EP1844113A2 - Method for applying integrated pre-treatment layers containing dicarboxylic acid olefin copolymers to metallic surfaces - Google Patents

Method for applying integrated pre-treatment layers containing dicarboxylic acid olefin copolymers to metallic surfaces

Info

Publication number
EP1844113A2
EP1844113A2 EP06707823A EP06707823A EP1844113A2 EP 1844113 A2 EP1844113 A2 EP 1844113A2 EP 06707823 A EP06707823 A EP 06707823A EP 06707823 A EP06707823 A EP 06707823A EP 1844113 A2 EP1844113 A2 EP 1844113A2
Authority
EP
European Patent Office
Prior art keywords
characterized
method according
mol
preferably
monomers
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Withdrawn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
EP06707823A
Other languages
German (de)
French (fr)
Inventor
Alexander Göthlich
Guido Vandermeulen
Markus Hickl
Michael Dornbusch
Helmut Witteler
Monica Fernandez Gonzalez
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
Priority to DE200510004292 priority Critical patent/DE102005004292A1/en
Priority to DE200510061317 priority patent/DE102005061317A1/en
Application filed by BASF SE filed Critical BASF SE
Priority to PCT/EP2006/050415 priority patent/WO2006079628A2/en
Publication of EP1844113A2 publication Critical patent/EP1844113A2/en
Application status is Withdrawn legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING 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
    • C09D135/00Coating 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 carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • C08F8/12Hydrolysis
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • C08F8/30Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • C08F8/34Introducing sulfur atoms or sulfur-containing groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • C08F8/44Preparation of metal salts or ammonium salts
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING 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
    • C09D123/00Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/18Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09D123/24Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having ten or more carbon atoms
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING 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
    • C09D133/00Coating 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04Homopolymers or copolymers of esters
    • C09D133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062Copolymers with monomers not covered by C09D133/06
    • C09D133/064Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • C09D5/082Anti-corrosive paints characterised by the anti-corrosive pigment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/10Copolymer characterised by the proportions of the comonomers expressed as molar percentages
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00Crosslinking
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04Homopolymers or copolymers of esters
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264Up to 3 mils
    • Y10T428/2651 mil or less

Abstract

The invention relates to a method for applying integrated pre-treatment layers with a thickness of between 1 and 25 μm to metallic surfaces, especially the surfaces of strip metals, by treatment with a composition containing at least one binding agent, a cross-linking agent, a fine-particle inorganic filler, and a dicarboxylic acid olefin copolymer. The invention also relates to metallic moulded bodies provided with one such integrated pre-treatment layer, and a formulation for carrying out the method.

Description

A method of applying dicarboxylic acid-olefin copolymers containing, integrated pretreatment layers on metallic surfaces

description

The present invention relates to a method for applying integrated pretreatment layers with a thickness of 1 to 25 microns on metallic surfaces, particularly the surfaces of strip metals, by treatment with a composition comprising at least one binder, crosslinking agents, a finely divided inorganic filler and a dicarboxylic acid-olefin includes -Copolymeres. It further relates to metallic shaped bodies, which are provided with such an integrated pretreatment layer, and a formulation for carrying out the method. For the production of thin-walled metallic workpieces such as Au tomobilteilen, body panels, appliance panels, facade panels, ceiling panels or window profiles are formed suitable metal sheets by means of suitable techniques such as punching, drilling, folding, profiling and / or deep drawing. Larger components such as automobile bodies are optionally joined together by welding of several individual parts. The raw material for this purpose normally long metal strips which are produced by rolling of the metal and for storage and transportation rollers (so-called "coils") are wound.

The metallic components mentioned must be protected as a rule against corrosion. Especially in the automotive sector, the requirements on the corrosion are onsschutz very high. On newer car models up to 30 years warranty against rust are now granted. Modern automobile bodies are produced in multistage operations and have a variety of different paint layers.

While the corrosion prevention treatment in the past, mainly in the finished metallic workpiece, such as a welded together automobile body has been made is made in more recent times, the corrosion protection treatment to an increasing extent on the band metal itself using "coil coating".

By "coil coating" is the continuous coating of metal strips, usually with liquid coating materials. In this case, 0.2 to 2 mm thick and up to 2 m wide metal strips at a speed of up to 200 m / min through a coil coating transported conditioning and thereby coated. for this purpose, cold rolled strips of soft steels or construction, electrolytically galvanized thin sheet, hot-dip galvanized steel strip or strips of aluminum or aluminum alloys Typical systems can be used, for example. comprise a feed station, a tape memory, a cleaning and pre-treatment zone, a first coating station along with baking oven and cooling zone, a second coating station with oven, laminating and cooling, and a tape storage and rewinder.

The coil coating process typically includes the steps of:

1. If necessary: ​​cleaning the metal strip of dirt that have accumulated during storage of the metal strip as well as temporary corrosion control oils, by means of cleaning baths.

2. application of a thin pre-treatment layer (<1 micron) in the dipping or spraying or roller application. This layer is to increase the corrosion resistance and serves to improve the adhesion of subsequent layers of paint on the metal surface. To this end, Cr (VI) -containing, Cr (III) -containing as well as chromate-free pretreatment baths.

. 3. Application of a primer ( "primer") by a roll method, the dry film thickness is usually about 5-8 microns Here, varnish systems are generally used solvent-based..

. 4. applying one or more top coat layers ( "topcoat") in the roller application method, the dry film thickness here is approximately 15 - 25 microns Here, varnish systems are also generally used solvent-based..

The layer structure of a metal strip coated in this way, for example, a coated steel strip is shown schematically in Figure 1. To the metal (1) are a conventional pretreatment layer (2), a primer (3) and one or several different topcoat layers (4) applied.

Thus coated metal strips are used, for example for the production of housings for the so-called white goods (refrigerators, etc.) as facade panels for building or the automotive industry.

The coating of the metal strips with the pretreatment layer (2) and a Grun- dation (3) is very complicated. Furthermore, the demand in the market is increasingly to Cr (VI) -free systems for corrosion protection. There has therefore been no lack of attempts to apply, instead of the separate application of a pretreatment layer (2) and the organic base coat (3) comprises a single integrated pretreatment layer (2 '), which takes over the functions of both layers. Such a layer structure is exemplary and shown schematically in Figure 2. The preparation of a coated metal strip is greatly simplified by such a single-stage process. Müller et al. disclose in "Corrosion Science, 2000, 42, 577-584" and "The Applied Macromolecular Chemistry 1994, 221, 177-185," the use of styrene-maleic acid copolymers as corrosion inhibitors for zinc and aluminum pigments.

EP-A 122 229, CA 990 060, JP 60-24384 and JP-A 2004-68065 discloses the use of copolymers of maleic acid and various other monomers such as styrene, other olefins and / or other vinyl monomers as corrosion inhibitors in aqueous systems.

EP-A 244 584 disclose the use of copolymers of modified maleic acid and styrene, sulfonated styrene, alkyl vinyl ethers, C2-Cβ-olefins and (meth) acrylamide as an additive to cooling water. The modified maleic acid units have attached via spacers functional groups such as -OH, -OR, -PO 3 H 2, -OPO 3 H 2, -COOH, -SO 3 H or, preferably, on.

EP-A 1288232 and EP-A 1,288,228 disclose copolymers of modified maleic acid and other monomers such as acrylates, vinyl ethers, or olefins, the modified maleic acid attached via spacers heterocyclic compounds have. The documents disclose the use of such polymers as corrosion inhibitors in aqueous systems such as cooling water circuits and as a constituent of coatings.

JP-A 2004-204243 and JP-A 2004-204244 disclose steel sheets with improved solderability, are then treated with an aqueous formulation to improve the solderability which first with tin and then with zinc and. The aqueous formulation comprises 100 to 800 g / l water-based acrylic resin, 50 to 600 g / l water-soluble rosins, 10 to 100 g / l of a corrosion inhibitor and from 1 to 100 g / l antioxidants. In an alternative embodiment of the invention, the formulation contains 100 - 900 g / l of a water-based polyurethane resin, from 10 to

100 g / l of a corrosion inhibitor and from 1 to 100 g / l antioxidants. As corrosion inhibitors amines can be used, as well as polymeric styrene-maleic anhydride copolymers. a polymer is preferably used, which comprises a maleic acid half-ester ammonium salt as a polymer unit. The formulations contain no encryption netzer and no fillers or pigments. The layers are dried at 90 0 C. The thickness of the coating is in each case 0.05 to 10 microns.

JP-A 2004-218050 and JP-2004-218051 disclose corresponding formulation as well as steel sheets coated therewith, with the formulations in this case additionally include still water dispersible SiOΣ. JP-A 60-219267 discloses a radiation-curable varnish formulation comprising 5 to 40% of a copolymer of styrene and unsaturated dicarboxylic acids or their monoesters, 5 to 30% phenolic resins, and 30 to 90% monomeric acrylates include. By means of the coating are removed by alkali rust protective films with a thickness of 5 to 50 microns available.

WO 99/29790 discloses compounds which heterocycles with at least two secondary nitrogen atoms include. In the compounds may also be copolymers of modified maleic acid and styrene or 1-octene, wherein the modified Maleinsäureinheiten mounted via spacers have Piperazineinhei- th. These are used for curing epoxy coatings at temperatures below 40 0 C. The document mentions corrosion protective coatings for steel with a layer thickness of 112-284 microns.

US 6,090,894 discloses copolymers of maleic acid or diesters and a-olefinsulfonates fin-carboxylic acids and given appropriate, other monomers and their further functionalization by reaction of COOH groups on the copolymer with epoxy compounds. The compounds can be used for the production of paints.

but none of the cited documents discloses a process for applying integrated corrosion protection layers, in particular no continuous process for applying integrated anticorrosive coatings on metals band.

DE-A 199 23 084 discloses a chromium-free aqueous coating compositions for one-stage coating comprising at least hexafluoro anions of Ti (IV), Si (IV) and / or Zr (IV), a water-soluble or water-dispersible film-forming binder and contains an organophosphoric. The composition may optionally also comprise a pigment and crosslinking agent.

WO 2005/078025 discloses integrated pretreatment layers and a method for applying integrated pretreatment layers containing as a corrosion inhibitor dithiophosphoric acid ester. Our as yet unpublished application DE 102005006233.4 discloses a method for applying integrated pretreatment layers which contain, as corrosion inhibitors dithiophosphinic acids. The use of polymeric corrosion inhibitor is not disclosed.

The object of the invention is to determine riding an improved method for producing integrated pretreatment layers, as well as improved integrated pretreatment layers sawn. Accordingly, a method for applying integrated pretreatment layers was found on metal surfaces, comprising at least the steps of

(1) applying a curable composition on the metallic surface, wherein the preparation contains at least

(A) 20 to 70 wt.% Of at least one thermally and / or photochemically crosslinkable binder system (A), (B) 20 to 70 wt.% Of at least one inorganic particulate filler having a mean particle size of less than 10 microns,

(C) from 0.25 to 40 wt.% Of at least one corrosion inhibitor, and

(D) optionally a solvent,

includes, with the proviso that the wt.% data on the sum of all

The components except the solvent refer, as well as

(2) thermal and / or photochemical crosslinking of the applied layer,

wherein it is in the anti-corrosion agent is at least one copolymer (C), which is built up from the following monomeric structural units:

(d) 70 to 30 mol% of at least one monoethylenically unsaturated hydrocarbon (da) and / or at least one monomer (db) selected from the group of functional groups X 1 modified monoethylenically unsaturated hydrocarbons (db ') and vinyl ethers (db'),

(C2) 30 to 70 mol% of at least one monoethylenically unsaturated dicarboxylic bonsäure having 4 to 8 C-atoms and / or its anhydride (c2a) and / or derivatives (c2b) thereof,

wherein the derivatives (c2b) esters of dicarboxylic acids with alcohols of the general formula HO-R 1 -X 2 n (I) and / or amides or imides with ammonia and / or amines of the general formula HR 2 NR 1 - X 2 is n (II), and the abbreviations have the following meanings:

R 1: (n + 1) -valent hydrocarbon group having 1 to 40 C atoms, in which non-adjacent C atoms by O and / or N may be substituted, R 2: H, Cr to Cio-hydrocarbon group or - ( R 1 -X 2 n) n: 1, 2 or 3

X 2: a functional group, and (c3) 0 to 10 mol% other ethylenically unsaturated monomers which are copolymerizable by (d) and (c2) different but with (d) and (c2),

and the amounts being based in each case lymer on the total amount of all monomer units in the Copo-.

In a preferred embodiment of the process is a continuous process for the coating of metal strips.

Furthermore, an apparatus suitable for carrying out the method formulation was found.

LIST OF FIGURES

Figure 1: section of a coated metal strip in two-stage pretreatment according to the prior art.

Figure 2: section through coated metal strip with the invention, integrated pretreatment.

Regarding the invention, the following may be stated specifically:

By means of the inventive method metallic surfaces with an integrated pretreatment layer can be provided. The integrated th pretreatment layers of the invention have a thickness of 1-25 microns.

It may in principle to the surfaces of any shape metallic body here. This may be to fully act existing body of metals, but the body can also be coated with metals and may themselves be composed of other materials, such as polymers or composites.

but particularly advantageously it may be sheet-like shaped body with a metallic surface, that is molded bodies whose thickness is substantially less than the extent in the other dimensions. Examples include plates, films, sheets, and particularly metal strips, as well as from -beispielsweise made by cutting, shaping and Fügen- components with a metallic surface, such as automobile bodies or parts thereof. The thickness or the wall thickness of such metallic materials is preferably less than 4 mm and, for example 0.25 to 2 mm. Using the method of the invention all kinds of metals can be coated in principle. but preferably it is non-noble metals or alloys, which are commonly employed as metallic materials of construction, and which must be protected against corrosion.

Preferably, the inventive method can be used to apply integrated pretreatment layers on the surfaces of iron, steel, zinc, zinc alloys, aluminum or aluminum alloys. In particular, it may be the surface of galvanized iron or steel. In a preferred exemplary form of the method is the surface of a metal strip, in particular electrolytically galvanized or hot-dip galvanized steel. This may be how to act galvanized steel strip on two sides both to one side.

Zinc or aluminum alloys and to their use for coating steel are known in the art. Depending on the intended application of the skilled worker selects the type and amount of alloying constituents. Typical constituents of zinc alloys comprise, in particular Al, Pb, Si, Mg, Sn, Cu or Cd. Typical constituents of aluminum alloys comprise, in particular, Mg, Mn, Si, Zn, Cr, Zr, Cu or Ti. The term "zinc alloy" is also intended Al / Zn alloys inclusion set SEN, in which Al and Zn in approximately equal amounts are present. with such alloys coated steel, the steel is commercially available. itself can be the usual, known in the art contain alloy components.

The term "integrated pretreatment layer" in the sense of this invention means that the coating of the invention is applied directly to the metal surface without any corrosion-inhibiting pretreatment such as passivation, applying a conversion layer or phosphating, particularly no treatment with Cr (VI) compounds is carried out . the integrated pretreatment layer combines the passivation layer with the organic primer and if necessary still further layers in a single layer. the term "metal surface" here is of course not to be equated with absolutely bare metal, but means the surface which is in common use of the metal formed inevitably in an atmospheric environment or during cleaning of the metal before the application of the integrated pre-treatment layer. The egg gentliche metal can, for example, still having a moisture film or a thin oxide or Oxidhydrathaut.

further coating layers may be advantageously applied directly to the integrated pretreatment layer without an additional organic primer to be applied beforehand. Of course, an additional organic undercoat, but in special cases possible, although preferably is absent. The type of further coating layers depends on the intended use of the metal.

In the inventively used formulations for applying integrated pretreatment layers, it may be preparations based on organic solvents, aqueous or predominantly aqueous Zubreitungen or solvent-free formulations both. The formulations comprise at least one thermally and / or photochemically crosslinkable binder system (A), at least one finely divided inorganic filler (B) and at least one anti-corrosion agent (C).

The term "crosslinkable binder system" refers below, is known in principle way those components of the formulation that are responsible for film formation. They form the thermal and / or photochemical curing a polymeric network. They include thermally and / or photochemically vernetzba- re components. the crosslinkable components may be of low molecular, oligomeric or polymeric. you have at least two crosslinkable groups generally crosslinkable groups can be reactive functional groups both. with groups of their kind ( "with themselves") or can react with complementary reactive functional groups. in this case, different configurations are possible in a basically known manner. The binder system may for example comprise a self not crosslinkable polymeric binder and one or more low molecular weight or oligomeric cross-linking agent (V). Alternatively, ann and the polymeric binder itself have crosslinkable groups that can react zer with other crosslinkable groups on the polymer and / or an additionally used crosslinking. Especially useful cross-linkable group-containing oligomers or prepolymers may be used, which are crosslinked to each other using cross-linking agents.

Thermally crosslinkable or curable binder systems crosslink upon heating of the coated layer to temperatures above room temperature. Such paint systems are referred to in the art as "baking varnishes". They have crosslinkable groups who can not or do not react at room temperature at least at a substantial rate, but only at higher temperatures. To implement the method according to the invention in particular, those comparable wettable binder systems, the only at temperatures above 60 0 C, preferably 80 0 C, crosslink more preferably 100 0 C and more preferably 120 0 C. Advantageously, such binder systems can be used, which at 100 to 250 0 C, preferably 120 to 220 0 C and network particularly preferably at 150 to 200 0 C. the binder systems (a) may be typical in the field of coil coating paints binder systems. the applied by means of coil coating paints layers must have sufficient flexibility . binder systems for coil coating materials therefore preferably soft segments au f. overall suitable binders or binder systems are known in principle to the expert. Of course, mixtures of different polymers can be used, provided that no undesirable effects on through the mixture. Examples of suitable binders include (meth) acrylate (co) polymers, partially saponified polyvinyl esters, polyesters, alkyd resins, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, polyamides, polyimides or polyurethanes. The skilled worker will make a suitable choice depending on the desired end use of the coated metal.

For thermosetting binder systems systems can be used to practice the invention preferably based on polyesters, epoxy resins, polyurethanes or acrylated distillates.

Binders based on polyesters can be constructed in a basically known manner from low molecular weight dicarboxylic acids and dialcohols and optionally further monomers. Other monomers include, in particular, a branching effect monomers, such as tricarboxylic acids or trialcohols. For use for coil coating generally polyesters are used with a relatively low molecular weight, preferably those having M n of 500 to 10,000 g / mol, preferably 1000 to 5000 g / mol and particularly preferably 2000 to 4000 g / mol.

The hardness and flexibility of the layers based on polyesters can be "soft" monomers are influenced in principle known manner by the choice of "hard" or. Examples of "hard" dicarboxylic acids include aromatic dicarboxylic acids or their hydrogenated derivatives such as isophthalic acid, terephthalic thal acid, phthalic acid, hexahydrophthalic acid or derivatives thereof, in particular anhydrides or esters thereof. Examples of "soft" dicarboxylic acids include in particular aliphatic 1, ω-dicarboxylic acids having at least 4 carbon atoms such as adipic acid, azelaic acid, sebacic acid or dodecanedioic acid. Examples of "hard" dialcohols include ethylene glycol, 1, 2-propanediol, neopentyl glycol or 1, 4-cyclohexanedimethanol. Examples of "soft" dialcohols include diethylene glycol, triethylene glycol, aliphatic sche1, ω-di-alcohols having at least 4 carbon atoms such as 1, 4-butanediol , 1, 6-hexanediol, 1-8-octanediols or 1, 12-dodecanediol. Preferred polyesters for carrying out the invention comprise at least a "soft" monomer.

Polyester coatings are commercially available. Details of polyesters are, for example, in "Paints and Coatings - Saturated Polyester Coatings" in Ullmann's Encyclopedia of Industrial Chemistry, 6 th Edt, 2000, Electronic Release Binder systems based on epoxides can be used for formulations of organic or aqueous-based... epoxy-functional polymers can in principle known manner by the reaction of epoxy-functional monomers such as bisphenol-A diglycidyl ether, bisphenol F diglycidyl ether or hexanediol diglycidyl ether can be prepared with alcohols such as bisphenol A or bisphenol F, soft segments that are in particular polyoxyethylene and / Epoxy-functional or polyoxypropylene segments. These may advantageously be incorporated by the use of ethoxylated and / or propoxylated bisphenol-A. the binder should preferably be free of chloride. polymers are commercially available, for example under the name of Epon ® or Epikote ®. Details of epoxy-functional polymers, for example, shown in shown in "Epoxy Resins" in Ullmann's Encyclopedia of Industrial Chemistry, 6 th Edt., 2000, Electronic Release

The epoxy-functional binder can be further functionalized. Epoxy resin-amine adducts can be obtained for example by reaction of the said epoxy-functional polymers with amines, especially secondary amines such as diethanolamine or N-methylbutanolamine.

Binders based on polyacrylates are particularly suitable for water-based formulations. Examples of suitable acrylates include emulsion polymers or copolymers, in particular anionically stabilized acrylic dispersions, obtainable in conventional manner from acrylic acid and / or acrylic acid derivatives, for example acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate or 2- ethylhexyl (meth) acrylate and / or vinyl aromatic monomers such as styrene, and optionally crosslinking monomers. The hardness of the binder may be "soft" by those skilled in basically known manner by the ratio of "hard" monomers such as styrene or methyl methacrylate and monomers such as Butylacry- lat or 2-ethylhexyl acrylate can be set. Particularly preferred for the production of acrylate monomers are used further having functional groups which can react with crosslinkers. This may be OH groups in particular. OH groups may be followed by hydrolysis to the polyacrylates are incorporated by the use of monomers such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate or N-methylolacrylamide or epoxy acrylates. Suitable polyacrylate dispersions are commercially available.

Binders based on polyurethane dispersions are particularly suitable for water-based formulations. Dispersions of polyurethanes can be obtained in prin- Piell known manner by incorporating to stabilize the dispersion in the polyurethane chain, ionic and / or hydrophilic segments. As the soft segments can preferably 20 to 100 mol%, based on the amount of all the diols, of höhermo--molecular diols, polyester diols preferably having a M n from about 500 to 5000 g / mol, preferably 1000 to 3000 g / mol. Particularly advantageously polyurethane dispersion can be used to practice the present invention containing bis (4-isocyanatocyclohexyl) -methane as the isocyanate component. DER-like polyurethane dispersions are disclosed for example in DE-A 199 14 896th Suitable polyurethane dispersions are commercially available.

Suitable crosslinking agents for the thermal crosslinking are known in the art in principle.

Suitable crosslinkers are, for example, on the basis of epoxides, in which two or more epoxy groups by means of a linking group are interconnected. Examples include low molecular compounds having two epoxy groups such as hexanediol diglycidyl ether, phthalic acid or cycloaliphathische connects fertilize such as 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate.

Also suitable as crosslinkers are highly reactive melamine derivatives such as hexamethylol melamine or corresponding etherified products such as hexamethoxymethylmelamine methyl melamine, hexabutoxymethylmelamine or optionally modified aminoplast resins. Such crosslinkers are commercially available, for example, as ® Luwipal (Fa. BASF AG).

Particularly preferred for embodiments of the invention, blocked polyisocyanates are used as crosslinking agents. In blocking the isocyanate group is reacted reversibly with a blocking agent. The blocking agent is split off again by heating to higher temperatures. Examples of suitable blocking agents are disclosed in DE-A 199 14 896, column 12, line 13 to column 13, line 2nd Particularly preferred blocked with ε-caprolactam polyisocyanates can be used.

To accelerate the crosslinking suitable catalysts can be added to the formulations known in principle way.

The skilled worker will, depending on the binder used and the desired result ER- an appropriate selection among the crosslinking agents. Of course, mixtures of different crosslinkers may be used, provided that the properties of the layer are not adversely affected thereby. The amount of crosslinker can advantageously 10 to 35 wt.%, Respectively with respect to the total amount of binder. The crosslinking of the epoxy-functional polymers can be done for example with crosslinkers based on polyamines such as diethylene triamine, amine adducts or polyaminoamides. For example, crosslinkers based on carboxylic anhydrides or the aforementioned crosslinkers based on melamine are advantageous. Preference is given in particular the blocked polyisocyanates already mentioned.

For the thermal crosslinking of acrylate dispersions, for example, the previously mentioned crosslinkers based on melamine or blocked isocyanates are used. Furthermore, even epoxy-functional crosslinking agents are suitable.

For the thermal crosslinking of polyurethane dispersions or polyesters for example, the above-mentioned crosslinking agents may based on melamine, blocked isocyanates or epoxy-functional crosslinkers.

The binder systems (A) comprise photochemically crosslinkable groups in photochemically crosslinkable preparations. The term "photochemical crosslinking" is intended to include the networking with all kinds of high-energy radiation such as UV, VIS, NIR or electron beams. It may in principle be all kinds act photochemically crosslinkable groups, preferably, these are but ethylenically unsaturated Groups.

typically oligomeric or polymeric photochemically crosslinkable binder systems include compounds with photochemically crosslinkable groups and, optionally, reactive diluents still deviated, usually monomers. Reactive WEI sen a lower viscosity than the oligomeric or polymeric crosslinking agent, and therefore take the role of a diluent in a radiation-curable system. For photochemical crosslinking, such binder systems further comprise, as a rule one or more photoinitiators.

Examples of photochemically crosslinkable binder systems include, for example, multifunctional (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, epoxy acrylates xy (meth) carbonate (meth) acrylates, polyether (meth) acrylates, optionally in combination with reactive diluents, such as methyl (meth) acrylate, butanediol diacrylate xandioldiacrylat, He or trimethylolpropane triacrylate. Exact details of suitable radiation-curable binders are described in WO 2005/080484 page 3, line 10 to page 16, line 35 shown. Suitable photoinitiators can be found in said font page 18, line 8 to page 19, line 10 degrees.

Of course, the embodiment of the present invention also can be used Bindemit- telsysteme combining can be thermally and photochemically cured (also called dual-cure systems known). The preparation used in this invention comprises 20 to 70 wt.% Of the binder system (A). The stated amounts are based on the sum of all components of the preparation, with the exception of the solvent or solvent mixture. Preferably, the amount is 30 to 60 wt.% And particularly preferably 40 to 50 wt.%.

The preparation used for the inventive process further comprises at least one finely divided inorganic filler (B). The filler may also comprise an additional organic coating, for example for waterproofing or hybrid drophilierung. The filler has an average particle size of less than 10 microns. Preferably, the average particle size is 10 nm to 9 microns and more preferably 100 nm to 5 microns. For round or approximately round particles, this figure refers to the diameter, wherein the irregularly shaped, such as, needle-shaped particles to the longest axis. With the Partikelgrö- SSE the primary particle size is meant. The skilled person will, of course, known that finely divided solids often agglomerate to form larger particles, which have to be intensively dispersed for use in the formulation. The particle size is selected by the expert according to the desired properties of the layer. It depends, for example, by the desired layer thickness. As a rule, the expert will choose smaller particles for a low layer thickness.

As fillers one hand, electrically conductive pigments or fillers are also suitable. Such additives serve to improve the weldability and to improve a subsequent coating with electrodeposition paints. Examples of suitable electri- cally conducting fillers and pigments include phosphides, vanadium carbide, titanium nitride, molybdenum sulfide, graphite, carbon black or doped barium sulfate. Metal phosphides are preferably used from Zn, Al, Si, Mn, Cr, Fe or Ni, used in particular iron phosphide. Examples of preferred metal phosphides include CrP, MnP, Fe 3 P, Fe 2 P, Ni 2 P, NiP or NiP 2. 3

It can also be used non-conductive pigments or fillers, such as finely divided amorphous silicon, aluminum or titanium oxides, which may also be doped with other elements. For example, modified amorphous silica can be used with calcium ions.

Other examples of pigments include anticorrosive pigments such as zinc phosphate, zinc metaborate or barium hydroxide monohydrate.

Of course, mixtures of different pigments can be used. The pigments are present in an amount of 20 to 70.% By weight. The exact amount will be determined by the skilled person depending on the desired properties of the layer. With the use of conductivity pigments, the amounts used are usually greater than with the use of non-conductive fillers. Preferred quantities of conductive pigments and fillers are from 40 to 70 wt.%, Preferred amounts by weight in non-conductive pigments 20 to 50.%.

Copolymer (C)

According to the invention, the composition as a corrosion inhibitor further comprises at least one copolymer (C). The copolymer is formed from the monomers (d) and (c2), and optionally (c3) constructed, it being understood that in each case several different monomers (d), (c2) or optional (c3) can be used. Except (d), (c2) and optionally (c3) are no other monomers present.

Monomers (d)

As the monomer (d) are 70 to 30 mol% of at least one monoethylenically unsaturated hydrocarbon (da) and / or at least one monomer (db) selected from the group of modified with functional groups X 1 monoethylenically unsaturated hydrocarbons (db ') and monoethylenically unsaturated ethers used (db "). the amount refers to the total amount of all monomer units in the copolymer.

(there)

The monomers (da) it may in principle be any hydrocarbon having an ethylenically unsaturated group. Can be, straight-chain or branched aliphatic hydrocarbons (olefins) and / or alicyclic hydrocarbons (cycloalkenes). It may also be hydrocarbons, which in addition to the ethylenically unsaturated group, aromatic radicals, especially vinyl aromatic compounds. Preferably is ethylenically unsaturated hydrocarbons, in which the double bond is located in α-position. As a rule, at least 80% of the monomers used should (da) have the double bond in α-position.

The term "hydrocarbons" is intended to also oligomers of propene or unbranched, or, preferably, branched C 4 - comprise up Cio-olefins which have an ethylenically un- saturated group in the Oligomers employed generally have a number average molecular weight M n of not more than 2300 g. / mol. preferred is M n from 300 to 1300 g / mol and particularly preferably 400 to 1200 g / mol. oligomers of isobutene, which still may comprise as the Como- noner optionally with other C3 to Cio-olefins are preferred. Such oligomers on the basis of isobutene are in folic constricting general usage, are referred to as "polyisobutene" as following. Polyisobutenes used should preferably have a content of double bonds in the α-position of at least 70%, more preferably at least 80%. Such polyisobutenes are -also-referred to as reactive polyisobutenes bekannnt in the art and commercially available.

Apart from the abovementioned oligomers are suitable for carrying out the invention as the vorliegen- (da) in particular, monoethylenically unsaturated hydrocarbons having 6 to 30 carbon atoms. Examples of such hydrocarbons include hexene, heptene, octene, nonene, decene, undecene, dodecene, tetradecene, hexadecene, octadecyl cen, eicosane, docosane, diisobutene, triisobutene or styrene.

unsaturated hydrocarbons having from 9 to 27, particularly preferably 12 to 24 carbon atoms, and for example, 18 to 24 carbon atoms are preferred monoethylenically used. Of course, mixtures of different hydrocarbons can be used. This may also be technical mixtures of different hydrocarbons, such as technical C2o-24 mixtures.

As the monomer (da) are especially preferred olefins, preferably 1-alkenes with the aforementioned numbers of C-atoms. The alkenes are preferably linear or at least substantially linear. By "substantially linear" is meant that it preferably is at any side groups are only methyl or ethyl groups only methyl groups.

Also particularly suitable are the oligomers mentioned preferred polyisobutenes. Surprisingly, the workability can thus be improved in aqueous systems straight. The oligomers are preferably but not used as the only monomer, but in a mixture with other monomers (da). It has proven useful, an oligomer content of 60 mol% with respect to the sum of all monomers (d) not to exceed. If present, the content is of oligomers is usually 1 to 60 mol%, preferably 10 to 55 and particularly preferably 20 to 50 mol%, and, for example, about 20 mol%. For combination with polyisobutenes are in particular olefins having 12 to 24 carbon atoms.

(db 1)

The modified with functional groups X 1 monoethylenically unsaturated hydrocarbons (d b ') can be, for all hydrocarbons having an ethylenically unsaturated group in principle, and in which one or more H atoms of the hydrocarbon are substituted by functional groups X 1 ,

It can act be alkenes, cycloalkenes or alkenes containing aromatic radicals. Preferably is ethylenically unsaturated hydrocarbons, in which the double bond is located in α-position. In general, the monomers (d b ') have from 3 to 30 carbon atoms, preferably 6 to 24 carbon atoms and most preferably 8 to 18 carbon atoms. They preferably have a functional group X. 1 It is preferable that the monomers (db ') are linear or substantially linear α-unsaturated-ω-functionalized alkenes having 3 to 30, preferably 6 to 24 and particularly preferably 8 to 18 carbon atoms and / or 4-substituted styrene.

With the functional groups X 1 (C) in the formulation advantageously, the solubility of the copolymer as well as the anchorage to the metal surface or in the binder matrix can be influenced. The skilled worker will, depending on the nature of the Bindemittelsys- tems and the metallic surface of a suitable choice of functional groups. The functional groups are preferably selected from the group consisting of -Si (OR 3) 3 (with R 3 = d- to C 6 alkyl), -OR 4, -SR 4, -NR 4 2l at least one - NH (C = O) R 4, COOR 4, - (C = O) R 4, -COCH 2 COOR 4, - (C = NR 4) R 4, - (C = N-NR 4 2) R 4, - (C = N-NR 4 - (C = O) -NR 4 2) R 4, - (C = N-OR 4) R 4, -0- (C = O) NR 4, -NR 4 (C = O) NR 4 2, -NR 4 (C = NR 4) NR 4, -CSNR 4 2, - CN, -PO 2 R 4 2, -PO 3 R 4 2, -OPO 3 R 4 2, (with R 4 = independently H, Ci act to Cβ alkyl, aryl, (earth) alkali salt) or -SO 3 H.

Particularly preferably, the groups X 1 to Si (OR 3) 3 (with R 3 = Cr to C6 alkyl), -OR 4, -NR 4 2, -NH (C = O) R 4, COOR 4, -CSNR 4 2, - CN, -PO 2 R 4 2, -PO 3 R 4 2, -OPO 3 R 4 2, (where R 4 = independently H, Ci to C6 alkyl, aryl, ( earth) AI potash) or -SO 3 H. very particular preference is COOH.

Examples of suitable monomers include (d b ') C 4 - to C 2 o- (α, ω) ethenyl carboxylic acids, such as vinyl acetic acid, or 10-Undecencarbonsäure, C 2 - to C 20 - (α, ω) -Ethenylphosphonsäuren such as vinylphosphonic acid, their mono- or diesters or salts, C 3 - to C 20 ethenylcarbonitriles such as acrylonitrile, allylnitrile, 1-butenenitrile, 2-methyl-3-butenenitrile, 2-methyl-2-butenenitrile, 1-, 2- , 3- or 4-Pentennitil or 1-hexenenitrile, 4-substituted styrenes such as 4-hydroxystyrene or 4-carboxystyrene. Of course, mixtures of several different monomers (d b ') can be used. It is preferable that in (d b ') by 10-unde- cencarbonsäure.

In the vinyl ethers (db ") is in principle known manner to ether of the general formula H 2 C = CH-OR 6 wherein R 6 is a straight, branched or cyclic, preferably aliphatic hydrocarbon group having 1 to 30 C atoms, preferably having 2 to 20 carbon atoms and particularly preferably 6 to 18 carbon atoms. They may also be modified vinyl ethers, in which where one or more H atoms in the group R substituted by functional groups X 1 6 are, wherein X 1 is as defined above preferably R 6 is a linear or substantially linear array, wherein optionally present func- tional groups is disposed X 1 is preferably terminal. of course, can also several different vinyl ethers (db ") be used.

Examples of suitable monomers (db ") include 1, 4-Dimethylolcyclohexanmonovinyl- ether, Ethylenglycolmonovinylether, diethylene glycol monovinyl ether, Hydroxybutylvinyl- ether, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, or t-butyl vinyl ether.

To prepare the copolymers used in this invention (C) only the monomers (da) or only the monomers (db) or a mixture of monomers

(Da) and (db) can be used. It is preferable that only monomers (da) or a mixture of (da) and (db). If it is a mixture of (da) and

(Db) is a mixture of is (da) and (d b ') is preferred. If a mixture is present, the amount of the monomers (db) is usually 0.1 to 60 mol% based on the sum of all the monomers (d), preferably 1 to 50 mol% and particularly preferably 5 to 30 mol%.

Monomers (c2)

Suitable monomers (c2) in the present invention are 30 to 70 mol% of at least one state-noethylenisch unsaturated dicarboxylic acid having 4 to 8 carbon atoms or anhydrides thereof (c2a) and / or derivatives (c2b) thereof. The amount refers to the total amount of all monomer units in the copolymer (C).

(C2a)

Examples of monoethylenically unsaturated dicarboxylic acids (c2a) include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, methylenemalonic acid or 4-cyclohexene-1, 2-dicarboxylic acid. The monomers may also be salts of the dicarboxylic acids and -if possible- act cyclic anhydrides thereof. Preferred as the monomer (da) are maleic acid or maleic anhydride.

(C2b)

The derivatives (c2b) of the monoethylenically unsaturated dicarboxylic acids are esters of dicarboxylic acids with alcohols of the general formula HO-R 1 -X 2 n (I) and / or amides or imides with ammonia and / or amines of the general formula HR 2 NR 1 -X 2 n (II). Preference is given by 1, ω-func tional alcohols or amines. This is at X 2 to an arbitrary functional group. Even with the functional groups X 2 can be influenced advantageously, the solubility of the copolymer (C) in the formulation as well as the anchorage to the metal surface or in the binder matrix. The skilled worker will, depending on the nature of the Bindemittelsys- tems and the metallic surface of a suitable choice of functional groups. It may be acidic groups or acid groups groups derived, for example. Specifically, it may, the functional group is a selected from the group consisting of -Si (OR 3) 3 (with R 3 = d- to C 6 alkyl), OR 4, -SR 4, -NR (4 2l -NH C = O) R 4, COOR 4, - (C = O) R 4, -COCH 2 COOR 4, - (C = NR 4) R 4, - (C = N-NR 4 2) R 4, - ( C = N-NR 4 - (C = O) -NR 4 2) R 4, - (C = N-OR 4) R 4, -0- (C = O) NR 4, -NR 4 (C = O ) NR 4 2,

-NR 4 (C = NR 4) NR 4, -CSNR 4 2l - CN, -PO 2 R 4 2, -PO 3 R 4 2, -OPO 3 R 4 2, (where R 4 = independently H, C to Cβ alkyl, aryl, (earth) alkali salt)) or -SO 3 H act. Preferably is -SH, -CSNH 2, -CN, -PO 3 H 2, or -Si (OR 3) 3 or salts thereof, and most preferably are -CN or -CSNH. 2

The number n of the functional groups X 2 in (I) or (II) is usually 1, 2 or 3, preferably 1 or 2 and particularly preferably (I).

In the formulas (I) and (II) is R 1 is a (n + 1) -valent hydrocarbon group having 1 to 40 carbon atoms having the OH group and the NHR 2 group with or connect the functional groups x2. In the group of non-adjacent C atoms may also be substituted by O and / or N. It is preferable that this is a 1 / "functional group.

In divalent linking groups R 1 may be preferably linear 1, ω-alkylene having from 1 to 20, preferably be 2 to 6 carbon atoms. Particularly preferred is 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene or 1, 6-hexylene radicals. Further preferably, it may be, which have O-atoms groups, for example, -CH 2 -CH 2 -O-CH 2 -CH 2 - or polyalkoxy of the general formula R 7 -CH 2 -CH - [- O-CH 2 - CHR 7 -] m -, where m is a natural number from 2 to 13 and R 7 is H or methyl. Examples of compounds (I) or (II) having such linking groups R 1 include HO-CH 2 -CH 2 -CSNH 2, HO-CH 2 -CH 2 - SH, H 2 N-CH 2 -CH 2 -CH 2 -Si (OCH) 3, H 2 N - (- CH 2 -) 6 CN, H 2 N-CH 2 -CH 2 -OH or H 2 N-CH 2 - CH 2 -O-CH 2 -CH 2 OH.

If the radical to bind more functional groups, more functional groups can be attached to the terminal carbon atom in principle. But preferably, R 1 in this case, on one or more branches. At the intersection, it may be a carbon atom or preferably a nitrogen atom. Examples of compounds (II) with such a residual are (hydroxyethyl) aminobismethylenephosphonic acid (IM) or (aminoethyl) aminobismethylenephosphonic acid (IIIa).

In the above formulas (I) and (II), R 2 is H, d- to Cio-hydrocarbon group, preferably a C to C 6 alkyl group or a group -R 1 -X 2 n, wherein R n 1 and X 2 are as defined above. Preferably, R 2 is H or methyl and more preferably H.

The derivatives (c2b) of the dicarboxylic acids may be esterified or amidated, respectively, both COOH groups of the dicarboxylic acid with the compounds (I) and / or (II). but only one of the two COOH groups is esterified or amidated vorzugt loading. An imide may naturally be formed only in common with 2 COOH groups. This is preferably around two adjacent COOH groups; but of course it can also be non-adjacent COOH groups.

Monomers (c3)

, the copolymers used in this invention (C) in addition yet O to 10 mol%, O preferably up to 5 mol%, particularly preferably from O to 3 mol% of other ethylene lenisch unsaturated monomers and (d) (c2) different but copolymerizable with (d) and (c2) contained as building blocks. Such monomers may be used required- to fine-tune the properties of the copolymer -if. Very particular preference no monomers (c3) are included.

Examples of monomers (c3) include in particular (meth) acrylic compounds such as (meth) acrylic acid or (meth) acrylester or hydrocarbons having conjugated double bonds such as butadiene or isoprene. The (meth) acrylester may also have further functional groups, such as OH or COOH groups. Furthermore, it may also be crosslinking monomers having two or more isolated ethylenically unsaturated double bonds. However, the copolymers should not be too greatly crosslinked. If crosslinking monomers are present, their amount should mol% with respect to the sum of all monomers, preferably 3 mol% and particularly preferably 2 mol% not normally exceed. 5

The amounts used according to the invention, monomers (d), (c2) and (c3) wur- those already mentioned. Preferably, the amounts of (d) are 35 to 65 mol%, and the amounts of (c2) 65 to 35 mol%, particularly preferably (d) is 40 to 60 mol%, and (c2) 60 to 40 mol% and very particularly preferably is (d) 45 to 55 mol%, and (c2) 55 to 45 mol%. For example, the amount of (d) and (c2) may be approximately 50 mol%. Preparation of the copolymers (C)

The preparation of the copolymers used in this invention (C) is preferably carried out by means of radical polymerization. see the implementation of a free-radical polymerization, including required apparatus is known in principle to the expert. The polymerization is preferably carried out using thermally decomposing polymerization initiators. Preferably, peroxides can be used as thermal initiators. However, the polymerization can of course also be performed photochemically.

Suitable monomers (c2a) are preferably used where chemically possible-the cyclic anhydrides of dicarboxylic acids. Maleic anhydride is particularly preferred.

As a solvent, preferably, aprotic solvents such as toluene, xylene, aliphatics, alkanes, benzine or ketones can be used. Insofar as monomers long chain mo- noethylenisch unsaturated hydrocarbons are used which have a boiling point higher, especially those with a boiling point higher than about 150 0 C, can also be carried out without solvent. The unsaturated hydrocarbons such themselves act as solvents.

The radical polymerization with thermal initiators can be at 60-250 0 C, preferably 80-200 0 C, most preferably be carried out at 100- 180 0 C and in particular at 130 to 170 0 C. The amount of initiator is 0.1 to 10 wt.%, Based on. The amount of monomers, preferably 0.2 to 5 wt.% By weight and particularly preferably 0.5 to 2.%. Usually an amount from about 1 wt.% Is recommended. The polymerization time is usually 1 - 12 hours, preferably from 2 - 1O h, and particularly preferably 4 - 8 hours. The copolymers can be isolated from the solvent by methods known to the skilled person, or alternatively are directly in solvent-free.

If the copolymers not on derivatives (c2b) are implemented, anhydride groups present usually to the corresponding Dicarbonsäureein- be hydrolyzed units. The procedure is aimed expediently according to the intended use of the copolymer.

Where the copolymer is to be used in an aqueous binder system, it is recommended to perform the hydrolysis in water. For this purpose, the copolymer containing anhydride groups can be introduced into water and hydrolysed expediently with gentle warming and the addition of a base. Temperatures of up to 100 0 C. have proved suitable bases are especially tertiary amines, such as dimethylethanolamine. The amount of base is generally from 0.1 to 2 equivalents (based on dicarboxylic anhydride units in the polymer), preferably 0.5 to 1.5 equivalents, and particularly preferably 0.7 - 1. 2 equivalents. Typically, one equivalent of base per anhydride is about used. The resulting aqueous solution or dispersion of the copolymer can be directly for the manufacture of crosslinkable lung preparation for the process can be used. Of course, the copolymers can be isolated following art methods known in principle.

Where the copolymer is to be used in a binder system based on organic solvents, the copolymer can be dissolved in an organic solvent such as THF, dioxane or toluene, or dispersed, and water is added in stoichiometrically necessary amounts, and the base. The hydrolysis can be carried out as described above with slight warming. Alternatively, after the hydrolysis in water but also a solvent exchange made the advertising.

include copolymers which are derivatives of monoethylenically unsaturated dicarboxylic acids (c2b), can in principle be prepared by two different synthetic routes. Firstly, the derivatives (c2b) can already be used as monomers for polymerization. These can advance in a separate synthetic step from the alcohols (I) or the functional amines (II) and the dicarboxylic acids or preferably their anhydrides.

In a preferred embodiment of the inventions as described above, first copolymers of the monomers (d) and the non-derivatized ethyle- cally unsaturated dicarboxylic acids (c2a) was prepared. the dicarboxylic acids are preferred for this purpose -if possible- in the form of their inner anhydrides used, maleic anhydride is particularly preferably used. After formation of the copolymer may in this synthesis variant, the copolymerized dicarboxylic acid, preferably the corresponding dicarboxylic anhydride units, and more preferably the maleic anhydride units in a polymer-analogous reaction with the functional alcohols HO-R 1 -X 2 n (I) and / or ammonia or the functional amines HR 2 NR 1 -X 2 n (II) are reacted.

The reaction can be carried out in bulk or preferably in a suitable aprotic solvent. Examples of suitable aprotic solvents include, in particular polar aprotic solvents such as acetone, methyl ethyl ketone (MEK), dioxane or THF, and optionally also non-polar hydrocarbons such as toluene or aliphatic hydrocarbons. In order to implement that can not submitted modified copolymer, for example, in the solvent and then the desired functional alcohol HO-R 1 -X 2 n (I), ammonia or the desired functional amine HR 2 NR 1 -X 2 n (II) in the desired amount are added. The reagents for functionalization can be zweckmä- ßigerweise previously dissolved in a suitable Lösmittel. The derivatization is preferably carried out under heating. Reaction times are 2 to 25 hours have been found. The use of primary amines or ammonia, the corresponding amides can be obtained at temperatures of up to 100 0 C., preferably while also increasing imides are formed at higher temperatures. At 130 to 140 0 C predominantly imides are already received. Preferably, the formation should be avoided by imide structures.

The amounts of the reagents used for the functionalization is directed depending on the desired degree of functionalization. has proven an amount of 0.5 to 1, 5 equivalents per dicarboxylic acid, preferably 0.6 to 1.2, particularly preferably 0.8 to 1, 1, and most preferably about 1 equivalent. Unless one less than 1 equivalent is used, remaining anhydride groups can be opened by hydrolysis in a second step.

Of course, also mixtures of several alcohols HO-R 1 -X to 2 n (II) can be used n (I) and / or ammonia or the functional amines HR 2 NR 1 -X. 2 Likewise, reaction sequences are possible in which first is reacted with an alcohol hol / ammonia / amine and after the reaction, a further alcohol hol / ammonia / amine component is used for the reaction.

The obtained organic solutions of the modified copolymers can be used directly for formulation of organic crosslinkable preparations. Of course the polymer by methods known well to the skilled in the art can also be isolated from.

For incorporation into aqueous formulations of the solution may conveniently be added to water and the organic solvents are removed by means known in the art methods.

The acidic groups of the polymer may be neutralized completely or partially. The pH of the copolymer solution should generally be at least 6, preferably at least 7, in order to ensure adequate solubility or -dispergier- bility. For non-functionalized copolymers of this value corresponds to about one equivalent of base per dicarboxylic acid unit. In the functionalized copolymer, the functional groups X 1 and X 2 naturally affect the solubility lichkeitseigenschaften with the copolymer. Examples of suitable bases for neutralization include Ammonik, alkali and alkaline earth, zinc oxide, linear, cyclic and / or branched Ci - Cβ mono-, di-, and trialkylamines, linear or branched Ci - Cβ mono-, di- or trialkanolamines, especially mono-, di- or trialkanolamines, linear or branched C - Cβ alkyl ethers of linear or branched Ci - Cβ mono-, di- or trialkanolamines, oligo- and polyamines, for example diethylenetriamine. The base can already be used subsequently or, advantageously, in the hydrolysis of anhydride groups.

The molecular weight M w of the copolymer is chosen by the skilled person depending on the desired end use. Proven a M w has of 1,000 to 100,000 g / mol, preferably from 1500 to 50,000 g / mol, particularly preferably 2,000 to 20,000 g / mol, most preferably 3,000 to 15,000 g / mol, and, for example, from 8000 to 14,000 g / mol.

To produce the integrated pretreatment layers one Copo- lymer (C) or a plurality of different copolymers (C) can be used. The skilled worker will make a particular selection possible in principle, the copolymer (C) according to the desired characteristics of the integrated pre-treatment layer. For the skilled worker it is obvious that not all types of copolymers (C) for all kinds of binder systems, solvent or metallic surfaces are equally well suited.

The copolymers used in this invention (C) are usually used in an amount of 0.25 to 40 wt.%, Preferably 0.5 to 30 wt.%, Particularly preferably 0.7 to 20 wt.% And very particularly preferably 1, 0 to 10 wt.% is used, aeration attracted to the amount of all components of the formulation except for the solvent.

As the component (D) the preparation as a rule comprises a suitable solvent, in which the components are dissolved and / or dispersed in order to allow a uniform application of the preparation to the surface. The solvents are removed prior to curing of the coating as a rule. but it is also possible in principle to make the formulation solvent-free or substantially solvent-free. This may be, for example powder coatings or to photocurable compositions.

Suitable solvents are those which are able to resolve the compounds of the present invention to disperse, suspend or emulsify. These may be organic solvents or water. Of course, mixtures of various organic solvents or mixtures of organic solvents can be used with water. The skilled worker makes an appropriate selection from the solvents possible in principle, depending on the desired end use and the type of compound used according to the invention. Examples of organic solvents include hydrocarbons such as toluene, xylene or mixtures such as are obtained in the refining of crude oil, such as hydrocarbon fractions with defined boiling, ethers such as THF or polyethers such as polyethylene glycol, ether alcohols such as butyl glycol, Etherglykolacetate acetate as Butylgklykol-, ketones such as acetone, alcohols such as methanol, ethanol or propanol.

Furthermore, preparations can be used comprising water or a predominantly aqueous solvent mixture. Among such mixtures are to be understood to comprise at least 50.%, Preferably at least 65 wt.% And particularly preferably at least 80 wt.% Include water. Other components are water-miscible solvents. Examples include monoalcohols such as methanol, ethanol or propanol, higher alcohols such as ethylene glycol or polyether polyols and ether alcohols such as butyl or methoxy propanol.

The amount of solvent is chosen by the skilled man depending on the desired properties of the preparation and the desired application method. 1 to 1: As a rule, the weight ratio of the layer components to the solvent is 10 10, preferably about 2: 1 without the invention being limited thereto. It is of course also possible first to prepare a concentrate and to dilute to the desired concentration only on site.

The formulation is prepared -if eingesetzt- by intensive mixing of the components of the preparation with the solvents. The skilled worker is aware of suitable mixing or dispersing. The copolymers are preferably used in the form of solutions or emulsions, resulting from the hydrolytic opening of the anhydride or the derivatization and optionally solvent exchange. Solvents in this synthesis stages should be chosen so that they are at least compatible with the binder system which is to be used, particularly advantageously the same solvent is used.

Of the components (A) to (C) and optionally (D) the preparation may further still comprise one or more excipients and / or additives (E). Such auxiliaries and / or additives are used to fine-tune the properties of the layer. Amount greater than a rule not 20 wt.% Based on. The sum of all components except for the solvent, preferably not 10%.

Examples of suitable additives are color and / or effect pigments, rheological aids, UV absorbers, light stabilizers, radical scavengers, initiators for radical polymerization, catalysts for the thermal crosslinking, photoinitiators and coinitiators, slip additives, polymerization inhibitors, defoamers, emulsifiers, degassing agents, wetting -, dispersants, adhesion promoters, leveling agents, film-forming auxiliaries, rheology control additives (thickeners), flame retardants, siccatives, anti-skinning agents, other corrosion inhibitors, waxes and Mattierungsmit- tel as known from the textbook "paint additives" by Johan Bieleman, Wiley-VCH, wine home, New York, 1998, or the German patent application DE 199 14 896 A1, column 13, line 56 to column 15, line 54, are known.

For performing the method according to the invention the preparation is applied to the metallic surface.

Optionally, the surface can be cleaned prior to treatment. If the inventions dung proper handling immediately after a metallic surface treatment, such as an electrolytic zinc coating or a Schmelztauchverzin- effect of steel strips, so the tapes can be accommodated in the control case without prior purification, the inventive treatment solution in contact. Were usually but mounted to be treated metal strips prior to coating of the invention and / or transported, are provided with anti-corrosion oils or dirty, so that cleaning prior to the coating of the invention is required. Cleaning can be done by the skilled person known methods with conventional cleaning agents.

The application of the preparation can be effected for example by spraying, dipping, pouring or rolling. After a dipping process can be allowed to drip the workpiece for removing excess composition; for sheets, metal foils or the like, excess formulation can also squeezing off or squeegeeing. The application with the preparation takes place generally at room temperature without the possibility of higher temperatures should be in principle.

Preference is given by the inventive method metal strips coated (often called "coil coating" hereinafter). In this case, the coating can be performed both on one side on both sides. It is also possible to coat the top and bottom by means of various formulations.

Most preferably, the coating takes place by means of a continuous process. Continuously operating coil coating lines are known in principle. usually they comprise at least one coating station, a TRO cken- or baking station and / or UV station and optionally further stations for pretreatment or aftertreatment, such as rinsing or Nachspülstationen. Examples of coil coating lines are found in in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 55, "Coil coating", or in German patent application DE 196 32 426 A 1. Of course, a different construction can be used be. the speed of the metal strip is selected by the expert according to the application and curing of the formulation used. have a rule proved speeds of 10 to 200 m / min, preferably 12 to 120 m / min, particularly preferably 14 to 100 m / min, most preferably 16 to 80 and especially 20 to 70 m / min.

For application to the metal strip, the preparation used in the invention, cross-linkable may be sprayed, poured or preferably rolled on. In the preferred roll coating, the rotating pick-up roll dips (pick-up roller) in a storage of the preparation used in the invention and so takes on the preparation to be applied. This is transferred from the pick-up roller directly or via at least one transfer roller to the rotating application roll. From the latter, the paint is transferred by same or opposite direction to the tape stripping. According to the invention the reverse stripping, or the reverse roller coating process of advantage and is therefore preferred. Preferably, the applicator roll has a circumferential speed which is 110 to 125% of the tape speed, and the receiving roll has a peripheral speed which is 20 to 40% of belt speed. However, the formulation used in the invention can be pumped directly into a gap between two zen WAI, which is referred to in the art as nip feed.

Following the application of the preparation used in the invention, any solvent present is removed may be in the layer and the layer is crosslinked. This can be done in two separate steps or simultaneously. To remove the solvent, the layer is preferably heated by means of a suitable device. The drying can also be effected by contact with a gas stream. Both methods can be combined.

The curing method depends on the nature of the binder system employed. It can take place thermally and / or photochemically.

In thermal curing, the applied coating is heated. This can preferably by convection heat transfer, carried out irradiation with near or far infrared, and / or bands on the basis of iron by electric induction.

The temperature required for curing depends in particular on the crosslinkable binder system. Highly reactive binder systems can be cured as less reactive binder systems at lower temperatures. As a rule, the cross-linking at temperatures of at least 60 0 C, preferably at least 80 0 C, particularly preferably made at least 100 0 C and most preferably at least 120 0 C. In particular, crosslinking can be at 100 to 250 0 C, preferably 120 to 220 0 C, and particularly preferably be carried out at 150 to 200 0 C. Is meant respectively the peak temperature found on the metal (peak metal temperature (PMT)), which (for example, non-contact infrared measurement or determination of the temperature with bonded test strips) can be measured by methods familiar to the skilled worker.

The heating time, ie the time of thermal curing varies depending upon the paint used in the invention. Preferably it is from 10 seconds to 2 minutes. If the convective heat applied substantially at the preferred tape speeds convection ovens a length of 30 to 50, especially 35 to 45 m, required. The convection temperature is of course higher than the temperature of the layer and can be up to 350 0 C.

The photochemical curing is carried out by means of actinic radiation. By actinic radiation is here and below, electromagnetic radiation, such as near infrared, visible light, UV radiation or X-rays or corpuscular radiation such as electron beams. for the photochemical curing of UV / VIS radiation is preferably used. Irradiation can if appropriate in the absence of oxygen, such. B. under an inert gas atmosphere, are carried out. The photochemical curing can under normal temperature conditions, that is carried out without heating of the coating, but it can also be at elevated temperatures for example at 40 to 150 0 C, preferably 40 to 130 0 C and in particular at 40 to 100 0 C are photochemically crosslinked.

The inventive method an integrated pretreatment layer on a metallic surface, particularly the surface of iron, steel, zinc or zinc alloys, aluminum or aluminum alloys is available. The exact structure and composition of the integrated pretreatment layer is not known to us. in addition to the crosslinked binder system (A) comprising the fillers, the copolymers (C) and optionally further components. In addition, can also have been extracted from the metal surface and redeposited components, such as conventional amorphous oxides of aluminum or of zinc and optionally other metals may be present.

The thickness of the integrated pre-treatment layer is 1 to 25 microns and is determined by the skilled person depending on the desired properties and the intended use of the layer. As a rule, a thickness has proved to 3-15 microns for integrated pretreatment layers. Preferably a thickness from 4 to 10 microns, and more preferably 5 to 8 microns. The thickness depends on the amount of each listed applied composition. For applications in the automotive sector can be dispensed after the application of the integrated pretreatment layer of the invention may even be in a cathodic dip coating (CDC). If the integrated pretreatment layer is also intended to replace the KTL, recommend somewhat thicker integrated pretreatment layers, for example with a thickness of 10 to 25 microns, preferably 12 to 25 microns.

further coating layers can not be applied to the provided with an integrated pretreatment layer metallic surface. Type and number of the required coating layers are determined by the skilled person depending on the desired use of the coated metal or metal molding. The integrated pretreatment layers of the invention can be recoated well and have good adhesion with the subsequent coating layers. Further coating films may be, for example, paints, films of color paints, varnishes or function. An example of a functional coating is a soft coating with a relatively high proportion of filler. This can be advantageously applied before the color and / or top coat to protect the metal and the integrated pretreatment layer from mechanical damage for example by scratching or stone chips.

The application of further lacquer layers can be made in the described coil coating system. There are then switched more application stations and, optionally, curing in a row. Alternatively, but rolled up after application and curing of the anticorrosion coating, the coated strip again and more layers are applied until a later date in other plants. The further processing of the coated metal coils can be done on site, or they can be transported for further processing to another location. Reservations can be provided for example with removable protective films.

With an integrated pretreatment layer provided tapes but can also first be -beispielsweise verabeitet to metallic mold parts by means of cutting, shaping and Fügen-. The joining can also be done by welding. The shaped article obtained can then be further lacquer layers with vershene as described above.

The invention therefore also provides shaped articles having a metallic surface, which are coated with an integrated pretreatment layer having a thickness of 1 to 25 microns, and moldings having layers further coatings in addition yet. The term "molded article" is intended to include both coated sheets, films or tapes as well as the obtained therefrom metallic components here. Such components are in particular those which can be used for paneling, facing or liner. Examples include automotive bodies or parts thereof , truck bodies, che framework for two-wheelers such as motorcycles or bicycles or parts for such vehicles, such as Schutzble- or, claddings for household appliances such as washing machines, dishwashers, clothes dryer, gas and electric cookers, microwave ovens, freezers or refrigerators, linings for technical devices or equipment, such as machines, switch cabinets, computer housings, or the like, components in the architectural field such as wall parts, facade elements te, ceiling panels, window or door profiles or partitions, furniture made of metallic material ies such as metal cabinets, metal shelves, parts of furniture or fittings. Furthermore, it can also be hollow articles for storing liquids or other substances, such as tins, cans or tanks.

The following examples illustrate the invention.

Part A - Synthesis of the copolymers used

Part I - synthesis of copolymers having anhydride groups

copolymer A

Copolymer of MSA / Ci2-olefin (molar ratio 1/1)

In a 2 l pilot-scale to be 176.4 g (1 mol 05) submitted to n-dodecene-1, sparged with nitrogen and heated to 150 0 C. Within 6h feed stream 1 of 147.1 g of melted maleic anhydride (80 0 C, 1, 50 mol) and a feed stream 2 of 4.1 g of di-tert-butyl peroxide (1% rel. To monomers) in 75.6 g (0.45 mol) of n-dodecene-1 are added dropwise. The reaction mixture is stirred for a further 2 h at 150 0 C. This gives a slightly yellowish solid resin.

copolymer B

Copolymer of maleic anhydride / C 2 olefin / styrene (molar ratio 1 / 0.9 / 0.1)

The procedure was as in Example 1, except that a mixture of 1, 35 mol of n-dodecene-1 and 0.15 mol of styrene was used in place of pure n-dodecene -1. copolymer C

Copolymer of MSA / Ci2-olefin / C2o-24-olefin (molar ratio 1 / 0.6 / 0.4)

In a 1500L pressure reactor with anchor stirrer, temperature control and nitrogen inlet, 36.96 kg C2o-24-olefin at 60 0 C and pumped in 31, is sucked 48 kg n-dodecene -1. The initial charge is heated to 150 0 C. Then, within 6 h of feed 1, consisting of 1 03 kg of di-tert-butyl peroxide, and feed 2, consisting of metered 30.57 kg of maleic anhydride melted. After the end of feed 1 and 2 is stirred for 2 hours at 150 0 C. At 150-200 mbar acetone and t-butanol is then distilled off.

copolymer D

Copolymer of maleic anhydride / C 2 olefin / polyisobutene 550 (molar ratio 1 / 0.8 / 0.2)

In a 2 l pilot-scale with anchor stirrer and internal thermometer, 363 g (0.66 mol) of highly reactive polyisobutene (α-olefin content> 80%) having a M n of 550 g / mol (Glissopal ® 550, Fa. BASF) and 323.4 g (2.11 mol) C 2 olefin under agitation and nitrogen gassing heated to 150 0 C. Subsequently, within 6 h, a feed stream 1, consisting of 323.4 g of maleic anhydride (80 0 C, 3.3 mol), and feed 2, consisting of 13.56 g of di-t-butyl peroxide (1% rel. To monomers) and 88.8 g (0.53 mol) Ci2-olefin added. After the end of feed 1 and 2 are a further 2 hours at 150 0 C. a solid yellowish polymer is obtained.

copolymer e

Copolymer of maleic anhydride / C 2 olefin / polyisobutene 1000 (molar ratio 1 / 0.8 / 0.2)

In a 2 l pilot-scale with anchor stirrer and internal thermometer, 600.0 g (0.6 mol) are highly reactive polyisobutene (α-olefin content> 80%) having a M n of 1000 g / mol (Glissopal ® 1000, Fa. BASF) and 322 5 g (1, 92 mol) Ci2-olefin under agitation and nitrogen gassing at 150 0 C heated. A feed stream 1, consisting of 294.0 g of maleic anhydride (80 0 C, 3.0 mol), and feed 2, consisting of 13.0 g of di-t-butyl peroxide (1% rel. Subsequently, to within 6 h monomers) and 80.6 g (0.48 mol) Ci2-olefin added. After the end of feed 1 and 2 are a further 2 hours at 150 0 C. a solid yellowish polymer is obtained. copolymer F

Copolymer of MSA / Ci2-olefin / 10-undecenoic acid (molar ratio 1/0, 9 / 0.1)

In a 2 l pilot-scale 554.4 g of n-dodecene-1 and 8.293 g (0.45 mol) of (3.3 mol) of 10-undecenoic acid, sparged with nitrogen and heated to 150 0 C. Within 6 h, a feed be molten from 1 441 g of maleic anhydride (80 0 C, 4.5 mol) and a feed stream 2 of 12 g of di-tert-butyl peroxide (1% rel. To monomers) in 126 g (0.75 mol ) n-dodecene-1 are added dropwise. The reaction mixture is stirred for a further 2 h at 150 0 C. This gives a slightly yellowish solid resin.

copolymer G

Copolymer of MSA / Cβ-olefin (molar ratio 1/1)

The procedure was as in Example 1, except that was used instead of n-dodecene-1 n-octene-1.

Part II hydrolytic ring opening of the resins / solvent exchange

General experimental 11-1

400 g of the copolymer resins used in each case A to G with anhydride groups are crushed, suspended in a 2 l pilot-scale in 1000 g water and heated to 100 0 C. Within one hour, 1 equivalent of base is used (based on the maleic hydride groups in the resin) was added dropwise and the mixture further 6 h at 100 0 C stirred until a solution or stable emulsion was obtained.

Solvent Exchange II-2

350 g of the aqueous solution from Procedure 1 are mixed in a reaction vessel with 400 g of butyl glycol. The water is subsequently distilled off at 50 to 60 0 C under reduced pressure.

Details of the polymers used in each case, the bases and the properties of the polymers obtained are summarized in Table 1 below. IM part functionalization of copolymers

General experimental 111-1

In a 2 l pilot-scale with anchor stirrer and internal thermometer, the respectively desired Maleinsäureeanhydrid-olefin copolymers A is introduced to G in an organic solvent and aerated with nitrogen. Then 1 equivalent of the respective desired hydroxy- or amino-functional compound (I) or (II) added dropwise over x y hours at 0 C.

Solvent Exchange:

Following the derivatization replacement of the organic solvent can be done against water. For this purpose, the product is treated with water and base to the desired pH. Subsequently, the organic solvent is distilled off under reduced pressure.

General experimental III-2:

In a 2 l pilot-scale with anchor stirrer and internal thermometer, the respectively desired Maleinsäureeanhydrid-olefin copolymers A to G and 1 equivalent of the respective desired hydroxy- or amino-functional compound (I) or (II) is initially charged, purged with nitrogen, and for x hours y 0 C stirred. Then the product is taken up in a suitable organic solvent.

Following the derivatization of an exchange of the organic solvent to water as described can be made.

Details of the polymers used in each case, the hydro- xy used or amino-functional compound (I) or (II) as well as the properties of the resulting derivatized copolymers are summarized in Table 2 below.

ω ω

Table 1: Aqueous emulsions of copolymers with unmodified dicarboxylic acid by hydrolytic ring opening according to general instruction 11-1

Note .: The K values ​​Cellulose-Chemie, Bd were respectively determined according to H. Fikentscher,. 13, pp 58-64 and 71-74 (1932) in 1

Wt .-% solution (aqueous solution or butyl glycol) at 25 ° C at pH uncorrected. The larger the K value, the greater the molecular weight of the polymer.

* Solvent exchange by hydrolysis in water - data not determined

ω

Table 2: With functionalized alcohols (I) or amines (II) derivatized copolymers DMEA: dimethyl ethanolamine, MEK: methyl ethyl ketone, BG: butylglycol

Part B - Performance Tests

application tests were mers with the resulting non-derivatized and derivatized maleic acid-olefin copolymer chain performed. Were carried out in 3 different coil coating lacquers based on epoxides, acrylates and polyurethanes tests.

Basisreze structure for coil coatin -Lack or anisch binders based E ox

The components were mixed in a suitable stirred vessel in the order listed and predispersed with a dissolver for ten minutes. The resulting mixture was transferred to a bead mill with cooling jacket and mixed with 1, 8 to 2.2 mm SAZ glass beads. The ground material was milled for 1h 30 'minutes. The millbase was separated from the glass beads.

The millbase was in the order given, 5.9 parts by weight of a blocked hexamethylene diisocyanate with stirring (Desmodur ® VP LS 2253 from. Bayer AG) and 0.4 parts by weight of a commercially available tin-free crosslinking catalyst (Borchi ® VP 0245, Fa. Borchers GmbH) ,

Base formulation for coil coating paint (aqueous) based acrylic binder

As the crosslinkable binder aqueous acrylate dispersion (solid content 30% wt.) Was an anionically stabilized with amines, used in the main monomers n-butyl acrylate, styrene, acrylic acid and hydroxypropyl methacrylate. In a suitable stirred vessel 5 parts by weight of a leveling agent with defoamer, 5.5 parts by weight of a melamine resin as a crosslinking agent were in the order given, 18.8 parts by weight of acrylate, 4.5 parts by weight of a dispersing additive, 1, (Luwipal 072 ®, BASF AG) , 0.2 parts by weight of a hydrophilized len fumed silica (Aerosil ® 200 V from Degussa), 3.5 parts by weight of talc Finntalc M5, 12.9 parts by weight of white pigment titanium rutile 2310, 8.0 parts by weight of Acrylatdisperpsion, 3.5 parts by weight with calcium ions modified silica (Shieldex ® from Grace Division), 4.9 parts by weight of zinc phosphate (Sicor ® ZP-BS-M company Waardals Kjemiske factories), 1, 2 parts by weight of black pigment (SICOMIX ® Black from BASF AG) were mixed with a dissolver predispersed for ten minutes. The resulting mixture was transferred to a bead mill with cooling jacket and mixed with 1, 8 to 2.2 mm SAZ glass beads. The ground material was ground for 45 minutes. The millbase was separated from the glass beads.

The ground material was added under stirring in the order indicated with 27 parts by weight of acrylate, 1, 0 parts by weight of a defoamer, 3.2 percent of a blocked sulfonic acid, 1, 5 parts by weight of a defoamer, and 1.0 parts by weight of a leveling assistant.

Base Formula for Coil Coating Material (Aqueous) Based on Polyurethane Binder:

As the crosslinkable binder an aqueous polyurethane dispersion (solids content 44 wt.%, Acid number of 25, M n of about 8000 g / mol, M w ca. 21000 g / mol) based on polyester diols (as soft segment M n about 2000 g / mol ), 4,4'-bis (isocyanatocyclohexyl) - methane and monomer having acidic groups and chain extenders.

In a suitable stirred vessel 5 parts by weight of a leveling agent with defoamer were in the order given, 18.8 parts by weight of the polyurethane dispersion, 4.5 parts by weight of a dispersing additive, 1, 5.5 parts by weight of a melamine resin as crosslinking agent (Luwipal ® 072, BASF AG), 0 (Degussa Aerosil® 200V), 3.5 parts by weight of talc Finntalc M5, 12.9 parts by weight of white pigment titanium rutile 2310, 8.0 parts by weight of the polyurethane dispersion, 3.5 parts by weight of modifiable 2 parts by weight of a hydrophilic fumed silica with calcium ions tes silica (Shieldex ® from Grace Division), 4.9 parts by weight of zinc phosphate (Sicor ® ZP-BS-M company Waardals Kjemiske factories), 1, 2 parts by weight of black pigment mixed (SICOMIX ® Black from BASF AG) and a dissolver for ten predispersed minutes. The resulting mixture was transferred to a bead mill with cooling jacket and having 1, 8 to 2.2 mm SAZ beads mixed comparable. The ground material was ground for 45 minutes. The millbase was separated from the glass beads. The millbase was added with stirring in the order indicated with 27 parts by weight of the polyurethane dispersion, 1, 0 parts by weight of a defoamer, 3.2 percent of an acid catalyst (blocked p-toluenesulfonic acid, Nacure ® 2500), 1, 5 parts by weight of a defoamer and 1, 0 sets weight of a flow aid comparable.

Addition of the copolymers used in this invention

The coil coating varnishes were each described 5 wt.% Of the above-described derivatized or non-derivatized copolymers (calculated as solid

Copolymer respect. The solid components of the formulation) was added. refer to the above-described solutions of the copolymers in butyl glycol, the aqueous solutions or emulsions described above were used for the organic coating on the basis of epoxides, for aqueous paints based on acrylate-distillates or epoxides used.

Coating of steel and aluminum sheets

For coating experiments, galvanized steel plates of type Z (OEHDG 2, Chemetall) and aluminum plates were AIMgSi (AA6016, Chemetall) was used. These were previously purified by known methods.

The described coil-coating materials by means of coating rods on in such a wet film thickness administered such that after curing in a continuous dryer at a circulating air temperature of 185 0 C and a temperature of 171 0 C coatings with a dry film thickness of 6 microns resulted.

For comparison purposes, coatings were prepared without the addition of the copolymers.

To test the corrosion inhibition effect of the coatings of the invention, the galvanized steel plates were the VDA alternating climate test (VDA test sheet 621-415 February 82) 10 weeks subjected.

In this test (see graph below), the samples are initially exposed for one day a salt spray test (5% NaCl solution, 35 ° C) and then 3 x alternately humid conditions (40 0 C, 100% rel. Humidity) and dry air ( exposed to 22 ° C, 60% rel. humidity). A cycle is terminated by a 2-day drying small imaphase. One cycle is shown schematically below. Initial Condensation water test Room condition

Salt spray test

35 ° C, 100% rh ASPO, 22 S C,

60% rh 60% rh W & RJT. 60% rh

1 day 1 day 1 day 1 day 1 day 2 days (8 hours / 16h) (8h / 16h) (8h / 16h) (8h / 16h)

1 week = 1 cycle

There are successively performed a total of 10 such load cycles.

After completion of the exposure to corrosion steel plates were visually evaluated by comparison with predetermined standards. It has both the formation of corrosion products on the undamaged paint surface and the infiltration inclination to edge and scribe mark.

The evaluation of the samples is based on a comparison with the control sample without the addition of corrosion-inhibiting copolymers.

The corrosion-inhibiting effect of the steel plates has also been made by a salt spray test according to DIN 50,021th

Aluminum plates of the acetic acid salt spray test ESS (DIN 50021, June 88) was performed. After end of corrosion exposure the panels evaluated visually. The circular delamination were evaluated on the entire paint surface.

For all tests, the paint layers were scratched; in the case of steel plates by the zinc layer through to the steel layer.

To evaluate the samples, the following grades were awarded:

0 corrosion damage as for the blank sample + less corrosion damage than the blank sample ++ at substantially less corrosion damage than the blank sample more corrosion damage than the blank sample

The results of the tests are shown schematically in Tables 3 to fifth ω

(O

Table 3: Corrosion tests with copolymers with non-derivatized dicarboxylic

O

Table 4: Corrosion tests with copolymers with the derivatized dicarboxylic acid

The examples show that under the present invention use of non-derivatized and derivatized MSA-olefin copolymers to improve the corrosion protection properties of the coil coating paints can be obtained. The improvement occurs on at least on one of the two substrates of aluminum or steel, as a rule will observed on both substrates.

Particularly good results are obtained by using longer chain olefins and using olefins having additional functional groups.

Claims

claims
1. A method for applying integrated pretreatment layers with a thickness of 1 to 25 microns to metallic surfaces at least comprising the steps of
(1) applying a curable composition on the metallic surface, wherein the preparation contains at least
(A) 20 to 70 wt.% Of at least one thermally and / or photochemically crosslinkable binder system (A),
(B) 20 to 70 wt.% Of at least one finely divided inorganic filler having a mean particle size of less than 10 microns,
(C) from 0.25 to 40 wt.% Of at least one corrosion inhibitor, and
(D) optionally a solvent,
includes, with the proviso that the wt.% figures relate to the sum of all components except the solvent, and
(2) thermal and / or photochemical crosslinking of the applied layer,
characterized in that it is in the anti-corrosion agent is at least one copolymer (C), which is built up from the following monomeric structural units:
(d) 70 to 30 mol% of at least one monoethylenically unsaturated hydrocarbon (da) and / or at least one monomer (db) selected from the group of functional groups X 1 modified monoethylenically unsaturated hydrocarbons (d b ') and ethers (db ") .
(C2) 30 to 70 mol% of at least one monoethylenically unsaturated dicarboxylic bonsäure having 4 to 8 C-atoms and / or its anhydride (c2a) and / or derivatives (c2b) thereof,
wherein the derivatives (c2b) esters of dicarboxylic acids with alcohols of the general formula HO-R 1 -X 2 n (I) and / or amides or imides with ammonia and / or amines of the general formula HR 2 NR 1 - X 2 n (II) is, and the abbreviations have the following meanings: R 1: (n + 1) -valent hydrocarbon group having 1 to 40 C atoms, in which non-adjacent C atoms by O and / or N substituted could be,
R 2: -: 1, 2, or 3 H, Cr to Cio hydrocarbon group, or (R 1 -X 2 n) n
X 2: a functional group, and
(C3) 0 to 10 mol% other ethylenically unsaturated monomers which are copolymerizable by (d) and (c2) are different, but with (d) and (c2),
wherein the amounts are each based on the total amount of all monomer units in the co-polymer.
2. The method according to claim 1, characterized in that it is in the metallic surface is the surface of steel, zinc or zinc alloys,
Aluminum or aluminum alloys is.
3. The method according to claim 1, characterized in that it is in the metallic surface is the surface of electrolytically galvanized or hot-galvanized steel.
4. The method according to any of claims 1 to 3, characterized in that it is at the metal surface is the surface of a metal strip, and is carried out the application of the integrated pretreatment layer with a continuous process
5. The method according to claim 4, characterized in that one carries out the coating by means of rolling, spraying or dipping process.
6. The method according to any one of claims 1 to 5, characterized in that the metallic surface is cleaned with the formulation in an additional purification step (0) before coating.
7. The method according to any one of claims 1 to 6, characterized in that one carries out the crosslinking thermally and binder systems selected from the groups of polyesters, epoxy resins, polyurethanes or polyacrylate and at least distillates using an additional crosslinking agent.
8. The method according to claim 7, characterized in that it is the crosslinker is a blocked isocyanate or a reactive melamine resin.
9. The method according to claim 7 or 8, characterized in that one carries out the crosslinking at a temperature of 100 0 C to 250 0 C.
10. The method according to any one of claims 1 to 9, characterized in that the thickness of the integrated pre-treatment layer is 3 to 15 microns.
11. The method according to any one of claims 1 to 10, characterized in that said monomer (c2a) is maleic acid and / or maleic anhydride.
12. The method according to any one of claims 1 to 11, characterized in that the copolymer (C) (da) comprises at least one monomer of the type.
13. The method according to claim 12, characterized in that the monomers (da) are monoethylenically unsaturated hydrocarbons having 6 to 30 carbon atoms.
14. The method according to claim 13, characterized in that the copolymer remains on the amount of all monomers (d) Any artwork least comprising 1 to 60 mol%, based a reactive polyisobutene.
15. The method according to claim 13, characterized in that the copolymer further comprises 1 to 60 mol%, based on the amount of all monomers (d), at least one functional group X 1 modified monoethylenically unsatu- rated hydrocarbon (db 1).
16. The method according to claim 15, characterized in that it concerns with the monomer (d b ') by 10-Undecencarbonsäure.
17. The method according to any one of claims 13 to 16, characterized in that the monoethylenically unsaturated hydrocarbons having 9 to 27 carbon atoms.
18. The method according to any one of claims 1 to 17, characterized in that it is the functional group X 2 is a selected from the group of
-Si (OR 3) 3 (with R 3 = d- to C 6 alkyl), -OR 4, -SR 4, -NR 4 2, COOR 4, - (C = O) R 4, -COCH 2 COOR 4, -CSNR 4 2l - CN, -PO 2 R 4 2, -PO 3 R 4 2, -OPO 3 R 4 2 (with R 4 = H, Ci to Ce alkyl or aryl), or -SO 3 H is.
19. A method according to any one of claims 1 to 17, characterized in that it is the functional group X 2 is a selected from the group consisting of -OH, -SH, -COOH, -CSNH 2, -CN, -PO 3 H 2 , -SO 3 H or salts thereof.
20, molded articles having a metallic surface, which is coated with an integrated pretreatment layer having a thickness of 1 to 25 microns, obtainable by a process according to any one of claims 1 to nineteenth
21. The molding according to claim 20, characterized in that it is in the metallic surface is of steel, zinc or zinc alloys, aluminum or aluminum alloys.
22. The molding according to claim 21, characterized in that the integrated pre-treatment layer is still overcoated with one or more coating layers.
23. The molding according to claim 22, characterized in that it is in the shaped body is an automobile body or body parts.
24. The molding according to claim 22, characterized in that it is in the mold body to components for cladding.
25. Preparation for applying integrated pretreatment layers on metallic surfaces comprising at least the following components:
(A) 20 to 70 wt.% Of at least one thermally and / or photochemically crosslinkable binder system (A), (B) 20 to 70 wt.% Of at least one inorganic particulate filler having a mean particle size of less than 10 microns,
(C) from 0.25 to 40 wt.% Of at least one corrosion inhibitor, and
(D) optionally a solvent,
with the proviso that the wt.% figures relate to the sum of all components except the solvent, and
characterized in that it is in the anti-corrosion agent is at least one copolymer (C), which is built up from the following monomeric structural units:
(d) 70 to 30 mol% of at least one monoethylenically unsaturated hydrocarbon (da) and / or at least one monomer (db) selected from the group of functional groups X 1 modified monoethylenically unsaturated hydrocarbons (d b '), as well as vinyl ethers (db "), (c2) 30 to 70 mol% of at least one monoethylenically unsaturated dicarboxylic bonsäure having 4 to 8 C-atoms and / or its anhydride (c2a) and / or derivatives (c2b) thereof,
wherein the derivatives (c2b) esters of dicarboxylic acids with alcohols of the general formula HO-R 1 -X 2 n (I) and / or amides or imides with ammonia and / or amines of the general formula HR 2 NR 1 - X 2 is n (II), and the abbreviations have the following meanings:
R 1: (n + 1) -valent hydrocarbon group having 1 to 40 C atoms, in which nonadjacent carbon atoms by O and / or N may be substituted,
R 2: H, Cr to Cio-hydrocarbon group, or - (R 1 -X 2 n) n: 1, 2 or 3 X 2: a functional group, and
(C3) 0 to 10 mol% other ethylenically unsaturated monomers different from (d) and (c2) different but with (d) and (c2) acrylates,
wherein the amounts are each based on the total amount of all monomer units in the co-polymer.
EP06707823A 2005-01-28 2006-01-24 Method for applying integrated pre-treatment layers containing dicarboxylic acid olefin copolymers to metallic surfaces Withdrawn EP1844113A2 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE200510004292 DE102005004292A1 (en) 2005-01-28 2005-01-28 Method for applying corrosion protection layer on metallic surfaces comprises treating the surface with a formulation having binding agent, pigment and/or filler and corrosion protecting agent, which is a thioamide group containing compound
DE200510061317 DE102005061317A1 (en) 2005-12-20 2005-12-20 Method for applying integrated pre-treatment layers, comprises applying cross linkable preparation containing e.g. corrosion protection agent, on metallic surface and thermally- and/or photochemically cross linking the layer
PCT/EP2006/050415 WO2006079628A2 (en) 2005-01-28 2006-01-24 Method for applying integrated pre-treatment layers containing dicarboxylic acid olefin copolymers to metallic surfaces

Publications (1)

Publication Number Publication Date
EP1844113A2 true EP1844113A2 (en) 2007-10-17

Family

ID=36147306

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06707823A Withdrawn EP1844113A2 (en) 2005-01-28 2006-01-24 Method for applying integrated pre-treatment layers containing dicarboxylic acid olefin copolymers to metallic surfaces

Country Status (8)

Country Link
US (1) US20080171195A1 (en)
EP (1) EP1844113A2 (en)
JP (1) JP2008528267A (en)
KR (1) KR20070112147A (en)
BR (1) BRPI0607291A2 (en)
CA (1) CA2595969A1 (en)
MX (1) MX2007009083A (en)
WO (1) WO2006079628A2 (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006079627A1 (en) * 2005-01-28 2006-08-03 Basf Aktiengesellschaft Method for applying corrosion protection layers comprising thioamides to metallic surfaces
KR100892192B1 (en) * 2008-01-11 2009-04-07 엘에스엠트론 주식회사 Die attachment adhesive film and resin composition for the same
DE102008059014A1 (en) 2008-05-28 2009-12-03 Basf Coatings Ag A process for coating metal strips
WO2011022395A1 (en) * 2009-08-17 2011-02-24 Berry Plastics Corporation Method of joining pipe segments using an adhesive composition
CN102153690B (en) * 2010-12-20 2013-06-12 广州天赐高新材料股份有限公司 Alternating or random copolymer containing polyquaternium lateral group and preparation method thereof
KR101249046B1 (en) 2010-12-28 2013-03-29 포항공과대학교 산학협력단 Polymer latex, composiotion for metal surface coating, metal complex, preparation method of composiotion for metal surface coating
JP6122387B2 (en) 2011-02-07 2017-04-26 ヴァルスパー・ソーシング・インコーポレーテッド The method of the coating composition as well as coatings for containers and other articles
US9981287B2 (en) 2012-04-18 2018-05-29 The Sherwin-Williams Company Low VOC, water-based coating compositions suitable for protecting metal containing substrates including food and beverage packages
KR20160147736A (en) 2014-04-14 2016-12-23 발스파 소싱 인코포레이티드 Methods of preparing compositions for containers and other articles and methods of using same
RU2655984C1 (en) * 2017-05-11 2018-05-30 Общество с ограниченной ответственностью "Компания Металл Профиль" Coating on the rolled steel application method

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2332202A (en) * 1997-12-09 1999-06-16 Courtaulds Coatings Curable epoxy resin compositions
FR2806089B1 (en) * 2000-03-09 2002-05-24 Atofina Use of a polymer was imidized maleic anhydride base in compositions for the surface treatment or coating and in inks and varnishes
AU2002219609B2 (en) * 2001-01-15 2007-03-15 Unitika Ltd Aqueous polyolefin resin dispersion
EP1715001B1 (en) * 2003-02-24 2008-05-07 Basf Se Polymers containg phosphonic acid / phosphoric acid groups for the treatment of metallic surfaces

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006079628A2 *

Also Published As

Publication number Publication date
JP2008528267A (en) 2008-07-31
WO2006079628A3 (en) 2006-12-07
US20080171195A1 (en) 2008-07-17
CA2595969A1 (en) 2006-08-03
WO2006079628A2 (en) 2006-08-03
BRPI0607291A2 (en) 2010-03-23
KR20070112147A (en) 2007-11-22
MX2007009083A (en) 2007-09-11

Similar Documents

Publication Publication Date Title
EP0952193B1 (en) Agent for treating metallic surface, surface-treated metal material and coated metal material
EP0980408B1 (en) Waterborne coating compositions for metal containers
CN1177952C (en) Surface treatment composition for metallic material and method for treatment
US6248819B1 (en) Thermosetting water-borne coating composition, method of forming a coating film using same, and method of forming a multilayer coating film
JP3865693B2 (en) Aluminum - zinc alloy plated steel sheet treated aqueous resin composition, coating method and an aluminum - zinc alloy plated steel sheet
EP1715001B1 (en) Polymers containg phosphonic acid / phosphoric acid groups for the treatment of metallic surfaces
AU2008225914B2 (en) Method for coating metal surfaces using an aqueous compound having polymers, the aqueous compound, and use of the coated substrates
EP1966411B1 (en) Aqueous dispersions containing ionomer resins and rust-preventive ionomeric coatings made therefrom
US5578669A (en) Water-based polyurethane coating composition
CN1070522C (en) Water borne zinc-rich primer compositions
EP0551568B2 (en) A method of coating a substrate with multiple layers of a coating
EP0787830B1 (en) Chromium-free composition for the treatment of metallic surfaces
CA2572333C (en) Method for the passivation of metal surfaces with polymers containing acid groups
US20030134973A1 (en) Waterborne latexes for anti-corrosive and solvent-resistant coating compositions
JP5377305B2 (en) How passivating metal surfaces using copolymers containing phosphoric and / or phosphonic acid groups and preparations for use therein
JPH06228796A (en) Preparation of multilayer coating
US7879158B2 (en) Nitrogenous polymers for metal surface treatment
US6767413B2 (en) Metal surface treating agent
CA2014539C (en) Water borne metallic coating composition
Athawale et al. Waterborne coatings based on renewable oil resources: an overview
CN1164706C (en) Epoxy ester emulsion and aqueous antirust primer with the said emulsion as base material
KR20030011871A (en) Water-based coating composition for inner surface of can and method of coating inner surface of can
JPH0680906A (en) Corrosion inhibitor
EP2013297B1 (en) Method for the application of corrosion-resistant layers to metallic surfaces
WO2005123849A1 (en) Radiation-curable, electrically conductive coating mixture

Legal Events

Date Code Title Description
AK Designated contracting states:

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

17P Request for examination filed

Effective date: 20070828

RAP1 Transfer of rights of an ep published application

Owner name: BASF SE

DAX Request for extension of the european patent (to any country) deleted
18W Withdrawn

Effective date: 20110516