1、ENISO7012-3April2025Peinturesetvernis-Dosagedesagentsdepreservationdanslesproduitsdepeinturediluablesaeau-Partie3:DosagedesisothiazolinonesenpotparCL-UVetCL-SM(ISO7012-3:2025)Beschichtungsstoffe-BestimmungvonKonservierungsmittelninWasserverdunnbarenBeschichtungsstoffen-Teil3:BestimmungvonIsothiazoli
2、nonenimGebindemitLC-UVundLC-MS-MS(ISO7012-3:2025)EUROPEANSTANDARDNORMEEUROPEENNEEuropaischenormICS87.040EnglishVersionPaintsandvarnishes-Determinationofpreservativesinwater-dilutablecoatingmaterials-Part3:Determinationofin-canisothiazolinoneswithLC-UVandLC-MS(ISO7012-3:2025)ThisEuropeanStandardwasap
3、provedbyCENon27March2025.CENmembersareboundtocomplywiththeCEN/CENELECInternalRegulationswhichstipulatetheconditionsforgivingthisEuropeanStandardthestatusofanationalstandardwithoutanyalteration.Up-to-datelistsandbibliographicalreferencesconcerningsuchnationalstandardsmaybeobtainedonapplicationtotheCE
4、N-CENELECManagementCentreortoanyCENmember.ThisEuropeanStandardexistsinthreeofficialversions(English,French,German).AversioninanyotherlanguagemadebytranslationundertheresponsibilityofaCENmemberintoitsownlanguageandnotifiedtotheCEN-CENELECManagementCentrehasthesamestatusastheofficialversions.CENmember
5、sarethenationalstandardsbodiesofAustria,Belgium,Bulgaria,Croatia,Cyprus,CzechRepublic,Denmark,Estonia,Finland,France,Germany,Greece,Hungary,Iceland,Ireland,Italy,Latvia,Lithuania,Luxembourg,Malta,Netherlands,Norway,Poland,Portugal,RepublicofNorthMacedonia,Romania,Serbia,Slovakia,Slovenia,Spain,Swede
6、n,Switzerland,TiirkiyeandUnitedKingdom.富EUROPEANCOMMITTEEFORSTANDARDIZATIONCOMITEEUROPEENDENORMALISATIONEuropaischeskomiteefurnormungCEN-CENELECManagementCentre:RuedelaScience23,B-1040BrusselsRef.No.ENISO7012-3:2025E2025CENAllrightsofexploitationinanyformandbyanymeansreservedworldwideforCENnationalM
7、embers.ContentsPageEuropeanforeword3EuropeanforewordThisdocument(ENISO7012-3:2025)hasbeenpreparedbyTechnicalCommitteeISO/TC35PaintsandvarnishesincollaborationwithTechnicalCommitteeCEN/TC139PaintsandvarnisheswthesecretariatofwhichisheldbyDIN.ThisEuropeanStandardshallbegiventhestatusofanationalstandar
8、d,eitherbypublicationofanidenticaltextorbyendorsement,atthelatestbyOctober2025,andconflictingnationalstandardsshallbewithdrawnatthelatestbyOctober2025.Attentionisdrawntothepossibilitythatsomeoftheelementsofthisdocumentmaybethesubjectofpatentrights.CENshallnotbeheldresponsibleforidentifyinganyorallsu
9、chpatentrights.Anyfeedbackandquestionsonthisdocumentshouldbedirectedtotheusersnationalstandardsbody/nationalcommittee.AcompletelistingofthesebodiescanbefoundontheCENwebsite.AccordingtotheCEN-CENELECInternalRegulations,thenationalstandardsorganizationsofthefollowingcountriesareboundtoimplementthisEur
10、opeanStandard:Austria,Belgium,Bulgaria,Croatia,Cyprus,CzechRepublic,Denmark,Estonia,Finland,France,Germany,Greece,Hungary,Iceland,Ireland,Italy,Latvia,Lithuania,Luxembourg,Malta,Netherlands,Norway,Poland,Portugal,RepublicofNorthMacedonia,Romania,Serbia,Slovakia,Slovenia,Spain,Sweden,Switzerland,Tiir
11、kiyeandtheUnitedKingdom.EndorsementnoticeThetextofISO7012-3:2025hasbeenapprovedbyCENasENISO7012-3:2025withoutanymodification.ISOInternationalStandardISO7012-3Firstedition2025-03Paintsandvarnishes一Determinationofpreservativesinwater-dilutablecoatingmaterials一Part3:Determinationofin-canIsothiazolinone
12、swithLC-UVandLC-MSPeinturesetvernisDosagedesagentsdepreservationdanslesproduitsdepeinturediluablesaeau一Partie3:DosagedesisothiazolinonesenpotparCL-UVetCL-SMReferencenumberISO7012-3:2025(en)COPYRIGHTPROTECTEDDOCUMENTISO2025Allrightsreserved.Unlessotherwisespecified,orrequiredinthecontextofitsimplemen
13、tation,nopartofthispublicationmaybereproducedorutilizedotherwiseinanyformorbyanymeans,electronicormechanical,includingphotocopying,orpostingontheinternetoranintranet,withoutpriorwrittenpermission.PermissioncanberequestedfromeitherISOattheaddressbeloworISO,smemberbodyinthecountryoftherequester.ISOcop
14、yrightofficeCP401Ch.deBlandonnet8CH-1214Vernier,GenevaPhone:+4122749Ol11Email:copyrightiso.orgWebsite:www.iso.orgPublishedinSwitzerlandContentsPageForewordiv1 Scope12 Normativereferences13 Termsanddefinitions14 Principle25 Apparatus25.1 General25.2 Equipmentforextractionandsamplepreparation25.3 LC-U
15、V/VISsystem35.4 LC-MS/MSorLC-MSsystem36 Reagentsandmaterials37 Sampling58 Procedure58.1 General58.2 LC-UV/VISmethod58.2.1 ExtractionofLC-UV/VIS58.2.2 OperationconditionsofLC-UV/VIS68.2.3 Blank68.2.4 InterferencesofLC-UV/VIS68.2.5 CalibrationofLC-UV/VIS68.2.6 DeterminationbyLC-UV/VIS78.3 LC-MSmethod7
16、8.3.1 ExtractionofLC-MS78.3.2 Furtherdilution78.3.3 Filtration88.3.4 OperationconditionsofLC-MS88.3.5 Blank88.3.6 InterferencesofLC-MS88.3.7 CalibrationofLC-MS88.3.8 DeterminationbyLC-MS99 Calculation910 Precision1010.1 General1010.2 RepeatabilityIimitJ1010.3 Reproducibilitylimit,/?1011 Testreport10
17、Annex A (informative)ExampleofLCconditions12Annex B (informative)ExampleofmultiplereactionmonitoringLC-MS/MSconditions15AnnexC(normative)CalculationofpreservativecontentwithstandardadditionforLC-MSmethod18Annex D (informative)Mechanicalmethodforhomogenizationandextraction20Annex E (informative)Resul
18、tsoftheinterlaboratorytest21Bibliography23ForewordISO(theInternationalOrganizationforStandardization)isaworldwidefederationofnationalstandardsbodies(ISOmemberbodies).TheworkofpreparingInternationalStandardsisnormallycarriedoutthroughISOtechnicalcommittees.Eachmemberbodyinterestedinasubjectforwhichat
19、echnicalcommitteehasbeenestablishedhastherighttoberepresentedonthatcommittee.Internationalorganizations,governmentalandnon-governmentallinliaisonwithISO,alsotakepartinthework.ISOcollaboratescloselywiththeInternationalElectrotechnicalCommission(IEC)onallmattersofelectrotechnicalstandardization.Thepro
20、ceduresusedtodevelopthisdocumentandthoseintendedforitsfurthermaintenancearedescribedintheISO/IECDirectives,Part1.Inparticular,thedifferentapprovalcriterianeededforthedifferenttypesofISOdocumentshouldbenoted.ThisdocumentwasdraftedinaccordancewiththeeditorialrulesoftheISO/IECDirectives,Part2(SeeWWW.is
21、o.org/directives).ISOdrawsattentiontothepossibilitythattheimplementationofthisdocumentmayinvolvetheuseof（八）patent(三).ISOtakesnopositionconcerningtheevidence,validityorapplicabilityofanyclaimedpatentrightsinrespectthereof.Asofthedateofpublicationofthisdocument,ISOhadnotreceivednoticeof（八）patent(三)whi
22、chmayberequiredtoimplementthisdocument.However,implementersarecautionedthatthismaynotrepresentthelatestinformation,whichmaybeobtainedfromthepatentdatabaseavailableatWWW.iso.org/patents.ISOshallnotbeheldresponsibleforidentifyinganyorallsuchpatentrights.Anytradenameusedinthisdocumentisinformationgiven
23、fortheconvenienceofusersanddoesnotconstituteanendorsement.Foranexplanationofthevoluntarynatureofstandards,themeaningofISOspecifictermsandexpressionsrelatedtoconformityassessment,aswellasinformationaboutISOsadherencetotheWorldTradeOrganization(WTO)principlesintheTechnicalBarrierstoTrade(TBT),Seewwwts
24、o.org/iso/foreword.htmLThisdocumentwaspreparedbyTechnicalCommitteeISO/TC35,Paintsandvarnishes,SubcommitteeSC16,Chemicalanalysis,incollaborationwiththeEuropeanCommitteeforStandardization(CEN)TechnicalCommitteeCEN/TC139,Paintsandvarnishes,inaccordancewiththeAgreementontechnicalcooperationbetweenISOand
25、CEN(ViennaAgreement).AlistofallpartsintheISO7012seriescanbefoundontheISOwebsite.Anyfeedbackorquestionsonthisdocumentshouldbedirectedtotheusersnationalstandardsbody.Acompletelistingofthesebodiescanbefoundatwww.iso.org/members.html.PaintsandvarnishesDeterminationofpreservativesinwater-dilutablecoating
26、materials一Part3:Determinationofin-canIsothiazolinoneswithLC-UVandLC-MS1 ScopeThisdocumentspecifiestheapparatusandtheanalyticalmethodsfordeterminingthecontentofin-canJsothiazolinonepreservativesinwater-dilutablecoatingmaterialsorrelatedproducts.Thisdocumentisalsoapplicabletopolymerdispersions.2 Norma
27、tivereferencesThefollowingdocumentsarereferredtointhetextinsuchawaythatsomeoralloftheircontentconstitutesrequirementsofthisdocument.Fordatedreferences,onlytheeditioncitedapplies.Forundatedreferences,thelatesteditionofthereferenceddocument(includinganyamendments)applies.ISO1513,PaintsandvarnishesExam
28、inationandpreparationoftestsamplesISO3696,WaterforanalyticallaboratoryuseSpecificationandtestmethodsISO15528,Paints,varnishesandrawmaterialsforpaintsandvarnishesSampling3 TermsanddefinitionsForthepurposesofthisdocument,thefollowingtermsanddefinitionsapply.ISOandIECmaintainterminologydatabasesforusei
29、nstandardizationatthefollowingaddresses: ISOOnlinebrowsingplatform:availableathttps:/www.iso.org/ObP IECElectropedia:availableathttps:WWW.eluctropediD.org/1.1readyforusestateofaproductwhenitismixedinaccordancewiththemanufacturersinstructionsinthecorrectproportionsandthinnedifrequiredusingthecorrectt
30、hinnerssothatitisreadyforapplicationbytheapprovedmethodSOURCE:ISO11890-2:2020,3.71.2water-dilutablecoatingmaterialwater-reduciblecoatingmaterialwater-basedcoatingmaterialwater-bornecoatingmaterialwater-thinnablecoatingmaterialDEPRECATED:waterpaintcoatingmaterialwhoseviscosityisreducedbytheadditionof
31、waterSOURCE:ISO4618:2023,3.2721.3detectionlimitofinstrumentthreetimesthestandarddeviationoftheresultobtainedintheblanktestusingaspecificinstrumentSOURCE:ISO8124-5:2015,3.51.4in-canpreservativebiocideusedtopreventgrowthofmicroorganismsduringstorageofastocksolutionofacoatingmaterialorwater-basedcoatin
32、gmaterial(3.2)SOURCE:ISO4618:2023,3.1414 PrincipleThesampleisextractedwithsuitabledilutionsolventusinganappropriatehomogenizationmethod,suchasultrasonicwaterbath.Theextractispurifiedbycentrifugation,afterwhichtheisothiazolinonesareidentifiedandquantifiedbyliquidchromatography(LC)incombinationwithult
33、raviolet/visible(UV/VIS)detectionordifferentmassspectrometrydetectors.Thisincludesliquidchromatography-tandemquadrupolemassspectrometry(LC-MS/MS)andliquidchromatography-singlequadrupolemassspectrometry(LC-MS).Forthepurposesofthisdocument,LCalsodesignateshigh-performanceliquidchromatography(HPLC)orul
34、tra-performanceliquidchromatography(e.g.UPLCorUHPLC).Atmosphericpressurechemicalionization(APCI)andelectrosprayionization(ESl)havebeenfoundsuitable.Otherionizationtechniquesandmassanalyserswithsufficientperformancecanalsobeused.NOTEThedifferencebetweentheresultsisexpectedtobesmallerthanthereproducib
35、ilitylimitsofthemethodsforastandardwater-bornecoatingsample.IntheinterlaboratorytestaccordingtoAnnexE,thedeterminationbytheLC-UV/VISmethodandtheLC-MSorLC-MS/MSmethodturnedouttodelivercomparableresultswithinthereproducibilitylimitsofthemethods,validatingtheabovestatement.Thisdocumentisgenerallyapplic
36、ableforn-octyl-4-isothiazolin-3-one(OlT)and4,5-dichloro-n-octyl-4-isothiazolin-3-one(DCOIT).However,thedocumentwasnotvalidatedforOITandDCOITintheinterlaboratorytest.Therearenationalstandardscoveringthesecompounds.5 Apparatus5.1 GeneralTheusuallaboratoryapparatusand,inparticular,thefollowingapparatus
37、statedin52to54shallbeused.5.2 Equipmentforextractionandsamplepreparation5.2.1 Highspeedcentrifuge,withanaccelerationatasuitablespeed.NOTEArotationspeedof(5000-30000)revolutionsperminute(rmin)hasbeenfoundsuitable.5.2.2 Ultrasonicwaterbath,withafrequencyfrom35kHzto45kHz.5.2.3 Analyticalbalance,capable
38、ofweighingtoanaccuracyof0,1mg.5.2.4 One-markvolumetricflask,of10ml,25ml,50mland100mlnominalcapacity.5.2.5 Pipettes,suitablesingle-volumepipettes,graduatedpipettesandPasteurpipettes.5.2.6 Centrifugetubes,withasuitablesnap/screwcap.5.2.7 Glassautosamplervials,withasuitablesnap/screwpre-slitcap,2ml.5.2
39、8 Syringe,minimumvolume2ml.5.2.9 Filtrationmembrane,about0,22mporesize.5.3 LC-UV/VISsystem5.3.1 LCsystem,equippedwithasampleinjectionsystem,asolventpumpingsystemcapableofmixingsolvents,asamplecompartmentcapableofmaintainingrequiredtemperatureandatemperature-controlledcolumncompartment,adegassingsys
40、temanddataprocessingsoftware.AnLCsystemthatcanperformattheflows,pressures,controlledtemperatures,samplevolumesandotherrequirementsofthedocumentshallbeused.5.3.2 Analyticalcolumn;reversephaseC18particlecolumnswereusedtodevelopthistestmethod.Anycolumnthatachievesadequateresolutionmaybeused.Theretentio
41、ntimesandorderofelutionmaychangedependingonthecolumnusedandshallbemonitored.5.3.3 UV/VISdetector,oroptionallyadiodearraydetector(DAD).5.4 LC-MS/MSorLC-MSsystem5.4.1 LCsystem,equippedwithasampleinjectionsystem,asolventpumpingsystemcapableofmixingsolvents,asamplecompartmentcapableofmaintainingrequired
42、temperatureandatemperature-controlledcolumncompartment,adegassingsystemanddataprocessingsoftware.AnLCsystemthatcanperformattheflows,pressures,controlledtemperatures,samplevolumes,andotherrequirementsofthedocumentshallbeused.5.4.2 Analyticalcolumn,asspecifiedin5.3.2.5.4.3 MS/MSorMS-systemlequippedwit
43、hAPCIorESI.Otherionizationtechniquesandmassanalyserswithsufficientperformancecanalsobeused.6 ReagentsandmaterialsDuringtheanalysis,unlessotherwisestated,useonlyreagentsofrecognizedanalyticalgradeandonlydistilledwaterorwaterofgrade1inaccordancewithISO3696.SolventsshallbeofasuitablequalityforLC-UV/VIS
44、andLC-MS,i.e.LC-MSgradeforLC-MSanalysis.6.1 Referencesubstances:methylisothiazolinone(MIT,CASRN1)2682-20-4)l5-chloro-2-methyl-4-isothiazolin-3-one(CMIT1CASRN26172-55-4)lll2-benzisothiazolin-3-one(BIT,CASRN2634-33-5).6.2 Methanol(CASRN67-56-1).6.3 Acetonitrile(CASRN75-05-8).6.4 Formicacid(CASRN64-18-
45、6).6.5 Aceticacid(CASRN64-19-7),99%massfraction,optionalforbetterrecoveryrates.NOTETheaceticacidisfoundusefultoimprovetherecoveryratebylooseningupthestructureoftheemulsionpaint.6.6 Ammoniumacetate(CASRN631-61-8).6.7 Precipitatingagent(optionalforbetterprecipitationwhenusingLC-UV/VIS),e.g.aluminiumsu
46、lfate98%,Carrezreagent.Aprecipitatingagent(e.g.aluminiumsulfate,Carrezreagent)canbeusedtocleanupthesamplesolutionaftertheextraction.Inthiscase,testsshallbecarriedouttoensurethattheuseoftheprecipitatingagentdoesnotreducetherecoveryrateascomparedtotheanalysiswithoutprecipitationagent.6.8 Dilutionsolve
47、nt,suitablefordilutingthesample.Itshallhaveapurityofatleast99%bymassorshallbeofknownpurity,anditshallnotcontainanysubstanceswhichinterferewiththedetermination,e.g.causingoverlappingpeaksinthechromatogram.Methanolandmixtureofwaterandmethanol(1:1byvolume)havebeenfoundsuitable.Alternatively,othersuitab
48、lesolventsmayalsobeused.Howeverlitshouldbeensuredthatthesampledoesnotagglomerate,whichcanleadtotheinclusionofpreservativesandthustoanalyticalerrors.6.9 Internalstandard(ISTD)forLC-MSmethod,whichshouldbeaddedattheextractionstepandtostandardworkingsolutions.Isotopelabelledinternalstandardsshouldbeusedasmuchaspossible.6.10 Calibrationstandardsolutions6.10.1 GeneralThecalibrationstandardsolutionsshouldbepre
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