PolySurF™Functional MonomersRadiation Curing Additives

for tomorrow’sTechnology

for tomorrow’sWorld

C H = C - C - O - - O - P - O H

OO

CH OR

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Chemicals BV

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Contents

1. Introduction 32. Properties 4 2.1 ADDAPT® PolySurF™ HP 4 2.2 ADDAPT® PolySurF™ HEOP 5 2.3 ADDAPT® PolySurF™ HPH 6 2.4 ADDAPT® PolySurF™ HPL 7 2.5 ADDAPT® PolySurF™ ACE 83. Application 9 3.1 Emulsion Polymerisation 9 3.1.1EmulsifiersandStabilisers 9 3.1.2PolySurF™–advantagesinEmulsionPolymerisation 9 3.1.3 Corrosion Resistant Primer Emulsion 10 3.2RadiationCuring 11 3.2.1RadiationCurableMetalandPlasticcoatings 11

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1. Introduction

Thereisanincreasingdemandforthedevelopmentanduseofenvironmentalfriendlierrawmaterialsandproductsduetolegislationand,eversoimportant:customerdemand.

Thecompositionanduseofsolventbasedproductssuchaspaint,adhesivesandprintinginkshasalreadychangeddramaticallybutneedfurtherchangesincomingyears.Thedemandfornew,environmentalfriendliersystemsisthereforestrongerthanever,notonlybasedonecologicalreasonsbutalsoduetoincreasingqualitydemand.

Ithasbeenshownthatasolutionforbothproblemsispossible:newwaterbasedsystemshavinglowornoemissionofvolatilematerialsshowingperformancematchingtheclassicsolventbasedsystems.Mainpartofthissuccesscanbeattributedtoanewgenerationofadditivesallowingmoreformulationfreedom.

ADDAPTChemicalsoffers,amongstother,anewgenerationoffunctionalmonomers/additivesforuseinemulsionpolymerisationoruseasadditivesinUV/EB-curablesystems.

ThisbrochuregivesanoverviewoftheADDAPT®PolySurF™productsforuseasadhesionpromoters,polymerisablestabilisers,polymerisableplasticizerandpolymerisablewettingagents.

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2. Properties

2.1 ADDAPT® PolySurF™ HP R=H

O O || || CH2 = C – C – O - - O - P - OR | | CH3 OR = Hydrophobic group

Av. Molecular Weight: 250

Suggested applications:

• RadiationCurablesystems.• Co-monomerinPolyAcrylicPigmentDispersants.• PolymerisableStabiliserforEmulsionPolymerisationProcesses.• Suggestedend-use:

Paints&Coatings(primers;wet-scrubimprovementofemulsionsetc.)Adhesives&BondingAgentsPigmentDispersantsPrintedCircuitBoard(PCB)–SolderMasks&EtchresistfilmPhotographicFilmDetergents&CleanersRadiationCurableMetalprimersandfinishesSuperabsorbents

Product benefits:

• ExcellentMechanicalStability–NonMigratory(EmulsionPolymerisation).• ExcellentPolyvalentcationtolerance(Ca2+etc.).• Improvedpropertiesover(Meth)acrylicacidinEmulsionPolymerisation.• Highlyreactive–goodcompatibilitywithAcrylicandMethacrylicesters.• ExcellentAdhesionPromotertoallmetalsubstrates,metal-oxides,glass,ceramicsand

concrete.• Impartsverygoodcorrosioninhibitingpropertiesafterpolymerisation.• GivesflameretardantpropertiesduetothePhosphorcontent.

Note: ADDAPT® PolySurF™ HP is not a surfactant and as such has no HLB-value.

Typical chemical and physical characteristics:

Appearance Clearliquid

Odour Sweetsmell

Viscosityat25ºC 1250 - 3500 mPa.s

Colour max.4Gardner

pH 0.5 to 3.0

Phosphorecontent ca.12%

Activecontent >99.5%

2.1 ADDAPT® PolySurF™ HEOP R=H

O O || || CH2 = C – C – O - - O - P - OR | | CH3 OR = 3.5 > EO < 4.5

Suggested applications:

• RadiationCurablesystems.• PolymerisableStabiliserforEmulsionPolymerisationProcesses.• Suggestedend-use:

Paints&Coatings(primers;wet-scrubimprovementofemulsionsetc.)Adhesives&BondingAgentsPigmentDispersantsPrintedCircuitBoard(PCB)–SolderMasks&EtchresistfilmPhotographicFilmDetergents&CleanersRadiationCurableMetalprimersandfinishesSuperabsorbents

Product benefits:

• ExcellentMechanicalStability–NonMigratory(EmulsionPolymerisation).• ExcellentPolyvalentcationtolerance(Ca2+etc.).• Improvedpropertiesover(Meth)acrylicacidinEmulsionPolymerisation.• Highlyreactive–goodcompatibilitywithAcrylicandMethacrylicesters.• ExcellentAdhesionPromotertoallmetalsubstrates,metal-oxides,ceramicsand

concrete.• Impartsgoodcorrosioninhibitingpropertiesafterpolymerisation.• Impartsfreeze/thawstability.

Typical chemical and physical characteristics: Appearance Clearliquid

Odour Sweetsmell

Viscosityat25ºC < 2000 mPa.s

Colour max.4Gardner

pH(1%solution) 1.6 to 2.0

Phosphorecontent 10.5%

Activecontent >99.5%

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2.3 ADDAPT® PolySurF™ HPH R = - (CH2 CH2O)10

O O || || CH2 = C – C – O - - O - P - OR | | CH3 OR = Hydrophobic group

Suggested applications:

• RadiationCurablesystems.• Co-monomerinPolyAcrylicPigmentDispersants.• PolymerisableStabiliserforEmulsionPolymerisationProcesses.• Suggestedend-use:

Paints&Coatings(Woodfinishes;Metalcoatings;MirrorBackingFilms)Adhesives&BondingAgentsPigmentDispersantsPrintedCircuitBoard(PCB)–SolderMasks&EtchresistfilmPhotographicFilmDetergents&CleanersRadiationCurableMetalprimersandWoodfinishes

Product benefits:

• ExcellentMechanicalStability–NonMigratory(EmulsionPolymerisation).• ExcellentPolyvalentcationtolerance(Ca2+etc.).• Improvedpropertiesover(Meth)acrylicacidinEmulsionPolymerisation.• Highlyreactive–goodcompatibilitywithAcrylicandMethacrylicesters.• VeryGoodAdhesionPromotertoallmetalsubstrates.• Impartsverygoodcorrosioninhibitingpropertiesafterpolymerisation.• ImproveswettingonmetalandwoodsubstratesinRadiationCurableSystems.

Note: ADDAPT® PolySurF™ HPH is not a surfactant and as such has no HLB-value.

Typical chemical and physical characteristics:

Appearance Clearliquid

Odour Sweetsmell

Viscosityat25ºC < 350 mPa.s

Colour max.2Gardner

pH < 3.0

Phosphoruscontent ca.6.5%

Activecontent >99.5%

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2.4 ADDAPT® PolySurF™ HPL R = - (CH2)10-12

O O || || CH2 = C – C – O - - O - P - OR | | CH3 OR = Hydrophobic group

Suggested applications:

• RadiationCurablesystems• Co-monomerinPolyAcrylicPigmentDispersants• PolymerisableStabiliserforEmulsionPolymerisationProcesses• Suggestedend-use:

Paints&CoatingsAdhesives&BondingAgentsPrintedCircuitBoard(PCB)–SolderMasks&EtchresistfilmPhotographicFilmRadiationCurableMetalprimersandfinishes

Product benefits:

• ExcellentNonMigratoryPlasticizer• Highlyreactive–goodcompatibilitywithAcrylicandMethacrylicesters• VerygoodAdhesionPromotertoallmetalsubstrates• VerygoodCorrosionInhibitorforMetalpastes(BronzeandAluminiumpastes)• Impartsverygoodcorrosioninhibitingpropertiesafterpolymerisation.

Typical chemical and physical characteristics:

Appearance Clearliquid

Odour Sweetsmell

Viscosityat25ºC 50 - 300 mPa.s

Colour max.2Gardner

pH 0.5 to 2.0

Phosphoruscontent ca.10%

Activecontent >99.5%

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2.5 ADDAPT® PolySurF™ ACE

O OH || | CH2 = CH – C – O - CH2 – CH – Versatic Acid

Suggested applications:

• RadiationCurablesystems.• Co-monomerinPolyAcrylicPigmentDispersants.• Co-monomerforEmulsionPolymerisationProcesses.• Suggestedend-use:

Paints&Coatings(Woodfinishes,Automotivefinishes)Adhesives&BondingAgentsPigmentDispersantsPrintedCircuitBoard(PCB)–SolderMasks&EtchResistfilmRadiationCurablefinishes

Product benefits:

• PolymerisableMonomerwithexcellentpigmentwettingproperties.• ADDAPT®PolySurF™ACEimprovesadhesiontoPolyolefin’s,PolyethyleneTherephtalate

andPolyvinylchloride.• ImpartsHydrophobicpropertiesinEmulsions.• Highlyreactive–goodcompatibilitywithVEOVA,Styrene,Acrylic,andMethacrylicesters.• GoodAcidresistance.• Containsareactivesec.OH-groupforimprovedintercoatadhesion.• ImpartsgoodUVstabilityinresinsafterpolymerisation.

Typical chemical and physical characteristics:

Appearance Clearliquid

Odour Acidicsmell

Viscosityat25ºC < 300 mPa.s

Colour max.2Gardner

pH 2.5 to 4.5

Tgofhomopolymer 0 °C

Activecontent >99.5%

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3. Application

3.1 Emulsion PolymerisationNaturallatexeshavebeenusedformanycenturies.Infact,syntheticrubberlatexes,whichwereamongthefirstcommercialproductsofemulsionpolymerisationprocesses,becameimportantasasubstitutefornaturalrubber.

Modernsyntheticlatexesfindapplicationascoatings,printingink,(pressuresensitive)adhesives,bindersinpaper,papercoatingandtextileproducts,medicalproductsandmanyotherareas.Theseproductsarenormallymarketedandusedinlatexform.Otherproductssuchaselastomersandengineeringplasticsareseparatedfromtheaqueousphasepriortouse.

Emulsionpolymersareproducedinawidevarietyofprocesses.Conventionalemulsionpolymerisationinvolvesthedispersionofanorganicmonomerinanaqueousphasewithanoil-in-wateremulsifierfollowedbypolymerisationwithafree-radicalinitiatorthatisnormallywater-soluble.Theproductisacolloidaldispersionofpolymerparticlescalledlatex.Thetermslatex,polymercolloidandemulsionpolymerareusedsynonymouslyinthisarticle.

Ingredientsforatypicalemulsionpolymerisationsysteminclude:

• Water–thecontinuousphase• Emulsifiers and Stabilisers• Monomer or Monomer Mixture• Initiator system• Minoringredients–additives(Defoamer,Biocideetc.)

ThechoiceofEmulsifiers,Stabilisers,monomersandcombinationsthereof,togetherwiththeinitiatorsystemwill,toalargeextend,determinetheend-propertiesoftheresultingpolymerlike:filmformation,flexibility,watersensitivityetc.

3.1.1 Emulsifiers and StabilisersEmulsifiers(surfactants)andStabilisersareusedinemulsionpolymerisationtooptimisecolloidalstabilityoftheemulsionduringpolymerisation,storageandapplicationincludingoptimisationofthefilmformationprocess.

Traditional Surfactantsincreasewatersensitivityofthefinalfilmduetosurfactantmigration(blooming)towardsthefilmsurface.Polymeric Surfactantswerelaunchedtoestablishanirreversibleabsorbedprotectivelayertotheparticlesurface.Althoughslow,migrationofthesesurfactantsishoweverstilllikelytooccur.Alsoincertaincasesthesepolymericsurfactanthavethetendencytore-emulsifyand/orgiverisetoanundesirablecontinuousplaticizingorsofteningeffect.

InadditiontoEmulsifiers,StabiliserslikeAcrylicacid,MethacrylicacidandItaconicacidareusedtofurtheroptimisethestabilityoftheemulsion.Majordrawbacksareincreasedwatersensitivity,poorpolyvalentcationstabilityandincaseofAcrylicacid,homo-polymerisationleadingtohighlywatersensitivepolyacrylatesoligomers.

3.1.2 PolySurF™ – advantages in Emulsion PolymerisationTheHydrophobicmoietynexttothePhosphonateinthePolySurF™productspreventsundesirablesaponificationassometimesobservedinSulfonatecontainingalternatives.

AsapolymerisableStabiliser,thePolySurF™HPachievesexceptionalmechanicalstabilityinemulsioncoatings.Itbecomesanintegralpartofthefilm,resistingleaching.Itimprovesadhesiontometalsurfacesandgivesanti-corrosionproperties.ItisanexcellentalternativeforAcrylicacid,improvingthetolerancetowardsCa2+-ions.

PolySurF™ HPHfunctionsasanethoxylatednon-ionicstabiliserrecommendablefornon-ionicstabilisedemulsions.Nexttobeingaverygoodadhesionpromoterformetalsurfaces,italsogivesverygoodwettingofmetalandwoodsurfaceswhenincorporatedintotheemulsionpolymer.

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PressureSensitiveAdhesivesforinstancehavebeennegativelyaffectedbythemovetowardswaterbasedformulations.Pooreradhesionwasattributedtothemigrationofsurfactantsintheemulsioncausingfailurebetweenadhesiveandsubstrate.IncorporationofPolySurF™HPHcouldovercomesuchproblems.

PolySurF™HPLcanbeusedasapolymerisableplasticizerviaemulsionpolymerisation.Becominganintegralpartofthefinalpolymer,nomigrationwilloccur.PolySurF™HPLcanalsoberecommendedforproductionofPVCviaemulsionpolymerisation.

3.1.3 Corrosion Resistant Primer Emulsion Description:VEOVA/AcrylatecopolymeremulsionshowinganexcellentlevelofsaltsprayresistancewhenformulatedinCorrosionResistantPrimers.

Number Amount (Kg) Raw materialInitial reactor chargeNo.1 1000.0 WaterdemiNo.2 200.0 ADDAPT®PEX™136(SeeNote1)No.3 7.0 ADDAPT® PolySurF™ HPNo.4 10.0 AmmoniumHydroxide25%No.5 2.0 PotassiumPersulphateNo.6 154.0 Waterdemi

Monomer pre-emulsionNo.7 1200.0 VEOVA 10No.8 600.0 MethylMethacrylateNo.9 140.0 ButylAcrylate(or2-EthylhexylAcrylate)No.10 200.0 ADDAPT®PEX™136(SeeNote1)No.11 8.0 PotassiumPersulphateNo.12 14.0 ADDAPT® PolySurF™ HPNo.13 20.0 Acrylicacid(SeeNote2)No.14 953.0 WaterDemiNo.15 4.0 ProxelXL2(oridentical)ex-ZenecaNo.16 21.4 AmmoniumHydroxide25%

Note1: ADDAPT®PEX™136,10%aqueoussolution,pH=9 Alkylethoxylatephosphateester(ADDAPTChemicalsBV)Note2: Dependingonstabilityandgritformation,ifpossibleavoidusageandsubstituteby

PolySurF™ HP.

ProcedureI. Charge(1)tothereactorandheatto80°Cunderaflowofnitrogen.II. Dissolve(2),(3),(4)and(5)inwater(6)andchargetothereactor.Meanwhilethe

reactorispurgedwithnitrogen.

III. Whenthetemperaturereaches80ºCagain,thenitrogenflowisstopped.IV. Mix(7),(8)and(9)andaddunderstirring(10),(11),(12),(13)and(14)untilastable

pre-emulsionisobtained.V. Add2.5%(volume)ofthispre-emulsiontothereactor(seed).VI. Afteraperiodoffiveminutes,theremainingpre-emulsionisaddedtothereactor

during3hoursat85ºC.VII. Afterdosage,keepthetemperatureat85°Cfortwohours.VII.CooldowntoT<30°Candadd(15)and(16).

PropertiesSolidcontentMFFTpHEmulsionViscosityEmulsion

45.0±0.5%15ºC8.0 ± 0.5450±75mPa.s(Brookfield)

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3.2 Radiation Curing

AdhesiontometalsandplasticsurfacesremainachallengingproblemofformulatorsofUV/EBcurablesystems.Inmanycases,thesesubstratesmustbecleanedorpre-treatedtoremoveresidualdirt,oiloroxidationresiduesthatexistsonthesurface.

Soiledsurfaceswillalsogivepoorwettingofthesurfacetherebynegativelyinfluencingadhesionandgiverisetosurfacedefectsofthefinalcoating.

Formulationsarethereforeaimedtodevelopsystemswhichnotonlywetthesurface,butuponcuring,exhibitlowshrinkagetominimizestressandtooptimisebondformationwiththesurfaceofthesubstrate.Althoughaproperchoiceoftheoligomerssystemplaysanimportantrole,useoffunctionaladditiveslikePolySurF™-productscanbringthefinaldesiredproperties.

Inparagraph3.2.1sometypicalformulations,usingPolySurF™productsasadditive,areshown.

3.2.1 Radiation Curable Metal and Plastic coatings

UV curable coating for Polycarbonate

1 SARTOMER,2CIBAadditives

UV curable clear coating for Aluminium

1 COGNIS-RCC13-429,2 CIBAadditives,3 BASF

Further formulations are available upon request.

The information in this bulletin is believed to be accurate, but all recommendations are made without warranty since the conditions of use are beyond ADDAPT Chemicals BV control. The listed proper-ties are illustrative only, and not product specifications unless stated otherwise. ADDAPT Chemicals BV disclaims any liability in connection with the use of information, and does not warrant against in-fringement by reason of the use of its products in combination with other material or in any process.

Component %Tris(2-Hydroxyethyl)IsocyanurateTriacrylate(SR-368)1 35.0 1.6HexanediolDiacrylate 29.0 PentaerythritolTetraacrylate 29.0 ADDAPT® PolySurF™ HPL 2.0 Darocure11732 3.0 Irgacure1842 2.0

Component %PolyesterAcrylateOligomer,lowMw.(1000)1 26.0ADDAPT® PolySurF™ HP 1.0ADDAPT® PolySurF™ HPH 2.0PHOTOMER® 40281 10.0PHOTOMER® 40391 20.0PHOTOMER® 40721 33.0PHOTOMER® 811 3.0Darocur11732 3.0Triethanolamine3 2.0

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CONTACT INFORMATION

ADDAPT Chemicals B.V.

Speltdijk15704RJHelmondTheNetherlands

Tel.:+31(0)492597575Fax: +31(0)492552955

E-mail:info@addapt-chem.comhttp://www.addapt-chem.com

LiabilityAll recommendations for the use of our products, whether given by us in writing, oral, or to be implied from the results of tests carried out by us, are based on the current state of our knowledge. Under no circum-stances shall Seller be liable for incidental, consequential or indirect damage for alleged negligence, breach of warranty, strict liability, tort or contract arising in connection with product(s). Seller’s sole liability for any claims shall be Buyer’s purchase price. Data and results are based on controlled lab work and must be confirmed by Buyer by testing for its intended conditions of use. The product(s) has/have not been tested for, and is/are therefore not recommended for, uses for which prolonged contact with mucous membranes, abraded skin or blood is intended, or for uses for which implantations within the human body is intended.

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