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NEWSLETTER TECHNICAT

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Determination of formaldehyde on textiles
on for of arise aboutthe methods determination formaldchyde textlesand Veryoftenquestions their difference thelr mportance exist methods. ng aboutthe currently an Forthisreason, overview is ationand correiatlons given. different is One of the both important methodsfor determiningformaldehyde lhc JapanLaw 112 (determination of free formaldehyde). '100", fower" as "ECOPROOF" European and like OekoTexStandard cal Manyecolog labels to I ke M&S" refer thismethod. and retailers we I aswell knownbrands Secondrmportantmelho(l is the AATCC 112'1998(rcleasedformaldehyde)' which is Law1-l2method to by required example M&S" in addition the Japan for The 3" method, Shiley Bu etin 4817'1975 (free formaldehyde)' hasc earlylost rmportancc veryrarely. and isrequired Law112 ml]lho'l methodto the Japan switched fromth s Shirley In 2000,M&S for example on The 4"'method, "De long" (free formaldehyde) is unifipotl.antfor the determinat of on formaldehyde textrles of on fabric depends the specificationseach abc on of Thc llmitvalue formaldehyde the textile and/orretailer. 100" asoneofthe mostimportant of the Asan example specification the OekoTexStandard is standards the followingl
Productclass directcontact

l apanLaw112

7s pprn

please lor ask end (for regarding uses, ons,especially informat moreexamples detailed Some of specifications eachretailer/label): 1 and Law'1'12) 300 ppm (AATCC 12) . M&S specifies llmitsof75 ppm (Japan and 300 ppm (no drrect . European limitsof 30 ppm (d rectskincontact) Flower specifies to lapanLaw112 both accordinq skincontact),

Overview of the different methods to determine formaldehvde


.:...].

:.*

b." *qr r<ln',|d,rer4


DtN EN tSO14184/1 DIN 54260 NF GO6-039-l MAS C18B
free

t r,t,:',
DtN EN ISO 14184/2 BS 6806-3 NF G06.039.2 M&S C18C rcleased
BS6806-2

DtN54260

free

free sodium sulphite


boric acid (buffersolution)

Reagent Treatmcnto, specifia, wM . . : i,.rar:,.

acetvl acetone

acev acetone
steam (abotlewater)

chromotropic acid water l+ wettinoaoent) 20 minutes


25'C 19r Iun-cut]

t hour

20 hourt

10 minutes

40 'c
Sampleweight 5 gr, but)
412/415 nm

50 "c
2 gr' ftut) 412nm

o-2'c

{cut) non titration

570nm

at wave

Valuebeyond chen slry

lbrmaldehyderelease.

B. F o r m a l d e h yd ei n F a b ri cs
l. Free Formaldehyde is monomeric formaldehldetha t Freeformaldehyde defineda s the uncombined are stoichiometric excesses that ma) exist in llnish solutions. lisually. its souroes h a ve b e e nincludedin the resin man u f a c t u rin gs t e p t o d riv e t h e re a c t io na n d / o r1 h e by amount arising from the eqLrilibriumestablished the parliculdr reactants. Frec formaldehydeis determined by suitable analytjcai titration procedurcs2. For m aldehyde Release !'ormaldehyde release, not to bc confuseduith frcc fbrmaldehyde. is the amount of lbrmaldehydc that escapesfrom a fabric into the atmosphere. lt is de ter m in edby the masonjar met h o d ,A A T CC T e s t Me t h o d I 1 2 . T h c mc t h o d c a lls for suspendingI gram offabric in a sealedquart masonjar containingdistilled water i nthe b o ttom.Thejarisincubatedf o r2 0 h o u rs a t . l9 ' C. ' lh e f o rDra ld e h y d e t h a t fabric. collects the water is analyzedand the results are reportedin ppm or prg/g in for determining formaldehyde fabric.For in test metbodsused There are other f'abric in examplethe Japanesemethod calls for titrating the free formaldehyde lhe iabfic oblaincd on by a cold procedure. Thc box below shorvsa comparisonol'1heresLrlts the same piece of fabric lested by the dillerent analytical proccdures.lhe fesulls me ob taine d b] the ltason j a r methoda re mu c h h ig h e r t h a n t h e J a p a n e s e t h o ds ot h e rcader is cautidncdTdtiesure of the details of what is being reportcdbefbrejunping to conclusions.

TABLE I I HCHO TEST METHOD COMPARISON


HCHO (opm) 57 250 151

Method Cold Sodium Sulfite MITI JapaneseLaw A A T C C1 r2 .1 9 8 3

8r8

1 09

lbl thc ia f t e s t u s u a ll) c a ll f o r lh e L rs co t a The a n a lytical procedLrres methodusing Nash Rcagcnl. l his pioccdurc is nol \ery reproduciblcli)f colorimetric low levels of IICHo \\ithor( cxtreme care. Mcthods using chromotropicacid lo develop the colofare more accurate.Recently.even more accuratemethodsrltilizing have been introduced. I I P L C te ch n iq ues 3. Linkages Responsible for HCHO Release 'I here arc three major t)'pesof formaldehyde lbr linkages th at arc fesponsiblc is cellulosehcltrifbrmal. Celhlosc relcasedlbrmaldehyde.The most labile linkagc rcadily picks up formaldehydefrorn the atnosphere and give a positive reirdingb) in a Fr t h e ja r 1e st. c e formaldeirydc solutio n s n d f o rma ld e h y d cma d c a ! a il. h le t ro n r sourc e s .A s c c o u clin k a g et lt a t c e n b e a s o u rc c l t h e N m ethylo lequilibrium are also ol gaseouslbrmaldehydeis uncured resin or pcndanl N'lnctlylol grrrups Tllcsc 1c\ l i n k ag e sa r c r ather labilc and easil,"- : c rtb a c k t o t h c ir s la rt illg rrlc ria ls l1 is lhat is a p p lic d a n d n la k c s u rc t h e le irc rro o1 d i f hcult to cur e 100%' the resin . p c nd a n tN- n e thylol groupsleli. Thcrefo rea ll la b ric s $ ill h r\ e s o mc .a n d t h e a ln o u n t will depend on how well the i'abric was curcd lhe third solll-ceol relclscd is f o r D r ald ch yd e thc crossiink itself. Th e f in is h rv iL ld e c o n p o s eu n d e r lh c la r t c s l condilionsand liberate (lH.O.
il.

Cellulose Hemiacetal
Ce]1-OCE,oE > CelL-OE + Cg,Ol

b. Pendent N-Methylols

-b-ncx"ox

r -8-"" *

"".o,
+ s o c E , N-C> EN c- + cE,ol

c,-Cellulose Crosslinks oE '99 ce ll- o-cs,N-t> ce]l-o E

4. Fabric pH and Formaldehyde Rclease e fab r ic pH has a great influenceon t h e md s o D-iatr s t re s u lt s .A s s e e nin f ig t lre lowestreleasevalues. Howevcr ilrhe pFI is alkalillc 20. a pll of7 will result in the o r aci dic.a ll else being equal, thc test will s h o w mu c h h ig h e r v a lu c s lf t h e s a rn e to swatch is resubjectcd the iar test?additionxl ib.maldehydc rvill be rclcascd ancl test values*ill be in the same ballpark as the first run. l he s$'atchu'ill continue to givc posilivereleasevalues until all the crosslinkshave been brokcn- Jhc shape o o f ih is iu r ve can be explainedbv an un d e rs t a n d in g l t h c lh re e lin k a ! : c s lh e t a re rclease. fb r e sp o n sib le r llCH() lt 0

Figure 45. Effect ofpH on CH'O Release.

3000

pg/q

r5uu

Th c ccllu losc hemiacetals are the o n e s t h a t mo s t e a s ily rc v c rt b a c k t o I I (' llo monomer. They are the ones that are releasedat lleu1ri]l pH. 'lihe penclentN' m e thylo ls are unstable at alkaline p H. I , a b ric t e s t e d u n d c r a lk a lin c p ll wo u ld lib e r a teb o th the hemiacetals and the p e n d e n tN mc t b ] lo ls . I J n d c ra c id ic c o n d it io |s . cr o sslin ks are broken so all three lin k a g e s \ v o u ld c o n t rib u t c t o t h c t o t a l a n o u n t cm i tted .

V. M-ETHODSOF REDUCING FORMAL-D-EHYDERELEASE


A number of approacheshave been tried io reduce HCHO release. lhese approaches range from afterwashingthe curedfabricto developing non-formaldehyde reactants- The section that follows vrill review some of the more important developments. A. Scave ngers Soa vengers are defined as ma t e ria ls c a p a b le o l re a c t in g \ \ ' it h mo n o mc n c fbrmaldehydeand tying it up. Scavengers are added to the finish l-orrnulation and can be grouped into t*o categodes.nitrogenouscompoundsand alcohols. Ihe t\\r groupscontrol [{CHO by different rrcchanisrrs. The nitroscnous additivcs not onl) r ca ct w i th HCHO to form N'methylo ls .b u t a ls o re a c t wit h t h c p c n d c n t N-mc t h y lo ls lL)form methylene bridges. lssentially they compete\"ith the oelluloseand when . e n o u g had ditive is present to lower H(lHO re le a s e c e llu lo s cc ro s slin k s a rc rc d u c c d resulting in lower DP performance. Additional N"lJ groups arc in thc labric turthor affecting chlorine damage and reduced lightfastness. Effective nitrogcnous scavengers are urea, ethylene urea and carbohydrazide.

|!

High boiling alcoholsalso acl as sca\engcrsand lou'cr HCHO rcleas Thcir mcchani;n involv;s cappingpc ndentN'm eth) lo l groups.Thc cappedc nd'groupsa r c ls o l n o r c sta b leth a n lhe hydroxymethylso t h e e q r. rilih riu m f t h e re v e rs c rc a e lir' rrs Thseadditivesalso competcwith crosslinkingso Dl'ratings are somc\!hal shiftecl. diminished. Not having N-H groups,hou'ever.mitigates lrgairst chlorinc rc\i\t Lnce arc lflictive alcoholscavcngers nitrcalcohols elh)lcnc and lighllastnessproblems. gllcol. diethyleneglycoland sorbitol. B. Nlodified DMDHELI approach 1i)r rcdncirrg DMDHEU has been the most strccessf'ul Moclil,ving modificd veisions \\'ele those madc frorn purcr IICHO release.-Among the tlrst starting materials and rigiaty controlling the stoichiometl) Later vcrsions lcd to alkylat;d DMDUETJand two typcs have bccomecommerciallyimportant products. nlethylatedand glycolatedDMDHETJ l. Mcthylrted DMDHEII

t D M D H l l l l has 4 reactivehydrox-vls ' [ h e 4 . 5 -rin gh ] d ro x )ls a re a s rc a c t iY e o Alkylating $'ith mcthanol can replacc alkylation as are the peldant N-methylols a n j rvhe r efio m I to 4 -OH groupsuith -OCH, P a rlia ll, v me t h ] la t c d DN' I DI lF I I f c t t f s to productsuhcre an averageof two lncthoxy groupsare attached'Irully mcthylatcd t r e i e r sr o p r o d u ctswbere all fotrr havc be e n rc a c le d lo a c c o n rp lis hh c la L lc r-t h c by r e a cti onm usl be driven to completion re n o v in g $ a t c r o l f e a c t io n lh is in ro lv c s making the l'ully meth y la t e d p ro d u c l mo re e x p t rls iv e a d isl i l l alio n step
EOCE, -{-c-N-cE,oB + 4CE3OS

,P

cE 'cg so oB

> cE3ocs?li-c-N-cE,ocE3 4 E'O

cs5
= 4, = 2,

-b--ca,

'

Ifhen CE3I{hen CE3-

P rodu c t i.s Fully Methylated MethYlated P loduc t j.s Partially ( UL F )

2 . Di eth- yle n e glycolated DMDHtrU

DMDHEIJ is made by rcacting 2 molesofdieth) lcnc gllcol ll))r(i)' Glycolaled rvith I rnoleotDMDHE(J.lt is olten rclerred to as a LZF(Llltra lo\! tornralclchltle) |lrc r e actan t. fhisp roduct cvohed tiom thc s u c c e s s lirle x p c rie n c e s n o t\e d n T )ll(l \ \ a s a d dedto th e fi ;ish lbrmulation P rccap p in gb e lo re i1 is a p p lie d in s u rc s lh a t t h e r' I)F'i srill are l1opendentN-methylo] groupsso the HCHO relcaseis evenlo$'cf lhr with cclluloseis not scvcrel) ,o crosslinking iunctionsas a leavinggtoup-du,ing "ut" irnpaircd. 112

-\TCE,OCE.CS,OCE,CE?OE BOCSTCE,OCS?CE,OCE,N' CE CE

I c

Bo

6s

C, Important Fatures of Alkylated DMDHEU ar DMDIIELIs ehar derto cur ethentheif Bo t hfu l l y a n dp a rti a l l ) me l h) lated l) pr to st cataly ar c needcd cur elhcse odLr cts P S co u n - r r e t h y l a te d u n te rp a rt.tro n ger as quir eas good their ur r - m elh) ' la1ed no1 ta me th vl a tcd .i Jtie' ; ; ; ; ; r ; i ; ; ; i ;'" "te ot exfcnse DP a! is de o i . ; ; i "; ; ; , ; . L o u e ri n g t fb rma l d eh) r elease accomplishedth.: ol-all releesc with the lowestfbrmaldchyde ."ri.lrrrLt"".ift" lf-Fs p,udr.. tchrics latcd as ' S "t a i "i "*i r, th e D P p e i fo rma n ce the Uf' Fs is still as good the un- elk\ of gir to fabficsu' ill c r alucsin applied w D MD IIE L I henpr oper ly "-rl"l s ,ll- "u o 0 u * e"r" n g e tfl h cfa h r icisunder cur edor ilthefabr ichasir nacidicp H ". a - i o i t-" Jtn d if f i "t o i t "r a .o " n i " i t;.ti e va l u e su 'i l lbchighcr M cthr lr tcLlDNlL) HIIr .r cbetrlcr ' l( l th r i{ \\r t n ""r "' *f i i '" .,f,rtfa tcd u n e 'b ci n diulr toiuOt' ngc ' r r dtlr clullr r r r cr lr - r lr tcJ at will gi\c l' abr ics 50 of belo$ glycol w u gi - O v fi U f U mo i l i ti cd i th d i ethylene Table 12 FormaldehYd Relase Comparison of Modifred DMDT]II
HCHO Release irs/g

I
I

DP Ratrngs
,l

DMDHEU Unmodified Partially Methylated Fully xlethylated Glycolated(UL!)

750- 1000 300 - 500 < 300 <50

3.0 3.0 3.25

types: where3 5 lowerfor the low release is somewhat I NOfe, Oe performance hav standar ds c acceptable r o r h i o h e rra ttn u sw e reo n cema rretplaceequir ements
releitte heen lo\ ered 1-6t ;n orJer lo me<l lo\ ihrmcldrhvde

ll3

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