EP2087036A2

EP2087036A2 - Compositions containing phosphonate-functional particles

Info

Publication number: EP2087036A2
Application number: EP07821621A
Authority: EP
Inventors: Christoph Briehn; Volker Stanjek; Martina Baumann; Silvia Jung-Rosetti
Original assignee: Wacker Chemie AG
Current assignee: Wacker Chemie AG
Priority date: 2006-11-10
Filing date: 2007-10-22
Publication date: 2009-08-12
Also published as: US20100063187A1; CN101522777A; WO2008055768A3; DE102006053156A1; WO2008055768A2; KR20090073155A; JP2010509416A

Abstract

The invention relates to a composition (Z) which contains (a) 0.02-200 parts by weight of particles (P) having at least one structural element of general formula =Si-L-P(O)(OR1)2, (b) 100 parts by weight of a binder (B), (c) 0-100 parts by weight of a curing agent (H) which is reactive to the binder (B), and (d) 0-1000 parts by weigh of a solvent or a solvent mixture, L being a bivalent aliphatic or aromatic hydrocarbon group with 1 to 12 hydrocarbon atoms as defined in claim 1 and R1 and R2 being defined as in claim 1. The invention also relates to composite materials (K) that can be produced from the composition and to the use thereof.

Description

Compositions containing phosphonate-functional particles

The invention relates to phosphonate functional particle-containing compositions, composite materials prepared therefrom and the use of the compositions.

Particles - especially nanoparticles - containing composite materials are state of the art. Corresponding coatings of composite materials are described for example in EP 1 249 470, WO 03/16370, US 20030194550 or US 20030162015. The particles lead to an improvement in the properties of the corresponding coatings, in particular with regard to their scratch resistance and optionally also their chemical resistance.

A common problem with the use of - usually inorganic - particles in organic matrix systems consists in a usually insufficient compatibility of particles and matrix. This can lead to the particles not being able to disperse sufficiently well in the matrix. In addition, even well-dispersed particles can settle at longer stand or storage times, possibly forming larger aggregates or agglomerates which can not or only poorly be separated into the original particles by an energy input. The processing of such inhomogeneous systems is in any case extremely difficult, often even impossible. Composite materials that have smooth surfaces after their application and curing can usually not be produced in this way, or can only be produced by cost-intensive processes.

Therefore, it is advantageous to use particles which have on their surface organic groups, which to a lead to better compatibility with the surrounding matrix and thus suppress unwanted agglomeration or aggregation of the particles. In this way, the inorganic particle is masked by an organic shell. In addition, particularly favorable composite properties can often be achieved if the organic functions on the particle surfaces are also reactive with respect to the matrix, so that they can react with the matrix under the respective curing conditions. It is thus possible to chemically incorporate the particles into the matrix during the curing of the composite, which often results in particularly good mechanical properties but also in an improved form

Chemical resistance results. Such systems are described, for example, in DE 102 47 359 A1, EP 0 832 947 A1 or EP 0 872 500 A1.

A disadvantage is the inadequate stability despite masking of the nanoparticles used in the prior art. This insufficient stability of the particles occurs on the one hand in the processing of the particles, in particular when concentrating the particle dispersions or a solvent exchange, on the other during the storage of the uncured particle dispersions to light. Indications of a lack of stability of the particles are an increase in viscosity, or the sedimentation of the particles, which often progresses until gelation. In addition, the described nanoparticles can not be isolated as redispersible solids due to the high agglomeration or aggregation tendency. The particles which can be produced according to the prior art fall on isolation, for example by spray drying, as

Particle agglomerates or aggregates, which also under energy input, for example by means of a bead mill or by ultrasonic treatment, not to achieve redispersing the original primary particle size. However, this would be particularly desirable in terms of storage, transport and in particular for possible processing of the powders in extrusion processes.

In the prior art, the surface-modified particles contained in the composite materials are prepared by reacting particles having free silanol (SiOH) or metal hydroxide functions with alkoxysilanes or their hydrolysis and condensation products containing unreactive groups, e.g. Alkyl or aryl radicals, or reactive organic functions, e.g. Vinyl, (meth) acrylic, carbinol, etc. included. The silanes used in the art for particle functionalization are typically di- or trialkoxysilanes.

If these silanes are used for surface functionalization, a siloxane shell is formed around the particle in the presence of water after hydrolysis and condensation of the resulting silanols. In Macromol. Chem. Phys. 2003, 204, 375-383, the formation of such a siloxane shell around a SiO ₂ -

Particles described. The problem here may be that the siloxane shell formed still has a large number of SiOH functions on the surface. The stability of such SiOH functional particles is among the

Conditions of manufacture and storage, even in the presence of the binder, often given only limited.

The production of core-shell particles which are free of alkoxysilyl and silanol groups on their surface and consequently have a lower tendency to agglomerate is taught by the documents EP 0 492 376 A and DE 10 2004 022 406 A. For this purpose, in a first step Cocondensation of various Silanes and siloxanes, wherein at least one silane or siloxane carries methacrylic groups, generates a siloxane particle, to which a polymethyl methacrylate shell is grafted in the subsequent step by reaction with methyl methacrylate. The resulting particles show excellent compatibility in organic polymers such as polymethylmethacrylate and PVC. These siloxane graft polymers also have the advantage that they are redispersible with a suitable composition and thickness of the grafted shell. However, they have the disadvantage of being relatively expensive to produce, which leads to high production costs.

Because of their broad applicability, particle-reinforced paints, which are described, for example, in EP 0 768 351, EP 0 832 947, EP 0 872 500 or DE 10247359, represent a particularly important type of composite material. Surface-modified particles are used as reinforcing fillers have sufficient compatibility with the paint matrix. By introducing the surface-modified particles, in particular the scratch resistance of paints can be significantly increased.

However, the handling of the particles, especially when in the form of a highly concentrated dispersion, is extremely difficult due to their described limited stability. In addition, it is not possible to isolate the particles, since the agglomerates which form in the course of the drying do not revert back to the original particle size, i. the size of the primary particles, can be separated. In addition, the mechanical hardnesses - and in particular the scratch resistance - of the particle-reinforced coatings are not sufficient for many applications.

For a particularly important type of paint, for another To improve the scratch resistance is sought by an addition of particles, a coating resin of hydroxy-functional prepolymers, in particular of hydroxy-functional polyacrylates and / or polyesters, used in the paint curing with an isocyanate-functional hardener (polyurethane coatings) and / or a melamine (melamine) for reaction to be brought. The polyurethane coatings are characterized by particularly good properties. In particular, polyurethane coatings have superior chemical resistance, while melamine coatings generally have better scratch resistance. Typically, these types of paints are used in particularly high-quality and demanding fields of application, for example as clearcoats or topcoats for OEM coatings in the automotive and vehicle industry. Likewise, most automotive refinish topcoats are of such systems. The layer thicknesses of these coatings are typically in the range from 20 to 50 μm.

In polyurethane paint systems, a distinction is generally made between the so-called 2K and 1K systems. The former consist of two components, one of which consists essentially of the Isocyanathärter, while the paint resin is contained with its isocyanate-reactive groups in the second component. Both components must be stored and transported separately and may only be mixed shortly before processing, since the finished mixture has only a very limited pot life. Often cheaper, therefore, are the so-called 1K systems, which consist of only one component in which there is a hardener with protected isocyanate groups in addition to the paint resin. 1K coatings are thermally cured, whereby the protecting groups of the isocyanate units are cleaved off and the deprotected isocyanates are then cleaved with the Resin can react. Typical baking temperatures of such ^1- component paints are 120-160 ° C. Melamine paints are generally 1-component paints, and the baking temperatures are typically in a comparable temperature range.

Especially with these high-quality paints, a further property improvement would be desirable. This applies in particular to vehicle topcoats. Above all, the achievable scratch resistance of conventional car paints is not yet sufficient, so that it can be used e.g. In the washing line by particles in the washing water to a noticeable scratching of the paint comes. In the long term, the gloss of the paint is sustainably damaged. Here would be desirable formulations that can achieve better scratch resistance.

A particularly advantageous way of achieving this object is the use of particles which have on their surface organo-functions which are reactive with the paint resin or with respect to the hardener. In addition, these lead

Organ functions on the particle surface to mask the particles and thus improve the compatibility of particles and paint matrix.

Such particles with suitable organ functions are already known in principle. Like their use in coatings, they are described, for example, in EP 0 768 351, EP 0 832 947, EP 0 872 500 or DE 10247359.

In fact, the scratch resistance of paints can be significantly increased by the incorporation of such particles. However, in all of the methods described in the prior art when using these particles are still not optimal Results achieved. In particular, the corresponding coatings have such high particle contents that the use of such paints in large series finishes will be difficult to realize, for reasons of cost alone.

In WO 01/09231, paint-containing paint systems are described, which are characterized in that there are more particles in a surface segment of the paint than in a bulk segment. The advantage of this particle distribution is the comparatively low particle concentration, which is needed for a significant improvement in the scratch resistance. The desired high affinity of the particles to the paint surface is achieved by applying a silicone resin as a surface-active agent to the particle surfaces. A disadvantage of this method, however, is the fact that not only the silicone resin modification of the particles, but also the preparation of the silicone resins required for this purpose is itself technically complex. The latter is particularly problematic because it is necessary to achieve a good scratch resistance, the silicone resins with

Organo-functions, e.g. Carbinol functions to provide, over which the appropriately modified particles can be chemically incorporated in the lacquer hardening in the paint. Such functionalized silicone resins are not available commercially or only to a very limited extent. Above all, though, is the

Selection of the possible organ functions with this system relatively limited. Therefore, in this system, as well as in all other systems according to the prior art, no optimal results are achieved.

The object of the invention was therefore the development of a composition for a composite material, which overcomes the disadvantages of the prior art. The invention provides a composition (Z) comprising (a) 0.02-200 parts by weight of particles (P) which contain at least one structural element of the general formula [1],

≡Si-LP (O) (OR ¹ ) 2 ^[1] '

exhibit,

(b) 100 parts by weight of a binder (B),

(c) 0-100 parts by weight of a curing agent (H) which is reactive with the binder (B), as well as

(D) 0-1000 parts by weight of a solvent or a solvent mixture, wherein

L is a divalent optionally substituted by carbinol, amino, halogen, epoxy, phosphonato, thiol, (meth) acrylato, carbamato groups substituted aliphatic or aromatic hydrocarbon radical having 1 to 12 carbon atoms, the carbon chain by non-adjacent oxygen atoms, Sulfur atoms, or NR ^ - groups may be interrupted,

R! Hydrogen, a metal cation, an ammonium cation of

Formula -N (R ^) ^ ⁺ , phosphonium cation of the formula -P (R ^) 4+ or an optionally with carbinol, amino, halogen,

Epoxy, phosphonato, thiol, (meth) acrylato, carbamato, ureido groups substituted aliphatic or aromatic hydrocarbon radical having 1 to 12 carbon atoms, whose carbon chain may be interrupted by non-adjacent oxygen atoms, sulfur atoms, or NR ^ groups, and

R ^ is a hydrocarbon radical having 1-8 carbon atoms mean.

Composite materials (K) which can be produced from the composition (Z) are likewise provided by the invention.

In one embodiment of the invention, the particles (P) in addition to functions of the general formula [1] additionally also at least one organofunctional group (F), which is reactive with the binder (B) or the curing agent (H).

In a preferred embodiment of the invention, the composite materials (K) are coating systems which can be prepared from a coating composition (Z) comprising (a) 0.02-60 parts by weight of particles (P) containing at least one structural element of the general formula [1] .

≡Si-LP (O) (OR ¹ J ₂ ^[1] '

c) 100 parts by weight of a hydroxyl-functional paint resin (B), c) 1-100 parts by weight of a paint curing agent (H) containing isocyanate groups selected from free isocyanate groups and protected isocyanate groups which upon thermal treatment with elimination of a protective group Releasing isocyanate function, d) 0-1000 parts by weight of a solvent or a solvent mixture.

The invention is based on the discovery that the

Composite materials (K) prepared from the compositions (Z) have excellent mechanical properties. In addition, the preparation of the compositions (Z) is due to the high stability of the particles (P) contained in the compositions (Z) compared to the methods of the prior art significantly easier. Due to the presence of the structural elements of the general formula [1], the particles (P) have an extremely low agglomeration or

Aggregation tendency, which makes it possible to handle the particles (P) in dispersions with high solids content. Depending on the type of particle modification, it is sometimes possible to isolate the particles (P) as a solid and to redisperse them in the composition (Z).

The binder (B), the hardener (H) and the particles (P) - if they have organofunctional groups (F) which are reactive with the binder or the curing agent - preferably have sufficiently many reactive groups that in curing the compositions (Z) to the composite materials (K) can form a three-dimensionally crosslinked polymer network.

L preferably represents a bivalent alkyl radical of 1-8

Carbon atoms or an aryl or heteroaryl radical having 1-10 carbon atoms; L is particularly preferably a methylene or propylene radical. When R ^ - is preferably an alkyl radical having 1-6 carbon atoms, in particular methyl or ethyl radical. R 1 is preferably an alkyl radical, in particular methyl, ethyl or butyl radical.

The composition (Z) preferably contains at least 0.05 parts by weight, more preferably at least 0.1 parts by weight of particles (P). In very advantageous

Embodiments of the invention contains the composition (Z) at least 0.3 parts by weight, in particular at least 0.5 parts by weight of particles (P). The composition (Z) preferably contains at most 50 parts by weight, more preferably at most 25 parts by weight of particles (P). In very particularly advantageous embodiments of the invention, the composition (Z) contains at most 10 parts by weight, in particular at most 5 parts by weight of particles (P).

The particles (P) preferably have a specific surface area of from 0.1 to 1000 m 2 / g, more preferably from 10 to 500 m 2 / g (measured by the BET method according to DIN EN ISO 9277 / DIN 66132). The average size of the primary particles is preferably less than 10 microns, more preferably less than 1000 nm, wherein the primary particles as aggregates (definition according to DIN 53206) and agglomerates (definition according to DIN 53206) may be present, depending on the external shear stress (eg due to the measurement conditions) can have sizes from 1 to 1000 μm, and the average particle size is determined by means of transmission electron microscopy (TEM) or the hydrodynamic equivalent diameter by means of photon correlation spectroscopy.

In a particular embodiment of the invention, particles are used as described in WO 2004/089961 but additionally have structural elements of the general formula [1].

In the particles (P), the structural elements of the general formula [1] can be covalently bonded via ionic or van der Waals interactions. Preferably, the structural elements of the general formula [1] are covalently attached. In a preferred embodiment of the invention, the particles (P) are formed by reaction of particles (P1) with functions selected from metal-OH, metal-O-metal, Si-OH,

Si-O-Si, Si-O metal, Si-X, metal-X, metal-OR ³ , Si-OR ³ with silanes (S) or their hydrolysis, alcoholysis and

Reacted condensation products which have at least one structural element of the general formula [1] and at least one reactive silyl group

≡Si-Y

which are reactive with the surface functions of the particle (P1), wherein R 1 represents an optionally substituted alkyl radical, X represents a halogen atom and

Y represents a halogen, a hydroxy or alkoxy group, a carboxylate or an enolate.

R 1 is preferably an alkyl radical having 1 to 10, in particular 1 to 6 carbon atoms. The radicals methyl, ethyl, n-propyl and i-propyl are particularly preferred. X is preferably fluorine or chlorine. The radicals Y are preferably a halogen, hydroxyl or alkoxy groups. The radicals Y are particularly preferably chlorine atoms, hydroxyl, ethoxy or methoxy radicals.

Are used for the preparation of the particles (P) particles (Pl), which have functions that are selected from metal-OH, Si-OH, Si-X, metal-X, metal-OR ³ , Si-OR ³ , so takes place the attachment of the silanes (S) by hydrolysis and / or condensation. If in the particle (Pl) exclusively metal O metal, metal O-Si or Si-O-Si functions, can the covalent attachment of silanes (S) by an equilibration reaction. The procedure and the catalysts required for the equilibration reaction are familiar to the person skilled in the art and have been described many times in the literature.

Alternatively, the attachment of the structural elements of the general formula [1] can take place during the particle synthesis.

In a preferred embodiment of the invention, the silanes (S) used for modifying the particles (P1) have a structure of the general formula [2],

(R ⁴ O) ₃ _ _a R ⁴ _a Si (CR ⁵⁾ _n -P (O) (OR ⁶⁾ ₂ [2]

where a is 0, 1 or 2 and n is 1, 2 or 3,

R5 is hydrogen, an optionally substituted aliphatic or aromatic hydrocarbon having 1-6

Represents carbon atoms and R ^ and R ° have the meanings of R ^.

In this case, n preferably assumes the value 1 or 3, particularly preferably the value 1. a is preferably 0 or 2, more preferably a is 2. R 1 is preferably one

Methyl or ethyl radical, R ^ is preferably hydrogen and R ° is preferably methyl or ethyl radical.

The silanes (S) or their hydrolysis or condensation products used for modifying the particles (P1) are preferably present in an amount greater than 1% by weight (based on the particles (P)), preferably greater than 5% by weight, particularly preferred greater than 8 wt .-% used.

In the production of the particles (P) from particles (P1), in addition to the silanes (S) or their hydrolysis and condensation products, it is additionally possible to use other silanes (S1), silazanes (S2), siloxanes (S3) or other compounds (L) become. The silanes (S1), silazanes (S2), siloxanes (S3) or other compounds (L) are preferably reactive toward the functions of the surface of the particle (P). The silanes (S1) and siloxanes (S3) have either silanol groups or hydrolyzable silyl functions, the latter being preferred. The silanes (S1), silazanes (S2) and siloxanes (S3) may have organic functions (F) which are reactive towards the binder (B) or the curing agent (H), but silanes (S1), Silazanes (S2) and siloxanes

(S3) are used without organ functions. The silanes and siloxanes (S) can be used as a mixture with the silanes (S1), silazanes (S2) or siloxanes (S3). In addition, the particles can also be successively functionalized with the different silane types.

Suitable compounds (L) are, for example, metal alcoholates, e.g. Titanium (IV) isopropoxide or aluminum (III) butanolate, protective colloids such as e.g. Polyvinyl alcohols, cellulose derivatives or vinylpyrrolidone-containing polymers and emulsifiers such. ethoxylated alcohols and phenols (alkyl radical C4-C18, EO grade 3-

100), alkali metal and ammonium salts of alkyl sulfates (C ^ -CI _Q),

Sulfuric acid and phosphoric acid esters and alkyl sulfonates. Particularly preferred are succinic acid esters and alkali alkyl sulfates and polyvinyl alcohols. It is also possible to use a plurality of protective colloids and / or emulsifiers as a mixture. Preferably, the proportion by weight of the silanes (S1), silazanes (S2), siloxanes (S3) and compounds (L) is based on the total amount consisting of the silanes (S) and (S1), silazanes (S2), siloxanes (S3) and compounds (L) is formed, at least 1 wt .-%, particularly preferably at least 5% by weight. In a further particularly preferred embodiment of the invention, the use of the compounds (S1), (S2), (S3) and (L) is completely dispensed with.

Particular preference is given to mixtures of silanes (S) with silanes (S1) of the general formula [3],

(R ⁷ O) ₄ _ _a _ _b (Z) _a Si (R ⁸ ) _b [3],

or their hydrolysis or condensation products, wherein

Z is halogen atom, pseudohalogen radical, Si-N-bonded amine radical,

Amide radical, oxime radical, aminoxy radical or acyloxy radical, a 0, 1, 2 or 3, b 0, 1, 2 or 3, R 'have the meanings of R ^

R8 is an aliphatic or aromatic hydrocarbon radical having 1 to 12 carbon atoms, whose carbon chain may be interrupted by non-adjacent oxygen atoms, sulfur atoms, or NR ^ groups and optionally also has an organofunctional group (F), compared to the binder (B) or the Hardener (H) is reactive, and a + b is less than or equal to 4.

In this case, a is preferably 0, 1 or 2, while b is preferably 0 or 1. R 'is preferably a methyl or ethyl radical. Z is preferably a chlorine atom. R ^ is preferably a radical containing functional groups of the carbinol type, amine, (meth) acrylate, epoxy, thiol, isocyanato, ureido and / or carbamate.

As silazanes (S2) or siloxanes (S3) are particularly preferably hexamethyldisilazane or hexamethyldisiloxane or linear siloxanes which carry side or terminal organofunctional groups used.

Particularly preferred are the silanes (S1) which carry an organofunctional group (F) which are reactive with the binder (B) or hardener (H). Examples of such silanes (S1) are amino-functional silanes, such as, for example, aminopropyltrimethoxysilane, cyclohexylaminomethyltrimethoxysilane,

Phenylaminomethyltrimethoxysilane, silanes having unsaturated functions such as vinyltrimethoxysilane, methacrylatopropyltrimethoxysilane, methacrylatomethyltrimethoxysilane, epoxyfunctional silanes such as glycidoxypropyltrimethoxysilane, mercapto functional silanes such as

Mercaptopropyltrimethoxysilane, silanes that have a masked NCO group and release an NCO function upon deprotection upon thermal treatment, and silanes that release carbinol or amine functions upon reaction with a particle (P1).

For reasons of technical handling, suitable oxides (c1) are oxides having a covalent bond fraction in the metal-oxygen bond, preferably oxides of the 3.

Main group, such as boron, aluminum, gallium or indium oxides, the 4th main group, such as silica, germanium dioxide, tin oxide, tin dioxide, lead oxide, lead dioxide, or oxides of 4. Subgroups such as titanium oxide, zirconium oxide and hafnium oxide. Further examples are nickel, cobalt, iron, manganese, chromium and vanadium oxides.

In addition, metals with oxidized surface, zeolites (a list of suitable zeolites can be found in: Atlas of Zeolite Framework Types, 5th edition, Ch. Baerlocher, W.M. Meier D. H. Olson, Amsterdam: Elsevier 2001), silicates, aluminates, aluminophosphates, titanates and

Aluminum phyllosilicates (eg bentonites, montmorillonites, smectites, hectorites), the particles (P 1) preferably having a specific surface area of from 0.1 to 1000 m 2 / g, particularly preferably from 10 to 500 m 2 / g (measured by the BET standard) Method according to DIN 66131 and 66132). The particles (P1), which preferably have an average diameter of less than 10 .mu.m, more preferably less than 1000 nm, can be present as aggregates (definition according to DIN 53206) and agglomerates (definition according to DIN 53206), which depends on the external shear stress (eg due to the measurement conditions) sizes may have from 1 to 1000 microns. The mean particle size is determined by

Transmission electron microscopy (TEM) or the hydrodynamic equivalent diameter determined by means of photon correlation spectroscopy.

In a preferred embodiment of the invention, colloidal silicon or metal oxides which are generally present as a dispersion of the corresponding submicron-sized oxide particles in an aqueous or organic solvent are used as particles (P1). Among other things, the oxides of the metals aluminum, titanium, zirconium, tantalum,

Tungsten, hafnium and tin or the corresponding mixed oxides are used. Particularly preferred are silica sols. As a rule, the silica sols are 1-50% by weight Solutions, preferably 20-40 wt .-% solutions. In addition to water, typical solvents are, above all, alcohols, in particular alcohols having 1 to 6 carbon atoms, frequently also isopropanol but also other usually low molecular weight alcohols, for example methanol, ethanol, n-propanol, n-butanol, isobutanol and t-butanol. Likewise, organosols in polar aprotic solvents such as methyl ethyl ketone or aromatic solvents such as toluene are available. The average particle size of the silica particles (P1) is generally 1-100 nm, preferably 5-50 nm, more preferably 8-30 nm.

Examples of commercially available silica sols which are suitable for the preparation of the particles (P) are silica sols of the product series LUDOX® (Grace Davison), Snowtex® (Nissan Chemical), Klebosol® (Clariant) and Levasil® (HC Starck), silica sols in organic solvents such as IPA-ST (Nissan Chemical) or those silica sols which can be prepared by the Stöber process.

Starting from the colloidal silicon or metal oxides (P1), the preparation of the particles (P) can be carried out by various processes. However, it is preferably carried out by addition of the silanes (S) or their hydrolysis or condensation products - optionally in a solvent and / or in mixtures with other silanes (S1), silazanes (S2) or siloxanes (S3) - to the particle (P1). or its solution in an aqueous or organic solvent. The reaction is generally carried out at temperatures of 0-200 ⁰ C, preferably at 20-80 ⁰ C and particularly preferably at 20-60 ⁰ C. The reaction times are typically from 5 min to 48 h, preferably from 1 to 24 h. Alternatively, it is also possible to add acidic, basic or heavy metal-containing catalysts. These are preferably used in traces (<1000 ppm). Especially However, preference is given to dispense with the addition of separate catalysts.

Optionally, the addition of water is preferred for the reaction of the particles (P1) with the silanes (S).

Since colloidal silicon or metal oxides are often present in aqueous or alcoholic dispersion, it may be advantageous to exchange the solvent or solvents during or after the preparation of the particles (P) for another solvent or for another solvent mixture. This can be done for example by distillative removal of the original solvent, wherein the new solvent or solvent mixture in one or in several steps before, during or even after the

Distillation can be added. Suitable solvents may be, for example, water, aromatic or aliphatic alcohols, wherein aliphatic alcohols, in particular aliphatic alcohols having 1 to 6 carbon atoms (eg methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, the various regioisomers of Pentanols and hexanols), esters (eg ethyl acetate, propyl acetate, butyl acetate, butyl diglycol acetate, methoxypropyl acetate), ketones (eg acetone, methyl ethyl ketone), ethers (eg diethyl ether, t-butyl).

Butylmethylether, THF), aromatic solvents (toluene, the various regioisomers of xylene but also mixtures such

Solvent naphtha), lactones (e.g., butyrolactone, etc.) or lactams

(eg N-methylpyrrolidone). In this case, aprotic solvents or solvent mixtures which consist exclusively or at least partly of aprotic solvents are preferred. The modified particles (P) obtained from the particles (P1) can be prepared by common methods such as for example, by evaporation of the solvents used or by drying, for example in a spray dryer, thin-film evaporator or condenser, are isolated as a powder. Alternatively, it is possible to dispense with isolation of the particles (P).

In addition, in a preferred procedure, following the production of the particles (P), processes for deagglomerating the particles can be used, such as pin mills or devices for grinding sifting, such as

Pin mills, hammer mills, countercurrent mills, bead mills, ball mills, impact mills or devices for grinding sifting.

In a further preferred embodiment of the invention, as particles (P1) are organopolysiloxanes of the general formula [4],

[R ⁹ 3SiO _1/2 ] i [R ⁹ 2SiO 2/2] j [R ⁹ SiO ₃ Z ₂ Ik [SiO ₄ Z ₂ Ii [4]

used, where

R ^ is an OH function, an optionally halogen, hydroxyl, amino, epoxy, thiol, (meth) acrylic, carbamate, ureido or NCO-substituted hydrocarbon radical having 1-18 carbon atoms, wherein the carbon chain may be interrupted by non-adjacent oxygen, sulfur, or NR 2 -O- groups;

R ^ O the meanings of R ^, i, j, k, 1 denote a value of greater than or equal to 0, with the proviso that i + j + k + 1 are greater than or equal to 3, in particular at least 10, and that at least 1 Rest R ^ represents an OH function. The preparation of the particles (P) from the organopolysiloxanes (P1) of the general formula [4] takes place as described above.

Particularly preferred as particles (P1) is fumed silica prepared in a flame reaction from organosilicon compounds, e.g. of silicon tetrachloride or methyldichlorosilane, or hydrogentrichlorosilane or hydrogenmethyldichlorosilane, or other methylchlorosilanes or alkylchlorosilanes, also in admixture with

Hydrocarbons, or any volatilizable or sprayable mixtures of organosilicon compounds, as mentioned, and hydrocarbons, e.g. in a hydrogen-oxygen flame, or even a carbon monoxide oxygen flame is produced. The production of

Silica can be carried out optionally with and without the addition of water, for example in the step of purification; preferred is no addition of water. Pyrogenic silica or silica is known for example from Ullmann's Encyclopedia of Industrial Chemistry 4th Edition, Volume 21, page 464. The unmodified fumed silica has a BET specific surface area, measured according to DIN EN ISO 9277 / DIN 66132 of

10 m ^ / g to 600 m ^ / g, preferably from 50 m ^ / g to 400 m ^ / g.

The preparation of the particles (P) from fumed silica can be carried out by various methods. In a preferred

Method, the dry powdery fumed silica directly with the finely divided silanes (S) - optionally in admixture with other silanes (Sl),

Silazanes (S2), siloxanes (S3) or compounds (L) - implemented. Processes which are suitable for the production of particles (P) from fumed silica are known and have been described many times. Thus, for example, all processes described in WO 2006/018144, in which preferably powdered silica is functionalized, can also be used for the preparation of the particles (P) according to the invention. The fumed silica is preferably reacted with silanes (S), which preferably correspond to the formula [2], and optionally additional other silanes (S1), silazanes (S2), siloxanes (S3) or other compounds (L).

In another preferred method, the fumed silica is not powdered but in dispersions in water or typical industrially used solvents such as alcohols such as methanol, ethanol, i-propanol, such as ketones, such as acetone, methyl ethyl ketone, such as ethers, such as diethyl ether, THF, Hydrocarbons such as pentane, hexanes, aromatics such as toluene or other volatile solvents such as hexamethyldisiloxane or mixtures thereof with silanes (S) and optionally the silanes (Sl), silazanes (S2), siloxanes (S3) or compounds (L) implemented.

The process can be carried out continuously or batchwise and be composed of one or more steps. Preferred is a continuous process. Preferably, the modified fumed silica is prepared by a process in which the silica (1) is mixed in one of the abovementioned solvents, (2) with the silanes (S) and optionally the silanes (S1), silazanes (S2), siloxanes (S3) or compounds (L) is reacted, and (3) freed of solvents, excess silanes and by-products.

The dispersion (1), reaction (2) and drying (3) are preferably carried out in an atmosphere with less than 10% by volume of oxygen, more preferably less than 2.5% by volume, best results are achieved with less than 1% by volume of oxygen. The mixing (1) can by means of conventional mixing units such

Anchor stirrer or bar stirrer. Optionally, the mixing under high shear by means of dissolvers, rotor-stator assemblies, optionally with direct metered addition into the shear gap, by means of ultrasonic generators or by means of grinding units such as ball mills. Optionally, various of the above aggregates can be used in parallel or sequentially.

For the reaction (2) of the silanes (S) and optionally of the silanes (S1), silazanes (S2), siloxanes (S3) or compounds (L) with the silica, these are added in pure form or as a solution in suitable solvents of the silica dispersion and homogeneously mixed. The addition of the silanes (S) and optionally of the silanes (S1), silazanes (S2), siloxanes (S3) or compounds (L) can be carried out in the container used to prepare the dispersion or in a separate reaction vessel. If the silanes are added in the dispersing container, this can take place parallel to or after completion of the dispersion. If appropriate, the silanes (S) and optionally the silanes (S1), silazanes (S2), siloxanes (S3) or compounds (L) dissolved in the dispersing medium can be added directly in the dispersing step. Optionally, water is added to the reaction mixture. Optionally, the reaction mixture acidic catalysts such as Bronsted acids such as liquid or gaseous HCl, sulfuric acid, phosphoric acid or acetic acid, or basic

Catalysts such as Brönsted bases such as liquid or gaseous ammonia, amines such as NEt3 or NaOH added.

The reaction step is at a temperature of 0 ⁰ C to 200 ° C, preferably 10 ⁰ C to 180 ⁰ C and more preferably carried out from 20 ⁰ C to 150 ⁰ C.

The removal of solvents, excess silanes (S) and optionally silanes (S1), silazanes (S2), siloxanes (S3) or compounds (L) and by-products (3) can be carried out by means of dryers or by spray drying. Optionally, an annealing step to complete the reaction may be connected to the drying step.

In addition, after the drying processes for mechanical densification of the silica can be used, such as press rolls, grinding units, such as edge mills and ball mills, continuously or discontinuously, compaction by screws or screw mixer,

Screw compressors, briquetting, or compacting by suction of the air or gas content by suitable vacuum methods.

In a further particularly preferred procedure, processes for the mechanical densification of the silica are used following the drying, such as compression by suction of the air or gas contents by suitable vacuum methods or pressure rollers or combination of both methods.

In addition, in a particularly preferred procedure, following the drying, processes for deagglomerating the silica can be used, such as pin mills, hammer mills, countercurrent mills, impact mills or devices for grinding sifting.

In a further preferred method for producing the Particles (P) are the particles (P) via a cohydrolysis of organosilanes (S) with other silanes (S4) or compounds (L). As silanes (S4) it is possible to use all hydrolyzable silanes and silanes containing hydroxysilyl groups. Likewise, siloxanes or

Silazane are used. Typical examples of suitable silanes (S4) are tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane or trimethylethoxysilane. Of course, different mixtures of different silanes (S4) can be used. Mixtures can be used which, in addition to the silanes (S), contain only silanes (S4) without additional organ functions, as well

Mixtures containing in addition to the silanes (S) and silanes (S4) without additional organo-function and silanes (S4) with additional organo function. In the preparation of the particles (P) via cohydrolysis, the various silanes can be added together or successively.

The compositions (Z) may contain one or more different types of particles (P), for example modified silica and modified alumina.

As binder (B) both inorganic and organic polymers are used. Examples of such polymer matrices (B) are polyethylenes, polypropylenes, polyamides, polyimides, polycarbonates, polyesters, polyetherimides, polyethersulfones, polyphenylene oxides, polyphenylene sulfides, polysulfones (PSU), polyphenylsulfones (PPSU), polyurethanes, polyvinyl chlorides, polytetrafluoroethylenes (PTFE), polystyrenes (PS ), Polyvinyl alcohols (PVA), polyether glycols (PEG), Polyphenylene oxides (PPO), polyaryletherketones, epoxy resins, polyacrylates, polymethacrylates and silicone resins.

Polymers which are likewise suitable as binders (B) are oxidic materials which are accessible by customary sol-gel processes known to the person skilled in the art. According to the sol-gel process, hydrolyzable and condensable silanes and / or organometallic reagents are hydrolyzed by means of water and if appropriate in the presence of a catalyst and hardened by suitable methods to give the silicatic or oxidic materials.

When the silanes or organometallic reagents carry organofunctional groups (such as epoxy, methacrylic, amine groups) that can be used for crosslinking, these modified sol-gel materials can additionally be cured via their organic moiety. The curing of the organic fraction may - optionally after addition of further reactive organic components - u.a. thermally or by UV irradiation. For example, as sol-gel materials are suitable as matrix (B), which are accessible by reaction of an epoxy-functional alkoxysilane with an epoxy resin and optionally in the presence of an amine curing agent. Another example of such inorganic-organic polymers are sol-gel materials (B), which can be prepared from amino-functional alkoxysilanes and epoxy resins. By introducing the organic fraction, for example, the elasticity of a sol-gel film can be improved. Such inorganic-organic polymers are described, for example, in Thin Solid Films 1999, 351, 198-203.

It is also possible to use reactive resins as binders (B). Reactive resins are included Understood compounds having one or more reactive groups. Examples which may be mentioned here as reactive groups are hydroxy, amino, isocyanate, epoxide, mercapto groups, ethylenically unsaturated groups and moisture-crosslinking alkoxysilyl groups. In

In the presence of a suitable hardener (H) or an initiator, the reactive resins can be polymerized by thermal treatment, actinic radiation and / or (air) moisture. The reactive resins may be present in monomeric, oligomeric and polymeric form. Examples of common reactive resins are: hydroxy-functional resins, e.g. hydroxyl-containing polyacrylates or polyesters which can be crosslinked with isocyanate-functional hardeners (H); acrylic and methacrylic functional resins which can be cured thermally, by actinic radiation or by an amino-functional hardener (H) after addition of an initiator; Epoxy resins that can be crosslinked with amine hardeners (H); vinyl-functional siloxanes which can be crosslinked by reaction with a SiH-functional hardener (H); SiOH-functional siloxanes which can be cured by a polycondensation.

The binders (B) are preferably carbinol, (meth) acrylate, epoxy and isocyanate functional resins. For the preparation of coating systems, the coating resins used are preferably hydroxyl-containing prepolymers, particularly preferably hydroxyl-containing polyacrylates or polyesters. Such suitable for the paint preparation hydroxyl-containing polyacrylates and polyesters are well known to those skilled in and widely described in the relevant literature. They are manufactured by many manufacturers and distributed commercially. Other suitable binders (B) are mixtures of various matrix polymers, corresponding copolymers, and monomeric, oligomeric and polymeric reactive resins.

As hardener (H), the compounds typically used for the abovementioned binders (B) are used. Examples of suitable hardeners are amino-, epoxy-, isocyanato-functional monomers, oligomers or polymers.

The compositions (Z), which are used in particular as a coating system, may be 1-component (1K) or 2-component (2K) systems. In the first case, hardeners (H) are preferably compounds which have protected isocyanate groups. In the second case, preferred hardeners (H) are compounds with free ones

Isocyanate groups used. Both in IK and in 2K paints are used as isocyanates diisocyanates and / or polyisocyanates, which may have been previously provided with the respective protective groups. In principle, all customary isocyanates are used, as described in the

Literature are often described. Common diisocyanates are, for example, diisocyanatodiphenylmethane (MDI), both in the form of crude or industrial MDI and in the form of pure 4,4'- or 2, 4 'isomers or mixtures thereof, tolylene diisocyanate (TDI) in the form of its various regioisomers,

Diisocyanatonaphthalene (NDI), isophorone diisocyanate (IPDI), perhydrogenated MDI (H-MDI), tetramethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1,3-diisocyanato-4- methylcyclohexane or hexamethylene diisocyanate (HDI). Examples of polyisocyanates are polymeric MDI (P-MDI), triphenylmethane triisocyanate and also all isocyanurate or biuret trimers of the diisocyanates listed above. In addition, it is also possible to use further oligomers of the abovementioned isocyanates with blocked NCO groups. All di- and / or polyisocyanates can be used individually or in mixtures. Preference is given here to the isocyanurate and biuret trimerates of the comparatively UV-stable aliphatic isocyanates, particularly preferably the trimers of HDI and IPDI.

Are hardened as (H) isocyanates with protected

Isocyanate groups are used, protecting groups are preferred which are cleaved at temperatures of 80 to 200 ⁰ C, more preferably at 100 to 170 ⁰ C. Suitable protecting groups are secondary or tertiary alcohols, such as isopropanol or t-butanol, CH-acidic compounds such as diethyl malonate, acetylacetone, ethyl acetoacetate, oximes such as formaldoxime, acetaldoxime, butanoxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime or diethylene glycol, lactams such as caprolactam, Valerolactam, butyrolactam, phenols such as phenol, o-methylphenol, W-alkylamides such as N-methylacetamide, imides such as phthalimide, secondary amines such as diisopropylamine, imidazole, 2-isopropylimidazole, pyrazole, 3,5-dimethylpryazole, 1, 2, 4 Triazole and 2,5-dimethyl-1,2,4-triazole. Preferably, protecting groups such as butane oxime, 3, 5-dimethylpyrazole, caprolactam,

Diethyl malonate, methyl malonate, acetoacetic ester, diisopropylamine, pyrrolidone, 1, 2, 4-triazole, imidazole and 2-isopropylimidazole used. Particular preference is given to using protective groups which allow a low stoving temperature, for example diethyl malonate, dimethyl malonate, butane oxime, diisopropylamine, 3,5-dimethylpyrazole and 2-isopropylimidazole. The ratio of - possibly blocked -

Isocyanate groups to the isocyanate-reactive groups of paint resin (B) in the composition (Z) is usually 0.5 to 2, preferably 0.8 to 1.5 and particularly preferably 1.0 to 1.2.

Other suitable hardeners (H) are mixtures of different hardeners (H).

The compositions (Z) may also contain common solvents and the additives and additives customary in formulations. To call here would be u.a. Leveling agents, surface-active substances, adhesion promoters, light stabilizers such as UV absorbers and / or radical scavengers, thixotropic agents and other solids and fillers. To produce the respective desired property profiles of both the compositions (Z) and the composites (K), such additives are preferred.

The preparation of the composite materials (K) is preferably carried out in a two-stage process. In a first stage, the compositions (Z) are prepared by mixing the particles (P), the binder (B) and optionally the hardener (H) and other additives and additives. In a second step, the

Compositions (Z) by curing, i. by drying, by reaction between the binder (B) and hardener (H), by (air) moisture and / or by treatment with thermal or actinic radiation in the composite materials (K).

In a preferred embodiment for the preparation of the compositions (Z), the binder (B), the particles (P) and optionally the hardener (H) and, if appropriate, further additives dissolved or dispersed in a solvent or a solvent mixture. Solvent or solvent mixtures having a boiling point or boiling range of up to 120 ° C at 0.1 MPa are preferred. Suitable solvents are ethers such as THF, alcohols such as methanol, ethanol, isopropanol, esters such as butyl acetate, aromatic hydrocarbons such as toluene and xylenes, linear and branched aliphatic solvents such as pentane, hexane, dodecane and dimethylformamide, dimethylacetamide, methoxyproyl acetate, dimethyl sulfoxide , N-methyl-2-pyrrolidone and water. In order to disperse the particles (P) in the composition (Z) it is possible to use further additives and additives usually used for dispersion. These include Brönsted acids, such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, trifluoroacetic acid, acetic acid, methylsulfonic acid, Bronsted bases, such as triethylamine and ethyldiisopropylamine. In addition, all commonly used emulsifiers and / or protective colloids can be used as further additives. Examples of protective colloids are polyvinyl alcohols, cellulose derivatives or vinylpyrrolidone-containing polymers. Common emulsifiers are, for example, ethoxylated alcohols and phenols (alkyl radical C4-C18, EO grade 3-100), alkali metal and ammonium salts of alkyl sulfates (C3-C18), sulfuric acid and phosphoric acid esters and alkyl sulfonates. Particularly preferred are succinic acid esters as well as alkali alkyl sulfates and polyvinyl alcohols. It is also possible to use a plurality of protective colloids and / or emulsifiers as a mixture. Preference is given to the dispersion of the

Particle (P) requires no additives.

For dispersing the particles (P) in the composition (Z) it may be helpful to carry out the incorporation of the particles by means of a bead mill, ultrasonic treatment or other common agitators.

Alternatively, the compositions (Z) as well as the composites (K) can be prepared in a melt or extrusion process from particles (P), binder (B) and optionally a hardener (H) and other additives.

Alternatively, the composition (Z) can be prepared by modifying particles (P1) in the binder (B) or in a mixture of binder (B), hardener (H) and optionally further additives. For this purpose, the particles (P1) are dispersed in the binder (B) and subsequently reacted with the silanes (S) to form the particles (P).

In a preferred method, the compositions (Z) are prepared by adding the particles (P) during a mixing process as a powder or as a dispersion in a suitable solvent. In addition, however, a further method is preferred in which first of all a masterbatch is produced from the particles (P) and one or more components of the composition (Z), with particle concentrations> 15% by weight, preferably> 25% by weight and particularly preferably> 30% by weight. In preparing the compositions (Z), this masterbatch is then mixed with the remaining components. If a particle dispersion is used in the preparation of the masterbatch, it may be advantageous if the solvent of the particle dispersion is removed in the course of the preparation of the masterbatch, for example via a distillation step, or exchanged for another solvent or solvent mixture. If the compositions contain (Z) aqueous or organic solvents, the corresponding solvents are optionally removed after preparation of the composition (Z). The removal of the solvent is preferably carried out by distillation. Alternatively, the solvent may remain in the composition (Z) and be removed by drying in the course of the preparation of the composite material (K).

For the preparation of the composite materials (K), the compositions (Z) are preferably wound on a substrate. Further processes are immersion, spraying, casting and extrusion processes. Suitable substrates include i.a. Glass, metal, wood, silicon wafers and plastics such as e.g. Polycarbonate, polyethylene, polypropylene, polystyrene and PTFE.

If the compositions (Z) contain reactive resins (B), the curing preferably takes place after addition of a curing agent (H) or initiator by actinic radiation or thermal energy. The curing conditions correspond to those of the particle-free compositions.

If the particles (P) carry organofunctional groups which are reactive towards the binder (B) or the curing agent (H), then the particles (P) can be covalently bonded to the binder (B) or the hardener.

The particles (P) may have a distribution gradient in the composite material (K) or be homogeneously distributed. In a particular embodiment of the invention, the concentration of particles (P) at the coating / air interface is higher than in the bulk segment and at the coating / substrate interface. As an interface Coating / air is understood to mean the near-surface layer which has a thickness of at most 150 nm. Alternatively, the concentration of particles (P) at the coating / substrate interface may be higher than in the bulk segment and at the coating / air interface. The coating / substrate interface is understood to be the near-surface layer which has a maximum thickness of 150 nm. In a further preferred embodiment of the invention, the concentration of particles (P) is higher both at the coating / air interface and at the coating / substrate interface than in the bulk segment. Depending on the matrix system selected, both a homogeneous distribution and an uneven distribution can occur For example, the particles increase mechanical stability, chemical resistance, corrosion stability and adhesion.

Due to the outstanding chemical, thermal and mechanical properties of the composite materials (K) produced therefrom, the compositions (Z) can be used in particular as adhesives and sealants and as sealants, potting compounds and dental compounds.

Particularly preferably, the composite materials (K) produced from the compositions (Z) serve as scratch-resistant clearcoats or topcoats, especially in the automotive industry as OEM and refinish paints. The application of the compositions (Z) can be carried out by any methods such as dipping, spraying, and casting. Also an application of the compositions (Z) to a basecoat for a "wet on wet" method is possible. Curing is generally carried out by heating under the particular conditions required (2K coatings typically at 0-100 ⁰ C, preferably at 20 -80 ⁰ C, IK Paints at 100-200 ⁰ C preferably at 120-160 ⁰ C). Of course, the curing of the composition (Z) can be accelerated by the addition of suitable catalysts. Particularly suitable catalysts are acidic, basic and also heavy metal-containing compounds.

All the above symbols of the above formulas each have their meanings independently of each other. In all formulas, the silicon atom is tetravalent.

Unless otherwise indicated, all amounts and percentages are by weight, all pressures are 0.10 MPa (abs.) And all temperatures are 20 ^° C.

Example 1: Synthesis of phosphonate-functional particles from an aqueous silica sol.

A solution of 1.96 g Diethylphosphonatomethyl- dimethylmethoxysilane in 40 ml of methoxypropyl acetate was added dropwise within 10 min with vigorous stirring to 14.0 g of an aqueous silica sol (LUDOX® AS 40 from Grace DAVISON, 24 nm, 40 wt .-%) and the mixture heated at 60 ⁰ C for 4 h. Subsequently, the resulting milky emulsion was concentrated in vacuo until a transparent silica sol was obtained. The mean particle size of the modified silica sol, determined by means of dynamic light scattering (Zetasizer Nano from Malvern), was 32 nm. After distilling off the solvent, 7.16 g of a colorless solid were obtained, which could be redispersed by stirring in isopropanol. The average particle size of the silica sol in isopropanol was 44 nm.

Example 2: Synthesis of phosphonate-functional particles from an organic silica sol. A mixture consisting of 480 g of a silica sol in isopropanol (IPA-ST from NISSAN CHEMICAL, 12 nm, 30 wt .-%) and 48.0 g Diethylphosphonatomethyl-dimethylmethoxysilane was heated to 60 ⁰ C for 6 h. The mean particle size of the modified silica sol, determined by means of dynamic light scattering (Zetasizer Nano from MALVERN), was 13 nm. After distilling off the solvent, 191 g of a colorless solid were obtained which could be redispersed by stirring in both acetone and isopropanol. The mean particle size of the silica sol in isopropanol was 14.5 nm.

Example 3: Synthesis of Phosphonate-Functional Particles Having Protected Isocyanate Functions.

A mixture consisting of 48.0 g of a silica sol in isopropanol (IPA-ST from NISSAN CHEMICAL, 12 nm, 30% by weight), 4.32 g Diethylphosphonatomethyl-dimethylmethoxysilane and 0.48 g of the protected isocyanatosilane heated to 60 ⁰ C for 6 h.

The mean particle size of the modified silica sol, determined by means of dynamic light scattering (Zetasizer Nano from MALVERN), was 12 nm. After distilling off the solvent, 184 g of a colorless solid were obtained which could be redispersed by stirring in both acetone and isopropanol. The average particle size of the silica sol in isopropanol was 23 nm. Example 4: Preparation of a particle-reinforced epoxy resin.

7.48 g of the powdery particle described in Example 2 were dispersed in 30 ml of acetone. The transparent silica sol was then added dropwise to a solution of 30.0 g of DER 332 epoxy resin (DOW CHEMICAL) and 8.00 g of 4-aminophenylsulfone in 100 ml of acetone. After distilling off the solvent under reduced pressure, the low-viscosity mixture was poured into an aluminum pan and cured at 190 ^° C. for 30 minutes and at 240 ^° C. for 3 hours. A transparent solid having a thickness of 6 mm was obtained. Electron micrographs showed that the particles used are isolated in the composite.

Example 5: Preparation of a particle-containing IK-PU coating formulation

To prepare a coating formulation, an acrylate-based coating polyol having a solids content of 52% by weight and an OH value of 156 (Parocryl® 54.4 from BASF AG) with Desmodur® BL 3175 SN from Bayer AG (butanoxime-blocked polyisocyanate, having a FG of 75 Wt .-% and a blocked NCO content of 11.1%). Furthermore, 1% by weight of dibutyltin dilaurate (1% in butyl acetate) and 1% by weight of TEGO ADDID® 100 from TEGO AG (flow control agent based on polydimethylsiloxane, 10% strength solution in butyl acetate) are mixed in, and the modified silica sols of the examples 1-3, whereby coating formulations were obtained with about 60 wt .-% solids content. The amounts of the respective components used are listed in Table 1. The initially slightly cloudy mixtures are stirred for 24 h at room temperature to give clear coating formulations (blends 2-5).

Table 1. Parocryl® Desmodur® Modified Particle

54.4 BL 317ϊ Silica sol content (in

SN (50 wt -. ^S 3 in wt .-%)

Acetone) **

Mixture 1 10, 00 g 6.03 g 0.0 g 0, 0

(Comparison* )

Blend 2 10.00 g 6, 03 g 0.3 g 1.5

(Particles out

Example 2)

Mixture 3 10, 00 g 6.03 g 0.3 g 1.5

(Particles out

Example D

Blend 4 10.00 g 6, 03 g 0.6 g 3.0

(Particles out

Example 2)

Mixture 5 10, 00 g 6.03 g 0.6 g 3.0

(Particles out

Example 3)

* not according to the invention

** particles of Examples 1-3 which were isolated as powder were used in

Acetone predispersed.

Example 6: Preparation of a particle-containing 2K PU coating formulation

To prepare a coating formulation, an acrylate-based coating polyol having a solids content of 65% by weight and an OH value of 180 (Parocryl® 49.5 from BASF AG) is diluted with 20% by weight of butyl acetate, mixed with the modified silica sol of Examples 2 or 3, and Stirred for 24 hours at room temperature. After addition of the hardener component Basonat 100 from BASF Coatings (aliphatic polyisocyanate based on isocyanurated hexamethylene diisocyanate, NCO content 22% by weight) and 1% by weight of ADDID® 100 from TEGO AG (leveling agent based on polydimethylsiloxane, 10% strength solution in butyl acetate) the mixture is stirred for a further 5 hours to give clear coating formulations (blends 7-10) with about 50% by weight solids. The quantities of the respective components used are listed in Table 2.

Table 2.

* not according to the invention ** Powder-isolated particles of Examples 1-3 were predispersed in acetone.

Example 7. Preparation and Evaluation of Paint Films from the Blends of Examples 5 and 6

The coating compositions from Examples 5 and 6 are in each case by means of a film applicator Coatmaster® 509 MC Fa. Erichsen with a doctor blade of gap height 120 microns on a glass plate geräkelt. Subsequently, the resulting coating films are dried in a circulating air dryer for 30 minutes at 70 ° C and then for 30 min at 150 ⁰ C. From blends 1-10 of Examples 5 and 6 optically flawless, smooth coatings are obtained. The gloss of the coatings is determined with a gloss meter Micro gloss 20 ° from Byk and is in all paints between 160 and 170 gloss units.

The scratch resistance of the cured coating films produced in this way is determined using a scouring tester according to Peter-Dahn. For this, a scouring fleece Scotch Brite® 2297 with an area of 45 x 45 mm and a weight of 500 g is weighted. With this, the paint samples are scratched with a total of 50 strokes. Both before and after completion of the scratching tests, the gloss of the respective coating is measured with a gloss meter Micro gloss 20 ° from Byk. As a measure of the scratch resistance of the respective coating, the loss in gloss was determined in comparison with the starting value:

not according to the invention

The results show that even small contents of the particles (P) lead to a significant increase in the scratch resistance of the corresponding coating. In addition, an increase in scratch resistance is observed for paints containing particles (P) which have functions (F) which are reactive with the binder (B) (paint samples from blends 5 and 10).

Claims

claims

1. containing composition (Z)

(a) 0.02-200 parts by weight of particles (P) containing at least one structural element of the general formula [1],

≡Si-LP (O) (OR ¹ J ₂ ^[1] '

(b) 100 parts by weight of a binder (B),

(d) 0-1000 parts by weight of a solvent or solvent mixture, wherein L is a divalent optionally substituted with carbinol, amino, halogen, epoxy, phosphonato, thiol, (meth) acrylato, ureido, carbamato groups aliphatic or aromatic hydrocarbon radical having 1 to 12 carbon atoms, the carbon chain of which may be interrupted by nonadjacent oxygen atoms, sulfur atoms, or NR 1 - groups,

R! Hydrogen, a metal cation, an ammonium cation of

Formula -N (R 1) 4+, phosphonium cation of the formula -P (R 1) 4 ^"1" or an optionally with carbinol, amino, halogen, epoxy, phosphonato, thiol, (meth) acrylato , Carbamato, ureido groups substituted aliphatic or aromatic hydrocarbon radical having 1 to 12 carbon atoms, whose carbon chain may be interrupted by non-adjacent oxygen atoms, sulfur atoms, or NR ^ - groups, and

R ^ is a hydrocarbon radical having 1-8 carbon atoms.

2. Composition (Z) according to claim 1, in which the particles (P) in addition to functions of the general formula [1] additionally also have at least one organofunctional group (F) which is resistant to the binder (B) or the hardener (H) is reactive.

3. Composition (Z) according to claim 1 or 2, wherein L is a methylene or propylene radical.

4. The composition (Z) of claims 1 to 3 wherein R 1 is an alkyl radical of 1-6 carbon atoms.

5. Composition (Z) according to claim 1 to 3, wherein the particles (P) have a specific surface of 10 to 500 m ^ / g, measured by the BET method according to DIN EN ISO 9277 / DIN 66132.

6. Composite materials (K) which can be produced from the composition (Z) according to claims 1 to 5.

7. Composite materials (K) according to claim 6, which are coating systems which can be prepared from a coating composition (Z) comprising, (a) 0.02-60 parts by weight of particles (P) containing at least one structural element of the general formula [1] .

≡Si-LP (O) (OR ¹ ) 2 ^[1] '

b) 100 parts by weight of a hydroxyl-functional paint resin (B), c) 1-100 parts by weight of a paint curing agent (H), the Contains isocyanate groups which are selected from free isocyanate groups and protected isocyanate groups which release an isocyanate function upon thermal treatment with elimination of a protective group, d) 0-1000 parts by weight of a solvent or a solvent mixture.

8. Use of the compositions (Z) according to claim 1 to

5 as adhesives and sealants as well as sealing, potting and dental compounds and paints.