EP1036215A2 - Chromium-free corrosion protection agent and method for providing corrosion protection - Google Patents

Chromium-free corrosion protection agent and method for providing corrosion protection

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Publication number
EP1036215A2
EP1036215A2 EP98965188A EP98965188A EP1036215A2 EP 1036215 A2 EP1036215 A2 EP 1036215A2 EP 98965188 A EP98965188 A EP 98965188A EP 98965188 A EP98965188 A EP 98965188A EP 1036215 A2 EP1036215 A2 EP 1036215A2
Authority
EP
European Patent Office
Prior art keywords
corrosion protection
protection agent
agent according
corrosion
ions
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.)
Ceased
Application number
EP98965188A
Other languages
German (de)
French (fr)
Inventor
Stefan Küpper
Reinhard Seidel
Brigitte Calaminus
Christina Hirsch
Alf Ruggieri
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1036215A2 publication Critical patent/EP1036215A2/en
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • 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
    • C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
    • C09D191/06—Waxes
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • 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
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates

Definitions

  • the present invention relates to a chromium-free corrosion protection agent and a corrosion protection method for the treatment of surfaces made of hot-dip galvanized or electrolytically galvanized steel, alloy-galvanized steel or of aluminum and its alloys. It is particularly suitable for surface treatment in conveyor systems.
  • galvanized or alloy-galvanized steel strips are either simply oiled or phosphated or chromated if higher corrosion stresses are to be expected.
  • these measures are not sufficient in the case of particularly high corrosive loads such as ship transport in a salty sea atmosphere or storage in a tropical environment.
  • the best temporary corrosion protection measure known in the prior art is chromating, in which the metal surfaces are coated with a layer containing chromium (III) and / or chromium (VI) with a layer of generally about 5 to about 15 mg / m 2 Chrome plated. Because of the known toxicological problems of chromium compounds, this process is disadvantageous and complex from the aspects of occupational safety, ecology and the necessary disposal.
  • Phosphating as an alternative measure for temporary corrosion protection can undesirably change the appearance of the metal surfaces.
  • phosphating is complex in terms of plant technology, since depending on the substrate material it requires an additional activation step and, as a rule, a passivation step after the phosphating step. Passivation is often carried out with chromium-containing treatment solutions, which also results in the disadvantages mentioned above of using chromium-containing treatment solutions.
  • metal strips are increasingly being processed, which are already provided with a corrosion protection layer by the manufacturer of the strips. Such materials are known for example under the names Durasteel R , Bonazinc R and Durazinc R.
  • the organic coating consists of polymer systems such as epoxy or polyurethane resins, polyamides and polyacrylates. Solid additives such as silica, zinc dust and soot improve the protection against corrosion and, due to their electrical conductivity, allow the metal parts coated with layers with a thickness of approximately 0.3 to approximately 5 ⁇ m to be electrically welded and electrolytically painted.
  • the coating of the substrate materials is generally carried out in a two-stage process which is complex in terms of plant technology, in which the inorganic conversion layer is first produced and then the organic polymer film is applied in a second treatment stage.
  • US Pat. No. 5,344,504 describes a coating process for galvanized steel, in which the substrate is brought into contact with a treatment solution having the following composition: 0.1 to 10 g / l of a tetra- or hexafluoro acid of boron, silicon, Titanium and zircon or hydrofluoric acid, about 0.015 to about 6 g / l cations of cobalt, copper, iron, manganese, nickel, strontium or zinc and optionally up to about 3 g / l of a polymer selected from polyacrylic acid, poly methacrylic acid and their esters.
  • the pH of this treatment solution is in the range from about 4 to about 5.
  • WO 95/14117 also describes a method for treating surfaces made of zinc or aluminum or their alloys.
  • the surfaces are brought into contact with a treatment solution with a pH value below 3, which contains a complex between a metal oxoion and a heteroion.
  • the metal oxoion is selected from molybdate, tungstate and vanadate.
  • the heteroion is selected from phosphorus, aluminum, silicon, manganese, magnesium, zirconium, titanium, tin, cerium and nickel.
  • the treatment solution also contains an organic film former which is compatible with the other components of the solution. Examples of suitable film formers are polyacrylates, such as, in particular, polymers of methyl methacrylate, n-butyl acrylate, hydroxyethyl acrylate and glycerol propoxy triacrylate.
  • EP-A-694 593 recommends treating the metal surfaces with a treatment solution which contains the following components: an organic polymer or copolymer in which 0.5 to 8% of the monomers carry groups which can form compounds with metal ions, complex cations or Anions of aluminum, calcium, cerium, cobalt, molybdenum, silicon, vanadium, zircon, titanium, trivalent chromium and zinc, an oxidizing agent such as nitric acid, perchloric acid or hydrogen peroxide and an acid such as oxalic acid, acetic acid, boric acid, phosphoric acid, sulfuric acid, nitric acid or Hydrochloric acid.
  • an organic polymer or copolymer in which 0.5 to 8% of the monomers carry groups which can form compounds with metal ions, complex cations or Anions of aluminum, calcium, cerium, cobalt, molybdenum, silicon, vanadium, zircon, titanium, trivalent chromium and zinc
  • an oxidizing agent such as
  • WO 95/04169 teaches the treatment of metal surfaces with a treatment solution which contains at least the following components: fluorocomplexes of titanium, zirconium, hafnium, silicon, aluminum and boron, metal ions selected from cobalt, magnesium, manganese, zinc, nickel, tin, copper , Zircon, iron and strontium, phosphates or phosphonates and water-soluble or water-dispersible organic film formers.
  • EP-A-792 922 describes a chromium-free corrosion-inhibiting coating composition which contains a film-forming organic polymer and (i) a salt selected from esters of rare earth metals, alkali or alkaline earth metal adadate and furthermore (ii) a borate salt of an alkaline earth metal.
  • a film-forming organic polymer and (i) a salt selected from esters of rare earth metals, alkali or alkaline earth metal adadate and furthermore (ii) a borate salt of an alkaline earth metal.
  • preferred polymers are epoxides including polyimide-based epoxies, polyurethanes, acrylic polymers and alkyd-based systems.
  • this coating composition must therefore contain at least one borate and a further component, which can be a vanadate.
  • the invention relates to a chromium-free anti-corrosion agent containing water and a) 0.5 to 10 g / l hexafluoro anions of titanium (IV) and / or zirconium (IV), b) 5 to 15 g / l vanadium ions, c) 0, 5 to 2 g / l of transition metal ions d) 30 to 150 g / l of phosphoric acid and / or phosphonic acid and e) optionally other active ingredients or auxiliaries.
  • the transition metal ions are preferably selected from manganese ions of oxidation state 2 to 7, iron ions and cobalt ions.
  • Preferred concentration ranges of components a) to c) are: a) 1 to 3 g / l hexafluoro anions of titanium (IV) and / or zirconium (IV), b) 6 to 10 g / l vanadium ions and c) 0.6 up to 1.2 g / l transition metal ions.
  • the pH of the anticorrosive agent is in the range from 0.5 to 2.5, preferably in the range from 1.0 to 2.1 and in particular in the range from 1.4 to 2.0.
  • Such an agent dissolves the metal surfaces, so that an incorporated treatment bath can additionally contain cations that originate from the treated substrates. Examples of this are zinc and aluminum and optionally further alloy components such as iron, nickel and copper.
  • the anti-corrosion agent can contain other auxiliaries or active ingredients.
  • it can additionally contain about 0.5 to about 10 g / l, in particular about 1 to about 5 g / l, of non-complex-bound fluoride ions as a further active ingredient.
  • These can be used as hydrofluoric acid or as a soluble fluoride such as, for example, alkali metal or ammonium fluoride. Regardless of the compound used, the fluoride ions at the pH of the anti-corrosion agent will largely be present as undissociated hydrofluoric acid.
  • the corrosion protection agent can additionally contain about 1 to about 30 g / l, in particular about 10 to about 25 g / l, of a conductivity pigment as a further active ingredient.
  • a conductivity pigment as a further active ingredient.
  • suitable conductivity pigments are: carbon black, graphite, molybdenum sulfide, barium sulfate doped with tin or antimony and iron phosphide. Iron phosphide (Ferrophos, Fe 2 P) is particularly preferred. It is preferably used in amounts of about 20 g / l.
  • the corrosion protection agent can additionally contain about 0.5 to about 50 g / l polyethylene wax as a further active ingredient.
  • the wax components make the coating lubricious and thus improve the forming behavior of the substrates treated with the anti-corrosion agent. As a result, it is not necessary in the case of forming processes to apply forming oils to the surfaces.
  • the corrosion protection agent preferably additionally contains about 15 to about 200 g / l, in particular about 50 to about 150 g / l, of an organic film former.
  • an organic film former ensures that no components of the corrosion protection layer formed by the action of the corrosion protection agent are detached in subsequent cleaning processes. In conjunction with the polyethylene wax, the organic film former further improves the forming behavior.
  • the organic film former can be selected, for example, from epoxy resins, polyurethane resins and polymers or copolymers of styrene, butadiene, acrylic acid, methacrylic acid and / or maleic acid and the esters of these acids or from precursors of these polymers. Film formers which crosslink at a temperature below 180 ° C. and in particular below 170 ° C. are preferred.
  • the organic film formers can be dissolved or dispersed in the anti-corrosion agent.
  • An example of this is an aqueous mixture of sodium polyacrylate and polyacrylic acid, which is commercially available with a solids content of 51% by weight and has a pH in the range from 2 to 3.
  • Film formers based on acrylic acid and / or methacrylic acid and their esters with alcohols having 1 to about 6 carbon atoms are preferred. These polymers or copolymers preferably have a glass transition temperature in the range from 20 to 25 ° C.
  • the organic film-forming agent can be an epoxy resin that can be formulated in one component with an integrated hardener or in two components with a separate hardener. Water-dilutable systems are preferably chosen for this. Amines or polyamines are particularly suitable as hardeners for the epoxy resins.
  • the epoxy resins are generally marketed as aqueous dispersions with resin contents in the range between about 50 and about 60%.
  • these dispersions contain small amounts of organic solvents such as isopropanol or methoxypropanol. Furthermore, they usually contain an emulsifier, which can also be directly condensed onto the epoxy resin. If such two-component epoxy resin systems are used in the context of the present invention, the epoxy resin dispersion mixed with the inorganic corrosion protection components on the one hand and the hardener component on the other hand can be stored in two separate containers and transported to the place of use. The two components are then mixed together shortly before use.
  • An alternative to such two-component formulations are single-component epoxy resin systems that contain an integrated hardener.
  • the integrated hardener can be an amine adduct, for example, which only cleaves the free amine when heated and thereby initiates the hardening process.
  • the anti-corrosion agent can contain about 0.5 to about 2% by weight of a silane-based adhesion promoter.
  • silane-based adhesion promoter examples include aminopropyltriethoxysilane and glycidoxypropyltrimethoxysilane.
  • the corrosion protection agent preferably contains 2 to 8 g / l zinc ions.
  • the invention relates to a method for the corrosion-protective treatment of surfaces of galvanized or alloy-galvanized steel or of aluminum or its alloys, characterized in that the surfaces are treated with a corrosion protection agent according to the invention described above for a period of time in the range from 2 to 60 seconds Brings contact and then with or without Intermediate rinsing with water at a substrate temperature (“peak metal temperature”) in the range from 50 to 180 ° C. dries.
  • the method can therefore be used on the one hand on galvanized or alloy-galvanized steel.
  • the steel may have been coated electrolytically or in a hot dip process with zinc or a zinc alloy.
  • Zinc / nickel, zinc / iron and zinc / aluminum alloys are particularly suitable as zinc alloys.
  • the process is suitable for treating surfaces made of aluminum or its alloys.
  • aluminum alloys are generally used instead of pure aluminum.
  • the main alloy components are zinc, magnesium, silicon and copper.
  • the method is suitable on the one hand as a pretreatment before painting. However, it can also be used for corrosion protection of metal parts that are not subjected to subsequent painting.
  • the process creates a passivation layer on the metal surface that protects the base metal from corrosion even without an additional layer of paint.
  • the process is particularly suitable for treating metal strips in strip systems.
  • the action times of the treatment agent until the start of drying are then in the range of a few seconds, for example between about 1 and about 20 and in particular between about 4 and about 12 seconds.
  • the corrosion protection agent can be applied to the metal surfaces in various ways known in the art.
  • the anti-corrosion agent can be sprayed onto the metal surfaces or the surfaces can be wetted by immersing them in the treatment agent. In both cases, it is preferable to lay excess treatment solution on a predetermined wet film layer, which leads to the desired dry layer layer of approximately 0.5 to approximately 5 g / m 2 and in particular approximately 0.8 to approximately 3 g / m 2 .
  • the anti-corrosion agent is preferably applied to the metal strips with application rollers, such as are known, for example, as chemcoaters.
  • application rollers such as are known, for example, as chemcoaters.
  • the desired one Set the wet film thickness directly.
  • the anti-corrosion agent remains on the belt with the desired wet film thickness and is dried in without intermediate rinsing. The drying takes place in preheated ovens, by heating by induction or by the action of infrared rays in such a way that the substrate has a temperature (“peak metal temperature”) in the range from about 50 to about 180 ° C. and in particular in the range from about 100 to about 170 ° C.
  • an optional organic film former hardens.
  • the strips can be brought into contact with the treatment solution according to the invention without prior cleaning.
  • the metal strips to be treated were stored and / or transported before the coating according to the invention, they are usually provided with anti-corrosion oils or at least so far soiled that cleaning before the treatment according to the invention is necessary. This can be done with weakly to strongly alkaline cleaners customary in the prior art, with aluminum and its alloys also with acidic cleaners.
  • Tables 1 and 2 contain exemplary corrosion protection agents according to the invention. They were produced by mixing the individual components together in the order mentioned at room temperature. The pH was adjusted with additional phosphoric acid if necessary. Sheets made of hot-dip galvanized and electrolytically galvanized steel were used as the substrate. These were cleaned with a commercially available strong alkaline cleaner before treatment with the anti-corrosion agent. The application to the metal surfaces was carried out with a paint spinner at 550 revolutions / minute. The exposure time before the start of drying was 15 seconds. The drying / baking of the coating was carried out at a substrate temperature (“peak metal temperature”) of 100 ° C. place the coated test trays in a convection oven heated to 300 ° C for 20 seconds.
  • peak metal temperature 100 ° C.
  • test panels were partially subjected to a salt spray test in accordance with DIN 5002155 without further painting. After a test period of 48 hours, the corrosion was visually assessed on 3 sample plates treated in the same way. Sheets without corrosion received the grade 0, sheets with more than 50% corrosion the grade 5. The results are summarized in Table 3. A degree of corrosion ⁇ 3 is considered acceptable.
  • Table 1 Composition of the anti-corrosion agents (parts by weight)
  • Table 2 Composition of other anti-corrosion agents (parts by weight)
  • HDG hot-dip galvanized steel
  • ZE electrolytically galvanized steel

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

Abstract

The invention relates to a chromium-free aqueous corrosion protection agent for treating galvanised or alloy galvanised steel surfaces or aluminium surfaces. Said agent contains the following essential constituents: a) 0.5 to 10 g/l hexafluoro-anions of titanium (IV) and/or zircon (IV), b) 5 to 15 g/l vanadium ions, c) 0.5 to 2 g/l transition metal ions, preferably Mn, Fe, Co, d) 30 to 150 g/l phosphoric acid and/or phosphonic acid. The inventive corrosion protection agent preferably also contains an organic film former, especially with a polyacrylate base; and a conductivity pigment. The agent is particularly suitable for treating metal strips in order to protect them against corrosion, with or without subsequent painting, and is preferably applied in such a way as to produce a dry layer coating of 0.5 to 5 g/m<2> on the surface.

Description

"Chromfreies Korrosionsschutzmittel und Korrosionsschutzverfahren" "Chromium-free corrosion protection agent and corrosion protection process"
Die vorliegende Erfindung betrifft ein chromfreies Korrosionsschutzmittel und ein Korrosionsschutzverfahren zur Behandlung von Oberflächen aus schmelz- tauchverzinktem oder elektrolytisch verzinktem Stahl, legierungsverzinktem Stahl oder aus Aluminium und seinen Legierungen. Es ist insbesondere geeignet zur Oberflächenbehandlung in Bandanlagen.The present invention relates to a chromium-free corrosion protection agent and a corrosion protection method for the treatment of surfaces made of hot-dip galvanized or electrolytically galvanized steel, alloy-galvanized steel or of aluminum and its alloys. It is particularly suitable for surface treatment in conveyor systems.
Als Maßnahme zum temporären Korrosionsschutz werden beispielsweise verzinkte oder legierungsverzinkte Stahlbänder entweder einfach nur eingeölt oder bei zu erwartenden höheren Korrosionsbeanspruchungen phosphatiert oder chromatiert. Bei besonders hohen korrosiven Beanspruchungen wie zum Beispiel Schiffstransport in salzhaltiger Seeatmosphäre oder Lagerung in tropischer Umgebung sind diese Maßnahmen jedoch nicht ausreichend. Die beste im Stand der Technik bekannte temporäre Korrosionsschutzmaßnahme ist eine Chromatierung, bei der die Metalloberflächen mit einer Chrom(lll)- und/oder Chrom(VI)-haltigen Schicht mit einer Schichtauflage von in der Regel etwa 5 bis etwa 15 mg/m2 Chrom überzogen werden. Wegen der bekannten toxikologischen Probleme von Chromverbindungen ist dieses Verfahren unter den Aspekten des Arbeitsschutzes, der Ökologie und der erforderlichen Entsorgung nachteilig und aufwendig. Eine Phosphatierung als alternative Maßnahme zum temporären Korrosionsschutz kann das Aussehen der Metalloberflächen in unerwünschter Weise verändern. Außerdem ist eine Phosphatierung anlagentechnisch aufwendig, da sie je nach Substratmaterial eine zusätzliche Aktivierungsstufe und in der Regel nach der Phosphatierung eine Passivierungsstufe erfordert. Dabei erfolgt die Passivierung häufig mit chromhaltigen Behandlungslösungen, wodurch sich die vorstehend genannten Nachteile der Anwendung chromhaltiger Behandlungslösungen auch hier ergeben. In der Automobil- und Haushaltsgeräteindustrie werden in zunehmendem Maße Metallbänder verarbeitet, die bereits beim Hersteller der Bänder mit einer Korrosionsschutzschicht versehen sind. Derartige Materialien sind beispielsweise unter dem Namen DurasteelR, BonazincR und DurazincR bekannt. Sie tragen eine dünne organische Beschichtung über einer Konversionsschicht, beispielsweise einer Chromatier- oder Phosphatierschicht. Die organische Beschichtung besteht aus Polymersystemen wie beispielsweise Epoxy- oder Polyurethanharzen, Polyamiden und Polyacrylaten. Feste Additive wie Kieselsäuren, Zinkstaub und Ruß verbessern den Korrosionsschutz und erlauben es aufgrund ihrer elektrischen Leitfähigkeit, die mit Schichten einer Dicke von etwa 0,3 bis etwa 5 μm überzogenen Metallteile elektrisch zu schweißen und elektrolytisch zu lackieren. Die Beschichtung der Substratmaterialien erfolgt in der Regel in einem anlagentechnisch aufwendigen Zweistufenprozeß, bei dem zuerst die anorganische Konversionsschicht erzeugt und anschließend in einer zweiten Behandlungsstufe der organische Polymerfilm aufgebracht werden.As a measure for temporary corrosion protection, for example, galvanized or alloy-galvanized steel strips are either simply oiled or phosphated or chromated if higher corrosion stresses are to be expected. However, these measures are not sufficient in the case of particularly high corrosive loads such as ship transport in a salty sea atmosphere or storage in a tropical environment. The best temporary corrosion protection measure known in the prior art is chromating, in which the metal surfaces are coated with a layer containing chromium (III) and / or chromium (VI) with a layer of generally about 5 to about 15 mg / m 2 Chrome plated. Because of the known toxicological problems of chromium compounds, this process is disadvantageous and complex from the aspects of occupational safety, ecology and the necessary disposal. Phosphating as an alternative measure for temporary corrosion protection can undesirably change the appearance of the metal surfaces. In addition, phosphating is complex in terms of plant technology, since depending on the substrate material it requires an additional activation step and, as a rule, a passivation step after the phosphating step. Passivation is often carried out with chromium-containing treatment solutions, which also results in the disadvantages mentioned above of using chromium-containing treatment solutions. In the automotive and household appliance industry, metal strips are increasingly being processed, which are already provided with a corrosion protection layer by the manufacturer of the strips. Such materials are known for example under the names Durasteel R , Bonazinc R and Durazinc R. They have a thin organic coating over a conversion layer, for example a chromating or phosphating layer. The organic coating consists of polymer systems such as epoxy or polyurethane resins, polyamides and polyacrylates. Solid additives such as silica, zinc dust and soot improve the protection against corrosion and, due to their electrical conductivity, allow the metal parts coated with layers with a thickness of approximately 0.3 to approximately 5 μm to be electrically welded and electrolytically painted. The coating of the substrate materials is generally carried out in a two-stage process which is complex in terms of plant technology, in which the inorganic conversion layer is first produced and then the organic polymer film is applied in a second treatment stage.
Im Stand der Technik sind bereits Versuche bekannt, einstufige Beschichtungsverfahren einzusetzen, bei denen die anorganische Konversionsbehandlung und die Beschichtung mit einem organischen Polymerfilm mit einer einzigen Behandlungslösung erfolgt. Beispielsweise beschreibt die US-A-5 344 504 ein Beschichtungsverfahren für verzinkten Stahl, bei dem das Substrat mit einer Behandlungslösung mit folgender Zusammensetzung in Kontakt gebracht wird: 0,1 bis 10 g/l einer Tetra- bzw. Hexafluorosäure von Bor, Silicium, Titan und Zirkon oder Flußsäure, etwa 0,015 bis etwa 6 g/l Kationen von Cobalt, Kupfer, Eisen, Mangan, Nickel, Strontium oder Zink und fakultativ bis zu etwa 3 g/l eines Polymers ausgewählt aus Polyacrylsäure, Poiymethacrylsäure und deren Estern. Der pH-Wert dieser Behandlungslösung liegt im Bereich von etwa 4 bis etwa 5.Attempts are already known in the prior art to use single-stage coating processes in which the inorganic conversion treatment and the coating with an organic polymer film take place with a single treatment solution. For example, US Pat. No. 5,344,504 describes a coating process for galvanized steel, in which the substrate is brought into contact with a treatment solution having the following composition: 0.1 to 10 g / l of a tetra- or hexafluoro acid of boron, silicon, Titanium and zircon or hydrofluoric acid, about 0.015 to about 6 g / l cations of cobalt, copper, iron, manganese, nickel, strontium or zinc and optionally up to about 3 g / l of a polymer selected from polyacrylic acid, poly methacrylic acid and their esters. The pH of this treatment solution is in the range from about 4 to about 5.
Die WO 95/14117 beschreibt ebenfalls ein Verfahren zum Behandeln von Oberflächen aus Zink oder Aluminium oder deren Legierungen. Hierbei werden die Oberflächen mit einer Behandlungslösung mit einem pH-Wert unterhalb von 3 in Berührung gebracht, die einen Komplex zwischen einem Metalloxoion und einem Heteroion enthält. Dabei ist das Metalloxoion ausgewählt aus Molybdat, Wolframat und Vanadat. Das Heteroion ist ausgewählt aus Phosphor, Aluminium, Silicium, Mangan, Magnesium, Zirkon, Titan, Zinn, Cer und Nickel. Weiterhin enthält die Behandlungslösung einen organischen Filmbildner, der mit den übrigen Komponenten der Lösung kompatibel ist. Als Filmbildner kommen beispielsweise Polyacrylate wie insbesondere Polymere von Methylmethacrylat, n-Butylacrylat, Hydroxyethylacrylat und Glycerinpropoxytriacrylat in Betracht.WO 95/14117 also describes a method for treating surfaces made of zinc or aluminum or their alloys. The surfaces are brought into contact with a treatment solution with a pH value below 3, which contains a complex between a metal oxoion and a heteroion. The metal oxoion is selected from molybdate, tungstate and vanadate. The heteroion is selected from phosphorus, aluminum, silicon, manganese, magnesium, zirconium, titanium, tin, cerium and nickel. The treatment solution also contains an organic film former which is compatible with the other components of the solution. Examples of suitable film formers are polyacrylates, such as, in particular, polymers of methyl methacrylate, n-butyl acrylate, hydroxyethyl acrylate and glycerol propoxy triacrylate.
Die EP-A-694 593 empfiehlt die Behandlung der Metalloberflächen mit einer Behandlungslösung, die folgende Komponenten enthält: ein organisches Polymer oder Copolymer, bei dem 0,5 bis 8 % der Monomere Gruppen tragen, die mit Metallionen Verbindungen bilden können, komplexe Kationen oder Anionen von Aluminium, Calcium, Cer, Cobalt, Molybdän, Silicium, Vanadium, Zirkon, Titan, dreiwertiges Chrom und Zink, ein Oxidationsmittel wie Salpetersäure, Perchlorsäure oder Wasserstoffperoxid und eine Säure wie beispielsweise Oxalsäure, Essigsäure, Borsäure, Phosphorsäure, Schwefelsäure, Salpetersäure oder Salzsäure.EP-A-694 593 recommends treating the metal surfaces with a treatment solution which contains the following components: an organic polymer or copolymer in which 0.5 to 8% of the monomers carry groups which can form compounds with metal ions, complex cations or Anions of aluminum, calcium, cerium, cobalt, molybdenum, silicon, vanadium, zircon, titanium, trivalent chromium and zinc, an oxidizing agent such as nitric acid, perchloric acid or hydrogen peroxide and an acid such as oxalic acid, acetic acid, boric acid, phosphoric acid, sulfuric acid, nitric acid or Hydrochloric acid.
Die WO 95/04169 lehrt die Behandlung von Metalloberflächen mit einer Behandlungslösung, die mindestens folgende Komponenten enthält: Fluorokomplexe von Titan, Zirkon, Hafnium, Silicium, Aluminium und Bor, Metallionen ausgewählt aus Cobalt, Magnesium, Mangan, Zink, Nickel, Zinn, Kupfer, Zirkon, Eisen und Strontium, Phosphate oder Phosphonate sowie wasserlösliche oder wasserdispergierbare organische Fiimbildner.WO 95/04169 teaches the treatment of metal surfaces with a treatment solution which contains at least the following components: fluorocomplexes of titanium, zirconium, hafnium, silicon, aluminum and boron, metal ions selected from cobalt, magnesium, manganese, zinc, nickel, tin, copper , Zircon, iron and strontium, phosphates or phosphonates and water-soluble or water-dispersible organic film formers.
Die EP-A-792 922 beschreibt eine chromfreie korrosionsinhibierende Beschichtungszusammensetzung, die ein filmbildendes organisches Polymer sowie (i) ein Salz ausgewählt aus Estern von seltenen Erdmetallen, Alkali- oder Erdalkalivanadat und weiterhin (ii) ein Boratsalz eines Erdalkalimetalls enthält. Als bevorzugte Polymere werden beispielsweise Epoxide einschließlich Polyimid- basierte Epoxide, Polyurethane, acrylische Polymere und Alkyd-basierte Systeme genannt. Diese Beschichtungszusammensetzung muß also außer dem organischen Filmbildner zumindest ein Borat und eine weitere Komponente enthalten, die ein Vanadat sein kann. Trotz des Standes der Technik besteht weiterhin Bedarf an verbesserten Beschichtungsverfahren für Metalloberflächen, bei denen zumindest eine anorganische Passivierschicht und vorzugsweise im gleichen Behandlungsschritt zusätzlich eine organische Polymerschicht auf die Metalloberflächen aufgebracht werden. Die Beschichtung soll das Ausstanzen und Umformen von Bauteilen aus den beschichteten Metallbändern erleichtem. Weiterhin sollen die Schichten, die nach dem Zusammenbau der Produkte, beispielsweise Fahrzeugkarosserien oder Haushaltsgeräte, üblichen Behandlungsschritte wie beispielsweise Reinigen unbeschadet überstehen und direkt überlackierbar sein. Die Schichten sollen jedoch auch ohne Lackierung einen ausreichenden Korrosionsschutz bewirken, so daß sie als Passivierung dienen können. Aus Gründen des Umwelt- und Arbeitsschutzes soll das Behandlungsverfahren ohne Einsatz von Chromverbindungen und möglichst auch unter Ausschluß von organischen Lösungsmitteln durchführbar sein.EP-A-792 922 describes a chromium-free corrosion-inhibiting coating composition which contains a film-forming organic polymer and (i) a salt selected from esters of rare earth metals, alkali or alkaline earth metal adadate and furthermore (ii) a borate salt of an alkaline earth metal. Examples of preferred polymers are epoxides including polyimide-based epoxies, polyurethanes, acrylic polymers and alkyd-based systems. In addition to the organic film former, this coating composition must therefore contain at least one borate and a further component, which can be a vanadate. Despite the prior art, there is still a need for improved coating methods for metal surfaces in which at least one inorganic passivation layer and preferably an additional organic polymer layer are applied to the metal surfaces in the same treatment step. The coating is intended to facilitate the punching out and reshaping of components from the coated metal strips. Furthermore, the layers which, after the assembly of the products, for example vehicle bodies or household appliances, should survive normal treatment steps such as cleaning undamaged and should be able to be painted over directly. However, the layers should provide adequate corrosion protection even without painting, so that they can serve as passivation. For reasons of environmental protection and occupational safety, the treatment process should be able to be carried out without the use of chromium compounds and, if possible, with the exclusion of organic solvents.
Die Erfindung betrifft ein chromfreies Korrosionsschutzmittel, enthaltend Wasser und a) 0,5 bis 10 g/l Hexafluoro-Anionen von Titan(IV) und/oder Zirkon(IV), b) 5 bis 15 g/l Vanadiumionen, c) 0,5 bis 2 g/l Übergangsmetallionen d) 30 bis 150 g/l Phosphorsäure und/oder Phosphonsäure sowie e) fakultativ weitere Wirk- oder Hilfsstoffe.The invention relates to a chromium-free anti-corrosion agent containing water and a) 0.5 to 10 g / l hexafluoro anions of titanium (IV) and / or zirconium (IV), b) 5 to 15 g / l vanadium ions, c) 0, 5 to 2 g / l of transition metal ions d) 30 to 150 g / l of phosphoric acid and / or phosphonic acid and e) optionally other active ingredients or auxiliaries.
Vorzugsweise sind die Übergangsmetallionen ausgewählt aus Manganionen der Oxidationsstufe 2 bis 7, Eisenionen und Cobaltionen.The transition metal ions are preferably selected from manganese ions of oxidation state 2 to 7, iron ions and cobalt ions.
Bevorzugte Konzentrationsbereiche der Komponenten a) bis c) sind: a) 1 bis 3 g/l Hexafluoro-Anionen von Titan(IV) und/oder Zirkon(IV), b) 6 bis 10 g/l Vanadiumionen und c) 0,6 bis 1 ,2 g/l Übergangsmetallionen. Der pH-Wert des Korrosionsschutzmittels liegt im Bereich von 0,5 bis 2,5, vorzugsweise im Bereich von 1 ,0 bis 2,1 und insbesondere im Bereich von 1 ,4 bis 2,0. Ein derartiges Mittel löst die Metalloberflächen an, so daß ein eingearbeitetes Behandlungsbad zusätzlich Kationen enthalten kann, die aus den behandelten Substraten stammen. Beispiele hierfür sind Zink und Aluminium sowie gegebenenfalls weitere Legierungskomponenten wie beispielsweise Eisen, Nickel und Kupfer.Preferred concentration ranges of components a) to c) are: a) 1 to 3 g / l hexafluoro anions of titanium (IV) and / or zirconium (IV), b) 6 to 10 g / l vanadium ions and c) 0.6 up to 1.2 g / l transition metal ions. The pH of the anticorrosive agent is in the range from 0.5 to 2.5, preferably in the range from 1.0 to 2.1 and in particular in the range from 1.4 to 2.0. Such an agent dissolves the metal surfaces, so that an incorporated treatment bath can additionally contain cations that originate from the treated substrates. Examples of this are zinc and aluminum and optionally further alloy components such as iron, nickel and copper.
Dem Fachmann ist geläufig, daß die vorstehend genannten Komponenten Reaktionen miteinander eingehen können und daß sie in der Behandlungslösung in der Form vorliegen, die unter den genannten Bedingungen für den pH-Wert stabil sind. Beispielsweise werden die Hexafluoroanionen teilweise in Form der freien Säuren vorliegen. Die Vanadiumionen werden großenteils als VO2 +- Kationen vorliegen, können jedoch auch teilweise zu Polykationen kondensiert sein.The person skilled in the art is familiar with the fact that the components mentioned above can react with one another and that they are present in the treatment solution in the form which is stable for the pH under the conditions mentioned. For example, some of the hexafluoro anions will be in the form of the free acids. The majority of the vanadium ions will be present as VO 2 + cations, but can also be partially condensed to form polycations.
Zusätzlich kann das Korrosionsschutzmittel weitere Hilfs- oder Wirkstoffe enthalten. Beispielsweise kann es als weiteren Wirkstoff zusätzlich etwa 0,5 bis etwa 10 g/l, insbesondere etwa 1 bis etwa 5 g/l nicht komplexgebundene Fluoridionen enthalten. Diese können als Flußsäure oder als lösliches Fluorid wie beispielsweise Alkalimetall- oder Ammoniumfluorid eingesetzt werden. Unabhängig von der eingesetzten Verbindung werden die Fluorid-Ionen bei dem pH-Wert des Korrosionsschutzmittels zum größten Teil als undissozierte Flußsäure vorliegen.In addition, the anti-corrosion agent can contain other auxiliaries or active ingredients. For example, it can additionally contain about 0.5 to about 10 g / l, in particular about 1 to about 5 g / l, of non-complex-bound fluoride ions as a further active ingredient. These can be used as hydrofluoric acid or as a soluble fluoride such as, for example, alkali metal or ammonium fluoride. Regardless of the compound used, the fluoride ions at the pH of the anti-corrosion agent will largely be present as undissociated hydrofluoric acid.
Weiterhin kann das Korrosionsschutzmittel als weiteren Wirkstoff zusätzlich etwa 1 bis etwa 30 g/l, insbesondere etwa 10 bis etwa 25 g/l eines Leitfähigkeitspigments enthalten. Hierdurch werden die elektrische Schweißbarkeit und die elektrolytische Lackierbarkeit der mit dem Korrosionsschutzmittel behandelten Substrate verbessert. Als Leitfähigkeitspigment kommen beispielsweise in Betracht: Ruß, Graphit, Molybdensulfid, mit Zinn oder Antimon dotiertes Bariumsulfat sowie Eisenphosphid. Eisenphosphid (Ferrophos, Fe2P) ist besonders bevorzugt. Es wird vorzugsweise in Mengen von etwa 20 g/l verwendet. Weiterhin kann das Korrosionsschutzmittel als weiteren Wirkstoff zusätzlich etwa 0,5 bis etwa 50 g/l Polyethylenwachs enthalten. Die Wachsanteile machen die Beschichtung gleitfähig und verbessern so das Umformverhalten der mit dem Korrosionsschutzmittel behandelten Substrate. Hierdurch ist es bei Umformprozessen nicht erforderlich, auf die Oberflächen Umformöle aufzubringen.Furthermore, the corrosion protection agent can additionally contain about 1 to about 30 g / l, in particular about 10 to about 25 g / l, of a conductivity pigment as a further active ingredient. This improves the electrical weldability and the electrolytic paintability of the substrates treated with the anti-corrosion agent. Examples of suitable conductivity pigments are: carbon black, graphite, molybdenum sulfide, barium sulfate doped with tin or antimony and iron phosphide. Iron phosphide (Ferrophos, Fe 2 P) is particularly preferred. It is preferably used in amounts of about 20 g / l. Furthermore, the corrosion protection agent can additionally contain about 0.5 to about 50 g / l polyethylene wax as a further active ingredient. The wax components make the coating lubricious and thus improve the forming behavior of the substrates treated with the anti-corrosion agent. As a result, it is not necessary in the case of forming processes to apply forming oils to the surfaces.
Vorzugsweise enthält das Korrosionsschutzmittel zusätzlich etwa 15 bis etwa 200 g/l, insbesondere etwa 50 bis etwa 150 g/l eines organischen Filmbildners. Hierdurch bildet sich bei der Verwendung des Korrosionsschutzmittels eine gemischte anorganisch/organische Beschichtung auf den behandelten Metalloberflächen aus, die neben der Korrosionsschutzfunktion auch die Wirkung eines Primers hat. Die vorbehandelten Metallteile können somit direkt überlackiert werden. Unabhängig hiervon bewirkt der organische Filmbildner, daß bei nachfolgenden Reinigungsprozessen keine Bestandteile der durch die Einwirkung des Korrosionsschutzmittels gebildeten Korrosionsschutzschicht herausgelöst werden. In Verbindung mit dem Polyethylenwachs verbessert der organische Filmbildner das Umformverhalten weiter.The corrosion protection agent preferably additionally contains about 15 to about 200 g / l, in particular about 50 to about 150 g / l, of an organic film former. As a result, when the anti-corrosion agent is used, a mixed inorganic / organic coating forms on the treated metal surfaces, which in addition to the anti-corrosion function also has the effect of a primer. The pre-treated metal parts can thus be painted over directly. Irrespective of this, the organic film former ensures that no components of the corrosion protection layer formed by the action of the corrosion protection agent are detached in subsequent cleaning processes. In conjunction with the polyethylene wax, the organic film former further improves the forming behavior.
Der organische Filmbildner kann beispielsweise ausgewählt sein aus Epoxidharzen, Polyurethanharzen und Polymeren oder Copolymeren von Styrol, Butadien, Acrylsäure, Methacrylsäure und/oder Maleinsäure sowie den Estern dieser Säuren oder aus Vorläufern dieser Polymere. Dabei sind Filmbildner bevorzugt, die bei einer Temperatur unterhalb 180 °C und insbesondere unterhalb 170 °C vernetzen. Die organischen Filmbildner können in dem Korrosionsschutzmittel gelöst oder dispergiert sein. Ein Beispiel hierfür ist eine wäßrige Mischung von Natriumpolyacrylat und Polyacrylsäure, die mit einem Feststoffgehalt von 51 Gew.-% kommerziell erhältlich ist und einen pH-Wert im Bereich von 2 bis 3 aufweist. Bevorzugt sind Filmbildner auf der Basis Acrylsäure und/oder Methacrylsäure sowie deren Estern mit Alkoholen mit 1 bis etwa 6 C- Atomen. Vorzugsweise weisen diese Polymere oder Copolymere eine Glasübergangstemperatur im Bereich von 20 bis 25 °C auf. Weiterhin kann der organische Filmbildner ein Epoxidharz darstellen, das einkomponentig mit integriertem Härter oder zweikomponentig mit getrenntem Härter formulierbar ist. Vorzugsweise wählt man hierfür wasserverdünnbare Systeme. Als Härter für die Epoxidharze sind insbesondere Amine oder Polyamine geeignet. Die Epoxidharze kommen in der Regel als wäßrige Dispersionen mit Harzgehalten im Bereich zwischen etwa 50 und etwa 60 % in den Handel. In der Regel enthalten diese Dispersionen geringe Mengen organischer Lösungsmittel wie beispielsweise Isopropanol oder Methoxypropanol. Weiterhin enthalten sie in der Regel einen Emulgator, der auch direkt an das Epoxidharz ankondensiert sein kann. Setzt man im Sinne der vorliegenden Erfindung solche Zweikomponenten- Epoxidharz-Systeme ein, kann man die Epoxidharz-Dispersion vermischt mit den anorganischen Korrosionsschutzkomponenten einerseits und die Härterkomponente andererseits in zwei getrennten Gebinden lagern und zum Anwendungsort transportieren. Die beiden Komponenten werden dann erst kurz vor der Anwendung miteinander vermischt. Eine Alternative zu solchen Zweikomponenten-Formulierungen bilden einkomponentige Epoxidharzsysteme, die einen integrierten Härter enthalten. Der integrierte Härter kann beispielsweise ein Aminaddukt sein, das erst bei Erhitzen das freie Amin abspaltet und hierdurch den Härtungsprozeß einleitet.The organic film former can be selected, for example, from epoxy resins, polyurethane resins and polymers or copolymers of styrene, butadiene, acrylic acid, methacrylic acid and / or maleic acid and the esters of these acids or from precursors of these polymers. Film formers which crosslink at a temperature below 180 ° C. and in particular below 170 ° C. are preferred. The organic film formers can be dissolved or dispersed in the anti-corrosion agent. An example of this is an aqueous mixture of sodium polyacrylate and polyacrylic acid, which is commercially available with a solids content of 51% by weight and has a pH in the range from 2 to 3. Film formers based on acrylic acid and / or methacrylic acid and their esters with alcohols having 1 to about 6 carbon atoms are preferred. These polymers or copolymers preferably have a glass transition temperature in the range from 20 to 25 ° C. Furthermore, the organic film-forming agent can be an epoxy resin that can be formulated in one component with an integrated hardener or in two components with a separate hardener. Water-dilutable systems are preferably chosen for this. Amines or polyamines are particularly suitable as hardeners for the epoxy resins. The epoxy resins are generally marketed as aqueous dispersions with resin contents in the range between about 50 and about 60%. As a rule, these dispersions contain small amounts of organic solvents such as isopropanol or methoxypropanol. Furthermore, they usually contain an emulsifier, which can also be directly condensed onto the epoxy resin. If such two-component epoxy resin systems are used in the context of the present invention, the epoxy resin dispersion mixed with the inorganic corrosion protection components on the one hand and the hardener component on the other hand can be stored in two separate containers and transported to the place of use. The two components are then mixed together shortly before use. An alternative to such two-component formulations are single-component epoxy resin systems that contain an integrated hardener. The integrated hardener can be an amine adduct, for example, which only cleaves the free amine when heated and thereby initiates the hardening process.
Als weiteren Wirk- oder Hilfsstoff kann das Korrosionsschutzmittel etwa 0,5 bis etwa 2 Gew.-% eines Haftvermittlers auf Silan-Basis enthalten. Beispiele hierfür sind Aminopropyltriethoxysilan und Glycidoxypropyltrimethoxysilan.As a further active ingredient or auxiliary, the anti-corrosion agent can contain about 0.5 to about 2% by weight of a silane-based adhesion promoter. Examples include aminopropyltriethoxysilane and glycidoxypropyltrimethoxysilane.
Weiterhin enthält das Korrosionsschutzmittel vorzugsweise 2 bis 8 g/l Zinkionen.Furthermore, the corrosion protection agent preferably contains 2 to 8 g / l zinc ions.
In einem weiteren Aspekt betrifft die Erfindung ein Verfahren zur korrosionsschützenden Behandlung von Oberflächen von verzinktem oder legierungsverzinktem Stahl oder von Aluminium oder seinen Legierungen, dadurch gekennzeichnet, daß man die Oberflächen für eine Zeitdauer im Bereich von 2 bis 60 Sekunden mit einem vorstehend beschriebenen erfindungsgemäßen Korrosionsschutzmittel in Kontakt bringt und anschließend mit oder ohne Zwischenspülung mit Wasser bei einer Substrattemperatur („Peak Metal Temperature") im Bereich von 50 bis 180 °C trocknet.In a further aspect, the invention relates to a method for the corrosion-protective treatment of surfaces of galvanized or alloy-galvanized steel or of aluminum or its alloys, characterized in that the surfaces are treated with a corrosion protection agent according to the invention described above for a period of time in the range from 2 to 60 seconds Brings contact and then with or without Intermediate rinsing with water at a substrate temperature (“peak metal temperature”) in the range from 50 to 180 ° C. dries.
Das Verfahren kann also zum einen auf verzinktem oder legierungsverzinktem Stahl eingesetzt werden. Dabei kann der Stahl elektrolytisch oder im Schmelztauchverfahren mit Zink oder einer Zinklegierung beschichtet worden sein. Als Zinklegierungen kommen insbesondere Zink/Nickel-, Zink/Eisen- und Zink/Aluminiumlegierungen in Betracht. Zum anderen eignet sich das Verfahren zur Behandlung von Oberflächen aus Aluminium oder seinen Legierungen. Im Automobilbau und Haushaltsgerätebereich werden in der Regel nicht Reinaluminium, sondern Aluminiumlegierungen eingesetzt. Die wichtigsten Legierungskomponenten sind Zink, Magnesium, Silicium und Kupfer.The method can therefore be used on the one hand on galvanized or alloy-galvanized steel. The steel may have been coated electrolytically or in a hot dip process with zinc or a zinc alloy. Zinc / nickel, zinc / iron and zinc / aluminum alloys are particularly suitable as zinc alloys. On the other hand, the process is suitable for treating surfaces made of aluminum or its alloys. In the automotive and household appliance sectors, aluminum alloys are generally used instead of pure aluminum. The main alloy components are zinc, magnesium, silicon and copper.
Das Verfahren eignet sich zum einen als Vorbehandlung vor einer Lackierung. Es kann jedoch auch zum Korrosionsschutz von Metallteilen eingesetzt werden, die keiner nachfolgenden Lackierung unterzogen werden. Durch das Verfahren wird auf der Metalloberfläche eine Passivierungsschicht erzeugt, die das Grundmetall auch ohne eine zusätzliche Lackschicht vor Korrosion schützt.The method is suitable on the one hand as a pretreatment before painting. However, it can also be used for corrosion protection of metal parts that are not subjected to subsequent painting. The process creates a passivation layer on the metal surface that protects the base metal from corrosion even without an additional layer of paint.
Besonders ist das Verfahren zur Behandlung von Metallbändern in Bandanlagen geeignet. Die Einwirkungszeiten des Behandlungsmittels bis zum Beginn der Trocknung liegen dann im Bereich von wenigen Sekunden, beispielsweise zwischen etwa 1 und etwa 20 und insbesondere zwischen etwa 4 und etwa 12 Sekunden. Der Auftrag des Korrosionsschutzmittels auf die Metalloberflächen kann auf unterschiedliche, im Stand der Technik bekannte Arten erfolgen. Beispielsweise kann das Korrosionsschutzmittel auf die Metalloberflächen aufgespritzt oder können die Oberflächen durch Eintauchen in das Behandlungsmittel benetzt werden. In beiden Fällen ist es vorzuziehen, überschüssige Behandlungslösung auf eine vorbestimmte Naßfilmauf läge, die zur erwünschten Trockenschichtauflage von etwa 0,5 bis etwa 5 g/m2 und insbesondere von etwa 0,8 bis etwa 3 g/m2 führt, einzustellen. Vorzugsweise trägt man das Korrosionsschutzmittel auf die Metallbänder mit Auftragswalzen, wie sie beispielsweise als Chemcoater bekannt sind, auf. Hierbei läßt sich die erwünschte Naßfilmdicke direkt einstellen. In allen Fällen verbleibt das Korrosionsschutzmittel mit der erwünschten Naßfilmdicke auf dem Band und wird ohne Zwischenspülung eingetrocknet. Das Eintrocknen erfolgt in vorbeheizten Öfen, durch Erwärmung mittels Induktion oder durch Einwirkung von Infrarotstrahlen derart, daß das Substrat eine Temperatur („Peak Metal Temperature") im Bereich von etwa 50 bis etwa 180 CC und insbesondere im Bereich von etwa 100 bis etwa 170 °C annimmt. Hierbei härtet ein fakultativ eingesetzter organischer Filmbildner aus.The process is particularly suitable for treating metal strips in strip systems. The action times of the treatment agent until the start of drying are then in the range of a few seconds, for example between about 1 and about 20 and in particular between about 4 and about 12 seconds. The corrosion protection agent can be applied to the metal surfaces in various ways known in the art. For example, the anti-corrosion agent can be sprayed onto the metal surfaces or the surfaces can be wetted by immersing them in the treatment agent. In both cases, it is preferable to lay excess treatment solution on a predetermined wet film layer, which leads to the desired dry layer layer of approximately 0.5 to approximately 5 g / m 2 and in particular approximately 0.8 to approximately 3 g / m 2 . The anti-corrosion agent is preferably applied to the metal strips with application rollers, such as are known, for example, as chemcoaters. Here, the desired one Set the wet film thickness directly. In all cases, the anti-corrosion agent remains on the belt with the desired wet film thickness and is dried in without intermediate rinsing. The drying takes place in preheated ovens, by heating by induction or by the action of infrared rays in such a way that the substrate has a temperature (“peak metal temperature”) in the range from about 50 to about 180 ° C. and in particular in the range from about 100 to about 170 ° C. Here, an optional organic film former hardens.
Erfolgt die erfindungsgemäße Behandlung unmittelbar nach einer elektrolytischen Verzinkung oder einer Schmelztauchverzinkung der Stahlbänder, so können die Bänder ohne vorherige Reinigung mit der erfindungsgemäßen Behandlungslösung in Kontakt gebracht werden. Wurden die zu behandelnden Metallbänder vor der erfindungsgemäßen Beschichtung jedoch gelagert und/oder transportiert, so sind sie in der Regel mit Korrosionsschutzölen versehen oder zumindest so weitgehend verschmutz, daß eine Reinigung vor der erfindungsgemäßen Behandlung erforderlich ist. Dies kann mit im Stand der Technik gebräuchlichen schwach bis stark alkalischen Reinigern, bei Aluminium und seinen Legierungen auch mit sauren Reinigern erfolgen.If the treatment according to the invention is carried out immediately after electrolytic galvanizing or hot dip galvanizing of the steel strips, the strips can be brought into contact with the treatment solution according to the invention without prior cleaning. However, if the metal strips to be treated were stored and / or transported before the coating according to the invention, they are usually provided with anti-corrosion oils or at least so far soiled that cleaning before the treatment according to the invention is necessary. This can be done with weakly to strongly alkaline cleaners customary in the prior art, with aluminum and its alloys also with acidic cleaners.
Ausführungsbeispieleembodiments
Die Tabellen 1 und 2 enthalten beispielhafte erfindungsgemäße Korrosionsschutzmittel. Sie wurden hergestellt, indem die einzelnen Komponenten in der genannten Reihenfolge bei Raumtemperatur zusammen gemischt wurden. Der pH-Wert wurde erforderlichenfalls mit zusätzlicher Phosphorsäure eingestellt. Als Substrat wurden Bleche aus schmelztauchverzinkten und aus elektrolytisch verzinktem Stahl verwendet. Diese wurden vor der Behandlung mit dem Korrosionsschutzmittel mit einem handelsüblichen stark alkalischen Reiniger gereinigt. Der Auftrag auf die Metalloberflächen erfolgte mit einer Lackschleuder bei 550 Umdrehungen/Minute. Die Einwirkdauer bis zum Beginn der Trocknung betrug 15 Sekunden. Das Trocknen/Einbrennen der Beschichtung erfolgte bei einer Substrattemperatur („Peak Metal Temperature") von 100 °C. Hierzu wurden die beschichteten Probebleche für 20 Sekunden in einen auf 300 °C aufgeheizten Umlufttrockenschrank gelegt.Tables 1 and 2 contain exemplary corrosion protection agents according to the invention. They were produced by mixing the individual components together in the order mentioned at room temperature. The pH was adjusted with additional phosphoric acid if necessary. Sheets made of hot-dip galvanized and electrolytically galvanized steel were used as the substrate. These were cleaned with a commercially available strong alkaline cleaner before treatment with the anti-corrosion agent. The application to the metal surfaces was carried out with a paint spinner at 550 revolutions / minute. The exposure time before the start of drying was 15 seconds. The drying / baking of the coating was carried out at a substrate temperature (“peak metal temperature”) of 100 ° C. place the coated test trays in a convection oven heated to 300 ° C for 20 seconds.
Die behandelten Probebleche wurden teilweise ohne weitere Lackierung einem Salzsprühtest nach DIN 5002155 unterzogen. Nach 48 Stunden Prüfdauer wurde die Korrosion an jeweils 3 gleichbehandelten Probeblechen visuell begutachtet. Bleche ohne Korrosion erhielten die Note 0, Bleche mit mehr als 50 % Korrosion die Note 5. Die Ergebnisse sind in Tabelle 3 zusammengestellt. Ein Korrosionsgrad < 3 wird als akzeptabel angesehen. The treated test panels were partially subjected to a salt spray test in accordance with DIN 5002155 without further painting. After a test period of 48 hours, the corrosion was visually assessed on 3 sample plates treated in the same way. Sheets without corrosion received the grade 0, sheets with more than 50% corrosion the grade 5. The results are summarized in Table 3. A degree of corrosion <3 is considered acceptable.
Tabelle 1 : Zusammensetzung der Korrosionsschutzmittel (Gewichtsteile)Table 1: Composition of the anti-corrosion agents (parts by weight)
1) Wäßrige Dispersion eines Copolymers von Estern von Alkoholen mit 1 bis 6 C-Atomen mit Acrylsäure und Methacrylsäure, 46 % Feststoff1) Aqueous dispersion of a copolymer of esters of alcohols with 1 to 6 carbon atoms with acrylic acid and methacrylic acid, 46% solids
2) entspricht 10 Gew.-Teile Feststoff bezogen auf Gesamtformulierung 2) corresponds to 10 parts by weight of solid, based on the total formulation
Tabelle 2: Zusammensetzung weiterer Korrosionsschutzmittel (Gewichtsteile) Table 2: Composition of other anti-corrosion agents (parts by weight)
Tabelle 3: Korrosionsschutzwirkung (Korrosionsgrad nach 48 Stunden Salzsprühtest)Table 3: Corrosion protection effect (degree of corrosion after 48 hours of salt spray test)
1) HDG = Schmelztauchverzinkter Stahl ZE = Elektrolytisch verzinkter Stahl 1) HDG = hot-dip galvanized steel ZE = electrolytically galvanized steel

Claims

Patentansprüche claims
1. Chromfreies Korrosionsschutzmittel, enthaltend Wasser und1. Chromium-free corrosion protection agent containing water and
a) 0,5 bis 10 g/l Hexafluoro-Anionen von Titan(IV) und/oder Zirkon(IV), b) 5 bis 15 g/l Vanadiumionen, c) 0,5 bis 2 g/l Übergangsmetallionen d) 30 bis 150 g/l Phosphorsäure und/oder Phosphonsäure sowie e) fakultativ weitere Wirk- oder Hilfsstoffea) 0.5 to 10 g / l hexafluoro anions of titanium (IV) and / or zirconium (IV), b) 5 to 15 g / l vanadium ions, c) 0.5 to 2 g / l transition metal ions d) 30 up to 150 g / l phosphoric acid and / or phosphonic acid and e) optionally other active ingredients or auxiliaries
2. Korrosionsschutzmittel nach Anspruch 1 , dadurch gekennzeichnet, daß die Übergangsmetallionen ausgewählt sind aus Manganionen der Oxidationsstufe 2 bis 7, Eisenionen und Cobaltionen.2. Corrosion protection agent according to claim 1, characterized in that the transition metal ions are selected from manganese ions of the oxidation state 2 to 7, iron ions and cobalt ions.
3. Korrosionsschutzmittel nach einem oder beiden der Ansprüche 1 und 2, dadurch gekennzeichnet, daß es als weiteren Wirkstoff zusätzlich 0,5 bis 10 g/l nicht komplex gebundene Fluoridionen enthält.3. Corrosion protection agent according to one or both of claims 1 and 2, characterized in that it additionally contains 0.5 to 10 g / l of non-complexly bound fluoride ions as a further active ingredient.
4. Korrosionsschutzmittel nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es als weiteren Wirkstoff zusätzlich 1 bis 30 g/l eines Leitfähigkeitspigments enthält.4. Corrosion protection agent according to one or more of claims 1 to 3, characterized in that it additionally contains 1 to 30 g / l of a conductivity pigment as a further active ingredient.
5. Korrosionsschutzmittel nach Anspruch 4, dadurch gekennzeichnet, daß das Leitfähigkeitspigment ausgewählt ist aus Ruß, Graphit, Molybdänsulfid, dotiertem Bariumsulfat und Eisenphosphid.5. Corrosion protection agent according to claim 4, characterized in that the conductivity pigment is selected from carbon black, graphite, molybdenum sulfide, doped barium sulfate and iron phosphide.
6. Korrosionsschutzmittel nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es als weiteren Wirkstoff zusätzlich 0,5 bis 50 g/l Polyethylenwachs enthält.6. Corrosion protection agent according to one or more of claims 1 to 5, characterized in that it additionally contains 0.5 to 50 g / l polyethylene wax as a further active ingredient.
7. Korrosionsschutzmittel nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es als weiteren Wirkstoff zusätzlich 15 bis 200 g/l eines organischen Filmbildners enthält.7. Corrosion protection agent according to one or more of claims 1 to 6, characterized in that it additionally 15 to 200 g / l as a further active ingredient contains an organic film former.
8. Korrosionsschutzmittel nach Anspruch 7, dadurch gekennzeichnet, daß der organische Filmbildner ausgewählt ist aus Epoxidharzen, Polyurethanharzen und Polymeren oder Copolymeren von Styrol, Butadien, Acrylsäure, Methacrylsäure und/oder Maleinsäure sowie Estern dieser Säuren.8. Corrosion protection agent according to claim 7, characterized in that the organic film-forming agent is selected from epoxy resins, polyurethane resins and polymers or copolymers of styrene, butadiene, acrylic acid, methacrylic acid and / or maleic acid and esters of these acids.
9. Korrosionsschutzmittel nach Anspruch 8, dadurch gekennzeichnet, daß der organische Filmbildner ein Copolymer von Estern von Acrylsäure und Methacrylsäure mit Alkoholen mit 1 bis 6 C-Atomen darstellt.9. Corrosion protection agent according to claim 8, characterized in that the organic film former is a copolymer of esters of acrylic acid and methacrylic acid with alcohols having 1 to 6 carbon atoms.
10. Korrosionsschutzmittel nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß es einen pH-Wert im Bereich von 0,5 bis 2,5 aufweist.10. Corrosion protection agent according to one or more of claims 1 to 9, characterized in that it has a pH in the range from 0.5 to 2.5.
11. Verfahren zur korrosionsschützenden Behandlung von Oberflächen von verzinktem oder legierungsverzinktem Stahl oder von Aluminium oder seinen Legierungen, dadurch gekennzeichnet, daß man die Oberflächen für eine Zeitdauer im Bereich von 1 bis 60 Sekunden mit einem Korrosionsschutzmittel nach einem oder mehreren der Ansprüche 1 bis 10 in Kontakt bringt und anschließend mit oder ohne Zwischenspülung mit Wasser bei einer Substrattemperatur im Bereich von 50 bis 180 °C trocknet.11. A method for the corrosion-protective treatment of surfaces of galvanized or alloy-galvanized steel or of aluminum or its alloys, characterized in that the surfaces for a period in the range from 1 to 60 seconds with an anti-corrosion agent according to one or more of claims 1 to 10 in Brings contact and then dries with or without intermediate rinsing with water at a substrate temperature in the range of 50 to 180 ° C.
12.Verfahren nach Anspruch 11 , dadurch gekennzeichnet, daß man auf der Oberfläche eine Trockenschichtauflage von 0,5 bis 5 g/m2 erzeugt. 12. The method according to claim 11, characterized in that a dry layer layer of 0.5 to 5 g / m 2 is produced on the surface.
EP98965188A 1997-12-05 1998-11-26 Chromium-free corrosion protection agent and method for providing corrosion protection Ceased EP1036215A2 (en)

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