FluorescentBrighteningagents

FBA
TheFluorescentBrighteningagentsoperatebythephenomenaoffluorescence InordertounderstandthemechanismofFBAitisnecessarytounderstandFluorescence Fluorescence istheemissionoflightbyasubstancethathasabsorbedlightorotherelectromagnetic radiation.Itisaformofluminescence .Inmostcases,theemittedlighthasalongerwavelength,and thereforelowerenergy,thantheabsorbedradiation.

Other names of FBA

Opticalbrighteners, opticalbrighteningagents(OBAs), fluorescentbrighteningagents (FBAs) or fluorescentwhiteningagents(FWAs) are dyes thatabsorblightinthe UV andvioletregion (usually340370 nm)ofthe EMspectrumandreemitlightintheblueregion(typically420470 nm). Fluorescentactivityisashorttermorrapidemissionresponse,unlikephosphorescence,whichisa delayedemission.Theseadditivesareoftenusedtoenhancetheappearanceofcolor of fabric and paper causinga"whitening"effect,makingmaterialslooklessyellowbyincreasingtheoverallamount ofbluelightreflected.

Resonance Fluorescence

However,whentheabsorbedelectromagneticradiationisintense,itispossiblefor one electrontoabsorbtwo photons;this 2photon canleadtoemissionofradiationhavinga shorterwavelengththantheabsorbedradiation.Theemittedradiationmayalsobeofthe samewavelengthastheabsorbedradiation,termed"resonancefluorescence". Themoststrikingexamplesoffluorescenceoccurwhentheabsorbedradiationisinthe ultraviolet regionofthe spectrumandthusinvisibletothehumaneye,andtheemittedlight isinthevisibleregion.

What are FBA

Typeofdye Dyesabsorbcolor andreflectsomecolors FBAaretypeofFluorescentDyes Reemitabsorbedlightintolonger Wavelength FBAabsorbUVandemitsinblueviolet Absorption340380nm,Emission425 450nm

What does FBA do?

FBAincreasestheapparentreflectanceofthearticleinthebluevioletregionofthe Spectrum.Treatedmaterialremitsmorelightinthevisibleregionthandoesanuntreated whitesampleandthusappearswhiterthanwhite.

How does it work

AnefficientFBAmustabsorbstronglyintheultravioletregionandmustalsoreemitamajor proportionoftheabsorbedenergyasvisiblelight,thatis,itmusthaveahighfluorescence efficiency. Althoughfluorescencecanoccurfromthesigmabonds ofmanyorganiccompounds,strong fluorescenceisassociatedwithpibondedelectrons. AllFBAsthereforecontainaconsiderablenumberof conjugateddoublebonds.

Brightenersarecommonlyaddedto laundrydetergents toreplacewhiteningagents removedduringwashingandtomaketheclothesappearcleaner.Opticalbrightenershave replacedBluing whichwasformerlyusedtoproducethesameeffect.Somebrightenerscan causeallergicreactionswhenincontactwithskin,dependingontheindividual. Brightenersareusedinmanypapers,especiallyhighbrightnesspapers,resultingintheir stronglyfluorescentappearanceunderUVillumination.Paperbrightnessistypically measuredat457 nm,wellwithinthefluorescentactivityrangeofbrighteners.

Paperusedforbanknotesdoesnotcontainopticalbrighteners,soacommonmethodfor detecting counterfeitnotesistocheckforfluorescence. Opticalbrightenershavealsofoundusein cosmetics.Oneapplicationistoformulasforwashingand conditioninggreyorblondehair,wherethebrightenercannotonlyincreasetheluminanceandsparkle ofthehair,butcanalsocorrectdull,yellowishdiscolorationwithoutdarkeningthehair.Someadvanced faceandeyepowderscontainopticalbrightener microsphere thatbrightenshadowedordarkareasof theskin,suchas"tiredeyes".

Stilbenes as FBA

Themostcommonclassesofchemicalswiththispropertyarethe stilbenes andolder,non commercial fluorescentchemical suchas umbelliferone,whichabsorbenergyinthe UV portionofthespectrumandreemititintheblueportionofthevisiblespectrum.A whitesurfacetreatedwithanopticalbrightenercanemitmorevisiblelightthanthatwhich shinesonit,makingitappearbrighter.Thebluelightemittedbythebrightenercompensates forthediminishingblueofthetreatedmaterialandchangesthehueawayfromyellowor brownandtowardwhite. Thereareapproximately400brightenertypeslistedintheColor Index,butlessthan90are actuallyproducedcommerciallyandonlyahandfularecommerciallyimportant.

Types of FBA used

FBA productionforpaper,textilesanddetergentsisdominatedbyjustafewdi andtetrasulfonated triazolestilbenes andadisulfonated stilbenebiphenyl.Thesearesubjecttofadingwhenexposedlong termtoUV,duetotheformationofopticallyinactivestilbene cisisomersfoundatthecenter ofthe molecule.Exposedtogasesandespeciallyoxygentheywillfadetoo,likemostdyecolorants.All brightenershaveextendedconjungation and/oraromaticity,allowingforelectronmovement.Some nonstilbene brightenersareusedinmorepermanentapplicationssuchaswhiteningsyntheticfiber.

Types of Brighteners

Basicclasstypesofbrightenersinclude: Triazine stilbene (di,tetra orhexasulfonated) Coumarins Imidazolines Diazoles Triazoles Benzoxazolines Biphenylstilbenes

Different types of FBA

Different FBAs

MostFBAsare"derivativesofstilbene...biphenylandfivemembered heterocyclics,suchas triazoles,oxoazoles orimidazoles....sixmembered heterocyclics,suchascoumarins, naphthalimide,pyrazine,ortriazine ." Theextensivepisystemsoftheseoftenheterocyclic aromaticcompoundsareassociatedwiththecloselyspacedelectronicenergylevelsthat allowforenergytransitionswithinthevisiblerange(e.g.n>pitransitions). Table1tothe rightshowssomeofbasestructuresthatFWAsarederivedfrom.

Booster for FBA

Brightenerscanbe"boosted"bytheadditionofcertain polyols likehighmolecular weight PEG orpolyvinylalcohol .Theseadditivesincreasethevisiblebluelightemissions significantly.Brightenerscanalsobe"quenched".Toomuchuseofbrightenerwilloftencause agreeningeffectasemissionsstarttoshowabovetheblueregioninthevisiblespectrum. Besidestheformationofcis isomerinstilbenecontainingbrighteners(onlythetransisomer isopticallyactive),continuedexposuretoUVcontaininglightwillactuallycleavethe moleculeandstarttheprocessofdegradation.

Total use of FBA

In2006,textilesstillaccountedfor25%ofworldwidefluorescentbrighteneruse (1). Syntheticsandplasticsaccountedforanadditional5%oftotaluse. Fluorescentbrightenersaretypicallyincorporatedintofabricsandplasticsviadyingduring manufactureto"enhanceaestheticsandconsumerappeal." Onceincorporated,these brightenersimprovecolorationandalsodisguisefading. Awiderangeofcolored fabricsthatcanbetreatedtoappearbrighter. Optimally,eachfabric andshadeistreatedwiththefluorescentbrightenerthatwillbestenhancetheoriginal fabric'shueorbasedye,makingitmorevibrant. Forexample,somebrightenersgiveoff highlyfluorescentgreenishyellowshadesandwouldbeappropriateforgreenfabrics.

Usefulness of FBA

Forafluorescentbrightenerstobeconsideredparticularlyeffectiveandusefulforusein textiles,itmustpossessthefollowingthreecharacteristics: 1. fluorescentemissioninthedesiredrange (i.e.theygiveoffthecorrectcolor) 2. fastness towashing,perspiration,andsunlight(i.e.theylastlongbecausetheybondor adherewelltothebasematerial)and 3. nonhazardousproperties (i.e.humanscanbesafelyexposedtothem).

FBAsexhibitfluorescenceasaresultofspecificelectronicandvibrational transitions,shownin 1.AbsorptionofUVlight. TheFBAabsorbsUVlightasitisexcitedfromthegroundelectronicstatetotheexcitedelectronicstate (i.e.thetwocurvedMorseenergylevelsurfacesinthediagramtotheleft). Thevibrational states(i.e.the smallerenergylevelswithineachelectronicenergylevelinthediagramtotheleft)alsousuallychange becausetheinternuclear distancemustremainthesameduringthiselectronictransition(accordingtothe FrankCondonprinciple). 2.Radiationless energytransfer. TheFBAthenrelaxestoalowervibrational statewithintheexcitedelectronicstate,oftenmediatedbya collisionorvibrational/rotationalmotionwithinthemolecule. Noelectromagneticradiationisemittedas energyisgivenoffviasomekineticmotion.

Followed by

3.Emissionofvisiblelight. TheFBAthenrelaxesfromtheexcitedelectronicstatebackdowntothegroundexcited state. Becauseoftheradiationless energytransfer,theenergyofthelightemissionisless energeticthantheenergyoftheinitiallightabsorption. TheFBAinitiallyhadabsorbedUV light,butemitsvisiblelight

FBA for cotton

FluorescentBrightenersforcottonareTinopal, Thisisclaimedtogiveexcellentresultswhenappliedbytheexhaustionorpaddingmethods AnditsslightlyvioletshadeimpartsawhiteeffectofstrikingbrillianceItexhaustswithinapHrangeof 811orhigherSimilarlytheFBAsforpolyamide,polyestersandacrylicfibres