FileNo:NA/688June 1999
NATIONALINDUSTRIALCHEMICALSNOTIFICATIONANDASSESSMENTSCHEME
FULLPUBLICREPORT
TuftoneHB-580 /TuftoneHB-688/TuftoneHB-308
ThisAssessmenthasbeencompiledinaccordancewiththeprovisionsoftheIndustrialChemicals(NotificationandAssessment)Act1989(theAct)andRegulations.ThislegislationisanActoftheCommonwealthofAustralia.TheNationalIndustrialChemicalsNotificationandAssessmentScheme(NICNAS)isadministeredbytheNationalOccupationalHealthandSafetyCommissionwhich alsoconductstheoccupationalhealth safety assessment.TheassessmentofenvironmentalhazardisconductedbytheDepartmentoftheEnvironmentandtheassessmentofpublichealthisconductedbytheDepartmentofHealthandAgedCare.
Forthepurposesofsubsection78(1)oftheAct,copiesofthisfullpublicreportmaybeinspectedbythepublicattheLibrary,NationalOccupationalHealthandSafetyCommission,92-94ParramattaRoad,CamperdownNSW2050,betweenthefollowinghours:
Monday-Wednesday8.30am-5.00pmThursday8.30am-8.00pm
Friday8.30am-5.00pm
Copiesofthisfullpublicreportmayalsoberequested,freeofcharge,bycontactingtheAdministrationCoordinatoronthefaxnumberbelow.
ForenquiriespleasecontacttheAdministrationCoordinatorat:
StreetAddress:92ParramattaRdCamperdown,NSW2050,AUSTRALIA
PostalAddress:GPO Box58, Sydney2001, AUSTRALIA
Telephone:(61)(02)9577-9514 FAX(61)(02)9577-9465
Director
ChemicalsNotificationandAssessment
NA/688
FULLPUBLICREPORT
TuftoneHB-580 /TuftoneHB-688/TuftoneHB-308
1.APPLICANT
TheSharpCorporationofAustraliaPtyLtdof1HuntingwoodDrive,Huntingwood,NSW2148hassubmittedalimitednotificationstatementinsupportoftheirapplicationforanassessment certificate for the polymerin Tuftone HB-580/Tuftone HB-688/Tuftone HB-308.
2.IDENTITYOFTHECHEMICAL
ChemicalName:1,4-benzenedicarboxylicacid,polymerwith
1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid,dihydro-3-(tetrapropenyl)-2,5-furandione,ethenylbenzene,2-ethylhexyl-2-propenoateand
,’-[(1-methylethylidene)-di-4,1-phenylene]bis[-
hydroxypoly(oxy-1,2-ethanediyl)],
,’-[(1-methylethylidene)-di-4,1-phenylene]bis[-hydroxypoly[oxy(methyl-1,2-ethanediyl)]]and
2-propenoicacid,graft,bis(1-methyl-phenylethyl)peroxide-initiated
ChemicalAbstractsService(CAS)Registry No.:
149367-99-7
TradeNames:TuftoneHB-580,TuftoneHB-688,TuftoneHB-308
Number-Average
MolecularWeight(NAMW):2850
Weight-Average
MolecularWeight:40,020
MaximumPercentageofLow MolecularWeightSpecies
MolecularWeight500:MolecularWeight1000:
4.03
9.36
MolecularFormula:
(C3H6O)aC15H16O2.(C2H4O)cC15H16O2.C16H26O3.C8H6O4.C9H4O5.C8H8.C11H20O2.
C3H4O2
StructuralFormula:
WeightPercentageofIngredients:
ChemicalName1,4-benzenedicarboxylicacid (terephthalicacid)
1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid
(4-carboxyphthalicanhydride)
dihydro-3-(tetrapropenyl)-2,5-furandione(tetrapropenylsuccinicanhydride)ethenylbenzene
(styrene)
2-ethylhexyl-2-propenoate
(2-ethylhexylacrylate)
,’-((1-methylethylidene)di-4,1-phenylene)bis(-hydroxypoly(oxy-1,2-ethanediyl))
(bisphenolAbis(polyethyleneglycol)ether)
,’-((1-methylethylidene)di-4,1-phenylene)bis(-hydroxypoly (oxy(methyl-1,2-ethanediyl)))
(bisphenolAbis(polypropyleneglycol)ether)
2-propenoicacid
(acrylicacid)
bis(1-methyl-1-phenylethyl)peroxide
(dicumylperoxide)
dibutyltinoxide
MethodofDetectionandDetermination:
datafromgelpermeationchromatographyandinfraredspectroscopywereprovidedforthenotifiedpolymer
SpectralData:IRmajorcharacteristicpeaksat555,691, 826,1111,
1239,1457,1507, 1600,1726and2929cm-1
3.PHYSICALANDCHEMICALPROPERTIES
Appearance at 20°Cand101.3 kPa:
paleyellowpowder
ParticleSize:9.2%bymassissmallerthan75m
Particle sizerange ( m)% w/w
>40050.3
125-40033.8
75-1256.7
30-758.1
10-301.1
<100
MeltingRange:88-155°C
GlassTransitionTemperature:55-65°C(fromMaterialSafetyDataSheet)
SpecificGravity:1.12
VapourPressure:1.7x10-10kPaat25°C
WaterSolubility:<1mg/Lat20°C
PartitionCo-efficient(n-octanol/water):
nodatapresented;seecommentsbelow
HydrolysisasaFunctionofpH:nodatapresented;seecommentsbelowAdsorption/Desorption: nodatapresented;seecommentsbelowDissociationConstant: nodatapresented;seecommentsbelow
FlashPoint:notapplicable;chemicalisasolidatroomtemperature
FlammabilityLimits:thenotifiedchemicalisnotregardedasflammable,
butiscombustible
AutoignitionTemperature:noselfignitionbeforemelting
ExplosiveProperties:noexplosiveproperties(whensubjectedtothermaland
mechanicalsensitivitytesting)
Reactivity:nooxidisingproperties
CommentsonPhysico-ChemicalProperties
Tests wereperformedaccordingtotheECDirective92/69/EEC(EuropeanCommission,1992)andOECDtestguidelines(OECD,1981),atHuntingdonLifeSciencesLtd,Eye,Suffolk,England,exceptforthevapourpressureestimationwhichwascarriedoutat theDepartment ofPhysicalChemistry,TheUniversityofLeeds,Leeds,England. ThesefacilitiescomplywithUKPrinciples ofGoodLaboratoryPractice.Areportdetailingallthetestsperformedwassubmitted.
Testsforn-octanol/waterpartitioning,hydrolysis,soiladsorption/desorptionanddissociationwereconsideredimpracticalforthenotifiedpolymer,duetoitslowsolubilityinwater(<1mg/L)andn-octanol(<10mg/L), aswell asthelackofasuitablesubstance specificanalyticalmethod.Thesedatagapswereacceptedbecause:
- hydrolysisoftheesterandetherlinkagesofthepolymerwouldnotbeexpectedunderenvironmentalconditions;
- onthebasisofthepolymer'slowwatersolubilityitislikelytohaveahighlogPandtoadsorbto,orbeassociatedwith,soil/sedimentandorganicmatterandbeimmobileinsoil;and
- thepolymercontainsasmallamountoffreecarboxylicacidfunctionalitiesexpectedtohavetypicalacidity.
4.PURITYOFTHECHEMICAL
DegreeofPurity:97% w/w (95-100%)
Non-hazardousImpurities (>1%by weight):
Chemicalname:,’-((1-methylethylidene)di-4,1-phenylene)bis(-
hydroxypoly(oxy(methyl-1,2-ethanediyl))
Synonyms:bisphenolAbis(polypropyleneglycol)ether
Weightpercentage:3.1(range1-5)
CASNo.:37353-75-6
Notes:
Comments:maycauseskinandeyeirritation(fromMSDS)
Thisimpurityalsorepresentsthemaximumresidualmonomercontent.Therearenotoxicorhazardousimpuritiesinthechemical.
Fromthelistofpolymeringredients(i.e.presentedinsection2),thefollowinghavebeenincludedontheNationalOccupational Health andSafety CommissionsListof DesignatedHazardous Substances(NOHSC,1994a):
1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acidethenylbenzene
2-ethylhexyl-2-propenoate2-propenoicacid
bis(1-methyl-1-phenylethyl)peroxide.
Allareusedupduringthesynthesisofthenotifiedpolymer,leavinganon-hazardousproduct.
Additives/Adjuvants:none
5.USE,VOLUMEANDFORMULATION
Thenotifiedchemical is apolyester/styrene-acrylicgraftedpolymerandwill be used in theprintingindustry asabinderresinoftoner inprintersandcopiers. Itwillbeimported intoAustraliaasa component (50-55% and2%by weight)of formulatedtoner and developerproducts, in100gcartridges and700gbottles.Theamountsthatwillbeimportedover thenextfiveyearsareasfollows:
19993.2tonnes
20006.5tonnes
20018.0tonnes
20028.2tonnes
20037.9tonnes.
Allmanufacturing,formulationandpackagingofthetonerwillbeperformedpriortoimportation.
6.OCCUPATIONALEXPOSURE
Thenotifiedpolymerisacomponenttheimportedtonerproduct,whichisalsoinpowderform.Boxesoftonerwillbetransportedbyroadfordistributiontocustomersintheprintingindustry.Noreformulationorrepackagingwilltakeplace.Hence,noexposuretothenotifiedpolymer,ortoner,isexpectedduringtransportationandstorage.
OccupationalexposuretothenotifiedpolymerinAustraliawillprimarilyconcerntwomainworkercategories.Theseareprinter/cpierservicepersonnelandprintingstaffusingprintersandcopiers.
Dutiesofthe service personnel(approximately 800) will include cleaning the inside of themachine(particularlytheexterioroftheprocessingunit),servicingthemachine(particularly
theexterioroftheprocessingunit),servicingthemachineandreplacementofcopierdeveloper.Thenotifierestimatedtotalexposuretimefoeanindividualtobe47hoursperyear,basedon187servicesand0.25hoursperservice.Bothinhalationanddermalexposuretothetonerpowdermayoccurduringtheseactivities.Servicepersonnelmayearprotectivegloves,generallyoftheLatexdisposaltype.
Printing and/or officestaff (approximately450)will replacetheused toner. Tochangethetonercartridge of printers, the seal tape is removed and then the cartridge is placed into themachine.Duringprinting,thetonerwillbetransferredontothepaperandheat-cured.Sincetonerisloadeddirectlyintoalaserprinterorplanepapercopierwhenrequired,theprocessisquick,takingapproximatelyoneminute.Toneraddition/replacementwouldberequiredonceamonthonaverage.Theestimatedtotalexposuretimeforanindividualworkertoreplacethetoneris12 minutesper yearper machine.As a toner containeris sealed,the operatorwouldnotbeexposedatanytoneruntilthesealtapeisremoved
Inhalationanddermalexposuretothetonerpowdermayoccurduringtonerreplacement,particularlyintheeventofacontainerleakorspill.Printingandofficeworkerswould notnormallywearprotectiveequipment.
Exposuremayoccuruponhandlingprintedmatter.However,lessthan50mgoftonerisused persheetofpaperanditwouldnotbeseparatelyavailableforexposureordermaluptakeasitisfusedandfixedtotheprintedsurface.Theseconsiderationsindicatetherewouldbenohumanexposuretothenotifiedchemicalduringthehandlingofprintedmaterials.
7.PUBLICEXPOSURE
Publiccontactwillonlyoccurfromtouchingthefixedtoneronpaper.Thenotifierstatesthatthetonerisfusedtothepaperand,undernormalconditions,releasefromthe surfaceisunlikely tooccur. Consequently,the potentialforpublicexposure tothe notified polymerduringallphasesofitslifecycleisconsideredtobenegligible.
8.ENVIRONMENTALEXPOSURERelease
Thenotifiedpolymer, asacomponentofapre-formulatedtoner,willbeimportedincartridges andbottles. Undernormalusethetoneristransferredontoasheetofpaperwhereit isfirmlyfixedto the surfacebyheat. Thus the polymerwillbefixedintothe cured tonerandreleasetotheenvironmentwillbenegligible.Wastepapercontainingthetoner(andthusthenotifiedpolymer)willeventuallybesenttolandfill,recycledorincinerated.
Releaseofthenotifiedchemicalwillalsooccurthroughthedisposalofcartridgesandbotlestolanfill,whichwould bewidespread across Australia. Thenotifierhas indicatedthat 1g (i.e.0.15%)ofresiduewillbeleftinatonercartridge.Thisequatesto0.1goftonerremainingina
spentcartridge.However,between1to5%isamorerealisticestimateoftheamountofresidueremaininginacartridge(i.e.1-5g).Assumingthistobetheupperlimitoftonerresidueremaininginthecartridge, thenthemaximumquantityofpolymerreleasedin thismannerwouldbe2.5to2.75gpercartridge,representing220to231kgofthenotifiedpolymerperyear.
Inadditiontothisamountthenotifierindicatesthatapproximately10%(i.e.10 g fromeachcartridge) ofthetonerloadedintothephotocopierissenttoawastetonerbottle,which isremovedbythemaintenancetechnician.Thequantityofpolymerreleasedviathisroutewouldbe5to5.5gpercartridge,representingamaximumof440to462kgperyear.
Assuminganannualimportof8.2tonnesofthenotifiedpolymerperyear,themaximumquantityofpolymerreleaseduetothedisposalofusedcartridgesandwastebottlestolandfillwillbe660to693kgperyear.
Environmentalreleaseduringtransportduetoaccidentalspillagewillbelimitedbecausethetonerissuppliedinsmallvolumecartridges.
Environmentalexposuretothenotifiedpolymercouldoccurduringdisposalorrecyclingofpapercontainingthepolymer(seebelow).
Fate
Thepolymerwillmostlikelysharethefateofitspapersubstrate andberecycledordisposedofvialandfillorincineration.Thesmallquantitiesofresidualtonerinspentcontainerswillalsobedisposedofbylandfill.Polymerdisposedoftolandfillisunlikelytoleachorcontaminate surfacewaterbecauseofitslowwatersolubilityandexpected highpartitioncoefficient.
PaperrecyclingisagrowingindustryinAustralia.Wastepaperisrepulpedusingavarietyof alkalis,wateremulsifiableorganicsolventsanddispersing,bleachingandwettingagentstoenhancethefibreseparation,inkdetachmentfromthefibresandpulpbrightnessandthewhiteness ofthe paper. After pulping,the contaminants andthe inkare separatedfrom thefibresbypumpingthestockthroughvariousheatwashing,screening,cleaning,flotationanddispersionstages.The notifier has provided no data on the likelybehaviour of the polymerduringtherecyclingprocess.Thehydrolysisofesterlinkagesunderalkalineconditionswillbeminimalduetothelowsolubilityofthepolymer.Thepolymerthereforeislikelytosurvivethe paperrecyclingconditions,eitherremainingboundtothepulporbecomingassociatedwiththesludge.Inthelattercase,thepolymerwillarriveinlandfillwhereitcanbeexpectedtoremainintact,orbedestroyedthroughincineration.
Biologicalmembranesarenotpermeabletopolymersofverylargemolecularsizeandthereforebioaccumulationofthenotifiedpolymerisnotexpected(Gobasetal.,1986;Anlikeretal., 1988).
9.EVALUATIONOFTOXICOLOGICALDATA
Notoxicologicaldatawereprovidedforthenotifiedpolymer.Thisisacceptableforpolymersofnumber-averagemolecularweight(NAMW)ofgreaterthan1000daltons.
HoweveraccordingtotheMaterialSafetyDataSheet(MSDS)forAR-330ND/330SD/330DVblackdeveloperandAR-330NT/330ST/330TblacktonerwhicharesimilarproductswereshowntobenonmutagenicwhentestedwithSalmonellatyphimuriumandEscherichiacoliintheAmestestandanacuteoraltoxicityofLD505000mg/kgandacuteinhalationtoxicity ofLC506.42mg/L.
10.ASSESSMENTOFENVIRONMENTALEFFECTS
Noecotoxicologicaldatawereprovidedforthenotifiedpolymer.Thisisacceptableforpolymersofnumber-averagemolecularweight(NAMW)ofgreaterthan1000daltons.
11.ASSESSMENTOFENVIRONMENTALHAZARD
The majority ofnotifiedpolymershouldnotenter the environment untilitisincorporatedintothe heat-cured toner matrix and fixed to paper.Disposalof the waste paper containingthetonerwouldnormallyoccurthroughlandfill,recyclingorincineration.Inlandfillthetoner(andthusthenotifiedpolymer) shouldremainfixedtothepapersubstrateandremainimmobile.Incinerationproducts ofthenotifiedpolymershouldnotproduceanenvironmentalhazard.Afterrecycling,thetonerwilleitherremainboundtothepulporbecomeassociatedwithsludge.Thesludgewouldbedestinedtolandfillwherethetonercouldpersistbutremainboundtothesludgeandimmobile..
Accidentalspillageofthepolymer,eitherduringreplacementofcartridgesorduringtransport,shouldresultinpowderwastesbeingsenttoeitherlandfillorincinerationfacilities. Spentcartridgescontainingresiduesoftonerarelikelytobesenttolandfill.Asaworstcase,amaximumof693kgofthenotifiedpolymercouldbesenttolandfillatmaximum importquantities.ThedisposalofcartridgeswouldbewidespreadacrossAustralia.
The notified polymer is not likely to present a concern to the environmentwhen it is stored,transported andusedinthe proposedmannerbecausethe environmental exposure andtheoverallenvironmentalhazardshouldbenegligible.
12.ASSESSMENTOFPUBLICANDOCCUPATIONALHEALTHANDSAFETYEFFECTS
There isnotoxicological dataavailableonthe notifiedpolymer.However,the notifier hasdeterminedthatneitherthenotifiedpolymer,northetoner,wouldbeahazardoussubstance,undertheNationalOccupationalHealthandSafetyCommissionsApprovedCriteriafor
ClassifyingHazardousSubstances(NOHSC,1994b).TheMSDSforAR-330ND/330SD/330DVblackdeveloperandAR-330NT/330ST/330Tblacktonerreporttoxicitydataforasimilartoner,namelyverylowacuteoraltoxicity(LD505000mg/kg)andacuteinhalationtoxicity(LC506.42mg/L)andanegativeAmestest.
The particle size ofthe notified polymer is above the respirable range (i.e. all particles are
>10m in size). However, approximately20-25%w/w of particles arewithin the inspirablerange(<180m)andmaybelodgedintheupperrespiratorytractandleadtorespiratoryirritation.Themainresidualmonomerofthe notifiedchemicalmaycauseskinandeyeirritation.However,asitisnotahazardoussubstanceandispresent inthepolymerpreparationat3.1%,itisunlikelytobeasourceofirritationintheimportedtonerproduct.
OccupationalHealthandSafety
Tonerpowdercontainingthe notifiedpolymer willbeusedbyindustrialprintingfirms.Trainingonhowtohandletheprocessunitandtonercartridge/bottle(containingthenotifiedpolymer)willbegiventoallpersonnelconcerned.Todatetherearenorecordsofinjuriesordiseasesrelatedtoworkersexposedtothetestsubstance.
Servicepersonnel(approximately800)maybeexposedtothenotifiedpolymerwhencleaningprinter/copierequipmentandreplacingcopierdeveloper;however,asthenotifiedpolymerorthetonerproductisnothazardous,theriskofadversehealtheffectsislow.Disposableglovesmaybeworntopreventskinirritationandworkersshouldavoidanygenerationofdustwhenhandlingthetoner.
Printingstaff(approximately450),whowillperformadditionsoftonerandreplacementofausedtoner container(cartridgeorbottle),areexpected tobeexposedinfrequentlytothenotifiedpolymerasthetonercontainerissealedandloadeddirectly intoaprinting machine.Uponapplicationtothepaper,thetonerisfusedtothesurfaceandreleaseisunlikelytooccur.Therefore, the riskof adversehealth effects toprinting personnelis very lowand noprotectiveequipmentisrequired.Nevertheless,anygenerationofdustshouldbeavoided.
Spiltresiduesshouldbesweptupmanuallyorusinganindustrialvacuumcleanerandplacedwithinawastecontainer.
Given theseconsiderations, thechemicalwillnotposeasignificanthealthhazardintheoccupationalenvironment.
Workershandlingprintedpaperarenotatriskofadversehealtheffectsbecausethepolymerisfixedtothepaperandnotavailableforexposureordermaluptake.
ThereisaNOHSCexposurestandardforcarbonblack,acomponentintheimportedproduct.Employersareresponsibleforensuringthattheexposurestandard(3mg/m3, time weightedaverage),isnotexceededintheworkplace.
PublicHealth
Basedonitsusepattern,physico-chemicalpropertiesandlowtoxicity,thenotifiedpolymerwillnotposeasignificanthazardtopublichealth.
13.RECOMMENDATIONS
Tominimiseoccupationalexposuretothe notifiedpolymer,thefollowingguidelinesandprecautionsshouldbeobserved:
- Avoidgenerationofdustcloudswhenhandlingthetoner;
- Serviceoperatorsshouldweardisposable,rubbergloveswhenhandlingtoner;
- Spillageofthenotifiedchemicalshould beavoided.Spillages shouldbecleaneduppromptlywithabsorbentswhichshouldbeputintocontainersfordisposal;
- Goodpersonalhygieneshouldbepractisedtominimisethepotentialforingestion;
- AcopyoftheappropriateMSDSshouldbeeasilyaccessibletoemployees.
TheNOHSCexposurestandardforcarbonblackshouldnotbeexceededintheworkplace.
14.MATERIALSAFETYDATASHEET
TheMSDSforTuftoneHB-580,AR-330NT/330ST/330T(blacktoner)andAR-330/330SD/330DV(blackdeveloper)wereprovidedinaformatconsistentwiththeNationalCodeofPracticeforthePreparationofMaterialSafetyDataSheets(NOHSC,1994c).
TheseMSDSwereprovidedbytheapplicantaspartofthenotificationstatement.Itisreproducedhere asamatter of public record.The accuracy of thisinformationremains theresponsibilityoftheapplicant.
15.REQUIREMENTSFORSECONDARYNOTIFICATION
Underthe Act, secondarynotificationofthenotifiedchemicalshall berequiredifanyofthecircumstancesstipulatedundersubsection64(2)oftheActarise.Nootherspecificconditionsareprescribed.
16.REFERENCES
AnlikerR,MoserPandPoppingerD(1988)Bioaccumulationofdyestuffsandorganicpigmentsinfish.Relationshipstohydrophobicityandstericfactors.Chemosphere17(8),1631-1644.
EuropeanCommission(1992)MethodsfortheDeterminationofPhysico-ChemicalProperties,PartA,CommissionDirective92/69/EC.OfficialJournal oftheEuropeanCommunitiesNo.L383A,December1992.
GobasFAPC,OpperhuizenAandHutzingerO(1986)Bioconcentrationofhydrophobicchemicalsin fish:relationshipwithmembranepermeation.EnvironmentalToxicologyandChemistry5,637-646.
NationalOccupationalHealthandSafetyCommission(NOHSC,1994a)List ofDesignatedHazardousSubstances[NOHSC:10005(1994)].AustralianGovernmentPublishingService,Canberra.
NationalOccupationalHealthandSafetyCommission(NOHSC,1994b)ApprovedCriteriaforClassifyingHazardousSubstances[NOHSC:1008(1994)].AustralianGovernmentPublishingService,Canberra.
National OccupationalHealthand Safety Commission (NOHSC, 1994c)NationalCodeofPracticeforthePreparationofMaterialSafetyDataSheets[NOHSC:2011(1994)].AustralianGovernmentPublishingService,Canberra.
OrganisationforEconomicCo-operationandDevelopment(OECD,1981)OECDGuidelinesforTestingofChemicals.OECD,Paris.