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SiliconeSurface-ActiveAgents

By 
DonnaPerry 
DowCorningCorporation 

DowCorningSiliconeSolutions
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SiliconeSurface-ActiveAgents 
byDonnaPerry 
DowCorningCorporation 
Introduction
Surface-activeagentsarechemicalsthat
reducethesurfaceenergyofamaterial
towhichtheyareaddedbyabsorptionat
theair/liquidinterface.Theincreasing
popularityofwaterbornecoatingspresents
acontinuingchallengeforformulators.
Thereistheneedtoformulatemore
environmentallyacceptableproductsto
complywithgovernmentregulationson
VOCs,toreduceflammabilityandto
generallyreducethehazardprofileof
coatingsystems.
Incomparisonwithsolvent-borne
systems,waterbornecoatingsexhibita
muchhighersurfacetension.Thisresults
fromwaterhavingasurfacetensionof
72.4mN/m.Asaresult,waterborne
coatingsexhibitpoorsubstratewetting
capabilitieswhencomparedtosolvent-
basedequivalents.Thehighsurface
tensionofwaterisduetoitspolarityand
thecohesivehydrogenbondingbetween
thewatermolecules.
Additivesorsurface-activeagents,
suchassiliconepolyethers,areusedto
modifythesurfacepropertiesofwater-
bornecoatingstoachievethedesired
flow,levellingandwettingperformance.
Siliconepolyethershavetraditionally
beenusedinthecoatingareaforsurface
modification,butalongwiththesetypes
ofmaterials,DowCorninghasintro-
ducednovelfunctionalitiestobroaden
applicationsandimprovesurfactant
performance.
Thispapercoversthetraditional
performanceattributesofthesilicone
polyetheradditiveclass,whilealso
introducingnovelcarbinolfunctional
materialsandtheirdifferences.
SurfaceTensionEffectsin
WaterborneCoatings
Surfacetensioncanbeconsideredin
variousways,butperhapsbestasa
resultoftheforcesofattractionexisting
betweenthemoleculesofaliquid.Itis
measuredbytheforceperunitlength
actinginthesurfaceatrightanglestoan
elementofanylinedrawninthesurface
(mN/m).
Wettingistheeffectofdisplacing
onefluidfromthesubstratesurfaceby
anotherliquid.Ingeneral,theliquid
musthavethesameoralowersurface
tensionthanthesubstrate;otherwise,
nowettingwillbeachieved.Thiswill
produceapositivespreadingcoefficient
andleadtoagoodcoating.Thiscan
bebestexpressedinequation(1).By
additionofthecorrectadditive,the
surfacetensionofthecoatingcanbe
modifiedtoimprovesubstratewetting.
Theadditiveactsbyloweringthe
surfacetensionofthecoating,enabling
ittowet-outoverthesubstrate.
Levellingistheprocessofeliminating
thesurfaceirregularitiesofacontinuous
liquidfilmundertheinfluenceofthe
liquid’ssurfacetension.Levellingisan
importantstepinobtainingasmoothand
uniformfilm.Concentrationandsurface
tensiongradientsincoatingsarethe
maincausesofpoorlevelling,which
developasthecoatingdries,dueto
variationsindryingrates.Additionof
theappropriateadditivewillmodifythe
surfacetension.Forinstance,asilicone
additivewillmigratetotheliquid/air
interface,givinganevensurfacetension
acrossthefilmduringthedrying
process,thusreducingsurfacetension
gradients.
Wettingandlevellingaretherefore
totallydifferentprocesses.Thoughthe
surfacetensionofthecoatingplaysan
importantroleinbothprocesses,the
effectsofsurfacetensiononspreadingis
oppositetothatobservedinlevelling.
Substratewettingcanbesubdivided
intotwodistinctcategories:“spreading
wetting”and“adhesionwetting.”
Spreadingwettingisnecessaryforeven
coverageofappliedfilms,inparticular,
forthelow-surface-energysubstratesof
manyplastics.
Adhesionwettingisdefinedinequation
(2).Itisimportant,forexample,in
printingprocessesinwhichitis
undesirablefortheappliedinktospread
acrossasurfaceandthenmergewith
othercolors.
Spreadingwetting:
S
(Spreadingcoeff.)
=-

G
Spreading
/A
= γ 
Substrate
- γ 
Substrate/Liquid
- γ 
Liquid
= γ 
Liquid
(cos θ - 1) (1)
When γ 
Substrate/Liquid
> 0 , spreading will occur spontaneously.
Adhesionwetting:
W
A(Work of adhesion)
= -

G
Adhesion
/ A
= γ 
Substrate
+ γ 
Liquid
- γ 
Substrate/Liquid
= γ 
Liquid
(cos θ +1) (2)
(γ (gamma) = Surface tension)
(θ  (theta) = Contact angle)

Figure1:Molecularstructureofarake-typesiliconesurfactant.
CH
3
CH
3
(CH
3
)
3
–Si–O–( Si–O)
x
-(Si–O)
y
–Si–(CH
3
)
3
CH
3
(CH
2
)
3
(OCH
2
CH
2
)
n
OR

Figure3:Molecularstructureofatrisiloxanesurfactant.
CH
3
(CH
3
)
3
–Si–O–Si–O- Si –(CH
3
)
3
(CH
2
)
3
(OCH
2
CH
2
)
n
OR

Figure2:MolecularstructureofanABA-typesiloxanesurfactant.
CH
3
CH
3
CH
3
RO(CH
2
CH
2
O)
n
(CH
2
)
3
–Si–O–( Si–O)
x
–Si–(CH
2
)
3
(OCH
2
CH
2
)
n
OR
CH
3
CH
3
CH
3
SiliconesasSurface-Active
Agents
Ofthevarioussurface-activechemistries
currentlyavailable,thispaperwill
mainlyconcentrateonaclassof
materialscalledsiliconepolyethers
andtheintroductionofnovelcarbinol
materialsbasedonsimilarstructures.
Thisfamilyofcopolymersisusedto
providemultifunctionalbenefitsin
waterbornesystems.Themainusesof
siliconepolyethersininksandcoatings
includede-foaming,de-aerating,
improvedsubstratewettingandlevel-
ling,andenhancedslipproperties
1,2
.
Thethreemostcommonmolecular
structuresforsiliconesurfactantsare
rake-typecopolymers,ABAcopolymers
andtrisiloxanesurfactants.These
areillustratedinFigures1,2and3
respectively,andtheperformanceof
thesestructureswillbedescribedintwo
typesofcoatings.
Siliconesarehighlysurfaceactiveduet
theirlowsurfacetensioncausedbythe
largenumberofmethylgroupsanddue
tothesmallintermolecularattractions
betweenthesiloxanehydrophobes.
Thesiloxanebackboneofthemolecule
ishighlyflexible,whichallowsfor
maximumorientationoftheattached
groupsatinterfaces.
Siliconepolyethersarenon-ionicand
havebothahydrophilicpart(low-
molecular-weightpolymerofethylene
oxideorpropyleneoxideorboth)and
ahydrophobicpart(themethylated
siloxanemoiety).Thenewcarbinol-
functionalmaterialsalsoincorporate
o
ahydrophilicspeciesonthemand
functionunderthesameprinciplesin
whichthetraditionalsiliconepolyethers
do.Thepolyethergroupsareeither
ethyleneoxideorpropyleneoxide,
andareattachedtoasidechainofthe
siloxanebackbonethroughahydro-
silylationorcondensationprocess.They
canformarake-like,combstructure,or
linearstructure.Siliconepolyethersare
stableupto320-256°F(160-180°C).
Thereisagreatdegreeofflexibilityin
designingthesetypesofpolymers.A
verywidevarietyofco-polymersis
possiblewhenthetwochemistriesare
combined.
Theycanbevariedbymolecularweight,
molecularstructure(pendant/linear)and
thecompositionofthepolyetherchain
(EO/PO),andtheratioofsiloxaneto
polyether.Themolecularweight
influencestherateofmigrationtothe
interface.Theincreasedmolecular
weightofapolymertypicallyleadstoan
increasedviscosity,butmayalsogive
greatersubstantivitytosurfacesand
improvedshinelevel.Othervariables
includeabsenceorpresenceoffunction-
alityorendgroupsonthepolyether
fragments.
Dependingontheratioofethyleneoxide
topropyleneoxide,thesemoleculescan
bewatersoluble,dispersibleorinsolu-
ble;obviously,forefficientwetting,
thesesurfactantsneedtohavegood
solubilityinsolution.Assurfactants,
theyhavetheabilitytoproduceand
stabilizefoamdependingontheir
structure.Conversely,iftheirsolubility
parametersarelow,theybehaveasanti-
foamingagents.
Thedifferentstructuresaffecthowthe
moleculescanpackataninterface.With
pendanttypesinaqueousmedia,the
siliconebackbonealignsitselfwiththe
interface,leavingthepolyalkyleneoxide
groupsprojectingintothewater.Linear
typesformaveryflattened“W”
alignmentwherethecentralsilicone

portionofthemoleculealignswiththe
interfaceandtheterminalgroupsarein
theaqueousphase.Theamountstobe
addedvarybetween0.01%and0.5%of
thetotalformulation.
Thispaperwillnowdiscussthebehavior
ofsiliconepolyethers,alongwith
comparisonstosiliconeswithnovel
carbinolfunctionalitiesinwater,together
withsomestudiesincoatingformula-
tions.Theresultsarecomparedwith
otheradditivesthatarecurrentlyused
incoatings.
SiliconePolyethersas
WettingAgents
Inthisstudy,thethreedifferentsiloxane
surfactantsdescribedabovewere
evaluatedinaqueoussolution,ina
water-basedprintingink,andinawater-
basedpolyestercoating,incomparison
withfluorosurfactantsandacetylenic
glycols,whicharealsousedaswetting
agents.Toachievegoodwettinganda
positivespreadingcoefficient,the
surfacetensionofthecoatingmustbe
lowerthanthecriticalsurfacetension
ofthesubstrate.
Waterhasatypicalsurfacetensionof
72mN/mand,ascanbeseenfrom
TableI,allthesurfactantstestedreduced
thesurfacetensionofthesystem,and,
asaresult,theaqueousmediumwetted
moreefficiently.Forthesiliconesurfac-
tants,thebestresultswereachieved
withproductA,alow-molecular-weight
material.TrisiloxaneAgaveaverylow
figurethatwasimprovedbythefluoro-
surfactant.
Thecriticalmicelleconcentration
(CMC)istherequiredlevelofproduct
toinitiatetheformationofmicellesin
thebulkofaliquid.Uptothispoint,the
surfactantaddedtothewatermigrated
totheliquid/airinterfacetoformafilm
thatreducedthesurfacetension.Thelow
CMCforAshoweditshighpacking
efficiencyattheinterface,inthemuch
lowerlevelrequiredincomparisontothe
otherproducts.
TableI:EquilibriumsurfacetensionwithaKrüssK10Ttensiometerandaplatinum
Wilhelmyplate,additiveconcentrations0.1%.
Surfactant EquilibriumSurfaceTension(nM/m) CMC(%)
TrisiloxaneA 20.5 0.008
ABASiloxaneB 29.0 0.025
RakeSiloxaneC 29.9 0.018
Fluorosurfactant
EthoxylatedAcetylenicDiol
17.5
25.3
0.030
0.050
Inthiscontext,itisimportantto
understandthedifferencebetween
equilibriumanddynamicsurface
tension.Foranequilibriumsurface
tensionmeasurement,aplatinumplate
isimmersedinatestsolutionandthen
slowlywithdrawn.Theforcerequired
toremovetheplatefromthesolution
isameasureofthesurfacetensionof
thatliquid.
Dynamicsurfacetensioncanbe
measuredbyaninstrumentthatbubbles
airthroughthetestliquidatanincreas-
ingrate,duringwhichthemaximum
pressurethatisrequiredtoforma
bubbleismeasured.Asthebubblerate
increasesfrom1bubblepersecondto
10,thetimetocreatethenewinterface
(liquid/air)decreases.Thisiseffectively
measuringhowquicklythesurfactant
lowersthesurfacetension.
Thedynamicmethodismorerepresen-
tativeofthecoatingapplication,for
example,spraying.Underthesecircum-
stances,itisimportanttoknowhow
quicklyasurfactantcanmigrateto
newlyformedinterfaces.Anideal
surface-activeagentwouldprovide
excellentsurfacetensionreduction
underbothequilibriumanddynamic
conditions.
Figure4showsdynamicsurfacetension
resultsfortheabovematerialsat0.1%
inwater.TrisiloxaneAgivesbetter
performancethantheothersilicone
polyethers,butdoesnotgivethevery
lowvaluesachievedbyeitherthe
fluorosurfactantsorethoxylated
acetylenicglycols.However,itmust
berememberedthatdynamicsurface
tensionrepresentsonlyoneaspectof
thetotalphenomenon.
m
N
/
m
 
Figure4:Dynamicsurfacetension,maximumbubblepressure(KrüssBP1),
0.1%inwater.
70  
C Additive, 0.1º 
60  
B Additive, 0.1º 
50  
A Additive, 0.1º 
40  
F Surfactant, 0.1º 
30  
Ethoxylated  
Acetylenic Diol,  
20  
0.1º 
1 2 3 4 5   6 7 8 9 10  
Bubble Frequency (Hertz) 
Figure5:Contactanglemeasurement.
Figure6.ContactanglemeasurementwithaVCA2000video
contactangleequipment,additiveconcentrationat0.1%inwater.
120 
Control 
100
(
°
)
B Additive 
C
o
n
t
a
c
t

A
n
g
l
e

80 
C Additive 
60 
Ethoxylated  
Acetylenic Diol 
40 
A Additive 
20
F Surfactant 

32   34   36   38   40   42   44  
Surface Energy of Substrate (mN/m  )
Inpractice,notonlytheconditionsatthe
air/liquidinterfaceareofinterestbut
alsotheconditionsattheliquid/substrate
interface.Ingeneral,thesmallerthe
contactangleproducedbyasystem,
thebetterthesubstratewetting.The
equipmentusedtomeasurethecontact
angle,theta(θ),wasaVCA2000
instrumentthatautomaticallydispensed
aminutedropletoftheliquidtobe
measuredandthenphotographedthe
dropletafterasetperiod,orcouldbe
programmedtotakeanumberof
photographsandmeasurecorrespond-
ingcontactanglesafterregulartime
intervals.Thistechniqueenabledthe
monitoringofdropletsspreadingon
non-poroussurfaces.
Whenθisgreaterthan90degrees,as
inFigure5,thenbeadingornon-wetting
isoccurring,asisshownbywateron
aplasticsurfacesuchashigh-density
polyethylene.Ifθislessthan90
degrees,asshowninFigure5,then
wettingisoccurring;thesmallerthe
angle,thebetterthewettingprocess.
Spontaneouswettingoccurswhenθ=0,
thedropletimmediatelyspreadingto
formaverythincontinuousfilmonthe
substratewitheffectivelynocontact
anglecapableofbeingdetermined.
Figure6showsthebehaviorofthesame
surfactantsonarangeoflow-energy
substratessuchaspolyethyleneand
polypropylene.Forwetting,ithasbeen
shownthatthemostefficientsilicone
andallowforveryefficientpackingat
interfaces.Forcriticallow-energy
substrates,onlythetrisiloxanesurfactant
Aallowsperfect(spontaneous)wetting
andexcellentspreading.
polyetheristrisiloxane
A,whichhasthreeSi
atomswithpendant
ethyleneoxide.Thelow
molecularweightand
sizegivegreater
mobilityinsolution
Extendingthisperformancebehavior
nowintopracticallifeapplications,the
effectsofthesesurfactantsinawater-
basedflexographicinkformulationare
showninFigure7.Theadditionof
siloxanesurfactantAshowsexcellent
substratewettingperformanceonplastic
foil,followedbythefluorosurfactant.
ThesiloxanesurfactantsBandC,which
haveadifferentstructureandahigher
molecularweight,donotimprovethe
wettingbehavior.Itcanbeseenthatthe
acetylenicglycolhasonlyasmallimpact
onthewettingbehavior.
Anysurfactantmoleculehasthepotential
togeneratefoamthatisundesirablein
manyapplications.Figure8showsthe
densitymeasurementsafterahighshear
stirtest,whichgiveanindicationofair
entrapmentintheink.Thesiloxane

Figure7:Flexographicprintingink,additiveconcentration
0.5%,wetting/appearanceperformanceafterapplication
onplasticfoil(surfaceenergy34mN/m)bydrawdown12
micron,ratedonascalefrom1–5.
5
4




 
e
t
t
i
n
g
*
a
n
c
e
/
W

p
p
e
a
r2 
A


Control  Trisiloxane A  ABA B  Rake C  Acetylenic   F Surfactant 
Glycol 
*Rating from 1-5, 1÷excellent 
Figure8:Flexographicprintingink,additiveconcentration
0.5%,densitymeasurementafterdissolverstirringtest
(5minutesat2800rpm)asameasureofrateoffoam
development.
0.95
0.9
)






 
D
e
n
s
i
t
y

i
n

(
g
/
c
m
30.85 
0.8 
0.75
0.7 
0.65
0.6 
Control  Rake  ABA B  Trisiloxane A  Acetylenic   F Surfactant 
Glycol 
Density without stirring: 1.10 g/cm

TableII:Contactangledata.
Sample WaterContactAngle
AcrylicBinder 43
Binderwith1%ABA 34
Binderwith1%NovelABA <15
Binderwith1%NovelResin <15
surfactantC(rake)actsonlyasalow-
to-moderatefoamenhancercompared
tothefluorosurfactant.Whatisalso
interestingisthatsiloxanesurfactant
B,thesiliconeproductwiththehighest
molecularweight,isperformingasa
de-aerator.
SiliconesasSlipAdditives
Sliprepresentsthelubricationofadry
coatingsurface.Giventhatthefunction
ofacoatingisoftentoprotectthe
underlyingsurfacefromdamagewhile
maintainingasatisfactoryappearance,
itisclearthatthecoatingitselfmustbe
capableofresistingmechanicaldamage.
Thisiswhereslipisimportant.Itis
oftenreferredtoasmarresistance,rather
thanabrasionresistance.Inthelatter,the
bulkmechanicalpropertiesofthefilm
areimportant,inadditiontothesurface
lubricity.
Slipadditivesmustreducefrictionat
thecoatingsurface.Athinlayerofa
materialwithlowinter-molecular
forcesiscapableofachievingthis.
Theslipadditiveshouldbesufficiently
compatiblewiththecoatingbefore
applicationtoavoidseparation.After
application,itshouldnotcausefisheyes
orotherdefectsassociatedwithnon-
wettingoftheadditivebythecoating.
However,therehastobesomedegreeof
incompatibilitytodrivetheadditiveto
thesurfaceofthecoatingfilmduring
drying.
Siliconepolyethersareimportantas
slipagentsduetotheirstructure.The
ratiooftheEO/POsegmentshastobe
carefullycontrolledtoachievethe
requiredcompatibilitybalance.Too
lowapolyethercontentmayleadtothe
de-wettingdefectsalreadymentioned.
Ontheotherhand,highpolyether
contentcanrenderthecopolymertoo
soluble,withnodrivingforcetogetit
tothecoatingsurfaceduringdrying.
Figure9:Effectofmolecularweightonslipperformance
ofsilicone-polyethercopolymersinwater-reducible
polyesterstovingpaint(A:lowmolecularweight;B:high
molecularweight).
35
30
25





S
l
i
p

A
n
g
l
e

(
°
)
20 
15 
10 


Control  Trisiloxane A 0.1º  Rake B 0.1º 
Aspreviouslydescribedforwetting,the
architectureofthecopolymerhasa
profoundeffectonitsbehaviorasaslip
additive.Optimizedstructureshavebeen
identifiedbydesignedexperimentation
togivethedesiredcombinationof
compatibilityandslipperformance.
Compatibilityisparticularlyimportant
inclearcoatings,whereglossreduction
orhazeisnotacceptable.
Figure9showsslipangleresultsfor
silicone-polyethercopolymersAandB
inwater-reduciblestovingpaint.The
maindifferencebetweenthecopolymers
isoverallmolecularweight.Both
productscontainpendantpolyether
groups.Itcanbeseenthattrisiloxane
Ahasalmostnoimpactonslip.Thisis
believedtobeduetotheveryshort
natureofitssiliconechains.Aminimum
amountofdimethylsiloxyunitsisrequired
togivenoticeablechangesinslip.This
requirementismetinrakestructureB,
whichshowsanimprovedslip.
NovelCarbinolFunction
SiliconesinComparison
toTraditionalSPEsin
ArchitecturalCoatings
Thepurposeoflookingatnewfunction-
alitieswastodetermineifwecould
improvehydrophilicitybeyondwhatwe
wereseeinginthetraditionalsilicone
polyethersthatwouldlendthemselvesto
moreeasy-cleansurfacedevelopment.
Inthisstudy,twonovelcarbinol
functionalitymaterialswerecomparedto
atraditionalsiliconepolyetherofsimilar
degreeofpolymerization(Dp)andits
performancetowarddirtreleaseinan
architecturalbinder.Eachsamplewas
dopedintoanacrylic-basedbinderby
weightofresin,andsurfaceappearance
andpropertieswerecharacterized.With
theincorporationofthenovelcarbinol
functionality,thedatashowsanincrease
inthehydrophilicityofthecoatingas
comparedtothetraditionalSPE(Table
II).Thisyieldswhatwasseenasan
TableV:Dirtreleasecharacteristicsafteroutdooraging.
DirtRelease 
Propertiesafter1008 
Sample HoursWeathering 
SG30Neat -
SG30with1%ABA 0
SG30with1%NovelABA +
SG30with1%NovelResin ++

6
0
°
G
l
o
s
s
,

B
a
s
e
T
x
a
n
e
r
i
s
i
l
o
T
x
a
n
e

r
i
s
i
l
o
e
l
w
i
t
h

N
o
v
A


A
B
A

A
B
e
l
w
i
t
h

N
o
v
R
e
s
i
n

w
i
t
h

N
o
v
e
l
C
o
m
p
e
t
i
t
o
r
 
S
a
m
p
l
e
Figure10:Marresistanceasafunctionofgloss.
100  
90  
80  
70  
60  
50 
40 
Initial  250 Rubs 
Formulation  
TableIII:Dirt-releasecharacteristicsthroughsimple
spraymethod.
Sample DirtReleaseProperties
Binder 0
Binderwith1%ABA +
Binderwith1%NovelABA ++
Binderwith1%NovelResin ++
TableIV:Dirtpickupandpencilhardness.
Pencil
Formulation DirtPickup Hardness
Binder 0 3B
Binderwith1%ABA - 4/5B
Binderwith1%NovelABA
Binderwith1%NovelResin
-
-
4/5B
4B
thoughwiththeadditionofthetradi-
tionalABAmaterialstherewasaslight
improvementoverthebaselinebutnotas
greatastheunagedsamples.Thenovel
ABAmaterialsstillshowedsignificant
improvement,whiletheresinous
materialsshowedexcellentdirt-release
characteristics(TableV).
NovelCarbinolFunctional
SiliconesinComparisonwith
TraditionalSPEsinOverprint
VarnishApplications
Abaselineformulationforageneral-
purposeoverprintvarnishwasobtained
byJohnsonPolymers.Theformulation
wasrunwithandwithouttheAerosol
OT-75,notingnodifferencesinthe
wet-outperformance,andwasomitted
foralltherunswiththeadditionofthe
additives.Theappearanceandwet-out
oftheOPVwerenotaffectedbythe
incorporationofthesiloxaneadditive,
eitherstandardorwiththenovel
functionality.
SampleswerecoatedontoLenteacharts
andrunfor250cyclesonaSutherland
rubtesterwithglossbeingdocumented
priorandafterrubstodetermineeach
formulation’sresistancetomar.The
initialpointtobenotedwasanincrease
intheinitialglosswithsiloxane
incorporation,excludingthestandard
ABAandtheBYKmaterialbench-
markedagainst.Enhancementwas
higherinthosecontainingthenovel
functionality.Therewasalsobettermar
resistanceoverallwithallthesesamples,
versusthebaselinematerial.
increaseinthedirt-releaseabilityofthe
coatingthroughsimplewaterspraying.
Thisincreaseinhydrophilicitywasseen
inboththeABA-structuredmaterialsas
wellasresinous-basedsiloxanes.
Afterasimpledrawdownandcuretime,
thecoatingsweredustedwithalayerof
dirtandsprayedwithwatertonotethe
dirt-releasingproperties.Withthe
additionoftheABAsiliconepolyether
structure,therewasanenhancementof
thedirt-releaseproperties,butthis
enhancementwasevengreaterinthose
samplesincorporatingthenewcarbinol
functionality(TableIII).Onethingtobe
notedisthattheadditionofthesilicone
surfactants,eitherwiththenewcarbinol
materialorthetraditionalpolyethers,
doescauseaslightsofteningofthe
coatingitself,whichactuallycorrelates
intoaninitialdirtpickupthatisslightly
enhancedovertheneatacrylicbinder
(TableIV).
Durabilityofthishydrophilicityisa
knowndeficiency,giventhecurrent
additivesfunctionbymigratingtothe
surfaceandcanoftenwashawayover
anextendedtimewithexposuretothe
environment.Aftersubjectingthe
coatingstoexternalweatheringexposure
for1008hours,thedirt-releaseperfor
mancedecreased.TheneatSG30
samplenolongerreleaseddirtaseasily,
-
C
o
F
Figure11:CoefficientoffrictiondataonOPVsamples.
0.25 
0.2 
0.15 
B
a
s
e
0.1 
0.05 

T
r
i
s
i
l
o
x
a
n
e
T
r
i
s
i
l
o
x
a
n
e

Formulation  
w
i
t
h

N
o
v
e
l
Static CoF  Kinetic CoF 
A
B
A


A
B
A

w
i
t
h

N
o
v
e
l
R
e
s
i
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modifiedtoimprovesubstratewetting.
Inparticular,thetrisiloxanestructure
givesthebestequilibriumsurface
tensionreductionandexcellentwetting
toplasticsurfacesandotherlow-energy
substrates.Thismaterialhasthegreatest
capacityforloweringtheliquid/solid
interfacialtension.Thehigher-molecular
weightsiloxanesurfactants,withrake
andlinearstructures,givemoderate
wetting.However,materialsofthese
typescanbeusedtoprovideother
benefits,forinstancemarresistance,
slipandde-aeration.Theincorporation
ofaresinousmaterialwithfunctionality
canalsoyieldahighersubstantivityin
acoatingthatislikelydesiredwhena
coatingisbeingexposedtolong-term
weatheringeffects.Theadditionofnovel
functionalitiesinplaceofthelinear
polyethersalsocanenhancetheproper
tiesofthesiliconepolyethermaterials;
researchisbeingdonetofine-tunethese
functionalitiestothemostappropriate
applications.
-
-
Coefficientoffrictiondata(CoF)indicates
thatthemarresistanceimprovements
werenotduetoincreasingtheslipofthe
surface.Byindustrystandards,theslip
changethatwasdocumentediswithin
error.Thisindicatesapossibilityfor
applicationssuchasfloorvarnishwhere
marresistanceneedstobeincreased
withnoeffectontheCoForslipperiness
ofthesurface.TheCoFdatademon-
stratesthattheadditiveisnotresidingon
thesurfacebutpossiblyallowingthePE
waxtobetterorientateatthesurfaceand
yieldhighermarresistance.
Inlookingatthesurfacetensiondataof
thematerialsusedinthisstudythereis
actuallyverylittledifferencethatwould
indicatethisisthereasonwhythe
materialperformsthisway.
Workcontinuestooptimizethestruc-
turesandfindapplicationinwhichthey
canbeutilized.
Conclusions
Silicone-basedsurfactantsoffermany
benefitsinwaterbornecoatings.Bythe
additionofthecorrectsiliconesurfac
tant,thecoatingsurfacetensioncanbe
-
TableVI:Surfaceenergyofstandardand
modifiedsiloxanes.
SurfaceEnergyat1%
(Dynes/cm)
Trisiloxane 20.1 
TrisiloxanewithNovel 21.2 
ABA 24.6 
ABAwithNovel 23.8 
Resin notsoluble 
ResinwithNovel 26.4 
References
1
Schlachter,I.,andFeldmann-Krane,Georg,SiliconeSurfactants,Surfactants Sci.
Ser.,1998,74,p.201-239.
2
Scholz,W.,Verkroniek,10,13,1995.

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