Characterization of Surface Deposits on Human Hair

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j. Soc.Cosmet.hem., 1, 379-390 (November/December990)

Characterizationf surfacedeposits n humanhair fibers

H.-D. WEIGMANN, Y. K. KAMATH, S. B. RUETSCH,

P. BUSCH, and H. TESMANN, TRI/Princeton,P.O. Box 625,

Princeton, J 08542 (H.-D, W., Y.K.K., S.B.R.), and Henkel

KGaA, Di•)seldorf-Holthausen,ederal epublicf GermanyP.B.,H.T.).

Receivedeptember, 1990. Presentedn part at the8th InternationalWoolTextileResearchonj•rence,hristchurch,ewZealand, ebruary7-14, 1990.

Synopsis

The deposition, ubstantivity, ndbuildupof variousormulationsn the surface f untreated ndoxidizedhair fibershavebeen nvestigated singa combination f wettabilityscanning nd microfluorometry.Wettabilityscanning long he lengthof the fiber establishesariationsn surface nergy nd thuscanexploreonly ncreasesn surface overagesa resultof multiple treatments.On the otherhand, microfluoro-metry, which nvolvesncorporation f appropriateluorochromesnto the formulation,canprovide nfor-

mationabout he thicknessf surface eposits nd thuscanbe used o studybuildupphenomenauringmultiple applications.Multiple treatmentswith a formulation ontaining cationicpolymer n conjunc-tion with an anionic thersulfateurfactantead o buildupof surface epositsuringmultiple reatments.Thesedeposits re stronglyheldevenon unoxidized air fibers,and repeatedinsingdoesnot completelyremove hem. In contrast,a formulation ontaining eratin hydrolysate eposits n the scale aces f thehair surface,with no buildup in multiple applications. epositionof this materialon unoxidized ibersresultsn an increasen hydrophilicity f the fiber surfacehat appearso increaselightlywith multipletreatments, ossiblyeflectingmoreuniformdistribution n the surface.

INTRODUCTION

Deposition f compoundsn humanhair fiber surfacess usedextensivelyo modifyappearance, anageability, ndgrooming tyle.Knowledge f the extentand natureofthe depositions critical for the development f appropriate air care ormulations,sinceexcessiveuildupof suchmaterials anhavedetrimental ffects n the behaviorandesthesticsf the hairassembly.RI hasdeveloped ethodologieshat permitrapidassessmentf the distribution nd thickness f surface eposits n fibrousmaterials.The useof liquid membrane ettabilityscanning, ased n surface nergychangesproduced y a treatment, rovides profileof surfaceoveragelong he engthof a hairfiber (1). Microfluorometry,n the otherhand,whichrelieson the incorporationf

fluorochrome racers nto the formulation, is able to assesshe relative thicknessofsurfaceoatings. luorescentracers avebeenused xtensivelyn qualitative haracter-izationof surface eposits n wool ibers 2-4) andalsoon hair (5). The introduction f

microfluorometryith its ability o scanluorescencentensity cross fiberor along tslengthhasmade t possibleo quantify he distribution f surface eposits n fibers,at

379



380 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

leaston a relativebasis.Both techniquesnvolvescanning longthe length of a fiber,the level of resolution epending n the rate of scanning.Using a combination f thesetwo methods,we havestudied he deposition, ubstantivity, nd buildup of formula-tionscontaining ithera cationic olymeror a keratinhydrolysaten conjunction ithan anionic ethersulfate surfactant.

EXPERIMENTAL

MATERIALS

The European ark brownhair fibersused n thesestudieswererinsedextensivelyndemineralizedwater prior to treatment.The following ormulationswereprepared:

1) Cationic cellulose ether (CCE): 2% (0.5%)

Sodium aureth sulfate: 14% (14%)Demineralized 20: 84% (85.5%)pH 6.3

2) Keratin hydrolysateKer): 5%Sodium laureth sutfate: 14%

DemineralizedH20: 81%

pH 6.4

ELECTROBALANCECOMPUTER

O/

RECORDER

- o.+

MELM• BER

I

Figure 1. Experimental rrangementor the measurementf fiber wettabilityby the liquid membranemethod (1).



SURFACE DEPOSITS ON HAIR 381

The sodium aurethsulfatehasan EO numberof 2. The keratinhydrolysates CTFA"hydrolyzed nimalkeratin."

FIBER TREATMENT

Fibersweremounted n stainlessteel absandtreated or 5 min at 30øC n a gentlystirred solution. They were rinsed ive times, 1 min each, with 200 ml demineralized

water.After conditioninghe fibersovernight t 65% RH and2 IøC, a smallsegmentof each iberwas emovedor determining receding ontact ngleO• by immersionwettability 6), and he restof the fiberwasscannedsing he liquid membrane etta-bility method 1). To assesshe buildupof deposits n the fiber surface,he treatmentwasrepeatedhree imes; he two levelsof treatmentare ndicatedby 1 x and 4 x inthe figuresand tables.Fiber perimeterswere calculatedrom major and minor axesdetermined y microscopy.

LIQUID MEMBRANE WETTABILITY SCANNING

Our liquid membrane ettabilityscanning rocedureasbeendiscussedn a previouspublication 1). The experimental rrangements diagrammedn Figure 1. As theliquid membranemoves p the fiber, forces re generated t the two liquid surfaces,advancing nd receding; he net force s given by

F = P'yLv(COSa -- COS•),

whereP is the fiberperimeter,Yrv he surfaceension f the membraneiquid, andandO• thecontactnglesn theadvancingnd eceding odes. ssuminghatcosdeterminedn the separatemmersion xperiment, oesnot varyalong he fiberpermitscalculationf cos0•, a measuref surfacenergy.n these tudies e used emineral-izedwateras he membraneiquid. Although he assumptionhat equilibriumwetting

PHOTOMULTIPLIER I X-Y RECORDER

FILTER{360-IOOnm} ¾ j COMPUTER

]

Figure 2. Diagramof the Leitz MPV 1.1 microspectrophotometerith the PLOEMOPAK attachmentorfluorescence measurements.




conditions xist s an oversimplificationt the high scanning peeds sed,our experi-encehas been hat we can still achieveour objectiveof establishing if)•rencesn hairfiber surface nergy.

MICROFLUOROMETRY

In applyingmicrofluorometryo assesseposit hickness, suitable luorescentracer sincorporatednto the formulationeither prior to depositionor as an aftertreatment.Interactionsbetweenthe fluorescent robe and formulation components esult in in-

creasedluorescence,resumably ecausehangesn the microenvironmentf the tracermoleculecause n increasen its quantumefficiency.Assuming hat film thicknesssdirectlyproportionalo fluorescencentensitypermitsone to determine relative ilmthickness istribution;we have ested his assumptionor a numberof compoundsndhave found it to be correct.

The sodiumsalt of fluoresceinCIAY-73), alsoknown as uranine,provedan

N,

COONacheme. Uranine Na salt of fluorescein CIAY-73).

excellent racer or the formulationsnvestigated.Aqueous olutions f uranineexcitedat 450 to 490 nm emit brilliant green luorescencet 540 nm. Uranine 0.1%) wasincorporatednto the various ormulations, nd hair fibers5-cm long were mmersednthesesolutionsor 5 min at 30øC,eitheronceor five times, followedby oneor five1-min rinseswith water at 30øC.After five applications,achwith five rinses, ome

fiberswereretaggedwith 0.1% uraninesolution nd rinsedonce n water (both proce-dures or 5 min at 30øC).

To evaluate he treated samples,we useda Leitz MPV 1.1 microspectrophotometer,with a Ploemopakluorescencelluminatorattachment, chematicallyhown n Figure2. The distributionof deposits long he filament is characterizedy monitoring luo-rescencemissionntensityas he scanning tagemoves he specimenhrough he beamcircumscribedy a variablemeasuring iaphragm. n thesestudieswe useda 5-1•m x5-1•m beam ocused n the domeof the fiber and scanned .35 mm of fiber at 18 I•m/s.

RESULTS AND DISCUSSION

WETTABILITY SCANNING

Figures3a and 3b showwettabilityscans long he lengthof unoxidized nd oxidizedhair fiber specimens,espectively, nd after oneand four treatmentswith the formula-





384 JOURNAL OF THE SOCIETYOF COSMETICCHEMISTS

Table I

AveragedWettabilityParametercosOa) or UnoxidizedndOxidizedHair Fibers reatedWithFormulations ontainingCationicCellulose ther or Keratin Hydrolysate

Untreated Treated 1 x Treated 4 x

CCE: 0.5%

Unoxidized -0.22 -+ 0.17 -0.08 -+ 0.15 -0.02 -+ 0.15

Oxidized 0.06 -+ 0.14 0.43 +- 0.05 0.35 +- 0.05

CCE: 2%

Unoxidized -0.39 + 0.10 -0.24 + 0.07 -0.23 -+ 0.08

Oxidized -0.16 -+ 0.07 0.08 +- 0.10 -0.03 - 0.16

Ker: 5%

Unoxidized -0.43 + 0.10 -0.15 -+ 0.23 -0.15 +- 0.21

Oxidized -0.15 + 0.10 0.27 - 0.09 0.34 -+ 0.14

treatmentwith the lower concentration f CCE, there s considerablencreasen hydro-philicity, especiallyor the oxidized iber, but the increases significantlyess or thehigherconcentration. his may be associatedith the natureof the hemimicelleshatare formed between the cationic CCE and the anionic ethersulfate molecules. In all

cases,multiple treatmentshave ittle or no effect, suggestinghat there s either nobuildup of this complexor that surface overage asreachedts maximum n the firsttreatment.

Very similarchangesn wettability are observed fter treatmentwith a formulation nwhich he cationic olymer s replaced y a keratinhydrolysateFigure4). Againwe seean increasen hydrophilicityor decreasen hydrophobicity, hich s morepronouncedfor the oxidized iber surface.The hair fibersappear o be somewhatmore uniformlytreated,but again, little if any effectof multiple treatmentss observedn the wetta-bility scans r in the average alues ncluded n Table I.

MICROFLUOROMETRY

As pointed out earlier, wettability scanningmeasures hangesn surface nergyand

therefore andetermine nly the extentanduniformityof surface overage ut canmakeno statementabout deposit hickness.For this purpose,we tried microfluorometricscanning.A varietyof fluorescencemission atterns reobservedfteruntreatedibersare exposedo 0.1% aqueous raninesolutions; typical pattern is shown n Figure 5.Here a sharpdemarcationof scaleedges s seen, suggesting hat uraninepenetrateseither nto the endocuticlehroughbroken-off cale dges r between wo cuticlecellsinto the intercellularcement. However, studieswith other hair specimens roduced

differenturaninedeposition atternson untreated ibers, ranging rom weak, diffusefluorescencemanatingrom the surfaceo the appearancef a weak"honeycomb."hishoneycomb attern hasalsobeenobserved y Leaver 7), who hassuggestedhat it is

associatedith hair damage. t is apparentrom this variation n fluorescenceatternsobservedwith untreated ibers that the surface roperties f the fiber determine henatureof the adsorption f the fluorochrome.t is interesting o note in this contextthat multiple reatments ith uraninedo not cause ignificantntensificationf fluores-cence.




1.5

.5

-.5

-1

-1.5

-2

(a) Unoxidized

ß lx

_ ' 4x

1.5

.5

-.5

-1

-1.5

-2

4x

ß I I I

0 50 loo 150

Distance (mm)

Figure 4. Typicalwettability cans f unoxidizedndoxidized air fibers ftersingleor multiple reat-mentswith the formulationcontaining5% Ker.

Treatmentwith the formulationcontaining2% of the cationiccellulose ther causeslarge ncreasen fluorescencentensity, ndicatingextensive olymerdeposition n thefiber surface.After multiple treatmentshere s a significanturther ncreasen fluores-cence ntensity,suggesting buildup in deposit hickness.Again, variouspatternsofdepositionwere observed, he most frequent being the honeycomb attern seen nFigure 5. As the micrographsn Figure 5 indicate,additionaldeposition uring mul-




Untreated

2% CCE, Ix 2% CCE, 5x

5% Ker ix 5 % Ker 5x

Figure 5. Fluorescenceicrographsf hair fibers,untreated ndafteroneor five treatments ith a haircare formulation (280 X ).




tiple treatments ccursn locations here he polymer/surfactantomplexwasdepos-ited in the initial treatment,apparentlyeaving malldomains f the surface ncovered.This patternof deposition xplainswhy wettabilitydeterminationsftermultiple treat-mentsdo not detectan increasen surface overage.

We canestimate he relativeextentof deposition y scanning long he length of thefibersand obtainingan averageluorescencentensity or the scanning istance f 1.35mm. Characteristic cans f fibersafter various reatmentand rinsingprocedures reshownn Figure6. Multiple application roduces large ncreasen fluorescencenten-sity, which decreasesignificantly fter multiple rinses.This lossof intensityon risingeithersuggestsncomplete ubstantivityf the depositedolymer/surfactantomplex rreflectspartial extractionof the fluorescentracer rom the complex. t appears hatboth mechanismsontribute o the intensity oss,since eintroducinghe fluorochromeinto the complex fterextensiveinsingby immersinghe fibers n 0.1% uranine olu-

tion (5 min, 30øC,waterrinse) esultsn only partialrecovery f the fluorescenceintensity.

Average luorescencentensities or the various reatment and rinsing conditions n-volving he formulation ontaining .5% CCE, shown n Figure7a, seem o indicateaslight but significantbuildup. At the higher concentrationf CCE (2%, Figure 7b),multiple treatmentsead to much higherbuildup. Comparison ith the wettabilitydata or these reatmentconditionsTable ) demonstrateshe importance f usingbothmethods o characterize urfacemodification.Although wettability scanning howeddifferencesn surface nergy ftera single reatment, t couldnot detect he significant

7O

ol 50

z 40

LIJ

o 30

2o

o 10

e

DISTANCEFigure 6. Typical luorescencentensity cans f hair ibers ftervariousreatment ndrinsingprocedureswith the formulation ontaining % CCE: a) oneapplication, ne inse; b) oneapplication,iverinses;c)five applications, ne rinse; d) five applications,ive rinses; e) five applications,ive rinses, etagged(2. tag), rinsed.




z

z

z

o

70

60

50

4O

30

20

10

0

'70

60

50

40

(a) 0.5% CCE

I [ [ • I ' I ' I

3O

2O

10 (b) 2% CCE

I ' I ' I ' I ' I '

I appl. I appl. 5 appl. 5 appl. 2. tag

I wash 5wash I wash 5wash I wash

TREATMENTS

Figure 7. Average luorescencentensities f hair fibersafter reatment nd rinsingprocedures ith theformulations ontaining a) 0.5% CCE and (b) 2% CCE.




increasen film thickness fter multiple applicationshat was shownby microfluo-rometry.

The deposition f keratinhydrolysaten hair fibers esultsn a totallydifferentpicture

from that observed ith the cationic olymer. t appearshat Ker deposits trongly ndexclusively n scalesurfaces, nd oncedeposition asoccurred, ubsequentreatmentsdo not result n buildup. Figure5 clearlyshowshe scale urface eposition nd ack ofincreasen multiple reatments. his ackof buildup s alsoseenn the averageluores-cencentensities ftervarious reatment nd rinsingprocedureshown n Figure8.

CONCLUSIONS

Wettability scanning nd microfluorometry avebeenused o study he deposition nd

buildup of several ormulations n the surface f untreated nd oxidizedhair fibers.Treatmentswith formulations ontaining he cationicpolymerCCE in two concentra-tions result n significantadsorption n untreated ibers, with substantial uildup ofsurfacedeposits fter multiple treatments.Multiple rinsing appears o desorbonlysmallamounts f the deposited ompounds. ettability shows efinite houghuneven

7O

6O

5O

4O

3O

5% Ker

ILl

LIJ 20

LIJ 10n- Control0:D 0 I ' , ' , ' , ' ' '

ßJ I appl. I appl. 5 appl 5 appl 2. tag! ' '

I wash 5wash I wash 5wash I wash

TREATMENTS

Figure 8. Averageluorescencentensities f hair fibersafter reatment nd rinsingproceduresith theformulation ontaining5% Ker.




adsorption ut cannotdetect he buildupobserved ith microfluorometry. ettabilitymeasurementshow hat oxidized ibershavea stronger endency o adsorb nd retainsurface eposits, eflecting he higheraffinity between he cationicpolymerand nega-

tive chargesormedon the fiber surface uring oxidation.We havenot donemicro-fluorometric canning f oxidized ibers,sinceuranineprovednot to be a suitable iuo-rochromeor suchspecimens.

The formulation ontaining % keratinhydrolysateppearso deposit n the scaleacesof the fiber surface nd not to build up in multipleapplications. eposition f Ker onoxidized ibers esultsn a considerablencreasen surface ydrophilicity ftera singletreatment,with only a slight further ncrease fter multiple treatments. hese esultspossiblyeflecta moreuniformdistribution f the surface eposits n oxidized air.

REFERENCES

(1) Y. K. Kamath, C. J. Dansizer,S. Hornby, and H.-D. Weigmann, Surfacewettabilityscanning flong filamentsby a liquid membranemethod,TextileRes. ., 57, 205-213 (1987).

(2) j. Garcia-Dominguez, . R. Julia, A. de la Maza, J. M. Pujol, and J. Sanchez, method ordetermining he distributionof cationicshrink-resistantesinson wool,J. $oc.DyersColor.,92,433-439 (1976).

(3) F. R. Rothery and M. A. White, Determinationof the presence nd distributionof polymersonwool,J. Soc.DyersColor.,99, 11 (1983).

(4) U. Meyer, SelektiveMarkierungvon Filzfreiausrfistungenuf Wolle mit fluoreszierendenerbin-dungen,Textilveredl.,7, 440-446 (1982).

(5) H. Gottschalk,G. Hohm, and H. Kaminski,Verteilung on haarfestigendenolymeren uf Hu-

manhaar, roc. nternat.WoolText.Res.Conf.,Aachen,1975, Vol. III, pp. 349-358.(6) Y. K. Kamath, C. J. Dansizer,and H.-D. Weigmann,Wetting behavior f humanhair fibers, .

Appl.Polym. ci., 22, 2295-2306 (1978).(7) I. H. Leavet,CSIRO, Melbourne,Australia,personal ommunication.

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Characterization of Surface Deposits on Human Hair