1995-03-10 AT AT95103462T patent/ATE175365T1/en not_active IP Right Cessation
- 1995-03-15 US US08/404,713 patent/US5494535A/en not_active Expired - Fee Related
- 1995-03-16 JP JP7057058A patent/JPH0847666A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0274738A1 (en) * | 1986-12-29 | 1988-07-20 | Nihon Parkerizing Co., Ltd. | Method for forming coatings on aluminium surfaces |
| US5373076A (en) * | 1992-07-14 | 1994-12-13 | Air Products And Chemicals, Inc. | Functional oligomeric vinylformamides and vinylamines |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008053517A1 (en) | 2008-10-28 | 2010-04-29 | Henkel Ag & Co. Kgaa | Paint adhesion by polyvinylamines in acidic aqueous polymer-containing corrosion protection agents |
| WO2010049198A1 (en) * | 2008-10-28 | 2010-05-06 | Henkel Ag & Co. Kgaa | Paint adhesion by polyvinyl amines in acidic aqueous corrosion protection product containing polymers |
| US8142897B2 (en) | 2008-10-28 | 2012-03-27 | Henkel Kgaa | Paint adhesion by polyvinyl amines in acidic aqueous corrosion protection product containing polymers |
| RU2504601C2 (en) * | 2008-10-28 | 2014-01-20 | Хенкель Аг Унд Ко. Кгаа | Bonding paint layer with polyvinyl amines in polymer-containing aqueous acidic anticorrosion media |
| AU2009309946B2 (en) * | 2008-10-28 | 2015-02-05 | Henkel Ag & Co. Kgaa | Paint adhesion by polyvinyl amines in acidic aqueous corrosion protection product containing polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| US5494535A (en) | 1996-02-27 |
| JPH0847666A (en) | 1996-02-20 |
| DE4409306A1 (en) | 1995-09-21 |
| EP0672467B1 (en) | 1999-01-07 |
| ATE175365T1 (en) | 1999-01-15 |
| DE59504710D1 (en) | 1999-02-18 |
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