WO2018011308A1

WO2018011308A1 - Scuff resistant decorative surface coverings

Info

Publication number: WO2018011308A1
Application number: PCT/EP2017/067623
Authority: WO
Inventors: Emilie FAURE; Guillaume Fascella
Original assignee: Tarkett GDL SA
Current assignee: Tarkett GDL SA
Priority date: 2016-07-15
Filing date: 2017-07-12
Publication date: 2018-01-18
Anticipated expiration: 2019-01-15

Abstract

The present invention is related to decorative surface coverings, in particular floor or wall coverings, comprising one or more polymer layer(s) and a crosslinked top-layer, combining excellent anti-slip properties and scuff resistance. The invention is further related to a method for the preparation of such surface coverings.

Description

SCUFF RESISTANT DECORATIVE SURFACE COVERINGS

Field of the Invention

[0001] The present invention is related to decorative floor and wall coverings comprising a crosslinked topcoat showing improved anti-slip properties and scuff-resistance. The invention is further related to a method for the production of such surface coverings.

State of the Art

[0002] Surface covering materials, and especially surface covering materials adapted for use as floor and wall coverings, must frequently possess a wide range of sometimes contradictory properties and characteristics. For example, there has been an increasing demand for floor covering materials having improved scuff resistance. Furthermore, it is highly desirable for such floor covering materials to possess satisfactory anti-slip properties.

[0003] The term "scuff resistance" designates the ability of the wear surface to resist plastic flow when subjected to the force and frictional heat caused by the dragging of, for example, rubber or plastic soled shoes.

[0004] The term "slip-resistance" designates the ability of the wear surface to allow safe walking of a test person, the slope of the surface being increased from the initial horizontal state to the acceptance angle where the limit of safe walking is reached and the test person slips.

[0005] The current state of the art of floor covering materials presents either satisfactory anti slip properties or scuff resistance and relies primarily on the use of coating compositions, in particular polyurethane coating compositions, as topcoat.

[0006] The use of radiation curable polyurethane compositions as top layer for decorative surface coverings are for example disclosed in EP 0210620 (B1 ), US 4,100,318, US 4,393,187, US 4,598,009, US 5,543,232, US 6,586,108, US 2013/0230729, DE 4421559, FR 2,379,323, KR 100292584, KR 20010016758, JPH 06279566, CN 103242742 and WO 03/022552.

[0007] US 5,458,953 discloses a resilient surface covering, meeting standards of stain, mar, scuff, and soil resistance, the resilient surface covering comprising (a) a resilient support surface and (b) a resilient wear surface adhered to the resilient support surface, the resilient wear surface comprising an underlying wear layer base coat and an overlying wear layer top coat adhered to the wear layer base coat, the wear layer top coat comprising a hard, thermoset, polymeric UV-curable blend of acrylic or acrylate monomers.

[0008] US 5,401 ,560 relates to non-slip materials which are provided by coating a polymer sheet backing, preferably a polyvinyl chloride sheet, with mineral particles adhered to the backing by a radiation curable polyurethane binder material. The radiation cured polyurethane binder material is electron beam cured. A variety of mineral particles may be employed which will provide adequate frictional contact in use to prevent, or aid in the prevention of slippage. Examples of suitable mineral particles are aluminum oxide, silicon carbide, fumed silica and silica gel.

[0009] The preferred resin system is a combination of resin components, made from commercially available resins, with diluents and other components. The resin system(s) preferably comprise(s) a blend of two or more grades of urethane oligomers. In addition, one or more surfactants, preferably containing fluorocarbon material, may be added as wetting agents.

[0010] While polyurethane surface coatings have achieved a significant degree of success in the flooring industry, there has been a general recognition that several disadvantages are associated with such surface coverings. For example, it is generally accepted that polyurethane coatings can be formulated to possess a high degree of anti-scuff properties. However, it is equally well established that scuff-resistant polyurethane coatings generally exhibit poor anti-slip. Yet, both of these properties are extremely important for the production of a commercially successful surface covering, especially a surface covering which is exposed to the conditions encountered by flooring materials.

[0011] It is nevertheless possible to formulate polyurethane coating compositions that have improved anti-slip properties. Unfortunately, such improvements can generally only be obtained at the expense of scuff resistance. Therefore polyurethane coating compositions which are formulated to exhibit improved anti-slip properties will also generally exhibit unsatisfactory scuff resistance. Aims of the invention.

[0012] The present invention aims, in one aspect, at providing a decorative surface covering, in particular floor or wall covering, comprising one or more layer(s) comprising one or more polyolefin(s) and/or vinyl chloride (co)polymers and a radiation cured top-layer with good adhesion to the top of the surface layer of the one or more layer(s), the radiation cured top-layer combining excellent scuff-resistance and anti-slip properties.

[0013] A further aim of another aspect of the present invention is to provide a process for the production of such surface coverings.

Summary of the Invention.

[0014] The present invention discloses a decorative surface covering comprising one or more polymer layer(s) and a crosslinked top-layer, completely covering the top surface of the one or more polymer layers, the top-layer comprising: i. 40 to 90% by weight of crosslinked segments selected from the group consisting of polyurethane, polyester, polyether, (meth)acrylate (co)polymer, (hydrogenated) bisphenol based resin, novolac type resin and mixtures thereof, the crosslinks connecting the segments being of the poly (meth)acrylate, polyalkene or polyether type;

ii. 0.5 to 25% by weight of one or more types of micro-scale particle(s) with a volume median particle diameter (D50) comprised between 1 and 50 μιτι, preferably between 3 and 35 μιτι, more preferably 5 and 20 μιτι as obtained from laser light scattering measurements according to ISO 13320,

iii. 0.1 to 20% by weight of one or more compound(s) selected from the group consisting of silicones, fluorocarbons and olefin (co)polymers.

[0015] Preferred embodiments of the present invention disclose one or more of the following features:

- the crosslinked top-layer comprises:

- 40 to 90% by weight of cross-linked polyurethane segments (i.); - 0.5 to 25% by weight of one or more types of glass micro-scale particle(s) (ii.);

- 0.1 to 20% by weight of one or more compound(s) (iii.);

- the micro-scale particles (ii.) are glass micro-scale particles, preferably soda- lime-silica glass micro-scale particles;

- the one or more types of micro-scale particle(s) (ii.) comprise a coating selected from the group consisting of ester-, vinyl ester-, amide-, urethane-, (meth)acrylate and epoxy- based coatings;

- the one or more compounds(s) (iii.) comprise one or more polydimethylsiloxanes;

- the one or more compounds (iii.) comprise one or more silicones, up to 50% weight of the silicones being a crosslinked segment of the crosslinked top- layer, the remaining 50% by weight or more being present as additive;

- the crosslinked segments (i.) comprise acid functionalities selected from the group consisting of -SO₃H, -OSOsH, -COOH, -OPO₃H₂ and -OPO2HO-;

- the crosslinked segments (i.) are connected through poly(meth)acrylate type crosslinks having a degree of polymerization of at least 2;

- the one or more polymer layer(s) comprise(s) one or more polymers selected from the group consisting of polyvinyl halides, polyolefins and block copolymers comprising polymer blocks of one or more vinyl aromatic monomer(s) and polymer blocks of one or more alkylene(s);

- the decorative surface covering comprises an embossed structure;

- the volume median particle diameter (D50) of the micro-scale particles (ii.) is comprised between 0.02 and 500%, preferably between 0.04 and 350%, more preferably between 0.06 and 200% and most preferably between 0.08 and 100% of the crosslinked polyurethane layer thickness;

- the volume median particle diameter (D50) of the micro-scale particles (ii.) is comprised between 0.01 and 500%, preferably between 0.05 and 300%, more preferably between 0.1 and 100% and most preferably between 0.2 and 50% of the embossing depth;

- the decorative surface covering have a Slip Resistance, according to EN13893, corresponding to Slip Resistance Class equal to or superior to R9, preferably equal to or superior to R10, more preferably equal to or superior to R1 1 and a Scuff Resistance of 8 or higher, preferably of 10 or higher, more preferably of 12 or higher as assessed in a friction test apparatus with an Astral Rubber tool according to the method as disclosed in [0147] to [0151 ] of the detailed description.

[0016] The present invention further discloses a process for the preparation of the decorative surface covering, comprising the steps of:

- providing one or more polymer layer(s);

- applying a radiation curable coating formulation, comprising an ethylenically unsaturated or oxirane group comprising binder, micro- scale particles and one or more compounds selected from the group consisting of silicones, fluorocarbons and olefin (co)polymers, on the surface of the one or more polymer layer(s);

- irradiating the radiation curable coating formulation to form a crossl inked top-layer.

[0017] Preferred embodiments of the process for the preparation of the decorative surface covering disclose one or more of the following features:

- the radiation curable coating formulation comprises 30 to 90% by weight, preferably 40 to 80% by weight of a radiation curable binder and from 0.5 to 10% by weight, preferably from 2 to 8% by weight of at least one

photoinitiator, relative to the total weight of the formulation;

- the radiation curable binder comprises at least 10% by weight, preferably at least 15% by weight of one or more ethylenically unsaturated polyurethane, polyester, polyether, (meth)acrylate (co)polymer, (hydrogenated) bisphenol based resin, novolac type resin, and at most 60% by weight preferably at most 50% by weight of one or more reactive diluent(s);

- the radiation curable coating formulation comprises 0.5 to 25% by weight of one or more micro-scale particle(s) with a volume median particle diameter (D50) comprised between 1 and 50 μιτι and 0.1 to 20% by weight of one or more compounds selected from the group consisting of silicones,

fluorocarbons and olefin (co)polymers;

- the top surface of the one or more polymer layer(s) is subjected to a plasma treatment, preferably a corona plasma treatment. Brief Description of the Figure

[0018] Figure 1 illustrates the scuff resistance test on a decorative surface according to the state of the art.

Figure 2 illustrates the scuff resistance test on a decorative surface according according to the present invention.

Detailed Description of the Invention

[0019] The object of an aspect of the present invention is to provide decorative floor and wall coverings comprising a crosslinked top-layer combining excellent scuff-resistance and anti-slip properties. The crosslinked top-layer is obtained from radiation curing one or more radiation curable compositions.

[0020] In one embodiment, the decorative surface coverings of the present invention comprise a stack of layers, preferably comprising a backing layer, a decor layer, at least one wear layer all preferably comprising one or more olefin (co)polymers and/or one or more vinyl halide (co)polymers and a crosslinked top-layer on the top-surface of the wear layer.

[0021] Additional layers can be present. The additional layers can be used for a variety of purposes, such as for reinforcement.

[0022] In another embodiment the decorative surface coverings comprise one layer comprising one or more olefin (co)polymers and/or one or more vinyl halide (co)polymers and a cross-linked top-layer on the top-surface of the layer.

[0023] The one or more polyolefin (co)polymers comprise one or more homo and/or copolymers selected from the group consisting of an ethylene homopolymer, a propylene homopolymer, an ethylene copolymer comprising alpha-olefins, an olefin copolymer comprising vinyl carboxylate esters, an olefin copolymer comprising alkyl (meth)acrylates, a polyolefin elastomer and a polar group comprising polyolefin.

[0024] The one or more vinyl halide (co)polymers are selected from the group consisting of polyvinyl chloride homopolymers, and copolymers of vinyl chloride and one or more ethylenically unsaturated monomers selected from the group consisting of vinylidene chloride, (meth)acrylic acid esters, α,β-unsaturated dicarboxylic acid esters, vinyl alkanoates, and alkylenes. [0025] The one or more layer(s) further may comprise one or more styrene/olefin based elastomers.

[0026] The one or more layer(s) further may comprise organic or inorganic fillers, lubricants and additives.

[0027] The one or more layers optionally comprise(s) a primer layer and/or one or more prints.

[0028] The top-layer on the top surface of the one or more layer(s) is obtained from a radiation curable coating composition after being subjected to actinic irradiation, in particular ultra violet (UV) irradiation or electron irradiation (EB).

[0029] Two main technologies may be used for converting the radiation curable top-coat formulation. The first uses free radical species to initiate the polymerisation of reactive functional groups, more particularly ethylenically unsaturated double bonds. The second is based on the generation of very strong acids to initiate the cationic polymerisation of reactive functional groups such as for example, cyclic ethers such as oxirane or oxethane, preferably alicyclic epoxides, allyl ethers and vinyl ethers.

[0030] Preferably, the crosslinked top-coat is obtained from a radical initiated conversion of ethylenically unsaturated double bonds.

[0031] The radiation curable coating composition for being used in the present invention comprises:

I. 40 to 90% by weight of an ethylenically unsaturated or oxirane group

comprising binder;

II. 0.5 to 25% by weight of one or more types of micro-scale particle(s) with a volume median particle diameter (D50) comprised between 1 and 50 μιτι, preferably between 3 and 35 μιτι, more preferably 5 and 20 μιτι.

III. 0.1 to 20% by weight of one or more compounds capable of reducing the surface tension of the coating composition.

[0032] The radiation curable coating composition for being used in the present invention further may comprise:

- from 0 to 15% by weight preferably from 2 to 10% by weight of at least one photoinitiator optionally combined with at least one photoactivator. - from 2 to 35 % by weight, preferably from 5 to 30 % by weight of further additifs.

[0033] The radiation curable coating for being used in the present invention further may comprise up to 40% by weight of solvent. By solvent the present invention means organic solvent or mixtures of organic solvents and water. The solvents in general are flashed before subjecting the coating composition to actinic radiation. Examples of solvents are alcohols such as methanol, ethanol, propanol, t-butyl alcohol; ethers such as ethylene glycol dimethyl ether; ketones such as acetone; and mixtures of the solvents and water; i.e. compounds not capable of being incorporated into the crosslinked topcoat through a chemically reaction upon irradiation.

[0034] Flashing solvents may be accelerated by subjecting the coating to heating means such as convection heat or infrared irradiation.

[0035] The coating composition subjected to irradiation is substantially solvent-free. By substantially solvent-free, the present invention means that the coating composition comprises less than 5% by weight, preferably less than 2% by weight, more preferably less than 1 % by weight, most preferably less than 0.5% by weight of solvents.

[0036] The ethylenically unsaturated group comprising binder for being used in the radiation curable coating composition of the present invention comprises

- from 5 to 90 % by weight preferably from 15 to 70 % by weight of an

ethylenically unsaturated group comprising polyurethane, polyester, polyether, (meth)acrylate (co)polymer, (hydrogenated) bisphenol based resin, novolac resin and mixtures thereof

- from 0.1 to 10 % by weight preferably from 1 to 8 % by weight of at least one acidic adhesion promotor and

- from 5 to 90% by weight preferable from 15 to 70% by weight of at least one mono- and/or polyfunctional reactive diluent.

[0037] The oxirane group comprising binder for being used in the radiation curable coating composition of the present invention comprises - from 5 to 90 % by weight preferably from 15 to 80 % by weight of an oxirane functionalized (meth)acrylate (co)polymer, (hydrogenated) bisphenol based resin, novolac resin and mixtures thereof

- from 5 to 90% by weight preferable from 20 to 70% by weight of at least one mono- and/or polyfunctional oxirane, vinylether and/or allyl ether comprising reactive diluent.

[0038] The ethylenically unsaturated group comprising polyurethanes for being used in the binder of the present invention in generally are obtained from the reaction of:

a) at least one polyisocyanate,

b) at least one polymerizable ethylenically unsaturated compound containing at least one reactive group capable to react with isocyanate groups and

c) at least one compound which differs from compound (b) containing at least one reactive group capable to react with isocyanate groups.

[0039] By polyisocyanate compound (a) is meant to designate organic compounds comprising at least two isocyanate groups. The polyisocyanate compound usually comprises not more than three isocyanate groups. The polyisocyanate compound (a) is most preferably a di-isocyanate. The polyisocyanate compound is generally selected from aliphatic, cycloaliphatic, aromatic and/or heterocyclic polyisocyanates or combinations thereof.

[0040] Examples of polyisocynates are 1 ,3-cyclopentane, 1 ,4- cyclohexane and 1 ,2-cyclohexane diisocyanate, 4,4'-methylene-bis(cyclohexyl isocyanate) and isophorone diisocyanate (IPDI), 2-methylpentamethylene 1 ,5- diisocyanate (MPDI), hexamethylene diisocyanate (HDI), trimethylhexannethylene 1 ,6-diisocyanate (TMDI), in particular 2,2,4- and the 2,4,4 isomer and technical mixtures of both isomers.

[0041] Polymerizable ethylenically unsaturated compound (b) in general have one or more reactive groups capable to react with isocyanate groups and at least one ethylenically unsaturated group.

[0042] Compounds (b) in general contain one or more ethylenically unsaturated group such as acrylic or methacrylic group and essentially one nucleophilic function capable of reacting with isocyanate, such as a hydroxyl group. Preferred are (meth)acryloyl mono-hydroxy compounds, more particularly poly(meth)acryloyl mono-hydroxy compounds.

[0043] Compound (c), containing at least one reactive group capable to react with isocyanate groups, in general comprises monomeric mono- and/or polyols such as ethylene glycol, 1 ,2-propylene glycol, 1 ,4-butanediol, neopentyl glycol, hexanediol, trimethylolpropane and the like and/or mono- and/or polyamines such as ethylene diamine, hexamethylene diamine. Aminoalcohols such as ethanol amine may be used as well.

[0044] Compound (c) furthermore comprises oligomeric and/or polymeric hydroxy-functional compounds. These oligomeric and/or polymeric hydroxy-functional compounds are, for example, polyesters, polyesteramides, polyethers, silicon comprising polyols, rubber polyols, polyether-esters, polycarbonates, polyether carbonate polyols and polycarbonate polyesters having a functionality of from 1 .0 to 3.0 and in general having a number averaged molecular weight comprised between 500 and 15,000 g/mole, preferably between 1000 and 10,000 g/mole, more preferably between 2,000 and 8,000 g/mole.

[0045] Preferably the ethylenically unsaturated group comprising polyurethane is an ethylenically unsaturated group comprising aliphatic polyurethane, more preferably an acrylated aliphatic polyurethane.

[0046] The ethylenically unsaturated group comprising polyethers for being used in the binder of the present invention in generally are obtained from the reaction of a polyether polyol with (meth)acrylic acid.

[0047] The polyether polyols in general have a degree of ethoxylation of from 10 to 20, the degree of ethoxylation indicating the number of moles of ethylene oxide that have on average been added onto 1 mole of a polyhydric alcohol used as the starter molecule in accordance with well-known methods.

[0048] Besides ethylene oxide, minor amounts of propylene oxide may be used for the alkoxylation of the polyhydric alcohol.

[0049] The ethylenically unsaturated group comprising polyesters for being used in the binder of the present invention in generally are obtained from the reaction of (meth)acrylic acid with a hydroxyl functional polyester, obtained from reaction of a molar excess of polyols on polyacids, or from the reaction of glycidyl(meth)acrylate with a carboxyl functional polyester obtained from reaction of a molar excess of polyacids on polyols.

[0050] Examples of polyols for being used in the polyesters of the present invention are ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, 1 ,2-butanediol 1 ,3-butanediol, 1 ,4-butanediol, 1 ,5-pentanediol, neopentyl glycol, diethylene glycol, triethylene glycol, cyclohexane-dimethanol, glycerol, trimethylolethane, trimethylolpropane and tris-2-hydroxyethyl isocyanurate,

[0051] Examples of polyacids for being used in the polyesters of the present invention are phthalic acid, isophthalic acid, terephthalic acid, adipic acid, fumaric acids, itaconic acid, trimellitic acid, and the corresponding anhydrides.

[0052] The ethylenically unsaturated group comprising (meth)acrylate copolymers for being used in the binder of the present invention in generally are obtained from the reaction a (meth)acrylic copolymer or oligomer comprising epoxy, carboxyl, hydroxyl or isocyanate group(s) with one or more ethylenically unsaturated group containing compound(s) having a functional group that can react with the epoxy, carboxyl, hydroxyl or isocyanate group(s) of the (meth)acrylic copolymer or oligomer.

[0053] The (meth)acrylic copolymer or oligomer having epoxy, carboxyl, hydroxyl or isocyanate group(s) is for example obtained from the polymerization of (meth)acrylate alkyl ester having from 2 to 26 carbon atoms in the alkyl group, such as for example ethyl(meth)acrylate, propyl(meth)acrylate, n- butyl(meth)acrylate, isobutyl(meth)acrylate and (meth)acrylic monomers comprising an epoxy group such as glycidyl(meth)acrylate, an acid group such as (meth)acrylic acid an hydroxyl group such as hydroxyethyl(meth)acrylic or an isocyanate group such as 1 -(1 -isocyanato-1 -methylethyl)-4-(1 -methylethenyl) benzene.

[0054] The ethylenically unsaturated group comprising (hydrogenated) bisphenol based resins for being used in the binder of the present invention in general are obtained from reaction of (hydrogenated) bisphenol A or F based epoxy resins with (meth)acrylic acid. The ethylenically unsaturated group comprising novolac resins are obtained from reaction of epoxy novolac resins with (meth)acrylic acid. [0055] The resins comprising epoxy functional groups, as disclosed above, such as epoxy functionalized acrylic copolymers, the bisphenol A or F epoxy resins or the epoxy novolac resins, may be used, as such, in radiation- initiated cationic curable binders, though cycloaliphatic epoxy group comprising compounds, such as 3,4-epoxycyclohexyl for example obtained from the copolymerization of 3,4-epoxycyclohexylmethyl(meth)acrylate and one or more (meth)acrylate alkyl esters having from 2 to 26 carbon atoms in the alkyl group and oxetane group comprising compounds, for example obtained from the copolymerization of 3-oxetanylmethyl (meth)acrylate and one or more (meth)acrylate alkyl esters having from 2 to 26 carbon atoms in the alkyl group, are preferred.

[0056] The acidic adhesion promoting resins used in accordance with the invention, generally comprise one or more acid functionality and one or more (meth)acrylic functionality. The one or more acid functionality is selected from the group consisting of -SO₃H, -OSOsH, -COOH, -OPO₃H₂ and -OPO2HO-. Optionally the acidic hydrogen is substituted by an alkali metal or an ammonium base.

[0057] The acidic adhesion promotor is the reaction product of the one or more acid functionality comprising components with one or more functionalized (meth)acrylates.

[0058] Examples are ethylenically unsaturated polyesters and polyurethanes comprising one or more -SO3H, -OSO3H, -COOH, -OPO3H2 and - OPO2HO- functionality

Polyesters comprising one or more of the acid functionalities are prepared from one or more polyol components and one or more polybasic acid components, wherein at least one or more diol component and/or one or more dibasic acid component contain one or more -SO3H, -OSO3H, -COOH, and -OPO3H2 functionality.

[0059] Examples of -SO3H, -OSO3H and -COOH functionality comprising polybasic acid or polyol include 5-sulfoisophthalic acid, 2- sulfoisophthalic acid, 4-sulfophthalic acid, 3-sulfophthalic acid, a dialkyl 5- sulfoisophthalate, a dialkyl 2-sulfophthalate, an alkyl 4-sulfophthalic acid, an alkyl 3-sulfophthalic acid, dimethylolpropionic acid and a sodium, potassium or ammonium salt of these compounds. [0060] Polyesters comprising one or more phosphate groups in the polyester chain are prepared from condensation of one or more polyols and one or more polybasic acids in the presence of phosphoric acid.

[0061] Acid functional polyesters having one or more -SO3H, -OSO3H,

-COOH, -OPO3H2 and -OPO2HO- functionality are converted into ethylenically unsaturated polyesters having one or more of the acid functionalities through reaction with glycidyl(meth)acrylate or hydroxyethyl(meth)acrylate.

[0062] Mono- and/or polyfunctional reactive diluents, comprising ethylenically unsaturated group(s), that may be used in the radiation curable binder composition in accordance with the invention, are for example the (meth)acrylate esters of alcohols such as methanol, ethanol, 1 -propanol, 1 -butanol, 1 -pentanol, 1 -hexanol, 2-propanol, 2-butanol, 2-ethylhexanol, dihydrodicyclopentadienol, tetrahydrofurfuryl alcohol, 3,3,5-trimethylhexanol, octanol, decanol, dodecanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, 1 ,4- butanediol, neopentyl glycol, 2-ethyl-2-butylpropanediol, trimethylpentanediol, 1 ,3- butylene glycol, 1 ,4-cyclohexanedimethanol, 1 ,6-hexanediol, 1 ,2- and 1 ,4- cyclohexanediol, hydrogenated bisphenol A (2,2-bis(4- hydroxycyclohexyl)propane), glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, and the ethoxylated and/or propoxylated derivatives of the alcohols and the technical grade mixtures obtained during (meth)acrylation of the abovementioned compounds.

[0063] Further suitable reactive diluents are for example epoxy

(meth)acrylates, polyether (meth)acrylates, polyester (meth)acrylates and polycarbonate (meth)acrylates having a number average molecular weight preferable comprised between 500 and 5000 g.mol^"1.

[0064] Particularly preferred are reactive diluents comprising more than one ethylenically unsaturated group.

[0065] Mono- and/or polyfunctional reactive diluents, comprising oxirane group(s), that may be used in the radiation initiated cationic curable binder composition of the present invention include aliphatic, cycloaliphatic, aromatic or heterocyclic epoxies such as propylene oxide, styrene oxide, vinylcyclohexene oxide, vinylcydohexene dioxide, glycidol, butadiene oxide, diglycidyl ether of bisphenol A, oxetane, octylene oxide, phenyl glycidyl ether, 1 ,2-butane oxide, cyclohexeneoxide 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane- carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6- methylcyclohexane carboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, dicyclopentadiene dioxide, epoxidized polybutadiene, 1 ,4-butanediol diglycidyl ether, polyglycidyl ether of phenolformaldehyde resole or novolak resin, resorcinol diglycidyl ether, epoxy silicones, such as dimethylsiloxanes having cycloaliphatic epoxide or glycidyl ether groups, aliphatic epoxy modified with propylene glycol and dipentene dioxide.

[0066] Preferred epoxies include monofunctional epoxy monomers/oligomers such as epoxy grafted polyesters and bifunctional monomers such as limonene dioxide, epoxidized bisphenol-A, cycloaliphatic diepoxides such as bis(3,4-epoxycyclohexyl)adipate and polyfunctional monomers such as epoxidized soybean oil.

[0067] The oxirane group comprising binder further may comprise reactive diluents comprising vinyl ether or allyl ether groups such as vinyl ether monomers and oligomers which have at least one vinyl ether group -O-CR -CRH and/or at least one allyl ether group -O-CH2-CR'=CRH, wherein R and R' are each, independently, H or Ci-e -alkyl. Those where both R and R' are a hydrogen atom are preferred.

[0068] Examples of suitable vinyl ether comprising monomers and oligomers include ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, hydroxybutyl vinyl ether, propenyl ether of propylene carbonate, dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, butyl vinyl ether, ethyleneglycol monovinyl ether, diethyleneglycol divinyl ether, butanediol monovinyl ether, butane diol divinyl ether, hexane diol divinyl ether, ethylene glycol butyl vinyl ether, triethylene glycol methyl vinyl ether, cyclohexane dimethanol monovinyl ether, cyclohexane dimethanol divinyl ether, 2-ethylhexyl vinyl ether, poly-THF divinyl ether, polyethylene glycol divinyl ether and the like.

[0069] Examples of suitable allyl ether comprising monomers and oligomers include ethyl allyl ether, propyl allyl ether, isobutyl allyl ether, octadecyl allyl ether, hydroxybutyl allyl ether, propenyl ether of propylene carbonate, dodecyl allyl ether, cyclohexyl allyl ether, 2-ethylhexyl allyl ether, butyl allyl ether, ethyleneglycol monoallyl ether, diethyleneglycol diallyl ether, butanediol monoallyl ether, butane diol diallyl ether, hexane diol diallyl ether, ethylene glycol butyl allyl ether, triethylene glycol methyl allyl ether, cyclohexane dimethanol monoallyl ether, cyclohexane dimethanol diallyl ether, 2-ethylhexyl allyl ether, poly-THF diallyl ether, polyethylene glycol diallyl ether and the like.

[0070] Mixtures of oxirane, vinyl ether and allyl ether group comprising monomers an/or oligomers may also be used.

[0071] The microscale particles for being used in the radiation curable coating composition of the present invention include glass spheres, plastic particles such as polyamide or polytetrafluorethylene particles, silicon carbide, metal oxides, or salts thereof. Non-limiting examples of suitable metal oxides include silicon oxide, aluminum oxide, tin oxide, zinc oxide, bismuth oxide, titanium oxide, zirconium oxide, lanthanide ("rare-earth") oxides, mixtures thereof, and the like; other suitable metal salts such as calcium carbonate, calcium aluminate, magnesium aluminosilicate, potassium titanate, cerium ortho-phosphate, hydrated aluminum silicate, metal salt clays such as montmorillonite, illite, kaolin clay, halloysite, mixtures thereof, and the like; and mixtures of metal oxides with metal salts.

[0072] The term "micro-scale particles" refers to particles having a volume median particle diameter (D50) comprised between 1 and 50 μιτι, preferably between 3 and 35 μιτι, more preferably 5 and 20 μιτι.

[0073] The micro-scale particles may be used in combination with one or more nano-scale particles. The term "nano-scale particles" refers to particles having a volume median particle diameter (D50) of about 1 to about 100 nm.

[0074] The volume median particle diameter (D50) in general is measured by laser light scattering using the particle size analyzer (HORIBA 920) from (Horiba Scientific) according to ISO 13320.

[0075] The micro-scale particle particles preferably used in the radiation curable coating compositions of the present invention are micro glass spheres optionally in combination with fumed silica nano-scale particles. [0076] The micro-scale particles for being used in the present invention preferably comprise a coating selected from the group consisting of ester-, vinyl ester-, amide-, urethane-, (meth)acrylate- and epoxy- based coatings.

[0077] The average particle size is related to the layer thickness of the cross-linked coating and is comprised between 0.02 and 500%, preferably between 0.04 and 400%, more preferably between 0.06 and 300% and most preferably between 0.08 and 200% of the coating layer thickness.

[0078] Without being bound by any theory, the inventor is of the opinion that blocking of the micro-scale particles at the surface of the top-layer, upon crosslinking, contributes to the anti-slip properties.

[0079] The radiation curable coating composition of the present invention further comprises one or more compounds selected from the group consisting of silicones, fluorocarbons and olefin (co)polymers.

[0080] Preferably at least 10% by weight , more preferably at least 20% by weight, most preferably at least 30% by weight of the fluorocarbons, silicones and hydrocarbons comprises ethylenically unsaturated or oxirane groups.

[0081] The fluorinated compound for being used in the radiation curable coating composition of the present invention preferably is a polymer obtained from the polymerization of one or more fluorinated ethylenically unsaturated monomers wherein fluorine is derived from at least one substituent such as a (per)fluorinated linear or branched alkyl-substituent, a (per)fluorinated linear or branched alkylene-substituent and/or a (per)fluorinated (poly)alkyleneoxy- substituent and optionally one or more non-fluorinated ethylenically unsaturated monomers comprising substituents such as for example (poly)alkyleneoxy, hydroxyalkyl, carboxyl, amine, quaternary amine, sulfonate, sulfate, carboxylate, phosphate, phosphonate, alkylalkoxylate or aminocarboxylate substituents.

[0082] Alternatively the fluorinated compound may comprise a fluorinated tail selected from the group consisting of (per)fluorinated polyoxyalkylene; poly-1 ,1 -difluoroethylene; copolymers of tetrafluoroethylene and hexafluoropropylene; terpolymers of hexafluoropropylene, tetrafluoroethylene, and ethylene; and terpolymers of tetrafluoroethylene, hexafluoropropylene and 1 ,1 - difluorethylene, and a non-fluorinated head such as for example a polyoxyalkylene, hydroxyalkyl, carboxyl, amine, quaternary amine, sulfonate, sulfate, carboxylate, phosphate, phosphonate, alkylalkoxylate or aminocarboxylate comprising head group.

[0083] Optionally the fluorinated compounds comprise a linking group between the fluorinated portion and the non-fluorinated portion such as for example alkylene, arylene, sulfonamidoalkylene, carbonamidoalkylene, oxydialkylene, thiodialkylene or alkylenecarbama to.

[0084] The silicones for being used in the radiation curable coating composition of the present invention are preferably straight chain, cyclic, branched, dendritic, or network polysiloxane(s). Straight chain or a partially branched straight chain polysiloxanes are particularly preferred.

[0085] Unsubstituted monovalent hydrocarbyl groups and substituted monovalent hydrocarbyl groups are examples of the silicon-bonded organic groups.

[0086] The unsubstituted monovalent hydrocarbyl can be exemplified by C1-10 alkyl such as methyl, ethyl, n-propyl, isopropyl, butyl, t-butyl, hexyl, octyl, decyl; C3-io cycloalkyl such as cyclopentyl, cyclohexyl; C2-10 alkenyl such as vinyl, allyl, 5-hexenyl, 9-decenyl; C-6-10 aryl such as phenyl, tolyl, xylyl; and C7-10 aralkyl such as benzyl, methylbenzyl, phenethyl.

[0087] Preferred there among are the Ci-io alkyl, C-6-10 aryl, and C2-10 alkenyl, wherein methyl and phenyl are particularly preferred.

[0088] The substituted monovalent hydrocarbyl group can be exemplified by groups provided by replacing all or a portion of the hydrogen atoms in the aforementioned unsubstituted monovalent hydrocarbyl groups, and particularly in the Ci-io alkyl and phenyl, with a halogen atom, an epoxy functional group, a (meth)acrylic functional group, an amino functional group, a sulfur- containing functional group or a substituent group such as alkoxy, hydroxycarbonyl and alkoxycarbonyl.

[0089] Preferred there among is a (meth)acrylic functional, more preferred an acrylic functional group.

[0090] Preferred polysiloxanes include polymers and copolymers comprising dimethylsiloxane units, methylhydrogensiloxane units, diphenylsiloxane units, phenylmethylsiloxane units, dimethylhydrogensiloxane units and thmethylsiloxane units.

[0091] Polysiloxanes with pendant fluorinated groups may be used as well.

[0092] The hydrocarbon compound for being used in the radiation curable coating composition of the present invention preferably is a functionalized polyolefin, a functionalized vinyl aromatic polymer or a functionalized copolymer of one or more vinyl aromatic monomers and one or more alkene or alkadiene such as for example polyethylene, polypropylene, polystyrene or poly(ethylene-styrene) random copolymer, comprising a terminal functional group such as a hydroxyl, a carboxyl, an amine, a quaternary ammonium, an anhydride, an imidazolinium, sulfonium or a phosphonium group.

[0093] Photoinitiators that can be used in the radiation curable coating composition of the invention, can be substantially any photoinitiator.

[0094] The usual photoinitiators that generate free radicals when exposed to radiation energy include, for example, aromatic ketone compounds, such as benzophenones, alkylbenzophenones, Michler's ketone, anthrone halogenated benzophenones.

[0095] The radicals initiate the radical polymerization of the ethylenically unsaturated groups wherein the groups are converted in a poly(meth)acrylate and/or polyalkene, comprising the conversion product of at least two ethylenically unsaturated monomeric units.

[0096] There are several suitable photoinitiators commercially available from Ciba including Irgacure 184 (1 -hydroxy-cyclohexyl-phenyl-ketone), Irgacure 819 (bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide), Irgacure 1850 (a 50/50 mixture of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl-phosphine oxide and 1 -hydroxy-cyclohexyl-phenyl-ketone), Irgacure 1700 (a 25/75 mixture of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl-phosphine oxide and 2-hydroxy- 2-methyl-1 -phenyl-propan-1 -one), Irgacure 907 (2-methyl-1 [4- (methylthio)phenyl]-2-morpholonopropan-1 -one), Darocur MBF (a phenyl glyoxylic acid methyl ester), Irgacure 2020 Photoinitiator blend (20% by weight of phenylbis(2,3,6-trimethyl benzoyl)phosphine oxide and 80% by weight of 2- hydroxy-2-methyl-1 -phenyl-1 -propanone) and Darocur 4265 (a 50/50 mixture of bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide and 2-hydroxy-2-methyl-1 - phenyl-propan-1 -one). The foregoing lists are meant to be illustrative only and are not meant to exclude any suitable photoinitiators.

[0097] Photoactivators can be used in combination with the aforementioned photoinitiators. Photoactivators are well known in the art and are for example chosen from methylamine, tributylamine, methyldiethanolamine, 2- aminoethylethanolamine, allylamine, cyclohexylamine, cyclopentadienylamine, diphenylamine, ditolylamine, trixylylamine, tribenzylamine, n- cyclohexylethyleneimine, piperidine, N-methylpiperazine, 2,2-dimethyl-1 ,3-bis(3- N-morpholinyl)-propionyloxypropane, and mixtures thereof.

[0098] Suitable photoinitiators for cationic polymerization include those compounds which form aprotic acids or Bronstead acids upon exposure to UV and/or visible light and initiate cationic polymerization.

[0099] Examples of suitable cationic photoinitiators that may be used in the radiation curable coating composition of the present invention are aryldiazonium salts, diaryliodonium salts, triarylsulphonium salts, triarylselenonium salts, dialkylphenacyl sulphonium salts, aryloxydiarylsulphoxonium salts and dialkylphenacyl sulphoxonium salts. The counter anion in general is hexafluorophosphate, hexafluoro antimonite, hexafkluoro arsenate and tetrafluoroborate.

[0100] Photosensitizers that may be used in combination with the photocationic initiator include anthracene, perylene, phenothiazine, xanthone, thioxanthone and benzophenone.

[0101] The acids initiate the cationic polymerization of the oxirane, vinyl ether and/or allyl ether groups wherein the groups are converted in (co)polyether and/or (co)polyalkene comprising the reaction product of at least two monomeric units.

[0102] As is known in the art, additional additives can be used. Such additives include dispersing agents, flow aid agents, thickening agents, defoaming agents, deaerating agents, pigments, fillers, flattening agents, matting agents and wetting agents.

[0103] The radiation curable coating composition preferably used in the present invention comprises: - between 10 and 40% by weight, preferably between 15 and 35% by weight of a ethylenically unsaturated groups comprising polyurethane;

- between 20 and 60% by weight, preferably between 30 and 50% by weight of one or more ethylenically unsaturated group comprising diluents;

- between 0.2 and 2% by weight, preferably between 0.5 and 1 .5% by weight of an acidic adhesion promotor;

- between 3 and 8% by weight, preferably between 4 and 7% by weight of one or more photoinitiators;

- between 0.5 and 3.0% by weight, preferably between 1 .0 and 2.0% by weight of one or more photoactivators;

- between 5 and 30% by weight, preferably between 10 and 25% by weight of one or more additives;

- between 5 and 15% by weight, preferably between 7 and 12% by weight of micro-scale particles;

- between 1 and 5% by weight, preferably between 2 and 4 % by weight of one or more silicones;

- up to 40% by weight of solvent

[0104] The radiation curable coating composition preferably used in the present invention comprises:

- between 10 and 40% by weight, preferably between 15 and 35% by weight of a acrylated polyurethane;

- between 20 and 60% by weight, preferably between 30 and 50% by weight of one or more acrylated diluents;

- between 0.2 and 2% by weight, preferably between 0.5 and 1 .5% by weight of an acrylic group comprising acidic adhesion promotor;

- between 5 and 25% by weight, preferably between 10 and 20% by weight of one or more matting additives;

- between 0.2 and 2% by weight, preferably between 0.5 and 1 .5% by weight of one or more wetting additives between 5 and 15% by weight, preferably between 7 and 12% by weight of micro-scale glass beads;

- between 1 and 5% by weight, preferably between 2 and 4 % by weight of one or more silicones, wherein at least 10% by weight, preferably at least 20% by weight, more preferably at least 30% by weight of the silicones are coreactable with the acrylated polyurethane and diluents upon radiation;

- up to 40% weight of solvent.

[0105] The method comprises the following steps:

- step 1 ): providing one or more layer(s) comprising one or more olefin (co)polymers and/or one or more vinyl halide (co)polymers,

- step 2): applying and curing one or more radiation curable coating compositions.

[0106] A first embodiment of step 1 ) comprises providing one or more polyolefin comprising layers. The one or more polyolefin comprising layers preferably are produced via one or more processing machines comprising a series of calendar rolls, wherein one or more polyolefin comprising paste(s), are processed.

[0107] The set temperature of the calendering rolls in general is comprised between 140 and 200°C, preferably between 150 and 190°C, more preferably between 160 and 180°C.

[0108] The hot polyolefin comprising paste is prepared by compounding the one or more olefin (co)polymers, the filler(s), the lubricant(s) and one or more additives in a suitable heated mixer, for example in a twin screw or a single screw extruder, a mixing bowl with heated jacket, a Banbury mixer, continuous mixer, a ribbon mixer or any combination thereof to form a blend.

[0109] The polyolefin comprising paste is obtained from melt-mixing at an internal temperature comprised between 180 and 240°C, preferable between 190 and 230°C, more preferable between 200 and 220°C.

[0110] A second embodiment of step 1 ) comprises spreading out at least one vinyl chloride (co)polymer comprising plastisol on a backing layer and gelling the at least one plastisol layer at a temperature comprised between 130°C and 200°C. Hereto, the at least one vinyl chloride (co)polymer comprising plastisol is spread on a backing layer moving at around 15 to 25 meters per minute. [0111] For multilayer decorative surface coverings at least one vinyl chloride (co)polymer comprising plastisol is spread on the backing layer in several layers so that the floor covering is literally built up.

[0112] The multilayer product is first gelled by contact with one or more heated roll and then passed into an oven where they are gelled and fused at a temperature of from 130°C to 200°C.

[0113] Often the gelling is performed after the spreading of each individual layer starting with the base layer. After the gelling the next layer can be spread.

[0114] Typically vinyl chloride (co)polymer comprising plastisols are produced in batch processes using high shear mixing equipment. The mixing generally is performed for a period of from about 15 to about 60 minutes, whereupon the blend is cooled down. In general such process is used for making plastisols which are immediately further processed, since the high friction level of the mixing elements in the plastisol results in high local temperature increase which generally results in poor viscosity stability of the plastisol on storage.

[0115] On the other hand, storage stable plastisols can be prepared by blending the finely divided vinyl chloride (co)polymer, optionally other finely divided solid materials, liquid plasticizer blend and optionally other liquid materials in a blending tank with low shear. The pre-homogenized plastisol is recirculated from the blending tank through a dynamic mixer back into the blending tank. This recirculation is performed up to 10 times prior to discharging the final plastisol.

[0116] The vinyl chloride (co)polymer comprising plastisol may be a phthalate-free polyvinyl chloride comprising plastisol.

[0117] After gelling and fusing the at least one PVC plastisol composition, the PVC (multi)layer, standing at a temperature comprised between130 and 200°C, optionally is mechanically embossed.

[0118] Mechanical embossing is performed by pressing a texture into the plasticized polyvinyl chloride layer(s) or the polyolefin layer(s) before the application of the ethylenically unsaturated coating composition. Embossing is carried out at a pressure comprised between 10 and 25 kg. cm^-3 and surface temperature comprised between 130°C and 200°C. [0119] The apparatus for mechanically embossing a substrate in general includes a cooled embossing roller and a backup roller operatively positioned within the embossing roller such that a nip is formed between the backup roller and the embossing roller whereby the substrate may pass through the nip and engage the embossing roller for imparting a mechanically embossed pattern. The apparatus further includes a profilometer capable of quantifying the mechanically embossed pattern as the substrate is being embossed.

[0120] In general the texture obtained from mechanical embossing is characterized by a depth comprised between about 10 to 100 μιτι, a width comprised between about 125 to 400 μιτι, a wall angle (angle relative to surface) comprised between about 5 to 40 degrees and a frequency of about 4 to 20 features per cm.

[0121] After mechanical embossing the polyvinyl chloride layer(s) or the polyolefin layer(s) is (are) cooled down in order to homogeneously apply and cure the radiation curable coating composition of the present invention. The application and curing preferably is carried out at room temperature but can also be done at temperatures higher than room temperature.

[0122] The radiation curable coating composition is applied at a film thickness in general comprised between 3 and 30 microns, preferable between 8 and 20 microns.

[0123] For the preparation of the radiation curable coating composition, one or more components selected from the group consisting of micro- scale particle(s) and of one or more compounds selected from the group consisting of fluorocarbons, silicones, olefin (co)polymers, are admixed to the ethylenically unsaturated group comprising binder composition, the binder composition comprising one or more ethylenically unsaturated polymers, oligomers, monomeric diluents and optionally at least one acidic adhesion promotor.

[0124] To the radiation curable coating composition optionally are added one or more photoinitiators, one or more photoactivators and one or more further additives such as wetting agent and matting agents. Mixing can be carried out simply by stirring. Mixing the components can be carried out preferably directly before the application. [0125] The radiation curable compositions of the present invention may be applied onto the top-surface of the PVC or PVC-free under-layer by any suitable coating process known to those of ordinary skill in the art, for example by direct gravure coating, reverse gravure coating, offset gravure coating, smooth roll coating, curtain coating, air-knife coating, spray coating and combinations thereof.

[0126] After application the coating composition is subjected to actinic radiation such as ultraviolet (UV) radiation with a wavelength of for instance 250- 600 nm, whereupon crosslinking is completed.

[0127] Examples of radiation sources are medium and high-pressure mercury vapour lamps, lasers, pulsed lamps (flashlight), halogen lamps and excimer emitters.

[0128] Preferably, within the context of the present invention, one or more medium pressure mercury vapour UV radiators of at least 80 to 250 W/linear cm are used. Preferably the medium pressure mercury vapour UV radiator(s) is (are) positioned at a distance of from about 5 to 20 cm from the substrate. The irradiating time period preferably is comprised between 1 and 60 seconds for having a radiation dose in the range of from 80 to 3000 mJ/cm².

[0129] On the other hand the radiation curable coating composition can be cured by bombardment with high-energy electron beams (EB) at for instance 150-300 keV. For this particular case, the coating formulations that do not comprise photoinitiators or photoactivators. From economical point of view electron-beam curing yet is less attractive as the equipment is quite expensive.

[0130] To the top-surface of the one or more layers of step 1 ), standing at a temperature comprised between 20 and 60°C, the radiation curable coating composition according to the present invention, is homogeneously applied in step 2).

[0131] In a particular embodiment of the present invention, the top surface of the one or more layers is subjected to a plasma treatment, preferably a corona treatment, adjusted to provide a surface energy of at least 38 mlM/m, preferably of at least 40 mlM/m, more of at least 42 mlM/m, according to ASTM D2578.

[0132] Corona treatment is of particular interest for the one or more layers of step a) comprising one or more olefin (co)polymers. [0133] Corona plasma treatment ideally is done on-line immediately before initiation of step b), i.e. before application of the radiation curable coating composition.

Example

[0134] The following illustrative example are merely meant to exemplify the present invention but are not destined to limit or otherwise define the scope of the present invention.

[0135] A phthalate-free PVC plastisol, as in table 2, was prepared using any convenient method known to the one skilled in the art. The finely divided PVC polymer and other finely divided solid materials were dispersed in the liquid plasticizer blend forming a paste. On heating the dispersion to a temperature above 100°C, the polymer became soluble in the plasticizer whereupon the two phase dispersion was transformed into a single phase system.

[0136] The PVC plastisol was produced using high shear mixing equipment. The mixing was performed for a period of 35 minutes, whereupon the blend was cooled down.

[0137] In table 1 , the PVC resin micro-suspension is a blend of 60.00 parts of Lacovyl® PB 1704 H and 10 parts of Lacovyl® PB 1202 from Arkema ; the paste PVC resin extender is Vinnolit® EXT from Vinnolit; diisononyl cyclohexane is Hexamoll® DINCH from BASF; isononyl benzoate is Vestinol® INB from Evonik; the branched paraffin, including normal alkanes, isoalkanes and cyclics, is EXXSOM™ D100 from Exxon Mobil; liquid Ca/Zn stabilizer is Lankromark® LZC 393 from Akcros; epoxidized soya bean oil is Drapex® HSE from Galata Chemicals and air release additive is Byk® 3160 from Byk Chemie.

[0138] The PVC surface covering, according to the formulation as given in table 1 , was prepared by applying the procedure as described in paragraphs 109 to 1 14.

[0139] A radiation curable polyurethane coating composition, as in table 2, was prepared using any convenient method known to the one skilled in the art.

[0140] In table 2: the radiation curable polyurethane is Ebecryl^® 4666 from Allnex; the reactive diluent is Sartomer^® SR 506 D (isobornyl acrylate) from Arkema; the acidic adhesion promotor is Sartomer SR9054 (2-hydroxyethyl methacrylate phosphate) from Sartomer; the photoinitiator is a mixture comprising 60% by weight of Additol^® BP (benzophenone) from Allnex and 40% by weight of Irgacure^® 184 (l -hydroxy-cyclohexyl-phenyl-ketone)from BASF; the photoactivator is Agisyn^® 008 (tertiary amine) from DSM; the matting agent is a mixture comprising 34.9% by weight of Acemat^® 3600 (fine-grained polymer- treated precipitated silica) from Evonik, 34.9% by weight of Deuteron^® MK (matting agent - urea-methanal polymer) from Deuteron and 30.2% by weight of Orgasol^® 2002 DNAT 1 (spheroidal powder of polyamide 12) from Arkema; the wetting agent is Disperbyk^® 185 (acrylic copolymer) from Byk; the micro-scale particle is Microperl^® 050-20-217 (polyester and vinyl ester coated glass bead made from soda lime glass with a volume median particle size of 20 μιτι) from Solvitec; the silicone is a mixture of 50% by weight of Byk 333 (polydimethylsiloxane) from Byk and 50% by weight Tego RAD 2010 (linear difunctional acrylate silicone) both from Evonik

[0141] The PVC surface covering, was mechanically embossed at a pressure of about 15 kg. cm^-2 while standing at a temperature of about 160°C.

[0142] After cooling down the embossed layer stack to about room temperature, the radiation curable coating composition of table 2 was applied on the corona treated top surface and subsequently subjected for 6 seconds to irradiation with ultraviolet light emitted by a 160 W/cm medium pressure mercury vapor UV-bulb (Fusion UV Systems Ltd) with a total UV dose of 1500 mJ/cm² while standing at a temperature of 25°C.

[0143] The anti-slip properties of the decorative surface covering of the present invention were assessed according to EN 13893 "Testing of floor coverings - Determination of the anti-slip property - Workrooms and fields of activities with slip danger, walking method - Ramp test"

[0144] In this method a test person with test shoes walks forwards and backwards in an upright position over the floor covering to be tested, the slope of which is increased from the initial horizontal state to the acceptance angle ( = angle of inclination until the limit of safe walking is reached and the test person slips). The acceptance angle is determined on floor coverings on which a lubricant has been applied.

[0145] For this test method the below evaluation criteria apply:

Resistance class Acceptance angle in °

R9 6 to 10

R10 1 1 to 19

R1 1 20 to 27

R12 28 to 35

R13 Over 35 [0146] For the decorative surface covering prepared according to the method of the present invention, a resistance class equal to or superior to R9 was recorded.

[0147] The scuff resistance is assessed using a friction test apparatus wherein an Astral rubber tool with thickness of 5 mm and a width of 0.8 mm, while subjected to a loading of "Y" kg is moved "X" times over 25 cm over the test area at a speed of 0.40 m/s.

[0148] In the test the rubber tool, before touching the test panel (39x39 cm) is moved over 2 cm of abrasive paper (P600)

[0149] The complete test consists of:

[0150] After each test series (for example 6 times with a 9 kg loading) the test panel is visually evaluated, without cleaning, on a 0 to 3 scale where:

0 results in severe damage (top-layer is teared off, scuff is irreversible);

1 results in damage (marks clearly visible);

2 results in slight damage (marks slightly visible);

3 results in no visual damage (no marks at all);

wherein damage, in the present invention reflects the intensity of the marks left by the rubber.

[0151] Finally the test result of the respective series are added together for a final result comprised between 0 and 15.

[0152] In Figure 1 the scuff test is illustrated for a decorative surface covering of the state of the art; in Figure 2 the same scuff test is illustrated for a decorative surface covering according to the invention. The test results are reproduced without cleaning before and after the scuff test. [0153] In Figure 1 the leftmost mark corresponds to conditions as disclosed in the bottom row of the above table. The rightmost mark corresponds to conditions as disclosed in the top row of the above table. The marks in between correspond, going from left (second mark) to right (fourth mark), to the conditions as disclosed in rows 4, 3 and 2 respectively. As appears from Figure 2, the marks are barely or even not visible for the decorative surface covering of the invention.

[0154] For the decorative surface covering, prepared according to the method as described above, a final scuff resistance of 12 was recorded; the value for the final scuff resistance was obtained from:

[0155] The respective evaluations in the above table and the final scuff resistance value is the average of 3 measurements.

Claims

1 . A decorative surface covering, in particular floor or wall covering, comprising one or more polymer layer(s) and a crosslinked top-layer covering the top surface of the one or more polymer layers, said top-layer comprising:

i. 40 to 90% by weight of crosslinked segments selected from the group consisting of polyurethane, polyester, polyether, (meth)acrylate (co)polymer, (hydrogenated) bisphenol based resin, phenol formaldehyde resin and mixtures thereof, the crosslinks connecting said segments being of the poly (meth)acrylate, polyalkene or polyether type;

ii. 0.5 to 25% by weight of one or more types of micro-scale particle(s) with a volume median particle diameter (D50) comprised between 1 and 50 μιτι, preferably between 3 and 35 μιτι, more preferably 5 and 20 μιτι as obtained from laser light scattering measurements according to ISO 13320;

2. The decorative surface covering according to 1 wherein the crosslinked segments are polyurethane segments and the micro-scale particles are glass particles.

3. The decorative surface covering according to claim 1 or 2, wherein the micro- scale particles (ii.) are soda-lime-silica glass particles.

4. The decorative surface covering according to any of the preceding claims wherein the one or more types of micro-scale particle(s) (ii.) comprise a coating selected from the group consisting of ester-, vinyl ester-, amide-, urethane-, (meth)acrylate and epoxy- based coatings.

5. The decorative surface covering according to any of the preceding claims wherein the one or more compounds(s) (iii.) comprise one or more polydimethylsiloxanes.

6. The decorative surface covering according to any of the preceding claims, wherein the one or more compounds (iii.) comprise one or more silicones from which up to 50% weight are a crosslinked segment of the crosslinked top-layer.

7. The decorative surface covering according to any of the preceding claims wherein the crosslinked segments (i.) comprise acid functionalities selected from the group consisting of -SO₃H, -OSOsH, -COOH, -OPO₃H₂ and -OPO2HO-.

8. The decorative surface covering according to any of the preceding claims, wherein the crosslinked segments (i.) are connected through poly(meth)acrylate type crosslinks having a degree of polymerization of at least 2.

9. The decorative surface covering according to any of the preceding claims wherein the one or more polymer layer(s) comprise(s) one or more polymers selected from the group consisting of polyvinyl halides, polyolefins and block copolymers comprising polymer blocks of one or more vinyl aromatic monomer(s) and polymer blocks of one or more alkylene(s).

10. The decorative surface covering according to any of the preceding claims wherein the volume median particle diameter (D50) of the micro-scale particles (ii.) is comprised between 1/50 and 5, preferably between 1/25 and 3.5, more preferably between 1/10 and 1 of the crosslinked polyurethane layer thickness.

1 1 . The decorative surface covering, according to any of the preceding claims, having a Slip Resistance, according to EN13893, corresponding to Slip Resistance Class equal to or superior to R9, preferably equal to or superior to R10, more preferably equal to or superior to R1 1 .

12. The decorative surface covering, according to any of the preceding claims, having a Scuff Resistance of 8 or higher, preferably of 10 or higher, more preferably of 12 or higher as assessed in a friction test apparatus with an Astral Rubber tool.

13. The decorative surface covering according to any of the preceding claims, having a Slip Resistance, according to EN13893, corresponding to Slip Resistance Class equal to or superior to R9, preferably equal to or superior to R10, more preferably equal to or superior to R1 1 , and also having a Scuff Resistance of 8 or higher, preferably of 10 or higher, more preferably of 12 or higher as assessed in a friction test apparatus with an Astral Rubber tool.

14. Method for the preparation of the decorative surface coverings according to any of the preceding claims, e.g. a floor or wall covering, comprising the steps:

- providing one or more polymer layer(s);

- applying a radiation curable coating formulation, comprising an ethylenically unsaturated or oxirane group comprising binder, micro-scale particles and one or more compounds selected from the group consisting of silicones, fluorocarbons and olefin (co)polymers, on the surface of the one or more polymer layer(s);

- irradiating the radiation curable coating formulation to form a crosslinked top- layer;

and wherein the steps are carried out in such a way that a decorative surface covering as claimed in any one of the preceding claims is obtained.

15. The method according to claim 14 wherein the radiation curable coating formulation comprises 30 to 90% by weight, preferably 40 to 80% by weight of a radiation curable binder and from 0.5 to 10% by weight, preferably from 2 to 8% by weight of at least one photoinitiator, relative to the total weight of the formulation.

16. The method according to claim 14 or 15, wherein the radiation curable binder comprises at least 10% by weight, preferably at least 15% by weight of one or more ethylenically unsaturated polyurethane, polyester, polyether, (meth)acrylate (co)polymer, (hydrogenated) bisphenol based resin, phenol formaldehyde resin, and at most 60% by weight preferably at most 50% by weight of one or more reactive diluent(s).

17. The method according to any of claims 14 to 16 wherein the radiation curable coating formulation comprises 0.5 to 25% by weight of one or more micro-scale particle(s) with a volume median particle diameter (D50) comprised between 1 and 50 μιτι, preferably between 3 and 35 μιτι, more preferably 5 and 20 μιτι as obtained from laser light scattering measurements according to ISO 13320; and 0.1 to 20% by weight of one or more compounds selected from the group consisting of silicones, fluorocarbons and olefin (co)polymers.

18. The method according to any of claims 14 to 17 comprising the additional step of subjecting the top surface of the one or more polymer layer(s) to a plasma treatment, preferably a corona plasma treatment.