DE102006050748A1 - Paint binder, e.g. for two-component clearcoats, comprises a polymer matrix and a stabilised suspension of nano-particles made by milling inorganic particles with solvent in a high-energy mill and adding dispersant - Google Patents

Abstract

Paint binders (I) comprising a polymer-based matrix and a stabilised suspension of nano-particles in amounts of 0.5-25 wt.% particles based on 100 wt.% (I), in which the suspension is obtained by (a) milling the agglomerated and/or aggregated particles with a solvent in a high-energy mill at pressures from above 500 to about 10000 bar to form nano-scale fragments and (b) adding 1-25 parts by weight (pts. wt.) dispersant(s) to 100 pts. wt. particles to stabilise the particle surface. Independent claims are included for (1) a method for the production of (I) by making a polymer-based matrix and mixing it with a suspension (II) obtained as above, and optionally with other conventional additives (2) paint containing (I) (3) painted objects with a coating of hardened (I) .

Description

Polyester coatings, for example for the band plate coating are used, characterized by high flexibility and moderate scratch resistance. Flexibility is especially ensured by the T-Bend test, in which a coated sheet is bent by 180 ° C, proved. Isocyanate-cured Polyester lacquer coated sheets survive this test without Rip or delaminating the lacquer layer. In practice, they are increasing scratch resistant coatings, but no or little loss in their flexibility show, demanded. To improve the scratch resistance of the Increased degree of crosslinking but the flexibility is significantly reduced. By filling a varnish with particulate fillers also succeeds in improving the scratch resistance, however leads this measure depending on the particle size of the fillers in clearcoats to a haze, Matting and / or roughening of the paint surface. The introduction of particles in the paint formulation also goes with a loss of ductility accompanying the coating and expresses itself for example, by loss of gloss or matting effects during stretching or Bending painted substrates at stretched areas.

Out EP 1204701 B1 It is known that cured coatings having a plurality of particles, wherein a concentration of the particles within a surface region of the coating is greater than a concentration within the volume range, are more scratch resistant than urmodified coatings. The nanoparticles used are organosols with monodisperse silica particles. These paints are characterized by special binders and hardeners, which cause migration of the nanoparticles to the paint surface. The patentee documents the migration of the particles to the surface up to the phase boundary between paint and air by transmission electron micrographs (TEM images) and attributes the experimentally proven improvement in scratch resistance to the accumulation of nanoparticles on the surface. The patent also describes an embodiment in which there is still a thin particle-free binder layer over the particle-enriched layer. Both surface-modified and untreated particles can be used. (Page 6, paragraph 0047). However, if untreated particles are used, the varnish must contain a polysiloxane compound which, together with the nanoparticles, causes the scratch resistance to be improved. If no siloxanes are used, the particles agglomerate and do not produce the desired effect. (P.33, line 11).

In order to bring about the enrichment of the nanoparticles on the paint surface, a siloxane-containing formulation is used, which favors the separation of binders and nanoparticles. As nanoparticles, organosols are used which, in combination with the polysiloxanes, improve the scratch resistance. The amount of siloxane required to stabilize the monodisperse nanoparticles is comparatively high. Example 2A requires 10.3 parts by weight of polysiloxane for 6.7 parts by weight of SiO ₂ (values based on solids). In Example 1C, even 15.3 parts by weight of polysiloxane are needed for 6.7 parts by weight of SiO ₂ . Organosols are prepared by complex processes via the sol-gel process or via solvent exchange and surface modification of silica sols. The costs of organosols and polysiloxanes are very high in terms of paint costs for large-scale products and limit the range of application.

From farmer, Mehnert et al., Macromol. Mater. Closely. 2002, 287, 546-552 It is known that inorganic nanoparticles are modified with silanes and can be used in radiation-curable, highly crosslinked paints to improve the scratch resistance. The modified nanoparticles are better compatible with the coatings and can be coupled by reactive groups to the paint. If a tetrafunctional crosslinker is used, improved abrasion values are found. With soft monofunctional reactive diluents you will find an improvement only at high fill levels.

DE 10326538 describes abrasion-resistant coatings based on surface-modified nanoparticles and blocked isocyanates. The coatings have excellent abrasion resistance with high filler content. As modifiers for the nanoparticles, silanes containing erotic groups or precursors of such silanes are used.

DE 19920801 describes a two-stage coating that is cured both thermally and photochemically. The coating contains monodispersed nanoparticles of the type Highlink OG 103-31. After the first particle-free layer was only partially cured, is coated with the second particle-containing layer and then cured again. In one variant, pyrogenic silica (Aerosil) is used instead of the monodisperse particles. However, there is no exact indication of which Aerosil type was used.

US 5,853,809 describes a nanoparticle-containing coating comprising a carbamate functional silica obtained by reacting colloidal silica with a previously prepared carbamate functional silane. The coatings contain very high filler contents and show in the scratch test with a Crockmeter lower percentage loss of gloss than unfilled paints or coatings in which the silica filler was not reacted with the coupling reagent.

US 6,916,368 describes aluminosilicate coatings with largely spherical substantially unmodified particles and improved percent gloss retention after Crockmeter test. The coatings with 5 or 40% nanofiller are significantly cloudier than unfilled coatings due to the difference in refractive index in the scratched state.

WO 0245129 , (Nanophase) describes abrasion resistant films with surface modified nanocrystalline particles prepared by depositing one or more species of polysiloxanes, preferably star polymers on the particle surface. Abrasion-resistant films or films with increased pencil hardness are obtained, which have better transparency than films with microparticles.

WO 03040223 (Nanophase) describes compositions containing micro- and nanoparticles. Non-linear effects are found, but due to the content of microparticles, they do not have clear transparent films.

WO 03084871 (Nanophase) describes nonaqueous dispersions with nanoparticles wherein polymeric dispersing additives with repeating units and anchor groups, such. As polyvinylpyrrolidone be used for stabilization.

WO 0400916 A2 (Nanophase) describes long-term stable aqueous dispersions with metal oxide nanoparticles using water-soluble polymeric dispersing additives with pigment affinities and water-soluble groups. In some cases cyclic phosphates can also be used.

WO 2005119359 (Nanophase) describes scratch-resistant articles having a substantially transparent coating, wherein a dispersion of mostly non-agglomerated nanocrystalline primary particles, polymeric dispersant and surface-active material is used (page 5, 2nd paragraph). An object of the cited document is the migration of the nanoparticles to the phase interface and thereby the use of small amounts of nanoadditive to achieve increased scratch resistance. The substantially spherical nanoparticles have a non-porous structure. The stabilization and migration of the nanoparticles are significantly controlled by the nature of the polymeric dispersing additives having a molecular weight above 1000 used.

EP-A-0766997 describes a jet-blasting method for comminuting agglomerates and aggregates of nanoscale primary particles, in which two liquid jets are shot at pressures of up to 200 bar in several passes and at which the particles dispersed in the liquids are ground.

EP 943664 B1 describes a method for producing scratch-resistant coatings using agglomerates of nanoscale particles ground by the jet-blast method. The invention relates to nanoparticle-containing transparent paint binders containing based on the paint solids 0.5 to 25 wt .-% incorporated as a solid primary nanoscale particles prepared by jet jet dispersion of the nanoscale particles in the binder. ( EP 943664 B1 , 0016). It is disclosed that it may be advantageous to use also surface-modified particles or z. B. make a surface modification after deagglomeration. Preference is given to using pyrogenic silicic acids and particularly preferably surface-modified types which have a hydrophobic surface. Particularly preferred resins include polyester polyols. Blocked polyisocyanates come under consideration as hardeners. The compositions described allow improved scratch resistance with constant transparency and gloss. Subject of the EP 943664 B1 is also a process for the preparation of transparent nanoparticle-containing paint binders, characterized in that the preparation consisting of nanoparticles and paint binders is passed in at least one passage through a device having at least one nozzle or a slot gap, wherein the range for the dimensions and the constructive arrangement are given (ebda. 0034). In carrying out the process, a pressure of 5 to 50 MPa, preferably 7 to 30 MPa is used. However, the significant "destructuring and milling effects" occurring only at significantly higher grinding pressures can not be achieved. In EP 943 664 B1 the dispersants are particularly preferably oligomeric or polymeric organic Verbindun gene, such. B. resins and binders commonly used in paint and coating technology as further substances. The addition of resins and binders increases the viscosity of the formulations, which limits the maximum manageable concentration of nanoscale particles. In the preferred procedure, the powdery, primarily nanoscale particles are introduced into the solvent and diluted to less than 2000 mPas polyol component in a dissolver and deagglomerated. In the examples, fumed silicas produced only by flame pyrolysis are referred to as nanoscale particles. Silicas have a low refractive index, which does not deviate so much from the refractive indices of conventional coating resins. In the case of silicas, therefore, a content of non-nanoscale fractions is not as noticeable as with high-index metal oxides.

Among the in EP 943 664 given conditions only a deagglomeration, but no grinding takes place. Aggregates of nanoscale particles can not be broken at pressures up to 50 MPa. It is not possible with the described method to grind aggregated metal oxide particles.

Even though Numerous methods for the formulation of scratch-resistant coatings for a variety of Substrates are described, there is a need for scratch-resistant, abrasion resistant and transparent coatings that are opposite the unmodified only limited scratch-resistant formulations no significant deterioration of properties exhibit.

In particular, the haze of the paints in the most effective scratch-resistant additives based on high-index metal oxides, especially alumina is too high for use in clear transparent clearcoats. The use of small amounts of nanocrystalline primary particles ( WO 2005119359 ) does not allow the production of clear transparent lacquers with a low haze value.

Other Ways to achieve scratch-resistant coatings over high nanoparticle concentrations with low refractive indexes Pigments, such as. B. Organosilicasols have the disadvantage that the coatings in comparison to loose unmodified material significantly in flexibility. The effect of such massive interventions on adhesion, recoatability and long term properties are critical and still under investigation become.

For the practice Therefore, there is the demand for a scratch-resistant paint system with complete or at least largely preserving the most important paint properties. The desired Improvement should show up in a wide processing window and in an easy-to-use paint system. The use of large Siloxane quantities for the stabilization of nanoparticles in 2K and 1K PU coating systems is undesirable, da siloxanes, as known in the art in high dosage adhesion problems cause and instability and segregation of the liquid Paint leads can. One for the Practice not insignificant factor is the cost of the paint system.

A The object of the invention is to provide a nanoscale Particles modified paint binder for paint systems and one with nanoscale particles of modified varnish and a milling process for agglomerates nanoscale inorganic particles, that of inexpensive raw materials going out and on a production scale reproducible feasible is. Since both siloxanes and nanoscale particles such. B. Organosols represent a significant cost factor, they should already cause a sufficient effect in a small amount or be replaced by cheaper systems.

The previously known grinding process for the production of nanoscale particles, z. B. over Agitator ball mills lead themselves with hard little balls, z. B. of ceria or zirconia to a not negligible Abrasion that can not be removed from the regrind and clarity and transparency of the coatings produced therewith. (please refer also J. Winkler, color + lacquer, 2/2006),

This in EP 766 997 and EP 943 664 B1 described dispersing method operates at a pressure of 230 bar to possibly 500 bar, which does not allow grinding. In the EP 766 997 described apparatus with the specified geometry of the grinding chamber and the specified arrangement of the nozzles is not suitable to be operated at a higher pressure, since the liquid jets destroy the opposite nozzles after a short period of operation.

The patent literature describes scratch-resistant coatings which have a high proportion of monodisperse nanofillers. Although the use of aggregated fillers with at least partially microscale dimensions succeeds in increasing the hardness, the transparency and, above all, the clarity are greatly reduced due to the light scattering. Also systems of combinations nanoscale and mikroska Raw materials lose their transparency and clarity, if not to that extent.

It was now surprising found that the previously described problems with regard to a paint binder dissolved can be which is a matrix based on one or a plurality of polymers and stabilized to 100% by weight of the total binder Suspension of nanoscale particles, in a solid fraction of the Suspension measured amount of 0.5 to 25 wt .-%, and characterized in that the suspension of the particles is available by a) grinding the particles with the addition of a solvent in a high-pressure mill, under a pressure in the range of> 500 - about 10,000 bar agglomerates and / or aggregates of the particles in nanoscale Fragments decomposed; and b) adding one or more dispersing additives to stabilize the surface the milled particle, wherein the dispersing additive (s) in an amount of 1 to 25 parts by weight based on 100 parts by weight the particle is present (are).

• a) einem Harzsystem,
• b) einem Härtersystem,
• c) einem Füllstoffsystem,
• d) gegebenenfalls Lösemitteln und
• e) gegebenenfalls weiteren in Lacken und Beschichtungen üblichen Additiven, wobei zumindest die Bestandteile a) und c) aus dem Lackbindemittel stammen,

die Forderung nach transparenten Beschichtungen mit verbesserter Kratzfestigkeit und/oder verbesserter Abriebbeständigkeit erfüllen, wenn die Komponenten aus den im Folgenden beschriebenen Produktsystemen ausgewählt werden und die anorganischen Füllstoffe mittels eines Hochdruckmahlverfahrens als nanoskalige Partikel bereitgestellt werden. Ein geeignetes Hochdruckmahlverfahren arbeitet gemäß den in DE 10360766 vom 23.12.2003, "Verfahren und Vorrichtung zur Herstellung von Dispersionen" oder DE 102 04 470 C1 vom 5.02.2002 ( US 6,991,190 ) "Verfahren zur Herstellung von Dispersionen" beschriebenen Verfahrensweisen.The paint binders according to the invention can be formulated in the classical way to give paints or coating systems. Surprisingly, it has now been found that lacquers resulting from the formulation using the lacquer binder according to the invention consist of

• a) a resin system,
• b) a hardener system,
• c) a filler system,
• d) optionally solvents and
• e) optionally further customary in paints and coatings additives, wherein at least the components a) and c) come from the paint binder,

meet the requirement for transparent coatings having improved scratch resistance and / or improved abrasion resistance when the components are selected from the product systems described below and the inorganic fillers are provided as nanoscale particles by means of a high pressure milling process. A suitable high pressure grinding method operates according to the in DE 10360766 of 23.12.2003, "Method and apparatus for the preparation of dispersions" or DE 102 04 470 C1 from 5.02.2002 ( US 6,991,190 ) Procedures for Preparing Dispersions.

A Particularity of the paint binder / paint system according to the invention consists of the use of specially obtained nanoscale Particles useful in stabilized Suspension used in the present case. The term "nanoscale Particle "refers on such particles whose size as aggregates of primary particles determined on a scale in the nanometer range, that's the range from 1.0 to about 500 nm. It is in the size specification the primary particle aggregates determined by the average particle size d50 using Horiba LA 920 particle size analyzer. The nanoscale particle aggregates (primary particle aggregates) can become in coating systems according to the invention not to larger entities agglomerate (agglomerate / form agglomerates).

in the According to the invention paint binders are of particular interest, in which the nanoscale present in stabilized suspension Particles have a mean particle size d50 in the range of 0.05 up to 10 μm have determined by means of light scattering to Mie. Very particularly preferred are such paint binders, which are characterized in that the nanoscale particles have a d50 value in the range of 0.05 to 0.5 μm, preferably 0.1 to 0.5 μm exhibit. As already said, between the size of the primary particles, the size of the primary particle aggregates ("Nanoscale") and the size of the particle aggregates to be distinguished in stabilized suspension / dispersion.

A special embodiment of the paint binder of the invention is characterized in that the nanoscale particles consist of primary particles that are globular, a size in the range from 5 to 30 nm, and have a fractinity <3 as measured by N 2 adsorption in the pressure range p / p0 from 0.5 to 0.8.

Particles with the aforementioned properties can be recruited from a whole range of substance groups. Interesting lacquer binders have nanoscale particles selected from the group consisting of oxidic, nitridic and carbidic metal and semimetal compounds, as well as mixtures of two or more of the above. In this context, paint binders are particularly preferred in which the nanoscale particles are selected from the group consisting of alpha-alumina, gamma-alumina, delta-alumina, theta-alumina, zirconia, yttrium-doped zirconia, titania, rutile, anatase, brookite , Silica, antimony oxide, zinc oxide, cerium oxide, iron oxides, palladium dioxide, indium tin oxide, antimony tin oxide, spinel type compounds, aluminum spinels, iron spinels, chromium spinels, titanium spinels, cobalt spinels, ceramic particles, boron nitride, boron carbide, silicon carbide, silicon nitride, mixed compounds and mixed oxides of the above-mentioned elements, and mixtures comprising two or more of the above substances.

From special interest for in the paint binder according to the invention Particles to be used are their surfaces. That's how one stands out expedient embodiment the paint binder of the invention characterized in that the surface of the nanoscale particles by post-oxidation, adsorption, reactions on the surface or complexation of or with inorganic and / or organic reagents is modified. This can be surprising achieve positive properties in the finished coatings.

In In this context, such modifications of the paint binder particularly preferred in which the surface of the nanoscale particles with two or more different types of functional Groups is modified. This will stabilize the Supports suspension of the particles at each stage of processing.

• a) Alkyltrialkoxysilane der allgemeinen Formel R-Si-O-R'_{3 ,} wobei R ein aliphatischer oder gemischt aliphatisch/aromatischer Rest sein kann und Heteroatome ausgewählt aus der Gruppe N, O, S, Cl enthalten sein können, die auch die Hauptkette unterbrechen können; und wobei R' ein aliphatischer Rest ist;
• b) Hexamethyldisilazan und seine Derivaten;
• c) Silikonbasierten Verbindungen mit einer Hauptkette aus [SiR₂-O]-Bausteinen und davon abweichenden Endgruppen sowie [SiR,R'-O]-Bausteinen bei denen R' für eine auf die Hauptkette aufgepfropfte Seitenkette steht;
• d) Vinylischen Homo- oder Copolymeren oder Oligomeren mit funktionellen Gruppen, ausgewählt aus der Gruppe bestehend aus Cl, CO₂R mit R = H, Aryl oder Alkyl mit optional weiteren funktionellen Gruppen; OH, NH2, NR2, wobei R ein Wasserstoff, aliphatischer und/oder aromatischer Rest sein kann, der weitere Heteroatome enthalten kann; C=ONR₂, wobei R ein Wasserstoff, aliphatischer und/oder aromatischer Rest sein kann, der weitere Heteroatome enthalten kann;
• e) Blockcopolymeren mit einem Gehalt an polaren erotischen oder polaren aprotischen funktionellen Gruppen in mindestens einem der Blöcke;
• f) Polykondensaten, wie z.B. Polyester und Polyamiden;
• g) Verbindungen der allgemeinen Formel R-(CH₂-CH₂-X)_n-R', wobei R und R' für ggf. funktionell substituierte aliphatische und/oder aromatische Reste, X für O, NR mit R = H, Alkyl steht;
• h) Hyperverzweigten Oligomeren oder Polymeren wie z.B. Polyimine mit darauf aufgepfropften Polyether- und/oder Polyesterseitenketten, hyperverzweigten Polyglycerinen;
• i) Sternpolymeren;
• j) Verbindungen mit einer Polyethyleniminhauptkette und darauf aufgepfropften Seitenketten, ausgewählt aus der Gruppe: Polyether, Polyester;
• k) phosphorhaltigen Oligomeren, wie z. B. tego dispers 655; und Mischungen enthaltend wenigstens eine der Verbindungen a) bis k).

The paint binders of the invention are admixed with dispersing additives for stabilizing the suspension of the nanoscale primary particle aggregates. There are a number of additives for this purpose in question. Particularly preferred paint binders of the invention are characterized in that the added dispersing additive is selected from the group consisting of

• a) alkyltrialkoxysilanes of the general formula R-Si-O-R _'3, where R can be an aliphatic or mixed aliphatic / aromatic radical and hetero atoms selected from the group N, O, S, Cl may be included, which may also interrupt the main chain; and wherein R 'is an aliphatic radical;
• b) hexamethyldisilazane and its derivatives;
• c) silicone-based compounds having a backbone of [SiR ₂ -O] building blocks and end groups differing therefrom, and [SiR, R'-O] building blocks in which R 'is a side chain grafted onto the main chain;
• d) vinylic homo- or copolymers or oligomers having functional groups selected from the group consisting of Cl, CO ₂ R where R = H, aryl or alkyl with optionally further functional groups; OH, NH 2, NR 2, where R may be a hydrogen, aliphatic and / or aromatic radical which may contain further heteroatoms; C = ONR ₂ , where R can be a hydrogen, aliphatic and / or aromatic radical which can contain further heteroatoms;
• e) block copolymers containing polar erotic or polar aprotic functional groups in at least one of the blocks;
• f) polycondensates, such as polyesters and polyamides;
• g) Compounds of the general formula R- (CH ₂ -CH ₂ -X) _n -R ', where R and R' are optionally functionally substituted aliphatic and / or aromatic radicals, X is O, NR with R = H, alkyl stands;
• h) hyperbranched oligomers or polymers such as, for example, polyimines having polyether and / or polyester side chains grafted thereon, hyperbranched polyglycerols;
• i) star polymers;
• j) Compounds having a polyethyleneimine backbone and side chains grafted thereto selected from the group consisting of: polyethers, polyesters;
• k) phosphorus-containing oligomers, such as. B. tego dispers 655; and mixtures containing at least one of the compounds a) to k).

Also certain combinations of particulate material and dispersing additive can particularly suitable paint binders result. A special embodiment the paint binder of the invention comprises as nanoscale particle aluminum oxide and as dispersing additive phosphorus-containing oligomers. Here is as phosphate-containing oligomer tego dispers 655 very particularly preferred.

Next The grinding process in a high-pressure mill could be further treatment steps upstream / downstream. A special paint binder The invention is therefore characterized in that the suspension the particle available is by placing one in a high energy mill before the step of grinding Predispersing the particles in a liquid phase in a rotor-stator-run aggregate performs. this leads to to another unexpected improvement in the stability of the suspension.

The grinding process can also be supported by further measures. Thus, the addition of a solvent is essential. An expedient variant of the paint binder according to the invention is now characterized in that the solvent added for grinding is selected from the group consisting of aliphatic and cycloaliphatic compounds, aromatic and substituted aromati compounds, petroleum and gasoline fractions usable in paints, esters, lactones, ethers, glycol ethers, ketones, alcohols, mixtures of two or more of the abovementioned compounds and mixtures comprising at least one compound of the abovementioned substances.

Very Cheap for the Paint binder of the invention is also when the solvent a combination of solvents different boiling points and / or evaporation rate and / or different polarity includes. Special embodiments are characterized in that the solvent combination used Solvesso 150 / butylglycol and / or solvesso 150 / methoxypropylacetate and / or Solvesso 150 / dibasic ester mixture DBE and / or solvent combinations with xylene or butyl acetate.

Also with respect to the resin acting as a matrix, the paint binder the invention wide variations. Advantageous embodiments are characterized in that the matrix is selected from the group consisting of organic oligomers with free hydroxyl groups, the one for one Reaction with a hardener to disposal stand, organic polymers with free hydroxyl groups, which are responsible for a curing reaction are suitable combinations of the above-mentioned oligomers and polymers, and mixtures, the oligomers and / or polymers having free hydroxyl groups suitable for reaction with a curing agent disposal stand.

Weiterhind preferred paint binders are characterized in that the Matrix polyacrylate, polyester, polycaprolactone, polyether, polycarbonate, Polyurethane polyol resins, any mixtures of the above substances, or mixtures comprising at least one of the above polymeric substances exhibit. Of these, paint binders are particularly useful at the matrix comprises polyester resins and / or polyacrylate resins.

The Paint binders of the invention have a high transparency and enable high transparent coatings. Prefers the paint binders have a high transparency of more than 70% Transmission, more preferably more than 85% transmission, still more preferably more than 88%.

• i) eine Matrix auf Basis eines oder einer Mehrzahl von Polymeren bereitstellt;
• ii) die bereitgestellte Matrix mit einer stabilisierten Suspension nanoskaliger Partikel mischt; und
• iii) gegebenenfalls zur Mischung aus ii) weitere übliche Additive hinzufügt; wobei auf 100 Gew.-% des gesamten Bindemittels, nanoskalige Partikel in einer als Feststoffanteil der Suspension gemessenen Menge von 0,5 bis 25 Gew.-%, eingearbeitet werden; wobei sich das Verfahren dadurch auszeichnet, dass die Suspension der Partikel erhältlich ist durch a) Vermahlung der Partikel unter Zusatz eines Lösemittels in einer Hochdruckmühle, die unter einem Druck im Bereich von > 500 – etwa 10.000 bar Agglomerate und/oder Aggregate der Partikel in nanoskalige Fragmente zerlegt; und b) Zusatz eines oder mehrerer Dispergieradditive zur Stabilisierung der Oberfläche der gemahlenen Partikel, wobei das (die) Dispergieradditiv(e) in einer Menge von 1 bis 25 Gewichtsteilen, bezogen auf 100 Gewichtsteile der Partikel, vorhanden ist (sind).

The invention also relates to a process for the preparation of paint binders, in which process one

• i) provides a matrix based on one or a plurality of polymers;
• ii) mixing the provided matrix with a stabilized suspension of nanoscale particles; and
• iii) optionally adding to the mixture of ii) other conventional additives; wherein on 100 wt .-% of the total binder, nanoscale particles in a measured as a solids content of the suspension amount of 0.5 to 25 wt .-%, incorporated; wherein the method is characterized in that the suspension of the particles is obtainable by a) grinding of the particles with the addition of a solvent in a high pressure mill under a pressure in the range of> 500 - about 10,000 bar agglomerates and / or aggregates of the particles in nanoscale Fragments decomposed; and b) adding one or more dispersing additives to stabilize the surface of the milled particles, wherein the dispersing additive (s) is present in an amount of 1 to 25 parts by weight based on 100 parts by weight of the particles.

The Paint binders of the invention and according to the method of the invention available Paint binders can be very useful together with aliphatic polyisocyanates in two-component clearcoats use. Another preferred use of the paint binders refers to the combination with hardeners containing hydroxyl groups can be reacted for the production of coatings and Coatings. Here, the use in combination with hardeners is selected from the group consisting of polyisocyanates, capped polyisocyanates, Isocyanate prepolymers, melamines, silanes, silylgruppenhaltigen Compounds, mixtures of one or more of the above Compounds and mixtures containing at least one of the above Compounds include, more preferably.

to Invention belongs also a paint comprising a paint binder as described herein. Likewise belong to the invention painted objects having a coating from a hardened Lacquer containing / containing a lacquer binder as described herein.

• a) einem oligomeren oder polymeren Harz oder einer Mischung oligomerer und/oder polymerer Harze, die für die Lackhärtung nutzbare funktionelle Gruppen enthalten können,
• b) einem Härtersystem, das selbst oligomere Bestandteile enthalten kann
• c) einem Füllstoffsystem, das im wesentlichen aus einem nanoskaligen partikulären Füllstoff oder einer Mischung von im wesentlichen nanoskaligen partikulären Füllstoffen besteht, wobei die Füllstoffe ausgewählt werden aus der Gruppe anorganischer amorpher oder kristalliner Materialien oder an der Oberfläche organisch modifizierter anorganischer Materialien und wobei der Füllstoff oder die Mischung der Füllstoffe in einem Lösemittel vermahlen werden und zur Vermahlung eine Hochdruckmühle eingesetzt wird, die unter sehr hohem Druck Agglomerate und/oder Aggregate des Füllstoffs in nanoskalige Fragmente zerlegen kann und die Reaggregation bzw. Reagglomeration der Partikel durch Stabilisierung der Partikeloberfläche mit Silanen und/oder phosphorhaltigen Verbindungen; Silanen und/oder oligomeren Dispergieradditiven; oder Kombinationen phosphorhaltiger Verbindungen mit oligomeren Dispergieradditiven verhindert wird.
• d) optional einem Lösemittel oder einer Kombination von Lösemitteln und
• e) weiteren in Lacken und Beschichtungen üblichen Additiven, ausgewählt aus der Gruppe der Verlaufhilfsmittel, Netzmittel, Dispergiermittel, Antioxidantien, Härtungskatalysatoren, Trocknungsmittel, Reaktivverdünner, Pigmente, Trennmittel, Slipadditive, Haftungsvermittler, Silane, Phoshorverbindungen, Alkylphosphonate.

The invention will be explained in more detail below with reference to the description of the individual components / method steps:
The paints according to the invention consist of:

• a) an oligomeric or polymeric resin or a mixture of oligomeric and / or polymeric resins which may contain usable functional groups for the lacquer hardening,
• b) a hardener system which may itself contain oligomeric components
• c) a filler system consisting essentially of a nanoscale particulate filler or a mixture of substantially nanoscale particulate fillers, wherein the fillers are selected from the group of inorganic amorphous or crystalline materials or on the surface of organically modified inorganic materials and wherein the filler or the mixture of fillers are ground in a solvent and used for grinding a high-pressure mill, which can decompose agglomerates and / or aggregates of the filler into nanoscale fragments under very high pressure and the reaggregation or reagglomeration of the particles by stabilizing the particle surface with silanes and / or phosphorus-containing compounds; Silanes and / or oligomeric dispersing additives; or combinations of phosphorus-containing compounds with oligomeric dispersing additives is prevented.
• d) optionally a solvent or a combination of solvents and
• e) other customary in paints and coatings additives selected from the group of flow aids, wetting agents, dispersants, antioxidants, curing catalysts, drying agents, reactive diluents, pigments, release agents, slip additives, adhesion promoters, silanes, phosphorus compounds, alkyl phosphonates.

• a) Alkyltrialkoxysilane der allgemeinen Formel R-Si-O-R'_{3 ,} wobei R ein aliphatischer oder gemischt aliphatisch/aromatischer Rest sein kann und Heteroatome enthalten sein können, ausgewählt aus der Gruppe N, O, S, Cl, die auch die Hauptkette unterbrechen können; und wobei R' ein aliphatischer Rest ist.
• b) Hexamethyldisilazan.
• c) Silikonbasierte Dispergieradditive mit einer Hauptkette aus [SiR₂-O]-Bausteinen und davon abweichenden Endgruppen sowie [SiR,R'-O]-Bausteinen bei denen R' für eine auf die Hauptkette aufgepfropfte Seitenkette steht.
• d) Vinylischen Homo- oder Copolymeren oder Oligomeren mit funktionellen Gruppen, ausgewählt aus der Gruppe, Cl, CO2R mit R = H, Aryl oder Alkyl mit optional weiteren funktionellen Gruppen; OH, NH2, NR2, wobei R ein Wasserstoff, aliphatischer und/oder aromatischer Rest sein kann, der weitere Heteroatome enthalten kann; C=ONR2, wobei R ein Wasserstoff, aliphatischer und/oder aromatischer Rest sein kann, der weitere Heteroatome enthalten kann.
• e) Blockcopolymeren mit einem Gehalt an polaren erotischen oder polaren aprotischen funktionellen Gruppen in mindestens einem der Blöcke
• f) Polykondensaten, wie z.B. Polyester und Polyamiden
• g) Verbindungen der allgemeinen Formel R-(CH₂-CH₂-X)_n-R', wobei R und R' für ggf. funktionell substituierte aliphatische und/oder aromatische Reste, X für O, NR mit R = H, Alkyl steht.
• h) Hyperverzweigten Oligomeren oder Polymeren
• i) Sternpolymeren
• j) Verbindungen mit einer Polyethyleniminhauptkette und darauf aufgepfropften Seitenketten, ausgewählt aus der Gruppe: Polyether, Polyester.
• k) phosphorhaltigen Oligomeren, wie z. B. tego dispers 655

The coating system of the invention is further distinguished by the fact that the silanes used for surface stabilization, phosphorus compounds or oligomeric dispersing additives are selected from the group of

• a) alkyltrialkoxysilanes of the general formula R-Si-O-R _'3, where R can be an aliphatic or mixed aliphatic / aromatic radical and hetero atoms can be included, selected from the group N, O, S, Cl, may also interrupt the main chain ; and wherein R 'is an aliphatic radical.
• b) hexamethyldisilazane.
• c) Silicone-based dispersing additives having a backbone of [SiR ₂ -O] units and other end groups, and [SiR, R'-O] units where R 'is a side chain grafted onto the backbone.
• d) vinylic homo- or copolymers or oligomers having functional groups selected from the group Cl, CO2R with R = H, aryl or alkyl with optionally further functional groups; OH, NH 2, NR 2, where R may be a hydrogen, aliphatic and / or aromatic radical which may contain further heteroatoms; C = ONR2, where R can be a hydrogen, aliphatic and / or aromatic radical which can contain further heteroatoms.
• e) block copolymers containing polar erotic or polar aprotic functional groups in at least one of the blocks
• f) polycondensates, such as polyesters and polyamides
• g) Compounds of the general formula R- (CH ₂ -CH ₂ -X) _n -R ', where R and R' are optionally functionally substituted aliphatic and / or aromatic radicals, X is O, NR with R = H, alkyl stands.
• h) hyperbranched oligomers or polymers
• i) star polymers
• j) Compounds having a polyethyleneimine backbone and side chains grafted thereon selected from the group consisting of polyether, polyester.
• k) phosphorus-containing oligomers, such as. B. tego dispers 655

Essential for the Invention is the grinding of nanoscale fillers under very high pressure takes place, so that already particle aggregates, which under usual Dispersing processes not destroyed be broken down into their components.

Description of the grinding system according to the invention

A process has proven particularly suitable in which the dispersion is first carried out with an energy input of less than 1000 kJ / m ³ to form a predispersion (eg dissolver or rotor-stator machines), the predispersion in at least two Divide sub-streams, these sub-streams in a high-energy mill under a pressure of at least 500 bar sets, relaxed via a nozzle and meet in a gas- or liquid-filled reaction space and optionally repeated high energy milling one or more times.

By the presence of suitable surfactants in the Dispersion solution selected from groups a) to j) the newly created surfaces are stabilized and prevents reaggregation or reagglomeration of the particles.

Description of the paint system:

• • einem Harz oder einer Mischung von Harzen
• • einem Lösemittel oder einer Mischung von Lösemitteln
• • einem Härter oder einer Mischung von Härtern
• • Additiven
• • nanopartikulären Füllstoffen, sowie
• • weiteren in Lacken üblichen Komponenten

The paint system consists of:

• • a resin or a mixture of resins
• • a solvent or a mixture of solvents
• • a hardener or a mixture of hardeners
• • additives
• • nanoparticulate fillers, as well
• • other common components in paints

The components of the paint system are described to illustrate the invention:
Resins of the present invention are organic polymers having free hydroxyl groups available for reaction with a hardener; z. For example, polyester resins and polyacrylates.

Saturated polyester resins are usually prepared by condensation of saturated polycarboxylic acids, e.g. dicarboxylic acids, or their anhydrides or other esterifiable derivatives with polyols, e.g. Diols or triplets made. Their properties are largely dependent of type and proportions of the starting materials.

Examples for suitable acids or acid derivatives for the production of the polyesters are phthalic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, pyromellitic acid, dimer fatty acids, and / or Trimellitic acid, whose anhydrides and / or lower alkyl esters such as e.g. Methylester.

Examples for suitable Polyols are: ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, dipropylene glycol, Triethylene glycol, tetraethylene glycol, 1,4-butanediol, 1,3-butylethylpropanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, cyclohexanedimethanol, Glycerol, 1,6-hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, 1,2,6-Trihydroxyhexaerythrit, Trishydroxyethyl isocyanurate, pentaerythritol, sorbitol, mannitol, xylitol, 1,4-benzyldimethanol, 1,4-benzyldiethanol, 2,4-dimethyl-2-ethylhexan-1,3-diol, Dicidol.

The polyesters essential to the invention are prepared by known processes (see Dr. P. Oldring, Resins for Surface Coatings, Volume III, published by Sita Technology, 203 Gardiness House, Bromhill Road, London SW 184JQ, England 1987 ) produced by condensation.

The saturated according to the invention Polyester can an acid number between 0 and 10 mg KOH / g, preferably 0 to 5 mg KOH / g and especially preferably 0 to 3 mg KOH / g; a hydroxyl number between 3 and 80 mg KOH / g, preferably 10 to 50 mg KOH / g and more preferably 15 to 30 mg KOH / g.

The number-average molecular weights Mn of the linear or branched, preferably linear or slightly branched polyester lie between 2000 and 20,000; the glass transition temperature (Tg) between -20 ° C and + 60 ° C, preferably between -10 ° C and + 40 ° C,

The hardener system

When hardener components can Compounds that are reacted with hydroxyl groups can, be used. Suitable compounds are polyisocyanates, capped Polyisocyanates, Isocyanatprepolymere, melamines, silanes and silylgruppenhaltige Compounds, other compounds at room temperature or increased Temperature, optionally with the aid of a catalyst having hydroxyl groups Reaction under chain extension or networking.

suitable Connections are z. B. in: Bodo Müller / Ulrich Poth: paint formulation and Paint Recipe, Vincentz-Verlag Hannover, 2003, Part II, Chapter 2: baked enamels and specified in the literature cited therein.

Description of the filler system:

The filler system, which consists essentially of a nanoscale particulate filler or a mixture of substantially nanoscale particulate fillers, wherein the fillers are selected from the group of inorganic amorphous or crystalline materials or on the surface of organically modified inorganic materials is an essential component of the coatings of the invention and Coatings and is provided by careful dispersion and / or grinding in combination with suitable surface active components in nanoscale form.

Selection of suitable particles:

Suitable inorganic particles of a certain size and a specific structure. This is achieved by adding to the polymers ceramic particles with non-spherical morphology. These particles may consist of aggregates of globular primary particles (size of the primary particles: 5 to 30 nm), which have a fractality of less than 3, preferably less than 2.8, more preferably less than 2.5 in order to achieve the high surface area. The fractality was after in the DE1976840 method determined by N2 adsorption in the pressure range p / p0 of 0.5 to 0.8. The evaluation of the measurement results was carried out according to the fractal BET theory for the Mehrladungsadsorption according to the method specified by Pfeifer, Obert and Cole ( Proc. R. Soc. London, A423, 169 (1989) ,

The Particles are added in such a way that once set Particle distribution, only undergoes such changes, the the desired Improvement of the property profile only insignificantly changed.

The Capacities vary from 0.1 to 20 w%, preferably 0.2 to 10 w% and especially preferably 0.5 to 3% by weight, based on solid resin.

One suitable production method for particles with fractal structures is the flame pyrolysis process of Degussa AG for the production of pyrogenic oxides. Fractal structures can e.g. through aggregation spherical, ellipsoid, crystalline or irregularly shaped particles in the Manufacturing process, for example, in the flame pyrolysis in one be called Flame or formed immediately behind the hot flame. Particles having a fractal structure can, for. B. from aggregates of at least two and up to several hundred spherical, ellipsoidal, crystalline or irregularly shaped primary particles consist. However, there are also particles with fractal structures, which have been prepared by another method suitable. examples for other suitable processes are precipitation processes, hydrothermal Method or plasma method.

The particles according to the invention be through surface modification made compatible with the polymer matrix. The term surface modification includes post-oxidation, adsorption, surface reactions or Complexation of or with inorganic and / or organic Reagents.

In a particular embodiment are the particles modified so that these functional groups carry a positive interaction of the van der Waals type and / or Hydrogen bonding and / or electrostatic binding and / or ionic bonding and / or coordinative binding and / or covalent bonding, between the particle and allow the polymer.

In another particular embodiment the particles contain at least two, more preferably at least three functional groups of different reactivity to in all phases of the manufacturing and processing process a good To achieve binding of the particles to the polymer matrix.

Generally, oxidic, nitridic and carbidic metal and metalloid compounds are preferred:
Alumina (alpha, beta, delta, theta), zirconia, yttria-doped zirconia, titania, (rutile, anatase and brookite), silica, antimony oxide, zinc oxide, ceria, iron oxides, palladium dioxide, mixed oxides of the above elements. Furthermore, indium tin oxide, antimony tin oxide. Furthermore, spinel type materials such as aluminum, iron, chromium, titanium and cobalt spinels. In addition, the following ceramic particles such as boron nitride, boron carbide, silicon carbide, silicon nitride. Depending on the manufacturing process chosen, the oxidic particles also have free hydroxyl groups in different proportions in addition to the oxidic groups. The hydroxyl groups may preferably be reacted in a subsequent surface modification.

The Particles are surface-modified in a preferred embodiment, to ensure an adaptation to the polymer matrix. The surface modification can take place in several stages and already take place during the synthesis. A preferred method is the post-oxidation wherein the number the hydroxyl groups on the surface can be reduced. Obtained by this modification one particle with reduced aggregation behavior, which is characterized by good dispersibility.

In an embodiment According to the invention, the particles are surface-modified only in one step.

Especially the surface modification is preferred with two or more different functional groups. The first surface modification the particle can be after the particle synthesis z. B. by Reaction of pyrogenic oxides with reactive low molecular weight; functional take place oligomeric or reactive oligomeric substances. Examples for suitable Modifiers are silicon-containing compounds, such as. B. Silanes, substituted silanes, silicone oil, hexamethyldisilazane, alkyltrialkoxysilanes, Alkyltrihalosilanes, dialkyldialkoxysilanes, dialkyldihalosilanes, Trialkylalkoxysilanes, trialkylhalosilanes, glycidyloxypropyltrialkoxysilanes, Aminopropyltrialkoxysilanes, methacryloxypropyltrialkoxysilanes, per- and partially fluorinated alkyltrialkoxysilanes, silanes with further functional Groups.

Further suitable compounds are phosphorus-containing substances, such as. B. organically modified phosphates, phosphonates, di- or polyphosphorus compounds, Alkylphosphonates, phosphorus compounds with mixed organic Rests, mixtures of phosphorus compounds or oligomers and polymers with phosphate-containing radicals, such as. B. tego dispers 655 from Degussa, Eat. Phosphorus compounds are particularly effective for surface modification of alumina suitable but also be used on other pyrogenic oxides. For surface modification according to the invention Of alumina is usually sufficient from a modification step. In a preferred embodiment be alumina particles in one step with several Modifying agents surface-modified.

In an embodiment become dispersants for the modification used. In a particular embodiment become dispersants for the second modification used. Under dispersants are Means to understand the dispersing of particles in one Dispersing agent, the liquid Phase of a dispersion, by lowering the interfacial tension facilitate. The property of the dispersant, by lowering the interfacial tension between the solid and liquid Phase to facilitate dispersion of the particles, when the particles of the invention in an organic liquid be converted into a dispersion. The dispersants support the breaking up of agglomerates, wet or occupy as surface-active Materials the surface the particles to be dispersed and stabilize them against a undesirable Reagglomeration.

The optional second functionalization of the particles can be done together with the first functionalization, following the first functionalization or preferably before, during or after the dispersing process, before, at or after the grinding process according to the invention respectively. In a preferred embodiment, those for the second surface modification required substances before the dispersion process to a solvent-containing Dispersion of nanoscale fillers or their precursors or to a binder-containing dispersion the fillers or precursors added in organic solvents.

The Modifier for the second surface modification can identical to or different from those of the first modification be. Suitable modifiers for the second modification are the silicon compounds mentioned in the first modification, Phosphorus compounds and above In addition, oligomeric dispersing aids with suitable functional Groups. The selection of the functional groups has to be done that they do not or only to a minor extent intervene in the hardening process. apart from the chemical nature of the functional groups therefore plays also the accessibility and Location in the molecule a role. Contain preferred oligomeric dispersing aids aprotic polar groups, more preferably ether, ester and amide groups. Protic or ionic functional groups are favorable for the dispersion process, can however, if necessary with the curing system react. In the case of isocyanate curing, the content of erotic or ionic functional groups in the dispersant therefore not to neglect. It is possible, however to introduce a certain amount of erotic or ionic groups to improve the dispersing effect. This is especially true if the paint system is more tolerant of a change in resin-to-hardener ratio is. In the case of alumina, oligomeric dispersing additives with phoshorhaltigen residues, such. B. tego dispers 655 especially proven.

Detailed description of the dispersants:

• a) Alkyltrialkoxysilane der allgemeinen Formel R-Si-O-R'_{3 ,} wobei R ein aliphatischer oder gemischt aliphatisch/aromatischer Rest sein kann und Heteroatome ausgewählt aus der Gruppe N, O, S, Cl enthalten sein können, die auch die Hauptkette unterbrechen können; und wobei R' ein aliphatischer Rest ist.
• b) Hexamethyldisilazan und seine Derivate
• c) Silikonbasierte Dispergieradditive mit einer Hauptkette aus [SiR₂-O]-Bausteinen und davon abweichenden Endgruppen sowie [SiR,R'-O]-Bausteinen bei denen R' für eine auf die Hauptkette aufgepfropfte Seitenkette steht.
• d) Vinylischen Homo- oder Copolymeren oder Oligomeren mit funktionellen Gruppen, ausgewählt aus der Gruppe, Cl, CO₂R mit R = H, Aryl oder Alkyl mit optional weiteren funktionellen Gruppen; OH, NH2, NR2, wobei R ein Wasserstoff, aliphatischer und/oder aromatischer Rest sein kann, der weitere Heteroatome enthalten kann; C=ONR₂, wobei R ein Wasserstoff, aliphatischer und/oder aromatischer Rest sein kann, der weitere Heteroatome enthalten kann.
• e) Blockcopolymeren mit einem Gehalt an polaren erotischen oder polaren aprotischen funktionellen Gruppen in mindestens einem der Blöcke
• f) Polykondensaten, wie z.B. Polyester und Polyamiden
• g) Verbindungen der allgemeinen Formel R-(CH₂-CH₂-X)_n-R', wobei R und R' für ggf. funktionell substituierte aliphatische und/oder aromatische Reste, X für O, NR mit R = H, Alkyl steht.
• h) Hyperverzweigten Oligomeren oder Polymeren wie z.B. Polyimine mit darauf aufgepfropften Polyether- und/oder Polyesterseitenketten, hyperverzweigten Polyglycerinen,
• i) Sternpolymeren
• j) Verbindungen mit einer Polyethyleniminhauptkette und darauf aufgepfropften Seitenketten, ausgewählt aus der Gruppe: Polyether, Polyester.
• k) phosphorhaltigen Oligomeren, wie z. B. tego dispers 655

The silanes, phosphorus compounds or oligomeric dispersing additives used for surface stabilization are selected from the group of

• a) alkyltrialkoxysilanes of the general formula R-Si-O-R _'3, where R can be an aliphatic or mixed aliphatic / aromatic radical and hetero atoms selected from the group N, O, S, Cl may be included, which may also interrupt the main chain; and wherein R 'is an aliphatic radical.
• b) hexamethyldisilazane and its derivatives
• c) Silicone-based dispersing additives having a backbone of [SiR ₂ -O] units and other end groups, and [SiR, R'-O] units where R 'is a side chain grafted onto the backbone.
• d) vinylic homopolymers or copolymers or oligomers having functional groups selected from the group consisting of Cl, CO ₂ R where R = H, aryl or alkyl with optionally further functional groups; OH, NH 2, NR 2, where R may be a hydrogen, aliphatic and / or aromatic radical which may contain further heteroatoms; C = ONR ₂ , where R can be a hydrogen, aliphatic and / or aromatic radical which can contain further heteroatoms.
• e) block copolymers containing polar erotic or polar aprotic functional groups in at least one of the blocks
• f) polycondensates, such as polyesters and polyamides
• g) Compounds of the general formula R- (CH ₂ -CH ₂ -X) _n -R ', where R and R' are optionally functionally substituted aliphatic and / or aromatic radicals, X is O, NR with R = H, alkyl stands.
• h) hyperbranched oligomers or polymers such as, for example, polyimines having polyether and / or polyester side chains grafted onto them, hyperbranched polyglycerols,
• i) star polymers
• j) Compounds having a polyethyleneimine backbone and side chains grafted thereon selected from the group consisting of polyether, polyester.
• k) phosphorus-containing oligomers, such as. B. tego dispers 655

suitable Wetting and dispersing agents are e.g. from the Degussa AG, Essen under the trade name tego dispers, EFKA (now Ciba) or Byk Chemistry, Wesel available. Suitable silanes are from Degussa AG, business unit Aerosil & Silane, Rheinfelden available.

Suitable particulate fillers are, for. B. under the trade names Aerosil ^® , Aeroxide ^® , AdNano ^® or under the chemical name of the metal oxides at Degussa AG, Aerosil & Silane division available.

The milling process:

The nanoscale fillers be under very high pressure in solvents containing at least one contain low molecular weight, oligomeric or polymeric dispersing additive, through a nozzle pressed. When passing through the nozzle very high shear forces occur on and the material is relaxing at high speeds accelerated. Preferably, at least a partial stream through a second nozzle relaxed and the generated accelerated liquid jets on a Focused common point to impact due to larger units to grind. Here it is favorable when the liquid jets off the opposite direction collide. It becomes practical with optimal adjustment, the kinetic energy for grinding the Particles used or in heat converted, thereby avoiding too high abrasive damage to the grinding chamber walls becomes. However, since an optimal adjustment is difficult, when using an angle of 180 °, the opposite nozzle mounts damaged. To avoid this, either a small angle is used and thus reduces the effect and the grinding chamber walls must go through the constant Impact of not complete brazed particles are protected by hard materials, or it can be in a particularly preferred embodiment, 3 partial flows are selected and adjusted in one plane at an angle of 120 ° each. As a precaution, the metallic material is also replaced by hard materials Protected Mahlkammerwandung. When grinding is appropriate one preferably set high solids content.

to Grinding is a grinding unit used under high pressure Agglomerates and / or aggregates of the filler in nanoscale fragments can disassemble. Reaggregation or reagglomeration of the particles is achieved by stabilizing the particle surface with silanes and / or phosphorus-containing Links; Silanes and / or oligomeric dispersing additives; combinations phosphorus-containing compounds with oligomeric dispersing additives prevented.

One A suitable two-stage process is the predispersion of the nanomaterials in the liquid phase in a rotor-stator-continuous-unit, type Ystral Conti TDS and the subsequent one Milling the predispersion in a high energy mill at a pressure over 500 bar, preferably between 500 and 5000 bar and z. B. 2500 bar.

With the grinding process according to the invention, fractal nanoscale particles are obtained which on the one hand are small enough that they do not contribute significantly to the light scattering and thus to the turbidity of the material on the other hand have not yet lost their fractal character. The aim of the milling is therefore not the production of primary particles, wherein the composition of the dispersion after the wet-grinding can also have a content of primary particles. To stabilize the dispersions, the wetting and dispersing additives described above are used. Further explanations about the use and combination of suitable surfactants are given in the examples.

The solvent system:

optional can be a single solvent or a combination of solvents be used. The solvent for the Preparation of the nanoparticle dispersion should with the solvents be compatible in the paint. Suitable solvents are selected from the group: aliphatic and cycloaliphatic solvents, aromatic and substituted aromatic solvents, usual in paints Oil- and gasoline fractions, esters, lactones, ethers, glycol ethers, ketones, Alcohols and other usual in paints Solvents. Preferably, combinations of solvents are different Boiling point (evaporation number) and different polarity. Examples of suitable Solvent combinations are Solvesso 150 / butylglycol; Solvesso 150 / methoxypropyl acetate and Solvesso 150 / Dibasic ester mixture DBE; Solvent combinations with xylene or butyl acetate.

Other typical additives in paints:

optional can other customary in paints and coatings additives used come, selected from the group of flow control agents, wetting agents and dispersants, Antioxidants, curing catalysts, Drying agent, reactive diluent, Pigments, release agents, panty additives, skin preventatives, adhesion promoters, Silanes, phosphorus compounds, alkylphosphonates, corrosion inhibitors, defoamers,

Foam problems are suitable for deaerators, which are also used in diesel fuel:
Tego Antifoam MR 465
Tego Antifoam MR 467
Tego Antifoam MR 2057
Tego Flow ZFS 460

The Antifoam systems are partially used at levels between 6 ppm used up to 0.5% (flow).

Description of the coating process

The coating can be done on a laboratory scale according to the usual methods. Examples of metal coating on a production scale are the coating of strip sheets by the coil coating method and the can coating method for metal can coating. The curing of the paints can be done for economic reasons at very short times and high temperatures. The paints according to the invention are intended to develop their required properties under production conditions. A suitable method for the laboratory is doctoring. Depending on the hardener system, the layer is cured in a drying oven and heated between 130 ° C and 310 ° C using a box squeegee, a scraper blade or a wire squeegee. The wet film thickness is chosen such that a dry film results between 5 and 100 .mu.m, preferably 30 and 60 .mu.m thickness. The curing time can be between 60 minutes at low temperature and 30 seconds at the highest temperature. It is chosen according to the reactivity of the hydroxy-functional component and the hardener component according to the recommendations of the raw material manufacturers. Hints for suitable time / temperature combinations can be found in: Bodo Müller / Ulrich Poth: Paint formulation and paint formulation, Vincentz-Verlag Hannover, 2003, Part II, Chapter 2: stoving enamels

Description of the coating

An essential feature of the coating according to the invention is that clear transparent or substantially clear transparent coatings are obtained. Nanoscale fillers with a high refractive index naturally lead to greater haze for the same particle size than fillers with a refractive index close to the refractive index of the resin hardener system. After curing of the coating is left to stand for 24 h. Thereafter, the test of the paint properties. All paint properties are compared with the unmodified blank. The following coating properties were tested: MEK resistance, adhesion (cross-hatch), layer thickness, pendulum hardness according to König, Erichsen indentation, ball hardness, abrasion resistance (Taber Abraser, friction wheels CS 10, 1000 revolutions (standard), if required up to 5000 revolutions), wet rub test according to internal method, gloss before and after wet rub test, reflow after 2 h 60 ° C or 2 d RT, pencil hardness, Erichsen scratch hardness.

Description of the paint properties and her exam

The paints according to the invention are flexible and scratch-resistant, abrasion-resistant and / or abrasion-resistant as the unmodified paints. Prerequisite for increased scratch resistance and / or Abrasion resistance is the grinding, dispersion according to the invention and stabilization of the fractal, particulate fillers. If not sufficient Dispersion or improper stabilization are fractal particulate fillers not even enough dispersed barren can agglomerate. Furthermore, with insufficient grinding and the viscosity of the paint for optimal processing is too high. In both cases show the corresponding paints turbidities and the scratch resistance, scuff resistance and / or abrasion resistance is opposite the reduced unmodified paints. An important feature of the invention is therefore the stabilization of the high energy grinding produced nanoscale particles in the dispersion by the above surface-active Medium. The paints of the invention have the same or improved flexibility compared with unmodified paints at Erichsentiefung. The invention is explained in more detail with reference to the following examples.

Example 1:

Preparation of the suspensions and comparative suspensions as well as their properties:

Suspension 1 A (S1A):

15% AEROXIDE Alu ^® 65, 10% Hostaphat OPS relative to Al2O3, in xylene;
in a equipped with a jet mixer 100 l stainless steel batch tank 58.45 kg of xylene are placed and 1.05 kg Hostaphat OPS dissolved with stirring. Subsequently, during ongoing dispersing Ystral Conti-TDS 3 (stator slot: 4 mm ring and 1 mm ring, rotor / stator gap ca. 1 mm) under shear conditions, 10.5 kg of AEROXIDE Alu ^® 65 (BET 65 m ² / g), Manufacturer Fa. Degussa, placed in the batch tank. After completion of the addition is post sheared at 3000 U / min for 30 min. This predispersion is passed in two passes through the high-energy mill Sugino Ultimaizer HJP-25050 at a pressure of 2500 bar and diamond nozzles of 0.25 mm diameter and thereby intensively further ground.

• * Mit Entschäumer BYK-05;
• ** %-Angabe bezogen auf AEROXIDE bzw. AEROSIL;
• *** nur ca. 5,3% Feststoff konnten ohne Additive eingearbeitet werden da die Viskosität zu stark anstieg;
• **** nur ca, 3% Feststoff konnten ohne Additive eingearbeitet werden da die Viskosität zu stark anstieg;

The other examples were carried out analogously to the embodiment of suspension 1 A (S1A), the components being used in amounts corresponding to the table below. Percentages for the surface active material (values in parentheses) refer to the nanoparticle solids. description Xylene [kg] AEROXIDE ^® Alu 65 [kg] Hostaphate OPS [kg] Dynasylan ^® Glymo [kg] Dynasylan ^® OCTMO [kg] d ₅₀ [μm] S1A 58.45 10.5 1.05 - - 0.301 S1B 58.14 10.5 1.05 0.315 (3%) ** - 0.224 S1C 57.82 10.5 1.05 0.630 (6%) - 0.213 S1D 57.40 10.5 1.05 1.05 (10) - 0.192 S2A 64.23 5.6 - 0.168 (3%) - 4.2 S2B 64.12 5.6 - 0.28 (5%) - 3.0 S2C 63.84 5.6 - 0.56 (10%) - 2.7 S3D 63.28 5.6 - 0.56 (10%) 0.56 (10%) 2.6 description Xylene [kg] AEROXIDE ^® Alu C 805 [kg] Hostaphate OPS [kg] Dynasylan ^® Glymo [kg] Dynasylan ^® OCTMO [kg] d ₅₀ [μm] S4A 59.19 10.5 - 0.315 (3%) - 0.226 S4B 58.98 10.5 - 0.525 (5%) - 0.222 description Xylene [kg] AEROSIL ^® R 8200 [kg] Hostaphate OPS [kg] Dynasylan ^® Glymo [kg] Dynasylan ^® OCTMO [kg] d ₅₀ [μm] S5A * 56.0 14.0 0.56 (4%) 0.239 Comparative Examples Xylene [kg] AEROXIDE ^® Alu 65 [kg] Hostaphate OPS [kg] Dynasylan ^® Glymo [kg] Dynasylan ^® OCTMO [kg] d ₅₀ [μm] V1 66.3 3.7 - - - *** kg AEROSIL ^® 200 - - - V2 67.9 2.1 - - - ****

• * With defoamer BYK-05;
• **% value based on AEROXIDE or AEROSIL;
• *** only about 5.3% solids could be incorporated without additives because the viscosity increased too much;
• **** only about 3% solids could be incorporated without additives because the viscosity increased too much;

• a) Dispersionen ohne Dispergieradditiv und ohne Vermahlung auf der Hochenergiemühle
• b) Dispersionen mit Dispergieradditiv ohne Vermahlung auf der Hochenergiemühle

Further comparative dispersions (suspensions) were prepared:

• a) dispersions without dispersing additive and without grinding on the high-energy mill
• b) Dispersions with dispersing additive without grinding on the high-energy mill

The Dispersions were mixed with a dissolver for 15 min or with a dissolver for 30 min Rotor startor Pass shearing unit (Ystral Co.).

• * Mit Entschäumer BYK-05;
• ** %-Angabe bezogen auf AEROXIDE bzw. AEROSIL;
• *** nur ca. 5,3% Feststoff konnten ohne Additive eingearbeitet werden da die Viskosität zu stark anstieg;

The experiments prove that no reduction in the average particle size in the suspension is achieved by the use of conventional rotor-stator mixers or dissolvers, regardless of whether a dispersing additive was used or not. description Xylene [kg] AEROXIDE ^® Alu 65 [kg] Hostaphate OPS [kg] Dynasylan ^® Glymo [kg] Dynasylan OCTMO [kg] d ₅₀ [μm] VS1A 58.45 10.5 - - - 7.6 VS1B1 58.14 10.5 1.05 - - 4.7 VS1B2 58.45 10.5 1.05 0.315 (3%) ** - 0.332 VS1C 57.82 10.5 1.05 0.630 (6%) 7.84 VS1D 58.45 10.5 1.05 1.05 (10%) ** - 7.62 VS2A 64.23 5.6 - 0.168 (3%) - 6.17 VS2B 64.12 5.6 - 0.28 (5%) - n / A VS2C 63.84 5.6 - 0.56 (10%) - 6.85 VS3D 63.28 5.6 - 0.56 (10%) 0.56 (10%) n / A description Xylene [kg] AEROXIDE ^® Alu C 805 [kg] Hostaphate OPS [kg] Dynasylan ^® Glymo [kg] Dynasylan OCTMO [kg] d ₅₀ [μm] VS4A1 59.19 10.5 - - - 6.4 VS4A2 59.19 10.5 - 0.315 (3%) - 5.95 VS4B 58.98 10.5 - 0.525 (5%) - 8.6 description Xylene [kg] AEROSIL ^® R 8200 [kg] Hostaphate OPS [kg] Dynasylan Glymo [kg] Dynasylan OCTMO [kg] d ₅₀ [μPm] VS5A1 * 56.0 14.0 - - - 12.4 VS5A2 * 56.0 14.0 - 0.56 (4%) - 11.8

• * With defoamer BYK-05;
• **% value based on AEROXIDE or AEROSIL;
• *** only about 5.3% solids could be incorporated without additives because the viscosity increased too much;

The Determination of particle size and particle size distribution The nanoparticle dispersions were carried out by means of light scattering analysis according to Mie theory using a Horiba LA 920 laser scattered light spectrometer.

• *) Als Dispergieradditiv wurde Tego Dispers 655 eingesetzt.
• **) Absolut, bezogen auf Gesamtsystem

Further suspensions S6 to S10 were prepared by the same procedure in butyl acetate. Instead of the abovementioned surface-active compounds, only a polymeric dispersing additive based on a polyethyleneimine with polyether and polyester side chains grafted onto it (test product, Degussa AG, Essen) was used. The following dispersions were used: Nanoparticle dispersions in butyl acetate with polymeric dispersing additive: description nanoparticles Content of particles [%] Content of dispersing additive [%] **) d ₅₀ [μm] S6 Aerosil R9200 25.9 10 7.71 S7 Aerosil OX 50 39.5 10 0,179 S8 Aeroxide Alu C 36.0 10 0.104 S9 Aeroxide Alu 65 42.1 10 0,111 S10 Aeroxide Alu C 45 10 Tego Dispers 655 0.105 *)

• *) Tego Dispers 655 was used as the dispersing additive.
• **) Absolutely, relative to the overall system

There were further comparative dispersions (suspensions) were prepared.

• c) Dispersionen ohne Dispergieradditiv und ohne Vermahlung auf der Hochenergiemühle
• d) Dispersionen mit Dispergieradditiv ohne Vermahlung auf der Hochenergiemühle

For comparison, the following dispersions were prepared:

• c) dispersions without dispersing additive and without grinding on the high-energy mill
• d) dispersions with dispersing additive without grinding on the high-energy mill

The Dispersions were 15 min with a Dissolver Pendraulik LD 50 with 35 mm disc and 930 rpm dispersed. Without dispersing additive one received in part viscous pastes, so that not the same quantity of filler as could be achieved with dispersing additive.

The Experiments prove that with the conventional dispersing Dissolver no equivalent reduction of the mean particle size as in the Hochenergievermahlung is achieved, regardless of whether the dispersing additive was used.

• *) mehr als 7,6 Teile Alu C können wegen starken Viskositätsanstiegs ohne Dispergieradditiv nicht in die Dispersion eingearbeitet werden. Mit dem Dispergieradditiv ohne Hochenergievermahlung können maximal 26 Teile eingearbeitet werden. Mit Dispergieradditiv und Hochenergievermahlung können 36 Teile eingearbeitet werden.
• **) Dispergierung bei 4600 UpM, viskose Paste
• ***) Dispergierung bei 2800 UpM, viskose Paste
• ****) Dispergierung bei 1860 UpM, viskose Paste
• *****) Absolut, bezogen auf Gesamtsystem
• *****) der maximal einstellbare Feststoffgehalt ist 25% bei einem Gehalt von 4,5% polymerem Dispergieradditiv absolut. Oberhalb dieser Konzentration tritt puddingartige Verdickung auf.

In some cases, with the combination of dispersing additive and nanoparticles already a mean particle diameter of several 100 microns can be achieved. The high energy milling allows in these cases, but a further reduction to very small particle sizes. Comparative Experiments: Nanoparticle Dispersions in Butyl Acetate with Polymeric Dispersing Aid Dispersed on the Dissolver Without Milling with the High Energy Mill: description nanoparticles Content of particles [%] Content of dispersing additive [%] *****) d ₅₀ [μm] VS6-1 **) Aerosil R9200 45.0 - 9.75 VS6-2 Aerosil R9200 25.9 10 11.1 VS7-1 ***) Aerosil OX 50 20.4 - 0.479 VS7-2 Aerosil OX 50 39.5 10 0.291 VS8-1 Aeroxide Alu C 7.6 *) - 8.47 VS8-2 Aeroxide Alu C 26.0 *) 10 6.25 VS9-1 ****) Aeroxide Alu 65 8.7 - 6.91 VS9-2 Aeroxide Alu 65 42.1 10 0.194 VS10-1 Aeroxide Alu C 45 10 Tego Dispers 655 Dispersion can not be produced due to thickening VS10-2 *****) Aeroxide Alu C 25 4.5 Tego Dispers 655 6.85

• *) more than 7.6 parts of Alu C can not be incorporated into the dispersion because of a marked increase in viscosity without a dispersing additive. With the dispersing additive without high energy milling a maximum of 26 parts can be incorporated. With dispersing additive and high energy milling 36 parts can be incorporated.
• **) Dispersion at 4600 rpm, viscous paste
• ***) Dispersion at 2800 rpm, viscous paste
• ****) Dispersion at 1860 rpm, viscous paste
• *****) Absolutely, relative to the whole system
• *****) the maximum settable solids content is 25% with a content of 4.5% polymeric dispersing additive absolute. Above this concentration, pudding-like thickening occurs.

Example 2:

Paints, production and properties

The nanoparticle suspensions are mixed with resins and hardeners as well as other additives, if necessary dispersed again with a dissolver, allowed to stand for degassing, coated on sheets and thermally cured. The cure temperature / time combination is chosen to pass the MEK test but no yellowing due to over cure. The addition of the nanoparticles may make it necessary to slightly increase the curing time compared to the urmodified coatings. Usually was cured at 160 ° C and cure times between 10 and 30 minutes. The different compositions according to the invention are reproduced in the following tables. An inventive paint consists z. B. from a hydroxy-functional polyester, a phenol-formaldehyde resin, a solvent mixture, a curing catalyst, a flow control agent and a surface-modified nanoscale particulate filler (according to one of the particle suspensions / dispersions described above).

Examples of lacquers of polyester and phenol-formaldehyde resin:

• 1) Linearer gemischt aliphatisch/aromatischer Polyester, Mn = ca. 6000, OH-Zahl = 20, 50% in Hydrosol A 200 Naphthalin-frei
• 2) 39,5% SiO₂ in Butylacetat (Aerosil OX 50)
• 3) Pigment z. B. Kronos 2310
• 4) z. B. Cymel 303
• 5) saure Katalysatoren wie z. B. Nacure 2500
• 6) z. B. Disparlon 1984/50% in SN200
• 7) z. B. Glykole, Ester, Ether, Aromatenschnitte etc.

The following examples demonstrate the increase in hardness (pencil hardness) and scratch resistance (scratch hardness) by modification with nanoparticles. paint variation Comparison pigmented pigmented Comparison clearcoat clearcoat Lacquer 1 Lacquer 2 Lacquer 3 Lacquer 4 NVC 50.8 50.8 50.8 50.8 OH number 22 22 22 22 Networking 80:20 80:20 80:20 80:20 Polyester solution ¹ 48.6 46.5 64.1 59.0 Nano-dispersion S7 ² 8.2 10.4 TiO2 ³ 27.2 26.0 Phenol-formaldehyde resin ⁴ 6.1 5.9 8.3 7.7 Catalyst ⁵ 0.4 0.4 0.5 0.5 Flow control agent ⁶ 1.1 1.0 1.4 1.3 Solvent ⁷ 16.6 12.0 19.2 21.2 Viscosity DIN 4 118 sec 132 sec 103 sec 116 sec

• 1) Linear mixed aliphatic / aromatic polyester, Mn = about 6000, OH number = 20, 50% in Hydrosol A 200 naphthalene-free
• 2) 39.5% SiO ₂ in butyl acetate (Aerosil OX 50)
• 3) pigment z. Eg Kronos 2310
• 4) z. B. Cymel 303
• 5) acidic catalysts such as. Eg Nacure 2500
• 6) z. Eg Disparlon 1984/50% in SN200
• 7) z. As glycols, esters, ethers, aromatic cuts etc.

The paint formulations were applied as topcoats on a primer. The layer thickness is 20 microns, the oven temperature was 310 ° C at a residence time of 30 sec. Paint no. 1 2 3 4 substratum aluminum aluminum aluminum aluminum course very well Good Good Good MEK test > 100 > 100 > 100 > 100 pencil hardness F 2H FH 2H Erichsen scratch hardness 17 N 28 N 24 N 32 N

Comparative tests

For comparison, coatings with Aerosil OX 50 without dispersing additive and with Aerosil OX 50 with dispersing additive were each carried out without grinding on the high-energy mill. The comparative experiments prove that without grinding on the high-energy mill no improvement of the scratch hardness (scratch resistance) and the pencil hardness can be achieved. The comparison coatings dispersed with conventional dissolvers had specks through agglomerates, while the over the high energy mill dispersed coatings were optically flawless. OX 50 OX 50 + LA-D 1045 OX 50 OX 50 + LA-D 1045 paint variation Comparison pigmented pigmented Comparison clearcoat clearcoat Lacquer 5 Lacquer 6 Lacquer 7 Lacquer 8 NVC 50.5 50.5 50.5 50.5 OH number 21 21 21 21 Networking 80:20 80:20 80:20 80:20 Polyester solution ¹ 47.7 49.7 70.0 68.9 AEROSIL OX 50 ² 3.3 3.3 4.9 4.8 Dispersing additive LA-D 1045 1.2 1.7 TiO2 ³ 26.7 27.8 Phenol-formaldehyde resin ⁴ 6.1 6.4 9.0 8.8 Catalyst ⁵ 0.4 0.4 0.3 0.6 Flow control agent ⁶ 1.0 1.1 1.5 1.5 Solvent ⁷ 14.8 10.0 14.0 13.8 Viscosity DIN 4 139 s 155 s 105 s 112 s

The paint formulations were applied as topcoats on a primer. The layer thickness is 20 microns, the oven temperature was 310 ° C at a residence time of 30 sec. Paint no. 5 6 7 8th substratum aluminum aluminum aluminum aluminum paint surface matt, grooves matt, grooves cloudy, grooves cloudy, grooves course satisfying satisfying satisfying satisfying MEK test 100-2 100-2 > 100 > 100 pencil hardness F F FH H Erichsen scratch hardness 16 N 17 N 26 N 23 N

Claims (25)

Paint binder comprising a matrix based on one or a plurality of polymers and based on 100 wt .-% of the total binder, a stabilized suspension of nanoscale particles, in a measured as a solids content of the suspension amount of 0.5 to 25 wt .-%, characterized that the suspension of the particles is obtainable by a.) milling the particles with the addition of a solvent in a high-pressure mill which decomposes agglomerates and / or aggregates of the particles into nanoscale fragments under a pressure in the range of>500; and b.) adding one or more dispersing additives to stabilize the surface of the milled particles, wherein the dispersing additive (s) is present in an amount of 1 to 25 parts by weight based on 100 parts by weight of the particles. Paint binder according to claim 1, characterized that the nanoscale particles present in stabilized suspension a mean particle size d50 in Range of 0.05 to 10 microns have determined by means of light scattering to Mie. Paint binder according to claim 2, characterized the nanoscale particles have a d50 value in the range of 0.05 up to 0.5 μm, preferably 0.1 to 0.5 microns exhibit. Paint binder according to claims 1-3, characterized that the nanoscale particles consist of primary particles that are globular, a Size in the range from 5 to 30 nm, and a fractality <3, measured by N2 adsorption in the pressure range p / p0 from 0.5 to 0.8. Paint binder according to one of the preceding claims, characterized characterized in that the nanoscale particles are selected from the group consisting of oxidic, nitridic and carbidic metal and semi-metal compounds, and mixtures of two or more the above substances. Paint binder according to claim 5, characterized in that the nanoscale particles are selected from the group consisting alpha alumina, gamma alumina, delta alumina, theta alumina, zirconia, yttria doped zirconia, Titanium dioxide, rutile, anatase, brookite, silica, antimony oxide, Zinc oxide, cerium oxide, iron oxides, palladium dioxide, indium tin oxide, Antimony tin oxide, spinel-type compounds, aluminum spinels, Iron spinel, chrome spinel, titanium spinel, cobalt spinel, ceramic Particles, boron nitride, boron carbide, silicon carbide, silicon nitride, Mixed compounds and mixed oxides of the above-mentioned elements and mixtures containing two or more of the above substances exhibit. Paint binder according to one of the preceding claims, characterized characterized in that the surface the nanoscale particles by post-oxidation, adsorption, reactions on the surface or complexation of or with inorganic and / or organic reagents is modified. Paint binder according to claim 7, characterized that the surface the nanoscale particle with two or more different from each other Types of functional groups is modified. Coating binders according to one of claims 7 or 8, characterized in that the added dispersing additive is selected from the group consisting of a) alkyl trialkoxysilanes of the general formula R-Si-O-R _'3, where R can be an aliphatic or mixed aliphatic / aromatic radical and Heteroatoms selected from the group N, O, S, Cl may be included, which may also interrupt the main chain; and wherein R 'is an aliphatic radical; b) hexamethyldisilazane and its derivatives; c) silicone-based compounds having a backbone of [SiR ₂ -O] building blocks and end groups differing therefrom, and [SiR, R'-O] building blocks in which R 'is a side chain grafted onto the main chain; d) vinylic homo- or copolymers or oligomers having functional groups selected from the group consisting of Cl, CO ₂ R where R = H, aryl or alkyl with optionally further functional groups; OH, NH 2, NR 2, where R may be a hydrogen, aliphatic and / or aromatic radical which may contain further heteroatoms; C = ONR ₂ , where R can be a hydrogen, aliphatic and / or aromatic radical which can contain further heteroatoms; e) block copolymers containing polar erotic or polar aprotic functional groups in at least one of the blocks; f) polycondensates, such as. For example, polyesters and polyamides; g) Compounds of the general formula R- (CH ₂ -CH ₂ -X) _n -R ', where R and R' are optionally functionally substituted aliphatic and / or aromatic radicals, X is O, NR with R = H, alkyl stands; h) hyperbranched oligomers or polymers such. B. polyimines with grafted on Polether- and / or polyester side chains, hyperbranched polyglycerols; i) star polymers; j) Compounds having a polyethyleneimine backbone and side chains grafted thereto selected from the group consisting of: polyethers, polyesters; k) phosphorus-containing oligomers, such as. B. tego dispers 655; and mixtures containing at least one of the compounds a) to k). Paint binder according to claim 9, characterized in that that the nanoscale particles are alumina and the dispersing additive are phosphorus-containing oligomers. Paint binder according to claim 10, characterized in that that the dispersing additive is tego dispers 655. Paint binder according to one of the preceding claims, characterized in that the Sus is obtained by pre-dispersing the particles in a liquid phase in a rotor-stator-run-aggregate before the step of grinding in a high-energy mill. Paint binder according to one of the preceding claims, characterized in that the solvent added for grinding selected is selected from the group consisting of aliphatic and cycloaliphatic Compounds, aromatic and substituted aromatic compounds, can be used in paints and gasoline fractions, esters, lactones, ethers, glycol ethers, ketones, Alcohols, mixtures of two or more of the foregoing Compounds and mixtures containing at least one compound of comprise the aforementioned substances. Paint binder according to claim 13, characterized that the solvent a combination of solvents different boiling points and / or evaporation rate and / or different polarity includes. Paint binder according to claim 14, characterized that the solvent combination used Solvesso 150 / butylglycol and / or solvesso 150 / methoxypropylacetate and / or Solvesso 150 / dibasic ester mixture DBE and / or solvent combinations with xylene or butyl acetate. Paint binder according to one of the preceding claims, characterized characterized in that the matrix is selected from the group consisting from organic oligomers with free hydroxyl groups, which are responsible for a reaction with a hardener to disposal stand, organic polymers with free hydroxyl groups, which are responsible for a curing reaction are suitable combinations of the above-mentioned oligomers and polymers, and mixtures, the oligomers and / or polymers having free hydroxyl groups suitable for reaction with a curing agent disposal stand. Paint binder according to claim 16, characterized that the matrix polyacrylate, polyester, polycaprolactone, polyether, Polycarbonate, polyurethane polyol resins, any mixtures of above substances, or mixtures comprising at least having one of the above polymeric substances. Paint binder according to claim 16, characterized the matrix comprises polyester resins and / or polyacrylate resins. Paint binder according to one of the preceding claims high transparency of more than 85% transmission. Process for the preparation of paint binders according to one of the preceding claims, in which method one i) a matrix based on or a plurality of polymers; ii) the provided Matrix with a stabilized suspension of nanoscale particles mixed; and iii) optionally to the mixture of ii) other conventional additives adds; in which to 100 wt .-% of the total binder, nanoscale particles in an amount of 0.5 measured as the solid content of the suspension to 25 wt .-%, incorporated; characterized, that the suspension of the particles is obtainable by a) grinding the particle with the addition of a solvent in a high pressure mill, the under a pressure in the range of> 500 - about 10,000 bar agglomerates and / or aggregates of the particles decomposed into nanoscale fragments; and b) Addition of one or more dispersing additives for stabilization the surface the milled particle, wherein the dispersing additive (s) in an amount of 1 to 25 parts by weight based on 100 parts by weight the particle is present (are). Use of the paint binders according to one of the preceding claims 1 to 19 together with aliphatic polyisocyanates in two-component clearcoats. Use of the paint binders according to one of the preceding claims 1 to 19 in combination with hardeners, which can be reacted with hydroxyl groups, for Production of coatings and Coatings. Use according to claim 22 in combination with hardeners selected from the group consisting of polyisocyanates, capped polyisocyanates, isocyanate prepolymers, melamines, silanes, silylgruppenhal Compounds, mixtures of one or more of the above compounds and mixtures comprising at least one of the above compounds. Paint having a paint binder according to claims 1 to 19th Painted object exhibiting a plating a hardened one Paint according to claim 24th