Note: Descriptions are shown in the official language in which they were submitted.
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STYLING SHAMPOO COMPOSIT10NS WHICH DELIVER IMPROVED
HAIR CURL RETENTION AND HAIR FEEL
FIELD OF THE INVENTION
The present invention relates to hair styling shampoo compositions which
provide improved
styling performance and improved hair feel. More particularly, the present
invention relates to styling
shampoo compositions which contain a detersive surfactant component and a hair
styling polymer. The
compositions, once applied to hair, exhibit a Hair Feel Index (HFI) of at
least 0.65 and a Curl Retention
Value (CRV) of at least 70.
BACKGROUND OF THE INVENTION
Many hair shampoo compositions provide acceptable cleaning but provide little
or no styling
benefiu, e.g. body, hold, stiffness. To realize such benefits, separate
cleaning and styling products are
often used.
Recently, hair shampoo compositions have been developed which can provide
cleaning and styling
performance from a single product. Many of these products contain styling
polymers in a compatible
shampoo base. Three different types of styling polymers are used to deliver
styling performance:
dispersible polymers, latex polymers, and hydrophobic styling polymers
dispersed in a hydrophobic
volatile carrier.
The first type of styling polymer is a polymer which can be dispersed in the
aqueous shampoo
matrix. This dispersible styling polymer may form a complex, or coacervate
phase, with the detersive
surfactant component in the shampoo or form a coacervate phase upon dilution.
Upon dilution, the
coacervate phase deposits on the hair. As the hair dries, the dispersible
styling polymer entrapped in the
coacervate delivers style achievement and style retention performance to the
hair. Unfortunately, these
dispersible styling polymers are very similar, if not identical, to the
conditioning polymers used in 2-in-1
shampoo applications. As a result, when sufficient quantities are used to
deliver styling performance, the
resulting hair feel profile is unacceptable. The dispersible styling polymers
have no inherent adhesive
properties, consequently so much coacervate phase needs to be deposited on the
hair to give styling
performance that, after repeated usage, the hair is left overconditioned,
coated, and dirty feeling.
The second type of styling polymer is a latex polymer. The latex polymer is in
the form of a
colloidal suspension of polymer particles in the aqueous shampoo matrix. In
order to achieve adhesion
between hair fibers, the glass transition temperature, or Tg, of the latex
styling polymer must be
significantly below room temperature. As a result, the latex styling polymers
that give good styling
performance have unacceptable hair feel which can be characterized as sticky
and coated.
The third type of styling polymer is an adhesive, hydrophobic styling polymer.
To prepare a
styling shampoo with a hydrophobic styling polymer, the styling polymer is
fast dissolved in a volatile,
water-insoluble carrier and then incorporated into the shampoo base. The water
insoluble carrier thereafter
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helps disperse the hydrophobic styling polymer in the shampoo composition, and
also helps enhance
spreading of the hydrophobic styling polymer onto hair such that the polymer
sets and forms welds
between hair fibers. The enhanced spreading of the styling polymer onto the
hair results in improved
styling performance from the shampoo composition.
One method for further improving styling polymer deposition from a shampoo,
utilizing either type
of styling polymer, involves the use of cationic deposition polymers. These
cationic deposition polymers
improve the deposition efficiency of the styling polymers, which in turn also
improves styling
performance. The improved deposition from the cationic polymer can also allow
for reduction of the
amount of styling polymer formulated into the shampoo composition, thus
reducing raw material costs.
The problem has been that excessive amounts of such deposition polymers can
result in undesirably coated
or oily wet hair feel, and can cause the hair when dry to feel dirty and have
less body, less fullness.
Therefore, a need exists for styling shampoo compositions which provide good
style achievement
and style retention without the disadvantages of overconditioning, coated, or
dirty feeling compositions.
Surprisingly, the present invention provides hair styling shampoo compositions
having good styling
performance without being overconditioning, coated, or dirty feeling. The
resulting hair styles obtained
from using these compositions hold up well under the common stress conditions.
Importantly, such
compositions provide the benefit of allowing the user to achieve the desired
style without separate style
achievement products, such as mousses or gels, or to supplement their current
style achievement products
to more easily achieve the desired style. The styling compositions of the
present invention leave the hair
both feeling and looking natural. Also, these produce do not have the
disadvantage of causing the hair to
quickly resoil.
It has been found in the present invention that compositions having certain
properties, as defined
by a Hair Feel Index (HFI) and a Curl Retention Value (CRV), are particularly
useful for providing strong
styling performance in combination with good hair feel. 'The hair styling
compositions, when evaluated
while the hair is still wet, exhibit a Hair Feel Index (HFI) of at least 0.65
and a Curl Retention Value
(CRV) of at least 70. The compositions of the present invention provide the
recited benefits by utilizing a
hair styling polymer.
In view of the foregoing, it is therefore an object of this invention to
provide styling shampoo
compositions that provide good styling performance without unacceptable hair
feel. It is a further object
of this invention is to provide styling shampoo compositions containing a
detersive surfactant component
in combination with a styling polymer. It is another object of this invention
to provide methods for
evaluating styling performance and hair feel.
SUMMARY OF THE INVENTION
The present invention relates to sryfing shampoo compositions which comprise
from about 5°~° to
about 50% by weight of a surfactant selected from the group consisting of
anionic surfactants, zwitterionic
or amphoteric surfactants, and combinations thereof; from about 0.1% to about
10% by weight of a hair
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styling polymer: and from about 40% to about 94.9% by weight of water, wherein
the composition is
characterized by providing a Hair Feel Index (HFI) of at least 0.65 and a Curl
Retention Value (CRV) of at
least 70.
DETAILED DESCRIPTION OF THE INVENTION
The shampoo compositions of the present invention can comprise, consist of, or
consist
essentially of the essential elements and limitations of the invention
described herein, as well any of the
additional or optional ingredients, components, or limitations described
herein.
As used herein, the term "water-insoluble" refers to any material that has a
solubility in water at
25°C of less than about 0.5%, preferably less than about 0.3%, even
more preferably less than about 0.2%
by weight.
As used herein, the symbol " > " means greater than or equal to.
All percentages, parts and ratios are based on the total weight of the shampoo
compositions-of the
present invention, unless otherwise specified. All such weights as they
pertain to listed ingredients are
based on the active level and, therefore, do not include carriers or by-
products that may be included in
commercially available materials, unless otherwise specified.
The styling shampoo compositions of the present invention, including the
essential and some
optional components thereof, are described in detail hereinafter.
Detersive Surfactant Comt~onent
The styling shampoo compositions of the present invention comprise an
detersive surfactant
component to provide cleaning performance to the composition. The detersive
surfactant component in
turn comprises anionic detersive surfactant, zwitterionic or amphoteric
detersive surfactant, or a
combination thereof. Such surfactants should be physically and chemically
compatible with the essential
components described herein, or should not otherwise unduly impair product
stability, aesthetics or
performance.
Suitable anionic detersive surfactant components for use in the shampoo
composition herein
include those which are known for use in hair care or other personal care
cleansing compositions. The
concentration of the anionic surfactant component in the shampoo composition
should be sufficient to
provide the desired cleaning and lather performance, and generally range from
about 0.5% to about 50%,
preferably from about 5% to about 30%, more preferably from about 10% to about
25%, even more
preferably from about 12% to about 22%, by weight of the composition.
Preferred anionic surfactants suitable for use in the shampoo compositions are
the alkyl and alkyl
ether sulfates. These materials have the respective formulae ROS03M and
RO(C2H40)xS03M, wherein
R is alkyl or alkenyl of from about 8 to about 18 carbon atoms, x is an
integer having a value of from 1 to
10, and M is a canon such as ammonium, alkanolamines, such as triethanolamine,
monovaient metals,
such as sodium and potassium, and polyvalent metal canons, such as magnesium,
and calcium. Solubility
of the surfactant will depend upon the particular anionic detersive
surfactants and cations chosen.
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Preferably, R has from about 8 to about 18 carbon atoms, more preferably from
about I 0 to about
16 carbon atoms, even vmore preferably from about I2 to about 14 carbon atoms,
in both the alkyl and
alkyl ether sulfates. The alkyl ether sulfates are typically made as
condensation products of ethylene oxide
and monohydric alcohols having from about 8 to about 24 carbon atoms. The
alcohols can be synthetic or
they can be derived from fats, e.g., coconut oil, palm kernel oil, tallow.
Lauryl alcohol and straight chain
alcohols derived from coconut oil or palm kernel oil are preferred. Such
alcohols are reacted with between
about 0 and about 10, preferably from about 2 to about 5, more preferably
about 3, molar proportions of
ethylene oxide, and the resulting mixture of molecular species having, for
example, an average of 3 moles
of ethylene oxide per mole of alcohol, is sulfated and neutralized.
Specific non limiting examples of alkyd ether sulfates which may be used in
the shampoo
compositions of the present invention include sodium and ammonium salts of
coconut alkyl triethylene
glycol ether sulfate, tallow alkyl triethylene glycol ether sulfate, and
tallow alkyl hexaoxyethylene sulfate.
Highly preferred alkyl ether sulfates are those comprising a mixture of
individual compounds, wherein the
compounds in the mixture have an average alkyl chain length of from about 10
to about 16 carbon atoms
and an average degree of ethoxylation of from about 1 to about 4 moles of
ethylene oxide.
Other suitable anionic detersive surfactants are the water-soluble salts of
organic, sulfuric acid
reaction products conforming to the formula [ Rl-SOg-M ] where R1 is a
straight or branched chain,
saturated, aliphatic hydrocarbon radical having from about 8 to about 24,
preferably about 10 to about 18,
carbon atoms; and M is a cation described hereinbefore. Non limiting examples
of such detersive
surfactants are the salts of an organic sulfuric acid reaction product of a
hydrocarbon of the methane
series, including iso-, neo-, and n-paraffins, having from about 8 to about 24
carbon atoms, preferably
about 12 to about 18 carbon atoms and a sulfonating agent, e.g., S03, H2S04,
obtained according to
known sulfonation methods, including bleaching and hydrolysis. Preferred are
alkali metal and
ammonium sulfonated C 10 to C 1 g n-paraffins.
Still other suitable anionic detersive surfactants are the reaction products
of fatty acids esterified
with isethionic acid and neutralized with sodium hydroxide where, for example,
the fatty acids are derived
from coconut oil or palm kernel oil; sodium or potassium salts of fatty acid
amides of methyl tauride in
which the fatty acids, for example, are derived from coconut oil or palm
kernel oil. Other similar anionic
surfactants are described in U.S. Patent 2,486,921; U.S. Patent 2,486,922; and
U.S. Patent 2,396,278.
which descriptions are incorporated herein by reference.
Other anionic detersive surfactants suitable for use in the shampoo-
compositions are the
succinnates, examples of which include disodium N-octadecylsulfosuccinnate;
disodium faun 1
sulfosuccinate; diammonium lauryl sulfosuccinate; tetrasodium
N-(1,2-dicarboxyethyl~N-octadecylsulfosuccinnate: diamyl ester of sodium
suffosuccinic acid: dihexvl
ester of sodium sulfosuccinic acid; and dioctyl esters of sodium sulfosuccinic
acid.
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Other suitable anionic detersive surfactants include olefin sulfonates having
about 10 to about 24
carbon atoms. In this c6ntext, the term "olefin sulfonates" refers to
compounds which can be produced by
the sulfonation of alpha-olefins by means of uncomplexed sulfur trioxide,
followed by neutralization of
the acid reaction mixture in conditions such that any sulfones which have been
formed in the reaction are
hydrolyzed to give the corresponding hydroxy-alkanesulfonates. The sulfur
trioxide can be liquid or
gaseous, and is usually, but not necessarily, diluted by inert diluents, for
example by liquid SO~,
chlorinated hydrocarbons, etc., when used in the liquid form, or by air,
nitrogen, gaseous 502, etc., when
used in the gaseous form. The alpha-olefins from which the olefin sulfonates
are derived are mono-olefins
having from about 10 to about 24 carbon atoms, preferably from about 12 to
about 16 carbon atoms.
Preferably, they are straight chain olefins. In addition to the true alkene
sulfonates and a proportion of
hydroxy-alkanesulfonates, the olefin sulfonates can contain minor amounts of
other materials, such as
alkene disulfonates depending upon the reaction conditions, proportion of
reactants, the nature of the
starting olefins and impurities in the olefin stock and side reactions during
the suifonation process. A non
limiting example of such an alpha-olefin sulfonate mixture is described in
U.S. Patent 3,332,880, which
description is incorporated herein by reference.
Another class of anionic detersive surfactants suitable for use in the shampoo
compositions are
the beta-alkyloxy alkane sulfonates. These surfactants conform to the formula
ORS H
R' S03M
H H
where R1 is a straight chain alkyl group having from about 6 to about 20
carbon atoms, R2 is a lower alkyl
group having from about 1 to about 3 carbon atoms, preferably I carbon atom,
and M is a water-soluble
canon as described hereinbefore.
Preferred anionic detersive surfactants for use in the shampoo compositions
include ammonium
lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate,
triethylamine laureth sulfate,
triethanolamine lauryl sulfate, triethanolamine laureth sulfate,
monoethanolamine lauryl sulfate,
monoethanolamine iaureth sulfate, diethanolamine lauryl sulfate,
diethanolamine laureth sulfate, lauric
monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate,
potassium lauryl sulfate,
potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl
sarcosinate, lauryl sarcosine, cocoyl
sarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl
sulfate, sodium lauroyl
sulfate, potassium cocoyl sulfate, potassium lauryl sulfate, triethanolamine
lauryl sulfate, triethanolamine
lauryl sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauryl
sulfate, sodium tridecyl
benzene sulfonate, sodium dodecyl benzene sulfonate, and combinations thereof.
Suitable amphoteric or zwitterionic detersive surfactants for use in the
shampoo composition
herein include those which are known for use in hair care or other personal
care cleansing. Concentration
of such amphoteric detersive surfactants preferably ranges from about 0.5 % to
about 20%, preferably
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6
from about 1% to about 10%, by weight of the composition. Non limiting
examples of suitable
zwitterionic or amphoteric surfactants are described in U.S. Patents 5,104,646
(Bolich Jr. et al.), U.S.
Patent 5,106,609 (Bolich Jr. et al.),
Amphoteric detersive surfactants suitable for use in the shampoo composition
are well known in
the art, and include those surfactants broadly described as derivatives of
aliphatic secondary and tertiary
amines in which the aliphatic radical 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 water
solubilizing group such as carboxy, sulfonate, sulfate. phosphate, or
phosphonate. Preferred amphoteric
detersive surfactants for use in the present invention include
cocoamphoacetate, cocoamphodiacetate,
lauroamphoacetate, lauroamphodiacetate, and mixtures thereof.
Zwinerionic detersive surfactants suitable for use in the shampoo composition
are well known in
the art, and include those surfactants 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 such as carboxy, sulfonate, sulfate, phosphate or
phosphonate. Zwitterionics
such as betaines are preferred.
The shampoo compositions of the present invention may further comprise
additional surfactants
for use in combination with the anionic detersive surfactant component
described hereinbefore. Suitable
optional surfactants include nonionic surfactants. Any such surfactant known
in the art for use in hair or
personal care products may be used, provided that the optional additional
surfactant is also chemically and
physically compatible with the essential components of the shampoo
composition, or does not otherwise
unduly impair product performance, aesthetics or stability. The concentration
of the optional additional
surfactants in the shampoo composition may vary with the cleansing or lather
performance desired, the
optional surfactant selected, the desired product concentration, the presence
of other components in the
composition, and other factors well known in the an.
Non limiting examples of other anionic, zwitterionic, amphoteric or optional
additional
surfactants suitable for use in the shampoo compositions are described in
McCutcheon's, Emulsifiers and
Detergents, 1989 Annual, published by M. C. Publishing Co., and U.S. Patent
3,929,678, U.S. Patent
2,658,072; U.S. Patent 2,438,091; U.S. Patent 2.528,378,
StvIinQ ~olvmer
The shampoo compositions of the present invention comprise a hair styling
polymer.
concentrations of which range from about 0.1% to about 10%, preferably from
about 0.3% to about 7°,0.
more preferably from about 0.5% to about 5%, by weight of the composition.
These styling polymers
provide the shampoo composition of the present invention with hair styling
perfotlrtance by providing
polymeric deposits on the hair after application from a shampoo composition.
i
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Many such polymers are known in the art, including dispersible and water-
insoluble organic
polymers and water-insoluble silicone-grafted polymers, all of which are
suitable for use in the shampoo
composition herein provided that they also have the requisite features or
characteristics described
hereinafter. Such polymers can be made by conventional or otherwise known
polymerization techniques
well known in the art, an example of which includes free radical
polymerization.
Examples of suitable oreanic and silicone grafted polymers for use in the
shampoo composition
of the present invention are described in greater detail hereinafter. Examples
of dispersible polymers are
disclosed in, for example, U.S. Patent 5,391.368, which descriptions are
incorporated by reference herein.
Examples of latex polymers are disclosed in, for example, U.S. Patent
4,710,374.
1. Organic styling polymer
The hair styling polymers suitable for use in the shampoo composition of the
present invention
include organic hair styling polymers well known in the art. The organic
styling polymers may be
homopolvmers, copolymers, terpolymers or other higher polymers, but must
comprise one or more
polymerizable hydrophobic monomers to thus render the resulting styling
polymer hydrophobic and
water-insoluble as defined herein. The styling polymers may therefore further
comprise other water
soluble, hydrophillic monomers provided that the resulting styling polymers
have the requisite
hydrophobicity and water insolubility.
As used herein, the term "hydrophobic monomer" refers to polymerizable organic
monomers that
can form with like monomers a water-insoluble homopolvmer, and the term
"hydrophilic monomer" refers
to polvmerizable organic monomers that can form with like monomers a water-
soluble homopolymer.
The organic styling polymers preferably have a weight average molecular weight
of at least about
20,000, preferably greater than about 25,000, more preferably greater than
about 30,000, most preferably
greater than about 35,000. There is no upper limit for molecular weight except
that which limits
applicability of the invention for practical reasons, such a_s processing,
aesthetic characteristics,
fotTrtulateabiliry; etc. In general, the weight average molecular weight will
be less than about 10,000.000,
more generally less than about 5,000,000, and typically less than about
2.000,000. Preferably, the weight
average molecular weight will be between about 20.000 and about 2,000,000,
more preferably between
about 30,000 and about 1,000,000, and most preferably between about 40,000 and
about 500.000.
The organic styling polymers also preferably have a glass transition
temperature (Tg) or
crystalline melting point (Tm) of at least about -20°C, preferably from
about 20°C to about 80°C, more
preferably from about 20°C to about 60°C. Styling polymers
having these Tg or Tm values form styling
films on hair that are not unduly sticky or tacky to the touch. As used
herein, the abbreviation "Tg" refers
to the glass transition temperature of the backbone of the polymer, and the
abbreviation "Tm" refers to the
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crystalline melting point of the backbone, if such a transition exists for a
given polymer. Preferably, both
the Tg and the Tm, if any, are within the ranges recited hereinabove.
The organic styling polymers are carbon chains derived from polymerization of
hydrophobic
monomers such as ethylenically unsaturated monomers, cellulosic chains or
other carbohydrate-derived
polymeric chains. The backbone may comprise ether groups, ester groups, amide
groups, urethanes,
combinations thereof, and the like.
The organic styling polymers may further comprise one or more hydrophilic
monomers in
combination with the hydrophobic monomers described herein, provided that the
resulting styling polymer
has the requisite hydrophobic character and water-insolubility. Suitable
hydrophilic monomers include,
but are not limited to, acrylic acid, methacrylic acid, N,N-
dimethylacrylamide, dimethyl aminoethyl
methacrylate, quaternized dimethylaminoethyi methacrylate, methacrylamide, N-t-
butyl acrylamide,
malefic acid, malefic anhydride and its half esters, crotonic acid, itaconic
acid, acrylamide, acrylate
alcohols, hydroxyethyi methacrylate, diallyldimethyl ammonium chloride, vinyl
ethers (such as methyl
vinyl ether), maleimides, vinyl pyridine, vinyl imidazole, other polar vinyl
heterocyciics, styrene
suifonate, allyl alcohol, vinyl alcohol (such as that produced by the
hydrolysis of vinyl acetate after
polymerization), salts of any acids and amines listed above, and mixtures
thereof. Preferred hydrophillic
monomers include acrylic acid, N,N-dimethyl acrylamide, dimethylaminoethyl
methacrylate, quaternized
dimethyl aminoethyi methacrylate, vinyl pyrrolidone, salts of acids and amines
listed above, and
combinations thereof.
Suitable hydrophobic monomers for use in the organic styling polymer include,
but are not
limited to, acrylic or methacrylic acid esters of C1-Clg alcohols, such as
methanol, ethanol, methoxy
ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol, 2-
pentanol, 3-pentanol, 2-
methyl-1-butanol, 1-methyl-I-butanol, 3-methyl-1-butanol, 1-methyl-1-pentanol,
2-methyl-1-pentanol, 3-
methyl-1-pentanol, t-butanol{2-methyl-2-propanol), cyclohexanol, neodecanol, 2-
ethyl-1-butanol, 3-
heptanol, benzyl alcohol, 2-octanol, 6-methyl-1-heptanol, 2-ethyl-1-hexanol,
3,5-dimethyl-1-hexanol,
3,5,5-tri methyl-1-hexanol, 1-decanol, l-dodecanol, 1-hexadecanol, 1-octa
decanol, and the like, the
alcohols having from about 1 to about 18 carbon atoms, preferably from about 1
to about 12 carbon atoms;
styrene; polystyrene macromer; vinyl acetate; vinyl chloride; vinylidene
chloride; vinyl propionate; alpha-
methylstyrene; t-butylstyrene; butadiene; cyclohexadiene; ethylene; propylene;
vinyl toluene; and mixtures
thereof. Preferred hydrophobic monomers include n-butyl methacryiate, isobutyl
methacrylate, t-butyl
acrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, methyl
metltacrylate, vinyl acetate, and mixtures
thereof, more preferably t-butyl acrylate, t-butyl methacrylate, or
combinations thereof. Surprisingly, it
has been found that conventional styling polymers consisting of copolymers of
vinyl pyrrolidone and vinyl
acetate do not exhibit the curl retention benefits required of the present
invention.
The styling polymers for use in the shampoo composition preferably comprise
from about 20% to
100%, more preferably from about 50% to about 100%, even more preferably from
about 60% to about
CA 02317703 2002-10-03
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100%, by weight of the hydrophobic monomers, and may funher comprise from zero
to about 80% by
weight of hydrophilic monomers. The panicular selection and combination of
monomers for
incorporation into the styling polymer will help determine its formulational
properties. By appropriate
selection and combination of, for example, hydrophilic and hydrophobic
monomers, the styling polymer
can be optimized for physical and chemical compatibility with the selected
styling polymer solvent
described hereinafter and other components of the shampoo composition. The
selected monomer
composition of the organic styling polymer must, however, render the styling
polymer water-insoluble but
soluble in the selected styling polymer solvent described hereinafter. In this
context, the organic styling
polymer is soluble in the styling polymer solvent if the organic polymer is
solubilized in the solvent at 25°
C at the polymer and solvent concentrations of the shampoo formulation
selected. However, a solution of
the organic styling polymer and styling polymer solvent may be heated to speed
up solubility of the styling
polymer in the styling polymer solvent. Such styling polymer and solvent
formulation, including the
selection of monomers for use in the styling polymer, to achieve the desired
solubility is well within the
skill of one in the art.
Examples of preferred organic styling polymers include r-butyl acrylatel2-
ethylhexyl acrylate
copolymers having a weight/weight ratio of monomers of about 95/S, about
90/10, about 80/20, about
70/30, about 60/40, and about SO/S0; t-butyl acrylate/2-ethylhexyl
methacrylate copolymers having a
weightlweight ratio of monomers of about 95/S, about 90/10, about 80/20, about
70/30, about 60/40, and
about 50/50; r-butyl methacrylate/2-ethylhexyl actylate copolymers having a
weight/weight ratio of
monomers of about 95/5, about 90/10, about 80/20, about 70/30, about 60/40,
and about 50/50; r-butyl
methacrylate/2-ethylhexyl methacrylate copolymers having a weightlweight ratio
of monomers of about
9515, about 90/10, about 80/20, about 70130, about 60/40, and about SO/S0; r-
butyl ethacrylate/2-
ethylhexyf methacrylate copolymers having a weight/weight ratio of monomers of
about 95/5, about
90/10, about 80/20, about 70/30, about 60/40, and mixtures thereof.
Especially preferred polymers are t-butyl acrylate/Z-ethylhexyl methacrylate
copolymers having a
weight/weight ratio of monomers of about 9S/S, about 90/10, about 80/20, about
70/30, about 60/40, and
about SO/S0; t-butyl methacrylate/2-ethylhexyl methacrylate copolymers having
a weight/weight ratio of
monomers of about 95/S, about 90/10, about 80/20, about 70130, about 60140,
and about SO/S0; and
mixtures thereof.
Examples of other suitable styling polymers are described in Lt.S. Patent
4,272,511, to Papantoniou
et al., issued June 9, 1981; U.S. Patent 5,672,576, to Behrens et al., issued
September 30, 1997; and U.S.
Patent 4,196,190, to Gehman et al., issued April 1, 1980.
11. Silicone-crafted stvlin~ polymer
Other suitable styling polymers for use in the shampoo composition of the
present invention are
silicone-grafted hair styling resins. These polymers may be used alone or in
combination with the organic
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styling polymers described hereinbefore. Many such polymers suitable for use
in the shampoo
composition herein are known in the art. These polymers are characterized by
polysiloxane moieties
covalently bonded to and pendant from an uncross-linked polymeric carbon-based
backbone.
The backbone of the silicone-grafted polymer is preferably a carbon chain
derived from
polymerization of ethylenically unsaturated monomers, but can also be
cellulosic chains or other
carbohydrate-derived polymeric chains to which polysiloxane moieties are
pendant. The backbone can
also include ether groups, ester groups, amide groups, urethane groups and the
like. The poiysiloxane
moieties can be substituted on the polymer or can be made by co-polymerization
of polysiloxaj~e-
containing polymerizable monomers (e.g. ethylenically unsaturated monomers,
ethers, andlor epoxid. :)
with non-polysiloxane-containing polymerizable monomers. The silicone-grafted
styling polymers
preferably have a weight average molecular weight of at least about 10,000,
preferably greater than about
20,000, more preferably greater than about 35,000, most preferably greater
than about 50,000. The weight
average molecular weight of the silicone-grafted styling polymer is preferably
less than 300,000, more
preferably less than about 250,000, and most preferably less than about
150,000.
The silicone-grafted styling polymers for use in the shampoo composition
comprise "silicone-
containing" (or "polysiloxane-containing") monomers, which form the silicone
macromer pendant from
the backbone, and non-silicone-containing monomers, which form the organic
backbone of the polymer.
Preferred silicone-grafted polymers comprise an organic backbone, preferably a
carbon backbone
derived from ethylenically unsaturated monomers, such as a vinyl polymeric
backbone, and a polysiloxane
macromer (especially preferred are polydialkylsiloxane, most preferably
polydimethylsiloxane) grafted to
the backbone. As used hereinafter, the term "PDMS" refers to
polydimethylsiloxane. The polysiloxane
macromer should have a weight average molecular weight of at least about 500,
preferably from about
1,000 to about 100,000, more preferably from about 2,000 to about 50,000, most
preferably about 5,000 to
about 20,000. Organic backbones contemplated include those that are derived
from polymerizable,
ethylenically unsaturated monomers, including vinyl monomers, and other
condensation monomers (e.g.,
those that polymerize to form polyamides and polyesters), ring-opening
monomers (e.g., ethyl oxazoline
and caprolactone), etc. Also contemplated are backbones based on cellulosic
chains, ether-containing
backbones, etc.
Preferred silicone grafted polymers for use in the shampoo composition
comprise monomer units
derived from: at least one free radically polymerizable ethylenically
unsaturated monomer or monomers
and at least one free radically polymerizable polysiloxane-containing
ethylenically unsaturated monomer
or monomers.
The silicone grafted polymers suitable for use in the shampoo composition
generally comprise
from about 1% to about 50%, by weight, of polysiloxane-containing monomer
units and from about 50%
to about 99% by weight, of non-polysiloxane-containing monomers. The non-
polysiloxane-containing
CA 02317703 2000-07-06
WO 99/3876 PCT/US99/02311
monomer units can be derived from the hydrophilic and/or hydrophobic monomer
units described
hereinbefore.
The styling polymer for use in the shampoo composition can therefore comprise
combinations of
the hydrophobic andlor polysiloxane-containing monomer units described herein,
with or without
hydrophilic comonomers as described herein, provided that the resulting
styling polymer has the requisite
characteristics as described herein.
Suitable polymerizable polysiloxane-containing monomers include, but are not
limited to, those
monomers that conform to the formula:
X(Y)nSi(R)3-mZm
wherein X is an ethylenically unsaturated group copolymerizable with the
hydrophobic monomers
described herein, such as a vinyl group; Y is a divalent linking group; R is a
hydrogen, hydroxyl, lower
alkyl (e.g. CI-C4), aryl, alkaryl, alkoxy, or alkylamino; Z is a monovalent
siloxane polymeric moiety
having a number average molecular weight of at least about 500, which is
essentially unreactive under
copolymerization conditions, and is pendant from the vinyl polymeric backbone
described above; n is 0 or
1; and m is an integer from I to 3. These polymerizable polysiloxane-
containing monomers have a weight
average molecular weight as described above.
A preferred polysiloxane-containing monomer conforms to the formula:
O
II
X-C-O-(CH2)~ (0)p Si(R~~,~
wherein m is l, 2 or 3 (preferably m s 1); p is 0 or l; q is an integer from 2
to 6; RI is hydrogen, hydroxyl,
lower alkyl, alkoxy, alkylamino, aryl, or alkaryl (preferably R I is alkyl); X
conforms to the formula
C H=C-
I I
RZ Rs
wherein R2 is hydrogen or -COOH (preferably R2 is hydrogen); R3 is hydrogen,
methyl or -CH2COOH
(preferably R3 is methyl); Z conforms to the formula:
R5
I
R4 Si
I
Rs
r
wherein R4, R5, and R6 independently are lower alkyl, alkoxy, alkyiamino,
aryl, arylalkyl, hydrogen or
hydroxyl (preferably R4, R5, and R6 are alkyls); and r is an integer of about
5 or higher, preferably about
10 to about 1500 (most preferably r is from about 100 to about 250). Most
preferably, R4, R5, and R6 are
methyl, p=0, and q=3.
Another preferred polysiloxane monomer conforms to either of the following
formulas
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12
X (CHZ)s-Si(R~)3-m-Zm
(R2>n
or
X-CH2-(CHZ)s-Si(R~)3-m-Zrn
wherein: s is an integer from 0 to about 6, preferably 0, 1, or 2, more
preferably 0 or 1; m is an integer
from 1 to 3, preferably 1; R2 is C1-CIO alkyl or C7-CIO alkylaryl, preferably
C1-C6 alkyl or C7-C10
alkylaryl, more preferably C1-C2 alkyl; n is an integer from 0 to 4,
preferably 0 or t, more preferably 0.
The silicone grafted styling polymers suitable for use in the shampoo
composition preferably
comprise from about 50% to about 99%, more preferably from about 60% to about
98%, most preferably
from about 75% to about 95%, by weight of the polymer, of non-silicone
macromer-containing monomer
units, e.g. the total hydrophobic and hydrophilic monomer units described
herein, and from about 1% to
about 50%, preferably from about 2% to about 40%, more preferably from about
5% to about 25%, of
silicone macromer-containing monomer units, e.g. the polysiloxane-containing
monomer units described
herein. The level of hydrophilic monomer units can be from about 0% to about
70%, preferably from
about 0% to about 50%, more preferably from about 0% to about 30%, most
preferably from about 0% to
about I S%; the level of hydrophobic monomer units, can be from 30% to about
99%, preferably from
about 50% to about 98%, more preferably from about 70% to about 95%, most
preferably from about 85%
to about 95%.
Examples of some suitable silicone grafted polymers for use in the shampoo
composition herein
are listed below. Each listed polymer is followed by its monomer composition
as weight part of monomer
used in the synthesis:
(t) t-butylacrylatye/t-butyl-methacrylate/2-ethylhexyi-methacrylate/PDMS
macromer-
20,000 molecular weight macromer 31/27/32110
(ii) t-butylmethacrylate/2-ethylhexyl-methacrylateIPDMS macromer-15,000
molecular
weight macromer 75/10/15
(iii) t-butylmethacrylate/2-ethylhexyl-acrylate/PDMS macromer-10,000 molecular
weight
macromer 6511 SI20
(iv) t-butylacrylate/2-ethylhexyl-acrylate/PDMS macromer-14,000 molecular
weight
macromer 77111 /12
(v) t-butylacrylatel2-ethythexyl-methacrylate/PDMS macromer-13,000 molecular
weight
macromer 81 /9110
Examples of other suitable silicone grafted polymers for use in the shampoo
composition of the
present invention are described in EPO Application 90307528.1, published as
EPO Application 0 408 31 1
CA 02317703 2002-10-03
13
A2 on January 11, 1991, Hayama. et al.; U.S. Patent 5,061.481, issued October
29, 1991, Suzuki et al.;
U.S. Patent 5.106.609. Bolich et al., issued April 21, 1992; U.S. Patent
5,100,658, Bolich et al., issued
March 31. 1992: U.S. Patent 5,100,657, Ansher-Jackson. et al., issued March
31, 1992; U.S. Patent
5,104.646, Bolich et al., issued April 14, 1992; U.S. Serial No. 07/758,319,
Bolich et al. filed August 27,
1991, U.S. Serial No. 07/758,320, Torgerson et al., fled August 27; 1991.
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14
Properties of StyiinQ Shampoo Compositions
The styling shampoo compositions of the present invention exhibit specific
physical properties as
defined by the Hair Feel Index (HFI) and Curl Retention Index (CRV) which are
determined as described
below.
Compositions of the invention are characterized by having an HFI of at least
0.65 and a CRV of
at least 70. Preferred compositions are characterized by having an HFI of at
least 0.70 and a CRV of at
least 75. More preferred compositions are characterized by having an HFI of at
least 0.80 and a CRV of at
least 80.
MethodoloQV for Determining HFI and CRV:
The following applies in determining each value. The hair switches are made by
Advanced
Testing Laboratories (Cincinnati, OH). Also, the silicone containing non-
styling shampoo has the
following formulation:
Com ponent Weight
'/.
Ammonium Laureth-3 15.0
Sulfate
Ammonium Lauryl Sulfate5.0
Glycol Distearate 2.0
Dimethicone 1.5
Fragrance 0.7
Tricetyl Methylmonium0.5
Chloride
Cocamide MEA 0.85
Cetyl Alcohol 0.21
Stearyl Alcohol 0.09
Preservatives 0.3
Monosodium Phosphate0.1
Disodium Phosphate 0.2
Water 73.55
The silicone containing non-styling shampoo is prepared in the following
manner. A premix is
prepared by solubilizing the solids in half of the ammonium laureth-3 sulfate
and enough water such that
the premix is 50% of the finished batch. The target premix temperature is
74°C. Next the premix is
cooled to approximately 38°C. The dimethicone is emulsified as a
separate premix using a portion of the
ammonium laureth-3 sulfate. The dimethicone emulsion and the remaining
components are then added to
the batch with sufficient agitation to ensure a homogeneous composition.
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WO 99/38476 PCT/US99/0231 I
Additionally, all water is 38°C tap water with a grain of 7 to 1 1 and
a flow rate of 5.7 liters per
minute. Also, care is taken to avoid contamination of a given product with
another (e.g., by wearing clean
gloves).
a) Hair Feel Index:
The Hair Fee! Index (HFI) of a treated hair switch is determined by having
panelists evaluate
treated hair switches for two attributes, resistance and roughness, each on a
scale of 0 to 10. For
resistance, 0 is "no resistance" and 10 is "lots of resistance." For
roughness, 0 is "not rough" and 10 is
"extremely rough." The silicone containing non-styling shampoo is identified
as the internal control for
each attribute with an assigned value: 5.75 for resistance and 4.50 for
roughness.
The hair switches used in the procedure are 2 gmI15.25 cm long, flat, and
slightly bleached virgin
brown hair from DeMeo Brothers in New York. Each switch is approximately 3.8
cm wide and is secured
with a 2.5 cm high Plexiglas top.
In preparation for test product application, the switches are clipped together
in pairs and then
wetted with tap water. 2 cc of test product is applied to each pair of
switches and is massaged, or milked,
therein for 30 seconds such that the shampoo is distributed evenly throughout
the switch. Each pair of
switches is then rinsed with water for 30 seconds. The switch pair is then
turned around and another 2 cc
of test product is applied to each pair of switches and is massaged, or
milked, therein for 30 seconds,
followed by another 30 second rinse. This process of two treatments and two
rinses is defined as a cycle.
The switch pair is then unclipped, each individual switch is turned around so
that the sides facing each
other are now on the outside of the switch pair. The switch pair is then
reciipped and a second cycle is
applied. During the last two seconds of the second lather of this cycle, the
switch pair is combed through
once with a beautician's comb. The switch pair is then fumed around and a
third cycle is applied. The
switch pair is then unclipped, quickly rinsed, and then combed through once.
After rinsing, the excess
water is squeezed from each switch by running the index and middle fingers
along the length of the switch
with Earn pressure. The switches are placed on a foil covered tray and then
covered with foil to keep them
wet until the panelist is ready to evaluate them.
In preparation for control shampoo application, the switch pairs receive one
cycle as defined
above. The switch pair is then unclipped, quickly rinsed, and then combed
through once. After rinsing,
the excess water is squeezed from each switch by running the index and middle
fingers along the length of
the switch with firm pressure. The switches are placed on a foil covered tray
and then covered with foil to
!seep them wet until the panelist is ready to evaluate them. A total of 24
switches ase treated for each test
product and the control.
Each panelist receives a tray with a control switch (identified) and two to
three test products. The
test products are randomized to avoid any bias associated with order. The
panelists cleanse their fingertips
with isopropyl alcohol swabs and allow them to dry prior to performing the
evaluation. The control switch
is dipped into a beaker of warm water, the excess water is squeezed from each
switch by running the index
CA 02317703 2000-07-06
WO 99138476 PCT/US99/02311
16
and middle fingers along the length of the switch with moderate pressure, and
clipped to a horizontal bar.
The same procedure is then followed for each test product. Once the switches
are all hung on the bar, the
panelists begin their evaluation. For each attribute, the control is evaluated
first to establish a reference
point for the panelist. The score for the control is pre-recorded on the test
ballot.
First, the switches are evaluated for resistance. Slowly moving the index
finger and middle finger
along the switch, from top to bottom, the panelist feels for the presence of
absence of drag when moving
fingers down the hair switch. Each panelist records the resistance score.
Next, the switches are evaluated
for roughness. Slowly running the thumb and index finger along the switch,
from top to bottom, the
panelist feels for unevenness of the hair tress which would be associated with
brittle or straw-like hair.
Each panelist records the roughness score.
A minimum of twelve panelists evaluate the test product switches. The mean
resistance is
determined by averaging the resistance scores from each panelist for each test
product. The mean
roughness is determined by averaging the roughness scores from each panelist
for each test product. The
Resistance Index (Rel) is defined as the mean resistance score for each test
product indexed to the control
using the assigned resistance score for the control (5.75). The Roughness
Index (Rol) is defined as the
mean roughness score for each test product indexed to the control using the
assigned roughness score for
the control (4.50). The Hair Feel Index (HFI) is then defined by the following
equation:
HFI = (ReI + RoIy2.
b) Curl Retention Valae:
The Curl Retention Value (CRV) is predictive of perceived style/hold benefits
in styling
shampoos by measuring the amount of curl retention over time.
This procedure utilizes curly permed hair switches which are prepared in the
following manner.
First, 4 gm/20.3 cm long, round switches are rinsed with water for 30 seconds
and the excess water is
squeezed from the switch using the first two fingers. Next, 0.5 cc of Perfect
Comb Out waving lotion
(ZOTOS) is applied to the bottom 5 cm of each switch using a syringe. Each
switch is then divided into 3
equal sections. Once an end wrap is placed on the end of each section, each
section is then curled by
starting at the right side of a 0.95 cm diameter straight rod, wrapping the
hair tightly and spirally along the
length of the rod. Using a syringe, 8 cc of waving lotion is applied such that
the entire switch is covered.
The rolled switches are then placed in plastic bag or wrapped in cellophane 2
at a time. After 30 minutes,
the switches are unrolled and checked to see if the desired wave pattern has
been achieved. If not, the
switches are then re-rolled and spot checked every 2 minutes until the desired
wave pattern is achieved,
being careful not to exceed a total of 45 minutes. With the rods still intact,
the switches are then rinsed for
90 seconds and blotted with a paper towel to remove excess water. After blot
drying, 10 cc of 20 volume
peroxide is applied to each rolled switch. Five minutes later the rods are
removed from the switches. The
switches are rinsed with water for 1 minute, and blotted with a paper towel.
Without combing, the
switches are then laid flat on a Plexiglas tray and left to dry in a room at
ambient temperature and relative
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17
humidity. After 2 days, the switches are shampooed with Prell shampoo by
applying 4 cc of Prell
shampoo, lathering with for 30 seconds, rinsing with water for 30 seconds,
applying another 4 cc of Prell
shampoo, lathering for 30 more seconds, and rinsing with water again for 60
seconds. Each switch is
blotted three times with a paper towel.
Next, the various products and control compositions are applied to the
switches. For shampoo,
0.2 cc of shampoo is applied to each switch. The switch is lathered for 30
seconds and then rinsed for 30
seconds. A second 0.2 cc of shampoo is applied and the process is repeated, 30
seconds of lathering
followed by 30 seconds of rinsing. During the lathering, the end of each
switch is brought up to the top of
the switch and scrubbed, hair against hair, to generate lather during the
first 10 seconds. The switch is
milked for the remaining 20 seconds. Upon completion of product application,
each switch is combed
through once with a small tooth beautician's comb and the excess water is
squeezed from each switch by
running the thumb and forefinger along the length of each switch such that the
hair resembles a smooth,
flat ribbon. Four switches are treated per test product and control.
Next, the hair of each switch is curled using a 22 mm diameter, 70 mm tong
'magnetic' roller with
a matching cover. The hair of each switch is curled by starting at the right
side of the roller and wrapping
the hair tightly around the roller, catching the hair ends under the hair
strand as the hair is rolled with
tension spirally up the roller. It is important to use the same amount of
tension when curling all switch
samples in order to ensure like test conditions. Once each switch is rolled,
each roller is placed on end on
a Plexiglas tray in a convection air drying box for 3 hours at approximately
57°C to 60°C and at an
ambient relative humidity. Once drying is complete, the still-rolled switches
are placed in a 27°C/15%
relative humidity room and allowed to cool for about 30 minutes before the
rollers are removed from the
switches.
After cooling, the rollers are removed by carefully unrolling each switch. In
preparation for curl
fall measurements, each curled switch is hung vertically and grouped according
to test product. The initial
length of the curled switch (Lp) is measured from the lowest end of the clip
holding the switch to the end
of the switch. This measurement is taken to the nearest mm using a metric
ruler. The switches are then
placed in a 27°C I80% relative humidity room and the curl lengths are
remeasured at 30 minutes (L30) to
determine the curl fall. The Curl Retention Value (CRV) for a switch is
calculated using the followin'
formula:
CRV - L _ Lø0 x 100%
where L is the original length of the untreated switch; L30 is the length of
the test product or control curl
switch after 30 minutes; and LO is the length of the test product or control
switch at the time of roller
removal.
Optional Comt~onents
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l8
The shampoo compositions of the present invention may further comprise one or
more optional
components known for use in hair care or personal care products, provided that
the optional components
are physically and chemically compatible with the essential components
described herein, or do not
otherwise unduly impair product stability, aesthetics or perfbttrrance.
Individual concentrations of such
optional components may range from about 0.001 % to about 10% by weight of the
shampoo
compositions.
Non limiting examples of optional components for use in the shampoo
composition include anti
dandruff agents, conditioning agents (hydrocarbon oils, fatty esters,
silicones) dyes, nonvolatile solvents or
diluents (water soluble and insoluble), pearlescent aids, foam boosters,
additional surfactants or nonionic
cosurfactants, pediculocides, pH adjusting agents, perfumes, preservatives,
proteins, skin active agents,
sunscreens, vitamins, and viscosity adjusting agents.
The shampoo composition of the present invention preferably further comprises
a water
insoluble, volatile carrier for the hydrophobic styling polymer. 'The carrier
helps disperse the styling
polymer in the shampoo composition, and also helps enhance spreading of the
styling polymer onto hair
such that the polymer sets and forms a thin film onto the surface of the hair
shaft. The optional a water
insoluble, volatile carrier for the hydrophobic styling polymer is described
in more detail hereinafter.
The shampoo composition of the present invention preferably further comprises
select cationic
deposition polymers to improve the deposition efficiency of the styling
polymers, which in tutu also
improves styling performance. These optional cationic deposition polymers are
described in more detail
hereinafter.
The shampoo composition of the present invention preferably further comprises
a select stability
active to enhance the deposition efficiency of the hair styling polymer over
conventional stabilizers,
allowing for more formulation freedom to either lower the cationic deposition
polymer usage level, or to
incorporate new cationic deposition polymers with improved build-up profiles.
These optional select
stability actives are described in more detail hereinaRer.
The shampoo composition of the present invention preferably further comprises
select cationic
materials which act as spreading agents for the styling polymer/volatile
carrier droplets. These optional
cationic spreading agents are described in more detail hereinafter.
The shampoo composition of the present invention also preferably comprises
select polyalkylene
glycols to enhance hair feel and enhance styling performance. These optional
polyalkylene giycols are
described in more detail hereinafter.
The shampoo composition of the present invention also preferably comprises a
silicone hair
conditioning agent to enhance hair feel, especially the soft, silky feel of
dry hair. These optional silicone
hair conditioning agents are described in more detail hereinafter.
The shampoo composition of the present invention also preferably comprises
additional optional
agents which improve the performance and/or aesthetics of the composition.
These materials impact
CA 02317703 2000-07-06
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19
which shampoo components are solubilized by the surfactant component and how
much of each
component is solubilized,'influencing coacervate formation and composition.
These additional agents are
also entrapped in the coacervate, thus impacting styling performance and hair
feel both directly and
indirectly. These additional optional agents are described in more detail
hereinafter.
a) Volatile Carrier for the StvIinQ Pol men
The shampoo composition of the present invention may further comprise a
volatile carrier for
solubilizing the hair styling polymers described hereinbefore. The carrier
helps disperse the hair styling
polymer as water-insoluble fluid particles throughout the shampoo composition,
wherein the dispersed
particles comprise the styling polymer and the volatile carrier. Carriers
suitable for this purpose include
hydrocarbons; ethers, esters, amines, alkyl alcohols, volatile silicone
derivatives and combinations thereof,
many examples of which are well known in the art.
The volatile carrier must be water-insoluble or have a low water solubility.
The selected styling
polymer, however, must also be sufficiently soluble in the selected carrier to
allow dispersion of the hair
styling polymer and solvent combination as a separate, dispersed fluid phase
in the shampoo composition.
The carrier for use in the shampoo composition must also be a volatile
material. In this context,
the team volatile means that the carrier has a boiling point of less than
about 300°C, preferably from about
90°C to about 260°C, more preferably from about 100°C to
about 200°C (at about one atmosphere of
pressure).
The concentration of the volatile carrier in the shampoo composition must be
sufficient to
solubilize the hair styling polymer and disperse it as a separate fluid phase
in the shampoo composition.
Such concentrations generally range from about 0.10% to about 10%, preferably
from about 0.5% to about
8%, most preferably from about 1% to about 6%, by weight of the shampoo
composition, wherein the
weight ratio of styling polymer to cannier is preferably from about 10:90 to
about 70:30, more preferably
from about 20:80 to about 65:35, even more preferably from about 30:70 to
about 60:40. If the weight
ratio of styling polymer to carrier is too low, the lathering performance of
the shampoo composition is
negatively affected. If the ratio of polymer to solvent is too high, the
composition becomes too viscous
and causes difficulty in the dispersion of the styling polymer. The hair
styling agents should have an
average particle diameter in the final shampoo product of from about 0.05 to
about 100 microns, prefer-
ably from about I to about 25 microns, more preferably from about 0.5 to about
10 microns. Particle size
can be measured according to methods known in the art, including, for example
optical microscopy.
Preferred volatile carriers for use in the shampoo composition are the
hydrocarbon solvents,
especially branched chain hydrocarbon solvents. The hydrocarbon solvents may
be linear or branched,
saturated or unsaturated, hydrocarbons having from about 8 to about 18 carbon
atoms, preferably from
about 10 to about 16 carbon atoms. Saturated hydrocarbons are preferred, as
are branched hydrocarbons.
Nonlimiting examples of some suitable linear hydrocarbons include decane,
dodecane, decene, tridecene,
and combinations thereof. Suitable branched hydrocarbons include isoparaffms,
examples of which
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WO 99/38476 PCTIUS99/02311
include commercially available isoparaffins from Exxon Chemical Company such
as Isopar H and K
(C 1 I -C 1 ~ isoparaffins), and Isopar L (C 1 1-C I 3 isoparaffins).
Preferred branched hydrocarbons are
isohexadecane, isododecane, 2,5-dimethyl decane, isotetradecane, and
combinations thereof.
Commercially available branched hydrocarbons include Petmethyl 99A and IOIA
(available from
Preperse, Inc., South Plainfield, NJ, USA).
Other suitable carriers include isopropanol, butyl alcohol, amyl alcohol,
phenyl ethanol, benryl
alcohol, phenyl propanol, ethyl butyrate, isopropyl butyrate, diethyl
phthalate, diethyl malonate, diethyl
succinate, dimethyl malonate, dimethyl succinate, phenyl ethyl dimethyl
carbinol, ethyl-6-
acetoxyhexanoate, and methyl (2-pentanyl-3-oxy)cyciopentylacetate, and
mixtures thereof. Preferred
among such other suitable solvents are diethyl phthalate, diethyl malonate,
diethyl succinate, dimethyl
malonate, dimethyl succinate, phenylethyl dimethyl carbinol, ethyl-6-
acetoxyhexanoate, and mixtures
thereof.
Suitable ether carriers are the di(CS-C~) alkyl ethers and diethers,
especially the di(CS-C6) alkyl
ethers such as isoamyl ether, dipentyl ether and dihexyl ether.
Other suitable carriers for use in the shampoo composition the volatile
silicon derivatives such as
cyclic or linear poiydialkyisiloxane, linear siloxy compounds or silane. The
number of silicon atoms in
the cyclic silicones is preferably from about 3 to about 7, more preferably
about 3 to about 5.
The general formula for such silicones is:
R2
wherein RI and R2 are independently selected from C 1 to Cg alkyl, aryl or
alkylaryl and wherein n=3-7.
The linear polyorgano siloxanes have from about 2 to 7 silicon atoms and have
the general formula:
RI Ra R6
R,-Si- O Si-O Si-R7
R3 Rs Rg
n
wherein Rl, R~, R3, R4, R5, R6, R~ and Rg can independently be saturated or
unsaturated C1 - Cg alkyl,
aryl, alkyiaryl, hydroxyalkyl, amino alkyl or alkyl siloxy.
Linear siloxy compounds have the general formula:
CA 02317703 2000-07-06
W O 99/38476
21
R,
I I "-R6
Ri-Si-O-R7-O-Si
R3 R;
PCT/US99/02311
wherein R 1, R2, R3, R4, R5, and R6 are independently selected from saturated
or unsaturated C 1 to C7
alkyl, aryl and alkyl aryl and R7 is C1 to C4 alkylene.
Silane compounds have the general formula:
R~
R4-Si-R2 _
R3
wherein Rl, R2, R3, and R4 can independently be selected from Cl -Cg alkyl,
aryl, alkylaryl,
hydroxyalkyl and alkylsiloxy.
Silicones of the above type, both cyclic and linear, are offered by Dow
Corning Corporation,
Dow Corning 344, 345 and 200 fluids, Union Carbide, Silicone 7202 and Silicone
7158, and Stauffer
Chemical, SWS-03314.
The linear volatile silicones generally have viscosities of less than about 5
centistokes at 25°C
while the cyclic materials have viscosities less than about 10 centistokes.
Examples of volatile silicones
are described in Todd and Byers, "Volatile Silicone Fluids for Cosmetics",
Cosmetics and Toiletries, Vol.
91, January, 1976, pp. 27-32, and also in Silicon Compounds, pages 253-295,
distributed by Petrarch
Chemicals, which descriptions arc incorporated herein by reference.
b) Cationic Deposition Polymer
The shampoo compositions of the present invention may further comprise an
organic cationic
polymer as a deposition aid for the styling polymer component described
hereinafter. The concentration
of the cationic polymer in the shampoo composition ranges from about 0.025% to
about 3%, preferably
from about 0.05% to about 0.5%, more preferably from about 0.1% to about
0.25%, by weight of the
shampoo composition.
The cationic polymer for use in the shampoo composition of the present
invention contains cationic
nitrogen-containing moieties such as quaternary ammonium or cationic
protonated amino moieties. The
cationic protonated amines can be primary, secondary, or tertiary amines
(preferably secondary or
tertiary), depending upon the particular species and the selected pH of the
styling shampoo composition.
The average molecular weight of the cationic polymer is between about 10
million and about 5,000,
preferably at least about 100,000, more preferably at least about 200,000, but
preferably not more than
CA 02317703 2002-10-03
22
about 2 million, more preferably not more than about 1.5 million. The polymers
also have a cationic
charge density ranging from about 0.2 meqigm to about 7 meqigm , preferably at
least about 0.4 meqigm,
more preferably at least about 0.6 meq/gm, but also preferably less than about
5 meq/gm, more preferably
less than about 2 meqigm, at the pH of intended use of the shampoo
composition, which pH wilt generally
range from about pH 3 to about pH 9, preferably between about pH 4 and about
pH 7.
Any anionic counterions can be use in association with the cationic polymers
so long as the
polymers remain soluble in water, in the shampoo composition, or in a
coacervate phase of the shampoo
composition, and so long as the counterions are physically and chemically
compatible with the essential
components of the shampoo composition or do not otherwise unduly impair
product performance, stability
or aesthetics. Non limiting examples of such counterions include halides
(e.g., chlorine, fluorine,
bromine, iodine), sulfate and methylsulfate.
The cationic nitrogen-containing moiety of the cationic polymer is generally
present as a
substituent on all, or more typically on some, of the monomer units thereof.
Thus, the cationic polymer
for use in the shampoo composition includes homopolymers, copolymers,
tetpolymers, and so forth, of
quaternary ammonium or cationic amine-substituted monomer units, optionally in
combination with non-
cationic monomers referred to herein as spacer monomers. Non limiting examples
of such polymers are
described in the CTF.9 Cosmetic Ingredient Dictionary, 3rd edition, edited by
Estrin, Crosley, and Haynes,
(The Cosmetic, Toiletry, and Fragrance Association, lnc., Washington, D.C.
(1982)).
Non limiting examples of suitable cationic polymers include copolymers of
vinyl monomers
having cationic protonated amine or quaternary ammonium functionalities with
water soluble spacer
monomers such as acrylamide, methacrylamide, alkyl and dialkyi acrylamides,
alkyl and dialkyl
methacrylamides, alkyl acrylate, alkyl methacrylate, vinyl caprolactone or
vinyl pyrrolidone. The alkyl
and dialkyl substituted monomers preferably have from C 1 to C~ alkyl groups,
more preferably from C 1
to C3 alkyl groups. Other suitable spacer monomers include vinyl esters, vinyl
alcohol (made by
hydrolysis of polyvinyl acetate), malefic anhydride, propylene glycol, and
ethylene glycol.
Suitable cationic protonated amino and quaternary ammonium monomers, for
inclusion in the
cationic polymers of the shampoo composition herein, include vinyl compounds
substituted with dialkyl-
aminoalkyl acrylate, dialkylaminoalkyl methacrylate, monoalkylaminoalkyl
acrylate,
monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammonium salt,
trialkyl acryloxyalkyl
ammonium salt, diallyl quaternary ammonium salts, and vinyl quaternary
ammonium monomers having
cyclic cationic nitrogen-containing rings such as pyridinium, imidazolium, and
quatemized pyrrolidone,
e.g., alkyl vinyl imidazolium, alkyl vinyl pyridinium, alkyl vinyl pyrrolidone
salts. The alkyl portions of
these monomers are preferably lower alkyls such as the C l, C2 or C3 alkyls.
CA 02317703 2002-10-03
7~
Suitable amine-substituted vinyl monomers for use herein include
dialkylaminoalkyl acrylate,
dialkyiaminoalkyl methacrylate, dialkylaminoalkyl acrylamide. and
dialkylaminoalkyl methacrylamide,
wherein the alkyl groups are preferably C1-C7 hydrocarbyls, more preferably C1-
C3, alkyls.
Other suitable cationic polymers for use in the shampoo composition include
copolymers of 1-
vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazoiium salt (e.g., chloride salt)
(referred to in the industry
by the Cosmetic, Toiletry, and Fragrance Association. "CTFA", as
Polyquaternium-16), such as those
commercially available from BASF Wyandotte Corp. (Parsippany, New Jersey,
U.S.A_) under the
LUVIQUATTM tradename (e.g., LUV1QUAT FC 370); copolymers of 1-vinyl-2-
pyrrolidone and
dimethylaminoethyl methacrylate (referred to in the industry by CTFA as
Polyquaternium-11) such as
those commercially available from 1SP Corporation ( Wayne, New Jersey, U.S.A.)
under the GAFQUATT""
tradename (e.g., GAFQUAT 755N); cationic diallyl quaternary ammonium-
containing polymers,
including, for example, dimethyldiallylammonium chloride homopolvmer and
copolymers of acrylamide
and dimethyldiallylammonium chloride, referred to in the industry (CTFA) as
Polyquaternium 6 and
Polyquaternium 7, respectively; and mineral acid salts of amino-alkyl esters
of homopolymers and
copolymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms, as
described in U.S. Patent
4,009,256.
Other suitable cationic polymers for use in the shampoo composition include
polysaccharide
polymers, such as cationic cellulose derivatives and cationic starch
derivatives. Suitable cationic
polysaccharide polymers include those which conform to the formula
R'
A-O-f R-N'-R3X)
Rz
wherein A is an anhydroglucose residual group, such as a starch or cellulose
anhydroglucose residual; R is
an alkylene oxyalkylene, polyoxyalkylene, or hydroxyalkylene group, or
combination thereof; R1, R2, and
R3 independently are alkyl, aryl, alkylaryl, arylatkyl, alkoxyalkyl, or
alkoxyaryl groups, each group
containing up to about 18 carbon atoms, and the total number of carbon atoms
for each cationic moiety
(i.e., the sum of carbon atoms in R1, R2 and R_i) preferably being about 20 or
less; and X is an anionic
counterion as described in hereinbefore.
Preferred cationic cellulose polymers are those polymers available from
Amerchol Corp. (Edison,
NJ, USA) in their Polymer JR and LR series of polymers, as salts of
hydroxyethyl cellulose reacted with
trimethyl ammonium substituted epoxide, referred to in the industry (CTFA) as
Polyquatetnium 10.
Another type of preferred cationic cellulose includes the polymeric quaternary
ammonium salts of
hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted
epoxide, referred to in the
industry (CTFA) as Polyquaternium 24. These materials are available from
Amerchol Corp. (Edison, NJ,
USA) under the trade name Polymer LM-200.
i
CA 02317703 2002-10-03
74
Cnher suitable cationic polymers include cationic guar gum derivatives, such
as guar
hvdroxypropyltrimonium chloride, specific examples of which include the Jaguar
series commercially
available from Rhone-Poulenc Incorporated. Other suitable cationic polymers
include quaternary
nitrogen-containing cellulose ethers, some examples of which are described in
U.S. Patent 3,962,41 F.
Other suitable cationic polymers include
copolymers of etherified cellulose, guar and starch, some examples of which
are described in U.S. Patent
3,958,581,
The cationic polymers herein are either soluble in the shampoo composition, or
preferably are
soluble in a complex coaceryate phase in the shampoo composition formed by the
cationic polymer and
the anionic detersive surfactant component described hereinbefore. Complex
coacervates of the cationic
polymer can also be formed with other charged materials in the shampoo
composition.
Coacervate formation is dependent upon a variety of criteria such as molecular
weight, component
concentration, and ratio of interacting ionic components, ionic strength
(including modification of ionic
strength, for example, by addition of salts), charge density of the cationic
and anionic components, pH,
and temperature. Coacervate systems and the effect of these parameters have
been described, for example,
by J. Caelles, et al., "Anionic and Cationic Compounds in Mixed Systems",
Cosmetics & Toiletries, Vol.
106, April 1991, pp 49-54, C. J. van Oss, "Coacervation, Complex-Coacervation
and Flocculation", J.
Dispersion Science and Technology, Vol. 9 (S,ti), 1988-89, pp 561-573, and D.
J. Burgess, "Practical
Analysis of Complex Coacervate Systems", J. of Colloid and lnrerface Science,
Vol. 140, No. 1,
November 1990, pp 227-238.
It is believed to be particularly advantageous for the cationic polymer to be
present in the shampoo
composition in a coacervate phase, or to form a coacervate phase upon
application or rinsing of the
shampoo to or from the hair. Complex coacervates are believed to more readily
deposit on the hair. Thus,
in general, it is preferred that the cationic polymer exist in the shampoo
composition as a coacervate phase
or form a coacervate phase upon dilution. if not already a coacervate in the
shampoo composition, the
cationic polymer will preferably exist in a complex coacervate form in the
shampoo upon dilution with
water.
'Techniques for analysis of formation of complex coacervates are known in the
art. For example,
microscopic analyses of the shampoo compositions, at any chosen stage of
dilution, can be utilized to
identify whether a coacervate phase has formed. Such coacervate phase will be
identifiable as an
adc'itional emulsified phase in the composition. The use of dyes can aid in
distinguishing the coacervate
phase from other insoluble phases dispersed in the shampoo composition.
c) Select Stability Active
The shampoo compositions of the present invention may further comprise a
select crystalline.
hydroxyl-containing stabilizer. The stabilizer is used to form a crystalline
stabilizing network in the
emulsion that prevents the styling polymerivolatiie carrier droplets from
coalescing and the shampoo from
CA 02317703 2000-07-06
WO 99/38476 PCT/US99/02311
35
phase splitting. Additionally, significantly lower levels of the crystalline,
hydroxyl-containing stabilizer
need to be used relative tb traditional stability actives. This results in
enhanced deposition efficiency of
the hair styling polymer onto the hair as well as reduced interactions with
other shampoo components.
The stabilizers used herein are not surfactants. The stabilizers provide
improved shelf and stress
stability, but allow the styling polymedvolatile cattier emulsion to separate
upon lathering, and thereby
provide for increased styling polymer deposition onto the hair.
The stabilizer suitable for use in the shampoo compositions are characterized
by the general
formula:
OH
CH~O C (CH2)x CH (CH2)a CH3
O OH
CHO C (CH2)y CH (CH2)b CH3
OH
CH20 C (CH2)z CH (CHZ)c CH3
wherein: (x + a) is from between 1 I and 17,
(y + b) is from between I 1 and 17,
(z + c) is from between 11 and 17;
preferably: x=y=z=10, and
a=b~5.
The crystalline, hydroxyl-containing stabilizer comprises from about 0.005% to
about 2.0%,
preferably from about 0.05% to about 0.25% by weight of the composition. The
preferred suspending
agent for use in the compositions herein is trihydroxstearin available from
ltheox, Inc. (New Jersey, USA)
under the tradename Thixcin R
d) Cationic Spreading Aeent
The shampoo compositions of the present invention may further comprise select
cationic materials
which act as spreading agents. The spreading agents for use in the composition
are select quaternary
ammonium or protonated amino compounds defined in greater detail hereinafter.
These select spreading
agents are useful to enhance the morphology of the styling polymer deposit on
the hair so that more
efficient adhesion between hair fibers results in improved styling
performance. The concentration of the
select spreading agents in the composition range from about 0.05% to about 5%,
preferably from about
0.1% to about 2%, more preferably from about 0.5% to about 1.5%, by weight of
the shampoo
composition.
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WO 99/38476 PCT/US99/023I 1
26
The select spreading agents are quaternary ammonium or amino compounds having
2, 3 or 4 N-
radicals which are substituted or unsubstituted hydrocarbon chains having from
about 12 to about 30
carbon atoms, wherein the substituents includes nonionic hydrophilic moieties
selected from alkoxy,
poiyoxalkylene, alkylamido, hydroxyalkyl, alkylester moieties, and mixtures
thereof. Suitable hydrophile-
containing radicals include, for example, compounds having nonionic hydrophile
moieties selected from
the group consisting of ethoxy, propoxy, poiyoxyethylene, polyoxypropylene,
ethyiamido, propylamido,
hydroxymethyl, hydroxyethyl, hydroxypropyl, methylester, ethylester,
propylester, or mixtures thereof.
The select spreading agents are cationic and must be positively charged at the
pH of the shampoo
compositions. Generally, the pH of the shampoo composition will be less than
about 10, typically from
about 3 to about 9, preferably from about 4 to about 8.
Select cationic spreading agents for use in the composition include those
corresponding to the
formu la:
R +
Rd-N-R2 X-
R3
wherein R1, and R2 are independently a saturated or unsaturated, substituted
or unsubstituted, linear or
branched hydrocarbon chain having from about 12 to about 30 carbon atoms,
preferably from about 18 to
about 22 carbon atoms, and wherein the hydrocarbon chain can contain one or
more hydophilic moieties
selected from the alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl,
alkylester, and mixtures thereof; R3
and R4 are independently a hydrogen, or a saturated or unsaturated,
substituted or unsubstituted, linear or
branched hydrocarbon chain having from about 1 to about 30 carbon atoms, or a
hydrocarbon having from
about 1 to about 30 carbon atoms containing one or more aromatic, ester,
ether, amido, amino moieties
present as substitutents or as linkages in the chain, and wherein the
hydrocarbon chain can contain one or
more hydophilic moieties selected from the alkoxy, polyoxyalkylene,
alkylamido, hydroxyalkyl,
alkylester, and mixtures thereof; and X is a soluble salt forming anion
preferably selected from halogen
(especially chlorine), acetate, phosphate, nitrate, sulfonate, and
alkylsulfate radicals.
An example of a select spreading agent for use in the composition include
those corresponding to
the formula:
CH3 +
CH3(CH2)n-CH2-N-(CH2)nCH3 X
CH3
wherein n is from 10-28, preferably 16, and X is a water soluble salt forming
anion (e.g., CI, sulfate, etc.).
Other examples of select cationic spreading agents for use in the composition
include those
corresponding to the formula:
I I I
CA 02317703 2002-10-03
27
O Z3 O
R"-CNH(-CH2-)m-N -(-CHI-)n-NHCR'
Z,
wherein Z I and Z2 are independently saturated or unsaturated, substituted or
unsubstituted, linear or
branched hydrocarbons, and preferably Z1 is an alkyl, more preferably methyl,
and Z2 is a short chain
hydroxyalkyl, preferably hydroxvmethyl or hydroxyethyi; n and m are
independently integers from 1 to 4,
inclusive, preferably from 2 to 3, inclusive, more preferably 2: R' and R" are
independently substituted or
unsubstituted hydrocarbons, preferably C12-C20 alkyl or alkenyl; and X is a
soluble salt forming anion
(e.g., CI, sulfate, etc.).
Nonlimiting examples of suitable cationic spreading agents include
ditallowdimethyl ammonium
chloride, ditallowdimethyl ammonium methyl sulfate, dihexadecyl dimethyl
ammonium chloride, di-
(hydrogenated tallow) dimethyl ammonium chloride, dioctadecyl dimethyl
ammonium chloride, dieicosyl
dimethyl ammonium chloride, didocosyl dimethyl ammonium chloride, di-
(hydrogenated tallow) dimethyl
ammonium acetate, dihexadecyl dimethyi ammonium acetate, disallow dipropyl
ammonium phosphate,
disallow dimethyl ammonium nitrate, di-(coconutalkyl) dimethyi ammonium
chloride, ditallowamidoethyl
hydroxypropylmonium methosulfate (commercially available as Varisoft 238),
dehydrogenated
tallowamidoethyl hydroxyethylmonium methosulfate (commercially available as
Varisoft 110),
ditallowamidoethyl hydroxyethylmonium methosulfate (commercially available as
Varisoft 222), and
di(partially hardened soyoylethyl) hydroxyethylmonium methosulfate
(commercially available as
Armocare EQ-S). Ditallowdimethyl ammonium chloride, ditallowamidoethyl
hydroxypropylmonium
methosulfate, dehydrogenated tallowamidoethyl hydroxyethylmonium methosulfate,
ditallowamidoethyl
hydroxyethylmonium methosulfate, and di{panially hardened soyoylethyl)
hydroxyethylmonium
methosulfate are particularly preferred quaternary ammonium cationic
surfactants useful herein.
Other suitable quaternary ammonium cationic surfactants are described in M.C.
Publishing Co..
McCatcheion's Detergents & Emulsifiers, (North American edition 1979);
Schwartz, et al., Surface Acrive
Agents. Their Chemisrry and Technology, New York: lnterscience Publishers,
1949; U.S. Patent
3,155,591, to Hilfer, issued Nov. 3, 1964; U.S. Patent 3,929,678 to Laughlin
et al., issued December 30,
1975; U.S. Patent 3,959,461 to Bailey et al, issued May 25, 1976; and U.S.
Patent 4,387,090 to Bolich Jr.,
issued June 7, 1983.
e) Polvalkvlene Glycol
The shampoo compositions of the present invention may further comprise
selected poiyalkylene
glycols in amounts effective to enhance the conditioned feel of the hair, to
mitigate the coated hail feel
resulting from the cationic deposition polymer, and to enhance the styling
performance of the shampoo.
Effective concentrations of the selected polyethylene glycols range from about
0.025% to about 1.5°,'0.
CA 02317703 2000-07-06
WO 99/38476 PCT/US99/02311
28
preferably from about 0.05% to about 1.0%, more preferably from about 0.1% to
about 0.5%, by weight of
the shampoo composition.'
The polyalkylene glycols suitable for use in the shampoo compositions are
characterized by the
general formula:
H(OCH~CH)n OH
R
wherein R is hydrogen, methyl or mixtures thereof, preferably hydrogen, and n
is an integer having an
average value of from about 1,500 to about 25,000, preferably from about 2,500
to about 20,000, and more
preferably from about 3,500 to about 15,000. When R is hydrogen, these
materials are polymers of
ethylene oxide, which are also known as polyethylene oxides, polyoxyethylenes,
and polyethylene glycols.
When R is methyl, these materials are polymers of propylene oxide, which are
also known as
polypropylene oxides, polyoxypropylenes, and polypropylene glycols. When R is
methyl, it is also
understood that various positional isomers of the resulting polymers can
exist.
Specific examples of suitable polyethylene glycol polymers include PEG-14 M
wherein R is
hydrogen and n has an average value of about 14,000 (PEG-14 M is also known as
Polyox WSR~ N-3000
available from Union Carbide) and PEG-23 M wherein R is hydrogen and n has an
average value of about
23,000 (PEG-23 M is also known as Polyox WSR~ N-12K available from Union
Carbide).
Suitable polyalkylene polymers include polypropylene glycols and mixed
polyethylenelpoiypropylene glycols.
It has been found that these polyalkylene glycols, when added to the styling
shampoo
compositions described herein, enhance the conditioned hair feel by mitigating
the coated hair feel
resulting from deposition of the cationic deposition polymer. Moreover, these
polyalkene glycols also
significantly enhance the styling performance versus compositions formulated
without. polyethylene
glycols. This performance is especially surprising as polyalkene giycols are
not known to deliver any
styling performance to hair and a synergistic relationship with the other
styling shampoo components
could not be anticipated.
~ Silicone Hair Conditioning Agent
The shampoo compositions of the present invention may further comprise an
optional silicone
hair conditioning agent at concentrations effective to provide hair
conditioning benefits. Such
concentrations range from about 0.01% to about 10%, preferably from about 0.1%
to about 8%, more
preferably from about 0.1 % to about 5%, most preferably from about 0.2% to
about 3%, by weight of the
shampoo compositions.
The optional silicone hair conditioning agents are insoluble in the shampoo
compositions, and are
preferably nonvolatile. Typically it will be intermixed in the shampoo
composition so as to be in the form
of a separate, discontinuous phase of dispersed, insoluble particles, also
referred to as droplets. The
optional silicone hair conditioning agent phase will comprise a silicone fluid
hair conditioning agent such
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WO 99/38476 PCT/US99102311
29
as a silicone fluid and can also comprise other ingredients, such as a
silicone resin to improve silicone
fluid deposition efficiency or enhance glossiness of the hair (especially when
high refractive index (e.g.
above about I .46) silicone conditioning agents are used (e.g. highly
phenylated silicones).
The optional silicone hair conditioning agent phase may comprise volatile
silicone, nonvolatile
silicone, or combinations thereof. Typically, if volatile silicones are
present, it will be incidental to their
use as a solvent or carrier for commercially available forms of nonvolatile
silicone materials ingredients,
such as silicone gums and resins.
The optional silicone hair conditioning agents for use in the shampoo
compositions preferably
have a viscosity of from about 20 to about 2,000,000 centistokes, more
preferably from about 1,000 to
about 1,800,000 centistokes, even more preferably from about 50,000 to about
1,500,000 centistokes, as
measured at 25°C .
Optional silicone fluids include silicone oils which are flowable silicone
materials having a a
viscosity of less than 1,000,000 centistokes, preferably between about 5 and
1,000,000 centistokes, more
preferably between about 10 and about 100,000 centistokes, at 25°C.
Suitable silicone oils include
polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether
siloxane copolymers, and
combinations thereof. Other insoluble, nonvolatile silicone fluids having hair
conditioning properties can
also be used.
Optional silicone oils include polyalkyl or poiyaryl siloxanes which conform
to the following
formula (1)
R R R
R-$i-O Si-O Si-R
x
where R is aliphatic, preferably alkyl or alkenyl, or aryl, R can be
substituted or unsubstituted, and x is an
integer from 1 to about 8,000. Suitable unsubstituted R groups include alkoxy,
aryloxy, alkaryl, arylalkyl,
arylalkenyl, alkylamine, and ether-substituted, hydroxyl-substituted, and
halogen-substituted aliphatic and
aryl groups. Suitable R groups also include cationic amines and quaternary
ammonium groups.
The aliphatic or aryl groups substituted on the siloxane chain may have any
structure so tong as
the resulting silicones remain fluid at room temperature, are hydrophobic, are
neither irritating, toxic nor
otherwise harmful when applied to the hair, are compatible with the other
components of the shampoo
compositions, are chemically stable under normal use and storage conditions,
are insoluble in the shampoo
compositions herein, and are capable of being deposited on and conditioning
the hair.
The two R groups on the silicon atom of each monomeric silicone unit may
represent the same or
different groups. Preferably, the two R groups represent the same group.
Preferred alkyl and alkenyl substituents are C1-Cg alkyls and alkenyls, more
preferably from Cl-
C4, most preferably from CI-C2. The aliphatic portions of other alkyl-,
alkenyl-, or alkynyl-containing
CA 02317703 2000-07-06
WO 99138476 PCT/US99102311
30
groups (such as alkoxy, alkaryl, and alkamino) can be straight or branched
chains and preferably have
from one to five carbon atoms, more preferably from one to four carbon atoms,
even more preferably from
one to three carbon atoms, most preferably from one to two carbon atoms. As
.discussed above, the R
substituents hereof can also contain amino functionalities, e.g. alkamino
groups, which can be primary,
secondary or tertiary amines or quaternary ammonium. These include mono-, dl-
and tri- alkylamino and
alkoxyamino groups wherein the aliphatic portion chain length is preferably as
described above. The R
substituents can also be substituted with other groups, such as halogens (e.g.
chloride, fluoride, and
bromide), halogenated aliphatic or aryl groups, and hydroxy (e.g. hydroxy
substituted aliphatic groups).
Suitable halogenated R groups could include, for example, tri-halogenated
(preferably fluoro) alkyl groups
such as -Rl-C(F)3, wherein R1 is C1-C3 alkyl. Examples of such polysiloxanes
include polymethyl -3,3,3
trifluoropropylsiloxane.
Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyl and
phenyimethyl. The
preferred silicones are polydimethyl siloxane, polydiethylsiloxane, and
polymethylphenylsiloxane.
Polydimethylsiloxane is especially preferred. Other suitable R groups include
methyl, medtoxy, ethoxy,
propoxy, and aryloxy. The three R groups on the end caps of the silicone may
also represent the same or
different groups.
The nonvolatile polyalkylsiloxane fluids that may be used include, for
example,
polydimethylsiloxanes. These siloxanes arc available, for example, from the
General Electric Company in
their Viscasil R and SF 96 series, and from Dow Coming in their Dow Coming 200
series.
The polyalkylaryl siloxane fluids that may be used, also include, for example,
polymethylphenylsiloxanes. These siloxanes are available, for example, from
the General Electric
Company as SF 1075 methyl phenyl fluid or from Dow Corning as 556 Cosmetic
Grade Fluid.
The polyether siloxane copolymers that may be used include, for example, a
polypropylene oxide
modified poiydimethylsiloxane (e.g., Dow Corning DC-1248) although ethylene
oxide or mixtures of
ethylene oxide and propylene oxide may also be used. The ethylene oxide and
polypropylene oxide
concentrations must be sufficiently low to prevent solubility in water and the
composition hereof:
Suitable alkylamino substituted silicones include those which conform to the
following structure
(II)
r
wherein x and y are integers. This polymer is also known as "amodimethicone".
CA 02317703 2000-07-06
WO 99/38476 PCT/US99/02311
31
Suitable cationic silicone fluids include those which conform to the formula
(Ill)
(RI)aG;_a-Si-{-OSiG2)n-(-OSiGb(RI)2-b)m-O-SiG3-a(RI)a , wherein G is selected
from the group
consisting of hydrogen, phenyl, hydroxy, CI-Cg alkyl and preferably methyl; a
is 0 or an integer having
a value from 1 to 3, preferably 0; b is 0 or l, preferably l; the sum n+m is a
number from I to 2,000 and
preferably from 50 to I50, n being able to denote a number from 0 to 1,999 and
preferably from 49 to 149
and m being able to denote an integer from 1 to 2,000 and preferably from 1 to
10; R 1 is a monovalent
radical conforming to the formula CqH2qL in which q is an integer having a
value of from 2 to 8 and L is
selected from the following groups:
-N(R2)CH2-CH2-N(R2yl
-N(R2?2
-N(R2~A
-N(R2xH~-CH2-NR2H2A
in which R2 is selected from the gmup consisting of hydrogen, phenyl, benryl,
a saturated hydrocarbon
radical, preferably an alkyl radical containing from I to 20 carbon atoms, and
A is a halide ion.
An especially preferred cationic silicone corresponding to formula (III) is
the polymer known as
"trimethylsilylamodimethicone", of formula (IV):
m
Other silicone cationic polymers which can be used in the shampoo compositions
are represented
by the formula (V):
R4CH2-CHOH-CH2-N'(R3~Cl
R3
(R~~ i i- i i- Si-O-Si(R~
R3 ~ Ra
r s
i i
CA 02317703 2002-10-03
32
where R3 denotes a monovalent hydrocarbon radical having from 1 to 18 carbon
atoms, preferably an
alkyl or alkenyi radical such as methyl; R4 denotes a hydrocarbon radical,
preferably a C1=Clg alkylene
radical or a CI-Clg, and more preferably C1-Cg, alkyleneoxy radical; Q is a
halide ion, preferably
chloride; r denotes an average statistical value from 2 to 20, preferably from
2 to 8; s denotes an average
statistical value from 20 to 200, and preferably from 20 to 50. A preferred
polymer of this class is
available from Union Carbide under the name "UCAR SILICONE ALE 56."
Other optional silicone fluids are the insoluble silicone gums. These gums are
polyorganosiioxane materials having a viscosity at 25°C of greater than
or equal to 1,000,000 centistokes.
Silicone gums are described in U.S. Patent 4,152,416; Noll and Walter,
Chemistry and Technolo~v of
Silicones, New York: Academic Press 1968: and in General Electric Silicone
Rubber Product Data Sheets
SE 30, SE 33, SE 54 and SE 76 . The silicone gums will
typically have a mass molecular weight in excess of about 200.000, generally
between about 200,000 and
about 1,000,000, specific examples of which include polydimethylsiloxane,
(polydimethylsiloxane)
(methylvinylsiloxane) copolymer, poly(dimethylsiloxane) (diphenyl
siloxane)(methylvinylsiloxane)
copolymer and mixtures thereof.
Another category of nonvolatile, insoluble silicone fluid conditioning agents
ate the high
refractive index silicones, having a refractive index of at least about 1.46,
preferably at least about 1.48,
more preferably at least about 1.52, most preferably at least about 1.55. The
refractive index of the
polysiloxane fluid will generally be less than about 1.70, typically less than
about 1.60. In this context,
polysiloxane "fluid" includes oils as well as gums.
The high refractive index polysiloxane fluid includes those represented by
general Formula (1)
above, as well as cyclic polysiloxanes such as those represented by Formula
(VI) below:
R
Si
n
R
wherein R is as defined above, n is from about 3 to about 7, preferably from 3
to 5.
The high refractive index polysiloxane fluids contain a sufficient amount of
aryl-containing R
substituents to increase the refractive index to the desired level. which is
described above. In addition, R
and n must be selected so that the material is nonvolatile. as defined above.
Aryl-containing substituents -contain alicyclic and heterocyclic five and six
membered aryl rings.
and substituents containing fused five or six membered rings. The aryl rings
themselves can be
substituted or unsubstituted. Substituenu include aliphatic substituents, and
can also include alkoxv
substituents, .acyl substituents, ketones, halogens (e.g.. Cl and Br), amines.
etc. Exemplary aryl-containing
groups include substituted and unsubstituted arenes. such as phenyl, and
phenyl derivatives such as
CA 02317703 2002-10-03
33
phenyls with C 1-CS alkyl or alkenyl substituents, e.g.. ailylphenyl. methyl
phenyl and ethyl phenyl, vinyl
phenyls such as styrenyl, and phenyl alkynes (e.g. phenyl C2-C4 alkynes).
Heterocyclic aryl groups
include substituents derived from furan, imidazole, pyrrole, pyridine, etc.
Fused aryl ring substituents
include, for example. napthalene, coumarin, and purine.
In general. the high refractive index polysiloxane fluids will have a degree
of aryl-containing
substituents of at least about 15%, preferably at least about 20%, more
preferably at least about 25%, even
more preferably at least about 35%, most preferably at least about 50%.
'Typically, although it is not
intended to necessarily limit the invention, the degree of aryl substitution
will be less than about 90%,
more generally less than about 85%, preferably from about 55% to about 80%.
The polysiloxane fluids are also characterized by relatively high surface
tensions as a result of
their aryl substitution. In general, the polysiloxane fluids hereof will have
a surface tension of at least
about 24 dynes/cm2, typically at least about 27 dynes/cm2. Surface tension,
for purposes hereof, is
measured by a de Nouy ring tensiometer according to Dow Corning Corporate ?est
Method CTM 0461,
November 23, 1971. Changes in surface tension can be measured according to the
above test method or
according to ASTM Method D 1331.
Preferred high refractive index polysiloxane fluids have a combination of
phenyl or phenyl
derivative substituents (preferably phenyl), with alkyl substituents,
preferably CI-C4 alkyl (most
preferably methyl), hydroxy, Cl-C4 alkylamino (especially -R1NHR2NH2 where
each R1 and R2
independently is a CI-C3 alkyl, alkenyl, and/or alkoxy. High refractive index
polysiloxanes are available
from Dow Corning Corporation (Midland. Michigan, U.S.A.) Huls America
(Piscataway, New Jersey,
U.S.A.), and General Electric Silicones (Waterford, New York, U.S.A.).
References disclosing examples of some suitable silicone fluids for use in the
shampoo
compositions include U.S. Patent 2,826,551. U.S. Patent 3,964,500, U.S. Patent
4,364,837, British Patent
849,433. and Silicon Compounds, Petrarch Systems, Jnc. (1984),
Silicone resins can be included in the silicone conditioning agent. These
resins are highly
crosslinked polymeric siloxane systems. The crosslinking is introduced through
the incorporation of
trifunctional and tetrafunctional silanes with monofunctional or difunctional,
or both, silanes during
manufacture of the silicone resin. As is well understood in the art, the
degree of crosslinking that is
required in order to result in a silicone resin will vary according to the
specific silane units incorporated
into the silicone resin. In general, silicone materials which have a
sufficient level of trifunctional and
tetrafunctional siloxane monomer uniu (and hence, a sufficient level of
crosslinking) such that they dry
down to a rigid, or hard, film are considered to be silicone resins. The ratio
of oxygen atoms to silicon
atoms is indicative of the level of crosslinking in a particular silicone
material. Silicone materials which
have at least about 1.1 oxygen atoms per silicon atom will generally be
silicone resins herein. Preferably,
the ratio of oxygenailicon atoms is at least about 1.2:1Ø Silanes used in
the manufacture of silicone
CA 02317703 2002-10-03
34
resins include monomethyl-, dimethyl-, trimethyl-, monophenyl-, Biphenyl-,
methylphenyl-, monovinyl-,
and methylvinyl-chlorosilanes, and tetrachlorosilane, with the methyl-
substituted silanes being most
commonly utilized. Preferted resins are offered by General Electric as GE
SS4230 and SS4267.
Commercially available silicone resins will generally be supplied in a
dissolved form in a low viscosity
volatile or nonvolatile silicone fluid. The silicone resins for use herein
should be supplied and
incorporated into the present compositions in such dissolved form, as will be
readily apparent to those
skilled in the art.
Background material on silicones including sections discussing silicone
fluids, gums, and resins,
as well as manufacture of silicones, can be found in Encyclopedia of Polymer
Science and Engineering,
Volume 15, Second Edition, pp 204-308, John Wiley & Sons, Inc., 1989.
Silicone materials and silicone resins in particular, can conveniently be
identified according to a
shorthand nomenclature system well known to those skilled in the art as "MDTQ"
nomenclature. Under
this system, the silicone is described according to presence of various
siloxane monomer units which make
up rite silicone. Briefly, the symbol M denotes the monofunctional unit
(CH3)3Si0,5; D denotes the
difunctional unit (CH3)2Si0; T denotes the trifvnctional unit (CH3)Si01.5; and
Q denotes the quadri- or
tetra-functional unit Si02. Primes of the unit symbols, e.g., M', D', T, and
Q' denote substituents other
than methyl, and must be specifically defined for each occurrence. Typical
alternate substituents include
groups such as vinyl, phenyls, amines, hydroxyls, etc. The molar ratios of the
various units, either in
terms of subscripts to the symbols indicating the total number of each type of
unit in the silicone (or an
average thereof) or as specifically indicated ratios in combination with
molecular weight complete the
description of the silicone material under the MDTQ system. Higher relative
molar amounts of T, Q, T'
and/or Q' to D, D', M and/or M' in a silicone resin is indicative of higher
levels of crosslinking. As
discussed before, however, the overall level of crosslinking can also be
indicated by the oxygen to silicon
ratio.
?he silicone resins for use herein which are preferred are MQ, MT, MTQ, MDT
and MDTQ
resins. Thus, the preferred silicone substituent is methyl. Especially
preferred are MQ resins wherein the
M:Q ratio is from about 0.5:1.0 to about 1.5:1.0 and the average molecular
weight of the resin is from
about 1000 to about 10,000.
The weight ratio of the nonvolatile silicone fluid, having refractive index
below 1.46, to the
silicone resin component, when used, is preferably from about 4:1 to about
400:1, preferably this ratio is
from about 9:1 to about 200:1, more preferably from about 19:1 to about 100:1,
p2rticularly when the
silicone fluid component is a polydimethylsiloxane fluid or a mixture of
polydimethylsiloxane fluid and
polydimethylsiloxane gum as described above. Insofar as the silicone resin
forms a part of the same phase
in the compositions hereof as the silicone fluid, i.e. the conditioning
active, the sum of the fluid and resin
should be included in determining the level of silicone conditioning agem in
the composition.
g) Optional Aeents
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WO 99/38476 PCT/US99/02311
35
The shampoo compositions of the present invention may further comprise
additional materials
which improve the performance and/or aesthetics of the compositions of the
present invention. These
materials compete with other shampoo composition materials for solubilization
by the surfactant
component. As a result, they impact both the amount of coacervate which forms
upon dilution and the
composition of this coacervate. Additionally, the additional optional agents
are also entrapped in the
coacervate. The styling polymer/volatile carrier droplets are deposited onto
the hair by the coacervate,
thus these optional agents can be used to directly influence styling
performance by impacting the amount
of coacervate formed as well as hair feel by impacting the composition of the
coacervate.
Highly preferred optional agents includes crystalline materials that can be
categorized as acyl
derivatives, long chain amine oxides, or combinations thereof, concentrations
of which range from about
0.1% to about 5.0%, preferably from about 0.5% to about 3.0%, by weight of the
shampoo compositions.
These agents are described as suspending agents in U.S. Patent 4,741,855, and
U.S. Reissue Patent 34,584
(Grote et al.), which descriptions arc incorporated herein by reference. These
preferred materials include
ethylene glycol esters of fatty acids preferably having from about 16 to about
22 carbon atoms. More
preferred are the ethylene glycol stearates, both mono and distearate, but
particularly the distearate
containing less than about 7% of the mono stearate. Other suitable optional
agents include alkanol amides
of fatty acids, preferably having from about 16 to about 22 carbon atoms, more
preferably about 16 to 18
carbon atoms, preferred examples of which include stearic monoethanolamide,
stearic diethanolamide,
stearic monoisopropanolamide and stearic monoethanolamide stearate. Other long
chain acyl derivatives
include long chain esters of long chain fatty acids (e.g., stearyl siearate,
cetyl palmitate, etc.); glyceryl
esters (e.g., glyceryl distearate) and long chain esters of long chain alkanol
amides (e.g., stearamide
diethanolamide distearate, stearamide monoethanolamide stearate). Long chain
acyl derivatives, ethylene
glycol esters of long chain carboxylic acids, long chain amine oxides, and
alkanol amides of long chain
carboxylic acids in addition to the preferred materials listed above may be
used as suspending agents.
Other long chain acyl derivatives suitable for use as additional optional
agents include N,N-
dihydrocarbyl amido benzoic acid and soluble salts thereof (e.g., Na, K),
particularly N,N-
di(hydrogenated) C 16, C 1 g and tallow amido benzoic acid species of this
family, which arc commercially
available from Stepan Company (Northfield, Illinois, USA).
Examples of suitable long chain amine oxides include alkyl (C16-C22) dimethyi
amine oxides,
e.g., stearyl dimethyl amine oxide.
Method of Use .
The shampoo compositions of the present invention arc used in a conventional
manner for
cleansing and styling hair. An effective amount of the composition for
cleansing and styling the hair is
applied to the hair, that has preferably been wetted with water, and is then
rinsed ofd: Such effective
amounts generally range from about lgm to about SOgm, preferably from about
lgm to about 20gm.
CA 02317703 2000-07-06
WO 99/38476 PCT/US99/02311
36
Application to the hair typically includes working the composition through the
hair such that most or all of
the hair is contacted with the composition.
This method for cleansing and styling the hair comprises the steps of a)
wetting the hair with
water, b) applying an effective amount of the shampoo composition to the hair,
c) shampooing the hair
with the composition, and d) rinsing the composition from the hair with water.
These steps can be repeated
as many times as desired to achieve the cleansing and styling benefit desired.
The metleod is preferably
employed daily, every other day, or every third day, to provide and maintaat
the hair cleansing and styling
performance described herein.
Examola
The styling shampoo compositions illustrated in Examples I-X illustrate
specific embodiments of
the shampoo compositions of the present invention, but are not intended to be
limiting thereof. Other
modifications can be undertaken by the skilled artisan without departing from
alts spirit and scope of-dtis
invention. 'These exemplified embodiments of the styling shampoo compositions
of the present invention
provide cleansing of hair and improved hair styling performance.
The shampoo compositions illustrated in Examples I-X are prepared by
conventional formulation
and mixing methods, an example of which is set forth hereinbelow. All
exemplified amounts are listed as
weight percents and exclude minor materials such as diluents, filler, and so
forth, unless otherwise
specified.
Preparation
The styling shampoo compositions of the present invention may be prepared
using conventional
formulation and mixing techniques. The hair styling polymer should first be
dissolved in the volatile
carrier. This styling polymer/voiatile carrier premix may then be added to a
premix of the surfactants, or
some portion of the surfactants, and the solid components which has been
heated to melt the solid
components, e.g., about 87°C. This mixture is then pumped through a
high shear mill and cooled, and
then the remaining components are mixed in. Alternatively, the styling
polymer/volatile carrier premix
may be added to this final mix, after cooling. The composition should have a
final viscosity of from about
2000 to about 12,000 cps. The viscosity of the composition -can be adjusted
using soditun chloride or
ammonium xylenesulfonate as needed.
The styling polymer/volatile solvent premix, as exemplified in the following
examples, may be a
combination of styling polymerslsoivent as described hereinbelow.
Mixture A. w/w ratio
Styling Polymer: 40
t-butyl
acrylate/2-ethylhexyl
methacrylate
(90/10 wlw)
Volatile isododecane 60
Solvent:
Mixture B. w/w ratio
Styling Polymer:t-butyl acrylate/2-ethylhexyl methacrylateSO
(90/10 w/w)
Volatile isododecane 50
Solvent:
Mixture C. w1w ratio
CA 02317703 2000-07-06
WO 99/38476 PCTIUS9910231 I
. 37
Styling Polymer: t-butyl acrylatel2-ethylhexyl methacrylateJ PDMS macromer
(81/9/10 wlw; Polymer wt avg. M.W. = 100.000) 40
Volatile Solvent: isododecane 60
Component
Weight
I II III IV V
Ammonium Laureth Sulfate
9.0 9.0 9.0 9.0 9.0
Ammonium Lauryl Sulfate
3.0 3.0 3.0 3.0 3.0
Lauroamphoacetate
6.0 6.0 6.0 6.0 6.0
Mixture A
--- 4.0 4.0 4.0
Mixture B
4.0 __ ___ _ 4.0
Dehydrogenated Tallowamidoethyl
Hydroxyethylmonium
Methosuifate ( 1 )
-- --- 1.0 1.0
Ditallowamidoethyl Hydroxypropylmonium
Methosulfat
e
(2)
___ ___ 1.0
Citric Acid
1.0 0.881.0 1 I.0
Laureth 4 0
0.17 0.170.17 0.17 0,
Monosodium Phosphate t
7
-- 0.1
Disodium Phosphate ~ _ __
Glycol Distearate ___ 0.2
2.0 2.0 2.0 1.43 2.4
Cocomonoethanol amide
0.6 0.6 0.6 0.6 0.6
Fragrance
1.0 1.0 1.0 1.0 1.0
Cetyl Alcohol
--- 0.420.42 0.42
Trihydroxystearin
0.05 0.250.15 0.15 0.15
Polyquatemium 10 (JR30M)
0. 0.
Guar Hydroxypropyltrimonium ChlorideI I
(3) S S
0. 0.3 0.3 0.3 0.15
Dimethicone t
5
0.25 0.5 0.25 1.0 0.25
DMDM Hydantoin
0.2 0.2 0.2 0.2 0.2
Water
qs qs qs
( I ) Available under the tradename100 100 100
Varisoft 110 fr qs
Sh 100
qs
100
om ChemicalCo. ublin,,
erex (D Ohio USA)
(2) Available under the tradename
Varis
ft 238 fr
o
om Sherex Chemical Co. (Dublin,
Ohio, USA)
(3)Available under the tradename
Jaguar C-17 from Rh
P
one- oulenc.Cranbury, New sey, )
( Jer USA
Component
Weight
VI VII VIII IX X
Ammonium Laureth Sulfate
9.0 9.0 9.0 9.0 9.0
Ammonium Lauryl Sulfate
3.0 3.0 3.0 3.0 3.0
Lauroamphoacetate
6.0 6.0 6.0 6.0 6.0
Mixture A
4.0 - 4.0 4.0
Mixture B
--- 4.0
Mixture C "' "- _--
__- ___ w 4.0
Dehydrogenated Tallowamidoethyl
Hydroxyethyhnonium
Methosulfate (1)
1.0 0.8 1.0 1.0
PEG 14M
0.3 0.150.3
PEG 23M "' "'
Citric Acid ___
-'- 0.3 0.15
1.0 1.0 1.0 1.0 I.0
~~4
0.17 0.170.17 0.17 0.17
Glycol Distearate
2.0 1.432.0 1.43 2.0
Fm~o~
1.0 1.0 1.0 1.0 l.0
Cetyl Alcohol
0.42 --- 0.42 -- 0.42
Trihydroxystearin
O. 0.050.25 O. 0.15
Polyquatennium 10 (JR30M) I I
S S
0.15 - 0.15 0.
Guar Hydroxypropyltrimonium Chloride0 I
(3) 15
. 0.3 0.15 0.3 0.2
Dimethicone
0.25 0.251.0 0.25 ---
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WO 99/38476 PCT/US99/02311
38
DMDM Hydantoin 0.2 0.2 0.2 0.2 0.2
Water qs 100 qs 100 qs 100 qs 100 qs 100
( 1 ) Available under the tradename Varisoft 110 from Sherex Chemical Co.
(Dublin, Ohio, USA)
(3) Available under the tradename Jaguar C-17 from Rhone-Poulenc. (Cranbury,
New Jersey, USA)
