WO2019137853A1

WO2019137853A1 - Compositions comprising polymerizable vinyl compounds, inorganic or organic fillers and their use

Info

Publication number: WO2019137853A1
Application number: PCT/EP2019/050157
Authority: WO
Inventors: Ulrike Licht; Dirk Wulff
Original assignee: Basf Se
Priority date: 2018-01-09
Filing date: 2019-01-04
Publication date: 2019-07-18

Abstract

Described are compositions comprising at least one inorganic and/or organic filler and at least one polymerizable vinyl compound, wherein the polymerizable vinyl compound is selected from methylene malonates, methylene beta-ketoesters and methylene beta-diketones; and wherein the filler has functional groups selected from anionic groups and neutralizable acid groups. The compositions can be used for adhesives, sealants, vibration damping materials, underbody coatings and body fillers.

Description

Compositions comprising polymerizable vinyl compounds, inorganic or organic fillers and their use

Description

The invention relates to compositions comprising polymerizable vinyl compounds, inorganic or organic particulate fillers, especially acrylic polymer powder, wherein the polymerizable vinyl compound is selected from methylene malonates, methylene beta-ketoesters and methylene beta-diketones; and wherein the fillers have functional groups selected from anionic groups and neutralizable acid groups. The compositions can be used for example for adhesives, sealants, vibration damping materials, underbody coatings and body fillers.

The hardening of adhesives, sealants and coatings often require application of energy. Low temperature curing formulations are of increased interest due to energy saving needs and faster processes. Conventional low temperature fast curing systems like isocyanate/alcohol or epoxy/amine reactive adhesives and coatings are under regulatory pressure for environment, health and safety reasons due to the reactive isocyanate crosslinker. Therefore, it is an objec- tive to provide further isocyanate-free alternatives for low temperature reactive adhesives, seal- ants, vibration damping materials and coatings with a reasonable working time (pot life) at room temperature.

WO 2013/149168 describes composite and laminate articles made with laminate adhesives comprising methylene malonates, methylene beta-ketoesters or methylene beta-diketones and reinforcing or filler material, using relatively large amounts of adhesive in the examples.

WO 2013/149165 describes activating methods, e.g. by anionic mechanism, for initiating polymerization of methylene malonates and other polymerizable compositions, wherein the polymerization activator is carried in inactive engagement in the polymerizable composition.

WO 2013/059473 describes multifunctional monomers, including multifunctional methylene ma- lonate and methylene beta-ketoester monomers.

WO 2016/040012 describes a method of anionic polymerizing 1 , 1 -disubstituted alkenes, such as methylene malonates, in the presence of nonionic emulsifiers and bases in water.

Not pre-published patent application with application number EP16161811.1 describes compo- site film laminates for flexible packaging wherein the laminating adhesive comprises polymeriza- ble vinyl compounds selected from methylene malonates, methylene beta-ketoesters and meth- ylene beta-diketones. Aqueous anionic polyurethane dispersions may be used as primers with a molar ratio of anionic groups of the polyurethane to the vinyl groups of the polymerizable vinyl compounds of 1 : 10 to 1 : 1 million. Not pre-published patent application with application number EP 16197869.7 describes Polyu- rethane methylene malonate hybrid polymers.

US 9752059 B2 describes plastic bonding systems comprising methylene malonates as reac- tive components and a reaction initiator incorporated into the plastic material substrate.

US 9334430 describes encapsulated polymerization initiator particles. The particles are encap- sulated in a cured composition comprising 1 , 1 -disubstitued alkene compounds.

US 9718989 describes coating compositions comprising polyester macromers containing 1 ,1- dicarbonyl-substitued alkenes. The compositions may contain fillers for improving scratch re- sistance.

The object of the invention was to provide alternative, isocyanate-free, compositions, suitable for uses as adhesives, sealants, coatings, vibration damping materials, underbody coatings or body fillers.

It was found that vinyl compounds selected from methylene malonates, methylene beta-ketoes- ters and methylene beta-diketones polymerize anionically in the presence of inorganic or or- ganic fillers, where the fillers comprise either anionic groups or acid groups which upon neutrali- zation with a base form anionic groups. It was found in particular that mixtures from methylene malonate monomers or oligomers with some kind of organic fillers like acrylic dispersion pow- ders are fast curing at room temperature with reasonable pot life. Depending on the mixing ra- tio, 2-component compositions such as for example structural adhesives, sealants or coatings of different hardness can be formulated. The acrylic dispersion powders serve as initiators as well as tougheners and fillers.

It has been found that the object of the invention is achieved by a composition comprising

(A) at least one particulate filler selected from inorganic fillers and organic fillers; and

(B) at least one polymerizable vinyl compound,

wherein the polymerizable vinyl compound is selected from methylene malonates, methylene beta-ketoesters and methylene beta-diketones;

and wherein the filler has functional groups selected from anionic groups and neutralizable acid groups,

wherein if the composition comprises no organic fillers, then the composition is a vibration damping composition comprising 50% by weight or more of the at least one inorganic filler and at least 15% by weight of the at least one polymerizable vinyl compound.

The components (A) and (B) are blended without being dispersed in water or an organic sol- vent. Thus, the composition is not in the form of encapsulated particles, i.e. not in the form of particulate fillers encapsulated by cured vinyl compound.

Preferably, the polymerizable vinyl compounds are methylene malonates. The invention also provides the use of the composition for adhesives (preferably for structural adhesives), sealants, coatings, vibration damping materials, underbody coatings and body fill- ers. The invention also provides a method of forming a coating wherein a composition according to the invention is coated on a substrate and the anionic groups or the neutralized acid groups of the at least one filler are reacted with the at least one polymerizable vinyl compound.

The invention also provides cured material or cured coatings, comprising a composition accord- ing to the invention as defined herein, wherein the at least one polymerizable vinyl compound (B) has been polymerized.

Glass transition temperature (Tg) is determined by differential scanning calorimetry (ASTM D 3418-08, midpoint temperature, heating rate 20°C/min).

Room temperature is 20 °C, unless otherwise indicated.

The polymerizable vinyl compounds have one, two or more methylene groups =CH2.

Methylene malonates are compounds comprising at least one (e.g. one, two or more) group ~0-C(0)-C(C=CH₂)-C(0)-0~

Methylene beta-ketoesters are compounds comprising at least one (e.g. one, two or more) group ~C(0)-C(C=CH₂)-C(0)-0~

Methylene beta-diketones are compounds comprising at least one (e.g. one, two or more) group ~C(0)-C(C=CH₂)-C(0)~

Preferred methylene malonates are compounds of the formula

R¹-0-C(0)-C(C=CH₂)-C(0)-0-R²

Preferred methylene beta-ketoesters are compounds of the formula

R¹-C(0)-C(C=CH₂)-C(0)-0-R²

Preferred methylene beta-diketones are compounds of the formula

R¹-C(0)-C(C=CH₂)-C(0)-R²

wherein R¹, R² are each independently C1-C15 alkyl, C2-C15 alkenyl, halo-(C1-C15 alkyl), C3- C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl-(C1- C15 alkyl), heteroaryl or heteroaryl-(C1-C15 alkyl), or alkoxy-(C1-15 alkyl), each of which may be optionally substituted by C1-C15 alkyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl -(C1-C15 alkyl), heteroaryl, C1- C15 alkoxy, C1-C15 alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, ester or sulfonyl; or wherein R¹ and R² are taken together with the atoms to which they are bound to form a 5-7 membered heterocyclic ring which may be optionally substituted by C1-C15 alkyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl -(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio, hydroxyl, nitro, azido, acyloxy, carboxy, ester or sulfonyl. The polymerizable vinyl compounds can be monofunctional, i.e. have only a single vinyl group or they can be polyfunctional having two or more than two vinyl groups. Preferred polyfunctional polymerizable vinyl compounds are the formula:

wherein R¹, R² are each independently C1-C15 alkyl, C2-C15 alkenyl, halo-(C1-C15 alkyl), C3- C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl-(C1- C15 alkyl), heteroaryl or heteroaryl-(C1 -C15 alkyl), or alkoxy-(C1 -15 alkyl), each of which may be optionally substituted by C1-C15 alkyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl -(C1-C15 alkyl), heteroaryl, C1- C15 alkoxy, C1-C15 alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, ester or sulfonyl; or wherein R¹ and R² are taken together with the atoms to which they are bound to form a 5-7 membered heterocyclic ring which may be optionally substituted by C1-C15 alkyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl -(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio, hydroxyl, nitro, azido, acyloxy, carboxy, ester or sulfonyl;

[A]- represents -(CR^AR^B)_n-, -(CR^AR^B)n-0(C=0)-(CH₂)i-i5-(C=0)0-(CR^AR^B)_n-,

-(CH2)n-[CY]-(CH2)n, a polybutadienyl linking group, a polyethylene glycol linking group, a poly- ether linking group, a polyurethane linking group, an epoxy linking group, a polyacrylic linking group, or a polycarbonate linking group;

each instance of R^A or R^B is independently H, C1-C15 alkyl, C2-C15 alkenyl, a moiety represented by the formula:

wherein L is a linking group selected from the group consisting of alkylene, alkenylene, haloal- kylene, cycloalkylene, heterocyclylene, heterocyclyl alkylene, aryl-alkylene, heteroarylene or heteroaryl-(alkylene), or alkoxy-(alkylene), each of which may be optionally branched and each of which may be optionally substituted by alkyl, haloalkyl, cycloalkyl, halo cycloalkyl, heterocy- clyl, heterocyclyl-(alkyl), aryl, aryl -(alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, ester, each of which may be optionally branched;

R₃ is independently selected from the group defined in R₂ above;

[CY] represents an alkyl, alkenyl, haloalkyl, cycloalkyl, halo cycloalkyl, heterocyclyl, heterocy- clyl-(alkyl), aryl-(alkyl), heteroaryl or heteroaryl-(alkyl), or alkoxy-(alkyl) group;

n is an integer from 1 to 25;

m is an integer from 1 to 25, preferably from 2 to 25;

and each instance of Q represents -O- or a direct bond. Preferred compositions are those wherein the polymerizable vinyl compound is selected from compounds of the formula

R¹-0-C(0)-C(C=CH₂)-C(0)-0-R²

wherein R¹, R² are each independently C1 -C10 alkyl, for example methyl, ethyl, propyl, butyl, Pentyl, hexyl, heptyl, octyl etc, and wherein the alkyl groups can be linear, branched or cyclic; or wherein the polymerizable vinyl compound is selected from compounds of the formula

wherein R¹, R² are each independently C1 -C10 alkyl, for example methyl, ethyl, propyl, butyl, Pentyl, hexyl, heptyl, octyl etc., and wherein the alkyl groups can be linear, branched or cyclic;

A is selected from C1 -C10 alkylene and -X-Ph-U-, wherein X and Y are each independently C1 - C10 alkylene, most preferably methylene. C1 -C10 alkylene can be methylene, ethylene, propyl- ene, butylene, pentylene, hexylene etc.

Methods of making methylene malonates are described in WO 2014/1 10388, WO 2012/054616 and WO 2012/054633. Methods of making methylene beta-diketones are described in

WO 2013/059479. Methods of making methylene beta-ketoesters are described in

WO 2013/066629. Methods of making multifunctional vinyl compounds are described in WO 2013/059473.

Preferred organic fillers are acrylic polymer powders. The total amount of anionic groups and neutralizable acid groups of the acrylic polymer powder (including anionic groups and acid groups of additives such as for example of emulsifiers, protective colloids and spray-drying ad- ditives) is preferably from 10 mmol/kg to 1000 mmol or from 20 mmol/kg to 250 mmol/kg based on dry material. Preferred anionic and acid groups of the acrylic polymer powder are selected from carboxylate groups, sulfonate groups, phosphate groups and the respective acid groups. Most preferred are carboxylate groups, especially with sodium or potassium as counterion.

Acrylic polymers are polymers which are predominantly (more than 50 % by weight) made of (meth)acrylic acid esters. The term“(meth)acryl...” and similar designations are used as an ab- breviating notation for“acryl... or methacryl...”. The term“Cx alkyl (meth)acrylate” means alkyl (meth)acrylate with x C-atoms in the alkyl chain.

The acrylic polymer is preferably composed of

(a) at least 70% by weight of at least one monomer selected from esters of acrylic acid and es- ters of methacrylic acid,

(b) at least 0,1 % by weight of at least one ethylenically unsaturated monomer with at least one acid group,

and optionally monomers different from monomers (a) and (b). The acrylic polymer is composed preferably to an extent of at least 70% by weight, more prefer- ably to an extent of at least 75% by weight, e.g., from 80% to 99% by weight, or from 80 % to 95 % by weight, of one or more of monomers (a) selected from the group consisting of C1 to C20 alkyl (meth)acrylates, preferably C1 to C10 alkyl (meth)acrylates or C1 to C8 alkyl

(meth)acrylates. Examples include methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate, n-butyl methacrylate, n-hexyl acrylate, octyl acrylate, 2-propylheptyl acrylate and 2- ethylhexyl acrylate. Also suitable in particular are mixtures of the (meth)acrylic acid alkyl esters.

The acrylic polymer is composed preferably to an extent of from 0,1 to 15% by weight, e.g. from 0,1 to 10 % by weight or from 0,5 to 5 % by weight of ethylenically unsaturated monomers with at least one acid group (acid monomer). Ethylenically unsaturated acid monomers are, for ex- ample, ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids, and ethylenically unsaturated phosphonic acids such as vinylphosphonic acid. Ethylenically unsatu- rated carboxylic acids used are preferably alpha, beta-monoethylenically unsaturated monocar- boxylic and dicarboxylic acids having 3 to 6 C atoms in the molecule. Examples thereof are acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylacetic acid, and vinyllactic acid. Suitable ethylenically unsaturated sulfonic acids include, for example, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropane sulfonic acid, sulfopropyl acrylate, and sulfopropyl methacrylate. Preference is given to acrylic acid and methacrylic acid and a mixture thereof, particular preference to acrylic acid. The acid monomers can be used in the form of the free acids and also in a form partially or fully neutralized with suitable bases, for the polymerization. It is preferred to use aqueous sodium or potassium hydroxide solution or ammonia as neutralizing agent.

The acrylic polymer may optionally be composed of at least one further monomer (c), different from alkyl (meth)acrylates (a) and acid monomers (b). The further monomers (c) are preferably selected from the group consisting of vinyl esters of carboxylic acids comprising up to 20 C at- oms, vinylaromatics having up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols comprising 1 to 10 C atoms, aliphatic hydrocarbons having 2 to 8 C at- oms and one or two double bonds, and monomers with at least one hydroxy group, and mix- tures of these monomers. Vinyl esters of carboxylic acids having 1 to 20 C atoms are, for exam- pie, vinyl laurate, vinyl stearate, vinyl propionate, Versatic acid vinyl esters, and vinyl acetate. Suitable vinylaromatic compounds include vinyltoluene, alpha- and para-methylstyrene, alpha- butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene, and - preferably - styrene. Examples of nitriles are acrylonitrile and methacrylonitrile. The vinyl halides are ethylenically unsaturated corn- pounds substituted by chlorine, fluorine or bromine, preferably vinyl chloride and vinylidene chloride. Vinyl ethers include, for example, vinyl methyl ether or vinyl isobutyl ether. Vinyl ethers of alcohols comprising 1 to 4 C atoms are preferred. Hydrocarbons having 4 to 8 C atoms and two olefinic double bonds include butadiene, isoprene, and chloroprene. Further secondary monomers are, for example, monomers comprising hydroxyl groups, more particularly C1-C10 hydroxyalkyl (meth)acrylates, and also (meth)acrylamide. Further secondary monomers that may be mentioned include phenyloxyethylglycol mono(meth)acrylate, glycidyl acrylate, glycidyl methacrylate, and amino (meth)acrylates such as 2-aminoethyl (meth)acrylate.

The acrylic polymer is preferably composed of

(a) from 70 to 99% by weight of alkyl (meth)acrylates with 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms in the alkyl group,

(b) from 0,1 to 10 % by weight of acid monomers, selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylacetic acid, and vinyllactic acid, and

(c) from 0 to 20% by weight of ethylenically unsaturated monomers different from monomers (a) and (b).

The acrylic polymer powder may be prepared by well-known conventional means such as spray-drying of polymer dispersions. In the preparation of the polymer dispersions that may be spray dried to yield the polymer powders, the polymer content of the dispersion may vary for ex- ample from 40 to 65 wt. %. The acrylic polymers preferably have glass transition temperatures (Tg) of from -60 to +60 °C, preferably a Tg of less than +25 °C.

The glass transition temperature is determined by differential scanning calorimetry (ASTM D 3418-08, midpoint temperature, heating rate 20°C/min).

Suitable acrylic polymer powders are for examples those known for making plastisols, for exam- pie as described in EP 1 132217 or DE 10 2004 035937.

Preferred acrylic polymer powders are spray-dried emulsion polymerizates, preferably with core- shell structure. Polymers with core-shell structure are for example described in

US 2007/0259987 or in EP 1 162217. Polymer particles with core-shell structure consist of a core and at least one shell which are prepared successively in at least two separate steps. Typi- cally, the core and the shell(s) each have a different composition. The term "shell" is intended to mean that the statement in question can relate either to one shell or, if appropriate, to a plurality of shells present.

In one aspect of the invention the composition comprises inorganic fillers. Inorganic fillers are described in WO 2015/165753. Examples of suitable inorganic, highly anionic fillers include cal- cium carbonate, silica-treated calcium carbonate, magnesium carbonate, mica, silica, wollaston- ite, clay, bentonite, barium sulfate, glass powders, glass flakes, glass fibers, metal hydroxides such as for example aluminum hydroxide, microdolomite. Moderately anionic fillers are for ex- ample chalk, kaolin, perlite, talc.

Preferred inorganic fillers have anionic groups and preferably a pH of a 10 % by weight slurry in water of greater 7, preferably from 8 to 10. Especially, silicate and silicate-modified calcium car- bonate, clay and metal hydroxides provide anionic groups in high amounts. It is preferred to use flake-like fillers such as mica, for example, or rod-like fillers like wollastonite alone or in combi- nation with typical inorganic pigments such as calcium carbonate, kaolin, silica or talc. The ani- onic inorganic fillers can be combined with nonionic inorganic fillers and/or with organic fillers, for example fly ash, carbon black, graphite, titanium dioxide, iron oxide, finely ground quartz, alumina, kieselguhr.

The weight ratio of vinyl compound to the sum of inorganic and organic fillers (preferably acrylic polymer powder) is preferably 95:5 to 5 :95, more preferably from 80:20 to 20:80.

The compositions of the invention can be used for example as vibration damping compositions, also known as liquid applied sound dampening (LASD) mass. The vibration damping composi- tions preferably comprise

50 to 85 parts by weight of inorganic filler wherein at least 50 parts by weight are inorganic filler with anionic groups

0 to 20 parts by weight of organic filler, preferably acrylic polymer powder,

and 15 to 50 parts by weight of polymerizable vinyl compounds selected from methylene malo- nates, methylene beta-ketoesters and methylene beta-diketones, preferably methylene malo- nates.

A typical example is a ratio of 70 parts by weight of inorganic filler, 0 parts by weight of organic filler and 30 parts by weight of methylene malonates.

The compositions of the invention can be used as an underbody coating. When used as under- body coating, the compositions preferably comprise

0 to 50 parts by weight of inorganic filler wherein at least 50 parts by weight are inorganic filler with anionic groups

10 to 70 parts by weight of organic filler, preferably acrylic powder, and

30 to 90 parts by weight of polymerizable vinyl compounds selected from methylene malonates, methylene beta-ketoesters and methylene beta-diketones, preferably methylene malonates.

A typical example is a ratio of 10 parts by weight inorganic filler, 40 parts by weight acrylic poly- mer powder and 50 parts by weight methylene malonates.

The compositions of the invention can be used for example as a structural adhesive. When used as structural adhesive, the compositions preferably comprise

0 to 30 parts by weight of inorganic filler wherein at least 50 parts by weight are inorganic filler with anionic groups

10 to 50 parts by weight of organic filler, preferably acrylic polymer powder, and

The molar ratio of the sum of the anionic groups and the neutralizable acid groups of the fillers to the vinyl groups of the polymerizable vinyl compound is preferably smaller than 1 :1 , prefera- bly from 1 :100 to 1 :1000. The compositions of the invention can be used in the form of one-component compositions, op- tionally comprising conventional additives. In one-component compositions the filler has acid groups which can be converted into anionic groups by suitable neutralizing agents shortly be- fore, after or during application to a substrate or by contacting with a surface with anionic or basic functional groups. Polymerization of the vinyl compound can be achieved at room temper- ature (25 °C or less), simply by adding at least one base as neutralizing agent. The polymeriza- tion can be accelerated and/or completed by raising the temperature above room temperature.

The compositions of the invention can also be used in the form of two component compositions, wherein a first composition comprises at least one filler with anionic groups and a second corn- position comprises at least one polymerizable vinyl compound selected from methylene malo- nates, methylene beta-ketoesters and methylene beta-diketones. Each of the first and second compositions can optionally comprise conventional additives. The two components are mixed shortly before application on a substrate. Preferably, at least part of the reaction products are formed after application to the substrate and/or after film formation on a substrate.

Examples of optional additives include wetting agents, thickeners, protective colloids, UV-ab- sorber, light stabilizers, biocides, defoamers, tackifiers, anti-oxidants, metal deactivators, anti- static agents, reinforcement agents, filler materials, anti-fogging agents, propellants, plasticizer, lubricants, emulsifier, colorants, pigments, rheology modifying agents, impact modifier, adhe- sion modifier, optical brightener, flame retardants, anti-dripping agents, nucleating agents, pro- tective colloids, water, organic solvents, reactive diluents etc.

The compositions of the invention can be used for examples for adhesives, sealants, coatings, vibration damping materials, underbody coatings and body fillers. They can be used as binders for coatings or as binders for adhesives. The compositions, or appropriately formulated prepara- tions, can be applied to substrates which are to be bonded or coated, by means, for example, of knife coating, spreading, spraying etc. Typical coating techniques may be employed, examples being roller coating, reverse roller coating, gravure roller coating, reverse gravure roller coating, brush coating, rod coating, spray coating, air brush coating, meniscus coating, curtain coating or dip coating. After a short time for volatiles to evaporate (preferably after 1 to 60 seconds), the coated substrate may, in the case of adhesive applications, then be contacted with a second substrate, the temperature being for example from 20 to 200 °C, preferably 20 to 100 °C, and the pressure being for example from 0,1 to 3000 kN/m².

The coating can be applied for example in amounts of 0,1 to 2000 g/m² , preferably in amounts of 1 to 200 g/m². The coating thickness is preferably from 0,1 pm to less than 2000 pm, for ex- ample from 1 to 250 pm. In case solvent (e.g. water or organic solvent) containing coating for- mulations, the coating thickness is that of the dried coating after evaporation of the solvent.

The compositions of the invention are employed preferably without additional crosslinking agents, more particularly without isocyanate crosslinkers. Examples of suitable substrates in- elude metal, glass, plastics, wood, paper and card board. Examples of suitable substrates in- clude polymer films, more particularly of polyethylene (PE), oriented polypropylene (OPP), unor- iented polypropylene (CPP), polyamide (PA), polyethylene terephthalate (PET), polyacetate, PVC, cellophane, polymer films (vapor-)coated with metal, e.g., with aluminum (metalized films for short), or metal foils, of aluminum for example. The stated films and foils may be bonded with one another or with a foil or film of a different type, for example, polymer films with metal foils, different polymer films with one another, etc. The stated foils and films may also, for exam- pie, be printed with printing inks. The thickness of the substrate films may be, for example, from 5 to 100 pm, preferably from 5 to 40 pm.

The compositions can be applied to a surface of one substrate and hardened to form a coated substrate. Or the compositions can be applied to a surface of a first substrate, contacted with a second substrate of the same or a different nature and hardened to form a composite. Or the composition as such can be shaped and hardened to form a molded material. Preferably, fur- ther (preferably nonionic) inorganic or organic fillers are used for preparing molded materials.

Surface treatment of the film substrates prior to coating according to the invention is not abso- lutely necessary. Better results, however, may be obtained if the surface of the film substrates is modified prior to coating. In this case it is possible to employ typical surface treatments, an ex- ample being corona treatment, for the purpose of intensifying the adhesion effect. The corona treatment or other surface treatments are carried out to the extent required for sufficient wetta- bility with the coating composition. Typically, corona treatment of approximately 10 watts per square meter per minute is sufficient for this purpose. Alternatively or additionally it is also pos- sible, optionally, to use conventional primers or tie coats between film substrate and adhesive coating or pre-coating. Furthermore, other, additional functional layers may be present on the composite films, examples being barrier layers, print layers, color layers or varnish layers, or protective layers. These functional layers may be located externally, i.e., on the side of the film substrate facing away from the adhesive-coated side, or internally, between film substrate and adhesive layer.

Examples of other suitable substrates include rigid substrates like metals, glass, plastics (e.g. acrylonitrile-butadiene-styrene copolymerisate (ABS), polyamide (PA), polystyrene (PS), polyvi- nyl chloride (PVC), polycarbonate (PC), rubber), wood, chipboard, cardboard and polymer com- posites. Bonding or coating of these substrates may be done after surface treatment like plasma or corona treatment, etching, flame treatment or primer application, but is preferably done with- out any treatment.

The curing (hardening) of the compositions of the invention is preferably done at temperatures below 100 °C, most preferably at 15 to 30 °C or at ambient temperature.

The composition is preferably non-aqueous and solvent free. The term "nonaqueous" means more particularly that no aqueous polymer dispersions are used in preparing the compositions. The term "solvent-free" pertains to what are called "100 % systems", where the polymeric binder is used in bulk, in other words not as a solution or dispersion in an organic solvent. Preparation- related solvent residues of below 5 % by weight, for example, based on the polymeric binder, do no harm, since the waste air from the drying ovens can be sent to a downstream incineration facility.

Preferred uses of compositions which contain inorganic fillers are uses as vibration damping compositions. The vibration damping composition may be employed, for example, in vehicles, machines or motors of all kinds, more particularly road-going motor vehicles, automobiles, and rail vehicles, and also in boats, aircraft, electrical machines, construction machines, and build- ings. The vibration damping compositions of the invention have good performance properties in terms of good application qualities and good vibration-damping qualities.

The invention also provides a substrate at least partly coated with a vibration damping composi- tion as described herein.

The vibration damping composition of the invention preferably comprises

(a) 0 to 20 % by weight, preferably 0 to 10 % by weight of at least one acrylic polymer powder with anionic or neutralizable acid groups,

(b) 50 to 85 % by weight, preferably 60 to 80 % by weight of inorganic fillers with anionic or neutralizable acid groups, and

c) 5 to 50 % by weight of at least one polymerizable vinyl compound, wherein the polymeriza- ble vinyl compound is selected from methylene malonates, methylene beta-ketoesters and methylene beta-diketones; and

(d) 0 to 50 % by weight, preferably 0.1 to 20 % by weight of auxiliaries.

Examples of auxiliaries, which are used preferably to an extent of at least 0.1 % by weight, or from 0.2 % to 10 % by weight for example, include crosslinkers, thickeners, rheological addi- tives, resins, plasticizers, organic and inorganic pigments, cosolvents, stabilizers, wetting agents, preservatives, foam inhibitors, glass or plastics beads, hollow glass or plastics bodies, antifreeze agents, dispersants, antioxidants, UV absorbers, antistats, and pigment dispersants. Among the auxiliaries, one, two or a plurality may be used in combination. Examples of suitable cosolvents are ethylene glycol, ethylene glycol alkyl ethers (e.g., Cellosolve® products), diethy- lene glycol alkyl ethers (e.g., Carbitol® products), Carbitol acetate, Butylcarbitol acetate or mix- tures thereof. Examples of thickeners are polyvinyl alcohols, cellulose derivatives or polyacrylic acids, in amounts of, for example, 0.01 to 4 or of 0.05 to 1.5 or of 0.1 to 1 part by weight, based on 100 parts by weight of solids. Examples of dispersants are sodium hexametaphosphate, so- dium tripolyphosphates, or polycarboxyl ic acids. Examples of antifreeze agents are ethylene glycol or propylene glycol. Examples of foam inhibitors include silicones. Examples of stabilizers are polyvalent metal compounds such as zinc oxide, zinc chloride or zinc sulfate. The auxiliaries are preferably used at not less than 0.1 % by weight and are preferably selected from crosslink- ers, thickeners, rheological additives, resins, plasticizers, cosolvents, defoamers, preservatives, antifreeze agents, and pigment dispersants. The compositions of the invention are preferably solvent-free, in other words contain no organic solvents, or at any rate less than 5% by weight of organic solvents, having a boiling point of less than 200°C.

A single plasticizer or a mixture of two or more different plasticizers may be used. Examples of plasticizers are phthalates, such as diisodecyl phthalate, diethylhexyl phthalate, diisononyl phthalate, di-C7-C1 1 n-alkyl phthalate, dioctyl phthalate, tricresyl phosphate, dibenzyltoluene, and benzyl octyl phthalate. In addition it is also possible to use other compounds such as cit- rates, phosphates, adipates, benzoates, and esters of diisononylcyclohexanedicarboxylic acid (DINCH). The proportions may vary within wide ranges. In typical compositions, the plasticizers are present in fractions of 0,5 to 5 parts by weight, per 100 parts by weight of the mixture For conformity with the rheological requirements it is possible, moreover, to use solvents (such as hydrocarbons, for example) as diluents.

The quality of the vibration damping composition can be measured by measurement of the flex- ural vibrations by the resonance curve method in accordance with ISO 6721 -1 and ISO 6721 -3. One measure of the vibration-damping effect is the loss factor tan delta. With vibration damping compositions of the invention, the maximum value of the loss factor tan delta is situated prefera- bly in the range from -20 to +70°C. Where two or more different binders are used, there can be two or more maxima to the loss factor, at not less than two different temperatures. In this case it is preferred for all of the maxima of the loss factor to be situated within the range from -20 to +70°C. Where crosslinkers or hardeners are used, the values relate to the crosslinked or hard- ened vibration damping composition.

The invention also provides a method for damping oscillations or vibrations of components of vehicles or machines, by

(1 ) providing a vibration damping composition as described in more detail above, and

(2) applying the vibration damping composition to a component of a vehicle or of a machine, and subjecting it optionally to drying, hardening and/or crosslinking.

Application may take place in a usual way, as for example by brushing, rolling or spraying. The amount applied is preferably from 1 to 7 kg/m² or from 2 to 6 kg/m² after drying. Drying may take place at ambient temperature or, preferably, by application of heat. The drying temperatures are preferably from 20°C to 160°C or from 30°C to 80°C.

It is an advantage of the invention that a wide variety of different substrates can be bonded or coated ensuring effective adhesion of the adhesive or coating compositions to various sub- strates and producing a high strength in bonded assemblies. Mixture of different acrylic polymer powders and/or different methylene malonate compounds can be used to specifically select the desired reactivity and elasticity. Particular advantages of the products of the invention are the following in particular:

- enables isocyanate-free and crosslinker-free compositions

- enables 1 -component as well as 2-component systems

- high bond strength in short time

- low water uptake of cured mixtures

- curing at room temperature.

Examples Materials:

Monomer 1 :

Methyl-hexyl methylene malonate

Monomer 3:

Dihexyl methylene malonate

Structure A:

Diethyl poly(butylene malonate) Structure C:

Dicyclohexyl methylene malonate

Acronal® 3626 aqueous polymer dispersion made from n-butyl acrylate, acrylic acid and methyl methacrylate, BASF

Acronal® P5033 dispersible, cross-linking polymer powder based on an aqueous anionic co- polymer dispersion of acrylic acid ester and styrene, with anionic protective colloid, BASF

Vinnol® H 15/45 thickener polymer, terpolymer of vinylchloride, vinylacetate and dicarboxylic acid; Wacker.

Kane Ace® M410 acrylate powder, impact modifier based on pure acrylic copolymer core- shell rubber particles, Kaneka, pH of a 50% by weight slurry >7

Performance test - Shear Strength

About 1 g of the compositions are placed onto one of two stainless steel test pieces. For the de- termination of the lap shear strength, two test pieces are adhered to one another with an over- lap of 625 mm² using a 0,25 mm spacer wire. The test specimen is cramped for 24 h at room temperature (20 °C). Shear strength is measured with a universal tensile testing machine (Zwick/Roell) at room temperature and at a speed of 10 mm/min.

Performance test vibration damping, loss factor tan delta

For the purposes of assessing the vibration damping behavior, a measurement is made of the loss factor tan delta at 25^*C, in the manner described in WO 2007/034933 (in analogy to ISO 6721-1 and ISO 6721-3). The obtained vibration damping composition is coated on a reed- shaped sheet steel in 30 x 300 x 1.6 mm with a spatula such that the weight after drying is about 3 kg per m². Then, the coated composition is dried for 24 hours at 23°C. Thereby, test pieces for vibration damping measurement are prepared. Each of these test pieces for vibration damping measurement is measured for loss factor values at -20°C to +80°C. The loss factor value is calculated from half band width of each resonance point at 1 to 1000 Hz of mechanical impedance, based on midpoint excitation method. Then, the loss factor value at 200 Hz is deter- mined by interpolation method. The larger the loss factor value is, the higher the effect of de- creasing vibration damping energy is.

Performance test underbody coating:

The methylene malonate monomers are mixed with the filler components at room temperature and placed in a Teflon mold (11 cm x 8 cm x 2 mm). After curing 24 hours at 23°C, bone shaped test specimen (S2) are cut out and a tensile testing is performed according to DIN 53504 with a velocity of 200 mm/min.

Measurement of water uptake:

The water uptake is determined according to DIN EN ISO 62:2008. The freshly prepared mix- ture is placed in a rectangular mold (30 mm x 15 mm x 2 mm), cured at room temperature for 24 hours. The cured film is placed in deionized water at 23°C for 7 days. After 7 days the water up- take is determined gravimetrically.

Example 1

a) Acronal® 3626 is mixed with chalk powder (Omyacarb® 15 GU, Omya) in a weight ratio of 77:33 and spray dried.

b) 10 g of Monomer 1 are intensively mixed with 5 g of a polymer powder (Acronal® P5033) and 5 g of spry dried powder of 1 a) and applied to a stain less steel test piece for shear strength measurement.

Shear strength: 9,5 MPa

Example 2

10 g of Monomer 1 are intensively mixed with 7,5 g of a polymer powder (Acronal® P5033) and 2,5 g of spry dried powder of 1a) and applied to a stain less steel test piece for shear strength measurement.

Shear strength: 8,4 MPa

Example 3

6 g of Monomer 1 are homogenized over night with 2 g of Monomer 2 and thickener polymer Vinnol H 15/45 , Wacker. 2 g of Kane ACE M 410 are introduced, mixed, homogenized to form a paste and applied to a stain less steel test piece for shear strength measurement.

Shear strength: 4,9 MPa

Example 4: vibration damping composition

7g of a chalk powder (Microcarb® LB 10T, Reverte, ultramicronized surface treated calcium car- bonate) are mixed with 1 ,5 g of Monomer 1 and 1 ,5 g of Monomer 2 and well homogenized.

One part of the mixture is formed into a test rod for vibration damping tests and hardened within 8 hours at room temperature.

The loss factor tan delta reaches its maximum of 0,2 between 25°C and 30°C.

A second part of the mixture is used for water-uptake tests.

Water uptake: 1 % Example 5: vibration damping composition

7g of a Wollastonit powder (Vansil W10, calcium silicate, Vanderbilt Minerals) is mixed with 1 ,5 g of Monomer 1 and 1 ,5 g of Monomer 2 and well homogenized. One part of the mixture is formed into a test rod for vibration damping tests and hardened within 8 hours at room tempera- ture.

The loss factor tan delta reaches its maximum of 0,2 between 28°C and 32°C.

A second part of the mixture is used for water-uptake tests.

Water uptake: 1 %

Example 6: vibration damping composition

6,5 g of a chalk powder (Microcarb® LB 10T, Reverte, ultramicronized surface treated calcium carbonate) are mixed with 0,5 g of the powder of example 1 a. 1 ,5 g of Monomer 1 and 1 ,5 g of Monomer 2 are added and everything is well mixed to give a low viscous slurry.

The mixture is formed into a test rod for vibration damping tests and hardened within 3 hours at room temperature.

The loss factor tan delta reaches the maximum of 0,15 in a temperature interval of 30°C to 35°C.

Example 7: vibration damping composition

6,5 g of a chalk powder (Microcarb® LB 10T, Reverte, ultramicronized surface treated calcium carbonate) are mixed with 0,5 g of the powder of example 1 a. 2,5 g of Monomer 1 and 0,5 g of Monomer 4 are added and everything is well mixed to give a low viscous slurry. The mixture is formed into a test rod for vibration damping tests and hardened within 3 hours at room tempera- ture.

The loss factor tan delta reaches the maximum of 0,16 in a temperature interval of 30°C and 35°C.

Example 8: underbody coating and tensile test:

3 g of a chalk powder (Microcarb® LB 10T, Reverte, ultramicronized surface treated calcium carbonate) are mixed with 12 g of the powder of example 1 a. 7,5 g of Monomer 1 and 7,5 g of Monomer 4 are added and everything is well mixed to give a low viscous slurry.

The mixture is placed in a Teflon mold (11 cm x 8 cm x 2 mm) and cured at 23°C for 24 hours to give a tack-free film. Tensile strength is 3 N/mm² and elongation is 200%.

Example 9: vibration damping composition

14 g of a chalk powder (Microcarb® LB 10T, Reverte, ultramicronized surface treated calcium carbonate) are mixed with 3 g of Monomer 4 and 3 g of Structure C and 0,26 g of Structure A and well homogenized. 0,3g of a 10% solution of triisopropanol amine in trimethylol propane tri- methacrylate is added and homogenized. One part of the mixture is formed into a test rod for vibration damping tests and hardened within 8 hours at room temperature. The loss factor tan delta reaches its maximum of 0,1 between 5°C and 15°C.

Example 10: vibration damping composition

14g of a chalk powder (Microcarb® LB 10T, Reverte, ultramicronized surface treated calcium carbonate) are mixed with 1g of Monomer 4 and 1 g of Structure C and 4 g of Structure A and well homogenized. 0,3g of a 10% solution of triisopropanol amine in trimethylolpropane tri- methacrylate is added and homogenized. One part of the mixture is formed into a test rod for vibration damping tests and hardened within 8 hours at room temperature.

Example 1 1 : vibration damping composition

14g of a chalk powder (Microcarb® LB 10T, Reverte, ultramicronized surface treated calcium carbonate) are mixed with 2 g of Monomer 4 and 4 g of Structure C and 0,26 g of Structure A and well homogenized. 0,6 g of a 0,2% solution of sodium benzoate in ethanol is added and ho- mogenized. One part of the mixture is formed into a test rod for vibration damping tests and hardened within 8 hours at room temperature.

The loss factor tan delta reaches its maximum of 0,1 between 25°C and 35°C.

Example 12: vibration damping composition

14 g of a chalk powder (Microcarb® LB 10T, Reverte, ultramicronized surface treated calcium carbonate) are mixed with 6 g of Structure A and well homogenized. 0,3g of a 10% solution of triisopropanol amine in trimethylolpropane trimethacrylate is added and homogenized. One part of the mixture is formed into a test rod for vibration damping tests and hardened within 8 hours at room temperature.

Example 13: vibration damping composition

14g of a chalk powder (Microcarb® LB 10T, Reverte, ultramicronized surface treated calcium carbonate) are mixed with 4 g of Monomer 4 and 2 g of Structure C and 0,26 g of Structure A and well homogenized. 0,3g of a 10% solution of triisopropanol amine in trimethylolpropane tri- methacrylate is added and homogenized. One part of the mixture is formed into a test rod for vibration damping tests and hardened within 8 hours at room temperature.

The loss factor tan delta reaches its maximum of 0,1 between - 5°C and - 15°C.

Water uptake: 2,5%

Example 14: lap shear measurement

a) Acronal® 3626 is mixed with chalk powder (Omyacarb® 15 GU, Omya) in a weight ratio of 77:33 and spray dried. b) 3g of Oligomer Structure A is mixed with 1 ,5 g of powder a) and intensively mixed. 0,15 g g of a 10% solution of Triisopropanolamine in Trimethylolpropanetrimethacrylate is mixed in and the mass is applied to a stain less steel test piece for shear strength measurement. Shear strength: 2,5 MPa

Example 15: lap shear measurement

5 g of Oligomer Structure A is mixed with 1 g of Monomer 4; 2 g of a polymer powder (Acronal® P5033) is mixed in and additionally 2 g of Wollastonit powder (Vansil W10, calcium silicate, Vanderbilt Minerals). After intensively mixing, 0,6 g of a 10% solution of triisopropanol amine in trimethylolpropane trimethacrylate is mixed in and the mass is applied to a stain less steel test piece for shear strength measurement.

Shear strength: 2 MPa

Example 16: lap shear measurement

b) 5 g of Oligomer Structure A is mixed with 1 g of Monomer 4; 2 g of a polymer powder

(Acronal® P734) is mixed in and additionally 2 g of a). After intensively mixing, 0,3 g of a 10% solution of triisopropanol amine in trimethylolpropane trimethacrylate is mixed in and the mass is applied to a stain less steel test piece for shear strength measurement.

Shear strength: 2 MPa

Claims

1. Composition comprising

(B) at least one polymerizable vinyl compound,

wherein the polymerizable vinyl compound is selected from methylene malonates, meth- ylene beta-ketoesters and methylene beta-diketones;

and wherein the particulate filler has functional groups selected from anionic groups and neutralizable acid groups,

wherein the components (A) and (B) are blended without being dispersed in water or an or- ganic solvent,

2. Composition according to claim 1 , wherein the organic filler is an acrylic polymer powder.

3. Composition according to claim 1 , wherein the inorganic filler with anionic groups is se- lected from silicate-treated calcium carbonate, mica, silica, wollastonit, clay, barium sulfate, glass powders, glass flakes, glass fibers, chalk, aluminum hydroxide, perlite, kaolin.

4. Composition according to any of claims 1 to 3 wherein the weight ratio of vinyl compound to the sum of inorganic and organic fillers is from 95:5 to 5:95, preferably from 80:20 to 20:80.

5. Composition according to any of the preceding claims, wherein the molar ratio of the sum of the anionic groups and the neutralizable acid groups of the filler to the vinyl groups of the polymerizable vinyl compound is smaller than 1 :1 , preferably from 1 :100 to 1 :1000.

6. Composition according to any of the preceding claims, wherein the filler is an acrylic poly- mer powder having an amount of anionic groups or neutralizable acid groups from 10 mmol/kg to 1000 mmol/kg based on dry material and wherein the anionic groups are se- lected from carboxylate groups, sulfonate groups and phosphate groups or the respective acid groups.

7. Composition according to any of the preceding claims, wherein the polymerizable vinyl compound is a methylene malonate selected from compounds of the formula

R¹-0-C(0)-C(C=CH₂)-C(0)-0-R²

or wherein the polymerizable vinyl compound is a methylene beta-ketoester selected from compounds of the formula

R¹-C(0)-C(C=CH₂)-C(0)-0-R²

or wherein the polymerizable vinyl compound is a methylene beta-diketone selected from compounds of the formula

R¹-C(0)-C(C=CH₂)-C(0)-R² wherein R¹, R² are each independently C1-C15 alkyl, C2-C15 alkenyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl-(C1 -C15 alkyl), heteroaryl or heteroaryl-(C1 -C15 alkyl), or alkoxy-(C1 -15 alkyl), each of which may be optionally substituted by C1-C15 alkyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl -(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, car- boxy, ester or sulfonyl;

or wherein R¹ and R² are taken together with the atoms to which they are bound to form a 5-7 membered heterocyclic ring which may be optionally substituted by C1-C15 alkyl, halo- (C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1- C15 alkyl), aryl, aryl -(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio, hydroxyl, nitro, azido, acyloxy, carboxy, ester or sulfonyl.

8. Composition according to any of claims 1 to 6, wherein the polymerizable vinyl compound is selected from compounds of the formula:

wherein R¹, R² are each independently C1-C15 alkyl, C2-C15 alkenyl, halo-(C1-C15 al- kyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl or heteroaryl-(C1-C15 alkyl), or alkoxy-(C1-15 alkyl), each of which may be optionally substituted by C1-C15 alkyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl - (C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, ester or sulfonyl;

or wherein R¹ and R² are taken together with the atoms to which they are bound to form a 5-7 membered heterocyclic ring which may be optionally substituted by C1-C15 alkyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl- (C1-C15 alkyl), aryl, aryl -(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio, hy- droxyl, nitro, azido, acyloxy, carboxy, ester or sulfonyl;

-(CH₂)n-[CY]-(CH₂)n, a polybutadienyl linking group, a polyethylene glycol linking group, a polyether linking group, a polyurethane linking group, an epoxy linking group, a polyacrylic linking group, or a polycarbonate linking group;

each instance of R^A or R^B is independently H, C₁-C₁₅ alkyl, C₂-C₁₅ alkenyl, a moiety repre- sented by the formula:

wherein L is a linking group selected from the group consisting of alkylene, alkenylene, haloalkylene, cycloalkylene, heterocyclylene, heterocyclyl alkylene, aryl-alkylene, hetero- arylene or heteroaryl-(alkylene), or alkoxy-(alkylene), each of which may be optionally branched and each of which may be optionally substituted by alkyl, haloalkyl, cycloalkyl, halo cycloalkyl, heterocyclyl, heterocyclyl-(alkyl), aryl, aryl -(alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, ester, each of which may be optionally branched;

R₃ is independently selected from the group defined in R₂ above;

[CY] represents an alkyl, alkenyl, haloalkyl, cycloalkyl, halo cycloalkyl, heterocyclyl, heter- ocyclyl-(alkyl), aryl-(alkyl), heteroaryl or heteroaryl-(alkyl), or alkoxy-(alkyl) group;

n is an integer from 1 to 25;

m is an integer from 1 to 25;

and each instance of Q represents -O- or a direct bond.

9. Composition according to any of the preceding claims, wherein the polymerizable vinyl compound is selected from compounds of the formula

R¹-0-C(0)-C(C=CH₂)-C(0)-0-R²

wherein R¹, R² are each independently C1-C10 alkyl;

or wherein the polymerizable vinyl compound is selected from compounds of the formula

wherein R¹, R² are each independently C1-C10 alkyl,

A is selected from C1-C10 alkylene and -X-Ph-U-, wherein X and Y are each independently C1-C10 alkylene.

10. Composition according to any of the preceding claims, wherein the polymerizable vinyl compound is a methylene malonate.

1 1. Composition according to any of the preceding claims, wherein the organic filler is an

acrylic polymer powder composed of

(a) at least 70% by weight of at least one monomer selected from esters of acrylic acid and esters of methacrylic acid,

and optionally monomers different from monomers (a) and (b).

12. Composition according to claim 11 wherein the acrylic polymer is composed of

(a) from 70 to 99% by weight of alkyl (meth)acrylates with 1 to 12 carbon atoms in the alkyl group,

(b) from 0,1 to 10 % by weight of acid monomers, selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinyla- cetic acid, and vinyllactic acid and

(c) from 0 to 20% by weight of ethylenically unsaturated monomers different from mono- mers (a) and (b).

13. Composition according to any of the preceding claims, wherein the organic filler is an

acrylic polymer which is a spray-dried emulsion polymerizate containing additives for spay- drying, that have anionic groups or neutralizable acid groups.

14. Composition according to claim 13, wherein the acrylic polymer has a core-shell structure and the core is characterized by a Tg lower than 0°C and the shell is characterized by a Tg higher than 20°C.

15. Composition according to any of the preceding claims, wherein the weight ratio of inorganic fillers to acrylic polymer powder to methylene malonates is 0 to 50 parts by weight of inor- ganic fillers, 10 to 70 parts by weight acrylic polymer powder and 30 to 90 parts by weight of methylene malonates.

16. Composition according to any of claims 1 to 13, wherein the weight ratio of inorganic fillers to acrylic polymer powder to methylene malonates is 50 to 85 parts by weight of inorganic fillers, 0 to 20 parts by weight acrylic polymer powder and 15 to 50 parts by weight of meth- ylene malonates.

17. Composition according to any of the preceding claims, wherein the composition is in the form of a two-component system wherein a first component comprises the at least one filler with anionic groups and a second component comprises the at least one polymerizable vi- nyl compound; or wherein the composition is in the form of a one-component system wherein the filler has acidic groups which can be converted into anionic groups by suitable neutralizing agents shortly before, after or during application to a substrate or by contacting with a surface with anionic or basic functional groups.

18. Method of forming a coating, wherein a composition according to any of claims 1 to 17 is coated on a substrate and the anionic groups or the neutralized acid groups of the at least one filler are reacted with the at least one polymerizable vinyl compound.

19. Use of a composition according to any of claims 1 to 17 for adhesives, sealants, coatings, vibration damping materials, underbody coatings and body fillers.

20. Cured material or cured coating, comprising a composition according to any of claims 1 to 17, wherein the at least one polymerizable vinyl compound (B) has been polymerized.