Note: Descriptions are shown in the official language in which they were submitted.
WO 94/17166 PCT/US94/00354
~1533~3
CLEANSING COMPOSITIONS
The present invention relates to cleansing compositions. In
particular it relates to foam-producing personal cleansing compositions
suitable for simlllt~neously cle~n~in~ and conditioning the skin and/or the
hair and which may be used, for example, in the form of foam bath
preparations, shower products, skin cleansers, hand, face and body
cleansers, shampoos, etc.
BACK(~ROUND OF THE INVENTION
Foaming cosmetic compositions must satisfy a number of criteria
including cle~n~in~ power, fo~min~ properties, mildness/low irritancy
and physical stability. Oil-in-water emulsion systems typical of fo~minp
cosmetic compositions represent a particular challenge with respect to
stability and viscosity. While on one hand it is possible to llltilise agents
specifically to inrlllce appropriate viscosity, care must be taken to ensure
these agents work to m~int~in that viscosity over time. Certain fatty acids
are known to be effective in the achievement of matrix viscosity.
However this is generally dependant upon the fatty acid forming stable
complexes. It has been a particular problem that fatty acid added to
achieve stability/viscosity in an oil-in-water emulsion can result in a
reduction in viscosity over time. This is believed in part to be due to the
secondary formation of insoluble cryst~lline moieties which break down
the structure of the emulsion and lead to lower viscosity/thinnin~. The
aforementioned problems can be exaggerated when products are exposed
to extremes or variations of temperature.
Skin is made up of several layers of cells which coat and protect the
keratin and collagen fibrous proteins that form the skeleton of its
structure. The outermost of these layers, r~ferred to as the stratum
corneum, is known to be composed of 250 A protein bundles surrounded
by 80 A thick layers. Hair simil~rly has a protective outer coating
enclosing the hair fibre which is called the cuticle. Anionic surfactants
WO 94/17166 PCT/US94/00354
33 ~3
can penetrate the stratum corneum membrane and the cuticle and, by
delipidization destroy membrane integrity. This interference with skin
and hair protective membranes can lead to a rough skin feel and eye
irritation and may eventually permit the surfactant to interact with the
keratin and hair proteins creating irritation and loss of barrier and water
retention functions.
Ideal cosmetic cleansers should cleanse the skin or hair gently,
without defatting and/or drying the hair and skin and without irritating the
ocular mucosae or leaving skin taut after frequent use. Most lathering
soaps, shower and bath products, shampoos and bars fail in this respect.
Certain synthetic surl~c~nts are known to be mild. However, a
major drawback of most mild synthetic surfactant systems when
form~ te~l for shampooing or personal cle~n~in~ is poor lather
performance compared to the highest shampoo and bar soap standards.
Thus, surf~ct~nt~ that are among the mildest, such as sodium lauryl
glyceryl ether sulfonate, (AGS), are marginal in lather. The use of
known high sll~lsin~ anionic sur~ct~nts with lather boosters, on the other
hand, can yield acceptable lather volume and qualjty but, at the expense of
clinical skin m~ ness. These two facts make the surfactant selection, the
lather and mil-ln~ss benefit form~ tion process a ~ielic~te balancing act.
Despite the many years of research that have been expended by the
toiletries in~lstry on personal cle~ncin~, the broad mass of consumers
remain ~lies~tisfied by the mil~3ness of present day cle~ncin~ compositions,
fin~lins~, for example, that they have to apply a separate cosmetic lotion or
cream moislur~er to the skin after using a shower or bath preparation in
order to m~in~in skin suppleness and hydration and to counteract the
delipitli7in~ effect of the cleanser.
Thus a need exists for personal cle~n~in~ products which produce a
foam which is ablln-l~nt, stable and of high quality, which are effective
hair and skin cleansers, which will not dehydrate the skin or result in loss
of skin suppleness, and which will provide a level of skin conditioning
performance in a wash and rinse-off product which previously has only
been provided by a separate post-cle~ncin~ cosmetic moisturizer, which
WO 94/17166 PCT/US94/00354
~ 3 ~ ~
has good rinsibility characteristics, and which at the same time has stable
product and viscosity characteristics and remains fully stable under long
term and stressed temperature storage conditions.
.,
SUMMARY OF THE INVENTION
The subject of the present invention is a stable, foaming cle~n~in~
product suitable for personal cleansing of the skin or hair and which may
be used as foam bath and shower products, skin cleansers and shampoos
etc. According to one aspect of the invention, there is provided a
personal cle~n~in composition comprising:
(a) from about 5 % to about 50% by weight of one or more
surfactants selected from anionic, nonionic, amphoteric,
zwitterionic and cationic surfactants and mixtures thereof;
(b) from about 3 % to about 40~ by weight of an insoluble,
nonionic oil or wa~c or mixture of insoluble, nonionic oils OF
waxes;
(c~ from about ~.1% to about 8% by weight of fatty acid having
a weight - average chain length of from about 10 to about 18
carbon atoms;
(d) from about 1.5% to about 10% by weight of citric acid or
water soluble citrate salt or mixture thereof; and
(e) water.
In preferred embo~imt~ts of the invention comprising mi~tures of
anionic and amphoteric sur~ct~nts, the anionic surf~ct~nt and amphoteric
surf~ct~nt together comprise from about 5% to about 30% by weight of
the composition, and the weight ratio of anionic surf~ct~nt.amphoteric
surf~ct~nt is in the range from about r:s to about 20:1. Prefeldbly the
weight ratio of total surf~ct~nt: nonionic oil or wax is in the range from
about 10:1 to about 1:3. r~eferably also the composition is in the form of
an oil-in-water emulsion having a viscosity (Brookfield RVT, Helipath,
Spindle TB, S rmp, 25C, lmin) in the range from 10,000 to 40,000 cps
WO 94/17166 PCT/US94/00354
3~3
and a yield point of at least 50 dynes/cm2 (Brookfield RVT, Spindle
CP52, Plate Code A, 25C).
All concentrations and ratios herein are by weight of the cle~ncinp
composition, unless otherwise specified. Surfactant chain lengths are also
on a weight average chain length basis, unless otherwise specified.
The invention relates to a foam-producing cle~ncin~ composition
with superior physical and viscosity st~bility characteristics (across
temperature conditions) combined with excellent lathering, milclnçss to
the skin and hair, together with good cleansing ability and conditioning
performance. The invention also relates to a wash and rinse-off personal
cle~ncin~ product having the above stability, lathering, milt~ness,
rinsibility and conditioning benefits.
The cle~n~in~ compositions herein are based on a combination of
mild surfactants which in general terms can be selected from anionic,
amphoteric, nonionic and betaine surfactants and mixtures thereof. The
compositions preferably comprise a mixture of anionic, nonionic and
amphoteric surfactants and highly preferred` systems also incorporate a
betaine surfactant. Other suit~ble compositions within the scope of the
invention comprise mixtures of anionic with one or more nonionic or
betaine surfactants or mixture thereof; and mixtures of amphoteric with
one or more nonionic or betaine surf~ct~ntc or mi~cture thereof. The level
of each of the anionic and amphoteric surf~ct~n~s is generally in the range
from about 1% to about 20%, preferably from about 1% to about 15%,
and especially from about 2% to about 13% by weight of the composition.
The weight ratio of anionic surfactant:amphoteric surf~ct~nt, on the other
hand is generally from about 1:5 to about 20:1, preferably from about 1:2
to about 5:1, and especially from about 1:1 to about 2:1. The total level
of anionic and amphoteric surf~ct~ntc is generally about 5% to about
30%, l,refeldbly from about 8% to about 25% and especially from about
10% to about 20% by weight of the cle~ncing composition. The nonionic
or betaine surfactant, on the other hand, ~referably con.ctitl~teC from about
0.1% to about 20%, more preferably from about 0.1% to about 10% and
especially from about 1% to about 8 % by weight of the composition. The
total level of anionic, nonionic and amphoteric surf~ct~ntc is generally
WO 94/17166 PCT/US94/00354
5215~31 3
from about 5% to about 45%, more preferably from about 7% to about
40% by weight of the cleansing composition. The total level of
surfactant, inclusive of anionic, amphoteric, nonionic, betaine and other
surfactant components, is preferably from about 5% to about 50%, more
preferably from about 10% to about 35% by weight of composition.
Anionic surfactants suitable for inclusion in the compositions of the
invention can generally be described as mild synthetic detergent
surfactants and include ethoxylated alkyl sl-lfate~, alkyl glyceryl ether
sulfonates, methyl acyl taurates, fatty acyl glycinates, N-acyl gllltamates,
acyl isethionates, alkyl sulfosuccinates, alpha-sulfonated fatty acids, their
salts and/or their esters, alkyl ethoxy carboxylates, alkyl phosphate esters,
ethoxylated alkyl phosphate esters, acyl sarcosinates and fatty acid/protein
condensates, and mixtures thereof. Alkyl and/or acyl chain lengths for
these surfactants are C8-c22~ preferably C10-C18
Preferred for use herein from the viewpoint of optimllm milclness
and lathering characteristics are the salts of sulfuric acid esters of the
reaction product of 1 mole of a higher fatty alcohol and from about 1 to
about 12 moles of ethylene oxide, with sodium and m~Enesi~lm being the
preferred counterions. Particularly prefe~led are the alkyl sl~lf~te~
cont~inin~ from about 2 to 6, preferably 2 to 4 moles of ethylene o~ide,
such as sodium laureth-2 sulfate and sodium laureth-3 sulfate. In
preferred embo~liment~, the anionic surfactant contains at least about
50%, especially at least about 75% by weight of ethoxylated alkyl slllf~te.
Pr~ferr~d compositions for use herein also contain an amphoteric
surfact~nt. Amphoteric surf~ct~nts suitable for use in the compositions of
the invention include:
(a) imi~7olinium surfactants of formula
C H O R
1 ~ + ~
WO 94/17166 2 ~ 33~ PCT/US94/00354~
wherein R1 is C7-C22 alkyl or alkenyI, R2 is hydrogen or
CH2Z, each Z is independently C02M or CH2C02M, and
M is H, alkali metal, ~Ik~line earth metal, ammonium or
alkanol~mmonium; and/or ammonium derivatives of formula
(II)
C2H40H
RlCONH ( CH2 ) 2N CH2 Z
R2
wherein R1, R2 and Z are as defined above;
(b) aminoalkanoates of formula (III)
RlNH(CH2)nC02M
and imino~ lk~noates of formula (IV)
RlN[(CH2)mc02M]2
wherein n and m are numbers from 1 to 4, and Rl and M are
indepenrlently selected from the groups specified above; and
(c) mixtures thereof.
Suitable amphoteric surfactants of type (a) are marketed under the
trade name Miranol and Empigen and are understood to comprise a
complex mixture of species. Traditionally, the Miranols have been
described as having the general formula I, although the CTFA Cosmetic
Ingredient Dictionary, 4th Edition indicates the non-cyclic structure II. In
practice, a complex mixture of cyclic and non-cyclic species is likely to
exist and both definitions are given here for sake of completeness.
Preferred for use herein, however, are the non-cyclic species.
~WO 94/17166 215 ~ PCT/US94/00354
Examples of suitable amphoteric surfactants of type (a) include
compounds of formula I and/or II in which R1 is CgH17 (especially iso-
capryl), CgH1g and C11H23 alkyl. Especially preferred are the
compounds in which R1 is CgH1g, Z is C02M and R2 is H; the
compounds in which R1 is C11H23, Z is C02M and R2 is CH2C02M;
and the compounds in which R1 is C11H23, Z is C02M and R2 is H.
In CTFA nomenclature, materials preferred for use in the present
invention include cocoamphocarboxypropionate, cocoamphocarbo~y
propionic acid, and especially cocoampho~cet~te and cocoampho~ cet~te
(other~vise referred to as cocoamphocarboxyglycinate). Specific
commercial products include those sold under the trade names of
Empigen CDL60 and CDR 60 (Albright & Wilson), Miranol H2M Conc.,
Miranol C2M Conc. N.P., Miranol C2M Conc. O.P., Miranol C2M SF,
Miranol CM Special (Rhone-Poulenc); Alkateric 2CIB (Alkaril
Chemicals); Amphoterge W-2 (Lonza, Inc.); Monateric CDX-38,
Monateric CSH-32 (Mona Industries); Rewoteric AM-2C (Rewo
Chemical Group); and Schercotic MS-2 (Scher Chemicals).
It will be understood that a number of commercially-available
amphoteric surfactants of this type are m~nllf~ctured and sold in the form
of electroneutral complexes with, for example, hydroxide counterions or
with anionic sulfate or sulfonate surf~c~nts, especially those of the
slllf~te~ Cg-C1g alcohol, Cg-Clg ethoxylated alcohol or Cg-C1g acyl
glyceride types. Preferred from the viewpoint of milclness and product
stability, however, are compositions which are esse-nti~lly free of (non-
etho~cylated) slllf~te~l alcohol surfactants. Note also that the
concentrations and weight ratios of the amphoteric surfactants are based
herein on the uncomplexed forms of the surf~ct~nt~, any anionic
surf~c~nt counterions being considered as part of the overall anionic
surf~ct~nt component content.
- Fx~mples of suitable amphoteric surf~ct~nts of type (b) include
salts, especially the triethanolammonium salts and salts of N-lauryl-beta-
amino propionic acid and N-lauryl-imino-dipropionic acid. Such
materials are sold under the trade name Deriphat by Henkel and
WO 94tl7166 PCT/US94/00354
~ 33~ 8
Mirataine by Rhone-Poulenc. Amphoterics preferred for use herein,
however, are those of formula I and/or II.
The compositions of the invention also contain from about 3% to
about 40%, preferably from about 4% to about 20%, and more preferably
from about 5 % to about 15 ~ by weight of an insoluble nonionic oil or
wax or mixture thereof, the oil or wax being insoluble in the sense that it
is insoluble in the cle~n~in.f~ composition liquid matrix at a temperature of
25C. In addition, the oil or wax is present in composition in a level such
that the weight ratio of total surfactant:oil or wax is in the range from
about 10:1 to about 1:3" preferably from about 5:1 to about 1:2, and
especially from about 2:1 to about 1:1, this being preferred from the
viewpoint of providing personal cleansing compositions having optimum
lathering, mil-3n~cs, emolliency and rinsibility.
Suitable oils and waxes for use herein can be selected from water-
insoluble silicones inclusive of non-volatile polyallyl and polyaryl
siloxane gums and fluids, volatile cyclic and linear polyalkylsilo~sanes,
polyalkoxylated silicones, amino and quaternary ammonium modified
silicones, rigid cross-linked and reinforced silicones and mixhlres thereof,
C1-C24 esters of Cg-C30 fatty acids such as isopropyl myristate and cetyl
ricinoleate, beeswax, saturated and l~nc~ rated fatty alcohols such as
behenyl alcohol, hydrocarbons such as mineral oils, petrolatum and
squalene, fatty sorbitan esters (see US-A-3988255, Seiden, issued
October 26th 1976), lanolin and oil-like lanolin derivatives, ~nim~l and
vegetable trigiycerides such as almond oil, peanut oil, wheat germ oil,
lin.~ee~ oil, jojoba oil, oil of apricot pits, walnuts, palm nuts, pistachio
nuts, ses~ms seeds, rapeseed, cade oil, corn oil, peach pit oil, poppyseed
oil, pine oil, castor oil, soybean oil, avocado oil, safflower oil, coconut
oil, h~lemlt oil, olive oil, grapeseed oil, and sunflower seed oil, and C1-
C24 esters of dimer and trimer acids such as diisopropyl dimerate,
diisostearylm~ e, diisostearyldimerate and triisostearyltrimerate. Of the
above, highly preferred from .he viewpoint of optimum lathering and
mildness are the vegetable triglyceride oils.
rreferred from the viewpoint of conditioning effectiveness in a
rinse-off application are compositions in the form of oil-in-water
~WO 94/17166 21 !~ ~ 3 I ~ PCT/US94/00354
emulsions wherein the average size of the emulsion droplets is in the
range from about 1 to about 150 microns, preferably from about 2 to
about 50 microns. (Droplet size being measured by, for example, laser
diffraction using, e.g. a Malvern Series 2600.)
The oil or wax is preferably used herein in combination with a mild
surfactant system. Suitable mild surfactants include those having a
Relative SkiII Barrier Penetration Value of less than about 75, preferably
less than about 50 and more preferably less than about 40, Relative Skin
Barrier Penetration Value being measured according to the test method set
out in EP-A-0203750 (Incorporated herein by reference). Surf~ct~nts
which have Relative Barrier Penetration Values of greater than 75 can be
used along with the mild surfactant at low levels in the compositions of
this invention, as long as their use does not significantly change the
clinical skin mil~lness of the total cle~n.cin~ composition.
Thus according to another aspect of the invention, there is provided
a personal cle~n.cin.~ composition comprising:
(a) from about 5% to about 50% by weight of a mixed surfactant
system having a Relative Skin Barrier Penetration Value of
less than about 75;
~b) from about 3 % to about 40% by weight of an insoluble,
nonionic oil or wax or mixture of insoluble, nonionic oils or
waxes;
(c) from about 0.1 % to about 8% by weight of fatty acid having
a weight-average chain length of from 10 to 18 carbon atoms;
(d) from about 1.5% to about 10% by weight of citric acid or
water soluble citrate salt or mi~cture thereof; and
(e) water,
wherein the weight ratio of total surf~ct~n~ nonionic oil or wa~c is
in the range from about 10:1 to about 1:3, and wherein the composition is
WO 94/17166 PCT/US94/00354 ~
2~33~3 lo
in the form of an oil-in-water emulsion having a viscosity (Brookfield
RVT, Helipath, Spindle TB, 5 rmp, 25C, lmin) in the range from
10,000 to 40,000 cps and a yield point of at least 50 dynes/cm2
(Brookfield RVT, Spindle CP52, Plate Code A, 25C).
The compositions herein preferably also contain from about 0.1
to about 20~, more preferably from about 0.1% to about 10%, and
especially from about 1% to about 8% of a nonionic surf~ct~nt Preferred
herein from the viewpoint of optimum lathering and mil~lne~s are nonionic
surfactants selected from C12-C14 fatty acid mono- and lieth~nol~mi-les;
polyhydroxy fatty acid amide surfactants having the general formula (V~)
O Rg
Il I
R8~C N Z2
where Rg is H, Cl-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or
a mixture thereof, R8 is Cs-C31 hydrocarbyl and Z2 is a
polyhydroxyhydrocarbyl having a linear chain with at least 3 hydroxyls
directly connecte~l to said chain, or an alkoxylated derivative thereof; and
polyethyleneglycol glyceryl fatty ester surfactants having the formula
(VII)
RCOCH2 CH ( OH ) CH2 ( OCH2 CH2 ) nOH
wherein n is from about S ~o about 200, preferably from about 20 to about
100, more preferably from about 30 to about 85, and wherein R
comprises an aliphatic radical having from about 5 to 19 carbon atoms,
preferably from about 9 to 17 carbon atoms, more ~re~l~bly from about
11 to 17 carbon atoms, most preferably from about 11 to 14 carbon
atoms; and mixtures of said ethanol~mi~e, alkyl polyhydroxy fatty acid
amide and/or glyceryl fatty ester surf~ct~nt~s. Also highly preferred
herein are compositions which are essentially free of alkyl polysaccharide
sur~ct~nts, this being preferred from the viewpoint of m~ ness and
processability.
~WO 94/17166 11 PCT/US94/00354
The preferred polyhydroxy fatty acid amide surfactants are those in
which Rg is C1 4 alkyl, preferably methyl, and R8 is C7-C1g alkyl or
alkenyl, more preferably straight-chain Cg-C17 alkyl or alkenyl, or
mixture thereof; and Z2 is a polyhydroxyhydrocarbyl having a linear
hydrocarbyl chain with at least 3 hydroxyls directly connected to the
chain, or an alkoxylated derivative (preferably ethoxylated or
propoxylated) thereof. Z2 preferably will be derived from a reducing
sugar in a reductive ~min~tion reaction; more preferably Z2 is a glycityl.
Suitable reducing sugars include glucose, fructose, maltose, lactose,
galactose, mannose, and xylose. As raw materials, high dextrose corn
syrup, high fructose corn syrup, and high maltose corn syrup can be
ili~e~ as well as the individual sugars listed above. These corn syrups
may yield a mix of sugar components for Z2- It should be understood
that it is by no means intended to exclude other suitable raw materials.
Z2 prefeldbly will be selected from the group consisting of-
CH2(CHOH)n-CH20H,-CH(CH20H)-(CHOH)nl-CH20H,-CH2-
(CHOH)2(CHOR')(CHOH)-CH20H, where n is an integer from 3 to 5,
inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and
alkoxylated derivatives thereof. Most preferred are glycityls wherein n is
4, particularly-CH2-(CHOH)4-CH20H.
The most preferred polyhydroxy fatty acid amide has the formula
Rg(CO)N(CH3)CH2(CHOH)4CH20H wherein R8 is a C11-C17 straight
chain alkyl or alkenyl group.
Suitable glyceryl fatty ester surfactants include polyethyleneglycol
derivatives of glyceryl cocoate, glyceryl caproate, glyceryl caprylate,
glyceryl tallowate, glyceryl p~lm~te, glyceryl stearate, glyceryl laurate,
glyceryl oleate, glyceryl ricinoleate, and glyceryl fatty esters derived
from triglycerides, such as palm oil, almond oil, and corn oil, preferably
glyceryl tallowate and glyceryl cocoate.
Suitable surfactants of this class are commercially available from
Sherex Chemical Co. (Dublin, Ohio, USA) under their Varonic LI line of
surfactants. These include, for example, Varonic LI 2 (PEG 28 glyceryl
WO 94/17166 PCT/US94/00354~
~ 33~3 12
tallowate), Varonic LI 420 (PEG 200 glyceryl tallowate), and Varonic LI
63 and 67 (PEG 30 and PEG 80 glyceryl cocoates), and from Croda Inc.
(New York, USA) under their Crovol line of materials, such as Crovol A-
40 (PEG 20 almond glyceride), Crovol A-70 (PEG 60 almond glyceride),
Crovol M~0 (PEG 20 maize glyceride), Crovol M-70 (PEG 60 maize
glyceride), Crovol PK~0 (PEG 12 palm kernel glyceride), and Crovol
PK-70 (PEG 45 palm kernel glyceride). Especially preferred are
monotallowate and cocoate fatty ester derivatives of polyethylene glycol,
or mixtures thereof, particlllarly materials such as PEG 82 glyceryl
monotallowate and PEG 30 glyceryl cocoate, and mixtures thereof. Also
especially preferred herein is PEG (6) capric/caprylic glyceride (Softigen
767).
The compositions herein preferably also contain from about 0.1%
to about 20%, more preferably from about 0.1% to about 10%, and
especially from about 1% to about 8 % of a betaine surfactant. Betaine
surfactants suitable for inclusion in the composition of the invention
include alkyl betaines of the formula RsR6R7N+(CH2)nM (VIII) and
amido betaines of the formula (IX)
16
R5CO (CH2 ) m I (CH2 ) nM
R7
wherein Rs is C12-C22 alkyl or alkenyl, R6 and R7 are independently
Cl-C3 alkyl, M is H, alkali metal, ~Ik~line earth metal, ammonium or
~lk~nolammonium, and n, m are each numbers from 1 to 4. Preferred
betaines include cocoamidopropyldimethylcarboxymethyl betaine and
lauryl~mir~opropyldimethylcarboxymethyl betaine and Tego betaine.
The compositions of the invention also contain from about 0.1% to
about 8% preferably from about 0.5% to about 6%, and especially from
about 1.5% to about 5 % by weight of saturated acyl fatty acids having a
weight average chain length of from 10 to 18, preferably from 12 to 16
carbon atoms. Highly preferred is myristic acid. The fatty acid is
valuable both from the viewpoint of providing emolliency benefits and
,~WO 94/17166 . 2 1 ~ ~ 3 1 ~ PCT/US94/00354
also in combination with the citrate for controlling the viscosity of the
final composition.
The compositions of the invention preferably also contain a cationic
or nonionic polymeric skin or hair conditioning agent at a level from
about 0.01% to about 5%, preferably from about 0.04% to about 2% and
especially from about 0.05 % to about 1% . The polymer is found to be
valuable for enhancing the cre~miness and quality of the foam as well as
providing a hair or skin conditioning utility. In addition to the above the
polymer is found to be valuable for enhancing the mil~lness of the product
via mitigating the effects of harsher surfactant moieties.
Suitable polymers are high molecular weight materials (mass-
average molecular weight determined, for instance, by light scattering,
being generally from about 2,000 to about 3,000,000, preferably from
about 5,000 to about 1,000,000).
Useful polymers are the cationic, nonionic, amphoteric, and anionic
polymers useful in the cosmetic field. Preferred are cationic andl nonionic
polymers used in the cosmetic fields as hair or skin conditioning agents.
Representative classes of polymers include cationic and nonionic
polysaccharides; cationic and nonionic homopolymers and copolymers
derived from acrylic and/or methacrylic acid; cationic and nonionic
cellulose resins; cationic copolymers of ~limetllyldiallylammonium
chloride and acrylic acid; cationic homopolymers of
dimethyldiallylammonium chloride; cationic polyalkylene and
ethoxypolyalkylene imine~; quaternized silicones, and mixtures thereof.
By way of exemplification, cationic polymers suitable for use
herein include cationic guar gums such as hydroxypropyl trimethyl
ammonium guar gum (d.s. of from 0.11 to 0.22) available commercially
under the trade names Jaguar C-14-S(RTM) and Jaguar C-17(RTM) and
also Jaguar C-16(RTM), which contains hydroxypropyl substituents (d.s.
of from 0.8-1.1) in addition to the above-specified cationic groups, and
quaternized cellulose ethers available commercially under the trade names
Ucare Polymer JR and Celquat. Other suitable cationic polymers are
WO 94/17166 ~3, 14 PCT/US94/00354~
homopolymers of dimethyldiallyl~mmonium chloride available
commercially under the trade name Merquat 100, copolymers of dimethyl
aminoethylmethacrylate and acryl~mi(ie, copolymers of
dimethyldiallylannmonium chloride and acryl~mitle, available
commercially under the trade names Merquat 550 and Merquat S,
quaternized vinyl pyrrolidone acrylate or methacrylate copolymers of
amino alcohol available commercially under the trade name Gafquat, and
polyalkylenetmines such as polyethylenimine and ethoxylated
polyethylenimine.
The viscosity of the ~lnal composition (Brookfield RVT, Helipath,
Spindle T-B, 5 rpm, 25C, 1 min) is preferably in the range of from
about 10,000 to about 40,000 cps, more preferably from about 20,000 to
about 30,000 cps and a yield point (shear skess at zero shear rate) of at
least 50 dynes/cm2, preferably at least 100 dynes/cm2 (Brookfield RVT,
Spindle CP52, Plate Code A, 25C). Preferred compositions have non-
Newtonian viscosity characteristics. In highly preferred embo~im~nts,
the composition of the invention also display a shear stress versus
temperature profile such that (S4s-Ss)/Ss is less than about 0.4,
preferably less than about 0.2, and more preferably less than about 0.1,
where St is the shear stress in dynes/cm2 at temperature t(C) and at a
shear rate of 500 sec~1 (13rookfield RVT, Spindle CP52, Plate Code A).
Another essenti~l component of the compositions of the invention is
citric acid or water soluble citrate salt or mixtures thereof, especially Na,
K, NH4 salts, at a level from about 1.5% to about 10% by weight
preferably from about 2% to about 8% by weight, most preferably from
about 2.5% to about 6% by weight. Citrate is important for providing
improved physical and viscosity characteristics in combination with the oil
and fatty acid components.
It is a feature of the compositions of the invention that the particular
combination of ingredients employed therein give excellent stability even
in the presence of fatty acids which can display cryst~llis~tion
characteristics. Furthermore it is noted that this excellent stability is
~WO 94/17166 ~ 5~ 3 I 3 PCT/US94100354
observed even in the absence of known stabilising agents/viscosity
modifiers.
The cleansing compositions can optionally include a hair or skin
moisturizer which is soluble in the cleansing composition matrix. The
preferred level of moisturizer is from about 0.5% to about 20% by
weight. In preferred embodiments, the moisturizer is selected from:
1. water-soluble liquid polyols;
2. essential amino acid compounds found naturally occurring in
the stratum corneum of the skin; and
3. water-soluble nonpolyol nonocclusives and mixtures thereof.
Some examples of more preferred nonocclusive moisturizers are
glycerine, polyethylene glycol, propylene glycol, sorbitol, polyethylene
glycol and propylene glycol ethers of methyl glucose (e.g. methyl glucam-
20), polyethylene glycol and propylene glycol ethers of lanolin alcohol
(e.g. Solulan-75), sodium pyrrolidone carboxylic acid, lactic acid, urea,
L-proline, gl~ni~line, pyrrolidone, hydrolyzed protein and other collagen-
derived proteins, aloe vera gel and acet~mi~le MEA and mixtures thereof.
Of the above, glycerine is highly p,efelred.
An additional optional component of the composition of the
invention is an adduct prepared from vegetable oils cont~inin~ non-
conj~ qte~ polyllnc~hlrated fatty acid esters which are conjll~t~l and
el~i-iini7e-1 and then modified via Diels-Alder addition with a member of
the goup concicting of acrylic acid, fumaric acid and maleic anhydride.
The vegetable oil adduct preferably has the general formula (X).
fH2O (CO) R3
fHo ( co) (CH2 ) y ~ (CH2 ) XCH3
CH2O (CO) R4 Zl Zl
wherein ~, y are integers of from 3 to 9, R3 and R4 are independantly
selected from saturated and llnc~ rated C7-C22 hydrocarbyl, each Z
WO 94/17166 2~3~ 16 PCTIUS94/00354~
being CO2M and wherein M is H, or a salt forming cation, preferably
~lk~limetal, ammonium or alkanol ammonium. The adducts and their
preparation are described in US-A-4740367, the adducts being marketed
under the trade name` Ceraphyl GA (Van Dyke). The vegetable oil adduct
is preferably added from about 0.5 % to about 5 %, preferably from about
1% to about 4% by weight of the composition.
A number of further additional optional materials can be added to
the cle~n~in~ compositions. Such materials include proteins and
polypeptides and derivatives thereof; water-soluble or solubilizable
preservatives such as DMDM Hydantoin, Germall 115, methyl, ethyl,
propyl and butyl esters of hydroxybenzoic acid, EDTA, Euxyl (RTM)
K400, Bronopol (2-bromo-2-nitropropane-1,3-diol), sodium benzoate and
2-phenoxyethanol; other moisturizing agents such as hyaluronic acid,
chitin, and starch-grafted sodium polyacrylates such as Sanwet (RTM)
IM-1000, IM-1500 and IM-2500 available from Celanese Superabsorbent
Materials, Portsmith, VA, USA and described in US-A~,076,663;
solvents such as hexylene glycol and propylene glycol; anti-bacterial
agents such as Oxeco (phenoxy isopropanol); low temperature phase
modifiers such as ammonium ion sources (e.g. NH4 Cl); viscosity control
agents such as m~nesium sulfate and other electrolytes; colouring agents;
pearlescers and opacifiers such as ethylene glycol ~licte~-ate, TiO2 and
TiO2-coated mica; perfumes and perfume solubilizers etc; zeolites such as
Valfor BV400 and derivatives thereof; and Ca2+/Mg2+ sequestrants
such as polycarboxylates, aminopolycarboxylate, polyphosphates,
polyphosphonates, aminopolyphosphonates and gluconates etc. Water is
also present at a level preferably of from about 45% to about 92%
prefe.~bly at least about 60% by weight of the compositions herein.
The pH of the compositions is preferably from about 4 to about 8,
more preferably from about 4.5 to about 6.5.
~ WO 94/17166 PCT/US94/00354
17 21~3~13
The invention is illustrated by the following non-limiting examples.
In the examples, all concentrations are on a 100% active basis and
the abbreviations have the following designation:
Amphoteric 1 Empigen CDL 60 - an aqueous mixture of 23.5 %
cocoampho~cet~te(the amphoteric of formula I and/or
IV in which Rl is coconut alkyl, R2 is H, and Z is
CO2Na) and 1.35% cocoamphodiacetate (the
amphoteric of formula I and/or IV in which Rl is
coconut alkyl, R2 is CH2CO2Na and Z is CO2Na).
Amphoteric 2 Sodium N-lauryl-beta-amino-propionate.
Anionic 1 Sodium laureth-2 sl-lf~te
Anionic 2 Magnesium sodium laureth 3.6 sulfate
GA Polyhydroxy fatty acid amide of formula VII in which
R8 is Cll-C17 alkyl, Rg is methyl, and Z2 is
CH2(CHOH)4CH20H
DEA Coconut diethanol~mi~e
MEA Coconut monoethanol~mi~e
Betaine Cocoamidopropylc1imethylcarboxymethyl betaine
Polymer 1 Merquat 550 - Copolymer of acryl~mi~le and
- dimethyldiallyl ammonium chloride, m.wt. 2.5 x 106
(8% solution)
Polymer 2 Polymer JR-400 - hydroxyethylcellulose reacted with
epichlorohydrin and quaternized with trimethyl~mine,
m.wt. 4 x 106
WO 94/17166 PCT/US94/00354_
18
MA Myristic Acid
Ceraphyl GA Maleated Soyabean Oil marketed by Van Dyke
Preservative DMDM Hydantoin
Pearlescer Ethyleneglycoldistearate/eml~lsifier mixture
Oil Soyabean oil
Softigen 767 PEG(6) caprylic/capryl glycerate
Mg Magnesium sulfate heptahydrate
WO 94/17166 21 5 3 3 1 ~ PCT/US94/00354
19
Examples I to VII
The following are personal cleansing compositions in the form of shower
foam products and which are representative of the present invention:
II III IV V VI VII
..,
Arnphoteric 1 7.5 3.0 S.0 S.0 2.5 5.0 5.0
Amphoteric 2 - S.0 3.0 - S.0
Anionic 1 2.5 - 6.0 4.0 7.5 10.0 10.0
Anionic 2 S.0 9.0 4.0 6.0
GA - 1.0 - 2.0 2.0 - 2.5
DEA 3.0 1.0 - 2.0 1.0 3.0
MEA - - - - - - 3.0
Betaine - 2.0 2.0 1.0 2.5 2.5
Polymer 1 - 0.1 0.2 - 0.1 0.2
Polymer 2 0.2 0.1 - 0.2 0.1 - 0.2
Softigen 767 - - - - - 2.0 1.0
M~ 4.0 2.0 l.S 1.0 2.0 2.0 2.0
Ceraphyl GA 2.0 1.0 - - - 2.0 1.0
Oil 8.0 12.0 9.0 12.0 8.0 10.0 1 1.0
Preservative 0.15 0. lS 0.15 0.15 0.15 0.2 0.2
Pearlescer O.S - - 1.0 1.0 2.0 1.0
WO 94/17166 PCTIUS94/00354
33~3 20
II III IV V VI VII
Perfume 1.0 1.0 1.0 1.0 1.0 1.0 1.0
Glycerine - - - - - - 3.0
Mg 1.0 - - - 2.0
Sodium Citrate2.0 3.0 2.0 5.0 2.0 4.0 3.0
Water to 100
~ wo 94/17166 ~ ~ ~ 3 .~ 1 ~ PCT/US94tO0354
Compositions I to VII are prepared by forming a surfactant phase A
cont~inin~ a portion of the water, the anionic and amphoteric surfactants
and the rem~inin~ water-soluble, oil-insoluble ingredients, forming an oil
phase B cont~ining the MA, DEA, Softigen and oil, admixing B with A at
about 40-70C, cooling to ambient temperature, then ~ in~ the
rem~inin~ water, preservative and perfume. The average particle size of
the emulsion droplets is about S micron. (Malvern Series 2600 laser
diffraction). The compositions have a viscosity (Brookfield RVT,
Helipath, Spindle TB, 5 rmp, 25C, lmin) in the range from 10,000 to
40,000 cps and a yield point of at least 50 dynes/cm2 (13rookfield RVT,
Spindle CP52, Plate Code A, 25).
The cle~n~in~ products demonstrate excellent physical stability and
viscosity characteristics across temperature in addition to good lathering,
rinsibility and conditioning benefits.
