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SpeedofSettingandFilmFormationinWaterborneEmulsionAdhesives

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Speed of Setting and Film Formation in Waterborne Emulsion Adhesives


SpecialChem/Jun22,2005

EdwardM.Petrie,MemberofSpecialChemTechnicalExpertTeam

Introduction
MajorTypesofWaterborneAdhesives
TheUnexpectedCharacteristicsofWater
MechanismofFilmFormation
VariablesthatAffectDryingTime
Conclusion
Introduction

Theuseofwaterborneadhesives,especiallysyntheticemulsions,hasgrownenormouslyinrecenttimes.Thishasbeendrivenprimarilybytheneedtofindalternativesforsolventbasedadhesi
adverseenvironmentalconsequences.Otheradvantagesofwaterborneemulsionadhesivesincludetheiradhesiontoawidevarietyofsurfaces,rapidsettingspeedabilitytoadjustresistanceto
solventgoodmachiningpropertiesandeaseofcompounding.

Many polymers can be used in manufacturing waterborne emulsion adhesives with various balances of strength and flexibility. Thermoplastic polymers such as acrylic, vinyl acetate, an
copolymers make up a significant portion of this market. However, certain elastomers such as styrene butadiene rubber, neoprene, and polyurethane are also employed. Even waterborne ep
compete for certain niche applications. 1 The major submarkets for these types of adhesives are packaging and converting, followed by textiles, woodworking, building and construction, tran
consumer.

Althoughsyntheticadhesivebasedonwaterborneemulsionsareproducedinlargequantitiesandusedinawidevarietyofapplications,manyaspectsoftheirformulationandapplicationsuc
settingandfilmformationremainsomewhatofamystery.Thespeedatwhichtheseproductslosetheirwaterandformapractical,continuousadhesivefilmisveryimportantincertainhighvo
applicationssuchastextilemanufactureandpackaging.However,thisprocessisnotwellunderstoodandattemptstooptimizetherateofdryingareoftenunsuccessful.

Thisarticlewillconcentratemainlyonthemorepopularandhighervolumeemulsiongradesofwaterborneadhesives.Themechanismoffilmformationwillbedescribedandseveralfactorsth
influence setting speed and the rate of film formation will be reviewed. This includes factors such as the presence of certain additives, the latex particle structure, and the ambient conditions
conversionoftheproductfromabulkliquidintoacontinuousfilm.

MajorTypesofWaterborneAdhesives

Therearebasicallytwotypesofwaterborneadhesivessolutionsandemulsions.ThedefinitionsarepresentedinTable1.Specifictypesofsyntheticorganicresinsthatcanbeformulatedinto
andwaterdissolvedcoatingsareshowninTable2.Manybutnotalloftheseresinswillmakegoodadhesives.Thereareasurprisingnumberofsyntheticresinsthatcanbedispersedinwater,an
dispersedordissolvedinwaterdependingontheirmolecularweight,crosslinking,etc.
Type

Definition

CharacteristicsFlat

Lowsolidsconcentrationslowsettinglow
cost
Atwophasesystemconsistingofpolymerparticles(generallyabout0.11.0micronin
highsolidsconcentrationfastsetting
Emulsion
diameter)suspendedinwater
relativelyhighcost

Table1:MajorTypesofWaterborneAdhesives
Solution Asinglephasesystemconsistingofapolymer(<0.001micron)dissolvedinwater

Viscosity
Thick,syrupyviscositydependenton
molecularweight
Lowviscosityliquidindependenton
molecularweight

Molecular
Weight
5,00010,000
100,000
1,000,000

Bothsolutionandemulsionadhesivesbondviasimilarprocesses.Theyareappliedasaliquidandflowtowetoutthesubstrate.Theythengainviscosityandbondstrengthondrying.Theyca
liquidstotwoporoussubstratesandallowedtodryoncethesubstratesarematedaprocesscalled"wetbonding".Orelsetheycanbeappliedtothesubstrateanddriedintoasolidorsemis
adheresviapressureorcontact(pressuresensitiveandcontactadhesives),heat(laminatingadhesives),orchemicalactivation(e.g.,epoxy,polyurethane).
WaterDispersible
WaterSoluble
Acrylics
Acrylics
Alkyds
Alkyds
Bituminous
Ureaformaldehyde
Cellulosenitrate
Melamineformaldehyde
Celluloseacetate
Methylcellulose
Cellulosebutyrate
Hydroxylethylcellulose
Ethylcellulose
Carboxymethylcellulose
Epoxy
Phenolic
Fluorocarbons
Polyester
Hydrocarbon
Polyvinylalcohol
Neoprene(Polychloroprene)
Phenolic
Polyamide
Polyester
Polyethylene
Polyurethane
Polyvinylacetate
Styrenebutadiene

Table2:MajorSyntheticResinsUsedinWaterSolutionandEmulsionAdhesives

Certainadhesivecanbedriedcompletelyforshippingandstorageandthenremoistenedwithwaterorsolventatthetimeofapplicationtoprovideforpolymerflowandbondstrength.Thesearege
toasremoistenableadhesiveandarecommonlyusedontapes,labels,envelopes,anddecorativestickers.

Solutionwaterbasedadhesivesareusuallylowsolids,lowcostmaterialsthatarehydrophilicorwaterloving.Naturalpolymersthatareusedassolutionadhesivesincludestarch,dextrin,andca
polymersusedassolutionadhesivesincludepolyvinylalcoholandcertaincellulosics.Becausetheyhavesuchanexcellentaffinityforwater,thesesolutionpolymersreleasewaterveryslowly.A
aregenerallyslowersettinganddryingthantheiremulsionbasedcounterparts.

Ontheotherhand,emulsionadhesivesarehighsolidsandfastersettingbecausethepolymerisnotdissolvedinwaterbutmerelydispersed.Emulsionadhesiveformulationscontainlesswater
adhesivesandthewaterthatispresentisnotwellheldintheformulation.Asaresultemulsionsgenerallysetfasterthandosolutionadhesiveswhetherappliedonporousornonporoussubstrates

Becauseoftheneedtomaintainastableemulsionthatwillnotcoagulateorsettlewithtime,theformulationofanemulsiontypeofadhesivesystemcanbecomefairlycomplicated.Bytheirph
emulsions are sensitive to mechanical stresses, chemical phenomena, and temperature changes. However, these factors can be taken into account in their formulation and production. Comm
emulsionadhesivethereforeincludesurfactants,protectivecolloids,andthickeners.Solutionbasedwaterborneadhesivesontheotherhandarerelativelysimpletoformulate.

Becauseofthenecessityforadditivesandthecharacteristicsoftheemulsionpolymerizationprocess,emulsionadhesivesgenerallyhaveahighermaterialcostperkilogramofresin.However,th
bythefactthattheemulsionadhesiveformulationshaveagreaterconcentrationofpurepolymer.Becauseoftheirfastsettingcapabilityandhighsolidsconcentration,emulsionadhesivesare
higherinproductivitythansolutiontypes.

TheUnexpectedCharacteristicsofWater

Although low in molecular weight, water has a depressed vapor pressure. This strongly suggests that water's evaporation rate will be slow relative to most solvents utilized in solvent bo
EvaporationrateofwatercomparedwithvarioussolventsatambientconditionsaregiveninTable3.
Material

RelativeEvaporation BoilingPoint
Rate(1=fastest)
C

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SpeedofSettingandFilmFormationinWaterborneEmulsionAdhesives
Ethylether
Ethylacetate
Ethylalcohol
Methylethylketone
Water
Toluene
Butanol
Xylene
Cyclohexanone
Benzylalcohol

1
2.7

35
77

78

2.7
3040
4.5
20
9
22
500

80
100
110
119
142
156
200

Table3:RelativeEvaporationRateandBoilingPointsofVarious
SolventsComparedtoWater

Becausewaterisahydroxyloralcoholtypeofcompound,wemightexpectittohaveaboilingpointofabout65C.However,becauseofitsextremelyhighpolarity,ithasaconsiderablyhigh
100C.Thisprovideswaterwithsomeveryunexpectedcharacteristicsthatmustbetakenintoaccountwhendryingwaterbasedadhesives.Forexample,toluene,whichhasaslightlyhigherb
water,willevaporateinabout1/10thetimeofwater.

Theevaporationrateofwaterisgovernedbytemperature,therelativehumidity,andflowrateofairacrossthewater'ssurface.Atafixedtemperatureandflowrateofair,theevaporationofw
functionofrelativehumidityvaryingfromzeroat100%RHtoamaximumat0%RH.

Asaresultoftheincreasingcapacityforwatervapor,theevaporationrateofwaterincreasessharplywithincreasingtemperature.Higherairspeedsignificantlyincreasestheevaporationofw
mediumrelativehumidityyetastheairreachessaturation,theevaporationofwaterapproacheszeronomatterwhattheairspeed.

Theneedforadditionalenergyand/ortimetodrywaterbornecoatingsisoneofthemajordrawbacksofswitchingfromasolventbasedtoawaterborneadhesive.Asaresultsignificanteffortha
todeterminethemechanismofdryingandpossibleoptimizationstrategies.
Otherseriousdisadvantagesofearlywaterborneadhesivecoatingsincludethefollowing:
Corrosionofovens,dryingtowers,etc.duetowatervapor
Poorerperformanceoncecured,especiallyinmoistenvironments,duetothenatureofthebasepolymerandtheadditivesemployedinthewaterborneformulation
Freezinganddestabilizationofstoredproductduetoexposuretolowtemperatures.
Modernwaterborneadhesiveformulationshaveprovidedsignificantstridesinovercomingthelasttwoobjectivesandplacingwaterborneadhesivesystemsonaparwithsolventbornesystems.

MechanismofFilmFormation
Therearethreeprimaryphysicalprocesses,orstages,thatoccurduringfilmformationofawaterborneemulsionadhesive:
Evaporationofwaterandparticleordering
Particledeformationand
Interdifusionofpolymersacrossparticleparticleboundaries.

Theseprocessesareoftencombinedandsummarizedas"drying"and"fusion".Thekineticsofdryingversusthekineticsoffusionwillultimatelydeterminethespeedofformationandthequalityo

Anadhesivecoatinggoesfromonestagetotheotherviatheseprocesses:fromacolloidaldispersionofparticlesinwatertoaclosepackingofparticlestoadenselypackedarrayofdeforme
finallytoacontinuousmaterial.ThesestagesareillustratedinFigure1.

Figure1:Waterborneemulsionfilmformingstages.

Eachstagerequirestimeandisaffectedbythechemistryoftheadhesivesystemaswellastheambientconditionsatthetimeofcoating.However,theinitialstageisthelongestofthethreean
polymerhasreachedapproximately6070%volumefraction(Figure2).Thisarticlewillconcentrateonthedryingprocesssinceitwilloftendeterminetherateatwhichtheproductionoperationca
inapracticalshopenvironment.

Figure2:Schematicplotofwaterlossoccurringonemulsion
drying.3

The term drying generally refers to the evaporation of water and particle ordering (the first physical process noted above). However, "drying" can also refer to oxidative or chemical crosslin
adhesivesusethismechanismtospeedsetandimprovethefinalphysicalpropertiesoftheadhesive.Thisarticlewillnotconsidercrosslinkingsystems,so"drying"willonlybeusedtodenotelos

VariablesthatAffectDryingTime

Anumberoffactorshavebeenstudiedtodeterminetherateatwhichawaterborneadhesivedriesandgainsbondstrength.Manyofthesestudieshavefocusedondevelopinganoptimizedform
processthatwillenablerapidlymovingandprofitablecoatinglines.
Inactuality,onlyseveralfactorshaveexperimentallybeenshowntoinfluencedryingandfilmformation:

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SpeedofSettingandFilmFormationinWaterborneEmulsionAdhesives
Theambientconditions
Thepresenceofcertainsurfactantsandotheradditives
Thelatexparticlestructure.

Thesefactorsarediscussedbelow.
AmbientConditions

The effect of ambient conditions on drying has been summarized above. A quantitative investigation of the parameters on the drying of waterborne coatings show that the relative humidity
temperatureareofspecialsignificance,whiletheairrateandvariationofthewatersolventratiomakeonlyarelativelysmallcontributiontothedryingbehavior.Table4givesaquantitativeco
effectsoftheseparameterswithinthevariousrangesthatwereinvestigated.
Parameter

RangeInvestigated

Relativehumidity,%
Temperature,C
Airspeed,l/min
Watercontent,%
Other

1090
2040
1030
60100

EffectonEvaporationRate
%
60.2
20.2
1.6
<0.1
10.2

Table4:RelativeEffectsofParametersontheEvaporationTimeofPolymerWaterMixtures.2

Adhesivecoatingsfromemulsionscanbedriedathighertemperaturesandathigherheattransferratesthanthesolventbasedadhesivecoatings,althoughitisadvisabletokeepthetempera
stagesofdryingbelow100C.Manyemulsionadhesivesarecurableatelevatedtemperatures,andthelastdryingzonescanbeutilizedtocrosslinkthepolymer.

Thecombinationofhotairandinfraredradiationarewellsuitedfortheaccelerateddryingofwaterborneadhesivesandcoatings. 4Thisisprobablythemosteffectivevariationinformulationorpr
a large improvement in speed. The hot air primarily affects the coating surface while the IR radiation, depending on the wavelength can penetrate into the deeper layers of the coating.
favoredevaporationofwatercanbeachievedthroughirradiationintheOHbandregion.

Twosideddryinghasalsobeenshowntomaximizeheattransfer,controldryingrateandgivethewebuniformenergy.5Theaddedevaporationfromthewebsideimprovesthetotalevaporationra
theearlystagesofdrying.

Frequentlyadhesivesmustbedevelopedspecifictotheconvertingprocessemployed.Thenatureofthebondingprocessissospecificduetomachine,substrate,andclimatevariations,thatadh
developedespeciallyforacertaincombinationofprocessesandsubstrates.Acrylicemulsionpressuresensitiveadhesives,forexample,canbeutilizedtodayonvariousrollandextrusioncoatin
speedrequirementswillbedeterminedbythecoatingmethodasshowninTable5,andoptimizedformulationsareavailableforspecificapplications.
CoatingHead
Reversegravure
Curtaincoating

Nominalspeed Optimizedspeed
m/min
m/min
200300
700900
300500
7001000

Slotdie

300400

600700

Mayerrod
Reverseroll

100200
75150

250300
200250

Table5:CoatingSpeedsofAcrylicEmulsionPSAsonTypicalCoatingEquipment.6

Surfactants

Thereisevidencethatthepresenceofsurfactantsintheadhesiveaffectsthemechanismandrateofdryinginwaterborneemulsionadhesives.Incasesinwhichsurfactantsformacontinuousm
water / air interface and in which ambient air is moving, the evaporation rate of water is expected to be slower. Surfactant added to a soft latex has been noticed to increase the drying ra
hydrophilicpathwaysforthediffusionprocess.Inatleastonereport,theadditionofsurfactantshasbeencorrelatedwithslowerevaporationrates.7

Inmostcases,however,theeffectofthesurfactantondryingrateisnotwellunderstoodoreasilydetermined.Thesurfactantisadsorbedprimarilyatthepolymer/waterinterface,andasthewa
moresurfactantadsorbsatthepolymer/waterinterface,sothatacontinuousconcentrationofsurfactantinthewaterphaseismaintained.
Forexample,Isaacs8foundthatthepresenceofsodiumdodecylbenzenesulfonate(SDBS)acceleratedtheevaporationrateofwaterinthelatestagesofdryinginPVAclatex.Heattributedt
influenceofthesurfactantonflocculationandgelation,whichinturnaffectthesurfaceareaofevaporationfromthewatermeniscus.
Cosolvents

Organic solvents are sometimes added to the latex emulsion to improve the coatability and to help the coalescence of latex particles. However, this technique, is generally not favored due to
concerns.Thecoalescenceofthelatexparticlesisimprovedifthecosolventisthelasttoleavethepolymercoating,andasaresultthesettingspeedisgenerallynotimproved.
NatureofthePolymerParticle

The performance of an emulsion is very much based on the production process used to provide the emulsion. In fact possibly the most influential parameter in determining the drying rate o
emulsionisthepolymerrawmaterial.Inthecaseofsettingspeed,afastadhesivedemandsthatthefastestemulsionbechosen.

Important variables in the emulsion selection process are the type of polymer,emulsionsolids,glasstransitiontemperature,viscosity,andparticle size and distribution. The major parameters
emulsionpolymerizationprocessaretheparticlesizeandsizedistribution.Thesizeandpackingofthesepolymericspheresinanemulsionwillinfluencethewettack,earlystrength,andfilmform
oftheadhesivecoating.Thewidertheparticlesizedistribution,thehigherthesolidsmustbeatequivalentviscosities.

Thefastestemulsionsarealsothosethatarehighinsolidsatlowviscositiesandhaveahighplasticizerresponse.Emulsionsuppliershavedevelopedproductsspecificallyforfastproduction.Fo
product,whichhasshownhighwettackandexcellentspeedofset,isAirProducts'Airflex7200vinylacetateethyleneemulsion.Ithasa72%solidslevelwhilemaintainingviscosityinthe1500
Similaremulsionproductsareavailablefrommajorresinsuppliers,andmanyofthesecanbefoundintheSpecialChem4Adhesivesbasepolymerdatabase.

Conclusion

Unfortunately,thereisnoadditiveor"magicpill"tosignificantlyspeedthedryingofwaterborneemulsionadhesives.Themajorparametersthataffectdryingrateare(1)thenatureofthepolyme
adhesivelatexand(2)theambientconditionsthatareprevalentduringtheproductionprocess.Additivestoanadhesiveformulation,suchascosolvents,surfactants,ordehumidifyingagentshave
arelativelyminorandsometimescontradictoryeffectonthedryingspeedofwaterborneemulsionadhesives.

References
1.Petrie,E.M.,"WaterborneEpoxyAdhesives",SpecialChem4Adhesives.comNovember17,2004.
2.Doren,K.,et.al.,WaterborneCoatings,HanserPublications,NewYork,1994.
3.Steward,P.A.,et.al.,"AnOverviewofPolymerLatexFilmFormationandProperties",AdvancesinColloidandInterfaceScience,vol.86,2000,pp.195267.
4.Alimena,J.,"BetterDryingwithInfrared",ProcessHeating,May,2003.
5.DeSanti,E.A.,"DryingWaterbornePSAs",AdhesivesAge,September,1984,pp.4447.
6.RohmandHaas,AcrylicsEmulsionsCenter,SpecialChem4Adhesives.com,June2005.
7.Okubo,M.,et.al.,JournalofPolymerScience:Poly.Chem.Ed.,vol.19,1981,p.1.
8.Issacs,P.K.,JournalMacromolecularChemistry,vol.1(1),1966,p.163.

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