PRIMER FORMULATION FOR THERMOPLASTIC MATERIAL

Abstract

A primer composition for the surface treatment of a polymer substrate, consisting of at least one polymer binder, at least two different types of inorganic fillers, where each inorganic filler contains inorganic particles, and water.

Description

BE2024 / 5923 2 substratescontributetoeasierrecyclability,aligningwithsustainabilitygoalsinprinting processes.

[0003] However,printingwithaqueousinksonthermoplasticspresentschallengessuchas blocking,bleeding,adhesionissues,andlaminationdifficulties,duetotheinkformulation,the typeofsurfacetreatment,andtheinherentpropertiesofthethermoplasticsubstrate.Blocking5 occurswhenprintedsubstratessticktogetherunderpressure,heat,orhumidity,particularlyif theinkorprimerlayerremainstackyorinadequatelydried.Bleeding,ontheotherhand,refersto theundesirablespreadofinkbeyonditsintendedboundaries,resultinginblurryordistorted designsduetolackofinkabsorptionbythepolymericsubstrate.Thisresultsinpooredge definitionandreducedprintclarity,ultimatelycompromisingthequalityofthefinalprint.Further,10 thisissueisespeciallycommonwhenprintingwithaqueousinks,asthehydrophobicnatureof thermoplasticsandtheirsmoothsurfaceimpedecontrolledinkabsorption.

[0004] Thisnecessitatesinnovativesolutionstoimprovetheinteractionbetweentheaqueous inkandthepolymericsubstrate,especiallywithlowsurfaceenergysuchasthermoplastic substrates.15

[0005] Additionally,theextendeddryingtimeofaqueousinkscomplicatesproduction, particularlywhenlaminatingawear-resistantlayertothermoplasticsubstrates,asincomplete dryingcancompromiseadhesionandresultinpeelingordelamination.

[0006] Therefore,thereisaneedtoaddressthesechallenges.Effectivesolutionsmust simultaneouslyaddresslaminationcompatibility,inkbleeding,andblockingtoensurehigh-20 quality,durableprintsonthermoplasticmaterials. SUMMARYOFINVENTION

[0007] Thepresentinventionaimstoaddressproblemsoutlinedabovebyprovidingaspecially formulatedprimercompositionforsurfacetreatmentofpolymericsubstrateswithrelativelylow25 surfaceenergy,suchasthermoplasticsubstrates.Asurfacetreatmentisapreparatorystepthat modifiesthesurfacepropertiesofamaterial,suchasapolymericsubstrate,toenhanceits compatibilitywithsubsequentprocesses.Thesurfacetreatmentmayincludetheapplicationof primercompositionsforimprovedprinting,coating,orbonding.Thisprimercomposition enhancesthesurfacepropertiesofthermoplasticsubstrates,improvinginkadhesion,especially30 foraqueousinkformulations,bypromotinguniformwetting,minimizingdelamination,and reducingblockingandbleeding,therebyensuringhigh-quality,durableprintsonchallenging thermoplasticmaterials. 2024 / 5923 BE2024 / 5923 3

[0008] Althoughtheprimercompositionofthepresentinventionisspecificallyformulatedfor digitalprintingapplications,itisalsocompatiblewithconventionalprintingmethods,suchas offsetprinting,screenprinting,gravureprinting,andflexographicprintingandisintendedfor treatingthesurfaceofthermoplasticmaterialsorsubstrates.

[0009] Aspectsandembodimentoftheinventionprovideaprimercompositionforsurface5 treatmentapolymericsubstrate,aprimerlayer,ashapedarticle,amethodforthepreparationof theshapedarticle.

[0010] Accordingtoanaspectofthepresentinventionthereisprovidedaprimercomposition forsurfacetreatmentofapolymericsubstrate,comprising:atleastonepolymericbinder,atleast twodistincttypesofinorganicfillers,whereineachinorganicfillercomprisesinorganicparticles;10 andwater.

[0011] Inanembodiment,thepolymericbinderisselectedfromoneormoreacrylicpolymersor co-polymers.Thepolymericbindercanbeaself-crosslinkingacrylicpolymeroracrylicco- polymer.Further,theacrylicbindercanbeanacrylicself-crosslinkingdispersioncomprisinga self-crosslinkingacrylicpolymeroraself-crosslinkingacrylicpolymer.15

[0012] Inanembodiment,thepolymericsubstratecanbeathermoplasticsubstrateora thermoplasticsurface.Thepolymericsubstratecanbeathermoplasticsubstrateselectedfrom thegroupconsistingofpolyvinylchloride(PVC),polyolefin,polyester,polystyreneorpolyamide.

[0013] Thetwodistincttypesofinorganicfillersaredefinedasafirstinorganicfillerandsecond inorganicfiller.Inanembodiment,thefirstinorganicfillercomprisescalciumcarbonate20 particles.Inafurtherembodiment,thesecondinorganicfillerisselectedfromthegroup consistingofaluminiumhydroxideoxideparticles,orfrominorganicparticlescomprisingablend ofsilicaandkaoliniteparticles.

[0014] Inanembodiment,thesecondinorganicfilleroftheprimercompositiondescribed aboveisselectedfromthegroupconsistingofaluminiumhydroxideoxideparticles,orfrom25 inorganicparticlescomprisingablendofsilicaandkaoliniteparticles,oracompositematerial comprisingsilicaandkaoliniteparticles,whereinthesilicaparticlesaredepositedonkaolinite particles,orkaoliniteparticlesaredepositedonsilicaparticles.

[0015] Inanembodiment,theblendofsilicaandkaoliniteparticleshaveaparticlesize distributionwithamediandiameter(D50)rangingfrom0.5µmto10µm,preferablyfrom0.5µm30 to5µm.

[0016] Inanembodiment,theweightratiobetweenthefirstandsecondinorganicparticlesisin therangefrom1:1to30:1,preferablyfrom1:1to20:1,morepreferablyfrom1:1to10:1.2024 / 5923 BE2024 / 5923 4

[0017] Inanembodiment,theprimercompositioncomprisesoffrom5%to40%byweightof firstinorganicfillerrelativetothetotalweightoftheprimercomposition,whereinthefirst inorganicfillerisselectedformcalciumcarbonateparticles.

[0018] Inanembodiment,theprimercompositioncomprisesoffrom2%to15%byweightof secondinorganicfillerrelativetothetotalweightoftheprimercomposition,whereinthesecond5 inorganicfillerisselectedformthegroupconsistingofablendofsilicaandkaolinite,or aluminiumhydroxideoxideparticles.

[0019] Inanembodiment,theprimercompositioncomprisesoffrom20%to80%byweightof atleastonepolymericbinderrelativetothetotalweightoftheprimercomposition.

[0020] Inanembodiment,thecalciumcarbonateparticleshaveaparticlesizedistributionwith10 amediandiameter(D50)rangingfrom0.15µmto15µm,morepreferably0.2µmto10µm.

[0021] Advantageously,theatleasttwoinorganicfillersofthepresentprimercompositionmay comprisetwoormoredistincttypesofinorganicparticlesselectedfromofsilica,clay,calcium bicarbonate,aluminiumoxyhydroxide,andmicrochalk(calciumcarbonate),alumina,orablend ofsilicaandkaolinite.15

[0022] Inanembodiment,theprimercompositionofthepresentinventionhasasurface tensionintherangeoffrom20mJ / m²to80mJ / m²at20°C.

[0023] Inanembodiment,theprimercompositionofthepresentinventionhasaviscosityinthe rangeof100cPto400cPat25°C,measuredaccordingtoASTMD7042.

[0024] Inanembodiment,theprimercompositionformsasurfacewithasurfaceenergyofat20 least30mJ / m2uponcuring,preferablywithasurfaceenergyintherangebetween30mJ / m2and 50mJ / m2uponcuring.

[0025] Inanembodiment,theprimercompositionhasathicknessrangingoffrom1to50μm whenappliedwettothethermoplasticsubstrate / surface.

[0026] Inanembodiment,thereisprovidedaprimerlayerforpolymericsubstratecomprisinga25 primercompositionincludingatleastonepolymericbinder,atleasttwodistincttypesof inorganicfillers,whereineachinorganicfillercomprisesinorganicparticles;andwater,wherein theprimerlayerhasasurfaceenergyofatleast30mJ / m²,oratleast35mJ / m².

[0027] Inanembodiment,theprimerlayerhasapeelstrengthofatleast20N / 50mm, preferably30N / 50mm,asdeterminedinaccordancewithASTMD903.30

[0028] Accordingtoanotheraspectofthepresentinventionthereisprovidedaninkandprimer systemforimageformationonathermoplasticsubstratesurfacecomprising: 2024 / 5923 BE2024 / 5923 5 a.theprimercomposition,theprimercompositionforsurfacetreatmentofapolymeric substratepriortoapplyinganaqueousinkcomposition,theprimercomprisingatleastone polymericbinder,atleasttwodistincttypesofinorganicfillers,whereineachinorganicfiller comprisesinorganicparticles;andwater.and b.anaqueousinkcompositioncomprisingwaterandatleasttwodifferentwater-soluble5 organicsolvents,whereintheatleasttwodifferentwater-solubleorganicsolventareselected fromagroupconsistingofalkyldiols,andwhereineachwater-solubleorganicsolventhasa distinctsurfacetensionfallingintherangeoffrom10to80mN / mat20°C.

[0029] Accordingtoafurtheraspectofthepresentinvention,thereisprovidedashapedarticle comprising:apolymericsubstrate,andaprimerlayerformedthereon.Thisprimerlayerisformed10 fromaprimercompositionaccordingtothepresentinventionthatatleastpartiallycoversthe polymericsubstrate,andformstheprimerlayerupondrying.

[0030] Inanembodiment,theshapedarticlefurthercomprisesadecorativelayerappliedon topoftheprimerlayer,whereinthedecorativelayercomprisestheaqueousinkcomposition accordingtothepresentinvention.Optionally,theshapearticlemayfurthercompriseawear-15 resistantlayerappliedontopofthedecorativelayer.

[0031] Inanembodiment,theprimerlayeroftheshapedarticlehasapeelstrengthofatleast 20N / 50mm,andasurfaceenergyofatleast30mJ / m2.Further,inanembodiment,theprimer layerhasathicknessintherangeof1μmto20μm,preferablyintherangeof4μmto10μm.

[0032] Inanembodiment,thereisprovidedashapedarticlecomprising:apolymeric20 substrate,aprimerlayerappliedontothepolymericsubstrate,whereintheprimerlayer comprisestheprimercompositionhavingatleastonepolymericbinder,atleasttwodistinct typesofinorganicfillers,whereineachinorganicfillercomprisesinorganicparticles;andwater,a decorativelayerappliedontopoftheprimerlayer,whereinthedecorativelayercomprisesthe aqueousinkcomposition,whereintheaqueousinkcompositioncompriseswaterandatleast25 twodifferentwater-solubleorganicsolvents,whereintheatleasttwodifferentwater-soluble organicsolventareselectedfromagroupconsistingofalkyldiols,andwhereineachwater- solubleorganicsolventhasadistinctsurfacetensionfallingintherangeoffrom10to80mN / m at20°C,preferablyoffrom15to75mN / mat20°C,morepreferably20to75mN / mat20°C.

[0033] Accordingtoafurtheraspectofthepresentinvention,thereisprovidedamethodforthe30 preparationoftheshapedarticleasdescribedabove,themethodcomprisingprovidinga polymericsubstrate,applyinganinkandprimersystem(describedabove)byfirstapplyingthe primercompositionofthepresentinvention,thenprinting,preferablybydigitalprinting,a 2024 / 5923 BE2024 / 5923 6 decorativelayerontheprimedpolymericsubstratewiththeaqueousinkcomposition,dryingthe aqueousinkcompositiontoformaprintedpolymericsubstrate TERMSANDDEFINITIONS

[0034] Theterm“surfaceenergy”referstoameasureofthecohesiveandadhesiveforcesatthe surfaceofasolidmaterial.5

[0035] Theterm"D50"referstoaspecificpointintheparticlesizedistributionofamaterial, representingthemedianparticlediameter.

[0036] Theterm"printingsubstrate"referstoamaterialsurfaceontowhichimagesortextare printed,suchaspaper,fabric,plastic,ormetal.

[0037] Theterm"aqueous"denotesacompositionthatiswater-based,indicatingthatwater10 servesastheprimarysolventormedium.

[0038] Theterm“surfacetension”referstoameasureofthecohesiveforceswithintheliquid thatcauseittominimizeitssurfacearea.

[0039] Theterm“thermoplasticsubstrate”referstoasubstratemadeofathermoplastic polymer,suchasPVC,polyolefinorpolyester.15

[0040] Theterms“polymericsubstrate”and“polymericsubstratesurface”areusedherein interchangeably.

[0041] Theterm“primer"referstoacoatingappliedtothesurfaceofasubstratebeforeprinting toenhanceinkadhesion,durability,andprintqualityTheterms“primer”and“primer composition”,"and“primercoating“areusedhereininterchangeably.20

[0042] Theterm“dispersion”referstoasysteminwhichparticles(solids)ofonesubstanceare distributedthroughoutanothersubstance,typicallyformingahomogeneousmixtureorsolution. Forexample,thesolid(s)inadispersionofthepresentinventioncanbewithintherangeoffrom 25wt%to80wt%,preferablyoffrom25wt%to50wt%.

[0043] Theterm"aqueous"denotesacompositionthatisaqueous,indicatingthatwaterserves25 astheprimarysolventormedium.

[0044] Theterm"C3toC8"referstothelengthofthecarbonchain,indicatingthatthesediols containanywherefrom3to8carbonatoms.

[0045] Thewetweightpercentage,alsodescribedaswet-wtpercent,isexpressedasthewet weightoftherespectivecomponentoverthetotalwetweightoftheprimercomposition.30

[0046] Theterm“ASTM”standforAmericanSocietyforTestingandMaterials.

[0047] Theterm“aqueousink(s)"and"aqueousinkcomposition(s)”areusedherein interchangeably. 2024 / 5923 BE2024 / 5923 7

[0048] Theterm“non-poroussubstrate”hereinreferstoamaterialsurfacethatdoesnotallow liquidsorgases,likewaterandair,topassthroughit.Although,PVC(polyvinylchloride)is generallyconsiderednon-porous,likeanypolymer,canallowverysmallamountsofgasesor liquidstodiffusethroughitsstructure,althoughthispermeationistypicallyminimalandslow.

[0049] Throughoutthisdisclosure,allpartsandpercentagesarebyweight(wt%ormass%5 basedonthetotalweight)andalltemperaturesarein°Cunlessotherwiseindicated.

[0050] BriefDescriptionoftheDrawings

[0051] Toeasilyidentifythediscussionofanyparticularelementoract,themostsignificant digitordigitsinareferencenumberrefertothefigurenumberinwhichthatelementisfirst introduced.10

[0052] FIG.1illustratesblockingresultsofthetestwithdifferentbinderandinorganicfillers.1- acrylicself-crosslinkingdispersion,2-polyurethanebinder(BaybondPU404),3-polyurethane binder(DaotanVTW6421),4-boehmite(aluminiumoxidehydroxide(γ-AlO(OH))),5-nofiller,6- blendofsilicaand(lamellar)kaoliniteparticles;InFIG.1,theterm"secondfiller"refers specificallytothesecondinorganicfiller.15

[0053] FIG.2illustratesaninteractionplotforblockingresults.1-acrylicself-crosslinking dispersion,2-polyurethanebinder(BaybondPU404),3-polyurethanebinder(DaotanVTW6421), 4-boehmite(aluminiumoxidehydroxide(γ-AlO(OH))),5-nofiller,6-blendofsilicaandkaolinite particles;InFIG.2,theterm"secondfiller"refersspecificallytothesecondinorganicfiller.

[0054] FIG.3showsdelaminationresultsofthetestwithdifferentbindersandinorganicfillers.20 1-acrylicself-crosslinkingdispersion,2-polyurethanebinder(BaybondPU404),3-polyurethane binder(DaotanVTW6421),4-boehmite(aluminiumoxidehydroxide,γ-AlO(OH)),5-nofiller,6- blendofsilicaandkaoliniteparticles;InFIG.3,theterm"secondfiller"refersspecificallytothe secondinorganicfiller.

[0055] FIG.4illustratesaninteractionplotfordelaminationresults.1-acrylicself-crosslinking25 dispersion,2-polyurethanebinder(BaybondPU404),3-polyurethanebinder(DaotanVTW6421), 4-boehmite(aluminiumoxidehydroxide,γ-AlO(OH)),5-nofiller,6-blendofsilicaandkaolinite particles;InFIG.4,theterm"secondfiller"refersspecificallytothesecondinorganicfiller. DETAILEDDESCRIPTION30

[0056] Thepresentinventionrelatestoaprimercompositionformulatedforapplicationon polymericsubstrates,particularlythermoplasticsubstrates,toimprovetheirprintability, adhesion,anddurability,particularlywhenusingaqueousinksinprintingprocesses.Thisprimer 2024 / 5923 BE2024 / 5923 8 compositionaddresseskeychallengesinthermoplasticprinting:improvinglaminationbetween substrate,ink,andwear-resistantlayers,preventingblockingoftheprimerandinklayers, reducinginkbleeding,andblockingadditivemigration.

[0057] Theprimercompositionofthepresentinventionachievesthesebenefitsthrougha carefullyselectedpolymericbinderthatisoptimizedtoresolveblockingandbleedingissues.The5 polymericbindercanbepreferablyanacrylicpolymericbinderthatcanadheretothe hydrophobic,impervioussurfaceofthermoplasticmaterialsandmodifytheirsurface characteristicstoimprovecompatibilitywithaqueousinks.Duringapplication,theacrylicbinder mayformauniformfilmthatprovidesacontrolledsurfacetexture.Thistexturecontributestothe formationofamicro-porouslayerthatcanretainwatertemporarily,allowingtheaqueousink10 compositiontospreadandadhereproperlybeforedrying.However,thecohesivestrength (internalbindingforceswithinthepolymerfilm)oftheacrylicpolymericbindersmaynotbe sufficienttoprovidethedurabilityneededforstronglamination,forexampleduringandafterthe productionofproducts,suchasdecorativecoverings.

[0058] Tofurtherenhancetheperformanceoftheprimercomposition,blendsofpolymeric15 binders,suchasacombinationofacrylicpolymericbinderswithpolyurethane,canbeused.The additionofpolyurethanecanimprovecohesivestrengthandmechanicalstability,addressingthe limitationsofacrylicbindersalonewhilemaintainingsufficientflexibility.Moreover,suchblends maylowerthefilm-formingtemperatureofthebindersystem,enablingcuringatlower temperaturesandenhancingthecompatibilitywithvarioussubstrates.Thiscombinationensures20 strongadhesion,resistancetoblocking,andimprovedlaminationperformance,particularlyfor demandingapplications

[0059] Therefore,toensureoptimallaminationstrength,theprimercompositionalso incorporatesinorganicfillersinprecisequantitiesandratios.Further,theseinorganicfillerswhen dispersedintheacrylicpolymerservingasabinder,mayintroducemicro-poresintotheprimer25 layer.Theinorganicfiller-to-polymericbinderratiocanalsobecriticaltoachievingthedesired balancebetweenadhesion,flexibility,andlaminationstrength.Toomuchinorganicfiller(s)can maketheprimerlayerbrittle,whiletoolittlemaycompromiseitseffectivenessincreatinga micro-porouslayer.Also,theselectionofspecifictypesofinorganicfillerscanalsoinfluencethe primer'soverallperformance,includingitsadhesion,flexibility,andporosity.30

[0060] Substrate

[0061] Thesubstratetobetreatedwiththeprimercompositionofthepresentinventionis polymericsubstratepreferablywithrelativelylowsurfaceenergy(30-50mN / m),suchas 2024 / 5923 BE2024 / 5923 9 thermoplasticsubstrate.Thethermoplasticsubstratemayincludepolyolefinslikepolypropylene (PP)andpolyethylene(PE),polyesterslikepolyethyleneterephthalate(PET),andpolyvinyl chloride(PVC).Also,materialslikepolyamide(PA),polycarbonate(PC),fluoropolymers,and polystyrene(PS),canbenefitfromtheprimercompositiontoimproveprintability.Thesematerials areinherentlynon-porous,non-absorbent(essentiallywaterimpermeable).5

[0062] Theprimercompositioncanalsobeappliedtolaminatesubstrates,whichare composedofmultiplelayersofdifferentmaterial.Also,othersubstratesthatexhibita thermoplastic-likesurfacecanalsobeused,forexampleforexamplecoatedcanvasandcoated wovenornon-wovenfabrics,coatedsubstrates,suchaspaperorcardboardcoatedorlaminated withpolymericlayers.Thesematerialsarewidelyutilizedinpackaging,signage,decorative10 coverings,andvariousdecorativeorshapedarticles.Theprimercompositionenableseffective adhesionofaqueousinkcompositionstothesetypicallyhydrophobicsurfaces,overcoming challengessuchaspooraqueousinkabsorptionandadhesion,bymodifyingthesurface propertiesofthepolymeric(thermoplastic)substrate.

[0063] Thepolymericsubstratemightbepartofvariousproducts,includingfloorcoverings,15 wallcoverings,ceilingcoverings,oralternativesurfacecoverings,tarpaulins,andprintfilms.

[0064] Theprimercompositionofthepresentinventioncanbeparticularlysuitablefor thermoplasticsurfacessuchaspolyvinylchloride(PVC),butitisnotlimitedtothisapplication only,aspreviouslydescribed.

[0065] Thepolymericsubstratemaybeinformofathermoplasticfoil,film,printfilm,decor20 films;orfoamlayer,foamablesubstrate,polymerfilmlaminates,suchasflexiblepackaging laminates.Inanembodiment,thepolymericsubstrateisathermoplasticsubstrateselectedform thegroupsconsistingofpolyolefins,suchaspolypropylene(PP),polyethylene(PE),polyvinyl chloride(PVC),polyesters,suchaspolyethyleneterephthalate(PET),polyamide(PA)and polystyrene(PS).25

[0066] Inanembodiment,thepolymericsubstratetobetreatedwiththeprimercompositionof thepresentinventionispolyvinylchloride.Inapreferredembodiment,thepolymericsubstrateis polyvinylchloride(PVC).PVCisapopularmaterialfordecorativecoverings,inparticularafloor covering,ceilingcovering,wallcovering,oralternativesurfacecovering,tarpaulin,duetoits durability,flexibility,andresistancetoenvironmentalfactors.However,itsnon-porousandnon-30 absorbentnaturemakesitachallengingsubstrateforaqueousinks.Thenon-porousandnon- absorbent(essentiallywaterimpermeable)polymericsurfaceofthePVCdoesnotreadilyabsorb liquids,leadingtochallengesintheadherenceandeffectivedryingofaqueousinks.Therelatively 2024 / 5923 BE2024 / 5923 10 lowsurfaceenergyofPVC,comparedtoothermaterials,furtherimpactsitsadhesionproperties. Toaddressthesechallenges,theprimercompositionofthepresentinventionisappliedtothe PVCsurfacebeforethedecorativelayerisformed.

[0067] PolymericBinder

[0068] Inprimercompositions,thebinderplaysacrucialroleindeterminingtheprimer's5 performancecharacteristics,includingadhesion,durability,printqualityandcompatibilitywith substratesandtopcoats.Thebinderisessentiallythefilm-formingcomponentoftheprimer, responsibleforholdingthepigmentparticlestogetherandprovidingadhesiontothesurface beingcoated.

[0069] Thebinderisaresinorpolymerthatservesastheprimarycomponentintheprimer10 compositionofthepresentinvention.Itfacilitatesbothsubstrateadhesionandinkabsorptionfor jettedinkapplications.Typically,polyurethaneresinsand / oracrylicresinsareemployedfor thesepurposes.Suitablecompatiblebindersfortheprimercompositionmayincludenon-ionic water-insolublepolymersincolloidalparticleform,suchasacryliclatexes,acryliccopolymer, acrylicself-crosslinkingdispersions,polyurethane,ablendofacrylicpolymers / co-polymerswith15 polyurethane,vinylacetatecopolymerlatexes,polyester,orpolyamide.

[0070] Theprimercompositionofthepresentinventionmayincorporateablendofpolyacrylate (PA)andpolyurethane(PU)asthepolymerbinder,thatcanreducetheoverallfilm-forming temperatureofthebinderblend,enablingtheprimerlayertocureatlowertemperatures.Alower curingtemperatureallowsfortheformationoftheprimerfilmundermilderconditions,whichcan20 significantlyenhanceprintqualitybyminimizingthermalstressonthesubstrate.Further,despite thereductionincuringtemperature,thecombinationofpolyacrylateandpolyurethaneensures sufficientblockingpotential,i.e.,meaningitpreventsstickingtoothersurfaces,duetothe presenceofsufficienthardresin(polyacrylate)intheformulation.Thisensurestheprimerretains itsstructuralintegrityandresistancetounwantedadhesionortransferduringprocessingand25 use.Thesynergisticuseofpolyacrylate(PA)andpolyurethane(PU)bindersresultsinimproved processability,adhesionstrength,andfunctionaldurability.

[0071] Additionally,certainsolventscanbeincorporatedintotheprimercompositionto acceleratefilmformation,providinganalternativetoblendingpolyurethanewithpolyacrylate. Thesesolventscanlowerthefilm-formingtemperatureofthebinder,acceleratingfilmformation,30 especiallyinlow-temperatureenvironments.2024 / 5923 BE2024 / 5923 11

[0072] Inanembodiment,thepolymericbinderusedintheprimercompositioncanbeselected fromoneormoreacrylicpolymersoracrylicco-polymers,orablendofacrylicpolymersorco- polymerswithpolyurethane.

[0073] Theprimercompositionofthepresentinventionmaycompriseapolymericbinderthatis preferablyanacrylicpolymeroracrylicco-polymer.Byselectinganacrylic-basedresin,theissue5 ofblockingismitigatedduetotheabilityoftheacrylicresintoformatough,durable,andless tackyfilmupondrying,asshowninFigs1-4.Acrylicresinsoftenexhibithigherglasstransition temperatures(Tg)thanforexamplepolyurethanesandintrinsichardness,whichcontributeto improvedresistancetostickingoradheringunderconditionsofheatandpressure.

[0074] Inanembodiment,thepolymericbinderisanacrylicpolymerorco-polymer.Preferably,10 theacrylicpolymerorco-polymerisaself-crosslinkingacrylicpolymer.Theacrylicpolymeric binderiswell-suitedforpreventingblockingduetoitsabilitytomaintainhighcohesivestrength, andlowadhesiveproperties.Also,theacrylicbinderhasaninherentlypolarnatureandhasthe abilitytomodifythesurfaceenergyofthepolymericsubstrate,preferablythethermoplastic substrate.15

[0075] Inanalternativeembodiment,theprimercompositioncomprisesapolymericbinder, whereinthepolymericbinderisanacrylicself-crosslinkingdispersioncomprisingaself- crosslinkingacrylicpolymer.

[0076] Alternatively,theprimercompositionmaycompriseapolymericbinderwherethe polymericbinderisanacrylicself-crosslinkingdispersion.Theacrylicself-crosslinking20 dispersionisatypeofpolymerdispersioninwaterthatcanformacrosslinkednetworkupon curingordryingwithouttheneedforexternalcrosslinkers.Thesedispersionscanbetypically throughemulsionpolymerization,usingacrylicmonomers(e.g.,butylacrylate,methyl methacrylate)combinedwithfunctionalmonomerssuchashydroxyethylmethacrylateoracrylic acid.Theacrylicself-cross-linkingdispersioncomprisesaself-crosslinkingacrylicpolymer.25

[0077] Theself-crosslinkingacrylicpolymerisusuallyintheformofanaqueousdispersionor emulsionandistypicallytheproductofatleasttwomonomersthatreactwithoneanother. Furthermore,aself-crosslinkingacrylicpolymerreferstoaonepackacrylicthat,whilstunder ambientcure,canachievecuring,typicallyviaacarbonyl / aminereaction.Thiscanoccur betweenketonegroupsandbi-orpolyfunctionalaminecompoundshavinggroupsthatare30 reactivetowardscarbonylgroups.Theseacrylicpolymersexhibitenhancedresistanceproperties intheresultantdriedfilm. 2024 / 5923 BE2024 / 5923 12

[0078] Theself-crosslinkingacrylicpolymerasthepolymericbinderintheprimercomposition, providingbothfilm-formingpropertiesandcrosslinkingfunctionality.Thesepolymerscanbe derivedfromvariouschemistries,suchasstyrene-acrylicestercopolymers,styrene-acrylicester copolymerscontainingacrylamidegroups,orcopolymersbasedonacrylonitrile, methacrylamide,andacrylicesters.5

[0079] Inoneembodiment,theself-crosslinkingacrylicpolymerissynthesizedfromreactive monomers,includingatleastoneofmethylacrylicacid(MAA),methylmethacrylate(MMA),butyl acrylate,butylmethacrylate,styrene,ormethylstyrene.Theresultingpolymerisadvantageously astyrene-acrylicestercopolymer,whichprovidesabalanceofflexibility,durability,and chemicalresistance.10

[0080] Dependingupontheacrylictype,thecross-linkingreaction,mayalsobeinitiatedbythe evaporationofwaterupondrying,achangeofpHofthevehicle,orbycuringatelevated temperatureswherethecross-linkingreactionoccursfaster,orthereactivegroupsarede- blocked.

[0081] Someexamplespolymericbinderscomprisinganacrylicpolymerorcopolymer,may15 includeNeoCryl®A-1127,aself-cross-linkingacryliccopolymerdispersion.Joncryl®8053,aself- cross-linkingacryliccopolymer;Bayhydrol®A2846XP(anacrylicdispersion),RhoplexSG-10M( self-cross-linkingacrylicemulsion);CHP536(anAlkylphenolEthoxylates(APEOs),-freeself- cross-linkingacryliccopolymerdispersion)andAcronal®290D(acryliccopolymer).

[0082] Further,suitableacrylicpolymersorco-polymerscanbeselectedfromNeoCrylBT-20,20 MakrovilVI08,NeoCrylD-2204,Exopur4109,Vinamul3231,NeoCrylXK-205,andNeoCrylAl120.

[0083] SuitableexamplesofpolyurethanescanbeselectedformBaybondPU404,BaybondPU 501,Witcobond®W-290H,Sancure®861,waterborneurethane-acrylichybridresins.

[0084] Theprimercompositionofthepresentinventioningeneralmaycompriseoffrom20%to 80%byweightofatleastonepolymericbinderrelativetothetotalweightoftheprimer25 composition,preferablybetween30%to80%byweight,morepreferablybetween40%and80% byweight,evenmorepreferablybetween40%and70%byweight.

[0085] Inanembodiment,theprimercompositionofthepresentinventioncomprisesoffrom20 %to80%byweightofself-cross-linkingacrylicpolymerasabinder,relativetothetotalweight oftheprimercomposition.30

[0086] Inanembodiment,theprimercompositionofthepresentinventioncomprisesacrylic self-crosslinkingdispersioninanamountcomprisedbetween20%to80%byweightrelativeto 2024 / 5923 BE2024 / 5923 13 thetotalweightoftheprimercomposition,preferablybetween30%to80%byweight,more preferablybetween40%and70%byweight.

[0087] Filler

[0088] Variousfillerscanbeusedintheprimercomposition,e.g.,inorganicfillers,organic fillers.Fillersmaybeusedeitherindividuallyorinadmixture.Preferredfillersaresubstantially5 inertundertheconditionsencounteredwhenthecomponentsoftheinventionaremixed. Preferably,atleasttwoinorganicfillersareusedinthepresentprimercomposition.

[0089] Theinorganicfillerisaparticulateadditive,solid,thatisincorporatedtoimprove mechanicalperformance,adjustsurfacecharacteristics,optimizeapplicationproperties.The inorganicfillerofthepresentinventioncomprisesinorganicparticlesorblendofinorganic10 particles.Inanembodiment,eachinorganicfillerconsistsofinorganicparticlesorblendof inorganicparticles.Examplesofsuitableinorganicparticlesforuseasafirstand / orsecond inorganicfillerinclude,butarenotlimitedto,silica,alumina,aluminiumhydroxide,aluminium hydroxideoxideparticles,microchalk,blendofsilicaandkaolinite,dolomite,kaolin,kaolinite, clay,wollastonite,mica,talc,calciumbicarbonate,calciumcarbonate,Diatomaceousearth,15 calcinedclay,silicagel,fumedsilica,colloidalsilica,talc,fumedalumina,colloidalalumina, titaniumdioxide,zincoxide,zincsulphideandbariumsulphate.

[0090] Theprimercompositionofthepresentinventionmayalsocompriseasatleastone inorganicfiller,preferablytwoinorganicfillers,oranydispersion(s)ofinorganicmaterial(s), includingbutnotlimitedtosilica,alumina,aluminiumhydroxideoxideparticles,blendoffinely20 dividedsilica(SiO₂)andlamellarkaoliniteclay(atypeofaluminiumsilicate),clay,microchalk, calciumbicarbonate,calciumcarbonate.

[0091] Theparticlesizecanvaryfromthenanometrerangeuptoseveralmicrons.Inpreferred embodiments,theaverageparticlesizeofthefirstinorganicfiller,inparticularcalcium carbonateisbetween0.15µmand0.5µm,orbetween0.2µmand0.4µm.25

[0092] Theprimercompositionofthepresentinventioncomprisesatleasttwodistincttypesof inorganicfillers,whereineachinorganicfillercomprisesinorganicparticlesconfiguredto enhancemechanicalbondingandsurfaceroughness.Thetwodistincttypesofinorganicfillers aredefinedasafirstinorganicfillerandsecondinorganicfiller.Theadditionoftwodistinct inorganicfillersintheprimercompositionofthepresentinventionhasasynergisticeffect.30 Withoutbeingboundtoanyspecifictheory,itisproposedthatthetwoinorganicfillers,differing inparticlesize,shape,orchemicalcomposition,interacttoenhancemechanicalinterlockingat theinterfacebetweentheprimerlayerandthesubstrateorlaminate.Thisinteractionstrengthens 2024 / 5923 BE2024 / 5923 14 thebondandimprovestheoveralladhesion.Theadditionoftwoinorganicfillerswith complementarypropertiescanoptimizethesurfaceenergyandtexture,andlaminationstrength. Thismayreducetackinessandpreventblocking.Theratiobetweenthetwodistinctinorganic fillersplaysapivotalroleinachievingthesetechnicaleffects.Theweightratiobetweenthefirst inorganicfillerandthesecondinorganicfillerisbetween0.5:1to30:1,whereinthefirstinorganic5 filleriscalciumcarbonateparticles,andthesecondinorganicfillerisblendoffinelydivided silica(SiO₂)andlamellarkaoliniteparticles,oraluminiumhydroxideoxideparticles.

[0093] Forexample,theweightratiobetweenthefirstinorganicfillerandthesecondinorganic fillercanbebetween1:1to20:1,orbetween1:1and15:1,orbetween1:1and10:1,orbetween 1:1and8:1.10

[0094] Particularlythefirstinorganicfillercanbecalciumcarbonateormicrochalk.Preferably, thefirstinorganicfillercanbepresentinanamountbelow50wt%,morepreferablybelow40wt %(wet-weightpercent),evenmorepreferablybelow35wt%(wet-weightpercent)basedonthe totalcompositionoftheprimercomposition.Ahigheramountoffirstinorganicfillercanresultin irreversiblesedimentationoftheinorganicparticles.15

[0095] Theadditionoftwotypesofinorganicfillersselectedforexamplecalciumcarbonate particles(microchalk),blendoffinelydividedsilica(SiO₂)andlamellarkaoliniteparticles;or aluminiumhydroxideoxideparticles,totheprimercompositionincreasesthedelamination strengthoftheprimerlayerformedonthesubstrate.

[0096] Inanembodiment,thefirstinorganicfillercomprisescalciumcarbonateparticles(micro20 chalkparticles,(CASnumber471341)).Theinclusionofcalciumcarbonateparticlesenhances thelaminationstrength,improvingtheadhesionbetweenthethermoplasticsubstrate,theprimer layer,theinklayer,andthewear-resistantlayer.Microchalk,alsoknownasmicronizedchalkor micropowderchalk,referstoaformoffinelygroundchalk,comprisingasaprimarycomponent calciumcarbonate(CaCO₃).Themicrochalkisproducedthroughaprecisegrindingprocessthat25 reducestheparticlesizetoafinepowder,typicallywithamediandiameter(D50)rangingfrom greaterthan0.15µmto15µm,or0.2µmto10µm,morepreferablybetween0.2µmand0.4µm. Further,themicrochalkparticlesmayoptionallybesurfacemodifiedtoenhancetheirproperties, forexample,theymaybecoated.Thecalciumcarbonate(microchalk)particlesareusedasan inorganicfillerandcanhelpcontroltheporosityoftheprimerlayer.30

[0097] Thermoplasticsurfaces,suchasPVCsurfaces,havelowporosity,whichcanpose challengesforprimeradhesion.Calciumcarbonateparticleshelptoreduceblockinginprimer compositionsbyenhancingsurfacecharacteristics.Itsfineparticlesfillsmallvoidsandaugment 2024 / 5923 BE2024 / 5923 15 surfaceroughness,therebyfosteringamoreporoussubstratesurface.Thisincreasedporosity promotesbettermechanicalinterlockingbetweentheprimerandthethermoplasticsubstrate, suchasPVCsubstrate.Asaresult,theprimeradheresmoreeffectivelytothethermoplastic substrate,reducingthelikelihoodofsheetsstickingtogetherduringstorageorhandling.

[0098] Inanembodiment,theparticlesizedistributionofthecalciumcarbonate(microchalk)5 hasamediandiameter(D50)offrom0.1µm(micrometres)toabout10µm,asdeterminedusinga Nicomp380ParticleSizeremployingDynamicLightScattering(DLS)forthismeasurement.Very fineparticlestendtoagglomerate,whichcancreatedispersiondifficultiesandreducetheoverall effectivenessoftheprimercoating.

[0099] Inanembodiment,theparticlesizedistributionofthecalciumcarbonatehasamedian10 diameter(D50)offrom0.15µmto15µm,orfromabout0.2µmto10µm,orfromabout0.2µmto 5µm,orfromabout0.2µmto3µm,orform0.2µmto0.4µmasdeterminedusingaNicomp380 ParticleSizeremployingDynamicLightScattering(DLS)forthismeasurement.

[0100] Asmallersize(0.1µm-10µm)ofinorganicparticles,suchasCaCO₃,mayleadtodeeper penetrationwithintheprimercompositionand / orintotheporesofthesubstrate.Thisdeeper15 penetrationcanreducetheavailabilityoftheparticlesatthesurfaceoftheprimerlayer,thereby diminishingtheirfunctionalcontributionatthesurface.

[0101] Preferably,thesecondinorganicfillercanbepresentinanamountbelow20wt%(wet- weightpercent),morepreferablybelow15wt%(wet-weightpercent),evenmorepreferably below12wt%(wet-weightpercent)basedonthetotalcompositionoftheprimercomposition.20 Thewetweightpercentage,alsodescribedaswet-wtpercent,isexpressedasthewetweightof therespectivecomponentoverthetotalwetweightoftheprimercomposition.Thesecond inorganicfillercanbeselectedfromablendofsilica(SiO₂)andkaolinite,preferablylamellar kaolinite,orfromalumina,aluminumhydroxide,aluminiumhydroxideoxideparticles,or compositematerials.Examplesofcompositematerialsincludecompositematerialmadefroma25 combinationofsilicaandkaoliniteparticles,wheresilicaparticlescanbedepositedonto kaoliniteparticles,orviceversa.

[0102] Inanembodiment,thesecondinorganicfilleroftheprimercompositionisselectedfrom thegroupconsistingofaluminiumhydroxideoxideparticles,orfrominorganicparticles comprisingablendofsilicaandkaoliniteparticles,oracompositematerialcomprisingsilicaand30 kaoliniteparticles,whereinsilicaparticlesaredepositedonkaoliniteparticles,orkaolinite particlesaredepositedonsilicaparticles. 2024 / 5923 BE2024 / 5923 16

[0103] Thesecondinorganicfillercanbeablendofsilicaandkaoliniteparticleswithaformula: SiO2-Al2[(OH)4Si2O5]withparticlesizedistribution(D50)oflessthan2.4µm.

[0104] Theterm"lamellar"referstotheplate-likeorsheet-likestructureofthemineral. Kaoliniteisaclaymineralcomposedofalternatinglayersofsilicaandalumina.

[0105] Inanembodiment,thesecondinorganicfillercomprisesinorganicparticlesconsisting5 primarilyofanaturalblendoffinelydividedsilica(SiO₂)andlamellarkaolinite(atypeof aluminumsilicate).Thematerialtypicallycontainsapproximately82%silicondioxide(SiO₂)and 12%aluminumoxide(Al₂O₃),withtraceamountsofironoxide(Fe₂O₃).Theparticlestructure combinescorpuscular(spherical-like)silicawithplate-likekaolinite,resultinginaunique morphology.Theparticlesizedistributiond50canbeintherangebetween1.8μmand2.4μm,as10 measuredbyISO13320(particlesizewasmeasuredusinglaserdiffraction)andelectrical conductivityintherangebetween70and100μS / cm.Structurally,theparticlesexhibitahybrid morphology,combiningcorpuscularsilicawithplate-likekaolinite.Inanembodiment,theprimer compositioncomprisesanadmixtureofinorganicfillers,whereinthefirstinorganicfiller comprisescalciumcarbonateparticles(microchalk)andwhereinthesecondinorganicfiller15 comprisesablendoffinelydividedsilica(SiO₂)andlamellarkaolinite(atypeofaluminium silicate)(SILLITINZ89byHoffmannMineral).

[0106] Aluminumhydroxideoxideisalsoknownasaluminumoxidehydroxide,aluminum oxyhydroxide,oraluminahydrateandhastheformulaAIO(OH)(=Al2O3·H2O).Preferredtypesof aluminumhydroxideoxideforuseinthepresentinventioncanbeboehmiteand20 pseudoboehmite.

[0107] Boehmiteisamineralwithanorthorhombicunitcell(a=3.693Å,b=12.221Å,andc= 2.865Å),classifiedasγ-AlO(OH).Itscrystalstructureconsistsofdoublelayersofoxygen octahedrawithaluminumatomscentrallypositionedwithinthem.Theoutward-facingoxygen atomsarebondedviahydrogenbondstothehydroxylgroupsofadjacentoctahedrallayers.Due25 totheserelativelyweakhydrogenbonds,boehmiteispronetointercalation,theinclusionof smallmolecules,typicallywater,betweenitslayers.Thisintercalationincreasesthespacing alongthe

[010] directionandresultsinperfectcleavageperpendiculartothegeneraldirectionof thehydrogenbonding.Whenthespacinginthe

[010] directionincreasessignificantly,the materialisreferredtoaspseudoboehmite,whilepredominantlyamorphousformsarecommonly30 knownasboehmitegel. 2024 / 5923 BE2024 / 5923 17

[0108] Boehmitecanoccurnaturallyorbesynthesized.Itmaybeprecipitatedandgrownfrom solutionsofaluminumsaltsoraluminaunderhydrothermalconditionsorproducedviathe hydrolysisofaluminumalkoxides.

[0109] Inanalternativeembodiment,thesecondinorganicfillercomprisesaluminium hydroxideoxideparticlesforexampleselectedfromboehmiteparticles,pseudoboehmite5 particles,andcombinationsthereof,and / orhaveamedianparticlesize(D50)offrom0.02to20 µm,orfrom0.02µmto10µm,orfrom0.02µmto5µm,preferablyfrom0.03µmto0.3µm,more preferablyfrom0.05µmto0.2µm,andmostpreferablyfrom0.08µmto0.18µmasdetermined bylaserdiffractionaccordingtoISO13320:2020-01.

[0110] Inanembodiment,thesecondinorganicfilleroftheprimercompositioncomprises10 aluminiumhydroxideoxideparticleshavingaparticlesizedistributionwithamediandiameter (D50)rangingfrom0.5µmto10µm,preferablyfrom0.5µmto5µm,asdeterminedbylaser diffractionaccordingtoISO13320:2020-01.

[0111] TheD50valueisastatisticalmeasureusedtodescribetheparticlesizedistributionof theinkthatrepresentsthemedianparticlediameter,indicatingthat50%oftheparticlesinthe15 inkaresmallerthanthisvalue,and50%arelarger.Further,DLSisatechniqueformeasuringthe sizedistributionofsmallparticlessuspendedinaliquid.Itworksbyanalysingtheintensity fluctuationsoflaserlightscatteredbytheparticlesastheyundergoBrownianmotion.

[0112] Inanembodiment,theprimercompositioncomprisesaself-crosslinkingacrylic polymer,anadmixtureatleasttwodistincttypesofinorganicfillers,whereinthefirstinorganic20 fillercomprisescalciumcarbonateparticles(microchalk)andwhereinthesecondinorganicfiller comprisesablendoffinelydividedsilica(SiO₂)andlamellarkaolinite.

[0113] Inanembodiment,theprimercompositioncomprisesaanacrylicself-crosslinking dispersioncomprisingaself-crosslinkingacrylicpolymer,anadmixtureatleasttwodistincttypes ofinorganicfillers,whereinthefirstinorganicfillercomprisescalciumcarbonateparticles(micro25 chalk)andwhereinthesecondinorganicfillercomprisesablendoffinelydividedsilica(SiO₂)and lamellarkaolinite,andwater,whereintheweightratiobetweenthefirstinorganicfillerandthe secondinorganicfillerisbetween1:1and20:1,orbetween1:1and15:1,orbetween1:1and 10:1,orbetween1:1and8:1(wet-weightratio).

[0114] Inanalternativeembodiment,theprimercompositioncomprisesaself-crosslinking30 acrylicpolymeroraself-crosslinkingacrylicco-polymer,anadmixtureatleasttwodistincttypes ofinorganicfillers,whereinthefirstinorganicfillercomprisescalciumcarbonateparticles(micro 2024 / 5923 BE2024 / 5923 18 chalk)andwhereinthesecondinorganicfillercomprisesaluminiumhydroxideoxideparticles, andwater.

[0115] Inanembodiment,theparticlesizedistributionofthecalciumcarbonate(microchalk) hasamediandiameter(D50)greaterthan0.1micrometres(µm),asdeterminedusingaNicomp 380ParticleSizeremployingDynamicLightScattering(DLS)forthismeasurement.Veryfine5 particlestendtoagglomerate,whichcancreatedispersiondifficultiesandreducetheoverall effectivenessoftheprimercoating.Forexample,thecalciumcarbonateparticlescanhavea particlesizedistributionwithamediandiameter(D50)rangingfrom0.15µmto15µm,orfrom0.2 µmto10µm,orfrom0.2µmto5µm,orfrom0.2µmto3µm,orform0.2µmto1µm,orfrom0.2 µmto0.5µm,orform0.2µmto0.4µm.10

[0116] Theratiobetweenthepolymericbinderandthetwoinorganicfillersisfrom1:10to10:1, preferablyfrom1:5to9:1,morepreferablyfrom1:1to8:1.

[0117] Inanembodiment,theprimercompositionforthermoplasticsubstratesurface comprisesatleastonepolymericbinder,whereinthepolymericbinderisanacrylicself- crosslinkingdispersioncomprisingaself-crosslinkingpolymer,atleasttwodistincttypesof15 inorganicfillers,whereinthefirstinorganicfilleriscalciumcarbonateparticles,andthesecond inorganicfillerisablendofsilicaand(lamellar)kaolinite,andwater,wheretheratiobetweenthe polymericbinderandthetwoinorganicfillersisfrom1:5to9:1,preferablyfrom1:1to8:1.

[0118] Theprimercompositionmaycomprise5%to40%byweightofafirstinorganicfiller (calciumcarbonate),preferably10wt%to35wt%,morepreferably10wt%to32wt%,even20 morepreferably15wt%to30wt%.

[0119] Theprimercompositionmaycomprisebasedonthetotalweightoftheprimer composition:2%to15%byweightofasecondinorganicfiller,whereinthesecondinorganicfiller isablendofsilicaand(lamellar)kaolinite,preferably4wt%to15wt%,morepreferably5wt%to 10wt%.25

[0120] Alternatively,theprimercompositionmaycomprisebasedonthetotalweightofthe primercomposition:2%to15%byweightofasecondinorganicfiller,whereinthesecond inorganicfillerisanaluminiumoxidehydroxide(boehmite),preferably4to15wt%,more preferably5wt%to10wt%.

[0121] Inanalternativeembodiment,theprimercompositionforthermoplasticsubstrate30 surfacecomprisesbasedonthetotalweightoftheprimercomposition:20wt%to80wt% acrylicbinder,whereinthepolymericbinderisanacrylicself-crosslinkingdispersioncomprising aself-crosslinkingpolymer,5wt%to40wt%calciumcarbonateparticles,and2%to15%by 2024 / 5923 BE2024 / 5923 19 weightofthesecondinorganicfillerisablendofsilicaand(lamellar)kaolinite,andthebalance beingwater.

[0122] Inanembodiment,theprimercompositionforthermoplasticsubstratesurface comprisesbasedonthetotalweightoftheprimercomposition:20wt%to80wt%acrylic binder,whereinthepolymericbinderisanacrylicself-crosslinkingdispersioncomprisingaself-5 crosslinkingpolymer,5wt%to40wt%calciumcarbonateparticles,and2%to15%byweight ofthesecondinorganicfillerisaaluminiumoxidehydroxide(boehmite),andthebalancebeing water.

[0123] Additives

[0124] Theprimercompositioncanalsoincludeotherprimercomponents(additives)suchas10 surfactants,rheologymodifiers,defoamers,opticalbrighteners,biocides,pHcontrollingagents, dyes,corrosioninhibitors,coalescingagentsolventstoreducefilmformingtemperatureof binderemulsionsandthelikeandotheradditivesforfurtherenhancingthepropertiesofthe primercomposition.

[0125] Theprimercompositionofthepresentinventionfurthermaycompriseoneormore15 antifoamingadditivesinanamountcomprisedbetween0%and2%byweight,preferably between0.5and1.5%byweightofthetotalweightoftheprimerformulation.

[0126] Examplesofantifoamingagentsarepolysiloxanes,suchaspolymethylhydrogensiloxane orpolydimethylsiloxane,polyoxyalkylenepolysiloxaneblockcopolymers,graftedpolyoxyalkylene polysiloxaneblockcopolymersandmixturesthereofwithorganicoilssuchasmineraloilssuch20 asnaphthenicandparaffinicmineraloil,polypropyleneoxide,polybutadiene,certainoilsof vegetableoranimalorigin,andthelike.

[0127] Theprimercompositionofthepresentinventionofthepresentinventionfurthermay compriseoneormoresurfactantsinanamountcomprisedbetween0%and2%byweight, preferablybetween0.5and1.5%byweightofthetotalweightoftheprimerformulation.25

[0128] Examplesofsuitablesurfactantscanbeapolyethermodifiedsiloxane,sodiumdodecyl sulfate,polysorbate20(orpolyoxyethylene20sorbitanmonolaurate),Polysorbate40(or polyoxyethylene20sorbitanmonopalmitate),Polysorbate60(orpolyoxyethylene20sorbitan monostearate),Polysorbate80(orpolyoxyethylene20sorbitanmonooleate),alkyl polyglucosides,morepreferablypolyethermodifiedsiloxane,Surfynol(acetylenicdiol-based30 surfactants).

[0129] Further,theprimercompositionofthepresentinventionisanaqueousprimer composition,whereinthewaterservesastheprimarysolventorcarrierintheformulation. 2024 / 5923 BE2024 / 5923 20 Aqueousprimercompositionsofferseveraladvantages,includingbeingmoreenvironmentally friendlyduetoreducedvolatileorganiccompound(VOC)emissions.

[0130] Also,thepresentinventionrelatestoaprimercompositionthatcanbeusedtoimprove theadhesionandlaminationstrengthofaqueousinkscompositionappliedtopolymeric surfaces,preferablythermoplasticsurfaces,usedindecorativecoverings,suchasfloorsurface5 covering,ceilingsurfacecovering,wallsurfacecovering,andlaminatedflooringpanels. Laminatedflooringpanelsorfloorcoveringelementscancompriseasupportlayer,afoamed layer,adecorativelayeradheredtotheuppersurfaceofthefoamlayer,awear-resistantlayer, andabackinglayer.Thedecorativelayerisanaestheticlayercomprisingdesignsprintedwith aqueousinkcompositionsonthethermoplasticsubstrate.Insomeexamples,theaqueousink10 compositionmaybeappliedontheprimerlayerbydigitalprinting,suchinasinglepassormulti- passprinting.Employingtheprimercompositionofthepresentinventionforcoveringelementsor laminatedpanelsservesmerelyasanillustration;itshouldnotbeconstruedaslimitingthe invention'sapplicabilitytotheseexamplesalone.

[0131] Further,theprimerlayercomprisingtheprimercompositionofthepresentinvention15 mayenhancetheadhesionandfacilitatestheeffectivelaminationofthewear-resistantlayerto thethermoplasticsurfaceofthesubstratewheretheaqueousinkisapplied.Thewear-resistant layerservesasaprotectivetopcoatorlacquerforsurfacessuchaslaminatedflooringpanelsor otherdecorativecoverings,improvingtheirdurabilityandresistancetodamagefromdailyuse, includingscratches,stains,andabrasion.Inoneembodiment,thewearresistantlayer20 comprisesoneormorelayersofapolymericmaterial,suchasathermoplasticand / orthermoset polymericmaterial.Inoneembodiment,thewearresistantlayercomprisesatransparent polyvinylchloridelayer.Otherexamplesofthewearresistantlayerinclude,butarenotlimitedto, acrylicpolymers,polyolefins,melamineresinsandthelike.Thewearresistantlayercanbe translucent,andpreferablytransparent.Thewearresistantlayermayhaveathicknessof100μm25 to1000μm.

[0132] Surprisingly,theadhesionofthewear-resistantlayertotheremainderofthemulti-layer substratemaybefurtherenhancedbytheinclusionoftheprimerlayercomprisingtheprimer compositionofthepresentinventionthatfacilitatesbetterlaminationstrengthbetweenthe wear-resistantlayerandthethermoplasticsubstrate,asshowninFigs.3and4.Preferably,the30 thermoplasticsubstrateexhibitsapeelstrengthbetweenthedecorativelayerandthewear- resistantlayerofbetween20to120N / 50mm,morepreferablyoffrom25to115N / 50mm,and 2024 / 5923 BE2024 / 5923 21 mostpreferablyoffrom30to110N / 50mm,whenmeasuredforthecompleteproductbuild-up includingawear-resistantlayer,aprimerlayer,anddeterminedaccordingtoEN431:1994.

[0133] Further,theprimerlayerofthepresentinventionexhibitsapeelstrengthofatleast20 N / 50mm,preferably30N / 50mm,asdeterminedinaccordancewithASTMD903.Thiscan ensurestrongadhesionbetweenthesubstrateandsubsequentlayers.5

[0134] Inanembodiment,theprimercompositionofthepresentinventionisformulatedfor treatmentofpolyvinylchloride(PVC)surface / substrate.PVCiswidelyusedasamaterialfor decorativecoverings,includingfloorcoverings,ceilingcoverings,wallcoverings,andother surfacecoverings,duetoitsdurability,flexibility,andresistancetoenvironmentalfactors. However,itsnon-porousandwater-impermeablenaturepresentschallengesfortheadhesion10 anddryingofaqueousinks.Furthermore,therelativelylowsurfaceenergyofPVC,typically around35mN / m,furtherhindersproperinkadhesion.Theprimercompositioncanmodifythe surfacepropertiesofPVC,increasingitssurfaceenergytoapproximately50mN / m,thereby enablingimprovedaqueousinkwetting,adhesion,andoverallprintquality.

[0135] Methodofapplication15

[0136] Thepresentinventionfurtherrelatestoamethodofapplyingaprimercompositiontoa polymericsubstratesurface,specificallyathermoplasticsubstratesurface,suchas,butnot limitedto,polyvinylchloride(PVC)substrate,oraplasticizedfoamablePVCsubstrate.

[0137] Thepresentinventionalsorelatestoamethodforpreparingashapedarticle,suchasa decorativecovering.Themethodinvolvesthefollowingsteps:providingapolymericsubstrate;20 applyinganinkandprimersystemasdescribedherein,whichincludesfirstapplyingtheprimer compositionofthepresentinventiontothepolymericsubstratetoformaprimerlayer; subsequentlyprintingadecorativelayerontheprimedsubstrate,preferablyusingdigitalprinting withanaqueousinkcomposition;andfinally,dryingtheaqueousinkcompositiontoformthe finishedprintedpolymericsubstrate.25

[0138] Inanembodiment,theprimercompositionofthepresentinventionisappliedon polyvinylchloride(PVC)substrate / surface,followedbytheprintingoftheaqueousink composition.

[0139] Whenprimingthermoplasticfilmsubstrates,thesubstratemaybeflameorcorona treatedpriortocoating.Suchtreatmentofthesubstrateenablesgoodadhesionoftheprimer30 layerbyprovidingasuitablesurfaceenergyofthesubstrate.Ingeneral,highersurfaceenergyis associatedwithbetteradhesion.Theprimercompositionofthepresentinvention,upon 2024 / 5923 BE2024 / 5923 22 applicationandsubsequenttreatment,canelevatethepolymericsubstrate'ssurfaceenergy.For example,ifitisPVCsubstrate-tofallwithinthedesirablerangeof40to55mN / m.

[0140] Theprimercompositioncanbeappliedtothepolymeric / thermoplasticsubstratebyany ofanumberofcoatingmethods,includingflexographic,gravure,rod,spray,roll,curtainand knifecoatingmethods.Preferredmethodsareflexographic,gravureandrodcoatingmethods.5 Theapplicationoftheprimercanbeon-line(directlybeforedigitalprinting,aspartofa continuousoperation),oroff-line(wherethecoatingprocessoccursseparatelyfromthedigital printing,allowingtheprimertofullyadhereandcureonthesubstratewithoutimmediateprinting) withtheinkjetinkprintingprocess.

[0141] Theprimercompositioncanbeappliedasaliquidorsemi-liquidcoating.Theprimer10 compositioncanbeinawetstate,referringtoitsconditionimmediatelyafterbeingappliedtoa polymericsubstrate / surface,beforeanysubstantialdryingorcuringhastakenplace.

[0142] Afterbeingappliedinawetstate,theprimercompositionundergoesadryingprocessto formaprimerlayer.Thedryingprocessmayinvolvetheevaporationofthevolatilecomponents fromtheprimercomposition.15

[0143] Theprimercompositioncanbedriedwithaninfraredlamp,hotairorcombination thereof.Inanembodiment,theprimercompositionisdriedusinganovenwithhotairata temperaturerangingfrom30⁰Cto95⁰Cforatimeintherangebetweenabout0.5minand8 minutes,formingaprimerlayer.Subsequently,itcanbeprintedwithanaqueousinkcomposition formingadecorativelayerontheprimedsurfaceofthepolymericsubstratethroughmethodslike20 single-passprinting,ormulti-passprintingusinganaqueousinkcomposition,oreven conventionalprinting.Optionally,theprimedpolymericsubstrate,i.ethepolymericsubstrate withaprimerlayerdepositedonitssurface,withthedecorativelayercanthenbelaminatedto anothersubstrateorcoatedwithanadditionallayer.Forexample,awear-resistantlayermaybe appliedontopofthedecorativelayer.25

[0144] Theprimerlayerforpolymericsubstrateisthusobtainedbydryingaprimercomposition accordingtothepresentinventionwhereintheprimerlayercomprisesthepolymericbinderand inorganicfillersoftheprimercomposition.Thesurfaceoftheprimerlayerisnon-sticky,which meansthatthereisnoblockingoradhesiontoothersurfacesatroomtemperatureorincreased temperature,e.g.50-60⁰C,particularlytothebacksideofasubstratewhichiswoundorrollafter30 applicationanddryingoftheprimercompositionandoptionallyafterprinting.

[0145] Theprimerlayerfurtherreferstothesolidfilmformedonthesurfaceofapolymeric substrateaftertheapplicationanddryingoftheprimercompositionasdescribedinthepresent 2024 / 5923 BE2024 / 5923 23 invention.Thisprimerlayercomprisesthenon-volatilecomponentsoftheprimercomposition, includingthepolymericbinderandtheatleasttwodistinctinorganicfillers,whilewaterandother volatilesubstancesareremovedduringthedryingprocess.Theprimerlayerprovidesafunctional surfacewithpropertiessuchasenhancedadhesionandasurfaceenergyofatleast30mJ / m², makingitsuitableforsubsequentprocesseslikeprinting.5

[0146] Theprimerlayermayhaveathicknessintherangeof1μmto20μm,preferablyinthe rangeof2µmto15µm,morepreferablybetween4μmto10μm.Theprimerlayermaybeina formofafilm.andwithapeelstrengthofatleast20N / 50mm.

[0147] Further,thereisprovidedapolymericsubstrateatleastpartiallycoatedwiththeprimer compositionaccordingtothepresentinventionformingaprimerlayer,theprimerlayerpreferably10 comprisingatleastonepolymericbinderandatleasttwotypesofinorganicfillers,eachfiller consistingofinorganicparticles.Inanembodiment,theprimerlayermaycomprisefrom20%to 70%byweightacrylicpolymer / acrylicco-polymer,orablendacrylicpolymer / acrylicco-polymer andpolyurethane,from15%to80%byweightofcalciumcarbonateparticles,andfrom3%to30 %byweightblendofsilicaandkaoliniteparticles.Thisbasedonthedryweightofthe15 formulation,representingtheproportionsofsolidmaterialsaftertheevaporationofwateror solventsThekaoliniteparticlesintheblendcanbeaspecialtypeoflamellarkaoliniteparticles.

[0148] Oncetheprimerlayeriscompletelydried,,i.e.itcontainsminimaltonomoisture content(seeforexampleTable1and2),andthesubstrateisadequatelyprepared,theaqueous inkcompositionisthenprintedontothepolymericsubstrate.Thissequentialprocessensures20 theprimercomposition / layereffectivelypreparesthethermoplasticsurface,enhancingink adhesionandresultinginsuperiorprintqualitywithvividcoloursandsharppatterns.

[0149] Afterprimerapplication,thepolymericsubstrate,particularlyathermoplasticsubstrate, exhibitstwodistinctsurfaces:primer-treatedsideanduntreatedside.Theprimer-treatedsideis modifiedtoexhibithighsurfaceenergyandasubstantiallyhydrophilicnature,enablingeffective25 adhesionofaqueousinksandcoatings.Incontrast,theuntreatedside(backside)retainsits inherentlowsurfaceenergyandsubstantiallyhydrophobicproperties,ensuringminimal adhesionandcompatibilitywithwindingorstackingprocesses.Inordertopreventblocking,the surfaceenergyoftheprimer-treatedside(frontside)anduntreatedside(backside)ofthe substratemustdiffersufficiently.Furthermore,theadditionofinorganicfillerstotheprimer30 compositionintroducessurfaceroughness,whichreducesthenumberofcontactpointsand lowersadhesiveforces.Thisstructuralmodificationfurtherminimizestheriskofblocking, ensuringsmootherhandlingandstorageofthetreatedpolymericsubstrate.This,inturn, 2024 / 5923 BE2024 / 5923 24 minimizesblockingwhentheprimer-treatedsidecomesintocontactwiththeuntreatedside (backside)ofthesubstrate.

[0150] Thus,thecombinationofhighsurfaceenergyonthetreatedsideofthepolymeric substrateandlowsurfaceenergyontheuntreatedsideofthepolymericsubstrate,alongwiththe introductionofsurfaceroughness,mayeffectivelypreventblocking.5

[0151] Inanembodiment,theprimerlayermayhaveathicknessrangingoffrom1μmto50μm, 1μmto30μm,or1μmto20μm,or5μmto15μmwhenappliedtothepolymericsubstrate surface,preferablytothethermoplasticsubstratesurface,morepreferablytothePVCsubstrate surface.

[0152] Inanembodiment,thethicknessoftheprimercompositionwhenappliedonthe10 polymericsubstratesurfaceisbetween1μmand20μm,preferablybetween5μmand18μm, morepreferablybetween8μmand15μm,evenmorepreferablybetween9μmand13μm.

[0153] Inanembodiment,theprimercompositionhasasurfacetensionof20mJ / m²to80 mJ / m²at20°C,asmeasuredbyWilhelmyplatemethod.TheWilhelmyplatemethodcalculates thesurfacetension(γ)ofaliquidbymeasuringtheforce(F)exertedonaplatethatispartially15 immersedintheliquid.TheequationtodeterminethesurfacetensionusingtheWilhelmyplate methodis:γ=F / P⋅cosθwhere:γisthesurfacetensionoftheliquid(mN / m),Fistheforce measuredbythetensiometerastheplateiseitherimmersedinorwithdrawnfromtheliquid (Newtons),Pistheperimeteroftheplatethatcomesincontactwiththeliquid(inmeters(m)or centimetres(cm)),andθisthecontactanglebetweentheliquidandtheplate.TheASTM20 standardforthismethodisASTMD1331.

[0154] Inkandaprimersystem

[0155] Theprimercompositionofthepresentinventionisparticularlysuitableforusein combinationwithaqueousinkcompositions,enhancingtheiradhesionandperformanceon variouspolymericsubstrates.Theapplicationoftheaqueousinkcompositionontotheprimed25 polymeric(e.g.thermoplastic)substratefacilitatesthecreationofdecorativecoveringelements, includingbutnotlimitedtofloor,ceiling,andwallsurfacecoverings,aswellaslaminated flooringpanelsandtarpaulins.

[0156] Inafurtheraspectofthepresentinvention,thereisprovidedaninkandprimersystem forimageformationonathermoplasticsubstratesurfacecomprising:aprimercompositionfor30 surfacetreatmentofapolymericsubstratepriortoapplyinganaqueousinkcomposition,the primercompositioncomprisingatleastonepolymericbinder,atleasttwodistincttypesof inorganicfillers,whereineachinorganicfillercomprisesinorganicparticles;andwater;andan 2024 / 5923 BE2024 / 5923 25 aqueousinkcompositioncomprisingwaterandatleasttwodifferentwater-solubleorganic solvents,whereintheatleasttwodifferentwater-solubleorganicsolventareselectedfroma groupconsistingofalkyldiols,andwhereineachwater-solubleorganicsolventhasadistinct surfacetensionfallingintherangeoffrom10to80mN / mat20°C.

[0157] Further,theprimercompositionoftheinkandprimersystemdescribedabovemay5 comprisetwodistincttypesofinorganicfillers,denotedasafirstinorganicfillerandasecond inorganicfiller,whereinthefirstinorganicfillercomprisescalciumcarbonateparticles(chalkor microchalk)andthesecondinorganicfillercomprisesablendofsilicawith(lamellar)kaolinite.

[0158] Inthisinkandprimersystem,theprimercompositionandtheaqueousinkformulation aredesignedtoworksynergistically,ensuringreliableadhesion,sharpprintresolution,andlong-10 termdurability.Althoughinkjetordigitalprintingisthepreferredmethodforapplyingthe aqueousinkcompositionaspartofthedecorativelayer,alsoconventionalprintingmethodsmay beusedforapplyingtheaqueousinkcomposition.

[0159] Theapplicationoftheaqueousinkcompositionontotheprimedpolymeric,preferably thermoplastic,substratefacilitatesthecreationofdecorativecoveringelements,includingbut15 notlimitedtofloor,ceiling,andwallsurfacecoverings,aswellaslaminatedflooringpanelsand tarpaulins.

[0160] Theinkandprimersystemaccordingtothisaspectoftheinventionmayoptionally furthercompriseathirdwatersolubleorganicsolventselectedfromagroupconsistingofalkyl triolswithasurfacetensionfallingintherangeoffrom10to80mN / mat20°C.20

[0161] Theinkandprimersystemcanbeappliedtoapolymericsubstrate,specificallya thermoplasticsubstrateselectedfromthegroupconsistingofpolyvinylchloride,polyolefinor polyester,morepreferablyaPVCsubstrate

[0162] Also,thepresentinventionrelatestoanaqueousinkcompositionforforminganimage bymeansofdigitalprintingonapolymericsubstrate,wheretheaqueousinkcompositionisused25 incombinationwithaprimercomposition.

[0163] Inoneembodiment,theaqueousinkcompositionisappliedusingasingle-passprinting process,whichemployseitherasubstrate-widearrayofstationaryinkjetprintingheadsor multiplestaggeredinkjetprintingheadsarrangedtocovertheentirewidthofthesurface.Inthis process,theinkjetprintingheadsremainstationarywhiletheprimedsubstrateiscontinuously30 transportedbeneaththem.

[0164] Accordingtoanaspectofthepresentinventionforwhichprotectionissought,thereis providedanaqueousinkandprimersystemforimageformationonapolymericsubstratesurface 2024 / 5923 BE2024 / 5923 26 comprising:aprimercompositionfortreatingthepolymericsubstrate,whereintheprimer compositioncomprisesatleastatleastonepolymericbinder,atleasttwodistincttypesof inorganicfillers,whereineachinorganicfillercomprisesinorganicparticles,andwaterandan aqueousinkcompositionforimageformationonthepolymericsubstratetreatedwiththeprimer composition,whereintheaqueousinkcompositioncompriseswaterandatleasttwodifferent5 water-solubleorganicsolvents,whereintheatleasttwodifferentwater-solubleorganicsolvent areselectedfromagroupconsistingofalkyldiols,andwhereineachwater-solubleorganic solventhasadistinctsurfacetensionfallingintherangeoffrom10to80mN / mat20°C, preferablyoffrom15to75mN / mat20°C,morepreferably20to75mN / mat20°C.

[0165] Theaqueousinkcompositioncomprisesatleasttwodistinct(different)water-soluble10 organicsolvents,thatcanbedefinedasafirstwater-solubleorganicsolventandasecondwater- solubleorganicsolvent,andwhereineachwater-solubleorganicsolventmaydifferintermsof carbonchainlengthandmayincludedifferentsubstituents.

[0166] Inanembodiment,thealkyldiolsintheaqueousinkcompositionmayhavecarbonchain lengthsrangingfromC3toC8,preferablyC3toC6.15

[0167] Inanembodiment,theatleasttwowater-solubleorganicsolventshaveadistinctboiling pointfallingintherangeoffrom50°Cto450°Cat1atmosphere,morepreferably100°Cto350°C at1atmosphere.

[0168] Inanembodiment,theaqueousinkcompositioncomprisesoffrom5wt%to70wt%of atleasttwowater-solubleorganicsolvents,preferably10wt%to50wt%,morepreferablyof20 from20wt%to45wt%relativetothetotalweightoftheaqueousinkcomposition.

[0169] Advantageously,theaqueousinkcompositionmaycompriseatleasttwoalkyldiols, suchas1,2propanediol,1,3-propanediol,2-methyl-1,3-propanediol,1,2-butanediol,1,3- butanediol,1,4-butanediol,1,2-pentanediol,2,3-pentanediol,1,5-pentanediol,1,5hexanediol, 2,5-hexanediol,1,6-hexanediol,1,2-hexanediol,2,3-hexanediol,1,7-heptanediol,and1,8-25 octanediol.

[0170] Inanembodiment,thefirstwater-solubleorganicsolventis1,2-hexanediol.

[0171] Inanembodiment,thesecondwater-solubleorganicsolventisanalkyldiolwitha carbonchainlengthrangingfromC3toC4,suchas1,3-butanediol,1,2-propanediol,or2-methyl- 1,3-propanediol,preferably1,3-butanediol.30

[0172] Theaqueousinkcompositionofthepresentinkandprimersystemmayfurthercomprise athirdwater-solubleorganicsolvent.Thethirdwater-solubleorganicsolventcanbeselected 2024 / 5923 BE2024 / 5923 27 formthegroupconsistingofalkyltriols.Inanembodiment,thethirdwater-solubleorganic solventisglycerol.

[0173] Inanembodiment,theaqueousinkcompositionofthepresentinventioncomprises threedifferentwater-solubleorganicsolvents,eachidentifiedasafirst,second,andthirdwater- solubleorganicsolventsrespectively.Thethreewater-solubleorganicsolventsformasynergistic5 mixture,wheretheireffectsarebeingamplifiedoraltered,leadingtoenhancedsurfacetension reduction,wetting,andinkpenetrationcomparedtowhateachcompoundcouldachieve individually.

[0174] Inanembodiment,thereisprovidedanaqueousinkcompositionforimageformationon apolymericsubstrate,whereinthepolymericsubstrateissurfacetreatedwithaprimer10 compositionofthepresentinvention,whereintheaqueousinkcompositioncompriseswaterand threedifferentwater-solubleorganicsolvents,whereinthefirstandthesecondwater-soluble organicsolventsarealkyldiols,andthethirdwater-solubleorganicsolventisanalkyltriol,and whereineachofthefirst,secondandthirdwater-solubleorganicsolventshasadistinctsurface tensionfallingintherangeoffrom10to80mN / mat20°C.15

[0175] Inanembodiment,theaqueousinkcompositioncomprises1,2-hexanediolasthefirst water-solubleorganicsolvent,1,3-butanediolasthesecondwater-solubleorganicsolvent,and optionallyglycerolasthethirdwater-solubleorganicsolvent.

[0176] Further,theaqueousinkcompositionmaycompriseathirdwater-solubleorganic solventselectedfromagroupconsistingofalkyltriolswithasurfacetensionwithin10to8020 mN / mat20⁰C.Preferably,thethirdwater-solubleorganicsolventisalkyltriol,morepreferably thethirdwatersolubleorganicsolventisglycerol.

[0177] Inanembodiment,thereisprovidedanaqueousinkcompositionforimageformationon apolymericsubstrateaspartoftheinkandprimersystemofthepresentinvention,whereinthe polymericsubstrateistreatedwithaprimercompositionofthepresentinvention,whereinthe25 aqueousinkcompositioncompriseswaterandthreedifferentwater-solubleorganicsolvents, whereinthefirstandthesecondwater-solubleorganicsolventsarealkyldiols,andthethird water-solubleorganicsolventisanalkyltriol,andwhereineachofthefirst,secondandthird water-solubleorganicsolventshasadistinctsurfacetensionfallingintherangeoffrom10to 80mN / mat20°C.Further,inthisembodiment1,2-hexanediolisindicatedasafirstwatersoluble30 organicsolvent,1,3-butanediolisindicatedsecondwaterssolubleorganicsolvent,andglycerol isindicatedasathirdwatersolubleorganicsolvent.2024 / 5923 BE2024 / 5923 28

[0178] Inanembodiment,thereisprovidedanaqueousinkcompositionforimageformationon apolymericsubstrateaspartoftheinkandprimersystemofthepresentinvention,whereinthe polymericsubstrateistreatedwithaprimercompositionofthepresentinvention,whereinthe aqueousinkcompositioncompriseswater,1,2-hexanediol,1,3-butanediol,andglycerol.

[0179] Inafurtherembodiment,thereisprovidedanaqueousinkcompositionforimage5 formationonapolymericsubstrate,whereinthepolymericsubstrateistreatedwithaprimer compositionofthepresentinvention,whereintheaqueousinkcompositioncompriseswater, threewater-solubleorganicsolvents,aninkbinder,asurfactant,oneormorepigments,wherein thethreewater-solubleorganicsolventsare1,3-butanediol,1,2-hexanediolandglycerol.Further, inthisembodiment1,2-hexanediolisindicatedasafirstwatersolubleorganicsolvent,1,3-10 butanediolisindicatedsecondwaterssolubleorganicsolvent,andglycerolisindicatedasathird watersolubleorganicsolvent.

[0180] Theweightratioofglycerolto1,2-hexanediolbasedonthetotalweightoftheaqueous inkcompositionmaybebetween10:1to1:10,preferablybetween1:1and1:5.Inapreferred embodiment,theaqueousinkcompositionofthepresentinkandprimersystemcomprises115 wt%to3wt%glycerol,3wt%to5wt%1,2-hexanediol,and18to30wt%of1,3-butanediol,and therestwaterbasedonthetotalweightoftheinkcomposition.

[0181] Theaqueousinkcompositionmayfurthercompriseaninkcompositionbinder,a surfactant,oneormorepigments.Inanexemplaryembodiment,theinkcompositionbinderisan acrylicbasedbinder,suchasastyrene-acryliccopolymerdispersion.20

[0182] Inapreferredembodiment,theaqueousinkcompositionforimageformationona polymericsubstrate(e.g.PVC,polyester,orpolyolefin),thatistreatedwithaprimercomposition ofthepresentinvention,compriseswaterandthreedifferentwater-solubleorganicsolvents, whereinthefirstandthesecondwater-solubleorganicsolventsarealkyldiols,thethirdwater- solubleorganicsolventisalkyltriol,andwhereineachofthefirst,secondandthirdwater-25 solubleorganicsolventshasadistinctsurfacetensionfallingintherangeoffrom10to80mN / m at20°C,preferably15to75mN / mat20°C.morepreferablyoffrom20to75mN / mat20°C,even morepreferablyoffrom24to73mN / mat20°Candwhereintheaqueousinkcomposition comprisesrelativetothetotalweightofthecomposition,20wt%to40%byweightofwater- solubleorganicsolvents,8wt%to20wt%ofaninkcompositionbinder.Further,inthis30 embodiment1,2-hexanediolisindicatedasafirstwatersolubleorganicsolvent,1,3-butanediol isindicatedsecondwaterssolubleorganicsolvent,andglycerolisindicatedasathirdwater solubleorganicsolvent.2024 / 5923 BE2024 / 5923 29

[0183] Theaqueousinkcompositionoftheinkandprimersysteminthepresentinvetionmay haveaviscosityintherangeoffrom1.0cPto15.0cPat25°C,3cPto10cPat25°C,4.0cPto9.0 cPat25°C,4.0cPto8.0cPat25°C,4cPto7cPat25°C,4.1to6.6cPat25°C,preferably4.8to 6.1cPat25°C,morepreferably5to6.1cPat25°C,at25°C,asmeasuredbyAntonPaar viscometer,ASTMD7042.5

[0184] Theaqueousinkcompositionoftheinkandprimersysteminthepresentinvetionmay haveasurfacetensionintherangeoffrom15mN / mto45mN / mat25°C,morepreferably15 mN / mto43mN / mat25⁰C,15mN / mto40mN / mat25⁰C,18mN / mto38mN / mat25⁰C, 20mN / mto35mN / mat25⁰C,20mN / mto30mN / mat25°C,asmeasuredbyWilhelmyplate method.10

[0185] Theaqueousinkcompositionmaycompriseatleastonepigment.Pigmentssuitablefor beingusedarethosegenerallywell-knownintheartforaqueousinks.Theaqueousink compositionmaycompriseoneormorepigmentsforeachoftheCMYK(Cyan,Magenta,Yellow andblack)coloursandwithoutbeingparticularlylimitedtoanytype.

[0186] SomeexamplesofsuitablepigmentsarepigmentdispersionsthatcanincludeProJet15 ADP1000Black(CarbonBlack),ProJetADP1000Cyan(PigmentBlue15:3),ProJetADP1000 YellowLF(PigmentYellow155),ProJetADP1000Red(PigmentRed254)andProJetADP1000 Blue(PigmentBlue60)werealsoused.Pro-Jet®APD1000pigmentdispersionsareavailablefrom FUJIFILMImagingColorantsLimited.

[0187] Further,thepolymericsubstrateoftheinkandprimersystemcanbepreferablya20 thermoplasticsubstrateselectedformthegroupconsistingoffromthegroupconsistingof polyvinylchloride(PVC),polyolefin,polyester,polystyreneorpolyamide.Inanembodiment,the polymericsubstrateispolyvinylchloride(PVC).

[0188] Shapedarticle

[0189] Theinventionfurtherpertainstoashapedarticlecomprisingapolymericsubstrateand25 primercompositionaccordingtothepresentinvention,whereintheprimercompositionatleast partiallycoversthepolymericsubstrateandformsaprimerlayerupondrying.

[0190] Theprimercompositionoftheshapedarticlemaycomprisetwodistincttypesof inorganicfillers,afirstinorganicfillerandasecondinorganicfiller,whereinthefirstinorganic fillercomprisescalciumcarbonateparticles(chalkormicrochalk)andthesecondinorganicfiller30 comprisesablendofsilicawith(lamellar)kaolinite.Upondrying,thisprimercompositionformsa primerlayer.Thisprimerlayerhasapeelstrengthofatleast20N / 50mm,ensuringstrong adhesion,andasurfaceenergyofatleast30mJ / m²,whichfacilitatescompatibilitywiththe 2024 / 5923 BE2024 / 5923 30 aqueousinkcompositionorothercoatings.Additionally,theprimerlayerhasathicknessinthe rangeof1μmto20μm,preferablyintherangeof4μmto10μm.Optionally,ontopoftheprimer layer,adecorativelayercanbeappliedontoprovidecustomizabledesigns,colours,orpatterns, whereinthedecorativelayercomprisestheaqueousinkcompositionaccordingtothepresent invention.Further,awear-resistantlayercanbeappliedoverthedecorativelayer,offeringa5 protectionagainstabrasion,scratches,andotherformsofmechanicalwear.

[0191] Theshapedarticlemayalsoincludedesignflexibility,allowingittobeproducedin variousformssuchassheets,films,mouldedcomponents,orthree-dimensionalobjects.Its layeredconstructionensurescompatibilitywithprocesseslikethermoforming,injectionmolding, orlamination.10

[0192] Inanembodiment,thereisprovidedashapedarticlecomprising:apolymeric substrate,aprimerlayerappliedontothepolymericsubstrate,whereintheprimerlayer comprisestheprimercompositionhavingatleastonepolymericbinder,atleasttwodistinct typesofinorganicfillers,whereineachinorganicfillercomprisesinorganicparticles;andwater,a decorativelayerappliedontopoftheprimerlayer,whereinthedecorativelayercomprisesthe15 aqueousinkcomposition,whereintheaqueousinkcompositioncompriseswaterandatleast twodifferentwater-solubleorganicsolvents,whereintheatleasttwodifferentwater-soluble organicsolventareselectedfromagroupconsistingofalkyldiols,andwhereineachwater- solubleorganicsolventhasadistinctsurfacetensionfallingintherangeoffrom10to80mN / m at20°C,preferablyoffrom15to75mN / mat20°C,morepreferably20to75mN / mat20°C.20

[0193] Further,theaqueousinkcompositionmaycompriseathirdwater-solubleorganic solventselectedfromagroupconsistingofalkyltriolswithasurfacetensionwithin10to80 mN / mat20⁰C.Preferably,thethirdwater-solubleorganicsolventisalkyltriol,morepreferably thethirdwatersolubleorganicsolventisglycerol.

[0194] Further,thepolymericsubstrateusedintheshapedarticlesispreferablya25 thermoplasticsubstrateselectedformthegroupconsistingoffromthegroupconsistingof polyvinylchloride(PVC),polyolefin,polyester,polystyreneorpolyamide.

[0195] Theshapedarticlecanbeadecorativecoveringforwalls,floors,orceilingsor alternativecoverings.Itmayalsobeutilizedinoutdoorapplications,suchasprintedtarpaulins foradvertisementsorweather-resistantcovers.Otherexamplesincludecustom-printed30 laminatesforfurniture,automotiveinteriors,anddurablelabelsorsignageforindustrialuse.

[0196] Blockingtestandanalysis 2024 / 5923 BE2024 / 5923 31

[0197] Alaminatewasformedbysequentiallyapplyingaprimercompositionaccordingtothe presentinvention,anaqueousinkcomposition,andwear-resistantlayerontoathermoplastic substrate.Theprimercompositionwasappliedusingabarcoater(K-bar),achievingawetfilm thicknessofapproximately12µm.Theprimercompositionwasthendriedunderairventilation formingaprimerlayer.Aportionoftheprimedsubstratewasusedforperformingtheblocking5 test.

[0198] Fig.1showsamaineffectsplot(Y,X)(Yvs.X)illustratingtheresultsoftheblockingtest.

[0199] TheblockingtestwasperformedinaccordancewithISO24343-1.

[0200] WithreferencetoFig.2,thefollowingnumbersrepresent:1-acrylicself-cross-linking dispersion,2-polyurethanebinder(BaybondPU404),3-polyurethanebinder(DaotanVTW6421),10 4-boehmite,5-nofiller,6-blendofsilicaand(lamellar)kaoliniteparticles;Intheresults,ahigher valueontheY-axisindicatesbetterblockingresistance.Theresultsshowthatacrylicbinder1 achievesbetterblockingresistancecomparedtopolyurethanebinders2and3,asindicatedby thehighervaluesontheY-axis.Theadditionoftwoinorganicfillers(4or6)andcalcium carbonate(chalk)totheacrylicbinderalsodemonstratesapositiveeffectonblocking15 resistance.Theplotdemonstratesasynergisticeffectinenhancingblockingresistancethrough thecombinationofcalciumcarbonate(chalk)andablendofsilicawithkaolinite,orboehmite (aluminiumoxidehydroxide)particles,andalsoincombinationwiththeacrylicbinder.This improvementisattributedtothecreationofaroughersurfaceonthethermoplasticsubstrate.

[0201] Delaminationtest20

[0202] Alaminatewasformedbysequentiallyapplyingaprimercompositionaccordingtothe presentinvention,anaqueousinkcomposition,andwear-resistantlayerontoathermoplastic substrate.Theprimercompositionwasappliedusingabarcoater(K-bar),achievingawetfilm thicknessofapproximately12µm.Theprimercompositionwasthendriedunderairventilation formingaprimerlayer.Next,theaqueousinkcompositionwasappliedtotheprimed25 thermoplasticsubstrate(forexamplebyeitherusingaK-barorbydigitalprinting)resultingina wetfilmthicknessofapproximately6µm,followedbyair-drying.Finally,awear-resistantlayer wasappliedovertheink-coatedandprimedthermoplasticsubstratetocompletethelaminate.

[0203] Thelaminatewassubjectedtodelaminationteststoassessthebondingstrengthand durabilityofthelayeredstructureundervariousconditions.30

[0204] Fig.3demonstratesthattheuseofacrylicbinder1resultsinhigherdelamination comparedtopolyurethaneresins1and2.However,thedelaminationobservedwithacrylic binder1significantlydecreaseswheninorganicparticlessuchasboehmite4,orablendofsilica 2024 / 5923 BE2024 / 5923 32 andkaoliniteparticles6areincorporatedintotheprimercomposition.Thedelaminationis furtherreducedwhencalciumcarbonate(chalk)isaddedtotheacrylicbinderintheprimer composition.

[0205] Fig.3showsamaineffectsplot(Y,X)fordelaminationresultsofthetestwithdifferent binderandinorganicfillers.AhighervalueontheY-axisindicateslowerdelaminationorahigher5 peelstrength;

[0206] Withreferencet.