DE10139230A1 - Coating for multilayer coatings comprises a (meth)acrylate/vinyl aromatic dispersion, a polyurethane dispersion, a rheology aid, a polysiloxane antifoam agent, hydrophobic solid(s) and polyglycol(s) - Google Patents

Abstract

Coating comprises: (i) acrylate dispersion of a (meth)acrylate copolymer comprising 1-8C alkyl (meth)acrylates, vinyl aromatic monomers and (meth)acrylic acids; (ii) aqueous dispersion of a polyurethane; (iii) rheology aid; and (iv) mixture of a polysiloxane antifoam agent, hydrophobic solid(s) and polyglycol(s). Coating comprises: (i) an acrylate dispersion of a (meth)acrylate copolymer comprising 30-60 wt.% 1-8C alkyl (meth)acrylates, 30-60 wt.% vinyl aromatic monomers and 0.5-10 wt.% (meth)acrylic acids; (ii) an aqueous dispersion of a polyurethane of Mn 1000-30,000 Da and 0.05-1.1 polymerizable double bonds/mol. and monomer(s) radically polymerized using a water-insoluble initiator(s) in a wt. ratio of polyurethane:monomer(s) of 1:10-10:1; (iii) a rheology aid, preferably a synthetic polymer with ionic and/or associative groups and optionally an inorganic rheology aid; and (iv) a mixture of a polysiloxane antifoam agent, a hydrophobic solid(s) and a polyglycol(s).

Description

Field of the Invention

The present invention relates to new color and / or effect aqueous Coating materials that contain an aqueous binder Acrylate dispersion (i), an aqueous polyurethane resin dispersion (ii) and a Rheological aids (iii) included. The present invention also relates to a new process for the production of color and / or effect aqueous Coating materials. The present invention further relates to Use of the new color and / or effect aqueous Coating materials as water-based paints for the production of color and / or effect-giving multi-layer paintwork.

State of the art

• a) eine Acrylatdispersion mit einem Gehalt von 30 bis 60 Gew.-% C₁-C₈- Alkyl(meth)acrylaten, 30 bis 60 Gew.-% vinylaromatischen Monomeren und 0,5 bis 10 Gew.-% (Meth)acrylsäure, jeweils bezogen auf das Acrylatcopolymerisat, sowie
• b) eine Dispersion eines Polymeren, das erhältlich ist, indem in einer wäßrigen Dispersion eines Polyurethanharzes, das ein zahlenmittleres Molekulargewicht Mn von 1000 bis 30 000 Dalton aufweist und im statistischen Mittel pro Molekül 0,05 bis 1, 1 polymerisierbare Doppelbindungen enthält, ein ethylenisch ungesättigtes Monomer oder ein Gemisch aus ethylenisch ungesättigten Monomeren in Gegenwart eines wasserunlöslichen Initiators oder eines Gemischs aus wasserunlöslichen Initiatioren radikalisch polymerisiert wird, wobei das Gewichtsverhältnis zwischen dem Polyurethanharz und dem ethylenisch ungesättigten Monomeren bzw. dem Gemisch aus ethylenisch ungesättigten Monomeren zwischen 1 : 10 und 10 : 1 liegt, und
• c) ein Rheologiehilfsmittel, das vorzugsweise ein synthetisches Polymer mit ionischen und/oder assoziativ wirkenden Gruppen enthält, und gegebenenfalls zusätzlich ein anorganisches Rheologiehilfsmittel,

enthalten, sind aus der deutschen Patentanmeldung DE 197 30 535 A1 oder der internationalen Patentanmeldungen WO 99/10439 A bekannt. Diese bekannten farb- und/oder effektgebenden wäßrigen Beschichtungsstoffe können nicht näher spezifizierte Entschäumer enthalten. Color and / or effect aqueous coating materials used as binder components

• a) an acrylate dispersion with a content of 30 to 60 wt .-% C ₁ -C ₈ alkyl (meth) acrylates, 30 to 60 wt .-% vinyl aromatic monomers and 0.5 to 10 wt .-% (meth) acrylic acid , each based on the acrylate copolymer, and
• b) a dispersion of a polymer which is obtainable by ethylenically in an aqueous dispersion of a polyurethane resin which has a number average molecular weight Mn of 1000 to 30,000 daltons and which contains on average 0.05 to 1.1 polymerizable double bonds per molecule unsaturated monomer or a mixture of ethylenically unsaturated monomers is radically polymerized in the presence of a water-insoluble initiator or a mixture of water-insoluble initiators, the weight ratio between the polyurethane resin and the ethylenically unsaturated monomer or the mixture of ethylenically unsaturated monomers between 1:10 and 10: 1 lies, and
• c) a rheology aid which preferably contains a synthetic polymer with ionic and / or associative groups, and optionally additionally an inorganic rheology aid,

are known from German patent application DE 197 30 535 A1 or international patent applications WO 99/10439 A. These known color and / or effect aqueous coating materials can contain defoamers that are not specified in detail.

The known coating materials serve as water-based paints in the manufacture color and / or effect multi-layer paint systems of the type Basecoat / clearcoat using the wet-on-wet process. The essential The advantage of the known coating materials is that they adhere very well Clear coats, especially clear coats that are made from Two-component clearcoats and clearcoat slurries, have been produced. The very good interlayer adhesion is not due to the stress in the Constant water condensation climate impaired.

When applying the known coating materials, one observes from one comparatively high layer thickness of 15 µm (metallic water-based paints) or 30 µm (uni water-based paints) often causes the formation of stoves. These arise when applied water-based lacquer layers that are, for example, on a Motor vehicle body are pre-dried in a drying oven become. The water-based paint layers become solid; but they have to still give off solvents (water and cosolvents), but these from the drying film can no longer escape easily, but as small bubbles, some of which burst open, remain visibly in the film. This The problem is particularly with red or white water-based paints and Basecoats serious, since these only in a comparatively high Layer thickness have the required hiding power.

Defoamers, which are also used as anti-foaming agents (see Römpp Lexikon Lacke and Printing colors, Georg Thieme Verlag, Stuttgart, New York, 1998, pages 39 and 40, "Antifoam" or defoaming agents or foam inhibitors (cf. Johann Bieleman, "Lackadditive", Wiley-VCH, Weinheim, New York, 1998, Pages 101 to 113), have been known for a long time. defoamers are often not individual products, but compositions. One differentiates between liquid one-component systems or homogeneous solutions, Dispersions of hydrophobic solids in a carrier oil, aqueous or aqueous emulsions or suspensions and powder Defoamers.

Basically, the selection and the necessary dosage or the Effect of a defoamer on the composition of the Coating material depends. Type and stabilization have a particularly strong effect the binder, the pigment concentration and the structure and ionogenicity of the surfactant additives used for substrate and Pigment wetting. Therefore, an incorrectly selected defoamer can Coatings cause surface defects such as craters that do the same are undesirable as the disturbances caused by foam bubbles become.

A class of very effective defoamers is by modifying functionalized polydimethylsiloxanes accessible with hydrophobic polyethers. In this way, active ingredients which are active in spreading are obtained, which are in aqueous coating materials can be used. The hydrophobic stand out Polyether siloxanes characterized in that they have a high intolerance to have foaming medium, but selectively in the dried film are tolerated. This is the combination of high defoaming activity possible with a slight tendency to crater (see Johann Bieleman, "Lackadditive", Wiley- VCH, Weinheim, New York, 1998, "4.2.5 Formulation of Active Ingredients", pages 110 to 111). Whether - and if so to what extent - these defoamers the formation of Stoves or bladders, which are one of the numerous variants is about crater formation (see Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Kocher", page 326, and "Crater formation", pages 335 to 336), especially in the known aqueous Influencing coating materials positively or negatively is not specified.

Task and solution

The object of the present invention is to provide new colors and / or effects to provide aqueous coating materials which have the disadvantages of the prior art No longer have technology, but the color and / or effect Deliver coatings that no longer have a stove, even in thick layers show, so that also trouble-free coatings in the critical colors White and red with high opacity can be produced.

The new color and / or effect aqueous coating materials are said to mainly as water-based paints for the production of color and / or effect-giving multi-layer coatings according to the wet-on-wet process are suitable, with the relevant basecoats having very good adhesion to the Clear coats, especially those made from two-component clear coats and Clear varnish slurries produced have soffen. This liability should also apply exposure to moisture is retained.

• a) eine Acrylatdispersion, enthaltend mindestens ein (Meth)Acrylatcopolymerisat, das 30 bis 60 Gew.-% an C₁-C₈- Alkyl(meth)acrylaten, 30 bis 60 Gew.-% an vinylaromatischen Monomeren und 0,5 bis 10 Gew.-% (Meth)acrylsäure, jeweils bezogen auf das (Meth)Acrylatcopolymerisat, einpolymerisiert enthält,
• b) eine Dispersion eines Polymeren, das erhältlich ist, indem in einer wäßrigen Dispersion eines Polyurethanharzes, das ein zahlenmittleres Molekulargewicht Mn von 1000 bis 30 000 Dalton aufweist und im statistischen Mittel pro Molekül 0,05 bis 1,1 polymerisierbare Doppelbindungen enthält, ein ethylenisch ungesättigtes Monomer oder ein Gemisch aus ethylenisch ungesättigten Monomeren in Gegenwart eines wasserunlöslichen Initiators oder eines Gemischs aus wasserunlöslichen Initiatioren radikalisch polymerisiert wird, wobei das Gewichtsverhältnis zwischen dem Polyurethanharz und dem ethylenisch ungesättigten Monomeren bzw. dem Gemisch aus ethylenisch ungesättigten Monomeren zwischen 1 : 10 und 10 : 1 liegt,
• c) ein Rheologiehilfsmittel, das vorzugsweise ein synthetisches Polymer mit ionischen und/oder assoziativ wirkenden Gruppen enthält, und gegebenenfalls zusätzlich ein anorganisches Rheologiehilfsmittel, und
• d) eine Mischung aus mindestens einem Polysiloxan-Entschäumungsmittel, mindestens einem hydrophoben Feststoff und mindestens einem Polyglykol

enthalten und im folgenden als "erfindungsgemäße Beschichtungsstoffe" bezeichnet werden. Accordingly, the new color and / or effect aqueous coating materials have been found

• a) an acrylate dispersion containing at least one (meth) acrylate copolymer which contains 30 to 60% by weight of C ₁ -C ₈ alkyl (meth) acrylates, 30 to 60% by weight of vinyl aromatic monomers and 0.5 to 10 % By weight of (meth) acrylic acid, based on the (meth) acrylate copolymer, in copolymerized form,
• b) a dispersion of a polymer which is obtainable by ethylenically in an aqueous dispersion of a polyurethane resin which has a number average molecular weight Mn of 1000 to 30,000 daltons and which contains on average 0.05 to 1.1 polymerizable double bonds per molecule unsaturated monomer or a mixture of ethylenically unsaturated monomers is radically polymerized in the presence of a water-insoluble initiator or a mixture of water-insoluble initiators, the weight ratio between the polyurethane resin and the ethylenically unsaturated monomer or the mixture of ethylenically unsaturated monomers between 1:10 and 10: 1 lies,
• c) a rheology aid, which preferably contains a synthetic polymer with ionic and / or associative groups, and optionally additionally an inorganic rheology aid, and
• d) a mixture of at least one polysiloxane defoaming agent, at least one hydrophobic solid and at least one polyglycol

included and hereinafter referred to as "coating materials of the invention".

• A) auf eine mit einem üblichen Füller oder gegebenfalls mit einem bekannten wäßrigen Wasserbasislack, beispielsweise einem Dünnschichtfüller gemäß DE-A 44 38 504, vorbeschichtete Substratoberfläche, der erfindungsgemäße Beschichtungsstoff aufgebracht wird,
• B) auf die so erhaltene Basislackschicht ein geeigneter Klarlack aufgebracht wird und
• C) die Basislackschicht sowie gegebenenfalls die Füllerschicht bzw. die erste Basislackschicht zusammen mit der Klarlackschicht gehärtet wird.

The invention further encompasses processes for the production of color and / or effect multilayer coatings on substrate surfaces, in which

• A) the coating material of the invention is applied to a substrate surface precoated with a customary filler or, if appropriate, with a known aqueous water-based lacquer, for example a thin-layer filler according to DE-A 44 38 504,
• B) a suitable clear lacquer is applied to the base lacquer layer thus obtained and
• C) the basecoat and optionally the filler layer or the first basecoat is cured together with the clearcoat.

Further subjects of the invention are evident from the description.

Implementation of the invention

Component (i) consists of an aqueous dispersion of a (meth) acrylate copolymer which contains 30 to 60% by weight, based on the acrylate copolymer, of copolymerized C ₁ -C ₈ -alkyl (meth) acrylates, the linear and branched chains Derivatives can be used. Examples include in particular methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl and iso-propyl (meth) acrylate, n-butyl and iso-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate or Mixtures of these monomers called. (Meth) acrylamide monomers and their derivatives and (meth) acrylonitrile can also be used as further monomers.

The (meth) acrylate copolymer further contains copolymerized vinyl aromatic monomers. Can as vinyl aromatic monomers for example, styrene, alpha-alkyl styrene and vinyl toluene in an amount of 30 up to 60% by weight, based on the (meth) acrylate copolymer become.

The acrylate dispersion (i) can be prepared according to the state of the art Processes are made. The quantitative ratio between the monomers and the water can be selected so that the resulting dispersion has a solids content of preferably 30 to 60% by weight.

The preparation of the acrylate dispersion (i) is preferably carried out in the presence an emulsifier. An anionic is preferably used as the emulsifier Emulsifier used alone or in a mixture with others. examples for anionic emulsifiers are the alkali salts of sulfuric acid semi-esters of Alkylphenols or alcohols, furthermore the sulfuric acid semiesters of ethoxylated alkylphenols or ethoxylated alcohols, preferably the alkali salts of the sulfuric acid half-ester with 4 to 5 moles of ethylene oxide per mole converted nonylphenol, alkyl or aryl sulfonate, sodium lauryl sulfate, Sodium lauryl ethoxylate sulfate and secondary sodium alkane sulfonates, their Carbon chain contains 8 to 20 carbon atoms. The amount of the anionic Emulsifier is 0.1 to 5.0% by weight, based on the monomers, preferably 0.5 to 3.0% by weight. Furthermore, to increase the stability of the Acrylate dispersions (i) additionally a nonionic emulsifier of the type one ethoxylated alkylphenol or fatty alcohol, e.g. B. an addition product of 1 mole Nonylphenol and 4 to 30 moles of ethylene oxide mixed with the anionic Emulsifier can be used.

The minimum film formation temperature (MFT) of the (meth) acrylate copolymer is preferably between -30 ° C and 60 ° C, particularly preferably between 0 ° C and 30 ° C.

The (meth) acrylate copolymer preferably has a number-average Molecular weight Mn from 200,000 to 2,000,000 daltons, preferably from 300,000 to 1,500,000 Daltons, on (determination: Gel permeation chromatography with polystyrene as standard).

The acrylate dispersion in the coating material of the invention (i) can vary widely and depends on the requirements of the individual case. The content is preferably 1 to 30, more preferably 2 to 25, particularly preferably 3 to 20 and in particular 4 to 15% by weight, in each case based on the Total amount of the coating material of the invention.

Component (ii) of the coating material according to the invention consists of an aqueous dispersion of a polymer which, as in the German Patent application DE 43 39 870 A1 described, is obtainable by in a aqueous dispersion of a polyurethane resin, which is a number average Molecular weight Mn from 1000 to 30,000 daltons and in statistical Contains an average of 0.05 to 1.1 polymerizable double bonds per molecule ethylenically unsaturated monomer or a mixture of ethylenically unsaturated monomers in the presence of a water-insoluble initiator or a mixture of water-insoluble initiators is polymerized by free radicals, the weight ratio between the polyurethane resin and the ethylenically unsaturated monomers or the mixture of ethylenically unsaturated monomers is between 1:10 and 10: 1.

• a) einem Polyester- und/oder Polyetherpolyol mit einem zahlenmittleren Molekulargewicht von 400 bis 5000 Dalton oder einem Gemisch aus solchen Polyester- und/oder Polyetherpolyolen und
• b) einem Polyisocyanat oder einem Gemisch aus Polyisocyanaten, gegebenenfalls zusammen mit einem Monoisocyanat oder einem Gemisch aus Monoisocyanaten und
• c) einer Verbindung, die mindestens eine gegenüber Isocyanatgruppen reaktive und mindestens eine zur Anionenbildung befähigte Gruppe im Molekül aufweist oder einem Gemisch aus solchen Verbindungen oder
• d) einer Verbindung, die mindestens eine gegenüber NCO-Gruppen reaktive Gruppe und mindestens eine Poly(oxyalkylen)gruppe im Molekül aufweist, oder einem Gemisch aus solchen Verbindungen oder
• e) einer Mischung aus den Komponenten (c) und (d) und
• f) gegebenenfalls einer Verbindung, die neben einer polymerisierbaren Doppelbindung mindestens noch eine gegenüber NCO-Gruppen reaktive Gruppe enthält oder einem Gemisch aus solchen Verbindungen und
• g) gegebenenfalls einer Hydroxyl- und/oder Aminogruppen enthaltenden organischen Verbindung mit einem Molekulargewicht von 60 bis 399 Dalton oder einem Gemisch aus solchen Verbindungen,

ein Polyurethanharz, das ein zahlenmittleres Molekulargewicht Mn von 1000 bis 30 000 Dalton, vorzugsweise 1500 bis 20 000 Dalton aufweist und im statistischen Mittel 0,05 bis 1,1, vorzugsweise 0,2 bis 0,9 polymerisierbare Doppelbindungen enthält, hergestellt und in Wasser dispergiert wird. According to the German patent application DE 43 39 870 A1, the aqueous dispersion of the polyurethane resin, in which the ethylenically unsaturated monomer or the mixture of ethylenically unsaturated monomers is radically polymerized in the presence of a water-insoluble initiator or a mixture of water-insoluble initiators, can be prepared from

• a) a polyester and / or polyether polyol with a number average molecular weight of 400 to 5000 daltons or a mixture of such polyester and / or polyether polyols and
• b) a polyisocyanate or a mixture of polyisocyanates, optionally together with a monoisocyanate or a mixture of monoisocyanates and
• c) 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 or
• d) a compound which has at least one group which is reactive toward NCO groups and at least one poly (oxyalkylene) group in the molecule, or a mixture of such compounds or
• e) a mixture of components (c) and (d) and
• f) optionally a compound which, in addition to a polymerizable double bond, also contains at least one group which is reactive toward NCO groups, or a mixture of such compounds and
• g) optionally an organic compound containing hydroxyl and / or amino groups and having a molecular weight of 60 to 399 daltons or a mixture of such compounds,

a polyurethane resin which has a number average molecular weight Mn of 1000 to 30,000 daltons, preferably 1500 to 20,000 daltons and contains on average 0.05 to 1.1, preferably 0.2 to 0.9 polymerizable double bonds, and in water is dispersed.

The polyurethane resin can be both in substance and in organic Solvents are made.

The polyurethane resin can be achieved by the simultaneous implementation of all Output connections are made. In many cases, however, it is expedient to produce the polyurethane resin in stages. So it is for Example possible from the components (a) and (b) containing isocyanate groups Prepare prepolymer, which then with component (c) or (d) or (e) is implemented further. It is also possible to use components (a) and (b) and (c) or (d) or (e) and optionally (f) an isocyanate group-containing Prepare prepolymer, which then with component (g) to a higher molecular weight polyurethane resin can be implemented. Implementation with the Component (g) can be in substance or - as for example in the European Patent application EP 0 297 576 A1 described - carried out in water become. In cases where a compound is used as component (f) that contains only one group that is reactive toward isocyanate groups can be found in a first stage from (b) and (f) an isocyanate group-containing intermediate be produced, which then continue with the other components can be implemented.

The reaction of components (a) to (g) can also in the presence of Catalysts such. B. dibutyltin dilaurate, dibutyltin maleate and tertiary Amines are carried out.

The amounts of component (a), (b), (c), (d), (e), (f) and (g) to be used result from the number average molecular weight Mn and the target acid number. The polymerizable double bonds can by using polymerizable double bonds (a) Components and / or polymerizable double bonds (b) Components and / or component (f) introduced into the polyurethane molecules become. It is preferred to use the polymerizable double bonds via the Introduce component (f). It is also preferred to use acrylate, methacrylate or containing allyl ether groups as polymerizable double bonds Introduce groups into the polyurethane resin molecules.

As component (a), saturated and unsaturated polyester and / or Polyether polyols, especially polyester and / or polyether diols with a number average molecular weight of 400 to 5000 Daltons can be used. To the components (a) in detail are referred to DE 43 39 870 A1.

Component (b) can be aliphatic and / or cycloaliphatic and / or aromatic polyisocyanates are used. As examples of aromatic Polyisocyanates are phenylene diisocyanate, tolylene diisocyanate, Xylylene diisocyanate, biphenylene diisocyanate, naphthylene diisocyanate and Diphenylmethane diisocyanate called. Because of their good resistance to Ultraviolet light gives (cyclo) aliphatic polyisocyanates products with low tendency to yellowing. For the components (b) in detail, refer to the German patent applications DE 43 39 870 A1 or DE 199 14 896 A1, Column 4, line 26, referenced to column 5, line 33.

To stably disperse the polyurethane resin in question in water , it must contain hydrophilic groups. These hydrophilic groups are by component (c) or component (d) or component (e) inserted into the polyurethane resin.

The groups of component (c) capable of forming anions are placed before or while dispersing the polyurethane resin in water with a base, preferably ammonia or a tertiary amine, such as. B. Neutralizes dimethylethanolamine, triethylamine, tripropylamine and tributylamine, so that the polyurethane resin contains anionic groups after neutralization. In the case where only component (c) as hydrophilic groups supplying component is used, component (c) in such Amount used that the polyurethane resin has an acid number of 15 to 80 mg KOH / g, preferably 20 to 60 mg KOH / g.

In the case where only component (d) as hydrophilic groups delivering component is used, component (d) in such Amount used that the polyurethane resin 5 to 40 wt .-%, preferably 10th contains up to 30% by weight of oxyalkylene groups, with component (a) possibly Introduced oxyalkylene groups are included. In the case where the Component (e) is used as the component providing the hydrophilic group, the amounts of component (c) and (d) to be used correspond to the Mixing ratio between the above values for the cases in which component (c) or (d) as the sole supplier of hydrophilic groups be used.

Otherwise, the person skilled in the art can determine the amounts of component (c) to be used, (d) or (e) easily determined by simple routine tests. He must just use simple series tests to check the proportion of Hydrophilic groups must at least be a stable aqueous one Obtain polyurethane resin dispersion. Of course, it can also be general usual dispersing aids, such as. B. Use emulsifiers to the Stabilize polyurethane resin dispersions. The sharing of Dispersing aids are not preferred, however, because they generally result in Moisture sensitivity of the basecoats obtained is increased.

Compounds (two) are preferably used as component (c) contain groups reactive toward isocyanate groups in the molecule. suitable groups reactive towards isocyanate groups are in particular Hydroxyl groups, as well as primary and / or secondary amino groups. Suitable for Groups capable of forming anions are carboxyl, sulfonic and / or Phosphonic acid groups, with carboxyl groups being preferred. To the Components (c) are referred to in DE 43 39 870 A1.

With the help of component (d), poly (oxyalkylene) groups can be introduced into the polyurethane molecules as nonionic stabilizing groups. The following can be used as component (d): alkoxypoly (oxyalkylene) alcohols with the general formula R'O - (- CH ₂ -CHR "-O-) _n -H in the R 'for an alkyl radical having 1 to 6 carbon atoms, R "represents a hydrogen atom or an alkyl radical having 1 to 6 carbon atoms and n represents a number between 20 and 75.

Component (f) is used to introduce polymerizable double bonds into the polyurethane resin molecules. It is preferred to use as component (f) a compound which contains at least one group which is reactive towards NCO groups and a polymerizable double bond. Compounds which contain, in addition to a polymerizable double bond, two groups which are reactive toward NCO groups are particularly preferably used as component (f). As examples of groups reactive towards NCO groups, -OH, -SH,> NH and -NH ₂ groups are mentioned, with -OH,> NH and NH ₂ - groups being preferred.

As examples of compounds that are used as component (f) can be called: hydroxy (meth) acrylates, in particular Hydroxyalkyl (meth) acrylates such as hydroxyethyl, hydroxypropyl, hydroxybutyl or Hydroxyhexyl (meth) acrylate and 2,3-dihydroxypropyl (meth) acrylate, 2,3- Dihydroxypropyl monoallyl ether, glycerol mono (meth) acrylate, Glycerol monoallyl ether, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, Pentaerythritol monoallyl ether, pentaerythritol diallyl ether, trimethylolpropane monoallyl ether, Trimethyl propane mono (meth) acrylate and trimethylol propane diallyl ether. As Component (f) is preferably glycerol mono (meth) acrylate, Pentaerythritol di (meth) acrylate, pentaerythritol diallyether and trimethylolpropane mono (meth) acrylate used. Component (f) is particularly preferred Trimethylolpropane monoallyl ether, glycerol monoallyl ether and 2,3-Dihydroxypropansäureallylester used. It is preferred to have the (f) components at least contain two groups reactive towards NCO groups, chain-linked (not terminal) in the polyurethane molecules.

As component (g), for example, polyols with molecular weights between 60 and 399 daltons such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2- Propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butylene glycol, 1,6-hexanediol, Trimethylolpropane, castor oil or hydrogenated castor oil, di-trimethylolpropane ether, Pentaerythritol, 1,2-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, Bisphenol F, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, hydroxyethylated or hydroxypropylated bisphenol A, hydrogenated bisphenol A and their mixtures are used. The polyols are generally in Amounts of up to 30 wt .-%, preferably 2 to 20 wt .-%, based on the amount of component (a) and (g) used.

Di- and / or polyamines with primary and / or secondary amino groups are used. Polyamines are essentially Alkylene polyamines with molecular weights between 60 and 399 daltons. You can Bear substituents that are not reactive with isocyanate groups Have hydrogen atoms. Examples are linear or branched polyamines aliphatic, cycloaliphatic or aromatic structure and at least two primary amino groups. Hydrazine, ethylenediamine, Propylenediamine, 1,4-butylenediamine, piperazine, 1,4-cyclohexyldimethylamine, 1,6-hexamethylenediamine, trimethylhexamethylenediamine, menthandiamine, Isophoronediamine, 4,4'-diaminodicyclohexylmethane and aminoethylethanolamine. Preferred diamines are hydrazine, alkyl or cycloalkyl diamines such as Propylene diamines and 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane. It can polyamines can also be used as component (g) which have more than two Amino groups contained in the molecule. In these cases, however - e.g. B. by Use of monoamines - make sure that they are not cross-linked Polyurethane resins can be obtained. Such useful polyamines are Diethylenetriamine, triethylenetetramine, dipropylenetriamine and dibutylenetriamine. As An example of a monoamine is called ethylhexylamine.

• 1. (α) aliphatische oder cycloaliphatische Ester der Acrylsäure oder Methacrylsäure, die weder Hydroxyl- noch Carboxylgruppen enthalten oder ein Gemisch aus solchen Estern und
• 2. (β) mindestens eine Hydroxylgruppe im Molekül tragende ethylenisch ungesättigte Monomere oder ein Gemisch aus solchen Monomeren und
• 3. (γ) mindestens eine Carboxylgruppe im Molekül tragende ethylenisch ungesättigte Monomere oder ein Gemisch aus solchen Monomeren und
• 4. (δ) weitere von (α), (β) und (γ) verschiedene ethylenisch ungesättigte Monomere oder ein Gemisch aus solchen Monomeren und
• 5. (ε) polyungesättigte Monomere, insbesondere ethylenisch polyungesättigte Monomere

sowie Mischungen aus den Komponenten (α), (β), (γ), (δ) und (ε). The binder contained in component (ii) according to the invention can be obtained by free-radically polymerizing in the aqueous polyurethane resin dispersion described above an ethylenically unsaturated monomer or a mixture of ethylenically unsaturated monomers in the presence of a water-insoluble initiator or a mixture of water-insoluble initiators, the weight ratio between the polyurethane resin and the ethylenically unsaturated monomer or the mixture of ethylenically unsaturated monomers is between 1:10 and 10: 1, preferably between 1: 2 and 2: 1. The following can be used as ethylenically unsaturated monomers:

• 1. (α) aliphatic or cycloaliphatic esters of acrylic acid or methacrylic acid, which contain neither hydroxyl nor carboxyl groups or a mixture of such esters and
• 2. (β) at least one hydroxyl group in the molecule carrying ethylenically unsaturated monomers or a mixture of such monomers and
• 3. (γ) at least one carboxyl group in the molecule carrying ethylenically unsaturated monomers or a mixture of such monomers and
• 4. (δ) further ethylenically unsaturated monomers other than (α), (β) and (γ) or a mixture of such monomers and
• 5. (ε) polyunsaturated monomers, especially ethylenically polyunsaturated monomers

as well as mixtures of the components (α), (β), (γ), (δ) and (ε).

Mixtures are preferably used as ethylenically unsaturated monomers used, which from 40 to 100 wt .-%, preferably 60 to 90 wt .-% of Component (α), 0 to 30 wt .-%, preferably 0 to 25 wt .-% of Component (β), 0 to 10 wt .-%, preferably 0 to 5 wt .-%, whole particularly preferably 0% by weight of component (γ) and 0 to 50% by weight, preferably 0 to 30% by weight of component (δ) and 0 to 5% by weight, preferably 0% by weight of component (ε), the sum of the The proportions by weight of (α), (β), (γ), (δ) and (ε) always give 100% by weight.

As component (α) z. B. can be used: cyclohexyl acrylate, Cyclohexyl methacrylate, alkyl acrylates and alkyl methacrylates with up to 20 Carbon atoms in the alkyl radical, such as. B. methyl, ethyl, propyl, butyl, hexyl, Ethylhexyl, stearyl and lauryl acrylate and methacrylate or mixtures of these monomers.

As component (β) z. B. are used: hydroxyalkyl esters Acrylic acid, methacrylic acid or another alpha, beta-ethylenic unsaturated carboxylic acid. These esters can differ from an alkylene glycol derive that is esterified with the acid, or they can by reacting the Acid can be obtained with an alkylene oxide. As component (β) preferably hydroxyalkyl esters of acrylic acid and methacrylic acid, in which the Hydroxyalkyl group contains up to 6 carbon atoms, or mixtures of this hydroxy alkyl esters used. Examples of this can be found in DE 43 39 870 A1 be removed.

Acrylic acid and / or methacrylic acid are preferably used as component (γ) used. However, other ethylenically unsaturated acids with bis can be used to 6 carbon atoms in the molecule. As examples of such Acids include ethacrylic acid, crotonic acid, maleic acid, fumaric acid and Called itaconic acid.

As component (δ) z. B. used: vinyl aromatic Hydrocarbons such as styrene, alpha-alkyl styrene and vinyl toluene, acrylic and Methacrylamide and acrylonitrile and methacrylonitrile or mixtures thereof Monomers.

Compounds (ε) which have at least contain two radically polymerizable double bonds in the molecule. As Examples are: divinylbenzene, p-methyldivinylbenzene, o- Nonyldivinylbenzene, ethanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6- Hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Pentaerythritol di (meth) acrylate, allyl methacrylate, diallyl phthalate, butanediol divinyl ether, Divinyl ethylene urea, divinyl propylene urea, maleic acid diallyl ester, etc.

Water-insoluble initiators can be, for example, water-insoluble ones Azo compounds and water-insoluble peroxy compounds are used. As examples of water-insoluble azo compounds, 2,2-azo-bis- (isobutyronitrile), 2,2'-azo-bis- (isovaleronitrile), 1,1'-azo-bis- (cyclohexane carbonitrile) and 2,2'-azo-bis- (2,4-dimethylvaleronitrile). As examples of water-insoluble peroxy compounds are t-amylperoxyethylhexanoate, t- Butyl peroxyethyl hexanoate, dilauryl peroxide, dibenzoyl peroxide and 1,1-dimethyl-3- called hydroxybutyl (1) peroxyethyl hexanoate.

Polymerization regulators can of course also be added.

The polymerization of the ethylenically unsaturated monomer or the mixture from ethylenically unsaturated monomers can be carried out by the ethylenically unsaturated monomer or the mixture of ethylenically unsaturated monomers of the aqueous polyurethane resin dispersion slowly be added. It is possible to both the total amount of Add monomers at once as well as submit only a part and the Add the rest in the course of the reaction. The ones to be polymerized However, monomers can also be prepared using part of the Polyurethane resin dispersion and water are brought into a pre-emulsion, which then slowly Template is added. The inflow time of the monomers to be polymerized is generally 2 to 8, preferably about 3 to 4 hours.

The water-insoluble initiators can be added to the template or are added dropwise together with the monomers. You can also share be added to the template, which contains part of the monomers. The rest initiator is then metered in with the remaining monomers. The The reaction temperature results from the rate of decay of the initiator or initiator mixture and can optionally by suitable organic Redox systems are reduced. The polymerization of the ethylenic unsaturated monomer or the mixture of ethylenically unsaturated Monomers generally take place at a temperature of 30 to 100 ° C, especially at a temperature of 60 to 95 ° C. When working at overpressure the reaction temperatures can rise above 100 ° C.

The ethylenically unsaturated monomer or the mixture of ethylenically unsaturated monomers should be selected so that those described above Binder polymers obtained a hydroxyl number from 0 to 100 mg KOH / g, preferably 0 to 80 mg KOH / g, and an acid number of 10 to 40 mg KOH / g, preferably 15 to 30 mg KOH / g.

The solids content of the binder dispersion (ii) can vary widely and depends according to the requirements of the individual case. Preferably, the Solids content at 20 to 80, preferably 25 to 75, particularly preferably 30 to 70 and in particular 35 to 65 wt .-%, each based on the Binder dispersion (ii).

Likewise, the content of the coating materials of the invention Binder dispersion (ii) vary widely. It is preferably 5 to 50, preferably 7 to 35, particularly preferably 10 to 30 and in particular 15 to 25 % By weight, in each case based on the total amount of the invention The coating material.

As a rheology aid of component (iii) of the invention Coating material come in particular synthetic polymers with ionic and / or associative groups. examples for this are Polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinyl pyrrolidone, Styrene-maleic anhydride or ethylene-maleic anhydride copolymers and their derivatives or also hydrophobically modified ethoxylated urethanes or Polyacrylates. Carboxyl group-containing polyacrylate Copolymers with an acid number of 60 to 780 mg KOH / g, in particular of 200 to 500 mg KOH / g used. The rheology aid should coating material of the invention in particular at the pH used Give value the desired viscosity. Ionic ones are particularly suitable Acrylate dispersions that are present in the paint system before curing pH values form fibrous gels and thus over the other components or connect them loosely, which means that they can be Drying the paint a film-like structure is obtained. Particularly preferred polyacrylic acid dispersions are used, optionally with other Comonomers can be polymerized.

The rheology aid (iii) is in the coating material of the invention preferably in an amount of 0.01 to 5.0 wt .-%, in particular about 0.1 to 1 wt .-%, based on the solids content.

Other rheology aids include xanthan gum, Diurea compounds, polyurethane thickeners, bentonite, waxes and Wax copolymers and preferably ionic layered silicates and their mixtures suitable.

Mixtures of the above are particularly preferred as rheology aids (iii) mentioned synthetic polymers with ionic or associative Groups and the ionic layered silicates.

The coating materials of the invention further contain at least a mixture (iv) of at least one polysiloxane defoamer, at least a hydrophobic solid and at least one polyglycol.

Examples of suitable polysiloxane defoamers are modified with polyethers Polysiloxanes, as described, for example, in Johann Bieleman, "Lackadditive", Wiley- VCH, Weinheim, New York, 1998, "4.2.5 Formulation of active ingredients", pages 110 to 111.

Examples of suitable hydrophobic solids are hydrophobic silicas or Urea derivatives, as described, for example, in Johann Bieleman, "Lackadditive", Wiley-VCH, Weinheim, New York, 1998, "4.2.4.1 Defoamer", pages 107 to 109.

Examples of suitable polyglycols are commercially available polyethylene glycols, Polypropylene glycols or polyethylene-co-polypropylene glycols, which in statistical Contain 4 to 100 oxaalkanediyl groups in the molecule.

Mixtures (iv) are preferably used in an amount of 0.1 to 7% by weight, preferably 0.2 to 6.5% by weight, particularly preferably 0.3 to 6, very particularly preferably 0.4 to 5 and in particular 0.5 to 4.5% by weight, in each case based on used the solid of the coating material of the invention.

The mixtures (iv) are known products and are, for example distributed by Byk Chemie under the Byk ®-028 brand.

Last but not least, the coating materials of the invention contain color and / or effect pigments. The color and / or effect are preferably Pigments from the group consisting of organic and inorganic, colored, optically effecting, electrically conductive, magnetically shielding or fluorescent pigments, metal powders, anti-corrosion pigments, organic and inorganic, transparent or opaque fillers or Nanoparticles, but especially optically and color-giving Pigments, selected.

Examples of suitable effect pigments are metal flake pigments, such as commercially available aluminum bronzes, chromated according to DE 36 36 183 A1 Aluminum bronze, and commercially available stainless steel bronze, as well as non-metallic Effect pigments, such as pearlescent or interference pigments, platelet-like effect pigments based on iron oxide, which has a color of Has pink to brownish red or liquid crystalline effect pigments. In addition, on Römpp Lexicon Lacke und Druckfarben, 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 A1, EP 0 417 567 A1, 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, Chromium titanium yellow, cadmium sulfide, cadmium zinc sulfide, chrome yellow or bismuth vanadate.

Examples of suitable organic color pigments are monoazo pigments, Bisazo pigments, anthraquinone pigments, benzimidazole pigments, Quinacridone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, Dioxazine pigments, indanthrone pigments, isoindoline pigments, isoindolinone pigments, Azomethine pigments, thioindigo pigments, metal complex pigments, perinone pigments, Perylene pigments, phthalocyanine pigments or aniline black.

In addition, varnish and printing inks are published on Römpp Lexikon, 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", directed.

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 of metals and metal alloys Aluminum, zinc, copper, bronze or brass.

An example of a corrosion protective pigment is zinc phosphate.

Examples of suitable organic and inorganic fillers are chalk, Calcium sulfate, 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, varnish and printing inks, Georg, are added to Römpp Lexikon Thieme Verlag, 1998, pages 250 ff., "Fillers".

Mica and talc are preferably used if the scratch resistance of the Color and / or effect layers produced from the basecoats should 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 like chalk, dolomite calcium sulfate, or barium sulfate use because as a result, the viscosity and the flow behavior can 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, especially hydrophilic, nanoparticles on the Base of silicon dioxide, aluminum oxide, zinc oxide, zirconium oxide and the Polyacids and heteropolyacids of 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. Based on nanoparticles are particularly preferred of silicon dioxide used.

Hydrophilic fumed silicas are very particularly preferably used, whose agglomerates and aggregates have a chain structure and which by flame hydrolysis of silicon tetrachloride can be produced in a detonating gas flame are. These are, for example, from Degussa under the brand Aerosil® distributed. Precipitated water glasses such as Nanohektorite, for example, from Südchemie under the brand Optigel® or distributed by Laporte under the Laponite® brand, used.

The pigment concentration of the coating materials of the invention can be very high vary widely and depends primarily on the effect that is set and / or the hiding power of the coloring pigments. The total pigment concentration is preferably 3 to 65% by weight, based on the solid of the coating material of the invention.

The pigments can in any way the inventive Coating material can be added, e.g. B. as an aqueous slurry or as a paste. Such pastes preferably contain a grinding binder, preferably on Polyurethane base, such as that in the German patent applications Polyurethane resins described in DE 40 10 176 A1 or DE 41 07 136 A1, at least one of the rheology aids mentioned above, deionized water, at least one organic solvent and the pigment or a mixture from pigments. If aluminum-metallic effect pigments are used, so if necessary in solvents and possibly a mixture of water and wetting agent slurried or in the main binder or in another Auxiliary binder rubbed.

The coating materials of the invention can furthermore Crosslinking agents included. The crosslinking agents include, in particular crosslinkers known in the paint field, such as melamine resins, blocked Polyisocyanates and / or tris (alkoxycarbonylamino) triazines which can be used with free OH Groups can react. Examples of these suitable and further suitable Crosslinking agents are described in German patent application DE 199 24 170 A1, Column 10, line 51 to column 12, line 69.

The coating materials of the invention can also be crosslinking Auxiliary binders included.

Examples of suitable auxiliary binders are epoxy-functional and / or carboxyl functional components.

Examples of suitable epoxy functional components are (Meth) acrylate copolymers, the usual glycidyl compounds, such as. B. Glycidyl acrylate or glycidyl methacrylate copolymerized.

Examples of suitable carboxyl-functional constituents are carboxylic acids, in particular saturated, straight-chain, aliphatic dicarboxylic acids with 3 to 20 C atoms in the molecule, dodecane-1,12-diacid being preferred.

Polyvinyl alcohol may also be used as a further auxiliary binder be used. It was found that by adding Polyvinyl alcohol in an amount up to 10 wt .-%, preferably from 1 to 5% by weight, the compatibility with those applied to the basecoat layers Clear coat layers can be improved. Polyvinyl alcohol works Solvent-repellent, so that any solvents contained in clear lacquer layers or other components due to the repulsive effect of the Do not penetrate polyvinyl alcohol into the basecoat layers, i.e. H. "collapse", and can change the color and / or the metallic effect.

The coating materials of the invention can be used in addition to the above described polymers still other compatible water-dilutable resins included, such as B. aminoplast resins, polyesters, blocked polyurethanes, such as described for example in DE 41 07 136 A1, and polyurethanes, which in generally serve as grinding resins for the pigments or as additional binders.

To neutralize components (i) and (ii), amines (in particular Alkylamines), amino alcohols and cyclic amines, such as di- and triethylamine, Aminomethylpropanol, N, N-dimethylethanolamine, diisopropanolamine, morpholine, N-alkylmorpholine can be used. For neutralization be easy volatile amines preferred, particularly preferably ammonia. The watery Coating agent is usually adjusted to a pH between 6 and 9, preferably between 6.5 and 8.5, particularly preferably between 7.0 and 8.2.

The basecoat composition can contain organic solvents in an amount up to 15% by weight. Examples of organic solvents are Naphthalenes, petrol and alcohols are suitable. As another organic solvent the basecoats of the invention can be alkylene glycols, such as ethylene glycol, Propylene glycol, butylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentylglycol and other diols, such as dimethylolcyclohexane, and preferably butyl glycol or Contain ethylhexanol.

The coating materials of the invention can be used as a further component Film forming aids included. For example, come as film-forming aids Dicarboxylic acid dialkyl esters, high-boiling gasolines and naphthalenes, which have a boiling point above 100 ° C, preferably above 140 ° C.

The coating materials of the invention can also contain leveling agents contain. Examples of suitable leveling agents are with fluorocarbons modified, silicone-free polyacrylates, preferably with an acid number of 50 to 100 in particular 70 to 75 mg KOH / g. The leveling means are preferably located in organic solution of a solids content of 40 to 80 wt .-% before. Sec-butanol is preferably used as the solvent. The salary of the Coating materials according to the invention on these leveling agents can be wide vary; it is preferably 0.1 to 2, preferably 0.3 to 1.5 and in particular 0.5 to 1.2 wt .-%, each based on the solids of coating material of the invention. Leveling agents of this type are common and well-known products and are sold under the EFKA® brand by distributed by EFKA Chemicals.

The coating materials of the invention can optionally contain other auxiliaries and additives. Examples include catalysts Excipients, defoaming agents, dispersion aids, wetting agents, preferably carboxy-functional dispersants, antioxidants, UV absorbers, radical scavengers, Leveling agents, biocides and / or water retention agents.

Other suitable auxiliaries and additives are described in German Patent application DE 199 14 896 A1, column 14, line 26, to column 15, line 46, described.

If the coating materials of the invention also with actinic Radiation, especially UV radiation, should be curable, they can usual and known components curable with actinic radiation and Photoinitiators included. Examples of suitable ingredients and photoinitiators are in the German patent applications DE 199 08 013 A1, column 6, line 63, to column 9, line 21, or DE 198 18 735 A1, column 3, line 16, to column 7, line 35.

The coating materials of the invention generally have one Solids content of preferably 10 to 70 wt .-%. The solids content varies with the intended use of the invention Coating materials. For metallic water-based paints, for example preferably at 12 to 25% by weight. It is higher for plain water-based paints, for example preferably 25 to 60% by weight.

The production of the coating materials according to the invention has none methodological peculiarities, but takes place by mixing the ingredients described above. Mixing units, such as Stirred kettles, dissolvers, in-line dissolvers, agitator mills, static mixers, Gear rim dispersers or extruders can be used. If necessary worked under the exclusion of actinic radiation to damage the coating materials according to the invention, additionally with actinic radiation are curable to avoid.

The coating materials of the invention are preferably coated on a a conventional filler coated substrate surface or optionally one with a first, preferably aqueous, basecoat, for example a thin film filler, coated substrate surface, applied. As a fountain pen can be any physically well-drying known from the prior art Filler can be used. Preferred aqueous thin-layer fillers are those in Lacquers described in DE 44 38 504 A1 are used. Generally one leaves the Filler layer or the first basecoat layer used instead of the filler layer evaporate briefly before applying the coating materials of the invention.

After application of the filler or the first basecoat, the coating material according to the invention or the water-based paint in itself known manner, for example by spraying, brushing, dipping, flooding, Doctor blades or rollers on the substrate, such as metal, plastic, wood or glass applied.

The water-based lacquer layer according to the invention applied to the substrate generally with a suitable transparent top coat or varnished with a clear coat. Before applying the clear coat, let the Advantageously briefly evaporate the water-based lacquer layer, preferably 1 to 15 Minutes, especially 4 to 8 minutes, at a temperature of 60 to 100 ° C. The period of evaporation depends on the temperature and is wide Ranges adjustable.

All the usual and come as clearcoats for the production of clearcoats known one-component (1K) -, two-component (2K) - or Multi-component (3K, 4K) clear coats, powder clear coats, powder slurry clear coats or UV-curable clear coats.

Thermally curable one-component (1K) -, two-component (2K) - or Multi-component (3K, 4K) clearcoats are from the European patent applications DE 42 04 518 A1, 05 94 068 A1, 05 94 071 A1, 05 94 142 A1, 06 04 992 A1 or 05 96 460 A1 international patent applications WO 94/10211, WO 94/10212, WO 94/10213, WO 94/22969 or WO 92/22615 or the American Patents US 5,474,811 A, 5,356,669 A or 5,605,965 A are known.

One-component (1K) clearcoats are known to contain hydroxyl groups Binders and crosslinking agents such as blocked polyisocyanates, Tris (alkoxycarbonylamino) triazines and / or aminoplast resins. In another As a binding agent, they contain polymers with pendant carbamate and / or allophanate groups and carbamate and / or allophanate modified Aminoplast resins as crosslinking agents (cf. the American patents US 5,474,811 A, 5,356,669 A or 5,605,965 A1, the international Patent applications WO 94/10211, WO 94/10212 or WO 94/10213 or the European patent applications EP 0 594 068 A1, 0 594 071 A1 or 0 594 142 A1).

Two-component (2K) or multi-component (3K, 4K) clearcoats contain as essential components known to contain hydroxyl groups and Polyisocyanates as crosslinking agents, which are separated until they are used be stored.

Thermally curable powder clearcoats are, for example, from the German Patent application DE 42 22 194 A1, the product information from BASF Lacke + Farben AG, "Pulverlacke", 1990 or the company name of BASF Coatings AG "Powder coatings, powder coatings for industrial applications", January 2000, known.

Powder clear lacquers are known to contain essential components binders containing epoxy groups and polycarboxylic acids as crosslinking agents.

Examples of suitable powder slurry clearcoats are from US Pat 4,268,542 A1 and the patent applications DE 195 40 977 A1, DE 195 18 392 A1, DE 196 17 086 A1, DE-A-196 13 547, EP 0 652 264 A1, DE 196 18 657 A1, DE 196 52 813 A1, DE 196 17 086 A1 or DE-A-198 14 471 A1 are known.

Powder slurry clear coats are known to contain powder clear coats in an aqueous Medium dispersed.

Clearcoats, powder clearcoats and powder slurry curable with actinic radiation Clear lacquers are derived, for example, from European patent applications EP 0 928 800 A1, EP 0 636 669 A1, EP 0 410 242 A1, EP 0 783 534 A1, EP 0 650 978 A1, EP 0 650 979 A1, EP 0 650 985 A1, EP 0 540 884 A1, EP 0 568 967 A1, EP 0 054 505 A1 or EP 0 002 866 A1, the German patent applications DE 198 35 206 A1, DE 197 09 467 A1 , DE 42 03 278 A1, DE 33 16 593 A1, DE 38 36 370 A1, DE 24 36 186 A1 or DE 20 03 579 B1, the international patent applications WO 97/46549 or WO 99/14254 or the American patents US 5,824,373 A, US 4,675,234 A, US 4,634,602 A, US 4,424,252 A, US 4,208,313 A, US 4,163,810 A, US 4,129,488 A, US 4,064,161 A or US 3,974,303 A.

Clearcoats, powder clearcoats, curable thermally and with actinic radiation Powder slurry clearcoats are derived, for example, from patent applications DE 198 18 735 A1, WO 98/40170, DE 199 08 013 A1, DE 199 08 018 A1, EP 0 844 286 A1 or EP 0 928 800 A1.

In general, the clear coats are applied in a wet film thickness that after their curing clear coats with the necessary for their functions and advantageous layer thicknesses result. They are preferably 10 to 100, preferably 15 to 80, particularly preferably 20 to 75 and in particular 25 to 70 microns.

After application, the color and / or effect are Waterborne basecoats together with the clearcoat layers as well optionally with the filler layers thermally or thermally and with hardened actinic radiation.

Curing can take place after a certain rest period or flash-off time. she can a duration of 30 s to 2 h, preferably 1 min to 1 h and in particular 1 min to Have 45 min. The rest period is used, for example, for the course and for degassing the Layers and for evaporation of volatile constituents such as, if necessary existing solvent and / or water.

When curing with actinic radiation, a dose of 1000 to 2000, preferably 1100 to 1900, particularly preferably 1200 to 1800, very particularly preferably 1300 to 1700 and in particular 1400 to 1600 mJ / cm ^{2 is} preferably used. If necessary, this hardening can be supplemented with actinic radiation from other radiation sources. In the case of electron beams, work is preferably carried out under an inert gas atmosphere. This can be ensured, for example, by supplying carbon dioxide and / or nitrogen directly to the surface of the clear lacquer layer. In the case of curing with UV radiation, it is also possible to work under inert gas in order to avoid the formation of ozone.

For curing with actinic radiation, the usual and known Radiation sources and optical auxiliary measures applied. Examples of suitable ones Radiation sources are flash lamps from VISIT, high or low mercury low-pressure vapor lamps, which are optionally doped with lead, around a Open beam window up to 405 nm, or electron beam sources.

Thermal curing also has no special features in terms of method, but rather takes place according to the usual and known methods such as heating in a forced air oven in countercurrent or irradiation with IR and / or NIR lamps. advantageously, thermal curing takes place at temperatures from 90 ° C to 180 ° C.

Further examples of suitable hardening methods are from the German Patent application DE 198 18 735 A1, column 10, page 31, to column 11, line 33, known.

The coating materials or water-based paints according to the invention are excellent for the production of decorative, functional and / or protective coatings of motor vehicle bodies and parts thereof, Motor vehicles indoors and outdoors, buildings indoors and Outside, doors, windows and furniture as well as part of industrial Painting of small parts, coils, containers, packaging, electrotechnical Components and white goods suitable.

When repairing color and / or effect Multi-layer painting is possible, the inventive Coating materials without special pretreatment and / or aids on the surfaces to be repaired.

The color and / or effect multi-layer coatings according to the invention are what color, effect, gloss and D.O.I. (distinctiveness of the reflected image) concerns, of the highest optical quality, have a smooth, structure-free, hard, flexible and scratch-resistant surface, they are weather, chemical and etch resistant do not yellow and show no cracking and delamination of the layers.

Therefore, the substrates according to the invention, in particular bodies of Automobiles and commercial vehicles, buildings inside and outside, industrial components, including plastic parts, small parts, packaging, coils, white parts Goods and electrical components, or furniture, doors or windows, with at least a coating according to the invention are coated, special technical and economic benefits, especially a long service life, based on what they are for Makes users particularly attractive.

The following examples are intended to illustrate the invention.

Examples and comparative tests Examples a to 4 and comparative experiment Va The Production of Waterborne Basecoats According to the Invention (Examples 1 to 4) and a water-based lacquer not according to the invention (comparative search V1)

For the production of the water-based paints were each in a mixing vessel 3.38 parts by weight of water presented. With stirring, 12 Parts by weight of aqueous acrylic dispersion Acronal® 290D (BASF AG) (Component (i)), 20 parts by weight of aqueous polyurethane resin dispersion according to Example 1 of DE 43 39 870 A1 (component (ii)), and 0.07 for neutralization Parts by weight of 25% aqueous ammonia solution are added.

A mixture was added to the resulting mixture with vigorous stirring from 58 parts by weight of a white paste with a solids content of 37.19 parts by weight % and 2.82 parts by weight of a melamine resin (Cymel® 1133) were added.

• - bei Beispiel 1 0,5 Gewichtsteile,
• - bei Beispiel 2 1,0 Gewichtsteile,
• - bei Beispiel 3 1,5 Gewichtsteile und
• - bei Beispiel 4 2,0 Gewichtsteile der erfindungsgemäß zu verwendenden Entschäumer-Mischung (iv) Byk ®-028 der Firma Byk Chemie

eingemischt. Bei dem Vergleichsversuche V1 wurde keine Entschäumer- Mischung (iv) zugesetzt. Thereafter, 0.4 part by weight of Viscalex® HV30 from Allied Colloids (rheology aids), 0.5 part by weight EFKA® 772 from EFKA (leveling agent), 2.9 parts by weight of water and

• in example 1 0.5 parts by weight,
• - in example 2 1.0 parts by weight,
• - In Example 3 1.5 parts by weight and
• - In Example 4 2.0 parts by weight of the defoamer mixture (iv) Byk®-028 from Byk Chemie to be used according to the invention

mixed. No defoamer mixture (iv) was added in comparative experiment V1.

The resulting waterborne basecoats had the properties given in Table 1 : Table 1 Properties of the waterborne basecoats 1 to 4 according to the invention and of the waterborne basecoat V1 not according to the invention

Both the water-based paints 1 to 4 according to the invention and that not Water-based lacquer V1 according to the invention were outstanding for the production suitable for multi-layer paint.

Examples 5 to 8 and comparative experiment V2 The production of multi-layer coatings according to the invention (Examples 5 to 8) and a multi-layer coating not according to the invention (Comparative experiment V2)

For example 5, the waterborne basecoat 1 from example 1 was used.

For example 6, the water-based lacquer 2 from example 2 was used.

For example 7, the waterborne basecoat 3 from example 3 was used.

For example 8, the water-based lacquer 4 from example 4 was used.

For the comparative experiment V2, the waterborne basecoat V1 of the Comparative experiment V1 used.

For the production of the multi-layer coatings, a filler was first produced in the following manner:
0.5 g of Additol® XW395 (Hoechst AG), 1.8 g of a 50% strength solution were added to 30.9 g of a binder (31% solids content) prepared according to Example 1 of DE 44 38 504 A1 with vigorous stirring from tetramethyldecinol in butyl glycol, 0.2 g Aerosil® R805 (Degussa AG), 0.02 g color black (FW2 from Degussa AG), 0.3 g titanium rutile R900 (DuPont), 3.45 g heliogenic green L8730 (Fa.BASF AG), 0.35 g Bayferox (Fa.Bayer AG), 2.95 g Hostaperm-Yellow H3G (Fa.Hoechst AG), 4.0 g talc 10 MO (Luzenac), 3, 1 g of Blanc Fixe Plv. F (Fa. Sachtleben) and 7.5 g of deionized water. The resulting mixture was dissolvered for 20 minutes at a maximum temperature of 40 ° C. and then ground on a stirrer mill to a fineness of 10 to 15 μm (Hegemann wedge 25). 30.7 g of the binder prepared according to Example 1 of DE 44 38 504 A1 (31% solids content), 2.8 butylglycol, 0.45 g of Byk®-346 (Fa .Byk-Gulden), 0.9 g Byketol WS (Byk-Gulden), 1.5 g Shellsol® T (Shell), 4 g deionized water and 4.5 g of a 10% aqueous dimethylethanol solution added. For application, the thin-film filler was set to a viscosity of 30 seconds in the DIN4 flow cup with deionized water.

The thin film filler was applied with a commercially available electrocoat Painted body panels applied, vented for 5 minutes at 20 ° C and in an air oven held at 80 ° C for 5 minutes so that the dried Thin film fillers had a dry film thickness of about 15 µm. After this The body sheets coated in this way were also cooled to 20 ° C. coated the water-based paints. The waterborne basecoats were 5 Flashed off for minutes at 20 ° C and in a forced air oven for 5.5 minutes at 80 ° C kept so that dried waterborne basecoats a dry film thickness of about 15 µm resulted.

A powder slurry clearcoat according to the example of WO was applied to this structure 96/32452 painted. The resulting powder clearcoat layers were Minutes at 20 ° C and in a forced air oven for 5 minutes at one Object temperature of 50 ° C pre-dried. In conclusion, the Water-based lacquer layers and the clear lacquer layers for 30 minutes at 150 ° C baked. The dry film layer thickness of the clear lacquer layers was approx. 40 microns.

To determine the properties dependent on the layer thickness, the The above experiments are repeated, only that the water-based lacquer layers in Wedge shape were applied.

The essential application properties of the multi-layer coatings 5 to 8 according to the invention and the multi-layer coating V2 not according to the invention are summarized in Table 2. Table 2 Properties of the multi-layer coatings 5 to 8 according to the invention and of the multi-layer coating V2 not according to the invention

Claims (12)

1. Color and / or effect aqueous coating materials containing a) an acrylate dispersion containing at least one (meth) acrylate copolymer which contains 30 to 60% by weight of C ₁ -C ₈ alkyl (meth) acrylates, 30 to 60% by weight of vinyl aromatic monomers and 0.5 to 10 % By weight of (meth) acrylic acid, based on the (meth) acrylate copolymer, in copolymerized form, b) a dispersion of a polymer which is obtainable by ethylenically in an aqueous dispersion of a polyurethane resin which has a number average molecular weight Mn of 1000 to 30,000 daltons and which contains on average 0.05 to 1.1 polymerizable double bonds per molecule unsaturated monomer or a mixture of ethylenically unsaturated monomers is radically polymerized in the presence of a water-insoluble initiator or a mixture of water-insoluble initiators, the weight ratio between the polyurethane resin and the ethylenically unsaturated monomer or the mixture of ethylenically unsaturated monomers between 1:10 and 10: 1 lies, c) a rheology aid, which preferably contains a synthetic polymer with ionic and / or associative groups, and optionally additionally an inorganic rheology aid, and d) a mixture of at least one polysiloxane defoaming agent, at least one hydrophobic solid and at least one polyglycol. 2. Coating materials according to claim 1, characterized in that the Polysiloxane defoamers from the group with polyethers modified polysiloxanes is selected. 3. Coating materials according to claim 1 to 2, characterized in that the hydrophobic solid from the group consisting of hydrophobic Silicas and urea derivatives. 4. Coating materials according to one of claims 1 to 3, characterized characterized in that the polyglycol from the group consisting of Polyethylene glycols, polypropylene glycols and polyethylene-co- polypropylene glycols, the statistical average of 4 to 100 oxaalkanediyl Contain groups in the molecule is selected. 5. coating materials one of claims 1 to 4, characterized in that they contain the mixtures (iv) in an amount of 0.1 to 7% by weight the solid of the coating material of the invention. 6. Coating materials according to one of claims 1 to 5, characterized characterized in that it is a leveling agent selected from the group of with Fluorocarbons contain modified, silicone-free polyacrylates. 7. Coating materials according to claim 6, characterized in that the Polyacrylates have an acid number of 50 to 100 mg KOH / g. 8. Coating materials according to claim 6 or 7, characterized in that they the leveling agents in an amount of 0.1 to 2 wt .-%, each based on the solid of the coating material of the invention. 9. Use of the color and / or effect coating materials according to one of claims 1 to 8 as water-based paints for the production of color and / or multi-layer effect paint. 10. Use according to claim 9, characterized in that the Waterborne basecoats for the production of color and / or effect Multi-layer painting of motor vehicle bodies and parts thereof, Motor vehicles indoors and outdoors, buildings indoors and Outside, doors, windows and furniture as well as part of industrial Painting of small parts, coils, containers, packaging, electrotechnical Components and white goods are used. 11. A process for the production of color and / or effect multi-layer coatings on substrate surfaces, in which A) a color and / or effect aqueous coating material according to any one of claims 1 to 8 is applied to a substrate surface coated with a conventional filler or, if appropriate, with a known aqueous waterborne basecoat, after evaporation, which is also optionally allowed to evaporate, B) a suitable clear lacquer is applied to the water-based lacquer layer thus obtained and C) the water-based lacquer layers and optionally the filler layer or the first basecoat layer are cured together with the clear lacquer layer. 12. The method according to claim 11, characterized in that as a clear coat in the Stage (B) uses a two-component clear coat or a clear coat slurry becomes.