The evaluation of gloves for protection against

j. Soc.Cosmet. Chem.,41, 267-273 (September/October 1990) The evaluationof glovesfor protectionagainst cosmeticingredients ANDREW SAVAIDES, THOMAS SC...
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j. Soc.Cosmet. Chem.,41, 267-273 (September/October 1990)

The evaluationof glovesfor protectionagainst cosmeticingredients ANDREW SAVAIDES, THOMAS SCHULTZ, and LUDWIG SALCE, Dr. EverettC. McDonough Research Laboratories,

ZOTOSInternational Incorporated, Darien,CT 06820-1005. Received August16, 1990. Synopsis

The efficiency of vinyl, plastic,andlatextypegloveswasevaluatedbaseduponthe resistance permeation by the following cosmetic ingredients: ammonium thioglycolate(AMTG), glycerylmonothioglycolate (GMTG), and hydrogenperoxide.The permeationgloveresistance studiesincludedimmersionof the middle glovefinger containing10 ml deionizedwater into 19% GMTG, 12% AMTG, and 2.5% hydrogenperoxide.Aliquotswereanalyzedby HPLC and UV/visible. QuantitativeHPLC and UV/visible assayresultsindicatethat latex-typeglovesexhibit the highestpermeationresistance towardsthesecosmetic ingredients.Thus,with properuseof latexgloves,salontechnicians andcosmetologists may limit their exposure to theseingredients.

BACKGROUND

In the practiceof the art of hair caresalonoperatorsare oftenexposedto productsthat containreactiveingredients,that is, the cosmeticcompositionsthat containthe materials that permit color development,permanentwaving, and hair bleaching.While with occasional useof theseproductsthereis a minimal possibilityof a type of contact dermatitisto the client, the cosmeticJan canoftenbe in contactseveraltimesa day, and in rare instances,the dermismay becomeirritated.

It hasbeenreportedthat someof the chemicalagentsusedin the practiceof personal and beautycare can causevarying typesof contactdermatitis(1-3). The most notoriousof thesechemicalsare constituentsof detergents--for example,the saltsand ethersof lauryl sulfates.fragrance compositions, dyestuffssuchasderivativesof phenylenediamines,and mercaptans usedin permanentwaving. The appearance of irritancy has been documentedfor the practionersof the art, beauty salonoperators.In some casesthe clientsof the salon,who experience sporadiccontactwith thesematerials,may be atopicand hencesusceptibleto sensitizationresponses. In 1983 Storrs(4) indicatedthat the activeingredientsin acidand alkalinepermanentwavingcompositions, GMTG or AMTG, are allergens,althoughthe incidenceis low, lessthan 0.01-0.02% as determinedfrom epidemiological data presentedby various permanentwavesuppliers[presentedto the CosmeticIngredient Review Boardof the CTFA (5,6)]. In rare occurances the peoplewho performnumerouspermanent-waving processes eachday can becomesensitized.Storrs(7) supportsthe adviceof somepro267

268

JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

ducersof the permanent-waving products,namelyto useprotectivegloveswhile using theseproducts.

We address in this studythe efficiencyof variousglovetypesagainstpermeation specifically by mercaptansor hydrogenperoxide.The method of study is a chromatographicprotocolfor the assayof permeationof the cosmeticingredientstypicallyfound in permanent-wavingcompositions(thioglycolatesalts, thioglycolateesters,or hydrogenperoxide)through glovesmade from vinyl, plastics,and syntheticand latex rubbers.While both vinyl and latex glovesare commonlyavailable,the latter have better tactile feel and may be more usefulin actualpractice.

EXPERIMENTAL

Two separatetestingprotocolswere utilized. The first wasto determine,undercontrolled conditions,the relativeability of differentglove typesto resistpermeationof mercaptansor hydrogenperoxideunderstaticconditions.The secondmethodinvolved examining gloves for permeationof the cosmeticingredient under conditionsthat mimic actualuse.This wasachievedby stretchinga portionof the gloveoverstandard glasstubing to enforcean alterationof the glove material.

The glovesexaminedare detailedin Table I. Three typesfrom eachof the following categories weretested:nylon,vinyl, syntheticrubber,latexrubber,and plastic.We set as a caveatthat the glovesneededto havetactile propertiessuitablefor practicaluse. This requiredthat the gloveswere of no more than 5-mil thickness.The gloveswere then testedin salonsfor operatorpreference,and thosepreferedwere then subjectedto examination as to the bestat inhibitingpermeationof mercaptans and hydrogenperoxide.

GENERAL ANALYTICAL

PROCEDURES PROCEDURE

The analyticalprocedurefor examiningthe amountof mercaptanpermeationwasspectrophotometic,usinghigh-pressure liquid chromatographic separation with a reversedTable

I

Descriptionof Gloves* Example

Material

Size

A

Latex

Medium

B

Latex

Medium

C

Latex

Medium

D E F G H

Vinyl Vinyl Vinyl Heavy polyethylene Medium polyethylene

Medium Medium Medium Medium Medium

I

Trionic

Medium

* Examples A, B, andC represent latexglovesfromdifferentsuppliers,andD, E, andF represent vinyl glovesfrom differentsuppliers.

GLOVES FOR USE WITH

COSMETICS

269

phasecolumn(Partisil10 ODS-3 or 5 ODS-3), a WatersAssociates Model6000 system equippedwith a dual setof Model 510 pumps,a variablewavelengthdetector(Waters Associates ModelLambdaMax 480 setat 210 nm), a WatersModel6 UK injectorwith a 200-•tl loop, and a Digital CorporationModel 380 dataprocessing unit. CONDiTiONS

FOR CHROM^TO(3R^VH•C

^N^rYSES

High-pressure liquidchromatographic analysis of GMTG.' Column.'Partisil 10 ODS-3, 250 mm X 4.6 mm

Mobile phase: 20% CH3CN/80%H20; 1.2 ml/minute Detection.' 210 nm

High-pressure liquidchromatographic analysis ofAMTG: Column:Partisil 50DS-3, 100 mm X 4.6 mm Mobilephase.' O.005 M Tetrabutylammonium phosphate,pH 3.5 Detection.' 210 nm

Enhanceddetectionof the mercaptanwas achievedby trapping the mercaptidewith

5,5'-dithiobis-(2-nitrobenzoic acid) (DTNB) (Aldrich Chemical),preparedby dissolving30 mg DTNB in a solutionof 25 mg ethylenediaminetetraacetic acid tetrasodium salt (Aldrich Chemical)in 0.1 M tribasicsodiumcitrate/dibasic phosphate(Aldrich Chemical) in deionized water.

Aliquots of the interior of the glove(1.0-ml portions)were removedby glasspipette and mixed thoroughlywith 4.0 ml of 0.003% DNTB reagent.Absorbance measurementsat 412 nm againstdeionizedwater in quartz cuvetteswere recordedafter 15 minutes

of reaction time.

Calibrationcurveswere establishedby usingtriplicaterunsfor both techniques(HPLC and DNTB). The HPLC calibrationcurves(Fig. 1) gavea detectionlimit of 10 ppm for both mercaptans and the DNTB calibrationcurves(Fig. 2) gavea detectionlimit of 5 ppm with extrapolation capabilityto 2 ppm for GMTG and 3 ppm for AMTG.

lOO

.,a:: 8o --

.,a:: 6o 0

'• 4.0 0

0

20

I

50

;

100

150

PPM MERCAPTAN

AMTG

GMTG

Figure 1. HPLC calibrationgraphs.

200

250

270

JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

The concentration levelsof permeatedmercaptans into the gloveportionwereassayed by usingthe externalstandardquantitationtechniquefrom calibrationcurvesFig. 1 and Fig. 2. Table II and Table III list the concentrationlevelsof GMTG and AMTG foundinto the interiorportionof glovetype at differenttime intervals. PERMEATION

STUDIES

Two setsof experimentationwere devisedfor determiningthe amount of permeation through the gloves.

MethodA. A pressuregradientof 1:10 water to GMTG solutioncomposed of 19% glycerylmonothioglycolate basedon an 80% activecompositionin anhydrous glycerin wasdissolvedin an aqueouspH 8 solutionbufferedwith ammoniumcarbonate.The middlefingerportionof the glovewasexcisedandfilled with aleionized water(10 ml), followedby knotting the openend. The mixturewasplacedinto a 200-ml beakerand stirredwith a magneticstirrercappedwith a glasscover.The mixturewasstirredfor a given time intervaland then the gloveportion removedlong enoughto rinsethe exterior with aleionized water. The waterinsidethe gloveportionwasremovedwith a glass pipette and the contentsput into a glassvial. A 200-•1 portionwasanalyzedby HPLC. One milliliter of the remainingportionwasmixedwith 5 ml of the DNTB reagentand the mixture analyzedby u.v. method 1 but using410-nm detection. Table

II

HPLC Direct & DTNB Indirect AnalysisData of Glycerylmonothioglycolate (GMTG) and Ammonium Thioglycolate(AMTG) Time

Glove

0 min

10 min

30 min

60 min

Final

PN

ppm GMTG (HPLC direct)/ppmGMTG (DNTB indirect) A

0/0

0/0

0/0

0/0

B

0/0

0/0

0/0

0/0

24 hrs

31/

2.5 hrs 2.5 hrs 17 hrs 21 hrs

/< 2 /4.15 60/ 0/0

C

0/0

0/0

0/0

0/0

D E F G

0/0 0/0 0/0 0/0

0/0 0/0 0/0 0/0

0/0 0/0 0/0 0/0

0/0 0/0 0/0 0/0

H

0/0

0/0

0/0

0/0

21 hrs

0/0

I

0/0

0/0

0/0

0/0

43 hrs

0/0

ppm AMTG (HPLC direct)/ppmAMTG (DNTB indirect) A B C D

0/0 0/0 0/0 0/0

0/0 0/0 0/0 0/0

0/0 0/0 0/0 0/0

0/0 0/0 0/0 0/0

E

0/0

0/0

0/0

0/0

F

0/0

0/0

0/0

0/0

17 hrs

G H I

0/0 0/0 0/0

0/0 0/0 0/0

0/0 0/0 0/0

0/0 0/0 0/0

21 hrs

PN

=

Permeation

noted

24 17 17 19

hrs hrs hrs hrs

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