EP2079664A2

EP2079664A2 - Method for the production of surface-modified, nanoparticulate metal oxides, metal hydroxides and/or metal oxyhydroxides

Info

Publication number: EP2079664A2
Application number: EP07821146A
Authority: EP
Inventors: Andrey Karpov; Hartmut Hibst; Jutta Kissel; Bernd Bechtloff; Hartwig Voss; Kerstin Schierle-Arndt; Valerie Andre
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2006-10-11
Filing date: 2007-10-10
Publication date: 2009-07-22
Also published as: US20100003203A1; WO2008043790A3; WO2008043790A2; CN101563294A; TW200827410A; JP2010505736A; KR20090094068A

Abstract

The present invention relates to methods for the production of surface-modified, nanoparticulate particles of at least one metal oxide, metal hydroxide and/or metal oxyhydroxide and of aqueous suspensions of said particles. The invention also relates to the surface-modified, nanoparticulate particles of at least one metal oxide, metal hydroxide and/or metal oxyhydroxide and to the aqueous suspensions of said particles which can be obtained by these methods and their use for cosmetic sunscreen preparations, as stabilisers in plastics and as active antimicrobial active substance.

Description

Process for the preparation of surface-modified nanoparticulate metal oxides, metal hydroxides and / or metal oxide hydroxides

description

The present invention relates to processes for the preparation of surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide and of aqueous suspensions of these particles. Furthermore, the invention relates to the surface-modified nanoparticulate particles obtainable by these processes of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide and aqueous suspensions of these particles and their use for cosmetic sunscreen preparations, as a stabilizer in plastics and as an antimicrobial agent.

Metal oxides are used for a variety of purposes, such. As a white pigment, as a catalyst, as part of antibacterial skin protection creams and as an activator for the rubber vulcanization. In cosmetic sunscreens there are finely divided zinc oxide or titanium dioxide as UV-absorbing pigments.

Nanoparticles are particles of the order of nanometers. Their size is in the transition region between atomic or monomolecular systems and continuous macroscopic structures. In addition to their usually very large surface, nanoparticles are characterized by particular physical and chemical properties, which differ significantly from those of larger particles. For example, nanoparticles often have a lower melting point, absorb light only at shorter wavelengths, and have different mechanical, electrical, and magnetic properties than macroscopic particles of the same material. By using nanoparticles as building blocks, many of these special properties can also be used for macroscopic materials (Winnacker / Kuchler, Chemical Engineering: Processes and Products, (Ed .: R. Dittmayer, W. Keim, G. Kreysa, A. Oberholz ), Vol. 2: New Technologies, Chapter 9, Wiley-VCH Verlag 2004).

In the context of the present invention, the term "nanoparticles" refers to particles having a mean diameter of from 1 to 500 nm, determined by means of electron microscopy methods.

Nanoparticulate zinc oxide with particle sizes below about 100 nm is potentially suitable for use as a UV absorber in transparent organic-inorganic hybrid materials, plastics, paints and coatings. In addition, it can also be used to protect UV-sensitive organic pigments.

Particles, particle aggregates or agglomerates of zinc oxide, which are greater than about 100 nm, lead to stray light effects and thus to an undesirable decrease Transparency in the field of visible light. Therefore, the redispersibility, ie the convertibility of the nanoparticulate zinc oxide produced into a colloidal disperse state, is an important prerequisite for the abovementioned applications.

Nanoparticulate zinc oxide with particle sizes below about 5 nm show a blue shift of the absorption edge due to the size quantization effect (L. Brus, J. Phys. Chem. (1986), 90, 2555-2560) and are therefore suitable for use as UV absorbers in UV -A area less suitable.

The production of finely divided metal oxides, for example of zinc oxide, by dry and wet processes is known. The classical incineration method of zinc, known as the dry process (eg, Gmelin volume 32, 8th Ed., Supplementary Volume, pp. 772 et seq.), Produces aggregated particles with a broad size distribution. Although it is fundamentally possible to produce particle sizes in the submicrometer range by means of grinding processes, dispersions having average particle sizes in the lower nanometer range can only be obtained from such powders with great difficulty by virtue of the shearing forces which can be achieved being too low. Particularly finely divided zinc oxide is mainly produced wet-chemically by precipitation processes. The precipitation in aqueous solution generally yields hydroxide and / or carbonate-containing materials which must be thermally converted to zinc oxide. The thermal aftertreatment has a negative effect on fineness, since the particles are subjected to sintering processes which lead to the formation of micrometer-sized aggregates, which can only be broken down to the primary particles by grinding in an incomplete manner.

Nanoparticulate metal oxides can be obtained, for example, by the microemulsion method. In this method, a solution of a metal alkoxide is added dropwise to a water-in-oil microemulsion. In the inverse micelles of the microemulsion, whose size is in the nanometer range, the hydrolysis of the alkoxides to the nanoparticulate metal oxide takes place. The disadvantages of this method are, in particular, that the metal alkoxides are expensive starting materials, that in addition emulsifiers must be used and that the preparation of the emulsions with droplet sizes in the nanometer range represents a complex process step.

DE 199 07 704 describes a nanoparticulate zinc oxide prepared by a precipitation reaction. Here, the nanoparticulate zinc oxide is prepared starting from a zinc acetate solution via an alkaline precipitation. The centrifuged zinc oxide can be redispersed by addition of methylene chloride to a sol. The zinc oxide dispersions prepared in this way have the disadvantage that they have no good long-term stability owing to the lack of surface modification. In WO 00/50503 zinc oxide gels are described which contain nanoparticulate zinc oxide with a particle diameter of <15 nm and which are redispersible to sols. Here, the solids produced by basic hydrolysis of a zinc compound in alcohol or in an alcohol / water mixture are redispersed by the addition of dichloromethane or chloroform. The disadvantage here is that no stable dispersions are obtained in water or in aqueous dispersants.

In the publication from Chem. Mater. 2000, 12, 2268-74 "Synthesis and Characterization of Poly (vinylpyrrolidones) - Modified Zinc Oxide Nanoparticles" by Lin Guo and Shihe Yang, zinc oxide nanoparticles are surface-coated with polyvinylpyrrolidone. The disadvantage here is that coated with polyvinylpyrrolidone zinc oxide particles are not dispersible in water.

WO 93/21127 describes a process for producing surface-modified nanoparticulate ceramic powders. Here, a nanoparticulate ceramic powder is surface-modified by applying a low molecular weight organic compound, for example, propionic acid. This method can not be used for the surface modification of zinc oxide since the modification reactions are carried out in aqueous solution and zinc oxide dissolves in aqueous organic acids. Therefore, this method can not be used for the production of

Use zinc oxide dispersions; Moreover, zinc oxide in this application is also not mentioned as a possible starting material for nanoparticulate ceramic powders.

In WO 02/42201 a process for the preparation of nanoparticulate metal oxides is described, in which dissolved metal salts are thermally decomposed in the presence of surfactants. The decomposition takes place under conditions under which the surfactants micelles, in addition, depending on the selected metal salt may require temperatures of several hundred degrees Celsius to achieve the decomposition. The process is therefore very complex in terms of apparatus and energy.

In a publication in Materials Letters 57 (2003), pp. 4079-4082, P. Si et al. the production of nanoparticulate zinc oxide rods by co-grinding of solid zinc acetate with sodium hydroxide in the presence of polyethylene glycol as a nonionic dispersant. However, the process is too laborious for industrial application and the components are not mixed together as homogeneously as when starting from a solution.

In the publication in Inorganic Chemistry 42 (24), 2003, p. 8105-9, Z. Li et al. a process for preparing nanoparticulate zinc oxide rods by hydro-thermal treatment of [Zn (OH) ₄ ] ² "complexes in an autoclave in the presence of polyethylene glycol. The habit of the products makes them unsuitable for applications on the skin.

WO 2004/052327 describes surface-modified nanoparticulate zinc oxides in which the surface modification comprises a coating with an organic acid. DE-A 10 2004 020 766 discloses surface-modified nanoparticulate metal oxides prepared in the presence of polyaspartic acid. EP 1455737 describes surface-modified nanoparticulate zinc oxides in which the surface modification comprises a coating with an oligo- or polyethylene glycol acid. Due to the acids used, these products are not suitable for cosmetic applications as they may only be poorly tolerated by the skin.

It is an object of the present invention to provide surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide and their aqueous suspensions, the substances used for surface modification with regard to cosmetic applications, especially in the field of UV protection should have good skin compatibility and are ideally already tested and approved as components of cosmetic preparations. Another object of the invention was the development of processes for the preparation of these surface-modified nanoparticulate particles and their aqueous suspensions and for their use.

This object is achieved by surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide which are precipitated from a solution in the presence of a nonionic dispersant.

The invention thus provides a process for preparing surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide, where the metal or metals are selected from the group consisting of aluminum, magnesium, cerium, iron, manganese, cobalt, Nickel, copper, titanium, zinc and zirconium, comprising the steps

a) Preparation of a solution of water and at least one metal salt of the abovementioned metals (solution 1) and a solution of water and at least one strong base (solution 2), wherein at least one of the two solutions 1 and 2 contains at least one nonionic dispersant whose chemical structure comprising between 2 and 10,000 -CH 2 CH 2 O- groups,

b) mixing the solutions 1 and 2 prepared in step a) at a temperature in the range from 0 to 120 ^° C., wherein the surface-modified nanoparticulate ren particles and precipitate out to form an aqueous suspension of the solution,

c) separating the surface-modified nanoparticulate particles from the aqueous suspension obtained in step b), and

d) drying of the surface-modified nanoparticulate particles obtained in step c).

The metal oxide, metal hydroxide and metal oxide hydroxide may be both the anhydrous compounds and the corresponding hydrates.

The metal salts in process step a) may be metal halides, acetates, sulfates or nitrates or hydrates of the salts mentioned. Preferred metal salts are halides, for example zinc chloride or titanium tetrachloride, acetates, for example zinc acetate dihydrate and nitrates, for example zinc nitrate. A particularly preferred metal salt is zinc chloride or zinc nitrate.

The concentration of the metal salts in the solution 1 is generally in the range of 0.05 to 1 mol / l, preferably in the range of 0.1 to 0.5 mol / l, particularly preferably 0.2 to 0.4 mol / l

The strong bases to be used according to the invention may generally be any substances capable of having a pH in aqueous solution of from about 8 to about 13, preferably from about 9 to about 12, depending on their concentration. 5 to produce. These may be, for example, metal oxides or hydroxides as well as ammonia or amines. Preference is given to using alkali metal hydroxides such as sodium or potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide or ammonia. Particular preference is given to using sodium hydroxide, potassium hydroxide and ammonia. In a preferred embodiment of the invention, ammonia can also be formed by thermal decomposition of urea in situ during process steps a) and / or b).

The concentration of the strong base in the solution 2 prepared in process step a) is generally selected so that in the solution 2 a Hydroxylionenkon- concentration in the range of 0.1 to 2 mol / l, preferably from 0.2 to 1 mol / l and more preferably from 0.4 to 0.8 mol / l. Preferably, the hydroxyl ion concentration in solution 2 (c (OH-)) is chosen as a function of the concentration and the valence of the metal ions in the solution 1 (c (M ^{n +} )), so that they have the formula

n • c (Mn ⁺ ) = c (OH-) where c is a concentration and M ^{n + is} at least one metal ion of valency n. For example, in a solution 1 having a concentration of divalent metal ions of 0.2 mol / l, a solution 2 having a hydroxyl ion concentration of 0.4 mol / l is preferably used.

The nonionic dispersants according to the invention are surface-active substances whose chemical structure comprises between 2 and 10,000 -CH 2 CH 2 O- groups, preferably between 3 and 200 -CH 2 CH 2 O- groups. These groups are formed, for example, by addition of a corresponding number of ethylene oxide molecules to hydroxyl- or carboxyl-containing substrates and usually form one or more contiguous ethylene glycol chains, the chemical structure of the formula - (- CH 2 CH 2 θ-) _n - with n from about 2 to about 80 corresponds.

In a preferred embodiment of the invention, the nonionic dispersant used is at least one substance from one of the following groups:

Addition products of 2 to 80 moles of ethylene oxide and optionally 1 to 15 moles of propylene oxide with linear fatty alcohols having 8 to 22 carbon atoms (eg cetylstearyl alcohol), fatty acids having 12 to 22 carbon atoms,

Alkylphenols having 8 to 15 carbon atoms in the alkyl group,

Glycerol mono- and diesters, sorbitol mono- and diesters and sorbitan mono- and

-diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms, - alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl radical,

Castor oil and / or hydrogenated castor oil,

Partial esters based on linear, branched, unsaturated or saturated fatty acids having 12 to 22 carbon atoms,

Ricinoleic acid, 12-hydroxystearic acid,

Acetic acid,

Lactic acid,

glycerin,

Polyglycerol, - pentaerythritol,

dipentaerythritol,

sucrose,

Sugar alcohols (eg sorbitol),

Alkyl glucosides (eg methyl glucoside, butyl glucoside, lauryl glucoside), - polyglucosides (eg cellulose),

Wool wax alcohols having 24 to 36 carbon atoms,

Guerbet alcohols with 6 to 22 carbon atoms, as well Polyalkylene glycols whose structure comprises between 2 and 80 ethylene glycol units.

In a particularly preferred embodiment of the invention, at least one substance from one of the following groups is used as the nonionic dispersant:

Addition products of 2 to 80 moles of ethylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, - alkylphenols having 8 to 15 carbon atoms in the alkyl group, as well as castor oil (Ricinusöl) and / or hydrogenated castor oil.

Many of the present invention to be used non-ionic dispersants are under the brand name Cremophor ^® (Fa. BASF Aktiengesellschaft) Avail- borrowed commercially.

The ethylene oxide addition products can always also contain a small proportion of the above-listed free hydroxyl or carboxyl groups-containing substrates in technical quality. In general, this proportion is less than 20 wt .-%, preferably less than 5 wt .-%, based on the total amount of the dispersant.

The concentration of the nonionic dispersants in the solutions 1 and / or 2 prepared in process step a) is generally in the range from 0.1 to 20 g / l, preferably from 1 to 10 g / l, particularly preferably from 1 to 5 5 g / l.

A preferred embodiment of the process according to the invention is characterized in that the precipitation of the metal oxide, metal hydroxide and / or metal oxide hydroxide takes place in the presence of a nonionic dispersant which is obtained by reacting hydrogenated castor oil or fatty alcohols with about 35 to about 50 equivalents of ethylene oxide. In a particularly preferred embodiment of the invention Cremophor ^® CO 40 (Fa. BASF Aktiengesellschft), an addition product of 40 equivalents of ethylene oxide with hydrogenated castor oil or Cremophor ^® A 25 is (Fa. BASF Aktiengesellschaft), an addition product of 25 equivalents of ethylene oxide with cetyl stearyl alcohol , used as a nonionic dispersant.

The mixing of the two solutions 1 and 2 (aqueous metal salt solution and aqueous base solution) in process step b) takes place at a temperature in the range from 0 ^° C. to 120 ^° C., preferably in the range from 10 ^° C. to 100 ^° C., more preferably in the range from 15 ° C to 80 ° C. Depending on the metal salts used, mixing may be carried out at a pH in the range of 3 to 13. In the case of zinc oxide, the pH during mixing is in the range of 7 to 11.

The time for the mixing of the two solutions in process step b) according to the invention is in the range of 1 second to 6 hours, preferably in the range of 1 minute to 2 hours. In general, the mixing time is longer with discontinuous driving than with continuous driving.

The mixing in process step b) can be carried out, for example, by combining an aqueous solution of a metal salt, for example zinc chloride or zinc nitrate, with an aqueous solution of a mixture of a nonionic dispersant and an alkali metal hydroxide or ammonium hydroxide, in particular sodium hydroxide. Alternatively, an aqueous solution of a mixture of a nonionic dispersant and a metal salt, such as zinc chloride or zinc nitrate, may be combined with an aqueous solution of an alkali metal hydroxide or ammonium hydroxide, especially sodium hydroxide. Furthermore, an aqueous solution of a mixture of a nonionic dispersant and a metal salt, for example of zinc chloride or zinc nitrate, with an aqueous solution of a mixture of a nonionic dispersant and an alkali metal hydroxide or ammonium hydroxide, in particular sodium hydroxide, can be combined.

In a preferred embodiment of the invention, the mixing in process step b) is carried out by adding an aqueous solution of a mixture of a nonionic dispersant and an alkali metal hydroxide or ammonium hydroxide, in particular sodium hydroxide, to an aqueous solution of a metal salt, for example of zinc chloride or zinc nitrate, or Addition of an aqueous solution of an alkali metal hydroxide or ammonium hydroxide, in particular sodium hydroxide, to an aqueous solution of a mixture of a nonionic

Dispersant and a metal salt, such as zinc chloride or zinc nitrate.

During mixing or after mixing, the surface-modified nanoparticulate particles are formed, which precipitate out of the solution to form an aqueous suspension. Preferably, the mixing is carried out while stirring the mixture. After complete union of the two solutions 1 and 2, the stirring is preferably continued for a time between 30 minutes and 5 hours at a temperature in the range of 0 ⁰ C to 120 ⁰ C.

A further preferred embodiment of the method according to the invention is characterized in that at least one of the method steps a) to d) is carried out continuously. be performed. In continuous operation, the process step b) is preferably carried out in a tubular reactor.

Preferably, the continuous process is carried out in the form that the mixing in step b) takes place in a first reaction space at a temperature T1 in which an aqueous solution 1 of at least one metal salt and an aqueous solution 2 of at least one strong base are introduced continuously at least one of the two solutions 1 and 2 contains at least one nonionic dispersant whose chemical structure comprises between 2 and 10,000 -CH 2 CH 2 O- groups from which the suspension formed is continuously removed and transferred to a second reaction space for temperature control at a temperature T2, wherein the surface-modified nanoparticulate particles form.

As a rule, the continuous process is carried out in such a way that the temperature T2 is higher than the temperature T1.

The processes described in the introduction are particularly suitable for the preparation of surface-modified nanoparticulate particles of titanium dioxide and zinc oxide, in particular of zinc oxide. In this case, the precipitation of the surface-modified nanoparticulate particles of zinc oxide from an aqueous solution of zinc acetate, zinc chloride or zinc nitrate takes place at a pH in the range of 8 to 13 in the presence of a nonionic dispersant.

A further advantageous embodiment of the process according to the invention is characterized in that the surface-modified nanoparticulate particles of a metal oxide, metal hydroxide and / or metal oxide hydroxide, in particular of zinc oxide, have a BET surface area in the range from 25 to 500 m ² / g, preferably from 30 to 400 m ² / g, more preferably 40 to 300 m ² / g.

The invention is based on the finding that, by surface modification of nanoparticulate metal oxides, metal hydroxides and / or metal oxide hydroxides with nonionic dispersants, long-term stability of dispersions of the surface-modified nanoparticulate metal oxides, in particular in cosmetic preparations, without undesired changes in the pH during storage of these preparations is achieved can be.

The separation of the precipitated particles from the aqueous suspension in process step c) can be carried out in a manner known per se, for example by filtration or centrifugation. If necessary, prior to isolation of the precipitated particles, the aqueous dispersion may be applied by a membrane process such as nano-, ultra-,

Concentrated by micro- or cross-flow filtration and optionally of unwanted water-soluble components, for example alkali metal salts such as sodium chloride or sodium nitrate, are at least partially freed.

It has proved to be advantageous to carry out the removal of the surface-modified nanoparticulate particles from the aqueous suspension obtained in step b) at a temperature in the range from 10 to 50 ^° C., preferably at room temperature. It is therefore advantageous to optionally cool the aqueous suspension obtained in step b) to such a temperature.

In process step d), the resulting filter cake can be dried in a conventional manner, for example in a drying oven at temperatures between 40 and 100 ⁰ C, preferably between 50 and 80 ⁰ C under atmospheric pressure to constant weight.

A further subject of the present invention are surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide, where the metal or metals are selected from the group consisting of aluminum, magnesium, cerium, iron, manganese, cobalt, Nickel, copper, titanium, zinc and zirconium, and the surface modification comprises a coating with at least one nonionic dispersant, obtainable by the process described in the introduction.

The present invention furthermore provides surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide, in particular of zinc oxide, the surface modification comprising a coating with a nonionic dispersant having a BET surface area in the range from 25 to 500 m ² / g, preferably 30 to 400 m ² / g, particularly preferably 40 to 300 m ² / g.

According to a preferred embodiment of the invention, the surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide are coated with a nonionic dispersant which is an adduct of from 2 to 80 moles of ethylene oxide with linear fatty alcohols containing from 8 to 22 carbon atoms, alkylphenols with 8 to 15 carbon atoms in the alkyl group or castor oil and / or hydrogenated castor oil.

According to a further preferred embodiment of the present invention, the surface-modified nanoparticulate particles have a diameter of from 10 to 200 nm. This is particularly advantageous since good redispersibility is ensured within this size distribution. According to a particularly preferred embodiment of the present invention, the surface-modified nanoparticulate particles have a diameter of 20 to 100 nm. This size range is particularly advantageous because, for example, after redispersion of such zinc oxide nanoparticles, the resulting suspensions are transparent and thus do not influence the coloring when added to cosmetic formulations. In addition, this results in the possibility for use in transparent films.

Another object of the present invention is the use of surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide, in particular titanium dioxide or zinc oxide, which are prepared by the process according to the invention, as a UV protective agent in cosmetic sunscreen preparations, as a stabilizer in plastics and as an antimicrobial agent.

According to a preferred embodiment of the present invention, the surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide, in particular titanium dioxide or zinc oxide, are redispersible in a liquid medium and form stable suspensions. This is particularly advantageous because, for example, the suspensions prepared from the zinc oxide according to the invention need not be redispersed before further processing, but can be processed directly.

According to a preferred embodiment of the present invention, the surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide are redispersible in polar organic solvents and form stable suspensions. This is particularly advantageous, since this uniform incorporation, for example, in plastics or films is possible.

According to another preferred embodiment of the present invention, the surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide are redispersible in water and form stable suspensions there. This is particularly advantageous, since this opens up the possibility of using the material according to the invention, for example in cosmetic formulations, wherein the omission of organic solvents represents a great advantage. Also conceivable are mixtures of water and polar organic solvents.

Since numerous applications of the surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide according to the invention require their use in the form of an aqueous suspension, their isolation as a solid may optionally be dispensed with. A further subject of the present invention is therefore a process for preparing an aqueous suspension of surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide, where the metal or metals are selected from the group consisting of aluminum, magnesium, cerium, iron, Manganese, cobalt, nickel, copper, titanium, zinc and zirconium, comprising the steps

b) mixing the solutions 1 and 2 prepared in step a) at a temperature in the range from 0 to 120 ^° C., whereby the surface-modified nanoparticulate particles are formed and precipitate out of the solution to form an aqueous suspension, and

c) optionally concentrating the aqueous suspension formed and / or separating by-products.

With regard to a more detailed description of the implementation of method steps a) and b) and of the starting materials and process parameters used, reference is made to the remarks made above.

If necessary, the aqueous suspension formed in step b) can be concentrated in process step c), for example if a higher solids content is desired. The concentration can be carried out in a manner known per se, for example by distilling off the water (at atmospheric pressure or at reduced pressure), filtering or centrifuging.

Furthermore, it may be necessary to separate by-products from the aqueous suspension formed in step b) in process step c), namely, if these would interfere with the further use of the suspension. Suitable by-products are primarily salts dissolved in water which are formed in the inventive reaction between the metal salt and the strong base in addition to the desired metal oxide, metal hydroxide and / or metal oxide hydroxide particles, for example sodium chloride, sodium nitrate or ammonium chloride. Such by-products can be largely removed from the aqueous suspension, for example by means of a membrane process such as nano-, ultra-, micro- or cross-flow filtration. A further preferred embodiment of the method according to the invention is characterized in that at least one of the method steps a) to c) are carried out continuously.

A further subject of the present invention are aqueous suspensions of surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide, wherein the metal or metals are selected from the group consisting of aluminum, magnesium, cerium, iron, manganese, cobalt, nickel, Copper, titanium, zinc and zirconium, and the surface modification comprises a coating with at least one nonionic dispersant obtainable by the method described above.

According to a preferred embodiment of the invention, the surface-modified nanoparticulate particles in the aqueous suspensions are coated with a nonionic dispersant which is an adduct of from 2 to 80 moles of ethylene oxide with linear fatty alcohols containing from 8 to 22 carbon atoms and alkylphenols with 8 to 15 carbon atoms in the alkyl group or castor oil and / or hydrogenated castor oil.

Another object of the present invention is the use of aqueous suspensions surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide, in particular titanium dioxide or zinc oxide, which are prepared by the process according to the invention, as UV protectants in cosmetic sunscreen preparations, as a stabilizer in synthetic materials and as an antimicrobial agent.

The invention will be explained in more detail with reference to the following examples.

example 1

Preparation of nanoparticulate zinc oxide in the presence of Cremophor ^® CO 40 (adduct of 40 equivalents of ethylene oxide with hydrogenated castor oil)

Two aqueous solutions 1 and 2 were first prepared. Solution 1 contained 27.26 g of zinc chloride per liter and had a zinc ion concentration of 0.2 mol / l. In addition, the Solution 1 contained 4 g / l of Cremophor ^® CO 40th

Solution 2 contained 16 g of sodium hydroxide per liter and thus had a hydroxyl ion concentration of 0.4 mol / l.

In a glass reactor with a total volume of 12 I 4 l of the solution 1 were initially charged and stirred (250 rpm). In the stirred solution were with an HPLC pump (Knauer, type K 1800, pump head 1000 ml / min) 4 l of the solution 2 within 6 minutes at room temperature. This formed a white suspension in the glass reactor.

Immediately after completion of the metering, a suspension flow of 0.96 l / min was pumped from the suspension obtained via a riser pipe by means of a gear pump (Gather Industrie GmbH, D-40822 Mettmann) and heated to a temperature in a downstream heat exchanger within 1 minute heated to 85 ° C. The suspension obtained then passed through a second heat exchanger, in which the suspension was kept at 85 ° C. for a further 30 seconds. The suspension subsequently passed through a third and fourth heat exchanger in succession, in which the suspension was cooled to room temperature within a further minute.

The freshly prepared suspension was dissolved in a crossflow ultrafiltration

Laboratory equipment (Sartorius, type SF Alpha, PES cassette, cut off 100 kD) thickened by a factor of 15. Subsequent isolation of the solid powder was carried out using an ultracentrifuge (Sigma 3K30, 20,000 rpm, 40.700g) with subsequent drying at 50 ⁰ C.

In the UV-VIS spectrum, the powder obtained had the absorption band characteristic of zinc oxide at about 350-360 nm. In line with this, the X-ray diffraction of the powder showed only the diffraction reflections of hexagonal zinc oxide. From the half-width of the X-ray reflections a crystallite size was calculated, which lies between 16 nm [for the (102) -reflex] and 57 nm [for the (002) -reflex]. In the transmission electron microscopy (TEM), the obtained powder had an average particle size of 50 to 100 nm.

Example 2

Continuous preparation of nanoparticulate zinc oxide in the presence of Cre mophor ^® CO 40 (adduct of 40 equivalents of ethylene oxide with hydrogenated castor oil)

In a glass reactor with a total volume of 8 I 5 l of water at a temperature of 25 ° C were added and this stirred at a speed of 250 rpm. With further stirring, solutions 1 and 2 from Example 1 were pumped into the water reservoir via two separate inlet tubes, each at a metering rate of 0.48 l, using two HPLC pumps (Knauer, type K 1800, pump head 500 ml / min) / metered in continuously. This formed a white suspension in the glass reactor. At the same time, a suspension tube was removed from the glass reactor via a riser pipe by means of a gear pump (Gather Industrie GmbH, D-40822 Mettmann). pumped from 0.96 l / min and heated in a downstream heat exchanger to a temperature of 85 ° C within 1 minute. The suspension obtained then passed through a second heat exchanger, in which the suspension was kept at 85 ° C. for a further 30 seconds. Thereafter, the suspension successively passed through a third and fourth heat exchanger, in which the suspension was cooled to room temperature within a further minute.

The freshly prepared suspension was thickened by the factor 15 in a crossflow ultrafiltration laboratory system (Sartorius, type SF Alpha, PES cassette, cut off 100 kD). Subsequent isolation of the solid powder was carried out using an ultracentrifuge (Sigma 3K30, 20,000 rpm, 40.700g) with subsequent drying at 50 ⁰ C.

In the UV-VIS spectrum, the resulting powder exhibited the absorption band characteristic of zinc oxide at about 350-360 nm. In line with this, the X-ray diffraction of the powder showed only the diffraction reflections of hexagonal zinc oxide. From the half-width of the X-ray reflections, the crystallite size was calculated to be between 16 nm [for the (102) reflection] and 57 nm [for the (002) reflection]. In the transmission electron microscopy (TEM), the obtained powder had an average particle size of 50 to 100 nm.

Example 3

Preparation of nanoparticulate zinc oxide in the presence of Cremophor ^® A 25 (AnIa- delay product of 25 equivalents of ethylene oxide with cetyl stearyl alcohol)

Two aqueous solutions 1 and 2 were first prepared. Solution 1 contained 27.26 g of zinc chloride per liter and had a zinc ion concentration of 0.2 mol / l. In addition, the solution contained 1 4 g / l of Cremophor ^® A 25th

In a glass reactor with a total volume of 12 l 4 l of the solution 1 were presented and stirred (250 rpm). 4 l of the solution 2 were metered into the stirred solution with an HPLC pump (Knauer, type K 1800, pump head 1000 ml / min) within 6 minutes at room temperature. This formed a white suspension in the glass reactor.

Immediately after completion of the metering, a suspension flow of 0.96 l / min was pumped out of the suspension obtained via a riser pipe by means of a gear pump (Gather Industrie GmbH, D-40822 Mettmann) and discharged in a downstream Heat exchanger heated to a temperature of 85 ° C within 1 minute. The suspension obtained then passed through a second heat exchanger, in which the suspension was kept at 85 ° C. for a further 30 seconds. The suspension subsequently passed through a third and fourth heat exchanger in succession, in which the suspension was cooled to room temperature within a further minute.

In the UV-VIS spectrum, the resulting powder exhibited the absorption band characteristic of zinc oxide at about 350-360 nm. In line with this, the X-ray diffraction of the powder showed only the diffraction reflections of hexagonal zinc oxide. From the half-width of the X-ray reflections a crystallite size was calculated, which lies between about 15 nm [for the (102) -reflex] and about 60 nm [for the (002) -reflex]. In the transmission electron microscopy (TEM), the obtained powder had an average particle size of 50 to 100 nm.

Example 4

Continuous production of zinc oxide in the presence of Cre nanopertikulärem mophor ^® A 25 (adduct of 25 equivalents of ethylene oxide with Cetylsteary- lalkohol)

In a glass reactor with a total volume of 8 I 5 l of water at a temperature of 25 ° C were added and this stirred at a speed of 250 rpm. With further stirring, the solutions 1 and 2 from Example 1 by means of two HPLC pumps (Knauer, type K 1800, pump head 500 ml / min) via two separate inlet tubes into the water reservoir each with a dosing of 0.48 l / min continuously metered. This formed a white suspension in the glass reactor. At the same time, a suspension flow of 0.96 l / min was pumped out of the glass reactor via a riser pipe by means of a gear pump (Gather Industrie GmbH, D-40822 Mettmann) and within a minute to a temperature of 85 ° in a downstream heat exchanger C heated. The suspension obtained then passed through a second heat exchanger, in which the suspension was kept at 85 ° C. for a further 30 seconds. Thereafter, the suspension successively passed through a third and fourth heat exchanger, in which the suspension was cooled to room temperature within a further minute. The freshly prepared suspension was thickened by a factor of 15 in a crossflow ultrafiltration laboratory system (Sartorius, type SF Alpha, PES cassette, cut off 100 kD). Subsequent isolation of the solid powder was carried out using an ultracentrifuge (Sigma 3K30, 20,000 rpm, 40.700g) with subsequent drying at 50 ⁰ C.

In the UV-VI S spectrum, the resulting powder exhibited the characteristic absorption band for zinc oxide at about 350-360 nm. In line with this, the X-ray diffraction of the powder showed only the diffraction reflections of hexagonal zinc oxide. From the half-width of the X-ray reflections a crystallite size was calculated, which lies between about 15 nm [for the (102) -reflex] and about 60 nm [for the (002) -reflex]. In the transmission electron microscopy (TEM), the obtained powder had an average particle size of 50 to 100 nm.

Example 5

Batch Preparation of nanoparticulate zinc oxide in the presence of Cre mophor ^® A 25 (adduct of 25 equivalents of ethylene oxide with Cetylsteary- lalkohol)

1000 ml of a 0.4M solution of zinc nitrate were heated with stirring to 40 ⁰ C. Within 6 minutes, 1000 ml of a likewise heated to 40 ° C 0.8M sodium hydroxide solution containing an additional 4 g / l Cremophor ^® A 25, dosed and stirred for a further 2 hours. The precipitated, surface-modified product was filtered off, washed with water and the filter cake dried at 80 ⁰ C in a drying oven. In the UV-VIS spectrum, the powder obtained had the absorption band characteristic of zinc oxide at about 350-360 nm. In line with this, the X-ray diffraction of the powder showed only the diffraction reflections of hexagonal zinc oxide. From the half-width of the X-ray reflections a crystallite size was calculated which lies between 15 nm [for the (102) reflection] and 42 nm [for the (002) reflection]. In the transmission electron microscopy (TEM), the obtained powder had an average particle size of 50 to 100 nm.

Example 6

Batch Preparation of nanoparticulate zinc oxide in the presence of Cremophor ^® A 25 (adduct of 25 equivalents of ethylene oxide with Cetylsteary- lalkohol)

1000 ml of a 0.4M zinc nitrate solution, which additionally contained 2 g / l of Cremophor A 25, were heated to 40 ^° C. with stirring. Within 6 minutes 1000 ml of a likewise heated to 40 ⁰ C 0.8M sodium hydroxide solution, the additional 2 g / l Cremophor ^® A 25, were metered in and stirred for a further 2 hours. The precipitated, surface-modified product was filtered off, washed with water and the filter cake dried at 80 ⁰ C in a drying oven. In the UV-VIS spectrum, the powder obtained had the absorption band characteristic of zinc oxide at about 350-360 nm. In line with this, the X-ray diffraction of the powder showed only the diffraction reflections of hexagonal zinc oxide. From the half-width of the X-ray reflections, the crystallite size was calculated to be between 17 nm [for the (102) reflection] and 45 nm [for the (002) reflection]. In the transmission electron microscopy (TEM), the obtained powder had an average particle size of 40 to 80 nm.

Example 7

Use of nanoparticulate zinc oxide, prepared according to Example 1, for the preparation of a sunscreen lotions containing 5% by weight of zinc oxide

% Ingredients INCI

A 7.50 Uvinul MC 80 ethylhexyl methoxycinnamate

1, 50 Tween 20 polysorbate-20

3.00 Pationic 138 C sodium lauroyl lactylate

1, 00 Cremophor CO 40 PEG-40 Hydrogenated Castor OiI

1, 00 Cetiol SB 45 Butyrospermum Parkii (Shea Butter)

6.50 Finsolv TN C12-15 alkyl benzoates

B 5.00 Zinc oxide from example 1 Zinc Oxide

C 4.00 Glycerin 87% Glycerol

1, 00 D-panthenol 50 P panthenol, propylene glycol

0.30 Keltrol Xanthan gum

0.10 Edeta BD Disodium EDTA

2.00 Urea Urea

2.00 Simulgels NS Hydroxyethyl Acrylates / Sodium Acryloyldimethyl Taurate Copolymer, Squalane, Polysorbate 60

64.10 Water. Aqua the.

D 0.50 Lactic Acid Lactic Acid

0.50 Euxyl K 300 phenoxyethanol, methylparaben, butylparaben, ethylparaben, propylparaben, isobutylparaben

The phase A is heated to 80 ⁰ C, then the phase B is added, the mixture is homogenized for 3 minutes. Separately, phase C is heated to 80 ° C and stirred into the mixture of phases A and B. The mixture is cooled to 40 ⁰ C while stirring, then the phase D is added. The lotion is briefly posthumogenised. Example 8

Preparation of nanoparticulate zinc oxide in the presence of Cremophor ^® CO 40 (check-storage product of 40 equivalents of ethylene oxide with hydrogenated castor oil)

Two aqueous solutions 1 and 2 were first prepared. Solution 1 contained 54.52 g zinc chloride per liter and had a zinc ion concentration of 0.4 mol / l. In addition, the Solution 1 contained 4 g / l of Cremophor ^® CO 40th

The solution 2 contained 32 g of sodium hydroxide per liter and thus had a hydroxyl ion concentration of 0.8 mol / l.

Immediately after completion of dosing (Gather Industrie GmbH, D-40822 Mettmann Fa.) Was obtained from the obtained suspension through a riser pipe by means of a gear pump pumped a suspension flow of 0.96 l / min and preheated to 85 ⁰ C heat exchanger with a volume of 0.96 I transferred. The heat exchanger is preheated to the desired temperature with hot water before use. The suspension subsequently passed through a second and third heat exchanger in succession, in which the suspension was cooled to room temperature within a further minute.

The freshly prepared suspension was washed in a crossflow ultrafiltration laboratory equipment (Sartorius, type SF Alpha, PES cassette, cut off 100 kD) and thickened by a factor of 15. Subsequent isolation of the solid powder was carried out using an ultracentrifuge (Sorvall RC 6, Fa. Thermo Electron Corporation, 13000 rpm) with subsequent drying at 80 ⁰ C.

In the UV-VIS spectrum, the powder obtained had the absorption band characteristic of zinc oxide at about 350-360 nm. In the transmission electron microscopy (TEM), the obtained powder had an average particle size of 50 to 100 nm. Example 9

Two aqueous solutions 1 and 2 were first prepared. Solution 1 contained 54.52 g zinc chloride per liter and had a zinc ion concentration of 0.4 mol / l. Furthermore, the solution 1 still contained 8 g / l of Cremophor ^® CO 40th

In a glass reactor with a total volume of 12 I 4 l of the solution 1 were initially charged and stirred (250 rpm). 4 l of the solution 2 were metered into the stirred solution with an HPLC pump (Knauer, type K 1800, pump head 1000 ml / min) within 6 minutes at room temperature. This formed a white suspension in the glass reactor.

Immediately after completion of dosing (Gather Industrie GmbH, 40822 Mettmann Fa.) Was obtained from the obtained suspension through a riser pipe by means of a gear pump pumped a suspension flow of 0.96 l / min and preheated to 85 ⁰ C heat exchanger with a volume of 0 , 96 I transferred. The heat exchanger is preheated to the desired temperature with hot water before use. Subsequently, the suspension flowed through a second and third heat exchanger in succession, in which the suspension was cooled to room temperature within a further minute.

The freshly prepared suspension was washed in a crossflow ultrafiltration laboratory system (Sartorius, type SF Alpha, PES cassette, cut off 100 kD) and thickened by a factor of 15. Subsequent isolation of the solid powder was carried out using an ultracentrifuge (Sorvall RC 6, Fa. Thermo Electron Corporation, 13000 rpm) with subsequent drying at 80 ⁰ C.

In the UV-VIS spectrum, the resulting powder exhibited the absorption band characteristic of zinc oxide at about 350-360 nm. In the transmission electron microscopy (TEM), the obtained powder had an average particle size of 50 to 100 nm.

Example 10

Preparation of nanoparticulate zinc oxide in the presence of Cremophor ^® CO 40 (adduct of 40 equivalents of ethylene oxide with hydrogenated castor oil) Two aqueous solutions 1 and 2 were first prepared. Solution 1 contained 27.26 g of zinc chloride per liter and had a zinc ion concentration of 0.2 mol / l. Furthermore, the solution 1 still contained 2 g / l of Cremophor ^® CO 40th

Example 1 1

Two aqueous solutions 1 and 2 were first prepared. Solution 1 contained 27.26 g of zinc chloride per liter and had a zinc ion concentration of 0.2 mol / l. In addition, the Solution 1 contained 4 g / l of Cremophor ^® CO 40th Solution 2 contained 16 g of sodium hydroxide per liter and thus had a hydroxyl ion concentration of 0.4 mol / l.

Immediately after completion of dosing (Gather Industrie GmbH, 40822 Mettmann Fa.) Was obtained from the obtained suspension through a riser pipe by means of a gear pump pumped a suspension flow of 0.96 l / min and preheated to 85 ⁰ C heat exchanger with a volume of 0 , 96 I transferred. The heat exchanger is preheated to the desired temperature with hot water before use. The suspension subsequently passed through a second and third heat exchanger in succession, in which the suspension was cooled to room temperature within a further minute.

In the UV-VIS spectrum, the powder obtained had the absorption band characteristic of zinc oxide at about 350-360 nm. In the transmission electron microscopy (TEM), the obtained powder had an average particle size of 50 to 100 nm.

Example 12

Two aqueous solutions 1 and 2 were first prepared. Solution 1 contained 27.26 g of zinc chloride per liter and had a zinc ion concentration of 0.2 mol / l. Furthermore, the solution 1 still contained 8 g / l of Cremophor ^® CO 40th

The resulting powder had in the UV-VI S-S pectrum the characteristic of zinc oxide absorption band at about 350 - 360 nm. In the transmission electron microscopy (TEM), the obtained powder had an average particle size of 50 to 100 nm.

Example 13

Preparation of nanoparticulate zinc oxide in the presence of Cremophor ^® A 25 (adduct of 25 equivalents of ethylene oxide with cetyl stearyl alcohol)

Two aqueous solutions 1 and 2 were first prepared. Solution 1 contained 54.52 g zinc chloride per liter and had a zinc ion concentration of 0.4 mol / l. In addition, the solution contained 1 or 2 g / l of Cremophor ^® A 25th

The solution 2 contained 32 g of sodium hydroxide per liter and thus had a Hydroxylio- nenkonzentration of 0.8 mol / l.

In a glass reactor with a total volume of 12 I 4 l of the solution 1 were initially charged and stirred (250 rpm). 4 l of the solution 2 were metered into the stirred solution with an HPLC pump (Knauer, type K 1800, pump head 1000 ml / min) within 6 minutes at room temperature. This formed a white suspension in the glass reactor. Immediately after completion of dosing (Gather Industrie GmbH, 40822 Mettmann Fa.) Was obtained from the obtained suspension through a riser pipe by means of a gear pump pumped a suspension flow of 0.96 l / min and preheated to 85 ⁰ C heat exchanger with a volume of 0 , 96 I transferred. The heat exchanger is preheated to the desired temperature with hot water before use. Subsequently, the suspension flowed through a second and third heat exchanger in succession, in which the suspension was cooled to room temperature within a further minute.

Example 14

Two aqueous solutions 1 and 2 were first prepared. Solution 1 contained 54.52 g zinc chloride per liter and had a zinc ion concentration of 0.4 mol / l. In addition, the solution contained 1 4 g / l of Cremophor ^® A 25th

Immediately after completion of dosing (Gather Industrie GmbH, 40822 Mettmann Fa.) Was obtained from the obtained suspension through a riser pipe by means of a gear pump pumped a suspension flow of 0.96 l / min and preheated to 85 ⁰ C heat exchanger with a volume of 0.96 I transferred. The heat exchanger is preheated to the desired temperature with hot water before use. At- closing the suspension flowed through successively a second and third heat exchanger in which the suspension was cooled to room temperature within a further minute.

Example 15

Two aqueous solutions 1 and 2 were first prepared. Solution 1 contained 54.52 g zinc chloride per liter and had a zinc ion concentration of 0.4 mol / l. Furthermore, the solution 1 still contained 8 g / l of Cremophor ^® A 25th

Immediately after completion of dosing (Gather Industrie GmbH, 40822 Mettmann Fa.) Was obtained from the obtained suspension through a riser pipe by means of a gear pump pumped a suspension flow of 0.96 l / min and preheated to 85 ⁰ C heat exchanger with a volume of 0.96 I transferred. The heat exchanger is preheated to the desired temperature with hot water before use. Subsequently, the suspension flowed through a second and third heat exchanger in succession, in which the suspension was cooled to room temperature within a further minute. The freshly prepared suspension was washed in a crossflow ultrafiltration laboratory system (Sartorius, type SF Alpha, PES cassette, cut off 100 kD) and thickened by a factor of 15. Subsequent isolation of the solid powder was carried out using an ultracentrifuge (Sorvall RC 6, Fa. Thermo Electron Corporation, 13000 rpm) with subsequent drying at 80 ⁰ C.

Claims

claims

A process for producing surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide, wherein the metal or metals are selected from the group consisting of aluminum, magnesium, cerium, iron, manganese, cobalt, nickel, copper, titanium, Zinc and zirconium, including the steps

b) mixing the solutions 1 and 2 prepared in step a) at a temperature in the range from 0 to 120 ⁰ C, wherein the surface-modified nanoparticle-ventricular particles are formed and precipitate to form an aqueous suspension of the solution,

2. The method according to claim 1, characterized in that it is the metal salt is zinc chloride, zinc nitrate, zinc acetate or titanium tetrachloride.

3. The method according to any one of claims 1 or 2, characterized in that the strong base is an alkali metal hydroxide, an alkaline earth metal hydroxide or ammonia.

4. The method according to any one of claims 1 to 3, characterized in that the nonionic dispersant in its chemical structure between 3 and 200

-CH2CH2O- - groups.

5. The method according to any one of claims 1 to 4, characterized in that the nonionic dispersant contains one or more contiguous ethylene glycol chains whose chemical structure of the formula - (- CH2CH2θ-) _n - with n from about 2 to about 80 equivalent.

6. The method according to any one of claims 1 to 5, characterized in that it is the nonionic dispersant to an addition product of 2 to 80 moles of ethylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to alkylphenols having 8 to 15 carbon atoms in the alkyl group or on castor oil and / or hydrogenated castor oil.

7. The method according to any one of claims 1 to 6, characterized in that at least one of the method steps a) to d) is carried out continuously.

8. Surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide, wherein the metal or metals are selected from the group consisting of aluminum, magnesium, cerium, iron, manganese, cobalt, nickel, copper, titanium, zinc and zirconium , and the surface modification comprises a coating with at least one nonionic dispersant, obtainable by a process according to one of claims 1 to 7.

9. Surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide, the surface modification comprising a coating with a nonionic dispersant, having a BET surface area in the range from 25 to 500 m ² / g.

10. Surface-modified nanoparticulate particles as claimed in claim 8 or 9, wherein the nonionic dispersant is an adduct of from 2 to 80 moles of ethylene oxide with linear fatty alcohols containing from 8 to 22

Carbon atoms, alkylphenols having 8 to 15 carbon atoms in the alkyl group or castor oil and / or hydrogenated castor oil.

1 1. Use of surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide, which according to a

A method according to any one of claims 1 to 7 are available as UV protectants in cosmetic sunscreen preparations, as a stabilizer in plastics or as an antimicrobial agent.

Use of surface-modified nanoparticulate particles according to claim 11, wherein the particles comprise zinc oxide or titanium dioxide.

13. A process for the preparation of an aqueous suspension of surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide, wherein the metal or metals are selected from the group consisting of aluminum, magnesium, cerium, iron, manganese, Cobalt, nickel, copper, titanium, zinc and zirconium, comprising the steps

a) Preparation of a solution of water and at least one metal salt of the abovementioned metals (solution 1) and a solution of water and at least one strong base (solution 2), at least one of the two

Solutions 1 and 2 contains at least one nonionic dispersant whose chemical structure comprises between 2 and 10,000 -CH 2 CH 2 O- groups,

b) mixing the solutions 1 and 2 prepared in step a) at a temperature in the range from 0 to 120 ⁰ C, wherein the surface-modified nanoparticle tikulären particles are formed and precipitate to form an aqueous suspension of the solution, and

c) optionally concentrating the aqueous suspension formed and / or

Separation of by-products.

14. The method according to claim 13, characterized in that it is the metal salt is zinc chloride, zinc nitrate, zinc acetate or titanium tetrachloride.

15. The method according to any one of claims 13 or 14, characterized in that it is an alkali metal hydroxide, an alkaline earth metal hydroxide or ammonia in the strong base.

16. The method according to any one of claims 13 to 15, characterized in that the nonionic dispersant comprises in its chemical structure between 3 and 200 -CH2CH2O- groups.

17. The method according to any one of claims 13 to 16, characterized in that the nonionic dispersant contains one or more contiguous Ethy- lenglykolketten whose chemical structure of the formula - (- ChbCI-bO-Jn- with n of about 2 to about 80 corresponds.

18. The method according to any one of claims 13 to 17, characterized in that it is the nonionic dispersant to an addition product of

From 2 to 80 mol of ethylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to alkylphenols having 8 to 15 carbon atoms in the alkyl group or to castor oil and / or hydrogenated castor oil.

19. The method according to any one of claims 13 to 18, characterized in that at least one of the method steps a) to c) is carried out continuously.

20. Aqueous suspensions of surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide, wherein the metal or metals are selected from the group consisting of aluminum, magnesium, cerium, iron, manganese, cobalt, nickel, copper, titanium , Zinc and zirconium, and the surface modification comprises a coating with at least one nonionic dispersant obtainable by a process according to any one of claims 13 to 19.

21. Aqueous suspensions according to claim 20, wherein the nonionic dispersant to an addition product of 2 to 80 moles of ethylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, alkylphenols having 8 to 15 carbon atoms in the alkyl group or castor oil) and or hardened castor oil.

22. Use of aqueous suspensions of surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide obtainable by a process according to one of claims 13 to 19, as UV protectants in cosmetic sunscreen preparations, as a stabilizer in plastics or as antimicrobial active ingredient.

23. Use of aqueous suspensions according to claim 22, wherein the particles comprise zinc oxide or titanium dioxide.