PERSONAL WASH CLEANSER WITH MILD SURFACTANT SYSTEMS
COMPRISING DEFINED ALKANOYL COMPOUNDS AND DEFINED FATTY
ACYL ISETHIONATE SURFACTANT PRODUCT AND
OPTIONAL SKIN OR HAIR BENEFIT AGENT

The present invention relates to novel super mild surfactant compositions for use
in personal care cleanser (e.g., personal care liquid body cleansers or shampoos)
compositions, further optionally comprising skin or hair benefit agent. Use of
these surfactant combinations provides mildness comparable or superior to
compositions which provide mildness using very high amounts emollient oils.
Personal cleansing compositions which provide cleansing and personal care
benefits are known in the art, for example, liquid cleansing market. In order to
achieve superior mild and moisturizing skin benefit, very high levels (generally
higher than 30% by wt. of liquid compositions) of emollient oils are used in leading
marketed moisturizing compositions (e.g., Dove® Cream Oil or Olay® Ribbon
body wash compositions).
There has been a continuous effort to provide skin care benefits from personal
skin/hair cleanser compositions, for example, by delivering ever increasing
amounts of benefit agents such as silicone oil, petrolatum and triglyceride oils
from such cleansers. Some products use emollient oils as high as 50% by wt. or
more of the composition.
U.S. Patent No. 5,61 2,307 to Chambers et al. discloses, for example, use of a
single package containing separate stripe of cleansing agents and benefit agents
where benefit agent is as high as 50% of the package in order to deliver sufficient
benefit agent for efficient skin moisturizing and conditioning. Delivery of benefit
requires special packaging, complicated processing and high levels of benefit
agent.
U.S. Patent No. 5,965,500 to Puvvada discloses liquid compositions where the
level of emollient exceeds the level of surfactant.
Other references also require very high level of skin benefit agent to deliver skin
care benefits (U.S. Publication No. 2005/01 00570 A 1; U.S. Publication No.
2005/0143268 A 1; U.S. Publication No. 2006/0079420 A 1, all to Procter &
Gamble). The benefit of using very mild surfactant systems to minimize use of
benefit agent is not recognized. Further, neither use of such mild surfactant
systems in combination with benefit agent; nor means for ensuring deposition of
benefit agent in such compositions is recognized or disclosed.
Accordingly, there is a need for personal cleanser compositions (e.g., liquid
cleansers) which provide superior skin care benefit without requiring use of high
levels of benefit agent (using very mild surfactant systems). There is further a
need for compositions with mild surfactant systems comprising benefit agent and
a means for ensuring deposition.
Unpredictably, applicants have found that this aim can be achieved using
exceptionally mild surfactant mixtures. It is extremely surprising that the overall
level of surfactant can be increased (relative to different systems) while also
increasing mildness. Using surfactant systems of the invention, optionally in
combination with skin or hair benefit agent (particularly in the form of floes upon
dilution), it is possible to achieve significant mildness (as defined in standard
Patch Test as disclosed, for example, in the Protocol below) while using, for
example, much lower levels (e.g., 30% or less) of the types of occlusive emollient
oils (e.g., petrolatum, silicone) typically used for providing mildness benefits.
Clinical benefits are equal to or better than products tested which comprise, for
example, 40% or more petrolatum.
Various other mild cleanser compositions have been claimed. Various references
to Johnson & Johnson claim compositions comprising modified acrylic copolymers
and common anionic surfactants such as sodium trideceth sulfate (U.S. Patent
No. 7,1 9,059; U.S. Patent No. 7,098,1 80; U.S. Patent No. 7,084,104; U.S.
Publication No. 2005/0075256). U.S. Publication No. 2005/01921 88 to Wagner et
al. discloses surfactants with a structured domain comprising at least 70% of a
lamellar phase made using common surfactant mixtures such as sodium trideceth
sulfate and sodium laurylamphoacetate.
Compositions of the subject invention provide unique surfactant systems (using,
for example, alkanoyl glycinate and specified fatty acyl isethionate surfactant
products), preferably for use in compositions having little to no (e.g., 3% by wt. or
less, preferably 2% by wt. or less) alkyl sulfate surfactants (e.g., sodium alkyl
sulfate, sodium alkyl ether sulfate), which are common to many cleanser
compositions. In an optional embodiment, additional benefit agent (skin or hair
benefit agent) is used and, in particularly preferred embodiment, additional benefit
agent is delivered in the form of floes.
More specifically, one embodiment the present invention provides novel, super
mild personal cleanser (preferably liquid personal cleanser) compositions
comprising 1 to 30%, preferably 2 to 25% more preferably 3 to 20% by wt. of a
surfactant system comprising:
1) 20 to 85%, preferably 30 to 75% by wt. surfactant system of an
alkanoyl surfactant selected from the group consisting of alkanoyl
glycinate, alkanoyl sarcosinate and mixtures thereof, wherein the
alkyl group on the alkanoyl chain is Cs to C20, preferably C12 to
C16 straight chain alkyl (e.g., lauroyl, cocoyl or myristoyl
glycinate). Preferably this component comprises at least
alkanoyl glycinate although, as noted, alkanoyl sarcosinate alone
and mixtures of alkanoyl glycinate and alkanoyl sarcosinate are
contemplated. Cocoyl glycinate is a particularly preferred
component.
2) 5 to 70% surfactant system of a fatty acyl isethionate product
which product comprises 40 to 80% (of the product) fatty acyl
isethionate and 15 to 50% (of the product) free fatty acid and/or
fatty acid salt/soap (the product may also comprise isethionate
salts, typically present at less than 5% of the product and may
further comprise traces, e.g., typically less than 2% of product, of
other impurities).
In a second embodiment of the invention, the composition may further comprise:
1 to 60% by wt., preferably 2 to 40% by wt. skin or hair benefit agent. Benefit
agent typically has a particle size in the range of 0.01 to 30 microns
(micrometers).
In a particularly preferred embodiment, when hair or skin benefit agent is used,
there are also used (a) 0.1 to 1.5% cationic polymer (measuring for floe formation)
and 3% or less lauric acid (minimized to not impede floe formation).
In addition, greater than 25% and less than 45% of the fatty acyl isethionate is of
chain length (referring to the alkyl chain defining the fatty acyl) of greater than or
equal to Ci6; and greater than 50%, preferably greater than 60% of the chain
length of free fatty acid and fatty acid soap groups combined are of chain length
Ci6 to C20- These chain length ranges are important for providing lather and
mildness of resulting fatty acyl isethionate product. These critically defined fatty
acid isethionate products (which applicants describe in applicants' copending
application, U.S. Serial No. 12/577,425 to Tsar filed October 12, 2009) and
defined alkanoyl surfactants synergistically react to form unique ultra mild
surfactant systems of the invention. When further combined with optional skin or
hair benefit agent, particularly delivered in the form of floes, super mild
compositions are made.
Compositions meeting requirements of invention will have irritation score in a
Patch Test as % of the same irritation result using 5% solution of sodium dodecyl
sulfate (SDS) of less than 90% SDS, preferably 75% or less of SDS score, more
preferably 70% or less, more preferably 65% or less and more preferably 60% or
less of the SDS irritation score.
In a preferred embodiment of the invention, the compositions comprising the novel
mild surfactant system (optionally further comprising skin or hair benefit agent or
agents) noted above have 3% or less and preferably 2% or less, more preferably
1% or less alkyl sulfate anionic (e.g., sodium dodecyl sulfate or sodium lauryl
ether sulfate). In one embodiment, the composition will have substantially no
(e.g., 0.2% or less by wt., preferably none whatsoever except for possible
impurities) alkyl sulfate anionic.
In another preferred embodiment, surfactant compositions of the invention
(comprising 1 to 30% of personal cleanser) will comprise ( 1) 20 to 85% alkanoyl
surfactant; (2) 5 to 70% isethionate product as defined; (3) 20 to 80%, preferably
30 to 70% surfactant system of an amphoteric and/or zwitterionic surfactant (e.g.,
betaine and/or amphoacetate); (4) optional 1 to 60% skin or hair benefit agent and
(5) 3% or less, and preferably substantially no, anionic and nonionic surfactant
other than ( 1 ) and (2) as defined above in the personal cleanser composition (e.g.,
other than alkanoyl surfactant and isethionate product of ( 1 ) and (2)). Even when
the amount of total anionic is closer to 3% in this embodiment, most preferably the
amount of alkyl sulfate (alkyl sulfate component of the additional anionic)
specifically should be minimized as noted in the embodiment above, e.g., it should
comprise 1% or less of alkyl sulfate surfactant and, preferably, be absent.
In addition to having any additional anionic and nonionic surfactant be a maximum
3% by wt. of total liquid composition, the anionic and nonionic should be less than
30% of the total amount of glycinate, sarconsinate, isethionate product,
amphoteric and zwitterionic in the composition. In other words, 3% of total
cleanser composition or 30% of surfactants noted in the immediately preceding
sentence, whichever is lower, is the maximum total of anionic and nonionic
surfactant present.
If compositions contain skin or hair benefit agent (as in one embodiment of the
invention), it is further preferred the compositions comprise cationic polymer to
help deposition of said benefit agent (e.g., through formation of benefit
agent/polymer floes). However, in such embodiment, since lauric acid is found to
interact with isethionate product and interfere with formation of skin or hair benefit
agent/polymer floes, the applicants have found that there is a cap on the upper
level of lauric acid used.
These and other aspects, features and advantages will become apparent to those
of ordinary skill in the art from a reading of the following detailed description and
the appended claims. For the avoidance of doubt, any feature of one aspect of
the present invention may be utilized in any other aspect of the invention. It is
noted that the examples given in the description below are intended to clarify the
invention and are not intended to limit the invention to those examples per se.
Other than in the experimental example, or where otherwise indicated, all
numbers expressing quantities of ingredients or reaction conditions used herein
are to be understood as modified in all instances by the term "about".
Similarly, all percentages are weight/weight percentages of the total composition
unless otherwise indicated. Numerical ranges expressed in the format "from x to
y" are understood to include x and y. When for a specific feature multiple
preferred ranges are described in the format "from x to y" it is understood that all
ranges combining the different endpoints are also contemplated. Where the term
"comprising" is used in the specification or clams, it is not intended to exclude any
terms, steps or features not specifically recited. All temperatures are in degrees
Celsius (°C) unless specific otherwise. All measurements are in SI units unless
specified otherwise. All documents cited are - in relevant part - incorporated
herein by reference.
The present invention relates to novel, super mild surfactant compositions used in
personal care cleanser compositions such as, for example, liquid cleansers or
shampoos. Using the mild surfactant compositions of the invention (optionally
further comprising skin or hair benefit agent), it is possible to achieve extremely
mild compositions (measured, for example, by standard Patch testing) on par or
better than compositions which do not use the same surfactant systems and use
significantly higher levels of benefit agent to provide mildness benefit. As such, in
one embodiment the invention provides a method for enhancing mildness to
obtain composition comparable in mildness to compositions using great amounts
(e.g., 40% or more) emollient oil by specific selection of super mild surfactant
systems.
The present invention relates to personal care cleanser compositions comprising
1 to 30% by wt., preferably 2 to 25%, more preferably 3 to 20% by wt. of a
surfactant system comprising:
1) 20 to 85%, preferably 30 to 75% by wt. of surfactant system of
alkanoyl surfactant selected from the group consisting of alkanoyl
glycinate, alkanoyl sarconsinate and mixtures thereof wherein alkyl
chain on the alkanoyl is Cs to C20 alkyl chain;
2) 5 to 70%, preferably 10 to 60% by wt. surfactant system of a fatty
acyl isethionate product which product comprises 40 to 80% fatty
acyl isethionate and 15 to 50% free fatty acid and/or soap wherein
greater than 20% and less than 40% fatty acyl isethionate has chain
length greater than or equal to C16 and greater than 50% of fatty
acid and/or soap has chain length greater than or equal to Ci6 to C24.
In a second embodiment, the composition further comprises 1 to 60% by wt.,
preferably 2 to 40% by wt. skin or hair benefit agent.
In this embodiment, it is particularly preferred to use 0.1 to 1.5% cationic polymer
(to form floe); and that there be used 3% or less, preferably 2% or less lauric acid.
When cationic is used, cleansing compositions form cationic polymer/benefit
agent floes with length 5 micrometer or longer, preferably 10 or longer upon
dilution of cleansing composition with 50 times or more water.
While mixtures of alkanoyl glycinate and alkanoyl sarcosinate are contemplated,
in a preferred form, the compositions comprise alkanoyl glycinate only or at least
predominantly (at greater than 50%, preferably greater than 60%, more preferably
75% or greater of the mixture of the glycinate and sarcosinate). Broadly in this
embodiment, the ratio of alkanoyl glycinate to alkanol sarcosinate may be from at
least 1/3 to 1/0 (e.g., from at least one-quarter of mixture to all glycinate). As
noted, preferably the mixture is predominantly alkanoyl glycinate.
In a preferred embodiment discussed below, the compositions have little or
substantially no alkyl sulfate. In another embodiment, compositions have little or
no anionic and nonionic surfactant at all other than what is present in ( 1 ) and (2).
Compositions may further preferably comprise amphoteric and/or zwitterionic
surfactant.
Where skin or hair benefit agent are used, in a preferred embodiment, the
composition further comprises lauric acid, but the level of lauric acid is kept at 3%
by wt. or less (e.g., 0.01 to <3%), preferably 2.5%, most preferably 2.0% by wt. or
less, to avoid interference with floes formed from combination of skin or hair
benefit agent and cationic polymer (formed when cationic deposition polymers are
used).
Each of these embodiments is discussed in more detail below, together with other
ingredients which may be used in the composition of the invention.
Mild Anionic Surfactant Combination
The first required components of the surfactant system are alkanoyl surfactants
which can be alkanoyl glycinates, alkanoyl sarcosinates or mixtures thereof. The
alkyl group is Cs to C20, preferably C12 to C16 straight chain alkyl.
Preferred surfactants include cocoyl, lauroyl or myristoyl glycinate and cocoyl,
lauroyl or myristoyl sarcosinates. A preferred composition comprises use of only
alkanoyl glycinate, e.g., cocoyl glycinate.
A second required component of the mild surfactant system is fatty acyl
isethionate product. It was surprising to find that a combination of fatty acyl
isethionate product and alkanoyl surfactant(s) lead to enhanced mildness of the
cleanser compositions as measured by patch test and LCAT tests described in the
protocol section. There is an unexpected synergy between the two.
The preferred fatty acyl isethionate product comprises (in addition to other
components) both pure fatty acyl isethionate surfactant (e.g., 40 to 80% of the
product) as well as free fatty acid and/or fatty acid salt (e.g., 15 to 50%). In
addition, greater than 20%, preferably greater than 25% of the fatty acyl
isethionate and less than 45 wt. % are of chain length greater than or equal to C16;
and greater than 50%, preferably greater than 60% of the free fatty acid/soap is of
chain length C16 to C20.
The fatty acyl isethionate surfactant component is typically prepared by the
reaction of an isethionates salt such as alkali metal isethionates and an aliphatic
fatty acid having 8 to 20 carbon atoms and Iodine Value (measuring degree of
unsaturation) of less than 20 g, for example:
HOR SO M ► RCOOR S0 3H
where Ri is an aliphatic hydrocarbon radical containing 2 to 4 carbons; M is alkali
metal cation or metal ion (e.g., sodium, magnesium, potassium, lithium),
ammonium or substituted ammonium cation or other counterion; and R is an
aliphatic hydrocarbon radical having 7 to 24, preferably 8 to 22 carbons.
Depending on the processing conditions used, the resulting fatty acyl isethionate
product can be a mixture of 40 to 80% by weight of fatty acyl isethionates (which
formed from the reaction) and 50 to about 15 wt. %, typically 40 to 20 wt. % of free
fatty acids. In addition, product may contain isethionates salts which are present
typically at levels less than 5 wt. %, and traces (less than 2 wt. %) of other
impurities. Preferably, a mixture of aliphatic fatty acids is used for the preparation
of commercial fatty acyl isethionates surfactants. The resulting fatty acyl
isethionate surfactants (e.g., resulting from reaction of alkali metal isethionate and
aliphatic fatty acid) should have more than 20 wt. %, preferably more than 25%,
but no more than 40% wt., preferably 35% (on basis of fatty acyl isethionates
reaction product) of fatty acyl group with 16 or greater carbon atoms to provide
both lather and mildness of the resulting fatty acyl isethionate product. These
longer chain fatty acyl isethionate surfactants and fatty acids, i.e. fatty acyl group
and fatty acid with 16 or more carbons, form insoluble surfactant/fatty acid crystals
typically in water at ambient temperatures. While not wishing to be bound by
theory, it is believed that these long chain fatty acyl isethionate surfactants in the
product together with free long chain fatty acids in the product contribute to the
mildness of the fatty acyl isethionate product for skin cleanser applications.
Examples of commercial fatty acyl isethionate products that are particularly useful
in the subject invention are DEFI flakes and Dove® cleansing bar noodles
produced by Unilever. DEFI (Direct Esterification of Fatty Isethionate) flakes
typically contain about 68 to 80 wt. % of sodium fatty acyl isethionate and 15 to 30
wt. % free fatty acid. More than 25 wt. % and no more than 35% of fatty acyl
group of the resulting fatty acyl isethionate have 16 to 18 carbon atoms. Dove®
cleansing bar noodles are mixtures of DEFI flakes described above and long
chain (mainly Ci6 and Cis) fatty acid and fatty soap which contain about 40 to 55
wt. % of fatty acyl isethionate and 30 to 40 wt. % of fatty acid and fatty soap. Due
to the high level of long chain ( 16 or more carbons) fatty acyl isethionate and fatty
acid, these preferred fatty acyl isethionate surfactant products are extremely mild
and have very good emollient benefits to the skin.
A key aspect of the present invention is that the mild surfactant system selected
should be milder than a 0.5% solution of sodium dodecyl sulfate (SDS) measured
using the Patch Test method described in the product. Either surfactant mixture
of fully formulated liquid composition may be used although fully formulated liquid
is preferred. As noted, surfactant system that can be used for the application of
this invention should be significantly less irritating to the skin than a 0.5 wt. % SDS
solution. According to the definition, the comparison is made using a cumulative
irritation score. This is defined in the Patch Test method as having less than 90%,
preferably less than 85%, most preferably less than 80% of the cumulative
irritation score of the 0.5 wt. % SDS control solution (the higher the score, the
more irritating). Surfactant systems that meet the mildness criteria are found to
cause less damage to the skin during the use of a product. This makes it possible
to deliver superior skin repair and conditioning benefits without the need of
incorporating extremely high level of emollient oils as required in current leading
skin care body washes as shown in the examples disclosed in this invention; or
(for example, in embodiment where skin or hair benefit agents are definitely used),
to add equal amounts of oil and provide superior effect.
Liquid cleanser compositions that meet the criteria described above deliver similar
to or better than a high petrolatum-containing (greater than 45 wt. %) commercial
moisturizing body wash, e.g., Olay® Butter Ribbon, using 30 wt. %, or even as low
as 10 wt. % of petrolatum.
In order to ensure that this level of mildness is achieved, it is required that there
be no more than a maximum amount of certain specific anionics; or maximum
amount of combined anionic and nonionic surfactant (other than components ( 1 )
and (2)) present in the composition of the invention.
In particular, the compositions preferably have 3% or less, preferably 2% or less,
more preferably 1% or less of any alkyl sulfate anionic including alkyl sulfates
such as sodium dodecyl sulfates or alkoxylated sulfates such as lauryl ether
sulfate. In a preferred embodiment, the compositions will have 0.2% or less
anionic surfactant and, in particular 0.2% or less alkyl sulfate.
In another preferred embodiment, the compositions will comprise ( 1 ) 20 to 85% of
surfactant system alkanoyl surfactant; (2) 5 to 70% of surfactant system
isethionate product as defined above, (3) 20 to 80%, preferably 30 to 70% of
surfactant system amphoteric and zwitterionic surfactant; (4) optionally 1 to 60%
skin or hair benefit agent and (5) 3% or less anionic and nonionic altogether (other
than what is found in ( 1 ) and (2)) in the cleanser composition.
Another way to define substantial absence of anionic and nonionic surfactant is
that the sum of the two must comprise 30% or less of total amount of glycinate,
sarcosinate, isethionate product, amphoteric and zwitterionic present. Total
anionic and nonionic is therefore 3% or less of total composition, or 30% or less of
total surfactants noted in previous sentence, whichever is lower.
While the amount of surfactant used is constrained as noted above, examples of
surfactants which can be used are noted below.
The anionic surfactant may be, for example, an aliphatic sulfonates, such as a
primary alkane (e.g., C8-C22) sulfonates, primary alkane (e.g., C8-C22) disulfonate,
C8-C22 alkene sulfonate, C8-C22 hydroxyalkane sulfonate or alkyi glyceryl ether
sulfonate (AGS); or an aromatic sulfonate such as alkyi benzene sulfonate.
The anionic may also be an alkyi sulfate (e.g., C12-C18 alkyi sulfate) or alkyi ether
sulfate (including alkyi glyceryl ether sulfates). Among the alkyi ether sulfates are
those having the formula:
wherein R is an alkyi or alkenyl having 8 to 18 carbons, preferably 12 to 18
carbons, n has an average value of greater than at least 0.5, preferably between 2
and 3; and M is a solubilizing cation such as sodium, potassium, ammonium or
substituted ammonium.
The anionic may also be alkyi sulfosuccinates (including mono- and dialkyl, e.g.,
C 6-C22 sulfosuccinates); fatty acyl taurates, fatty acyl amino acids other than
lauroyl and cocoyl glycinate or sarcosinate, alkyi sulfoacetates, C8-C22 alkyi
phosphates, alkyi phosphate esters and alkoxyl alkyi phosphate esters, acyl
lactates, C8-C22 monoalkyl succinates and maleates, and fatty acyl isethionates.
Another class of anionics is carboxylates such as follows:
R-(CH2CH2O)nCO2M
wherein R is Cs to C2oalkyl; n is 0 to 10; and M is as defined above.
Another carboxylate which can be used is amido alkyl polypeptide carboxylates
such as, for example, Monteine LCQ® by Seppic.
The nonionic surfactants which may be used include in particular the reaction
products of compounds having a hydrophobic group and a reactive hydrogen
atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene
oxides, especially ethylene oxide either alone or with propylene oxide. Specific
nonionic detergent compounds are alkyl (C6 -C22) phenols-ethylene oxide
condensates, the condensation products of aliphatic (Cs-Cis) primary or
secondary linear or branched alcohols with ethylene oxide, and products made by
condensation of ethylene oxide with the reaction products of propylene oxide and
ethylenediamine. Other so-called nonionic detergent compounds include long
chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl
sulphoxides.
The nonionic may also be a sugar amide, such as a polysaccharide amide.
Specifically, the surfactant may be one of the lactobionamides described in U.S.
Patent No. 5,389,279 to Au et al. which is hereby incorporated by reference or it
may be one of the sugar amides described in Patent No. 5,009,814 to Kelkenberg,
hereby incorporated into the subject application by reference.
Preferred alkyl polysaccharides are alkylpolyglycosides of the formula:
R2O(C nH2nO)t(glycosyl) x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which alkyl groups
contain from about 10 to about 18, preferably from about 12 to about 14, carbon
atoms; n is 0 to 3, preferably 2; t is form 0 to about 10, preferably 0; and x is from
1.3 to about 10, preferably from 1.3 to about 2.7. The glycosyl is preferably
derived from glucose.
The zwitterionic and amphoteric surfactants which are used in preferred
embodiments of the invention are as noted below.
Zwitterionic surfactants are exemplified by those which can be broadly described
as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium
compounds, in which the aliphatic radicals can be straight or branched chain, and
wherein one of the aliphatic substituents contains from about 8 to about 18 carbon
atoms and one contains an anionic group, e.g., carboxy, sulfonate, sulfate,
phosphate, or phosphonate. A general formula for these compounds is:
wherein R2 contains an alkyl, alkenyl, or hydroxyl alkyl radical of from about 8 to
about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to
about 1 glyceryl moiety; Y is selected from the group consisting of nitrogen,
phosphorus, and sulfur atoms; R3 is an alkyl or monohydroxyalkyl group
containing about 1 to about 3 carbon atoms; X is 1 when Y is a sulfur atom, and 2
when Y is a nitrogen or phosphorus atom; R4 is an alkylene or hydroxyalkylene of
from about 1 to about 4 carbon atoms and Z is a radical selected from the group
consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
Examples of such surfactants include:
4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1 -carboxylate;
5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1 -sulfate;
3-[P,P-diethyl-P-3,6,9-trioxatetradexocylphosphonio]-2-hydroxypropane-1 -
phosphate;
Amphoteric surfactants which may be used in this invention include at least one
acid group. This may be a carboxylic or a sulphonic acid group. They include
quaternary nitrogen and therefore are quaternary amido acids. They should
generally include an alkyl or alkenyl group of 7 to 18 carbon atoms. They will
usually comply with an overall structural formula:
where R1 is alkyl or alkenyl of 7 to 18 carbon atoms; R2 and R3 are each
independently alkyl, hydroxyalkyl or carboxyalkyl of 1 to 3 carbon atoms; n is 2 to
4; m is 0 to 1; X is alkylene of 1 to 3 carbon atoms optionally substituted with
hydroxyl, and Y is -CO2- or -SO3-
Alkylamphoacetates and dialkylamphoacetates are also intended to be covered
among possible amphoteric compounds which may be used.
Examples of suitable amphoteric surfactants are alkyl betaines; amidoalkyl
betaines; amphocarboxylate derivatives such as (mono or di) alkylamphoacetate;
and amidoalkyl sultaines.
Cocamidopropybetaine, lauramidopropyl betaine, lauryl betaine, coco-betaine,
lauroamphoacetate, cocoamphoacetate, cocoamphopropionate, lauryl
hydroxysultaine and cocamidopropyl hydroxysultaine surfactants are particularly
useful and preferred for this application.
In another embodiment of the invention, the compositions seek to deliver skin or
hair benefit agent (in particular petrolatum for skin and silicone oil for hair, for
example) in the mild surfactant compositions of the invention (to ensure low
mildness scores measured, for example, by Patch Test) through use of small skin
or hair benefit agent particles in combination with cationic polymer combined with
minimizing use of lauric acid. This is described below.
Where skin or hair benefit agents are used, there are at least two possible ways to
deliver said skin or hair benefit agent onto the skin or hair during the use of the
products. One relates to delivery by floe formation. Benefit agent is delivered
through the interaction of small skin or hair benefit agent particles with cationic
polymers. In this case the skin or hair benefit agent particles in the liquid
composition should be in the range of 0.01 to 30 micrometers. Upon dilution of
the liquid composition with water at 50 times or more, i.e., during use of the liquid
product, these small particles interact with cationic polymers to form aggregates of
benefit agent/polymer floes with aggregate length of 10 up to several hundreds
micrometers. Cationic polymer such as modified polysaccharides including
cationic guar available from Rhone Poulenc under the trade name Jaguar C 13S,
Jaguar® C 14S, Jaguar® C 17, or Jaguar® C 16; BF® Guar C 17 from Lamberti, Aqua
D4091 ® or Aqua D4051 ® from Aqualon; cationic modified cellulose such as
UCARE Polymer JR 30® or JR 40® from Amerco are useful for this application.
Formation of benefit agent/polymer aggregates with length from 5, preferably 10
to several hundreds micrometers upon dilution with water is critical for efficient
delivery of benefit agent onto the skin. The applicants found that the benefit
agent/polymer floe formation is sensitive to the liquid composition containing fatty
acyl isethionate surfactant product of our invention, especially to the level of extra
lauric acid added into the liquid. To ensure efficient delivery of benefit agent using
cationic polymer as deposition aid, the amount of lauric acid added to the liquid for
better liquid properties (such as viscosity and lather) should be minimized. In
general, extra lauric acid added into liquids of this invention using cationic polymer
as deposition aid for skin or hair benefit agent (e.g., emollient oil) should be no
more than 3.0 wt. %, preferably no more than 2.5 wt. %, most preferably no more
than 2.0 wt. %.
Another way to deliver skin or hair benefit agent is through the direct contact of
the dispersed skin or hair benefit agent (e.g., droplets) with skin or hair during the
use of the product. In this case, the skin or hair benefit agent droplet size has to
be larger than 50 micrometers up to several thousand micrometers and the benefit
agent droplet should be viscous with viscosity more than 5,000 centipoises such
as petrolatum or thickened low viscosity oil as taught in U.S. Patent No.
5,804,540.
A preferred skin or hair benefit agent for the application of this invention for skin is
petrolatum and for hair is silicone. The total amount of skin or hair benefit agent in
the composition of this invention can be 1 to 60 wt. %, preferably 2 to 50 wt. %,
more preferably 3 to 35 wt. %.
Other suitable nutrients and moisturizers are noted below.
One class of ingredients is nutrients used to moisturize and strengthen, for
example, the skin. These include:
(a) vitamins such as vitamin A and E, and vitamin alkyl esters
such as vitamin C alkyl esters;
(b) lipids such as cholesterol, cholesterol esters, lanolin, sucrose
esters, and pseudo-ceramides;
(c) liposome forming materials such as phospholipids, and
suitable amphophilic molecules having two long hydrocarbon
chains;
(d) essential fatty acids, poly unsaturated fatty acids, and sources
of these materials;
(e) triglycerides of unsaturated fatty acids such as sunflower oil,
primrose oil, avocado oil, almond oil;
(f) vegetable butters formed from mixtures of saturated and
unsaturated fatty acids such as Shea butter;
(g) minerals such as sources of zinc, magnesium, and iron.
A second type of skin benefit agent is a skin conditioner used to provide a
moisturized feel to the skin. Suitable skin conditioners include:
(a) silicone oils, gums and modifications thereof such as linear and
cyclic polydimethylsiloxanes, amino, alkyl, and alkyl aryl
silicone oils;
(b) conditioning proteins such as milk proteins, silk proteins and
glutens;
(c) emollients such as esters of long chain fatty acids, such as
isopropyl palmitate and cetyl lactate.
A third type of benefit agent is deep cleansing agents. These are defined here as
ingredients that can either increase the sense of refreshment immediately after
cleansing or can provide a sustained effect on skin problems that are associated
with incomplete cleansing. Deep cleansing agents include:
(a) antimicrobials such as 2-hydroxy-,2 ,4'-trichlorodiphenylether
(DP300), 2,6-dimethyl-4-hydroxychlorobenzene (PCMX),
3,4,4'-trichlorocarbanilide (TCC), 3-trifluoromethyl-4,4'-
dichlorocarbanilide (TFC), benzoyl peroxide, zinc salts, tea tree
oil;
(b) anti-acne agents such as salicylic acid, lactic acid, glycolic
acid, and citric acid, and benzoyl peroxide (also an
antimicrobial agent);
(c) oil control agents including sebum suppressants, modifiers
such as silica, titanium dioxide, oil absorbers, such as micro
sponges;
(d) astringents including tannins, zinc and aluminum salts, plant
extracts such as from green tea and Witch-hazel (Hammailes),
(e) scrub and exfoliating particles, such as polyethylene spheres,
agglomerated silica, sugar, ground pits, seeds, and husks such
as from walnuts, peach, avocado, and oats, salts;
(f) cooling agents such as methanol and its various derivatives
and lower alcohols;
(g) fruit and herbal extracts;
(h) skin calming agents such as aloe vera
(i) essential oils such as jasmine, camphor, white cedar, bitter
orange peel, rye, turpentine, cinnamon, bergamot, citrus
unshiu, calamus, pine, lavender, bay, clove, hiba, eucalyptus,
lemon, starflower, thyme, peppermint, rose, sage, menthol,
cineole, sugenol, citral, citronelle, borneol, linalool, geranoil,
evening primrose, camphor, tymol, spirantol, penene, limonene
and terpenoid oils.
Other benefit agents that can be employed include anti-dandruff compounds such
as zinc pyrithione for shampoo application, anti-aging compounds, sunscreens,
and lightening agents.
When the benefit agent is oil, especially low viscosity oil, it may be advantageous
to pre-thicken it to enhance its delivery. In such case, hydrophobic polymers of
the type describe in U.S. Patent No. 5,804,540 (which is incorporated by
reference into the subject application) may be used.
Water soluble skin benefit agents
Water-soluble skin benefit agents is another optional ingredient that is highly
preferred to be include in the liquid compositions of the invention. A variety of
water-soluble skin benefit agents can be used and the level can be from 0 to 50
weight %, preferably 1 to 30%. The materials include, but are not limited to,
polyhydroxy alcohols such as glycerin, propylene glycol, dipropylene glycol,
sorbitol, pantenol and sugar; urea, alpha-hydroxy acid and its salt such as glycolic
or lactic acid; and low molecular weight polyethylene glycols with molecular weight
less than 20,000. Preferred water soluble skin benefit agents for use in the liquid
composition are glycerin and diglycerin.
Water soluble/dispersible polymers are an optional ingredient that is preferred to
be included in the liquid composition of the invention. The water soluble/or
dispersible polymer can be cationic, anionic, amphoteric or nonionic polymer with
molecular weight higher than 100,000 Dalton. These polymers are known to
increase the viscosity and stability of liquid cleanser compositions, to enhance inuse
and after-use skin sensory feels, and to enhance lather creaminess and lather
stability. When water insoluble skin benefit agent is used in this invention, the
water soluble/dispersible polymers are required to stably suspend the added skin
benefit agents. Amount of polymers used can be in the range of 0.1 up to 10 wt.
% depending on the composition of the liquid cleansers.
Examples of water soluble or dispersible polymers useful in the present invention
include the carbohydrate gums such as cellulose gum, microcrystalline cellulose,
cellulose gel, hydroxethyl cellulose, hydroxypropyl cellulose, sodium
carboxymethylcellulose, hydroxymethyl or carboxymethyl cellulose, methyl
cellulose, ethyl cellulose, guar gum, gum karaya, gum tragacanth, gum Arabic,
gum acacia, gum agar, xanthan gum and mixtures thereof; modified and nonmodified
starch granules with gelatinization temperature between 30 to 85°C and
pregelatinzed cold water soluble starch; polyacrylate; Carbopols; alkaline soluble
emulsion polymer such as Aculyn 28, Aculyn 22 or Carbopol Aqua SF1 ; cationic
polymer such as modified polysaccharides including cationic guar available from
Rhone Poulenc under the trade name Jaguar C 13S, Jaguar C14S, Jaguar C 17, or
Jaguar C 16; BF Guar 7 from Lamberti, Aqua D4091 or Aqua D4051 from
Aqualon; cationic modified cellulose such as UCARE Polymer JR 30 or JR 40
from Amerchol; N-Hance 3000, N-Hance 3 196, N-Hance GPX21 5 or N-Hance
GPX 196 from Hercules; synthetic cationic polymer such as MerQuat 100,
MerQuat 280, Merquat 281 and Merquat 550 by Nalco; cationic starches, e.g.,
StaLok® 100, 200, 300 and 400 made by Staley Inc.; cationic galactomannans
based on guar gum of Galactasol 800 series by Henkel, Inc.; Quadrisect Um-200;
and Polyquaternium-24.
Gel forming polymers such as modified or non-modified starch granules, xanthan
gum, Carbopol, alkaline-soluble emulsion polymers and cationic guar gum such
as Lamberti BF Guar C 17, and cationic modified cellulose such as UCARE
Polymer JR 30® or JR 40® are particularly preferred for this invention.
As discussed in co-pending application relating to benefit agent delivery through
floe formation, when such delivery is used, anionic polymer (e.g., Carbopol ®)
should be preferably minimized to reduce formulation costs.
Other Optional Components
In addition, the compositions of the invention may include 1 to 10% by wt.
optional ingredients as follows:
Perfumes; sequestering agents, such as tetra sodium
ethylenediaminetetraacetate (EDTA), EHDP or mixtures in an amount of 0.01 to
1%, preferably 0.01 to 0.05%; and coloring agents, opacifiers and pearlizers such
as zinc striate, magnesium stearate, Ί 2, EGMS (ethylene glycol monostearate)
or Lytron 621 (Styrene/Acrylate copolymer); all of which are useful in enhancing
the appearance or cosmetic properties of the product.
The compositions may further comprise antimicrobials such as 2-hydroxy-4,2'4'
trichlorodiphenyl ether (DP300); preservatives such as
dimethyloldimethylhydantoin (Glydant XL 1000), parabens, sorbic acid, etc.
Antioxidants such as, for example, butylated hydroxytoluene (BHT) may be used
advantageously in amounts of about 0.01 % or higher if appropriate.
Polyethylene glycols as conditioners which may be used include:
Polyox WSR-25 PEG 14M
Polyox WSR-N-60K PEG 45M, or
Polyox WSR-N-750 PEG 7M.
Another ingredient which may be included are exfoliants such as polyoxyethylene
beads, walnut shells and apricot seeds.
Examples
Protocol
Patch Test
This was randomized, double-blind study. A sufficient number of subjects were
recruited to ensure that 25 subjects completed the study. The 14-day cumulative
irritation test was conducted as follows. Patching occurred for 14 consecutive
days, except on Sundays. Patches applied on Saturday were left in place until
Monday, when freshly prepared patches were applied. The designated patch test
sites were approximately 2cm x 2cm on the intrascapular area of the back.
Approximately 0.2 ml_ of the test product was placed onto a Parke-Davis Readi-
Bandage® occlusive patch that measured 2 cm x 2 cm. Solutions were made by
diluting the cleansers to 25% w/w in distilled water. The patch was then applied to
the designated test site. The patches were secured with hypoallergenic tape
(Scanpor {Allerderm} as needed). A 0.5% sodium dodecyl sulfate (SDS) solution
was used as the control in the test.
Each day following application, the patches were removed, the sites evaluated
and identical patches reapplied to the same test sites. All evaluations were made
using the following 6-point scoring system:
0 = No evidence of any effect
+ = Barely perceptible (minimal, faint, uniform or spotty erythema)
numerically equivalent to 0.5
1 = Mild (pink, uniform erythema covering most of the contact site)
2 = Moderate (pink-red, erythema uniform in the entire contact site)
3 = Marked (bright red erythema with/without petechiae or papules)
4 = Severe (deep red erythema with/without vesiculation or weeping)
If a dermal reaction of 3 or 4 occur with any of the test articles at any point during
the study, further patch testing on that subject was terminated at the test site
involved, and the attained score was assigned to that site for the subsequent
scheduled test days.
Cumulative irritation scores, which were the sum of the numerical irritation grades
assigned daily during the 14-day test period, were calculated at the end of the
study to compare mildness of the test products. Based on the 26 subjects
completing the study, the highest "Cumulative Irritation Score" that could be
obtained was 1456 (26 subjects x 14 days x 4 [0-4 scoring scale]). The data were
statistically analyzed using Tukey-Kramer Comparison, and statistical significance
was determined at the 95% confidence level.
LCAT (Leg Controlled Application Technique)
LCAT clinical study was a randomized, double blind incomplete block design with
subjects 18-65 years of age (n=49) and was conducted according to Standard
Protocol #HPC CAT2004 Hill Top-Controlled Application Technique for Estimating
the Relative Mildness of Personal Cleansing Products. The study consisted of a
five-day conditioning phase followed by either a five-day or a seven-day product
application phase. Qualified subjects completed the five-day in-home conditioning
phase using unscented Dove bar according to their normal wash regime. During
the conditioning phase, subjects discontinued use of all moisturizers, lotions,
sunscreens, and washing appliances on or near their lower legs. Subjects having
dryness scores between 1.5-3.5 and erythema scores of <2.0 at the end of the
conditioning phase continued into five-day product application phase.
Each outer lower leg was divided and marked with a skin-marking pen into three 3
cm diameter test sited, for a total of 6 test sites. Product application consisted of
two wash sessions per day, morning and afternoon at least 3-hour apart, for days
1 to 4 or 1 to 6, and one wash session at morning on the fifth or seventh day
respectively for five day or seven day product application study. Each wash
session consisted of two washes performed in succession. During product
application, study personnel dispersed 0.2 ml of the designated liquid cleanser
onto a moistened Masslinn towel and squeezed slightly to generate lather. All test
sites were washed for 10 seconds, followed by a 90 second lather retention, 15
seconds rinse with warm water, and then patted dry with a Masslinn towel.
Visual evaluation of dryness and erythema were conducted three times daily
(before washed 1 and 3 and 2 hours after wash 4) and twice on last day of the
product application phase (before wash 1 and before final instrument readings).
Instrumental ServoMed was used to measure transepidermal water loss (TEWL)
done at baseline (Day 1 before wash 1) and endpoint (3 to 5 hours after the last
wash session on either Day 5 or Day 7 or when a test site was discontinued form
further product application). Skicon for the measurement of conductance and
Corneometer for capacitance reading were done twice daily (before wash 1 at
A.M., and 2 hours after wash 4 at P.M.) and at baseline and endpoint (3 to 5 hours
after the last wash session on either Day 5 or Day 7 or when a test site was
discontinued from further product application). Subjects continued using
unscented Dove® bar (formulation noted below) for all general bathing, excluding
the lower legs and continued not using moisturizers, lotions, sunscreens, or
washing appliances throughout the product application phase.
Unscented Dove® ingredient listing: sodium cocoyl isethionate, stearic acid,
sodium tallowate; or sodium palmitate, sodium stearate, water, sodium
isethionate, lauric acid, sodium C14-C16 olefin sulfonate, sodium cocoate or
sodium palm kernalate; sodium chloride, maltol, dipropylene glycol, tetrasodium
EDTA, tetrasodium etidronate, titanium dioxide.
Example 1
In order to demonstrate that there is a need to make milder cleanser formulations
(e.g., liquid cleansers) without using very large amounts of, for example,
petrolatum and mineral oil, the applicants compared patch test results of three (3)
leading commercial skin care body washes as set forth in Table 1 below. The
table ingredients and brief comments are set forth below.
Table 1: Patch Test Score of leading commercial skin care body wash liquids
Three leading commercial skin care liquid cleansers-i.e. Dove Deep Moisture
Body Wash (ingredient list: water, sunflower seed oil, sodium laureth sulfate,
cocamidopropyl betaine, glycerin, petrolatum, lauric acid, cocamide MEA,
fragrance, santalum album oil, guar hydroxypropyltrimonium chloride, lanolin
alcohol, PEG-30 dipolyhydroxystearate, DMDM hydantoin, EDTA, citric acid,
etidronic acid, T1O2); Olay® ultra moisture body wash (ingredient list: water,
petrolatum, ammonium laureth sulfate, ammonium lauryl sulfate, sodium
lauroamphoacetate, lauric acid, fragrance, trihydroxystearin, sodium chloride, guar
hydroxypropyltrimonium chloride, citric acid, DMDM hydatoin, sodium benzoate,
EDTA, niaciamide, PEG-14M, butyrospermum parki extract, tocopheryl acetate,
retinyl palmitate; and Olay® Butter ribbons body wash (ingredient list: water,
petrolatum, mineral oil, sodium trideceth sulfate, sodium lauryl sulfate, sodium
lauroamphoacetate, sodium chloride, trideceth-3, fragrance, simmondsia
chinensis (Jojoba) butter, citric acid, guar hydroxypropyltrimonium chloride,
acrylonitrile/methacrylonitrile/methylmethacrylate copolymer, isopentane, xanthan
gum, sodium benzoate, PEG-90M, disodium EDTA, methylchloro isothiazolinone,
methylisothiazolinone, sodium hydroxide, Red 7, Green 6) were evaluated in
patch test compared to the standard 0.5% SDS (Na dodecyl sulfate) solution. The
results are summarized in Table 1.
As shown in the table, the total irritation score for all three leading commercial skin
care body washes is higher than the 0.5% SDS solution. To achieve superior
moisturizing benefit, very high level of emollient oils, such as Olay Butter ribbon
containing more than 45% petrolatum and mineral oil, are used in these products.
The results clearly show that there is a need to make milder liquid as defined in
this invention, for skin care liquid cleanser application to achieve superior skin
cleansing and skin moisturizing benefit without the need of using very high level of
emollient oils as current leading commercial skin care body washes. The
examples of this invention noted below show that liquid cleanser compositions
containing the super mild surfactant system as defined in this invention, having
significantly lower level of petrolatum, can achieve similar or better skin care
benefit, as shown in clinical studies, than even a leading commercial body wash
containing more than 45% of emollient oils (Olay® Butter Ribbon).
Examples 2-5 and Comparatives A-F
The Examples in the table below (plus water to 100 wt%) were prepared for
mildness comparison using the Patch Test method. All the examples were
prepared by mixing all the ingredients except perfume and glydant plus at 70 to
75°C for 30 to 40 minutes to form a uniform mixture. Perfume and glydant plus
were added below 40°C. The pH of the samples was adjusted with NaOH or citric
acid solution to the range of 6.4 to 7.0 at the end of preparation.
Table 2 is set forth below:

The total irritation score as percentage compared to 0.5% SDS solution for each
sample is also given in Table 2 . Lower percentage of total cumulative irritation
score (by percentage) indicates milder surfactant system. As shown in the table,
Comparative Examples D, E and F containing high level of sodium alkyl ether
sulfates, mild synthetic surfactants widely claimed in mild liquid cleanser patents
and which are most widely used in current commercial mild personal care liquid
cleansers, all have very high total irritation score with numbers higher or almost
same as the 0.5% SDS solution even for the liquid (Comparative Example D),
containing 50 wt. % of NaLES and 50 wt. % amphoteric surfactant
(cocamidopropyl betaine). To make mild liquid composition with cumulative
irritation score significantly lower than 0.5% SDS solution (defined as less than
90% of 0.5% SDS total irritation score), alkyl ether sulfates level has to be
reduced (see Comparative B relative to Comparative F where reduction went from
99.6% to 87.6% score) or removed altogether (see Comparative C versus D, E
and F).
A surprising and unpredictable finding is that the combination of a fatty acyl
isethionate surfactant product to the liquid composition can enhance the mildness
of other synthetic surfactant (e.g., alkanoyi surfactants) when levels of anionic and
nonionic are minimized. This specific fatty acyl isethionate product contain about
50 wt. % of fatty acyl isethionate surfactant with about 30% of the fatty acyl group
equal to or longer than 16 carbon, and about 35 wt. % of linear fatty acid/linear
fatty soap in which about 79 wt. % of the fatty acid/fatty soap have 16 to 20
carbons. This is seen, for example, in comparing Comparative A (no isethionate
product) to Example 2 and Comparative C to Example 3 .
It was unexpected that the addition of any extra surfactants, which might be
examples to introduce irritation (fatty acyl isethionate surfactant product), can
enhance mildness of other synthetic surfactants.
The combination of this fatty acyl isethionate product with alkanoyi surfactant(s)
defined, however, provides synergy to lower the irritation of liquid cleanser.
Examples 6-8 and Comparatives G-J
In order to further show benefits of the invention, the applicants conducted LCAT
clinical tests for compositions set forth in the table below (plus water to 100 wt%):
Table 3
Example No. 6 7 8
Comparative Example G - H - - I J
Na fatty acyl isethionate product - 10 - 4 4 - -
HEBE noodle
Na cocoyl isethionate - 2 - - - - -
Na cocoamidopropyl betaine 5 5 4.4 4.4 4.8 5 2
Na lauryl amphoacetate
K cocoyl glycinate 5 5 - - - - -
Na cocoyl glycinate - - 4.6 4.6 2.5 - -
Na laurath ( 1EO) sulfate - - - - - 5
Na laurath (3EO) sulfate - - - - - - 9
Na lauryol sarcosinate - - - - 2.5 - 3
Cocomonoethanolamide - - - - - 1
Laurie acid 1 0 0.8 0.6 1.8 1 2.5
Cationic guar 0.1 0.3 0.4 0.5 - 0.1 0.35
Jaguar C13S
Cationic guar - - - - 0.5 - -
Lamberti cosmetic BF7
Glycerin 30 30 10 10 6 30 -
Petrolatum 18 20 30 30 10 18 40
Penreco Snow White
Indopol H1500 polybutene 2 - - - 2 2 -
Indopol H300 polybutene - - - - - - 3
Pure gel B990 starch 7 - 6.5 5 6 7 -
Perfume 1 1 1 1 1 1 1
LCAT clinica results
TEWL >R >R = >R = = >R
Conductance = >R >R >R >R = =
Visual dryness = >R >R >R = = =
CAPACITANCE >R >R >R >R = = =
ERYTHEMA >R >R >R >R = >R =
The seven samples with compositions shown in Table 3 were prepared using the
same procedure as described above for LCAT (Leg Controlled Application
Technique) clinical study. The LCAT clinical results conducted according to the
method disclosed in this patent are also summarized in Table 3 . In the LCAT
study, Olay Butter Ribbon Body Wash containing more than 45% petrolatum is
used as the control for comparison. A "=" sign indicates there is no significant
difference between the test sample and the Olay Ribbon Butter. A ">R" means
the test sample is significantly better than Olay butter Ribbon in that clinical
measurement. If the test sample is significantly worse than Olay Butter Ribbon,
"