DE102007030285A1 - New surface-modified particle, preferably inorganic particle with reactive group e.g. hydroxyl group at its surface useful e.g. as fillers and in coatings, plastics, cosmetics, adhesives and in sealants - Google Patents

Abstract

Surface-modified particle (A), preferably inorganic particle with reactive group such as hydroxyl group, at its surface and/or metal and/or semi-metal oxide, -hydroxide and/or -oxide hydroxide containing particle, preferably nano-particle, is new; where: the particle exhibits a polysiloxane based modifying agent at its surface, and the surface of the particle is chemically modified using a modifying agent (a polysiloxane compound), preferably under the formation of covalent bonds. Surface-modified particle (A), preferably inorganic particle with reactive group such as hydroxyl group, at its surface and/or metal and/or semi-metal oxide, -hydroxide and/or -oxide hydroxide containing particle, preferably nano-particle, is new; where: the particle exhibits a polysiloxane based modifying agent at its surface, and the surface of the particle is chemically modified using a modifying agent (a polysiloxane compound of formula ((R 1> xR 2> 3 - xSiR 3>) yR 4>)), preferably under the formation of covalent bonds. R 1>monovalent 1-18C (preferably 1-3C) organic residue; R 2>linear, branched or cyclic 1-6C (preferably 1-2C)-alkoxy (containing OH group or hydrolyzable group), halo (preferably Cl) or 1-4C (preferably 2C) carboxylic acid; R 3>linear or branched, preferably linear 1-8C alkylene (containing oxygen or at least bivalent organic residue), alkylene ether, alkylene thioether, alkylene polyether (preferably based on ethylene oxide, propylene oxide, butylene oxide or styrene oxide or mixtures of oxides or based on statistical or block polyethers), arylene polyether, alkylene polyester, or organic aliphatic or aromatic or arylaliphatic group (preferably containing urethane- and/or urea groups in addition to ester- and/or ether groups); R 4>single- or multiple bond residue containing polydialkylsiloxane with 4-200 silicon units and with 1-18C-alkyl at the silicon atom, where the alkyl is partially substituted with modifying groups (G) (preferably polar modifying groups) such as (poly-)ether containing group (G1) (preferably based on at least alkylene oxide), polyester containing group (G2), arylalkyl containing (G3) and perfluorinated alkyl containing group (G4); x : 0-2, preferably 0; and y : 1-10, preferably 2-5.

Description

The The present invention relates to surface-modified particles, in particular inorganic based particles with reactive or reactive, in particular silane-reactive or siloxane-reactive surfaces, in particular hydroxyl-containing Surfaces, and / or of metal or semimetal oxides and / or hydroxides existing or containing particles, preferably nanoparticles, which on their surface have a polysiloxane-based modifier, in particular on their surface with a polysiloxane-based modifier, preferably with the formation of chemical, in particular covalent bonds implemented and a corresponding production method for them surface-modified Particle.

Farther For example, the present invention relates to the use of these surface-modified ones Particles, in particular in coating materials and coating systems, especially paints, inks and the like, in dispersions of all Art, in plastics, in foams, in cosmetics, in particular Nail varnishes, in adhesives, in sealants, etc. Furthermore For example, the present invention relates to the use of these surface-modified ones Particles as fillers, especially in the aforementioned systems.

It also concerns the present invention equally systems, in particular coating materials and coating systems, in particular paints, inks and the like, Plastics, foams and cosmetics, in particular nail varnishes, which these surface modified Contain particles. Finally are The present invention also provides novel dispersions, which these surface modified Particles in a carrier or dispersing medium contain.

Of the Use of particles, in particular nanoparticles, is in coating and dispersion systems the person skilled in the art known in principle: So offers the Use of nanoparticles as filler for coating systems the advantage that a Coating material desired Properties (such as increased scratch resistance), without that at the same time negative side effects have to be taken into account (such as poor Transparency).

It is known that the Incorporation of nanoparticles in coating materials, for example for improving the mechanical properties of coating systems, for example, UV-curable Coating systems, leads.

For example, in the EP 1 236 765 A1 describes a method for modifying nanoscale silica particles with alkoxysilanes, which cause an improvement in the mechanical properties after incorporation into a corresponding UV-curable coating system. In other highly networked systems, such as As in epoxy resins, also positive effects are found. The improvement of the mechanical properties is essentially due to the binding of the nanoparticles to the surrounding matrix via chemical bonds. Due to the chemical bonding of the particles to the organic matrix, depending on the degree of filling of the coating materials with such nanoparticles, an increasing embrittlement is observed which, depending on the application area, is detrimental to the coating. If the known nano-scale fillers based on silica are not bound to the organic matrix, the desired effect of improving the mechanical properties in UV-curable or epoxy-based coating systems is far from being so pronounced.

Next Silikananopartikeln can be used in other types of nanoparticles Install coating materials for their mechanical properties to optimize. By adding, for example, nanoscale alumina (for example, the market products NANOBYK-3600 or NANOB K-3601 of BYK-Chemie GmbH, Wesel, Germany) in UV-curable Coating systems will significantly improve the abrasion resistance without influence on the flexibility reached the system. The alumina is not in this case attached to the organic matrix of the coating system. The Stabilization of the nanoparticles in the paint matrix takes place via commercially available wetting and dispersing additives.

Coating systems which are not UV-curable or based on epoxy systems can equally through Addition of nanoparticles can be optimized in their scratch resistance.

So is in the US Pat. No. 6,593,417 a method is described in which silica particles are used in combination with a polysiloxane in a two-component polyurethane varnish. The polysiloxane has reactive groups which can bond with the paint matrix via covalent groups. The attachment of the polysiloxane to the nanoparticles occurs only via coordinative interactions. The special combination The nanoparticles and polysiloxane particles cause the nanoparticles to orient themselves towards the coating / air interface, where they lead to a mechanical reinforcement, which manifests itself in increased scratch resistance. A disadvantage is the orientation of the nanoparticles to the coating / air interface, since the top layer is first removed by stress of the coating by weathering and use and thus decreases the effectiveness over time.

The US 5,853,809 A teaches that an improvement in the scratch resistance of coating systems, as z. B. used in automotive finishes can be done by the incorporation of modified nanoparticles. The modification of the nanoparticles, for example, by a functional polyurethane in such a way that the polymer enters into a covalent bond with the nanoparticle surface. Furthermore, the polymeric shell of the nanoparticles modified in this way is able to form covalent bonds with the binder system of the coating material. Statements about the embrittlement of the paint system, especially at high nanoparticle contents, are not met.

The Improve known from the prior art modified nanoparticles although the scratch resistance of the paints in which they are used; however, especially in non-radiation-curing, especially UV-curing, systems the attachment of nanoparticles via To critically evaluate the modification to the paint matrix: Due to the binding of the nanoparticles to the lacquer matrix, the Network density of the cured Paint film increased, resulting in an increased brittleness of the paint film leads.

From the DE 195 40 623 A1 nanoscale filler particles are known which are dispersed in a polymeric matrix. Surface modifiers include silanes, in particular organoalkoxysilanes. The surface modifiers are low molecular weight compounds having a molecular weight no greater than 500 daltons. The functional groups which have to carry such compounds depend on the surface groups of the nanoscale particles and on the desired interaction with the matrix. The modified particles therefore have an affinity for the matrix.

Of the The present invention is therefore based on the object surface-modified Particles, in particular nanoscale surface-modified particles, to provide, which in particular for use in the aforementioned Suitable systems and those associated with conventional particles Disadvantages at least largely avoid or at least mitigate, as well as to provide a corresponding manufacturing method for such particles.

A Another object of the present invention is to be seen in a new, efficient surface modification of particles of the type mentioned in the beginning, in particular nanoparticles, provide.

Of Another object of the present invention is to provide the particles, in particular nanoparticles, as a stable dispersion in suitable dispersing or carrier media (eg solvents, Water etc.), as used for example in the paint industry will be available to deliver. These new dispersions should also have a high particle content over a high storage stability feature. The tendency of these particle dispersions, in particular nanoparticle dispersions, for sedimentation or gelation should advantageously be excluded. Furthermore, the dispersions, in particular when used for the production of coating materials be advantageously, inter alia, an increase in the scratch resistance the cured one Coatings cause. A possible reactivity of the new surface-modified Particles, in particular nanoparticles, compared to the systems in which they are used, in particular with respect to the binder components the paint system used, should be minimized as possible, preferably about the tendency to embrittlement of the cured Avoid paint film. In particular, the surface modification across from the systems in which the surface-modified particles be used, for example, compared to a paint matrix, if possible inert or as possible be little reactive.

Finally lies another object of the present invention in the provision a manufacturing process for the new surface-modified Particles, in particular nanoparticles, which are in a simple manner carry out leaves and broad can be varied, in particular in this way new surface-modified Particles, in particular nanoparticles, and their dispersions for different Custom-made applications to disposal to deliver.

The Applicant has now surprisingly found that the above-described problem can be solved in an efficient manner, if particles, in particular inorganic based particles with reactive or reactive, preferably silane-reactive or siloxane-reactive groups, especially hydro xyl groups, on their surface and / or consisting of metal and / or Halbmetalloxiden, hydroxides and / or oxide hydroxides or containing particles, preferably nanoparticles, with a polysiloxane-based modifier, preferably with the formation of chemical, especially covalent bonds, reacting, which have higher molecular weight, are preferably linear, is inert to a surrounding matrix and is equipped with modifying, especially polar groups. In this way, surprisingly, the dispersibility of the particles can be improved, improve the surface modification over known systems and control the polarities improved.

to solution the problem described above proposes the present invention thus surface-modified Particles according to claim 1. Further, advantageous properties are the subject of the dependent claims 2 to 11th

Another The present invention is a process for the preparation the surface-modified according to the invention Particles according to claim 13. Further, advantageous properties are the subject of the method claims.

In turn Another object of the present invention is the use the surface-modified according to the invention Particles as fillers according to claim 18th

One in turn another object of the present invention is the Use of the surface-modified according to the invention Particles in coating materials and coating systems, in particular paints, Paints and the like, in dispersions of all kinds, in plastics, in foams, in cosmetics, especially nail varnishes, in adhesives and in sealants according to claim 19th

Of In addition, the present invention likewise relates to dispersions, which the surface-modified according to the invention Particles in a carrier or dispersion medium according to claim 20.

Finally are in turn, another object of the present invention coating materials and Coating systems, in particular paints, inks and the like, Plastics, foams, cosmetics, in particular nail polishes, adhesives as well as sealants containing the surface-modified particles of the invention contained, according to claim 21st

The The present invention will be described in more detail below with reference to the surface-modified Particles, in particular nanoparticles, are explained. The relevant ones versions apply to the remaining aspects or objects of the present invention - inventive production method, use according to the invention, inventive dispersions etc. - accordingly, so that the Avoid unnecessary Repetitions also for the other aspects or objects The present invention can be referred to.

• • x = 0 bis 2 einschließlich der Grenzen, insbesondere x = 0;
• • y = 1 bis 10 einschließlich der Grenzen, insbesondere y = 2 bis 5;
• • R¹ = einbindiger organischer Rest, bevorzugt mit 1 bis 18 Kohlenstoffatomen, insbesondere 1 bis 10 Kohlenstoffatomen, vorzugsweise 1 bis 3 Kohlenstoffatomen;
• • R² = OH-Gruppe oder hydrolysierbare Gruppe enthaltend oder bestehend aus:
• – einer linearen oder verzweigten oder cyclischen Alkoxygruppe mit 1 bis 6 Kohlenstoffatomen, insbesondere 1 bis 2 Kohlenstoffatomen,
• – einem Halogenatom, insbesondere Chloratom oder
• – einem Carbonsäurerest mit 1 bis 4 Kohlenstoffatomen, insbesondere 2 Kohlenstoffatomen;
• • R³ = Sauerstoff oder mindestens zweibindiger organischer Rest enthaltend oder bestehend aus:
• – einem linearen oder verzweigten, vorzugsweise linearen Alkylenrest, insbesondere mit 1 bis 8 Kohlenstoffatomen,
• – einem Alkylenether,
• – einem Alkylenthioether,
• – einem Alkylenpolyether, bevorzugt auf Basis von Ethylenoxid, Propylenoxid, Butylenoxid oder Styroloxid oder Mischungen der Oxide oder auf Basis eines statistischen oder Blockpolyethers,
• – einem Arylenpolyether,
• – einem Alkylenpolyester oder
• – einer organischen aliphatischen oder aromatischen oder arylaliphatischen Gruppe, insbesondere wobei die Gruppe neben Ester- und/oder Ethergruppen auch Urethan- und/oder Harnstoffgruppen enthält;
• • R⁴ = ein- oder mehrbindiger Rest enthaltend oder bestehend aus einem Polydialkylsiloxan mit 4 bis 200 Si-Einheiten und mit C₁-C₁₈-Alkylgruppen an den Siliciumatomen, wobei die C₁-C₁₈-Alkylgruppen teilweise und jeweils unabhängig voneinander durch eine oder mehrere der folgenden modifizierenden Gruppen (G), vorzugsweise polaren modifizierenden Gruppen (G), ersetzt bzw. substituiert sind (d. h. mit anderen Worten gegen diese Gruppe ausgetauscht sind, insbesondere mittels Pfropfung), ausgewählt aus den nachfolgend unter (i) bis (iv) aufgeführten modifizierenden Gruppen (G1) bis (G4):
• (i) (Poly-)Ethergruppen enthaltende Gruppe (G1), insbesondere auf Basis mindestens eines Alkylenoxids,
• (ii) Polyestergruppen enthaltende Gruppe (G2),
• (iii) Arylalkylgruppen enthaltende Gruppe (G3),
• (iv) perfluorierte Alkylgruppen enthaltende Gruppe (G4).

The present invention accordingly provides, according to a first aspect of the present invention, surface-modified particles, in particular inorganic-based particles with reactive or reactive, preferably silane-reactive or siloxane-reactive groups, in particular with hydroxyl groups, on their surface and / or metal and / or metal surfaces. or semimetal oxides, hydroxides and / or oxide hydroxides existing or containing these particles, preferably nanoparticles, wherein the particles have on their surface a polysiloxane-based modifier, in particular on its surface with a polysiloxane-based modifier, preferably with the formation of chemical, in particular covalent bonds implemented are, wherein the surface-modified particles are characterized in that the modifying agent is a polysiloxane of the following general empirical formula (R ¹ _x R ² _3-x SiR ³ ) _y R ⁴ is, where in the empirical formula mean:

• • x = 0 to 2 including the limits, in particular x = 0;
• • y = 1 to 10 including the limits, in particular y = 2 to 5;
• • R ¹ = monovalent organic radical, preferably having 1 to 18 carbon atoms, in particular 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms;
• R ² = OH group or hydrolyzable group containing or consisting of:
• A linear or branched or cyclic alkoxy group having 1 to 6 carbon atoms, in particular 1 to 2 carbon atoms,
• A halogen atom, in particular chlorine atom or
• A carboxylic acid radical having 1 to 4 carbon atoms, in particular 2 carbon atoms;
• R ³ = oxygen or at least divalent organic radical containing or consisting of:
• A linear or branched, preferably linear, alkylene radical, in particular having 1 to 8 carbon atoms,
• An alkylene ether,
• An alkylene thioether,
• An alkylene polyether, preferably based on ethylene oxide, propylene oxide, butylene oxide or styrene oxide or mixtures of the oxides or based on a random or block polyether,
• An arylene polyether,
• An alkylene polyester or
• An organic aliphatic or aromatic or arylaliphatic group, in particular where the group also contains urethane and / or urea groups in addition to ester and / or ether groups;
• R ⁴ = mono- or mehrbindiger radical containing or consisting of a polydialkylsiloxane having 4 to 200 Si units and having C ₁ -C ₁₈ alkyl groups on the silicon atoms, wherein the C ₁ -C ₁₈ alkyl groups partially and each independently one or more of the following modifying groups (G), preferably polar modifying groups (G), are substituted or substituted (ie in other words replaced by this group, in particular by grafting) selected from the following under (i) to ( iv) modifying groups (G1) to (G4):
• (i) (poly) ether group-containing group (G1), in particular based on at least one alkylene oxide,
• (ii) group containing polyester groups (G2),
• (iii) arylalkyl group-containing group (G3),
• (iv) perfluorinated alkyl group-containing group (G4).

advantageous Embodiments of the present invention will become apparent from the dependent claims and ancillary claims.

A significant peculiarity of the present invention must be seen in the preferably polar modification of the group R ⁴ : As described above, the alkyl groups of the polydialkylsiloxane (ie the C ₁ -C ₁₈ alkyl groups on the silicon atoms) are partially and independently modified by a modifying, preferably polar group (G) replaced or replaced (eg by means of grafting). Surprisingly, this on the one hand, the dispersibility of the particles according to the invention verbes sert. On the other hand, the polarity can be selectively controlled in this way, so that in this way the application properties can be tailored. Finally, the surface modification is decisively improved in this way, in particular with regard to the desired application properties (eg scratch resistance of paints, etc.). The modifying groups (G) for the group R ⁴ are to be selected in such a way that they are advantageously compatible with respect to the application systems or application matrix and their ingredients (for example lacquer matrix), in particular inert or at most as slightly reactive as possible. The preferably polar modification groups (G) can be introduced, for example, by grafting into the radical R ⁴ (for example by means of hydrosilylation or addition reaction or by condensation reaction) starting from commercially available starting materials; this is known to the skilled person as such and will be described in more detail below.

Especially preferred embodiments with regard to the selection of the modification groups (G) are the subject the claims 2 to 5.

A special embodiment the surface-modified according to the invention Particle is the subject of claim 6.

A special performance increase of the particles according to the invention can be through additional surface modifications with silanes according to the object the claims Reach 11 and / or 12.

The Particle size of the particles according to the invention, especially nanoparticles, is in the range of 0.1 to 1000 nm, in particular 0.5 to 500 nm, preferably 1 to 350 nm, more preferably 2 to 200 nm, more preferably below 100 nm, especially preferably below 50 nm. The particle sizes can according to the invention by means of Transmission electron microscopy can be determined.

As nanoparticles according to the invention finely divided solids having a particle size in the aforementioned particle size range (ie in the range of 0.1 to 1000 nm, in particular 0.5 to 500 nm, preferably 1 to 350 nm, more preferably 2 to 200 nm, more preferably below 100 nm , most preferably below 50 nm). As mentioned above, the determination of the particle sizes in the context of the present invention can be carried out in particular by means of transmission electron microscopy (TEM). To determine the particle size of the particles or nanoparticles according to the invention, a TEM examination: The corresponding nanoparticle dispersions are usually diluted for this purpose, applied to a carbon black (in particular 600 mesh carbon film) and dried; the analysis is then carried out in each case, for example, with a LEO 912 transmission electron microscope. The evaluation of the TEM images is z. B. digitally performed with a software of the company analySIS Soft Imaging System GmbH. The particle diameter is generally calculated in each case for at least 1000 particles by correlating the measured area of the particles or nanoparticles with an area-like circle. Then the mean value is calculated from the results.

The claimed particles, in particular nanoparticles, are in general inorganic particles, on whose surfaces reactive or reactive, preferably silane-reactive or siloxane-reactive groups, in particular hydroxyl groups, are located or arranged, which for the chemical, preferably covalent attachment of the modifier are required; d. H. the on the surface the reactive or reactive groups located to be modified particles have to be able to react with the modifier. Next Hydroxyl groups, which are preferred according to the invention, are also others silane and / or siloxane-reactive groups into consideration, for. B. halogens (such as fluorine or chlorine) or halogen-containing groups Etc.

Especially if the particles consist of at least one metal and / or half metal oxide, -oxidhydroxid and / or hydroxide or contain this; come too Mixtures or combinations of various metal and / or semimetal oxides, oxide hydroxides and / or hydroxides (eg particles, that of mixed metal and / or Halbmetalloxiden, oxide hydroxides or hydroxides exist). For example, the oxides, Hydroxides and / or oxide hydroxides of aluminum, silicon, zinc and / or titanium etc. for the production of modified particles or Attract nanoparticles. Furthermore, oxide hydroxides, such as aluminum oxide, according to the specified method modify. equally Also suitable are other inorganic materials, in particular inorganic salts such as phosphates, sulfates, halides, carbonates etc. optionally in a mixture of the abovementioned metal and / or Semi-metal oxides, oxide hydroxides and / or hydroxides. According to the invention preferred however, are metal and / or semi-metal oxides, oxide hydroxides and / or hydroxides of the aforementioned type.

Of the Production process of the particles used according to the invention, in particular the oxidic or hydroxidic or oxidic hydroxide particles, especially nanoparticles, can be over a variety of methods, such. For example, ion exchange processes, Plasma processes, sol / gel process, precipitation, comminution (e.g. by grinding) or flame hydrolysis, etc., take place; it is irrelevant according to the invention by which method the oxide or hydroxide particles be prepared, d. H. According to the invention can be produced arbitrarily Surface modification of particles of the aforementioned type.

The found, novel surface-modified Particles, in particular nanoparticles, are used in the present Invention also as particles according to the invention or as nanoparticles according to the invention designated. The new dispersions of the particles according to the invention or nanoparticles are also within the scope of the present invention as inventive dispersions designated.

In Knowledge of the prior art was completely surprising and for the expert is not foreseeable that the previously described tasks, which are the basis of the present invention, by the particles according to the invention, by the production method according to the invention, by the dispersions of the invention and the rest, previously described inventive objects could be solved.

The Production of the particles according to the invention and the dispersions of the invention settles in simple manner without the use of expensive methods or procedures carry out.

The nanoparticles according to the invention are suitable for example the production of z. B. thermally curable, radiation-curing or two-component coating systems, of thermoplastics, from Foam Etc.

By the provision of the dispersions of the invention has succeeded an easily handled particle concentrate, in particular nanoparticle concentrate, to disposal to ask, which z. B. easy to the most diverse Paint systems can be dosed to the desired Effect, for example, of improved mechanical resistance, such as Scratch resistance, to achieve.

In addition to the ease of metering the dispersions of the invention is also a good Sta stability of the dispersions against settling and gel formation, especially at high solids contents.

The particles according to the invention, In particular, nanoparticles are advantageously modifying Groups occupied so that, if necessary remaining, functional reactive groups on the particle surface so far are shielded that one Reaction of these groups with other steric functional groups establish no longer takes place.

The surface of the particles according to the invention, in particular nanoparticles, is covered with at least one type of modifying group. The structure of the modifying groups is shown below:
The modifying group is chemically, preferably covalently, attached to the particle surface. The modifying group has various structural elements that can build up at least one chemical, in particular covalent, bond with the particle surface. Furthermore, the modifying group consists of a spacer which can not react with the particle surface and is also substantially inert to the matrix (eg other paint components, plastic components, etc.). The spacer part of the modifying group may e.g. Example, be formed from a polymer, for example, having a number average molecular weight, for example in the range of 300 to 5,000 daltons. The structure of the spacer radical is preferably linear.

This means that the modifying agent is composed of at least one or more anchor groups which are reactive with respect to the particle surface and also a polydialkylsiloxane (= constituent of the above-defined radical R ⁴ ). The anchor groups with the connecting structures may be attached to the ends of the polydialkylsiloxane or may be present as side groups on the polydialkylsiloxane.

The structure of the modifier used according to the invention can be represented schematically as an example, in the example shown, three different polar substituents or modifying groups (G) for the radical R ⁴ (= polydialkylsiloxane) in the representation was chosen (Regarding the meaning of the substituents may be made to the above statements and to the claims.):

The index a describes the number of anchor groups, and the indices b, c, d ... describe the number of preferably polar substituents or modifying groups (G) in the side group of the polydialkylsiloxane R ⁴ , where:
a ≥ 1
b + c + d + ... ≥ 1

As previously described, may additionally a surface modification the particle with silanes according to claim 11 and / or 12, which are generally alike at least attached a chemical, in particular covalent bond to the particle surface are and advantageously over have one or more spacer parts. For details on this can the claims to get expelled.

The Production of the nanoparticles according to the invention can by simply mixing the modifier with a particulate, especially nanoparticulate, Powder done. It should be ensured that preferably a chemical, in particular covalent attachment of the modifier to the surface of the Nanoparticles takes place. The conditions for this depend on the reactivity of each other functional groups to be reacted and can easily be determined by the person skilled in the art become. If a reaction does not take place already at room temperature, For example, by annealing the mixture of nanoparticulate powder and modifier at a temperature of about 80 ° C over a Period of about one hour a chemical, especially covalent Connection of the modifier can be achieved.

The preparation of the modifier used according to the invention is familiar to the person skilled in the art and can be carried out, for example, in the following way:
Starting from commercially available open-chain and cyclic polydimethylsiloxanes and Si-H-functional polydimethylsiloxanes, it is possible to use an equilibration reaction (as used, for example, in US Pat Noll, "Chemistry and Technology of Silicones", Wiley / VCH Weinheim, 1984 , is described) produce Si-H-functional polydimethylsiloxanes, which can be implemented in further steps to the modifying reagent used in the invention. In the context of the present invention, the number of Si-H groups in the Si-H-functional polydimethylsiloxane must be at least two (at least one Si-H group for attachment of the anchor group (R ¹ _x R ² _3-x SiR ³ ) _y and at least one Si-H group needed for the polar modification).).

By known methods can be unsaturated compounds such as 1-octene, 1-decene, 1-dodecene, 1-hexadecene and 1-octadecene, to Si-H-containing Polysiloxanes by means of suitable catalysts, such as. Hexachloroplatinic acid, Speyers Catalyst, platinum divinyltetramethyldisiloxane complex or in the presence of supported materials applied platinum compounds, attach; the hydrosilylation conditions are generally known, preferably the hydrosilylation temperature between room temperature and 200 ° C, preferably 50 and 150 ° C, depending on the catalyst used.

Analogous for the attachment of alkenes alternatively, however, other compounds with unsaturated Groups in terms of hydrosilylation of Si-H groups are added. For example can Polyalkylene glycol allyl alkyl ethers (eg, polyglycol AM types, Clariant GmbH) or trialkoxyvinylsilane (eg Dynasylan VTMO or Dynasylan VTEO, Degussa AG) on Si-H groups be added.

Farther can For example, addition compounds of lactones, such as. Ε-caprolactone and / or δ-valerolactone, of ethylenically unsaturated Alcohols, such as. Allyl alcohol, hexenol, allyl glycol or vinyl hydroxybutyl ether, be added to Si-H groups. These compounds can be, for example be alkylated or acylated.

Next The possibility the addition of ethylenically unsaturated compounds to Si-H groups continues to offer the opportunity hydroxy-functional compounds via a condensation reaction to couple to Si-H-functional polydimethylsiloxanes. Because of this known processes can be, for example, polyalkylene glycol monoalkyl ethers (e.g., butylpolyethylene glycol) to Si-H groups with elimination of hydrogen gas condense. As a catalyst for this reaction can be For example, use zinc acetylacetonate. In analog form can also other substituents, such as ester group-containing groups into the polydimethylsiloxane.

to Modification of Si-H-functional polydimethylsiloxanes may include hydrosilylation reactions and Condensation reactions performed become. It is also possible the existence combined method is used to modify the modifier manufacture.

in the Difference to the hydrosilylation (formation of a Si-C bond) arises by the condensation reaction an Si-O linkage.

In this way, the radical R ⁴ can be modified by the polar groups (G), as listed, for example, under (i) to (iv) of claim 1.

The particles according to the invention, especially nanoparticles, can For example, be applied directly in paints and plastics. The particles according to the invention, In particular, nanoparticles, but are particularly suitable for Preparation of dispersions z. As in water, solvents, plasticizers, waxes, mineral oils and reactive diluents and other media, as usual Be used in the paint and plastics industry.

The Preparation of the dispersions of the invention is carried out by incorporating appropriately modified in the desired dispersion or carrier medium or dispersants using conventional dispersing aggregates, such as B. tooth colloid mills, Dissolvers, ultrasonic dispersers, etc.

By Addition of the modifier in a particle dispersion, in particular Nanoparticle dispersion, a dispersion of the invention is obtained. at This procedure should also ensure that a chemical, in particular covalent attachment of the modifier to the particle surface, in particular Nanoparticle surface, takes place. The transfer of a dispersion according to the invention from one to another dispersion medium, for example, succeeds by distillation. By using suitable entraining agents, a low-boiling azeotrope with the dispersing medium to be removed form such processes can be easily optimized.

Of the Particle content of the dispersions according to the invention, measured as incineration residue, can be up to about 40% can be increased without it for gel formation or for a significant sedimentation comes.

The dispersions according to the invention can at least one additional Containing substances from the field of typical coatings additives, Binder or crosslinking agent is derived. For example, here are Wetting and dispersing additives or additives for controlling the rheological Properties, but also defoamers, To name light stabilizers and catalysts.

The particles according to the invention, especially nanoparticles, and the dispersions of the invention are pronounced widely applicable. The wide applicability in combination with the extremely good Effectiveness of the particles according to the invention, in particular nanoparticles, and exceed the dispersions of the invention Particles, in particular nanoparticles, and dispersions of the state the technology by far.

The Application of the particles according to the invention, in particular nanoparticles, and dispersions by addition in existing systems, which z. B. to paints, adhesives, plastics, etc be further processed. By adding even small quantities the particles according to the invention, in particular nanoparticles, or the dispersions of the invention will be an extraordinary increased mechanical resistance at the same time increased resistance against chemical influences the ultimately resulting coating or molding achieved.

Surprisingly become the processing properties of paints and plastics only insignificantly influenced, so no new optimization of external parameters must be done in these applications.

The particles according to the invention, especially nanoparticles, and their dispersions are outstanding for the Use in coating materials, plastics, adhesives, Sealants etc.

Further Embodiments, modifications and variations of the present invention are for the person skilled in the art readily discernible when reading the description and realizable without him while leaving the scope of the present invention.

The The present invention will become apparent from the following embodiments However, which illustrates the present invention in no way restrict should.

EXAMPLES

1. Preparation of Modifiers ("Modifiers 1-11") 1 2 3 4 5 6 raw material Manufacturer A Baysilone oil MH 15 GE Bayer 24.71 24.71 24.7 1 25.50 26.93 22.82 B Dynasylan VTMO Degussa 16.73 16.73 16.7 3 17.26 18.23 15,45 C Uniox MUS 15 NOF Europe 24.71 22.32 C Unilube MB 40 S NOF Europe 24.71 17.97 C Unilube MA 170 T NOF Europe 24.7 1 30.46 D 1-octene 33.76 33.76 33.7 6 34.84 36.79 31.18 e Karstedt cat 0.2% WC Heraeus 0.08 0.08 0.0 8th 0.08 0.08 0.08 7 8th 9 10 11 raw material Manufacturer A MDH29D86M see Note 40.21 40.21 40,20 44.52 33.26 B Dynasylan VTMO Degussa 6.46 6.46 6.46 7.15 5.34 C Uniox MUS 15 NOF Europe 40.21 - C Unilube MB 40 S NOF Europe 40.21 33.82 C Unilube MA 170 T NOF Europe 40.24 50.54 D 1-octene 13.03 13.03 13.03 14.43 10.78 e Karstedt cat 0.2% WC Heraeus 0.08 0.08 0.08 0.08 0.08

General manufacturing instructions:

In a 250 ml four-necked flask with stirrer, thermometer, reflux condenser and Inert gas connection is (A), heated under nitrogen to 80 ° C and mixed with (E). Subsequently is added dropwise within 40 minutes (B). Thereafter, the reaction mixture is for 30 minutes at 120 ° C touched, and then it will over a period of 20 minutes (C) added dropwise. After the end of the addition the reaction mixture is stirred at 120 ° C for a further 30 minutes. Subsequently, will (D) over a period of 150 minutes dripped and then 60 minutes touched.

Annotation:

2. Herstellung der Nanopartikelkonzentrate ("Nanopartikelkonzentrate 1-11") Produktname Hersteller Menge/g A Köstrosol 2040AS CWK-Bad Köstritz 75,00 B 1-Methoxy-2-propanol 75,00 C Dynasylan PTMO Degussa 1,64 D Methoxypropylacetat 80,00 E Dynasylan OCTMO Degussa 1,17 F Modifizierungsmittel (1-11) 0,60 G Disperbyk-168 BYK-Chemie 65,00 The silicone MDH29D86M (see graph) can be easily by an equilibration reaction, as in Noll "Chemistry and Technology of Silicones", Wiley / VCH Weinheim, 1984 described, represent.

2. Production of Nanoparticle Concentrates ("Nanoparticle Concentrates 1-11") product name Manufacturer Amount / g A Köstrosol 2040AS CWK-Bad Köstritz 75.00 B 1-methoxy-2-propanol 75.00 C Dynasylan PTMO Degussa 1.64 D methoxypropylacetate 80,00 e Dynasylan OCTMO Degussa 1.17 F Modifier (1-11) 0.60 G Disperbyk-168 BYK-Chemie 65,00

General manufacturing instructions:

In a 250 ml four-necked flask with stirrer, thermometer and reflux condenser (A) and mixed with (B). It is then heated to 70.degree and (C) added. After a reaction time of 90 minutes (D) added. Then vacuum is applied, and it will be at a Temperature of 70 ° C 100 g solvent mixture separated. Now, successively (E) and (F) are added and for 120 minutes at 70 ° C touched. Subsequently is added (G). By separation of 60 g of solvent mixture in vacuo achieved a nanoparticle content of 21.7%.

3. Application examples ("Application examples 1-11 ")

• Macrynal SM 515/70BAC (Hydroxyfunktionelles Polyacrylat): UCB
• TinStab BL277 (Dibutylzinndilaurat): Akcros Chemicals
• Desmodur N 3390 (aliphatisches Polyisocyanat): Bayer AG

Two-car repair system Component 1 comparison sample Application Example 1-11 Macrynal SM515 / 70BAC 46.7 46.7 methoxypropylacetate 8.3 8.3 butyl glycol 1.3 1.3 TinStab BL277 (1% solution in butyl acetate) 0.2 0.2 butyl 10.1 10.1 Nanoparticle concentrate 1-11 ---- 5.3 Component 2 comparison sample Application Example 1-11 Desmodur N 3390 26.5 26.5 butyl 6.9 6.9

• Macrynal SM 515 / 70BAC (hydroxyfunctional polyacrylate): UCB
• TinStab BL277 (dibutyltin dilaurate): Akcros Chemicals
• Desmodur N 3390 (aliphatic polyisocyanate): Bayer AG

The components of the respective components were thoroughly mixed. Immediately before the Be layering, the two components 1 and 2 were mixed. The application of the coating system was carried out by a spray application on PMMA plates (200 mm × 400 mm). After a flash-off time of one hour at room temperature, forced drying was carried out at 60 ° C. for a period of 12 hours. The achieved layer thickness of the coating was about 45 microns.

The scratch resistance was using a crockmeter device (Type CM-5, ATLAS) tested for scratch resistance. To The coated panels were treated with a polishing cloth from the company 3M (3M polishing paper, grade: 9 mic) reproducibly stressed (Contact force: 9 N). The evaluation of scratch resistance was carried out by measuring the gloss of the claimed sites in Comparison to the gloss of an unstressed spot on the test plate. As a result, the residual gloss was expressed in percent (%). The shine was with the micro-TRI-Gloss device determined by BYK-GARDNER. The observation angle was on 85 ° set.

The quality of the paint surface, in particular the course of the coating material, was assessed visually on the basis of a scale of 1-5. A value of 1 corresponds to a very good course of the paint, a value of 5 corresponds to a poor paint course, which shows up in an orange peel-like surface. Residual gloss /% course Comparative example 10 5 Application example 1 81 4 Application Example 2 86 2 Application example 3 84 4 Application Example 4 75 4 Application Example 5 83 2 Application Example 6 69 2 Application example 7 80 4 Application Example 8 68 4 Application Example 9 85 2 Application Example 10 67 2 Application Example 11 53 2

4. Preparation of the modifier ( "Modifiers 12 ")

In a 250 ml four-necked flask equipped with heating, internal thermometer, stirrer, reflux condenser and protective gas connection, 100 g of Si-H-functional polysiloxane having the following average structure were placed:

This Silicone leaves simply by an equilibration reaction, as with Noll "chemistry and Technology of Silicones ", Wiley / VCH Weinheim, 1984 described.

The Silicone is heated to 70 ° C under nitrogen, and it becomes 10 ppm hexachloroplatinic acid added. Subsequently 251 g of a poly (oxyethylene) glycol-a-methyl-o-allyl ether (Uniox PKA - 5009, NOF Europe) was added so that the Reaction temperature 80 ° C does not exceed. Thereafter, the addition of 73 g of vinyltrimethoxysilane (e.g., Geniosil XL10, Wacker Chemie GmbH). It is important to ensure that the reaction temperature Does not exceed 80 ° C. After the addition, the reaction mixture is stirred for one hour at 80.degree. Subsequently, will Applied vacuum and about 2 g of unreacted vinyltrimethoxysilane or volatile Components of the polysiloxane separated by distillation. The product is low viscous and has a slightly amber color.

5. Preparation of the Nanoparticle Concentrate ( "Nanoparticles concentrate 12 ") and a corresponding one comparison

In a kitchen mixer 40 g nanoscale alumina are presented and with 4 g Modification reagent from the previous preparation example ("modifier 12"). Subsequently, will Homogenize the mixture for 1 minute. The with modifying reagent occupied powder is annealed at 80 ° C for one hour. In a solution 56.8 g of methoxypropyl acetate and 3.2 g of wetting and dispersing agent (BYK-9077, BYK-Chemie GmbH), 40 g of the modified nanoparticles are stirred in and subsequently dispersed with ultrasound. The dispersion thus obtained is of low viscosity and does not show any tendency to gelation or sedimentation 28 days storage.

6. Application example

• 1: Sartomer Company, Inc.
• 2: LAMBERTI S.p.A. chemical specialties

UV Clear component zero sample comparison Application Example 12 Sartomer SR-368 ¹ (isocyanurate triacylate) 27 g 27 g 27 g Sartomer SR-494 ¹ (ethoxylated pentaerythritol tetraacrylate) 9 g 9 g 9 g Sartomer CD-501 ¹ (trimethylolpropane triacrylate) 27 g 27 g 27 g Sartomer SR-238 ¹ (1,6 hexanediol diacrylate) 27 g 27 g 27 g Esacure KB1 ² 5 g 5 g 5 g benzophenones 5 g 5 g 5 g Nanoparticle Dispersion 12 0 g 0 g 2.5 g Modifier 12 0 g 0.1 0 g

• 1: Sartomer Company, Inc.
• 2: LAMBERTI SpA chemical specialties

The individual components of the clearcoat become intense with each other mixed and over a period of at least 12 hours at room temperature on one stored in a dark place.

The Varnishes were coated with a 25 μm spiral squeegee applied to PVC plates and then flashed for 15 minutes. The curing The coatings were carried out on a UV system. Total were the coatings twice at a belt speed of 5.0 m / min treated with an irradiation intensity of 120 W / cm.

After a storage period of three days, the coated PVC panels were soiled with KIWI shoe polish (KIWI brown). After 30 and 60 minutes or after 24 hours, the shoe polish was removed by hand with a dry cloth and the tested site visually evaluated. test time zero sample Comparison (silicone only) Application Example 12 30 minutes light soiling Strong stain no soiling 60 minutes heavy soiling, paint is attacked Strong stain no soiling 24 hours very heavy soiling, paint is partially detached very heavy soiling, paint is attacked no soiling

Claims (21)

Surface-modified particles, in particular inorganic-based particles having reactive groups, in particular hydroxyl groups, on their surface and / or consisting of metal and / or Halbmetalloxiden, hydroxides and / or oxide hydroxides or containing particles, preferably nanoparticles, wherein the particles on their surface a polysiloxane-based modifying agent, in particular have been reacted on its surface with a polysiloxane-based modifying agent, preferably with the formation of chemical, in particular covalent bonds, characterized in that the modifying agent is a polysiloxane of the following general empirical formula (R ¹ _x R ² _3-x SiR ³ ) R ⁴ is, where in the empirical formula mean: • x = 0 to 2 including the limits, in particular x = 0; • y = 1 to 10 including the limits, in particular y = 2 to 5; • R ¹ = monovalent organic radical, preferably having 1 to 18 carbon atoms, in particular 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms; • R ² = OH group or hydrolyzable group containing or consisting of: - a linear or branched or cyclic alkoxy group having 1 to 6 carbon atoms, in particular 1 to 2 carbon atoms, - a halogen atom, in particular chlorine atom or - a carboxylic acid radical having 1 to 4 carbon atoms , in particular 2 carbon atoms; R ³ = oxygen or at least divalent organic radical containing or consisting of: a linear or branched, preferably linear alkylene radical, in particular having 1 to 8 carbon atoms, an alkylene ether, an alkylene thioether, an alkylene polyether, preferably based on ethylene oxide, Propylene oxide, butylene oxide or styrene oxide or mixtures of oxides or based on a random or block polyether, - an arylene polyether, - an alkylene or - an organic aliphatic or aromatic or arylaliphatischen group, in particular where the group in addition to ester and / or ether groups also urethane and or urea groups; R ⁴ = mono- or mehrbindiger radical containing or consisting of a polydialkylsiloxane having 4 to 200 Si units and having C ₁ -C ₁₈ alkyl groups on the silicon atoms, wherein the C ₁ -C ₁₈ alkyl groups partially and each independently one or more of the following modifying groups (G), preferably polar modifying groups (G), are substituted or substituted, selected from the modifying groups (G1) to (G4) listed below under (i) to (iv): (i ) (Poly) ether group-containing group (G1), in particular based on at least one alkylene oxide, (ii) polyester group-containing group (G2), (iii) arylalkyl group-containing group (G3), (iv) perfluorinated alkyl group-containing group (G4). Surface-modified particles according to Claim 1, characterized in that the (poly) ether group-containing group (G1) is based on at least one alkylene oxide of the general formula

wherein the radical R 'denotes a hydrogen atom, a phenyl radical or an alkyl radical, in particular an alkyl radical having 1 to 4 carbon atoms, or based on a mixture of at least two of these alkyls is formed lenoxide; and / or • that the (poly) ether groups containing group (G1) has a molecular weight in the range of 116 to 15,000 daltons, preferably in the range of 160 to 4,000 daltons, more preferably in the range of 250 to 2,500 daltons; and / or that the ratio of the mass of the poly (di) alkylsiloxane and that of the modifying group (G1) is in the range from 12: 1 to 0.07: 1, preferably in the range from 2: 1 to 0.5: 1 , lies. Surface-modified particles according to claim 1 or 2, characterized in that • the polyester group-containing group (G2) is an aliphatic and / or cycloaliphatic and / or aromatic polyester group or a group containing this group; and / or • that the polyester group-containing group (G2) at least three groups

contains; and / or • that the group (G2) containing polyester groups has a molecular weight in the range from 344 to 4,000 daltons, preferably in the range from 500 to 2,000 daltons, particularly preferably in the range from 500 to 1,500 daltons; and / or that the ratio of the mass of the poly (di) alkylsiloxane and that of the modifying group (G2) is in the range from 1: 5 to 1: 0.05, preferably in the range from 1: 2 to 1: 0.2 , lies. surface-modified Particles according to one of the preceding claims, characterized in that the arylalkyl groups group (G3) containing a phenylpropyl group, in particular a 2-phenylpropyl group, or a group containing this group. surface-modified Particles according to one of the preceding claims, characterized in that the perfluorinated ones Alkyl group-containing group (G4) is a perfluorinated alkyl group having 3 to 8 carbon atoms or a group containing this group Group is and / or that the perfluorinated alkyl group-containing group (G4) represents a tetrahydroperfluoroalkyl group, in particular a 1,1,2,2-tetrahydroperfluoroalkyl group, preferably having 3 to 8 carbon atoms, or a group containing this group Group is. Surface-modified particles, in particular inorganic-based particles having reactive groups, in particular hydroxyl groups, on their surface and / or consisting of metal and / or Halbmetalloxiden, hydroxides and / or oxide or existing hydroxides containing particles, preferably nanoparticles, in particular according to one of the preceding claims in which the particles have on their surface a polysiloxane-based modifier, in particular have been reacted on their surface with a polysiloxane-based modifier, preferably with the formation of chemical, in particular covalent bonds, characterized in that the modifier is a polysiloxane of the following general empirical formula (R ¹ _x R ² _3-x SiR ³ ) _y R ⁴ is, where in the empirical formula mean: • x = 0 to 2 including the limits, in particular x = 0; • y = 1 to 10 including the limits, in particular y = 2 to 5; • R ¹ = monovalent organic radical, preferably having 1 to 18 carbon atoms, in particular 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms; R ² = OH group or hydrolyzable group containing or consisting of: a linear or branched or cyclic alkoxy group having 1 to 6 carbon atoms, in particular 1 to 2 carbon atoms, a halogen atom, in particular chlorine atom, or a carboxylic acid radical having 1 to 4 Carbon atoms, in particular 2 carbon atoms; R ³ = oxygen or at least divalent organic radical containing or consisting of: a linear or branched, preferably linear alkylene radical, in particular having 1 to 8 carbon atoms, an alkylene ether, an alkylene thioether, an alkylene polyether, preferably based on ethylene oxide, Propylene oxide, butylene oxide or styrene oxide or mixtures of the oxides or based on a random or block polyether, - an arylene polyether, - an alkylene polyester or An organic aliphatic or aromatic or arylaliphatic group, in particular where the group also contains urethane and / or urea groups in addition to ester and / or ether groups; R ⁴ = mono- or mehrbindiger radical containing or consisting of a polydialkylsiloxane having 4 to 200 Si units and having C ₁ -C ₁₈ alkyl groups on the silicon atoms, wherein the C ₁ -C ₁₈ alkyl groups partially and each independently one or more of the following modifying groups (G), preferably polar modifying groups (G), are substituted or substituted, selected from the modifying groups (G1) to (G4) listed below under (i) to (iv): (i ) (Poly) ether group-containing group (G1), in particular based on at least one alkylene oxide, particularly preferably based on at least one alkylene oxide of the general formula

wherein the radical R 'denotes a hydrogen atom, a phenyl radical or an alkyl radical, in particular an alkyl radical having 1 to 4 carbon atoms, or based on a mixture of at least two of these alkylene oxides, in particular wherein the (poly) ether groups containing group (G1) a Molar mass in the range of 116 to 15,000 daltons, preferably in the range of 160 to 4,000 daltons, more preferably in the range of 250 to 2,500 daltons, and / or in particular wherein the ratio of the mass of the poly (di) alkylsiloxane and the modifying group (G1) is in the range of 12: 1 to 0.07: 1, preferably in the range of 2: 1 to 0.5: 1. (ii) polyester group-containing group (G2) selected from aliphatic and / or cycloaliphatic and / or aromatic polyester groups or groups containing these groups, preferably having at least three groups

in particular wherein the group (G2) containing polyester groups has a molecular weight in the range from 344 to 4,000 daltons, preferably in the range from 500 to 2,000 daltons, more preferably in the range from 500 to 1,500 daltons, and / or in particular wherein the ratio of the mass of Poly (di) alkylsiloxane and that of the modifying group (G2) in the range of 1: 5 to 1: 0.05, preferably in the range of 1: 2 to 1: 0.2. (iii) Arylalkyl group-containing group (G3), preferably phenylpropyl group, especially a 2-phenylpropyl group, or a group containing this group; (iv) perfluorinated alkyl group-containing group (G4), preferably perfluorinated alkyl group having 3 to 8 carbon atoms and / or tetrahydroperfluoroalkyl group, especially 1,1,2,2-tetrahydroperfluoroalkyl group, preferably having 3 to 8 carbon atoms, or group containing this group. surface-modified Particles according to one of the preceding claims, characterized in that the proportion the modifier 0.01 to 50 wt.%, In particular 0.05 to 30 wt .-%, preferably 0.1 to 15 wt .-%, based on the total weight the surface modified Particle is. surface-modified Particles according to one of the preceding claims, characterized in that the particles are inorganic based particles with reactive groups on their surface, in particular with silane-reactive and / or siloxane-reactive groups, preferably selected from the group of hydroxyl groups, halogen atoms and halogen atoms containing groups, particularly preferably hydroxyl groups, and / or that the Particles inorganic based particles with hydroxyl groups on their surface are. surface-modified Particles according to one of the preceding claims, characterized in that the particles at least one oxide, hydroxide and / or oxide hydroxide at least a metal or semi-metal or mixtures or combinations consist of such compounds or contain these compounds, in particular of at least one oxide, hydroxide and / or oxide hydroxide of aluminum, silicon, zinc and / or titanium or these Contain connections. Surface-modified particles according to one of the preceding claims, characterized in that the particles have particle sizes, in particular determined by means of transmission electron microscopy, in the range from 0.1 to 1000 nm, in particular 0.5 to 500 nm, preferably 1 to 350 nm, more preferably 2 to 200 nm, more preferably below 100 nm, most preferably below 50 nm. Surface-modified particles according to one of the preceding claims, characterized in that the particles additionally with a silane of the general empirical formula R ⁶ _{(4-x ')} SiR ⁵ _x' in the formula, mean: x '= 1 to 3 inclusive of the limits; R ⁵ = monovalent linear or branched or cyclic organic radical having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms; R ⁶ = hydroxyl group or hydrolyzable group containing or consisting of: a linear or branched or cyclic alkoxy group having 1 to 6 carbon atoms, in particular 1 to 2 carbon atoms, a halogen atom, in particular chlorine atom, or a carboxylic acid radical having 1 to 4 carbon atoms, preferably 2 carbon atoms. Surface-modified particles according to one of the preceding claims, characterized in that the particles additionally with a silane of the general empirical formula R ⁷ _{(4-x ")} Si (R ⁸ -R ⁹ R ¹⁰ ) _x" are modified, wherein in the empirical formula mean: x '= 1 to 3 inclusive of the limits; R ⁷ = hydroxyl group or hydrolyzable group containing or consisting of: a linear or branched or cyclic alkoxy group having 1 to 6 carbon atoms, in particular 1 to 2 carbon atoms, a halogen atom, in particular chlorine atom, or a carboxylic acid radical having 1 to 4 carbon atoms, preferably 2 carbon atoms; R ⁸ = oxygen or at least divalent organic radical containing or consisting of: a linear or branched, preferably linear alkylene radical, in particular having 1 to 8 carbon atoms, an alkylene ether, an alkylene thioether, an alkylene polyether, preferably based on ethylene oxide, Propylene oxide, butylene oxide or styrene oxide or mixtures of oxides or based on a random or block polyether, - an arylene polyether, - an alkylene or - an organic aliphatic or aromatic or arylaliphatischen group, in particular where the group in addition to ester and / or ether groups also urethane and or urea groups; • R ⁹ = divalent organic group, in particular having a molecular weight in the range of 130 to 5000 daltons, containing or consisting of: - a polyether group, preferably containing or consisting of ethylene oxide, propylene oxide, butylene oxide or styrene oxide or mixtures of these oxides, - an aliphatic and or cycloaliphatic and / or aromatic polyester group, preferably having at least three groups

R ¹⁰ = alkyl group or acetoxy group or a radical -OR ¹¹ , wherein R ^{11 is} an alkyl group having 1 to 18 carbon atoms, or a radical -O-CO-NH-R ¹² , wherein R ^{12 is} an alkyl group having 1 to 18 carbon atoms , Process for the preparation of the surface-modified particles according to Claims 1 to 12, in which particles, in particular inorganic-based particles having reactive groups, in particular hydroxyl groups, are present on their surface and / or of metal and / or semimetal oxides, hydroxides and / or oxide hydroxides or particles containing them, preferably nanoparticles, are reacted with a polysiloxane-based modifying agent, preferably converted to form chemical bonds, in particular covalent bonds, characterized in that the modifying agent used is a polysiloxane of the following general empirical formula (R ¹ R ² _3-x SiR ³ ) _y R ⁴ is used as defined in any one of the preceding claims. Method according to claim 13, characterized in that that this Modifying agent in amounts of 0.01 to 50 wt.%, In particular 0.05 to 30 wt .-%, preferably 0.1 to 15 wt .-%, based on the total weight of the surface-modified particles obtained, is used. A method according to claim 13 or 14, characterized in that the particles additionally with a silane of the general empirical formula R ⁶ _{(4-x ')} SiR ⁵ _x' as defined in claim 11. Method according to one of claims 13 to 15, characterized in that the particles additionally with a silane of the general empirical formula R ⁷ _{(4-x '')} Si (R ⁸ -R ⁹ -R ¹⁰ ) _{x ''} modified as defined in claim 12. Method according to one of claims 13 to 16, characterized that as Particles inorganic based particles with reactive groups, in particular Hydroxyl groups, on their surface be used and / or that as Particles such or with at least one oxide, hydroxide and / or Oxide hydroxide of at least one metal or semi-metal or from or with mixtures or combinations of such compounds, in particular particles of or with at least one oxide, hydroxide and / or oxide hydroxide of aluminum, silicon, zinc and / or Titans, are used, and / or that as particles from such or with at least one inorganic salt, in particular phosphate, Sulfate, halide and / or carbonate, optionally in admixture with at least one metal and / or half metal oxide, oxide hydroxide and / or Hydroxide can be used. Use of surface-modified particles according to the claims 1 to 12 as fillers. Use of surface-modified particles according to the claims 1 to 12 in coating materials and coating systems, in particular Lacquers, paints and the like, in dispersions of all kinds, in plastics, in foams, in cosmetics, especially nail varnishes, in adhesives and in sealants. Dispersions containing surface-modified particles according to the claims 1 to 12 in a carrier or dispersing medium. Coating materials and coating systems, in particular Lacquers, paints and the like, plastics, foams, cosmetics, in particular nail varnishes, adhesives and sealants, containing surface-modified Particles according to the claims 1 to 12.