Butvar® polyvinyl butyral resin

Properties and uses

ContentsContents

1 Introduction

1 Uses

1 Technicalsupportforspecificapplications

2 Properties

2 Chemistry

6 Producttypes

6 Butvar:therightresinsolution

13 Compatibility

15 Insolubilizingreactions

17 Applications

17 Wireenamels

17 Surfacecoatings

17 Washprimers

17 Militaryspecificationwashprimers

18 Nonspecificationwashprimers:

B-1030withButvar

18 Single-packagewashprimer:

B-1011withButvar

19 Chromate-freewashprimerswithButvar

20 Metalcoatings

21 Woodfinishes

21 Protective wash coats and sealers

21 Knot sealers

22 Adhesives

22 Structural adhesives

22 Phenolic resins

22 Expoxies and other thermosetting resins

23 High-strength bonding procedure

23 Performance characteristics

23 Adhesive strengths

24 Hot melt adhesives

24 Textilecoatings

24 Advantagesastextilecoating

25 Ceramicbinderapplications

26 Tapecasting

26 Thickfilms

27 Tonersandprintinginks

28 Storage and handling

28 Storage

28 ToxicityandFDAstatus

28 Qualitycontrol

29 Material sources

Introduction

Polyvinylbutyralresinsareemployedinawidearrayofindustrialandcommercialapplications.Theseuniqueresinsofferimpressiveperformance,aswellasoutstandingversatility.

Butvar®polyvinylbutyralresinshaveacombinationof

propertiesthatmakethemakeyingredientinavarietyof

successfulformulations.Someofthesepropertiesforwhich

Butvariswidelyusedareoutstandingbindingefficiency,

opticalclarity,adhesiontoalargenumberofsurfaces,and

toughnesscombinedwithflexibility.

SolutiaofferssixgradesofButvarresinsthatcoverabroad

rangeofchemicalandphysicalproperties.Theseresins

aregenerallywellsuitedeitherasamajoringredientof

aformulationorinsmallerquantitiestoenhancethe

propertiesofotherresins.

Uses SomeoftheapplicationsinwhichButvarisavital

ingredientinclude:

•Ceramicbinders

•Inks/drytoners

•Woodcoatings

•Washprimers

•Compositefiberbinders

•Structuraladhesives

•Otherdiverseuses

ButvarresinwaspioneeredbyMonsantointhe1930sas

thekeyingredientforautomotivesafetyglassinterlayers.

Itstillenjoyswidespreaduseinautomotiveand

architecturalapplicationsforlaminatedsafetyglass.

Technical support for specific applications Solutia’stechnicalsupportandresearchstaffforButvar

resinscanassistinyourspecificapplicationneeds.The

CustomerServiceCenterat1-800-964-5224standsready

toreceiveyourordersforsamplesandtechnicalliterature,

aswellaspurchaseordersforshipmentofButvarresin.

1

Properties

ChemistryAcetals,suchaspolyvinylbutyral,areformedbythe

well-knownreactionbetweenaldehydesandalcohols.The

additionofonemoleculeofanalcoholtoonemoleculeof

analdehydeproducesahemiacetal.Hemiacetalsarerarely

isolatedbecauseoftheirinherentinstabilitybut,rather,are

furtherreactedwithanothermoleculeofalcoholtoforma

stableacetal.

Polyvinylacetalsarepreparedfromaldehydesandpolyvinyl

alcohols.Polyvinylalcoholsarehighmolecularweightresins

containingvariouspercentagesofhydroxylandacetate

groupsproducedbyhydrolysisofpolyvinylacetate.

Theconditionsoftheacetalreactionandtheconcentration

oftheparticularaldehydeandpolyvinylalcoholusedare

closelycontrolledtoformpolymerscontainingpredetermined

proportionsofhydroxyl,acetate,andacetalgroups.Thefinal

productmayberepresentedbythefollowingstylizedstructure.

TheproportionsofA,B,andCarecontrolled,andtheyare

randomlydistributedalongthemolecule.

2

H

R — C + R1 — OH

O Alcohol

Aldehyde

H

R — C (— OR1)2 + H

2O

Acetal

H

H C3H

7

HCH2

CH2 — C

C

C

O O

PV Butyral

A

H

CH2 — C

OH

PV Alcohol

B

H

CH2 — C

O

C

CH3

O

PV Acetate

C

H

R — C — OR + R1 — OH

OH

Hemiacetal

Alcohol

3

Table 1.PhysicalpropertiesofButvar®resins(white,free-flowingpowder)

Property Units ASTM method B-72 B-74 B-76 B-79 B-90 B-98

Volatiles,amax % — 3.5 3.0 5.0 5.0 5.0 5.0

Molecularwt(weightaverageinthousands)

— (1) 170–250 120–150 90–120 50–80 70–100 40–70

Solutionviscosity15%byweight

cp (2) 7,000–14,000 3,000–7,000 500–1,000 100–400 600–1,200 200–400

Solutionviscosity10%byweight

cp (2) 1,600–2,500 800–1,300 200–450 75–200 200–400 75–200

Ostwaldasolutionviscosity

cp (3) 170–260 37.0–47.0 18.0–28.0 9.0–16.0 13.0–17.0 6.0–9.0

Specificgravity23˚/23˚(±0.002)

— D792–50 1.100 1.100 1.083 1.083 1.100 1.100

Burningrate ipm D635–56T 1.0 1.0 1.0 1.0 0.9 0.9

Refractiveindex(±0.0005)

— D542–50 1,490 1.490 1.485 1.485 1.490 1.490

Waterabsorption(24hours)

% D570–59aT 0.5 0.5 0.3 0.3 0.5 0.5

Hydroxylacontentexpressedas%polyvinylalcohol

— — 17.5–20.0 17.5–20.0 11.5–13.5 11.0–13.5 18.5–20.5 18.0–20.0

Acetatecontentexpressedas%polyvinylacetate

— — 0–2.5 0–2.5 0–2.5 0–2.5 0–2.5 0–2.5

Butyralcontentexpressedas%polyvinylbutyral,approx.

— — 80 80 88 88 80 80

aSpecification properties

All properties were determined by ASTM methods except the following:

• Molecular weightwasdeterminedviasizeexclusionchromatographywithlow-anglelaserlightscattering(SEC/LALLS)methodofCottsandOuanointetra-hydrofuran.b

• Solution viscositywasdeterminedin15%byweightsolutionsin60:40toluene:ethanolat25˚C,usingaBrookfieldViscometer.Alsoin10%solutionin95%ethanol@25˚CusinganOstwald-Cannon-FenskeViscometer.

• Ostwald solution viscosityforeachproducttypemeasuredwithanOstwald.Cannon-FenskeViscometer.Thesolventsandsolidslevelsusedareasfollows:

ProductPercent solids Solvent

Temperature (C˚)

B-72 7.5Anhydrousmethanol

20

B-76,B-79 5.0SD29ethyl

alcohol25

B-74,B-90,B-98 6.0Anhydrousmethanol

20

bP. Dublin, ed., Microdomains In Polymer Solutions (New York: Plenum Press, 1985), pp. 101-119.

bP. Dublin, ed., Microdomains In Polymer Solutions (New York: Plenum Press, 1985), pp. 101-119.

4

Table 2.ChemicalpropertiesofButvar®resins

Property Units ASTM method B-72 B-74 B-76 B-79 B-90 B-98

Resistance to:

Weakacids — D543-56T E E E E E E

Strongacids — D543-56T E E E E E E

Weakbases — D543-56T E E E E E E

Strongbases — D543-56T E E E E E E

Organic solvents:

Alcohols — D543-56T P P P P P P

Chlorinated — D543-56T G G F F G G

Aliphatic — D543-56T E E F F E E

Aromatic — D543-56T F F P P F F

Esters — D543-56T F F P P F F

Ketones — D543-56T F F P P F F

Key:E–excellentG–goodF–fairP–poor

Table 3.MechanicalpropertiesofButvarresins

Property Units ASTM method B-72 B-74 B-76 B-79 B-90 B-98

Tensile strength:

Yield 103psi D638-58T 6.8–7.8 6.8–7.8 5.8–6.8 5.8–6.8 6.3–7.3 6.3–7.3

Break 103psi D638-58T 7.0–8.0 7.0–8.0 4.6–5.6 4.6–5.6 5.7–6.7 5.6–6.6

Elongation:

Yield % D638-58T 8 8 8 8 8 8

Break % D638-58T 70 75 110 110 100 110

Modulusofelasticity(apparent)

105psi D638-58T 3.3–3.4 3.3–3.4 2.8–2.9 2.8–2.9 3.0–3.1 3.1–3.2

Flexuralstrength,yield 103psi D790-59T 12–13 12–13 10.5–11.5 10.5–11.5 11–12 11–12

Hardness, Rockwell:

M — D785-51 115 115 100 100 115 110

E — D785-51 20 20 5 5 20 20

ImpactstrengthIzod,notched½"x½"

ft.lb./in. D256-56 1.1 1.1 0.8 0.8 0.9 80

*Specification properties

5

Table 4.ThermalpropertiesofButvar®resins

Property Units ASTM method B-72 B-74 B-76 B-79 B-90 B-98

Flowtemperature,1,000psi

ºC D569-59 145–155 135–145 110–115 110–115 125–130 105–110

Glasstransitiontemperature(Tg)

ºC (4) 72–78 72–78 62–72 62–72 72–78 72–78

Ash content at 550ºC:

Innitrogen % (5) <3.0 <3.0 <2.0 <2.0 <3.0 <3.0

Inair % (5) <1.0 <1.0 <0.75 <0.75 <0.75 <0.75

Heatdistortiontemperature

ºC D648-56 56–60 56–60 50–54 50–54 52–56 45–55

Heatsealingtemperature ºF (6) 220 220 200 200 205 200

Table 5.ElectricalpropertiesofButvar®resins

Property Units ASTM method B-72 B-74 B-76 B-79 B-90 B-98

Dielectric constant:

50cps — D150-59T 3.2 3.2 2.7 2.7 3.2 3.3

103cps — D150-59T 3.0 3.0 2.6 2.6 3.0 3.0

106cps — D150-59T 2.8 2.8 2.6 2.6 2.8 2.8

107cps — D150-59T 2.7 2.7 2.5 2.5 2.7 2.8

Dissipation factor:

50cps — D150-59T 0.0064 0.0064 0.0050 0.0050 0.0066 0.0064

103cps — D150-59T 0.0062 0.0062 0.0039 0.0039 0.0059 0.0061

106cps — D150-59T 0.027 0.027 0.013 0.013 0.022 0.023

107cps — D150-59T 0.031 0.031 0.015 0.015 0.023 <0.24

Dielectric strength (l" thickness):

Shorttime v/mil D149-59 420 420 480 480 450 400

Step-by-step v/mil D149-59 400 400 390 390 370 380

*Specification properties

• Glass transition temperature (Tg)wasdeterminedbyDifferentialScanningCalorimeter(DSC)overarangeof30˚Cto100˚Condriedgranularresin.

• Ash contentoftheThermalGravimetricAnalysis(TGA)wasdeterminedasaweightlossversustemperatureprofileconductedataheatingrateof10˚C/min.

• Heat-sealing temperaturewasdeterminedona1-mildriedfilmonpapercastfroma10%solutionin60:40toluene:ethanol.Adwelltimeof1.5secondsata60psilinepressurewasusedontheheatsealer.

Product types ThepropertiesofthevarioustypesofButvar®resinsare

describedinTables1through5.Theresinsareofferedina

varietyofmolecularweightrangesandviscosities.B-76and

B-79havealowerhydroxylcontentthantheotherButvar

resins.Thispermitsbroadersolubilitycharacteristics.

Asageneralrule,thesubstitutionofbutyralgroupsfor

acetategroupsresultsinamorehydrophobicpolymerwith

ahigherheatdistortiontemperature.Atthesametime,the

polymer’stoughnessandadhesiontovarioussubstratesis

considerablyincreased.Theoutstandingadhesionofthe

polyvinylbutyralresinsisaresultoftheirterpolymer

constitution.Becauseeachmoleculepresentsthechoiceof

threedifferentfunctionalgroupstoasurface,theprobability

ofadhesiontoawidevarietyofsubstratesisincreased

substantially.

Althoughpolyvinylbutyralresinsnormallyarethermoplastic

andsolubleinarangeofsolvents,theymaybecrosslinked

throughheatingandwithatraceofmineralacid.Crosslinking

isgenerallycausedbytransacetalizationbutalsomay

involvemorecomplexmechanisms,suchasareaction

betweenacetateorhydroxylgroupsonadjacentchains.

Asapracticalmatter,crosslinkingofthepolyvinylbutyrals

iscarriedoutbyreactionwithvariousthermosettingresins,

suchasphenolics,epoxies,ureas,diisocyanatesand

melamines.Theavailabilityofthefunctionalhydroxylgroups

inButvarresinsforcondensationsofthiskindisan

importantconsiderationinmanyapplications.Incorporation

ofevenasmallamountofButvarresinintothermosetting

compositionswillmarkedlyimprovetoughness,flexibility,

andadhesionofthecuredcoating.

Polyvinylbutyralfilmsarecharacterizedbyhighresistance

toaliphatichydrocarbons,mineral,animal,andvegetable

oils(withtheexceptionofcastorandblownoils).They

withstandstrongalkalisbutaresubjecttosomeattackby

strongacids.However,whenemployedascomponentsof

curedcoatings,theirstabilitytoacids,aswellassolvents

andotherchemicals,isimprovedgreatly.Butvarwill

withstandheatingupto200˚Fforprolongedperiodswith

littlediscoloration.

Butvar: the right resin solutions Butvarbrandresinsgenerallyaresolubleinalcohols,glycol

ethers,andcertainmixturesofpolarandnonpolarsolvents.

ArepresentativelistofButvarsolventscanbefoundin

Table6.Ingeneral,ButvarB-98resinwillshowthesame

generalcompatibilitycharacteristicsasB-90and,therefore,

shouldproveadvantageouswherephysicalandchemical

propertiesofB-90aredesiredbutlowersolutionviscosities

arenecessary.ThesameistrueforButvarB-79inrelation

toB-76.

Whenanalcoholistheonlysolvent,theviscosityofa

Butvarsolutionincreasesasthemolecularweightofthe

alcoholincreases.Blendsofalcoholswitharomaticsolvents

providethebeststartingpointforthedevelopmentof

solventsystems.Wherealcohols,suchasethylorisopropyl,

areemployedeitheraloneorinamixturewithothersolvents,

usethe95%grades.Thepresenceofwatergiveslowersolution

viscositiesthansolutionsutilizinganhydrousalcohols.

Butvarsolutionsshowverymarkedviscosityincreasesasresin

solidsincrease.ThiseffectisshowninGraphs3through10.

ThelowerhydroxylcontentofButvarB-76andB-79permits

solubilityinawidervarietyoforganicsolventsascompared

totheothergradesofButvar.Onenotableexception,

however,istheinsolubilityofButvarB-76andB-79in

methanol.AllothertypesofButvarcontainsufficient

hydroxylgroupstoallowforsolubilityinalcoholandin

hydroxyl-containingsolvents.Thepresenceofbothbutyral

andhydroxylgroupspermitssolutioninmixturesofalcohol

andaromatics.

ViscositiesofButvarresinsolutionscontainingmixedsolvents

dependontheratioofalcoholtoaromatic.Viscositycurves

forButvarB-76,B-90,andB-98inGraph2showminimum

pointsinthegeneralvicinityof50%alcohol:50%aromatic.

6

7

Table 6.SolubilityofButvar®resins

SolventButvara

B-72, B-74Butvarb

B-76, B-79Butvarb

B-90, B-98

Aceticacid(glacial) S S S

Acetone I S SW

2-Butoxyethanol S S S

n-butylacetate I S PS

n-butylalcohol S S S

n-butylpropionate I S I

Cyclohexanone S S S

Diacetonealcohol PS S S

Diisobutylketone I SW I

Dimethylesters PSc S PSc

N,N-dimethylacetamide S S S

N,N-dimethylformamide S S S

Dimethylsulfoxide S S S

Ethylacetate,85% S S S

Ethylacetate,99% I S PS

Ethylalcohol,95%oranhydrous S S S

Ethylenedichloride SW S SW

Isophorone PS S S

Isopropylacetate I S I

Isopropylalcohol,95%oranhydrous S S S

Methylacetate I S PS

Methylalcohol S SW S

Methylamylketone SW S PS

Methylethylketone PS S PSc

Methylisoamylketone I S SW

Methylisobutylketone I S I

Methylpropylketone SWc S SWc

Methylenechloride PS S S

N-methyl-2-pyrrolidone S S S

Naphtha(lightsolvent) I SW I

Propylpropionate I S I

Propylenedichloride S S S

Tetrachloroethylene SW SW SW

Tetrahydrofuran S S S

Toluene SW SW SW

Toluene:ethylalcohol,95%(60:40byweight) S S S

1,1,1-trichloroethane SW S SW

Xylene I PS SWa5% solids solution agitated for 24 hours at room temperatureb10% solids solution agitated for 24 hours at room temperaturecClear solution at 50º–80ºC

Key:S–solublePS–partiallysolubleI–insolubleSW–swells

AcommonsolventforalloftheButvar®resinsisa

combinationof60partstolueneand40partsethanol

(95%)byweight.TheviscositiesofalltheButvarresins

inthissolventblendareshowninGraphs2and3.The

viscositiesofButvarresinsinalcoholsareshowninGraphs

4through8.Graphs9and10presenttheviscositiesof

Butvarresinsin2-Butoxyethanol.

ForcompositionsofButvar,methylalcoholwilltendtogive

thelowestviscosityand,therefore,willpermittheuseof

highersolidswhenusedasacomponentofasolventblend.

Whenmuchmorethan10%to15%alcoholisusedina

formulationforsprayapplication,blushingmayresult.

ThesolventblendsinTable7aresuggestedforallButvar

grades.Theyareusefulasstartingpointsinthedevelopment

ofsolventblendsfortheothertypes.

Selectionofasuitablesolventsysteminvolvesanumber

offactors.End-useandapplicationtechniqueusedwill

necessitateconsiderationofsolutionviscosity,cobweb

formation,blushing,evaporation,solventrelease,andtoxicity

characteristics.Inmostcases,thechoiceofcomponentsof

solventblendwillinvolvecompromisesinatleastsomeof

thesefactorssothatadesiredcombinationofproperties

maybeobtained.

Aliphatichydrocarbonscanbetoleratedinonlyverysmall

proportions.Aromatichydrocarbons,alcohols,esters,ketones,

andhalocarbons,whennotactivesolvents,aregenerally

satisfactoryasdiluentsorlatentsolvents.Solventblends

aremorelikelytobesuccessfulwhentheirmeansolubility

parameterandhydrogenbondingfallwithintheranges

showninGraph1andTable8.

TheButvarresinscanbedissolvedquiterapidlyusing

conventionaltechniques.Toensurethoroughanduniform

wettingofallparticles,itisimportanttoaddtheresin

slowlytothesolventsystemwithadequatestirring.With

somemixedsolvents,itmaybedesirabletoslurrytheresin

inthehydrocarbonorothernonsolventcomponentandadd

themoreactivesolventcomponentstotheslurryunder

adequateagitation.

8

Table 7.SuggestedsolventblendsforButvar®resins

A B C D

Diacetonealcohol 22.5% 20.0% 15.0% —

n-butylalcohol 22.5 20.0 15.0 —

Ethylalcohol,95% 10.0 20.0 20.0 55.0%

Xylene 45.0 40.0 30.0 —

Toluene — — 20.0 45.0

Total 100.0 100.0 100.0 100.0

Relativeviscosity High Medium Low Low

Relativeevaporationrate Slow Medium Medium Veryfast

Applicationtechnique Spray Dip,roll Dip,roll Brush

Dryingtechnique Bake Bake Bake Airdry

9

Graph 1.HansensolubilityparametersofButvar®resinsa

Polyvinyl butyral Hansen solubility parameters

Dispersive δD (MPaa)

Polar δP (MPaa)

H-bonding δH (MPaa)

Sphere radius(MPaa)

●B-90andB-98 21.72 7.85 14.55 15.0

●B-72andB-74 21.19 8.70 14.02 13.7

●B-76andB-79 17.72 7.18 12.62 9.7

aHSPiP Software, Version 4.0.08, 2013.

Ingeneral,solventsorsolventmixtureshavingδD,δP,andδHcoordinateswithinapolymersphere,RED≤1,aresolvents;thoseoutsideaspherearenonsolvents.Relative Energy Difference (RED) = [4(δD2-δD1)2+(δP2-δP1)2+(δH2-δH1)2]½/Sphere Radius

Table 8.Hansensolubilityparametersforcommonsolventsandsolventmixturesa

Solvent Solvent ratio (wt%)Dispersive δD (MPaa)

Polar δP (MPaa)

H-bonding δH (MPaa)

Acetone 100 15.5 10.4 7.0

2-butoxyethanol 100 16.0 5.1 12.3

n-butylacetate 100 15.8 3.7 6.3

Diisobutylketone 100 16.0 3.7 4.1

N,N-dimethylacetamide 100 16.8 11.5 9.4

N,N-dimethylacetamide/xylene 60/40 17.2 7.2 7.3

Dimethylsulfoxide 100 18.4 16.4 10.2

Dioxane 100 17.5 1.8 9.0

Dioxane/tetrahydrofuran 50/50 17.1 3.9 8.5

Ethanol 100 15.8 8.8 19.4

Ethanol/water 95/5 15.8 8.2 20.5

Ethylacetate/ethylalcohol 99/1 15.8 5.3 7.3

Ethylenedichloride 100 18.0 7.4 4.1

Ethyleneglycol 100 17.0 11.0 26.0

Isopropanol 100 15.8 6.1 16.4

Isopropanol/water 98/2 15.8 6.3 16.8

Methanol 100 14.7 12.3 22.3

Methylamylketone 100 16.2 5.7 4.1

Methylenedichloride 100 17.0 7.3 7.1

Methylisobutylketone 100 15.3 6.1 4.1

Propyleneglycolmonomethylether 100 15.6 6.3 11.6

Propyleneglycolmonomethyletheracetate 100 15.6 5.6 9.8

Tetrahydrofuran 100 16.8 5.7 8.0

Toluene 100 18.0 1.4 2.0

Toluene/ethanol 50/50 16.9 5.2 11.0

Trichloroethane 100 16.8 4.3 2.0

Xylene 100 17.8 1.0 3.1

Xylene/N,N-dimethylacetamide 50/50 17.2 6.1 6.6aCharles M. Hansen, Hansen Solubility Parameters: A User’s Handbook, 2nd Edition, CRC Press (2007).

D H

P

30

24

18

12

6

30

24

18

12

6

6

27

24

2118

15

12

18

24

30

Graph 2.ViscositiesofButvarintoluene-ethanol(95%)(15%solids)

Graph 3.ViscositiesofButvarin60/40toluene-ethanol(95%)(byweight)

1,800

1,600

1,400

1,200

1,000

800

600

400

200

00 20 40 60 80

Toluene

100 80 60 40 20

Ethanol

Solvent composition by weight

Broo

kfie

ld V

isco

sity

at

25ºC

-cp

— B-76

— B-90

— B-98

100,000

10,000

1,000

100

10

10 5 10 15 20 25 30

Broo

kfie

ld V

isco

sity

at

25ºC

-cp

Percent total solids

— B-72

— B-76

— B-79

— B-90

— B-98

10

11

Graph 4.ViscositiesofButvarinmethanol Graph 5.Butvarinethanol(95%)

Graph 6.Butvarinethanol(95%)

100,000

10,000

1,000

100

10

10 5 10 15 20 25 30

Broo

kfie

ld V

isco

sity

at

25ºC

-cp

Percent total solids

— B-72

— B-90

— B-98

100,000

10,000

1,000

100

100 5 10 15

Broo

kfie

ld V

isco

sity

at

25ºC

-cp

Percent total solids

— B-72

— B-74

100,000

1,000

100

100 5 10 15

Broo

kfie

ld V

isco

sity

at

25ºC

-cp

Percent total solids

— B-76

— B-79

— B-90

— B-98

12

Graph 7.Butvarinn-Butanol

Graph 8.Butvarinn-Butanol

Graph 9.Butvarin2-Butoxyethanol

Graph 10.Butvarin2-Butoxyethanol

100,000

10,000

1,000

100

100 5 10 15

Broo

kfie

ld V

isco

sity

at

25ºC

-cp

Percent total solids

— B-72

— B-74

10,000

1,000

100

100 5 10 15

Broo

kfie

ld V

isco

sity

at

25ºC

-cp

Percent total solids

— B-76

— B-79

— B-90

— B-98

10,000

1,000

100

100 5 10 15

Broo

kfie

ld V

isco

sity

at

25ºC

-cp

Percent total solids

— B-76

— B-79

— B-98

100,000

10,000

100

1,000

100 5 10 15

Broo

kfie

ld V

isco

sity

at

25ºC

-cp

Percent total solids

— B-72

— B-74

— B-90

Compatibility ThecompatibilityofButvar®polyvinylbutyralresinswith

plasticizers,modifiers,andothervariousresinsiswell

established.Butvarreadilylendsitselftocompoundingwith

otheradditivestoenhanceitsphysicalandchemicalproperties.

Plasticizersareoftenusedtoimpartimprovedflexibilityover

abroadertemperaturerange.SeeTable9.

13

Table 9.PlasticizersforButvar®resin

Type Name or trademarkKnown Butvar:plasticizer

compatibility level

Hexanoate EastmanTEG-EH(triethyleneglycoldi-2-ethylhexanoate) 1:1

Adipate Santicizer®97(dialkyladipate) 4:1

Santicizer367(dihexyladipate) 3:1

Dioctyladipate(DOA) 4:1

Blownlinseedoil Linseedoil —

Citrate Tributylcitrate —

Phosphate Santicizer141(2-ethylhexyldiphenylphosphate) 1:1

Santicizer148(isodecyldiphenylphosphate) 1:1

Santicizer154(Tert-butylphenyldiphenylphosphate) 1:1

Santicizer143(triarylphosphateesterblend) 1:1

Tricresylphosphate(TCP) 1:1

Triphenylphosphate(TPP) 2:1

Phthalate Santicizer261(alkylbenzylphthalate) 2:1

Santicizer278(alkylbenzylphthalate) 4:3

Santicizer160(butylbenzylphthalate) 1:1

Dibutylphthalate(DBP) 1:1

Dialkylphthalate 4:1

Dioctylphthalate(DOP) 4:1

PEglycolether Pycal™94 —

Polyester Paraplex™RGA-8 —

Processcastoroil #15,#30,#40 2:1

Rawcastoroil #1Castor 1:1

Ricinoleate Flexricin™P3(butylricinoleate) 2:1

Rosinderivatives Hercolyn™ —

Sebacate Dibutylsebacate —

Sulfonamide Ketjenflex™8(n-ethyltoluenesulfonamide) 1:1

Ketjenflex™9S(toluenesulfonamide) 2:1

Thevaluesgiveninthistableareaguidetothecompatibilitylimitsoftheplasticizersinthevariousresinsshown.(Ifnovalueisgiven,thelimitisunknown.)Thehighestconcentrationtestedwas100phr.Wherethevalueisgivenas1:1,someplasticizer/resincombinationsmayhaveevengreatercompatibility.However,sincethevaluesgivenapplytoaresintype,thecompatibilitywithaparticularcommercialgradeshouldbecheckedwhenevaluatingaspecificcompound,particularlyiftheplasticizercontentoftheformulationistobeneartheceilingvalueindicated.

CrosslinkerssuchasSantolink®phenolicandResimene®amino

resinsareusedtoimpartgreatertoughnessandthermalresistance.

Table10depictsthecompatibilityofButvar®polyvinylbutyral

resinswithothermodifiersandresins.

14

Table 10.CompatibilityofButvarwithvariousresinsa

SolventButvar

B-76, B-79Butvar B-72, B-74,

B-90, B-98

Acrylate — I I

Alkyd Beckosol™11-035 P P

Duraplex™11-804 P P

Cellulose Celluloseacetate I I

Celluloseacetatebutyrate P P

Ethylcellulose P P

Nitrocellulose,RS™ C C

Nitrocellulose,SS™ C C

Chlorinatedrubber — I I

Coumarone-indene — I I

Epoxy Epi-Rez™540-C C C

Epon™1001F,1007F C C

Araldite™6069 C C

Fossil Damar C C

Isocyanate Desmodur™APStabil C C

Melamineformaldehyde Resimene®717and881 P P

Resimene®730and741 P P

Phenolic OxyChem™02620,92600,29107 C C

Durite™P-97 C C

Methylon™75-108 C C

Santolink®EP560(butyletherified) C C

SP-1044resin C C

Rosinderivatives Pentalyn™H P P

Staybelite™ester10 C P

Vinsol™ C C

Shellac — C C

Silicone DC840 C P

DCZ6018 C P

Sulfonamid Ketjenflex™MH P P

Ureaformaldehyde Resimene®918 P P

Vinylchloridecopolymer VAGH,VAGD P IaRefers to film compatibility provided mutual solvents are used.

Key: C–compatibleinallproportionsP–partiallycompatibleI–incompatible

Insolubilizing reactionsManyapplicationsforthevinylacetalresinsinvolvecuring

withathermosettingresintoobtainthebalanceofproperties

desired.Thefreehydroxylgroupsinvinylacetalresinspresent

apointofchemicalreactivitythroughwhichtheresinsmay

beinsolubilized.Ingeneral,anychemicalreagentorresinous

materialwhichreactswithsecondaryalcoholswillreactwith

thepolyvinylbutyraltoinhibitsolubility.

Thepropertiesofcoatingsvarygreatlywiththetypeand

amountofcrosslinkingagentused.

15

OH

OHOH

CH3

BUTVAR

BUTVAR

BUTVAR

BUTVAR

PHENOLIC

H+

(R)HOH2 CC H 2OH

OH

CH3

O

O OH

CH3

(R)H2 CC H2

OH

CH3

OH

BUTVAR

EPOXY

BUTVAR

CH2 CH

CH CH2

CHOC

CH3

CH3

CH3 OH

CH3

CCH2 CH2O O CH2 CH2OCH2 CH

OH

CH

O O

C

O

O

O

O

C

X

C

O

O

CH2

C

O

O

Typical epoxy resin

Reactionwithphenolics

Reactionwithepoxies(anhydridecure)

16

Reactionwithdialdehydes

Reactionwithmelamines

Reactionwithisocyanates

CH CH2 CH

OH OH

O

O

OH OH

HC H+

CH

CH CH2 CH

O O

CH CH2 CH

HC

CH

OO

CH CH2 CH

BUTVAR

BUTVAR

O

N N

O

HO

OH

BUTVAR

BUTVAR

BUTVAR

BUTVAR

MELAMINERESIN

HOH2C

NH 2

CH2OHNH NHNH HN(R)C CC C

N

C

N N

NH2

C

N

N N

H2C

NH2

CH2NH NHNH HN(R)C CC C

N

C

N N

NH2

C

N

H+

O

OH

R

NCO

OH

NCO

O

NH

C

C O

O

R

NH

BUTVAR

DIISOCYANATE

BUTVAR

BUTVAR

BUTVAR

Tertiary amine

Applications

Wire enamelsButvar®resinsmaybeusedtoovercoatmagnetwiresothat

coilsmadefromthatwirecanbecementedwithheatorby

solventactivation.

Coiledorshapedmagnetwirewithapolyvinylbutyral

overcoatistoughandflexible.Thepresenceofhydroxyl

groupsinthepolyvinylbutyralmoleculepermitsthe

polyvinylbutyralnotonlytocrosslinkwithitselfbutalso

tocrosscurewithphenolicorisocyanateresin.

Theoverallbalanceofphysicalandchemicalpropertieshas

madethistypeofovercoatbasedonButvaraleaderinthe

fieldformanyyears.

Surface coatingsTheButvarvinylacetalresinmaybeusedaloneorin

combinationwithawidevarietyofresinstogivefunctional

surfacecoatingcompositions.Filmswhichmaybeairdried,

baked,orcuredatroomtemperatureareobtainedbyproper

compounding.Thepresenceofhydroxylgroupsinthe

polymermoleculenotonlyenablesgoodwettingofmost

substratesbutalsofurnishesareactivesiteforchemical

combinationwiththermosettingresins.

Wash primers Inprotectivecoatingsformetal,thebestknownvinyl

acetalapplicationisin“washprimers,”alsoreferredto

as“metalconditioners.”Comparedwithothercorrosion

inhibitingmaterials,washprimersareuniqueandmore

effectivebecausetheyoffer,inasingletreatment,several

meansofpreventingcorrosion.Theseanticorrosiveprimers

applyeasier,adherebetter,anddryfasterthanthemore

conventionalmaterials.

Theactionofwashprimersoversteel,forexample,is

asfollows:

•First,anironoxideandzincphosphatefilm,similartothat

formedinthecommonphosphatingprocesses,isdeposited

onthemetal.

•Second,thesewashprimersprovideacontinuoussupply

ofchromateionstorepairpinholesinthephosphatefilm,

eliminatingtheneedforaspecialchromaterinse.

•Third,thepolyvinylbutyralfilmischemicallyboundinthe

inorganiclayersthroughachromiumcomplex,providing

additionalmechanicalprotectiontothemetalsurface.

Ineffect,thistypeofprimeractuallyphosphatizesthemetal

atthesurface,suppliesacorrosioninhibitingpigmentina

tenaciouslyadheringbinder,anddriestotakemosttopcoats.

Washprimersarewidelyusedonavarietyofmetal

structures,suchasstoragetanks,ships,airplanes,etc.

Highwaydepartmentsalsohaveshownakeeninterest

inthesecoatingsforbridges,damlocks,andinparticular,

highwayguardrails.Infinishingtrucksorhousetrailers

fabricatedofphosphatedorgalvanizedsteel,oraluminum,

washprimersprovidecorrosionresistanceandadhesion

undersingle-coatstyrenatedalkydandothermodified

alkydenamels.Onmetalthatissubjecttoimmersionand

corrosionconditions,washprimersarespecifiedunder

urethaneandvinyltopcoats.

Military specification wash primersTheU.S.NavyBureauofShipshaslongrecognizedtheneed

fortheuseofthewashprimerasasurfacepretreatmentfor

metalspriortosubsequentpainting.MilitarySpecification

DOD-P-15328DentitledPrimer, Pretreatmentisrequiredto

beusedonallmetalsurfaces.Thisprimerisatwo-package

systemcontainingButvarB-90inasolventsystemconsisting

ofnormalbutanolandeitherethanolorisopropanol.By

comparison,theDepartmentoftheAirForceandtheU.S.

NavyBureauofNavalWeaponshaveapprovedaslightly

differentpretreatmentformulationdesignatedCoating

Compound, Metal Pretreatment, Resin-AcidMIL-C-8514C

(ASG).ThissystemspecifiestheuseofeitherButvarB-76or

ButvarB-90inasolventsystemconsistingofbutanoland

ethanol.Specificdetailsofbothwashprimersystemscanbe

foundintheparticularspecificationinvolved.

17

Nonspecification wash primers: B-1030 with ButvarWashprimerB-1030formulationisatwo-packagesystem

basedonButvarB-76resinandathermosettingphenolic

resin.Thisformulationwasdesignedtogivehigherearly

waterresistancethanthewell-knownmilitaryspecification

washprimers.CoatingsbasedonformulationB-1030exhibit

reducedtendencytoblisterandtoloseadhesioninhigh

humidity.TheB-1030formulationalsohasnonsettling

characteristics.Incontrasttotheolderwashprimer

formulations,B-1030doesnotdisplayhardpigmentsettling

ofthebasegrind.

ThethermosettingresincontentoftheB-1030formulation

notonlyincreaseswaterresistancebutalsocontributesto

reducedsolventsensitivity.Thus,goodadhesionandcorrosion

resistanceareretainedunderalkyd,alkyd-nitrocellulose,

acrylic,andvinyltopcoats,andalsounderepoxy,urethane,

polyvinylacetate,andalkydmelaminetopcoats.

Single-package wash primer: B-1011 with ButvarWashprimerB-1011isaclear,greensingle-packageprimer

alsoknownasa“reacted”washprimer.BasedonButvar

B-90resin,ithasexcellentstabilityinbothconcentrated

anddilutedformsandairdriestoclearglossyfilmsofvery

lowcolor.Filmsoftheprimerpossessgoodadhesionto

steel,phosphatedsteel,galvanizedsteel,brass,copper,wood,

stainlesssteel,andchromeplate.Althoughdesignedto

enhanceadhesion,thiscoatingalsofunctionsasacorrosion-

inhibitingprimerforavarietyoftopcoatsbutinmanycases,

mayaffordprotectionasthesolecoating.

18

Table 11.WashprimerB-1030withButvar

A. Base grind Percent by weight

1.Toasolutionof: ButvarB-76 1.24

Ethanol,95% 9.35

Methylethylketone 9.97

2.Add: Basiczincchromatepigment 11.52

Celite™266 4.82

3.GrindtoHegmanfinenessof6,N.S.scale

4.Addsolutionof: ButvarB-76 7.39

Ethanol,95% 23.08

Methylethylketone 24.63

Santolink®EP560 8.00

Total 100.00

5.Grindfor30minutesandpackage

B. Reducer Percent by weight

Phosphoricacid,85% 7.50

n-butanol 92.50

Total 100.00

Mixforseveralminutesandpackage

Reduced primer properties (Pigmentgrindtoreducer;1:1byvolume)

NVM 19%

Weightpergallon 7.5lb

Coverage 533sq.ft./galat0.3milsdry

Potlife 8–12hours

Chromate-free wash primers with Butvar Traditionalwashprimerformulationshavegenerally

employedzincchromateastheanticorrosivepigment.

Duetotoxicityconcernsassociatedwithchromates,

alternativeanticorrosivepigments,suchaszincmolybdate,

borate,orborophosphate,aresuggested.Substitutionof

thesepigmentsforzincchromateonanequalweightor

volumebasisaresuggestedstartingpointsforreformulation.

Achromate-freewashprimerbasedonU.S.Government

specificationDOD-P-15328DisshowninTable13.

19

Table 12.WashprimerB-1011withButvar

Material Percent by weight

A. Acetone 44.40

Anhydrousethanol 36.30

ButvarB-90 11.00

B. 85%phosphoricacid(U.S.P.) 0.72

Water 6.48

C. Chromicacid(99+%) 0.37

Water 0.73

Total 100.00

Properties

NVM 12%

Viscosity 21sec.,No.4Fordcup

Lb/gal 7.0

Coverage 384sq.ft./galat0.3milsdry

Table 13.Sherwin-Williamschromate-freewashprimer

A. Base grind DOD-P-15328DMoly-White

X92Butvar**

B-90, B-98

Pounds Pounds Gallons

ButvarB-90 56.0 56.0 6.10

n-butanol 125.0 125.0 18.48

Isopropanol,99% 353.0 353.0 53.80

Moly-WhiteX92 — 39.7 1.70

Basiczincchromate 54.0 1.70

Magnesiumsilicate,MP40-27 8.0 8.0 0.34

Furnaceblack 0.6 0.6 0.34

Water,DI 15.0 15.0 1.80

— — 82.26

B. Reducer

Phosphoricacid,85% 28.0 28.0 2.0

Water,DI 25.0 25.0 3.0

Isopropanol,99% 99.0 99.0 15.0

— — 20.0

Alternativechromate-freepigmentsarePhosGuard®J-0800fromMineralPigmentsCorporationandBorogardZBfromU.S.Borax.

Metal coatingsButvar®resinsareusedinawidevarietyofmetalcoating

applicationsincombinationwithotherresintypes,such

asphenolics,epoxies,isocyanates,melamines,ureas,etc.

Whenusedwiththesevariousmodifyingresins,Butvarcan

improvecoatinguniformity,minimizecratering,improve

adhesion,andincreasecoatingtoughnessandflexibility.

Theseresincombinationscanbecompoundedtoproduce

bakedcoatingswithgoodchemicalresistance,whichalso

willwithstandpostforming.Applicationsofsuchcoatings

canbemadebyconventionalmethodsincludingbrush,

spray,dip,fluidizedbed,etc.End-useapplicationsinclude

drumandcanlinings,aswellasthewidevarietyofmetallic

substrates,whicharecoatedbythefluidizedbedtechnique.

CurablecoatingscontainingButvarresinmaybeformulated

tomeettheextractabilityrequirementsoftheU.S.Foodand

DrugAdministrationforindirectfoodadditiveuses.

Metalcoating2009isoneexampleoftheuseofButvar

incombinationwithotherresins—inthiscasephenolic

andepoxy—toproduceanexcellentcoating.Thisparticular

combinationprovidesexcellentabrasionresistance,

toughness,flexibility,adhesion,andchemicalresistance.

Specificapplicationtestshaveshownthatthissystem

shouldmakeoutstandingcanordrumlinings.

20

Table 14.Metalcoating2009

Material Percent by weight

Diacetonealcohol 17.4

n-butanol 17.4

Ethanol,95% 7.7

Xylol 34.7

Santolink®EP560 5.1

Epon™1007F 13.0

Butvar®B-90 2.0

10%phosphoricacid(inabovesolvents)

2.7

Total 100.0

Properties

NVM 20%

Application:sprayorroller

Curecyclesequence:Roomtemperature.Drying15minutes,followedby30minutesat190˚Fand20minutesat400˚F.

Wood finishes Protective wash coats and sealers

Butvar®resiniswidelyusedasacomponentofwash

coatsandsealersinwood-finishingoperations.Itprovides

goodholdout,intercoatadhesion,moistureresistance,

flexibility,toughness,andimpactresistancetothecoating

system.Inaddition,thewoodsubstrateisprotectedagainst

discolorationwhenButvarisusedinthefinish.Combinations

involvingnitrocellulose,shellac,andshellacesteralongwith

otherresintypesareusedwithButvarundermanyofthe

commontopcoats(Table15).Butvarisparticularlyeffective

forimprovingtheholdoutofpolyesterandpolyurethane

coatings,aswellasprotectingthewoodsubstrateagainst

colorchangescausedbylight.

Thefollowingstartingformulationisrepresentativeofthe

kindofwoodsealerorwashcoatthatcanbecompounded

fromButvar.

Knot sealers

Thepolyvinylbutyralresinsareexcellentbarriersto

bleedingofterpenaceousmatterfromknots,heartwood,

androsinducts.TheWesternPineAssociationhasdeveloped

asuperiorknotsealerbasedonButvar.Thesystemconsists

ofacombinationofButvarandphenolicresins(Table16).

Theprecedingformulationisdesignedforbrushapplication.

However,ithasbeenadaptedtoapplicationfromanaerosol

spraycan,givingthesameoutstandingperformanceasthe

brushappliedsystem.

21

Table 15.Sealer/washcoatwithButvar

Material Percent by weight

ButvarB-98 6.1

Nitrocellulose,RS™,¼second 9.2

Butylacetate 32.9

Ethanol,anhydrous 5.5

Isopropanol,99% 10.9

Methylisobutylketone 8.8

Xylol 13.3

Toluol 13.3

Total 100.0

Table 16.WesternPineAssociationknotsealer,WP578

Material Percent by weight

ButvarB-90 3.3

Durite™P-97 40.0

Ethanol,95% 56.7

Total 100.0

Properties

NVM 23.3%

Application:brush

Properties

NVM 12.5%

Viscosity20sec.,

No.4Fordcup

Cure cycle sequence: Room temperature. Drying 15 minutes, followed by 30 minutes at 190˚F and 20 minutes at 400˚F. Application: Spray or roller

Adhesives Structural adhesives

Structuraladhesivesoriginallyweredevelopedforusein

theaircraftindustrytoreplacerivetsandothermethodsof

joiningandfastening.Refinementsinformulatingstructural

adhesivesledtotheiruseinbondingbrakelinings,inthe

electricalandelectronicindustriesonprintedcircuits,in

structuralcompositefiberbindersforaerospaceor

antiballisticapplications,andinthearchitecturalfieldfor

themanufactureofinteriorandexteriorcurtainwalls.

CombinationsofButvar®resinwiththermosettingresins

havelongbeeninuseinbondingaircraftcomponents—

infact,thesystemwasthefirstsyntheticresinadhesive

tobeusedforbondingmetalsinstructuralapplications.

Phenolic resins

Insomestructuraladhesiveformulations,Butvarresinsare

combinedwithalkalinecatalyzedphenoliclaminatingresins,

suchasDurite™LS-433orPlyophen™22-023.Comparedwith

othergeneraltypesofstructuraladhesivesystems(epoxy-

phenolicandsyntheticrubber-phenolic),thePVB-phenolic

givesthehighestshearstrengthvaluesattemperaturesup

to250˚F.OtheroutstandingpropertiesofthePVB-phenolic

systemincludehighpeelstrengthatverylowtemperatures,

excellentdielectricproperties,andexceptionallygoodcreep

resistanceasmeasuredbytheabilityofthebondtocarry

sustainedloadsforextendedperiodsoftime.

Polyvinylbutyral-phenolicratiosoffrom10:1to10:20have

beenusedsuccessfullyforstructuraladhesives,although10:5

seemstobethebestratioforacompromiseofproperties.

Astheamountofphenolicisreduced,thecuredadhesive

becomesmoreflexible,andinmostcases,peelstrength

increases.Inaddition,becauseoftheincreasedthermoplastic

natureofthesystem,thehightemperatureshearstrengthis

reduced.Theseeffects,i.e.,increasedpeelandreducedhigh

temperatureshearstrength,occurwhenthecuretimeis

shortenedorthecuretemperatureislowered.

Structuraladhesivesbasedonpolyvinylbutyralresinscan

beappliedasasolution,anunsupportedfilm,asupported

filmonpaperorcloth,orasamixtureofliquidandsolid.1

Inasolutionadhesivesystem,thechoiceofsolventsis

importantbothforviscositycontrolofthesolutionand

properdryingandfilmingcharacteristics.Properdryingof

theadhesivefilmisveryimportant,asonlyasmallamount

ofresidualsolventcanaffectgreatlythevariousfinal

properties.Yetthesolventcannotbesovolatilethat

blushingoccurs.Sprayedfilmsaremuchmoresensitiveto

blushingthanbrushedorroller-coatedfilms.Forbrushing,

solventsintheboilingrangeof75˚to100˚Careadvised

becausetheycanberemovedbyairdryingandthenforce

dryingfor30to60minutesat105˚C.Solutionsforspraying

cantoleratesmallamountsofhigherboilingsolvents,such

asxyleneandbutanol.

Viscosityoftheadhesivesolutionaffectsthesmoothness

andthethicknessofthefinalbrushedorsprayedfilm.

Forbrushing,theproperviscosityisobtainedatthe

followingsolidscontent(witha10:5PVB:phenolicratio):

ButvarB-90,21%;ButvarB-72,16%to18%.Forspraying,

thesolidscontentshouldbereducedtoobtainnonblushing,

noncobwebbingfilms.

Epoxies and other thermosetting resins

Butvarresinsarecompatiblewithmanyepoxyresinsand

canconfersuchimprovementsonepoxy-basedsystemsas

increasedimpactresistanceandpeelstrength.Inepoxy

systems,asinphenolicsystems,thevinylacetalresinscan

serveasbothcoreactantandflexibilizer.

Theadditionofsmallamountsofcompatibleplasticizerto

anadhesivesystemcombiningavinylacetalresinwitha

thermosettingresinincreasestheflexibilityandimpact

resistanceofthebondwithonlyslightsacrificeinhigh

temperatureshear.Thisincreasedflexibilityismostevident

whenpeelingthickadherendsandathighpeelingspeeds.

Thetackorheatsealtemperatureoftheuncuredadhesive

alsoisappreciablyloweredbytheadditionofplasticizer.

Adhesiveswithpressuresensitivepropertiesintheuncured

statecanbedevelopedwhich,whencured,willhave

temperatureshearbondstrengthofmorethan1,000psi.

22

1See U.S. Patent 2,499,134.

High-strength bonding procedure

Forhigh-strengthbonds,substratecleaningisvery

important.Usuallytheremovalofsurfacecontamination,

suchasoilfilm,dust,etc.,issufficient.Suchcleaning

normallyisachievedbysolventorbydetergentwash.

However,forhigheststrengthbonds,chemicalsurface

preparationisemployed.Thefollowingmetalsrequire

thepreparationnoted:

•Aluminumalloys—acidoxidation

•Copper—alkalineoxidation

•Steel—apicklingbathtoremoveoxidescale

Careshouldbetakentoavoidtouchingthecleanedpanels

orexposingthemtoanycontaminatedatmosphere.The

adhesiveshouldbeappliedtothecleanedsurfaceassoon

aspossible.

Adrygluelineof3to10milshasbeenfoundquite

satisfactory.Withsolventsystems,thisthicknessusually

canbeachievedwith2to4brushedcoatsofadhesiveon

eachadherend.Withverythingluelines,evenpressuremust

beappliedtothelaminateduringcuresothatconsistent

bondsbeobtained.Thickergluelineshavegreaterflowand

absorbunequalcuringpressures.

Performance characteristics

Thequalityofastructuralbondforaparticularapplication

isusuallydescribedintermsofitsshearstrength,peel

strength,creepproperties,fatiguestrength,and

environmentalresistance.Inaircraftapplications,high

temperatureshear,fatigueresistance,creep,andoilandgas

resistancearemostimportant.Inprintedcircuits,peel

strength,blisterresistance,anddielectricpropertiesareof

primaryimportance.Forarchitecturaluse,highpeelstrength

andlong-termresistancetodeadloadandextremesof

atmosphericenvironmentaretheoutstandingrequirements.

AdhesivesbasedonButvar®resinsexcelinallofthese

characteristics.

Therequirementsandmethodsfortestingadhesivesfor

aircraftapplicationsarepresentedinMilitarySpecifications

MM-A-132andMIL-A-25463-30.Testmethodsfor

architecturalandprintedcircuitapplicationsarecontained

invariousASTMandNEMAspecifications.

Adhesive strengths

TypicaltestvaluesforphenolicbondsofButvarresins

measuredbythesetechniquesareinTable17.

Table 17.Adhesivesstrengths

Amount of PSI shear strength at Peel at 72ºFVinyl acetal phenolic, phra Cure 72ºF 180ºF 250ºF 300ºF lb/in. width

ButvarB-72 50 30min,330ºF 6,000 4,000 1,400 500 25–30

ButvarB-90 50 30min,330ºF 5,700 2,800 1,000 — 30–35

ButvarB-72 100 20min,300ºF 5,000 3,300 1,100 — 35–40aphr = parts per hundred resin

Testprocedures:Shear—aluminumtoaluminumasperMIL-A-8431Peel—6-milaluminumto64-milaluminumpeeledat5inchesperminute

23

Hot melt adhesives

Butvar®makesanexcellentbaseforhotmeltadhesives

evenwheredifficult-to-bondsurfacesareinvolved.Themany

typesofButvarresinsallowthebestmatchtoindividual

applications.Forexample,ButvarB-98canbeformulatedto

produceahotmeltwithlowviscositycharacteristics.B-72

canbeusedtoproduceanadhesivewithsimilarchemical

propertiesbuthigherviscosity.Othertypes,suchasB-76,

areavailabletoproduceadhesiveswherelesscrosslinkingis

desirable.

Table18showsastartingformulationforahotmeltbased

onButvar.

Textile coatings OneoftheuniqueusesofButvarpolyvinylbutyralresinis

inthetextilecoatingfield.Itcanbecompoundedtomake

fabricswaterresistantandstainresistantwithoutnoticeably

affectingtheappearance,feel,drape,andcolorofthefabric.

Tablecloths,drapes,slipcovers,showercurtains,aprons,

smocks,andchildren’sbibsaresomeofthemorecommon

itemswhichcanbeprepared.Outsidethehome,fabrics

coatedwithButvarserveasrainwear,porchfurniture

upholstering,awnings,andbeachaccessories.

Butvar,whichprovidesatransparentfilm,canbeapplied

topracticallyallcommonfabrics.Cotton,wool,silk,nylon,

viscoserayon,andothersyntheticscanbesuccessfully

coated.Asarule,almostanyfairlytightwovenfabricwith

aflatsurfacecanbemadewaterandstainresistantwith

acoatingbasedonButvar.

Advantages as textile coating TheadvantagesofButvarasatextilecoatingresinstem

fromthefollowingproperties:

•Transparency:Butvarcanbemadeintoaclear,colorless

coatingwithexcellentlightresistanceandaging

characteristics.

•Adhesion:Aftercuring,Butvaradheresreadilytopractically

allfabrics,includingthosenormallyconsidereddifficultto

coat,suchasnylon,viscoserayon,andfiberglass.

•Handandappearance:AcoatingwithButvarhasthesoft,

warm,flexiblefeelofanuncoatedfabric,yetpossessesall

thefunctionalcharacteristicsofcoatedfabrics.

•Functionalproperties:Butvarcombinestheseattributes

withfunctionalpropertiescomparabletothoseofthebest

textilecoatingmaterialsinthefield.Duringthedryingand

curingoperations,Butvaristransformedtoanelastomer

whichbecomesapermanentpartofthefabric.

FabricscoatedwithproperlycompoundedandcuredButvar

haveoutstandingsoftnessandflexibilitywithouttackiness

oflowsofteningtemperatures.Theyhaveexcellentchemical

andwaterresistance.FilmsofButvarresinaretoughandwill

resistabrasionandwear.Coatingscanbeappliedfromhigh

solidssolutionsmadewithcommonsolvents.Clearcoatings

withButvarmaybeappliedfromsolutionsofupto35%

solids;pigmentedcoatingsmaybeashighas45%solids.

SolutionsofButvarareideallysuitedtocoatingwitheither

rubberorpyroxylinspreaders.Solidscontentcanbehigh

andthesolventsfastevaporating.Thematerialwillflowwell

afterbeingspread.Formostapplications,alightcoating

averaging1½ozdrytothesquareyardisrecommended.The

solutionofButvar,whichcanbepreparedinasolvent

mixtureofalcoholandnaphtha,isappliedingenerallytwo

tofivepasses,dependingonthetypeoffabricandthe

coatingoperation.Thisisfollowedbyaflattopcoatto

removeglossandtacknormallyassociatedwithcoated

fabrics.Usuallytwotopcoatsarerequiredforasmooth,

skip-freecoating.

Thefirsttwocoatsshouldbelowinviscosityforproper

penetrationofthecoatingintothefiberinterstices.The

relationshipbetweendepthofpenetrationandcoating

viscositywillnecessarilydependonthefabricconstruction

andmustbedeterminedonthebasisoftrials.Ifan

excessivelyhighcoatingviscosityisusedfortheinitial

coats,peeladhesion,Mullen,andotherphysicaltest

propertieswillsuffer.Experiencehasshownthatsuperior

coatingsareproducedbymanythincoatsratherthan

byafewheavyapplications.24

Table 18.Typicalhotmeltformulation

Material Parts by weight

ButvarB-76 10

Santicizer®160 10

Castorwax™ 35

Poly-Pale™Ester#1 26

Staybelite™Ester#10 19

Total 100

Butvarisuniqueamongvinylresinsinitsabilitytobecured

inamannersomewhatanalogoustorubber.Curingimproves

bothheatandsolventresistanceandadhesiontothefabric.

CuringButvarisaccomplishedbyincorporatingcrosslinking

resins,suchasurea,phenolics,melamines,andisocyanates.

Sincethereactioninvolvesthehydroxylgroupsonthe

chainofButvar,onlyasmallamountofamodifyingresin

isneededtoincreasesubstantiallytheheatandsolvent

resistanceoftheButvarresin.

Aformulationincorporatingsuchacrosslinkingresinis

showninTable19.

Coatedstocksarecuredafterallcoatshavebeenapplied.

Prematurecuringofanycoatduetooverheatingwillreduce

theadhesionofsubsequentcoats.Thetimerequiredfor

curingwilldependontheresinsandthecatalystsemployed

andonthetemperatureofthecuringoven.Curetimewill

varyfromapproximatelyonehourat250˚Ftofiveminutes

orlessat350˚F.

CoatingswithButvarhavebeencuredsatisfactorilyinfestoon

dryersat200˚F,insteamheatedovensat300˚F,ingasovens,

andevendryercans.Inallcases,overheatingshouldbe

avoidedtopreventlossofplasticizerandstiffening.

Aproperlycoatedandcuredfabricwillbewaterresistant;

willberesistanttoinkstains,coffee,tea,cookingoils,and

fats;andwillhaveexcellentwashability.Mostsoilingscanbe

wipedawaywithadampcloth.Shouldtheuncoatedside

requirelaundering,neutralsoapandwarmwatershouldbe

used.Thecoatedfabriccanbeironedontheuncoatedside.

CoatingsbasedonButvarcannotbedrycleaned.Such

treatmentwillremovetheplasticizerandleaveastiff,harsh

coatingwhichwillbreakonflexing.

Ceramic binder applicationsButvarpolyvinylbutyralresinsarerecognizedasthe

binderofchoiceintheprocessingofceramictapecast

materials.Theresinimpartsexcellentgreenstrengthand

flexibilitytotheceramictape.Itiscompatiblewithmany

commonsolventsandplasticizersandburnsoutcleanly

duringsintering.

Butvarresinsalsoareusedasabindermediuminthick

filmprocessing.Butvarisformulatedinthesolventvehicle

usedtodepositthecircuitpatternontheceramicsurface.

TheprimaryadvantagesofusingButvarresinsaretheir

solubilityinawiderangeofsolventsanduniformadhesion

toconductivemetals.

Table 19.Typicaltextilecoatingformulation

Material Parts by weight

ButvarB-72 48.0

Tricresylphosphate 48.0

Ethanol95% 84.2

Toluene 64.8

Water 8.0

Resimene®AQ-7550 3.5

p-toluenesulfonicacid 0.7

p-nonylphenol 0.2

Compounding

1.Combinesolventsandplasticizer.

2.AddButvarB-72withstirring;heatifdesiredtospeedsolution.

3.Coolbatch,blendinp-nonylphenol,ResimeneAQ-7550,andp-toluenesulfonicacidinthatorder.

Compound properties

Percentsolids 39%

Viscosity(freshlymade) ca70,000cps

Viscosity(24hours) ca75,000csp

Cure cycle sequence: Room temperature. Drying 15 minutes, followed by 30 minutes at 190˚F and 20 minutes at 400˚F. Application: Spray or roller

25

Tape castingButvarisregardedasthebinderofchoicefortheceramic

tapecastingprocessduetothefollowingbenefits:

•Butvarresinsprovideexcellentgreenstrengthtothe

unifiedtape.

-Butvarallowsmultipletapestobelaminatedin

thegreenstage.

-LowButvarconcentrationsallowforhigherdensity

substratesafterfiring.

•Butvarissolubleinmanyvolatileyetinexpensivesolvents.

-FlexibilityinchoosingButvarproducttypesandload

levelsforawiderangeinbindersolutionviscositiesand,

therefore,ceramicslipviscosities.

•Butvariscompatiblewithmanyoftheplasticizersused

inceramicsystems.

-Choosefromdialkylphthalates,benzylphthalates,

adipates,orphosphatescommonlyused.

•Butvarburnsoutcleanlywithaminimumofwarpage

tothefiredpart.

-Theproductshrinksuniformly.

-Lowgelcontentminimizessurfacedefects.

•Butvarhasnaturaldispersingpropertiesandiscompatible

withcommondispersingagents,suchasfishoilsor

phosphateesters.

Themedium-to-lowmolecularweightresins,Butvar

B-76,B-79,B-90,orB-98,arerecommendedforusein

tapecastingprocesses.

Atypicaltapecastingformulationbasedon100gmsof

solidceramicpowderisshowninTable20.

PremixthefishoilinthetolueneandMEKandaddtoball

mill.AddAluminaandballmillforonehour.AddSanticizer

160andButvarB-79.Millanadditional24hours.Pour,

de-airforseveralminutes,andcast.

•AdditionalButvarcanbeaddedtomostformulationsto

improveinterfilmlaminationinamultilayersubstrate.

•Amicrofiltrationsystemisgenerallyusedwith

binder/solventsystems.Afivemicronorfinerfilteris

recommended.

Thick filmsButvarresinscanbeusedasthebindermediuminvehicle

formulationsforthickfilmpastes.Ourlowestmolecular

weightresins,ButvarB-79andB-98,arerecommendedfor

eithersilkscreenorsteelscreenprocesses.Theadvantages

ofusingButvarinthickfilmsinclude:

•Butvarisanexcellentbinderanddispersantforthe

conductivemetalsusedinthickfilms.

•ThickfilmswithButvarcanbecofiredwiththegreen

tapeinlaminatedceramicsubstrates.

•Bindercompatibilityproblemsareminimizedforcofiring

systemswhenButvarisusedinboththickfilmprocessing

andasthebinderintheceramictapecastingprocess.

Theapparentglasstransitiontemperature(Tg)was

determinedbyDifferentialScanningCalorimeter(DSC).

TheThermalGravimetricAnalysis(TGA)wasaweightloss

versustemperatureprofileconductedataheatingrateof

10˚C/min.

26

Table 20.Typicaltapecastingformulation

Component Parts by weight

Alumnina 100.0

ButvarB-79 5.0

Santicizer®160 4.3

BlownMenhadenOilZ-3visc. 2.0

Toluene 14.4

MEK 14.4

Table 21.Thermalproperties

UnitsTest

method

Butvar B-76 B-79

Butvar B-90 B-98

Glasstransitiontemperature(Tg)

C DSC 62–72 72–78

Ashcontentat550ºC

Innitrogen % TGA <2.0 <3.0

Inair % TGA <0.75 <0.75

Toners and printing inksButvarresinshavebeenusedinprintinginkformulations

formanyyears.AllButvarresinsarealcoholsolubleand

areoftenusedinsolvent-basedgravureandflexographic

inkformulationstoimproveflexibility,adhesion,and

toughness.ThesolubilitycharacteristicsofButvarB-79and

B-76inaromaticandotherfast-dryingsolventsallowfor

compoundingatlowconcentrationsinhighspeed,high

qualityprintingapplications.Thesepropertieshavealso

enabledButvartobeusedininkformulationsforthickfilm

conductivepastes,printerribbons,andpeninks,aswellasin

themanufactureofoffsetprintingplatesandotherprinting

technologyapparatus.

Butvaralsoservesthetonerindustryasasecondarybinder.

Polyvinylbutyralisaddedtotheformulationstoincrease

viscosityandtoimprovefilmintegrityoverthefuserroll.

TheoveralltoughnessofButvarenhancestheintegrity

ofthetonerduringthemillingprocessandextendedmachine

operation.Thisminimizestheleveloffineswithoutdetracting

fromtheflowproperties.

27

Graph 11.Butvar®resinthermolysisprofiles:ThermalGravimetricAnalysis(TGA)

Graph 12.Butvar®resinthermolysisprofiles:ThermalGravimetricAnalysis(TGA)

In nitrogen

In air

100

90

80

70

60

50

40

30

20

10

050 100 150 200 250 300 350 400 450 500 550

Wei

ght

(wt

perc

ent)

Temperature (ºC) Heating rate: 10ºC/min

100

90

80

70

60

50

40

30

20

10

050 100 150 200 250 300 350 400 450 500 550

Wei

ght

(wt

perc

ent)

Temperature (ºC) Heating rate: 10ºC/min

100

90

80

70

60

50

40

30

20

10

050 100 150 200 250 300 350 400 450 500 550

Wei

ght

(wt

perc

ent)

Temperature (ºC) Heating rate: 10ºC/min

100

90

80

70

60

50

40

30

20

10

050 100 150 200 250 300 350 400 450 500 550

Wei

ght

(wt

perc

ent)

Temperature (ºC) Heating rate: 10ºC/min

Storage Environmentsofhighheatandhumidityshouldbeavoided.

Toxicity and FDA statusButvar®resinsareregulatedbytheU.S.FoodandDrug

Administrationunderpartsof21CodeofFederalRegulations

foruseasindirectfoodadditives.Butvarresinalsohasbeen

subjectedtoacutetoxicityandmutagenicitystudies.Details

onspecificcoverageofindividualstudiesareavailableon

request.

Quality controlToobtaintheoutstandingqualitycharacteristicsof

Butvar,Solutiamaintainsstatisticalprocesscontrolover

themanufacturingprocess.Inaddition,toensurethat

youreceivehighlyuniformmaterialwitheachshipment,

thefinishedproductisanalyzedindetailtobecertainit

conformstoourrigidspecifications.

Storage and handling

28

Table 22.Packaginginformation

Container type B-72 B-90, B-76 B-98, B-79, B-74

61-gallonfiberdrum 145lb(66kg) 140lb(63kg) 135lb(61kg)

Material sources

29

Product designation Owner and/or supplier

Araldite6069 CibaGeigyCorporation

BasiczincchromateLanscoColorsRockwoodPigmentsNA,Inc.

Beckosol11-035 ReichholdChemicals,Inc.

BlownMenhadenOilZ-3visc.WernerG.SmithInc.

R.E.Mistler,Inc.

BorogardZB U.S.Borax

2-Butoxyethanol(Eastman™EBsolvent) EastmanChemicalCompany

Butvar®resins EastmanChemicalCompany

Butylacetate EastmanChemicalCompany

Butylalcohol EastmanChemicalCompany

Butylbenzylphthalate FerroCorporation

CastorOil#1(raw),#15,#30,#40 CasChemInc.

Castorwax CasChemInc.

Celite266 ImerysFiltration

Celluloseacetate EastmanChemicalCompany

Celluloseacetatebutyrate EastmanChemicalCompany

Chlorinatedrubber HerculesInc.

Chromicacid(chromiumtrioxide) J.T.BakerInc.

DC840 DowCorningCorporation

DCZ6018 DowCorningCorporation

DesmodurAPstabil BayerMaterialScience

Diacetonealcohol ShellChemicalCorporation

Dibutylphthalate BASF

Dibutylsebacate HallStar

Dihexyladipate FerroCorporation

Dimethylesters Invista

Dioctylphthalate EastmanChemicalCompany

Duraplex11-804 ReichholdChemicals,Inc.

DuriteP-97,LS-433 BordenChemicalCompany

Epi-Rez540-C Solvay

Epon1001F,1007F Momentive

2-ethylhexyldiphenylphosphate FerroCorporation

Flexricin-P3 CasChemInc.

Furnaceblack ColumbianChemicals

Hercolyn PinovaSolutions

Isophorone DowChemicalCompany

Isopropanol EastmanChemicalCompany

Ketjenflex8,9S,MH Axcentive

Product designation Owner and/or supplier

LinseedoilAristaChemicalInc.ReichholdChemicals,Inc.

MagnesiumsilicateMP40-27 SpecialtyMinerals

Methylacetate EastmanChemicalCompany

Methylalcohol AirProductsandChemicalsInc.

Methylethylketone ShellChemicalCorporation

Methylisobutylketone EastmanChemicalCompany

Methylon75-108 OxyChem

Moly-WhiteX92 Sherwin-WilliamsChemical

Naphtha ShellChemicalCorporation

NitrocelluloseRS,SS DowWolffCellulosics

OxyChem02620,92600,29107 OxyChem

p-nonylphenol BoddinChemiehandel

Paraplex®RGA-8 HallStar

PentalynH EastmanChemicalCompany

PhosGuard®J-0800 RockwoodPigmentsNA,Inc.

Phosphoricacid,85%U.S.P. Astaris

Plyophen22-023 OxyChem

Poly-Paleester#1 HerculesInc.

Pycal94 ICIAmericasInc.

Resimene®717,730,741,881AQ-7550and918

CytecInd.

SP-1044resin SchenectadyChemicalsInc.

Santicizer®plasticizers FerroCorporation

Santolink®EP560 CytecInd.

Shellac RPMInternationalInc.

Staybeliteester#10 EastmanChemicalCompany

Tributylcitrate MorflexChemicalCompany

TricresylphosphateFMCCorporationAkzoChemicalsInc.

Triethyleneglycoldi-2-ethylhexanoate(Eastman™TEG-EH)

EastmanChemicalCompany

Triphenylphosphate Triway

VinylchloridecopolymerVAGH,VAGD(UCARsolutionvinylresin)

DowChemicalCompany

Vinsol PinovaSolutions

Xylol(xylene) ExxonCompany,USA

Zincborate U.S.Borax

Zincborophosphate RockwoodPigmentsNA,Inc.

Zincmolybdate Sherwin-WilliamsChemical

Eastman Chemical CompanyCorporate HeadquartersP.O. Box 431Kingsport, TN 37662-5280 U.S.A.

Telephone:U.S.A. and Canada, 800-EASTMAN (800-327-8626)Other Locations, (1) 423-229-2000Fax: (1) 423-229-1193

Eastman Chemical Latin America9155 South Dadeland Blvd.Suite 1116Miami, FL 33156 U.S.A.

Telephone: (1) 305-671-2800Fax: (1) 305-671-2805

Eastman Chemical B.V.Fascinatio Boulevard 602-6142909 VA Capelle aan den IJsselThe Netherlands

Telephone: (31) 10 2402 111Fax: (31) 10 2402 100

Eastman (Shanghai) Chemical Commercial Company, Ltd. Jingan Branch1206, CITIC SquareNo. 1168 Nanjing Road (W)Shanghai 200041, P.R. China

Telephone: (86) 21 6120-8700Fax: (86) 21 5213-5255

Eastman Chemical Japan Ltd.MetLife Aoyama Building 5F2-11-16 Minami AoyamaMinato-ku, Tokyo 107-0062 Japan

Telephone: (81) 3-3475-9510Fax: (81) 3-3475-9515

Eastman Chemical Asia Pacific Pte. Ltd.#05-04 Winsland House3 Killiney RoadSingapore 239519

Telephone: (65) 6831-3100Fax: (65) 6732-4930

www.eastman.com

BVR-001 11/13

Although the information and recommendations set forth herein are presented

in good faith, Eastman Chemical Company and its wholly owned subsidiary

Solutia Inc. make no representations or warranties as to the completeness or

accuracy thereof. You must make your own determination of their suitability

and completeness for your own use, for the protection of the environment,

and for the health and safety of your employees and purchasers of your

products. Nothing contained herein is to be construed as a recommendation

to use any product, process, equipment, or formulation in conflict with any

patent, and we make no representations or warranties, express or implied, that

the use thereof will not infringe any patent. NO REPRESENTATIONS OR

WARRANTIES, EITHER EXPRESS OR IMPLIED, OF MERCHANTABILITY, FITNESS

FOR A PARTICULAR PURPOSE, OR OF ANY OTHER NATURE ARE MADE

HEREUNDER WITH RESPECT TO INFORMATION OR THE PRODUCT TO WHICH

INFORMATION REFERS AND NOTHING HEREIN WAIVES ANY OF THE SELLER’S

CONDITIONS OF SALE.

Safety Data Sheets providing safety precautions that should be observed when

handling and storing our products are available online or by request. You

should obtain and review available material safety information before handling

our products. If any materials mentioned are not our products, appropriate

industrial hygiene and other safety precautions recommended by their

manufacturers should be observed.

© 2013 Eastman Chemical Company. Eastman and The results of insight are

trademarks of Eastman Chemical Company. Butvar is a trademark of Solutia

Inc., a subsidiary of Eastman Chemical Company. As used herein, ® denotes

registered trademark status in the U.S. only. All other trademarks are the

property of their respective owners.