DE102005041380A1 - Use of alkoxylated fatty alcohols in pseudoplastic clearcoat slurries, pseudoplastic clearcoat slurry, process for their preparation and their use - Google Patents

Abstract

Use of wetting agents selected from the group consisting of alkoxylated fatty alcohols with 8 to 15 carbon atoms in the alkyl radical and a statistical average of 3 to 19 oxaalkanediyl groups in the molecule, in pseudoplastic clearcoat slurries; Structurally viscous clearcoat slurry containing solid and / or highly viscous particles which are dimensionally stable under storage and application conditions and have the following monomodal particle size distribution measured using the laser diffraction method: DOLLAR A D (v, 0.1) = 0.8 to 1.2 μm; DOLLAR A D (v, 0.5) = 1.5 to 2.5 µm; DOLLAR AD (v, 0.9) = 2.5 to 3.6 mum and DOLLAR A Span = {[D (v, 0.9)] - [D (v, 0.1)]} / [D ( v, 0.5)] = 0.8 to 1.5: DOLLAR A Process for producing the pseudoplastic clearcoat slurry and its use.

Description

Territory of invention

The The present invention relates to the novel use of alkoxylated Fatty alcohols in pseudoplastic clearcoat slurries. It also concerns the present invention provides a novel pseudoplastic clearcoat slurry. Of Furthermore, the present invention relates to a new method for the preparation of a pseudoplastic clearcoat slurry. Not least The present invention relates to the use of the novel pseudoplastic clearcoat slurry for the Automobile painting, the automotive refinishing, painting of buildings in the interior and exterior, the painting of doors, Windows and furniture as well as industrial painting, including coil coating, containers Coating, small parts painting, impregnation and / or coating electrotechnical components and the painting of white goods.

Out International Patent Application WO 03/010247 is a pseudoplastic Clearcoat slurry containing solid and / or high viscosity, under storage and application conditions dimensionally stable particles and at least one wetting agent selected from the group consisting from alkoxylated fatty alcohols having 16 to 18 carbon atoms in the alkyl radical and on average at least 20 oxaalkanediyl groups in the molecule.

The known pseudoplastic clearcoat slurry has good filterability and good gear pump handling on. It provides clearcoats that have very good optical properties (Appearance) and have a high chemical resistance.

It However, it has been shown that the particle size distribution of the known pseudoplastic clearcoat slurry after their preparation comparatively is wide, changes over time and only after a storage period stabilized by several weeks. D. h., The known pseudoplastic Clearcoat slurry shows an aging effect. This aging effect but must be considered by the manufacturer and user to disadvantages to avoid what the logistical effort in the production, the handling and the application increases.

In addition, must the known pseudoplastic clearcoat slurry in its stability to sedimentation, their filterability and their gear pump handling further improved become.

Not last need those prepared from the known pseudoplastic clearcoat slurry Clearcoats in their chemical stability, weathering resistance and the occurrence of paint defects, like craters or micro disorders (Starry sky), steadily improving.

task

task The present invention is a new pseudoplastic clearcoat slurry to provide their performance characteristics profile in comparison to that of the known pseudoplastic clearcoat slurry is further improved.

Especially should the particle size distribution the new pseudoplastic clearcoat slurry after its preparation be relatively tight, do not change over time and already immediately after their production and not after one Storage time of several weeks to be stable. That is, the new pseudoplastic Clearcoat Slurry no longer show any aging effect, resulting in Manufacturers and users of the logistical effort in the production, Handling and application can be reduced.

In addition, should the known pseudoplastic clearcoat slurry in its stability to sedimentation, their filterability and their gear pump handling further improved be.

Not last should be from the known pseudoplastic clearcoat slurry prepared clearcoats in their chemical stability, weather resistance and the occurrence of paint defects, like craters or micro disorders (Starry sky), be further improved.

solution

Accordingly, became the new use of wetting agents, selected from the group consisting from alkoxylated fatty alcohols having 8 to 15 carbon atoms in the Alkyl radical and on average 3 to 19 Oxaalkandiyl groups in the molecule, found in pseudoplastic clearcoat slurries, below referred to as "inventive use" becomes.

In addition, the novel pseudoplastic clearcoat slurry comprising solid and / or highly viscous particles which are dimensionally stable under storage and application conditions was subjected to the following monomodal particle size distribution measured by the laser diffraction method:
D (v, 0.1) = 0.8 to 1.2 μm;
D (v, 0.5) = 1.5 to 2.5 μm;
D (v, 0.9) = 2.5 to 3.6 microns and
Span = {[D (v, 0.9)] - [D (v, 0.1)]} / [D (v, 0.5)] = 0.8 to 1.5;
found.

in the The new pseudoplastic clearcoat slurry is referred to below as the "slurry according to the invention".

Further Invention objects go out of the description.

Advantages of invention

in the With regard to the prior art, it was surprising for the expert and unpredictable that underlies the present invention lying task can be solved by the use of the invention could.

In particular, surprised that the object underlying the present invention by the slurry of the invention solved could be.

In front but surprised everyone that the use according to the invention the provision of the slurry of the invention in particular allowed a simple and very reproducible way.

The inventive slurry had a narrow particle size distribution which did not change over time and already immediately after the preparation of the slurry of the invention and not only after storage period of several weeks was stable. That is, the slurry of the invention showed no aging effect, causing the manufacturer and Users of logistical effort in the manufacture, handling and the application could be reduced.

Besides, pointed the slurry of the invention a significantly improved stability to sedimentation, a significant improved filterability and significantly improved gear pump handling on.

Not last were the clearcoats prepared from the slurry according to the invention in their chemical stability and weather resistance significantly improved. If any Lack of paint, such as Craters or micro disorders (Starry sky), only very isolated on.

Full Description of the invention

in the Framework of the use according to the invention wetting agents are selected from the group consisting of alkoxylated fatty alcohols with 8 to 15 carbon atoms in the alkyl radical and in the statistical average 3 to 19 oxaalkanediyl groups in the molecule, in pseudoplastic clearcoat slurries used.

Preferably contains the alkyl group of the alkoxylated fatty alcohol 9 to 15, preferably 10 to 14, more preferably 5 to 15 and especially 13 carbon atoms.

The alkyl radical can be linear or branched. Preferably, it is branched. In particular, the alkyl radical is isotridecyl (iC ₁₃ H ₂₇ ).

Of the contains alkoxylated fatty alcohol on a statistical average preferably 5 to 15, preferably 7 to 14, especially preferably 8 to 12 and in particular 10 oxaalkandiyl groups in the molecule.

Preferably the oxaalkanediyl groups are selected from the group consisting of 1-oxapropane-1,3-diyl, 1-oxabutane-1,4-diyl, 1-oxabutane-1,3-diyl, 1-oxapentane-1,5-diyl or 1-oxapentane-1,3-diyl, preferably 1-oxapropane-1,3-diyl and 1-oxabutane-1,3-diyl, selected.

Especially the oxaalkanediyl group is 1-oxapropane-1,3-diyl (ethylene oxide group).

The present invention to be used alkoxylated fatty alcohols are commercially available wetting agents and are sold for example by BASF Aktiengesellschaft under the brand name Lutensol ^® TO. [- (- CH ₂ CH ₂ O-) ₁₀ -H iC ₁₃ H ₂₇ O], and Lutensol ^® 109 (mixture of 85% Lutensol ^® TO 10 and 15% water) in particular are Lutensol ^® TO 10th

in the Framework of the use according to the invention may be the amount of the invention to use Wetting agents in the pseudoplastic clearcoat slurries vary widely. It is a very particular advantage of the use according to the invention, that comparatively small amounts of wetting agents are used can, to achieve the advantages of the invention. Preferably, the to be used according to the invention Wetting agent in an amount of 0.01 to 2.5, preferably 0.05 to 2.4, particularly preferably 0.1 to 2.2, very particularly preferably 0.15 to 2 and in particular 0.2 to 1.8 wt .-%, each based on a given clearcoat slurry used.

In addition to the invention to be used Wetting agents can in international patent application WO 03/010247, page 9, Line 17, to page 10, line 18, described wetting agent, selected from the group consisting of alkoxylated fatty alcohols with 16 to 18 carbon atoms in the alkyl radical and in the statistical average at least 20 oxaalkanediyl groups in the molecule, be used.

• (i) erfindungsgemäß zu verwendenden Netzmitteln zu
• (ii) zusätzlichen Netzmitteln

breit variieren. Vorzugsweise liegt das Verhältnis (i) : (ii) bei 9 : 1 bis 1 : 9, bevorzugt 2,5 7,5 bis 7,5 : 2,5, besonders bevorzugt 4,5 : 6,5 bis 6,5 : 4,5 und insbesondere 1.The ratio of

• (i) Wetting agents to be used according to the invention
• (ii) additional network resources

vary widely. Preferably, the ratio (i): (ii) is 9: 1 to 1: 9, preferably 2.5 7.5 to 7.5: 2.5, more preferably 4.5: 6.5 to 6.5: 4,5 and in particular 1.

It is a further particular advantage of the use according to the invention, that even with the use of additional wetting agents the total amount the wetting agent in the preferred ranges given above can be held.

The use according to the invention is aimed at pseudoplastic clearcoat slurries.

The as "pseudoplastic" referred to viscosity behavior describes a condition, on the one hand, the needs of the spray application and on the other hand, the requirements for storage and sedimentation Account taken: In the moved state, such as when pumping over the pseudoplastic clearcoat slurry in the ring line of the paint shop and during spraying, takes the pseudoplastic clearcoat slurry has a low viscosity state a, which ensures a good processability. Without shearing stress however, the viscosity increases and guaranteed in this way, that of the already on the substrate to be painted Lack located a reduced tendency to run on vertical surfaces shows ("runners") in the same way leads the higher viscosity in the unmoved state, such as during storage, to that one Settling the solid particles mostly is prevented or a re-stirring during storage time only weak deposited pseudoplastic clearcoat slurry is guaranteed.

The pseudoplastic clearcoat slurries suitable for use in the invention can be considered be of different composition. Preferably the slurries according to the invention described below are used.

• – D (v, 0,1) = 0,8 bis 1,2 μm, vorzugsweise 0,9 bis 1,1 μm und insbesondere 0,95 bis 1,1 μm;
• – D (v, 0,5) = 1,5 bis 2,5 μm, vorzugsweise 1,6 bis 2,4 μm und insbesondere 1,7 bis 2,3 μm;
• – D (v, 0,9) = 2,5 bis 3,6 μm, vorzugsweise 2,6 bis 3,5 μm und insbesondere 2,7 bis 3,5 μm und
• – Span = {[D (v, 0,9)] – [D (v, 0,1)]}/[D (v, 0,5)] = 0,8 bis 1,5, vorzugsweise 0,9 bis 1,4 und insbesondere 0,95 bis 1,3.

The slurries according to the invention contain solid and / or highly viscous particles which are dimensionally stable under storage and application conditions and have the following monomodal particle size distribution measured by the laser diffraction method:

• D (v, 0.1) = 0.8 to 1.2 μm, preferably 0.9 to 1.1 μm and in particular 0.95 to 1.1 μm;
• D (v, 0.5) = 1.5 to 2.5 μm, preferably 1.6 to 2.4 μm and in particular 1.7 to 2.3 μm;
• D (v, 0.9) = 2.5 to 3.6 μm, preferably 2.6 to 3.5 μm and in particular 2.7 to 3.5 μm and
• Span = {[D (v, 0.9)] - [D (v, 0.1)]} / [D (v, 0.5)] = 0.8 to 1.5, preferably 0.9 to 1.4 and especially 0.95 to 1.3.

The laser diffraction method is a common and well-known method for the measurement of particle sizes and their distribution and can be carried out for example using the Mastersizer ^® from Malvern Instruments.

The to be used according to the invention Particle size distribution the slurry of the invention can be adjusted in any way. Preferably results the particle size distribution due to the use according to the invention. This means that the inventive slurry preferably the one described above to be used according to the invention Wetting agents, particularly preferably in the amounts indicated above, contains.

• – die aus den deutschen Patentanmeldungen DE 195 40 977 A1 oder DE 19832 2 06 A1 bekannten, mit Hilfe von Mahl- und Dispergierverfahren hergestellten, thermisch oder mit aktinischer Strahlung härtbaren Klarlack-Slurries,
• – die aus der deutschen Patentanmeldung DE 199 59 923 A1 bekannten, mit Hilfe von Primärdispersionsverfahren hergestellten, thermisch oder thermisch und mit aktinischer Strahlung härtbaren Klarlack-Slurries,
• – die aus den internationalen Patentanmeldungen WO 97/45476, WO 98/45356 oder WO 00/17256, dem amerikanischen Patent US 4,056,653 A oder den deutschen Patentanmeldungen DE 100 06 673 A1 oder DE 100 18 581 A1 bekannten thermisch oder thermisch und mit aktinischer Strahlung härtbaren Klarlack-Slurries, die mit Hilfe von Schmelzeemulgierverfahren hergestellt werden, oder
• – die aus den deutschen Patentanmeldungen DE 198 41 842 A1 , DE 196 17 086 A1 oder DE 199 08 018 A1 oder DE 100 55 464 A1 oder der europäischen Patentanmeldung EP 0 899 282 A1 bekannten, mit Hilfe von Sekundärdispersionsverfahren hergestellten, thermisch oder thermisch und mit aktinischer Strahlung härtbaren Klarlack-Slurries

als Basis für die erfindungsgemäßen Slurries in Betracht.Otherwise, the slurries according to the invention can have a wide variety of material compositions. For example

• - from the German patent applications DE 195 40 977 A1 or DE 19832 2 06 A1 known clearcoat slurries prepared by means of grinding and dispersing methods, thermally curable or with actinic radiation,
• - from the German patent application DE 199 59 923 A1 known clearcoat slurries prepared by primary dispersion methods, thermally or thermally curable and with actinic radiation,
• - those from international patent applications WO 97/45476, WO 98/45356 or WO 00/17256, the American patent US 4,056,653 A or the German patent applications DE 100 06 673 A1 or DE 100 18 581 A1 known thermally or thermally curable and with actinic radiation clearcoat slurries, which are prepared by means of melt emulsification, or
• - from the German patent applications DE 198 41 842 A1 . DE 196 17 086 A1 or DE 199 08 018 A1 or DE 100 55 464 A1 or the European patent application EP 0 899 282 A1 known, prepared by secondary dispersion methods, thermally or thermally curable and with actinic radiation clearcoat slurries

as a basis for the slurries according to the invention into consideration.

Of these, the German patent applications DE 198 41 842 A1 or DE 199 08 018 A1 or DE 100 55 464 A1 known, prepared by secondary dispersion methods, thermally or thermally and curable with actinic radiation, free of organic solvents or substantially free clearcoat slurries of advantage and are therefore preferably used according to the invention.

All particularly preferred are those prepared by the secondary dispersion method Clearcoat slurries containing the special ones described below Methacrylate copolymers as binders in the dimensionally stable Contain particles.

The inventive slurry contains dimensionally stable particles. In the context of the present invention means "dimensionally stable" that the particles under the usual and known conditions of storage and use of clearcoat slurries, if any, only slightly agglomerate and / or disintegrate into smaller particles, but also under the influence of shear forces essentially their original ones Preserve form. It can the particles are highly viscous and / or solid. Preferably, the dimensionally stable particles.

Preferably has the slurry according to the invention a content of potentially ionic groups of 0.05 to 1, preferably 0.05 to 0.9, preferably 0.05 to 0.8, particularly preferably 0.05 to 0.7 and in particular 0.05 to 0.6 meq / g of solids. Preferably, the Quantity of neutralizing agents chosen so that the degree of neutralization at 100%, preferably below 80%, more preferably below 60% and especially below 50%.

The chemical nature of the binder is usually in this regard not restrictive, as long as herein ion-forming groups are included, which have a Neutralization can be converted into salt groups and thereby take over ionic stabilization of the particles in water can.

Suitable anionic groups are acid groups such as carboxylic acid, sulfonic acid or phosphonic acid groups, in particular carboxylic acid groups, into consideration. Accordingly, bases such as alkali metal hydroxides, ammonia or amines are used as the neutralizing agent. Alkali metal hydroxides can be used only to a limited extent, since the alkali metal ions are not volatile during firing and can cloud the film due to their incompatibility with organic substances and lead to loss of gloss. Therefore are Ammonia or amines are preferred. In the case of amines, tertiary amines are preferred. Examples include N, N-dimethylethanolamine or aminomethylpropanolamine (AMP) called.

When Cation-forming groups are primary, secondary or tertiary amines into consideration. Accordingly, become as a neutralizing agent, in particular low molecular weight organic acids such as formic acid, acetic acid, dimethylolpropionic acid or lactic acid used.

For the preferred one Use of the slurry according to the invention in the automotive topcoat as unpigmented clearcoats Polymers or oligomers with acid groups preferred as ion-forming groups, since these so-called anionic Binders usually have a better resistance to yellowing than have the class of cationic binders.

But cationic binders with cationic groups such as amino groups are in principle also usable, provided the field of application their typical secondary properties such as their tendency to yellowing coped.

Examples for suitable Binders are random, alternating and / or block-structured linear and / or branched and / or comb-like (co) polymers of ethylenically unsaturated Monomers, polyaddition resins and / or polycondensation resins. To these terms will be supplementary on Römpp Lexicon Paints and Printing Inks, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "polyaddition" and "polyaddition resins (Polyadducts) " and pages 463 and 464, "Polycondensates", "Polycondensation" and "Polycondensation Resins", as well as Pages 73 and 74, "Binders".

Examples suitable (co) polymers are (meth) acrylate (co) polymers or partially saponified polyvinyl esters, in particular (meth) acrylate copolymers.

Examples suitable polyaddition resins and / or polycondensation resins Polyesters, alkyds, polyurethanes, polylactones, polycarbonates, polyethers, Epoxy resins, epoxy resin-amine adducts, polyureas, polyamides, Polyimides, polyester-polyurethanes, Polyether-polyurethanes or polyester-polyether-polyurethanes.

These Oligomers and polymers are known in the art, and numerous suitable compounds are available on the market.

According to the invention (Meth) acrylate copolymers, the polyesters, the alkyd resins, the Polyurethanes and / or the acrylated polyurethanes of advantage and are therefore preferred.

Highly suitable (meth) acrylate copolymers and processes for their preparation are described, for example, in the German patent application DE 199 08 018 A1 , Page 9, line 44, to page 10, line 53, in the European patent application EP 0 767 185 A1 , the German patents DE 22 14 650 B1 or DE 27 49 576 B1 and the American patents US 4,091,048 A . US 3,781,379 A . US 5,480,493 A . US 5,475,073 A or US 5,534,598 A or in the standard work Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume 14/1, pages 24 to 255, 1961 described. Suitable reactors for the copolymerization are the customary and known stirred tanks, stirred tank cascades, tube reactors, loop reactors or Taylor reactors, as described, for example, in the patent applications DE 1 071 241 B1 . EP 0 498 583 A1 or DE 198 28 742 A1 or in the article by K. Kataoka in Chemical Engineering Science, Vol. 50, No. 9, 1995, pp. 1409-1416.

Well suitable polyesters and alkyd resins and their preparation are For example, in the standard work Ullmann's Encyclopedia of technical chemistry, 3rd edition, volume 14, Urban & Schwarzenberg, Munich, Berlin, 1963, pages 80 to 89 and pages 99 to 105, as well as in the books: "Résines Alkydes-Polyester" by J. Bourry, Paris, Publisher Dunod, 1952, "Alkyd Resins "by C. R. Martens, Reinhold Publishing Corporation, New York, 1961, and "Alkyd Resin Technology "by T. C. Patton, Intersience Publishers, 1962.

Highly suitable polyurethanes and / or acrylated polyurethanes and their preparation are described, for example, in the patents EP 0 708 788 1A1 . DE 44 01 544 A1 or DE 195 34 361 A1 described.

Very particular advantages result for the slurries according to the invention, if their dimensionally stable particles contain at least one methacrylate copolymer as binder, which, based on a given Neth methacrylate copolymer, at least 90, preferably at least 95 and in particular at least 99 wt .-% methacrylate comonomers, including containing potentially ionic groups methacrylate comonomers, in copolymerized form.

Preferably it is the potentially ionic groups containing (Meth) acrylate comonomers to acrylic acid, beta-carboxyethyl acrylate and / or methacrylic acid, especially methacrylic acid. Preferably become the (ionic) group-containing (meth) acrylate comonomers copolymerized in an amount in the methacrylate copolymers, that the content of the particles described above is potentially ionic groups can be easily adjusted. Preferably they are in an amount of 0.1 to 3, preferably 0.2 to 2.8, particularly preferably 0.3 to 2.6, very particularly preferably 0.4 to 2.4 and in particular 0.5 to 2.2 wt .-%, each based on a given Methacrylatcopolymerisat, in the methacrylate copolymers in copolymerized form.

Preferably the methacrylate copolymers have a glass transition temperature Tg of at most 50 ° C; there should the glass transition temperature Tg preferably not lower than 0, preferably 10 and in particular 20 ° C.

Preferably becomes the glass transition temperature Tg of the methacrylate copolymers via at least one of reactive functional groups and of potentially ionic groups free Methacrylate comonomer set. The glass transition temperature is preferred Tg over at least two, especially two, of reactive functional Groups and of potentially ionic groups free Methacrylatcomonomeren set. Preferably, the glass transition temperatures Tg of the respective homopolymers of reactive functional groups and from potentially ionic groups of free methacrylate comonomers by a maximum of 40 ° C from each other.

Examples more suitable of reactive functional groups and of potential ionic groups of free methacrylate comonomers are methyl, ethyl, n-propyl, n-butyl, i-butyl-tert-butyl, n-pentyl, isoamyl, cyclopentyl, n-hexyl and cyclohexyl methacrylate. Of these, i-butyl methacrylate (glass transition temperature Tg of the homopolymer: 53 ° C) and n-butyl methacrylate (glass transition temperature Tg of the homopolymer: 20 ° C) advantageous and are therefore used with particular preference.

The Amount of those to be used in the invention Copolymerized copolymer of methacrylate, of reactive functional Groups and of potentially ionic groups free Methacrylatcomonomeren can vary widely. It is essential that the amount is chosen that the resulting methacrylate copolymers the above described glass transition temperature Tg have. Preferably, the amount is at least 50, preferably at least 55, more preferably at least 60, especially preferably at least 65 and in particular at least 70 wt .-%, respectively based on a given methacrylate copolymer.

there can the weight ratio the most preferably used methacrylate comonomer n-butyl methacrylate and i-butyl methacrylate vary widely. Preferably, the weight ratio is n : i at 10: 1 to 1:, preferably 8: 1 to 1: 4, more preferably 6: 1 to 1: 2, most preferably 5: 1 to 1: 1.5 and in particular 4: 1 to 1: 1.

These it is the slurries according to the invention to physically curable, The methacrylate copolymers contain no or only one for the crosslinking negligible number of reactive functional groups.

These it is the slurries according to the invention thermally self-crosslinking, contain the methacrylate copolymers the complementary reactive functional described below Groups for thermal crosslinking and / or reactive functional groups, the "with oneself", d. H. Groups of their own Kind, can network.

These it is the slurries according to the invention curable with actinic radiation, can they Methacrylate copolymers reactive functional groups with at least contain a activatable with actinic radiation bond. These reactive functional groups are in the methacrylate copolymers the curable with actinic radiation slurries according to the invention mandatory if the slurries no further radiation-curable Contain ingredients.

If the slurries according to the invention are dual-cure slurries, the Me Thacrylatcopolymerisate reactive functional groups for thermal crosslinking and / or reactive functional groups containing at least one activatable with actinic radiation bond. The reactive functional groups having at least one bond activatable with actinic radiation are compulsorily contained in the methacrylate copolymers of the dual-cure slurries according to the invention if the dual-cure slurries contain no further radiation-curable constituents.

Examples suitable to be used according to the invention complementary reactive functional groups are in the following overview compiled. 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 '' are the same or different aliphatic radicals or are together with one another aliphatic or heteroaliphatic ring linked.

Overview: Examples of complementary reactive functional groups

The Selection of the respective complementary reactive functional For a group groups, first of all, it depends on the fact that they belong to the Preparation of the binders and in the production, storage, the application and the melting of the slurries according to the invention no unwanted Reactions, in particular no formation of polyelectrolyte complexes or premature crosslinking, entering and / or curing with do not disturb actinic radiation or inhibit, and second, thereafter, in what temperature range is the crosslinking to be held.

Preferably become in the slurries of the invention Crosslinking temperatures of 60 to 180 ° C applied. It will therefore preferably binders with thio, hydroxyl, N-methylolamino N-alkoxymethylamino, imino, carbamate and / or allophanate groups, preferably hydroxyl groups, on the one hand, and preferably crosslinking agents with anhydride, epoxy, blocked and unblocked, in particular blocked, isocyanate, urethane, methylol, methylolether, siloxane, Carbonate, amino, hydroxy and / or beta-hydroxyalkylamide groups, preferably blocked isocyanate, carbamate and / or N-alkoxymethylamino groups, on the other hand applied.

in the Cases of self-crosslinking slurries according to the invention contain the Binders, in particular methylol, methylol ether and / or N-alkoxymethylamino groups.

Complementary reactive functional groups responsible for the use in the thermally externally crosslinking slurries according to the invention and the dual-cure slurries according to the invention in particular are well suited, are hydroxyl groups on the one hand and blocked Isocyanate groups on the other hand.

The functionality the binder with respect of the above-described reactive functional groups vary very widely and depends in particular on the density of the network, which one wants to achieve, and / or according to the functionality of each applied crosslinking agents. For example, in the case of hydroxyl-containing Binders the OH number preferably at 20 to 300, preferably 40 to 250, more preferably 60 to 200, most preferably 80 to 190 and in particular 90 to 180 mg KOH / g.

The above-described complementary reactive functional Groups can after the usual and known methods of polymer chemistry incorporated into the binder become. This can be achieved, for example, by the incorporation of methacrylate comonomers, which carry the corresponding reactive functional groups, and / or with the help of polymer-analogous reactions.

• – Hydroxyalkylester der Methacrylsäure, die sich von einem Alkylenglykol ableiten, das mit der Säure verestert ist, oder die durch Umsetzung der Methacrylsäure mit einem Alkylenoxid wie Ethylenoxid oder Propylenoxid erhältlich sind, insbesondere Hydroxyalkylester der Methacrylsäure, in denen die Hydroxyalkylgruppe bis zu 20 Kohlenstoffatome enthält, wie 2-Hydroxyethyl-, 2-Hydroxypropyl-, 3-Hydroxypropyl-, 3-Hydroxybutyl- oder 4-Hydroxybutylmethacrylat; oder Hydroxycycloalkylester wie 1,4-Bis(hydroxymethyl)cyclohexan-, Octahydro-4,7-methano-1H-inden-dimethanol- oder Methylpropandiolmonomethacrylat; oder Umsetzungsprodukte aus cyclischen Estern, wie z.B. epsilon-Caprolacton und diesen Hydroxyalkylmethacrylaten;
• – Umsetzungsprodukte aus Methacrylsäure mit dem Glycidylester einer in alpha-Stellung verzweigten Monocarbonsäure mit 5 bis 18 C-Atomen je Molekül, insbesondere einer Versatic^®-Säure, oder anstelle des Umsetzungsproduktes eine äquivalenten Menge Methacrylsäure, die dann während oder nach der Polymerisationsreaktion mit dem Glycidylester einer in alpha-Stellung verzweigten Monocarbonsäure mit 5 bis 18 C-Atomen je Molekül, insbesondere einer Versatic^®-Säure, umgesetzt wird;
• – Aminoethylmethacrylat oder N-Methylaminoethylmethacrylat, die auch der Einführung von potentiell ionischen Gruppen dienen können;
• – N,N-Di(methoxymethyl)aminoethylmethacrylat oder N,N-Di(butoxymethyl)aminopropylmethacrylat;
• – Methacrylsäureamide wie Methcrylsäureamid, N-Methyl-, N-Methylol-, N,N-Dimethylol-, N-Methoxymethyl-, N,N-Di(methoxymethyl)-, N-Ethoxymethyl- und/oder N,N-Di(ethoxyethyl)-methacrylsäureamid;
• – Methacryloyloxyethyl-, propyl- oder butylcarbamat oder -allophanat; weitere Beispiele geeigneter Methacrylatcomonomere, welche Carbamatgruppen enthalten, werden in den Patentschriften US 3,479,328 A , US 3,674,838 A , US 4,126,747 A , US 4,279,833 A oder US 4,340,497 A beschrieben;

Examples of suitable methacrylate comonomers having reactive functional groups are methacrylate comonomers bearing at least one hydroxyl, amino, alkoxymethylamino, carbamate, allophanate or imino group per molecule, such as

• Hydroxyalkyl esters of methacrylic acid derived from an alkylene glycol esterified with the acid or obtainable by reacting the methacrylic acid with an alkylene oxide such as ethylene oxide or propylene oxide, in particular hydroxyalkyl esters of methacrylic acid in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl or 4-hydroxybutyl methacrylate; or hydroxycycloalkyl esters such as 1,4-bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1H-indenedimethanol or methylpropanediol monomethacrylate; or to reaction products of cyclic esters, such as epsilon-caprolactone and these hydroxyalkyl methacrylates;
• - Reaction products of methacrylic acid with the glycidyl ester of an alpha-branched monocarboxylic acid having 5 to 18 carbon atoms per molecule, in particular a Versatic ^® acid, or instead of the reaction product an equivalent amount of methacrylic acid, which then during or after the polymerization reaction with the glycidyl ester an alpha-branched monocarboxylic acid having 5 to 18 carbon atoms per molecule, in particular a Versatic ^® acid, is reacted;
• Aminoethyl methacrylate or N-methylaminoethyl methacrylate, which may also serve to introduce potentially ionic groups;
• N, N-di (methoxymethyl) aminoethyl methacrylate or N, N-di (butoxymethyl) aminopropyl methacrylate;
• Methacrylamides, such as methacrylamide, N-methyl-, N-methylol-, N, N-dimethylol-, N-methoxymethyl-, N, N-di (methoxymethyl) -, N-ethoxymethyl- and / or N, N-di ( ethoxyethyl) -methacrylsäureamid;
• Methacryloyloxyethyl, propyl or butyl carbamate or allophanate; Further examples of suitable methacrylate comonomers containing carbamate groups are disclosed in patents US 3,479,328 A . US 3,674,838 A . US 4,126,747 A . US 4,279,833 A or US 4,340,497 A described;

In subordinate quantities the reactive functional groups for thermal crosslinking via other olefinically unsaturated Monomers, such as the corresponding acrylates, allylamine, allyl alcohol or polyols, such as trimethylolpropane mono or diallyl ether or Pentaerythritol mono-, di- or triallyl ether.

The Binders of dual-cure slurries can be calculated on a statistical average at least one, preferably at least two, group (s) having at least containing activatable with actinic radiation bond (s) per molecule.

in the The scope of the present invention is under a with actinic Radiation activatable bond understood a bond at Irradiation with actinic radiation becomes reactive and with others activated bonds of their type polymerization reactions and / or Crosslinking reactions that after radical and / or ionic Mechanisms expire. 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 particularly advantageous and therefore very particular according to the invention preferably used. The brevity In the following, they are referred to as "double bonds".

Therefore contains the preferred according to the invention Group a double bond or two, three or four double bonds. If more than one double bond is used, the double bonds can be conjugated be. It is according to the invention however, it is advantageous if the double bonds are isolated, in particular each for themselves terminal, in the group in question. It is according to the invention with particular advantage two, in particular one, double bond to use.

The Dual-cure binder contains on average at least one of those described above actinic radiation activatable groups. This means, that functionality of the binder in this regard, i.e., for example two, three, four, five or more, or not integer, i.e. equal, for example 2.1 to 10.5 or more. Which functionality one chooses, depends on the Requirements placed on the respective dual-cure slurries become.

Become statistically more than one with actinic radiation activatable group applied per molecule, the groups are structurally different or the same Structure.

are structurally different from each other, this means in the context of the present invention that two, three, four or more, in particular but uses two groups activatable with actinic radiation which are of two, three, four or more, but especially derive two, monomer classes.

Examples suitable groups are (meth) acrylate, ethacrylate, crotonate, Cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbornenyl, Isoprenyl, isopropenyl, allyl or butenyl; Dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, Allyl or butenyl ether groups or dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, Allyl or butenyl ester groups, but especially acrylate groups.

Preferably, the groups are urethane, urea, allophanate, ester, ether and / or amide groups, but in particular via ester groups, bound to the respective basic structures of the binders. This is usually done by conventional and known continuous polymer-analogous reactions such as the reaction of pendant glycidyl groups with olefinically unsaturated comonomers containing an acid group of pendant hydroxyl groups with the halides of these comonomers, isocyanates containing hydroxyl groups with double bonds such as vinyl isocyanate, methacryloyl isocyanate and / or 1 - (1-isocyanato-1-methylethyl) -3- (1-methylethenyl) benzene (TMI ^® from CYTEC) or of pendant isocyanate groups with the hydroxyl-containing comonomers described above.

It can in the particles, however, also mixtures of purely thermally curable and purely actinic radiation curable binders become.

method for the preparation of the preferably used methacrylate copolymers are from the above cited patent applications, patents and References known. Particularly preferred are the methacrylate copolymers produced under pressure.

Of the Content of the dimensionally stable particles on the above-described Binders can vary widely. Preferably, it is in the case the thermally externally crosslinking or the thermally externally crosslinking and curable with actinic radiation slurries according to the invention from 5 to 80, preferably from 6 to 75, particularly preferably from 7 to 70, most preferably 8 to 65 and in particular 9 to 60 wt .-%, each based on the solid the slurries according to the invention. In the case of the physically curable and the curable with actinic radiation, but especially the physically curable, Slurries according to the invention can the content is up to 100 wt .-% amount.

The dimensionally stable particles of thermal or thermal and with actinic radiation curable slurries invention can Crosslinking agents containing the complementary reactive functional groups for the thermal crosslinking and / or reactive functional groups with at least one activatable with actinic radiation bond exhibit.

• – Aminoplastharze, wie sie beispielsweise in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, Seite 29, »Aminoharze«, dem Lehrbuch „Lackadditive" von Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, Seiten 242 ff., dem Buch „Paints, Coatings and Solvents", second completely revised edition, Edit. D. Stoye und W. Freitag, Wiley-VCH, Weinheim, New York, 1998, Seiten 80 ff., den Patentschriften US 4 710 542 A1 oder EP 0 245 700 A1 sowie in dem Artikel von B. Singh und Mitarbeiter "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry", in Advanced Organic Coatings Science and Technology Series, 1991, Band 13, Seiten 193 bis 207, beschrieben werden,
• – Carboxylgruppen enthaltende Verbindungen oder Harze, wie sie beispielsweise in der Patentschrift DE 196 52 813 A1 oder 198 41 408 A1 beschrieben werden, insbesondere 1,12-Dodecandisäure,
• – Epoxidgruppen enthaltende Verbindungen oder Harze, wie sie beispielsweise in den Patentschriften EP 0 299 420 A1 , DE 22 14 650 B1 , DE 27 49 576 B1 , US 4,091,048 A oder US 3,781,379 A beschrieben werden,
• – Tris(alkoxycarbonylamino)triazine, wie sie in den Patentschriften US 4 939 213 A , US 5 084 541 A , US 5 288 865 A oder der Patentanmeldung EP 0 604 922 A beschrieben werden,
• – blockierte Polyisocyanate, wie sie beispielsweise in den Patentschriften US 4,444,954 A1 , DE 196 17 086 A1 , DE 196 31 269 A1 , EP 0 004 571 A1 oder EP 0 582 051 A1 beschrieben werden, oder
• – beta-Hydroxyalkylamide wie N,N,N',N'-Tetrakis(2-hydroxyethyl)adipamid oder N,N,N',N'-Tetrakis(2-hydroxypropyl)adipamid.

Crosslinking agents which are suitable are all crosslinking agents customary in the field of light-stable clearcoats. Examples of suitable crosslinking agents are

• Aminoplast resins, as described, for example, in Rompp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, page 29, "Aminoharze", the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pages 242 et seq. , the book "Paints, Coatings and Solvents", secondly revised edition, Edit. D. Stoye and W. Freitag, Wiley-VCH, Weinheim, New York, 1998, p. 80 et seq., Patents US 4,710,542 A1 or EP 0 245 700 A1 and in the article by B. Singh and coworkers "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry" in Advanced Organic Coatings Science and Technology Series, 1991, Volume 13, pages 193 to 207,
• - Carboxyl-containing compounds or resins, as described for example in the patent DE 196 52 813 A1 or 198 41 408 A1, in particular 1,12-dodecanedioic acid,
• - Epoxy-containing compounds or resins, as described for example in the patents EP 0 299 420 A1 . DE 22 14 650 B1 . DE 27 49 576 B1 . US 4,091,048 A or US 3,781,379 A to be discribed,
• - Tris (alkoxycarbonylamino) triazines, as described in the patents US 4,939,213 A . US 5 084 541 A . US 5 288 865 A or the patent application EP 0 604 922 A to be discribed,
• - blocked polyisocyanates, as described for example in the patents US 4,444,954 A1 . DE 196 17 086 A1 . DE 196 31 269 A1 . EP 0 004 571 A1 or EP 0 582 051 A1 be described, or
• Beta-hydroxyalkylamides such as N, N, N ', N'-tetrakis (2-hydroxyethyl) adipamide or N, N, N', N'-tetrakis (2-hydroxypropyl) adipamide.

The Crosslinking agents described above may be used singly or as a mixture be used from at least two crosslinking agents. Offer according to the invention the blocked polyisocyanates and / or tris (alkoxycarbonylamino) triazines, in particular the blocked polyisocyanates, particular advantages and are therefore used with particular preference.

Of the Content of the dimensionally stable particles of the slurry of the invention The crosslinking agents can also vary and judge widely primarily based on the functionality and amount of binder on the one hand and the functionality the crosslinking agent on the other hand. It is preferably at 10 to 95, preferably 12 to 94, more preferably 14 to 93, all particularly preferably from 16 to 92 and in particular from 18 to 90% by weight, in each case based on the solids the slurry of the invention.

The Dimensionally stable particles of the slurry according to the invention can be used in addition the essential ingredients described above additives as commonly used in clearcoats. It is essential that these additives are the glass transition temperature Do not significantly lower the Tg of the binder.

Examples suitable additives are those of the binders described above and crosslinking agents various polymers, catalysts for crosslinking, defoamers, Adhesion promoters, additives for improving the substrate wetting, Additives for improving surface smoothness, matting agents, light stabilizers, Corrosion inhibitors, biocides, flame retardants or polymerization inhibitors, especially photoinhibitors, as described in the book "Lackadditive" by Johan Bielemann, Wiley-VCH, Weinheim, New York, 1998.

• – die in den europäischen Patentanmeldungen 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 oder EP 0 002 866 A1 , den deutschen Patentanmeldungen 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 oder DE 20 03 579 B1 , den internationalen Patentanmeldungen WO 97/46549 oder WO 99/14254 oder den amerikanischen Patentschriften 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 oder US 3,974,303 A beschriebenen, zur Verwendung in UV-härtbaren Klarlacken und Pulverklarlacken vorgesehenen Bindemittel;
• – mit aktinischer Strahlung härtbare Reaktivverdünner, wie die in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, auf Seite 491 unter dem Stichwort »Reaktivverdünner« beschriebenen; oder um
• – Photoinitiatoren, wie sie in Römpp Chemie Lexikon, 9. erweiterte und neubearbeitete Auflage, Georg Thieme Verlag Stuttgart, Bd. 4, 1991, oder in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag Stuttgart, 1998, Seiten 444 bis 446, beschrieben werden.

In addition, the dimensionally stable particles may contain other than the binders described above, curable with actinic radiation components as additives, if inventive slurry should be curable thermally and with actinic radiation or with actinic radiation alone. These are for example

• - in the 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 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 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 described binders for use in UV-curable clearcoats and powder clearcoats;
• Reactive diluents curable with actinic radiation, such as those described in Römpp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, on page 491 under the heading "reactive diluents"; or to
• Photoinitiators, as described in Rompp Chemie Lexikon, 9th extended and revised edition, Georg Thieme Verlag Stuttgart, Vol. 4, 1991, or in Rompp Lexikon Lacke and printing inks, Georg Thieme Verlag Stuttgart, 1998, pages 444 to 446 described ,

The inventive slurry can be in the watery Phase also contain additives.

Preferably these are nonionic and / or ionic thickeners. As a result, the tendency of the comparatively large fixed Particles effectively encountered sedimentation.

Examples nonionic thickeners are hydroxyethyl cellulose and polyvinyl alcohols. So-called nonionic associative thickeners are in a variety of choices also available on the market. They usually consist of water-dilutable polyurethanes, which Reaction products of water-soluble Polyether diols, aliphatic diisocyanates and monofunctional hydroxylic compounds having an organophilic radical.

Also commercially available are ionic thickeners. These usually contain anionic groups and are based in particular on special polyacrylate resins with acid groups, partially or completely can be neutralized.

Examples of suitable thickeners to be used according to the invention are from the textbook "Lackadditive" by Johan Bielemann, Wiley-VCH, Weinheim, New York, 1998, pages 31 to 65, or the German patent application DE 199 08 018 A1 , Page 13, line 18, to page 14, line 48, known.

For the slurry according to the invention it may be advantageous if both of the thickener types described above contained herein. In most cases, however, a thickener is enough, in particular a nonionic thickener, from to the desired pseudoplastic To adjust behavior.

The Amount of thickener to be added and, if two different Thickener applied, the ratio of ionic to nonionic Thickeners depend on the desired viscosity of the slurry according to the invention, in turn of the needed sedimentation and the special needs the spray application can be specified. The expert can therefore the amount of thickener and optionally the ratio of Thickener types to each other based on simple considerations if necessary Determine the help of preliminary tests.

Preferably, for the pseudoplastic behavior of the slurry of the invention, a viscosity range of 50 to 1500 mPas at a shear rate of 1000 s ^-1 and 150 to 8000 mPas at a shear rate of 10 s ^-1 and from 180 to 12000 mPas at a shear rate of 1 s ^-1 set.

The aqueous phase of the slurry of the invention may further contain crosslinkable flow control agents in the film. Examples of suitable constituents of this type are thermally curable reactive diluents such as positionally isomeric diethyloctanediols or hydroxyl-containing hyperbranched compounds or dendrimers as described in the German patent applications DE 198 05 421 A1 . DE 198 09 643 A1 or DE 198 40 405 A1 to be discribed.

The inventive slurry can be in their watery Phase still at least one, especially one, water-soluble Salt preferably in an amount of 0.1 to 50 mmol per 1,000 g in the slurry of the invention contained contained water. The salt is residue-free or substantially residue-free decomposable. This means that it does not contain any residues or decomposition Residues in one Amount that forms no adverse technical effects in the Clearcoats of the invention causes.

The Salt can be decomposed with the help of heat and / or actinic radiation be. Preferably, it is thermally decomposable. It is preferred under the conditions of hardening from the slurries of the invention prepared clearcoat films according to the invention decomposable. It is according to the invention advantageous if the salt decomposes at temperatures above 100 ° C. is. Preferably, the decomposition of the salt is 250, preferably 200, more preferably 190 and in particular 180 ° C ended.

at the decomposition of the salt can the most diverse organic, inorganic and organometallic Form decomposition products. So it can be with the decomposition products to fleeting elements, neutral organic or inorganic hydrogen compounds, organic and inorganic bases, organic and inorganic acids or Oxides act.

Examples for volatile elements are phosphorus, sulfur, nitrogen or oxygen, especially nitrogen.

Examples for neutral Organic and inorganic hydrogen compounds are water or hydrocarbons, especially water.

Examples for organic and inorganic bases are ammonia, methylamine, dimethylamine or trimethylamine, especially ammonia.

Examples for organic and inorganic acids are formic acid, Acetic acid, Propionic acid, oxalic acid, citric acid, tartaric acid, hydrochloric acid, hydrogen bromide, Phosphoric acid, phosphorous acid, sulfamic acid, Sulfuric acid, sulphurous acid, thiosulfuric, HSCN or hydrogen sulfide, especially acetic acid.

Examples for oxides are carbon dioxide, sulfur dioxide, sulfur trioxide or phosphorus oxides, especially carbon dioxide.

Preferably if a salt is selected its decomposition products are not or only slightly toxic and / or are not corrosive or only slightly corrosive. Prefers is selected in a sentence, as decomposition products water, nitrogen, carbon dioxide, ammonia and organic acids forms.

Especially the salt is preferred from the group of ammonium salts, especially preferably from the group consisting of salts of ammonia and of organic amines with organic and inorganic acids.

Especially the ammonium salt is selected from the group consisting of ammonium carbonate, Ammonium thiocyanate, ammonium sulfamate, ammonium sulfite monohydrate, ammonium formate, Ammonium acetate, ammonium hydrogen oxalate monohydrate, diammonium oxalate monohydrate, Ammonium citrate and ammonium tartrate selected. These are in turn Ammonium carbonate and ammonium acetate very particularly advantageous and Therefore, according to the invention are very special preferably used.

Preferably, the slurry according to the invention is completely or substantially free of organic solvents. "Completely free" means that the content of the inventive slurry of organic solvents un below the detection limits of the conventional and known methods of qualitative and quantitative detection of organic solvents. "Substantially free" means that the content of the slurries according to the invention of organic solvents is so low that it does not adversely affect the performance properties of the slurry.

Preferably is the content, in each case based on the slurry according to the invention, <5 wt .-%, preferably <2.5 wt .-% and in particular <1 Wt .-%.

Preferably, the slurry according to the invention by the German patent application DE 199 08 018 A1 , the German patent DE 198 41 842 C2 or the German patent application DE 100 55 464 A1 produced known secondary dispersion process.

at This method is the ionically stabilizable binder and the crosslinking agents and optionally the additives in organic solution mixed and with the help of neutralizing agents in water dispersed. Then it is diluted with water while stirring. It initially forms one Water-in-oil emulsion off, on further dilution in an oil-in-water emulsion turns. This point is generally related to solids contents of <50% by weight on the emulsion, and is externally at a greater waste the viscosity while the dilution recognizable.

The oil-in-water emulsion can also directly by the melt emulsification of the binder and the crosslinking agent and optionally the additives in water getting produced.

It is according to the invention advantageous if the wetting agents to be used according to the invention the organic solution and / or the water before or during be added to the emulsifying. Preferably, they become the organic solution added.

The thus obtained, still solvent-containing Emulsion is subsequently freed by azeotropic distillation of solvents.

It is according to the invention advantageous if the solvents to be removed at a distillation temperature below 70 ° C, preferably below 50 ° C and in particular below 40 ° C be distilled off. If necessary, the distillation pressure chosen here, that at higher boiling solvents this temperature range is maintained.

in the In the simplest case, the azeotropic distillation can be accomplished thereby be that the emulsion at room temperature in an open vessel during several Days stir.

in the preferred case is the solvent-containing Emulsion is freed from the solvents by vacuum distillation.

The evaporated or distilled off amount of water and solvents are replaced by water to avoid high viscosities. The Addition of the water can be done before, after or during the Evaporation or distillation by adding in portions.

To Loss of solvents the glass transition temperature rises Tg of the dispersed particles, and it forms in place of previous solvent-containing Emulsion is a dispersion, i. the slurry of the invention, from.

The to be used according to the invention Salts can in different ways in the slurries or their precursors according to the invention be introduced. For example, the salts may be conventional and known clearcoat slurries are added, whereby the slurries of the invention result. You can also the organic solution of constituents of the powder slurry according to the invention added become. Preferably, they are before emulsifying the organic solution dissolved in the water.

Possibly the particles of the slurry according to the invention are in the wet state mechanically comminuted, which is also referred to as wet grinding. Preferably, conditions are used in this case that the temperature of the grind 70, preferably 60 and especially does not exceed 50 ° C. Preferably the specific energy input during the milling process 10 to 1,000, preferably 15 to 750 and in particular 20 to 500 Wh / g.

For wet grinding can A variety of devices are applied, the high or generate low shear fields.

Examples suitable devices that produce low shear fields are common and known stirred tank, Slit homogenizers, microfluidizers or dissolvers.

Examples suitable devices that produce high shear fields are common and known agitator mills or Inline dissolver.

Especially preferred are the devices which generate high shear fields, applied. Of these, the agitator mills according to the invention are particularly advantageous and are therefore used with very particular preference.

As a general rule When wet grinding the slurry according to the invention by means of suitable Devices, such as pumps, in particular gear pumps, the above supplied devices and driven in a circle over it, until the desired Particle size reached is.

The inventive slurry advantageously has a solids content of 10 to 60 wt .-%, in particular from 20 to 50 wt .-%, on.

Preferably, the slurry of the invention is filtered before use. For this purpose, the usual and known filtration devices and filters are used, as they come into consideration for the filtration of the known clearcoat slurries. The mesh size of the filter can vary widely and depends primarily on the particle size and the particle size distribution of the particles of the slurry according to the invention. The person skilled in the art can therefore easily determine the suitable filters on the basis of this physical parameter. Examples of suitable filters are monofilament surface filters or bag filters. These are available on the market under the brands ^Pong® or ^Cuno® . Preference is given to using bag filters with mesh sizes of 25 to 50 μm, for example ^Pong® 25 to ^Pong® 50.

to Preparation of the clearcoats of the invention is the slurry of the invention applied to the substrate to be coated. Here do not need special measures to be taken, but the application can according to the usual and known methods are carried out, which is another particular advantage the slurry of the invention is.

To their application, the slurry of the invention dries on and easily shows at the processing temperature, usually at room temperature, a filming. That is, the slurry of the invention applied as a wet layer airs at room temperature or slightly elevated temperatures with release of water from where the particles contained therein their original Change shape and flow together. As a result, the tendency to "mudcracking" is extremely low.

In the subsequent baking step is now largely anhydrous Layer brought to crosslinking. In some cases, it may be beneficial the course process and the networking reaction with a temporal To run off offset by a Stufenheizprogramm or a so-called Aufheizrampe is driven. The for the present examples adequate crosslinking temperature is between 120 and 160 ° C. The corresponding Burning time is between 20 and 60 minutes.

In the case of the dual-cure slurry according to the invention, the thermal curing is supplemented by curing with actinic radiation, the usual and known radiation sources and processes, as described, for example, in German Patent Application DE 198 18 735 A1 , Column 10, line 31 to column 11, line 22, can be applied. These methods and devices can also be used for the curing of the actinic radiation curable slurry of the invention.

The This resulting clearcoat has excellent performance Properties on. So it adheres firmly to all common and well-known basecoat films or on substrates such as metal, glass, wood, ceramics, stone, concrete or plastic. It is high gloss, smooth, scratch resistant, weather resistant, chemical stable and also in high layer thicknesses free of disturbances, such as stress cracks or cooker. When loaded with moisture, it shows no blushing more. About that It is also free of micro-disorders and shows no annoying optical effects, such as a metallic effect-like Starry sky.

Especially but has the slurry of the invention a very good filterability with a very good gear pump handling.

In front However, all the dimensionally stable particles of the slurry of the invention have Already immediately after their production an advantageously close Particle size distribution, which does not change over time, or the change is so marginal that the beneficial application properties the slurry of the invention not affected by this.

Because of This advantageous property profile is the slurry according to the invention excellent for the automotive OEM, the automobile refinishing, the Painting of buildings in the interior and exterior, the painting of doors, Windows and furniture as well as industrial painting, including coil coating, containers Coating, the painting of small parts, the impregnation and / or coating electrotechnical components or the paint of white Goods, suitable. Here it is mainly for the production of clearcoats in the context of multicoat color and / or effect paint systems used according to the usual and known wet-on-wet process of basecoats and the slurry of the invention getting produced.

at the wet-in-wet process, the slurry of the invention without problems with numerous basecoats, in particular waterborne basecoats, be combined without problems, such as cracking, lack of Wettability and poor intercoat adhesion, occur.

The inventive slurry can surprisingly also as an adhesive for the production of adhesive layers and as a sealant for the production of seals, in particular to the aforementioned technical Areas are used.

she but can also be used as starting material for the production of molded parts and slides are used.

Production Example 1

The production of a Methacrylate copolymer (binder)

39,75 Parts by weight of methyl ethyl ketone were placed in a reaction vessel equipped with stirrer, Reflux condenser, oil heater, Nitrogen inlet tube and two feed vessels, presented and heated to 78 ° C.

hereafter was from the first feed vessel during 6.75 h is an initiator solution from 4 parts by weight of methyl ethyl ketone and 5 parts by weight TBPEH evenly metered.

15 Minutes after the initiator dosing began, the second was taken Feed vessel a monomer mixture from 27.5 parts by weight of n-butyl methacrylate, 9.15 parts by weight i-butyl methacrylate, 12.75 parts by weight of hydroxyethyl methacrylate and 0.6 parts by weight of methacrylic acid are added uniformly over 6 hours. Subsequently was the monomer with 0.25 parts by weight of methyl ethyl ketone and the feed vessel with 0.5 Rinsed parts by weight of methyl ethyl ketone. After completion of the Initiatorzulaufs the relevant feed vessel was also rinsed with 0.5 parts by weight of methyl ethyl ketone.

you let the Reaction mixture while still 3 h at 78 ° C afterreact. Subsequently were the fleeting ones Units removed by vacuum distillation until a solids content of 70% by weight. Thereafter, the resin solution was discharged. She had a viscosity from 7.0 to 10.0 dPas (solid resin 60% xylene at 23 ° C). The acid number was 9.0 to 11.0 and the hydroxyl number was 110 mg KOH / g of solid resin.

Production Example 2

The production of a blocked polyisocyanate based on hexamethylene diisocyanate (Crosslinking agent)

534 parts by weight Desmodur ^® N 3300 (commercial isocyanurate of hexamethylene diisocyanate from Bayer AG) and 200 parts by weight of methyl ethyl ketone were placed in a reaction vessel and on Heated to 40 ° C. To the solution was added, with cooling, 100 parts by weight of 2,5-dimethylpyrazole, waiting for the exothermic reaction to disappear. Thereafter, with continued cooling, 100 parts by weight of 2,5-dimethylpyrazole were added again. After renewed decay of the exothermic reaction, an additional 66 parts by weight of 2,5-dimethylpyrazole were added. Thereafter, the cooling was turned off, causing the reaction slowly heated to 80 ° C. It was held at this temperature until its isocyanate content had dropped below 0.1%. Thereafter, the reaction mixture was cooled and discharged.

The resulting solution of the blocked polyisocyanate had a solids content of 81% by weight (1 h at 130 ° C) and a viscosity of 3.4 dPas (70% in methyl ethyl ketone; plate and cone viscometer at 23 ° C) on.

Examples 1

The production of a Clearcoat slurry and a clearcoat of this

961.8 parts by weight of the Methacrylatcopolymerisatlösung of Preparation Example 1 and 484.6 parts by weight of the solution of the blocked polyisocyanate of Preparation Example 2 were mixed together at room temperature in an open stirring vessel for 15 minutes. To the resultant mixture 21.5 parts by weight of Tinuvin ^® 400 and 10.7 parts by weight of Tinuvin ^® 123 (commercially available light stabilizers from Ciba Specialty Chemicals, Inc.) and 1.5 parts by weight of Lutensol ^® TO 10 (ethoxylated fatty alcohol having 13 carbon atoms in the alkyl radical and an average of 10 ethylene oxide groups in the molecule from BASF Aktiengesellschaft), after which the mixture was stirred at room temperature for 30 minutes. Subsequently, 0.86 parts by weight of dibutyltin dilaurate and 4.68 parts by weight of dimethylethanolamine were added. The resulting mixture was stirred for another two hours at room temperature.

Subsequently was with 735 parts by weight of deionized water containing 1.462 parts by weight Ammonium acetate dissolved were, in small portions. After a break of 15 minutes An additional 780 parts by weight of deionized water were inside of 30 minutes evenly given.

The resulting aqueous Emulsion was diluted with 739 parts by weight of deionized water. hereafter she was the same on a rotary evaporator under vacuum Quantity of a mixture of volatile organic solvents and water removed until the solids content was 37 wt .-% (1 h at 130 ° C).

90 parts by weight of Acrysol ^® RM-8W were stirred (commercial nonionic associative thickener from Rohm & Haas) and 1.57 parts by weight Baysilon ^® Al 3468 (commercial leveling agent from Bayer AG) into the slurry to adjust the desired intrinsic viscosity.

The resulting clearcoat slurry had a pronounced pseudoplasticity. With the laser diffraction method (instrument Mastersizer ^® from Malvern) measured particle size distribution was as follows:
D (v, 0.1) = 0.98 μm;
D (v, 0.5) = 1.86 μm;
D (v, 0.9) = 3.28 μm and
Span = {[D (v, 0.9)] - [D (v, 0.1)]} / [D (v, 0.5)] = 1.24.

The Particle size distribution changed not over time, d. h., the clearcoat slurry showed no signs of aging anymore.

The Clearcoat slurry was extremely shear stable, as evidenced by the gear pump test could be. For this purpose, a laboratory apparatus was used in the the clearcoat slurry of a shear load by pumping in a circle was suspended. 500 g of the clearcoat slurry were introduced into a 1 liter storage tank.

Subsequently was she over an 80 cm long plastic tube with an inside diameter of 0.5 cm with a delivery rate of 600 ml / min at a pressure of 5 bar pumped five times in a circle. The advancement carried out by means of a gear pump (company Barmag, 6 ccm).

The Clearcoat slurry remained very easy to filter even after the shear load.

When Test Panels Steel sheets were used, with a usual and well-known, cathodic coated and baked electrocoating coated had been. On the electrocoats were each a Layer from a usual and known water filler BASF Coatings AG a layer of a conventional and well-known, black Water-based paint from BASF Coatings AG applied wet-on-wet. After application, the layers each became 80 ° C for 10 Minutes pre-dried.

In A first series was the unloaded, filtered clearcoat slurry in wedge shape on the test sheets applied. Subsequently the resulting clearcoat slurry layer was used together with the pre-dried water filler layer and the pre-dried water-based paint layer at 150 ° C during 23 Minutes burned. The dry film thickness of the resulting Clearcoating was 20 to 70 μm. At the lower edge of the part formed, due to the application on the vertical test plates an edge bead of a dry film thickness of 140 microns.

In a second series was the loaded, filtered clearcoat slurry processed in the same way.

The Clearcoats of the first or second series were in terms of their performance characteristics completely equivalent. They pointed an excellent course, a brilliant shine, an excellent chemical stability and excellent scratch resistance. They were free of agglomerates, Specks, micro disorders (Starry sky), blushing as well as craters in the area and on the edge.

Claims (27)

Use of wetting agents selected from the group consisting of alkoxylated fatty alcohols with 8 to 15 carbon atoms in the alkyl radical and in the statistical average 3 to 19 oxaalkanediyl groups in the molecule in pseudoplastic clearcoat slurries. Use according to claim 1, characterized the alkyl radical contains 9 to 15 carbon atoms. Use according to claim 2, characterized the alkyl radical contains 10 to 14 carbon atoms. Use according to one of Claims 1 to 3, characterized in that the alkoxylated fatty alcohol has a statistical average of 5 to 15 oxaalkanediyl groups in the molecule contains. Use according to one of Claims 1 to 4, characterized the alkoxylated fatty alcohol has a statistical average of 7 to 14 oxaalkanediyl groups in the molecule contains. Use according to one of claims 1 to 5, characterized the alkoxylated fatty alcohol has an average of 8 to 12 oxaalkanediyl groups in the molecule contains. Use according to one of claims 1 to 6, characterized the oxaalkanediyl groups are selected from the group consisting of 1-oxapropane-1,3-diyl, 1-oxabutane-1,4-diyl, 1-oxabutane-1,3-diyl, 1-oxapentane-1,5-diyl or 1-oxapentane-1,3-diyl, selected become. Use according to claim 7, characterized that the oxaalkanediyl groups from the group consisting of 1-oxapropane-1,3-diyl and 1-oxabutane-1,3-diyl. Use according to claim 9, characterized that the oxaalkandiyl group 1-Oxapropane-1,3-diyl (ethylene oxide group). Use according to one of claims 1 to 10, characterized that the pseudoplastic clearcoat slurries for the automotive finish, the automotive refinishing, the painting of buildings in the Indoor and outdoor, the painting of doors, Windows and furniture as well as industrial painting, including coil coating, containers Coating, small parts painting, impregnation and / or coating electrotechnical components and the painting of white goods be used. Use according to claim 11, characterized in that the pseudoplastic clearcoat slurries for the production of clearcoats in the context of multicoat color and / or effect paint systems be used. Pseudoplastic clearcoat slurry containing solid and / or high viscosity, under storage and application conditions dimensionally stable particles with the following with the laser diffraction method measured monomodal particle size distribution: D (v, 0,1) = 0.8 to 1.2 μm; D (v, 0.5) = 1.5 to 2.5 μm; D (v, 0.9) = 2.5 to 3.6 μm and Span = {[D (v, 0,9)] - [D (v, 0.1)]} / [D (v, 0.5)] = 0.8 to 1.5. Pseudoplastic clearcoat slurry according to claim 13, characterized in that D (v, 0.1) = 0.9 to 1.1 μm; D (v, 0.5) = 1.6 to 2.4 μm; D (v, 0.9) = 2.6 to 3.5 μm and Span = {[D (v, 0,9)] - [D (v, 0.1)]} / [D (v, 0.5)] = 0.9 to 1.4. Pseudoplastic clearcoat slurry according to Claim 13 or 14, characterized in that D (v, 0.1) = 0.95 to 1.1 μm; D (v, 0.5) = 1.7 to 2.3 μm; D (v, 0.9) = 2.7 to 3.5 μm and Span = {[D (v, 0,9)] - [D (v, 0.1)]} / [D (v, 0.5)] = 0.95 to 1.3. Pseudoplastic clearcoat slurry according to one of claims 13 to 15, characterized in that it comprises at least one wetting agent, as in any of the claims 1 to 10 defines. Pseudoplastic clearcoat slurry according to claim 16, characterized in that it contains the wetting agents in an amount of 0.01 to 2.5 wt .-%, each based on the pseudoplastic clearcoat slurry, contains. Pseudoplastic clearcoat slurry according to one of claims 13 to 17, characterized in that it comprises at least one water-soluble Salt that is residue-free or almost residue-free is decomposable, contains. Pseudoplastic clearcoat slurry according to one of claims 13 to 18, characterized in that it at least one additional Wetting agent, selected from the group consisting of alkoxylated fatty alcohols with 16 to 18 carbon atoms in the alkyl radical and in the statistical average contains at least 20 oxaalkanediyl groups in the molecule. Pseudoplastic clearcoat slurry according to one of claims 13 to 19, characterized in that they are thermally or thermally and curable with actinic radiation is. Pseudoplastic clearcoat slurry according to one of claims 13 to 20, characterized in that the dimensionally stable particles as binders contain methacrylate copolymers, which, based to a given methacrylate copolymer, at least 90% by weight Methacrylate comonomers, including potentially ionic groups (Meth) acrylate comonomers, incorporated in copolymerized form. Pseudoplastic clearcoat slurry according to claim 21, characterized in that the methacrylate copolymers, based to a given methacrylate copolymer, greater than 99% by weight of methacrylate comonomers, including (meth) acrylate comonomers containing potentially ionic groups, incorporated in copolymerized form. Pseudoplastic clearcoat slurry according to Claim 21 or 22, characterized in that the potentially ionic groups containing methacrylate comonomers from the group consisting of Acrylic acid, beta-carboxyethyl and methacrylic acid, selected become. Pseudoplastic clearcoat slurry according to one of claims 13 to 23, characterized in that it is from organic solvents essentially or completely free is. Structurally viscous clearcoat slurry according to any one of claims 13 to 24, characterized in that it is characterized by 1) emulsifying an organic solution of components of the clearcoat slurry in water, whereby a Emul 2) removal of the organic solvent or organic solvents and 3) partial or complete replacement of the removed solvent volume by water is produced. Pseudoplastic clearcoat slurry according to claim 25, characterized in that the wetting agent or wetting agent and the extra Wetting agent before the process step 1) of the organic solution and / or the Water is or will be added. Pseudoplastic clearcoat slurry according to one of claims 13 to 26, characterized in that they are used for automotive OEM finishing, the automotive refinishing, the painting of buildings in the Indoor and outdoor, the painting of doors, Windows and furniture as well as industrial painting, including coil coating, containers Coating, the small parts painting, the impregnation and / or coating electrotechnical Components and the painting of white goods is usable. Pseudoplastic clearcoat slurry according to claim 27, characterized in that they are for the production of clearcoats in the context of multicoat color and / or effect paint systems is usable.