EP1417040A2

EP1417040A2 - Aqueous functional coating material and integrated method for production of coloured or effect-generating multi-layer coatings

Info

Publication number: EP1417040A2
Application number: EP02730277A
Authority: EP
Inventors: Ekkehard Sapper
Original assignee: BASF Coatings GmbH
Current assignee: BASF Coatings GmbH
Priority date: 2001-05-28
Filing date: 2002-05-24
Publication date: 2004-05-12
Anticipated expiration: 2022-05-24
Also published as: CA2442545C; EP1417040B1; US6942902B2; WO2002096572A2; DE10124576A1; ATE313389T1; DE50205367D1; DE10124576B4; ES2255613T5; US20040077750A1; EP1417040B2; MXPA03009170A; WO2002096572A3; ES2255613T3; CA2442545A1

Abstract

A wet-on-wet process for producing multicoat color and/or effect coating systems is disclosed. The process involves using aqueous functional coating materials comprising (A) at least one crosslinkable binder, (B) at least one separate, water-soluble and/or -dispersible crosslinking system which independently effects partial or complete crosslinking in and/or on the matrix of the wet, drying and/or dried films (2) of the aqueous functional coating materials before the binders (A) crosslink completely; and (C) at least one pigment.

Description

Aqueous functional coating materials and integrated process for the production of color and / or effect multi-layer coatings

The present invention relates to a new integrated wet-on-wet method for producing color and / or effect multi-layer coatings, the at least one functional layer and at least one color and / or effect uni-coat or alternatively at least one color and / or effect base coat and contain at least one clear coat. In addition, the present invention relates to new aqueous functional coating materials for the production of multicolor paint or effect paint.

Integrated wet-on-wet processes are understood to mean coating processes in which at least two different coating materials are applied one above the other in at least two layers, the lower layer or the lower layers only being dried, but not completely crosslinked, after which the layers are cured together.

Integrated wet-on-wet processes for the production of color and / or effect multi-layer coatings which contain at least one functional layer and at least one color and / or effect single-coat finish or alternatively at least one color and / or effect base coat and at least one clear coat known. With these integrated procedures

(1) aqueous functional coating materials are applied to primed or unprimed substrates, after which (2) the resulting layers of the aqueous functional coating materials are dried without fully hardening,

(3) the dried layer (2) is coated with water-based paints, after which

(4) the resulting water-based lacquer layers (3), without fully hardening, coated with clear lacquers, after which

(5) the layers (2), (3) and (4) harden together, which results in the functional layers, the color and / or effect basecoats and the clearcoats.

Reference is made, for example, to German patent application DE 44 38 504 A1.

s

The aqueous functional coating materials used here are physically curable and contain, as a binder, a water-dilutable polyurethane resin with an acid number of 10 to 60 and a number average molecular weight of 4,000 to 25,000. The polyurethane resin can be prepared by aa) a polyester and / or polyether polyol with a number average molecular weight of 400 to 5,000 or a mixture of such polyester and / or polyether polyols, bb) a polyisocyanate or a mixture of polyisocyanates, cc) a compound, which has at least one group which is reactive towards isocyanate groups and at least one group capable of forming anions, or a mixture of such compounds and optionally dd) an organic compound containing hydroxyl and / or amino groups and having a molecular weight of 40 to 400 or a mixture of such Compounds are reacted with each other and the resulting reaction product at least is partially neutralized. The aqueous functional coating materials also contain pigments and / or fillers, the ratio of binder to pigment being between 0.5: 1 and 1.5: 1. They can also contain minor amounts of aminoplast resins or polyisocyanates.

The known aqueous functional coating materials allow the production of particularly thin filler coatings,

Stone chip protection primers or functional layers without loss of stone chip resistance or deterioration in covering the unevenness of the primed substrate. The known wet-on-wet process is therefore particularly economical and ecological.

It is disadvantageous that the known wet-on-wet process is limited to the use of a special type of polyurethane and therefore offers no alternatives in this regard. Nevertheless, because of the numerous economic, ecological and technical advantages offered by the aqueous functional coating materials known from DE 44 38 504 A1 and the wet-on-wet process made possible by them, efforts are made to remove the usual and known so-called stoving fillers to replace the aqueous functional coating materials.

However, this substitution is not readily possible, because in the production of the color and / or effect multi-layer coatings according to DE 44 38 504 A 1 there is often an effect and / or color shift compared to the color and / or effect multi-layer coatings, in the case of which Production of one and the same water-based paints applied to baked-on filler coatings (cf., for example, German patent application DE 199 30 552 A1) and thereon were hardened. This also prevents the use of one and the same waterborne basecoat in the two processes in one company.

Another integrated wet-on-wet method is known from European patent application EP 0 871 552 A1. In this known integrated method

(A) a water-based lacquer (ii), which contains an aqueous polymer dispersion as film-forming agent, is applied to a substrate surface coated with an aqueous functional coating material (i),

(B) a suitable clear lacquer is applied to the layer obtained in step (A) and

(C) the layer of the aqueous functional coating material (i) and the layer of the water-based lacquer (ii) are baked together with the clear lacquer layer,

wherein the waterborne basecoat (ii) contains an aqueous polymer dispersion containing

(x) a (meth) acrylate copolymer based on 30 to 60% by weight of C 1 -C ₈ -alkyl (meth) acrylate monomers, 30 to 60% by weight of vinyl aromatic monomers and 0.5 to 10% by weight

(Meth) acrylic acid and

(y) a non-associative thickener which contains a (meth) acrylate copolymer based on (Cι-Ce) -based alkyl (meth) acrylate and (meth) acrylic acid. The coloring and / or effect multi-layer coatings produced by these integrated processes can be repaired very well, and the composition of the functional coating materials (i) is also not materially restricted. However, this does not apply to waterborne basecoats (ii), which are necessarily aqueous dispersions of (meth) acrylate copolymers based on the constituents (x) and (y). This is the only way to ensure that clear coats based on powder slurry clear coats can also be used for the production of the multi-layer coats without causing mud cracking.

There is therefore a need for a wet-on-wet process which has the advantages of the prior art without showing its disadvantages and which allows the stoving fillers to be substituted without great expenditure on material, apparatus and process technology, without this an effect and / or color shift occurs in the water-based paints.

Aqueous functional coating materials which contain at least one saturated, unsaturated and / or grafted with olefinically unsaturated compounds, ionically and / or nonionically stabilized polyurethane as binders and pigments are known from German patent applications DE 199 14 896 A1, DE 199 53 445 A. 1, DE 199 53 203 A 1 or DE 199 53 446 A 1. They can be cured thermally or thermally and with actinic radiation. Thermal curing can be done by self-crosslinking or external crosslinking.

DE 199 14 896 A1 was based on the object of providing new polyurethane dispersions which have no or only a very slight tendency to form coagulates. The object of DE 199 53 446 A 1 was to provide new olefinically unsaturated hydrophilic or hydrophobic polyurethanes which have a particularly high grafting activity and are easily obtainable. It was also based on the task of providing new graft copolymers based on the new polyurethanes.

The patent applications DE 199 53 445 A 1 and DE 199 53 2 03 A 1 were essentially based on the task of providing aqueous and non-aqueous self-crosslinking functional coating materials, adhesives and sealants based on polyurethane with very good application properties. In particular, the self-crosslinking functional coating materials, in particular the aqueous self-crosslinking functional coating materials, especially the self-crosslinking waterborne basecoats, should not crack when they are processed in the wet-on-wet process, even when using powder clearcoat slurries (mud cracking) or stove or Cause needlesticks. The new functional coating materials are said to have very good storage stability, excellent application properties, such as a very good flow and a very low tendency to run even with high layer thicknesses. The multicoat paint systems produced in this way are said to have an excellent overall optical impression and high chemical, yellowing and weather resistance. Last but not least, there should no longer be any delamination of the layers after the water jet test. All of these advantages should be able to be achieved without having to accept an increase in the emission of organic compounds.

The aqueous functional coating materials of DE 199 53 445 A1, DE 199 53 203 A1 or DE 199 53 446 A1 can also be used, inter alia, as * Filler can be used. However, they are preferably used as water-based paints. Whether and, if so, to what extent the known aqueous functional coating materials as fillers are able to substitute conventional and known stoving fillers in a wet-on-wet process without an effect and / or color shift occurring not known. In addition, the known aqueous functional coating materials do not contain a separate, water-soluble and / or dispersible crosslinking system which partially or completely crosslinks itself in and / or on the matrix of wet, drying and / or dried layers of the aqueous functional coating materials, before the layers are completely cross-linked. There are also no indications from the patent applications which could stimulate the person skilled in the art to add such a system to the aqueous functional coating materials.

Aqueous multicomponent systems based on hydroxyl-containing polyurethanes and polyisocyanates are known from German patent applications DE 199 04 317 A1 and DE 198 55 125 A1. The aqueous multicomponent systems can contain radiation-curable binders, reactive diluents and photoinitiators. Thus, zvyei have separate networking systems side by side. The aqueous multicomponent systems can also be used as fillers. However, because of their high reactivity, the polyurethanes and the polyisocyanates begin to crosslink immediately after application of the aqueous multicomponent systems, so that curing with actinic radiation cannot be carried out in such a way that it is essentially complete before the matrix of the layers has been completely thermally cured , Both injury mechanisms therefore run in parallel, or curing with actinic radiation is carried out after thermal curing. The German patent application DE 199 04 317 A 1 was based on the object of providing aqueous multicomponent systems which, in particular during prolonged storage, are to a lesser extent or not at all attacked and destroyed by microorganisms.

The German patent application DE 198 155 125 A 1 was based on the object of providing aqueous multicomponent systems which are easy to produce, homogeneous, easy to handle, low in solvent, boil-proof, splash-proof and stable with forced drying and which provide matt coatings which have no surface defects and gray veils but are weather-resistant and petrol-resistant.

Accordingly, the person skilled in the art was also unable to find any information from these patent applications to use two different crosslinking systems next to one another in an aqueous filler based on polyurethane, in order to prevent a shift in the effect and / or color of the waterborne basecoats when conventional stoving finishes are replaced by the aqueous fillers based on polyurethane.

The thermal crosslinking of functional coating materials by means of the complementary keto groups and hydrazide groups is known per se. The use of these complementary reactive functional groups in aqueous functional coating materials based on polyurethanes is not described in the above-mentioned German patent applications.

The object of the present invention is to provide a new wet-on-wet process for producing color and / or effect-giving ^' r multi-layer coatings, which has the economic, technical and ecological advantages of the German patent application DE 44 38 504 A 1 or European Patent application EP 0 871 552 A 1 known method and which allows to substitute stoving filler without great material, apparatus and process engineering effort, without this causing an effect and / or color shift in the water-based paints.

In addition, it was the object of the present invention to provide a new aqueous functional coating material which is outstandingly suitable for the production of coloring and / or effect-giving multi-layer coatings, it being used for the production of functional layers, fillers, stone chip protection primers,

Solid-color topcoats and basecoats, but especially functional layers, can be used. Above all, however, the new aqueous functional coating material should be suitable for the new wet-on-wet process.

Accordingly, the new wet-on-wet process for the production of color and / or effect multi-layer coatings, the at least one functional layer and at least one color and / or effect coating color or alternatively at least one color and / or effect base coat and at least one clear coat included, with the process

(1) aqueous functional coating materials applied to primed or unprimed substrate, after which

(2) the resulting layers of the aqueous functional coating materials are dried without fully hardening, (3) the dried layers (2) of the aqueous functional coating materials are coated with aqueous solid-color topcoats, after which

(4) the layers (2) and (3) harden together, resulting in the functional layers and the solid-color coatings;

or alternatively

(3) the dried layers (2) of the aqueous functional coating materials are coated with water-based paints, after which

(5) the layers (2), (3) and (4) harden together, resulting in the functional layers, the basecoats and the clearcoats;

or alternatively

(3) the dried layer (2) of the aqueous functional coating materials is coated with water-based paints,

(3) the resulting water-based lacquer layers (3) and the dried layers (2) harden together, resulting in the functional layers and the basecoats, and

(4) the basecoats are coated with clearcoats, after which (5) the clear lacquer layers (4) harden, whereby the clear lacquers result;

characterized in that containing aqueous functional coating materials

(A) at least one crosslinkable binder,

(B) at least one separate, water-soluble and / or - dispersible crosslinking system which partially or completely crosslinks for itself in and / or on the matrix of the wet, drying and / or dried layers (2) of the aqueous functional coating materials before fully crosslink the binders (A), and

(C) at least one pigment,

used.

In the following the new wet-on-wet process for the production of color and / or effect multi-layer coatings as

"Process according to the invention" referred to

In addition, the new aqueous functional coating materials were found to contain

(A) at least one crosslinkable binder,

(B) at least one separate, water-soluble and / or - dispersible crosslinking system which is made in and / or on the matrix of the wet, drying and / or dried layers (2) partially or completely crosslinked the aqueous functional coating materials for themselves before the binders (A) completely crosslinked, and

(C) at least one pigment.

In the following, the new aqueous functional coating materials are referred to as "functional coating materials according to the invention".

Further objects of the invention result from the description.

In view of the prior art, it was surprising and unforeseeable for the person skilled in the art that the object on which the present invention is based could be achieved with the aid of the method according to the invention, in particular with the aid of the functional coating materials according to the invention. It was particularly surprising that the effect and / or color shifts of

Waterborne basecoats, which had often occurred during the replacement of conventional stoving fillers with aqueous functional coating materials based on polyurethane, by adding a separate, water-soluble and / or dispersible one

Crosslinking system which is capable of partially or completely crosslinking itself in and / or on the matrix of wet, drying and / or dried layers of aqueous functional coating materials before the binders (A) completely crosslink completely could become. Above all, it was surprising that the process according to the invention and in particular the functional coating materials according to the invention provided functional layers which had a high resistance to stone chips even in layer thicknesses which are unusually small for fillers. The new ones showed Functional layers provide excellent interlayer adhesion between the primers and the water-based paints.

The process according to the invention is used to produce multi-layer coatings which give color and / or effect on primed or unprimed substrates.

The new multi-layer paint and / or effect paint systems contain at least one functional layer and at least one color and / or effect paint finish or alternatively at least one color and / or effect base coat and at least one clear coat,

Functional layers i. S. of the present invention are filler coatings i. See the German patent application DE 44 38 504 A

1 or the European patent application EP 0 871 552 A1, which have a high stone chip protection effect even in unusually thin layer thicknesses and, moreover, often also contribute to the color and / or effect. All substrates whose surface is covered by the

Use of heat and / or actinic radiation in the hardening of the layers thereon is not damaged. The substrates preferably consist of metals, plastics, wood, ceramic, stone,

Textiles, fiber composites, leather, glass, glass fibers, glass and rock wool, mineral and resin-bound building materials, such as gypsum and cement boards or roof tiles, as well as composites of these materials.

Accordingly, the method according to the invention and the functional coating materials according to the invention are not only for applications in the fields of automotive OEM painting and

Motor vehicle refinishing is particularly suitable, but also come for the coating of buildings inside and outside and of doors, windows and furniture, for industrial painting, including coil coating, container coating and the impregnation and / or coating of electrical components, as well as for the painting of white goods, inclusive Household appliances, boilers and radiators. In the context of industrial painting, they are suitable for painting practically all parts and objects for private or industrial use such as household appliances, small parts made of metal, such as screws and nuts, hubcaps, rims, packaging, or electrotechnical components such as motor windings or transformer windings.

In the case of electrically conductive substrates, primers can be used which are produced in a customary and known manner from electrocoat materials. Both anodic and cathodic electrocoat materials, but in particular cathodic electrocoat materials, are suitable for this. However, they can also have a cathodically deposited electrodeposition coating which is not thermally hardened, but is merely dried or partially hardened. The electrocoating or electrocoating layer can then be overcoated with the functional coating materials according to the invention or the functional coating materials to be used according to the invention. These can then be cured together with the electrocoat layer (wet-on-wet process).

Examples of suitable cathodic electrocoating materials and, if appropriate, wet-on-wet processes including electrocoating materials are described in Japanese Patent Application 1975-142501 (Japanese Patent Application Laid-Open No. 52-065534 A2, Chemical Abstracts Section No. 87: 137427) or US Pat 4,375,498 A 1, US 4,537,926 A 1, US 4,761, 212 A 1, EP 0 529 335 A 1, DE 41 25 459 A 1, EP 0 595 186 A 1, EP 0 074 634 A1, EP 0 505 445 A1, DE 42 35 778 A1, EP 0 646 420 A1, EP 0 639 660 A1, EP 0 817 648 A1, DE 195 12 017 C1 , EP 0 192 113 A 2, DE 41 26476 A 1 or WO 98/07794.

In the case of non-functionalized and / or non-polar plastic surfaces, these can be subjected to a pretreatment in a known manner, such as with a plasma or with flame treatment, or can be provided with a hydro primer before coating.

In the first step of the method according to the invention, at least one, in particular one, functional coating material according to the invention is applied to a substrate.

The functional coating material according to the invention contains at least one, in particular one, binder (A). The composition of the binders (A) is not restricted. They can also be oligomers or polymers.

Oligomers are understood to mean resins which contain at least 2 to 15 monomer units in their molecule. Polymers are understood to mean resins which contain at least 10 recurring monomer units in their molecule. In addition to these terms, reference is made to Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, »Oligomere«, page 425.

Preferably, the binder (A) selected from the group consisting of physically, thermally curable with aktinicher radiation, or thermally and with actinic radiation or crosslinkable statistical ^", alternating and / or block, constructed, linear and / or branched and / or comb (Co) polymers of ethylenically unsaturated monomers, and polyaddition resins and Polycondensation resins selected. These terms are supplemented by Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "Polyaddition" and "Polyadditionharze (polyadducts)", and pages 463 and 464, "Polycondensates", "Polycondensation" and "Polycondensation Resins".

Examples of highly suitable (co) polymers (A) are (meth) acrylate copolymers and partially saponified polyvinyl esters, in particular (meth) acrylic) copolymers.

Examples of suitable polyaddition resins and / or

Polycondensation resins (A) are polyesters, alkyds, polyurethanes, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, polyamides or polyimides.

Of these, the polyurethanes (A) are advantageous, which is why they are preferably used. The polyurethanes (A) are particularly preferably selected from the group consisting of saturated, unsaturated and grafted with olefinically unsaturated compounds, ionically or nonionically and ionically and nonionically stabilized polyurethanes.

Polyurethanes (A) are known per se and are described, for example, in

- German patent application DE 199 14 896 A1, column

Lines 29 to 49, column 4, line 23, to column 11, line 5, and column 19, line 12, to column 20, line 6,

German patent application DE 44 38 504 A 1, page 2, line 58, to page 4, line 40, i. V. m. Page 5, line 24, to page 7, line

33 German patent application DE 199 04 624 A 1, page 2, line 35, to page 5, line 46, i. V. m. Page 1, line 36, to page 8, line 14,

German patent application DE 41 07 136 A 1, page 2, line 23, to page 4, line 35, i. V. m. Page 5, lines 23 to 59,

German patent application DE 199 04 317 A1, page 9, line 44, to page 12, line 11, i. V. m. Page 16, line 58, to page 17,

Line 2,

described in detail. In addition, reference is made to the German patent applications cited at the beginning.

The content of binders (A) in the functional coating materials according to the invention can vary widely and depends on the requirements of the individual case. The content is preferably 10 to 80, preferably 15 to 78, particularly preferably 20 to 76, very particularly preferably 25 to 74 and in particular 30 to 72% by weight, in each case based on the solid of the functional coating material.

The functional coating materials according to the invention further contain at least one, in particular one, separate, water-soluble and / or dispersible crosslinking system (B).

In the context of the present invention, the term “separately” clarifies that the crosslinking system takes place independently or essentially independently of the crosslinking of the binder (A). It is important here that the separate crosslinking system (B) in and / or on the matrix of the wet, drying and / or dried layers from the Functional coating materials according to the invention are partially or completely crosslinked for themselves before the binders (A), in particular the polyurethanes (A), completely crosslink and thus completely crosslink the layers as a whole.

The separate crosslinking system (B) to be used according to the invention can be of any composition as long as it fulfills the requirement essential to the invention. In other words, the separate crosslinking system (B) to be used according to the invention can be selected on the basis of the composition of the aqueous functional coating materials based on the binders (A) described above, in particular the polyurethanes (A).

The separate crosslinking system (B) is preferably selected from the group consisting of physically, thermally, with actinic radiation and thermally and with actinic radiation curable crosslinking systems.

Electromagnetic radiation, preferably near infrared (NIR), visible light, UV radiation or X-rays, in particular UV radiation, and / or corpuscular radiation, in particular electron radiation, are preferably used as actinic radiation.

The separate crosslinking system (B) is preferably selected from the group consisting of crosslinking systems curable thermally or thermally and with actinic radiation. The crosslinking systems (B) can be thermally self- and / or externally crosslinking.

In the context of the present invention, the term “physical hardening” means the hardening of the invention using separate crosslinking system (B) by filming, for example, on the surface of the matrix of the layers of the functional coating materials according to the invention, the linkage via loop formation of the polymer molecules of the binders (for the term cf.Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Binders", pages 73 and 74). Or the filming takes place via the coalescence of particles from the separate crosslinking system (B) (cf. Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, »Hardening«, pages 274 and 275). No crosslinking agents are usually necessary for this. If necessary, the physical hardening can be supported by atmospheric oxygen, heat or by exposure to actinic radiation.

The selection of a physically curing separate crosslinking system (B) depends on the temperature at which the functional coating material according to the invention itself films or is thermally crosslinked. Physically curing separate crosslinking systems (B) are selected whose minimum film formation temperature (MFT) (cf.Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998 "Minimum film formation temperature", page 391) is below the minimum film formation temperature or the crosslinking temperature of the invention Functional coating materials or the binder (A). The person skilled in the art can therefore easily determine suitable physically curing separate crosslinking systems (B) for a given physically, thermally or thermally and with actinic radiation-curing functional coating material according to the invention on the basis of his general specialist knowledge, possibly with the aid of simple preliminary tests. In the context of the present invention, the term “self-crosslinking” denotes the property of the crosslinking system (B) to be used according to the invention “to undergo crosslinking reactions with itself”. The prerequisite for this is that both types of complementary reactive functional groups are already present in at least one constituent are necessary for crosslinking, or reactive functional groups which can react with themselves.On the other hand, such separate crosslinking systems (B) are referred to as crosslinking, in which one type of complementary reactive functional groups in a binder and the other type in a hardener In addition, reference is made to Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Hardening", pages 274 to 276, in particular page 275, below.

Examples of suitable complementary reactive functional groups to be used according to the invention are summarized in the following overview. In the overview, the variable R stands for an acyclic or cyclic aliphatic, an aromatic and / or an aromatic-aliphatic (araliphatic) radical; the variables R and R stand for the same or different aliphatic radicals or are linked to one another to form an aliphatic or heteroaliphatic ring.

Overview: Examples of complementary functional groups

Binders and crosslinking agents or crosslinking agents and binders -SH -C (0) -OH

-NH ₂ -C (0) -0-C (0) -

-OH -NCO

-0- (CO) -NH- (CO) -NH ₂ -NH-C (0) -OR

-0- (CO) -NH ₂ -CH ₂ -OH

-NH-CH ₂ -0-R

-NH-CH ₂ -OH

-N (-CH ₂ -0-R) ₂

-NH-C (0) -CH (-C (0) OR) ₂

-NH-C (0) -CH (-C (0) OR) (- C (O) -R)

-NH-C (0) -NR'R "

> Si (OR) ₂

O

-CH-CH ₂ OC oo

-CH-CH2

-C (0) -OH O -CH-CH ₂

-C (0) -N (CH ₂ -CH ₂ -OH) ₂

-0-C (0) -CR ⁵ = CH ₂ -OH

-0-CR = CH ₂ -NH ₂

-C (0) -CH ₂ -C (0) -R

-CH = CH ₂

> C = 0 -C (0) -NH-NH ₂

The selection of the complementary reactive functional groups depends on the temperature range in which the complete hardening of the matrix of the layers of the functional coating materials according to the invention, which also includes the binders (A), in particular the polyurethanes (A), takes place. So the thermal curing of the separate crosslinking system (B) at lower temperatures expire if the functional coating materials according to the invention are functional coating materials curable thermally or thermally and with actinic radiation. The person skilled in the art can therefore easily select the appropriate complementary reactive functional groups for a given functional coating group according to the invention, based on his general specialist knowledge, if necessary with the aid of simple orienting experiments.

Examples of suitable constituents for the separate or crosslinking systems (B) which are curable thermally or thermally and with actinic radiation and which contain the complementary reactive functional groups described above are described, for example, in

German patent application DE 199 30 067 A1, page 3, lines 23 to 56, i. V. m. Page 4, lines 23, to page 7, lines 19, page 7, lines 20, page 9, line 20, page 9, lines 21 to 29, page 9, line 49, to page 11, line 37, page 11, lines 38 to 68, page 12, lines 30 to 55, and page 16, line 50, to page 17, line 13,

German patent application DE 199 14 896 A1, column 11, line 6, to column 13, line 55,

- German patent application DE 199 04 317 A1, page 3, line

64, to page 2, line 2, i. V. m. Page 4, line 7, to page 9, line 43, and page 15, lines 33 to 49, i. V. m. Page 16, lines 30 to 45, or German patent application DE 198 18 735 A1, column two, pages 21 to 46, column 3, to column 6, line 33, and column 6, line 55, to column 7, line 35,

described in detail.

Curing with actinic radiation takes place with the aid of reactive functional groups which contain at least one, in particular one, bond which can be activated with actinic radiation.

In the context of the present invention, a bond which can be activated with actinic radiation is understood to mean a bond which becomes reactive when irradiated with actinic radiation and which undergoes polymerization reactions and / or crosslinking reactions with other activated bonds of its type which take place according to radical and / or ionic mechanisms. Examples of suitable bonds are carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon single bonds or double bonds. Of these, the carbon-carbon double bonds are particularly advantageous and are therefore used with very particular preference in accordance with the invention. For the sake of brevity, they are referred to below as "double bonds".

Accordingly, the group preferred according to the invention contains one double bond or two, three or four double bonds. If more than one double bond is used, the double bonds can be conjugated. According to the invention, however, it is advantageous if the double bonds are isolated, in particular each individually in the group in question here. According to the invention it is from it is particularly advantageous to use two, in particular one, double bond.

Examples of suitable groups are (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyf, allyl or butenyl groups; Dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups, but especially acrylate groups.

Examples of suitable components for separate crosslinker systems (B) curable with actinic radiation are described in detail in German patent application DE 197 36 083 A1, page 7, line 3, to page 8, line 38.

The selection of the separate crosslinking systems (B) curable with actinic radiation depends primarily on the wavelength range in which the bonds which can be activated with actinic radiation are activated. This wavelength range should lie outside the range with which the functional coating materials according to the invention are cured. For a given functional coating material according to the invention which is curable with actinic radiation, the person skilled in the art can therefore easily select suitable crosslinking systems (B) curable with actinic radiation on the basis of his general specialist knowledge, possibly with the aid of simple orienting experiments.

Of the separate crosslinking systems (B) to be used according to the invention described above, those which are thermally crosslinkable via keto groups and hydrazide groups are particularly advantageous. They are therefore particularly preferred according to the invention used. As already mentioned, the aqueous functional coating materials are referred to as the functional coating materials according to the invention.

The particularly preferred separate crosslinking system (B) is externally crosslinking or self-crosslinking.

The particularly preferred externally crosslinking separate crosslinking system (B) contains at least one constituent (B 1) which on average contains at least two, preferably at least three, keto groups in the molecule. In addition, the particularly preferred externally crosslinking separate crosslinking system (B) contains at least one constituent (B 2) which on average contains at least two hydrazide groups in the molecule. The particularly preferred externally crosslinking, separate crosslinking system (B) preferably consists of a constituent (B 1) and a constituent (B 2). The ratio of the two components (B 1) and (B 2) can vary very widely and depends on the functionality of the two complementary components.

The constituent (B 1) is preferably selected from the group consisting of oligomers and polymers which contain terminal or lateral or terminal and lateral keto groups. Suitable oligomers and polymers come from the polymer classes described above for binders (A), with (meth) acrylate copolymers (B 1) being particularly advantageous and therefore being used with particular preference.

The constituents (B 2) are preferably selected from the group consisting of low molecular weight compounds with at least two

Hydrazide groups and oligomers and polymers, the terminal or contain lateral or terminal and lateral hydrazide groups, selected. Suitable oligomers and polymers come from the polymer classes described below. The low molecular weight compounds with two hydrazide groups in the molecule are preferably used.

Examples of suitable low molecular weight compounds with two hydrazide groups are the dihydrazides of organic dicarboxylic acids, such as phthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid, sebacic acid or adipic acid. Adipic acid dihydrazide is particularly preferably used.

In a further preferred embodiment, the particularly preferred self-crosslinking separate crosslinking systems (B) contain at least one constituent (B 3) which, from the group consisting of oligomers and polymers, has a statistical average of at least two, in particular at least three, terminal or lateral or terminal and contain lateral keto groups and at least two, in particular at least three, terminal or lateral or terminal and lateral hydrazide groups in the molecule, or they consist of this component (B 3).

In addition to the keto groups, the preferred separate crosslinking systems (B) can also have at least one of the above-described complementary reactive functional groups for thermal crosslinking and / or at least one of the above-described reactive functional groups which contain at least one bond which can be activated with actinic radiation. These reactive functional groups can then crosslink the separate crosslinking systems (B) with the matrix of the layers of the functional coating materials according to the invention are used.

The particularly preferred separate crosslinking systems (B), which can crosslink via keto groups and hydrazide groups, are commercially available substances and are, for example, in the form of aqueous dispersions under the Acronal ® brand, in particular Acronal ® A 603 or A 627, or under the Luhydran ® brand , in particular Luhydran ® LR 8950 or 8975, from BASF Aktiengesellschaft, under the Viacryl ® brand, in particular Viacryl ® VSC 6270, 6286 or 6295, from the Solutia company or under the Setalux ® brand, in particular Setalux ® 6810 AQ-25 or XL 1141, sold by Akzo. The aqueous dispersions are crosslinked in particular with adipic acid dihydrazide. In general, the adipic dihydrazide content of the aqueous dispersions is up to 10% by weight, based on the solids content of the aqueous dispersions.

The content of the separate crosslinking systems (B) in the functional coating materials according to the invention can vary very widely and depends on the requirements of the individual case. The functional coating materials according to the invention preferably contain, based on the solid, 1 to 50, preferably 2 to 48, particularly preferably 3 to 44, very particularly preferably 4 to 42 and in particular 5 to 40% by weight of (B).

The functional coating materials according to the invention contain at least one pigment (C).

The pigments (C) are preferably selected from the group consisting of color and / or effect, fluorescent, electrically conductive and magnetically shielding pigments, metal powders, organic and inorganic, transparent and opaque fillers and nanoparticles selected.

The pigment (C) content of the functional coating materials according to the invention can vary widely. The content is preferably selected so that the quantitative ratio of pigments (C) to binders (A) and to the oligomers and polymers which may be present in the separate crosslinking systems (B) (pigment / binder ratio) is 0.1: 1 to 3 : 1, preferably 0.2: 1 to 2.8: 1, particularly preferably 0.3: 1 to 2.5: 1, very particularly preferably 0.3: 1 to 2: 1 and in particular 0.3: 1 to 1.5: 1.

Examples of suitable effect pigments are metal flake pigments such as commercially available aluminum bronzes, aluminum bronzes chromated according to DE 36 36 183 A1, and commercially available stainless steel bronzes as well as non-metallic effect pigments, such as pearlescent or interference pigments, platelet-shaped effect pigments based on iron oxide, or a shade of pink from brown has or liquid crystalline effect pigments. In addition, Römpp Lexikon Lacquers and Printing Inks, Georg Thieme Verlag, 1998, pages 176, "Effect Pigments" and pages 380 and 381 "Metal Oxide Mica Pigments" to "Metal Pigments", and the patent applications and patents DE 36 36 156 A1, DE 37 18 446 A1, DE 37 19 804 A1, DE 39 30 601 A1, EP 0 068 311 A1, EP 0 264 843 A1, EP 0 265 820 A1, EP 0 283 852 A1, EP 0 293 746 A 1, EP 0 417 567 A 1, US 4,828,826 A or US 5,244,649 A.

Examples of suitable inorganic color pigments are

White pigments such as titanium dioxide, zinc white, zinc sulfide or lithopone; Black pigments such as carbon black, iron-manganese black or spinel black;

Colored pigments such as chromium oxide, chromium oxide hydrate green, cobalt green or Ultramarine green, cobalt blue, ultramarine blue or manganese blue, ultramarine violet or cobalt and manganese violet, iron oxide red, cadmium sulfoselenide, molybdate red or ultramarine red; Iron oxide brown, mixed brown, spinel and corundum phases or chrome orange; or iron oxide yellow, nickel titanium yellow, chrome titanium yellow, cadmium sulfide, cadmium zinc sulfide, chrome yellow or bismuth vanadate.

Examples of suitable organic coloring pigments are monoazo pigments, bisazo pigments, anthraquinone pigments, benzimidazole pigments, quinacridone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, indanthrone pigments, azomethane pigments, iso-pigment pigments, iso-pigment pigments

Thioindigo pigments, metal complex pigments, perinone pigments,

Perylene pigments, phthalocyanine pigments or aniline black.

In addition, Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 180 and 181, "Iron Blue Pigments" to "Iron Oxide Black", pages 451 to 453 "Pigments" to

»Pigment volume concentration«, page 563 »Thioindigo pigments«, page 567 »Titanium dioxide pigments«, pages 400 and 467, »Naturally occurring pigments«, page 459 »Polycyclic pigments«, page 52, »Azomethine pigments«, »Azo pigments« , and page 379, “Metal complex pigments”.

Examples of fluorescent pigments (daylight pigments) are bis (azomethine) pigments.

Examples of suitable electrically conductive pigments are titanium dioxide / tin oxide pigments. Examples of magnetically shielding pigments are pigments based on iron oxides or chromium dioxide.

Examples of suitable metal powders are powders made from metals and metal alloys aluminum, zinc, copper, bronze or brass.

Examples of suitable organic and inorganic fillers are chalk, calcium sulfates, barium sulfate, silicates such as talc, mica or kaolin, silicas, oxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such as plastic powder, in particular made of polylamide or polyacrylonitrile. In addition, reference is made to Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 250 ff., "Füllstoffe".

Mica and talc are preferably used if the scratch resistance of the coatings produced from the powder coatings according to the invention is to be improved.

It is also advantageous to use mixtures of platelet-shaped inorganic fillers such as talc or mica and non-platelet-shaped inorganic fillers such as chalk, dolomite, calcium sulfate or barium sulfate, because this allows the viscosity and the flow behavior to be adjusted very well.

Examples of suitable transparent fillers are those based on silicon dioxide, aluminum oxide or zirconium oxide.

Suitable nanoparticles are selected from the group consisting of hydrophilic and hydrophobic, in particular hydrophilic, nanoparticles based on silicon dioxide, aluminum oxide, zinc oxide,

Zirconium oxide and the polyacids and heteropolyacids from Transition metals, preferably of molybdenum and tungsten, with a primary article size <50 nm, preferably 5 to 50 nm, in particular 10 to 30 nm. The hydrophilic nanoparticles preferably have no matting effect. Nanoparticles based on silicon dioxide are particularly preferably used.

Hydrophilic pyrogenic silicon dioxides are very particularly preferably used, the agglomerates and aggregates of which have a chain-like structure and which can be produced by flame hydrolysis of silicon tetrachloride in a detonating gas flame. These are sold, for example, by Degussa under the brand Aerosil ®. Precipitated water glasses, such as nanohectorites, which are sold, for example, by Südchemie under the Optigel ® brand or by Laporte under the Laponite ® brand, are also used with particular preference.

In addition, the functional coating materials of the invention may also contain at least one additive (D) as is usually used in the field of functional coating materials.

Examples of suitable additives are molecularly dispersible dyes, light stabilizers such as UV absorbers and reversible radical scavengers (HALS); antioxidants; low and high boiling ("long") organic solvents; Venting means; Wetting agents; emulsifiers; slip additives; polymerization inhibitors; Crosslinking catalysts; thermolabile free radical initiators; reactive diluents curable thermally and with actinic radiation; Adhesion promoters; Leveling agents; film-forming aids; Rheology aids (thickeners); Flame retardants; Corrosion inhibitors; waxes; driers; Biocides and / or matting agents; like for example in the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, or in German patent application DE 199 14 896 A1, column 14, page 26, to column 15, line 46, are described in detail.

In terms of method, the production of the functional coating materials according to the invention has no special features, but takes place by mixing the constituents described above in customary and known mixing units, such as stirred kettles, Ultraturrax, inline dissolvers, extruders or kneaders.

In terms of method, the application of the functional coating materials according to the invention also has no peculiarities, but can be done by all customary application methods, such as Spraying, knife coating, brushing, pouring, dipping, trickling or rolling. Spray application methods are preferably used, such as, for example, compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), if appropriate combined with hot spray application, such as hot air hot spraying. These application methods can of course also be used for the application of solid-color topcoats, waterborne basecoats and clearcoats.

After application, the layers of the functional coating materials according to the invention are dried without completely curing them. Temperatures of 20 to 80, preferably 20 to 70 and in particular 20 to 65 ° C. are preferably used here. Drying can be supported by laminar air currents. Drying times of 30 seconds to two hours, preferably one minute to one hour and in particular one minute to 45 minutes, are preferably used. According to the invention, during this process step, the separate, water-soluble and / or dispersible crosslinking system (B) partially or completely crosslinks on and / or in the matrix of the wet, drying and / or dried layers before the binders (A) crosslink completely. If the separate crosslinking systems (B) can also or only be hardened with actinic radiation, the layers are irradiated with actinic radiation.

Radiation sources such as high or low pressure mercury vapor lamps, which may be doped with lead to open a radiation window up to 405 nm, or electron beam sources are suitable for irradiation with actinic radiation. Further examples of suitable methods and devices for curing with actinic radiation are described in German patent application DE 198 18 735 A1, column 10, lines 31 to 61.

In the further course of the process according to the invention, the dried layer of the functional coating material according to the invention is coated with at least one, in particular one, aqueous solid-color topcoat, resulting in a solid-color topcoat layer. The application methods described above can be used. Examples of suitable aqueous solid-color topcoats are described in the patent applications cited at the outset, in particular in German patent application DE 199 14 896 A1, column 1, lines 29 to 49. Subsequently, the solid-color topcoat layer and the dried layer and, if appropriate, the dried electrocoat layer are cured together physically, thermally or thermally and with actinic radiation, in particular thermally or thermally and with actinic radiation. The curing processes described above are used. The thermal curing can be carried out in conventional and known convection ovens or with the help of IR lamps. The result is a multi-layer coating according to the invention, which comprises at least one, in particular one, functional layer and at least one, in particular one, coloring and / or effect-giving solid-color coating.

As an alternative to this, in the further course of the process according to the invention the dried layer is coated with at least one, in particular a waterborne basecoat, so that a

Water-based paint layer results. Examples of suitable waterborne basecoats are described in the patent applications cited at the outset, in particular in German patent application DE 199 14 896 A1, column 1, lines 29 to 49. The waterborne basecoat is then dried without fully hardening. The drying methods described above can be used.

In the further course of the process according to the invention, at least one, in particular one, clear lacquer is applied to the dried water-based lacquer layer, resulting in a clear lacquer layer. Examples of suitable clear coats are described in the patent applications mentioned at the outset, in particular in German patent application DE 199 14 896 A1, column 17, line 57, to column 18, line 30. If it is not powder coatings, the application methods described above can be used. Examples of suitable application processes for powder coatings are described, for example, in the product information from Lacke + Farben AG, "Powder coatings", 1990.

Subsequently, the dried layer of the functional coating material according to the invention, the water-based lacquer layer and the clear lacquer layer and optionally the

Electrocoating layer preferably thermally or thermally and with actinic radiation cured using the methods and devices described above. This results in a multi-layer paint and / or effect coating according to the invention, which comprises at least one functional layer, at least one color and / or effect water-based coating and at least one clear coat.

In a further variant of the method according to the invention, the dried layer of the functional coating material according to the invention and the water-based lacquer layer are cured together. Subsequently, at least one clearcoat is applied to the resulting waterborne basecoat, after which the resulting clearcoat layer (s) are cured, it being possible to use the methods and devices described above. This also results in a color and / or effect according to the invention

Multi-layer coating of the structure described above

The coloring and / or effect multi-layer lacquers according to the invention produced with the aid of the method according to the invention have an excellent flow, a uniformly smooth surface, a high interlayer adhesion and excellent optical properties (appearance). Compared to color and / or effect multi-layer coatings that do not have a functional layer i. S. of the present invention, but only have a stoving filler coating, no or only slight effect and / or color shifts occur when using the same waterborne basecoat. Examples and comparative experiment

Production Example 1

The preparation of an aqueous dispersion containing a polyurethane (A)

For the examples and the comparative search, the aqueous dispersion of a polyurethane (A) according to that described in German patent application DE 44 38 504 A1, page 5, lines 24 to 42, »1. Manufacture of water-borne polyurethane resins; 1.1 Polyurethane resin «, specified regulation.

Examples 1 and 2 and comparative experiment V1

The production of the functional coating materials 1 and 2 according to the invention (Examples 1 and 2) and of the functional coating material V1 not according to the invention

(Comparative experiment V1)

The functional coating materials 1 and 2 according to the invention and the functional coating material V1 not according to the invention were produced by mixing the constituents given in table 1 in the order given and homogenizing them.

Table 1: The composition of the functional coating materials 1 and 2 according to the invention (examples 1 and 2) and of the functional coating material V1 not according to the invention (comparative test V1)

Components examples: 1 V1

Pigment paste:

Polyurethane dispersion of preparation example 1 32, 1 32,

32, 1st

Additol® XW 395 (commercially available leveling agent from Solutia) 0.48 0.48

0.48

Surfactant S (commercial wetting agent from BASF Aktiengesellschaft) 0.5 0.5

0.5

Aerosil® R 972 (commercially available fumed silica from Degussa) 0.34 0.34

0.34

Aerosil® R 805 (commercially available fumed silicon dioxide from Degussa) 1.02 1.02

1.02

Deionized water 1.45 1.45

1.45

Flame black 101 (commercial carbon black from the company Degussa) 0.9 0.9

0.9

Sicomix black 00-6190 (commercially available black pigment from Degussa) 2.4 2.4

2.4

Talc 10 MO Micro (commercially available filler from Luzenac de France) 3.6 3.6 3.6

Titan Rutil R 900-28 (commercially available

Titanium dioxide pigment from DuPont) 0.76 0.76

0.76

Aluminum silicate ASP 200 (commercially available filler from Engelhard) 5.8 5.8

5.8

Deionized water 1, 4 1, 4

1, 4

Deionized water 1, 3 1, 3

1, 3

letdown:

Viacryl © VSC 6295 (commercially available aqueous dispersion of a methacrylate copolymer which can be crosslinked with adipic acid dihydrazide;

Manufacturer: Solutia) 9.9 19.8 Polyurethane dispersion of preparation example 1 16.5

32.1

Cymel® 1133 (commercial melamine resin from Dyno-Cytec) 0.9 0.9

0.9

Pluriol® P900 (commercially available polyether polyol from BASF Aktiengesellschaft) 0.8 0.8

0.8

Byk ® 346 (commercially available silicone surfactant from Byk Chemie) 0.4 0.4 0.4

Byketol ® WS (commercial additive from Byk Chemie) 0.8 0.8

0.8

Serad ® FX 1010 (commercially available rheology aid from Servo Delden) 10 10

10

Deionized water 9.1 15.25

2.95

Solids content: 35.84 35.86

35.81 Pigment-binder ratio: 0.64 0.5

0.89

Examples 3 and 4 and comparative tests V2 and V3

The production of multi-layer coatings according to the invention (Examples 3 and 4) and a multi-layer coating not according to the invention (comparative search V2)

The functional coating material of example 1 was used for example 3 and the functional coating material of example 2 was used for example 4.

The functional coating material from comparative test V1 was used for comparative test V2.

For the production of the multi-layer coatings, steel panels were coated with a customary and known cathodic electrodeposition coating. A commercially available filler (Ecoprime® 130 from BASF Coatings AG) was applied pneumatically to the electrocoating and then baked at 130 ° C. for 30 minutes, so that a filler coating resulted.

Half of the coated surface of the steel panels was coated with the functional coating materials of Examples 1 and 2 (Examples 3 and 4) and of Comparative Experiment V1 (Comparative Experiments V2), so that half of the conventional filler coating always remained visible. The resulting layers of the functional coating materials of Examples 1 and 2 and of Comparative Experiment C1 were dried at 60 ° C. for 10 minutes. The entire coated surfaces of the steel sheets were then coated with a commercially available water-based lacquer in the color brilliant silver from BASF Coatings AG and dried at 60 ° C. for 10 minutes. The two layers were then baked in a forced air oven at 130 ° C. for 30 minutes.

The resulting multicoat paint system according to the invention of Examples 3 and 4 and the resulting multicoat paint system of the comparative test V2, which was not according to the invention, were directly compared colorimetrically with the standard “baked-in Ecoprime® 130 / waterborne basecoat”. This resulted in a color shift D of only 2.9 in the multi-layer coating of Example 3 according to the invention and a color shift D of only 1.5 in the multi-layer coating of Example 4 according to the invention, whereas the multi-layer coating of Comparative Experiment V2 not in accordance with the invention resulted in a color shift D of 6.3 showed.

Claims

Aqueous functional coating materials and processes for the production of color and / or effect multi-layer coatings

1. Wet-on-wet process for the production of coloring and / or effect-giving multi-layer lacquers, the at least one functional layer and at least one color and / or effect-giving uni-coat or alternatively at least one coloring and / or effect-giving base coat and at least one

Clear coat included, with the process

(1) aqueous functional coating materials applied to primed or unprimed substrates, after which

(2) the resulting layers of the aqueous functional coating materials are dried without fully hardening,

(3) the dried layers (2) of the aqueous functional

Coating materials coated with aqueous solid-color topcoats, after which

or alternatively

(3) the dried layers (2) of the aqueous functional coating materials are coated with water-based paints, after which (4) the resulting water-based coating layers (3), without curing them completely, are coated with clearcoats, after which

or alternatively

(4) the resulting water-based coating layers (3) and the dried layers (2) harden together, resulting in the functional layers and the basecoats, and

(5) coated the waterborne basecoats with clearcoats, after which

(6) the resulting clearcoat layers (5) cure, resulting in the clearcoats;

characterized in that containing aqueous functional coating materials

(A) at least one crosslinkable binder, (B) at least one separate, water-soluble and / or - dispersible crosslinking system which partially or completely crosslinks for itself in and / or on the matrix of the wet, drying and / or dried layers (2) of the aqueous functional coating materials before crosslink the binders (A), and

(C) at least one pigment,

used.

2. The method according to claim 1, characterized in that the binders (A) are selected from the group consisting of saturated, unsaturated and grafted with olefinically unsaturated compounds, ionically or nonionically and ionically and nonionically stabilized polyurethanes.

3. The method according to claim 1 or 2, characterized in that the crosslinking system (B) from the group consisting of physically, thermally, with actinic radiation and thermally and with actinic radiation curable crosslinking systems is selected.

4. The method according to claim 2 or 3, characterized in that the crosslinking system (B) from the group consisting of thermally or thermally and with actinic radiation curable crosslinking systems is selected.

5. The method according to claim 4, characterized in that the crosslinking system (B) from the group consisting of thermal external and self-crosslinking networking systems is selected.

6. The method according to claim 5, characterized in that the crosslinking system (B) is thermally crosslinked via keto groups and hydrazide groups.

7. The method according to any one of claims 1 to 6, characterized in that the pigments (C) from the group consisting of color and / or effect, fluorescent, electrically conductive and magnetically shielding pigments, metal powders, organic. and inorganic, transparent and opaque fillers and nanoparticles can be selected.

8. The method according to any one of claims 1 to 7, characterized in that for the preparation of the primer applied to the substrates electrocoat materials, the resulting electrocoat layers, without curing them completely, with the aqueous functional coating materials and the solid-color topcoats or alternatively with the aqueous Functional coating materials, the waterborne basecoats and the clearcoats, after which all the layers together or the electrocoat layers, the layers of the functional coating materials and the waterborne basecoats together and the clearcoat layers cured separately.

9. Aqueous functional coating materials containing

(A) at least one binder, (B) at least one separate, water-soluble and / or - dispersible crosslinking system which partially or completely crosslinks for itself in and / or on the matrix of the wet, drying and / or dried layers (2) of the aqueous functional coating materials before crosslink the binders (A), and

(C) at least one pigment

and wherein the networking system (B)

(B 1) at least one constituent which on average contains at least two keto groups in the molecule, and

(B 2) at least one constituent which contains on average at least two hydrazide groups in the molecule,

and or

(B 3) at least one constituent which contains on average at least two keto groups and at least two hydrazide groups in the molecule,

includes or consists of.

10. Aqueous functional coating materials according to claim 9, characterized in that the binders (A) are selected from the group consisting of saturated, unsaturated and grafted with olefinically unsaturated compounds, ionically or nonionically and ionically or nonionically stabilized polyurethanes.

11. Aqueous functional coating materials according to claim 9 or 10, characterized in that the pigments (C) from the group consisting of color and / or effect, fluorescent, electrically conductive and magnetically shielding pigments,

Metal powders, organic and inorganic, transparent and opaque fillers and nanoparticles can be selected.

12. Aqueous functional coating materials according to one of claims 9 to 11, characterized in that the pigment-binder ratio is 0.1: 1 to 3: 1.

13. Use of the aqueous functional coating materials according to one of claims 9 to 12 for the production of color and / or effect multi-layer coatings.

14. Use according to claim 13, characterized in that the aqueous functional coating materials are used for the production of functional layers, fillers, stone chip protection primers, solid-color coatings and basecoats.