New high-charge density hydrophobically modified cationic HEC

Transcription

j, Cosmet.
Sd., 58, 421-434 (July/August2007)
New hioh-charoedensityhydrophobically
modifiedcationic
HECpolymersfor improvedco-deposition
of benefitaoents
and seriousconditioninofor problemhair
T. V. DROVETSKAYA,
E. F. DIANTONIO,
R. L. KREEGER,
J. L. AMOS, and D. P. FRANK, Amercho/Corporation,
A Subsidiary
of TheDow Chemical
Company,
171 RiverRoad,
Piscataway,
NJ 08854.
Synopsis
A seriesof newhigh chargedensityPolyquaternium-671
(PQ-67)polymers
havebeenprepared
and
evaluated
in shampoo
formulations.
Thesenewcompositions
represent
an additionto the familyof highviscosityquaternized
hydroxyethylcellulose
(HEC) polymerswith cationicsubstitutionof trimethylam-
moniumanddimethyldodecyl
ammonium
2 (Figure1A)described
in (1) and(2). Theevaluation
protocol
includedobjectivelab methodsand subjectivepanelstudieson differenthair types.Commercialcondi-
tioning
polymers:
PQ-67(Polymers
SoftCAT
LM3)
andcationic
guar
4 (Jaguar
C-13S
©5)wereusedasperformance benchmarks.
It wasfoundthat increasing
the cationicchargedensityof the PQ-67 polymersabove1.45 meq/g(equivalent of 2 weight-percent
(wt.%) nitrogen)resultedin a several-fold
boostof their co-deposition
ability.
Theseexperimental,
high chargedensityPQ-67 polymerswereshownto deliversilicones
and otherperformanceingredientsfrom shampoo
formulations
moreefficientlythan anyotherpolymercurrentlyavailable on the market for rinse-offhair cleansing/conditioning
applications.The polymersalso provided
improvedwet and/ordry conditioning,
volme control,and couldbe instrumentalin achievingsleek
lookinghair andimprovedcontrol/manageability
of unrulyor frizzyhair.The high chargedensityPQ-67
polymersare alsoideallysuitedfor highly-fragranced
surfactant-based
formulasthat are usedin aromatherapyandspaproducts
dueto their superiorabilityto deliverfragrance.
BACKGROUND
Hair is a diverse substratethat comes in different shapes,colors and textures. Its
properties
andappearance
varyfor differentracesandagegroups,asdo the benefitsthat
consumers
are seekingin new hair care products.As more and more consumersare
shampooing,
grooming,coloring,bleachingor waving/straightening
their hair, they are
Addressall correspondence
to T. V. Drovetskaya.
JHydrophobically
modified
cationic
conditioning
HEC polymers.
2Supplied
byAmerchol
Corporation/Dow
Chemical
Company
underthetradenameSoftCAT
TMSLandSK.
3 Supplied
by Amerchol
Corporation/Dow
Chemical
Company.
4 Guarhydroxypropyltrimonium
chloride.
5 Supplied
by Rhodia.
421
422
JOURNAL OF COSMETIC SCIENCE
A.PQ-67
•+"'
C,•I•I-CH,C
I'
B.PQ-•O
•O-(CH2CH20)i(CH2Ct
HCH)•H
OH
CH
-'•
( HO
C,•}+.H•H,C
i-
•O-(CH2CHzO)i(CH2(•H
CH)•H
)7)
• n(o•O•)n
O
Hc,• oOH
(CH2C
H20
)x'(CH2C
H(•.H)œH
.
CHjI•-CH
3 CI
C•H•s
Figure 1. Cationic conditioningHEC polymers.
also damagingit, and thus the needfor productsthat can mitigate and repair this
damageis increasingdramatically.The currentofferingof cationicconditioningpolymersis quite broadand is expanding,with HEC-basedpolymersrepresentinga significant portion of this market. Varying structuralparametersof thesepolymers,suchas
molecularweight, cationicand hydrophobicsubstitutionand/or the degreeof ethoxylation significantlyimpactstheir performanceon hair and createsthe much needed
diversityof propertiesand benefits.This paper describesthe impact of the charge
substitution(CS)in combinationwith the hydrophobic
substitution(HS) on the depositionpropertiesand overallconditioningof PQ-67 polymers.New compositional
featuresenhancedthe performance
of the experimentalhigh chargedensityPQ-67 polymers,whichwerefoundsuperiorwhencomparedto anyof the competitivebenchmarks
usedin this studyin depositionof performance
ingredientsand for overallconditioning.
This performance
makesthe new structures
a valuableadditionto the family of cationic
conditioningpolymers.Thesepolymerswere found to be especiallyusefulto manage
hair types that benefit from volume control and
extra-conditioning,suchas unruly,
6
difficult-to-managehair or for Asianhair types.
RESULTS
POLYMER
AND
DISCUSSION
COMPOSITION
New experimentalhigh chargedensityPQ-67 polymersbelongto the family of high
viscosityquaternizedhydroxyethylcellulose(HEC) derivativeswith cationic substitution of trimethyl ammoniumand dimethyldodecylammonium(Figure 1A) describedin
(1) and (2) and recently commercializedfor personalcare applicationsby Amerchol
Corporationand the Dow ChemicalCompanyunderthe trade nameof PolymersSoftCAT TMSL and SK. Similar to the commerciallyavailablegrades,experimentalPQ-67
samples
described
in thispaperwereproducedby reactingHEC polymerswith 3-chloro2-hydroxypropyldodecyldimethyl
ammonium chloride and 2,3-epoxypropyltrimethyl
ammoniumchloridein aqueousisopropanol
(2). In this work we usedpolymersmadeof
a high viscosityHEC with the degreeof ethoxylationsimilar to one of commercially
c,Wearecurrently
inprogress
evaluating
performance
ofexperimental
highcharge
density
PQ-67polymers
on Asian hair.
2006 TRI/PRINCETON
CONFERENCE
423
availablePQ-67 gradessuchasPolymers
SoftCATSLandSK. Lowlevelsof hydrophobic
dimethyldodecyl
ammoniumsubstitution(HS •< 0.01) wereusedto impart hydrophobic characterto thesepolymers.
Severalstructuralparametersof cationiccellulosicether derivatives,suchas PQ-67
(Figure 1A) and their non-hydrophobic
structuralanalogs,PQ-10 (Fig. lB) polymers
havea profoundimpacton theirperformance
on hairandskin.Theseparameters
include
molecularweight (Mw), cationiccharge(CS), as well as the degreeof the side chain
substitutionwith ethyleneoxide (EO MS). Examplesof such structure-performance
relationships
for PQ-10 polymersin surfactantsystemswere previouslydescribedin
industrysources
(3-6). On the otherhand,the structuralpotentialof PQ-67 compositionsis muchlessexploredandunderstood.
In additionto the structuralfeaturesalready
presentin PQ-10, the structureof PQ-67 polymersoffersonemorevariable-thedegree
of hydrophobic
substitution(HS), whichis anotherusefultool for modifying,controlling, and improvingcertainperformance
aspectsof thesepolymerson hair (1) and skin
(7). The newresultspresented
belowdemonstrate
that increasing
the cationicchargeto
above2 wt.% N in the hydrophobically
modifiedquaternizedHEC polymers,suchas
PQ-67, resultedin a severalfold boostof their depositionand deliveryproperties,
and
significantlyimprovedthe overallperformance
of thesepolymerson hair, especially
non-chemically
treated,coarse,difficult to manageand unruly hair types.
The highchargedensityPQ-67 polymerswereevaluated
in shampoo
formulations
using
objectivequantitativelab methodsand subjectivepanel evaluationon hair tresses.
Commercialconditioningpolymers:PQ-67 with chargedensitylessthen 1.45 meq/g
(SoftCATTMSL and SK) and cationicguar (Jaguar
© C-13S)wereusedasperformance
benchmarks.
PERFORMANCE
IN SHAMPOOS
WITH
SILICONES
The principalintent of shampooing
is to cleanthe hair. However,productsthat are
designedsolelyfor cleansingcanleavehair tangledand unmanageable
whenwet, and
raspydry and dull-lookingupon drying ((1) and references
therein).
As previouslydescribed
in (1), manyconditioningpolymersandvariousotherperformanceingredients,e.g. insolublesilicones,
canimprovethe hair conditionby reducing
the combingfriction of hair and providinga soft, smoothfeel and healthy, shiny
appearance.
Cationicpolymers,suchasPQ-10, PQ-67, and cationicguar, areknownto
workin theseways,in thesesystems,
aloneor in combination
with otheractives.They
are assumedto form a polymersurfactant
complex(coacervate
phase)that separates
and
precipitatesontothe hair during the rinse-offcycle(1,8-10). Coacervates
canoptionally
incorporateperformanceingredientssuchas silicones,fragrance,sunscreens,
and other
benefitagentsthusassisting
in their deposition
on hair (1,3,4). Experimental
polymers
describedin this paperare conjecturedto performalongthis line.
Depositionof silicones
onhair hasbeenevaluatedin two shampoo
systems
that included
differentsurfactantbasesand differenttypesof silicones:Shampoo
Formulation
A containingsodiumlaurethsulfate(SLES)/disodiumcocamphodiacetate
(DSCADA), 1 wt.%
424
dimethicone
with an average
particlesize-0.3 microns,
7 andconditioning
polymers
incorporated
at 0.25% levelandShampoo
Formulation
B containingsodiumlaurethsulfate
(SLES)/disodium
laurethsulfosuccinate
(DSLSS)/cocamidopropyl
betaine(CAPB),1 wt.
% dimethiconol
with average
particlesize-0.5 micron
s andconditioning
polymers
incorporated
at 0.2% level.Depositionof siliconesfrom shampooformulationsdepends
upon many factors;type of silicone,its averageparticle size,the surfactantbase,the
presence
andtypeof cationicpolymersareamongstthe mostimportant(6,11). Hair type
canalsoplay a significantrolein the deposition
of silicones
and, therefore,impactthe
choiceof cationicpolymersto assistin and/orcontrolthisdeposition.
Forexample,aswe
previouslydescribedin (1) and the SoftCAT product literature, the low to medium
chargedensity(-1.0 to 1.45 wt.% N) PQ-67 polymersideallysuitthe needsof bleached
damagedhair. They do not overloadthis susceptible-to-cationic-deposition
hair type
while maximizingthe depositionof muchneededsiliconeascomparedto cationicguar
and PQ-10 polymers.Depositionof siliconeon virgin hair aswell ason any "intermediate" hair type variessignificantlydependingon a specificshampooformulation.Examplesof systemswherehigh-viscosityhigh-chargePQ-10 gradesoutperformedtheir
cationicguar counterpartshave beenpreviouslydescribedin (11). As we showlater,
Shampoo
Formulation
B alsofalls into this category.At the sametime, the Shampoo
Formulation
A yieldedsignificantlybettersiliconedepositionon Europeanvirgin brown
hairwhenformulated
withcationic
guar.
9 Oneofthegoalsofthepresent
studywasto
furtherexploreandtune structuralparameters
of PQ-67 polymersin orderto closethis
gap. We, therefore,beganour investigationwith the Formulation
A, wherethe shortcomingwasfirst identified,and then expendedour evaluationscopeto includeother
systems.
Conditioningperformance
of two prototypeshampoo
systems
described
belowis largely
dueto the presence
of silicones
and their ability to reachhair and staybehind(in small
amounts)after the rinse-offcycleis complete.Ability to depositsiliconeis therefore
crucialin thesesystemsandgreatlycontributesto the overallconditioningeffect.On the
otherhand,the contributionof the cationicconditioningpolymersandotheringredients
foundin shampoos
canalsoplay an importantrole in the overallperformance.
In order
to accountfor theseeffectsandmakesurethat the performance
differences
arelikely to
be noticedand appreciated
by the end consumer,
we includedsubjectivepanelstudies
on hair tresses in our evaluation.
Performance
in Shampoo
Formulation
A
Siliconedeposition.The total amount of siliconedepositedon hair treated with the
ShampooFormulationA was measuredusing atomic absorptionspectrophotometry.
Commercial
European
virginhair•øwaswashed
twotimes
TM
witheachformulation.
The
7 DowCorning
© Emulsion
1664(supplied
by DowCorning)is a non-ionic
emulsion
of highmolecular
weight polydimethylsiloxane
with 50% siliconecontent.
sDowCorning
© Emulsion
1785(supplied
by DowCorning)
is an anionic
emulsion
of highmolecular
weight polydimethylsiloxane
with 60% siliconecontent.
9Notethattheexactsame
shampoo
formulation
withlowercharge
density
PQ-67polymers
(SoftCAT
SL
grade)yieldedsuperiordeposition
of silicones
on single-bleached
hair compared
to cationicguar(1).
mAll hairusedin thisworkanddescribed
in thispaperwassupplied
byInternational
HairImporters
Co.
•J Consecutive
washings,
nodryingin-between.
2006 TRI/PRINCETON
CONFERENCE
425
siliconewas extractedfrom the hair by a 50/50 (v/v) methyl isobutyl ketone/toluene
solution.The siliconecontent was measured,and then the microgramsof siliconeper
gram of hair wascalculated.
Depositionof siliconeon Europeanvirgin brown hair from the prototypeShampooA
formulatedwith PQ-10 polymers,PQ-67 polymers,and cationicguar is shownon
Figure2A. Accordingto this data,increasingthe chargesubstitutionin PQ-10 polymers
(HS = 0) resultedin moresiliconedepositedon hair. A moderateincreasefrom N45 to
95 microgramsof siliconeper gram of hair was observed.This trend becamemore
pronouncedin the PQ-67 group comparedto PQ-10. The sameincreaseof cationic
chargefrom -1.0 to 1.8 wt.% N resultedin a severalfold boostof siliconedeposition
from PQ-67 formulas:from -45 to 215 microgramsof silicone.
700 /
Ai
600
500
400
3OO
200
100
0
HS= 0 (PQ.10)
LowHS(PQ-67)
Cat.guar
[]%N~1.8
I
I D%N
~1.0 []%N~1.25
3600-
30002400-
1800-
•
.
001 I
Low HS
Medium HS
HighHS
Cat.guar
B%N-1.25
B%N-1.45
B%N~1.8
[]%N~2.1
!a%N-2.5
I
Figure 2. Siliconedepositionfrom ShampooFormulationA on Europeanvirgin brown hair. A. Polymers
PQ-10 and PQ-67 with CS of 1.0-1.8 wt.% N. B. PQ-67 with CS 1.25-2.5 wt.% N and cationicguar.
426
a.
'-
500
0
O.07wt.%
0.15wt.%
0.25wt.%
I[3Cat.
guar
[]PQ-67,
Medium
HS[]PQ-67,
High
HS1
Cationic guar
PQ-67,
PQ-67,
%N-2.1,
%N-2.5,
Medium
HS
Medium
HS
¸ 1wt.%
silicone
[]0.3wt.%
silicone]
Figure 3. Siliconedepositionon Europeanvirgin brown hair: formulationswith fractionalamountsof
PQ-67 polymeror silicone.A. Formulationswith 0.007 to 0.25 wt.% Polymerand I wt. % Silicone.B.
Formulationswith 0.25 wt.% Polymer and 0.3 to 1 wt.% Silicone.
Furtherstudiesrevealedthat evenminimal amountof hydrophobe,suchas,for example,
the low level hydrophobicsubstitutionpresentin the commercialproductsSoftCAT
SL-5, SK-M, and SK-H, was sufficientto observethe significantboost in silicone
depositionbetweenPQ-10 and PQ-67 polymers.At the sametime, varying HS in
polymerswith the CS corresponding
to 1.0-1.8 wt.% N did not resultin significant
changesin siliconedeposition.As discussed
earlierand accordingto the data presented
on Figure 2A, the prototypebenchmarkFormulationA preparedwith cationicguar
depositedsignificantlymore silicone(-675 microgramsiliconeper gram of hair) on
virgin brownhair comparedto eithergroupof cationiccellulosicpolymers.In orderto
closethis gap, we focusedon the PQ-67 structureswith the idea of combiningthe
impactsof CS and HS on depositionperformance.The chargesubstitutionwasfurther
increased
and high chargedensitypolymerswerepreparedat threelevelsof hydrophobic
substitution:
low,medium,
andhigh•2 (Fig.2B).According
to thedatapresented
in
Figure 2B, a step-change
in siliconedepositionon hair from PQ-67 shampoos
occurred
when the chargesubstitutionin polymersexceeded2 wt.% cationicnitrogen. Experi-
mentalhigh chargedensityPQ-67 polymersdeposited
up to -3,500 microgramsilicone
per gramEuropeanvirgin brownhair, dependingon their CSandHS. They significantly
outperformedotherPQ-67 andcationicguarbenchmarks
usedin the study.In a second
studya series
ofhighcharge
density
PQ-67•3shampoos
wereformulated
withfractional
amountsof polymer (0.07-0.25 wt.%) or silicone(0.3 wt.%). These shampooswere
evaluatedfor siliconedepositionin comparisonto completeformulations(Shampoo
FormulationA) containing0.25 wt.% cationicguar and 1 wt.% silicone.Accordingto
Figure 3A, the amountof depositedsiliconewasproportionalto the amountof the high
chargedensityPQ-67 polymeraddedto the formulation.Lessthen one third of the
PQ-67 amount(0.07 wt.% versus0.25 wt.%) wasenoughto matchthe siliconedeposition from the cationicguar formula. In addition, data presentedon Figure 3B shows
that the formulationcontainingonethird of the amountof silicone(0.3 wt.% versus1.0
wt.% siliconein a "complete"ShampooFormulationA) and high chargedensityPQ-67
polymersyieldedsiliconedepositionon hair that was similar to the depositionfrom a
"complete"formulationcontainingcationicguar.
•2 All polymers
described
in thispaperhadHS < 0.01.
•3 PQ-67polymers
containing
2.5 wt.% N.
2006 TRI/PRINCETON
A. Baseline (untreated)
CONFERENCE
B. Before combing
427
C. After combing
.-=
.
...
.
.
:
PQ-67
Cationic guar
PQ-67
Cationic guar
Figure 4. Volume and frizz control.
Subjectivepanelevaluationon tresses.To confirmthat the effectsdescribedabovewere
perceivableto humansubjects,pairsof commercialfrizzy hair tresses
wereshampooed,
dried overnightand distributedto five expertpanelistsskilledin evaluatingconditioning and other propertiesof hair. Each pair had one tresstreated with Shampoo
A
formulated
witha highcharge
density
PQ-67polymer
TMandonetresstreated
witha
control shampoocontainingcationicguar. Panelistswere askedto evaluatethree attributes:they wereaskedto chooseonehair swatchin eachpair that had lessvolume/
frizz, waseasierto combandfelt smoother/softer.
Eachpanelistperformedevaluations
twice on differentpairsof hair tresses.Photosof the swatcheswere taken beforetreatment (Figure4A), after treatmentbeforecombing(Figure4B), and after repeated
combing(Figure4C).
As shownin Figure4, the high chargedensityPQ-67 formulationprovidedexcellent
volumecontrolfor frizzy hair. Its superiorperformance
comparedto the cationicguar
controlwas clearlynoticeablebeforeand after the hair was combed(Figure 4). The
resultsof the subjectivepanel evaluationare presentedin Figure 5A. The study confirmed that the PQ-67 formulationwas perceivedby panelistsas providing better
volumecontrol
(10/10)andalsosignificantly
improving
dryfeel(8/10)15anddrycomb
(9/10)•6offrizzyhairagainst
thecationic
guar.Aspreviously
discussed,
thehighcharge
densityPQ-67 polymersweresignificantlymoreefficientin depositingsilicones
on hair
comparedto the cationicguarcontrol(Figure3B). Therefore,a secondpanelevaluation
studywasconductedto comparea completeformulationwith cationicguar to a sample
formulation
containing
a PQ-67polymer
17andonlyaboutonethirdof theamount
of
silicone (0.3 wt.% versus 1.0 wt.%). Hair tresses treated with the formulations were
evaluatedwet anddry in pairsin the samewayasdescribed
above.The resultsof wet/dry
comband feel propertyevaluations
are presentedin Figure 5B. It wasfound that the
high chargedensityexperimentalPQ-67 polymerusedin this studysignificantlyim-
PQ-67polymer
with%N -2.5 andmedium
HS wasusedin thisstudy.
Exactsignificance
level= 89% (binomial
distribution).
Exactsignificance
level= 98%(binomial
distribution).
PQ-67polymer
with 2.5 wt.%,mediumHS.
428
Dry Comb
Dry Feel
Less Volume
IraCationic
guar[]PQ-67,
%N~2.5,Medium
HSI
Next day:
10-
El
Wet
Wet Feel
Comb
Dry
Comb
Dry Feel
Less
PQ-67
Cationic guar
Volume
I1:1
Cationic
guar! PQ-67,
%N2.5,Medium
HSI
Figure 5. Subjectivepanelevaluationon œrizzy
hair. A. ShampooFormulationA: 0.25 wt.% polymer,1
wt.% silicone.B. Shampoo
FormulationA: 0.25 wt.% PQ-67, 0.07 wt.% siliconeversus0.25 wt.% cationic
guar, 1.0 wt.% silicone.
proved
bothdrycombandfeel(8/10)t8 and,possibly,
wetfeeloffrizzyhairdespite
the
fact that it wasusedin a systemwith threetimeslesssiliconecomparedto the cationic
guar formulation.On the day of the evaluation,after all the manipulationson hair were
completedthe panelistswerenot ableto seedifferences
in volume.Nevertheless,
oneday
later hair tresses
treatedwith the cationicguarformulashowedsignificantlymorefrizz
andunwanted
volume
•9Figure5B,whilethePQ-67formulation
continued
toprovide
much
needed volume
and frizz control.
Performance
in Shampoo
Formulation
B
Siliconedeposition.The total amount of siliconedepositedon Europeanvirgin hair
Exactsignificance
level= 89% (binomialdistribution).
Frizzandvolumeincrease
aretypicalto thishairtypeandcanbecaused
byatmospheric
moisture.
2006 TRI/PRINCETON
CONFERENCE
429
looo
400
,
0
UCARE
JR-30M
........
-•'
........
:•:•
'"SoftCAT
SK-MH
SoftCAT
SK-H
i
PQ-67
PQ-•7
%N- 2.1%N-2.5
Cat.
guar
Com m e rcial
2-in-1
sham poo
Figure 6. Siliconedepositionfrom ShampooFormulationB on Europeanvirgin brownhair.
treatedwith ShampooFormulationB wasmeasured
followingthe proceduredescribed
above.PolymersPQ-10 (UCARETMJR-30M), PQ-67 (SoftCATTMSK-MH and H), and
cationicguar(JaguarC-13S©) wereusedasbenchmarks.
A marketleadingcommercial
shampooproduct that had an SLES/DSLSS/CAPBsurfactantbase,dimethiconol,and
guar hydroxypropyltrimethylammoniumchloridelistedon the ingredientlabel wasalso
includedin the studyasan additionalbenchmark.The resultsobtainedfor the silicone
depositionfrom eachformulationare presentedin Figure 6. It hasbeenfoundthat the
PQ-10 polymerwith medium-highcationiccharge(UCARETMJR-30M, %N -1.8) and
PQ-67 polymerwith medium cationiccharge(SoftCATrM SK-H, 1.45 wt.% N) outperformedcationicguarn the prototypeformulationB. Theyyieldedsiliconedeposition
in the rangeof-430 and 490 micrograms
of siliconeper gram of hair, respectively,
whichwascloseto the amountdeliveredby the commercialshampooproductthat listed
an SLES/DSLSS/CAPB
surfactant
systemandcationicguar:-460 micrograms
of silicone.
Experimentalhigh chargedensityPQ-67 polymersdescribedin this paperdelivered
significantlymoresilicone(-850 and 1,100 micrograms,
respectively,
dependingon the
CS) showingagaina significantincreasein siliconedepositionover the benchmarks.
Subjectivepanel evaluationon tresses.In order to further validate the outstanding
conditioningperformance
of the high chargedensityPQ-67 polymersin the prototype
ShampooFormulationB, a sampleshampoocontainingone of thesepolymers(-2.1
wt.% N, mediumHS) wascomparedto the market-leadingcommercialshampooused
in the siliconedepositionstudy(Figure7A). Pairsof Europeanvirgin brownhair tresses
werepreparedasdescribedaboveanddistributedto panelists.The hair wasevaluatedfor
wet/dry comband feel properties.Accordingto the resultspresentedin Figure 7A, the
panelistspreferredtheprototypeFormulationB containinga high chargedensityPQ-67
polymer
overthecommercial
shampoo
forbothwetcomb(9/10)20andfeel(8/10).TM
20Exactsignificance
21Exactsignificance
distribution).
430
10•
ß-
108-
8
6-
•.6
,,-
4
.
z
..
'•,t.•'
o
Wet
Comb
Wet
Feel
. .... -3 •.
Dry Comb
Dry Feel
0
Wet Comb
Wet Feel
Dry Comb
Dry Feel
[E]Commercial
shampoo
BPQ-67,
2.5wt.%N,Medium
HS]I[]Cationic
guar []PQ-67,
2.1wt.%N,Medium
HS}
Figure 7. Subjectivepanelevaluationon Europeanvirgin hair. A. ShampooFormulationB: PQ-67 versus
commercialshampoo.B. ShampooFormulationB: PQ-67 versuscationicguar.
After the hair dried,panelists'choicesindicatedno statisticaldifferencein dry comband
feel betweenswatches
(Figure7A). A secondpanelstudywasconductedto comparethe
Shampoo
Formulation
B madewith a highcharge
densityPQ-67polymer
22to an
identical
formulation
containing
cationic
guar.
23Asexpected
fromthesilicone
depositiondata,the PQ-67 formulationoutperformed
the guarcontrolin bothcombandfeel
in the wet and dry state, Figure 7B.
DEPOSITION
OF FRAGRANCE
Fragranceis anotherimportant performanceingredientbesidessiliconesthat greatly
contributesto the overallaesthetics
of shampooproductsand their acceptance
by consumers.Delivery of long-lastingfragranceto the hair from rinse-offformulationssuch
as shampoosand conditionersrepresentsa seriouschallenge.The high chargedensity
PQ-67 polymersthat demonstrated
remarkableperformance
in assistingthe deposition
of siliconeson hair werealsotestedfor depositionof fragrancefrom a shampooformu-
lation.WhiteTeaFragrance
24wasformulated
at 1 wt.%in anSLES/DSCADA
25prototypeshampoo
formulationalongwith 0.4 wt.% cationicconditioningpolymer.The
fragrance
deposition
fromashampoo
containing
ahighcharge
density
PQ-67polymer
26
wasevaluated
against
similarshampoos
containing
nopolymer,
SoftCAT
SK-MH,27and
cationicguar in a seriesof subjectivepanel evaluationstudieson Europeanvirgin hair
tresses conducted in the same manner as described above. The results of these studies are
summarizedin Figure8. It wasshownthat the high chargedensityPQ-67 polymerused
in this studyimproveddepositionof the white tea fragranceon virgin brownhair and
thatthedifference
wasperceivable
to thepanelists
in all threecases
(9/1()2• or 8/1029).
_,2PQ-67polymer
with 2.1 wt. %N andmediumIIS wasusedin thisstudy.
23JaguarC-I 3S.
24Provided
by Fragrance
Resources,
Inc.
25Thesamesurfactant
system
asusedin theShampoo
Formulation
A.
26PQ-67polymer
with 2.5 wt.%N andmediumIlS.
27SoIkCAT
SK-MHwasfoundto delivermorefragrance
onskinfromrinse-off
formulations
compared
to
other PQ-67 and PQ-10 polymersand cationicguar (SoftCATSK Conditioning
Polymers,
productbrochure
issuedby AmercholCorporation/DowChemicalCompany(2005)).
2• ExactSignificance
29ExactSignificance
distribution).
2006 TRI/PRINCETON
CONFERENCE
431
9
!
!
ß::L•x,.,,. ßßß
0
PQ-67 vs. blank
PQ-67 vs.
SoftCAT
SK-MH
PQ-67 vs.
Cat. guar
Figure 8. Fragrancedepositionon Europeanvirgin brown hair, wet subjectives.
Coacervate
studies.
In orderto understandthe origin of the step-changeboostin assisted
depositionof performanceingredientsobservedfor the high chargedensity PQ-67
polymers,their coacervate
formationwas studiedin clearshampoosystemsformulated
withnosilicone
and0.3 wt.% polymer
in a SLES/DSCADA
surfactant
3øbaseand0.3
wt.% polymer.Haze measurements
wereperformedusingthe Nippon Denshoku300A
hazemeterin a 50 mm path lengthcell.As discussed
above,cationicpolymersareknown
to form coacervateswith anionic surfactants.Clear in a concentrated form, surfactant
solutionswith PQ-10 and PQ-67 cationicpolymersbecomehazyupon dilution. This
haziness,which is an indicator of coacervateformation, was measured over a dilution
rangeof 0-10 and haze (coacervate)
curveswere studies.As shownin Figure 9, the
coacervate
curvesof PQ-67 polymerswith wt.% N rangingfrom 1.25 to 2.5% changed
their shapeandpositiondependingon charge.In the rangeof 1.25 up to 1.8 wt.% N,
their shapeprogressively
evolvedfrom lowerand broadercurves(low CS) to higherand
"sharper"(narrower)curves(higherCS). In addition, thesecurvesprogressively
shifted
toward
the lower dilution
ratio.
This trend was earlier noticedand describedfor the PQ-10 polymers,such as, for
example
UCARE'rM
LR-30M(%N -1.0) andJR-30M(%N -1.8).• On thecontrary,
the hazecurvesfor the high chargedensityPQ-67 polymerswith % N above2.0 did not
follow the sametrend. They becamehigher and broaderat the sametime (Figure 9)
extendingovera broaderrangeof dilution comparedto their 1.8% N predecessor.
This
is a knownindicatorof morecoacervate
beingformedthat raisesexpectations
of superior
deposition/co-deposition
and conditioningperformance.Therefore,theseobservations
arein agreementwith earlierfindingsfrom the siliconeandfragrancedepositionstudies
30Thesamesurfactant
system
asusedin theShampoo
Formulation
A.
31UCARET
M productliterature,
Amerchol
Corporation.
432
lOO
-O-
8o
%N ~ 1.25
--O-- %N ~ 1.45
ß
60
N
• 40
--e--
%N ~ 1.8
--Z•
%N ~ 2.1
•
%N ~ 2.5
2o
i
1.0
3.3
Dilution
5.0
Ratio
7.5
10.0
Figure 9. Coacervate
formationin shampoos
containingPQ-67 polymers.
describedin this paper.This providessomeinsightson the mechanisticaspectsof the
high chargedensityPQ-67 polymers'outstandingperformance.
OTHER
PROPERTIES
IN
SHAMPOOS
As shownabove,novel high chargedensityPQ-67 polymersdemonstratedimproved
overallperformanceand, in particular,showedoutstandingability to depositbenefit
agentson hair from shampooformulations.At the sametime, thesepolymerswerefound
to retain the goodqualitiesof the PQ-10 and their lower chargedensityPQ-67 coun-
terparts,
suchasenabling
crystal
clearformulations,
32showing
noexcessive
build-up
on
hair33(asshown
onFigure10),andhaving
nonegative
impact
onfoam
'•4(asshown
on
Figure 11).
CONCLUSIONS
A seriesof new experimentalhigh chargedensityPQ-67 polymerswere preparedand
evaluatedin shampooformulations.Thesenewcompositions
demonstrated
outstanding
performancein assistingdepositionof performanceingredientssuch as siliconeand
fragranceon humanhair. They were foundsuperiorcomparedto PQ-10, lowercharge
densityPQ-67 polymers,and cationicguar benchmarks.In severalstudiesexperimental
polymersoutperformedthe cationicguar benchmarkevenwhenlesspolymeror silicone
32Measuring
lessthan4% hazeonNipponDenshoku
300Ahazemeter,
50 mmpathlength,
0.3• polymer.
33Theamountofdeposited
polymer
wasassessed
bydetecting
theamountof anionicRed80 dyeboundto
the cationicpolymerdepositedto the hair as describedin (1). The depositionvalueswere normalizedper
amount of polymer depositedafter one wash. The prototype formulation included 0.3 wt.• polymer
(experimental
high chargedensityPQ-67 polymerwith 2.1 wt.% N andmediumhydrophobic
substitution,
UCAREr• JR-30M (PQ-10), or Jaguar
© C-13S) in a SLES/DSCADA
surfiictant
base.
34Quantitative
foammeasurements
wereperformed
asdescribed
in (12):all foamgenerated
whileshampooing a hair tresswas collectedand weighed and then its volume and density were calculated.).The
prototypeformulationincluded0.3 wt.% polymer(experimental
high chargedensityPQ-67 polymerwith
2.1 wt.% N and mediumhydrophobic
substitution,
UCARETMJR-30M (PQ-10), or Jaguar
© C-13S)in a
SLES/DSCADA
surfactant
base.
2006 TRI/PRINCETON
CONFERENCE
433
1.75
1.5
1.25
1
1 wash
3 washes
5 washes
I .•bCationic
guar
• PQ-10
-•- PQ-67
I
Figure 10. Polymerdepositionon Europeanvirgin brownhair. Red 80 ArtionicDye Test.
o
35
x
30
E
m
25
ß• 20
•
15
E 10
E
5
o
>
•..:
•
.'
0
No Polymer
Cat. guar
PQ-10
PQ-67
Figure 11. Foamvolumeand densitymeasurement.
wasusedin the formulationcontainingPQ-67. Along with excellentoverallconditioning, shampoos
formulatedwith newPQ-67 polymersprovidedimprovedvolumecontrol
and manageabilityto problemhair--a much neededbenefitfor anti-frizz/smoothing
formulasand productsthat target sleekhair look. Perceivableimprovementin delivery
of fragranceto the hair was also substantiated.This could also make the polymers
434
describedherewell suitedfor aromatherapyand spaformulas.Accordingto the performancedatapresentedin thispaper,the newhigh chargedensityPQ-67 polymersshould
be recommended
for a rangeof hair typesthat would benefitfrom enhanceddeposition,
premium conditioningand volume control: from normal, not chemicallytreated to
problemhair (frizzy, unruly, coarseetc.) as well as Asian hair types.
REFERENCES
(1) T.V. Drovetskaya,R.L. Kreeger,J. L. Amos, and C.B. Davis, Effectsof low-level hydrophobic
substitutionon conditioningpropertiesof cationiccellulosicpolymersin shampoosystems,J.Cosmet.
Sci.,55(Suppl.),S195-S205(2004).
(2) R. L. Kreegerand S. Zhou, Celluloseethers,International
PatentApplication
WO 2005/000903 (2006).
(3) M. Gamez-Garcia,Polycationsubstantivityto hair, IFSCC, 4, 99-107 (2001).
(4) W. Li and S.L. P. Jordan,Cationiccellulosicpolymerswith multifunctionaland outstanding
performancefor personalcare,Cosmet.
Toilerr.Manufact.Worldwide,1-4 (2003).
(5) S. Zhou, C. Xu, J. Wang, P. Golas,J. Batteas,andL. Kreeger,Phasebehaviorof cationichydroxyethyl
cellulose-sodium
dodecylsulfatemixtures:Effectsof molecularweight and ethyleneoxidesidechain
lengthof polymers,Langmuir,20, 8482-8489 (2004).
(6) W. Li, J. Amos,S.Jordan,A. Theis,andC. Davis,Selectingthe optimumsiliconeparticlesize/cationic
polymer structureto maximize shampooconditioningperformance,
J. Cosmet.
Sci., 57(2), 178-180
(2006).
(7) X. Zhang,L. Kreeger,L. Kosensky,
C. Barbelto,andJ. Amos,Effectof cationichydroxyethylcellulose
polymerarchitectureon triglyceridedepositionfrom bodywashes,IFSCC Congress
(2004).
(8) R. Y. Lochhead,
"Shampoos,"
in TheChemistry
andManufacture
ofCosmetics,
3• ed.,M. L. Schlossman,
Ed. (Allured PublishingCorporation,CarolStream,IL, 2002), Vol. 2, pp. 277-326.
(9) R.Y. Lochhead,Conditioningshampoo,SoapCosmet.
Chem.Spec.,42-49 (October1992).
(10) E. D. Goddard,"Polymer/Surfactant
Interactionin Applied Systems,"in Principles
ofPolymer
Science
and
Technology
in Co•metic•
andPersonal
Care,E. D. GoddardandJ. V. Grubber,Eds.(MarcelDekker,New
York, 1999), pp. 18l.
(11) B. G. Johnsonand S. Van Oycke,Towardsoptimumhair conditioning,Personal
Care,17-19 (2006).
(12) W. Li, S. L. P. Jordan,X. Zhang,J. Amos, and C. Davis, Synergisticeffectsof high molecularweight
polyethyleneoxide(PEO) andcationiccel]ulosic
polymerson conditioningpropertiesof hair andskin
careproducts,Cosmet.
Toiletr.Manufact.Worldwide, 31-34 (2004).

New high-charge density hydrophobically modified cationic HEC

Transcription

Similar documents