Bonding paint layer with polyvinyl amines in polymer-containing aqueous acidic anticorrosion media. RU patent 2504601.

FIELD: chemistry.

SUBSTANCE: agent contains water and fluorine-containing complex titanium and/or zirconium ions, an anticorrosion pigment, an organic polymer or copolymer which is water-soluble or water-dispersible, which as such in an aqueous solution in concentration of 50 wt % has pH ranging from 1 to 3. The agent also contains a polyvinyl amine with molecular weight greater than 100000 g/mol but not greater than 1000000 g/mol, the degree of acylation of the polyvinyl amines being not less than 80%.

EFFECT: invention improves bonding of a hardened ground coating with a metal surface and subsequent organic coatings.

14 cl, 2 tbl

The present invention relates to the water, not containing chromium and tool for priming coating of metal surfaces, which for the improvement of adhesion of cured anticorrosive primers with the metal surface and the subsequent organic coating contains at least one organic polymer and copolymer at least partially acylated . The invention of advanced relates to a method for anticorrosive primers with the corresponding invention of a product, and also for application of other organic coatings, in particular those based on polyurethane resins and/or on the basis of isocyanates and diols or polyols, and made in such a way metal tape or cutoff from it a piece of sheet metal that can be subjected to moldable.

The prior art known to a large number of curing primer compositions, not containing chromium, which are suitable for the formation of the metallic surfaces corrosion-resistant coating a few microns thick. Such priming funds are usually acidic aqueous solutions, which provide for transformation of inorganic metal surface and coating it with an organic binder tool, which then hardens, being in contact with priming agent. In this way the obtained thin organic-inorganic hybrid coatings, which already provide significant protection against corrosion.

So, laid out the description of the invention to Germany's application DE 10 2006 039 633 is water anticorrosion mean for priming metal coating of painted surfaces, which has a value of pH in the range from 1 to 3, contains water and

a) fluorine-containing complex ions titanium and/or zirconium,

(b) at least one anticorrosive pigment,

C) at least one organic polymer, water soluble or in the water in this area pH, and as such, in aqueous solution at a concentration of 50% by weight has a value of pH in the range from 1 to 3.

According to the instructions of a patent document DE 10 2006 039 633, this corrosion-resistant tool set lime of the metal belt status can be used as high-grade coating, protecting from corrosion. However, for optimal barrier actions against the corrosive environments and desired mechanical and optical properties covered with a metal tape also need additional coverage of system of organic binder, that is, application of additional paint system. An optional secondary coverage is also mentioned in the patent document DE 10 2006 039 633, although the characteristics of the clutch with the usual fine lacquers are not optimal, so that secondary coating can easily crumble from the inside and lose their functionality.

Thus, the task of the present invention is to improve the adhesion of organic coating paint systems, metal surfaces, in particular with the surfaces of zinc and zinc alloys by means of cure corrosion-resistant, but not containing chromium primer products containing organic binder, and to gain sufficient traction on paint systems, especially paint systems based on polyurethane resins.

When it talks about « coverage», it means that the metal surface before handling the relevant invention corrosion protection agent is not subject to any additional processing for protection against corrosion. Moreover, this invention corrosion product should be applied or metal surface. This treatment represents a first measure corrosion protection of metal surface. This should definitely preferably after applying the relevant invention of anticorrosion means to put on a metal surface for more decorative and/or to protect against corrosion coating, such as ordinary lacquers for coating dipping, spraying or coating powders.

Specification of the patent EP 0 672 467 presents an interim flushing phosphate-treated metal surfaces solution acylated before conducting coating to improve traction inflicted by dipping varnishes from phosphated metal surface. Application of acylated in water anticorrosive vehicle containing organic binder for anticorrosive primers if this is not mentioned, nor the suitability of acylated as an amplifier coupling system-specific organic binders.

Underlying the invention task unexpectedly solved by not containing chromium, cure of anticorrosion means for priming metal coating of painted surfaces, which has a value of pH in the range from 1 to 3, contains water and

a) fluorine-containing complex ions titanium and/or zirconium,

(b) at least one anticorrosive pigment,

C) at least one organic polymer, water soluble or in the water in this area pH, and as such, in aqueous solution at a concentration of 50% by weight has a pH value in the field from 1 to 3,

moreover, the tool also contains

d) at least one water soluble or in water organic polymer or copolymer, which does not constitute an organic polymer or copolymer, corresponding to a component), and that has at least one link with the General structural formula (I):

and the remains R 1 and R 2 , independently, choose from hydrogen and/or an alkyl group, containing not more than 6 carbon atoms.

Suddenly, in the presence of water-soluble or in water organic polymer or copolymer under component d) in the known prior art acid the containing components), clearly increases with both the adhesion of cured priming funds with metal painted surface and adhesion of organic coating lacquer with primer coating.

Under according to the invention understand all , substituted on the nitrogen atom, and the loose .

As appeared, in particular a positive effect on the adhesion of cured anticorrosive primers from the painted surface has a presence and amides in organic polymer or copolymer, respectively the General structural formula (I). Accordingly, preferable with such relevant invention priming funds, which contains at least one organic polymer and copolymer under component d), which has at least one link with the General structural formula (I), in which the remainder R 1 choose from hydrogen or methyl group, and the remainder R 2 is the hydrogen atom, in particular whenever thus replaced all links with the General structural formula (I).

The organic polymer and copolymer component d), along with the links with the General structural formula (I), may contain any other links, for example, fragments of vinyl alcohols and products esterification, and . However, due to easier accessibility and greater efficiency to increase the adhesion of varnish, as a component d) is preferred , amino which at least partially, are and, mainly, .

In addition, it was found that increase of links according to the General structural formula (I) in an organic polymer or copolymer component d) adhesion of the coating on metal painted surface by means of cured priming means of continuously improving. In this regard, as the organic polymer component d) therefore preferable with the degree of acylation of not less than 50%, preferably not less than 80%, and especially not less than 90%.

Moreover, respectively invention was found that, as in the corresponding invention vehicle as a component d) use , amino which at least partially, are , the best results in relation to the paint coating adhesion are achieved when their molecular mass is preferably more than 10,000, especially preferably more than 100,000, but mostly not more than 1,000,000 g/mol, especially preferably no more than 500000 g/mol.

Accordingly, for the solution put in a basis of invention tasks best suited with a molecular weight of more than 100,000 g/mol, but not more than 500,000 g/mol, and the degree of acylation of not less than 90%, and therefore is especially preferred.

The following are more specific explained versions of components a-C) of the relevant invention cure anticorrosion means.

Fluorine-containing complex ions titanium and/or zirconium under component a) the relevant invention, mostly represent complex ions. You can enter them in the form of free acids or in the form of salts, soluble in anticorrosive tool. To bring the pH of the acid value is best to enter fluorine-containing complex ions in the form of acids. Fluorine-containing complex ions in the tool can also contain less than 6 fluorine atoms on a complex molecule. For example, this can be achieved by the fact that in addition to complex ions impose other connection or salt ions titanium and/or zirconium in a position to form . For example, should be called or . On the other hand, anti-corrosion agent can have a surplus of free of fluoride ions, exceeding the number of available complex ions, which, for example, can be introduced in the form of hydrofluoric acid.

Anticorrosive pigment b) preferably represents a dispersed organic or inorganic compound that by impeding the diffusion («barrier pigment») delays the diffusion of water and/or other corrosive agents through the coating, or can allocate molecules or ions with anti-corrosion effect. As a corrosion resistant pigment preferably applied connection with the properties of cation-exchange substance. In particular, preferably compound containing cations two - or polyvalent metal able to exchange ions of alkaline metals. Preferred exchangeable cations are cations of metals such as Ca, Ce, Zn, Sr, La, Y, Al and Mg. Especially preferred anti-corrosion pigments based on silicate with a layered or spatial mesh structure that contain similar exchange cations. For example, anticorrosive pigment may be a synthetic amorphous silicon acid, which, at least partly, is in the form of its salts with the ability to exchange ions of calcium. To meet additionally discussed below desirable thickness of a layer of hardened anti-corrosion products, the average particle size of anticorrosive pigment (D50-value, for example, determined by the methods of light scattering) varies in the range from 0.5 to 10 microns, especially in the area from 1 to 4 microns.

Organic polymer that is selectable as a component), has its own inherent in it, the property is build in an aqueous solution at a concentration of about 50% by weight of pH value in the range from 1 to 3, preferably in the region of 1.5 to 2.5, and in particular in the area from 1.8 to 2.2. This requires that the polymer in water solution had the group, causing acid reaction, which give a solution of polymer pH value in this area, without the need to regulate the pH value addition of extra acids.

The presence of a component) makes anticorrosion mean «», that is, causes hardening of anticorrosion means on a metal surface. It may be a purely physical way due to evaporation of water and/or solvent (which may be designated as «film formation»). It is however preferable to cure is based, at least partially, on a chemical reaction («present»), in which the molecular mass of the polymer or copolymer with) increases. Examples of such reactions are reactions of polymerization, e.g. the double C=C-relations, or condensation reaction. These reactions can be initiated in a thermally or the impact of rich radiation energy (for example, electron beam irradiation, gamma rays, ultraviolet or visible light). In the framework of the present invention as a component with a) preferably use the polymer and copolymer, thermal effects and/or evaporation of water and/or solvent. Summing heat may be fulfilled by the carrier (such as a pre-heated surface or hot air), or via infrared radiation.

Organic polymer or a copolymer with) in the simplest case contains monomer with ethylene saturation capable of radical polymerization.

For example, the following may be used monomers with ethylene saturation: monomers, such as styrene and [alpha]-methylstyrene, esters of mono - and dicarboxylic acids with one of ethylene saturation in the [alpha]-[beta]-position having predominantly from 3 to 6 carbon atoms, in particular, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and acid with aliphatic alcohols having mostly from 1 to 12, preferably from 1 to 8 With the atoms in features such as methyl, ethyl, n-butyl, , , , , , , and 2- esters of acrylic and methacrylic acids, or di-n-butyl complex diesters fumaric and maleinovoj acids.

Organic polymer or a copolymer C) preferably contains at least one monomer selected from acrylic acid, methacrylic acid ester acrylic acid ester methacrylic acid, and has at least one type of functional groups selected from epoxy, , hydroxyl, carboxyl, phosphoric acid groups and fragments of esters of phosphoric acid.

In particular, preferably synthesize so that it contains at least two monomers selected from acrylic acid, methacrylic acid ester acrylic acid ester methacrylic acid, associated with at least one monomer selected from the ester acrylic acid ester methacrylic acid, polymer has at least one type of functional groups selected from epoxy, , hydroxyl, carboxyl, phosphoric acid groups and fragments of esters of phosphoric acid.

The preferred polymers or copolymers, which bear group or fragments of esters of phosphoric acid, and the content of monomers in polymers, which are group or fragments of esters of phosphoric acid, varies in particular in the area of 0.5 to 4, especially preferably in the region of 1 to 2 molar percent.

In addition to groups or fragments of esters of phosphoric acid, polymer or copolymer, preferably there is at least one additional group chosen from epoxy groups, groups, carboxyl groups and hydroxyl groups. The content of hydroxyl groups in polymers or copolymer constitutes from 0.5 to 3.5 mg/g polymer. Especially preferred polymer contains group or fragments of esters of phosphoric acid, carboxyl groups and hydroxyl groups.

Next, is preferable to the polymer and copolymer, except for hydroxyl, carboxyl, phosphoric acid groups or fragments of esters of phosphoric acid, additionally contain fragments of carboxylic acid amides, and N-atoms in a fragment of a carboxylic acid amide associated with at least one remnant, preferably at least one remnant. Especially preferred polymers that have group or fragments of esters of phosphoric acid, and additionally as the hydroxyl group and a carboxyl group, and named movie carboxylic acid amides.

Examples of such monomers are hydroxy-C1-C8- esters of methacrylic and acrylic acids, such as n-hydroxyethyl-, n-hydroxypropyl - or n- and-methacrylate and compounds such as N-, and esters of phosphoric acid and and .

Adding able to form chelate complexes of organic compounds f) are recommended, especially when, polymer with) has groups.

Anticorrosion mean preferably contains phosphate ions as an additional component e). They can be introduced in the form of phosphoric acid and/or in the form of its salts. With the introduction of phosphoric acid may be a need to regulate the pH value of anticorrosion means to the desired level by adding base of passive substances. As a base of passive substances is proposed to use oxides or carbonates below-named metals, is preferably the presence of the corresponding metal ions. Regardless of what form make phosphate ions in the processing tool, depending on the pH value is set to an appropriate balance between different particles. For the following quantitative data regarding the preferred composition of anticorrosion means adopted the simplified assumption that the phosphate ions are in the form of phosphoric acid.

In addition, the invention of a corrosion-proof tool may contain ions of manganese and/or magnesium as an additional component f). Thus preferably the presence of manganese ions. In this case, magnesium ions may be in addition to ions of manganese, that even is preferred. These metal ions preferably introduced in anti-corrosion agent in the form of phosphates because oxides, hydroxides or carbonates these metals interact with phosphoric acid. These oxides, hydroxides or carbonates can also serve as a base of passive components to the presence of phosphoric acid to adjust the pH value to the desired area.

In addition, the invention of anticorrosion mean preferably contains as an additional component g) at least one organic compound capable of formation of chelate complexes. Capable of formation of chelate complexes of organic compounds (molecules or ions) are, for example, -especially acid, acid, diphosphonic acids and esters of phosphoric acid, as well as, where appropriate, their salts. Selected examples are acid, amino-Tris( acid), -Penta( acid), (2-hydroxyethyl)amino-bis( acid), Ethylenediamine-tetrakis( acid), -tetrakis( acid), (2-ethylhexyl)-( acid), n--bis( acid), cyclohexane-1,2-diamine-tetrakis( acid), -( acid), N,N-bis-(3-aminopropyl)-amino-hexacis( acid).

For more specific examples are named in the stone-description of the invention to application DE 10 2006 039 633, in paragraph [0014].

It is also preferable to anticorrosion mean as a component h) additionally contain and/or ions. Their preferably introduced in the form of salts of ammonium or of alkali metals.

In addition, it is preferable to have the anticorrosion mean as a component i) in addition to contain at least one cation selected from ions of zinc, cobalt, Nickel, vanadium and iron. Keep in mind ions are soluble in the anticorrosive, and not such ions, which are associated in the anticorrosive pigment b) as of exchanging cations. As the above ions of manganese and/or magnesium, these cations also preferably introduced in the form of phosphate. Again, this can be due to the fact that oxides, hydroxides and carbonates of these ions react with phosphoric acid. In particular, preferably corrosion product contains zinc ions.

Next, is preferable to anticorrosion mean as a component j) additionally contain at least one restorer selected from ions of iron(II) and hydroxylamine, salts or connections, hydroxylamine. This applies in particular when the corrosion product contains ions of manganese(II).

By definition, anticorrosion mean that contains at least the components (a), b), C) and d). Each additional optional components from (e) to (j) improve certain properties in the profile specifications of the invention of anticorrosion means. So in particular, it is preferable that anticorrosion mean contain at least one, mainly at least 2, and in particular preferably at least 3 of the optional components of e) to (j). For example, especially preferably anticorrosion mean contain as phosphate ions and ions of manganese and/or magnesium. It is also preferable to corrosion at the same time contain phosphate ions and at least one organic compound capable to form chelate complexes. In the optional preferred embodiment, the corrosion-resistant tool contains ions of manganese and/or magnesium, and additionally at least one cation selected from ions of zinc, cobalt, Nickel, vanadium and iron. If there are ions of manganese(II), anticorrosion mean preferably additionally contains a restorer i).

In the optional preferred embodiment, the corrosion product contains at least one of the components of e), f), g) and i) together with and/or tungstate ions.

Especially preferred corrosion product contains at least one representative of each of the components of e), f), g), h) and i).

Optional anticorrosion mean may contain additives with dispersant properties, which, for example, are known for grinding pigment pastes the manufacture of paint materials.

Anticorrosion mean in a ready to use condition preferably includes components with the following levels of content in weight percentage, based on all anticorrosion mean:

water: from 25 to 69.6% by weight,

a) fluorine-containing complex ions titanium and/or zirconium, per or, respectively, acid: in General, from 0.3 to 3% by weight, preferably from 0.5 to 2% by weight,

b) corrosion protection(nye) pigment(s): in General from 5 to 25% by weight, preferably in General, from 10 to 20% by weight,

C) organic polymer, water soluble or in the water in this area of pH values, which as such in aqueous solution at the content of 50% by weight has a value of pH in the range from 1 to 3 from 25 to 50 per cent, by weight, preferably from 30 to 40% by weight

d) acylated : in General, from 0.1 to 5% by weight, preferably from 0.5 to 2% by weight,

In addition to these components, there may be additional active or auxiliary substances, for example, the above additional polymers and/or supplements with dispersing properties. It goes without saying that the content of separate components chosen in such a way that together they constitute 100%. This is also true, when in addition to these components a) to (j) present additional components. In a preferred embodiment, the corrosion product contains, in addition to water components from a) to d), and one or more of the components of e) to (j), if necessary with the addition of the above-mentioned additional polymers and additives. It should be noted that for these ion components must be appropriate counterions. For example, and/or ions are mainly used in the form of salts of ammonium or of alkali metals. However, in General, is preferable to an anticorrosive means, in addition to existing as of fluorinated anion complexes (a), anionic groups in the anticorrosive pigment b) and in polymers or copolymers C) and (d), phosphatic ions (e), and, if necessary, anions of organic compounds (g), are able to form chelate complexes, failed to provide any other anions. Under this condition, it is guaranteed that after application and curing of anticorrosion means in a layer no salt, which dissolve easily in water and which weaken the anti-corrosion effect.

In particular, corresponding to the invention of a corrosion-proof tool must contain less organic compounds, such as organic solvents, which are volatile in the conditions of hot drying and fall into the surrounding air as «volatile organic compounds, VOC». Accordingly, it is preferable that anticorrosion mean contain not more than 5% by weight, preferably no more than 2% by weight, and especially not more than 0,5% by weight of organic compounds that at atmospheric pressure have a boiling point of magnitude below 150 C. and, to a maximum of 150 degrees C.

For reasons of wide applicability, the speed of production and consumption it is desirable that the metal surface coated with corrosion protection agent subjected to hardening at temperature not above 150 degrees C. Accordingly, organic polymer or a copolymer C) preferably a property, that he is cured at a temperature not above 150 C, preferably not above 100 C, within no more than 60 seconds, preferably no more than 30 seconds. The mentioned temperature constitute a material temperature of a metal substrate is coated with corrosion protection agent.

Therefore, additional aspect of the present invention also refers to a method of coating on the metal tape with the corresponding invention corrosion protection agent, preferably with such a wet film thickness on the moving metal band that cures by heating of a metal tape obtains a layer with thickness from 0.5 to 10 microns, preferably from 1 to 5 microns. The temperature of the tape is preferably maximum 150 C, preferably as high as 100 degrees, if The duration of a maximum of 60 seconds, preferably as much as 30 seconds.

After curing, corresponding to the invention of anticorrosion means on a metal substrate is obtained casing layer already has a good grip and providing protection from corrosion, which is particularly well suited for subsequent coating of organic coating systems based on surface binding polymers or copolymers according d) of the relevant invention of products, especially for paint systems based on polyurethane resins and/or on the basis of isocyanates and diols or polyols.

Accordingly, the method according to the invention, in particular also covers the additional coating products containing the system of organic binder on the basis of polyurethane resins and/or on the basis of isocyanates and diols or polyols, cured corresponding to the invention of a corrosion-proof tool, and curing of the coating funds. Application of additional, mainly organic coating layers primarily serves to strengthen protection against corrosion of a metal surface due to a higher barrier to action against aggressive compounds and environments. In addition, coatings provide improved abrasion resistance and also decorative purposes as a result of mixing of pigments, such as optical masking the surfaces of metal painted products or make color paints. Prerequisite for long-term stability, total cover, made of a variety of cover funds, is a good grip hardened cover of the funds with one another and on the boundary surface with metal painted surface. In the corresponding invention method achieved these properties and mutual compatibility of organic coating layers and system binder, and as a secondary coverage on anticorrosive vehicle according to the invention, as already mentioned, the preferable system of a binder based on polyurethane resins and/or on the basis of isocyanates and diols or polyols.

Corresponding to the invention of the method of coating on metal surfaces preferably can be applied to the metal strips, selected among the tapes from the zinc or zinc alloy, iron, or iron alloys, aluminium or aluminium alloys, and also from the steel belts, covered with zinc or zinc alloys or aluminium or aluminium alloys. The especially preferably primer coating selected tapes of zinc and zinc alloys, steel belts, covered with zinc and zinc alloys, thanks to improved adhesion of metal painted surface.

In addition, the present invention includes made relevant to the invention way, the metal strip or separated from her sheet metal, which can be subjected to moldable. The preferable such metallic ribbon, which in addition to coverage of the relevant invention funds has cured secondary coating with a top product containing system binder on the basis of polyurethane resins and/or on the basis of isocyanates and diols or polyols.

Application examples:

Then, in the order of the example, not only lists the corresponding invention corrosion protection agents, but also described their implementation in the relevant invention of the method, which provide secondary coverage with a product containing system binder on the basis of polyurethane resins or on the basis of isocyanates and diols or polyols. The effectiveness of the cover system in respect of its adhesion characteristics demonstrated in the so-called trial of boiling, and is associated with comparable with coating systems according to prototype.

Table 1 Composition of water priming all sample songs

Components*

Designation

Quantity/weight.% #

H 2 6 TiF

Modified calcium oxide silicon

Acrylic resin

-1,1- acid

* According to the nomenclature of components in the description # Share amounting to the difference between the sum of the parts by weight of components and 100%, falls on the water

Table 1 gives basic composition of the water of anticorrosion means according to prototype described in the patent document DE 10 2006 039 633.

Relevant to the invention of the funds are obtained by adding the appropriate quantity of partially .

It was shown that in the so-called «trial by boiling» especially remarkable suitable are those corrosion protection agents which improve adhesion with organic top lacquer based on polyurethane resin in respect of basic composition V1, who, as the polymer additives contain with high molecular weight (B1, B3-B5: >10000 g/mol), in each case in particular, preferably a high degree of acylation (B3, B4: >70%).

1. Not containing chromium anticorrosion mean for anticorrosive primers metal painted surfaces, which has a value of pH in the range from 1 to 3 containing water and a) fluorine-containing complex ions titanium and/or zirconium, (b) at least one anticorrosive pigment, c) at least one organic polymer and copolymer, water soluble or in the water in the selected area of pH, and as such, in aqueous solution at a concentration of 50% by weight has a value of pH in the range from 1 to 3, characterized in that it additionally contains d) at least one with a molecular weight of more than 100,000 g/mol, but not more than 1,000,000 g/mol, while the degree of acylation is not less than 80%.

2. The tool according to claim 1, wherein the amino group in component d) are .

3. The tool according to claim 2, characterized in that the molecular mass component d) is not more than 500000 g/mol.

4. Means of one of the preceding paragraphs, characterized in that the degree of acylation component d) is not less than 90%.

5. The tool according to claim 1, wherein the water-soluble or dispersable in water organic polymers or copolymers of component C) synthesized from one or more monomers from acrylic acid, methacrylic acid ester acrylic acid ester of methacrylic acid and have at least one type of functional groups selected from epoxy, , hydroxyl, carboxyl, phosphoric acid groups and fragments of esters of phosphoric acid.

6. Means of claim 5, wherein the water-soluble or dispersable in water organic polymers or copolymers of component C) contain at least one monomer selected from the ester acrylic acid ester of methacrylic acid.

7. Tool on one of the claims 5 or 6, wherein the content of monomers, which are group or fragments of esters of phosphoric acid in polymers or copolymers component) varies in the range from 0.5 to 4, preferably in the region of 1 to 2 mol.%.

8. The tool according to claim 1, characterized in that it is ready to application of state includes components with the following levels of content in weight percentage per all anti-corrosive medium: water from 25 to 69.6% by weight a) fluorine-containing complex ions titanium and/or zirconium per or respectively acid in General from 0.3 to 3% by weight, preferably from 0.5 to 2% by weight, b) corrosion protection(nye) pigment(you) in General from 5 to 25% by weight, preferably in General, from 10 to 20% by weight c) organic polymer water-soluble or in the water in the selected area of pH values, which as such in aqueous solution at the content of 50% by weight has a value of pH in the range from 1 to 3 from 25 to 50 per cent, by weight, preferably from 30 to 40% by weight, d) acylated in General from 0.1 to 5% by weight, preferably from 0.5 to 2% by weight, e) phosphate ions per phosphoric acid from 0 to 5% by weight, preferably from 0.5 to 4% by weight, f) ions of manganese and/or magnesium in General from 0 to 2% by weight, preferably from 0.1 to 1% by weight, g) organic(-Kie) connection(opal), capable of(institutional) form chelate complexes in General from 0 to 5% by weight, preferably from 0,5 to 3% by weight, h) and/or ions per salt in General from 0 to 1% by weight, preferably from 0.05 to 0.5% by weight, i) cations, selected from ions of zinc, cobalt, Nickel, vanadium and iron, in General, from 0 to 1% by weight, preferably from 0.1 to 0.5% by weight, j) reducing selected from ions of iron (II) and hydroxylamine, salts or connections, hydroxylamine, in General, from 0 to 0.1% by weight, preferably from 0.005 to 0.05% by weight.

9. The tool according to claim 1, characterized in that it contains no more than 5% by weight, preferably no more than 2% by weight and in particular not more than 0,5% by weight of organic compounds that at atmospheric pressure have a boiling point of not above 150 degrees C.

10. The method of coating on the metal strip, wherein the anticorrosion mean one of claims 1 to 9 lead in contact with degreased and cleaned by a metal band, and, after curing, anticorrosive means of the metal belt receive the thickness of the layer in the region of 0.5 to 10 microns, preferably from 1 to 5 microns.

11. The method according to paragraph 10, characterized in that after drying of anticorrosion means cause and additional cover a means of containing the system of organic binder on the basis of polyurethane resins and/or on the basis of isocyanates and diols or polyols.

13. Metal tape coated, wherein the coating is applied in a way one of .10-12.

14. Metallic coated sheet, the resulting separation from metal coated, which, if necessary, subject to moldable, wherein the coating is applied in a way one of .10-12.