File No: NA/398Date: 30 November 1996

NATIONALINDUSTRIALCHEMICALSNOTIFICATIONANDASSESSMENTSCHEME

FULLPUBLICREPORT

PolymerinAstacinTopLD6601

ThisAssessmenthasbeencompiledinaccordancewiththeprovisions oftheIndustrialChemicals(NotificationandAssessment)Act1989(theAct),andRegulations.ThislegislationisanActoftheCommonwealthofAustralia.TheNationalIndustrialChemicalsNotificationandAssessmentScheme(NICNAS)isadministeredbyWorksafeAustraliawhichalsoconductstheoccupationalhealthsafetyassessment.TheassessmentofenvironmentalhazardisconductedbytheDepartmentoftheEnvironment,Sport,andTerritoriesandtheassessmentofpublichealthisconductedbytheDepartmentofHealthandFamilyServices.

Forthepurposesofsubsection78(1)oftheAct,copiesofthisfullpublicreportmaybeinspectedbythepublicattheLibrary,WorksafeAustralia,92-94ParramattaRoad,CamperdownNSW2050,betweenthehoursof10.00amand12.00noonand2.00pmand4.00pmeachweekdayexceptonpublicholidays.

ForEnquiriespleasecontacttheAdministrationCoordinatorat:

StreetAddress: 92Parramatta RdCamperdown, NSW 2050,AUSTRALIA

PostalAddress:GPOBox58,Sydney2001,AUSTRALIA

Telephone:(61)(02)9577-9466 FAX (61)(02) 9577-9465

Director

ChemicalsNotificationandAssessment

NA/398

FULLPUBLICREPORT

PolymerinAstacinTopLD6601

1.APPLICANT

BASFAustraliaLtdof500PrincesHighwayNOBLEPARKVIC3174hassubmittedalimitednotificationstatementinsupportoftheirapplicationforanassessmentcertificate forPolymerinAstacinTopLD 6601.

2.IDENTITYOFTHECHEMICAL

PolymerinAstacinTopLD6601isnotconsideredtobehazardousbasedonthenatureofthechemicalandthedataprovided. Thereforethechemicalname,CASnumber,molecularandstructuralformulae,molecularweight,spectraldataanddetailsofthepolymercompositionhavebeenexemptedfrompublicationintheFullPublicReportandtheSummaryReport.

OtherName:PolymerinAstacinTopLD6601

MethodofDetection

andDetermination:thepolymerhasbeenisolatedbygelpermeationchromatography(GPC),andidentifiedbyinfraredspectroscopy

3.PHYSICALANDCHEMICALPROPERTIES

Thepolymeritselfwillneverbeisolated. Thefollowingdatarefertotheimportedproduct,AstacinTopLD6601(containing30%polymer,8%2-pyrrolidinone1-methyl-and0.8%proxelXLZinwater),unlessotherwisestated.

Appearanceat 20°C

and101.3kPa:clear,slightlyyellowaqueousdispersion

BoilingPoint:~100°C(asforwater)

Meltingpoint:thesolidificationtemperatureis0C

300C(forthe polymer)

Density:1042kg/m3

VapourPressure:2.3 kPaat20°C (water)

basedonthehighmolecularweight;thepolymeritselfisexpectedtohavelowvapourpressure

WaterSolubility:thepolymerisinsolubleinwaterbasedoncomparisonwithsimilarpolymers;thepolymerdispersioncanbedilutedwithwaterinallproportions

PartitionCo-efficient

(n-octanol/water):notdetermined

HydrolysisasaFunction

ofpH:notdetermined;thepolymerisnotexpectedtoreadilyhydrolysebasedonanalogywithotherpolymers

Adsorption/Desorption:notdetermined;uponevaporationthedispersion

isexpectedtobecomeviscousandtacky andbindtosoil

DissociationConstant:notdetermined;thepolymerisnotconsideredto

besolubleinwater

FlashPoint:nonewhentestedupto100C

FlammabilityLimits:thewaterbaseddispersionisnotexpectedtobe

flammableAutoignitionTemperature:200°CExplosiveProperties: noneexpected

Reactivity/Stability:thepolymerisnotconsideredreactive

CommentsonPhysico-ChemicalProperties

Thenotifierclaimsthatbycomparisonwithsimilarsyntheticpolymers,thenotifiedpolymerwillbeinsolubleinwater. Thepolymerismanufacturedasadispersioninwater,whichisclaimedcanbedilutedwithwaterinallproportions. ThewatersolubilityofthepolymerwilldependonthepHofthemedium. AtlowpHvalues,atwhichthepolymerexistspredominantlyinthecarboxylicacidform,thesolubilityinwateris expected to be very low.However,at high pH (above 8) thehydrophilicityofthepolymerwillbehigherasitexistsinasaltform. However,thereisonly6%ofthisfunctionality. Therefore,thewatersolubilityisstillpredictedtobelow.

Thenotifierclaimsthatinformationfromsimilarmaterialsindicatesthathydrolyticdecompositionofthismaterialishighlyunlikely. ItisconsideredthatthenotifiedpolymerisunlikelytoundergohydrolyticdecompositionintheenvironmentalpHrange(1).

Duetothecomplexnatureofthepolymerthepartitioncoefficient,adsorption/desorption,anddissociationconstantwillbedifficulttomeasure. Thepolymerwillhaveahighpartitioncoefficientincarboxylicacidformagainduetolowwatersolubility. Adsorptivityhasastrongnegativecorrelationwithsolubility.Lowsolubilityofpolyurethanessuggeststhattheywillhavehighadsorptivitycoefficients. Asthewaterandtriethylamineareremovedbyevaporation,itbecomesviscousandtackyandthepolymerwillbindtosoilandbecomefixed.

ThepolymercontainsdissociablecarboxylicacidgroupsandthepKaisexpectedtobeintherangeof3to 5.

4.PURITYOFTHECHEMICALDegreeofPurity:98%

Non-hazardousImpurities

(>1%byweight):none

5.USE,VOLUMEANDFORMULATION

Thenotifiedpolymerwillbeusedaspartofaformulationintendedasaspecificaftertanningagentintheleatherindustry. Theformulation(30%polymerdispersioninwaterand2-pyrrolidinone1-methyl-)willenhancethewater,oilandstainrepellancyoftheleather.

Thepolymerwillbeimportedonlyasa30%dispersionatarateoflessthan100tonnesperyearforthefirstfiveyears.

6.OCCUPATIONALEXPOSURE

ThepolymerdispersionwillarriveintoAustraliain120kgopenheadpolyethylenedrumsaspartofamixedloadofchemicals. Thenotifierestimatesthat1to2peoplewillbeinvolvedinreceivingtheimportatthedockand1to2transportdriverswillbeinvolvedinroadtransportfromthedocktotheimporter’swarehouseinVictoria. Atthewarehouse1to3storepersonswillunloadthecontainer. Thedispersionwillthenbedistributedbyroadtoapproximately5tanneriesthroughtAustralia. Exposureoftransportandstoragepersonnelisexpectedonlyintheeventofaccidentalspillage.

Ateachtannery1to3operatorswillunloadthedrum(s)ofdispersionand1to4operatorswillbeinvolvedinweighingtheproductandmixingitwithotheringredients(usuallywater,butmayinclude“normalfinishingbinders”)toafinalpolymerconcentrationofapproximately20%. Themixingprocesswillbeconductedintheproductionareaandisexpectedtoinvolveoneworkerfor10minutes/day. Theproductionareaisexpectedtobefittedwithlocalexhaustventilation.

Themixwillbeappliedtoleatherhidesatambienttemperaturebyarotogravureorspraymachineatarateof40g/m2. Dailypolymerusageisanticipatedtobe10to20kgofnotifiedchemical. Applicationwillbeconductedbyonetotwoworkersforupto8hours/day. Cleaningoftherotogravuremachinerywillbeconductedoncedailyandwillinvolvetheremovalofapproximately0.3kgpolymerfromtheroller.

Theapplicationareaisexpectedtobefittedwithlocalexhaustventilation.

Themainoccupationalrouteforworkersinvolvedinweighing,mixingandtransferoperations,aswellasproductapplication,machinerymaintenanceandmachinecleaning,willbedermal. Accidentaleyecontactmayalsooccurduetosplashes.Inhalationalexposureisunlikelyduetothelowvapourpressureofthepolymerdispersion. However,thereisapossibilityofexposureduringapplicationbyspraymachine

7.PUBLICEXPOSURE

Thereisnegligiblepotentialforpublicexposuretothenotifiedpolymerarisingfromleathertreatmentprocesses. Theremaybewidespreadpubliccontactwiththenotifiedpolymeronthesurfaceoftreatedleathergoods,butitsadhesiontothesubstrateandphysico-chemicalpropertieswillbesufficienttoprecludeabsorptionacrosstheskinorotherbiologicalmembranes.

8.ENVIRONMENTALEXPOSURERelease

Thereshouldbenoreleasetotheenvironmentduringtransportandstorage

exceptinamajoraccident.

Thenotifierclaimsthatwhenthenotifiedpolymerproductisappliedbyrotogravuremachines,nooverspreadwilloccur. Theonlylossesarethroughcleaningtheapplicationequipment. Rotogravuremachinesarecleanedonceaday. Wastewaterwashingsarecollectedandtreatedinthecompany'seffluenttreatmentplant.Thewasteistreatedtoseparatethesolidsandthewastewaterisflocculatedanddesludgedbeforedischargetothesewer.

Whenthepolymerproductisappliedbyspraymachine,appropriatefiltersareinstalled to filter outanyoverspraythat may occur. The notifierdid notgiveanindicationtotheextentofthisoverspray. Thefilterswillbedisposedoftoapproveddisposalsites.

Minorspillsanddripsduringaboveoperationsarecontainedandsoakedupwithearthorsandanddisposedofappropriately. Iflargespillsoccurtheywillbedivertedtotheplant'swastewatertreatmentplantforappropriatetreatmentsuchasflocculation.

Fate

The fate ofthe bulk ofthe polymerwillbe tied tothe fate ofthe finished leather.Leatherthathasbeentreatedwiththepolymerisexpectedtobeusedinmakingleatherproducts. Mostofthetreatedleatherwillbelandfilled,eitherastrimmingsduringthemakingofleatherarticlesorwhenthegoodsarefinallydisposedof.

Thewastesolutionfromthecleaningofrotogravuremachinesisdivertedtothecompany'swastewatertreatmentplantwherethesmallamountofpolymerisflocculatedanddesludgedbeforedischargetothesewer. DraftANZECCGuidelines(forTanningandRelatedIndustries)(4)statesthattreatmentofwastestobedisposedoftosewershouldachievethequalityrequiredbythetreatmentplantfortradewastes. Releaseofthepolymertotheaquaticenvironmentwouldthereforebenegligible.

Wastecontainingthepolymer,generatedduringtrimming,shavingandbuffingoftreatedhides,andassludgefromwastewatertreatmentisexpectedtobedisposedofthroughlandfillorincineration. Incinerationwilldestroythepolymer.

As stated inthe MaterialSafety Data Sheet(MSDS), degradabilityhas beenestimatedat20to70%dissolveorganiccarbonreduction(OECDTG302BModifiedZahn-WellensTestforInherentBiodegradability)basedonproductsofa“similarstructureandcomposition”. Thestructuresofthesechemicalswerenotsightedduringenvironmentalassessment.

9.EVALUATIONOFTOXICOLOGICALDATA

No datawereprovided. Toxicological dataarenotrequired accordingtothe Act forpolymerswithNAMWgreaterthan1000.

10.ASSESSMENTOFENVIRONMENTALEFFECTS

Noecotoxicologydatawereprovided,whichisacceptableforpolymersofNAMWgreaterthan1000accordingtotheAct. Suchpolymersaretoolargetocrossbiologicalmembranes(5,6,7).

ThecompanyhasprovidedthefollowingresultsintheMSDS. Thesearederivedfromproductsof“similarstructureandcomposition”. Toxicity tofish,(GoldenOrfe,Leuciscusidus):96 hLC50greater than500 mg/L.Toxicityto bacteria (Warburgtest):greaterthan100mg/L. Reportsandchemicalstructureswerenotmadeavailable.

11.ASSESSMENTOFENVIRONMENTALHAZARD

Mostofthepolymerwillbedisposedoftolandfillwiththeleathertowhichitiscured. Therewillbenoenvironmentalhazardfromsuchcuredpolymer.

Thenotifierestimatesthateachtannerywilldisposeupto0.3kgofAstacinTopLD6601dailytoitswastewatertreatmentplantthroughthecleaningofrotogravuremachinesattheendoftheday. WithAstacinTopLD6601containing30%ofthenotifiedpolymer,thetotalannualdischargeofthepolymertothetreatmentplantsofall5tanneriesisestimatedat170kg. Thisislessthan1%ofthemaximumannualimport. Mostofthisistrappedinthecompany'swastewatertreatmentplantanddisposedofaslandfillorincineration. This,andthelowaquatictoxicityofthepolymer,indicatesalowhazardtotheaquaticenvironment.

Smallamountsofthepolymerarrivinginlandfillinanuncuredform,iethatcontainedinfiltersfromthesprayapplicationprocess,fromwasteduringtheaftertanningprocessandthatadsorbedtosludgeinthewastewatertreatmentplant,arelikelytoremainboundtosoil. Incinerationofsuchwastewilldestroythepolymerproducingwaterandoxidesofcarbonandnitrogen.

Overall,theenvironmentalhazardfromtheproposedimportratesanduseofthepolymerisnegligible.

12.ASSESSMENTOFPUBLICANDOCCUPATIONALHEALTHANDSAFETYEFFECTS

ThenotifiedpolymerhasaNAMWgreaterthan1000andisthereforeunlikelytocrossbiologicalmembranesandcausesystemiceffects. However,ithasahighpercentageoflowmolecularweightspeciesgreaterthan1000(10.2%)and500(6.3%). Thepolymerisstable,haslowvolatilityunderambientconditions,isnon-flammable,hasnoexplosivepropertiesandisnotexpectedtoreactwithothermaterials.

Thenotifiedpolymerhasalowlevelofresidualmonomers,whichareknowntocauseskinandeyeirritation,sensitisationandrespiratoryeffectsaswellasbeingflammable. AllresidualmonomersarepresentatconcentrationsbelowthethresholdrequiringclassificationaccordingtoWorksafeAustralia’sApprovedCriteriaforClassifyingHazardousSubstances(Approved Criteria) (8).

Onecomponent2-pyrrolidine1-methyl-ofthepolymerdispersionhasthepotentialtocauseskinandeyeirritation. Itconstitutesupto8%inAstacinTopLD6601andislessthantheconcentrationthreshold(10%)listedforclassificationofmixturesaccordingtoWorksafeAustralia’sListofDesignatedHazardousSubstances(2).

Therewillbenoworkerexposureduringtransportandstorageoperationsunlessthereisanaccidentalspill. TheproceduresoutlinedintheMSDS(personneltowearprotectiveclothing,gogglesandgloves;spillstobecontainedandsoakedupwithabsorbentmaterialandplacedinclosedlabeliedcontainers)willbeadequatetominimiseexposureduringclean-upoperations.

Duringthechemical’suseasanaftertanningagent,workerexposuremayoccurduringweighing,mixingandopentransferoperationsaswellasduringoperation,maintenanceandcleaningoftherotogravuremachinary. Theproductwillbeusedatambienttemperaturesinaliquidformonly. Asthepolymerisexpectedtohavealowvapourpressureanditisunlikelythataerosolsormistswillbegeneratedduringuse,thepotentialforinhalationalexposurewillbenegligible. Themostlikelyroutesofexposureduringusewillthereforebeskinandeyecontact. The useofprotectiveclothing,eyeprotectionandgloveswillreducetheexposurelevels. Giventhelowhazardsassociatedwiththepolymerriskstoworkersshouldbe low.

ThereisnegligiblepotentialforpublicexposuretoPolymerinAstacinTopLD6601arisingfromleathertreatmentprocess. Theremaybewidespreadpubliccontactwiththenotifiedpolymeronthesurfaceoftreatedleathergoods,butitsadhesiontothesubstrateandphysico-chemicalpropertieswillbesufficienttoprecludeabsorptionacrosstheskinorotherbiologicalmembranes.

13.RECOMMENDATIONS

TominimiseoccupationalexposuretoPolymerinAstacinTopLD6601,thefollowingguidelinesandprecautionsshouldbeobserved:

  • Safepracticesforhandlinganychemicalformulation,shouldbeadheredtoandinclude:

-minimisingspillsandsplashes:

-practisinggoodpersonalhygiene;and

-practisinggoodhousekeepingandmaintenanceincludingbundingoflargespillswhichshouldbecleaneduppromptlywithabsorbentsandputintocontainersfordisposal.

  • Inaddition,whenhandlingtheimportedformulationAstacinTopLD6601,protectiveclothingconformingtoandusedinaccordancewithAustralianStandard(AS)2919(9)andprotectivefootwearconformingtoAustralian/NewZealand Standard(AS/NZS)2210(10)shouldbewornasamatterofcourse. Itisadvisablewhenhandlingthepolymersolutiontowearchemical-typegoggles(selectedandfitted)accordingtoAS1336(11)andmeetingrequirementsofAS/NZS1337(12)andimpermeableglovesAS2161-1978(13),tominimiseexposuretoother,hazardous,constituentsoftheformulation.
  • AcopyoftheMSDSshouldbeeasilyaccessibletoemployees.

14.MATERIALSAFETYDATASHEET

TheMSDSfortheproductcontainingthenotifiedchemicalwasprovidedinaccordancewiththeNationalCode of Practice for thePreparationof MaterialSafetyData Sheets(14).

ThisMSDSwasprovidedbytheapplicantaspartofthenotificationstatement. It isreproducedhereasamatterofpublicrecord. Theaccuracyofthis informationremainstheresponsibilityoftheapplicant.

15.REQUIREMENTSFORSECONDARYNOTIFICATION

UndertheAct,secondarynotificationofthenotifiedpolymershallberequiredifanyofthecircumstancesstipulatedundersubsection64(2)oftheActarise. Nootherspecificconditionsareprescribed.

16.REFERENCES

1.NationalOccupationalHealthandSafetyCommission1994,ListofDesignatedHazardousSubstances[NOHSC:10005(1994)],GovernmentPublishingServicePubl.,Canberra.

2.AustralianNationalOccupationalHealthandSafetyCommission1995,‘AdoptedNationalExposureStandardsforAtmosphericContaminantsintheOccupationalEnvironment’,[NOHSC:1003(1995)], inExposureStandardsforAtmosphericContaminantsintheOccupationalEnvironment:GuidanceNoteandNationalExposureStandards,AustralianGovernmentPublishingService

3.Browning,S.B.1983, SurfaceCoatingsRawMaterialsandTheirUse.Volume 1,TheNewSouthWalesUniversityPress,NSW,Australia.pp263-293.

4.ANZECCand ARMCANZ, 1995, “Draft Effluent Management GuidelinesforTanneryandRelatedIndustries-December1995”,CommonwealthofAustralia,Canberra.

5.Nabholz, J.V.,Miller,P. andZeemanM. 1993,EnvironmentalRiskAssessmentofNewSubstancesundertheToxicSubstancesControlActSectionFive.InLandisWG,HughesJSLewis,MA(Eds),EnvironmentalToxicologyandRiskAssessment,AmericanSocietyforTesting andMaterials,ASTMSTP 1179,Philadelphia.pp 40-55.

6.Anliker, R., Moser,P and Poppinger,D., 1988, Bioaccumulation of dyestuffsandorganicpigmentsinfish. Relationshipstohydrophobicityandstericfactors.Chemosphere17(8):pp1631-1644.

7.Gobas,F.A.P.C.,OpperhuizenAandHutzingerO,1986,Bioconcentrationofhydrophobicchemicalsinfish:relationshipwithmembranepermeation.EnvironmentalToxicologyandChemistry5:pp637-646.

8.NationalHealthandSafetyCommission1994,ApprovedCriteriaforClassifyingHazardousSubstances[NOHSC:1008(1994)],AustralianGovernmentPublishingServicePubl.,Canberra.

9.StandardsAustralia,1987, AustralianStandard2919-1987,IndustrialClothing,StandardsAssociationofAustraliaPubl.,Sydney.

10.StandardsAustralia,StandardsNewZealand1994, Australian/ NewZealand Standard2210-1994OccupationalProtectiveFootwear,Part1:Guide to Selection,CareandUse. Part 2:Specifications,StandardsAssociationofAustraliaPubl.,Sydney, StandardsAssociationofNewZealandPubl.Wellington.

11.StandardsAustralia1994,AustralianStandard1336-1994,Eye protectionintheIndustrialEnvironment,StandardsAssociationofAustraliaPubl.,Sydney.

12.StandardsAustralia/StandardsNewZealand1992,Australian/NewZealandStandard1337-1992,EyeProtectorsforIndustrialApplications,StandardsAssociationofAustraliaPubl.,Sydney,StandardsAssociationofNewZealandPubl,Wellington.

13.StandardsAustralia1978,AustralianStandard2161-1978, Industrial SafetyGlovesandMittens(excludingElectricalandMedicalGloves),StandardsAssociation ofAustraliaPubl.,Sydney.

14.NationalOccupationalHealthandSafetyCommission1994,NationalCodeofPracticeforthePreparationofMaterialSafetyDataSheets[NOHSC:2011(1994)],AustralianGovernmentPublishingService,Canberra.

Attachment 1

TheDraizeScaleforevaluationofskinreactionsisasfollows:

ErythemaFormationRatingOedemaFormationRating

No erythema0Nooedema0

Veryslighterythema(barelyperceptible)

1Veryslightoedema(barely1

perceptible)

Well-definederythema2Slightoedema(edgesofareawell-2

definedbydefiniteraising

Moderatetosevereerythema3Moderateoedema(raisedapprox.13

mm)

Severeerythema(beetredness)4Severeoedema(raisedmorethan14

mmand extendingbeyondareaofexposure)

TheDraizescaleforevaluationofeyereactionsisasfollows:

CORNEA

OpacityRatingArea of CorneainvolvedRating

Noopacity0 none25%orless(notzero)1

Diffusearea,detailsof irisclearlyvisible

Easilyvisibletranslucentareas,detailsofirisslightlyobscure

1slight25%to50%2

2mild50%to75%3

Opalescentareas,nodetailsofirisvisible,sizeofpupilbarelydiscernible

3

moderate

Greaterthan75%4

Opaque,irisinvisible4severe

CONJUNCTIVAE
Redness / Rating / Chemosis / Rating / Discharge / Rating
Vesselsnormal / 0 none / No swelling / 0 none / No discharge / 0 none
Vesselsdefinitely / 1 / Anyswellingabove / 1slight / Anyamountdifferent / 1slight
injectedabovenormal / slight / normal / fromnormal
Morediffuse,deeper / 2mod. / Obviousswelling / 2mild / Discharge with / 2mod.
crimsonredwith / withpartialeversion / moisteningoflids
individualvesselsnot / oflids / andadjacenthairs
easilydiscernible / Swellingwithlids / 3mod. / Discharge with / 3
Diffusebeefyred / 3 / half-closed / moisteningoflids / severe
severe / Swellingwithlids / 4 / andhairsandconsiderablearea
half-closedto
completelyclosed / severe / around eye

IRIS

ValuesRating

Normal0 none

Foldsabovenormal,congestion,swelling,circumcornealinjection,irisreactstolight1slightNoreactiontolight,haemorrhage,grossdestruction 2severe