1、InternationalStandardISO7012-1Firstedition2025-04Paintsandvarnishes一Determinationofpreservativesinwater-dilutablecoatingmaterials一Part1:Determinationofin-canfreeformaldehydePeinturesetvernisDosagedesagentsdepreservationdanslesproduitsdepeinturediluablesaYeau一Partie1:DosageduformaldehydeIibreenpotRef
2、erencenumberISO7012-l:2025(en)COPYRIGHTPROTECTEDDOCUMENTISO2025Allrightsreserved.Unlessotherwisespecified,orrequiredinthecontextofitsimplementation,nopartofthispublicationmaybereproducedorutilizedotherwiseinanyformorbyanymeans,electronicormechanical,includingphotocopying,orpostingontheinternetoranin
3、tranet,withoutpriorwrittenpermission.PermissioncanberequestedfromeitherISOattheaddressbeloworISO,smemberbodyinthecountryoftherequester.ISOcopyrightofficeCP401Ch.deBlandonnet8CH-1214Vernier,GenevaPhone:+41227490111Email:copyrightiso.orgWebsite:www.iso.orgPublishedinSwitzerlandPageContentsForewordv1 S
4、cope12 Normativereferences13 Termsanddefinitions14 Principle34.1 General34.2 Equilibriaofin-canfreeformaldehydeinthecoatingmatrix34.3 Equilibriaofin-canfreeformaldehydeduringextraction34.4 Equilibriaofin-canfreeformaldehydeduringderivatization34.5 PrincipleofMethodA:Derivatizationwithacetylacetone(A
5、CAC)combinedwithphotometricdetection34.5.1 DerivatizationwithACAC34.5.2 Detectionandquantificationwithaspectralphotometer44.6 PrincipleofMethodB:Derivatizationwithdinitrophenylhydrazine(DNPH)combinedwithliquidchromatography(LC)separationandUV/VISdetection44.6.1 DerivatizationwithDNPH44.6.2 Separatio
6、n,detectionandquantificationwithLC-UV/VIS44.7 PrincipleofMethodC:Liquidchromatography(LC)separationfollowedbypost-columnderivatizationwithACACandsubsequentquantificationwithUV/VISdetection44.7.1 Separationoffreeformaldehydebyliquidchromatography44.7.2 Post-columnderivatizationwithacetylacetone(ACAC)
7、andquantificationwithUV/VISdetection45 Apparatus423.4.55.5.5.LHGeneralapparatus4Apparatusforextraction4ApparatusformethodA5ApparatusformethodB55.5.1 LCHPLCorultra-performanceliquidchromatography(UHPLC)system55.5.2 Appropriatecolumn55.6ApparatusformethodC65.6.1 LCHPLCorultra-performanceliquidchromato
8、graphy(UHPLC)systemwithpost-columnreactor65.6.2 Appropriatecolumn(e.g.RPC8,RPC18column)66 Reagentsandmaterials66.1 General.66.2 Generalreagents66.2.1 Demineralizedwater66.2.2 Formaldehydesolution66.2.3 Formaldehydestocksolution66.2.4 Formaldehydeworkingsolutionsforcalibration66.2.5 Carrezsolutions(o
9、ptional)76.3 MethodA:ReagentsforderivatizationwithACAC76.4 MethodB:ReagentsforderivatizationwithDNPH76.5 MethodC:Reagentsforpost-columnderivatizationwithACAC76.6 Reagentsfortitrationofformaldehydestandard87 Procedure87.1 Sampling87.2 Extraction87.3 AnalysisanddetectionofMethodA97.3.1 Procedureforder
10、ivatizationwithACAC97.3.2 Photometricanalysisofcalibrationsolutions97.3.3 Samplemeasurementforphotometricanalysis107.3.4 Quantificationofthein-canfreeformaldehydecontent107.4 AnalysisanddetectionofMethodB107.4.1 ProcedureforderivatizationwithDNPH107.4.2 Operationconditions117.4.3 Blankdetermination1
11、17.4.4 Analysisofcalibrationsolution117.4.5 Samplemeasurement117.4.6 Qualitycheck127.4.7 Calculationofin-canfreeformaldehydecontent127.5 AnalysisanddetectionofMethodC127.5.1 Operationconditions127.5.2 Blankdetermination127.5.3 Analysisofcalibrationsolution127.5.4 Samplemeasurement137.5.5 Qualitychec
12、k137.5.6 Calculationofin-canfreeformaldehydecontent138 Precision148.1 General148.2 Repeatabilitylimit,r148.3 Reproducibilitylimit,R149 Testreport14Annex A (normative)Titrationmethodsforthedeterminationofformaldehydecontent16Annex B (informative)ExampleofHPLCconditionsformethodB18Annex C (informative
13、)ExampleofHPLCconditionsformethodC19Annex D (informative)Resultsoftheinterlaboratorytest20Bibliography21ForewordISO(theInternationalOrganizationforStandardization)isaworldwidefederationofnationalstandardsbodies(ISOmemberbodies).TheworkofpreparingInternationalStandardsisnormallycarriedoutthroughISOte
14、chnicalcommittees.Eachmemberbodyinterestedinasubjectforwhichatechnicalcommitteehasbeenestablishedhastherighttoberepresentedonthatcommittee.Internationalorganizations,governmentalandnon-governmental,inliaisonwithISO,alsotakepartinthework.ISOcollaboratescloselywiththeInternationalElectrotechnicalCommi
15、ssion(IEC)onallmattersofelectrotechnicalstandardization.TheproceduresusedtodevelopthisdocumentandthoseintendedforitsfurthermaintenancearedescribedintheISO/IECDirectives,Part1.Inparticular,thedifferentapprovalcriterianeededforthedifferenttypesofISOdocumentshouldbenoted.Thisdocumentwasdraftedinaccorda
16、ncewiththeeditorialrulesoftheISO/IECDirectives,Part2(seeWWW.iso.org/directives).ISOdrawsattentiontothepossibilitythattheimplementationofthisdocumentmayinvolvetheuseof（八）patent(三).ISOtakesnopositionconcerningtheevidence,validityorapplicabilityofanyclaimedpatentrightsinrespectthereof.Asofthedateofpubl
17、icationofthisdocument,ISOhadnotreceivednoticeof（八）patent(三)whichmayberequiredtoimplementthisdocument.HoweverlImplementersarecautionedthatthismaynotrepresentthelatestinformation,whichmaybeobtainedfromthepatentdatabaseavailableatWWW.iso.org/patents.ISOshallnotbeheldresponsibleforidentifyinganyorallsuc
18、hpatentrights.Anytradenameusedinthisdocumentisinformationgivenfortheconvenienceofusersanddoesnotconstituteanendorsement.Foranexplanationofthevoluntarynatureofstandards,themeaningofISOspecifictermsandexpressionsrelatedtoconformityassessment,aswellasinformationaboutISOsadherencetotheWorldTradeOrganiza
19、tion(WTO)principlesintheTechnicalBarrierstoTrade(TBT),seeWWW.iso.org/iso/foreword.htmLThisdocumentwaspreparedbyTechnicalCommitteeISO/TC35,Paintsandvarnishes,SubcommitteeSC16,Chemicalanalysis,incollaborationwiththeEuropeanCommitteeforStandardization(CEN)TechnicalCommitteeCEN/TC139,Paintsandvarnishes,
20、inaccordancewiththeAgreementontechnicalcooperationbetweenISOandCEN(ViennaAgreement).AlistofallpartsintheISO7012seriescanbefoundontheISOwebsite.Anyfeedbackorquestionsonthisdocumentshouldbedirectedtotheusersnationalstandardsbody.Acompletelistingofthesebodiescanbefoundatwww.iso.orH/members.htmLPaintsan
21、dvarnishesDeterminationofpreservativesinwater-dilutablecoatingmaterials一Part1:Determinationofin-canfreeformaldehyde1 ScopeThisdocumentspecifiestheapparatusandanalyticalmethodsfordeterminingtheconcentrationofin-canfreeformaldehydeinwater-dilutablecoatingmaterials.Thisdocumentcanalsobeappliedtopolymer
22、dispersions.ThedeterminationmethodAforin-canfreeformaldehydedescribedinthisdocumentisonlyoflimitedsuitabilityforpigmentedsystems,astheinherentcolorationofthematerialcanhaveaninfluenceonthedetection.2 NormativereferencesThefollowingdocumentsarereferredtointhetextinsuchawaythatsomeoralloftheircontentc
23、onstitutesrequirementsofthisdocument.Fordatedreferences,onlytheeditioncitedapplies.Forundatedreferences,thelatesteditionofthereferenceddocument(includinganyamendments)applies.ISO1513,PaintsandvarnishesExaminationandpreparationOftestsamplesISO3696,WaterforanalyticallaboratoryuseSpecificationandtestme
24、thodsISO15528,Paints,varnishesandrawmaterialsforpaintsandvarnishesSampling3 TermsanddefinitionsForthepurposesofthisdocument,thefollowingtermsanddefinitionsapply.ISOandIECmaintainterminologydatabasesforuseinstandardizationatthefollowingaddresses: ISOOnlinebrowsingplatform:availableathttps:WWW.iso.org
25、/obp IECElectropedia:availableathttps:WWW.electropedia.org/1.1readyforusestateofaproductwhenitismixedinaccordancewiththemanufacturersinstructionsinthecorrectproportionsandthinnedifrequiredusingthecorrectthinnerssothatitisreadyforapplicationbytheapprovedmethodSOURCE:ISO11890-2:2020,3.71.2in-canfreefo
26、rmaldehydecontentconcentrationofformaldehydewhichisavailableinthecoatingasanin-canpreservativef3.9asdeterminedby： methodAofthisdocument,i.e.photometricdetectionafterderivatizationwithacetylacetone; methodBofthisdocument,i.e.liquidchromatographydetectionafterderivatizationwithDNPH(2,4-dinitrC)PhenyI-
27、hydrazine);or methodCofthisdocumenti.e.liquidchromatographydetectionwithpost-columnderivatizationwithacetylacetone;wherewaterisusedasanextractionsolventforallthreemethodsNote1toentry:In-canfreeformaldehydecontentcorrespondstotheamountofformaldehydeinmilligrams,basedon1kgofcoatingmaterial(3.4)orpolym
28、erdispersion,whichisavailableunboundinthesampleatthetimeofderivatization.Note2toentry:Sincethefreeformaldehydeisinequilibriumwithboundformaldehydeandtheequilibriumcanbeinfluencedbythesolvent,thecontentoffreeformaldehydeinwatercandifferfromthatinanothersolvent.Thisdefinitionforin-canfreeformaldehydec
29、ontentisonlyvalidwithrespecttowaterastheextractionsolvent.1.3in-cantotalformaldehydecontentconcentrationoffreeandboundformaldehydeinthecoatingmaterial(3.4)1.4coatingmaterialDEPRECATED:coatingproduct,inliquid,pasteorpowderform,that,whenappliedtoasubstrate,formsalayerpossessingprotective,decorativeand
30、/orotherspecificpropertiesSOURCE:ISO4618:2023,3,481.5water-dilutablecoatingmaterialwater-reduciblecoatingmaterialwater-basedcoatingmaterialwater-bornecoatingmaterialwater-thinnablecoatingmaterialDEPRECATED:waterpaintcoatingmaterial(3.4)whoseviscosityisreducedbytheadditionofwaterSOURCE:ISO4618:2023,3
31、2721.6formaldehydedepotsubstancecompoundthatreleasesformaldehydeoveralongperiodoftime1.7extinctionattenuationofalightbeamtraversingamediumthroughabsorptionandscatteringNote1toentry:Extinctiondependsonthewavelengthoftheradiation.SOURCE:ISO13320:2020,3.1.91.8preservativesubstancethatpreventsthegrowth
32、ofundesirablemicroorganismsSOURCE:ISO8124-7:2015,3.61.9in-canpreservativebiocideusedtopreventgrowthofmicroorganismsduringstorageofastocksolutionofacoatingmaterial(3.4)orwater-basedcoatingmaterial(3.5)SOURCE:ISO4618:2023,3.1414 Principle4.1 GeneralThisdocumentdescribesthreemethodsforthedeterminationo
33、fin-canfreeformaldehydeincoatingmaterialswhichhavebeenvalidatedtoshowcomparableresultsforselectedsampleswithrespecttotheircomparabilitylimitsstatisticallyformethodsAandBandwithasinglecomparisonformethodC.4.2 Equilibriaofin-canfreeformaldehydeinthecoatingmatrixWhenaformaldehydedepotsubstanceisaddedto
34、acoatingmaterial,equilibriumisestablishedbetweentheformaldehydeboundtotheformaldehydedepotsubstanceandthein-canfreeformaldehyde.ThisequilibriumdependsonthepHvalue,thecoatingmatrix,theformaldehydedepotsubstanceandthetemperature.Furthermore,inwater-dilutablecoatingmaterials,thereisalsoequilibriumbetwe
35、enthein-canfreeformaldehydeandthematrixitself.Thein-canfreeformaldehydecanundergoavarietyofequilibriumreactions,e.g.withwatertoformahydrateorwithotherformaldehydemoleculestoformtrimers.Adistinctionshallbemadeinacoatingmaterialbetweenthein-cantotalformaldehydecontentandtheincanfreeformaldehydecontent
36、Inthisdocument,thein-canfreeformaldehydecontentisunderstoodtobetheformaldehydeconcentrationdeterminedbyeither: methodA,i.e.derivatizationwithacetylacetoneandsubsequentphotometricdetectionandquantification; methodB,i.e.derivatizationwithDNPHandsubsequentdetectionandquantificationwithliquidchromatogr
37、aphy-ultraviolet/visiblelightdetector(LC-UV/VIS)analysis;or methodC,i.e.liquidchromatography(LC)separationfollowedbypost-columnderivatizationwithacetylacetoneandsubsequentquantificationwithultraviolet/visiblelightdetector(UV/VIS)detection.4.3 Equilibriaofin-canfreeformaldehydeduringextractionInaddit
38、iontotheequilibriainthecoatingmatrixmentionedin42duringextraction,theequilibriumofincanfreeformaldehydeisalsoaffectedbytheextractionsolvent.Dependingonthenatureoftheextractionsolvent,thesample/solventratio,extractiontimeandpHvalue,theequilibriumofboundandfreein-canformaldehydecanbeshiftedtoeithersid
39、e.Therefore,itiscrucialtoselecttheappropriateextractionsolventandextractionconditions.4.4 Equilibriaofin-canfreeformaldehydeduringderivatizationThein-canfreeformaldehydeintheextract(orafterchromatographicseparation)isderivatizedbychemicalreactionwithaderivatizingagentThereactionisalsoanequilibriumre
40、action.Toensurecompletederivatization,anexcessofderivatizationagentisadded.4.5 PrincipleofMethodA:Derivatizationwithacetylacetone(ACAC)combinedwithphotometricdetection4.5.1 DerivatizationwithACACInordertoenablephotometricdetectionofformaldehyde,derivatizationshallbecarriedout.Derivatizationintroduce
41、sachromophoreafterreactionwithformaldehyde,whichhasthepropertytoabsorbultraviolet(UV)orvisible(VlS)light.Thederivatizationisperformedpriortothephotometricanalysis(pre-columnderivatization).In-canfreeformaldehydeisderivatisedto3,5-diacetyl-l,4-dihydrolutidinebyusingACACandammoniumions(Hantzschreactio
42、n).Theabsorptionmaximumofthecompoundisatawavelengthof412nm.4.5.2 DetectionandquantificationwithaspectralphotometerAspectralphotometerisappliedtoquantifytheformaldehyde-ACACreactionproduct,which,inturn,canbeusedtocalculatetheconcentrationofin-canfreeformaldehydeinthecoatingmatrix.4.6 PrincipleofMetho
43、dB:Derivatizationwithdinitrophenylhydrazine(DNPH)combinedwithliquidchromatography(LC)separationandUV/VISdetection4.6.1 DerivatizationwithDNPHThein-canfreeformaldehydecanbederivatizedwithDNPHleadingtotheformationofacompoundthatcanbeseparatedbyliquidchromatographyanddetectedwithaUV/VIS-detectorat360nm
44、4.6.2 Separation,detectionandquantificationwithLC-UV/VISLiquidchromatographyisappliedtoseparatethedifferentaldehyde-DNPHreactionproducts.SubsequentUV/VISdetectionisusedtoidentifyandquantifytheconcentrationoftheformaldehyde-DNPHreactionproduct,whichenablesthecalculationofthein-canfreeformaldehydecon
45、tentinthecoatingsample.IfderivatizationwithDNPHisused,thedeterminationofin-canfreeformaldehydecontentshallbeperformedbyLC-UV/VISanalysis,sincethereactionwithDNPHisalsosensitivetootheraldehydes,whichcaninterferewhenusingadeterminationwithaspectralphotometer.4.7 PrincipleofMethodC:Liquidchromatography
46、LC)separationfollowedbypost-columnderivatizationwithACACandsubsequentquantificationwithUV/VISdetection4.7.1 SeparationoffreeformaldehydebyliquidchromatographyLiquidchromatographyisperformedpriortoderivatization.Itisappliedtoseparatefreeformaldehydefromallothercomponentspresentinthewaterextracttoavo
47、idinterferencesinthedetection.4.7.2 Post-columnderivatizationwithacetylacetone(ACAC)andquantificationwithUV/VISdetectionToenabledetectionoftheseparatedformaldehyde,derivatizationisperformedasdescribedin4.5.LinthiscasebymixingACACtothecolumnoutlet.Quantificationisdonein-linewithUV/VISdetectionatthemaximumabsorptionoftheformaldehydeACACreactionproduct,i.e.412nm.5 Apparatus5.1 GeneralTheusuallaboratoryapparatusand,inparticular,thefollowingapparatusstatedin52to56shallbeused.5.2 Generalapparatus5.2.1 Precisionscale,capableofweighingtoanaccuracyof0,0001g.5.2.2 Suitablevolumetricflasksforcal
