(10) DE 10 2007 030 285 A1 02/107/2008

Specification

[0001] The present invention relates to surface modified particles, in particular inorganic based particles having reactive and/or reactable surfaces, in particular silane reactive and/or siloxane reactive surfaces, in particular surfaces containing hydroxyl groups, and/or particles comprising or consisting of metal or semimetal oxides and/or hydroxides, preferably nanoparticles, which on their surface have a polysiloxane based modifier, in particular having been reacted on their surface with a polysiloxane based modifier, preferably with the formation of chemical bonds, in particular covalent bonds, and also to a suitable method for producing said surface modified particles.

[0002] Furthermore, the present invention relates to the use of these surface modified particles, especially in coating materials and coating systems, in particular paints, inks and the like, in dispersions of all kinds, in plastics, in foams, in cosmetics, in particular nail varnishes, in adhesives, in sealants, etc. Furthermore, the present invention relates to the use of these surface modified particles as fillers, in particular in the aforementioned systems.

[0003] In addition, the present invention also relates to systems, in particular coating materials and coating systems, in particular paints, inks and the like, plastics, foams and cosmetics, in particular nail varnishes, which contain these surface modified particles. Finally, the subject matter of the invention also consists of novel dispersions, which contain these surface modified particles in a carrier or dispersion medium.

[0004] In principle, the person skilled in this art knows about the use of particles, in particular nanoparticles, in coating systems and dispersion systems from the state of the art. Thus, the use of nanoparticles as fillers for coating systems offers the advantage of imparting to a coating material the desired properties (such as enhanced scratch resistance) without having to accept simultaneously negative side effects (such as poor transparency).

[0005] It is known that the incorporation of nanoparticles in coating materials leads, for example, to an improvement in the mechanical properties of the coating systems, for example, coating systems that can be cured by means of ultraviolet light.

[0006] Therefore, the EP 1 236 765 A1 discloses, for example, a method for modifying nanoscaled silica particles with alkoxysilanes. Once these particles have been incorporated into a suitable coating system, which can be cured with ultraviolet light, they affect an improvement in the mechanical properties. Positive effects are also found in other high quality cross-linked systems, such as epoxide resins. The improvement of the mechanical properties is explained in essence by the bonding of the nanoparticles to the surrounding matrix by way of chemical bonds. Owing to the chemical bonding of the particles to the organic matrix an increasing embrittleness is observed - as a function of the degree to which the coating materials are filled with this type of nanoparticle. Depending on the area of applicant, this feature is disadvantageous for the coating. To the extent that the prior art nanoscaled silica-based fillers are not bonded to the organic matrix, the desired effect of improving the mechanical properties in UV curing and/or epoxide based coating systems is not anywhere near as pronounced.

[0007] Besides the silica nanoparticles, other types of nanoparticles can also be incorporated into the coating materials in order to optimize their mechanical properties. By adding, for example, nanoscaled aluminum oxide (for example, the commercial products NANOBYK 3600 and/or NANOBYK 3601 of BYK-Chemie GmbH, Wesel, Germany) to coating systems, which can be cured with ultraviolet light, the abrasion resistance can be significantly improved without influencing the flexibility of the system. In this case the aluminum oxide is not bonded to the organic matrix of the coating system. The nanoparticles in the coating matrix are stabilized with commercially available wetting and dispersion additives.

[0008] Similarly the coating systems, which cannot be cured with ultraviolet light or are not based on epoxide systems, can be optimized in terms of their scratch resistance with the addition of nanoparticles.

[0009] Therefore, the US 6 593 417 A describes a method, in which silica particles in combination with a polysiloxane are used in a two component polyurethane coating. The polysiloxane has reactive groups, which can bond with the coating matrix by means of covalent groups. The polysiloxane bonds to the nanoparticles only by means of coordinative interactions. The special combination consisting of nanoparticles and polysiloxane results in the nanoparticles orienting themselves in relation to the interface of coating and air, as a result of which this interface is mechanically strengthened. This mechanical strengthening is manifested in turn in an enhanced scratch resistance. The drawback is the orientation of the nanoparticles in relation to the interface of coating and air, since the stress, to which the coating is exposed owing to the influence of weather and use, abrades, first of all, the uppermost layer. Hence, the effectiveness of the uppermost layer decreases over time.

[0010] The US 5 853 809 A teaches that the scratch resistance of the coating systems, as used, for example, in the topcoat of automobiles, can be improved by incorporating modified nanoparticles. The modification of the nanoparticles is carried out by means of a functional polyurethane in such a manner that the polymer enters into a covalent bond with the nanoparticle surface. Furthermore, the polymer sheath of the nanoparticles that are modified in this way is in a position to enter into covalent bonds with the binder system of the coating material. However, this document does not address the embrittlement of the coating system, especially in the case of high nanoparticle contents.

[0011] The modified nanoparticles, which are known from the state of the art, do improve the scratch resistance of coatings, in which they are incorporated, but in systems, which do not cure with radiation, in particular UV curing systems, the bonding of the nanoparticles to the coating matrix via modification must be evaluated as extremely dubious. Bonding the nanoparticles to the coating matrix increases the network density of the cured coating film, a state that results in higher embrittlement of the coating film.

[0012] The DE 195 40 623 A1 discloses nanoscaled filler particles, which are dispersed in a polymer matrix. Silanes, in particular organoalkoxysilanes, are described, inter alia, as the surface modifiers. The surface modifiers are low molecular compounds having a molecular weight, which is no higher than 500 Dalton. The functional groups, which must carry this type of compound, conform with the surface groups of the nanoscaled particles and with the desired interaction with the matrix. Thus, the modified particles exhibit an affinity for the matrix.

[0013] Therefore, the object of the present invention is to provide surface modified particles, in particular nanoscaled surface modified particles, which are especially suitable for use in the aforementioned systems and which at least largely avoid or at least minimize the drawbacks associated with the conventional particles, as well as to provide a suitable method for producing such particles.

[0014] Another object of the present invention is to provide a new, efficient surface modification of particles of the aforementioned genre, in particular nanoparticles.

[0015] Furthermore, the object of the present invention is to provide the particles, in particular nanoparticles, as a stable dispersion in suitable dispersion and/or carrier mediums (for example, solvents, water, etc.), as used, for example, in the coating industry. These new dispersions are to exhibit a high storage stability even in the case of a high particle content. The tendency of these particle dispersions, in particular the nanoparticle dispersions, to form sedimentation and/or a gel should be ruled out in an advantageous manner. Furthermore, the dispersions, in particular if they are used for producing coating materials, should affect advantageously, inter alia, an increase in the scratch resistance of cured coatings. Any reactivity of the new surface modified particles, in particular the nanoparticles, to the systems, in which they are incorporated, in particular to the binder components of the coating system that is used, should be minimized as much as possible, preferably in order to avoid the tendency towards embrittlement of the cured coating film. In particular the surface modification should be as inert as possible and/or as little reactive as possible to the systems, in which the surface modified particles are used, for example, with respect to a coating matrix.

[0016] Finally another object of the present invention is to provide a method for producing the new surface modified particles, in particular nanoparticles. In this case the method can be carried out easily and can be widely varied, in particular in order to tailor in this way the new surface modified particles, in particular nanoparticles, and their dispersions to a variety of application purposes.

[0017] At this point the applicant has found surprisingly that the above described problem can be solved in an efficient way if the particles, in particular the inorganic based particles having reactive and/or reactable, preferably silane reactive and/or siloxane reactive groups, in particular hydroxyl groups, on their surface, and/or particles comprising or consisting of metal and/or semimetal oxides, hydroxides and/or oxide hydroxides, preferably nanoparticles, are reacted with a polysiloxane based modifier, preferably with the formation of chemical bonds, in particular covalent bonds, said modifier exhibiting a higher molecular weight, being preferably linearly constructed, being inert with respect to the surrounding matrix and being provided with modifying groups, in particular polaric groups. In this way the dispersing property of the particles can be surprisingly improved; the surface modification with respect to the known systems can be improved; and the polarities can be controlled in an improved way.

[0018] In order to solve the problem described above, the present invention proposes the surface modified particles as claimed in claim 1. Other advantageous properties are the subject matter of the respective dependent claims 2 to 11.

[0019] An additional subject matter of the present invention is a method for producing the inventive surface modified particles as claimed in claim 13. Other advantageous properties are the subject matter of the method-related dependent claims.

[0020] In turn an additional subject matter of the present invention is the use of the inventive surface modified particles as fillers, as claimed in claim 18.

[0021] An additional subject matter of the present invention is the use of the inventive surface modified particles in coating materials and coating systems, in particular paints, inks and the like, in dispersions of all kinds, in plastics, in foams, in cosmetics, in particular nail varnishes, in adhesives and in sealants, as claimed in claim 19.

[0022] Furthermore, the subject matter of the present invention also consists of dispersions, which contain the inventive surface modified particles in a carrier or dispersion medium, as claimed in claim 20.

[0023] Finally an additional subject matter of the present invention consists of coating materials and coating systems, in particular paints, inks and the like, plastics, foams, cosmetics, in particular nail varnishes, adhesives and sealants, which the inventive surface modified particles contain, as claimed in claim 21.

[0024] The present invention is explained in detail below by means of the inventive surface modified particles, in particular nanoparticles. The respective data apply correspondingly to the other aspects and/or subject matters of the present invention - the inventive production method, the inventive use, the inventive dispersions, etc., so that in order to avoid unnecessary repetition even for the other aspects and/or subject matters of the present invention reference can be made thereto.

[0025[ Therefore, the subject matter of the present invention, according to a first aspect of the present invention, consists of surface modified particles, in particular inorganic based particles having reactive and/or reactable, preferably silane reactive and/or siloxane reactive groups, in particular having hydroxyl groups, on their surface, and/or particles comprising or consisting of metal and/or semimetal oxides, hydroxides and/or oxide hydroxides, preferably nanoparticles. In this case the particles exhibit 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 bonds, in particular covalent bonds. Therefore, the surface modified particles are characterized in that the modifier is a polysiloxane of the following general empirical formula (R¹_x R²_3-x SiR³)_yR⁴, where in the empirical formula

• x = 0 to 2 including the limits, in particular x = 0;

• y = 1 to 10 including the limits, in particular y = 2 to 5;

• R¹ = monovalent organic group, preferably having 1 to 18 carbon atoms, in particular 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms;

• R² = 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 group having 1 to 4 carbon atoms, in particular 2 carbon atoms;

• R³ = oxygen or at least bivalent organic group, containing or consisting of:

- a linear or branched, preferably linear alkylene group, in particular having 1 to 8 carbon atoms,

- an alkylene ether,

- an alkylene thio ether,

- an alkylene polyether, preferably on the basis of ethylene oxide, propylene oxide, butylene oxide or styrene oxide or mixtures of oxides or on the basis of a static or block polyether,

- an arylene polyether,

- an alkylene polyester or

- an organic aliphatic or aromatic or arylaliphatic group, in particular where the group contains not only ester and/or ether groups, but also urethane and/or urea groups;

• R⁴ = monovalent or polyvalent group containing or consisting of a polydialkyl siloxane having 4 to 200 Si units and having C₁ - C₁₈ alkyl groups at the silicon atoms, where the C₁ - C₁₈ alkyl groups are replaced and/or substituted to some extent and respectively independently of each other by one or more of the following modifying groups (G), preferably polaric modifying groups (G), (that is, in other words are exchanged for this group, in particular by grafting), selected from the following modifying groups (G1) to (G4), which are listed under (i) to (iv):

(i) (poly) ether groups-containing group (G1), in particular on the basis of at least one alkylene oxide,

(ii) polyester groups-containing group (G2),

(iii) arylalkyl groups-containing group (G3).

(iv) perfluorated alkyl groups-containing group (G4).

[0026] Advantageous configurations of the present invention are disclosed in the dependent claims and secondary claims.

[0027] The preferably polaric modification of the group R⁴ must be regarded as the decisive feature of the present invention. As described above, the alkyl groups of the polydialkyl siloxane group (that is, the C₁ - C₁₈ alkyl groups at the silicon atoms) are replaced and/or substituted to some extent and independently of each other by a modifying, preferably polaric group (G) (for example, by grafting). Surprisingly, on the one hand, the dispersing property of the inventive particles is improved in this way. On the other hand, the polarity can be controlled in a targeted way so that in this way even the application properties can be tailored to the application. Finally in this way the surface modification is significantly improved, in particular in terms of the targeted application properties (for example, scratch resistance of coatings, etc.). The modifying groups (G) for the group R⁴ are selected in such a manner that they are advantageously compatible, inert or at least as little reactive as possible, with respect to the application systems and/or the application matrix and their content materials (for example, coating matrix). The preferably polaric modification groups (G) can be introduced, for example, by grafting into the group R⁴ (for example, by means of hydrosilylation and/or addition reaction or by means of condensation reaction), starting from commercially available starting products; the person skilled in this art is aware of the afore-stated, which shall be described below in greater detail.

[0028] Especially preferred embodiments with respect to the selection of modification groups (G) are the subject matter of claims 2 to 5.

[0029] An especially preferred embodiment of the inventive surface modified particles is the subject matter of claim 6.

[0030] A special increase in the performance of the inventive particles can be achieved by an additional surface modification with silanes, according to the subject matter of claims 11 and/or 12.

[0031] The particle size of the inventive particles, in particular nanoparticles, lies in a range of 0.1 to 1,000 nm, in particular 0.5 to 500 nm, preferably 1 to 350 nm, furthermore preferably 2 to 200 nm, particularly preferred below 100 nm, very particularly preferred below 50 nm. The particle sizes may be determined, according to the invention, by means of transmission electron microscopy.

[0032] Nanoparticles are defined, according to the invention, as fine particulate solids having a particle size in the aforementioned particle size range (that is, in a range of 0.1 to 1,000 nm, in particular 0.5 to 500 nm, preferably 1 to 350 nm, furthermore preferably 2 to 200 nm, particularly preferred below 100 nm, very particularly preferred below 50 nm). As stated above, the particle sizes may be determined, according to the present invention, in particular by means of transmission electron microscopy (TEM). In order to determine the particle size of the inventive particles and/or nanoparticles, a TEM examination may be conducted. For this purpose the corresponding nanoparticle dispersions are usually diluted, applied on a carbon grid (in particular, 600 mesh carbon film), and dried. Then the analysis can be done, for example, with a LEO 912 transmission electron microscope. The TEM images are evaluated, for example, digitally with software from the company analySIS Soft Imaging System GmbH. The particle diameters are generally calculated for at least 1,000 particles by correlating the measured area of the particles and/or nanoparticles with a circle having the same area. Then the average value is formed from the results.

[0033] The claimed particles, in particular nanoparticles, are generally inorganic particles, on the surfaces of which are located and/or arranged reactive and/or reactable, preferably silane reactive and/or siloxane reactive groups, in particular hydroxyl groups, which are needed for the chemical, preferably covalent bonding of the modifier. That is, the reactive and/or reactable groups, which are located on the surface of the particles, which are to be modified, must be capable of reacting with the modifier. Besides the hydroxyl groups, which are preferred according to the invention, other silane and/or siloxane reactive groups are also suitable, for example halogens (such as fluorine or chlorine) or groups, containing halogen atoms, etc.

[0034] In particular, the particles comprise or contain at least a metal and/or semimetal oxide, oxide hydroxide and/or hydroxide. Even mixtures or combinations of different metal and/or semimetal oxides, oxide hydroxides and/or hydroxides may be used (for example, particles, which comprise mixed metal and/or semimetal oxides, oxide hydroxides and/or hydroxides). For example, the oxides, hydroxides and/or oxide hydroxides of aluminum, silicon, zinc and/or titanium, etc. can be used for producing modified particles and/or nanoparticles. Furthermore, oxide hydroxides, such as aluminum oxide hydroxide, can be modified in accordance with the cited method. Similarly other inorganic materials, in particular inorganic salts, such as phosphates, sulfates, halogenides, carbonates, etc., are also suitable - optionally in a mixture the aforementioned metal and/or semimetal oxides, oxide hydroxides and/or hydroxides. However, metal and/or semimetal oxides, oxide hydroxides and/or hydroxides of the aforementioned kind are preferred, according to the invention.

[0035] The production process of the particles, which are used according to the invention, in particular the oxidic and/or hydroxidic and/or oxide hydroxidic particles, in particular nanoparticles, can be carried out by means of a wide variety of methods, such as ion exchange processes, plasma processes, sol/gel method, precipitation, comminution (for example, by grinding) or flame hydrolysis etc. It is immaterial, according to the invention, as to which method is used to produce the oxidic and/or hydroxidic particles. That is, the surface of any arbitrarily produced particle of the aforementioned kind can be modified, according to the invention.

[0036] The inventive, novel surface modified particles, in particular nanoparticles, are also called, according to the present invention, the inventive particles and/or the inventive nanoparticles. The new dispersions of the inventive particles and/or nanoparticles are also called, according to the present invention, the inventive dispersions.

[0037] Being aware of the state of the art, it came as a total surprise and was unpredictable by the person skilled in the art that the above described problem, on which the present invention is based, could be solved by the inventive particles, by the inventive production method, by the inventive dispersions and the other, above described inventive subject matters.

[0038] The production of the inventive particles and the inventive dispersions can be carried out in a simple way without the use of complicated methods or processes.

[0039] The inventive nanoparticles are suitable, for example, for the production of, for example, thermally curable, radiation curing or two component coating systems, thermoplastics, foams, etc.

[0040] By making available the inventive dispersions it is possible to provide an easy to manipulate particle concentrate, in particular nanoparticle concentrate, which can be easily metered, for example, into a very wide variety of coating systems, in order to achieve the desired effect, for example, an improved mechanical stability, such as scratch resistance.

[0041] Besides the ease with which the inventive dispersions can be metered, a good stability of the dispersions to settling and gel formation, in particular even in the case of high solid contents, could also be found.

[0042] The inventive particles, in particular nanoparticles, are covered advantageously with modifying groups in such a manner that any still existing, functional reactive groups on the particle surface are shielded to such an extent that a reaction of these groups with other functional groups no longer takes place for steric reasons.

[0043] The surface of the inventive particles, 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 bonded chemically, preferably covalently to the particle surface. The modifying group exhibits a variety of different structural elements, which can build with the particle surface at least a chemical bond, in particular a covalent bond. Furthermore, the modifying group consists of a spacing member, which cannot undergo a reaction with the particle surface and is largely inert to the matrix (for example, other coating constituents, plastic constituents, etc.). The spacing member of the modifying group may be formed, for example, by a polymer, having, for example, an average molecular weight, for example, in a range of 300 to 5,000 Dalton. In this case the structure of the spacing group is constructed preferably in a linear manner.

[0044] This means that the modifier is constructed from at least one or more anchor groups, which are reactive to the particle surface, as well as a polydialkyl siloxane ( = component of the above defined group R⁴). The anchor groups with the connecting structures may be attached to the ends of the polydialkyl siloxane as well as exist as a side group on the polydialkyl siloxane.

[0045] The structure of the modifier, used according to the invention, can be rendered schematically as follows by way of an example. In the illustrated example three different polaric substituents and/or modifying groups (G) were selected for the group R⁴ (= polydialkyl siloxane) in the drawing. (With respect to the meaning of the substituents reference is made to the above description as well as the patent claims.)

[see figure]

Polydialkyl siloxane

[0046] The index a describes the number of anchor groups; and the indices b, c, d ... describe the number of preferably polaric substituents and/or modifying groups (G) in the side group of the polydialkyl siloxane R¹, where

a ³ 1

b + c + d + ... ³ 1.

[0047] As described above, a surface modification of the particles can also be carried out, according to claim 11 and/or claim 12, with silanes, which are generally bonded in the same way to the particle surface by means of at least one chemical bond, in particular a covalent bond, and exhibit advantageously one or more spacing members. For more details reference is made to the patent claims.

[0048] The production of the inventive nanoparticles may be carried out by simply mixing the modifier with a particulate, in particular nanoparticulate, powder. At the same time it must be ensured that preferably a chemical, in particular covalent bonding of the modifier to the surface of the nanoparticles takes place. The conditions are governed by the reactivity of the functional groups, which are to be reacted with one another, and may be easily determined by the person skilled in this art. If a reaction does not take place as early as at room temperature, then a chemical, in particular covalent bonding of the modifier can be achieved, for example, by heating the mixture comprising nanoparticulate powder and modifier at a temperature of approximately 80 deg. C for a period of approximately one hour.

[0049] The person who is skilled in this art is familiar with the production of the modifier, used according to the invention. This production may be carried out, for example, in the following way.

Starting from commercially available open chained and cyclical polydimethyl siloxanes and Si-H functional polydimethyl siloxanes, the Si-H functional polydimethyl siloxanes can be produced by means of an equilibrium reaction (as described, for example, in Noll, "Chemistry and Technology of Silicones", Wiley/VCH Weinheim, 1984). In the subsequent steps said Si-H functional polydimethyl siloxanes can be reacted to form the modification reagent, used according to the invention. Within the scope of the present invention, the number of Si-H groups in the Si-H functional polydimethyl siloxane must amount to at least two. (At least one Si-H group is needed for bonding the anchor group (R¹_x R²_3-xSiR³)_y and at least one Si-H group for bonding the polaric modification).

[0050] Unsaturated compounds, such as 1-octene, 1-decene, 1-dodecene, 1-hexadecene, and 1-octadecene, can be attached by known methods to Si-H containing polysiloxanes by means of suitable catalysts, such as hexachloroplatinic acid, Speyer catalyst, platinum divinyl tetramethyl disiloxane complex or in the presence of platinum compounds, which are applied on the carrier materials. The hydrosilylation conditions are universally known; preferably the hydrosilylation temperature ranges between room temperature and 200 deg. C, preferably from 50 to 150 deg. C, depending on the catalyst that is used.

[0051] Analogous to the attachment of alkenes, but as an alternative, other compounds having unsaturated groups may also be added in the sense of a hydrosilylation to the Si-H groups. For example, polyalkylene glycol allyl alkyl ether (for example, polyglycol AM types, Clariant GmbH) or trialkoxy vinyl silane (for example, Dynasylan VTMO or Dynasylan VTEO, Degussa AG) may be added to the Si-H groups.

[0052] Furthermore, addition compounds of lactones, such as e-caprolactone and/or d-valerolactone at ethylenically unsaturated alcohols, such as allyl alcohol, hexenol, allyl glycol or vinyl hydroxy butyl ether, may be added, for example, to the Si-H groups. These compounds may be, for example, alkylated or acylated.

[0053] Furthermore, besides the possibility of the addition of ethylenically saturated compounds to Si-H groups, there is the possibility of coupling hydroxy functional compounds to the Si-H functional polydimethyl siloxane by way of a condensation reaction. Owing to these known methods polyalkylene glycol monoalkyl ether (for example, butyl polyethylene glycol) can be condensed at the Si-H groups while simultaneously splitting off the hydrogen gas. One example of a catalyst for this reaction is zinc acetyl acetonate. Other substituents, such as ester group-containing groups in the polydimethyl siloxane, may also be introduced in an analogous manner.

[0054] In order to modify the Si-H functional polydimethyl siloxanes, hydrosilylation reactions and condensation reactions may be carried out. Similarly it is possible to use a combined method in order to produce the modifier.

[0055] In contrast to hydrosilylation (formation of a Si-C bond), condensation reactions produce an Si-O coupling.

[0056] In this manner the group R⁴ may be modified by the polaric groups (G), as listed, for example, under (i) to (iv) of claim 1.

[0057] The inventive particles, in particular nanoparticles, may be used, for example, directly in paints and plastics. However, the inventive particles, in particular nanoparticles, are also especially suitable for producing dispersions, for example, in water, solvents, plasticizers, waxes, mineral oils and reactive thinners and other carrier mediums, such as used conventionally in the paint and plastics industry.

[0058] The inventive dispersions are produced by incorporating in a suitably modified manner into the desired dispersion and/or carrier medium or dispersing agent with the use of conventional dispersing aggregates, such as toothed colloid mills, dissolvers, ultrasound dispersers, etc.

[0059] An inventive dispersion is obtained through the addition of the modifier to a particle dispersion, in particular a nanoparticle dispersion. This method must also ensure that a chemical, in particular covalent bonding of the modifier to the particle surface, in particular nanoparticle surface, takes place. The transfer of an inventive dispersion from one dispersion medium to another is achieved, for example, by means of distillation. Such methods can be easily optimized by using suitable entrainers, which form a low boiling azeotrope with the dispersing medium to be removed.

[0060] The particle content of the inventive dispersions, measured as a residue on ignition, may be raised to values ranging up to more than 40% without the possibility that a gel will form or that any noteworthy sedimentation will occur.

[0061] In this case the inventive dispersions may contain at least one additional substance, which originates from the area of conventional paint additives, binders or cross-linking agents. Some examples that can be mentioned here are wetting and dispersing additives and/or additives for controlling the rheological properties, but also defoamers, light stability agents and catalysts.

[0062] The inventive particles, in particular nanoparticles, and the inventive dispersions have a very wide range of application. The wide applicability in combination with the extremely good efficiency of the inventive particles, in particular nanoparticles, and the inventive dispersions outclass by far particles, in particular nanoparticles, and dispersions of the state of the art.

[0063] The inventive particles, in particular nanoparticles, and the dispersions can be applied by adding them to existing systems, which are further processed, for example, into paints, adhesives, plastics, etc. The addition of just small amounts of the inventive particles, in particular nanoparticles, and/or the inventive dispersions results in an extremely enhanced mechanical stability with simultaneously higher stability to chemical influences of the coating and/or molded part, obtained in the final end.

[0064] Surprisingly the processing properties of the paints and plastics are affected only negligibly so that no new optimization of the external parameters must take place in the event of these applications.

[0065] The inventive particles, in particular nanoparticles, and their dispersions exhibit excellent properties for use in coating materials, plastics, adhesives, sealants, etc.

[0066] Additional embodiments, modifications and variations of the present invention can be easily identified by the person skilled in the art in his reading of the specification and can be implemented without abandoning the scope of the present invention.

[0067] The present invention is illustrated by means of the following embodiments, which, however, do not restrict the present invention in any way.

Embodiments:

[0068]

1. Production of the 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 Kat 0.2%	W.C. Heraeus	0.08	0.08	0.0	8	0.08	0.08	0.08

			7	8	9	10	11
	Raw Material	Manufacturer
A	MDH29D8 6M	see comments	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 170T	NOF Europe			40.24		50.54
D	1-octene		13.03	13.03	13.03	14.43	10.78
E	Karstedt Kat 0.2%	W.C. Heraeus	0.08	0.08	0.08	0.08	0.08

General Production Protocol:

[0069] (A) is placed into a 250 ml four necked flask with agitator, thermometer, reflux cooler and protective gas outlet, heated under nitrogen to 80 deg. C, and treated with (E). Then (B) is added drop by drop in a period of 40 minutes. Thereafter the reaction mixture is stirred for 30 minutes at 120 deg. C, and then (C) is added drop by drop over a period of 20 minutes. After completion of the addition, the reaction mixture is stirred for another 30 minutes at 120 deg. C. Then (D) is added drop by drop over a period of 150 minutes and thereafter stirred for 60 minutes.

Comments:

[0070] The silicone MDH29D86M (see chart) can be shown by means of an equilibrium reaction, as described in Noll, "Chemistry and Technology of Silicones", Wiley/VCH Weinheim, 1984.

[see figure]

2. Production of the Nanoparticle Concentrates ("Nanoparticle Concentrates 1 - 11")

	Product Name	Manufacturer	Amount / g
A	Köstrosol 2040AS	CWK Bad Köstritz	75.00
B	1-methoxyl-2-propanol		75.00
C	Dynasylan PTMO	Degussa	1.64
D	Methoxypropyl acetate		80.00
E	Dynasylan OCTMO	Degussa	1.17
F	Modifier (1 - 11)		0.60
G	Disperbyk 168	BYK Chemie	65.00

General Production Protocol:

[0071] (A) is placed into a 250 ml four necked flask with agitator, thermometer, and reflux cooler and mixed with B. Then heated to 70 deg. C, and treated with (C). After a reaction period of 90 minutes, (D) is added. Thereafter a vacuum is applied; and at a temperature of 70 deg. C, 100 g of a solvent mixture are separated off. At this point (E) and (F) are added in succession and stirred for 120 minutes at 70 deg. C. Thereafter (G) is added. A nanoparticle content of 21.7% is obtained by separating off 60 g of solvent mixture.

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

[0072]

Two Component Automobile Repair System

Component 1	Reference Sample	Application Example 1 - 11
Macrynal SM515/70BAC	46.7	46.7
Methoxypropyl acetate	8.3	8.3
Butyl glycol acetate	1.3	1.3
TinStab BL277 (1% solution in butyl acetate)	0.2	0.2
Butyl acetate	10.1	10.1
Nanoparticle concentrate 1-11	--	5.3

Component 2	Reference Sample	Application Example 1 - 11
Desmodur N 3390	26.5	26.5
Butyl acetate	6.9	6.9

Macrynal SM 515/70BAC (hydroxy functional polyacrylate): UCB

TinStab BL277 (dibutyl tin dilaurate): Acros Chemicals

Desmodur N 3390 (aliphatic polyisocyanate): Bayer AG

[0073] The constituents of the respective components were mixed intensively. Directly before the coating process, the two components 1 and 2 were mixed. The coating system was applied by a spray application on PMMA plates (200 mm x 400 mm). After a venting period of one hour at room temperature, forced air drying was conducted at 60 deg. C over a period of 12 hours. The targeted layer thickness of the coating was approximately 45 mm.

[0074] The scratch resistance was tested with a crockmeter device (CM-5 model, ATLAS). To this end the coated plates were stressed in a reproducible manner with a polishing cloth from the company EM (3M polishing paper, grade 9 mic) (application force: 9 N). The scratch resistance was evaluated by measuring the gloss of the stressed spots in comparison with the gloss of a non-stressed spot on the test plate. As the result, the residual gloss was given in percent (%). The gloss was determined with the micro TRI gloss device from the company BYK GARDNER. The viewing angle was set at 85 deg.

[0075] The quality of the coating surface, in particular the contour of the coating material, was evaluated by eye using a scale of 1 to 5. A value of 1 is equivalent to a very good contour of the coating; a value of 5 is equivalent to a poor coating contour, which is manifested in a surface that resembles an orange peel.

	Residual Gloss / %	Contour
Reference 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. Production of the Modifier ("Modifier 12")

[0076] 100 g of Si-H functional polysiloxane having the following average structure were placed into a 250 ml four necked flask with heater, internal thermometer, agitator, reflux cooler and protective gas outlet.

[see figure]

[0077] This silicone can be shown in a simple way by means of an equilibrium reaction, as described in Noll, "Chemistry and Technology of Silicones", Wiley/VCH Weinheim, 1984.

[0078] The silicone was heated under nitrogen to 70 deg. C. Then 10 ppm of hexachloroplatinic acid are added. Then 251 g of a poly(oxythylene) glycol-a-methyl-o-ally ether (Uniox PKA - 5009, NOF Europe) are added in such a manner that the reaction temperature does not exceed 80 deg. C. Thereafter, 73 g of vinyl trimethoxysilane (for example, Geniosil XL10, Wacker Chemie GmbH), are added. In so doing, it must be observed that the reaction temperature does not exceed 80 deg. C. Following the addition, the reaction mixture is stirred for one hour at 80 deg. C. Then a vacuum is applied; and approximately 2 g of unreacted vinyl trimethoxysilane and/or slightly volatile constituents of polysiloxane are removed by distillation. The product exhibits low viscosity and has a slightly amber-like coloration.

5. Production of the Nanoparticle Concentrate ("Nanoparticle Concentrate 12") and a corresponding Comparison

[0079] 40 g of nanoscaled aluminum oxide are placed into a kitchen mixer and treated with 4 g of modification reagent from the preceding production example ("modifier 12"). Then the mixture is homogenized for 1 minute. The powder, which is coated with the modification reagent, is heated for one hour at 80 deg. C. 40 g of the modified nanoparticles are stirred into a solution comprising 56.8 g of methoxypropyl acetate and 3.2 g of wetting and dispersing agents (BYK 9077, BYK Chemie GmbH) and then dispersed with ultrasound. The dispersion that is obtained in this way exhibits low viscosity and does not show any tendency to form a gel and/or sedimentation after 28 days of storage.

6. Application Example

[0080]

Ultraviolet Clear Coating

Component	Null Sample	Reference	Application Example 12
Sartomer SR-368 (isocyanurate triacylate)	27 g	27 g	27 g
Sartomer SR-494¹ (ethoxylated pentaerythritol tetraacylate)	9 g	9 g	9 g
Sartomer CD-501¹ (trimethylolpropane triacylate)	27 g	27 g	27 g
Sartomer SR-238¹ (1,6 hexanediol diacrylate)	27 g	27 g	27 g
Esacure KB1¹	5 g	5 g	5 g
Benzophenone	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 S.p.A. chemical specialties

[0081] The individual components of the clear coating are mixed together intensively and stored in a dark place at room temperature for a period of at least 12 hours.

[0082] The coatings were applied with a 25 mm spiral doctor blade on PVC plates and then vented for 15 minutes. The coatings were cured in a UV system. Altogether the coatings were treated twice with an irradiation intensity of 120 W/cm at a belt speed of 5.0 m/min.

[0083] After a storage period of three days the coated PVC plates were soiled with shoe polish of the tradename KIWI (KIWI brown). After 30 and 60 minutes and/or after 24 hours, the shoe polish was removed by hand with a dry cloth; and the tested spot was evaluated by eye.

Test Duration	Null Sample	Reference (only silicone)	Application Example 12
30 minutes	slightly soiled	extremely soiled	no soiling
60 minutes	extremely soiled. Coating is attacked.	extremely soiled	no soiling
24 hours	very extreme soiling. Coating is partially detached.	very extreme soiling. Coating is attacked.	No soiling

Patent Claims

1. Surface modified particles, in particular inorganic based particles having reactive groups, in particular hydroxyl groups, on their surface, and/or particles comprising or consisting of metal and/or semimetal oxides, hydroxides and/or oxide hydroxides, preferably nanoparticles, where the particles exhibiting on their surface a polysiloxane based modifier, in particular having been reacted on their surface with a polysiloxane based modifier, preferably with the formation of chemical bonds, in particular covalent bonds,

characterized in

that the modifier is a polysiloxane of the following general empirical formula (R¹_x R²_3-x SiR³)R⁴, where in the empirical formula

• x = 0 to 2 including the limits, in particular x = 0;

• y = 1 to 10 including the limits, in particular y = 2 to 5;

• R¹ = monovalent organic group, preferably having 1 to 18 carbon atoms, in particular 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms;

• R² = 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 group having 1 to 4 carbon atoms, in particular 2 carbon atoms;

• R³ = oxygen or at least bivalent organic group, containing or consisting of:

- a linear or branched, preferably linear alkylene group, in particular having 1 to 8 carbon atoms,

- an alkylene ether,

- an alkylene thio ether,

- an alkylene polyether, preferably on the basis of ethylene oxide, propylene oxide, butylene oxide or styrene oxide or mixtures of oxides or on the basis of a static or block polyether,

- an arylene polyether,

- an alkylene polyester or

- an organic aliphatic or aromatic or arylaliphatic group, in particular where the group contains not only ester and/or ether groups, but also urethane and/or urea groups;

• R⁴ = monovalent or polyvalent group containing or consisting of a polydialkyl siloxane having 4 to 200 Si units and having C₁ - C₁₈ alkyl groups at the silicon atoms, where the C₁ - C₁₈ alkyl groups are replaced and/or substituted to some extent and respectively independently of each other by one or more of the following modifying groups (G), preferably polaric modifying groups (G), selected from the following modifying groups (G1) to (G4), which are listed under (i) to (iv):

(i) (poly) ether groups-containing group (G1), in particular on the basis of at least one alkylene oxide,

(ii) polyester groups-containing group (G2),

(iii) arylalkyl groups-containing group (G3).

(iv) perfluorated alkyl groups-containing group (G4).

2. Surface modified particles, as claimed in claim 1, characterized in

• that the (poly) ether groups-containing group (G1), on the basis of at least one alkylene oxide of the general formula

[see figure]

where the group R¹ is a hydrogen atom, a phenyl group or an alkyl group, in particular an alkyl group having 1 to 4 carbon atoms, or is formed on the basis of a mixture of at least two of these alkylene oxides; and/or

• that the (poly) ether groups-containing group (G1) exhibits a molar mass in a range of 116 to 15,000 Dalton, preferably in a range of 160 to 4,000 Dalton, particularly preferred in a range of 250 to 2,500 Dalton; and/or

• that the ratio between the mass of poly(di)alkyl siloxane and that of the modifying group (G1) is in a range of 12 : 1 up to 0.07 to 1, preferably in a range of 2 : 1 up to 0.5 : 1.

3. Surface modified particles, as claimed in claim 1 or 2, characterized in

• that polyester groups-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 groups-containing group (G2) contains at least three groups

[see figure] and/or [see figure];

and/or

• that the polyester groups-containing group (G2) exhibits a molar mass in a range of 344 to 4,000 Dalton, preferably in a range of 500 to 2,000 Dalton, particularly preferred in a range of 500 to 1,500 Dalton; and/or

• that the ratio between the mass of poly(di)alkyl siloxane and that of the modifying group (G2) is in a range of 1 : 5 up to 1 : 0.05, preferably in a range of 1 : 2 up to 1 : 0.2.

4. Surface modified particles, as claimed in any one of the preceding claims, characterized in

that the arylalkyl groups-containing group (G3) is a phenylpropyl group, in particular a 2-phenylpropyl group, or a group containing this group.

5. Surface modified particles, as claimed in any one of the preceding claims, characterized in

that the perfluorated alkyl groups-containing group (G4) is a perfluorated alkyl group having 3 to 8 carbon atoms or a group containing this group; and/or that the perfluorated alkyl groups-containing group (G4) is 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.

6. Surface modified particles, in particular inorganic based particles having reactive groups, in particular hydroxyl groups, on their surface, and/or particles comprising or consisting of metal and/or semimetal oxides, hydroxides and/or oxide hydroxides, preferably nanoparticles, in particular as claimed in any one of the preceding claims, where the particles exhibiting on their surface a polysiloxane based modifier, in particular having been reacted on their surface with a polysiloxane based modifier, preferably with the formation of chemical bonds, in particular covalent bonds,

characterized in

that the modifier is a polysiloxane of the following general empirical formula (R¹_x R²_3-x SiR³)_yR⁴, where in the empirical formula

• x = 0 to 2 including the limits, in particular x = 0;

• y = 1 to 10 including the limits, in particular y = 2 to 5;

• R¹ = monovalent organic group, preferably having 1 to 18 carbon atoms, in particular 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms;

• R² = 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 group having 1 to 4 carbon atoms, in particular 2 carbon atoms;

• R³ = oxygen or at least bivalent organic group, containing or consisting of:

- a linear or branched, preferably linear alkylene group, in particular having 1 to 8 carbon atoms,

- an alkylene ether,

- an alkylene thio ether,

- an alkylene polyether, preferably on the basis of ethylene oxide, propylene oxide, butylene oxide or styrene oxide or mixtures of oxides or on the basis of a static or block polyether,

- an arylene polyether,

- an alkylene polyester or

- an organic aliphatic or aromatic or arylaliphatic group, in particular where the group contains not only ester and/or ether groups, but also urethane and/or urea groups;

• R⁴ = monovalent or polyvalent group containing or consisting of a polydialkyl siloxane having 4 to 200 Si units and having C₁ - C₁₈ alkyl groups at the silicon atoms, where the C₁ - C₁₈ alkyl groups are replaced and/or substituted to some extent and respectively independently of each other by one or more of the following modifying groups (G), preferably polaric modifying groups (G), selected from the following modifying groups (G1) to (G4), which are listed under (i) to (iv):

(i) (poly) ether groups-containing group (G1), in particular on the basis of at least one alkylene oxide, particularly preferred on the basis of at least one alkylene oxide of the general formula

[see figure]

in particular where the (poly) ether groups-containing group (G1) exhibits a molar mass in a range of 116 to 15,000 Dalton, preferably in a range of 160 to 4,000 Dalton, particularly preferred in a range of 250 to 2,500 Dalton; and/or

in particular, where the ratio between the mass of poly(di)alkyl siloxane and that of the modifying group (G1) is in a range of 12 : 1 up to 0.07 to 1, preferably in a range of 2 : 1 up to 0.5 : 1.

(ii) polyester groups-containing group (G2), selected from aliphatic and/or cycloaliphatic and/or aromatic polyester groups or groups, containing these groups, preferably with at least three groups

[see figure] and/or [see figure];

in particular where the polyester groups-containing group (G2) exhibits a molar mass in a range of 344 to 4,000 Dalton, preferably in a range of 500 to 2,000 Dalton, particularly preferred in a range of 500 to 1,500 Dalton; and/or in particular where the ratio between the mass of poly(di)alkyl siloxane and that of the modifying group (G2) is in a range of 1 : 5 up to 1 : 0.05, preferably in a range of 1 : 2 up to 1 : 0.2;

(iii) arylalkyl groups-containing group (G3), preferably phenylpropyl group, in particular a 2-phenylpropyl group, or a group containing this group;

(iv) perfluorated alkyl groups-containing group (G4), preferably perfluorated alkyl group having 3 to 8 carbon atoms; and/or tetrahydroperfluoroalkyl group, in particular a 1,1,2,2-tetrahydroperfluoroalkyl group, preferably having 3 to 8 carbon atoms, or a group containing this group.

7. Surface modified particles, as claimed in any one of the preceding claims, characterized in

that the modifier content is 0.01 to 50 % by wt., in particular 0.05 to 30 % by wt., preferably 0.1 to 15 % by wt., based on the total weight of the surface modified particles.

8. Surface modified particles, as claimed in any one of the preceding claims, characterized in

that the particles are inorganic based particles having reactive groups on their surface, in particular having silane reactive and/or siloxane reactive groups, preferably selected from the group of hydroxyl groups, halogen atoms and halogen atoms-containing groups, particularly preferred hydroxyl groups; and/or that the particles are inorganic based particles having hydroxyl groups on their surface.

9. Surface modified particles, as claimed in any one of the preceding claims, characterized in

that the particles comprise at least an oxide, hydroxide and/or oxide hydroxide of at least one metal or semimetal or mixtures or combinations of such compounds or contain these compounds, in particular comprise at least one oxide, hydroxide and/or oxide hydroxide of aluminum, silicon, zinc and/or titanium, or these compounds.

10. Surface modified particles, as claimed in any one of the preceding claims, characterized in

that the particles exhibit particle sizes, in particular determined by means of transmission electron microscopy, in a range of 0.1 to 1,000 nm, in particular 0.5 to 500 nm, preferably 1 to 350 nm, furthermore preferably 2 to 200 nm, particularly preferred below 100 nm, very particularly preferred below 50 nm.

11. Surface modified particles, as claimed in any one of the preceding claims, characterized in

that the particles are modified additionally with a silane of the general empirical formula R⁶_(4-x1) SiR⁵_x, where in the empirical formula

• x¹ = 1 to 3 including the limits,

• R⁵ = monovalent linear or branched or cyclic organic group having 1 to 18 carbon atoms, in particular 1 to 6 carbon atoms, especially preferred 1 to 3 carbon atoms;

• R⁶ = 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 group having 1 to 4 carbon atoms, preferably 2 carbon atoms.

12. Surface modified particles, as claimed in any one of the preceding claims, characterized in

that the particles are modified additionally with a silane of the general empirical formula R⁷_(4-x11) Si(R⁸-R⁹R¹⁰)_x11, where in the empirical formula

• x¹¹ = 1 to 3 including the limits,

• R⁷ = 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 group having 1 to 4 carbon atoms, preferably 2 carbon atoms.

• R⁸ = oxygen or at least divalent organic group containing or comprising:

- a linear or branched, preferably linear alkylene group, in particular having 1 to 8 carbon atoms,

- an alkylene ether,

- an alkylene thio ether,

- an alkylene polyether, preferably on the basis of ethylene oxide, propylene oxide, butylene oxide or styrene oxide or mixtures of oxides or on the basis of a static or block polyether,

- an arylene polyether,

- an alkylene polyester or

- an organic aliphatic or aromatic or arylaliphatic group, in particular where the group contains not only ester and/or ether groups, but also urethane and/or urea groups;

• R⁹ = divalent organic group, in particular having a molar mass in a range of 130 to 5,000 Dalton, containing or comprising:

- a polyether group, preferably containing or comprising 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 with at least three groups

[see figure] and/or [see figure];

• R¹⁰ = alkyl group or acetoxy group or a group -O-R¹¹, where R¹¹ is an alkyl group having 1 to 18 carbons atoms, or a group -O-CO-NH-R¹², where R¹² is an alkyl group having 1 to 18 carbon atoms.

13. Method for producing the surface modified particles, as claimed in any one of the claims 1 to 12, wherein the particles, in particular inorganic based particles having reactive groups, in particular hydroxyl groups, on their surface, and/or particles comprising or consisting of metal and/or semimetal oxides, hydroxides and/or oxide hydroxides, preferably nanoparticles, having been reacted with a polysiloxane based modifier, preferably with the formation of chemical bonds, in particular covalent bonds,

characterized in

that a polysiloxane of the following general empirical formula (R¹ R²_3-x, SiR³)_yR⁴ is used as the modifier, as defined in any one of the preceding claims.

14. Method, as claimed in claim 13, characterized in that the modifier is used in quantities of 0.01 to 50 % by wt., in particular 0.05 to 30 % by wt., preferably 0.1 to 15 % by wt., based on the total weight of the surface modified particles obtained.

15. Method, as claimed in claim 13 or 14, characterized in

that the particles are modified additionally with a silane of the general empirical formula R⁶_(4-x1) SiR⁵_x, as defined in claim 11.

16. Method, as claimed in any one of the claims 13 to 15, characterized in

that the particles are modified additionally with a silane of the general empirical formula R⁷_(4-x11) Si(R⁸-R⁹R¹⁰)_x11, as defined in claim 12.

17. Method, as claimed in any one of the claims 13 to 16, characterized in

that inorganic based particles having reactive groups, in particular hydroxyl groups, on their surface, are used as the particles; and/or that such particles comprising or consisting of at least one oxide, hydroxide and/or oxide hydroxide of at least one metal or semimetal or comprising and/or having mixtures or combinations of such compounds, in particular particles comprising and/or having at least one oxide, hydroxide and/or oxide hydroxide of aluminum silicon, zinc and/or titanium, are used as the particles, and/or that such particles comprising and/or having at least one inorganic salt, in particular phosphate, sulfate, halogenide and/or carbonate, optionally in a mixture with at least one metal and/or semimetal oxide, oxide hydroxide and/or hydroxide, are used as the particles.

18. Application of surface modified particles, as claimed in claims 1 to 12, as fillers.

19. Application of surface modified particles, as claimed in claims 1 to 12, in coating materials and coating systems, particular paints, inks and the like, in dispersions of all kinds, in plastics, in foams, in cosmetics, in particular nail varnishes, in adhesives, in sealants, etc.

20. Dispersions, containing surface modified particles, as claimed in claims 1 to 12, in a carrier or dispersion medium.

21. Coating materials and coating systems, in particular paints, inks and the like, plastics, foams, cosmetics, in particular nail varnishes, adhesives, and sealants, containing surface modified particles, as claimed in claims 1 to 12.

No Sheet of Drawings to follow.