EP1606362A2 - Polymeres azotes pour le traitement de surfaces metalliques - Google Patents

Polymeres azotes pour le traitement de surfaces metalliques

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Publication number
EP1606362A2
EP1606362A2 EP04720004A EP04720004A EP1606362A2 EP 1606362 A2 EP1606362 A2 EP 1606362A2 EP 04720004 A EP04720004 A EP 04720004A EP 04720004 A EP04720004 A EP 04720004A EP 1606362 A2 EP1606362 A2 EP 1606362A2
Authority
EP
European Patent Office
Prior art keywords
acid
metal surface
passivation layer
water
component
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.)
Withdrawn
Application number
EP04720004A
Other languages
German (de)
English (en)
Inventor
Frank Dietsche
Helmut Witteler
Matthias KLÜGLEIN
Frank Klippel
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.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1606362A2 publication Critical patent/EP1606362A2/fr
Withdrawn legal-status Critical Current

Links

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
    • C23C22/48—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
    • C23C22/53—Treatment of zinc or alloys based thereon
    • 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
    • B05D7/142—Auto-deposited coatings, i.e. autophoretic coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/088—Autophoretic paints
    • 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
    • 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
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified

Definitions

  • the present invention relates to a passivation layer on a metal surface which contains a nitrogen-containing polymer, a method for forming this passivation layer and the use of a composition comprising a water-soluble, nitrogen-containing polymer for passivation of a metal surface, a lacquer structure on a metal surface, comprising the passivation layer mentioned and a Painting and a method for forming this paint structure and a surface made up of a metal surface and the passivation layer according to the invention.
  • Metallic materials especially iron and steel, are usually galvanized to protect them from corrosive environmental influences.
  • the protection against corrosion of the zinc is based on the fact that it is even less noble than the metallic material and therefore initially only attracts the corrosive attack, ie it acts as a sacrificial layer.
  • the metallic material itself remains intact as long as it is continuously covered with zinc and the mechanical functionality is retained over longer periods than with non-galvanized parts.
  • the corrosive attack of such a zinc layer can in turn be delayed by applying a passivation layer. This is particularly the case with galvanized parts, both for parts that are subsequently painted and for those that are used without painting.
  • Aluminum surfaces are also often provided with a passivation layer, especially if they are subsequently to be painted.
  • the passivation layer delays the corrosive attack on the metal surface and at the same time serves to improve the adhesion of any lacquer layers to be applied.
  • the term conversion layer is often used synonymously.
  • passivation layers have been obtained on zinc or aluminum surfaces, usually by immersing the workpiece to be protected in aqueous acidic solutions of CrO 3 . The workpiece is protected against corrosion after immersion and drying. When immersed, part of the metal to be protected dissolves and immediately forms an oxidic film on the metal surface. This film is similar to the oxide film that is already present on many metals, but is denser and better adherent than this.
  • This Cr (VI) treatment is optimal in terms of passivation. The time until white rust formation of an unpainted galvanized sheet is extended by Cr (VT) treatment from less than 1 hour to more than 100 hours.
  • DE-A 100 05 113 relates to an application solution which contains phosphoric acid and / or at least one fluoric acid of one or more elements from the group Zr, Ti, Hf and Si or their respective anions and a homo- or copolymer of vinylpyrrolidone and a process for the corrosion protection treatment a metal surface, the metal surface being brought into contact with a homo- or copolymer of vinylpyrrolidone.
  • known passivation agents based on fluorometalates of Zr, Ti, Hf or Si homo- or copolymers of vinylpyrrolidone are added to improve the corrosion protection.
  • JP-A 04231679 relates to anti-corrosion agents for surfaces made of copper or copper alloys, the copper surface being first treated with an alcoholic solution containing polyvinylimidazole and then with a solution containing a zinc salt. This treatment of corrosion protection till- 'and improves the heat resistance of the copper surface.
  • DE-A 44 09 306 relates to a method for modifying cleaned or chemically pretreated metal surfaces with aqueous solutions, organic polymers containing amino groups, in particular with polyvinylamines.
  • the object of the present invention is to provide a passivation layer on a metal surface which meets the following requirements:
  • the layer should generally not be hydrophobic
  • a passivation layer on a metal surface obtainable by bringing the metal surface into contact with a composition which contains a water-soluble, nitrogen-containing polymer, the polymer being a base and an aqueous solution of the polymer with the addition of one or more salts of the base metal forms a precipitate at pH ⁇ 7.
  • the passivation layer according to the invention is characterized in that it already has an excellent corrosion-inhibiting effect in the form of a very thin layer.
  • Any metal surface can generally be used as the metal surface. Suitable metal surfaces are generally technically customary materials selected from the group consisting of steel, cast iron, zinc, aluminum, magnesium and alloys of these metals with one another or with other alloy components. Zinc and aluminum as well as alloys of these metals with other alloy components are particularly preferred, a surface of zinc or zinc alloys generally being obtained by a galvanizing process of a metallic material such as iron or steel.
  • metal surfaces that are not pretreated. However, it is preferred that the metal surfaces have at least been cleaned prior to contacting the composition containing a water-soluble, nitrogen-containing polymer.
  • the cleaning preferably includes degreasing the metal surface. Suitable cleaning or degreasing processes are known to the person skilled in the art.
  • the polymer particularly preferably contains> 50% by weight of vinylimidazole and optionally at least one further monomer.
  • the term polymer means both homopolymers and copolymers.
  • the polymer (component A) used according to the invention very particularly preferably contains the following components:
  • N-vinyl lactams for example N-vinyl caprolactam, N-vinyl pyrrolidone and N-vinyl piperidone, are suitable as component Ab
  • vinyl pyridines and vinyl pyridine N-oxides are suitable as further vinyl heteroaromatics
  • suitable vinyl esters are, for example, vinyl acetate and vinyl propionate and suitable C 1 -C 4]
  • o-Alkyl (meth) acrylates are methyl, ethyl and butyl acrylate or the corresponding methacrylates.
  • Monoethylenically unsaturated compounds which contain at least one acid group, for example a carboxyl group, a sulfonic acid group or a phosphonic acid group, are suitable as component Ac.
  • Compounds suitable as component Ac are, for example, acrylic acid, methacrylic acid, dimethacrylic acid, ethyl acrylic acid, crotonic acid, allylacetic acid and vinyl acetic acid.
  • monoethylenically unsaturated dicarboxylic acids are suitable as component Ac, for example maleic acid, fumaric acid, itaconic acid, mesaconic acid, methylene malonic acid, citraconic acid, maleic anhydride, itaconic anhydride and methylene malonic anhydride, the anhydrides usually hydrolyzing to the corresponding dicarboxylic acids when introduced into water.
  • Monomers containing sulfonic acid groups for example 2-acrylamido-2-methylpropanesulfonic acid, (meth) acrylic acid-3-sulfopropyl ester, vinylsulfonic acid, methallylsulfonic acid and allylsulfonic acid, and monomers containing phosphonic acid groups, such as vinylphosphonic acid, can also be used as component Ac.
  • the monomers mentioned as component Ac can be used either alone or as a mixture with one another.
  • Ac monomers selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, 2-acrylarnido-2-methylpropanesulfonic acid, vinylsulfonic acid, acrylic or methacrylsulfonic acid 3-sulfopropyl ester and vinylphosphonic acid are preferably used as component Ac.
  • the monomers used as component Ac can either be in the form of the free acids or, which is preferred, in the form of their alkali metal, alkaline earth metal or Ammonium salts are used.
  • Preferred alkali metal salts are sodium and potassium salts
  • preferred alkaline earth salts are magnesium and calcium salts.
  • the water-soluble, nitrogen-containing polymer is homopolyvinylimidazole, i.e. the polymer is composed of 100% by weight of N-vinylimidazole.
  • the weight average molecular weight (Mw) of the water-soluble, nitrogen-containing polymer used according to the invention is generally 1000 to 1,000,000 g / mol, preferably 10,000 to 150,000 g / mol. In the case of homopolyvinylimidazole used with very particular preference, this has a molecular weight of generally 5,000 to 200,000 g / mol.
  • the molecular weight (Mw) was determined by means of gel permeation chromatography using a polystyrene standard.
  • Copolymers are generally to be understood as meaning those compounds which have at least 3 repeat units, preferably more than 10 repeat units.
  • the water-soluble, nitrogen-containing polymer used according to the invention can be produced in any manner known to the person skilled in the art. For example, one is
  • Emulsion polymerization or solution polymerization for example in toluene, water or ethanol. Furthermore, it is possible to prepare the water-soluble, nitrogen-containing polymer used according to the invention by precipitation polymerization from an organic solvent, such as alkanes or cycloalkanes, or in accordance with the process disclosed in DE-A 43 42 281.
  • an organic solvent such as alkanes or cycloalkanes
  • the preferably used water-soluble, nitrogen-containing polymer which is composed of> 50% by weight vinylimidazole and, if appropriate, at least one further monomer, and the very particularly preferably used homopolyvinylimidazole are preferably prepared by a process in accordance with the process disclosed in DE-A 43 42 281 ,
  • the metal surface is preferably brought into contact with a composition containing a) a water-soluble, nitrogen-containing polymer as defined above, as component A;
  • component C optionally at least one surface-active compound, at least one emulsifier and / or at least one dispersant, as component C.
  • the water-soluble, nitrogen-containing polymer used as component A has already been defined above.
  • this polymer is generally used in an amount of 0.01 to 100 g / 1, preferably 0.01 to 70 g / 1, particularly preferably 0.01 to 50 g / 1, based on 1 1 each Composition used.
  • Component B is water or another solvent which is suitable for dissolving or dispersing, suspending or emulsifying the polymer (component A).
  • a solvent is understood to mean a liquid matrix in which the various constituents of the composition according to the invention are present as finely as possible. Such a fine distribution can, for example in the sense of a molecularly disperse distribution, be a real solution of the ingredients in the solvent.
  • solvent also includes liquid matrices in which the ingredients are distributed in the form of an emulsion or dispersion, i.e. do not form a molecularly disperse solution.
  • Suitable solvents are water and water-miscible and water-immiscible solvents.
  • Suitable water-miscible solvents are, for example, primary or secondary mono- or polyalcohols with 1 to about 6 C-
  • Atoms such as methanol, ethanol, propanol, isopropanol, n-butanol, iso-butanol, pentanol, Hexanol, cyclohexanol or glycerin.
  • water-miscible solvents low molecular weight ketones such as acetone or methyl ethyl ketone or ether alcohols such as diethylene glycol or triethyl glycol.
  • solvents which are immiscible or only slightly miscible with water.
  • ethers such as diethyl ether, dioxane or tetrahydrofuran, aromatic solvents such as toluene or xylene, halogenated solvents such as dichloromethane, chloroform or carbon tetrachloride and optionally substituted aliphatic solvents, which include, for example, the higher homologues of the abovementioned alcohols and ketones and paraffin hydrocarbons.
  • the solvents mentioned above can be used individually or as a mixture of two or more of the solvents mentioned.
  • water is used as the solvent, optionally in a mixture with one or more of the above-mentioned, preferably water-soluble solvents.
  • a solvent is to be used which contains water and a water-immiscible solvent, the solvent can, for example, contain an emulsifier in order to enable an essentially stable W / O or O / W emulsion.
  • the proportion of water in such a mixture is preferably at least about 30% by weight or more, for example at least about 40 or at least about 50% by weight.
  • the water content is at least about 75% by weight.
  • Suitable combinations of water and water-miscible solvents are, for example, water / methanol, water / ethanol, water / propanol or water / isopropanol.
  • a mixture of water and ethanol is preferred in the context of the present invention, the water content preferably being greater than about 75% by weight, for example greater than about 80 or about 85% by weight.
  • a composition according to the invention contains at least one solvent which has a water content of at least about 50% by weight.
  • the composition preferably used according to the invention as an aqueous solution generally has a pH of from 1 to 6, with narrower pH ranges being chosen depending on the substrate and type of application and the duration of action of the composition used according to the invention on the surface of the base metal.
  • the pH value for the treatment of bare metal surfaces is preferably set to the range from 2 to 6, for the treatment of aluminum surfaces preferably to the range from 2 to 4 and for the treatment of steel, zinc or galvanized steel preferably to the range from 3 to 6 5 a.
  • Surfaces of a base metal that have already been pretreated and which, for example, carry a phosphate layer, are preferably brought into contact with a composition used according to the invention having a pH of 3.5 to 5.
  • the amount of water or another solvent depends on whether the composition according to the invention is a ready-to-use composition or a concentrate, and on the particular application. Basically, the quantity results from the concentrations of the individual components specified for the ready-to-use composition.
  • the composition according to the invention can additionally contain surface-active compounds, emulsifiers and / or dispersants.
  • Suitable surface-active compounds are surfactants, which can be cationic, anionic, zwitterionic or nonionic.
  • Suitable surfactants are, for example, alkyl and alkenyl alkoxylates of the R-EO n / PO m type, where R is generally linear or branched C 6 -C 3 o-alkyl radicals, preferably C 8 -C 20 -alkyl radicals and EO for an ethylene oxide unit and PO stands for a propylene oxide unit, where EO and PO can be arranged in any order and n and m are independently> 1 and ⁇ 100, preferably> 3 and ⁇ 50, for example E ulan®, Lutensol® and Plurafac® (der BASF), alkylphenol ethoxylates, EO / PO block copolymers (Pluronic®, from BASF), alky
  • composition used according to the invention contains, in addition to components A, B and optionally C:
  • Lantanoids as component D, and / or
  • At least one acid selected from the group consisting of phosphoric acid, sulfuric acid, sulfonic acids, nitric acid, hydrofluoric acid and hydrochloric acid as
  • component H further auxiliaries and additives as component H.
  • compositions are suitable for passivating, in particular phosphating, the metal surfaces mentioned in the present application.
  • Suitable as component D are salts, acids and bases based on transition metal cations, transition metal oxo anions, fluorometalates or lanthanoids.
  • Suitable transition metal cations are, in particular, fluorometalates of Ti (IV), Zr (IV), Hf (IV) and / or Si (IV), suitable lanthanides, in particular Ce. Tungsten and molybdates are also suitable.
  • compositions according to the present application containing component D are particularly suitable for either a corrosion-protective layer on a
  • component A has an excellent corrosion protection effect in the compositions according to the invention.
  • the use of component A in the compositions used according to the invention leads to such good corrosion protection properties that the addition of component D is not necessary.
  • compounds of component D are therefore not contained in the compositions used according to the invention.
  • the amount of component D is - if component D is contained in the compositions according to the invention - preferably 0.02 to 20 g / 1.
  • compositions according to the invention can also contain at least one acid selected from the group consisting of phosphoric acid, sulfuric acid, sulfonic acids such as methanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, m-nitrobenzenesulfonic acid, naphthalenesulfonic acid and derivatives thereof, nitric acid, hydrofluoric acid and hydrochloric acid.
  • the type of acid used depends on the type of treatment of the metal surface.
  • phosphoric acid is generally used in phosphating baths for phosphating steel surfaces.
  • the composition used according to the invention is a phosphating solution.
  • non-layer-forming phosphating solutions which are solutions that have no divalent metals.
  • Such "non-layer-forming" phosphating solutions are, for example, in the form of an iron phosphating solution.
  • the phosphating solutions contain ions of divalent metals, e.g. B. zinc and / or manganese, the phosphating solutions ⁇ are available as so-called “forming” phosphating solutions.
  • Compositions containing nitric acid according to the present application are particularly suitable for the surface treatment of zinc and its alloys, while hydrofluoric acid-containing compositions are particularly suitable for the surface treatment of aluminum and its alloys.
  • the amount of acid used can vary depending on the application. In general, if component E is contained in the compositions according to the invention, 0.2 to 200 g / 1, preferably 2 to 100 g / 1, of component E are used.
  • Component F is contained in the compositions according to the invention, 0.2 to 200 g / 1, preferably 2 to 100 g / 1, of component E are used.
  • compositions used according to the invention can contain at least one further corrosion inhibitor.
  • Suitable corrosion inhibitors are selected from the group consisting of butynediol, benzotriazole, aldehydes, amine carboxylates, amino and nitrophenols, amino alcohols, aminobenzimidazole, aminoimidazolines, aminotriazole, benzimidazolamines, benzothiazoles, derivatives of benzotriazole, various boranol acid esters, such as boranol acid esters, with boronic acid amines such as boronic acid amines, such as boronic acid amines, such as boronic acid amines, such as boronic acid amines, such as boronic acid amines, such as boronic acid amines, such as boronic acid amines, such as boronic acid amines, such as boronic acid amines, such as boronic acid amines, such as boronic acid amines, such as boronic
  • Butynediol and benzotriazole are preferably used as further corrosion inhibitors.
  • the corrosion inhibitors if they are used at all in the compositions, are used in an amount of generally 0.01 to 50 g / 1, preferably 0.1 to 20 g / 1, particularly preferably 1 to 10 g / 1.
  • compositions used according to the invention are preferably Cr (VI) -free, particularly preferably the compositions used according to the invention contain no compounds according to Component G. If the compounds mentioned (component G) are nevertheless used, preference is given to using compounds selected from Fe, Z ⁇ , Zr and Ca. The amount of these compounds in the compositions is - if these compounds are present at all - generally 0.01 to 100 g / 1, preferably 0.1 to 50 g / 1, particularly preferably 1 to 20 g / 1.
  • the compositions used according to the invention can contain further auxiliaries and additives.
  • auxiliaries and additives include conductivity pigments or conductive fillers e.g. Iron phosphide, vanadium carbide, titanium nitride, carbon black, graphite, molybdenum disulfide or barium sulfate doped with tin or antimony, with iron phosphide being preferred.
  • conductivity pigments or conductive fillers are added to the compositions used according to the invention to improve the weldability of the metal surfaces to be treated or to improve a subsequent coating with electrocoat materials.
  • silica suspensions can be used, in particular when the compositions are used to treat aluminum-containing surfaces.
  • additives are generally in finely divided form, i.e. their average particle diameters are generally 0.005 to 5 ⁇ m, preferably 0.05 to 2.5 ⁇ m.
  • the amount of auxiliaries and additives is generally 0.1 to 50, preferably 2 to 35% by weight, based on the total mass of the compositions according to the invention.
  • compositions used according to the invention may further contain additives to improve the forming behavior, for example wax-based derivatives based on natural or synthetic waxes, e.g. Waxes based on acrylic acid, polyethylene, polytetrafluoroethylene (PTFE) waxes or wax derivatives or paraffins and their oxidation products.
  • Waxes based on acrylic acid, polyethylene, polytetrafluoroethylene (PTFE) waxes or wax derivatives or paraffins and their oxidation products.
  • compositions used according to the invention can contain polymer dispersions based on styrene, 4-hydroxystyrene, butadiene, acrylic acid, acrylic acid esters, acrylic acid amides, acrylates, methacrylic acid, Contain methacrylic acid esters, methacrylic acid amides, methacrylates and derivatives of acrylamide. It is also possible that the compositions used according to the invention contain polyurethane dispersions and polyester urethane dispersions or polyurea dispersions.
  • compositions used according to the invention are polyethylene glycols, polypropylene glycols, copolymers of ethylene oxide and copolymers of propylene oxide.
  • compositions used according to the invention are used for passivation (conversion layer formation), in particular no-rinse conversion layer formation, that is to say processes with a reduced number of rinsing operations, for example on galvanized steel and aluminum.
  • passivation layer according to the invention is formed on the metal surface.
  • compositions used according to the invention can optionally additionally contain a complexing agent as component I.
  • Suitable complexing agents are e.g. Ethylenediaminetetraacetic acid (EDTA), ethylenediamine (ED), citric acid and salts of the compounds mentioned.
  • compositions used according to the invention can optionally contain at least one acid or an alkali metal or alkaline earth metal salt of the corresponding acid, preferably selected from the group consisting of HNO 3 , H 2 SO 4 , H 3 PO 4 , formic acid and acetic acid as component K.
  • the acid is generally used in an amount of 0.5 to 700 g / 1, preferably 5 to 280 g / 1.
  • compositions used according to the invention can contain further additives as component L.
  • Suitable additives are 1- (2-methylpyridinium) -2-ethylsulfobetaine, 1,1-dimethyl-2-propynyl-1- ⁇ umin, 1-pyridinium-2-ethylsulfobetaine, 1-pyridinium-2-hydroxy-3 - propylsulfobetaine, 1-pyridinium-3-propylsulfobetaine, 2,2'-dichlorodiethyl ether, 2,5-dimethyl-3-hexyne-2,5-diol, 2-butyne-l, 4-diol, 2-butyne-l , 4-diol ethoxylate, 2-butm-l, 4-dio_propoxylate, 3- (2-benzothiazolylthio) -l-propane-sulfonic acid Na salt, 3,3'-dithio-bis- (l-
  • the passivation layer according to the invention contains, apart from the water-soluble nitrogen-containing polymer, metal ions of the base metal, in particular aluminum and zinc or alloy metal ions of alloy metals with aluminum or zinc, no further metals.
  • the compositions used to produce the passivation layer contain no metals or metal compounds.
  • passivation layers are obtained which have excellent corrosion stability.
  • the layer thickness of the passivation layer according to the invention formed on the surface of a base metal is preferably ⁇ 3 ⁇ m.
  • the layer thickness is particularly preferably 0.01 to 3 ⁇ m, very particularly preferably 0.1 to 3 ⁇ m.
  • the thickness of the layer is determined by differential weighing before and after the action of the composition used according to the invention on the metal surface, on the assumption that the layer has a specific density of 1 kg / 1.
  • “layer thickness” is always understood to mean a size determined in this way, regardless of the specific density of the layer.
  • the water-soluble, nitrogen-containing polymer used according to the invention can be present in solution, emulsion, suspension or as an aerosol in the process according to the invention.
  • the polymer (component A) is preferably present in the compositions used in the process according to the invention in aqueous solution.
  • the type of application corresponds to the usual technical methods.
  • the metal surface is preferably brought into contact with compositions used according to the invention by spraying the composition onto the metal surface or by dipping the metal surface into the composition.
  • the particularly preferred application method used depends on the number, size and shape of the parts to be treated. Accordingly, the contacting is preferably carried out by means of a spraying, rolling or dipping process.
  • compositions according to the present application containing phosphoric acid as component E can be applied by a “roll-on” or “dry-in-place” or “no-rinse” method are, wherein the phosphating composition used according to the invention is applied to the metal strip and dried without rinsing, a polymer film being formed.
  • Another subject of the present application is a method comprising the steps:
  • the contacting of the metal surface with the water-soluble, nitrogen-containing polymer used according to the invention is the passivation step, in particular a phosphating step, which is carried out by methods known to the person skilled in the art.
  • the passivation layer according to the invention is formed on the metal. If in step e)
  • Preferred water-soluble, nitrogen-containing polymers (component A) have already been named above.
  • Washing with water takes place between the individual process steps in order to avoid contamination of the solution required for the subsequent step with components of the solution used in the previous step.
  • the composition used according to the invention is generally either sprayed onto the metal surface or transferred onto the surface by application rollers. This is followed by an exposure time which is generally in the range from 2 to 20 seconds, without further action Intermediate rinsing a drying of the composition used according to the invention, for example in a heated oven.
  • step a) The steps of cleaning (step a)) and contacting the metal surface in the presence of the water-soluble, nitrogen-containing polymer (component A) (step e)) used according to the invention can also be carried out in one step, ie with a formulation which, in addition to the customary cleaning agents also contains the composition used according to the invention.
  • the process according to the invention is generally carried out at a temperature of 5 to 100 ° C., preferably 10 to 80 ° C., particularly preferably 15 to 45 ° C.
  • compositions which are preferably used and polymers (component A) which are preferably used in the compositions have already been mentioned above.
  • Metal surfaces which are preferably used and processes which are preferably carried out for passivating the metal surfaces have likewise already been mentioned above.
  • the metal surface provided with the passivation layer according to the invention can be provided with a varnish after the method steps a) to g).
  • the painting is carried out according to methods known to those skilled in the art.
  • a powder coating or an electrolytic, in particular cathodic, dip coating can be used as the coating.
  • Another object of the present application is thus a lacquer build-up on a metal surface comprising at least one passivation layer X according to the invention and at least one lacquer layer, preferably several lacquer layers, as layer (s) Y.
  • passivation layer and preferred embodiments of the passivation layer have already been mentioned above.
  • Suitable layers of lacquer are known to the person skilled in the art.
  • the lacquer structure according to the invention can contain a multi-layer lacquer coating (several lacquer layers) with further layers.
  • a multi-layer coating can be constructed from at least one of the following layers, which can typically be arranged as follows:
  • a pigmented and / or layer W provided with effect substances • a layer Z selected from the group of primers, basecoat, primer, pigmented lacquer or lacquer provided with effect substances.
  • a layer Z selected from the group of primers, basecoat, primer, pigmented lacquer or lacquer provided with effect substances.
  • lacquers which are customary for these purposes and are known to the person skilled in the art are suitable as color and / or effect lacquers in the layer Z and / or W. These can be curable physically, thermally, with actinic radiation or thermally and with amine radiation (dual-cure).
  • They can be conventional basecoats, waterborne basecoats, essentially solvent-free and water-free liquid basecoats (100% systems), essentially solvent-free and water-free solid basecoats (pigmented powder coatings) or essentially solvent-free pigmented powder coating dispersions (powder slurry basecoats). They can be thermally or DualCure-curable, and self- or externally cross-linking.
  • One or more, preferably 1 to 3, particularly preferably 1 to 2 and very particularly preferably a coloring and / or effect-imparting lacquer can be used in the layers.
  • Essentially solvent-free means that the coating material in question has a residual volatile solvent content of ⁇ 2.0% by weight, preferably ⁇ 1.5% by weight and particularly preferably ⁇ 1.0% by weight. It is of particular advantage if the residual content is below the gas chromatographic detection limit.
  • Water-based paints such as those described in patent applications EP 0 089 497 AI, EP 0 256 540 AI, EP 0 260 447 AI, EP 0 297 576 AI, WO 96/12747, EP 0 523 610 AI, EP are particularly preferably used in the multi-layer coatings 0 228 003 AI, EP 0 397 806 AI, EP 0 574 417 AI, EP 0 531 510 AI, EP 0 581 211 AI, EP 0 708 788 AI, EP 0 593 454 AI, DE-A-43 28 092 AI, EP 0 299 148 AI, EP 0 394 737 AI, EP 0 590 484 AI, EP 0 234 362 AI, EP 0 234 361 AI, EP 0 543 817 AI, W095 / 14721, EP 0 521 928 AI, EP 0 522 420 AI, EP 0 522 419 AI, EP 0 649 865 AI, EP 0 5
  • the color and / or effect coatings described above can be used not only for the production of color and / or effect base coatings, but also for color and / or effect combination effect layers.
  • This is to be understood as a coating which fulfills at least two functions in a color and / or effect multi-layer coating. Functions of this type are, in particular, protection against corrosion, the imparting of adhesion, the absorption of mechanical energy and the coloring and / or effects. Above all, it serves Combination effect layer of the absorption of mechanical energy and the coloring and / or effect at the same time; it therefore fulfills the functions of a filler paint or stone chip protection primer and a base coat.
  • the combination effect layer preferably also has a corrosion protection effect and / or an adhesion-promoting effect.
  • Typical thicknesses of the layer (W) and / or (Z) range from 0.1 to 2000 ⁇ m, preferably 0.5 to 1000 ⁇ m, particularly preferably from 1 to 500 ⁇ m, very particularly preferably from 1 to 250 ⁇ m and in particular from 10 up to 100 ⁇ m.
  • the lacquers which can be used in the multi-layer lacquers can contain coloring and / or effect pigments. All paint-typical pigments of organic or inorganic nature are suitable as color pigments. Examples of inorganic or organic color pigments are titanium dioxide, micronized titanium dioxide, iron oxide pigments, carbon black, azo pigments, phthalocyanine pigments, quinacridone and pyrrolopyrrole pigments.
  • effect pigments are particularly characterized by a platelet-like structure.
  • effect pigments are: metal pigments, e.g. made of aluminum, copper or other metals; Interference pigments, e.g. metal oxide coated metal pigments, e.g. titanium dioxide coated or mixed oxide coated aluminum, coated mica, e.g. titanium dioxide coated mica and graphite effect pigments.
  • UV-curable pigments and, if appropriate, also fillers can advantageously be used, for example to improve the hardness. These are with radiation-curable compounds, e.g. acrylic functional silanes, coated pigments / fillers, which can thus be included in the radiation hardening process.
  • the paint structure according to the invention is generally carried out by a method comprising the steps:
  • step b) A method for forming the passivation layer and preferred embodiments of this method have already been mentioned above. Suitable coating processes as step b) are known to the person skilled in the art. The following examples further illustrate the invention.
  • Test sheets galvanized steel, 20 ⁇ m zinc were passivated using a passivation method mentioned in Table 1. The service life was determined in the salt spray test.
  • white spots generally form more than 1 mm in diameter (Zn or Al oxide, so-called white rust)
  • the service life is specified as the time after which the damage pattern has reached rating grade 8 in DIN EN ISO 10289 from April 2001, Appendix B, page 19.
  • Test sheets galvanized steel, 20 ⁇ m zinc are immersed in the solution for 1 minute and dried by hanging overnight. The layer thickness D is partially determined by differential weighing. The service life is determined in the salt spray test.
  • the thickness of the layer is determined by differential weighing before and after the composition used according to the invention has acted on the metal surface and on the assumption that the layer has a specific density of 1 kg / l.
  • layer thickness is always understood to mean a size determined in this way, regardless of the specific density of the layer.
  • Immersion at a higher temperature (e.g. at 60 ° C) or in more concentrated solutions, even in nitric acid of a different concentration compared to the examples mentioned above, can further improve the service life in the corrosion test.
  • An increase in the concentration of the polymer leads to an increase in the service life.
  • the concentration of the polymer is preferably ⁇ 5% by weight.
  • An aqueous zinc chloride solution forms a white, insoluble precipitate with aqueous polyvinylimidazole solution over wide concentration ranges, generally from as little as 0.5% by weight of the polymer.
  • the K value is the Fikentscher constant for identifying the average molecular weight, cf. H.-G. Elias, Macromolecules Vol. 1, 5th Edition, Hüthig & Wepf Verlag, Basel 1990, page 99.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne une couche de passivation sur une surface métallique, obtenue par mise en contact de la surface métallique avec une composition renfermant un polymère azoté hydrosoluble. L'invention concerne en outre une surface, constituée par une surface métallique et par la couche de passivation selon l'invention, un procédé de formation d'une couche de passivation sur une surface métallique, l'utilisation d'une composition renfermant un polymère azoté hydrosoluble, pour la passivation d'une surface métallique, et une structure sur une surface métallique, comprenant une couche de passivation selon l'invention et d'autres couches de vernis.
EP04720004A 2003-03-13 2004-03-12 Polymeres azotes pour le traitement de surfaces metalliques Withdrawn EP1606362A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10310972A DE10310972A1 (de) 2003-03-13 2003-03-13 Stickstoffhaltige Polymere für die Metalloberflächenbehandlung
DE10310972 2003-03-13
PCT/EP2004/002623 WO2004081128A2 (fr) 2003-03-13 2004-03-12 Polymeres azotes pour le traitement de surfaces metalliques

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EP1606362A2 true EP1606362A2 (fr) 2005-12-21

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US (1) US7879158B2 (fr)
EP (1) EP1606362A2 (fr)
JP (1) JP4357527B2 (fr)
KR (1) KR20050115901A (fr)
CN (1) CN1759152A (fr)
BR (1) BRPI0407941A (fr)
CA (1) CA2518077A1 (fr)
DE (1) DE10310972A1 (fr)
MX (1) MXPA05008515A (fr)
WO (1) WO2004081128A2 (fr)

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BRPI0407941A (pt) 2006-02-21
DE10310972A1 (de) 2004-09-23
MXPA05008515A (es) 2005-10-20
JP4357527B2 (ja) 2009-11-04
WO2004081128A2 (fr) 2004-09-23
KR20050115901A (ko) 2005-12-08
US7879158B2 (en) 2011-02-01
CN1759152A (zh) 2006-04-12
WO2004081128A3 (fr) 2004-10-28
JP2006520852A (ja) 2006-09-14
CA2518077A1 (fr) 2004-09-23
US20060162820A1 (en) 2006-07-27

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