KR20070030777A - Curable composition containing surface-modified particles - Google Patents

Abstract

The present invention relates to a curable composition Z comprising binder BM having at least one ethylenically unsaturated group and also particles P having at least one ethylenically unsaturated group on its surface and containing radicals of the general formula (1):

[Formula 1]

-SiR ² _2- (CR ³ ₂ ) _n -ADC

[In the meal,

R ² is - ₁₂ and the hydrocarbon radical (wherein the carbon chain may be interrupted by groups of the non-adjacent oxygen, sulfur or _{^{NR 4), - (CR 3}} 2) n -ADC or C ₁

R ³ is hydrogen or C _{1 - 12} hydrocarbon radical and (wherein the carbon chain may be interrupted by groups of the non-adjacent oxygen, sulfur or NR ^4),

R ⁴ is hydrogen or C _{1 -} is a hydrocarbon radical of _12,

A is oxygen, sulfur, = NR ⁴ or = N- (DC),

D is in each case C _{1 - 12} and a carbonyl group, an alkylene, cycloalkylene or sub-tolylene radical (wherein the carbon chain is to be non-adjacent oxygen, sulfur or NR ⁴ groups blocked by available),

C is a terminal unsaturated group,

n is at least 1].

Curable composition, ethylenically unsaturated group

Description

Curable composition containing surface-modified particles {CURABLE COMPOSITION CONTAINING SURFACE-MODIFIED PARTICLES}

The present invention relates to a curable composition comprising a binder having at least one ethylenically unsaturated group, and also particles having at least one ethylenically unsaturated group on its surface, and also to the use for coating the composition.

Free-radically curable coating compositions are known which comprise nanoscale fillers surface-modified with organic radicals and which cure with high mechanical hardness and chemically resistant coatings. In coating compositions of this kind, appropriate modification of the particle surface ensures the compatibility of the particles with the surrounding polymer matrix. Moreover, if the particle surface has the proper reactivity to the matrix, it can react with the binder system under certain curing conditions of the coating system, and during the curing process it is possible to chemically introduce the particles into the matrix, Frequently a positive effect on a profile.

Free-radical curable, particle-reinforced coating compositions are described in particular in US Pat. No. 4,455,205 A and US Pat. No. 4,189,508 A, for example, by reacting colloidal silicon dioxide with 3-methacryloyloxypropyltrimethoxysilane, By successive exchange of aqueous and / or alcoholic solvents with free-radical crosslinkable organic binders. Coating compositions of this kind can be used to coat thermoplastic substrates.

US 6306502 B discloses a coating composition for anti-scratch coatings which can be prepared from colloidal silicon dioxide and free-radically polymerizable silanes. The binder used in this case is (meth) acryloyloxyalkyl-functional isocyanurate. DE 102 00 928 A1, for example, after the dispersing step in dipentaerythritol pentaacrylate, hydrophilic pyrogenic silicon dioxide, with 3-methacryloyloxypropyltrimethoxysilane, aluminum butoxide, and water A curable organic dispersion comprising surface-modified nanoparticles, prepared by mixing, is disclosed. Dispersions of this kind can in particular also be used as coating materials, but also as adhesives and sealants.

According to the prior art, the particles contained in the coating system include particles having free silicon hydroxide (SiOH) or metal hydroxide (MeOH) functional groups, and ethylenic unsaturated such as vinyl, (meth) acryloyl, etc. as the reactive organic functional groups. It is prepared by reacting with an alkoxysilane containing group. A feature common to all silanes used in particle functionalization in the prior art is that they have di- or trialkoxysilyl groups, as for example for methacrylatopropyltrimethoxysilane.

When di- or trialkoxysilanes are used for surface functionalization, after hydrolysis and condensation of the silanol obtained, a siloxane shell is formed around the particles in the presence of water. Macromol. Chem. Phys. 2003, 204, 375-383 discloses the formation of siloxane shells of this kind surrounding SiO ₂ particles. The problem here may be the fact that the formed siloxane shell still has a large number of SiOH functional groups on the surface. Under manufacture and storage, even in the presence of a binder, where appropriate, the stability of SiOH-functional particles of this kind is limited. There may be aggregation and aggregation of particles. The limited stability of the dispersions involved makes it more difficult to produce materials with renewable properties. Moreover, large amounts of reactive organic functional groups in the siloxane husk are three-dimensionally shielded, making it impossible for particles to adhere to the reactive binder through this action. Ideally, however, all reactive organic functionalities attached to the particle surface should be available for covalent introduction into the matrix.

As a result, all known binder systems containing particles have the disadvantage of exhibiting properties that are often difficult to reproduce, in both cured and uncured forms. In particular, however, the mechanical hardness of the cured coatings—and especially the scratch resistance—are still inadequate for many applications.

It is therefore an object of the present invention to provide a coating system which is curable with actinic radiation or which is no longer having the disadvantages of known systems.

The present invention provides a curable composition Z comprising binder BM having at least one ethylenically unsaturated group and also particles P having at least one ethylenically unsaturated group on its surface and containing radicals of the general formula (1):

-SiR ² _2- (CR ³ ₂ ) _n -ADC

[In the meal,

R ² is - ₁₂ and the hydrocarbon radical (wherein the carbon chain may be interrupted by groups of the non-adjacent oxygen, sulfur or _{^{NR 4), - (CR 3}} 2) n -ADC or C ₁

R ³ is hydrogen or C _{1 - 12} hydrocarbon radical and (wherein the carbon chain may be interrupted by groups of the non-adjacent oxygen, sulfur or NR ^4),

R ⁴ is hydrogen or C _{1 -} is a hydrocarbon radical of _12,

A is oxygen, sulfur, = NR ⁴ or = N- (DC),

D is in each case C _{1 - 12} and a carbonyl group, an alkylene, cycloalkylene or arylene radicals (wherein the carbon chain is to be non-adjacent oxygen, sulfur or NR ⁴ groups blocked by available),

C is an ethylenically unsaturated group,

n is at least 1].

The composition Z for curing comprises particle P surface-modified by a reactive radical of formula 1 containing an ethylenically unsaturated group, the reactive radical having three organic radicals to which the silyl group is attached via a CC bond, further bonding It is distinguished by the fact that it is attached to the particle surface through Thereby, the scratch resistance of the composition Z for curing is greatly increased compared to known particle-containing compositions.

Particle P is preferably preparable by reaction with the following (a) and (b), and optionally (c):

(a) selected from metal oxides, metal-silicon mixed oxides, silicon dioxides, colloidal silicon dioxides and organopolysiloxane resins and combinations thereof, Me-OH, Si-OH, Me-O-Me, Me-O-Si, Particles P1 of a substance having a functional group selected from Si-O-Si, Me-OR ¹ and Si-OR ¹ ,

(b) organosilane B of formula (2) and / or its hydrolysis and / or condensation products,

(R ¹ O) R ² ₂ Si- (CR ³ ₂ ) _n -ADC,

(c) water,

[In the meal,

R ¹ is hydrogen or C _{1 -} is (in this case, the carbon chain may be interrupted by groups of the non-adjacent oxygen, sulfur or NR ⁴⁾ ₆ hydrocarbon radical,

Me is a metal atom,

R ² , R ³ , A , D , C and n are as defined above].

The use of the monofunctional organosilane B of formula 2 allows the particles to be functionalized, even in the absence of water. In this case, it is possible in the stoichiometric reaction that substantially all MeOH and / or SiOH groups on the particle surface are saturated with organosilane B. Thus, remaining MeOH and / or SiOH groups that can limit the stability of the particles can be largely avoided. Freely available Me-O-Me, Me-O-Si or Si-O-Si groups can also be functionalized by reaction with organosilane B in stoichiometric reactions.

Likewise, particle P is preferably preparable by cohydrolyzing organosilane B of formula (2) with alkoxysilane B * of formula (3):

(R ⁵ O) _4-m (R ⁶ ) _m Si

[In the meal,

R ⁵ R ¹ Has the definition of

R ⁶ Is a hydrocarbon radical which may be substituted,

m represents a value of 0, 1, 2 or 3.

The hydrocarbon radical R ¹ is preferably an alkyl, cycloalkyl or aryl radical, in particular a methyl, ethyl or phenyl radical, more preferably a methyl or ethyl radical. R ² is preferably an alkyl, cycloalkyl, aryl or arylalkyl radical, in particular a methyl, ethyl or phenyl radical, more preferably a methyl radical. R ³ is preferably hydrogen or an alkyl, cycloalkyl, aryl or arylalkyl radical, in particular a methyl radical, and in certain preferences the radical R ³ is hydrogen. n preferably represents a value of 1, 2 or 3. In certain preferences n = 1. ₆ is an unsaturated alkyl radical, in particular vinyl, one by one or methacrylate with acrylic _- C is preferably a C _{2 -12,} more preferably C _2. The (-ADC) group is preferably the following radicals: OC (O) C (CH ₃ ) = CR ³ ₂ , OC (O) CH = CR ³ ₂ , NHC (O) C (CH ₃ ) = CR ³ ₂ Or NHC (O) CH = CR ³ ₂ . In certain preferred embodiments it is a radical OC (O) C (CH ₃ ) = CR ³ ₂ or OC (O) CH = CR ³ ₂ . The preferred radical in R ⁵ has been described in the preferred radicals R ^1. R ⁶ is preferably, for example, C _{1 -} there, is functionalized or non neunghwa ₁₂ as an aromatic or aliphatic saturated or unsaturated hydrocarbon radical. Preferred radicals for R ⁶ are described in preferred radicals R ² . In addition, R ⁶ may represent positive CR ³ ₂ -ADC; That is, in this case, organosilane B of formula (2) is the same as alkoxysilane B * .

Preferred examples of alkoxysilane B * are tetraethoxysilane, tetramethoxysilane, methyl trimethoxysilane, dimethylmethoxysilane, phenylmethyldimethoxysilane, phenyltrimethoxysilane, and vinyltrimethoxysilane.

Composition Z is preferably used as a coating. In this regard, in certain preferences, they serve to improve the scratch resistance of the coated surface. Coatings obtainable from the composition Z by curing are those particles which have been surface-modified with conventional trifunctional alkoxysilanes, such as, for example, methacrylatopropyltrimethoxysilane and / or hydrolysis and / or condensation products thereof. It has higher mechanical hardness and improved scratch resistance than comparable coatings it contains.

In view of the high reactivity of the alkoxysilane B having a methylene spacer between the alkoxysilyl group and the heteroatom (n = 1), the compound is particularly suitable for functionalizing the particles P1 having SiOH or MeOH. For the preparation of particle P , equilibrium of Me-O-Me-, Me-O-Si, and Si-O-Si-functionalized particles with alkoxysilane B can be carried out. The reaction with the alkoxysilane B of the particle P1 is completed quickly.

The binder BM contained in the composition Z should preferably contain at least one reactive group initiated by actinic radiation or heat treatment, which are free-radical, cationic or with the structure of the polymer, themselves and with the reactive particles. Anionic polymerization can be carried out. Reactive groups are groups containing ethylenically unsaturated groups, in particular vinyl groups, methacrylate groups, acrylate groups and acrylamide groups. In this relationship, the binder BM may comprise monomers, oligomers or other polymer compounds.

Examples of suitable monomer and oligomeric compounds are hexanediol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, triethylene glycol diacrylate and the like. Examples of suitable polymeric binders BM are (meth) acrylic copolymers having ethylenically unsaturated groups, polyester (meth) acrylates, unsaturated polyesters, urethane (meth) acrylates, and silicone (meth) acrylates.

By actinic radiation is meant electromagnetic radiation in the infrared (NIR), visible, ultraviolet (UV) and also X-radiation regions.

Composition Z is suitable for all metal oxide and metal mixed oxide particles (e.g., aluminum oxides such as corundum, aluminum mixed oxides with other metals and / or silicon, titanium oxides, zirconium oxides, iron oxides, etc.) , Silicon oxide compounds (eg, colloidal silica, pyrogenic silica, precipitated silica, silica sol) or some valences of silicon are provided with organic radicals (eg silicone resins) It is noteworthy in the fact that it consists of the particle P1 . Furthermore, the particles P1 can, on the surface thereof, through which the reaction can take place with organosilane B so that they are metal hydroxide (MeOH), silicon hydroxide (SiOH), Me-O-Me, Me-O-Si and / Or it is noteworthy in the fact that it has a Si—O—Si functional group. Particle P1 preferably has an average diameter of less than 1000 nm, more preferably less than 100 nm and the particle size is measured by transmission electron microscopy.

In one preferred embodiment of the invention, the particles P1 consist of pyrogenic silica. In a further preferred embodiment of the invention, the particles P1 used are colloidal silicon oxides or metal oxides, which are preferably in the form of dispersions of corresponding oxide particles of submicron size in aqueous or organic solvents. In this relationship, in a preferred embodiment, it is possible to use oxides of metal aluminum, titanium, zirconium, tantalum, tungsten, hafnium, and tin. A preference is given to using an aqueous SiO ₂ sol, which preferably reacts with the organosilane B of formula (2).

Likewise, in a preferred embodiment, particle P1 composed of a silicone resin of the formula

^{_{(R 7 3 SiO 1/2}} ) e (R 7 2 SiO 2/2) f (R 7 SiO 3/2) g (SiO 4/2) h

[In the meal,

R ⁷ is OR ⁸ functional groups, OH functional groups, optionally halogen-, hydroxyl -, amino-, epoxy-, thiol-, (meth) _acryloyl-1 or _C-18 of NCO- substituted hydrocarbon radicals (wherein The carbon chain can be blocked by nonadjacent oxygen, sulfur or NR ⁴ groups),

R ⁸ is C _{1 - 18} is a monovalent hydrocarbon radical optionally substituted with,

e represents a value of zero or more,

f represents a value of zero or more,

g represents a value of zero or more,

h represents a value of 0 or more, provided that the sum of e + f + g + h is 1 or more, preferably 5 or more].

It is possible to use one or more different particle type P for the composition Z. Thus, for example, it is possible to produce coating systems comprising nanoscale corundum in addition to nanoscale SiO ₂ .

The amount of particles P contained in the coating system is preferably at least 5% by weight, more preferably at least 10% by weight, very preferably at least 15% by weight, and preferably at most 90% by weight, based on the total weight. to be.

Composition Z is preferably prepared in a two step process. In the first step, particle P is produced. In the second step the functionalized particles P are introduced into the binder BM .

In one preferred process, particle P obtained by reacting particle P1 with organosilane B is purified before being introduced into binder BM . This approach is particularly useful when the impurities that occur during the manufacturing process have an adverse effect on the profile of the properties of the (cured) coating. For example, particle P can be purified by precipitating the particles and then washing them with a suitable solvent.

In another process, composition Z is prepared by functionalizing particle P1 with silane B in the presence of binder BM . In both manufacturing processes, particles P1 can be present in an aqueous or else anhydrous solvent in dispersion and in the solid state.

If an aqueous or non-aqueous dispersion of the particles P1 is used, the corresponding solvent is generally removed after the particles P or P1 are introduced into the binder BM . The removal of the solvent is preferably carried out distillatively and can occur before or after the reaction of the particles P1 with silane B.

Examples of the silane B used in the preferred examples include methacrylatomethyldimethylmethoxysilane, methacrylatomethyldimethylethoxysilane, methacrylatopropyldimethylmethoxysilane, methacrylatopropyldimethylethoxysilane, and acrylatomethyl Dimethylmethoxysilane, acrylatomethyldimethylethoxysilane, acrylatopropyldimethylmethoxysilane and acrylatopropyldimethylethoxysilane.

In functionalizing the particles, it is possible to use one silane B either individually or as a mixture of different silanes B or else as a mixture of silane B and other alkoxysilanes.

Moreover, the composition Z may comprise conventional solvents and also typical additives and additives in the formulation. Examples above include light stabilizers such as flow control aids, surface-active substrates, adhesion promoters, UV absorbers and / or free-radical scavengers, thixotropic agents, and also further solids and fillers ( fillers). For both the composition and the cured material, additives of this kind are preferred in order to produce a profile of certain desirable features. This is especially true when composition Z is used as a coating. Coatings of such formulations may additionally also include dyes and / or pigments.

Curing of the composition Z is preferably accomplished by conventional methods known to those skilled in the art, under conditions requiring ethylenically unsaturated groups, by actinic radiation or by thermally initiated free-radical polymerization reactions.

For example, the polymerization takes place by UV irradiation, followed by the addition of suitable photoinitiators such as, for example, Darocur ^® 1178, Darocur ^® 1174, Irgacure ^® 184, Irgacure ^® 500. The photoinitiator is typically used in amounts of 0.1 to 5% by weight. The polymerization reaction can be carried out thermally, for example following the addition of an organic peroxide, such as peroxydicarboxylic acid, or an azo compound, such as azobisisobutyronitrile.

In one particularly preferred embodiment of the invention, composition Z comprises at least one photoinitiator and the coating is cured by UV radiation. In a further particularly preferred embodiment of the invention, the composition Z is cured by an electron beam.

The coating obtained after the composition Z has cured has significant mechanical properties. For example, there is a significant improvement in scratch resistance compared to known materials.

The invention further provides for the use of the composition Z in coating any desired substrate. Examples of preferred substrates include acidic materials such as glass, such as metals, wood or polycarbonates, polybutylene terephthalate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polypropylene. Include the same plastic.

The applied coating acts to improve scratch resistance, abrasion resistance, chemical stability or otherwise affect adhesive properties.

Composition Z can be applied by any desired technique such as dipping, spraying, and casting. Application by the "wet on wet" method is also possible.

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

In the examples below, unless otherwise indicated, all amounts and percentages are by weight, all pressures are 0.1 Mpa (abs.) And all temperatures are 20 ° C.

Example  One:

20.00 g of SiO ₂ organic sol (IPA-ST ^® from Nissan Chemicals, 30 wt.% SiO ₂ , 12 nm) was added dropwise and mixed with 2.00 g of methacrylatomethyldimethylmethoxysilane over one minute. The mixture was heated at 60 ° C. for 16 h. After the mixture was cooled to room temperature, 15.00 g of hexanediol diacrylate was added and then isopropanol was distilled off under reduced pressure. The clear dispersion contained 29 wt% SiO ₂ .

Example  2:

20.00 g of an aqueous SiO ₂ sol (Grace Davison Company LUDOX ^® AS 40, 40 _{wt% SiO 2, pH = 9.1,} 22 nm) to, the 15 ml over the course of 60 minutes with ethanol, of 2.00 g over 5 min The mixture was added dropwise with methacrylatomethyldimethylmethoxysilane and the mixture was heated at 60 ° C. for 16 hours. After the mixture was cooled to room temperature, 15.00 g of hexanediol diacrylate was added and then ethanol and water were distilled off as azeotrope. The clear dispersion contained 29 wt% SiO ₂ .

Example  3:

20.00 g of SiO ₂ organic sol (IPA-ST ^® from Nissan Chemicals, 30 wt.% SiO ₂ , 12 nm) was added dropwise and mixed with 2.00 g of methacrylatomethyldimethylmethoxysilane over one minute. The mixture was heated at 60 ° C. for 16 h. After the solvent was distilled off, the residue was washed with 100 ml (5 × 20 ml) of pentane. A dispersion of 2.90 g of the resulting solid in 10 ml of ethanol was mixed with 7.10 g of HDDA and the solvent was distilled off. This gave a transparent dispersion with 29 wt% content of SiO ₂ .

Comparative example  One:

26.7 g of SiO ₂ organic sol (IPA-ST ^® from Nissan Chemicals, 30 wt.% SiO ₂ , 12 nm) is mixed with 15.00 g of hexanediol diacrylate over a course of 1 minute and the mixture is 30 After stirring for minutes, isopropanol was distilled off under reduced pressure. The clear dispersion contained 35 wt% SiO ₂ .

Comparative example  2:

20.00 g of an aqueous SiO ₂ sol (Grace Davison Company LUDOX ^® AS 40, 40 _{wt% SiO 2, pH = 9.1,} 22 nm) to, the 20 ml over the course of 60 minutes with ethanol, of 2.00 g over 5 min The mixture was added dropwise with methacrylatomethyltrimethylmethoxysilane and the mixture was heated at 60 ° C. for 16 hours. After the mixture was cooled to room temperature, 15.00 g of hexanediol diacrylate was added and then ethanol and water were distilled off as azeotrope. The clear dispersion contained 35 wt% SiO ₂ .

Comparative example  3:

A water mixture of 20.00 g of SiO ₂ organic sol (Nissan Chemicals Co. IPA-ST ^®, 30 wt% SiO _2, 12 nm) and 10 g, over the course of one minute, 2.00 g of methacrylic gelato trimethoxy It was added dropwise with silane and mixed. The mixture was heated at 60 ° C. for 16 h. After the mixture was cooled to room temperature, 15 g of hexanediol diacrylate was added and then isopropanol and water were azeotropically distilled off. The clear dispersion contained 29 wt% SiO ₂ .

Example  4:

Preparation of Coating Film

Coatings composed of coating materials from Examples 1, 2, 3 and Comparative Examples 1, 2 and 3 and also pure 1,6-hexanediol diacrylate, having a coating bar having a slot height of 80 μm , Corichmaster ^® 509 MC film-drawing appratus from Erichsen, respectively, was applied to the glass plate (glass plate). The resulting coating film was then cured under nitrogen in Dr. Honle's UVA Cube, Model UVA-Print 100 CV1, with a lamp output of 60 mW / cm ² and a 60 second irradiation period. All coating formulations produced a visually attractive and smooth coating. The gloss of all five coatings-measured using a Micro gloss 20 ° glossometer from Byk-was about 155 gloss units for all six coating materials.

Example  5:

Of coating film scratch  Evaluation of resistance

The scratch resistance of the coating film prepared according to Example 4 was measured using a Peter-Dahn abrasion-testing instrument. To the intention was to load the [Scotch Brite ^® 07558 abrasion nonwoven] it has an area of 45 × 45 mm to the weight of 1 kg and scratch using 500 strokes (strokes). For both before and after the start of the scratch test, the gloss of each coating was measured using a Micro gloss 20 ° glossometer from Byk. As a measure of the scratch resistance of each coating, the loss of gloss was confirmed (mean value from three coating samples in each case):

Loss of Gloss in Peter-Dan Scratch Test Coating samples Loss of gloss Example 1 15 ± 4% Example 2 10 ± 5% Example 3 <5% Comparative Example 1 78 ± 7% Comparative Example 2 25 ± 5% Comparative Example 3 43 ± 5% 1,6-hexanediol diacrylate 75 ± 10%

The curable compositions of the present invention have high mechanical hardness and improved scratch resistance.

Claims (10)

A curable composition Z comprising binder BM having at least one ethylenically unsaturated group and also particles P having at least one ethylenically unsaturated group on its surface and containing radicals of the general formula (1): [Formula 1] -SiR ² _2- (CR ³ ₂ ) _n -ADC [In the meal, R ² is - ₁₂ and the hydrocarbon radical (wherein the carbon chain may be interrupted by groups of the non-adjacent oxygen, sulfur or _{^{NR 4), - (CR 3}} 2) n -ADC or C ₁ R ³ is hydrogen or C _{1 - 12} hydrocarbon radical and (wherein the carbon chain may be interrupted by groups of the non-adjacent oxygen, sulfur or NR ^4), R ⁴ is hydrogen, or C _{1 -} is a hydrocarbon radical of _12, A is oxygen, sulfur, = NR ⁴ or = N- (DC), D is in each case C _{1 - 12} and a carbonyl group, an alkylene, cycloalkylene or sub-tolylene radical (wherein the carbon chain is to be non-adjacent oxygen, sulfur or NR ⁴ groups blocked by available), C is an ethylenically unsaturated group, n is at least 1]. The composition Z according to claim 1, wherein particle P is preparable by reaction with (a) and (b), and optionally (c): (a) selected from metal oxides, metal-silicon mixed oxides, silicon dioxides, colloidal silicon dioxides and organopolysiloxane resins and combinations thereof, Me-OH, Si-OH, Me-O-Me, Me-O-Si, Particles P1 of a material having functions selected from Si-O-Si, Me-OR ¹ and Si-OR ¹ , (b) organosilane B of formula (2) and / or its hydrolysis and / or condensation products, [Formula 2] (R ¹ O) R ² ₂ Si- (CR ³ ₂ ) _n -ADC, (c) water, [In the meal, R ¹ is hydrogen or C _{1 -} is (in this case, the carbon chain may be interrupted by groups of the non-adjacent oxygen, sulfur or NR ⁴⁾ ₆ hydrocarbon radical, Me is a metal atom, R ² , R ³ , A , D , C and n are as defined in claim 1]. The composition Z of claim 1, wherein the particle P is preparable by cohydrolyzing the organosilane B of formula 2 with an alkoxysilane B * of formula 3: [Formula 3] (R ⁵ O) _4-m (R ⁶ ) _m Si [In the meal, R ⁵ R ¹ Has the definition of R ⁶ Is a hydrocarbon radical which may be substituted, m represents a value of 0, 1, 2 or 3. 4. The composition Z according to claim 2, wherein the hydrocarbon radical R ¹ is a methyl, ethyl or phenyl radical. The group according to any one of claims 1 to 4, wherein the (-ADC) group is OC (O) C (CH ₃ ) = CR ³ ₂ , OC (O) CH = CR ³ ₂ , NHC (O) C (CH ^₃₎ = CR _{3 2} or ^{NHC (O) CH = CR 3} 2 in that the composition Z. The composition Z according to any one of claims 1 to 5, wherein the ethylenically unsaturated group in the binder BM is capable of free-radical, cationic or anionic polymerization. The composition Z according to any one of claims 1 to 6, wherein the ethylenically unsaturated groups in the binder BM can be polymerized by actinic radiation or by heat treatment. The composition Z according to any one of claims 1 to 7, wherein the ethylenically unsaturated group in the binder BM is selected from vinyl groups, methacrylate groups, acrylate groups and acrylamide groups. The composition Z of claim 1, wherein particle P1 has an average diameter of less than 1000 nm and the particle size is determined by transmission electron microscopy. Use of the composition Z of any one of claims 1 to 9 for coating a substrate.