Note: Descriptions are shown in the official language in which they were submitted.
CA 02319800 2000-09-29
-1-
THERMOPLASTIC ELASTOMERIC COPOLYMERS AND HAIR AND SKIN CARE
COMPOSTIONS CONTAINING THE SAME
This application has been divided out of Canadian Patent
Application Serial No. 2,165,767 filed June 30, 1994.
TECHNICAL FIELD
The present invention relates to water or alcohol soluble or
dispersible thermoplastic elastomeric copolymers and to cosmetic and
pharmaceutical compositions containing these copolymers. These copolymers
are useful for hair setting and styling purposes. A particularly useful
application for these. copolymers is in hair spray and mousse
compositions. This invention further relates to copolymers useful for
incorporating into cosmetic and pharmaceutical compositions for topical
application to the skin. Skin care compositions containing these
copolymers are useful for delivering and/or transdermally transporting a
wide variety of active ingredients to and/or through the skin.
BACKGROUND OF THE INVENTION
In the hair care area, the desire to have hair retain a particular
style or shape is widely held. Such style retention is generally
accomplished by either of two routes: permanent chemical alteration of
the hair fiber or temporary alteration of hair style or shape. A
temporary alteration is one which can be removed by water or by
shampooing. Temporary style alteration has generally been accomplished by
application of a composition to dampened hair after shampooing and/or
conditioning and prior to drying and/or styling. Products in the form of
mousses, gels, lotions, or sprays are most commonly used for this
purpose. Once the desired style is achieved, spray products are commonly
used to help retain the style. These various hair care products utilize a
variety of gums and resins for providing styling and retention. However,
the gums and resins currently used tend to feel either too sticky or too
stiff upon the hair. Also, these gums and resins do not wash out as
easily as desired. Therefore, the need exists for improved styling and
style retention materials which provide a strong,
CA 02319800 2000-09-29
lasting, hold without being either too stiff or too sticky, and
yet which are easily removed by shampooing. Furthermore, because
most hair care styling compositions are water and/or alcohol
based, it is necessary that these materials have good solubility
or dispersibility in these bases.
Thermoplastic elastameric copolymers are well known. These
copolymers combine thermoplastic properties, which give them
solubility and strength, with rubber-like elastic properties,
which give them flexibility and shape retention. However, despite
10 these highly desirable properties, most thermoplastic elastomeric
copolymers are generally insoluble or poorly soluble in water
and/or alcohol systems and would not be suitable in hair care
compositions. Therefore, thermoplastic elastomeric copolymers
having good water and/or alcohol solubility would be useful for
developing improved hair care compositions.
In the present invention new classes of thermoplastic
elastomeric copolymers have been developed which have the desired
flexibility, strength, and elastic properties and yet are readily
soluble and/or dispersible in water and/or alcohol systems.
20 Furthermore, these materials provide hair care compositions which
leave the hair feeling natural, i.e. not stiff.
In addition to the hair care benefits provided by these
copolymers, it has been found that these materials are also useful
for incorporation into a wide variety of cosmetic and
25 pharmaceutical Compositions for topical application to the skin.
These copolymers provide topical coapositions which are sore
easily and uniforvly spread upon the skin, which feel good upon
the skin, and yet which are highly substantive. Furthermore,
these copolymers are useful for enhancing the penetration of a
38 wide variety of cosuetlc and phan~aceutical actives Into the skin,
or alternatively, through the skin for systemic delivery.
It is an object of the present invention to provide novel,
water an4/or alcohol soluble and/or dispersible thermoplastic
elastomeric copolymers.
CA 02319800 2000-09-29
-3-
It is another object of the present invention to provide novel
thermoplastic elastomeric copolymers useful in hair care compositions.
It is another object of the present invention to provide novel
hair care compositions having improved styling and/or hold properties
and having improved aesthetics.
It is another object of the present invention to provide novel
thermoplastic elastomeric copolymers useful in topical skin care
cosmetic and pharmaceutical compositions.
It is another object of the present invention to provide novel
topical cosmetic and pharmaceutical compositions useful for delivering
a wide variety of cosmetic materials and pharmaceutical actives to
and/or through the skin.
These and other objects will become readily apparent from the
detailed description which follows.
SUMMARY OF THE INVENTION
The present invention relates to a water or alcohol soluble or
dispersible thermoplastic elastomeric copolymer having a backbone and
one or more polymeric side chains, said copolymer formed from the
copolymerization of randomly repeating A and B units and corresponding
to the formula
[A]a [B]b
wherein
(i) A is at least one polymerizable monomer unit corresponding
to the formula
0
X - C - CR5 = CHR6
wherein X is selected from the group consisting of -OH,
-OM,-OR4, -NH2, -NHR4, and -N(R4)z; M is a cation selected from
the group consisting of Na+, K+, Mg++, Ca++, Zn++, NHa+,
alkylammonium, dialkylammonium, trialkylammonium, and
tetraalkylammonium; each R4 is selected from the group consisting
of H, C~-Ca straight or branched chain alkyl, and N. N,-
CA 02319800 2000-09-29
-4-
dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2
ethoxyethyl; and R5 and R6 are independently selected from the
group consisting of H, C~-Ca straight or branched chain
alkyl, methoxy, ethoxy, and 2-hydroxyethoxy, 2-methoxyethyl,
2-ethoxyethyl;
(ii) B is at least one hydrophilic macromonomer unit
copolymerizable with A corresponding to the formula
RO -[-CH2CH2N-]m-CH2
C=0 CH=CH2
R'
wherein R and R' are independently selected from the group
consisting of H and C~-Ca straight or branched chain alkyl; and m
is an integer from about 10 to about 2000; and
(iii) a is an integer of about 100 or greater and b is an
integer of about 2 or greater; and wherein said copolymer has a
weight average molecular weight greater than about 10,000, and
wherein said copolymer exhibits two distinct Tg values, said
first Tg corresponding to said backbone and having a value less
than about 0°C, and said second Tg corresponding to said side
chains and having a value greater than about 25°C.
CA 02319800 2000-09-29
-5-
In further embodiments, the present invention Telates to hair
care compositions, especially hair setting and styling
compositions, containing these copolymers.
In further embodiments, the present invention relates to
cosmetic and pharmaceutical compositions containing these
copolymers for topical.application to the skin for the delivery of
cosmetic materials and pharmaceutical actives onto, into and/or
10 through the skin.
All percentages and ratios used herein are by weight of the
total composition and ail measurements made are at 25oC, unless
otherwise designated. The invention hereof can comprise, consist
of, or consist essentially of, the essential as well as optional
15 ingredients and components described herein.
DETAILED DESCRIPTION Of THE INV NTInN
The feral 'thermoplastic elastomeric copolymer' as used herein
means that the copolymer has both thermoplastic and elastomeric
properties. The term 'thermoplastic elastomeric copolymer' is one
20 fau,iliar to those of ordinary skill in polymer science. By
'thermoplastic' is meant that upon heating, the copolymer softens
and upon cooling it rehardens; upon being subject to stress it
begins to flow and upon removal of stress it stops flowing. 8y
'elastomeric' is want that the copolymer has an elastic modulus
25 such that the copolymer exhibits a resistance to deformation and
has limited extensibility and retraction. In other words, the
copolymer tends to recover its size and shape after deformation.
The term 'macromonomer' is one familiar to those of ordinary
skill in polymer science, and is used to describe a polymeric
material containing a polymerlzable moiety. A macromonomer is a
macromolecular mono.er. A macromonomer is essentially a very
large type of monoaer building~block~unFit which can be used in a
polymerization reaction to fora polymers with itself, with other
monomers, or with other macromonomsrs.
CA 02319800 2000-09-29
-6-
The term 'water or alcohol soluble or dispersible' as used
herein means that these copolymers are either freely soluble in or
dispersible (as a stable suspension) in at least one of the
following solvents, or alternatively, in any combination of one of
the following solvents: water, methanol, ethanol, and isopropanol.
By 'soluble' is meant that the copolymer is soluble in the solvent
= or solvents at 25oC at a concentration of at least about-20 mg/ml,
more preferably about 50 mg/mL, and most preferably about 100
mg/ml. By 'dispersible' is meant that the copolymer forms a
10 stable, uniform suspension (without the addition of further
materials such as emulsifiers) when combined with the solvent or
solvents at 25oC at a concentration of at least about 20 mg/ml,
more preferably about 50 mg/ml, and most preferably about 100
mg/ml.
15 Thermoplastic Elastomeric Cooolvmers
The copolymers of the present invention are characterized in
having an elastomeric or flexible backbone and rigid,
thermoplastic, hydrophilic side chains. This combination of both
elastomeric and thermoplastic moieities in a single copolymer
20 provides the unique and useful properties of these materials. The
copolymers of the present invention, can also be referred to as
'graft copolymers' because they can be prepared from the
capolymeritation of monomer units and macromonmer units. In other
words, the macromonomer is 'grafted' or incorporated into the
25 copolymer.
These copolymers exhibit two distinct in~iscible phases.
itithout being limited by theory, it is believed that the
hydrophilic side chains of these copolymers are closely associated
with each other, thereby existing in one phase, while the backbone
30 of the copolymer remains in a separate phase. A consequence of
this phase ianiscibility is that these copolymers exhibit two
distinct glass transition temperatures or, 'Tg's', for the
backbone and the side chains. Tg is a well known ter°ei of art in
polymer science used to describe the temperature at which a
35 polymer or portion thereof undergoes a transition from a solid or
CA 02319800 2000-09-29
_. -
brittle material to a liquid or rubber-like material. Glass
transition temperatures can be measured using standard techniques
that are well known to the polymer scientist of ordinary skill in
the art. One particularly useful technique for determining glass
5 transitions is differential scanning calorimetry (also known as
DSC). The glass transition phenomenon in polymers is described in
Tntrnrluetier~ to Polymer Science and Technoloav: An SPE Textbook,
(eds. H.S. Kxufman and J.J. Falcetta), (John wiley ~ Sons: I477).
The Tg of the backbone of the copolymers herein (i.e. that
part of the copolymer not containing the side chains) should be
less than about OoC. Preferably the Tg of the backbone should be
from about -IOoC to about -130oC, more preferably from about -20oC
to about -125oC, and most preferably from about -55oC to about
-120oC. The Tg of the side chain of the copolymers (i.e. that
15 part of the copolymer not containing the backbone) is greater than
about 20oC. Preferably the Tg of the sidechain should be from
about 25oC to about 200oC, more preferably from about 30oC to
about 175oC, and most preferably from about 35oC to about 150oC.
Because these copolymers possess two distinct Tg's, these
20 copolymers are useful in hair styling and setting compositions.
liithout being limited by theory, it is believed that when these
copolymers are subjected to temperatures above both Tg's, they are
essentially liquid and can provide great flexibility during the
styling process (e. g., when curling irons, blow driers, and other
25 heat sources are applied to the hair). Upon cooling of the
copolymer to room temperature (e.g., when the heat source is
removed from the hair) the copolymer is then at a temperature that
is typically between both Tg's, and the copolymer possesses
structural rigidity from the macromonomer side chains, and yet has
30 flexibility from the backbones, and can provide a strong, yet
flexible, hair hold or style retention.
furthermore, at skin temperatures, these copolymers would be
at a temperature which is essentially between both Tg's. these
copolymers can enhance the film forming properties of skin care
CA 02319800 2000-09-29
_8_
coiapositions, and provide benefits shuch as better and a~ore even
distribution upon the skin.
The copolymers of the present invention are formed from the
copolymerizatton of randomly repeating A and B units, preferably
wherein the A units are selected from at least one polymerizable,
ethylenically unsaturated monomer unit, and the B units are
selected from at least- one hydrophilic macromonomer unit which
contains an ethylenically unsaturated moiety which is
copolymerizable with A. In typical embodiments of these
copolymers, the backbone is primarily derived frog the
ethylenically unsaturated portion of the A monomer unit and the
ethylenically unsaturated portion of the B macromonomer unit. The
side chains are derived from the non-copolymerized portions of the
macromonomer. The A and B units can be selected from a wide
vairety of structures as long as the limitations of the copolymer
are met (e.g., solubility, Tg's, and molecular weights)
The A monomer units of the copolymers of the present
invention can comprise from about 40X to about 90x, more
preferably from about 50x to about 85X, and most preferably from
about 60X to about 80X, by weight, of the copolymers.
The hydrophilic B macromonomer units can comprise from about
10Z to about 60x, more preferably from about 15x to about 50x, and
a~ost preferably frog about 20x to about 40X, by weight of the
copolymers.
The copolymers of the present invention have a weight average
molecular weight of at least about 10,000. There is no upper
limit for molecular weight except that which limits appltcability
of the invention for practical reasons, such as viscosity,
processing, aesthetic characteristics, formulation compatibility,
etc. In general, the weight average molecular weight is less than
about 5,000,000, more generally less than about 2,500,000, and
typically less than about 1,500,000. Preferably, the weight
average molecular weight is froei about 10,000 to about 5,000,000,
oars preferably from about T5,000 to about 1,000,000, even more
CA 02319800 2000-09-29
_g_
preferably from about 100,000 to about 850,000, and most
preferably from about 125,000 to about 750,000.
Alternatively, the copolymers of the present invention can
also be represented by the formula
(AJaI~Jb
wherein A and B are as described herein, and where a 1s an integer
of about 100 or greater, preferably a is an integer from about 100
to about 3000, more preferably from about 250 to about 2000, and
most preferably from about 350 to about 1500, and b is an integer
10 of about 2 or greater, preferably from about 2 to about 50, more
preferably from about 2 to about 20, and most preferably from
about 2 to about 10. In this formula, it is expressly intended
that even though ranges are provided for the subscripts a and b,
these subscripts are not intended to strictly limit the polymers
15 herein so long as the physical propoerties of the polymers are
achieved. when the copolymers herein are described by the formula
disclosed in this paragraph it has been found useful to describe
the copolymers by the m number average molecule weights. In
_ general, the number average molecular weight is less than about
20 2,500,000, more generally less than about 1,500,000, and typically
less than about 1,000,000. Preferably, the number average
molecular weight is from about 15,000 to about 1,000,000, more
preferably froa~ about 20,000 to about 500,000, and most preferably
frog about 25,000 to about 250,000.
30
CA 02319800 2000-09-29
-10-
By appropriate selection and combination of the particular A
and B units and by the choice of specific relative ratios of the
5 units yell within the ability of one of ordinary skill in the art,
the copolymers can be optimized for various physical properties
such as solubility, Tg's, and the like, and for compatibility with
other ingredients commonly used in hair care and skin care
applications.
10 lihen the copolymers of the present invention are Incorporated
into hair and/or skin care compositions, the copolymers typically
comprise from about O.lx to about 25x, preferably from about 0.5%
to about 20x, more preferably from about lx to about 10%, and most
preferably from about 2% to about 5X of the composition, although
15 higher or lower amounts can be used depending upon the particular
application.
Monoeier 'A' Unii~
The 'A' monomer unit is selected from polymerizable monomers,
preferably ethylenically unsaturated monomers. Either a single A
20 monomer or~combinations of two or more A monomers can be utilized.
For example, if two different A monomers are polymerized with a 8
macromonomer, the resulting copolymer could be described as a
terpolymer. In either case, the monomers are selected to meet the
requirements of the copolymer. By 'polymerizable', as used
25 herein, is meant monomers that can be polymerized using any
conventional synthetic techniques. Monomers that are
poiymerizable using conventional free radical initiated techniques
art preferred. the term 'ethylenically unsaturated' is used
herein to mean monomers that contain at least one polymeritable
30 carbon-carbon double bond (which can be ~ano~, di-, tri-, or
tetra-substituted).
Ths A monomer units of the copolymers of the present
invention can comprise from about 40% to about 90x, more
preferably from about 50x to about 85x, and most preferably from
35 about 60'x to about 80%, by weight, of the copolymers.
CA 02319800 2000-09-29
-11-
The ethylenically unsaturated A monomer units preferably can
be described by the following formula
0
X - C- CRS = CHR6
S
wherein X is selected from the group consisting of -OH, -0l1, -OR4,
-NH2, -NHR4, and -N(R4)Z; M is a catlon selected from the group
consisting of Na+, K+, Mg++, Ca++, Zn++, HH4+, alkylammonium,
dialkylammonium, trialkylanmonium, and tetralkylartenonium; each R4
10 is independently selected from the group consisting of H, C1-Cg
straight or branched chain alkyl, N,N-dimethylaminoethyl,
2-hydroxyethyl, 2-methoxyethyl, and 2-ethoxyethyl; and RS and R6
are independently selected from the group consisting of H, C1-C8
straight or branched chain alkyl, methoxy, ethoxy,
15 2-hydroxyethoxy, 2-methoxyethyl, and 2-ethoxyethyl.
. Representative noniimiting examples of monomers useful herein
include acrylic acid and salts, esters, and amides thereof. The
salts can be derived from any of the common nontoxic metal,
ammonium, or substituted ammonium counter ions. The esters can be
20 derived from C1.40 straight chain, C3-40 branched chain, or C3-40
carbocyclic alcohols; from polyhydric alcohois having from about 2
to about 8 carbon atoms and from about 2 to about 8 hydroxy groups
(nonlimiting examples of which include ethylene glycol, propylene
glycol, butylene glycol, hexylene glycol, glycerin, and
25 1,2,6-hexanetriol); from amino alcohols (nonlimiting examples of
which include aminoethanol, dimethylaminoethanol, and
diethylaminoethanol, and their quaternized derivatives); or from
alcohol ethers (nonliaiting examples of which include
methoxyethanol, and ethoxy ethanol)., The asides can be
30 unsubstituted, N-alkyl or H-alkylamino mono-substituted, or
N,N-dialkyl or N,H-dialkylamino di-substituted, wherein the alkyl
or alkylamino group can be derived from C1-4p straight chain,
C3~40 branched chain, or C3-40 carbocylic moietfes. Additionally,
the alkylan~ino groups can be quaternized. Also useful as monomers
35 are substituted acrylic acids and salts, esters, and amides
CA 02319800 2000-09-29
-12-
thereof (wherein the substituents are on the two and three carbon
positions of the acrylic acid and are independently selected froo
the group consisting of C1-4 alkyl, -CN, -COOH (e. g., methacrylic
acid, ethacrylic acid, and 3-cyano acrylic acid). The salts,
esters, and amides of these substituted acrylic acids can be
defined as described above for the acrylic acid salts, esters, and
amides. Other useful monomers include vinyl and aliyl esters of
C1-,0 straight chain, C3-40 branched chain, or C3-40 carbocylic
carboxylic acids; vinyl and allyl halides (e. g., vinyl chloride
10 and allyl chloride); vinyl and allyl substituted heterocylic
compounds (e. g., vinyl pyrridine and allyl pyridine); vinylidene
chloride; and hydrocarbons having at least one carbon-carbon
double bond (e. g., styrene, alpha-methyistyrene, t-butylstyrene,
butadiene, isoprene, cyclohexadiene, ethylene, propylene,
15 1-butane, 2-butane, lsobutylene, vinyl toluene); and mixtures
thereof.
Preferred A monomers useful herein include those selected
froa~ the group consisting of acrylic acid, methacrylic acid,
ethacrylic acid, methyl acrylate, ethyl acrylate, Q-butyl
20 acrylat~e, ~q-butyl acrylate, ~-butyl acrylate, 2-ethylhexyl
acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate,
n-butyl methacrylate, j,~-butyl methacrylate, ~,-butyl
methacrylate, 2~ethylhexyi methacrylats, decyl methacrylate,
methyl ethacrylate, ethyl ethacrylate, n-butyl ethacrytate,
25 j~-butyl ethacrylate, ~-butyl sthacrylate, 2-ethylhexyt
ethacrylate, decyl ethacrylats, 2,3-dihydroxypropyl acrylate,
Z,3-dihydroxypropyl methacrylate, 2-hydroxyethyi acrylate,
Z-hydroxypropyl acrylate, hydroxypropyl methacrylate, glyceryl
monoacrylate, giyceryl monomethacrylats,
30 acryiamide, meethacrylan~ide, ethacrylan~ide, N~methyl acrylaoida,
N,H-diaiethyl acryiamide, N,N-dimethyl methacryla~aids,
H-ethylacrylamide, N-isopropyl acrytamide, N-butyl acrylamide,
N-~-butyl acrylamide, N,ti-di-n-butylacrylaeide,
H,ti-disthylacrylamide, N-octyl acrylan~ide, N-octadecyl acrylaaide,
35 N-phenyl acrylamide, H-methyl methacrylamide,
CA 02319800 2000-09-29
-13-
N-ethylmethacrylamide. N-dodecylmethacrylamide, N,N-dimethylaminoethyl
acrylamide, quaternized N,N-dimethylaminoethyl acrylamide, N,N-
dimethylaminoethyl methacrylamide, quaternized N,N-dimethylaminoethyl
methacrylamide, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl
methacrylate, quaternized N.N-dimethylaminoethyl acrylate,
quaternized N,N-dimethylaminoethyl methacrylate, 2-hydroxyethyl
acrylate, 2-hydroxyethyl methacrylate. 2-hydroxyethyl ethacrylate,
glyceryl acrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate,
2-methoxyethyl ethacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl
methacrylate. 2-ethoxyethyl ethacrylate, malefic acid, malefic anhydride
and its half esters, crotonic acid, itaconic acid, angelic acid,
diallyldimethyl ammonium chloride, vinyl pyrrolidone methyl vinyl ether.
methyl vinyl ketone, maleimide, vinyl pyridine, vinyl imidazole, vinyl
furan, styrene sulfonate, allyl alcohol, vinyl alcohol, vinyl
caprolactam, and mixtures thereof.
More preferred A monomers are those selected from the group
consisting of methyl acrylate, methyl methacrylate, methyl ethacrylate,
ethyl acrylate, ethyl methacrylate, ethyl ethacrylate, n-butyl acrylate,
n-butyl methacrylate, n-butyl ethacrylate, 2-ethylhexyl acrylate, 2-
ethylhexyl methacrylate, 2-ethylhexyl ethacrylate, N-octyl acrylamide, 2-
methoxyethyl acrylate, 2-hydroxyethyl acrylate, N.N-dimethylaminoethyl
acrylate, and mixtures thereof.
Most preferred A monomers for the embodiment of the present
invention are those selected from the group consisting of n-butyl
acrylate, 2-ethylhexyl acrylate, N-octyl acrylamide. 2-methoxyethyl
acrylate, 2-hydroxyethyl acrylate, N,N-dimethylaminoethyl acrylate, and
mixtures thereof.
Hydrophilic "B" Macromonomer Units
A macromonomer is a large monomer unit, i.e. a macromolecular
monomer, which can be further polymerized with itself, with other
conventional monomers, or with other macromonomers. The term
"macrononomer" is one that is familiar to the polymer chemist of
ordinary skill in the art. The hydrophilic "B" macromonomer units
CA 02319800 2000-09-29
-14-
of the present invention are very large monomer building blocks
which can be formed from the polymerization of smaller monomer
units. The 8 macromonomers encompass a wide variety of
structures and are copolymerizable with the A monomer. Either a
single B macromonomer or combinattons of two or more B
macromonomers can be utilized. In either case, the macromonomers
are selected to meet the requirements of the copolymer.
The hydrophilic B macromonomers comprise from about lOX to
about 60X, more preferably from about 15x to about 50X, and most
10 preferably from about ZOx to about 40x, by weight of the
copolymers.
By the term 'copolymerizable' as used herein is meant B
macromonomers that can be reacted with the A monomer in a
polymerization reaction using any conventional synthetic
15 techniques. 'Copolymerization' is a tern of art used to refer to
the simultaneous polymerization of two or more different monomers.
In the present invention, B macromonomers that are copolymerizable
with A monomers using conventional free radical initiated
techniques are preferred. By the term 'hydrophilic' as used
20 herein is meant B macromonomers that are soluble in or have an
affinity for water and/or other polar, water-soluble solvent
materials (e.g., methanol, ethanol, propanol, isopropanol and the
like). "Hydrophilic' is also a tens of art used to described a
substance having a strong tendency to absorb water which results
25 in the swelling, solubilization, or dispersion of the substance in
water. W thout being limited by theory, the hydrophilic B
macrortanoaier units are believed to contribute to the overall water
or alcohol soluble or dispersible properties of the copolymers.
B a~acromono~oers that are useful herein contain an
30 ethylenically unsaturated oioiety that is copoiyinerizable with the
A mono~er. The tera 'sthylenically unsaturated" is used herein to
mean B macroa~ono~ners irhat contain it least one carbon-carbon
double bond (which can be mono-, dt-, tri-, or tetra-substituted).
Typically, the preferred B macromonomers are those that are
35 endcapped with the ethylenically unsaturated moiety. 8y
CA 02319800 2000-09-29
-15-
'endcapped' as used herein is ~oeant that the ethylenically
unsaturated moiety is at or near a terminal position of the
macromonomer. However, this definition of 'endcapped' is not
intended to limit the macromonomer to only those macromonomers
5 which terminate in a carbon-carbon double bond (whether mono-,
di-, tri-, or tetra-substituted).
The hydrophilic 8 macromonomers of the present invention can
be synthesized utilizing a variety of standard synthetic
procedures familiar to the polymer chemist of ordinary skill in
10 the art,. Furthermore, these macromonomers can be synthesized
starting from commercially available polymers. Typically the
weight average molecular weight of the macromonomer is from about
1000 to about 200,000, more preferably from 1500 to about 30,000,
and most preferably from about 2000 to about 25,000.
15 For example, the hydrophilic 8 macromonomers can be
synthesized by the polymerization (acid, bass, free radical, or
auto-initiated)-of a hydrophilic monomer to farm a polymer which
is subsequently reacted with or 'endcapped' with a structural unit
E, containing the ethylenically unsaturated moiety.
20 Alternatively, the B macromonomers can be synthesized starting
with commercially available hydrophilic polymers which are
'endcapped' with the structural unit E. In yet another
alternative, the B macromonoa~er can be synthesized by starting
with the structural unit E, and polymerizing onto it the desired
25 hydrophilic monomer units. It is to ba understood that in this
third alternative, the ethylenically unsaturated moiety of the E
unit is not consumed in the synthesis but its integrity is
preserved for subsequent copolymerization of tht B macromonomer
with tht A monomer units. All of the synthetic alternatives are
30 merely illustrative in that any other suitable synthetic
procedures can be utilized to prepare the 8 ~acromonomers and
copolymers of the present invention.
The B ~nacromonomers can be described by the following
formula
35 [ I jn - [ X jm - E.
CA 02319800 2000-09-29
-16-
X is a hydrophilic monomer unit, and m is an integer from
about 10 to about 2000, preferably from about 15 to about 300, and
more preferably from about 20 to about 250, so that the
macromonomer meets the weight average molecular weight
requirements set forth above. Preferred is when X is a
hydrophilic monomer unit selected from the group consisting of
oxazolines, H-alkyloxazolines, alkylene glycols,
N-vinylpyrrolidones, N-allylpyrrolidones, vinylpyridines,
allylpyridiens, vinylcaprolactams, allylcaprolactams,
10 vinylimidazoles, allylimidaoles, vinylfurans, allylfurans,
vinyltetrahydrofurans, ailyltetrahydrofurans, and mixtures
thereof. More preferred is wherein X is a monomer unit selected
from the group consisting of H-alkyloxazolines, alkylene glycols,
and mixtures thereof. Most preferred is wherein X is a monomer
15 unit selected from N-alkyloxazolines.
E is a structural unit containing the ethylenically
unsaturated moiety or 'endcapping' group. Preferred is when E is
selected from the group consisting of vinyl, allyl, acryloyl,
methacryloyl, ethacryloyl, styryl, 3-vinylbenzyl, ~-vinyibenzyl,
20 3-vinylbenzoyi, 4-vinylbentoyl, I-butenyl, I-propenyi, isobutenyl,
isoprenyl, cyclohexyl, cylcopentyl, and mixtures thereof. More
preferred is when E is selected from the group consisting of
vinyl, aliyl, acryloyl, methacryloyl, ethacryloyi, 3-vinylbenzyl,
~-vinylbenZyl, 3-vinylbenzoyl, t-vinylbenzoyl, 1-butenyl,
25 I-propenyl, isobutenyl, and mixtures thereof. !lost preferred is
when E is selected from the group consisting of vinyl, ally!,
acryioyl, methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl,
and Fixtures thereof.
I is an optionally present chemical moiety. In other words,
30 ~ is an integer selected from zero and one. Without being limited
by theory, I can be derived froo a chemical initiator or solvent
used in the synthesis of the B macromonomer. Honiimiting examples
of such initiators from which I can be derived include hydrogen
ion, hydrogen radical, hydride ion, hydroxide ion, hydroxyl
35 radical, peroxide radical, peroxide anion, C1~20 carbocations,
CA 02319800 2000-09-29
-17-
C1-20 carbanions, CI-20 carbon radicals, C1-20 aliphatic and
aromatic aikoxy anions, ammonium ion, and substituted ammonium
tons (e.g., C1-20 alkyl and C1-ZO alkoxy substituted). I can be
derived from any useful solvent, nonlimiting examles of which
5 inlcude water, methanol ethanol, propanol, isopropanol, acetone,
hexane, dichloromethane, chlorofora, benzene, and toluene.
Nonlimiting examples of I include chemical moieties selected from
the group consisting of H, CI-C6 alkyl, phenyl, 4-methyiphenyl,
and benzyl; preferably H, methyl, ethyl, and phenyl; and more
10 preferably H, methyl, and ethyl.
Representative examples of classes of endcapped B
macromonomers useful herein include those selected from the group
consisting of endcapped poly(N-alkyloxazolines), endcapped
polyalkylene glycol monoalkyl 'ethers, endcapped
15 ~pol~y(H-vinylpyrrolidones), endcapped ,poly(N-allylpyrrolidones),
endcapped polyvinyipyridines, endcapped polyallylpyridines,
~endcapped polyvinylcaprolactams, endcapped poiyallylcaprolactams,
endcapped polyvinylimidazoles, endcappped polyallylimidazoles,
endcapped polyvinylfurans, endcapped polyvinyltetrahydrofurans,
ZO endcapped polyallylfurans, endcapped polyacrylic acids, endcapped
polymethacrylic acids, endcapped polyallyltetrahdyrofur~ns, and
mixtures thereof.
Preferred are eacromonomers selected froa~ the group
consisting of endcapped poly(N-alkyloxazolines), endcapped
23 polyalkylene glycol monoaikyl ethers, and Aixtures thereof.
l~lore preferred ire endcapped poly(N-alkyloxazoline)
macromonomers.
Exaa~ples of endcapped poly(N-alkyioxazoline) nacroaonomers
are those having the following chemical formula:
30
R -~-NCHyCH2-j~-0-E
C~0
35
R'
CA 02319800 2000-09-29
-18-
wherein R and R' are independently selected frog H or C1-8
straight or branched chain alkyl, more preferably R and R' are
independently selected froo H, methyl, or ethyl; and most
preferably R is methyl and R' is ethyl. E is a copolymerizable,
ethylenicaily unsaturated moiety (i.e. the endcapping gaiety).
Preferred is when E is selected from the group consisting of
vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, styryl,
3-vinyibenzyl, ~-vinylbenzyl, 3-vinylbenzoyl, i-vinylbenzoyl,
I-butenyl, I-propenyl, isobutenyl, isoprenyi, cyclohexyl,
L0 cylcopentyl, and mixtures thereof. More preferred is when E is
selected from the group consisting of vinyl, allyl, acryloyl,
methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl,
3-vinyibenzoyl, 4-vinylbenzoyl, I-butenyl, I-propenyl, isobutenyl,
and mixtures thereof. Most preferred is when ~ is selected from
15 the group consisting of vinyl, allyl, acryloyl, methacryloyl,
ethacryloyl, styryl, 3-vinylbenzyl, t-vinylbenzyl, and mixtures
thereof. In the above structure 4 is preferably an integer from
about 10 to about 2000, more preferably from about 15 to about
300, and most preferably from about 20 to about 250.
20 ~ Alternatively, other examples of endcapped
poly(N-alkyloxazolint) macromonomers ire those having the
following chemical formula:
R- 0 -[-CH2CH2N-I~ - CHZ
C~0
CH=CH2
R'
30 wherein R and R' are independently selected frog the group
consisting of H or CI-8 straight or branched chain alkyl, more
preferably R and R' are independently selected from H, methyl, or
ethyl; and most preferably R is H and R' is ethyl. In the above
structure m is an integer from about I0 to about 2040, more
35
CA 02319800 2000-09-29
-19-
preferably from about 15 to about 300, and most preferably from
about 20 to about 250.
Highly preferred examples of endcapped poly(R-alkyloxazoline)
macromonomers useful herein include acryloyl endcapped
5 poly(2-ethyl oxazoline), methacryloyl endcapped poly(2-ethyl
oxatoline), styryl endcapped poly(2-ethyloxazoline), acryloyl
endcapped poiy(2-methyl oxazoline), methacryloyi endcapped
poly(2-methyl oxazoline), 3-vlnyibenzoyl endcapped
poly{2-methyloxazoline), 4-vinylbenzoyl endcapped
poly(2-methyloxazoline), and mixtures thereof.
The endcapped poly(N-alkyloxazoline) macroioonomers can be
synthesized using standard synthetic procedures which involve
polymerizing, usually under acid-catalyzed conditions, an
H-alkyloxazol.ine to yield a poiy(N~alkyloxazoline) alcohol. This
15 alcohol can then be subsequently endcapped, ea~ploying standard
reaction procedures, with the desired ethylenically unsaturated
moiety using a reactive or activated form of an endcapping group.
Suitable activated endcapping groups include vinyl, allyl,
1-propenyl, 3-vinylbenzyi, 4-vinylbenzyl, 3-vinylbenzoyl, and
20 4-vinylbenzoyl halides (c. g. chlorides, bromides, and iodides),
and the acid chlorides and bromides derived frog acrylic acid,
methacrylic acid, and ethacrylic acid. ~, e.g., S.I. Shoda et
al., 'Synthesis and Surfactant Property of Copolymers Having a
Poly{2-Oxazol ine) Graft Chain', Journal of Polv~ner Scien ~~ Part
25 A; Polymer Che~ni:try, vol. 30, pp. 1489-1494 (1992); T. Saegusa et
al., 'Macromoiecular Engineering on the Basis of the
Polymerization of 2-Oxazolines, I~la,kromol. Cheis., liacron~ol Svmn ,
vol. 51., pp. 1-10 (1991); S. Kobayashi et al., llacronalecylg~, vol
22, pp. 2878-2884 (1989), and U.S. Patent No. 4,011,376, to
30 T~lia et al., issued March 8, 1971; and U.S. Patent No.
3,786,116, to Milkovich et al., issued January 15, 1974.
Alternatively the poiyoxazoline macromononeers can be
synthesized by polymerizing the monomers onto an appropriate
endcapping group. For example, the vinyl benzyl endcapped
CA 02319800 2000-09-29
2U-
polyoxazolines can be prepared by polymerizing Z-ethyl-Z-oxazoltne
onto a mixture of 3-vinylbenzyl and 4-benzylchlorides. egg
EXArIPIE III.
Also highly useful herein are endcapped polyalkylene glycol
5 monoalkyl ether macromonomers corresponding to the following
general chemical formula
R'-[OCHZ-CHJp-0-E
R3
wherein R' is selected from CI-C40 straight or branched chain
alkyl, more preferably from CI-t8 straight or branched chain
alkyl, most preferably from C1~C4 straight or branched chain
alkyl, and most preferably methyl; R3 is selected from hydrogen,
methyl, ethyl, or n-propyl, more preferably from hydrogen or
15 methyl, most preferably froa~ H. E is a copolymerizable,
ethylenically unsaturated moiety (i.e. the endcapping moiety),
Preferred is when E is selected fros the group consisting of
vinyl, ally!, acryloyl, methacryloyl, ethacryloyl, styryl,
3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl,
ZO 1-butenyl,. 1-propenyl, isobutenyl, isoprenyl, cyclohexyl,
cylcopentyl, and mixtures thereof. More preferred is when E is
selected froo the group consisting of vinyl, ally!, acryioyl,
methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl,
3-vinytbenzoyl, 4-vinylbenzoyl, 1-butenyl, 1-propenyl, isobutenyl,
25 and ~i xtures thereof . !lost preferred i s when E i s sei ected froa~
the group consisting of vinyl, ally!, acryloyl, methacryloyl,
ethacryloyl, styryl, 3-vinylbenzyl, 4-vinylbenzyl, and mixtures
thereof: In the above structure, s is as described previously,
wherein a~ is preferably an integer froo about 20 to about 2000,
30
more preferably froo about 30 to about 750, and a~ost preferably
frog about 40 to about 500. It is to be understood that in the
above structure, that when R3 is other than hydrogen that various
isoaers of the resulting a~acromonort~er ire possible depending upon
the orientation of the individual glycol eoieties. Therefore, the
35 structure depicted above for these endcapped polyalkylene glycol
CA 02319800 2000-09-29
-21-
- ~nonol kayl ethers i s a general one that i s not intended to 1 imi t
these materials to any one particular isomeric structure.
Highly preferred examples of endcapped polyalkylene glycol
monoalkyl ethers useful herein inlcude acryloyl endcapped
polyethylene glycol monomethyl ether, 3-vinylbenzoyl endcapped
polyethylene glycol monomethyl ether, 4-vinylbenzoyl endcapped
polyethylene glycol monomethyl ether, methacryleyl endcapped
polyethylene glycol monomethyl ether, and mixtures thereof.
The endcapped polyalkylene glycol monoalkyl ethers can be
synthesized from the polyalkylene glycol monoalkyl ether and the
reactive or activated form of an endcapping group employing
standard reaction procedures. Suitable activated endcapping
groups include vinyl, allyl, 3-vinylbenzoyl, and 4-vinylbenzoyl
halides (e. g, chlorides, bromides, and iodides), and the acid
chlorides and bromides derived from acrylic acid, methacrylic
acid, and ethacrylic acid. The polyalkylene glycol monoalkyl
ether can be synthesized from the corresponding polyalkylene
glycol using any of the alkylating agents well known in the art
(e. g., methyl iodide, methyl bromide, diazomethane, methyl
sulfate, ethyl iodide). Polyethylene glycols of various molecular
weight ranges, as well as their methyl ethers are commercially
available from Aldrich Chemical Company and Union Carbide
Corporation. Alternatively, the polyalkylene glycols can be
synthesized from the corresponding alkylene oxides and alkylene
glycois~using standard synthetic
procedures (e.g., the acid or
base catalyzed polymerization of ilkylene oxides).
Svn- s of the Cooolvm r
In general, the copolymers can be made by free radical
polymerization of the A monomers with the B macromonomers. It is
not intended to necessarily exclude from this invention any
copolymers made by means other than free radical polymerization,
so long as the product has the desired physical properties. The
copolymers herein contain randomly repeating monomer units and
macromonomer uniis.
35'
CA 02319800 2000-09-29
.22.
The general principles of free radical polymerization
methods are well understood. See, for example, Odian, 'Principles
of Polymerization', 2nd edition, John liiley t Sons, 1981, pp.
179-318. The desired monomers and macromonomers are all placed in
a reactor, along with a sufficient amount of a mutual solvent so
that when the reaction is complete the viscosity of the reaction
is reasonable. Typical monomer and macromonomer loadings are from
about lOx to about SOx, on a weight basis. Undesired terminators,
especially oxygen, can be removed as needed. This is done by
evacuation or by purging with an inert gas, such as argon or
nitrogen. The initiator is introduced and the reaction brought to
the temperature needed for initiation to occur, assuming thermal
initiators are used. Nonlimiting examples of suitable initiators
include those selected from the group consisting of azo
initiators, peroxide initiators, redox initiators, a~
photochemical inittstors. The polymerization is allowed to
proceed as long as needed for a high level of conversion to be
achieved, typically from a few hours to a few days. The solvent
is then removed, usually by evaporation or by precipitating the
copolymer by addition of a nonsolvent. The copolymer can be
further purified, as needed utilizing a variety of techniQues
including filtration, extraction, trituration, e~embrane
separation, gel permeation chromatography, and like.
There are nuuerous variations on these procedures which ire
=5 entirely up to the discretion of the synthetic chemist (e. g.,
choice of degassing eiethod and gas, choice of initiator type,
extent of conversion, reaction loading, etc). The choice of ini
tiator and solvent are often deteroined by the requirements of the
particular Aonomers and aiacromonoawer used, because different
,~~n and macromonomers have different solubilities and
different reactivities to a specific initiator.
The copolymers of the present invt_ntion can also be
synthesized by first preparing the backbone from the
polyiaerization of_ suitable monomers, followed by further
polymerization of the backbone with suitable hydrophilic monomers
CA 02319800 2000-09-29
-23-
to fo no the polymeric side chains. This alternative procedure for
synthesizing the copolymers herein is illustrated in EXNiPIE VIII
below.
Analysis of the copolymer reaction product and the extracted
materials, and the purified copolya»r can bs per~oeired by
conventional analysis techniques known in the art. Thsss include,
for example, nuclear magnetic resource (WiR), infrared molecular
, spectroscopies,, gel psrmsation/sizs exclusion chromatography,
membrane osmometry, and atoo~ic absorption and eaission
spectroscopies.
Hair Cart and Tooical Skin Carp ~..~.,~iti.....
The copolymers of the present invention can be fornulated
into a wide variety of product types, including sousses, gels,
lotions, tonics, sprays, shaspoos, conditioners, rinses, hand and
~y lotions, facial aaisturizers, sunscnsns, anti-acne
preparations, topical analgesics, sascaras, and the tike. The
carriers and additional coaiponsnts required to formulate such
products vary with product type and can be routinely chosen by one
skilled in the art. The following is a description of sons of
?0 these carriers and additional components.
Carriers
Hair Care C_o~npositions
The hair care coepositions of the present invention can
comprises_ a carrier, or a efxtun of such carriers, which are
suitable for application to the hair. The carriers are present at
_ free abort 0.5'i to about 9g.5ii, preferably froo about 5.0~G to
about 99.5it, mono preferably free :bout 10.0 to about 98.0x, of
the co~position. As used herein, the phrase 'suitable for
application to hair' e~eans that the carrier doss not drags or
negatively affect the aesthetics of hair or cause irritation to
the underlying skin.
Carriers suitable for use with hair care compositions of the
pnssnt invention include, for exaapls, those used in the
for~lation of hair sprays, saussea, tonics, gels, shaepoos,
conditioners, and rinses. The choice of appropriate carrier will
CA 02319800 2000-09-29
-24-
also depend on the particular copolymer to be used, and whether
the product formulated is meant to be left on the surface to which
1t is applied (e. g., hair spray, mousse, tonic, or~gel) or rinsed
off after use (e. q., shampoo, conditioner, rinse).
The carriers used herein can include a ride range of
components conventionally used in hair care compositions. The
carriers can contain a solvent to dissolve or disperse the
particular copolymer being used, with water, the C1-C6 alcohols,
and mixtures thereof being preferred; and water, methanol,
10 ethanol, isopropanol, and mixtures thereof being more preferred.
The carriers can also contain a wide variety of additional
materials inlcuding, but not limited to acetone, hydrocarbons
(such as isobutane, hexane, decene), halogenated hydrocarbons
(such as Freons), linalool, esters (such as ethyl acetate, dibutyl
15 phthalate), and volatile silicon derivatives (especially siloxanes
such as phenyl pentamethyl disiloxane, methoxypropyl heptamethyl
cyclotetrasiloxane, chloropropyi pentamethyl disiloxane, hydroxy-
propyl pentamethyl disiloxane, octamethyl cyclotetrasiloxane,
decamethyl cyclopentasiloxane, cyclomethicone, and dimethicone
20 having for example, a viscosity at 25'C of about 15 centipoise or
less), and mixtures thereof, when the hair care composition is a
hair spray, tonic, gei, or mousse the preferred solvents include
water, ethanol, volatile silicone derivatives, and mixtures
thereof. The solvents used in such mixtures may be miscible or
25 i,nsiscible with each other. Mousses and aerosol hair sprays can
also utilize my of the conventional propellants to deliver the
material as a foam (in the case of a mousse) or as a fine, uniform
spray (in the cast of an aerosol hair spray). Examples of
suitable propellants include materials such as trichloro-
30 fluoromethane, dichlorodifluoromethane, difluoroethane,
dimethylether, propane, n-butane or isobutane. A tonic or hair
spray product having a low viscosity may also utilize an emul-
sifying agent. Examples of suitable emulsifying agents include
nonionic, cationic, anionic surfactants, or mixtures thereof.
35 Fluorosurfactants are especially preferred, particularly if the
CA 02319800 2000-09-29
-25-
product is a hair spray composition and most especially if it is a-
spray composition having relatively low levels of volatile organic
solvents, such as alcohols, and relatively high levels of water
(e.g., in excess of about 10X, by reight water). If such an
5 emulsifying agent is used, it is preferably present at a level of
from about O.O1X to about 7.5X of the composition. The level of
propellant can be adjusted as desired but is generally from about
3X to about 30X of mousse compositions and from about 15X to about
50X of the aerosol hair spray compositions.
10 Suitable spray containers are well known in the art and
include conventional, non-aerosol pump sprays i.e., 'atomizers,'
aerosol containers or cans having propellant, as described above,
and also pump aerosol containers utilizing compressed air as the
propellant. Pump aerosol containers are disclosed, for example,
15 in U.S. Patents 4,077,441, March 7, 1978, Olofsson and 4,850,577,
July 25 . 1989, TerStege, and also in Canadian Serial
No. 2.129.968, Gosselin, Lund, Sojka, and Lefebvre, "Consumer
Product Package Incorporating A Spray Device Utilizing
Large Diameter Bubbles". Pump aerosols hair sprays using
20 compressed air are also currently marketed by The Procter
& Gamble Company under their tradename UIDAL SASSOON AIRSPRAY~
hair sprays.
lihere the hair care compositions are conditioners and rinses
the carrier can include a wide variety of conditioning materials.
25 y~here the hair care compositions are shampoos, the carrier can
include surfactants, suspending agents, thickeners etc. Various
additional components useful in hair cars compositions ire
described in U.S. Patent No. 5,106,609, to Bolich, Jr. et al.,
issued April 21, 1992; and U.S. Patent No. 4,387,090, to Bolich,
30 Jr. issucd June 7, 1983.
Some of these additional components are described below.
Topical Skin Care Compositions
The topical cosmetic and pharmaceutical compositions of the
present invention can comprise a carrier. The carrier should be
35 ~cosmetlcally and/or pharmaceutically acceptable', which means
CA 02319800 2000-09-29
-26-
that the carrier is suitable for topical application to the skin,
has good aesthetic properties, is compatible with the copolymers
of the present invention and any other components, and will not
cause any untoward safety or toxicity concerns.
5 The carrier can be in a wide variety of forms. For exaople,
emulsion carriers, including, but not lioited to, oil-in-water,
water-in-oil, water-in-oil-in-water, and oil-in-water-in-silicone
emulsions, ire useful herein. These emulsions can cover a broad
range of viscosities, e.g, from about 100 cps to about 200,000
10 cps, These emulsions can also be delivered in the form of sprays
using either mechanical pump containers or pressurized aerosol
containers using conventional propellants. These carriers can
also be delivered in the form of a mousse. Other suitable topical
carriers include anhydrous liquid solvents such as oils, alcohois,
15 and si 1 i cones (e . g. , mi neral of 1, methanol , ethanol , i sopropanol
,
dimethicone, cyclomethicone, and the like); aqueous-based single
phase liquid solvents (e.g., hydro-alcoholic solvent systems); and
thickened versions of these anhydrous and aqueous-based single
phase solvents (e. g., where the viscosity of the solvent has been
20 increased to fore a solid or semi-solid by the addition of
appropriate gums, resins, waxes, polymers, salts, and the like).
Examples of topical carrier systems useful in the present
invention are described in the following four references:
'Sun
25 Products Formulary' ~osmetic~ il Toiletries, vol. 105, pp. 122-139
(December 1990); 'Sun Products Formulary', ~,Qseretics 8 Toiletries,
vol. 102, pp. 117-136 (March 1987); U.S. Patent No. 4,960,764 to
Figueroa et al., issued October 2, 1990; and U.S. Patent No.
4,25~,105 to Fukuda et al., issued Harch 3, 1981.
30 The carriers of the skin care compositions can c~nprise from
about 50x to about 99x by weight of the coisposltions of the
present invention, preferably fro4 about 75x to about 99x, and
most preferably froo about 85x to about 95x.
Preferred cosawtically and/or pharmaceut1ca11y acceptable
35 topical carriers include hydro-alcoholic systems and oil-in-water
CA 02319800 2000-09-29
-27-
emulsions. When the carrier is a hydro-alcoholic system, the
carrier can comprise from about 1% to about 99x of ethanol,
isopropanol, or mixtures thereof, and from about IX to about 9fx
of eater. More preferred is a carrier comprising from about 5x to
5 about 60x of ethanol, isopropanol, or mixtures thereof, and from
about 4fX to about 95x of water. Especially preferred is a
carrier comprising from about 20X to about 50x of ethanol,
isopropanol, or mixtures thereof, and frog about 50x to about 80%
of water. When the carrier is an oil-in-water emulsion. the
10 carrier can include any of the cortmon excipient ingredient. for
preparing these emulsions. ~ Additional components useful in
formulating these topical compositions are further described
below.
Additional Comconents
A wide variety of additional components can be employed in
the hair care and topical skin compositions herein. Non-limiting
examples include the following:
Pharmaceutical Actives
The compositions of the present invention, especially the
20 topical skin care compositions, can eomprise a safe and effective
amount of a pharmaceutical active. The phrase 'safe and effective
amount', as used herein, means an amount of an active high enough
to significantly or positively modify the condition to be treated,
but low enough to avoid serious side effects (at a reasonable
25 benefit/risk ratio), within the scope of sound medical ,~udgea~ent.
A-safe and effective amount of the pharmaceutical active will vary
with the specific active, the ability of the composition to
penetrate the active through the skin, the amount of composition
to be applied, the particular condition being treated, the age and
30 physical condition of the patient being treated, the severity of
the condition, the duration of the treatment, the nature of
concurrent therapy, and like factors.
Ths pharmaceutical actives which can be used in the
coapositions of the present invention preferably comprise from
35 about O.lx to about 20% by weight of the compositions, more
CA 02319800 2000-09-29
_28_
preferably from about O.lx to about lOx, and most preferably from
about O.lx to about 5X. Mixtures of pharmaceutical actives may
also be used.
Honlimiting examples of pharmaceutical actives can include
the following:
Useful pharmaceutical actives in the compositions of the
present invention include anti-acne drugs: Anti-acne drugs
preferred for use in the present invention include the
keratolytics such ~as salicylic acid, sulfur, lactic acid,
10 glycolic, pyruvic acid, urea, resorcinol, and N-acetylcysteine;
retinoids such as retinoic acid and its derivatives (e.g., cis and
traps); antibiotics and antimicrobials such as benzoyl peroxide,
octopirox, erythromycin, zinc, tetracyclin, triclosan, azelaic
acid and its derivatives, phenoxy ethanol and phenoxy proponol,
15 ethylacetate, clindamycin and meclocycline; sebostats ,such as
flavinoids; alpha and beta hydroxy acids; and bile salts such as
scymnol sulfate and its derivatives, deoxycholate, and cholate.
Preferred for uss herein is salicylic acid.
Useful pharmacetuical actives in the compositions of the
20 present invention include non-steroidal anti-inflammatory drugs
(NSAIDS). The NSAI05 can be selected from the following
categories: propionic acid derivatives; acetic acid derivatives;
fena~ic acid derivatives; biphenylcarboxylic acid derivatives; and
oxica~s. A11 of these NSAIDS are fully described in the U.S.
25 Patent 4,985,459 to Sunshine et al., issued January 15, 1991.
Most preferred are the
propionic NSAIDS including but not limited to Aspiri n',
acetaa~inophen, Ibuprofen, naproxen, benoxaprofen, flurbi.profen,
fenoprofen, fenbufen, ketoprofen, indoprofen, pirprofen,
30 carprofen, oxaprozin, pranoprofen, ~iroprofen, tioxaprofen,
suprofen, ~loinoprofen, tiaprofenic acid, fluprofen and bucioxic
acid. Als4 useful are the steroidal anti-inflammatory drugs
including hydrocortisone and the like.
Useful pharmaceutical actives in the compositions of the
35 present invention include antipruritic drugs. Antipruritic drugs
CA 02319800 2000-09-29
_29_
preferred for inclusion in compositions of the present invention
include pharaaceutically-acceptable salts of methdilizine and
trimeprazine.
Useful pharmaceutical actives in the compositions of the
5 present invention include include anesthetic drugs. Anesthetic
drugs preferred for inclusion in compositions of the present
invention include pharmaceutically-acceptable salts of lidocaine,
bupivacaine, chlorprocaine, dibucaine, etidocaine, mepivacaine,
tetracaine, dyclonine, hexylcaine, procaine, cocaine, ketamine,
10 pramoxine and phenol.
Useful pharmaceutical actives in the compositions of the
present invention include antimicrobiai drugs (antibacterial,
antifungal, antiprotozoal and antiviral drugs). Antimicrobial
drugs preferred for inclusion in compositions of the present
15 invention include pharmaceutically-acceptable salts of p-lactam
drugs, quinolone drugs, ciprofloxacin, norfioxacin, tetracycline,
erythromycin, amikacin, triclosan, doxycycline, capreomycin,
chlorhexidine, chlortetracycline, oxytetracycline, clindamycin,
ethambutol, metronidazole, pentamidine, gentamicin, kanamycin,
ZO lineomycin, a~ethacycline, methenamine, minocycline, neomycin,
netilmicin, paromomycin, streptomycin, tobramycin, miconazole and
amanfadine. Antimicrobial drugs preferred for inclusion in
compositions of the present invention include tetracycline
hydrochloride, erythromycin estoiate, erythromycin stearate
25 (salt), amikacin sulfate, doxycyclint hydrochloride, capreoa~ycin
sulfate, chlorhtxidine gluconate, chlorhexidine hydrochloride,
chlortetracycline hydrochloride, oxytetracycline hydrochloride,
clinda~nycin hydrochloride, tthambutol hydrochloride, metronidazole
hydrochloride, pentamidine hydrochloride, gentamicin sulfate,
30 kanamycin sulfate, lineomycin hydrochloride, methacycline
hydrochloride, methenaa~ine hippuratt, methenamine mandelatt,
minocycline hydrochloride, ne~ycin sulfate, netilmicin sulfate,
paromomycin sulfate, streptomycin sulfate, tabramycin sulfate,
miconaZOie hydrochloride, amanfadine hydrochloride, amanfadine
35
CA 02319800 2000-09-29
-30-
sulfate, triclosan, octopirox, parachlorometa xylenol, nystatin,
tolnaftate and clotrimazole.
Also useful herein are sunscreening agents. A wide variety
of sunscreenlng agents are described in U.S. Patent Ho. 5,087,445,
5 to Haffey et al., issued February 11, 1992; U.S. Patent No.
5,073,372, to Turner et al., issued December 11, 1991; U.S. Patent
No. 5,073,371, to Turner et ai. issued December 17, 1991; and
Segarin, et al., at Chapter VIII, pages 189 et seq., of Cosmetics
Sc i ence and Iechnol a~ .
10 Preferred among those sunscreens which are useful in the
compositions of the instant invention are those selected fram the
group consisting of 2-ethylhexyl p-methoxycinnamate, 2-ethylhexyl
N,N-dimethyl-p-aminobentoate, p-aminobenzoic acid,
2-phenyibenzimidazole-5-sulfonic acid, octocrylene, oxybenzone,
15 homomenthyl saiicylate, octyl salicylate,
4,4'-methoxy-~-butyldibenzoylmethane, 4-isopropyl
dibenzoylmethane, 3-benzylidene camphor, 3-(4-methylbenzylidene)
camphor, titanium dioxide, zinc oxide, silica, iron oxide, and
mixtures thereof.
20 Still other useful sunscreens are those disclosed in U.S.
Patent No. 4,937,370, to Sabatelli, issued June 26, 1990: and U.S.
Patent No. 4,999,186, to Sabatelli et al., issued March 1Z, 1991.
The sunscreening agents disclosed therein have, in a
single molecule, two dtstinct chromophore Aoieties which axhibit
25 different ultra-violet radiation absorption spectra. One of the
chro~ophore moieties absorbs predominantly in the UVB radiation
range and the other absorbs strongly in the UVA radiation range.
These sunscreening agents provide higher efficacy, broader UV
absorption, lower skin penetration and longer lasting efficacy
30 relative to conventional sunscreens. Especially preferred
examples of these sunscreens include those selected from the group
consisting of 4-N,N~(2~ethylhexyl)methylaminobenzoic acid ester of
2,4-dihydroxybenzophenone, 4-N,N-(2-ethylhexyl)methylaminobenzoic
CA 02319800 2000-09-29
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acid ester with 4-hydroxydibenzoylmethane, 4-ti, H- (2-ethylhexyl)-
methylaminobenzoic acid ester of Z-hydroxy-4-(2-hydroxyethoxy)ben-
zophenone, 4-N,N-(2-ethylhexyl)-methylamtnobenzoic acid ester of
4-(2-hydroxyethoxy)dibenzoylmethane, and o~txtures thereof.
6eneraliy, the sunscreens can comprise from about O.Sx to
about ZO% of the compositions useful herein. Exact amounts will
vary depending upon the 'sunscreen chosen and the desired Sun
Protection Factor (SPF). SPF is a cortmonly used measure of
photoprotection of a sunscreen against erythema. egg Fe ral
10 Rea-, Vol. 43, No. 166, pp. 38206-38269, August 25, 1978.
Also useful in the present invention are sunless tanning
agents including dihydroxyacetone, giyceraldehyde, indoles and
their derivatives, and the like. These sunless tanning agents aay
also be used in combination with the sunscreen agents.
15 Other useful actives include skin bleaching (or lightening)
agents including but not limited to hydro4uinone, ascorbic acid,
ko,)ic acid and sodium metabisulfite.
Other useful actives which are especially useful for hair
care compositions include anti-dandruff actives such as zinc
20 pyrithione, octopirox, seleniua~ disulfide, sulfur, coal tar, and
the like.
Conditioners
Conditioning agents useful herein, and especially useful for
hair~care coaroositions, include hydrocarbons, silicone fluids, and
25 cationic materials.
The hydrocarbons can be either straight or branched chain and
can contain froa about 10 to about 16, preferably frog about 12 to
about 16 carbon atoa~s. Examples of suitable hydrocarbons are
decane, dodecane, tetradecane, tridecane, and mixtures thereof.
30 Silicone conditioning agents useful hero n can include either
cyclic or linear polydimethylsiloxanes, pheny and alkyl phenyl
silicones, and silicone copolyols. The linear volatile silicones
generally have viscosities of less than about 5 centistokes at
CA 02319800 2000-09-29
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25oC, while the cylic materials have viscosities less than about
centistokes.
Cationic conditioning agents useful herein can include
quaternary ammonium salts or the salts of fatty amines. Preferred
quaternary ammonium salts are dialkyl dimethyl ammonium chlorides,
wherein the alkyl groups have from 12 to 22 carbon atoms and are
derived from long-chain fatty acids. Representative examples of
quaternary ammonium salts include ditallow dimethyl ammonium
chloride, ditallow dimethyl ammonium methyl sulfate, dihexadecyl
10 dimethyl ammonium chloride, and di(hydrogenated tallow) ansnonium
chloride. Other qauternary ammonium salts useful herein are
dicationics such as tallow propane dianmonium dichloride.
Quaternary imidazolinium salts are also useful herein. Examples
of such materials are those imidazolinium salts containing C12-22
15 alkyl groups such as
1-methyl-1-[(stearoylamide)ethyl]-2-heptadecyl-4,
5-dihydroimidazolinium chloride,
1-methyl-1-[(palmitoylamide)ethyl]-2-octadecyl-4,5-dihydroimidazo-
linium chloride and
20 1-methyl-1-((tallowamids)-ethyl]-2-tallow-imidazolinium methyl
sulfate. Also useful herein are salts of fatty amines. Examples
of such compounds include stsarylamine hydrochloride, soyamine
hydrochloride, and stsarylaa~ine formats. Useful conditioning
agents are disclosed in U.S. Patent No. 4,387,090, to Bolich,
25 issued June 7, 1983.
Mumectants and Moisturizers
The compositions of the present invention can contain one or
more humectant or moisturizing materials. A variety of these
maters al s can be empi oyed and each can be present at a 1 suet of
30 fros about O.lx to about 20lC, more preferably from about lx to
about lOx and most preferably froa~ about 2x to about 5x. These
materials include urea; guanidine; glycolic acid and glycolate
salts (s. g. ammonium and quaternary alkyl ammonium); lactic acid
and lactate salts (e. g. ammonium and quaternary alkyl ammonium);
35 aloe very in any of its variety of forms (e.g., aloe vera gel);
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polyhydroxy alcohols such as sorbitol, glycerol, hexanetriol,
propylene glycol, butylene glycol, hexylene glycol and the like;
polyethylene glycols; sugars and starches; sugar and starch
derivatives (e. g., alkoxyiated glucose); hyaluronic acid;
5 lactamide monoethanolamine; acetamide monoethanolamine; and
mixtures thereof. Preferred humectants and moisturizers are
glycerol, butylene glycol, hexylene glycol, and mixtures thereof.
Surfactants
The. compositions of the present invention, especially the
10 shampoo and conditioner compositions, can contain one or more
surfactants. These surfactants are useful ad,~uncts for the
carriers of the present compositions, and are not required for
solubilizing or dispersing the copolymers of the present
invention. For a shampoo, the level is preferably from about
15 1pX to about 30X, preferably from 12X to about 25X, of the
composition. For conditioners, the preferred level of surfactant
is from about O.ZX to about 3X. Surfactants useful in
compositions of the present invention include anionic, nonionic,
cationic, zwitterionic and amphoteric surfactants. A wide variety
20 of surfactants useful herein are disclosed in U.S. Patent No.
5,151,209, to Mc Call et al., issued September 29, 1992; U.S.
Patent No. 5,151,210, to Steuri et al., issued September 29,
1992; and U.S. Patent No. 5,120,532, to halls et al., issued June
9, 1992 .
25 Nbnlimiting examples of theca surfactants include anionic
surfactants such as alkyl and alkyl ether sulfates. Theca
materials typically have the respective formulae ROS03M and
RO(C2N40)xS03M, wherein R is alkyl or alkenyl of from about 10 to
about 20 carbon atoms, x is 1 to 10, and !i is a water-soluble
30 can on such as anraonium, sodium, potassium and triethanolamine.
Another suitable class of anionic surfactants are the water-
solubla salts of the organic, sulfuric acid reaction products of
the general formula:
R1-S03-M
35
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wherein R1 is chosen from the group consisting of a straight or
branched chain, saturated aliphatic hydrocarbon radical having
from about 8 to about 24, preferably about 12 to about 18, carbon
atoms; and M is a can on. Additional examples of anionic
synthetic surfactants which come within the terms of the present
invention 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; sodium or
potassium salts of fatty acid amides of methyl tauride in which
the fatty acids, for example, are derived from coconut oil. Still
other anionic synthetic surfactants include the class designated
as succinamates, olefin sulfonates having about 12 to about 24
carbon atoms, and B-alkyloxy alkane sulfonates. Many additional
nonsoap synthetic anionic surfactants ire described in
pc~~+~heon's Detergents and Emulsifiers. 1984 Annual, published
by Allured Publishing Corporation.
Also U.S. Patent 3,929,678, t.aughlin et al., issued
December 30, 1975, discloses many other anionic as well as other
surfactant types.
Nonionic surfactants useful herein are preferably used in
combination with an anionic, amphoteric or zwitterionic
surfactant. Thsse nonionic surfactants can be broadly defined as
compounds produced by the condensation of alkylene oxide groups
(hydrophilic in nature) with an organic hydrophobic compound,
which may-be aliphatic or alkyl aromatic in naturc.
Cationic surfactants useful in compositions of the present
invention are disclosed in the following documents:
M.C. Publishing Co.,
~rmtcheon's Detera~~ts 8 Emulsifiers, (North Averican edition
1979); SchwartZ. et al., Surface Active Agents, Their Chemistry
and Technologic, New York: Interscisnce Publishers, 1949; U.S.
Patent 3,155,591, Hilfer, issued November 3, 1964; U.S. Patent
3,929,678, Laughlin, et al., issued December 30, 1975; U.S. Patent
3,959,461, Bailey, et al., issued May 25, 1976; and U.S. Patent
4,387,090, Bolich, Jr., issued June 7, 1983. If included in the
CA 02319800 2000-09-29
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compositions of the present invention, the cationic surfactant is
present at from about 0.05X to about 5x.
Zwitterionic surfactants are exemplified by those which can
be broadly described as derivatives of aliphatic quaternary
ammonium, phosphonium, and sulfonium compounds, in which the
aliphatic radicals can be straight or branched chain, and wherein
one of the aliphatic substituents contains from about 8 to about
18 carbon atoms and one contains an anionic water-solubilizing
group, e.g., carboxy, sulfonate, sulfate, phosphate, or
phosphonate. Other zwitterionics such as betaines are also useful
in the present invention. Examples of betaines include the high
alkyl betaines, such as coco dimethyl carboxymethyl betaine,
- lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha
carboxyethyl betaine, cetyi dimethyi carboxymethyl betaine, lauryl
bis-(2-hydroxyethyl) carboxymethyl betaine, stearyl bis-(2
hydroxypropyl) carboxymethyl betaine, oleyl dimethyl~ gamna-
carboxypropyl betaine, lauryl bis-(2-hydroxypropyl)alpha-
carboxyethyl betaine, coco dimethyl sulfopropyl betaine, stearyl
dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine,
lauryl bis-(2-hydroxyethyl) sulfopropyl betaine, and amidobetaines
and amidosulfobetaines (wherein the RCONH(CH2)3 radical is at-
tached to the nitrogen atom of the betaine).
Examples of amphoteric surfactants which can be used in the
2S co~ositions of the present invention are those which are 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 at~os and one contains an anionic water
solubilizing group, e.g., carboxy, sulfonate, sulf~tl, phosphate,
or phosphonate. Examples of compounds falling Within this defini-
tion are sodium 3-dodecyl-aminopropionate, sodium 3-dodecylamino-
propane sulfonate, N-alkyltaurines such as the one prepared by
reacting dodecylamine with sodium isethionate according to the
teaching of U.S. Patent 2,658,072, H-higher alkyl aspartic acids
such as those produced according to the teaching of U.S. Patent
CA 02319800 2000-09-29
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2,438,091, and the products sold under the trade name 'Miranol'
and described in U.S. Patent 2,528,378.
Carboxviic Acid Cooolvmer Thickeners
Another component useful in the compositions herein is a
5 carboxylic copolymer thickener. These crosslinked polymers
contain one or more monomers derived from acrylic acid,
substituted acrylic acids, and salts and esters of these acrylic
acids and the substituted acrylic acids, wherein the crosslinking
agent contains two or more carbon-carbon double bonds and is
10 derived from a polyhydric alcohol. The preferred polymers for use
herein are of two general types. The first type of polymer is a
crosslinked homopolymer of an acrylic acid monomer or derivative
thereof (e.g., wherein the acrylic acid has substituents on the
two and three carbon positions independently selected from the
15 group consisting of C1-4 alkyl, -CN, -COOH, and mixtures thereof).
The second type of polymer is a crosslinked copolymer having a
first monomer selected from the group consisting of an acrylic
acid monomer or derivative thereof (as just described in the
previous sentence), a short chain alcohol (i.e. a C1-4) acrylate
20 ester monomer or derivative thereof (e. g., wherein the acrylic
acid portion of the ester has substituents on the two and three
carbon positions independently selected from the group consisting
of CI_4 alkyl, -CH, ~CODE1, and mixtures thereof), and mixtures
thereof; and a second monomer which is a long chain alcohol (i.e.
25 C8-40) acrylate ester monomer or derivative thereof (e. g., wherein
the acrylic acid portion of the ester has substituents on the two
and three carbon positions independently selected from the group
consisting of CI_4 alkyl, -CN, -COOH, and a~ixtures thereof).
Coebinations of these two types of polymers are also useful
30 herein.
In the first type of crosslinked homopolyaiers the monomers
are preferably selected from the group consisting of acrylic acid,
methacrylic acid, ethacryitc acid, and mixtures thereof, with
acrylic acid being most preferred. In the second type of
35 crosslinked copolymers the acrylic acid monomer or derivative
CA 02319800 2000-09-29
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thereof is preferably selected from the group consisting of
acrylic acid, methacrylic acid, ethacrylic acid, and mixtures
thereof, with acrylic acid, methacrylic acid, and mixtures thereof
being most preferred. The short chain alcohol acrylate ester
5 monooier or derivative thereof is preferably selected from the
group consisting of C1_4 alcohol acrylate esters, C1_4 alcohol
methacrylate esters, C1_4 alcohol ethacrylate esters, and mixtures
thereof, with the C1_4 alcohol acrylate esters, C1_4 alcohol
methacrylate esters, and mixtures thereof, being most preferred.
10 The long chain alcohol acrylate ester monomer is selected from
C8_40 alkyl acrylate esters, with C10-30 alkyl acryiate esters
being preferred.
The crosslinking agent in both of these types of polymers is
a polyalkenyl polyether of a polyhydric alcohol containing more
15 than one alkenyl ether group per molecule, wherein the parent
polyhydric alcohol contains at least 3 carbon atoms and at least 3
hydroxyl groups. Preferred crosslinkers ire those selected from
the group consisting of allyl ethers of sucrose and allyl ethers
of pentaerythritol, and mixtures thereof. These polymers useful
20 in the present invention are more fully described in U.S. Patent
No. 5,087,445, to Haffey et al., issued February 11, 1992; U.S.
Patent No. 4,509,949, to Huang et al., issued April 5, 1985; U.S.
Patent No. 2,798,053, to Broom, issued July 2, 1957; which are
incorporated by reference herein. ~~, CTFA International
25 c~~~t;~ Ingredient Dictionary, fourth edition, 1991, pp. 12 and
80.
Exaa~les of coaoercially availble hompolymers of the first
type useful herein include the carbomers, which are homopolymers
of acrylic acid crosslinked with allyl ethers of sucrose or
30 pe~taerytritol. The carbomers are available as tha CarbopolR 900
series froa~ B.F. Goodrich. Examples of commercially available
copolymers of the second type useful herein include copolymers of
C10-30 alkyl acrylates with one or more uonomers of acrylic acid,
methacrylic acid, or one of their short chain (i.e. C1_~ aicoholj
35 esters, wherein the crosslinking agent is an allyl ether of
CA 02319800 2000-09-29
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sucrose or pentaerytritol. These copolymers are known as
acrylates/C10-30 alkyl acrylate crosspolymers and are commerically
available as CarbopolR 1342, Pemulen"TR-1, and Pemolen TR-2, from
B.F. Goodrich. In other words, examples of carboxylic acid
polymer thickeners useful herein are those selected from the group
consisting of carbomers, acrylates/C10-C30 alkyl acrylate
crosspolymers, and mixtures thereof.
The compositions of the present can comprise from about
0.025x to about lx,~ more preferably from about 0.05X to about
10 0.75x and most preferably from about O.IOX to about 0.50X of the
carboxylic acid polymer thickeners.
Emulsifiers
The compositions herein can contain various emulsifiers.
These emulsifiers are useful for emulsifying the various carrier
15 components of the compositions herein, and are not required for
solubiliiing or dispersing the copolymers of the ' present
invention. Suitable emulsifiers can include any of a wide variety
of nonionic, cationic, anionic, and zwitterionic emulsifiers
disclosed in the prior patents and other references. _Sge
20 I~IcCutcheon's, Qetergents and EmuTsifier~, North American Edition
(1986), published by Allured Publishing Corporation; U.S. Patent
No. S,OlI,681 to Ciotti et al., issued April 30, 1991; U.S. Patent
No. 4,421,769 to Dixon et al., issued December 20, 1983; and U.S.
Patent No. 3,755,560 to Dickert et al., issued August 28, 1973.
25 Suitable eawlsifier types include esters of glycerin, esters
of propylene glycol, fatty acid esters of polyethylene glycol,
fatty acid esters of polypropylene glycol, esters of sorbitol,
esters of sorbitan anhydrides, carboxylic acid copolymers, esters
and ethers of glucose, ethoxylated ethers, ethoxylated alcohols,
30 alkyl phosphates, polyoxyethylene fatty ether phosphates, fatty
acid amides, acyl lactylates, soaps and mixtures thereof.
Suitable emulsifiers can include, but are not limited to,
polyethylene glycol 20 sorbitan monolaurate (PolysorbateT" 20),
CA 02319800 2000-09-29
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polyethylene glycol 5 soya sterol, Steareth 20, CetearethTH20,
PPG-2 methyl glucose ether distearate, CetethT~lO, Polysorbate 80,
cetyl phosphate, potassium cetyl phosphate, diethanolamine cetyl
phosphate, Polysorbate 60, glyceryl stearate, PEG-100 stearate.
and mixtures thereof.
The emulsifiers can be used individually or as a mixture of
two or more and can compri se from about O.1X to about 10X, more
preferably from about 1X to about 7X, and most preferably from
about 1X to about 5X of the compositions of the present invention.
10 Emol 1 i en~,~
The compositions useful in the methods of the present
invention can also optionally comprise at least one emollient.
Examples of suitable emollients include, but are not limited to,
volatile and non-volatile silicone oils, highly branched
15 hydrocarbons, and non-polar carboxylic acid and alcohol esters,
and mixtures thereof. Emollients useful in the instant invention
are further described in U.S. Patent No. 4,919,934, to Oeckner.et
al., issued April 24 1990.
The emollients can typically comprise in total from about 1X
20 to about 50X, preferably from about 1X to about 25X, and more
preferably from about lx to about lOX by weight of the
compositions useful in the present invention.
Additional Components
A variety of additional components can be incorporated into
25 the compositions herein. Hon-limiting examples of these
additional components include vitamins and derivatives thereof
(e. g:, ascorbic acid, vitamin E, tocopheryl acetate, retinoic
acid, retinol, retinoids, and the like); low pH thickening agents
(e.g. polyacrylamide and C13-14 isoparaffin and laureth-7,
30 available as Sepigel~ from Seppic Corporation; polyquaternium and
mineral oil, available as Salcare SC92, from Allied Colloids;
crosslinked methyl quaternized dimethylaminomethacrylate and
mineral oil, available as Salcare SC95 from Allied Colloids;
resins; gums and thickeners such as xanthan gum, carboxymethyl
CA 02319800 2000-09-29
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cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose,
alkyl-modified hydroxyalkyl celluloses (e. g. long chain alkyl
modified hydroxyethyl celluloses such as cetyl
hydroxyethylcellulose), and magnesium aluminum silicate; cationic
polymers and thickeners (e. g., cationic guar gum derivatives such
as guar hydroxypropyltrimonium chloride and hydroxypropyl guar
hydroxypropyltrimonium chloride, available as the Jaguar C series
from Rhone-Poulenc; polymers for aiding the film-forming
properties and substantivity of the composition (such as a
10 copolymer of eicosene and vinyl pyrrolidone, an example of which
is available from GAF Chemical Corporation as GanexR V-220);
suspending agents such as ethylene glycol distearate and the like;
preservatives for maintaining the antimicrobial integrity of the
compositions; skin penetration aids such as OMSO,
15 1-dodecylatacycloheptan-2-one (available as Atone from the Upjohn
Co.) and the like; antioxidants; chelators and sequestrants; and
aesthetic components such as fragrances, colorings, essential
oils, skin sensates, astringents, skin soothing agents, skin
healing agents and the like, nonlimiting examples of these
20 aesthetic components include panthenot and derivatives (e. g. ethyl
panthenol), pantothenic acid and its derivatives, clove oil,
menthol, caa~phor, eucalyptus oil, eugenol, menthyl lactate, witch
hazel distillate, allantoin, bisabalol, dipotassium
glycyrrhizinat~ and the like.
25 Method of Usinci Hair and Skin Care Compositions
The hair care and skin care compositions of the present
invention are used in conventional ways to provide the desired
benefit appropriate to the product such as hair styling, holding,
cleansing, conditioning and the like for hair care compositions
30 and benefits such as moisturization, sun protection, anti-acne,
anti-wrinkling, artificial tanning, analgesic, and other cosmetic
and pharmaceutical benefits for skin cars compositions. Such
methods of use depend upon the type of composition employed but
generally involve application of an effective amount of the
35 product to the hair or skin, which may then be rinsed from the
CA 02319800 2000-09-29
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hair or skin (as in the case of shampoos and some conditioning
products) or al 1 owed to remai n on the hai r ( as i n the case of spray,
mousse, or gel products). or allowed to remain on the skin (as in the
case of the skin care compositions). By "effective amount" is meant an
amount sufficient to provide the benefit desired. Preferably, hair
rinse, mousse, and gel products are applied to wet or damp hair prior
to drying and styling of the hair. After such compositions are applied
to the hair, the hair is dried and styled in the usual ways of the
user. Hair sprays are typically applied to dry hair after it has
already been dried and styled. Cosmetic and pharmaceutical topical skin
care compositions are applied to and rubbed into the skin.
The following examples further illustrate preferred embodiments
within the scope of the present invention. The examples are given
solely for the purposes of illustration and are not to be construed as
limitations of the present invention as many variations of the
invention are possible without departing from its spirit and scope.
EXAMPLES
The following examples further describe and demonstrate
embodiments within the scope of the present invention and the parent
application. The examples are given solely for the purpose of
illustration and are not to be construed as limitations of the present
invention, as many variations thereof are possible without departing
from the spirit and scope of the invention.
Ingredients are identified by chemical or CTFA name.
EXAMPLE 1
S~mthesis of Poly(2-ethyl-2-oxazoline) Alcohol
To a solution of 50 g (0.5044 mol) of 2-ethyl-2-oxazoline
in 50 mL of acetonitrile is added 0.92 g (0.0048 mol) of methyl-
p-toluenesulfonate at 0°C under a nitrogen atmosphere. The reaction
mixture is heated at 80°C for 20 hours and the resulting
polymer solution is then refluxed with 2.3 mL distilled water
in the presence of 5.6 g (0.0528 mol) of sodium carbonate for
24 hours. The solvents are removed under vacuum. The residue is
CA 02319800 2000-09-29
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extracted with 300 mL of dichloromethane for 24 hours, and the
insolubles are removed by suction filtration. The
dichloromethane is then evaporated to yield about 48 g {96x yield)
of poly(2-ethyl-2-oxatoline) alcohol.
EXAMPLE II
Synthesis of Acrvlate-Canoed Polvl2-ethyl-2-oxazoline) Alcohol
Macromonomer
To a solution of 48 g of poly(2-ethyl-2-oxazoline) alcohol
(from EXAMPLE I) and 1.0 g (0.01056 mol) of triethylamine in 80 mL
10 of dichloromethane is added dropwise a solution of 0.95 g (0.01056
mol) of acryloyl chloride at OoC under a nitrogen atmosphere. The
reaction mixture is then stirred at room temeprature for 36 hrs,
and the resulting solution is then suction filtered to remove the
insolubles. The solvent and any unreacted triethylamine are
15 removed by evaporation under vacuum. The resulting solid is then
redissolved in 200 ml of dichloromethane, filtered, and evaporated
under vacuum to yield about 45.6 g (95X yield) of the
macromonomer.
Using an analogous procedure the methacrylate and ethacrylate
20 endcapped macromonomers are prepared by replacing the acryloyl
chloride with an equivalent molar amount of methacryloyl chloride
and ethacryloyl chloride, respectively.
EXAlIPLE III
c~~th.~i5 of Yinvlbenzvl-Cacced Polv(2-ethyl-2-oxazolinel Alcohol
25 Macromonomer
To a solution of 50 g (0.5044 mol) of 2-ethyl-2-oxazoline in
50 ml of acetonitrite is added a mixture of 0.3816 g (0.0025 mol)
of meta and paravinylbenzylchlorides (available from Aldrich
Chemical Co.), 0.562 g (0.0037 mol) of sodium iodide and 0.06 g
30 (0,00023 mot) of H,H'-Biphenyl-~-phenylenediamine. The solution
.is then heated at 90oC for 16 hours. To the resulting reaction
product is added 100 mL of dichloromethane and the solution is
filtered and then precipitated in 800 ml of ether, The
precipitate product is collected by vacuum filtration and dried
35
CA 02319800 2000-09-29
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under vacuum at ambient temperature to yield about 45 g (90X
yield) of the macromonomer.
EXAh1 P L E I Y
5 5vnthesis of Acrvlate-Canoed Polv(ethvlene glvcol)methvl ~Fther
hlacromonomer
To a solution of 50 g (0.01 mol) of polyethylene
glycol)methyl ether having an average molecular weight of about
5000 (commercially available from Aldrich Chemical Co.) and 4.05 g
10 (0_04 mol) of triethylamine in 400 mL of dichloromethane is added
dropwise at OoC under a nitrogen atmosphere a solution of 2.26 g
(0.025 mol) of acryloyl chloride dissolved in 25 ml of
dichloromethane. The reaction mixture is then stirred at room
temeprature for 36 hrs, and the resulting solution is then suction
15 filtered to remove the insolubles. The solvent and any unreacted
triethylamine are removed by evaporation under vacuum. The
resulting solid is then redissolved in 300 mL of dichloromethane,
filtered, and evaporated under vacuum to yield about 50 g (100X
yield) of the macromonomer.
20 The above procedure is varied using other polyethylene
glycol)alkyl ethers (e. g. methyl, ethyl, 2-sthylhexyl, decyl,
dodecyl, cetyl, stearyl, lauryl, and myristyl wherein the polymer
has an average molecular weight varying from about 1000 to about
200,000) to obtain the analogous acrylate-capped ~acromonomers.
25 Additionally, the methacrylate and ethacrylate endcapped
macromonoaiers are prepared by replacing the acryloyl chloride with
an equivalent molar amount of methacryloyl chloride and
ethacryloyl chloride, respectively.
30
Synthesis of Polv(n-butyl acrvlate)-ql~aft-oolv(2-ethyl-2-oxazo-
line) Thermoplastic Elastomeric C~yolvmer
To a solution of 16.0 g (0.1248 mol) of 0-butyl acrylate, and
4 g of acrylate capped poly(2-ethyl-2-oxazoline) macromonomer
35
CA 02319800 2000-09-29
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(from Example II) in 100 ml of acetone is added 0.03 g (0.00018
mol) of azoisobutyronitrile (AIBN) initiator. The resulting
solution is refluxed slowly for about 20 hours. The reaction is
then quenched by the addition of about 5 mL of methanol. The
5 solution is then poured into a Teflon' pan and the acetone is
evaporated at room temperature under a fume hood. The resulting
polymer film is redissovled in ethanol, filtered, and the ethanol
is then evaporated to yield about 18.4 g of the thermoplastic
elastomeric copolymer.
10 Alternatively, by varying the monomers and macromoners used,
this procedure is used to prepare other copolymers of the present
invention.
EXAMPLE VI
15 Synthesis of Polv(n-bud,vl-co-2-methoxvethvlacrvlatel-craft-oolv(2-
~,~hvl 2 oxazolinel Thermoplastic Elastomeric CoXiolvmer~ Method I
To a solution of 4.5 g (0.035 mol) of ~-butyl acrylaEe, 2.5 g
(0.0192 mol) of 2-methoxy ethylacrylate and 3 g
poly(2-ethyl-2-oxazoline) macromonomer (from Example II) in 40 ml
20 of acetone is added 0.05 g of AI6N irritator. The resulting
solution is refluxed slowly for about 20 hours. The reaction is
then quenched by the addition of about 5 ml of methanol. The
solution is then poured into a teflon pin and the acetone is
evaporated at room temperature under a fume hood. The resulting
25 polymer film is redissovled in ethanol, filtered, and the ethanol
is then evaporated to yield about 9.5 g of the thermoplastic
elastomeric copolymer.
Alternatively, by~varying the nwnomers and macromoners used,
this procedure is used to prepare other copolymers of the present
30 invention.
EXAMPLE VII
Svnthe~is of Polv(n-butyl- co-2-methoxvethvla crv~iatel-oraft -oolv(2-
2thv1 2 oxazolinel plastic ElastomericCopolymer: thod
Thermo Me II
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To a 500 ml round-bottomed flask is added 20.8 g (0.1623 mol)
of n-butyl acrylate, 11.2 g (0.0861 mol) of 2-methoxyethyl
acrylate, 0.30 g (0.002 mol) ~-vinylbenzyl chloride, and 0.02 g
(0.0012 mol) of azoisobutyronitrile (AIBN) irritator, in 200 ml of
acetone. The resulting solution is refluxed slowly for about 24
hours. The reaction is then quenched by the addition of about 5
ml of methanol and cooled to room temperature. The solvents are
removed by rotary evaporation and the resulting polymer is
dissolved in 250 mL of dry acetonitrile. Next 20.0 g (0.2018 mol)
0,.- 2-ethyl-2-oxazoline and 0.44 g (0.0029 mol) of sodium iodide is
added and the solution is heated to 90oC for 20 hours. The
. resulting solution is filtered and the solvent is evaporated to
yield about 45.0 g (86X yield) of the thermoplastic elastomeric
copolymer.
Alternatively, by varying the monomers used, this procedure
is used to prepare other copolymers of the present invention.
EXAMPLE VIII
Synthesis of Polvln-butyl co 2 ldimethvlaminoiethvl metharrvlatel
craft-oolvl2-ethyl-2-oxazolinel Thermoplastic Elast merit
To a solution of 7.Z g (0.0561 mol) of 0-butyl acrylate, 4.8
g (0.0305 mol) of 2-(dimethylamino)ethyl methacrylate, and 8.0 g
poly(2-ethyl-2-oxazoline) macromonomer (from Example II) in 80 ml
of acetont is added 0.01 g of AIBN irritator. The resulting
solution is refluxed slowly for about 24 hours. The reaction is
then quenched by the addition of about 5 mL of methanol. The
solution is then poured into a teflon pan snd the acetone is
evaporated at room temperature under a fume hood. The resulting
polymer film is redissovled in ethanol, filtered, and the ethanol
is then evaporated to yield about 18.4 g of the thermoplastic
elastomeric copolymer.
Alternatively, by varying the monomers and macromoners used,
this procedure is used to prepare other copolymers of the present
invention.
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EXAMPLE IX
~ nthesis of Methyl Quaternized Polv(n-butyl-co-2-(dimethvlaminol-
~~vl methacrvlatelaraft-y~olv(2-ethyl-2-oxazoline) Thermoplastic
Flash Copolymer
5 To l0 grams of the copolymer from EXAMPLE VIII dissovled in
80 grmas of ethanol is added dropwise 4.32 g (0.0281 mole) of
dimethylsulfate. The resulting solution is stirred for 2 hours at
room temperature. The solvent is removed by rotary evorpation to
yield about 10 grams of the methyl quaterniied copolymer.
10
Hai r~Sora_v
Hair spray compositions are prepared from the following
components utilising conventional mixing techniques.
15 Ingredients ~.9nc x
9 ~ ~ Q
water QS 100 QS 100 QS 100 QS 100
Ethanol (SOA 40) 79.0 79.0 79.0 90.0
Copolymer of Example VI1 4.0 4.0 3.0 3.0
20 Fragrance 0.1 0.2 --- ---
These products ire prepared by first dissolving the polymer
in the ethanol with stirring. The water and fragrance are then
added with stirring. The resulting hsir spray compositions can
25 then be packaged .in a nonaerosol spray pump. Alternatively, the
compositions can be combined with conventional propellants and
packaged in an aerosol spray.
These hair sprays are useful for application to the hair to
provide a styling and holding benefit.
30
1 Alternatively, spray compositions are prepared using the
copolymers of Examples V and VIII.
35
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EXAMPLE X1
geduced Volatile Organic Content Hairsorav
Hair spray compositions are prepared from the following
components utilizing conventional mixing techniQues.
Ingredients V~gight x
Q
Water QS 100 QS 100 QS 100- QS 100
Ethanol (SDA 40) 54.0 54.0 54.0 54.0
Copolymer of Example VI1 4.0 3.0 4.0 3.0
Fragrance 0.05 O.Z --- ---
These products are prepared by first dissolving the polymer
in the ethanol with stirring. The water and fragrance are then
added with stirring. The resulting hair spray compositions can
15 then be packaged in a nonaerosol spray pump. Alternatively, the
compositions can be combined with conventional propellants and
packaged in an aerosol spray.
These hair sprays are useful for application to the hair to
provide a styling and holding benefit.
1 Alternatively, spray compositions are prepared using the
copolymers of Examples V and VIII.
~XA~tPLE
~usse XII
Mousse compositions are prepared
from the
following
coa~ohents utilizing convent ional mixingtechniques.
t Weight
x
s A
Ingredien
Water QS 100 QS 100 QS 100
Copolymer of Example VIII1 3.00 2.50 3.50
Lauramide DEA 0.33 0.33 0.33
SodiuA Methyl Oleyl Taurate I.67 1.67 1.67
DMOM Hydantoin 0.78 0.78 0.78
pisodium DTA 0.20 0.20 0.20
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Polyoxyalkylated isostearyl
Alcohol2 0.10 0.10 0.10
Fragrance 0.10 0.10 0.10
Propellant3 7.0 7.0 7.0
5
These products are prepared by first dissolving the polymer
in water with stirring. The remaining ingredients, except the
propellant, are' then added with stirring.
The resulting mousse concentrate can then be combined with
10 conventional propellants (e.g., Propellant A46) and packaged in an
aerosol spray.
These mousses are useful for application to the hair to
provide a styling and holding benefit.
15 1 Alternatively, mousse compositions are prepared using the
copolymers of Examples V and and VI.
2Available as Aerosurf~" 66-E10:
3Available as a mixture of 82.46x isobutane, I6.57X propane, and
O.OOIX butane.
20
Hair Tonic
Hair ionic compositions are prepared from the following
25 components utilizing conventional mixing techniques.
Ingredients weight ~
9
Ethanol (SOA 40) QS 100 QS 100 QS 100
Copolymer of Example UI1 0.75 1.00 1.25
30 Fragrance 0.10 0.20 0.30
These products are prepared by dissolving the polymer in the
ethanol with stirring and then adding the fragrance and any
colors.
35
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These hair tonics are useful for application to the hair to
provide a styling and holding benefit.
1 Alternatively, tonic compositions are prepared using the
copolymers of Examples Y and VIII.
EXAMPLE XIY
Hair Conditioner
A hair conditioner composition is prepared from the following
components utilizing conventional mixing techniques.
Ingredient Weight x
Stvlina Agent Premix
Copolymer of Example IX 1.00
Silicone Premix
Silicone gum, GE SE761 0.30
Octamethyl cyclotetrasiloxane 1.70
Main MixMix
water QS100
Cetyl Alcohol 1.00
Quaternium 182 0.85
Stearyl Alcohol 0.70
Hydroxethyl cellulose 0.50
Ceteareth-20 0.35
Fragrance 0.20
Dimethicone copolyol 0.20
Citric Acid 0.13
Methylchloroisothiazolinone (and)
~thylisothiazolinone 0.04
Sodium Chloride 0.01
The product is prepared by co~aixing all the Main Mix
ingredients, heating to about 60oC with mixing, and colloid
milling while cooling to about 45oC. At this temperature, the two
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premixes are add separately with moderate agitation and the
resultant conditioner is allowed to cool to room temperature.
This product is useful as a rinse off hair conditioner.
5 1 Commercially available from General Electric.
2 Dimethyl Di(Hydrogenated Tallow) Ammonium Chloride
EXAMP! E XV
Shampoo Composition
10 A shampoo composition is prepared from the following
components utilising conventional mixing techniques.
Ingredients Weight x
~tvlina Agent
15 copolymer from Example IX 1.00
Premi xx
Silicone gum 0.50
Dimethicone, 350 cs fluid 0.50
20
Main Mix
water OS100
Artmoniua~ lauryl sulfate 11.00
Cocamide MEA 2.00
25 Ethylene glycol distearate 1.00
Xanthan Guar 1.20
Methy-lchloroisothiaZOlinone (and)
methylisothiatolinone 0.0~
Citric Acid to pH 4.5 as needed
30
The Main Mix is prepared by first dissolving the xanthan gum
in the water with conventional mixing. The remaining Main Mix
ingredients are added and the Main Mix is heated to 150oF with
agitation for 1/2 hour. The Styling Agent and the Premix are then
35 added sequentially with about 10 minutes of agitation between
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51-
additions, and the entire mixture isstirred while the batch is
cooled to room temperature. For varied particile size, the
Styling AGent and Premix can be added at different times using
either or both high shear mixing (high speed dispersator) or
5 normal agitation.
This shampoos is useful for cleansing the hear and for
providing a styling benefit.
Example XYI
10 Anti-Acne Ccomposition
An anti-acne composition is made by combining the following
components using conventional mixing technology.
15 Ingredient Neiaht x
hater QS100
5aiicylic Acid 2.0
Copolymer from Example VI1 2.0
Ethanol (SOA 40) 40.0
20
The compositon display skin penetration of the salicylic acid
as well as improved skin reel and residue characteristics and is
useful for the treatment of acne.
25 1 Alternatively, the anti-acne compositions are prepared using the
copolymers of Examples VIII and IX.
30
35
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Example XVII
Topical Anal esic Composition
A topical analgesic composition is made by combining the
following ingredients utilizing conventional mixing techniques.
j,naredient W, eight x
Hater, Purified QS100
Ibuprofen Z.0
Copolymer from Example YII 2.0
Ethanol (SDA 40) 20.0
IO
The compositions display skin penetration of the ibuprofen
active as well as improved skin feel and residue characteristics
together with excellent moisturizing, emolliency, rub-in and
absorption characteristics.
15
I Alternatively, the topical analagesic compositions are prepared
using the copolymers of Examples VIII and IX.
I~camule XYIII
20 c~~nless Tannins Composition
A composition for sunless tanning is made by combining the
following ingredients utilizing conventional a~ixing techniques.
25
Pha-
hater qs 100
Copolymer from Example YI1 2.00
Carbomer 9342 0.20
30 Carbomer 9803 0.15
Acrylic Acid Copolymer4 0.15
Phase B
PPG-20 Methyl Glucose Ether
35 Distearate 2.00
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Tocopheryl Acetate 1.20
Mineral Oil 2.00
Stearyl Alcohol 1.00
Shea Butter 1.00
5 Cetyl Alcohol 1.00
Ceteareth-20 2.50
Ceteth-2 1.00
Ceteth-10 1.00
10 ph
DEA-Cetyl Phosphate 0.75
Phase D
Dihydroxyacetone 3.00
15
Phase E
8utylene Glycol Z.00
OMOh Hydantoin (and)
Iodopropynyl Butylcarbamate 0.25
20
Phase F
Fragrance 1.00
Cyclomethicone 2.00
25 In a suitable vessel the Phase A ingredients are dispersed in
the water and heated to 75-85oC. In a separate vessel the Phase B
ingredients are combined and heated to 85-90oC until melted.
Next, the DEA-Cetyl Phosphate is added to the liquid Phase B and
stirred until dissolved. This mixture is then added to Phase A to
30 form the emulsion. The emulsion is cooled to 40-45oC with
continued mixing. Next, in a separate vessel, the
dihydroxyacetone is dissolved in water and the resulting solution
is mixed into the emulsion. In another vessel, the Phase E
ingredients are heated with mixing to 40-45oC until a clear
35 solution is formed and this solution is then added to the
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emulsion. Finally, the Phase F ingredients are added to the
emulsion with mixing, which is then cooled to 30-35oC, and then to
room temperature.
Thi s emul sion i s useful for topical appl ication to the skin
5 to provide an artificial tan.
1 Alternatively, the artificial tanning compositions are prepared
using the copolymers of Examples VIII and IX.
2 Available as CarbopolR 934 from B.F. Goodrich.
10 3 Available as CarbopolR 980 from B.F. Goodrich.
4 Available as Pemulen TR1 from B.F. Goodrich.
EXAMPLE XIX
15 Sunscreen Com~iosition
An oil-in-water emulsion is prepared by combining the
following components utilizing conventional mixing techniques.
Ingredients - W_e_i hq t x
ZO Phase A
Water QS100
Carbomer 9541 0.24
Carba~er 13422 0.16
Copolymer from Exmaple VII3 1.75
25 Disodium EDTA 0.05
Phase 8
Isoarachidyl Neopentanoate4 2.00
PVP Eicosene Copoiymer5 Z.00
30 Octyl Methoxycinnaa~ate 7.50
Octocryl ere 4 . 00
Oxybenzone 1.00
Titanium Dioxide 2.00
Cetyl Palmitate 0.75
35 Stearoxytrimethylsilane
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(and) Stearyl Alcohol6 0.5'0
Glyceryl Tribehenate7 0.75
Dimethicone 1:00
Tocopheryl Acetate 0.10
DEA-Cetyl Phosphate 0.20
Phase C
Water 2.00
Triethanolamine 99x 0.60
phase D
Water 2.00
Butylene Glycol 2.00
DMDM Hydantoin (and)
15 Iodopropynyl Butylcarbamate8 0.25
dl Panthenol 1.00
Ph
Cyclomethicone 1.00
I Available as CarbopolR 954 from B.F. Goodrich.
2 Available as CarbopolR I342 from B.F. Goodrich.
3 Alternatively, the sunscreen compositions are prepared using the
copolymers of Examples VIII and IX.
25 4 Available as Elefac~I-205 from 8ernel Chemical.
5 Available as GaneX Y-220 frog GAF Corporation.
6 Available as DC 580 Wax from Dow Corning.
7 Available as SynchrowaX NRC from Croda.
8 Available as GlydantT~Plus from LonZa.
In a suitable vessel tha Phase A ingredients are dispersed in
the water and heated to 75-85oC. In a separate vessel the Phase B
ingredients (except OEA-Cetyl Phosphate) are combined and heated
to 85-90oC until melted. Next, the DEA-Cetyl Phosphate is added
to the liquid Phase B and stirred until dissolved. This mixture
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is then added to Phase A to form the emulsion. The Phase C
ingredients are combined until dissolved and then added to the
emulsion. The emulsion is then cooled to 40-45oC with continued
mixing. In another vessel, the Phase 0 ingredients are heated
5 with mixing to 40-45oC until a clear solution is formed and this
solution is then added to the emulsion. Finally, the emulsion is
cooled to 35oC and the Phase E ingredient is added and mixed.
This emulsion is useful for topical application to the skin
to provide protection from the harmful effects of ultraviolet
10 radiation.
EXAMPLE XX
Facial Moisturizer
A leave-on facial emulsion composition containing a cationic
15 hydrophobic surfactant is prepared by combining the following
components utilizing conventional mixing techniques.
Ingredient l~gi~ t x
Mater QS100
ZO Copolymer from Example VI1 1.00
Glycerin 3.00
Cetyl Palmitate 3.00
Cetyl Alcohol 1.26
Quaternium22 1.00
25 Glyceryl Monohydroxy Stearate 0.74
Dimethicons 0.60
Stearic Acid 0.55
Octyldodecyl hyristate 0.30
Potassium Hydroxide 0.20
30 Carbomer 1342 0.125
Tetrasodius EDTA 0.10
OMDM Hydantoin and Iodopropynyl
Butyl Carbamate 0.10
Carboaier 951 0.075
35
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This emulsion is useful for application to the skin as a
moisturizer.
Alternatively, the moisturizers are prepared using the
copolymers of Examples VIII and IX.
