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
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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