EP1919970A1 - Polymer composition for corrosion protection - Google Patents

Abstract

The invention relates to a composition for coating metal surfaces, which contains a binding component, a corrosion inhibitor polymer based on an ethylenical mono- and dicarboxylic acid and, optionally, additional ethylenical monomers, a solvent component and, optionally, cross-linked components and pigment/filling components. The invention also relates to methods for the production thereof, and to a method for coating a metal surface with the help of said composition, metal surfaces coated according to said method and to the use of the composition as a base coat, in particular, during coil coating or for atmospheric corrosion protection. After drying, the applied layer has, preferably, a thickness of at least 3,1 ?m and is thicker than a normal pre-treated layer.

Description

Polymer composition for corrosion protection

description

The present invention relates to compositions for coating metallic surfaces, to processes for their preparation and to processes for coating a metallic surface with the aid of the composition, coated metallic surfaces obtainable thereby and the use of the polymer composition.

For the production of flat metal workpieces such as automotive parts, body panels, equipment panels, cladding, ceiling panels or window profiles suitable metal sheets are formed by known techniques such as punching, drilling, folding, profiling and / or deep drawing. Larger components, such as automobile bodies are optionally joined together by welding several items. The raw material for this purpose are usually long metal bands, which are produced by rolling the metal and unwound for storing and transporting into coils (so-called "coils"). The said metallic components must be protected against corrosion as a rule. Especially in the automotive sector, the demands on today's corrosion protection are very high. Newer car types now offer up to 30 years rust prevention warranty. Modern automotive bodies are manufactured in multi-stage processes and have a variety of different layers. In this case, a steel sheet is usually coated in a first step with zinc or a zinc alloy. This can be done galvanically or by immersion in liquid zinc, so-called hot-dip galvanizing. To improve the corrosion resistance of the zinc layer itself, a predominantly inorganic pretreatment layer is subsequently applied. This may be a phosphatization and / or chromating with chromium (VI) or chromium (III) compounds. Chromium and phosphate-free pretreatment layers are also known. The pretreatment layer is also called a conversion layer or passivation layer. It is usually very thin. Typically, the thickness of such a pretreatment layer is well below 1 μm. Typical thicknesses are 2 to 100 nm. In addition to improving the corrosion resistance of the zinc layer, the pretreatment layer should also improve the adhesion between metal and subsequent paint layers. An organic primer is then applied to the pretreatment layer.

This is followed by the actual paint layers. In the case of automobiles, the body is then usually coated with an electrodeposition paint and closing with the so-called filler. The surfacer layer is a comparatively thick, soft layer that is intended to prevent rockfall or the like from destroying the underlying layers. Finally, some or more color coat layers and a clear coat layer are applied to the filler for protection. For other applications, other lacquer layers and / or coating sequences above the base coat are common.

While the anticorrosive treatment in the past has been performed substantially on the finished metallic workpiece such as a welded automobile body, corrosion-inhibiting treatment is increasingly being performed on the band metal itself. Here, at least the pretreatment layer and the organic base coat is already applied to the strip metal (so-called coil coating). Only then are parts punched out, shaped and optionally welded together. Therefore, increased demands are placed on the applied layers, since they are also exposed to punching, forming and welding processes, whereby no quality losses with respect to the layers should occur.

Coil coating is the continuous coating of metal strips with mostly liquid broomsticks, whereby metal strips 0.2 to 2 mm thick and up to 2 m wide are conveyed at speeds of up to 200 m / min For example, cold-rolled strip made of soft steels or structural steels, electrolytically galvanized sheet steel, hot-dip galvanized steel strip, or strips of aluminum or aluminum alloys may be used, typically a feed station, a strip accumulator, a cleaning machine and pretreatment zone, a first coating station together with a baking oven and the following cooling zone, a second coating station with oven, laminating station and cooling as well as a belt store and rewinder.

The coil coating process usually comprises the following process steps:

1. If necessary: Cleaning the metal strip of dirt accumulated during storage of the metal strip and of temporary anticorrosive oils with the aid of cleaning baths.

2. Application of a thin pretreatment layer (<1 μm) by dipping or spraying or by roller coating. This layer is intended to increase the corrosion resistance and serves to improve the adhesion of subsequent paint layers on the metal surface. For this purpose, Cr (VI) -containing, Cr (III) -containing as well as chromate-free pretreatment baths are known.

3. Application of a Primer by Roll Application The dry film thickness is usually around 5 to 8 μm

Solvent-based paint systems used.

4. Application of one or more top coats ("top coat") using the roll application method The dry film thickness here is about 15-25 μm, where solvent-based coating systems are also generally used.

In addition to the coil coating described above as corrosion protection of metals, the metallic material is provided with corrosion protection only in its final form in the case of severe (atmospheric) corrosion protection. These are, for example, steel structures with larger dimensions, such as bridges, metallic components on houses, large-scale industrial plant parts and the like. Due to their size and sometimes also their weight, some coating methods, such as dipping, are not possible. Also, a pretreatment layer is often dispensed with. Nevertheless, in order to obtain a sufficient corrosion protection, thicker primer coating layers are typically applied in comparison to the "coil coating".

In principle, however, a pretreatment layer is also possible here.

As stated above, many compositions for the pretreatment layer are inorganic in nature. To improve the properties of these pretreatment layers, numerous systems have been proposed. Organic systems play an increasingly important role here.

WO-A 2004/074372, for example, describes a solution polymer for the pretreatment whose corrosion inhibition-active component is a copolymer of various ethylenically unsaturated monomer units.

Here, the pretreatment layer should be at most 3 microns.

A comparable system and its production are described in the German patent applications with the application numbers DE-A 10 2004 041 127 and DE-A 10 2004 041 142. Here, a polymer is available as a polymeric corrosion inhibitor from a monoethylenically unsaturated mono- and dicarboxylic acid and optionally further ethylenically unsaturated comonomers used.

To ensure the most flexible possible corrosion protection, which can be used for example in coil coating as well as heavy corrosion protection, it would be desirable to provide corrosion inhibitors as described above not only for the pretreatment layer, but also generally as a corrosion inhibiting additive to coating compositions of metallic surfaces, eg. As paints in general and in particular for the base coat, so z. B. if necessary, could be dispensed with the pretreatment layer such as the atmospheric corrosion protection or to further improve the corrosion protection when using such a pretreatment layer.

It is therefore an object of the present invention to provide a composition useful as a coating of metallic surfaces, e.g. B. can be used as a coating and in particular as a primer while containing a corrosion protection component based on a corrosion inhibitor polymer.

The object is achieved by a composition for coating metallic surfaces see containing

A 15 to 70 wt .-% based on the total weight of the composition of a binder component;

B 0.1 to 40 wt .-% based on the total weight of the composition of a corrosion protection component containing at least one corrosion inhibitor polymer obtainable from the polymerization of at least the monomers of the composition

B1 0.1 to 95 wt .-% based on the total amount of the monomers used to form the corrosion inhibitor polymer of at least one monoethylenically unsaturated monocarboxylic acid;

and at least one monomer selected from B2 and B3, wherein

B2 0.1 to 70 wt .-% based on the total amount of the monomers used to form the corrosion inhibitor polymer of at least one ethylenically unsaturated dicarboxylic acid of the general formula

(HOOC) R ¹ C = CR ² (COOH) (I), and / or R ¹ R ² C = C (- (CH ₂ ) _n -COOH) (COOH) (II),

or the corresponding carboxylic acid anhydrides and / or other hydrolyzable derivatives, wherein R ¹ and R ² independently of one another are H or a straight-chain or branched, optionally substituted alkyl radical having 1 to 20 C atoms, or in the case of (I) R ¹ and R ² together represent an optionally substituted alkylene radical having 3 to 20 carbon atoms, and n represents an integer of 0 to 5;

B3 0.1 to 70% by weight, based on the total amount of monomers used, of forming the corrosion inhibitor polymer of at least one other ethylenically unsaturated comonomer other than B1 and B2;

C 5 to 84.9 wt .-% based on the total weight of the composition of a solvent component;

D 0 to 30 wt .-% based on the total weight of the composition of a crosslinkable component;

E 0 to 70 wt .-% based on the total weight of the composition of a

Pigment / filler.

F optionally further components.

It was surprisingly found that the composition described above, in which hitherto the corrosion protection component B was used only for a pretreatment layer for corrosion inhibition of metal surfaces, as coating of metallic surfaces, eg. B. as a paint and especially as a primer and can be used accordingly. It was additionally surprising that a corrosion-inhibiting effect is ensured by a layer consisting of the composition according to the invention which, after drying, has a thickness of at least 3.1 .mu.m.

The metallic surface can be a surface of sheets, foils, plates and in particular metal strips, but also building constructions, scaffoldings, bridges or the like, as is the case with atmospheric corrosion protection. The metallic surface may furthermore be surfaces of shaped articles which can be used, for example, for cladding, veneering or lining. Examples include automobile bodies or parts thereof, truck bodies, frames for bicycles such as motorcycle wheels or bicycles or parts for such vehicles such as fenders or panels, linings for household appliances such as washing machines, dishwashers, clothes dryers, gas and electric stoves, microwave ovens, freezers or refrigerators , Cladding for technical equipment or facilities such as machinery, cabinets, computer cases or the like, building elements in the architectural sector such as wall parts, facade elements, ceiling elements, window or door profiles or partitions, furniture made of metallic materials such as metal cabinets, metal shelves, parts of furniture or Forged. Furthermore, it may also be hollow body for storage of liquids or other substances, such as cans, cans or tanks.

The starting material for the coating can also be a metallic semi-finished product. The term "semifinished product" is in a manner known in principle for prepared or prepared raw materials for production, which are usually present in larger dimensions. As a rule, these are exclusively semi-finished metal. It may be a single-layer material or a material in which several layers of different metals follow one another.

The term "semi-finished metal product" is also intended to include composite materials which have at least one metallic surface and in which at least one metallic layer is connected to at least one non-metallic layer. For example, it can be a metal foil connected to a plastic film.

The metals, in particular the metal sheets or strips, may, for example, be iron or steel, zinc, magnesium, aluminum, tin, copper or alloys of these metals with one another or with other metals. The steels can be both low-alloyed and high-alloyed steels.

They are preferably materials with metallic surfaces of zinc or zinc alloys or aluminum or aluminum alloys and tin. In particular, it may be the surface of galvanized iron or steel. In a preferred embodiment, it is the surface of a band metal, in particular bands of electrolytically galvanized or hot-galvanized steel. Of course, the term "galvanized" or "aluminized" also includes coating with zinc or aluminum alloys. Suitable alloys for coating metal strips are known to the person skilled in the art. Depending on the desired application, the person skilled in the art selects the type and quantity of alloy constituents. Typical constituents of zinc alloys include in particular Al, Mg, Pb, Fe, Mn, Co, Ni, Si, Mg, Sn, Cu or Cd, preferably Al and / or Mg. It may also be Al / Zn alloys, in Al and Zn are present in approximately the same amount. The coatings may be substantially homogeneous coatings or also coatings with concentration gradients. For example, it can be galvanized steel, which was additionally vapor-deposited with Mg. As a result, a surface zinc / Mg alloy can arise. Steel coated with the described alloys is commercially available. In particular, typical constituents of aluminum alloys include Mg, Mn, Si, Zn, Cr, Zr, Cu or Ti. Of course, the metallic surfaces to be treated may also have thin oxide / hydroxide and / or carbonaceous surface layers or layers of similar construction. Such layers usually form on metallic surfaces in contact with the atmosphere alone and are included in the term "metallic surface".

The metallic surface can also be protected against corrosion. For example, it may be oiled with anticorrosive oils, have a temporary anticorrosive coating or be provided with a peelable protective film. Of course, combinations of these measures are possible. If protective films are present, these are generally removed before coating with the composition according to the invention. Temporary coatings and / or oils can also be removed if necessary.

The composition according to the invention for coating the metallic surfaces contains several components.

Binder component A

The binder component may consist of one or more binders. In general, the person skilled in the art knows which binders are suitable. Particularly suitable binders for use in coil coating are, for example, (meth) acrylate (co) polymers, partially saponified polyvinyl esters, polyesters, alkyd resins, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, polyamides, polyimides or polyurethanes , Of course, mixtures can also various polymers are used, provided that there are no unwanted effects by the mixture.

The binder component A hereinafter referred to in principle known manner those proportions of the composition (formulation), which are responsible for the film formation. They form a polymeric network during thermal and / or photochemical curing. They include thermally and / or photochemically crosslinkable components. The crosslinkable components may be low molecular weight, oligomeric or polymeric. They usually have at least two crosslinkable groups. Crosslinkable groups can be either reactive functional groups that can react with groups of their type ("with themselves") or with complementary, reactive functional groups. In this case, different combination possibilities are conceivable in a manner known in principle. The binder system may comprise, for example, a self-crosslinkable polymeric binder and one or more low molecular weight or oligomeric crosslinkers (V). Alternatively, the polymeric binder itself can have crosslinkable groups which can react with other crosslinkable groups on the polymer and / or on an additionally used crosslinker. It is also particularly advantageous to use oligomers or prepolymers containing crosslinkable groups which are crosslinked to one another using crosslinkers.

Thermally crosslinkable or curing binder systems crosslink on heating the applied layer to temperatures above room temperature. Such lacquer systems are also referred to by the person skilled in the art as "stoving lacquers." They have crosslinkable groups which do not react at room temperature or at least not at a substantial rate but only at relatively high temperatures at temperatures above 60 ° C, preferably 80 ⁰ C, more preferably 100 ⁰ C and more preferably cross-link 120 ° C. Advantageously, such binder systems are used, which at 100 to 250 ⁰ C, preferably 120 to 220 ° C and more preferably at 150 to 200 ° C crosslink.

Preference is given to using polyester or epoxy resins or epoxy resin-amine adducts. Suitable polyesters are, in particular, condensates of low molecular weight dicarboxylic acids and dialcohols. Examples of suitable dicarboxylic acids include aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, aliphatic-aliphatic such as dimer fatty acids, ie reaction products of unsaturated fatty acids with each other, cycloaliphatic dicarboxylic acids such as 1,4- or 1,3-cyclohexanedicarboxylic acid, tricyclodecanedicarboxylic acid and aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid or phthalic acid. Of course, it is also possible to use derivatives of dicarboxylic acids. Particularly suitable are anhydrides such as phthalic anhydride, hexahydrophthalic anhydride or tetrahydrophthalic anhydride.

Examples of suitable dialcohols include aliphatic alcohols, such as, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-butanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1-methylpropanediol 1, 3, 2 Butyl 2-ethylpropanediol, pentanediols, hexanediols, octanediols, dodecanediol, Hydroxy-pivalinsäureneo- pentylglykolester, cycloaliphatic alcohols such as 1,4- or 1, 3-cyclohexanedimethanol, TCD-alcohol and bis (4-hydroxycyclohexyl) methane or -propane and dimer diols (hydrogenated dimer fatty acids). It is of course also possible in a known manner to use derivatives of alcohols, for example esters, in particular the corresponding methyl or ethyl esters.

In addition to linear binders and branched binders can be used. Suitable monomers for producing branching include tricarboxylic acids or their anhydrides, such as trimellitic anhydride or trimesic acid, and trialcohols, such as trimethylolalkanes, for example trimethylolethane or trimethylolpropane.

The polyesters may preferably be reacted completely or partially with isocyanate-terminated polyesters by reaction with polyisocyanates.

The OH number of the polyesters used is usually about 10 to about 200 mg KOH / g, preferably 15 to 120 mg KOH / g, more preferably 20 to 80 mg KOH / g and for example about 50 mg KOH / g. The molecular weights are usually from 400 to 10,000 g / mol, preferably from 500 to 5000 g / mol and more preferably from 1000 to 4000 g / mol.

Epoxy-functional polymers can be prepared by the reaction of epoxy-functional monomers such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether or hexanediol diglycidyl ether with phenols such as bisphenol A, bisphenol F and / or alcohols such as ethoxylated or propoxylated bisphenol A. epoxy-functional Polymers are commercially available, for example under the name Epon ^® or Epikote ^®.

Epoxide resin-amine adducts can be obtained by reaction of said epoxy-functional components with phenols or aliphatic or cycloaliphatic dicarboxylic acids, acidic polyesters or alcohols, thiols and amines, especially secondary amines such as diethanolamine or N-methylbutanolamine.

Furthermore, emulsion polymers can also be used. These are particularly suitable for water-based formulations. Examples of suitable emulsion polymers or copolymers include acrylate dispersions obtainable in the usual manner from acrylic acid and / or acrylic acid derivatives, for example acrylic esters and / or styrene. Also suitable are dispersions of polyurethanes prepared from aromatic and / or aliphatic diisocyanates and polyesters or aliphatic soft segments.

In particular for thermosetting systems, binder systems based on polyesters, epoxy resins, polyurethanes or acrylates may preferably be used to carry out the invention.

Binder based on polyesters can be constructed in a manner known in principle from low molecular weight dicarboxylic acids and dialcohols and optionally other monomers. Further monomers include in particular branching monomers, for example tricarboxylic acids or trialcohols. For use in coil coating, polyesters having a comparatively low molecular weight are generally used, preferably those having M _{n of} from 500 to 10 000 g / mol, preferably from 1000 to 5000 g / mol and more preferably from 2000 to 4000 g / mol.

The hardness and flexibility of the polyester-based layers can be influenced in a manner known in principle by the selection of "hard" or "soft" monomers. Examples of "hard" dicarboxylic acids include aromatic dicarboxylic acids or their hydrogenated derivatives such as, for example, isophthalic acid, terephthalic acid, phthalic acid, hexahydrophthalic acid or derivatives thereof, in particular their anhydrides or esters Examples of "soft" dicarboxylic acids include in particular aliphatic α, ω-dicarboxylic acids having at least 4 C 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 1, ω-dialcohols having at least 4 C 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 one "soft" monomer.

Polyester for coatings are commercially available. Details of polyesters are shown, 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 on an organic or aqueous basis. Epoxy-functional polymers can be prepared in a manner known in principle by the reaction of epoxy-functional monomers such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether or hexanediol diglycidyl ether with alcohols such as, for example, bisphenol A or bisphenol F. Particularly suitable soft segments are polyoxyethylene and / or polyoxypropylene segments. These can be advantageously incorporated by the use of ethoxylated and / or propoxylated bisphenol A. The binders should preferably be chloride-free. Epoxy-functional polymers are commercially available, for example under the name Epon ^® or Epikote ^®. Details of epoxy-functional polymers are shown, for example, in "Epoxy Resins" in Ullmann's Encyclopedia of Industrial Chemistry, 6 ^th Edt., 2000, Electronic Release

The epoxy-functional binders can also be further functionalized. As already mentioned above, epoxy resin-amine adducts can be obtained, for example, by reaction of said epoxy-functional polymers with amines, in particular secondary amines such as, for example, 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 acrylate dispersions, obtainable in a conventional manner from acrylic acid and / or acrylic acid derivatives, for example acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate or 2-ethylhexyl (meth) acrylate and / or vinylaromatic monomers such as styrene and optionally crosslinking monomers. The hardness of the binder can be adjusted by the skilled worker in a manner known in principle by the ratio of "hard" monomers such as styrene or methmethacrylate and "soft" monomers such as butyl acrylate or 2-ethylhexyl acrylate. Particularly preferred for the preparation of acrylate dispersions continue to be monomers used which have functional groups which can react with crosslinkers. These may in particular be OH groups. OH groups can be generated by the use of monomers such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate or N- Methylolacrylamide or also of epoxy acrylates followed by hydrolysis in the Polyac- rγlate be incorporated. 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 a manner known in principle by incorporating ionic and / or hydrophilic segments in order to stabilize the dispersion in the PU chain. As soft segments, preferably 20 to 100 mol%, based on the amount of all diols, of higher molecular weight diols, preferably polyester diols, having a M _n of about 500 to 5000 g / mol, preferably 1000 to 3000 g / mol can be used. Polyurethane dispersion which contain bis (4-isocyanatocyclohexyl) methane as isocyanate component can be used to particular advantage for carrying out the present invention. Such polyurethane dispersions are disclosed, for example, in DE-A 199 14 896. Suitable polyurethane dispersions are commercially available.

Suitable crosslinkers (V) for thermal crosslinking are known in principle to the person skilled in the art.

Suitable crosslinking agents are, for example, based on epoxides in which two or more epoxy groups are linked together by means of a linking group. Examples include low molecular weight compounds having two epoxy groups such as hexanediol diglycidyl ether, phthalic acid diglycidyl ether or cycloaliphatic compounds such as 3,4-Epoxicyclohexancarbonsäure 3 ', 4'-epoxycyclohexylmethylester.

Also suitable as crosslinking agents are highly reactive melamine derivatives, such as, for example, hexamethylolmelamine or corresponding etherified products, such as hexamethoxymethylmelamine, hexabutoxymethylmelamine or also, if appropriate, modified aminoplast resins. Such crosslinkers are commercially available, for example as Luwipal ^® (Fa. BASF AG).

Particularly preferred for carrying out the invention are blocked polyisocyanates used as crosslinking agents. In blocking, the isocyanate group is reversibly reacted with a blocking agent. The blocking agent is split off again when heated to higher temperatures. Examples of suitable blocking agents are disclosed in DE-A 199 14 896, column 12, line 13 to column 13, line 2. Particular preference may be given to using ε-caprolactam blocked polyisocyanates. To accelerate the crosslinking, suitable catalysts can be added to the formulations in a manner known in principle.

Depending on the binder used and the desired result, the person skilled in the art makes a suitable choice among the crosslinkers. Of course, mixtures of different crosslinkers can be used, provided that the properties of the layer are not adversely affected. The amount of crosslinker may advantageously be 10 to 35% by weight relative to the total amount of the binder.

The crosslinking of the epoxy-functional polymers can be carried out, for example, with crosslinkers based on polyamines, for example diethylenetriamine, amine adducts or polyaminoamides. Crosslinking agents based on carboxylic anhydrides or the already mentioned crosslinkers based on melamine are advantageous, for example. Preference is given in particular to the already mentioned blocked polyisocyanates.

For thermal crosslinking of the acrylate dispersions, it is possible to use, for example, the already mentioned crosslinkers based on melamine or blocked isocyanates. Furthermore, epoxy-functional crosslinkers are also suitable.

For the thermal crosslinking of polyurethane dispersions or polyesters, it is possible, for example, to use the already mentioned crosslinkers based on melamine, blocked isocyanates or epoxy-functional crosslinkers.

The binder component A comprises photochemically crosslinkable groups, especially in the case of photochemically crosslinkable compositions. The term "photochemical crosslinking" is intended to include crosslinking with all types of high-energy radiation, such as, for example, UV, VIS, NIR or electron radiation, and may in principle involve all types of photochemically crosslinkable groups, but is preferably ethylenically unsaturated Groups.

Photochemically crosslinkable binder systems generally comprise oligomeric or polymeric compounds with photochemically crosslinkable groups and optionally also reactive diluents, generally monomers. Reactive thinners have a lower viscosity than the oligomeric or polymeric crosslinkers, and therefore play the role of thinner in a radiation-curable system. For photochemical crosslinking, such binder systems furthermore generally comprise one or more photoinitiators. Examples of photochemically crosslinkable binder systems include, for example, multifunctional (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, epoxy (meth) acrylates, carbonate (meth) acrylates, polyether (meth) acrylates, if appropriate in combination with reactive diluents such as Methyl (meth) acrylate, butanediol diacrylate, hexanediol diacrylate or trimethylolpropane triacrylate. More details on suitable radiation-curable binders are shown in WO 2005/080484 page 3, line 10 to page 16, line 35. Suitable photoinitiators can be found in the said document page 18, line 8 to page 19, line 10.

Of course, binder systems which can be thermally and photochemically cured (also known as dual-cure systems) can also be used to carry out the present invention.

The composition of the invention contains 15 to 70 wt .-% of the binder component A. In particular, for the coil coating 20 to 70 wt .-% are suitable. The weight percentages are based on the total weight of the composition according to the invention. The proportion by weight is preferably from 30 to 60% by weight and more preferably from 40 to 50% by weight.

In particular for the atmospheric corrosion protection, the binder components A curable under atmospheric conditions may be the binder systems customary in the field of anticorrosive coatings and coatings. Such binders or binder systems are known in principle to the person skilled in the art. Of course, it is also possible to use mixtures of different binder systems, provided that the mixture does not have any undesired effects.

In the following, the term "binder system" designates, in a manner known in principle, those components of the composition (formulation) which are responsible for the formation of the image.

The term "curable under atmospheric conditions" means that the binder systems have the property, after application to the surface, to cure under normal ambient conditions, eg, at room temperature, in the presence of air and ordinary humidity, without the use of additional equipment or equipment Depending on the environment, they are more than 0 to 40 ° C., preferably 5 to 35 ° C. and, for example, 15 to 25 ° C. It is clear to the person skilled in the art that the time until the complete curing of the same binder system depends on the actual binder Ambient conditions may be different. Depending on the type of binder system used, the curing can proceed according to various mechanisms. For example, it may be a purely physical curing, caused by the evaporation of the solvent used. It may also be an oxidative cure by reaction of the binder system with the oxygen of the air. Finally, it can also be a chemical crosslinking (reactivity). Reactive binder systems include crosslinkable components. The crosslinkable components may be low molecular weight, oligomeric or polymeric. These may preferably be 1K or 2K systems. Reactive crosslinking systems also include moisture-curing binder systems in which the humidity acts as a hardener component. Of course, a binder system can also cure by a combination of different curing methods. In 2-component systems, the binder and hardener components are mixed in a manner known in the art prior to use of the formulation.

For carrying out the invention, aqueous-soluble or organic-soluble binder systems can be used. They are preferably water-based binder systems.

Binder systems for anticorrosion coatings, in particular anticorrosive systems based on water, are known in principle to the person skilled in the art. These may be, for example, epoxy resins, polyacrylates, styrene-acrylate polymers, polyesters, alkyd resins, polyurethanes of the styrene-butadiene polymers.

The amount of binder A in the formulation is 15 to 70% by weight, based on the amount of all components of the formulation including the solvent. It is determined by the skilled person depending on the desired properties of the coating. The amount, in particular for the atmospheric corrosion protection agent, is preferably from 20 to 60% by weight and more preferably from 25 to 50% by weight.

Preferred binder systems for atmospheric corrosion protection are described below.

Polyacrylates or Styrene-Acrylate Copolymers (A1)

In a preferred embodiment of the invention, the binder system is an aqueous or predominantly aqueous dispersion of polyacrylates or styrene-acrylate copolymers (A1). Aqueous dispersions of polyacrylates or styrene-acrylate copolymers (A1) for the preparation of anticorrosive coatings are known in principle to the person skilled in the art. The aqueous dispersions of the polyacrylates (A1) may be both primary dispersions and secondary dispersions. Suitable polyacrylates contain as main monomers at least one alkyl (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate or 2-ethylhexyl (meth) acrylate. They may preferably have, as further main monomers, vinylaromatics, in particular styrene. The amount of the main monomers together is generally at least 60% by weight, preferably at least 80% by weight. In addition to the stated alkyl (meth) acrylates as main monomer, styrene-acrylate copolymers generally comprise at least 30% by weight, preferably at least 40% by weight and more preferably about 50% by weight of styrene. The polyacrylates or styrene-acrylate copolymers (A1) may additionally comprise further comonomers, in particular those with functional groups such as hydroxyl, carboxy or carboxamide groups. Examples include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, (meth) acrylamide or hydroxyalkyl (meth) acrylates. Other comonomers are preferably acidic comonomers. Furthermore, optionally also crosslinking monomers in small amounts, usually less than 4 wt.%, Preferably less than 2 wt.%, To be present. Examples include butanediol (meth) acrylate, hexanediol di (meth) acrylate or allyl acrylate.

Polyacrylates (A1) can be prepared in a manner known in principle by means of emulsion polymerization. Further details of such polymers and their preparation are disclosed, for example, in EP-A 157 133, WO 99/46337, or in "Paints and Coatings, 2.5.Acrylic Coatings" in Ullmann's Encyclopedia of Technical Chemistry, 6th Edition 2000, Electronic Release. The person skilled in the art makes a suitable choice of the polyacrylates (A1) which are possible in principle, depending on the desired properties of the layer.

Particularly suitable for carrying out the invention in the field of atmospheric corrosion protection are styrene-acrylate copolymers which contain as main monomers at least one elastomeric acrylate such as, for example, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl acrylate or 2- Ethylhexyl (meth) acrylate in admixture with styrene and as a minor monomer at least one acidic monomer, such as (meth) acrylic acid. For use as binders for the formulation, the acid groups may be wholly or partially neutralized with suitable bases such as ammonia.

The polyacrylates used should as a rule have a glass transition temperature T ₉ in the range from 0 to 60 ^° C., preferably in the range from 5 to 40 ^° C. (measured according to the DSC method according to DIN EN ISO 11357). The glass transition temperature can be selected by the person skilled in the art in a manner known in principle by the choice and the quantitative ratio of hard and soft monomers.

Are preferred for practicing the invention can also polyacrylates (A1) nm with an average particle size of 50 nm to 400, particularly preferably 80 nm to 250 nm (as measured by the Malvern ^® Autosizer 2 C).

Suitable acrylate or styrene-acrylate dispersions for the production of corrosion protective coatings are available commercially, for example as Acronal ^® S 760 or Acronal ^® LR 8977 (Fa. BASF Aktiengesellschaft) or Acronal ^® Optive 410 (Fa. BASF Corporation).

Styrene-alkadiene polymers (A2)

In a second preferred embodiment of the invention, the binder system is an aqueous or predominantly aqueous dispersion of styrene-alkadiene polymers (A2).

Aqueous dispersions of styrene-alkadiene polymers (A2) for the preparation of anticorrosive coatings are known in principle to those skilled in the art and are described, for example, in EP-A 47380. It may preferably be primary dispersions but also secondary dispersions.

Suitable polymers (A2) comprise as main monomers styrene and at least one conjugated aliphatic diene (alkadiene). The alkadienes may, for example, be butadiene, isoprene, 1,3-pentadiene or dimethylbutadiene. The styrene can also be substituted with alkyl groups. Examples include α-methylstyrene or 4-methylstyrene. Preferably, the main monomers are styrene and butadiene. In general, the polymers contain at least 20% by weight of styrene and 20% by weight of alkadienes, the amount of the main monomers together being generally at least 60% by weight, preferably at least 80% by weight. The quantities are in each case based on the sum of all monomers. You may also have other comonomers. On the one hand, mention may be made here of ethylenically unsaturated carboxylic acids and / or disaccharides such as, for example, (meth) acrylic acid, maleic acid or itaconic acid. They may also be ethylenically unsaturated carboxylic acid nitriles such as (meth) acrylonitrile and also alkyl (meth) acrylates such as methyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl acrylate or 2-ethylhexyl (meth) acrylate act. Styrene-alkadiene polymers (A2) can be prepared in a manner known in principle by means of emulsion polymerization. Further details of styrene-butadiene polymers for coating materials and their preparation are disclosed, for example, in "Paints and Coatings, 2.4.8. Polystyrene and Styrene Copolymers" in Ullmann's Encyclopaedia of Technical Chemistry, 6th Edition 2000, Electronic Release.

Particularly suitable for carrying out the invention are styrene-butadiene polymers which comprise as minor monomer one or more acidic monomers, such as, for example, (meth) acrylic acid, preferably in an amount of from 0.5 to 5% by weight. For use as binders for the formulation, the acid groups may preferably be neutralized completely or partially with suitable bases such as, for example, ammonia.

The styrene-butadiene polymers (A2) used should as a rule have a glass transition temperature T ₉ in the range from 0 to 60 ^° C., preferably in the range from 5 to 40 ^° C. The glass transition temperature can be selected by a person skilled in the art in a manner known in principle by the selection and the ratio of hard and soft monomers.

Styrene-butadiene polymers (A2) having an average particle size of from 50 nm to 400 nm, more preferably from 80 nm to 250 nm, may also be used to carry out the invention.

Polyurethanes (A3)

In a third, preferred embodiment of the invention, the binder system, in particular for atmospheric corrosion protection, is an aqueous or predominantly aqueous dispersion of polyurethanes (A3).

Aqueous dispersions of polyurethanes (A3) for the preparation of corrosion protection coatings are known in principle to the person skilled in the art. Details of polyurethanes for coating materials and their preparation are disclosed, for example, in "Paints and Coatings, 2.9 Polyurethane Coatings in" Ullmann's Encyclopedia of Technical Chemistry, 6th Edition 2000, Electronic Release The aqueous dispersions of polyurethanes (A3) can be both primary dispersions how to act on secondary dispersions.

Polyurethanes for aqueous dispersions can be synthesized in a manner known in principle from customary diisocyanates and diols. With regard to good film formation and elasticity, diols with a number average in particular are used for this purpose Molecular weight M _n of about 500 to 5000 g / mol, preferably about 1000 to 3000 g / mol in question. Both polyether and polyester diols can be used for this purpose. The amount of such higher molecular weight diols is usually 10 to 100 mol% with respect to the sum of all diols. The desired hardness and elasticity of the film can be controlled by using, in addition to the diol already mentioned, low molecular weight diols with a number average molecular weight M _n of about 60 to 500 g / mol.

In order to build up polyurethanes for aqueous dispersions, moreover, monomers are used which comprise at least one isocyanate group or an isocyanate-reactive group and additionally at least one hydrophilic group. These may be nonionic groups such as, for example, polyoxyethylene groups, acidic groups such as COOH, sulfonate or phosphonate groups or basic groups such as amino groups. They are preferably acidic groups. For use as binders for the formulation, the acid groups may preferably be neutralized in whole or in part with suitable bases. Preferred for this purpose are ammonia or amines. Further details of such polyurethane dispersions and their preparation are described in detail in WO 2005/005565, page 4, line 13 to page 14, line 14. Further examples of suitable polyurethanes are disclosed in US 5,707,941 or in WO 2004/101638, in particular page 2, line 31 to page 14, line 11.

It may also be modified polyurethanes. For example, it may be oxidatively curing urethane alkyds. For example, triglycerides of unsaturated fatty acids can be partially hydrolyzed for production. The resulting OH group can react with the isocyanate groups in polyurethane production.

Polyurethanes (A3) having an average particle size of not more than 1000 nm, preferably less than 500, particularly preferably less than 200 nm, and in particular 20 to 200 nm, may furthermore be used to carry out the invention.

Alkyd resins (A4)

In a fourth, preferred embodiment of the invention, the binder system, in particular for the atmospheric corrosion protection, is an aqueous or predominantly aqueous dispersion of alkyd resins (A4).

Aqueous dispersions of alkyd resins (A4) for the preparation of corrosion protection coatings are known in principle to the person skilled in the art. Alkyd resins (A4) are oxidative curing polycondensation of polyols and polybasic carboxylic acids in which at least one OH group of the polyol is esterified with fatty oils and / or natural and / or synthetic mono- or polyunsaturated fatty acids, wherein at least one of the polyols used tri- or höherfunktio- have to be.

Examples of preferred polyhydric alcohols include glycerol, pentaerythritol, t-methylolethane, trimethylolpropane, various diols such as ethane / propanediol, diethylene glycol, neopentyl glycol.

Preferred polybasic carboxylic acids are phthalic acid (anhydride) (PSA), isophthalic acid, terephthalic acid, trimellitic anhydride, adipic acid, azelaic acid, sebacic acid, particularly preferably phthalic acid (anhydride).

As the oil component or fatty acid, for example, drying oils such as linseed oil, oiticica oil or wood oil, semi-drying oils such as soybean oil, sunflower oil, safflower oil, ricinoleic or tall oil, non-drying oils such as castor oil, coconut oil or peanut oil or free fatty acids of the above oils consideration.

The molecular weight M _{n of} typical alkyd resins is between 1500 and 20 000 g / mol, preferably between 3500 and 6000 g / mol. The acid number is preferably 2 to 30 mg KOH / g, with water-dilutable resins also 35-65 mg KOH / g. The OH number is generally up to 300, preferably up to 100 mg KOH / g.

The term "alkyd resins" is also intended to include modified alkyd resins such as styrene-modified alkyd resins, urethane alkyds, urethane oils or epoxy resin-modified alkyd resins Such modified alkyd resins are known to those skilled in the art.

Further details of alkyd resins (A4) for coating materials and their preparation are described, for example, in "Paints and Coatings, 2.6. Alkyd Coatings" in Ullmann's Encyclopedia of Technical Chemistry, 6th Edition 2000, Electronic Release and in "Paint Formulation and Paint Formulation", ed. Ulrich Zorll, p. 188 et seq., Curt R. Vinzentz Verl., Hanover, 2003.

The alkyd resins (A4) used should as a rule have a glass transition temperature T ₉ in the range from 0 to 60 ^° C., preferably from 5 to 40 ^° C.

As binder component A, other binders or exclusively binders based on waxes can be used in addition to the already mentioned binders. Again, the wax is preferably in dispersed finely divided form.

The term "wax" is known to the person skilled in the art and is described, for example, in Römpp-Lexikon "Paints and printing inks", Georg Thieme Verlag, Stuttgart, New York 1998, p. 615/616 or "Ullmann's Encyclpedia, 6th Edition, Electronic Release; Waxes; 1.2. The person skilled in the art also includes PTFE waxes here, even though they are actually not waxes in the sense of the definition (see, for example, Römpp, pages 466/467) The term "wax" encompasses both the actual wax and the wax Formation of a wax dispersion optionally used adjuvants. The person skilled in waxes for use in aqueous dispersions are known, and he makes a suitable choice.

Preferred waxes are oligomeric or polymeric substances which have a molecular weight greater than 200 g / mol, preferably greater than 400 g / mol, and which have a weight fraction of more than 60% by weight of structural elements selected from the group of

• (-CH ₂ -CH ₂ -)

• (-CH ₂ -CH * :) • (-CH ₂ -CH (CH ₃ ) -)

• (-CH ₃ )

• (CR ₂ -CR ₂ ) and (CR ₂ -CR (CR ₃ ))

where R is H and / or F, and provided that said structural elements are joined together to predominantly comprise units of at least 12 directly linked carbon atoms. Of course, a mixture of different waxes can be used.

The waxes may also have acid functions, in particular carboxylic acid groups which may be neutralized or unneutralized. Waxes with one

Acid number <200 mg KOH / g are preferred. Particularly preferred is an acid number of 3 to 80 mg KOH / g. Waxes having a melting point are preferred.

Particularly preferred is a melting point of 40 to 200 ⁰ C. In particular, is a

Melting point of 60 to 120 ° C is preferred.

Examples of suitable waxes for carrying out the present invention include

[CAS numbers in square brackets]:

• polyethylene wax [9002-88-4] • paraffin wax [8002-74-2] • montan wax and montan wax raffinates, for example [8002-53-7]

• Polyethylene-polypropylene waxes

• polybutene waxes

• Fischer-Tropsch waxes • Camauba wax

Oxidized waxes, for example oxidized polyethylene wax according to [68441-17-8]

Copolymeric polyethylene waxes, for example copolymers of ethylene with acrylic acid, methacrylic acid, maleic anhydride, vinyl acetate, vinyl alcohol for example [38531-18-9], [104912-80-3], [219843-86-4] or copolymers of the

Ethylene with several of these monomers

Polar modified polypropylene waxes, for example [25722-45-6]

Microcrystalline waxes, for example microcrystalline paraffin waxes [63231-60-7] montan acids, for example [68476-03-9]

• Metal salts of montan acids, for example sodium salts [93334-05-5] and calcium salts [68308-22-5]

• esters of long-chain carboxylic acids with long-chain alcohols, for example octadecyl stearate [2778-96-3] • montanic acid esters of polyhydric alcohols, for example o montan wax glycerides [68476-38-0], also partially hydrolyzed o montanic acid esters of trimethylolpropane [73138-48-4], also partially saponified o montanic acid ester of 1,3-butanediol [73138-44-0], also partially saponified o montanic acid ester of ethylene glycol [73138-45-1], also partially saponified

Montan wax ethoxylates, for example [68476-04-0]

Fatty acid amides, for example erucamide [112-84-5], oleamide [301-02-0] and 1,2-ethylenebis (stearamide) [110-30-5]

Long-chain ethers, for example octadecylphenyl ether.

Furthermore, mixtures of waxes are suitable, for example

• mixtures of octadecyl stearate and partially hydrolyzed montanic acid esters of polyhydric alcohols • mixtures of paraffin waxes and partially hydrolyzed montanic acid esters of polyhydric alcohols and / or montanic acids

• Blends of polyethylene wax and polyethylene glycol.

Particularly preferred waxes are those which, because of their delivery state, are particularly easy to incorporate into the formulation for the process according to the invention such as micronized waxes and / or wax dispersions.

Micronized waxes are particularly finely divided powders having an average particle size of preferably less than 20 .mu.m, particularly preferably from 2 to 15 .mu.m. Wax dispersions are aqueous preparations of waxes which contain water, optionally further water-miscible solvents, spherical wax particles and, as a rule, auxiliaries. Preferred wax dispersions for use in the present invention have a particle size below 1 μm, preferably 20 to 500 nm, particularly preferably 50 to 200 nm. Micronized waxes and finished wax dispersion are commercially available.

Auxiliaries are used in wax dispersions, for example, to ensure the dispersibility of the wax and its storage stability. The auxiliaries may be, for example, bases for the neutralization or partial neutralization of acid functions in the wax, for example alkali metal hydroxides, ammonia, amines or alkanolamines. Acid groups can also be neutralized or partially neutralized with cations, for example Ca ⁺⁺ or Zn ⁺⁺ . Furthermore, they can be surface-active substances, preferably nonionic surfactants or anionic surfactants. Examples of nonionic surfactants include ethoxylates and propoxylates based on alcohols and hydroxyaromatics and their sulfation and sulfonation products. Examples of anionic surfactants include alkylsulfonates, arylsulfonates and alkylarylsulfonates.

Particularly suitable for carrying out the present invention are wax dispersions having a pH of less than 7, preferably having a pH of less than 6.

Other useful binders for binder component A are disclosed in US-B 6,403,826.

The binder component A may further contain silanes, as disclosed in WO-A 01/07679. Here are described of the formula XR ²² Si (OR ²¹ J ₃ silanes wherein each R ²¹ is selected from the group consisting of hydrogen, Ci _-6 alkyl, and C _2-6 alkanoyl; R ²² is a Ci.io-alkanediyl, optionally substituted with hydroxyl, amine or thiol groups and / or interrupted by an amine, ether or thioether bridge and X is a reactive group selected from the group consisting of NH ₂ - glycidoxy, - (meth) acryloyloxy, -vinyloxy, thiol and Urea is.

Corrosion protection component B The corrosion protection component B may contain one or more corrosion inhibitors. However, it contains at least one corrosion inhibitor polymer obtainable from the polymerization with at least the monomer B1 and at least one monomer selected from B2 and B3.

Preferably, the polymerization is carried out only with the monomers B1, B2, or B1, B3 or B1, B2, B3. In particular, it is preferably a terpolymer of the monomers B1, B2 and B3.

The monomer B1 is at least one monoethylenically unsaturated monocarboxylic acid. Of course, mixtures of several different ethylenically unsaturated monocarboxylic acids can also be used.

Examples of suitable monoethylenically unsaturated monocarboxylic acids B1 include acrylic acid, methacrylic acid, crotonic acid, vinylacetic acid or C 1 -C ₄ monoesters of monoethylenically unsaturated dicarboxylic acids. Preferred monomers are acrylic acid and methacrylic acid, particularly preferred is acrylic acid.

There are used 0.1 to 95 wt .-% of the monomer B1, in particular 30 to 70 wt .-%, wherein the amount is based on the total amount of all monomers used for the formation of the corrosion inhibitor polymer. Preferably, 40 to 65 wt .-% of the monomer B1, more preferably 45 to 62 wt .-% and most preferably 50 to 60 wt .-% are used.

The monomer B2 is at least one monoethylenically unsaturated dicarboxylic acid of the general formula (HOOC) R ¹ C = CR ² (COOH) (I) and / or R ¹ R ² C = C (- (CH ₂ ) _n -COOH ) (COOH) (II).

It is also possible to use mixtures of several different monomers B2. In the case of (I), it may be the ice and / or the trans form of the monomer. The monomers can also be used in the form of the corresponding carboxylic anhydrides or other hydrolyzable carboxylic acid derivatives. If the COOH groups are arranged in cis form, it is particularly advantageous to use cyclic anhydrides.

R ¹ and R ² independently of one another are H or a straight-chain or branched, optionally substituted alkyl radical having 1 to 20 C atoms. The alkyl radical preferably has 1 to 4 C atoms. R ¹ or R ² is particularly preferably H and / or a methyl group. The alkyl radical may optionally also be Have these substituents, provided that they have no negative impact on the application properties of the corrosion inhibitor polymer or the composition of the invention.

In the case of the formula (I) R ¹ and R ² may furthermore together represent an alkylene group having 3 to 20 C-atoms, which may be further substituted also optional. Preferably, the ring formed from the double bond and the alkylene radical comprises 5 or 6 carbon atoms. Examples of alkylene radicals include, in particular, a 1,3-propylene or a 1,4-butylene radical which may also have further alkyl groups as substituents. N is an integer from 0 to 5, preferably 0 to 3 and most preferably 0 or 1.

Examples of suitable monomers B2 of the formula (I) include maleic acid, fumaric acid, methylfumaric acid, methylmaleic acid, dimethylmaleic acid and optionally the corresponding cyclic anhydrides. Examples of formula (II) include methylenemalonic acid and itaconic acid. Preference is given to using maleic acid or maleic anhydride and itaconic acid.

When monomers B2 are used, from 0.1 to 70% by weight, in particular from 0.5 to 65% by weight, are used, the amount being based on the total amount of all monomers used for the formation of the corrosion inhibitor polymer. Preference is given to using from 10 to 65% by weight of the monomers B2, more preferably from 10 to 62% by weight, particularly preferably from 15 to 61% by weight and very particularly preferably from 20 to 60% by weight. Preferred ranges are also 12 to 55 wt .-% of the monomers B2, more preferably 15 to 40 wt .-% and in particular 17 to 25 wt .-%.

If monomers B3 are used, from 0.1 to 70% by weight are used, the amount being based on the total amount of all monomers used for the formation of the corrosion inhibitor polymer.

The monomers B3 are used for fine control of the properties of the copolymer. Of course, several different monomers B3 can be used. They are selected by the skilled person depending on the desired properties of the copolymer. The monomers B3 are also free-radically polymerizable.

Preferably, these are also monoethylenically unsaturated monomers. In special cases, however, small amounts of monomers with several polymerizable groups can be used. As a result, the copolymer can be crosslinked to a small extent. The monomers B3 may be both acidic and / or basic and / or neutral monomers. Preference is given to neutral monomers and / or acidic monomers.

In the event that several monomers B3 are used, it is preferred to use 0.1-40% by weight of monomers containing acid groups, in particular P-containing and sulfonic acids, and 0-30% by weight of other monomers.

Examples of suitable monomers B3 include, in particular, monomers which contain phosphoric acid and / or phosphonic acid groups. Particularly noteworthy here are vinylphosphonic acid, monovinyl phosphonate, allylphosphonic acid, monoesters of phosphoric acid, 3-butenylphosphonic acid, mono (3-butenyl) phosphoric acid, (4-vinyloxybutyl) phosphoric acid, phosphonoxyethyl acrylate, phosphonoxyethyl methacrylate, Phosphoric acid mono (2-hydroxy-3-vinyloxypropyl) esters, phosphoric mono (1-phosphonoxymethyl-2-vinyl-oxyethyl) esters, phosphoric mono (3-allyloxy-2-hydroxypropyl) esters, phosphoric acid mono - [2- (allyloxy-1-phosphonoxymethylethyl)] ester, 2-hydroxy-4-vinyloxymethyl-1, 3,2-dioxaphosphole, 2-hydroxy-4-allyloxymethyl-1,3,2-dioxaphosphole. It is also possible to use salts and / or esters, in particular C 1 -C ₈ mono-, di- and optionally trialkyl esters of the monomers containing phosphoric acid and / or phosphonic acid groups.

Also suitable are monomers containing sulfonic acid groups, such as, for example, allylsulfonic acid, methallylsulfonic acid, styrenesulfonate, vinylsulfonic acid, allyloxybenzenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid or 2- (methacryloyl) ethylsulfonic acid or their salts and / or esters.

Other acidic monomers include e.g. Maleinsäurehalbamide.

Examples substantially neutral monomers B3 Ci-Ci _δ -alkyl or CrC include ₄ hydroxyalkyl esters of (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, Butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate or butanediol-1,4-monoacrylate, (methyl) styrene, maleimide or maleic acid N-alkylimide.

Also suitable are vinyl or allyl ethers, e.g. Methyl vinyl ether, ethyl vinyl ether,

Propyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, vinyl cyclohexyl ether, vinyl 4-hydroxybutyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2- (di- ethylamino) ethyl vinyl ether, 2- (di-n-butyl-amino) ethyl vinyl ether or methyl diglycol vinyl ether or the corresponding allyl compounds. Also used may be vinyl esters such as vinyl acetate or vinyl propionate.

Examples of basic monomers include acrylamides and alkyl-substituted acrylamides, such as. As acrylamide, methacrylamide, N-tert-butylacrylamide or N-methyl (meth) acrylamide.

It is also possible to use alkoxylated monomers, in particular ethoxylated monomers. Especially suitable are alkoxylated monomers which are derived from acrylic acid or methacrylic acid and have the general formula (III)

in which the variables have the following meaning:

R ^{3 is} hydrogen or methyl;

R ⁴ - (CH ₂₎ ^ O- -CH ₂ -NR ⁷ -, -CHHD-CHz-CR ^ -CHHD- or -CONH-; -COO-

(Ester)

R ^{5 are} identical or different C ₂ -C ₄ -alkylene radicals which may be arranged blockwise or randomly, the proportion of ethylene radicals being at least 50 molar

% is;

R ^{6 is} hydrogen, C 1 -C ₄ -alkyl, -SO ₃ M or -PO ₃ M ₂ ;

R ^{7 is} hydrogen or -CH ₂ -CR ¹ = CH ₂ ;

R ⁸ -O- [R ⁵ -O] _n -R ⁶ , where the radicals - [R ⁵ -O] _n - of the other radicals contained in formula (IM) - [R ⁵ -O] _m - different could be;

R ^{9 is} hydrogen or ethyl;

M is alkali metal or hydrogen, preferably hydrogen,

m is 1 to 250, preferably 2 to 50, more preferably 3 to 10;

x is 0 or 1 and n, R ^{1 have} the meaning as in formula (II). Examples of crosslinking monomers include molecules having a plurality of ethylenically unsaturated groups, for example di (meth) acrylates such as ethylene glycol di (meth) acrylate or butanediol-1,4-di (meth) acrylate or poly (meth) acrylates such as t-methylolpropanetri (meth ) acrylate or else di (meth) acrylates of oligo- or polyalkylene glycols such as di-, tri- or tetraethylene glycol di (meth) acrylate. Further examples include vinyl (meth) acrylate or butanediol divinyl ether.

The person skilled in the art will find a suitable choice among the monomers B3, depending on the desired properties of the polymer and the desired application of the polymer.

As monomer B3 it is preferred to use monomers containing phosphonic acid and / or phosphoric acid groups, in particular vinylphosphonic acid or its salts and / or their C 1 -C ₈ esters. Particularly preferred as monomer B3 are vinylphosphonic acid or its salts; in particular vinylphosphonic acid.

The amount of all monomers B3 used together amounts to 0.1 to 70 wt .-%, in particular 0.2 to 65 wt .-%, based on the total amount of all monomers used for the formation of the corrosion inhibitor polymer. Preferably, the amount is 0.5 to 60 wt .-%, more preferably 1 to 50% and most preferably 2 to 40 wt .-%. In the case of the vinylphosphonic acid 10 to 30% are preferred, in particular 15 to 25 wt .-%. If crosslinking monomers B3 are present, their amount should as a rule not exceed 5% by weight, preferably 2% by weight, particularly preferably 1% by weight, based on the total amount of all monomers used for the process. It may for example be 10 ppm to 1 wt .-%.

As component B, a combination of the monomers acrylic acid (B1), maleic acid (B2) and vinylphosphonic acid (B3) is preferred.

Therefore, a preferred component B contains a corrosion inhibitor polymer obtainable from the polymerization of acrylic acid as monomer B1, maleic acid as monomer B2, and vinylphosphonic acid as monomer B3.

Further preferably, component B contains no further corrosion inhibitor polymers.

Also for this corrosion inhibitor polymer apply the aforementioned quantities. The monomers used can be radically polymerized in aqueous solution or in organic solvents or any mixtures.

The term "aqueous" means that the solvent or diluent used comprises water as the main constituent, but it may also contain portions of water-miscible organic solvents and, if appropriate, small amounts of emulsifiers, which may be advantageous in order to increase the solubility of certain monomers in particular of the monomers B3 in the reaction medium, but preferably no emulsifiers are present.

Accordingly, the solvent or diluent used has at least 50% by weight of water with respect to the total amount of the solvent. In addition, one or more water-miscible solvents can be used. Particular mention should be made here of alcohols, for example monoalcohols such as ethanol, propanol or isopropanol, dialcohols such as glycol, diethylene glycol or polyalkylene glycols or derivatives thereof. Preferred alcohols are propanol and isopropanol. The proportion of water is preferably at least 70% by weight, more preferably at least 80% by weight, particularly preferably at least 90% by weight. Most preferably, only water is used.

The term "organic solvent"("or organic solvent") means that the solvent or diluent used contains an organic solvent as the main constituent, but also amounts of water may also be present Examples of organic solvents include hydrocarbons, such as toluene, XyIoI or mixtures, as obtained, for example, in the refining of crude oil and commercially available, for example, as petroleum benzine, kerosene, Shellsol ^® , Solvesso ^® or Ricella ^® , ethers such as diethyl ether, tetrahydrofuran, dioxane, ether glycol acetates such as butylglycol acetate, ketones such as acetone Methyl ethyl ketone, alcohols, for example monoalcohols, such as methanol, ethanol, propanol or isopropanol, dialcohols, such as glycol, C 1 -C 10 monoalkyl or dialkyl glycols, diethylene glycol or polyalkylene glycols or derivatives thereof Preferred organic solvents are butylglycol, isopropanol, methanol, tetrahydrofuran, Dioxane, Petr oleic benzine and solvesso, more preferably butylglycol, isopropanol, petroleum benzine and solvesso, and most preferably butylglycol. The amount of the monomers used in each case is selected by the person skilled in the art such that the monomers are soluble in the particular solvent or diluent used. Accordingly, less soluble monomers are used by the skilled person only to the extent that they can be dissolved. Optionally, small amounts of emulsifiers may be added to increase the solubility. If inert monomers such. B. dicarboxylic acids or corresponding Dicar- bonsäureanhydride used, it has proven to be advantageous to carry out the reaction in the presence of bases. The polymerization is then carried out preferably in the presence of 2 to 19.9 mol% of at least one amine. This quantity indication relates to the total amount of all COOH groups of monocarboxylic acid B1 and dicarboxylic acids B2. Other, possibly existing acidic groups remain out of consideration. In other words, the COOH groups are thus partially neutralized. Of course, a mixture of two or more organic amines can be used.

The amines used may have one or more primary and / or secondary and / or tertiary amino groups and the corresponding number of organic groups. The organic groups may be alkyl, aralkyl, aryl or alkylaryl groups. Preference is given to straight-chain or branched alkyl groups. They may also have other functional groups. Such functional groups are preferably OH groups and / or ether groups. It is also possible to use amines which are not per se water-soluble, because in contact with the acidic monomers the formation of ammonium ions advantageously increases the water solubility. The amines can also be ethoxylated.

Examples of suitable amines include linear, cyclic and / or branched CrC ₈ - mono-, di- and trialkylamines, linear or branched Ci-C ₈ mono-, di- or trialkanolamines, especially mono-, di- or trialkanolamines, linear or branched d-Cs-alkyl ethers of linear or branched CrC ₈ mono-, di- or trialkanolamines, oligo- and polyamines such as diethylenetriamine.

The amines may also be heterocyclic amines such as morpholine, piperazine, imidazole, pyrazole, triazoles, tetrazoles, piperidine. Particularly advantageous can be used those heterocycles which have corrosion-inhibiting properties. Examples include benzotriazole and / or tolyltriazole. By this combination corrosion protection properties can be improved.

Furthermore, it is also possible to use amines which have ethylenically unsaturated groups, in particular monoethylenic amines. Such amines perform a dual function as an amine for neutralization as well as a monomer (B3). For example, allylamine can be used.

The person skilled in the art will make a suitable choice among the amines. Preference is given to amines having only one amino group. Further preferred are linear or branched CrC ₈ mono-, di- or trialkanolamines, particular preference is given to mono-, di- and triethanolamine and / or the corresponding ethoxylated products.

The amount of amine used is preferably 2 to 18 mol%, more preferably 3 to 16 mol% and particularly preferably 4 to 14 mol%. Very particularly preferred are 5 to 7 mol% and 11 to 14 mol%.

The amine may be added before or during the polymerization. It is preferably added already before or at the latest at the beginning of the polymerization. The base can be added either at once or in a time interval which corresponds at most to the total reaction time. In this case, the amine can be mixed with the monomer feed, either the monocarboxylic acid, the dicarboxylic acid or both, and metered in with them. In other words, the carboxylic acids are thus partially added in the form of the corresponding ammonium salts. Preferably, the amine is metered directly into the template. In order to carry out the polymerization, it has proven useful to introduce the dicarboxylic acid or, if appropriate, its cyclic anhydride and then to meter in the amine before further monomers and / or initiator are metered in, without the invention thus being fixed on this procedure.

The free-radical polymerization is preferably started by the use of suitable thermally activatable polymerization initiators. Alternatively, however, it can also be triggered by suitable radiation, for example. The free radical initiators should be soluble in the solvent of the reaction.

Among the thermally activatable polymerization initiators, preference is given to initiators having a decomposition temperature in the range from 30 to 150.degree. C., in particular from 50 to 120.degree. This temperature refers as usual to 10h half-life.

Initiators which can be used are all compounds which decompose into free radicals under the polymerization conditions, for example inorganic peroxo compounds, such as peroxodisulfates, in particular ammonium, potassium and preferably sodium peroxodisulfate, peroxosulfates, hydroperoxides, percarbonates and hydrogen peroxide and the so-called redox initiators. Preference is given to the use of initiators which are soluble in the solvent of the polymerization mixture. In some cases, it is advantageous to use mixtures of different initiators, for example mixtures of hydrogen peroxide and sodium or potassium peroxodisulfate. fat. Mixtures of hydrogen peroxide and sodium peroxodisulfate can be used in any proportion.

Suitable organic peroxy compounds are diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (o-toloyl) peroxide, succinyl peroxide, tert-butyl peracetate, tert-butyl permaleinate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl ple- sododecanoate, tert-butyl perbenzoate, tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy-2-ethylhexanoate and diisopropyl peroxydicarbamate ,

Preferred initiators are also azo compounds. These can be soluble, such as 2,2 ^1-azobis (4-methoxy-2,4-dimethyl valeronitrile) in organic solvents, dimethyl-2,2 ^1-azobis (2-methylpropionate), 1, 1'-azobis ( cyclohexane-1-carbo nitrile), 1 - [(cyano-1-methylethyl) azo] formamide, 2,2'-azobis (N-cyclohexyl-2-methylpro- pionamid), 2.2 ¹ azobis (2, 4-dimethyl valeronitrile), 2,2 ^1-azobis (2-methylbutyronitrile), 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2 ^1-azobis (N-butyl-2 -methylpropionamide).

Preferred water-soluble azo compounds are, for. 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2.2 ¹ azobis [2- (2-imidazolin-2-yl) propane] disulfide hydrates, 2.2 ¹ azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate, 2,2'-azo bis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl ] propane} dihydrochloride, 2,2'-azobis {2-methyl

N- [1, 1 -bis (hydroxymethyl) -2-hydroxyethyl] propionamide, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2 ^1-azobis [2- (2 -imidazolin-2-yl) propane] dihydrochloride, 2.2 ¹ azobis (2-methylpropionamide) dihydrochloride, 2.2 ¹ azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2-azobis ¹ [2- (2-imidazolin-2-yl) propane], 2,2'-

Azobis {2-methyl-N- [2- (1-hydroxybutyl)] propionamide}.

Further preferred initiators are also redox initiators. The redox initiators contain as oxidizing component at least one of the abovementioned peroxo compounds and, as reducing component, for example ascorbic acid, glucose, sorbose, ammonium or alkali metal hydrogen sulfite, sulfite, thiosulfate, hyposulfite, pyrosulfite, sulfide or sodium hydroxymethyl sulfoxylate. Preferably used as the reducing component of the redox catalyst ascorbic acid or sodium pyrosulfite. Relative to the employed in the polymerization amount of monomers 10 ^{~ 5} is used, for example, 1 x to 1 mol% of the reducing component of the redox catalyst.

In combination with the initiators or the redox initiator systems it is additionally possible to use transition metal catalysts, for example salts of iron, Cobalt, nickel, copper, vanadium and manganese. Suitable salts are, for example, iron (II) sulfate, cobalt (II) chloride, nickel (II) sulfate, copper (I) chloride. The reducing transition metal salt is usually used in an amount of 0.1 to 1000 ppm, based on the sum of the monomers. For example, combinations of hydrogen peroxide and iron (II) salts are particularly advantageous, such as a combination of 0.5 to 30% by weight of hydrogen peroxide and 0.1 to 500 ppm of FeSO ₄ .7H ₂ O, in each case based on the total the monomers.

Examples of suitable photoinitiators include acetophenone, benzoin ethers, benzyl alkyl ketones and their derivatives.

Preferably, thermal initiators are used, with azo compounds and peroxo compounds being preferred. Particularly preferred for polymerizations in aqueous solution are inorganic peroxo compounds, in particular hydrogen peroxide and especially sodium peroxodisulfate or mixtures thereof, optionally in combination with 0.1 to 500 ppm FeSO ₄ .7H ₂ O, and also 2,2'-azobis (2 - methylpropionamide) dihydrochloride. Very particular preference is given to hydrogen peroxide and sodium peroxodisulfate. Preferred organic solvent initiators are organic peroxides and azo compounds soluble in organic solvents. Particularly preferred are 2.2 ¹ -Azobis (2-methylbutyronitrile), 2.2 ¹ -Azobis (2,4-dimethyl valeronitrile) and Ditertbutylperoxid.

Of course, mixtures of different initiators can be used, provided they do not adversely affect. The amount is determined by the skilled person depending on the desired copolymer. As a rule, 0.05 wt .-% to 30 wt .-%, preferably 0.1 to 15 wt .-% and particularly preferably 0.2 to 8 wt .-% of the initiator with respect to the total amount of all monomers used.

In addition, suitable regulators, such as, for example, mercaptoethanol, can also be used in a manner known in principle. Preferably, no controllers are used.

Apart from this, the temperature can be varied within wide limits by the person skilled in the art, depending on the nature of the monomers used, the initiator and the desired copolymer. A minimum temperature of about 60 ^° C. has proven useful. The temperature can be kept constant during the polymerization or temperature profiles can also be run. Preferably, the polymerization temperature is 75 to 125 ° C, more preferably 80 to 120 ° C, most preferably 90 to 110 ° C and for example 95 to 105 ⁰ C.

The polymerization can be carried out in conventional free-radical polymerization apparatus. If one works above the boiling point of the water or the organic solvent or the mixture of water and other solvents, working in a suitable pressure vessel, otherwise it can be operated without pressure.

If an inert monomer such. As dicarboxylic acids or corresponding dicarboxylic anhydrides or vinylphosphonic acid is used, it has proven itself in the polymerization regularly to submit this monomer in the reaction vessel. After this, if necessary, the amine may be added. A person skilled in the art is a potential reaction of carboxylic acid anhydrides with nucleophilic reactants, the z. B. in the case of difunctional nucleophiles can lead to crosslinking monomer components known. He chooses the reaction conditions so that the desired products arise. Thereafter, the monocarboxylic acid, optionally further monomers B3 and the initiator, expediently also be metered in aqueous solution. Feed times of from 0.5 h to 24 h, preferably from 1 h to 12 h and particularly preferably from 2 to 8 h, have proven useful. In this way, the concentration of the more reactive monocarboxylic acids in the aqueous solution is kept relatively low. This reduces the tendency for the monocarboxylic acid to react with itself and results in a more uniform incorporation of the dicarboxylic acid units into the copolymer. After the feed of all monomers may also follow a post-reaction time, for example, from 0.5 to 3 hours. This ensures that the polymerization reaction proceeds as completely as possible. The completion can also be achieved by post-dosing polymerization initiator again.

Of course, the skilled person can also carry out the polymerization in other ways.

Not only carboxylic acid anhydrides but also other monomers used which have hydrolyzable groups, such as esters, may under some circumstances hydrolyze wholly or partly, depending on the polymerization conditions. The copolymers then contain the monomers copolymerized with the acid group resulting from the hydrolysis or else both unhydrolyzed groups and hydrolyzed groups next to one another. The synthesized copolymers can be isolated from the aqueous solution by conventional methods known to those skilled in the art, for example by evaporation of the solution, spray drying, freeze drying or precipitation. Of course, the polymers can also be purified by means of cleaning methods known to those skilled in the art, for example by ultrafiltration.

However, the copolymers are particularly preferably not purified at all after the polymerization but the resulting solutions of the copolymer solutions are used as such for the composition according to the invention.

However, it is quite possible to carry out the polymerization in an aqueous medium and to prepare a polymer solution in an organic solvent by a solvent exchange from an aqueous polymer solution. This can be done by methods known to those skilled in the art, for example by evaporation of the solution, spray drying, freeze drying or precipitation. Subsequently, the polymer is redissolved or dispersed in an organic solvent. Likewise, the replacement of the solvent can be carried out continuously, for. Example by adding a second solvent of a polymer solution in a first solvent and distilling off the first solvent. The addition of the second solvent can be carried out continuously or in portions or by a single addition.

The composition of the copolymers essentially corresponds to the ratio of the monomers used B1, B2 and optionally B3. As a rule, therefore, the copolymers comprise from 0.1 to 95% by weight of monomer units derived from the monoethylenically unsaturated monocarboxylic acid B1 and from 0.1 to 70% by weight of monomer units derived from the monoethylenically unsaturated dicarboxylic acid B2 of the general formula (HOOC) R ¹ C = CR ² (COOH) (I) and / or R ¹ R ² C = C (- (CH ₂ ) _n -COOH) (COOH) (II) and / or 0.1 to 70% by weight of monomer units derived from further ethylenically unsaturated comonomers B3 wherein R ¹ , R ² and n are as defined above.

If hydrolyzable derivatives of the monomers B2 and B3 are used, the polymer may also contain portions of unhydrolysed monomers, depending on the rate of hydrolysis and the conditions.

However, there are also other methods for preparing the corrosion inhibitor polymer for the anticorrosion component B.

The corrosion inhibitor polymer is soluble or at least dispersible in water or organic solvents, it being understood by those skilled in the art that the solubility of COOH-rich polymers can be highly pH dependent. The term "dispersible" means that the solution is not very clear, but the polymer is homogeneously distributed in it and does not settle. They are preferably copolymers which are soluble in the solvent.

The polymers according to the invention generally have a low pH. For mixing with components A and C, and optionally D, E and F, the polymer solution can either be used directly or the pH is adjusted by bases or acid addition.

A preferred pH range for mixing is as a rule 4 to 11, preferably 5 to 10 and particularly preferably 6 to 9, very particularly preferably 7 to 8.9.

If the pH of the polymer solution is lower after the polymerization, it can be increased by adding base. Bases for this are, for. As alkali and alkaline earth metal hydroxides, - carbonate, ammonia or amines.

The amines used may have one or more primary and / or secondary and / or tertiary amino groups and the corresponding number of organic groups. The organic groups may be alkyl, aralkyl, aryl or alkylaryl groups. Preference is given to straight-chain or branched alkyl groups. They may also have other functional groups. Such functional groups are preferably OH groups and / or ether groups. The amines can also be ethoxylated.

Examples of suitable amines include linear, cyclic and / or branched CrC ₈ - mono-, di- and trialkylamines, linear or branched CrC ₈ mono-, di- or trialkanolamines, in particular mono-, di- or trialkanolamines, linear or branched C 1 -C ₅ -alkyl ethers of linear or branched C 1 -C ₈ -mono-, di- or trialkanolamines, oligo- and polyamines such as, for example, diethylenetriamine.

The amines may also be heterocyclic amines such as morpholine, piperazine, imidazole, pyrazole, triazoles, tetrazoles, piperidine. It is particularly advantageous to use those heterocycles which have corrosion-inhibiting properties. Examples include benzotriazole and / or tolyltriazole. By this combination corrosion protection properties can be improved.

The same applies mutatis mutandis, if the pH is higher than the desired value. In this case, acids are added, such as. B. linear or branched C _r to C ₂₀ aliphatic, unsaturated or aromatic carboxylic acids, hypophosphorous acid, Phosphonic acids or derivatives, phosphoric acid or derivatives, sulfuric acid, sulfonic acid, such as methanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, m-nitrobenzenesulfonic acid, naphthalenesulfonic acid and derivatives thereof, nitric acid or hydrofluoric acid.

The molecular weight M _w (weight average) of the copolymers according to the invention is at least 1000 g / mol, preferably at least 3000 g / mol, more preferably at least 5000 g / mol and most preferably at least 10 000 g / mol. It is also possible to achieve molecular weights of more than 1 000 000 g / mol. Usually, M _{w is} 3000 g / mol to 150000 g / mol, preferably 5000 g / mol to 1 000 000 g / mol, more preferably 8000 g / mol to 750 000 g / mol and, for example, 15 000 g / mol up to 500 000 g / mol. The molecular weight is determined by the person skilled in the art according to the desired application.

Preferred polymers include acrylic acid and maleic acid or itaconic acid as monomers, and optionally other comonomers B3. Other comonomers may preferably be monomers containing phosphorous or phosphonic acid groups, for example vinylphosphonic acid or (meth) acrylic esters, for example methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth ) acrylate or hydroxyethyl (meth) acrylate.

Particular preference is given to copolymers which comprise acrylic acid, maleic acid and 5 to 40% by weight of monomers (B3) containing phosphonic acid and / or phosphoric acid groups. Monomer B3 is preferably vinylphosphonic acid or its salts and / or its CrC ₈ ester, particularly preferably vinylphosphonic acid.

For the formation of the corrosion inhibitor polymer for the anticorrosion component B of the composition according to the invention, preference may be given to using acrylic acid-maleic acid copolymers having a maleic acid content of 20.01 to 40% by weight, for example 25 to 40% by weight. Also preferred are terpolymers of 55 to 78, preferably 65 to 78 and more preferably 65 to 75 wt .-% acrylic acid, 20.01 to 34 wt .-%, preferably 21 to 34 and particularly preferably 22 to 30 wt. % Maleic acid and 1 to 24.99, preferably 2 to 24 and particularly preferably 5 to 22 wt .-% vinylphosphonic acid, which may also be partially present as their esters under certain circumstances.

For example, a terpolymer of 71 to 73 wt .-% acrylic acid, 23 to 25

% By weight of maleic acid and 3 to 5% by weight of vinylphosphonic acid. Further examples include terpolymers of 55 to 62% by weight of acrylic acid, 20.01 to 22 wt .-% of maleic acid and 16 to 24 wt .-% vinylphosphonic acid and terpolymers of 65 to 70 wt .-% acrylic acid, 21 to 25 wt .-% maleic acid and 6 to 12 wt .-% vinylphosphonic.

Copolymers having a higher molecular weight M _w are preferably used for the treatment of metallic surfaces, in particular those having M _{w of} from 1000 to 1.5 million g / mol, preferably from 5 000 to 1 million g / mol, particularly preferably from 10,000 to 800,000 g / mol and most preferably 20,000 to 500,000 g / mol. In the case of acrylic acid / maleic acid / vinylphosphonic acid terpolymers, preference is given to polymers having a molecular weight M _{w of} from 1,000 to 100,000 g / mol, preferably from 5,000 to 80,000 g / mol, particularly preferably from 10,000 to 50,000 g / mol and For example, be used from 15 000 to 30 000 g / mol.

Of course, any mixtures of different polymers can be used as component B.

The anticorrosion component B is present at a weight percentage, based on the total weight of the composition, of from 0.1 to 40% by weight. The proportion is preferably from 0.2 to 30, preferably 0.5 to 20, particularly preferably 1 to 10.

Solvent component C

The solvent component C consists of one or more solvents.

As a rule, a suitable solvent is used in which the components are dissolved and / or dispersed in order to allow a uniform application on the surface.

In the case of coil coating, it may be necessary to dispense with the use of the solvent.

Suitable solvents are those which are capable of dissolving, dispersing, suspending or emulsifying the compounds of the invention. These may be organic solvents or water. Of course, mixtures of different organic solvents or mixtures of organic solvents with water can be used. The person skilled in the art makes a suitable choice of the solvents which are possible in principle according to the type of components used for the composition according to the invention. Examples of organic solvents include hydrocarbons such as toluene, xylene or mixtures, as obtained, for example in the refining of crude oil, and for example, as petroleum benzine, kerosene, Solvesso ^®, Shellsol ^® or Ricella ^® commercially available, ethers, Etherglykolacetate such as butyl glycol acetate, ketones such as Acetone, alcohols such as methanol, ethanol or propanol.

Furthermore, the solvent component may be water or a predominantly aqueous solvent mixture. These are understood as meaning mixtures which comprise at least 50% by weight, preferably at least 65% by weight and particularly preferably at least 80% by weight of 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 glycol or methoxypropanol.

The amount of solvent is chosen by the skilled person depending on the desired properties of the composition of the invention and the desired application method. The composition can also be prepared first as a concentrate and diluted on site to the desired concentration.

The proportion by weight based on the total weight of the composition according to the invention is for the solvent component C 5 to 84.9 wt .-%. Preferably, this is 10 to 80, preferably 20 to 70 and most preferably 30 to 60 wt .-%.

Crosslinkable component D

The crosslinkable component D may contain one or more crosslinkers. Some crosslinkers have already been mentioned above. In particular when the composition according to the invention is used for coil coating, the presence of a crosslinker is advantageous. Typically, crosslinking occurs after application of the composition of the invention by thermal treatment. Photochemical (actinic) treatment is also possible. In the case of atmospheric corrosion protection, such a thermal treatment is often not feasible, so that preferably no crosslinking component D is present in the composition according to the invention for this application.

For the crosslinking component D, thermally crosslinking groups or photochemically crosslinking groups may be present. Suitable crosslinkers are included For example, crosslinking agents based on epoxides, in which two or more epoxy groups are linked to one another by means of a linking group. Examples include low molecular weight compounds having two epoxy groups, such as hexanediol diglycidyl ether, phthalic acid diglycidyl ester or cycloaliphatic compounds, such as 3,4-epoxycyclohexanecarboxylic acid S'-epoxycyclohexylmethyl ester.

Further examples of suitable crosslinkers include melamine type crosslinkers, e.g. B. at BASF Aktiengesellschaft commercially available crosslinkers Luwipal ^® series.

Blocked polyisocyanates are particularly preferably used as crosslinkers. In blocking, the isocyanate group is reversibly reacted with a blocking agent. The blocking agent is split off again when heated to higher temperatures. Examples of suitable blocking agents are disclosed in DE-A 199 14 896, column 12, line 13 to column 13, line 2. Particular preference is given to using ε-caprolactam-blocked polyisocyanates.

Suitable for photochemical crosslinking crosslinkers are, for example Dibasonat ^® - grades from BASF or oligomeric acrylates.

If a crosslinker is used separately, usually 0.5 to 10 wt .-%, preferably 1 to 8 wt .-% and particularly preferably 2 to 6 wt .-%, are used. Of course, it is also possible to use mixtures of different crosslinkers, provided that the properties of the layer are not adversely affected thereby.

Based on the total weight of the composition, the proportion by weight of the crosslinking component D is 0 to 30% by weight. If component D is to be present, its proportion is preferably 1 to 25, preferably 2 to 20, and very particularly preferably 5 to 15 wt .-%.

Pigment / filler component E

The pigment / filler component E may contain one or more pigments and / or fillers.

If a filler is used, it may also comprise an additional organic coating, for example for hydrophobing or hydrophilization. Of the

Filler should not exceed an average particle size of 10 microns. The average particle size is preferably 10 nm to 9 μm and is particularly advantageous. preferably 100 nm to 5 μm. In the case of round or approximately round particles, this information refers to the diameter, in the case of irregularly shaped particles, such as, for example, acicular particles, to the longest axis. The particle size means the primary particle size. It will be understood by those skilled in the art that finely divided solids often agglomerate into larger particles which must be dispersed intensively for use. The particle size is selected by the skilled person depending on the desired properties of the layer. It also depends, for example, on the desired layer thickness. As a rule, the person skilled in the art will select smaller particles for a small layer thickness.

Suitable fillers are on the one hand electrically conductive pigment or fillers in question. Such additives serve to improve the weldability and to improve a subsequent coating with electrodeposition paints. Examples of suitable electrically conductive fillers or pigments include phosphides, vanadium carbide, titanium nitride, molybdenum sulfide, graphite, carbon black or doped barium sulfate. Preference is given to using metal phosphides of Zn, Al, Si, Mn, Cr, Fe or Ni. Examples of preferred metal phosphides include CrP, MnP, Fe ₃ P, Fe ₂ P, Ni ₂ P, NiP or NiP _{2. 3} Iron phosphide are commercially available, for example under the name Ferrophos ^®.

It is also possible to use non-conductive pigments or fillers, such as, for example, finely divided amorphous silicon, aluminum or titanium oxides, which may also be doped with further elements. For example, calcium ion-modified amorphous silica can be used.

Further examples of pigments include anticorrosive pigments such as zinc phosphates and silicates, zinc metaborate or barium metaborate monohydrate, nanodisperse oxides and other anticorrosion pigments known to those skilled in the art, for example as described by MJ Austin in "Surface Coatings - Raw Materials and their Use", Vol. 1, 3rd Ed ., Chapman & Hall, London 1993, p. 409-434.

Of course, mixtures of different pigments can be used. The pigments are preferably used in an amount of 10 to 70 wt .-%. The exact amount will be determined by the skilled person depending on the desired properties of the layer. When using conductivity pigments, the amounts used are usually greater than when using non-conductive fillers. Preferred amounts of conductive pigments and fillers are 40 to 70 wt .-%, preferred amounts of non-conductive pigments 20 to 50 wt .-%.

Component E has a weight fraction based on the total weight of the composition of 0 to 70 wt .-%. Preferably, the proportion 5 to 60%, more preferably 10 to 50%, even more preferably 20 to 40% and most preferably 35% by weight.

Other components F

The composition according to the invention may also comprise one or more auxiliaries and / or additives. Such auxiliaries and / or additives are used for fine control of the properties of the layer. As a rule, its amount does not exceed 20% by weight, based on the total weight of the composition, preferably the proportion does not exceed 10% by weight.

Examples of suitable additives are coloring and / or effect pigments, reactive thinners for thermal curing or curing with actinic radiation, rheology aids, UV absorbers, light stabilizers, radical scavengers, initiators for free-radical polymerization, catalysts for thermal crosslinking, photoinitiators and -co-initiators, slip additives, polymerization inhibitors, defoamers, emulsifiers, degassing agents, wetting and dispersing agents, adhesion promoters, leveling agents, film-forming auxiliaries, rheology-controlling additives (thickeners), flame retardants, siccatives, skin-preventing agents, other corrosion inhibitors, waxes and matting agents, as also known from the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998 or the German patent application DE-A 199 14 896, column 13, line 56 to column 15, line 54, are known.

Suitable corrosion inhibitors are, for example, phosphonic acid, aminophosphates, organic and inorganic phosphates, for example of zinc, calcium and magnesium, vinylphosphonic acid and its salts, carboxylic acids and their salts and esters, alkanolamines and amines, benzotriazole and its structural derivatives such as, for example, tolytriazole, acetylenic derivatives, such as N ₁ N-dimethyl-2-propyn-1-amine, N, N-diethyl-2-propyn-1-amine, 1,1-dimethyl-2-propynyl-1-amine, N, N-diethyl- 4-amino-2-butyn-1-ol, 2,5-dimethyl-3-hexyne-2,5-diol, 3-hexyne-2,5-diol, 2-butyne-1,4-diolethoxylate, 2- Butyne-1,4-diol, 2-butyne-1,4-diol propoxylate, propargyl alcohol, propargyl alcohol ethoxylate, propargyl alcohol propoxylate, propylene sulfonic acid and their salts. Further suitable corrosion inhibitors are aldehydes, amine- and sodium-neutralized phosphoric esters of alkyl alcohols, amine carboxylates, amino and nitrophenols, amino alcohols, aminobenzimidazole, aminoimidazolines, aminotriazole, benzimidazolamines, benzothiazoles, boric acid esters with various alkanolamines such as boric acid diethanolamine ester, butynediol, quinoline derivatives, dibenzylsulfoxide , Dicarboxylic acids and their esters, diisobutenylsuccinic acid, dithiophosphonic acid, fatty amines and fatty acid amides, guanidine derivatives, urea and its derivatives, Laurylpyridinium chloride, maleic acid anides, mercaptobenzimidazole, N-2-ethylhexyl-3-aminosulfopropionic acid, phosphonium salts, phthalic acid amides, polyetheramines, sulfonium salts, sulfonic acids such as methanesulfonic acid, thioethers, thioureas, thiuram sulfides, cinnamic acid and their derivatives.

Preferred additives are dibutyltin dilaurate as a thermal crosslinking catalyst.

Another object of the present invention is the preparation of a composition according to the invention comprising the steps

a) contacting the components A, B, C and optionally D, E and F; and

b) mixing the components.

It is advantageous if in step a) the component A is supplied as a dispersion and the component B as a solution or emulsion.

The composition is prepared by intensive mixing of the components. The person skilled in the art is familiar with suitable mixing or dispersing aggregates.

Another object of the present invention is a method for coating a metallic surface containing the steps

(a) applying a layer to the metallic surface of a composition according to the invention;

(b) optionally crosslinking the applied layer; and

(c) drying the layer.

In the event that the crosslinking takes place thermally, the steps (b) and (c) can be combined into one step.

Prior to step (a), a pretreatment step may be performed. For applications in atmospheric corrosion protection, the pretreatment may preferably be carried out only in a mechanical cleaning, such as grinding, brushing, sand or dry ice blasting. In the case of coil coating, in addition to these pretreatment steps or alternatively, further steps may be taken. This includes chemical cleaning and the application of a pretreatment layer. This may also include the corrosion inhibitor component B described above.

When used for atmospheric corrosion protection, the coating can be applied by simply brushing, brushing, dabbing or spraying.

Especially with coil coating, modified treatment steps make sense.

Coil coating can also be cleaned before the layer is applied. If the treatment according to the invention takes place immediately after a metallic surface treatment, for example an electrolytic galvanizing or hot-dip galvanizing of steel strips, then the strips can normally be brought into contact with the composition according to the invention by coating without prior purification. However, if the metal strips to be treated have been stored and / or transported before the coating, they are generally provided with anticorrosive oils or at least so largely polluted that they should be cleaned before coating. The cleaning can be carried out according to methods known to the person skilled in the art with customary cleaning agents.

In the method according to the invention for applying the composition according to the invention, the application of the composition to the surface of the metal can take place, for example, by spraying, dipping or rolling.

After a dip process, you can drain the workpiece to remove excess preparation; in the case of metal sheets, metal foils or the like, excess preparation can also be squeezed or doctored off. The application with the spread is usually carried out at room temperature without that higher temperatures should be excluded in principle.

Metal strips (often referred to as "coil coating") are preferably coated by means of the method according to the invention, in which case the coating can be carried out both on one side and on both sides It is also possible to coat the top and bottom by means of different formulations.

Most preferably, the tape coating by means of a continuous process. Continuously working coil coating systems are known in principle. As a rule, they comprise at least one coating station, a drying or stoving station and / or UV station and, if appropriate, further stations. or post-treatment, such as rinsing or rinsing stations. Examples of coil coating systems can be found in Römpp Lexikon Lacke and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, page 55, "coil coating", or in the German patent application DE 196 32 426 A 1. Of course, differently constructed systems used become.

The speed of the metal strip is selected by the person skilled in the art in accordance with the application and curing properties of the preparation used. In general, rates of 10 to 150 m / min, preferably 12 to 120 m / min, more preferably 14 to 100 m / min, very particularly preferably 16 to 80 and in particular 20 to 70 m / min have been proven.

The application of the composition according to the invention can in any way, for. B. by spraying, casting or roller painting done. Roller coating is particularly advantageous of these application methods and is therefore preferably used according to the invention.

Each application step of roller painting can be carried out with several rollers. Preferably, two to four and in particular two rolls are used.

In roll painting, the rotating take-up roll (pick-up roll) dips into a supply of the paint according to the invention (the composition according to the invention) and thus takes over the paint to be applied. This is transmitted from the pickup roller directly or via at least one transfer roller to the rotating application roller. From this, the paint is transferred by rectified or reverse stripping on the tape.

The paint can also be pumped directly into a gap between two rollers, which is also referred to in the art as a nip feed.

According to the invention, the counter stripping or the reverse roller coating method is advantageous and is therefore preferred.

In roll coating, the speeds of revolution of the take-up roll and applicator roll can vary greatly from one coating process to the next. Preferably, the application roller has a rotational speed which is 110 to 125% of the belt speed, and the take-up roller has a revolution speed which is 20 to 40% of the belt speed. In the case of the particularly preferred coating of metal strips, the coating can be carried out both on one side and on both sides. Most preferably, the coating is carried out by means of a continuous process.

The coating can be carried out, for example, by means of a continuous strip coating system, as described in Rompp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 55, "Bandbeschichtung", or in German patent application DE 196 32 426 A 1. Of course, differently constructed systems can also be used.

Following the application of the composition used according to the invention, any solvent present in the layer is removed and the layer is crosslinked. This can be done in two separate steps but can be done simultaneously. To remove the solvent, the layer is preferably heated by means of a suitable device. Drying can also be done by contacting with a gas stream. Both methods can be combined.

The Aushärtemethode depends on the nature of the binder or the crosslinking agent and is usually thermally. However, the curing can also take place with actinic radiation or combined thermally and with actinic radiation. The common hardening with heat and actinic radiation is also referred to in the art as dual-cure. Actinic radiation is understood here and below to mean electromagnetic radiation, such as near infrared, visible light, UV radiation or X-radiation, in particular UV radiation, or corpuscular radiation, such as electron radiation.

During thermal crosslinking, the applied coating is heated. This may preferably be done by convective heat transfer, near or far infrared irradiation, and / or in iron-based ribbons by electrical induction.

The temperature required for curing depends in particular on the binder or crosslinker used. Very reactive crosslinkers can be cured at lower temperatures than less reactive crosslinkers. The temperature of the layer is usually between 120 and 250 ⁰ C for curing.

Very reactive binder systems can also be cured at lower temperatures than less reactive binder systems. As a rule, the cross-linking at temperatures of at least 60 ⁰ C is preferable, more preferably at least 100 ° C and particularly preferably at least 120 ° C BE DONE least 80 ° C men. In particular, the crosslinking at 100 to 250 ⁰ C, preferably 120 to 220 ⁰ C and particularly preferably be carried out at 150 to 200 ° C. This refers in each case to the peak temperature (peak metal temperature (PMT)) found on the metal, which can be measured by methods familiar to the person skilled in the art (for example non-contact infrared measurement or determination of the temperature with glued-on test strips).

The heating of the coating layers according to the invention in the thermal curing is preferably carried out by convection heat transfer, irradiation with near or far infrared and / or in bands based on iron by electrical induction.

The heating time, that is to say the duration of the thermal curing, varies as a function of the lacquer used according to the invention. Preferably, it is 10 seconds to 2 minutes.

If convection heat transfer is essentially used, circulating air furnaces having a length of 30 to 50, in particular 35 to 45, m are required at the preferred belt speeds. Preferably, the circulating air temperature is at 350 ⁰ C.

The thermal curing of the coating layers according to the invention can still be supported by the irradiation with actinic radiation.

Curing can, however, also be effected with actinic radiation alone, as described, for example, in German patent application DE 198 35 206 A1.

The photochemical curing takes place by means of actinic radiation. Actinic radiation is understood here and below to mean electromagnetic radiation, such as near infrared, visible light, UV radiation or X-radiation or corpuscular radiation, such as electron radiation. Preferably, UV / VIS radiation is used for the photochemical curing. The irradiation may optionally also in the absence of oxygen, for. B. under inert gas atmosphere, are performed. The photochemical curing can be carried out under normal temperature conditions, ie without heating the coating, but it can also be photochemically crosslinked at elevated temperatures, for example at 40 to 150 ⁰ C, preferably 40 to 130 ° C and especially at 40 to 100 ° C.

In the case of atmospheric corrosion protection cures after application to the

Surface the applied coating under atmospheric conditions. This can in the simplest case by the gradual evaporation of the solvent respectively. Depending on the nature of the binder used, other crosslinking processes can take place.

Depending on the thickness of the desired corrosion protection layer, the entire layer can be applied in a single operation, or it can also be several similar layers applied one after the other and each cured to achieve the desired total layer thickness of the corrosion protection layer.

After drying, the applied layer preferably has a thickness of at least 3.1 μm and is thus thicker than a conventional pretreatment layer.

For coil coating, the layer thickness is typically from 3.1 to 20 .mu.m, preferably from 4 to 15 .mu.m, more preferably from 4.5 to 10 .mu.m, and particularly preferably from 5 to 8 .mu.m.

In the case of atmospheric corrosion protection, the thickness of the layer after drying is typically 20 to 1000 μm, preferably 25 to 500 μm, more preferably 30 to 200 μm and most preferably 35 to 150 μm.

By means of the method according to the invention, a coating, in particular a base lacquer layer, can be obtained on a metallic surface, in particular the surface of iron, steel, zinc, aluminum, magnesium, tin, copper or alloys thereof.

The metal may preferably be a metal sheet or metal strip, in particular of galvanized steel, tin-plated steel, aluminized steel, aluminum or galvanized aluminum.

Another object of the present invention is a coated metallic surface, which is obtainable from the inventive method described above.

On the metallic surface with the primer lacquer layer even more lacquer layers can be applied. Preferably, after immersion, an electrocoating takes place. As such, the metallic surface to be coated may itself be the coating of another substrate.

This can be done in the same coil coater in which several application and optionally curing stations in succession are switched. Alternatively, however, the coated strip can be removed again after the application and the curing and further layers can be applied in other systems. After the coated ribbons have been produced, the coils to be coated can be wound and then further processed at another location; However, they can also be processed directly from the coil coating. So they can be laminated with plastics or provided with removable protective films.

For applications in the automotive sector, after application of the composition according to the invention, cathodic dip coating (KTL) may even be dispensed with. If the integrated pretreatment layer is also to replace the cathodic electrode, it is recommended to use somewhat thicker integrated pretreatment layers, for example with a thickness of 10 to 25 μm, preferably 12 to 25 μm.

On the provided with a composition according to the invention metallic surface even more paint layers can be applied. The type and number of required lacquer layers are determined by the skilled person depending on the desired use of the coated metal or metallic molded part. Further lacquer layers may be, for example, layers of colored lacquers, clearcoats or functional lacquers. An example of a functional paint is a soft paint with a relatively high proportion of filler. This can be advantageously applied before the color and / or topcoat to protect the metal and the integrated pretreatment layer from mechanical damage, for example by stone chipping or scratching.

However, the tapes provided with the primer lacquer layer can also first be comminuted without further painting and further processed into shaped parts. Various moldings can also be joined together by welding. Examples of suitable shaping processing methods are pressing and deep-drawing.

Molded parts may comprise coated sheets, foils or strips as well as the metallic components obtained therefrom.

Such components are, in particular, those which can be used for cladding, veneering or lining. Examples include automobile bodies or parts thereof, truck bodies, frames for two-wheeled vehicles such as motorcycles or bicycles or parts for such vehicles as, for example, protective panels or linings, linings for household appliances such as washing machines, dishwashers, tumble dryers, gas and electric stoves, microwave ovens, Freezers or refrigerators, covers for technical equipment or devices such as machines, control cabinets, computer housings or the like, architectural elements such as wall parts, facade elements, ceiling elements, window or door profiles or partitions, furniture made of metallic materials such as metal cabinets, metal shelves, parts of furniture or Beschllage. Furthermore, it may also be hollow body for storage of liquids or other substances, such as cans, cans or tanks.

The resulting profile elements and molded parts are scratch-resistant, corrosion-resistant, weather-resistant and chemically stable, and can easily be over-painted with a wide variety of paints.

The primer without conductive pigments can also be used as a KTL replacement. Layer thicknesses of about 10-15 μm are typically used here.

Another object of the present invention is the use of the composition of the invention as a primer, especially in coil coating or in atmospheric corrosion protection.

Examples

The metal substrate used is hot-galvanized steel ("HDG") and aluminum. HDG is commercially available from Chemetall (OEHDG / 2, according to DIN EN 10142 and 01147). Aluminum was also purchased from the company Chemetall and has the specification AA6016.

The paint systems used are three different primers. This is an organic solvent-based epoxy varnish and two waterborne acrylate and polyurethane varnishes.

The epoxy paint contains the following components:

44.25% Epoxy Binder Based on Bisphenol A 0.91% Binder Epoxy B

8.25% thinner butyl glycol

0.26% filler fumed hydrophilic silica (Aerosil ^® 200 V)

4.78% filler talc

17.81% white pigment: TiO ₂ rutile 4.95% corrosion inhibitor pigment: Ca-SiO ₂ 6.76% Corrosion inhibitor pigment: Zinc phosphate (ZP BS M) 1.65% Black pigment: Sicomix

9.73% 1K cross linker (blocked hexamethylene diisocyanate) 0.65% catalyst

acrylate

The acrylate dispersion is anionically stabilized (ammonia) and contains as monomers acrylic acid, methyl methacrylate, 4-hydroxystyrene, n-butyl acrylate, styrene, hydroxypropyl methacrylate, ethyl methacrylate.

Polyurethane dispersion (PUR)

The PU dispersion contains the oligomeric constituents 4,4'-bis (isocyanate-cyclohexal) methane type (M _n = 8,000, M _w = 21,000, FG = 44%, SZ = 25) as the isocyanate component and a polyester segment ( M _n = 2000, M _w = 5500 g / mol), both are chain extended with triethanolamine. Both binders (acrylate dispersion and polyurethane dispersion) are formulated in similar paint formulations as the epoxy binder.

Examples of Preparation of Polymeric Corrosion Inhibitors:

The K values were measured according to H. Fikentscher, Cellulose-Chemie, Vol. 13, pp. 58-64 and 71-74 (1932) in 1% strength by weight solution at 25.degree.

Example 1:

In a 6I pressure reactor with anchor stirrer, temperature control and nitrogen inlet, 486.3 g of maleic anhydride, 22.5 mg of ferrous sulfate are placed in one liter of deionized water. Under nitrogen atmosphere is heated to 115 to 120 ⁰ C. After reaching this temperature, 1725 g of acrylic acid in 1, 2251 deionized water, and within 5h, 115 g of 30% hydrogen peroxide solution and 257.5 ml deionized water are uniformly added within 4h. It is diluted with 191.3 g of deionized water and stirred at 120 ° C for 2 h. This gives a clear yellow solution having a solids content of 44.7% and a K value (1% in deionized water) of 28.4. 1146g of this solution is adjusted with N ₁ N-dimethylethanolamine to a pH of 8.5. Example 2:

In a 61 pressure reactor equipped with anchor stirrer, temperature control, nitrogen inlet and 2 feed points, 486.3 g of maleic anhydride, 22.5 mg iron (II) sulfate heptahydrate, and 1000 g of deionized water are presented. Under nitrogen atmosphere is heated to 115 to 120 ⁰ C. After reaching this temperature is within 5 hours Feed 1, consisting of 1725.0 g of acrylic acid, 66.33 g of vinylphosphonic (3 wt .-% based on maleic anhydride and acrylic acid) and 1344.8 g of deionized water, and within 6 Hours of feed 2, consisting of 115.0 g of hydrogen peroxide (30%) and 257.5 g of deionized water dosed uniformly. After the end of feed 1, a further 191.3 g of deionized water are added. The reaction mixture is stirred for a further 2 hours at 120.degree. During the polymerization, the pressure is maintained at 3 to 4 bar by gentle decompression. After cooling, a yellowish, clear polymer solution having a solids content of 45.2% and a K value (1% in deionized water) of 27.1. 850 g of this polymer solution are adjusted to pH 8.3 with N, N-dimethylethanolamine.

Example 3:

121.6 g of maleic anhydride are dissolved in 190 g of deionized water in a stirred pot with a paddle stirrer and internal thermometer and stirred for one hour under a nitrogen blanket at a slight reflux. 5.62 mg of iron (II) sulfate heptahydrate dissolved in 10 g of deionized water are added all at once and over 5 minutes, feed 1 consisting of 86.3 g of triethanolamine in 50.0 g of deionized water is added. Subsequently, feed 2 consisting of 431.3 g of acrylic acid, 55.2 g of hydroxyethyl acrylate in 336.0 g of deionized water in 4 h and feed 3 consisting of 40.2 g hydrogen peroxide (30%) and 112.0 g of deionized Water added in 5 h. After completion of the addition, the mixture is stirred for a further 2 hours under reflux conditions and cooled to room temperature. This gives a slightly yellowish, clear polymer solution having a solids content of 32.3%, a K value (1% in deionized water) of 46.1. 250 g of this solution are adjusted to pH 8.3 with triethanolamine.

Example 4:

In a stirred pot with paddle stirrer and internal thermometer, 99.9 g of itaconic acid are dissolved in 350 g of deionized water and treated with 3.488 mg of iron (II) sulfate heptahydrate. is heated to light reflux (internal temperature 98 ° C). Then within 5 h Feed 1, consisting of 267.3 g of acrylic acid, 20.4 g of vinylphosphonic acid and 812.0 g of deionized water, and within 6 h feed 2, consisting of 38.5 g of hydrogen peroxide in 350 g of water. After the end of feed 1, the mixture is stirred at 99.degree. C. for a further 2 h. This gives a colorless, clear polymer solution having a solids content of 19.3% and a K value (1% in deionized water) of 37.8. 250 g of this polymer solution are adjusted to pH 8.5 with N, N-dimethylethanolamine.

Example 5:

In a stirred pot with paddle stirrer and internal thermometer 49 g of maleic anhydride in 250 g of Pluriol A1000E (monomethylpolyethylene glycol, Mw 1000 / g / mol) are heated to 150 ⁰ C. Subsequently, feed 1, consisting of 144 g of acrylic acid, and within 5 h 30 min feed 2, consisting of 3.9 g of di-tert-butyl peroxide in 20 g of Lutensol A7 N (nonionic surfactant from BASF AG), are added within 5 h. After the end of feed 1 is stirred for a further 2 h at 150 ⁰ C. A yellow viscous polymer is obtained. One part was diluted with deionized water and adjusted to pH 8.5 with N ₁ N-dimethylethanolamine (solids content 22.9%).

Example 6:

74.9 g of itaconic acid, 57.7 g of Uniperol AC Type SE are dissolved in 262.5 g of deionized water in a stirred pot with paddle stirrer and internal thermometer and treated with 2.616 mg of iron (II) sulfate heptahydrate to give slight reflux (internal temperature 98 ° C). Feed 1, consisting of 200.5 g of acrylic acid, 15.3 g of vinylphosphonic acid, 27.8 g of hydroxyethyl acrylate and 609 g of deionized water, and within 6 h Feed 2, consisting of 28.9 g of hydrogen peroxide in 608, are then added within 5 h. 9 g of water added. After the end of feed 1, the mixture is stirred at 99.degree. C. for a further 2 h. This gives a colorless, clear polymer solution having a solids content of 19.3%. 942 g of this polymer solution are adjusted to pH 8.2 with N, N-dimethylethanolamine.

Example 7:

In a stirred pot with paddle stirrer and internal thermometer, 249 g of Pluriol A10R (allyl alcohol ethoxylate, commercial product of BASF AG) under nitrogen atmosphere Heated to 150 ⁰ C. Subsequently, feed 1, consisting of 36 g of acrylic acid and 52 g of styrene and within 5 h feed 2, consisting of 10.1 g of di-tertbutyl peroxide in 20 g of Lutensol A7 N (nonionic surfactant from BASF AG) are added within 5 h , After the end of feed 1 is stirred for a further 2 h at 150 ⁰ C. A yellow viscous polymer is obtained. It was diluted with 750 g of deionized water and adjusted to pH 9 with N, N-dimethylethanolamine (solids content 28.6%).

Example 8:

121.6 g of maleic anhydride and 152 g of vinylphosphonic acid are dissolved in 190 g of deionized water in a 2 l pilot stirrer with anchor stirrer and internal thermometer, sparged with nitrogen and stirred at 99.degree. C. for 1 h. Subsequently, 703 mg of iron (II) sulfate heptahydrate dissolved in 10 g of deionized water are added. Feed 5, consisting of 51.7 g of dimethylethanolamine in 50 g of deionized water, is then added over the course of 5 minutes and Feed 2, consisting of 430 g of acrylic acid in 455 g of deionized water, and Feed 6 within 6 h, within 5 h, consisting of 42.4 g of sodium peroxodisulfate in 160 g of water. After the end of feed 3, the mixture is stirred at 99.degree. C. for a further 2 h. This gives a yellow, clear polymer solution having a solids content of 47.1% and a K value (1% in deionized water) of 19.4. 400 g of this polymer solution are mixed with 40 g of deionized water and adjusted to pH 8.0 with 192 g of dimethylethanolamine. Solids content: 52.6%.

Example 9:

In a stirred pot with paddle stirrer and internal thermometer, 249 g of Pluriol A10R (allyl alcohol ethoxylate, commercial product of BASF AG) are heated to 150 ° C. under a nitrogen atmosphere. Subsequently, feed 1, consisting of 36 g of acrylic acid and 52 g of styrene and within 5 h feed 2, consisting of 10.1 g of di-tertbutyl peroxide in 20 g of Lutensol A7 N (nonionic surfactant from BASF AG) are added within 5 h , After the end of feed 1 is stirred for a further 2 h at 150 ⁰ C. A yellow viscous polymer is obtained. It was diluted with 200 g of butyl glycol (solids content 63.5%, K value (1% in butylglycol) 28.8).

Example 10: Approximately 400 g of Example 8 is freeze-dried prior to pH adjustment. The solid (201 g) is dissolved in 200 g of methanol. A solution having a solids content of 49.7% is obtained.

Example 11:

In a stirred tank with anchor agitator 7.161 kg maleic anhydride is dissolved in 5 kg of deionized water, then added 8.951 kg of vinylphosphonic in 12 kg of deionized water, and gassed with nitrogen and stirred for 1 h at 99 ° C. Subsequently, 41.40 g of iron (II) sulfate heptahydrate dissolved in 740 g of deionized water are added within 1 minute. Thereafter, feed 1, consisting of 5.088 kg of triethanolamine in 5.0 kg of deionized water is added within 5 minutes. Subsequently, feed 2, consisting of 25.322 kg of acrylic acid, and within 6 h Feed 4, consisting of 2.497 kg of sodium peroxodisulfate in 33.2 kg of deionized water is added within 5 h. After the end of feed 2 is rinsed with feed 3, consisting of 5 kg of deionized water. After the end of feed 4, stirring is continued for 2 hours at 99.degree. After cooling, a yellow, clear polymer solution having a solids content of 46.4% and a K value (1% in deionized water) of 18.4.

Example 12:

In a 2L pilot stirrer with anchor stirrer and internal thermometer 126.3 g of vinylphosphonic dissolved in 200 g of isopropanol, gassed with nitrogen and heated to 65 ° C with stirring. Subsequently, at 65-73 ° C within 5 h feed 1, consisting of 120 g of vinyl acetate and 360 g of acrylic acid, and within 6 h feed 2, consisting of 36.0 g of WAKO V-65 in 400 g of isopropanol. After about 3.5 hours, the polymer solution is diluted once more with 171 g of isopropanol. After the end of feed 2, the mixture is stirred at 68-73 ° C. for a further 4 h. This gives a colorless, clear polymer solution having a solids content of 47.0% and a K value (1% in methanol) of 19.7.

Example 13:

68.2 g of vinylphosphonic acid are dissolved in 471.2 g of dioxane in a 2 l pilot stirrer with anchor stirrer and internal thermometer, sparged with nitrogen and heated to 95 ° C. with stirring. Subsequently, at 95 ° C. within 4 h, feed 1, consisting of 508.8 g of lauryl acrylate and 100.9 g of acrylic acid, and within 5 h feed 2, best from 20.2 g of WAKO V-59 in 200 g of dioxane. After the end of feed 2, stirring is continued for 2 hours at 95.degree. This gives a colorless, cloudy polymer solution having a solids content of 51.0% and a K value (1% in tetrahydrofuran) of 17.6.

Example 14:

In a 2 l pilot stirrer with anchor stirrer and internal thermometer, 127.9 g of vinylphosphonic acid are dissolved in 430 g of dioxane, sparged with nitrogen and heated to 95 ° C. with stirring. Then at 95 ° C within 4 h feed 1, consisting of 318 g of lauryl acrylate and 189.2 g of acrylic acid, and within 5 h feed 2, consisting of 18.9 g of WAKO V-59 in 200 g of dioxane was added. The batch was diluted during the polymerization with a total of 220 g of deionized water and 135 g of dioxane. After the end of feed 2, the mixture is stirred at 90 ^° C. for a further 4 h. This gives a colorless, cloudy polymer solution having a solids content of 40.3% and a K value (1% in methanol) of 19.3.

The HDG surfaces are cleaned in a three-step process:

Solvent based degreasing (ethanol / ethyl acetate), alkaline cleaning (Henkel Rido- line C72, bath was adjusted to a value of 4.2 adjusted according to the protocol Henkel, 60 ⁰ C, 60 sec.) Followed by drying with compressed air. The same procedure was used for the aluminum surfaces.

The binder were mixed as indicated in the table below 5 wt .-% of a polymeric anticorrosion component B, and in such a film thickness on the metal plate surface with a doctor blade applied, and (in an oven at a peak metal temperature of 171 ⁰ C furnace temperature 181 to 183 ° C, 87 to 120 sec), so that a layer thickness after drying of 5 to 6 microns results.

The thus coated plates were subjected to the following tests:

Corrosion Test:

Salt Spray Test (SSK, DIN 50021) for Hot Galvanized Steel (HDG) Acetic Acid Salt Spray Test (ESS, ASTM B287) for Aluminum Climate Change Test (KWT) (VDA-Test Sheet 621 - 415 Feb82) for HDG: The appearance of the surface was examined, as was the sub-surface migration and the delamination of the paint at the scribe location.

Results for KWT, SSK and ESS are compared qualitatively in comparison to a blank (containing no polymeric corrosion protection component B). Legend for the test method:

A = test in acrylate-based primer P = test in PUR-based primer E = test in epoxy-based primer

Abbreviations:

AS Acrylic acid BG Butylglycol

DMEA dimethylethanolamine

HEA hydroxyethyl acrylate

IS itaconic acid

LA lauryl acrylate (mixture of C ₂ -C ₄ -alkanol esters) MS maleic acid

S styrene

VAc vinyl acetate

VPS vinylphosphonic acid

Polymers in aqueous solution for testing in acrylate- or PUR-based primer varnish:

Polymer solutions in organic solvents for testing in an epoxy-based primer:

Claims

claims

1. Composition for coating metallic surfaces containing

A 15 to 70 wt .-% based on the total weight of the composition of a binder component;

B 0.1 to 40 wt .-% based on the total weight of the composition of a corrosion protection component containing at least one corrosion inhibitor polymer obtainable from the polymerization of at least the monomers of the composition

B1 from 0.1 to 95% by weight, based on the total amount of monomers used, of the formation of the corrosion inhibitor polymer of at least one ethylenically unsaturated monocarboxylic acid,

and at least one monomer selected from B2 and B3, wherein

B2 0.1 to 70 wt .-% based on the total amount of the monomers used to form the corrosion inhibitor polymer of at least one ethylenically unsaturated dicarboxylic acid of the general formula

(HOOC) R ¹ C = CR ² (COOH) (I), and / or R ¹ R ² C = C (- (CH ₂ ) _n -COOH) (COOH) (II)

or the corresponding carboxylic acid anhydrides and / or other hydrolyzable derivatives, wherein R ¹ and R ² independently of one another are H or a straight-chain or branched, optionally substituted alkyl radical having 1 to 20 C atoms or in the case of (I) R ¹ and R ² common for an optionally substituted alkylene radical

3 to 20 carbon atoms, and n is an integer of 0 to 5;

B3 from 0.1 to 70% by weight, based on the total amount of monomers used, of forming the corrosion inhibitor polymer of at least one further ethylenically unsaturated comonomer other than B1 and B2;

C 5 to 84.9 wt .-% based on the total weight of the composition of a solvent component; D 0 to 30 wt .-% based on the total weight of the composition of a crosslinkable component;

E 0 to 70 wt .-% based on the total weight of the composition of a pigment / filler component;

F optionally further components

2. A composition according to claim 1, wherein at least one of the following conditions is met:

R ¹ , R ² are independently selected from the group consisting of H and CH ₃ ;

the ethylenically unsaturated dicarboxylic acid / anhydride B2 is maleic acid or its anhydride;

the at least one ethylenically unsaturated monocarboxylic acid B1 is acrylic acid or methacrylic acid.

3. Composition according to claim 1 or 2, characterized in that the at least one ethylenically unsaturated comonomer B3 phosphonic acid and / or phosphoric acid groups.

4. The composition according to any one of claims 1 to 3, characterized in that it is the ethylenically unsaturated comonomer B3 is nylphosphonic.

5. The composition according to any one of claims 1 to 4, characterized in that the corrosion inhibitor polymer is obtainable from the polymerization of the monomers B1, B2 or B1, B3 or B1, B2, B3.

6. A composition according to claim 5, characterized in that the corrosion inhibitor polymer is obtainable from the polymerization of the monomers B1, B2 and B3.

7. A composition according to claim 6, characterized in that B1 is acrylic acid, B2 is maleic acid and B3 is vinylphosphonic acid.

A composition according to any one of claims 5 to 7, characterized in that the corrosion inhibitor polymer is obtainable from the polymerization of the monomers of the composition

-B1 30-70% by weight

-B2 0.5-65% by weight

-B3 0.2-65% by weight.

9. A process for the preparation of a composition according to any one of claims 1 to 8 comprising the steps

a) contacting the components A, B, C and optionally D, E and F and

b) mixing the components.

10. The method according to claim 9, characterized in that the component A is fed in step a) as a dispersion and component B in step a) as a solution or emulsion.

11. A method of coating a metallic surface comprising the steps of:

(a) applying a layer to the metallic surface of a composition according to any one of claims 1 to 8;

(b) optionally, crosslinking the applied layer; and

(c) drying the layer.

12. The method according to claim 11, characterized in that before step (a), a pretreatment step takes place.

13. The method according to claim 11, characterized in that before step (a) no pretreatment step takes place.

14. The method according to claim 11 to 13, characterized in that the applied layer after drying has at least a thickness of 3.1 microns.

15. The method according to any one of claims 11 to 14, characterized in that it is the surface of iron, steel, zinc, aluminum, magnesium, tin, copper or alloys thereof in the metallic surface.

16. The method according to any one of claims 11 to 15, characterized in that it is the surface of metal sheets or metal strips in the metal surface.

17. The method according to claim 16, characterized in that it is in the sheet metal or metal strip to one selected from the group of galvanized steel, tinned steel, aluminized steel, aluminum or galvanized aluminum.

18. The method according to any one of claims 11 to 17, characterized in that after coating with the composition according to one of claims 1 to 8, an electrocoating is applied.

19. Coated metallic surface obtainable from a method according to one of claims 11 to 18.

20. Coated metallic surface according to claim 19, characterized in that the metallic layer is iron, steel, zinc, aluminum, magnesium, tin, copper or alloys thereof.

21. Coated metallic surface according to claim 19 or 20, characterized in that the applied layer after drying has at least a thickness of 3.1 microns.

22. A coated metallic surface according to any one of claims 19 to 21, character- ized in that from this at least one molded body selected from the group of parts of automobile bodies, truck bodies, linings for household appliances, cladding for technical equipment, components in the field of architecture or Furniture is made.

23. Use of a composition according to any one of claims 1 to 8 for the coating of metallic surfaces.

24. Use of component B as a corrosion protection additive in a coating composition.

25. Use of a composition according to any one of claims 1 to 8 as a primer.

26. Use according to claim 25, characterized in that the primer is used in coil coating.

27. Use according to claim 25, characterized in that the primer is used in atmospheric corrosion protection.