WO2018011308A1 - Revêtements de surface décoratifs résistants à l'abrasion - Google Patents

Revêtements de surface décoratifs résistants à l'abrasion Download PDF

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Publication number
WO2018011308A1
WO2018011308A1 PCT/EP2017/067623 EP2017067623W WO2018011308A1 WO 2018011308 A1 WO2018011308 A1 WO 2018011308A1 EP 2017067623 W EP2017067623 W EP 2017067623W WO 2018011308 A1 WO2018011308 A1 WO 2018011308A1
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weight
decorative surface
group
surface covering
layer
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PCT/EP2017/067623
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English (en)
Inventor
Emilie FAURE
Guillaume Fascella
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Tarkett Gdl
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Publication of WO2018011308A1 publication Critical patent/WO2018011308A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/02—Flooring or floor layers composed of a number of similar elements
    • E04F15/02172—Floor elements with an anti-skid main surface, other than with grooves
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/02—Flooring or floor layers composed of a number of similar elements
    • E04F15/10—Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials
    • E04F15/105—Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials of organic plastics with or without reinforcements or filling materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08J2461/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with monohydric phenols
    • C08J2461/10—Phenol-formaldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes

Definitions

  • 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.
  • shock 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • one or more surfactants preferably containing fluorocarbon material, may be added as wetting agents.
  • 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.
  • 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.
  • a further aim of another aspect of the present invention is to provide a process for the production of such surface coverings.
  • 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;
  • micro-scale particle(s) with a volume median particle diameter (D50) comprised between 1 and 50 ⁇ , preferably between 3 and 35 ⁇ , more preferably 5 and 20 ⁇ as obtained from laser light scattering measurements according to ISO 13320,
  • Preferred embodiments of the present invention disclose one or more of the following features:
  • the crosslinked top-layer comprises:
  • cross-linked polyurethane segments i.
  • - 0.5 to 25% by weight of one or more types of glass micro-scale particle(s) ii.
  • micro-scale particles are glass micro-scale particles, preferably soda- lime-silica glass micro-scale particles;
  • the one or more types of micro-scale particle(s) 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 -SO 3 H, -OSOsH, -COOH, -OPO 3 H 2 and -OPO2HO-;
  • 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.
  • the present invention further discloses a process for the preparation of the decorative surface covering, comprising the steps of:
  • 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);
  • 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
  • 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 ⁇ and 0.1 to 20% by weight of one or more compounds selected from the group consisting of silicones,
  • the top surface of the one or more polymer layer(s) is subjected to a plasma treatment, preferably a corona plasma treatment.
  • 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.
  • 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.
  • 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.
  • Additional layers can be present.
  • the additional layers can be used for a variety of purposes, such as for reinforcement.
  • 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.
  • 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.
  • 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, ⁇ , ⁇ -unsaturated dicarboxylic acid esters, vinyl alkanoates, and alkylenes.
  • the one or more layer(s) further may comprise one or more styrene/olefin based elastomers.
  • the one or more layer(s) further may comprise organic or inorganic fillers, lubricants and additives.
  • the one or more layers optionally comprise(s) a primer layer and/or one or more prints.
  • 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).
  • actinic irradiation in particular ultra violet (UV) irradiation or electron irradiation (EB).
  • 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.
  • the crosslinked top-coat is obtained from a radical initiated conversion of ethylenically unsaturated double bonds.
  • the radiation curable coating composition for being used in the present invention comprises:
  • micro-scale particle(s) with a volume median particle diameter (D50) comprised between 1 and 50 ⁇ , preferably between 3 and 35 ⁇ , more preferably 5 and 20 ⁇ .
  • D50 volume median particle diameter
  • the radiation curable coating composition for being used in the present invention further may comprise:
  • the radiation curable coating for being used in the present invention further may comprise up to 40% by weight of solvent.
  • 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.
  • 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.
  • Flashing solvents may be accelerated by subjecting the coating to heating means such as convection heat or infrared irradiation.
  • the coating composition subjected to irradiation is substantially solvent-free.
  • substantially solvent-free 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.
  • the ethylenically unsaturated group comprising binder for being used in the radiation curable coating composition of the present invention comprises
  • ethylenically unsaturated group comprising polyurethane, polyester, polyether, (meth)acrylate (co)polymer, (hydrogenated) bisphenol based resin, novolac resin and mixtures thereof
  • 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
  • the ethylenically unsaturated group comprising polyurethanes for being used in the binder of the present invention in generally are obtained from the reaction of:
  • 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.
  • 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.
  • IPDI isophorone diisocyanate
  • MPDI 2-methylpentamethylene 1 ,5- diisocyanate
  • HDI hexamethylene diisocyanate
  • TMDI trimethylhexannethylene 1 ,6-diisocyanate
  • 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.
  • 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.
  • ethylenically unsaturated group such as acrylic or methacrylic group
  • nucleophilic function capable of reacting with isocyanate, such as a hydroxyl group.
  • (meth)acryloyl mono-hydroxy compounds more particularly poly(meth)acryloyl mono-hydroxy compounds.
  • 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.
  • Compound (c) furthermore comprises oligomeric and/or polymeric hydroxy-functional compounds.
  • 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.
  • the ethylenically unsaturated group comprising polyurethane is an ethylenically unsaturated group comprising aliphatic polyurethane, more preferably an acrylated aliphatic polyurethane.
  • 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.
  • 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.
  • 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.
  • polyesters of the present invention examples include 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,
  • polyesters of the present invention examples include phthalic acid, isophthalic acid, terephthalic acid, adipic acid, fumaric acids, itaconic acid, trimellitic acid, and the corresponding anhydrides.
  • 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.
  • 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.
  • 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.
  • the resins comprising epoxy functional groups 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.
  • 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
  • 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 -SO 3 H, -OSOsH, -COOH, -OPO 3 H 2 and -OPO2HO-.
  • the acidic hydrogen is substituted by an alkali metal or an ammonium base.
  • the acidic adhesion promotor is the reaction product of the one or more acid functionality comprising components with one or more functionalized (meth)acrylates.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • (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 .
  • reactive diluents comprising more than one ethylenically unsaturated group.
  • 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-epoxies
  • 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.
  • 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
  • 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
  • Mixtures of oxirane, vinyl ether and allyl ether group comprising monomers an/or oligomers may also be used.
  • 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.
  • 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.
  • micro-scale particles refers to particles having a volume median particle diameter (D50) comprised between 1 and 50 ⁇ , preferably between 3 and 35 ⁇ , more preferably 5 and 20 ⁇ .
  • D50 volume median particle diameter
  • micro-scale particles may be used in combination with one or more nano-scale particles.
  • nano-scale particles refers to particles having a volume median particle diameter (D50) of about 1 to about 100 nm.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • substituents such as for example (
  • 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.
  • a fluorinated tail selected from the group consisting of (per)fluorinated polyoxyal
  • 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.
  • 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.
  • 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.
  • Unsubstituted monovalent hydrocarbyl groups and substituted monovalent hydrocarbyl groups are examples of the silicon-bonded organic groups.
  • 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.
  • C1-10 alkyl such as methyl, ethyl, n-propyl, isopropyl, butyl, t-butyl, hexyl, octyl, decyl
  • Ci-io alkyl C-6-10 aryl
  • C2-10 alkenyl wherein methyl and phenyl are particularly preferred.
  • 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.
  • Preferred there among is a (meth)acrylic functional, more preferred an acrylic functional group.
  • Preferred polysiloxanes include polymers and copolymers comprising dimethylsiloxane units, methylhydrogensiloxane units, diphenylsiloxane units, phenylmethylsiloxane units, dimethylhydrogensiloxane units and thmethylsiloxane units.
  • Polysiloxanes with pendant fluorinated groups may be used as well.
  • 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.
  • a functionalized polyolefin 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
  • Photoinitiators that can be used in the radiation curable coating composition of the invention can be substantially any photoinitiator.
  • 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.
  • 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.
  • 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 M
  • 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.
  • 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.
  • 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.
  • Photosensitizers that may be used in combination with the photocationic initiator include anthracene, perylene, phenothiazine, xanthone, thioxanthone and benzophenone.
  • 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.
  • additives can be used.
  • additives include dispersing agents, flow aid agents, thickening agents, defoaming agents, deaerating agents, pigments, fillers, flattening agents, matting agents and wetting agents.
  • 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;
  • the radiation curable coating composition preferably used in the present invention comprises:
  • silicones 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;
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the vinyl chloride (co)polymer comprising plastisol may be a phthalate-free polyvinyl chloride comprising plastisol.
  • the PVC (multi)layer standing at a temperature comprised between130 and 200°C, optionally is mechanically embossed.
  • 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.
  • 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.
  • the texture obtained from mechanical embossing is characterized by a depth comprised between about 10 to 100 ⁇ , a width comprised between about 125 to 400 ⁇ , 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • actinic radiation such as ultraviolet (UV) radiation with a wavelength of for instance 250- 600 nm
  • Examples of radiation sources are medium and high-pressure mercury vapour lamps, lasers, pulsed lamps (flashlight), halogen lamps and excimer emitters.
  • one or more medium pressure mercury vapour UV radiators of at least 80 to 250 W/linear cm are used.
  • 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/cm 2 .
  • the radiation curable coating composition can be cured by bombardment with high-energy electron beams (EB) at for instance 150-300 keV.
  • EB electron beams
  • 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.
  • step 2 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).
  • 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.
  • Corona treatment is of particular interest for the one or more layers of step a) comprising one or more olefin (co)polymers.
  • Corona plasma treatment ideally is done on-line immediately before initiation of step b), i.e. before application of the radiation curable coating composition.
  • 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.
  • the dispersion 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.
  • 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.
  • 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 EXXSOMTM 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.
  • a radiation curable polyurethane coating composition as in table 2, was prepared using any convenient method known to the one skilled in the art.
  • 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 ®
  • 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.
  • 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/cm 2 while standing at a temperature of 25°C.
  • 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"
  • 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.
  • test panel is visually evaluated, without cleaning, on a 0 to 3 scale where:
  • top-layer is teared off, scuff is irreversible
  • damage in the present invention reflects the intensity of the marks left by the rubber.
  • test result of the respective series are added together for a final result comprised between 0 and 15.
  • 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.
  • 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.
  • the marks are barely or even not visible for the decorative surface covering of the invention.

Abstract

La présente invention concerne des revêtements de surface décoratifs, en particulier des revêtements de sols ou muraux, comportant une ou plusieurs couche(s) polymère(s) et une couche supérieure réticulée, combinant d'excellentes propriétés anti-dérapantes et une excellente résistance à l'abrasion. L'invention concerne également un procédé de préparation de tels revêtements de surface.
PCT/EP2017/067623 2016-07-15 2017-07-12 Revêtements de surface décoratifs résistants à l'abrasion WO2018011308A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN109054730A (zh) * 2018-07-23 2018-12-21 深圳天鼎新材料有限公司 一种加成型灌封胶及其制备方法和使用方法
CN111379392A (zh) * 2018-12-29 2020-07-07 塔吉特Gdl公司 装饰性墙壁或地面覆盖物的安装方法

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FR2379323A1 (fr) 1977-02-04 1978-09-01 Forbo Forshaga Ab Procede perfectionne pour l'application de revetements de surfaces
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CN109054730A (zh) * 2018-07-23 2018-12-21 深圳天鼎新材料有限公司 一种加成型灌封胶及其制备方法和使用方法
CN111379392A (zh) * 2018-12-29 2020-07-07 塔吉特Gdl公司 装饰性墙壁或地面覆盖物的安装方法

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