EP2164806A2

EP2164806A2 - Hybrid nanoparticles

Info

Publication number: EP2164806A2
Application number: EP08785890A
Authority: EP
Inventors: Monica Fernandez Gonzalez; Richard Riggs; Simon Schambony; Rüdiger Sens; Wolfgang Best; James Reuben Brown
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2007-07-02
Filing date: 2008-06-30
Publication date: 2010-03-24
Also published as: CN101687662A; MX2009013925A; JP2010531907A; BRPI0812843A2; US20100184887A1; WO2009003981A3; WO2009003981A2

Abstract

The invention relates to particles which can be obtained by reacting compounds that can form inorganic nanoparticles with organic molecules containing functional groups and to the use of said particles for finishing deactivated organic polymers, in particular for stabilising said polymers against the action of UV radiation. The invention also relates to liquid formulations containing particles of this type, to methods for producing the particles and their liquid formulations, to powders that can be obtained from the aforementioned liquid formulations and also to liquid formulations that can be obtained by the deflocculation of the powder. The invention further relates to the use of nanoparticles, on the surface of which organic, light-absorbing compounds are bonded, for stabilising polymers against the action of light, radicals or heat.

Description

Hybrid nanoparticles

Description:

The present invention relates to particles obtainable by the reaction of compounds capable of forming inorganic nanoparticles with organic molecules containing functional groups, and the use of these particles to furnish inanimate organic polymers, in particular for stabilization against the action of UV radiation. Furthermore, the invention relates to liquid formulations containing such particles, as well as processes for the preparation of the particles and their liquid formulations. The present invention includes powders obtainable from the above liquid formulations and also liquid formulations obtainable by redispersing the powders.

Further embodiments of the present invention can be taken from the claims, the description and the examples. It is understood that the features mentioned above and those yet to be explained of the subject matter according to the invention can be used not only in the particular concretely specified combination but also in other combinations without departing from the scope of the invention. Preferred or very preferred are the embodiments of the present invention in which all features have the preferred or very preferred meanings.

The production of surface-modified nanoscale ceramic powders is known from WO 93/21127. The unmodified ceramic powder is dispersed in water and / or an organic solvent in the presence of a low molecular weight organic compound having a group capable of reacting and / or interacting with groups present on the surface of the powder particles. Specific examples of the low molecular weight organic compounds are certain mono- and polycarboxylic acids, mono- and polyamines, .beta.-dicarbonyl compounds, organoalkoxysilanes, or modified alkoxides. The surface modification with these low molecular weight organic compounds serves to control the agglomeration of the nanoscale particles.

EP 1 205 177 A2 and EP 1 205 178 A2 describe conjugates which can be used for the preparation of dermatological and cosmetic compositions. The conjugates include an inorganic pigment and an organic compound-based drug covalently linked to the inorganic pigment via a spacer group. The conjugates are prepared by binding the active ingredient via a spacer group to a preformed inorganic pigment.

WO 2006/099952 describes metal oxide particles which are provided with a shell based on at least one crosslinkable chromophore. The meta Loxide particles are initially charged and then provided with the shell containing crosslinkable chromophores.

WO 2007/017587 and WO 2007/017586 describe mixtures containing nanoparticles based on metal derivatives and organic compounds which contain a carboxyl or sulfonic acid group for use in cosmetic sunscreen formulations. The organic compounds are covalently attached to the nanoparticles via the carboxyl or sulfonic acid group. The mixtures are prepared by means of special alkoxy compounds which already contain the covalently bonded organic compounds.

WO 2005/120440 A1 describes particles comprising an inorganic network and organic compounds which are covalently bonded to the network via a spacer group, the organic compounds being present by co-polymerization during the preparation in the interior of the particles. The presence of organic molecules within an inorganic network can adversely affect the performance of these particles, for example, where interaction between the organic molecules and the particle environment is desired.

In the mentioned processes of the prior art, the production of the modified particles is often carried out either by the surface modification of existing particles, or by the reaction of already modified compounds. In one case, one is limited to existing particle sizes and in the other case, first modified compounds must be prepared. Both approaches, however, limit the possibilities for producing modified particles.

Furthermore, when equipping inanimate organic polymers with functional additives, for example with UV absorbers, the problem frequently arises that the functional additives leave the polymer matrix over time, for example by migrating to the surface of the polymer (migration). Furthermore, there is a need to increase the stability (lifetime) of functional additives in inanimate organic polymers.

It is an object of the present invention to provide modified particles based on a simple and controlled preparation, without the use of preformed particles or premodified compounds. A further object of the invention was to find further and improved production processes which allow efficient access to migration-stable functional additives with increased stability.

These and other objects are achieved, as apparent from the disclosure of the present invention, by the various embodiments of the method according to the invention, which are described below. It has surprisingly been found that these objects are achieved by particles P which are obtainable by the reaction of compounds V, which can form inorganic nanoparticles X, with organic molecules M which contain functional groups Z, the molecules M and the compounds V are present during the formation process of the particles P together.

Terms of the form C ₃ -Cb in the context of this invention designate chemical compounds or substituents with a certain number of carbon atoms. The number of carbon atoms can be selected from the entire range from a to b, including a and b, a is at least 1 and b is always greater than a. Further specification of the chemical compounds or substituents is made by expressions of the form Ca-Cb-V. V here stands for a chemical compound class or substituent class, for example for alkyl compounds or alkyl substituents.

Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, particularly preferably fluorine or chlorine.

Specifically, the collective terms given for the various substituents have the following meanings:

C 1 -C 20 -alkyl: straight-chain or branched hydrocarbon radicals having up to 20 carbon atoms, for example C 1 -C 10 -alkyl or C 2 -C 20 -alkyl, preferably C 1 -C 10 -alkyl, for example C 1 -C 3 -alkyl, such as methyl, ethyl, propyl , Isopropyl, or C 4 -C 6 -alkyl, n-butyl, sec-butyl, tert-butyl, 1, 1-dimethylethyl, pentyl, 2-methylbutyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2,2 -Dimethylpropyl, 1-ethylpropyl, hexyl, 2-methylpentyl, 3-methyl-pentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3 , 3-dimethylbutyl, 2-ethylbutyl, 1, 1, 2

Trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, or C ₇ ₀ CI -alkyl, such as heptyl, octyl, 2-ethyl-hexyl, 2, 4,4-trimethylpentyl, 1,1,3,3-tetramethylbutyl, nonyl or decyl and their isomers.

C 1 -C 20 -alkylcarbonyl: a straight-chain or branched alkyl group having 1 to 20 carbon atoms (as mentioned above) which is attached via a carbonyl group (-CO-), preferably C 1 -C 10 -alkylcarbonyl, such as, for example, formyl, acetyl, n- or iso Propionyl, n-, iso-, sec- or tert-butanoyl, n-iso-, sec- or tert-pentanoyl, n- or iso-nonanoyl, n-dodecanoyl.

Aryl: a mono- to trinuclear aromatic ring system containing 6 to 14 carbon ring members, e.g. As phenyl, naphthyl or anthracenyl, preferably a mono- to binuclear, more preferably a mononuclear aromatic ring system. Aryloxy is a mono- to trinuclear aromatic ring system (as mentioned above) which is attached via an oxygen atom (-O-), preferably a mono- to binuclear, particularly preferably a mononuclear aromatic ring system.

Arylalkyl is a mono- to trinuclear aromatic ring system (as mentioned above) which is attached via a C 1 -C 20 -alkylene group, preferably a mononuclear or dinuclear, more preferably a mononuclear aromatic ring system.

C 1 -C 20 -alkylene: straight-chain or branched hydrocarbon radicals having 2 to 20 carbon atoms, for example C 2 -C 10 -alkylene or C 2 -C 20 -alkylene, preferably C 2 -C 10 -alkylene, in particular methylene, dimethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene ,

Heterocycles: five- to twelve-membered, preferably five- to nine-membered, particularly preferably five- to six-membered, oxygen, nitrogen and / or sulfur atoms, ring rings optionally containing several rings such as furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, Dioxolyl, dioxyl, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.

C 1 -C 20 -alkoxy denotes a straight-chain or branched alkyl group having 1 to 20 carbon atoms (as mentioned above) which are bonded via an oxygen atom (-O-), for example C 1 -C 10 -alkoxy or C 2 -C 20 -alkoxy, preferably C 1 C10 alkyloxy, particularly preferably Ci-C3-alkoxy, such as methoxy, ethoxy, propoxy.

Heteroatoms are preferably oxygen, nitrogen, sulfur or phosphorus.

For the purposes of the present invention, the term "solvent" is also used for diluents The dissolved compounds are present either in solution, in suspension, in dispersed form or in emulsified form in the solvent or in contact with the solvent to understand.

"Liquid formulations" of the particles P according to the invention are solutions, dispersions, emulsions or suspensions of the particles P.

For the purposes of this application, "nanoparticles" are understood as meaning particles having a particle size of 1 nm to 1000 nm. The term "(nano) particle" also uses the term "(nano) particle". For the determination of the particle size of nanoparticles and of the particles P, a number of different methods are available to the person skilled in the art, which depend on the composition of the particles and can yield partly deviating results with respect to the particle size. For example, particle size can be determined by measurements using a transmission electron microscope (TEM), dynamic light scattering (DLS) or UV absorption wavelength measurements. Particle sizes are determined in the context of the present application, if possible, by means of the measurements of a transmission electron microscope (TEM). With an ideal spherical shape of the nanoparticles, the particle size would correspond to the particle diameter. It goes without saying that the agglomerates, which may have arisen as a result of a juxtaposition of nanoparticles, of the initially formed primary particles, may also be greater than 1000 nm.

According to the invention, the particles P are prepared by the reaction of compounds V which can form inorganic nanoparticles X with organic molecules M containing functional groups Z. The compounds V may all be the same or different. Furthermore, the organic molecules M, as well as the functional groups Z can all be the same or different. The particles according to the invention can therefore also be mixtures of different types of particles. Preferably, the compounds V are all the same. Particularly preferably, the compounds V are all the same and at the same time the organic molecules M are all the same.

The particles P according to the invention and the nanoparticles X can be both crystalline and amorphous or have varying proportions of crystalline and amorphous structures. The detection is carried out by TEM measurements or by X-ray powder diffraction measurements.

The stoichiometric composition of the particles P according to the invention containing the inorganic nanoparticles X and the organic molecules M can vary over a wide range, for example depending on the nature of the compounds V or the nature of the organic molecules M, as explained below.

As compounds V, in principle, all substances are in question, which are able to form inorganic nanoparticles X by chemical reactions.

For example, compounds V are substances which can form inorganic nanoparticles through a series of hydrolysis and condensation reactions (SoI-GeI process).

Preferred substances used as compounds V are those which lead to the formation of inorganic nanoparticles containing metal or semimetal oxides, metal or semimetal sulfides, selenides, nitrides, sulfates or carbonates. Particularly important Preferred compounds here are those compounds V which lead to the formation of inorganic nanoparticles containing metal or semimetal oxides, particularly preferably to metal oxides. For example, such compounds V contain the elements Si, Zn, Ti, Ce, Zr, Sn, Fe. Zn, Ti, Sn are preferred.

In one embodiment, the compounds V are Ti (OH) ₄ , Ti (OEt) ₄ , titanium tetrapropoxide (= Ti (OPr) ₄ ), titanium tetraisopropoxide (= Ti (OiPr) ₄ ), Zn (acetate) ₂ (= Zn ( OAc) ₂ ), Zn (methacrylate) 2, Zn (benzoate) 2, ZnCb, ZnBr ₂ , Zn (NOs) ₂ or SnCl ₄ . Zn (OAc) ₂ , Zn (NOs) ₂ , ZnCl ₂ , Ti (OiPr) ₄ or SnCl _{4 are} preferred.

In another embodiment of the particles according to the invention, compounds V, which are further metal salts, are used to form the inorganic nanoparticles.

The metal salts of 1 to 5 valent metal cations are preferably used here. The metal salts of 2 to 4 valent metal cations are particularly preferably used. Examples of suitable metal cations are alkali metal ions, alkaline earth metal ions, earth metal ions or transition metal ions. Preferred metal cations are Zn (II), Ti (IV), Ce (I), Ce (III), Zr (II), Sn (II), Sn (IV), Fe (II), Fe (III). Zn (II), Ti (IV) are particularly preferred.

Preferred are when the compounds V are metal salts as anions acetate, formate or benzoate. Particularly preferred is acetate.

As already mentioned above, preference is likewise given to those compounds V which are suitable for

Formation of inorganic nanoparticles containing metal oxides or mixtures thereof. Metal oxides of the form A _x Oy, where x is a number from the range of 1 to 3 and y is a number from the range of 1 to 5 and A is a metal, are particularly preferred. ZnO, TiO ₂ , ZrO ₂ , CeO ₂ , Ce ₂ O ₃ , SnO ₂ , SnO, Al ₂ O ₃ , SiO ₂ , or Fe ₂ O ₃ are very particularly preferred as metal oxides. In particular ZnO, TiO ₂ , ZrO ₂ , CeO ₂ , Ce ₂ O ₃ , SnO ₂ .

The particles P of the symbolic formula X-M according to the invention preferably obey, and the organic molecules M interact with the inorganic nanoparticles X on the basis of the compounds V. This interaction preferably takes place on the surface of the inorganic nanoparticles X and the particles according to the invention In this case, P correspond to surface-modified inorganic nanoparticles. Naturally, the symbolic formula XM denotes a variable composition of the particles P according to the invention over a wide range. This composition comprises the interaction of an organic molecule M with an organic nanoparticle X. Preferably, the symbolic see formula XM the interaction of several organic molecules M with an inorganic nanoparticle X.

The structure of the particles P according to the invention can generally vary over a wide range, for example depending on the nature of the compound V. For example, the organic molecules M may be distributed in the particle P or at the surface of the particle. The distribution of the organic molecules M in the particle P may be homogeneous or else heterogeneous. Preferably, the M are at or substantially at the surface of the particles P. The coating of the surface of the particles P with the organic molecules M can be present completely or partially, for example in the form of individual islands. More preferably, as already mentioned above, the organic molecules M are present essentially at the surface of the particles P. The structure of the particles P according to the invention may, in the regions in which no organic molecules M are present, correspond to the structure of the inorganic nanocrystals X which would be present if no organic molecules were present during the formation of the particles P. A determination of the distribution of the organic molecules M in the particles P is carried out, for example, by determining the crystallinity of the particles P by means of TEM measurements. For example, a distribution of the organic molecules M in the particles P generally disturbs the crystallinity of the particles P more than a distribution of the organic molecules M substantially at the surface of the particles P.

In many applications, the inorganic nanoparticles X can also be replaced by particles P according to the invention.

In general, the particles P contain from 0.1 to 99.9 wt .-% of the organic compounds M, based on the total weight of the particles P, preferably from 1 to 80 wt .-% and particularly preferably 5 to 70 wt .-% ,

The inorganic particles X and the particles P according to the invention preferably have a particle size of 1 nm to 1000 nm. The particle size of X and P is preferably from 1 nm to 100 nm. The particle size is particularly preferably from 1 nm to 50 nm, very particularly preferably from 1 nm to 30 nm and in particular from 1 nm to 20 nm.

The organic molecules M containing functional groups Z are preferably of low molecular weight, i. they have a molecular weight of less than 800 g / mol. More preferably, the molecular weight of the organic molecules is below 600 g / mol, in particular below 500 g / mol.

Preferably, the organic molecules M of the formula Y'-Z obey. Here, Y 'denotes a chemical structural unit (linker) via which, if appropriate after a chemical conversion of Y' to Y, the organic molecules are mixed with the inorganic Na. noparticles X interact. The particles according to the invention can therefore preferably be described by the following symbolic general formulas (I) and (II):

X-Y'-Z (I) or X-Y-Z (II).

For example, the chemical reaction of the linker Y 'to the linker Y is carried out by hydrolysis.

The nature of the interaction between Y 'and X or Y and X can be very different for different Y and Y'. For example, the linker may be covalently linked to the inorganic nanoparticle X. Furthermore, an electrostatic (ionic) interaction, an interaction via dipole-dipole forces or via hydrogen bonds bonds is possible. Preferably, the linker interacts covalently or electrostatically with X. Of course, the linker can also interact with the inorganic nanoparticle at several points, for example form a plurality of covalent bonds, or, in addition to a covalent bond, have further interactions with X, for example via hydrogen bridges.

For example, the linker corresponds to -Y-

(L1), R ¹ (L2) (L3)

- O- * -N- * -s- *

O (L4) O (L5) R ¹ O (L6)

- o-c-o- * - o-c- * -N-C- *

O (L7) O (L8) O (L9)

- o-s-o- * - o-s- * -s *

O O O

( ^* symbolizes the connection point to the functional group Z)

Here are

R ¹ is H, _Ci-C2 o alkyl, aryl, arylalkyl, heterocyclic, _{Ci-C2o-alkylcarbonyl,} R ^2, R ³ independently voneinenander O, C ₂ O-alkoxy, Ci-C2o-alkyl,

Aryl, arylalkyl, heterocycles, R ^{4 is} a single chemical bond, O, Ci-C2o-alkylene,

C ₁ -C ₂ -alkylene-R ⁵ R ⁵ O, N, S, N (R ⁶ ) -C =O, N-CO ₂ , O ₂ C, CO ₂ , O ₂ CN, OCO ₂ ,

R ⁶ OOR ⁶ R ⁶ OOR ⁶

I I l I l I l I l I

N-C, C-N, N-C-O, O-C-N,

O-C, C-O, O-C-O, N-C-N

R ^{6 is} H, C 1 -C ₂₀ -alkyl,

R ⁷ H, metal cation,

where the substituents R ¹ to R ⁴ and / or R ^{6 may} each be interrupted at any position by one or more heteroatoms, the number of these heteroatoms being interrupted roatoms is not more than 10, preferably not more than 8, very particularly preferably not more than 5 and in particular not more than 3, and / or in any position, but not more than five times, preferably not more than four times and particularly preferably not more than three times, by C 1 -C 20 -alkyl, C 1 -C 20 -alkoxy, aryl, aryloxy, heterocycles, heteroatoms or halogen may be substituted, which may also be substituted at most twice, preferably at most once with said groups. Metal cations are preferably mono-, di-, or trivalent metal cations, for example, alkali, alkaline earth, earth metal, transition metal cations. In particular, metal cations are Li ⁺ , Na ⁺ , K ⁺ , Ca ²⁺ and / or Mg ²⁺ . Of course, when it comes to the value of metal cations, it must be borne in mind that overall electro-neutrality remains guaranteed. For example, a divalent metal cation neutralizes two linkers L10. Formation of ionic interactions, for example salt bridges, between linkers L10 is possible.

Preferred linkers -Y- are L1, L5, L8, L10 or L14.

Preferred silane linkers are L14

(L15) (L16)

Et-O Et-O

- O-Si-CCCN- * - O- Si-Et-CCCO- * ά ^">" * "* _ _O ^H _Et ^H 2 ^H 2 H ₂

( ^* symbolizes the attachment site to the functional group Z) or (partially) hydrolyzed derivatives of these silane linkers L15 or L16.

In one embodiment of the particles according to the invention, the organic molecules M interact not only with the compounds V but also with one another. For example, the organic molecules M can interact with one another via electrostatic interactions or hydrogen bonds. It is also possible that the organic molecules M react with each other in a chemical reaction, before or after a possible chemical reaction with the inorganic nanoparticles. For example, this is possible in the form of a crosslinking reaction between the organic molecules M. This can take place before, during, or after the formation of the particles P. Such crosslinking preferably takes place when the organic molecules carry silane groups which are capable of condensation reactions. When the organic molecules M are present on the surface of the particles P, the crosslinking reaction can lead to the formation of a completely crosslinked shell, or even only partially crosslinked areas on the surface. The functional group Z of the organic molecule may be very different depending on the use of the particles of the invention. For example, the functional group Z comprises a chromophore that can absorb electromagnetic radiation. For example, such a chromophore is capable of absorbing IR, visible, or UV light. By way of example, such a chromophore can then emit the absorbed light again, optionally at a different wavelength (fluorescence or phosphorescence), or else emit the received light energy without radiation. Furthermore, combined processes of emission and radiationless deactivation are possible.

In addition to the UV absorbers, the functional group Z comprises, for example, stabilizers for organic polymers, auxiliaries for organic polymers, flame retardants, organic dyes, or IR dyes, fluorescent dyes, optical brighteners, antistatic agents, antiblocking agents, nucleating agents, antimicrobial additives.

The functional group Z preferably comprises a chromophore which absorbs UV light having a wavelength of less than 400 nm, in particular from 200 to 400 nm (UV absorber). Such a chromophore can therefore absorb, for example, UV-A (from 320 to 400 nm), UV-B (from 290 to 319 nm) and / or UV-C (from 200 to 289 nm). The chromophore preferably absorbs UV -A and / or UV-B light. Most preferably, the chromophore absorbs UV-A and / or UV-B light and deactivates the received light energy without radiation. For example, the functional group Z corresponds

( ^* symbolizes the attachment point to the linker Y or Y ') where

R is halogen, hydroxy, phenyl, C 1 -C 20 -alkyl, hydroxyphenyl,

C 1 -C 20 -alkoxy, aryl, aryloxy, amino, mono- or di-alkylamino, nitrile, Carboxylate, ester, thiol, sulfoxides, sulfonic acid, acyl, formyl, carbonyloxyalkyl, carbonylaminoalkyl, n is an integer in the range of 0 to 4

and the n substituents R can be the same or different independently of one another, and wherein the substituent R can be interrupted at any position by one or more heteroatoms, the number of these heteroatoms being not more than 10, preferably not more than 8, very particularly preferably not more than 5 and in particular not more than 3, and / or in any position, but not more than five times, preferably not more than four times and more preferably not more than three times, by Ci-C2o-alkyl, Ci-C2o Alkoxy, aryl, aryloxy, heterocycles, heteroatoms or halogen may be substituted, which may also be substituted at most twice, preferably at most once with said groups.

The particles P according to the invention preferably absorb light having a wavelength of 200 to 600 nm. Further preferably, the absorption spectrum of the particles according to the invention has at least one absorption maximum in the wavelength range from 200 to 600 nm. Particles of the invention preferably absorb UV-A and / or UV-B light. Most preferably, the particles according to the invention absorb UV-A and / or UV-B light and deactivate the absorbed light energy without radiation.

The UV absorbers used are preferably organic molecules M which have a linker Y or Y '.

UV absorbers are often commercial products. They are sold, for example, under the trademark Uvinul® by BASF Aktiengesellschaft, Ludwigshafen. The UVinul® light stabilizers comprise compounds of the following classes: benzophenones, benzotriazoles, cyanoacrylates, cinnamic acid esters, para-aminobenzoates, naphthalimides. In addition, other known chromophores are used, e.g. Hydroxyphenyltriazines or oxalanilides. Such compounds are used, for example, alone or in mixtures with other light stabilizers in cosmetic applications, for example sunscreens or for the stabilization of organic polymers. A particularly preferred UV absorber is 4-n-octyloxy-2-hydroxybenzophenone. Further examples of UV absorbers are:

substituted acrylates, such as, for example, ethyl or isooctyl-α-cyano-β, β-diphenylacrylate (mainly 2-ethylhexyl-α-cyano-β, β-diphenylacrylate), methyl-α-methoxycarbonyl-β-phenylacrylate, methyl α- methoxycarbonyl-β- (p-methoxyphenyl) acrylate, methyl or butyl α-cyano-β-methyl-β- (p-methoxyphenyl) acrylate, N- (β-methoxycarbonyl-β-cyanovinyl) -2-methylindoline, octyl -p-methoxycinnamate, isopentyl-4-methoxycinnamate, urocanic acid or its salts or esters; Derivatives of p-aminobenzoic acid, in particular their esters, for example ethyl 4-aminobenzoate or ethoxylated 4-aminobenzoic acid ethyl esters, salicylates, substituted cinnamates (cinnamates) such as octyl-p-methoxycinnamate or 4-isopentyl-4-methoxycinnamate, 2-phenylbenzimidazole-5 sulfonic acid or its salts.

2-hydroxybenzophenone derivatives, e.g. 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4, 2 ', 4'-trihydroxy, 2'-hydroxy-4,4' - dimethoxy-2-hydroxybenzophenone and 4-methoxy-2-hydroxybenzophenone-sulfonic acid sodium salt;

Esters of 4,4-diphenylbutadiene-1, 1-dicarboxylic acid, e.g. the bis (2-ethylhexyl) ester;

2-phenylbenzimidazole-4-sulfonic acid and 2-phenylbenzimidazole-5-sulfonic acid or salts thereof;

Derivatives of benzoxazoles;

Derivatives of benzotriazoles or 2- (2'-hydroxyphenyl) benztriazoles such as 2- (2H-benztriazol-2-yl) -4-methyl-6- (2-methyl-3- ((1,1,3,3 tetramethyl-1- (trimethylsilyloxy) disiloxanyl) propyl) phenol, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'- hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benztriazole, 2- [2'-hydroxy-5 '- (1, 1, 3,3-tetramethylbutyl) phenyl] benztriazole, 2- (2H) 3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2 - (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benztriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'- Di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- [3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl] benztriazole, 2- [3'-tert-butyl- 2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl] -5-chlorobenzotriazole, 2- [3'-tert-butyl-5' - (2- (2-ethylhexyloxy) carbonylethyl) -2'-hydroxyphenyl ] -5-chlorobenzotriazole, 2 [3'-tert-butyl-2'-hydroxy-5 '- (2-methoxyca rbonylethyl) phenyl] -5-chlorobenzotriazole, 2- [3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl] benztriazole, 2- [3'-tert-butyl-2'-hydroxy-5'- (2-octyloxycarbonylethyl) phenyl] benztriazole, 2- [3'-tert-butyl-5 '- (2- (2-ethylhexyloxy) carbonylethyl) -2'-hydroxyphenyl] benztriazole, 2- (3-tert. 3'-Dodecyl-2'-hydroxy-5'-methylphenyl) benztriazole, 2- [3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenyl] benzotriazole, 2,2' -Methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6-benztriazol-2-yl-phenol], the fully esterified product of 2- [3'-tert-butyl-5 '- (2 -methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300, [R-CH 2 CH 2 -COO (CH 2) 3] 2 with R equal to 3'-tert-butyl-4-hydroxy-5 ' 2H-benztriazol-2-yl-phenyl, 2- [2'-hydroxy-3 '- (α, α-dimethylbenzyl) -5' - (1,1,3,3-tetramethylbutyl) -phenyl] -benztriazole, 2- [2 ' -Hydroxy-3 '- (1,1,3,3-tetramethylbutyl) -5' - (α, α-dimethylbenzyl) phenyl] benzotriazole; Benzylidene camphor or its derivatives, as described, for. B. in DE-A 38 36 630 are called, for example, 3-Benzylidencampher, 3 (4'-methylbenzylidene) d-1-camphor;

α- (2-oxoborn-3-ylidene) toluene-4-sulfonic acid or its salts, N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) anilinium monosulfate;

Dibenzoylmethanes, e.g. 4-tert-butyl-4'-methoxydibenzoylmethane;

2,4,6-triaryltriazine compounds such as 2,4,6-tris {N- [4- (2-ethylhex-1-yl) oxycarbonylphenyl] amino} -1, 3,5-triazine, 4,4 ' - ((6- ((tert.

Butyl) aminocarbonyl) phenylamino) -1, 3,5-triazine-2,4-diyl) imino) bis (benzoic acid 2'-ethylhexyl ester);

2- (2-hydroxyphenyl) -1, 3,5-triazines, e.g. 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1 3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4 -propyloxyphenyl) -6- (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5 triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy) 3-butyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4 , 6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2 - [2-hydroxy-4 (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4- hexyloxyphenyl) -4,6-diphenyl-1, 3,5-triazine, 2- (2-hydroxy-4- methoxyphenyl) 4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1, 3,5-triazine, 2- (2-Hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1-oxy ) -2-hydroxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine.

Further suitable UV absorbers can be found in the document Cosmetic Legislation, Vol. 1, Cosmetic Products, European Commission 1999, pp. 64-66, to which reference is hereby made.

Suitable UV absorbers are also described in lines 14 to 30 ([0030]) on page 6 of EP 1 191 041 A2. These are incorporated herein by reference, and this reference is made to the disclosure of the present invention.

According to the invention, it is therefore possible to use particles P which contain organic UV absorbers as organic molecules for stabilizing polymers against the action of UV light. Another object of the present invention is a general method for stabilizing polymers against the action of light, radicals or heat, wherein the polymers nanoparticles are added to the surface organic, light-absorbing compounds, such as UV absorbers, are attached. This general method according to the invention can, of course, be carried out with the aid of the corresponding particles P of the invention, which have light-absorbing compounds substantially on their surface, but are not limited thereto. In general, it is possible to use all nanoparticles which have organic light-absorbing compounds on their surface, for example surface-modified nanoparticles. The preparation of such surface-modified nanoparticles is known, for example, from the documents WO 2006/099952 A2, EP 1 205 177 or WO 2007/017586. The examples of surface-modified particles of the documents WO 2006/099952 A2 (p.3 - page 16), EP 1 205 177 ([0013], [0071] - [0076]) or WO 2007/017586) [0012] [0055]) is explicitly referenced and these references are made to the disclosure of the present invention.

Another object of the invention is the use of nanoparticles, on the surface of organic, light-absorbing compounds are attached to stabilize polymers against the action of light, radicals or heat.

The incorporation of the nanoparticles, on the surface of which organic, light-absorbing compounds are bonded into polymers, can be effected by the same processes as the incorporation of the particles P according to the invention into polymers.

Due to the photocatalytic effect of the nanoparticles, the use of inorganic nanoparticles X, for example of nanoparticles based on ZnO and TiO.sub.2 in polymers, frequently leads to damage or destruction of the polymer matrix and thus to a deterioration in the properties of the polymers. The particles P of the invention have the advantage that the photocatalytic activity is reduced or completely suppressed when used as organic molecules M UV absorber.

The particles P produced by means of UV absorbers as organic molecules M, by the process according to the invention, have the further advantage that the UV absorbers are generally stabilized. By introducing the UV absorbers into the particles P according to the invention, the life of the UV absorbers is generally prolonged and premature photochemical destruction of the UV absorbers is prevented. This effect contributes to an effective reduction of the required amount of UV absorber.

Suitable organic molecules M are also stabilizers for organic polymers into consideration. The stabilizers are compounds that are organic polymers against degradation by exposure to oxygen, light (except UV) or Stabilize heat. They are also referred to as antioxidants or as light stabilizers, cf. Ullmanns, Encyclopedia of Industrial Chemistry, Vol. 3, 629-650 (ISBN-3-527-30385-5) and EP-A 1 1 10 999, page 2, line 29 to page 38, line 29. With such stabilizers virtually all organic polymers are stabilized, cf. EP-A 1 1 10 999, page 38, line 30 to page 41, line 35. This reference is made by reference to the disclosure of the present invention. The stabilizers described in the EP application belong to the class of compounds of pyrazolones, organic phosphites or phosphonites, sterically hindered phenols and sterically hindered amines (stabilizers of the so-called HALS type or HALS stabilizers, see Römpp, 10th edition, US Pat. Volume 5, pages 4206-4207 According to the invention, it is therefore possible to use particles P which contain stabilizers as organic molecules M for stabilizing polymers.

In a preferred embodiment, mixtures of particles P which contain as organic molecules M UV absorbers and certain auxiliaries for organic polymers are used. For example, these aids flame retardants, organic dyes, IR dyes, fluorescent dyes, optical brighteners, nucleating agents, antimicrobial additives. Depending on the field of application, the ratio of auxiliary agents to UV absorbers can vary widely. For example, the ratio of UV absorbers to auxiliaries is from 10: 1 to 1:10, preferably from 5: 1 to 1: 5, in particular from 2: 1 to 1: 2.

As organic molecules M are further aids for organic polymers into consideration. Auxiliaries are, for example, substances which at least largely prevent the fitting of films or molded parts made of plastics, so-called antifogging agents. In addition, suitable polymer additives are anti-fogging agents for organic polymers, from which, in particular, sheets or films are produced. Such polymer additives are described, for example, by F. WyNn, in Plastics Additives Handbook, 5th Edition, Hanser, ISBN 1-56990-295-X, pages 609-626. According to the invention, therefore, particles P which contain as organic molecules M adjuvants can be used as anti Use fogging or anti-fogging agents.

Other suitable organic molecules M are lubricants such as oxidized polyethylene waxes and antistatic agents for organic polymers. Examples of antistatic agents cf. the aforementioned reference F. WyNn, Plastics Additives Handbook, pp. 627-645.

Further suitable organic molecules M are flame retardants, which are described, for example, in Römpp, 10th edition, pages 1352 and 1353 and in Ullmanns, Encyclopedia of Industrial Chemistry, Vol. 14, 53-71. According to the invention, it is therefore possible to use particles P which contain flame retardants as organic molecules M as flame retardants for polymers. Commercial stabilizers and adjuvants are available, for example, under the trade names Tinuvin®, Chimassorb®, and Irganox® from Ciba, Cyasorb® and Cyanox® from Cytec, Lowilite®, Lowinox®, Anox®, Alkanox®, Ultranox®, and Weston® from Chemtura and Hostavin ® and Hostanox® from Clariant. Stabilizers and auxiliaries are described for example in Plastics Additives Handbook, 5th edition, Hanser Verlag, ISBN 1-56990-295-X.

Other organic molecules M are organic dyes that absorb light in the visible range, or optical brighteners. Such dyes and optical brighteners are described in detail in the prior art WO 99/40123, page 10, line 14 to page 25, line 25, which is incorporated herein by reference. While organic dyes have an absorption maximum in the wavelength range from 400 to 850 nm, optical brighteners have one or more absorption maxima in the range from 250 to 400 nm. Optical brighteners emit fluorescence radiation in the visible range when exposed to UV light. Examples of optical brighteners are compounds from the classes of bisstyrylbenzenes, stilbenes, benzoxazoles, coumarins, pyrenes and naphthalenes. Commercially available optical brighteners are sold under the trademarks Tinopal® (Ciba), Ultraphor® (BASF Aktiengesellschaft) and Blankophor® (Bayer). Optical brighteners are also described in Römpp, 10th edition, volume 4, 3028-3029 (1998) and in Ullmanns, Encyclopedia of Industrial Chemistry, Vol. 24, 363-386 (2003). According to the invention, it is therefore possible to use particles P which contain organic dyes or brighteners as organic molecules for coloring or lightening polymers.

Other suitable organic molecules M are IR dyes, which are sold for example by BASF Aktiengesellschaft as Lumogen® IR. Lumogen® dyes include compounds of the classes of perylenes, naphthalimides, or quaterylenes. According to the invention, it is therefore possible to use particles P which contain IR dyes as organic molecules as IR absorbers for polymers or for the invisible marking of polymers.

In particular, particles P which are obtainable by reacting compounds V which lead to the formation of ZnO in the presence of benzophenones are preferred.

In particular, particles P are also obtainable which are obtainable by reacting compounds V which lead to the formation of ZnO in the presence of salicylic acid.

Preference is further given to particles P which are obtainable by reacting compounds V which lead to the formation of ZnO in the presence of organic molecules M, of the formula Y'-Z or YZ, where Y is a silane linker (L14) and Function of a UV absorber has. Preference is further given to particles P which are obtainable by reacting compounds V which lead to the formation of OO 2 in the presence of organic molecules M of the formula Y'-Z or YZ, where Y is a carboxyl linker (L5) and Function of a UV absorber has.

Preference is furthermore given to particles P which are obtainable by reacting compounds V which lead to the formation of TiO 2 in the presence of organic molecules M of the formula Y'-Z or YZ, where Y is a sulfonic acid linker (L8) and Function of a UV absorber has.

Preference is furthermore given to particles P which are obtainable by reacting compounds V which lead to the formation of TiO 2 in the presence of organic molecules M of the formula Y'-Z or YZ, where Y is a silane linker (L14) and Function of a UV absorber has.

In particular, particles P which are obtainable by reacting compounds V which lead to the formation of ZnO in the presence of organic molecules M, of the formula Y'-Z or YZ, where Y is the linker L1 and Z is a group Z2, are also preferred ,

Preferred particles P according to the invention are those particles in which all features take on their preferred meaning.

Of course, the particles according to the invention can subsequently be modified on their surface by processes known from the prior art (EP 1 205 177 A2, WO 93/21127).

The particles P according to the invention are prepared by reacting compounds V which can form inorganic nanoparticles X with organic molecules M containing functional groups Z, the molecules M and the compounds V being present together during the formation process of the particles P. ,

As already explained above, inorganic nanoparticles can be formed with the aid of the compounds V. The formation of the inorganic nanoparticles X can also take place in the absence of the organic molecules M. According to the invention, however, the compounds V and the organic molecules M are co-present in the formation of the particles P. The organic molecules M preferably influence the formation of inorganic nanoparticles from the compounds V to the effect that in the reaction of the compounds V not the inorganic nanoparticles X, but the particles P according to the invention are formed. Most preferably, the remaining reaction conditions which would result in a reaction of the compounds V to the inorganic nanoparticles, except for the presence of the organic molecules M, unchanged. In one embodiment, the preparation of the particles P according to the invention comprises the following steps:

(a) providing the compound V optionally dissolved in a solvent and the organic molecules M optionally dissolved in a solvent. (b) mixing the compounds V with the organic molecules M optionally in a solvent.

(c) reacting the mixture of (b), optionally with the addition of further substances or further organic molecules M, optionally under the reaction conditions which would lead to the formation of nanoparticles X from compounds V, into particles P according to the invention.

(d) Optional isolation of particles P.

(e) Optional purification and work-up of the particles P.

(f) Optional further modification of the particles P.

(g) optionally redispersing the particles P.

In a preferred embodiment of the process according to the invention for the preparation of the particles P, the organic molecules M or the compounds V are dissolved in a solvent in step (a). Particularly preferably, both the compounds V and the organic molecules are dissolved in a solvent and are mixed in dissolved form, in particular the compounds V and the organic molecules M are dissolved in the same solvent.

Further preferred in the process according to the invention in step (c) is the addition of further substances, for example initiators or catalysts for the formation of the inorganic nanoparticles, or further organic molecules M. Initiators or catalysts for the formation of the inorganic nanoparticles are understood to be substances which initiate or accelerate the formation of the particles P. For example, as further substances bases, in particular EtONa, EtOK, EtOLi, PrONa, MeONa, NaOH, LiOH, KOH, trialkylamines, tetra-alkylammoniumhydroxide, or acids, in particular HCl, H2SO4, HNO3, acetic acid, or salts, in particular tetra-alkylammoniumhalogenide used

In step (c), further organic molecules M are preferably added. The addition of these further organic molecules M can be used to control the particle size of the particles P or to introduce additional functional groups Z into the particles P. In general, the particle size is dependent on the concentration of the organic molecules M, the higher the concentration of M, the lower the particle size of the particles P in general. By adding further organic molecules M, additional functional groups Z can be added to the TeN atoms. introduce P. The Zs can all be the same or different. Preferably, particles P with different Z can be produced by means of the process according to the invention. The particles P of the invention prepared with different Z generally have combined properties based on the different Z, on. For example, it is possible in this way to produce particles P which contain different UV absorbers and thus cover the entire required absorption spectrum. Further combinations of functional groups are, for example, flame retardants with dyes or UV absorbers with flame retardants. Depending on the desired field of application, further combinations can be selected. Such combinations often show synergies.

Very preferably, a solvent is used in the preparation process according to the invention in step (a) and in step (c) further substances are added or further molecules M are added.

In a preferred embodiment, the preparation of the particles P according to the invention comprises the following steps: (a) providing Zn (OAc) 2 and UV absorbers, (b) mixing Zn (OAc) 2 and UV absorbers in polar solvent, preferably ethanol or Water, (c) reacting the mixture of (b) in the presence of base, preferably NaOH or LiOH, to particles P of the invention. (D) optionally isolating the particles P. (e) optionally purifying and working up the particles P. (f) Optional further modification of the particles P. (g) optionally redispersion of the particles P.

In a further preferred embodiment, the preparation of the particles P according to the invention comprises the following steps: (a) providing Ti (OiPr) ₄ and UV absorbers, (b) mixing Ti (OiPr) ₄ and UV absorber in polar solvent, preferably ethanol or water, (c) reaction of the mixture of (b) in the presence of base, preferably NaOH or LiOH, to give particles P of the invention. (d) optionally isolating the particles P. (e) optionally purifying and working up the particles P. f) Optional further modification of the particles P. (g) Optional redispersion of the particles P.

In a further preferred embodiment, the preparation of the particles P according to the invention comprises the following steps: (a) Provision of TiiβOi6 (OEt) 32 according to the literature procedure (Sanchez C. et al., J. Am. Chem. Soc. 2005, 127, 4869-4878 , R. Schmid, A. Mosset and J. Galyy, J. Chem. Soc, Dalton Trans., 1991, 1999) and UV absorbers, (b) mixing Tii6θi6 (OEt) 32 and UV absorbers in polar solvent, preferably ethanol or water, (c) reaction of the mixture of (b) in the presence of base, preferably NaOH or LiOH, to particles P according to the invention. (d) optionally isolation of the particles P. (e) optionally purification and work-up of the particles P. f) Optional further modification of the particles P. (g) Optional redispersion of the particles P.

The optional further modification of the particles P (f) preferably comprises a chemical modification of the particles P, in particular on the organic molecules M, very preferably a chemical reaction on the functional groups Z. For example, in this embodiment of the method according to the invention, a (subsequent) Conversion of the functional group Z from an inactive to an active form possible.

Pressure and temperature are generally of minor importance for the preparation of the particles P according to the invention. The choice of temperature can have an influence on the particle size and depends naturally on the compounds V used. Usually, the reaction temperature in the range of - 5 ° C to 300 ⁰ C, often in the range of 10 to 150 ⁰ C. Preferably, the reaction is temperature in the range of 20 to 70 ⁰ C. The reaction is usually carried out at normal pressure or ambient pressure carried out. However, it can also be carried out in the pressure range of up to 50 bar.

The solids content of the liquid formulations according to the invention is determined to a first approximation by the particles P of the invention and varies depending on the application in a wide range. In general, the solids content is in the range from 1 to 90% by weight and in particular in the range from 5 to 70% by weight, based on the total weight of the liquid formulation.

The liquid formulations according to the invention can be used directly as such or after dilution. In addition, the liquid formulations of the invention may contain conventional additives (additives), for. As the viscosity-modifying additives (thickener, thickener), anti-foaming agents, bactericides, antifreeze and / or surface-active substances. The surface-active substances include protective colloids or low molecular weight emulsifiers (surfactants), the latter usually having a molecular weight below 2000 g / mol, in particular below 1000 g / mol (mass average), in contrast to the protective colloids. The protective colloids or emulsifiers may be anionic, nonionic, cationic or zwitterionic in nature.

In addition, the liquid formulations according to the invention can be formulated with conventional binders, for example aqueous polymer dispersions, water-soluble resins or with waxes.

The particles P according to the invention are contained in the liquid formulations and can be obtained from these liquid formulations (step (d) and (e) of the process according to the invention) by removing the volatile constituents of the liquid phase in powder form. In the powder particles of the invention may be present either isolated, in agglomerated form, or partially filmed. The powders according to the invention are accessible, for example, by evaporation of the liquid phase, freeze-drying or by spray-drying. Frequently, liquid formulations according to the invention are obtainable by redispersion (step (f) of the process according to the invention) of the powders according to the invention, for example in ethanol or toluene.

The liquid formulations according to the invention and the powders according to the invention obtainable therefrom by separation of the liquid phase have the advantage that they contain the organic molecules M in a controlled migration stable manner over a long period of time, ie. the organic molecules M are associated with the particles P over an extended period of time and are not released to the environment outside the particles P. Furthermore, the inorganic constituents of the nanoparticles are also frequently retained in the particles P by the modification with the organic molecules M and are not released into the environment. The organic molecules M and / or the inorganic nanoparticles are thus present in a form which is particularly advantageous for their application. This fact applies in particular to those liquid formulations or particle powders which contain a UV absorber. The migration stability can be measured, for example, by spray-drying the liquid formulation and then extracting the powder with tetrahydrofuran (THF) by determining the fraction of organic molecules M recovered by extraction. Furthermore, according to the invention, in the case of metal-containing inorganic nanoparticles, the metals are frequently prevented from leaving the particles P. Thus, for example, the toxic effect of the metal (cations) can be controlled.

The particles according to the invention in the form of their liquid formulations or powders are preferably used for finishing, for example for stabilizing, organic polymers. The particles can be incorporated for this purpose both as a liquid formulation, as well as a powder by the usual methods in the organic polymers. Mention may be made, for example, of the mixture of the particles with the organic polymers before or during an extrusion step. In general, it is also possible to incorporate other, for example surface-modified nanoparticles, together with the particles according to the invention or else alone, for example as additives or fillers, into organic polymers.

After incorporation of the particles P according to the invention into the organic polymers, the particles P are in the polymer matrix and the organic molecules are according to the invention stable to migration in the organic polymers. The migration stability can be applied analogously to the above-mentioned method (extraction with THF) for particle powder also on polymer powder containing particles P. Furthermore, the migration stability can be tested by optical determination. For this purpose, films are produced from the organic polymers containing the particles P, for example by extrusion, which are stored at elevated temperature (for example 60 ^° C.). After a certain period of time, for example one to two weeks, it can be determined by optical examination whether the particles P have migrated to the surface of the films (formation of visible deposits). Inanimate organic polymers here are any plastics, preferably thermoplastics, in particular films, fibers or shaped bodies of any desired shape. These are also referred to simply as organic polymers in the context of this application. Further examples of the equipment or stabilization of organic polymers with polymer additives can be found in the Plastics Additives Handbook, 5th edition, Hanser Verlag, ISBN 1-56990-295-X. The organic polymers are preferably polyolefins, in particular polyethylene or polypropylene, polyamides, polyacrylonitriles, polyacrylates, polymethacrylates, polycarbonates, polystyrenes, copolymers of styrene or methylstyrene with dienes and / or acrylic derivatives, acrylonitrile-butadiene-styrenes (ABS), polyvinyl chlorides, polyvinyl acetals , Polyurethanes or polyesters. Organic polymers may also be co-polymers, blends or blends of the above polymers. Particularly preferred polymers are polyolefins, in particular polyethylene or polypropylene.

In order to stabilize a thermoplastic polymer to UV exposure, one can proceed, for example, so that one first melts the polymer in an extruder, an inventively prepared UV absorber-containing particulate powder into the polymer melt at a temperature of for example 180 to 200 ⁰ C familiarization processed and produces a granulate from which then produced by known methods films, fibers or moldings, which are stabilized against the action of UV radiation.

Of course, within the scope of the use according to the invention it is also possible to use mixtures of different particles according to the invention. The particles of these mixtures may have the same or different compositions and size distributions. For example, particles containing UV absorbers can also be used together with other particles of the invention containing, for example, stabilizers for organic polymers such as antioxidants for stabilizing organic polymers and lacquer layers.

Of technical interest are, for example, such liquid formulations according to the invention or those thereof e.g. spray-dried powders containing particles of the invention containing at least one antioxidant, for example phenolic compounds such as pentaerythritol tetrakis [3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] (available, for example, as Irganox® 1010 from Ciba SC). Also of interest are particulate powders containing at least one organic polymer antistat or organic fogging inhibitor or organic polymer colorant.

Preference is given to liquid formulations according to the invention which contain UV absorbers and stabilizers. For use in equipment, for example for stabilizing organic polymers, the particles of the invention P can also be used together with other additive systems to improve the overall efficiency. For example, with conventional emulsion concentrates, suspension concentrates, suspoemulsion concentrates of polymer additives. By mixing the particles according to the invention with conventional preparations of the abovementioned polymer additives, the spectrum of activity is broadened on the one hand if the conventional preparation contains polymer additives other than the particles according to the invention. On the other hand, the advantages of the particles according to the invention are not lost by formulation with conventional polymer additive formulations, in particular the improved migration stability. Consequently, one can improve the performance of a conventional polymer additive formulation by formulation with particles P of the invention containing the same polymer additives. In particular, it is possible because of the improved migration stability with constant effectiveness to reduce the amount of additives used.

In a preferred embodiment, the particles P according to the invention are used together with further stabilizers for stabilizing polymers. In particular, UV absorbers, antioxidants, sterically hindered amines, nickel compounds, metal deactivators, phosphites, are used as further stabilizers for this purpose.

Phosphonites, hydroxylamines, nitrenes, amine oxides, benzofuranones, indolinones, thiosynergists, peroxide-destroying compounds or basic costabilizers used.

The liquid formulations according to the invention are associated with a number of further advantages. On the one hand, these are stable formulations of the particles P, for example of polymer additives. In particular, the phase separation problems and settling of the polymer additive observed in other formulations as well as in microdispersions or nanodispersions of the polymer additives are not observed, even under severe conditions such as occur in the case of organic polymers with polymer additives. The leaching of the polymer additive from the treated organic polymer when exposed to water is significantly reduced compared to other formulations. Furthermore, interactions of the polymer additives with other formulation ingredients or co-polymer additives, as commonly encountered in conventional formulation, are not observed. In addition, the degradation of the polymer additives by substrate or environmental influences, such as pH of the environment or UV radiation is slowed down or even completely prevented. Surprisingly, a reduced effectiveness of the polymer additives by incorporation into a polymer matrix is generally not observed.

A further advantage of the production method according to the invention is that the particle size of the particles P according to the invention can be adjusted in a controlled manner. In particular, as mentioned above, the concentration of organics in see molecules M in the mixture with the compounds V set the particle size of the particles P targeted. For example, by the use of salicylic acid, in the presence of compounds V, which lead to the formation of ZnO nanoparticles, particle sizes of 2 to 10 nm can be adjusted with the addition of base, for example NaOH, depending on the concentration of salicylic acid. The larger the concentration of the organic molecules, the smaller the particle size of the particles P of the invention. For example, with a molar ratio of Zn (OAc) 2: salicylic acid of 1: 0.5, particle sizes of about 2 nm can be obtained. With a molar ratio of Zn (OAc) 2: salicylic acid of, for example, 1: 0.1, particle sizes of about 5 nm are obtained.

By repeatedly adding various amounts of organic molecules M (step (c) of the production method of the present invention), the particle size and composition of the particles P can be further varied. By way of such a variation of the particle size, the properties of the particles P can also be adjusted. For example, nanoparticles based on ZnO or TiO 2 have different UV absorptions depending on the particle size. According to the invention, therefore, for example, the UV absorption properties of the particles P can vary depending on the use. Further properties which can be set by the skilled person by routine experiments are, for example, the solubility properties of the particles P or the transparency of the materials containing the particles P.

The production process of the particles P according to the invention allows very efficient access to the particles. The particles according to the invention are present, for example, as constituents of liquid formulations or of powders and can easily be incorporated into organic polymers.

The particles of the invention are particularly suitable for the equipment, for example against static charge or fogging and / or stabilization, for example against oxidation, exposure to UV rays, heat and / or light, of organic polymers.

The following examples are intended to illustrate the invention without, however, limiting it.

Examples:

All equivalents (eq) are molar equivalents. Room temperature (RT): 21 ^° C.

Comparative Example 1: ZnO nanoparticles

A 1 molar ethanolic sodium hydroxide solution (1 eq) was added to a 0.03 molar ethanolic zinc acetate solution (1 eq) and the mixture was stirred at room temperature. The growth of zinc oxide nanoparticles was monitored by UV spectroscopy. The particles grew continuously and after some time precipitated in the solution.

Analysis: TEM showed crystalline ZnO particles of about 4 to 5 nm particle size.

Using lithium hydroxide, smaller (from 2 to 3 nm) and larger (from 5 to 10 nm) particles were obtained using potassium hydroxide.

Example 1 :

ZnO modified with a chromophore

Ethanolic solutions of sodium hydroxide (1 eq), zinc acetate (1 eq) and 2,6-dihydroxy-4-methyl-3-acetylpyridine (UV absorbing chromophore) (0.5 eq) were mixed and the mixture stirred at room temperature. After 1 hour of reaction at room temperature, the solution was concentrated to dryness to obtain surface-modified ZnO nanoparticles. This solution remained stable for several months without the particles continuing to grow.

A powder obtained from a part of the solution could be redispersed in ethanol.

Production (including powder):

300 ml (9 mmol) of zinc acetate ^* 2H 2 O (0.03 molar solution in ethanol, absolute) were initially charged and 9 ml (9 mmol) of sodium hydroxide (1 molar solution in ethanol, absolute) and 150 ml (4.5 mmol) of 2,6-dihydroxy at room temperature -4-methyl-3-acetylpyridine (0.03 molar solution in methanol). The solution immediately turns light brown. After 1 h reaction at room temperature, the product solution was concentrated on a rotary evaporator at room temperature and 0-10mbar within 3 h to dryness.

This gave 2.8 g of a light brown, fine solid (powder).

analytics:

UV spectroscopy of the redispersed powder showed the absorption of ZnO and the organic chromophore. The absorption edge of the modified ZnO had a much lower wavelength (about 330 nm) than the unmodified ZnO of the Comparative Example 1 (about 380 nm) - this confirmed the smaller particle size.

TEM showed in the comparative experiment 1 crystalline ZnO nanoparticles, without surface modification, with 4 to 5 nm particle size. The ZnO particles modified with the UV absorber had a particle size of 2 to 3 nm according to TEM.

Solid NMR showed that there was no free UV absorber left. The entire UV absorber is present in bound form.

Analogously, this experiment could be carried out for similar chromophores with similar results:

AK ZnO: absorption edge modified ZnO

AK ZnO: 340 nm AK ZnO: 340 nm

AK ZnO: 330 nm AK ZnO: 335 nm AK ZnO: 335 nm

Example 2:

ZnO and silane linker

A mixture of a zinc acetate solution (1 eq, 0.03 molar ethanolic solution), sodium hydroxide solution (1 eq, 1 molar ethanolic solution) and 3-aminopropyltriethoxysilane (0.5 eq, 0.03 molar solution in ethanol) was added stirred at room temperature for 24 hours. The mixture was then centrifuged and the separated solid washed several times with methanol.

analytics:

¹ H NMR shows no more SiOEt groups, TEM shows very small (from 2 to 3 nm) crystalline modified ZnO particles, TGA (room temperature to 600 ⁰ C) shows a mass loss of about 40%, corresponding to the organic content.

Using lithium hydroxide, smaller (from 1 to 2 nm) and larger (from 5 to 10 nm) particles were obtained using potassium hydroxide.

Concentrations and ratios of the reagents were varied to obtain additional products.

Reactions at RT:

Zinc acetate as 0.03 molar ethanolic solution. NaOH as a 1 molar ethanolic solution. LiOH as 0.25 molar ethanolic solution. 3-aminopropyltriethoxysilane (96%, from Fluka) as a 0.03 molar methanolic solution. 3- (methacryloxy) propyltrimethoxysilane (97%, Alfa Aesar) as 0.03 molar methanolic solution. Solution: solution.

MOI

Behavior of sol. Ratio of silane (c / LM) Zn: (after 24 h) Zn: OH- silane first clear solution.

NaOH 1: 1 3-aminopropyltriethoxysilane 1: 2 then cloudy / sediment

NaOH 1: 1 3-aminopropyltriethoxysilane 1: 2 turbid / sediment first clear sol.

NaOH 1: 1 3-aminopropyltriethoxysilane 1: 1 then cloudy / sediment

3

NaOH 1: 1 (methacry-1: 2 clear solution loxy) propyltrimethoxysilane

3

NaOH 1: 1 (methacrylo-1: 1 clear solution xy) propyltrimethoxysilane

LiOH 1: 3 3-aminopropyltriethoxysilane 1: 2 clear sol.

LiOH 1: 3 3-aminopropyltriethoxysilane 1: 1 clear sol.

3

LiOH 1: 3 (methacry-1: 2 clear solution loxy) propyltrimethoxysilane

LiOH 1: 3 3- 1: 1 clear sol.

Reactions at 60 ^° C.

Example 3:

Silane-cinnamic acid chromophore

A mixture of triethylamine (1.5 eq) and 3-aminopropyltriethoxysilane (1 eq) was dissolved in dichloromethane and treated with cinnamic acid chloride solution (1 eq). The mixture was stirred at room temperature for 24 h. Subsequently, the product solution was washed several times with water, dried and the solvent was stripped off.

The desired structure was confirmed by ¹ H-NMR: δ _H (CDCl ₃ ) 0.70 (2H, t, CH ₂ Si), 1.25 (9H, t, 3 x CH ₃ ), 1.72 (2H, m, CH ₂ CH ₂ Si), 3.39 (2H, q, CH ₂ NH), 3.85 (6H, q, 3 x OCH ₂ ), 6.10 (1H, s, NH), 6.48 (1H, d, CH = C), 7.3- 7.4 (3H, m, Ar), 7.45-7.55 (2H, m, Ar) and 7.62 (1H, d, CH = C).

Example 4:

Silane cyanoacrylate chromophore

A mixture of triethylamine (1.5 eq) and 3-aminopropyltriethoxysilane (1 eq) was dissolved in dichloromethane and 3,3-diphenyl-2-cyanoacryloyl chloride (1 eq) was added. The mixture was stirred at room temperature for 24 h. Subsequently, the product solution was washed several times with water, dried and the solvent was removed. The desired structure was confirmed by ¹ H-NMR: δ _H (CDCl ₃ ) 0.55 (2H, t, CH ₂ Si), 1.35 (9H, t, 3 x CH ₃ ), 1.50 (2H, m, CH ₂ CH ₂ Si),, 3.20 (8H, m, 3 x OCH ₂ + CH ₂ N), 7.0-7.5 (1OH, m, Ar), and 1.8 (1H, q, NH)

Example 5:

ZnO with cinnamic acid silane

A mixture of zinc acetate (1 eq, 0.03 molar ethanolic solution), sodium hydroxide (1 eq, 1 molar ethanolic solution) and cinnamate (0.5 eq, 0.155 molar ethanolic solution) shown above was stirred for 24 hours at room temperature. Thereafter, the solvent was stripped off to obtain the particles.

analytics:

TEM shows modified crystalline ZnO having a particle size of 2 to 3 nm.

UV-vis spectrum shows cinnamic acid absorption at λ _ma χ 270nm.

Example 6:

ZnO with cyanoacrylamide silane

A mixture of zinc acetate (1 eq, 0.03 molar ethanolic solution), sodium hydroxide (1 eq, 1 molar ethanolic solution) and cyanoacrylamide-silane (0.5 eq, 0.155 molar ethanolic solution) was stirred for 24 hours at room temperature. Thereafter, the solvent was stripped off to obtain the particles.

Analytics: TGA (room temperature to 600 ⁰ C) shows a mass loss of about 40%, corresponding to the organic content.

TEM shows modified crystalline ZnO with a particle size of 2 to 3 nm. UV-vis spectrum shows the cyanoacrylate absorption at λ _ma χ 295 nm.

Example 7:

TiO ₂ with chromophore in ethanol General rule:

To an ethanolic solution of a UV-absorbing chromophore (0.1-1 eq) was distilled. Water (0.7-14 eq) added. Titanium tetraisopropoxide (1 eq) was added dropwise to this solution at room temperature with stirring. After 1 hour of reaction at room temperature, the solution was concentrated to dryness to obtain the particles. The resulting product was redispersed in ethanol.

The solution remained stable for several months without the particles continuing to grow.

Experimental Example:

59 mg (0.24 mmol) of 3,3-diphenyl 2-cyanoacrylic acid were dissolved in 10 ml of ethanol. 21.4 μl (1.19 mmol) of dist. Water was added. Subsequently, 100 μl (0.34 mmol) of titanium tetraisopropoxide are added to this solution while stirring. After 1 h reaction at room temperature, the product solution was concentrated on a rotary evaporator at RT and 0-10 mbar to dryness.

The same reaction was carried out in different molar ratios of titanium tetraisopropoxide: water: chromophore: from 1: 0.7: 0.1 to 1: 14: 1.

The following chromophores were reacted analogously:

λ _max 310 nm λ _max ~ 380 nm λ _max ~ 380 nm

analytics: UV spectra in ethanol: Absorption of the O2 and the chromophore are both observed. Particle size determination by laser diffraction: particle size from 1 to 6 nm.

Claims

Hybrid nanoparticle patent claims:

1. Particles P obtainable by reacting compounds V capable of forming inorganic nanoparticles X with organic molecules M containing functional groups Z, wherein the molecules M and the compounds V are co-present during the formation process of the particles P. ,

2. Particles according to claim 1, characterized in that the particles P have a particle size of 1 nm to 50 nm.

3. Particles according to claim 1 or 2, characterized in that the inorganic nanoparticles X contain metal oxides.

4. Particles according to claim 3, characterized in that the nanoparticles X metal oxides of the general formula A _x O _y , where x is a number from the range of 1 to 3 and y is a number in the range of 1 to 5 and

A is a metal or contain their mixtures.

5. Particles according to claim 4, wherein the metal oxides ZnO, TiÜ2, ZrÜ2, CeÜ2, Cβ2θ3, Snθ2, SnO, Al2O3, Si02, or Fβ2θ3 are θder the mixtures of these metal oxides.

6. Particles according to claims 1 to 5, wherein the particles P obey the symbolic formula X-M and the organic molecules M are located substantially on the surface of the particles P.

Particles according to claim 6, wherein the organic molecules M are of the formula Y'-Z and Y 'denotes a chemical moiety (linker) via which the organic molecules M interact with the inorganic nanoparticles X.

8. Particles according to claim 6, wherein the organic molecules M conform to the formula YZ, Y denotes a chemical structural unit (linker), via which the organic molecules interact with the inorganic nanoparticles X and Y has arisen after a chemical reaction from Y '.

9. Particles according to claims 7 or 8, corresponding to the symbolic general formulas (I) or (II):

X-Y'-Z (I)

X-Y-Z (II), where -Y'- or -Y- are given by,

(L1), R ¹ (L2) (L3)

- 0- * - N- * -s *

O (L4) O (L5) R ¹ O (L6)

I I o -c-o- * - o-c- * -N-C- *

O (L7) O (L8) O (L9)

^■ oso- * - os- * -s- *,

I i

O O O

O (L10) O (LH) O (L12)

-o-p- * - O-P- * - p- *,

OR ⁷

and " ^* " denotes the attachment to the functional group Z, wherein

R ¹ is H, _Ci-C2 o alkyl, aryl, arylalkyl, heterocyclic, _{Ci-C2o-alkylcarbonyl,}

R ² , R ^{3 are} independently of each other O, C 1 -C 20 -alkoxy, C 1 -C 20 -alkyl,

Ci-C ₂ o-Alkylen-R ⁵

R ^{5 is} O, N, S, N (R ⁶ ) -C =O, N-CO ₂ , O ₂ C, CO ₂ , O ₂ CN, OCO ₂ , R ⁶ OOR ⁶ R ⁶ OOR ⁶

I I l I l I l I l I

N-C, C-N, N-C-O, O-C-N,

OOOR ⁶ OR ⁶

O-C, C-O, O-C-O, N-C-N

R ^{6 is} H, C 1 -C ₂₀ -alkyl,

R ^{7 are} H, metal cations, and wherein the substituents R ¹ to R ⁴ and / or R ^{6 may} each be interrupted at any position by one or more heteroatoms, the number of these heteroatoms not exceeding 10, preferably not more than 8, most preferably not more than 5 and in particular not more than 3, and / or in any position, but not more than five times, preferably not more than four times and more preferably not more than three times, by Ci-C2o-alkyl, d -

C2o-alkoxy, aryl, aryloxy, heterocycles, heteroatoms or halogen may be substituted, which may also be substituted at most twice, preferably at most once with said groups.

10. Particles according to claims 1 to 9, characterized in that the organic molecules M have a molecular weight of less than 800 g / mol.

1 1. Particles according to claims 7 to 10, corresponding to the general formulas

X-Y'-Z or XYZ with -Z

(* symbolizes the attachment point to the linker Y or Y '] where R is halogen, hydroxy, phenyl, C 1 -C 20 -alkyl, hydroxyphenyl,

C 1 -C 20 -alkoxy, aryl, aryloxy, amino, mono- or di-alkylamino, nitrile, carboxylate, esters, thiol, sulfoxides, sulfonic acid, acyl, formyl, carbonyloxyalkyl, carbonylaminoalkyl n is an integer from the range from 0 to 4

and the n substituents R independently of one another may be identical or different, and where the substituent R may be interrupted at any position by one or more heteroatoms, the number of these heteroatoms being not more than 10, preferably not more than 8, most preferably not more than 5 and in particular not more than 3, and / or in any position, but not more than five times, preferably not more than four times and more preferably not more than three times, by Ci-C2o-alkyl, Ci -C 2o-alkoxy, aryl, aryloxy, heterocycles, heteroatoms or halogen may be substituted, these also being at most twice, preferably at most once with said

Groups can be substituted.

12. Particles according to claims 1 to 1 1, characterized in that the particles P absorb electromagnetic radiation in the wavelength range of 200 to 600 nm.

13. Particles according to claim 12, characterized in that the absorption spectrum of the particles P has an absorption maximum in the wavelength range of 200 to 600 nm.

14. Powder containing particles according to claims 1 to 13.

15. Liquid formulations containing particles according to claims 1 to 13.

16. A process for the preparation of particles according to claims 1 to 13, comprising the following steps:

(a) providing the compound V optionally dissolved in a solvent and the organic molecules M optionally dissolved in a solvent,

(b) mixing the compounds V with the organic molecules M optionally in a solvent,

(c) reacting the mixture of (b), optionally with addition of further substances or further organic molecules M, optionally under the reaction conditions which would lead to the formation of nanoparticles X from compounds V, to particles P according to the invention, (d) optionally isolating the Particles P,

(e) optionally purifying and working up the particles P,

(f) optionally further modification of the particles P,

(g) optionally redispersing the particles P.

17. The method according to claim 16, characterized in that the compounds V and the organic molecules are dissolved in step (a) in a solvent and in step (b) are mixed in dissolved form.

18. The method according to claims 16 or 17, characterized in that in step (c) as further substances initiators or catalysts for the formation of the inorganic nanoparticles X are added.

19. The method according to claims 16 to 18, characterized in that in step (c) further organic molecules M are added.

20. The method according to claims 16 to 19, characterized in that the inorganic nanoparticles X are metal oxides.

21. The method according to claim 20, characterized in that the metal oxides X, ZnO, TiO ₂ , ZrO ₂ , CeO ₂ , Ce ₂ O ₃ , SnO ₂ , SnO, Al ₂ O ₃ , SiO ₂ or Fe ₂ O ₃ or mixtures from these metal oxides are.

22. A method for controlling the particle size, characterized in that particles are prepared by a method according to claims 16 to 21.

23. A method for suppressing the photocatalytic activity of inorganic nanopatics X, characterized in that particles are prepared according to claims 1 to 13, being used as organic molecules M UV absorber.

24. A process for the stabilization of UV absorbers, characterized in that the UV absorbers are introduced as organic molecules M in particles P according to claims 1 to 13.

25. A process for the stabilization of polymers against the action of light, radicals or heat, characterized in that the polymers mixtures containing particles according to claims 1 to 13, are added in an amount sufficient to stabilize the polymers

26. A process for the stabilization of polymers against the action of UV light, characterized in that the polymers mixtures containing particles according to claims 12 or 13 are added in an amount sufficient to stabilize the polymers.

27. A process for the stabilization of polymers according to claims 25 or 26, characterized in that the mixtures in addition to the particles further stabilizers.

28. A process for the stabilization of polymers according to claim 27, characterized in that the further stabilizers UV absorbers, antioxidants, hindered amines, nickel compounds, metal deactivators, phosphites, phosphonites, hydroxylamines, nitrenes, amine oxides, benzofuranones, indolinones, thiosynergists, peroxide are destructive compounds or basic costabilizers.

29. Use of particles P according to claims 12 or 13 for the stabilization of polymers against the action of light.

30. Use of particles according to claims 12 or 13 as UV absorbers in cosmetic applications.

31. A method for stabilizing polymers against the action of light, free radicals or heat, characterized in that the nanoparticles are added to the polymer, on the surface of organic, light-absorbing compounds are attached.

32. Use of nanoparticles, on the surface organic, light-absorbing compounds are attached to stabilize polymers against the action of light, radicals or heat.