Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02413276 2002-12-16
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METHODS OF ENHANCING DELIVERY
OF OIL-SOLUBLE SKIN CARE ACTIVES
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of co-pending U.S. Application No.
09/613,266
filed July 10, 200'0, incorporated herein by reference, and to which this
application claims the
benefit of priority.,
TECHNICAL FIELD
This invention relates to the field of water-in-oil emulsion compositions
containing
silicone elastomers. More particularly, this invention relates to a method of
using water-in-
silicone emulsion compositions containing silicone elastomers to enhance the
delivery of oil-
soluble skin care actives into the skin.
BACKGROUND
Numerous skin care compositions are known in the art containing oil-soluble
actives such
as terpene alcohols, phytosterols, anti-acne actives, beta-hydroxy acids,
vitamin B3 compounds,
retinoids, anti-oxidants/radical scavengers, chelators, flavonoids, anti-
inflammatory agents, anti-
cellulite, and topical anesthetics, that are known to provide skin benefits.
Extremely popular are
oil-in-water and water-in-oil emulsion compositions that may include a variety
of oil-soluble skin
care actives in the oil phase of the emulsion. In general, the oil phase is
comprised of organic
oils, such as mineral oil. However, water-in-oil emulsion compositions tend to
impart an oily feel
to the skin and are thus undesirable from a consumer standpoint.
In addition, when such oil-soluble skin care actives are present in the oil
phase of an oil-
in-water or water-in-oil emulsion, it is often difficult to formulate such
that the actives leave
("partition out oP') the oil phase when the composition is applied to the
skin. Therefore, less of
the active present in the composition is actually delivered into the skin and
the efficacy of such
oil-soluble skin care actives is limited.
Therefore, there exists a need to improve the efficacy of compositions
containing oil-
soluble skin care actives. It is believed that the amount of active delivered
into the skin (i.e. "skin
penetration" of the active), is primarily controlled by two factors; 1)
concentration of the active in
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the oil; and 2) solubility of the active in the oil versus solubility of the
active in the skin. The
latter factor leads to a dynamic equilibrium on the skin surface.
One way of increasing the delivery of skin care actives into the skin is to
increase the
amount of the oil-soluble skin care actives) present in the composition.
However, this leads to
increased cost, increased possibility of adverse reactions with other
ingredients, and the potential
for greater skin irritation.
An alternative approach is to decrease the solubility of the oil-soluble
active in the oil
phase which would then lead to an increase in the amount of active that
partitions out of the oil
phase and into the skin. Unfortunately, oil-soluble skin care actives are
inherently very soluble in
oil which makes it difficult to decrease the solubility enough to produce such
an effect. In
addition, modifying the solubility of the oil-soluble active in the oil would
have a negative effect
on the concentration of the active in the oil phase; i.e., the amount of
active would be lower. As
discussed above, the concentration of the active in the composition is also a
factor in skin
penetration.
One way to improve the oily feel of water-in-oil emulsions is to replace the
organic oil
discontinuous phase with a silicone oil. Silicone provides a smooth, non-oily
feel to the skin.
The broad class of silicone elastomers, including both emulsifying and non-
emulsifying silicone
elastomers is well-known in the art for formulating stable skin care
compositions with a variety of
benefits. See, e.g., U.S. Patents Nos. 5,412,004, U.S. 5,654,362, 5,889,108,
and 5,811,487.
Specific combinations of silicone elastomers.are also known, such as the
combination
taught by U.S. Patent 6,221,979, for solubilizing water-soluble and oil-
soluble skin care actives in
order to achieve a uniform composition.However, oil-soluble skin care actives
are poorly soluble
in silicone.
Therefore, there is a need for a skin care composition that can provide
improved delivery
of oil-soluble skin care actives into the skin and also impart good aesthetic
benefits.
SUMMARY
The present invention relates to topical water-in-oil compositions useful for
enhancing the
delivery of oil-soluble skin care actives. The compositions comprise a
silicone oil, a silicone
elastomer and an oil-soluble skin care active. Preferably, the oil-soluble
skin care active is
selected from terpene alcohols, phytosterols, anti-acne actives, beta-hydroxy
acids, vitamin B3
compounds, retinoids, anti-oxidants/radical scavengers, chelators, flavonoids,
anti-inflammatory
agents, anti-cellulite, topical anesthetics, and mixtures thereof.
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The present invention also relates to methods of enhancing the delivery of oil-
soluble skin
care actives into the skin.
DETAILED DESCRIPTION
While the specification concludes with the claims particularly pointing and
distinctly
claiming the invention, it is believed that the present invention will be
better understood from the
following description.
All percentages and ratios used herein are by weight of the total composition
and all
measurements made are at 25°C, unless otherwise designated.
As used herein, the "skin care products" are those used to treat or care for,
or somehow
moisturize, improve, or clean the skin. Products contemplated by the phrase
"skin care products"
include, but are not limited to moisturizers, personal cleansing products,
occlusive drug delivery
patches, nail polish, powders, wipes, hair conditioners, skin treatment
emulsions, shaving creams
and the like.
The term "ambient conditions" as used herein refers to surrounding conditions
under
about one atmosphere of pressure, at about 50% relative humidity, and at about
25°C. unless
otherwise specified.
The compositions of the present invention can include, consist essentially of,
or consist
of, the components of the present invention as well as other ingredients
described herein. As
used herein, "consisting essentially of means that the composition or
component may include
additional ingredients, but only if the additional ingredients do not
materially alter the basic and
novel characteristics of the claimed compositions or methods.
All percentages, parts and ratios axe based upon the total weight of the skin
care
compositions of the present invention, unless otherwise specified. All such
weights as they
pertain to listed ingredients are based on the active level and, therefore, do
not include carriers or
by-products that may be included in commercially available materials, unless
otherwise specified.
All publications cited herein axe hereby incorporated by reference in their
entirety.
In any embodiment of the present invention, the skin care actives useful
herein can be
categorized by the benefit they provide or by their postulated mode of action.
However, it is to be
understood that the actives useful herein can in some instances provide more
than one benefit or
operate via more than one mode of action. Therefore, classifications herein
are made for the sake
of convenience and are not intended to limit the active to that particular
application or
applications listed.
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The term "keratinous tissue," as used herein, refers to keratin-containing
layers disposed
as the outermost protective covering of mammals (e.g., humans, dogs, cats,
etc.) which includes,
but is not limited to, skin, lips, hair, toenails, fingernails, cuticles,
hooves, etc.
The term "dermatologically-acceptable," as used herein, means that the
compositions or
components thereof so described are suitable for use in contact with mammalian
keratinous tissue
without undue toxicity, incompatibility, instability, allergic response, and
the like.
The term "safe and effective amount" as used herein means an amount of a
compound or
composition sufficient to significantly induce a positive benefit, preferably
a positive keratinous
tissue appearance or feel benefit, or positive hair appearance or feel
benefit, including
independently or in combinations the benefits disclosed herein, but low enough
to avoid serious
side effects, i.e., to provide a reasonable benefit to risk ratio, within the
scope of sound judgment
of the skilled artisan.
"Signs of skin aging" include, but are not limited to, all outward visibly and
tactilely
perceptible manifestations as well as any other macro or micro effects due to
skin aging. Such
signs may be induced or caused by intrinsic factors or extrinsic factors,
e.g., chronological aging
and/or environmental damage. These signs may result from processes which
include, but are not
limited to, the development of textural discontinuities such as wrinkles and
coarse deep wrinkles,
skin lines, crevices, bumps, large pores (e.g., associated with adnexal
structures such as sweat
gland ducts, sebaceous glands, or hair follicles), or unevenness or roughness,
loss of skin
elasticity (loss and/or inactivation of functional skin elastin), sagging
(including loss and/or
damage to functional subcutaneous muscle tissue and including puffiness in the
eye area and
jowls), loss of skin firmness, loss of skin tightness, loss of skin recoil
from deformation,
discoloration (including undereye circles), blotching, sallowness,
hyperpigmented skin regions
such as age spots and freckles, keratoses, abnormal differentiation,
hyperkeratinization, elastosis,
collagen breakdown, and other histological changes in the stratum corneum,
dermis, epidermis,
the skin vascular system (e.g., telangiectasia or spider vessels), and
underlying tissues, especially
those proximate to the skin.
It is desirable to have one or more oil-soluble skin care actives present in
skin care
compositions (for example, moisturizing creams and lotions) to provide skin
care benefits such as
regulating the condition of skin. However, it is also desirable to increase
the delivery potential of
a given active. The use of a silicone elastomer enhances the delivery
potential of oil-soluble skin
care actives and thereby increases the efficacy of a particular active.
The present invention is also useful for therapeutically regulating visible
and/or tactile
discontinuities in mammalian skin, including discontinuities in skin texture
and color. For
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example, the apparent diameter of pores decreases, the apparent height of
tissue immediately
proximate to pore openings approaches that of the interadnexal skin, the skin
tone/color becomes
more uniform, and/or the length, depth, and/or othex dimension of lines and/or
wrinkles are
decreased.
The compositions of the present invention are also useful for regulating the
condition of
skin and especially for regulating keratinous tissue condition. Regulation of
skin condition,
namely mammalian and in particular human skin condition, is often required due
to conditions
which may be induced or caused by factors internal and/or external to the
body. Examples
include, enviromnental damage, radiation exposure (including ultraviolet
radiation), chronological
aging, menopausal status (e.g., post-menopausal changes in skin), stress,
diseases, etc. For
instance, "regulating skin condition" includes prophylactically regulating
and/or therapeutically
regulating skin condition, and may involve one or more of the following
benefits: thickening of
skin (i.e., building the epidermis and/or dennis and/or sub-dermal (e.g.,
subcutaneous fat or
muscle) layers of the skin and where applicable the keratinous layers of the
nail and hair shaft) to
reduce skin atrophy, increasing the convolution of the dermal-epidermal border
(also known as
the rete ridges), preventing loss of skin elasticity (loss, damage and/or
inactivation of functional
skin elastin) such as elastosis, sagging, loss of skin recoil from
deformation; non-melanin skin
discoloration such as under eye circles, blotching (e.g., uneven red
coloration due to, e.g.,
rosacea) (hereinafter referred to as "red blotchiness"), sallowness (pale
color), discoloration
caused by telangiectasia or spider vessels.
As used herein, prophylactically regulating skin condition includes delaying,
minimizing
and/or preventing visible and/or tactile discontinuities in skin (e.g.,
texture irregularities in the
skin which may be detected visually or by feel).
As used herein, therapeutically regulating skin condition includes
ameliorating, e.g.,
diminishing, minimizing and/or effacing, discontinuities in skin.
The compositions of the present invention provide additional benefits,
including stability,
absence of significant (consumer-unacceptable) skin irritation and good
aesthetics.
It has now surprisingly been found that by adding a silicone elastomer to a
water-in
silicone composition, that delivery of an oil-soluble skin care active may be
enhanced as
compared to traditional oil-in-water and/or water-in-oil compositions. Such
compositions also
have good aesthetic properties and are pleasing to consumers. The present
inventors have found
that a water-in-silicone composition containing silicone elastomers in the oil
phase provides
enhanced delivery of oil-soluble skin care actives, such as, terpene alcohols,
phytosterols, anti-
acne actives, beta-hydroxy acids, vitamin B3 compounds, retinoids, anti-
oxidants/radical
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scavengers, chelators, flavonoids, anti-inflammatory agents, anti-cellulite,
and topical anesthetics
into the skin.
Without being limited by theory, it is believed that although the oil-soluble
skin care
active may be stably formulated into the silicone oil phase with the aid of
the silicone elastomer,
that the presence of both a silicone oil and silicone elastomer create a non-
preferred environment
for the oil-soluble skin care active. Therefore, upon application of the
composition to the skin,
the oil-soluble skin care active partitions out of the silicone elastomer and
is delivered into the
skin. The partitioning out effect leads to greater delivery of the oil-soluble
active into the skin
than if the active was present in a conventional oil phase.
The present invention also relates to methods of enhancing the penetration of
oil-soluble
skin care actives by applying to the skin, a composition containing silicone
elastomers.
The compositions of the present invention contain a silicone oil, a silicone
elastomer, and
an oil-soluble skin care active. Preferred compositions of the present
invention are water-in-
silicone oil emulsion compositions containing a silicone elastomer and an oil-
soluble skin care
active in the continuous oil phase.
The compositions herein may also include a ~ wide variety of other
ingredients. The
compositions of the present invention, are described in detail hereinafter.
I. Oil-Soluble Skin Care Active
The compositions of the present invention contain a safe and effective amount
of an oil-
soluble skin care active. An "oil-soluble active" may be defined as any active
material that is
immiscible with water. Preferably, the composition contains from about 0.001%
to about 40%,
by weight of the composition formed, of the oil-soluble skin care active, more
preferably from
about 0.01% to about 40%, even more preferably from about 0.05% to about 30%,
and still more
preferably from about 0.1% to about 20%, more preferably from about 0.1% to
about 10%
Non-limiting examples of oil-soluble actives that may be used in the present
invention
include oil-soluble terpene alcohols, phytosterols, anti-acne actives, beta-
hydroxy acids, vitamin
B3 compounds, retinoids, anti-oxidants/radical scavengers, chelators,
flavonoids, anti-
inflammatory agents, anti-cellulite agents, topical anesthetics, and mixtures
thereof. A preferred
oil-soluble skin care active for use herein is farnesol.
a) Oil-soluble Terpene Alcohols
As used herein, "terpene alcohol" refers to organic compounds composed of two
or more
5-carbon isoprene units [CHZ=C(CH3)-CH=CHZ] with a terminal hydroxyl group.
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Examples of oil-soluble terpene alcohols that are useful herein include
farnesol,
derivatives of farnesol, isomers of farnesol, geraniol, derivatives of
geraniol, isomers of geraniol,
phytantriol, derivatives of phytantriol, isomers of phytantriol, and mixtures
thereof. Preferred for
use herein is farnesol.
~ i) Farnesol and Derivatives thereof
Farnesol is a naturally occurring substance which is believed to act as a
precursor and/or
intermediate in the biosynthesis of squalene and sterols, especially
cholesterol. Farnesol is also
involved in protein modification and regulation (e.g., farnesylation of
proteins), and there is a cell
nuclear receptor which is responsive to farnesol.
Chemically, farnesol is [2E,6E]-3,7,11-trimethyl-2,6,10-dodecatrien-1-of and
as used
herein "farnesol" includes isomers and tautomers of such. Farnesol is
commercially available,
e.g., under the names farnesol (a mixture of isomers from Dragoco, 10 Gordon
Drive, Totowa,
New Jersey) and trans-trans-farnesol (Sigma Chemical Company, P. O. Box 14508,
St. Louis,
Missouri). A suitable derivative of farnesol is farnesyl acetate which is
commercially available
from Aldrich Chemical Company, P. O. Box 2060, Milwaukee, WI.
ii) Geraniol and derivatives thereof
Geraniol is the common name for the chemical known as 3,7-dimethyl-2,6-
octadien-1-ol.
As used herein, "geraniol" includes isomers and tautomers of such. Geraniol is
commercially
available from Aldrich Chemical Company (P. O. Box 2060, Milwaukee, WI).
Suitable
derivatives of geraniol include geranyl acetate, geranylgeraniol, geranyl
pyrophosphate, and
geranylgeranyl pyrophosphate, all of which are commercially available from
Sigma Chemical
Company, P. O. Box 14508, St. Louis, MO. For example, geraniol is useful as a
spider vessel/
red blotchiness repair agent, a dark circle/puffy eye repair agent, sallowness
repair agent, a
sagging repair agent, an anti-itch agent, a skin thickening agent, a pore
reduction agent, oil/shine
reduction agent, a post-inflammatory hyperpigmentation repair agent, wound
treating agent, an
anti-cellulite agent, and regulating skin texture, including wrinkles and fine
lines.
iii) Phytantriol and derivatives thereof
Phytantriol is the common name for the chemical known as
3,7,11, l5,tetramethylhexadecane-1,2,3,-triol. Phytantriol is commercially
available from BASF
(1609 Biddle Avenue, Whyandotte, MI). For example, phytantriol is useful as a
spider vessel/ red
blotchiness repair agent, a dark circle/puffy eye repair agent, sallowness
repair agent, a sagging
repair agent, an anti-itch agent, a skin thickening agent, a pore reduction
agent, oil/shine reduction
agent, a post-inflammatory hyperpigmentation repair agent, wound treating
agent, an anti-cellulite
agent, and regulating skin texture, including wrinkles and fine lines.
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b) Phytosterols
Phytosterol and derivatives thereof are known for providing skin lightening
benefits.
Non-limiting examples of oil-soluble phytosterol derivatives include (3-
sitosterol, campesterol,
brassicasterol, lupenol, a-spinasterol, stigmasterol, their derivatives, and
combinations thereof.
More preferably, the phytosterol derivative is selected from the group
consisting of (3-sitosterol,
campesterol, brassicasterol, stigmasterol, their derivatives, and combinations
thereof.
Phytosterols are generally found in the unsaponifiable portion of vegetable
oils and fats
and are available as free sterols, acetylated derivatives, sterol esters,
ethoxylated or glycosidic
derivatives. More preferably, the phytosterols are free sterols. As used
herein, "phytosterol"
includes isomers and tautomers of such and is commercially available from
Aldrich Chemical
Company (Milwaukee, Wisconsin), Sigma Chemical Company (St. Louis, Missouri),
and
Dragoco (Totowa, NJ).
c) Oil-Soluble Vitamin Compounds
A number of vitamins known by those in the art for providing various skin
benefits are
oil-soluble and some or all of their derivatives are oil-soluble. As such,
these oil-soluble vitamin
compounds are useful as oil-soluble skin care actives herein. Non-limiting
examples of such oil-
soluble vitamin compounds include retinoids, vitamin B3 compounds, vitamin C
(e.g. ascorbyl
palmitate), vitamin D, vitamin K, vitamin E, and mixtures thereof. Preferred
for use herein are
retinoids, vitamin B3 compounds, which are discussed in more detail below.
i) Retinoids
As used herein, "retinoid" includes all natural and/or synthetic analogs of
Vitamin A or
retinol-like compounds which possess the biological activity of Vitamin A in
the skin as well as
the geometric isomers and stereoisomers of these compounds. Non-limiting
examples of retinoids
useful herein include retinol, retinol esters (e.g., C~ - C22 alkyl esters of
retinol, including retinyl
palmitate, retinyl acetate, retinyl propionate), retinal, andlor retinoic acid
(including all-trans
retinoic acid and/or 13-cis-retinoic acid), preferably retinoids other than
retinoic acid. These
compounds are well known in the art and are commercially available from a
number of sources,
e.g., Sigma Chemical Company (St. Louis, MO), and Boerhinger Mannheim
(Indianapolis, IN).
Other suitable retinoids are tocopheryl-retinoate [tocopherol ester of
retinoic acid (trans- or cis-),
adapalene {6-[3-(1-adamantyl)-4-methoxyphenyl]-2-naphthoic acid}, and
tazarotene (ethyl 6-[2-
(4,4-dimethylthiochroman-6-yl)-ethynyl]nicotinate). Preferred retinoids are
retinol, retinyl
palmitate, retinyl acetate, retinyl propionate, ,retinal and combinations
thereof, but any oil-soluble
retinoid may be used herein.
ii) Oil-Soluble Vitamin B3 Compounds
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Oil-soluble Vitamin B3 compounds are particularly useful for regulating skin
condition.
Non-limiting examples of oil-soluble B3 compounds useful herein include
nicotinic acid esters,
including non-vasodilating esters of nicotinic acid (e.g., tocopheryl
nicotinate), Examples of
suitable vitamin B3 compounds are well known in the art and are commercially
available from a
number of sources, e.g., the Sigma Chemical Company (St. Louis, MO); IC1V
Biomedicals, Inc.
(Irvin, CA) and Aldrich Chemical Company (Milwaukee, WI).
iii) Oil-Soluble Vitamin E compounds
Vitamin E and several derivatives thereof are known to be especially useful as
anti-oxidants/radical scavengers. Such antioxidants/radical scavengers are
especially
useful for providing protection against UV radiation which can cause increased
scaling or
texture changes in the stratum corneum and against other environmental agents
which can
cause skin damage.
Nonlimiting examples of oil soluble vitamin E compounds include tocopherol
(vitamin E), tocopherol sorbate, tocopherol acetate, and other esters of
tocopherol.
Preferred anti-oxidants/radical scavengers are selected from tocopherol
sorbate,
tocopherol acetate, and mixtures thereof. Also useful herein are the class of
materials,
tocotrienols, which are related to vitamin E.
d) Anti-Acne Actives
Non-limiting examples of oil-soluble anti-acne actives include resorcinol and
erythromycin.
e) Beta-Hydroxy Acids
Nonlimiting examples of oil-soluble beta-hydroxy acids include salicylic acid
and
derivatives thereof such as the octanoyl derivative. Beta-hydroxy acids are
known to provide
anti-acne and anti-aging benefits.
f) Chelators
As used herein, "chelator" or "chelating agent" means an active agent capable
of
removing a metal ion from a system by forming a complex so that the metal ion
cannot readily
participate in or catalyze chemical reactions. The inclusion of a chelating
agent is especially
useful for providing protection against UV radiation which can contribute to
excessive scaling or
skin texture changes and against other environmental agents which can cause
skin damage.
Exemplary oil-soluble chelators that are useful herein are disclosed in U.S.
Patent No.
5,487,884, issued 1/30/96 to Bissett et al.; International Publication No.
91/16035, Bush et al.,
published 10/31/95; and International Publication No. 91/16034, Bush et al.,
published 10/31/95.
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Preferred oil-soluble chelators useful in compositions of the subject
invention are furildioxime,
furilmonoxime, and derivatives thereof.
g) Flavonoids
Flavonoid compounds are broadly disclosed in U.S. Patents 5,686,082 and
5,686,367,
both of which are herein incorporated by reference. Nonlimiting examples of
flavonoids useful
herein include isoflavones, flavanones selected from the group consisting of
unsubstituted
flavanones, mono-substituted flavanones, and mixtures thereof; chalcones
selected from the group
consisting of unsubstituted chalcones, mono-substituted chalcones, di-
substituted chalcones, tri-
substituted chalcones, and mixtures thereof; flavones selected from the group
consisting of
unsubstituted flavones, mono-substituted flavones, di-substituted flavones,
and mixtures thereof;
one or more isoflavones; coumarins selected from the group consisting of
unsubstituted
coumarins, mono-substituted coumarins, di-substituted coumarins, and mixtures
thereof;
chromones selected from the group consisting of unsubstituted chromones, mono-
substituted
chromones, di-substituted chromones, and mixtures thereof; one or more
dicoumarols; one or
more chromanones; one or more chromanols; isomers (e.g., cis/trans isomers)
thereof; and
mixtures thereof. By the term "substituted" as used herein means flavonoids
wherein one or more
hydrogen atom of the flavonoid has been independently replaced with a
hydroxyl, C1-C8 alkyl, or
C1-C4 alkoxyl.
Examples of suitable flavonoids include, but are not limited to, unsubstituted
flavanone,
mono-hydroxy flavanones (e.g., 2'-hydroxy flavanone, 6-hydroxy flavanone, 7-
hydroxy
flavanone, etc.), mono-alkoxy flavanones (e.g., 5-methoxy flavanone, 6-methoxy
flavanone, 7-
methoxy flavanone, 4'-methoxy flavanone, etc.), unsubstituted chalcone
(especially unsubstituted
trans-chalcone), mono-hydroxy chalcones (e.g., 2'-hydroxy chalcone, 4'-hydroxy
chalcone, etc.),
di-hydroxy chalcones (e.g., 2',4-dihydroxy chalcone, 2',4'-dihydroxy chalcone,
2,2'-dihydroxy
chalcone, 2',3-dihydroxy chalcone, 2',5'-dihydroxy chalcone, etc.), and tri-
hydroxy chalcones
(e.g., 2',3',4'-trihydroxy chalcone, 4,2',4'-trihydroxy chalcone, 2,2',4'-
trihydroxy chalcone, etc.),
unsubstituted flavone, 7,2'-dihydroxy flavone, 3',4'-dihydroxy naphthoflavone,
4'-hydroxy
flavone, 5,6-benzoflavone, and 7,8-benzoflavone, unsubstituted isoflavone,
daidzein (7,4'-
dihydroxy isoflavone), 5,7-dihydroxy-4'-methoxy isoflavone, soy isoflavones (a
mixture extracted
from soy), unsubstituted coumarin, 4-hydroxy coumarin, 7-hydroxy coumarin, 6-
hydroxy-4-
methyl coumarin, unsubstituted chromone, 3-formyl chromone, 3-formyl-6-
isopropyl chromone,
unsubstituted dicoumarol, unsubstituted chromanone, unsubstituted chromanol,
and mixtures
thereof..
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Preferred for use herein are unsubstituted flavanone, methoxy flavanones,
unsubstituted
chalcone, 2',4-dihydroxy chalcone, isoflavones, and mixtures thereof. Most
preferred are
unsubstituted flavanone, unsubstituted chalcone (especially the trans isomer),
isoflavones, and
mixtures thereof.
Flavonoid compounds useful herein are commercially available from a number of
sources, e.g., Indofine Chemical Company, Inc. (Somerville, New Jersey),
Steraloids, Inc.
(Wilton, New Hampshire), NovaSoy from Archer Daniels Midland Co. (Decatur,
Illinois),.and
Aldrich Chemical Company, Inc. (Milwaukee, Wisconsin).
Mixtures of the above flavonoid compounds may also be used.
h) Anti-Inflammatory A~,ents
Nonlimiting examples of oil-soluble anti-inflammatory agents useful herein
include steroidal anti-
inflammatory agents, such as the corticosteroids (e.g. hydrocortisone), and
oil soluble
nonsteroidal anti-inflammatory agents, such as the propionic acid derivatives
(e.g. ibuprofen,
naproxen,and/or ketoprofen).
Mixtures of oil-soluble anti-inflammatory agents may also be employed, as well
as the
dermatologically acceptable salts and esters of these agents. For example,
etofenamate, a
flufenamic acid derivative, is particularly useful for topical application.
Non-limiting examples of so-called "natural" anti-inflammatory agents useful
herein
include those obtained as an extract by suitable physical and/or chemical
isolation from natural
sources (e.g., plants, fungi, by-products of microorganisms) or can be
synthetically prepared. For
example, candelilla wax, bisabolol (e.g., alpha bisabolol), and/or plant
sterols (e.g., phytosterol),
may be used.
i) Anti-Cellulite A_
Non-limiting examples of oil-soluble anti-cellulite skin care actives useful
herein include
the oil soluble xanthine compounds such as caffeine.
j) Topical Anesthetics
Non-limiting examples of oil-soluble topical anesthetic drugs include
benzocaine,
lidocaine, and pharmaceutically acceptable salts thereof.
II. Silicone Elastomer
The compositions of the present invention also include from about 0.1% to
about 30%, by
weight of the composition, of a silicone elastomer component. Preferably, the
composition
includes from about 0.1% to about 30%, more preferably from about 0.5% to
about 10%, by
weight of the composition, of the silicone elastomer component All such
percentages as they
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pertain to the silicone elastomer are based on the amount of elastomer and
therefore, do not
include carriers or by-products that may be included in commercially available
materials.
Commercially available silicone elastomers are often introduced into the
overall composition in
solution with a silicone oil. Such silicone oil amounts are considered in the
overall percentages of
silicone oil present in the compositions of the present invention.
Suitable for use herein are silicone elastomers which can be emulsifying or
non-
emulsifying crosslinked siloxane elastomers or mixtures thereof. No specific
restriction exists as
to the type of curable organopolysiloxane composition which can serve as
starting material for the .
crosslinked organopolysiloxane elastomer. Examples in this respect are
addition reaction-curing
organopolysiloxane compositions which cure under platinum metal catalysis by
the addition
reaction between SiH-containing diorganopolysiloxane and organopolysiloxane
having silicon-
bonded vinyl groups; condensation-curing organopolysiloxane compositions which
cure in the
presence of an organotin compound by a dehydrogenation reaction between
hydroxyl-terminated
diorganopolysiloxane and SiH-containing diorganopolysiloxane; condensation-
curing
organopolysiloxane compositions which cure in the presence of an organotin
compound or a
titanate ester, by a condensation reaction between an hydroxyl-terminated
diorganopolysiloxane
and a hydrolyzable organosilane (this condensation reaction is exemplified by
dehydration,
alcohol-liberating, oxime-liberating, amine-liberating, amide-liberating,
carboxyl-liberating, and
ketone-liberating reactions); peroxide-curing organopolysiloxane compositions
which thermally
cure in the presence of an organoperoxide catalyst; and organopolysiloxane
compositions which
are cured by high-energy radiation, such as by gamma-rays, ultraviolet
radiation, or electron
beams.
Addition reaction-curing organopolysiloxane compositions are preferred for
their rapid
curing rates and excellent uniformity of curing. A particularly preferred
addition reaction-curing
organopolysiloxane composition is prepared from:
(A) an organopolysiloxane having at least 2 lower alkenyl groups in each
molecule;
(B) an organopolysiloxane having at least 2 silicon-bonded hydrogen atoms in
each
molecule; and
(C) a platinum-type catalyst.
With regard to the above, component (A) is the basic component of the silicone
elastomer-generating organopolysiloxane, and curing proceeds by the addition
reaction of this
component with component (B) under catalysis by component (C). This component
(A) must
contain at least 2 silicon-bonded lower alkenyl groups in each molecule; an
excellent cured
product will not be obtained at few than two lower alkenyl groups because a
network structure
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will not be formed. Said lower alkenyl groups are exemplified by vinyl, allyl,
and propenyl.
While the lower alkenyl groups can be present at any position in the
molecular, their presence at
the molecular terminals is preferred. The molecular structure of this
component may be straight
chain, branched straight chain, cyclic, or network, but a straight chain,
possibly slightly branched,
is preferred. The molecular weight of the component is not specifically
restricted, and thus the
viscosity may range from low viscosity liquids to very high viscosity gums. In
order for the cured
product to be obtained in the form of the rubbery elastomer, it is preferred
that the viscosity at 25
degrees Centigrade be at least 100 centistokes. These organopolysiloxanes are
exemplified by
methylvinylsiloxanes, methylvinylsiloxane-dimethylsiloxane copolymers,
dimethylvinylsiloxy-
terminated dimethylpolysiloxanes, dimethylvinylsiloxy-terminated
dimethylsiloxane-
methylphenylsiloxane copolymers, dimethylvinylsiloxy-terminated
dimethylsiloxane-
diphenylsiloxane-methylvinylsiloxane copolymers, trimethylsiloxy-terminated
dimethylsiloxane-
methylvinylsiloxane copolymers, trimethylsiloxy-terminated dimethylsiloxane-
methylphenylsiloxane-methylvinylsiloxane copolymers, dimethylvinylsiloxy-
terminated
methyl(3,3,3-trifluoropropyl) polysiloxanes, and dimethylvinylsiloxy-
terminated
dimethylsiloxane-methyl(3,3,-trifluoropropyl)siloxane copolymers.
Component (B) is an organopolysiloxane having at least 2 silicon-bonded
hydrogen
atoms in each molecule and is a crosslinker for component (A). Curing proceeds
by the addition
reaction of the silicon-bonded hydrogen atoms in this component with the lower
alkenyl groups in
component (A) under catalysis by component (C). This component (B) must
contain at least 2
silicon-bonded hydrogen atoms in each molecule in order to function as a
crosslinker.
Furthermore, the sum of the number of alkenyl groups in each molecule of
component (A) and the
number of silicon-bonded hydrogen atoms in each molecule of component (B) is
to be at least 5.
Values below 5 should be avoided because a network structure is then
essentially not formed.
No specific restriction exists on the molecular structure of this component,
and it may be
any of straight chain, branch-containing straight chain, cyclic, etc. The
molecular weight of this
component is not specifically restricted, but it is preferred that the
viscosity at 25 degrees
Centigrade be 1 to 50,000 centistokes in order to obtain good miscibility with
component (A). It
is preferred that this component be added in a quantity such that the molar
ratio between the total
quantity of silicon-bonded hydrogen atoms in the instant component and the
total quantity of all
lower alkenyl groups in component (A) falls within the range of (1.5:1) to
(20:1). It is difficult to
obtain good curing properties when this molar ratio falls below 0.5:1. When
(20:1) is exceeded,
there is a tendency for the hardness to increase to high levels when the cured
product is heated.
Furthermore, when an organosiloxane containing substantial alkenyl is
supplementarily added for
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the purpose of; for example, reinforcement, it is preferred that a
supplemental addition of the
instant SiH-containing component be made in a quantity offsetting these
alkenyl groups. This
component is concretely exemplified by trimethylsiloxy-terminated
methylhydrogenpolysiloxanes, trimethylsiloxy-terminated dimethylsiloxane-
methylhydrogensiloxane copolymers, and dimethylsiloxane-methylhydrogen-
siloxane cyclic
copolymers.
Component (C) is a catalyst of the addition reaction of silicon-bonded
hydrogen atoms
and alkenyl groups, and is concretely exemplified by chloroplatinic acid,
possibly dissolved in an
alcohol or ketone and this solution optionally aged, chloroplatinic acid-
olefin complexes,
chloroplatinic acid-alkenylsiloxane complexes, chloroplatinic acid-diketone
complexes, platinum
black, and carrier-supported platinum.
Component C is added preferably at 0.1 to 1,000 weight parts, and more
preferably at 1 to
100 weight parts, as platinum-type metal proper per 1,000,000 weight parts of
the total quantity of
components (A) plus (B). Other organic groups which may be bonded to silicon
in the
organopolysiloxane forming the basis for the above-described curable
organopolysiloxane
compositions are, for example, alkyl groups such as methyl, ethyl, propyl,
butyl, and octyl;
substituted alkyl groups such as 2-phenylethyl, 2-phenylpropyl, and 3,3,3-
trifluoropropyl; aryl
groups such as phenyl, tolyl, and xylyl; substituted aryl groups such as
phenylethyl; and
monovalent hydrocarbon groups substituted by, for example, the epoxy group,
the carboxylate
ester group, the mercapto group, etc.
Examples of the production of the organopolysiloxane elastomer powder are as
follows:
an organopolysiloxane composition as described above (additional-curable,
condensation-curable,
or peroxide-curable) is mixed with water in the presence of a surfactant
(nonionic, anionic,
cationic, or amphoteric), and, after mixing to homogeneity in a homomixer,
colloid mill,
homogenizer, propeller mixer, etc., this is cured by discharge into hot water
(temperature at least
50 degrees Centigrade) and is then dried; the organopolysiloxane composition
(addition-curable,
condensation-curable, or peroxide-curable) is cured by spraying it directly
into a heated current;
the powder is obtained by curing a radiation-curable organopolysiloxane
composition by spraying
it under high energy radiation; the organopolysiloxane composition (addition-
curable,
condensation-curable, peroxide-curable) or high energy-curable
organopolysiloxane composition
is cured, the latter by high energy radiation, and the product is then
pulverized using a known
pulverizer such as, for example, a ball mill, atomizer, kneader, roll mill,
etc., to thereby form the
powder.
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The compositions of the present invention may include an emulsifying
crosslinked
organopolysiloxane elastomer, a non-emulsifying crosslinked organopolysiloxane
elastomer, or a
mixture thereof. The term "non-emulsifying," as used herein, defines
crosslinked
organopolysiloxane elastomers from which polyoxyalkylene units are absent. The
term
"emulsifying," as used herein, means crosslinked organopolysiloxane elastomers
having at least
one polyoxyalkylene (e.g., polyoxyethylene or polyoxypropylene) unit.
Preferred emulsifying
elastomers herein include polyoxyalkylene modified elastomers formed from
divinyl compounds,
particularly siloxane polymers with at least two free vinyl groups, reacting
with Si-H linkages on
a polysiloxane backbone. Preferably, the elastomers are dimethyl polysiloxanes
crosslinked by
Si-H sites on a molecularly spherical MQ resin. Emulsifying crosslinked
organopolysiloxane
elastomer can notably be chosen from the crosslinked polymers described in US
Patents
5,412,004 (issued 5/2/95) ; 5,837,793 (issued 11/17/98); and 5,811,487 (issued
9/22/98), all of
which are herein incorporated by reference in their entirety. In addition, an
emulsifying elastomer
comprised of dimethicone copolyol crosspolymer (and) dimethicone is available
from Shin Etsu
under the tradename KSG-21.
The silicone elastomers of the present invention may be further processed by
subjecting
them to a high shear (approximately 5,000 psi) treatment in the presence of a
solvent for the
silicone elastomer via a Sonolator with or without recycling in from 1 to 60
passes in order to
result in a particular average particle size of silicone elastomer. Less than
10 passes results in an
average particle size ranging from about 20 to 200 microns. From 10 to 60
passes results in an
average particle size of less than 20 microns as measured by the Horiba LA-
910. As used herein,
the term "particle size" of the elastomer represents the elastomer particle
size in its swelled state.
By "swelled," as used herein, means that the elastomer particles have extended
beyond their
normal size and shape by virtue of their absorption of the solvent compound.
Preferably, the non-emulsifying elastomers are dimethicone/vinyl dimethicone
crosspolymers. Such dimethicone/vinyl dimethicone crosspolymers are supplied
by a variety of
suppliers including Dow Corning (DC 9040 and DC 9041), General Electric (SFE
839), Shin Etsu
(KSG-15, 16, 18 [dimethicone/phenyl vinyl dimethicone crosspolymer]), and
Grant Industries
(GRANSILTM line of elastomers). Cross-linked organopolysiloxane elastomers
useful in the
present invention and processes for making them are further described in U.S.
Patent 4,970,252 to
Sakuta, et al., issued November 13, 1990; U.S. Patent 5,760,116 to Kilgour, et
al., issued June 2,
1998; U.S. Patent 5,654,362 to Schulz, Jr., et al. issued August 5, 1997, all
of which are herein
incorporated by reference. Additional crosslinked organopolysiloxane
elastomers useful in the
CA 02413276 2002-12-16
WO 02/03930 PCT/USO1/21602
present invention are disclosed in Japanese Patent Application JP 61-18708,
assigned to Pola
Kasei Kogyo KK.
Commercially available elastomers preferred for use herein are Dow Coming's
9040
silicone elastomer blend, Shin Etsu's KSG-21, and mixtures thereof
III. Silicone Oil
The compositions of the present invention contain a safe and effective amount
of a
silicone oil. Preferably, the composition contains from about 5% to about 99%,
by weight of the
composition formed, of the silicone oil, more preferably from about 15% to
about 95%, even
more preferably from about 20% to about 90%, and still more preferably from
about 25% to about
85%.
Non-limiting examples of common silicone oils that may be used in the present
invention
include cyclomethicone, dimethicone, and mixtures thereof.
The compositions of the present invention may be anhydrous. By "andhydrous" is
meant
that the composition contains less than 5% of water, preferably less than 1%.
In such anhydrous
systems, the composition may contain a combination of silicone oil, silicone
elastomer, and oil-
soluble active.
The compositions of the present invention may also contain an aqueous phase
and be in
the form of, for example, a water-in-oil emulsion. Emulsions according to the
present invention
generally contain an aqueous phase and a lipid or oil. Lipids and oils may be
derived from
animals, plants, or petroleum and may be natural or synthetic (i.e., man-
made). The lipid or oil is
preferably a silicone oil. Emulsions preferably further contain from about 1 %
to about 10%, more
preferably from about 2% to about 5%, of an emulsifier, based on the weight of
the carrier.
Emulsifiers may be emulsifying silicone elastomers, silicone emulsifiers,
nonionic, anionic or
cationic. Suitable emulsifiers are disclosed in, for example, McCutcheori s
Detergents and
Emulsifiers, North American Edition, pages 317-324 (1986). The emulsifier is
preferably a
emulsifying silicone elastomer, silicone emulsifier or combination thereof.
Suitable emulsions may have a wide range of viscosities, depending on the
desired
product form. Preferably the viscosity is from about 5,000 centipoise to about
100,000 centipoise.
The emulsion can contain a variety of optional components. As will be
understood by the
skilled artisan, a given component will distribute primarily into either the
water or oil/silicone
phase, depending on the water solubility/dispersibility of the component in
the composition.
Preferably, the compositions of the present invention contain an aqueous phase
and are in
the form of a water-in-silicone oil emulsion. Even more preferably, the
composition is a water-in-
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silicone emulsion wherein the oil phase comprises at least 51%, by weight of
the oil phase, of
silicone oil. Water-in-silicone emulsions are described more fully below.
Water-in-Silicone Emulsion
Water-in-silicone emulsions contain a continuous silicone phase and a
dispersed aqueous
phase.
(a) Continuous silicone phase
Preferred water-in-silicone emulsions of the present invention comprise from
about 25%
to about 90%, preferably from about 27% to about 80%, more preferably from
about 30% to
about 70%, by weight of the composition formed, of a continuous silicone
phase. The continuous
silicone phase exists as an external phase that contains or surrounds the
discontinuous aqueous
phase described hereinafter.
The continuous silicone phase contains an organopolysiloxane oil for use in
the
composition. Such organopolysiloxane oil may be volatile, non-volatile, or a
mixture of volatile
and non-volatile silicones. The term "nonvolatile" as used in this context
refers to those silicones
that are liquid under ambient conditions and have a flash point (under one
atmospheric of
pressure) of or greater than about 100°C. The term "volatile" as used
in this context refers to all
other silicone oils.' Suitable organopolysiloxanes can be selected from a wide
variety of silicones
spanning a broad range of volatilities and viscosities. Examples of suitable
organopolysiloxane
oils include polyalkylsiloxanes, cyclic polyalkylsiloxanes, and
polyalkylarylsiloxanes.
Polyalkylsiloxanes useful in the composition herein include polyalkylsiloxanes
with
viscosities of from about 0.5 to about 1,000,000 centistokes at 25°C.
Such polyalkylsiloxanes can
be represented by the general chemical formula R3Si0[R2Si0]xSiR3 wherein R is
an alkyl group
having from one to about 30 carbon atoms (preferably R is methyl or ethyl,
more preferably
methyl; also mixed alkyl groups can be used in the same molecule), and x is an
integer from 0 to
about 10,000, chosen to achieve the desired molecular weight which can range
to over about
10,000,000. Commercially available polyalkylsiloxanes include the
polydimethylsiloxanes,
which are also known as dimethicones, examples of which include the Vicasil~
series sold by
General Electric Company and the Dow Corning~ 200 series sold by Dow Corning
Corporation.
Specific examples of suitable polydimethylsiloxanes include Dow Corning~ 200
fluid having a
viscosity of 0.65 centistokes and a boiling point of 100°C, Dow
Corning~ 225 fluid having a
viscosity of 10 centistokes and a boiling point greater than 200°C, and
Dow Corning~ 200 fluids
having viscosities of 50, 350, and 12,500 centistokes, respectively, and
boiling points greater than
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200°C. Suitable dimethicones include those represented by the chemical
formula
(CH3)3Si0[(CH3)2Si0]x[CH3RSi0]ySi(CH3)3 wherein R is straight or branched
chain alkyl
having from two to about 30 carbon atoms and x and y are each integers of 1 or
greater selected to
achieve the desired molecular weight which can range to over about 10,000,000.
Examples of
these alkyl-substituted dimethicones include cetyl dimethicone and lauryl
dimethicone.
Cyclic polyalkylsiloxanes suitable for use in the composition include those
represented by
the chemical formula [SiR2-O]n wherein R is an alkyl group (preferably R is
methyl or ethyl,
more preferably methyl) and n is an integer from about 3 to about 8, more
preferably n is an
integer from about 3 to about 7, and most preferably n is an integer from
about 4 to about 6.
When R is methyl, these materials are typically referred to as
cyclomethicones. Commercially
available cyclomethicones include Dow Corning~ 244 fluid having a viscosity of
2.5 centistokes,
and a boiling point of 172°C, which primarily contains the
cyclomethicone tetramer (i.e. n=4),
Dow Corning~ 344 fluid having a viscosity of 2.5 centistokes and a boiling
point of 178°C,
which primarily contains the cyclomethicone pentamer (i.e. n=5), Dow Corning~
245 fluid
having a viscosity of 4.2 centistokes and a boiling point of 205°C,
which primarily contains a
mixture of the cyclomethicone tetramer and pentamer (i.e. n=4 and 5), and Dow
Corning~ 345
fluid having a viscosity of 4.5 centistokes and a boiling point of
217°, which primarily contains a
mixture of the cyclomethicone tetramer, pentamer, and hexamer (i.e. n=4, 5,
and 6).
Also useful are materials such as trimethylsiloxysilicate, which is a
polymeric material
corresponding to the general chemical formula [(CH2)3Si01/2]x[Si02]y, wherein
x is an integer
from about 1 to about 500 and y is an integer from about 1 to about 500. A
commercially
available trimethylsiloxysilicate is sold as a mixture with dimethicone as Dow
Corning~ 593
fluid.
Dimethiconols are also suitable for use in the composition. These compounds
can be
represented by the chemical formulas R3Si0[R2Si0]xSiR20H and
HOR2Si0[R2Si0]xSiR20H
wherein R is an alkyl group (preferably R is methyl or ethyl, more preferably
methyl) and x is an
integer from 0 to about 500, chosen to achieve the desired molecular weight.
Commercially
available dimethiconols are typically sold as mixtures with dimethicone or
cyclomethicone (e.g.
Dow Corning~ 1401, 1402, and 1403 fluids).
Polyalkylaryl siloxanes are also suitable for use in the composition.
Polymethylphenyl
siloxanes having viscosities from about 15 to about 65 centistokes at
25°C are especially useful.
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Preferred for use herein are organopolysiloxanes selected from the group
consisting of
polyalkylsiloxanes, alkyl substituted dimethicones, cyclomethicones,
trimethylsiloxysilicates,
dimethiconols, polyalkylaryl siloxanes, and mixtures thereof. More preferred
for use herein are
polyalkylsiloxanes and cyclomethicones. Preferred among the polyalkylsiloxanes
are
dimethicones.
As stated above, the continuous silicone phase may contain one or more non-
silicone
oils. Concentrations of non-silicone oils in the continuous silicone phase are
preferably
minimized ox avoided altogether so as to further enhance the delivery of the
oil-soluble skin care
active. Suitable non-silicone oils have a melting point of about 25°C
or less under about one
atmosphere of pressure. Examples of non-silicone oils suitable for use in the
continuous silicone
phase are those well known in the chemical arts in topical personal care
products in the form of
water-in-oil emulsions, for example, mineral oil, vegetable oils, synthetic
oils, and semisynthetic
oils.
(b) Di~ersed aqueous phase
The topical compositions of the present invention may also comprise from about
10% to
about 75%, by weight of the composition formed, of a dispersed aqueous phase.
In emulsion
technology, the term "dispersed phase" is a term well-known to one skilled in
the art which means
that the phase exists as small particles or droplets that are suspended in and
surrounded by a
continuous phase. The dispersed phase is also known as the internal or
discontinuous phase. The
dispersed aqueous phase is a dispersion of small aqueous particles or droplets
suspended in and
surrounded by the continuous silicone phase described hereinbefore.
The aqueous phase can be water, or a combination of water and one or more
water soluble
or dispersible ingredients. Preferably, the aqueous phase contains greater
than about 50% of
water, by weight of the aqueous phase. Nonlimiting examples of such optional
ingredients
include thickeners, acids, bases, salts, chelants, gums, water-soluble or
dispersible alcohols and
polyols, buffers, preservatives, water-soluble skin care actives, water-
dispersible skin care actives,
sunscreening agents, colorings, and the like. Water-soluble and water-
dispersible skin care
actives are more fully described below under optional ingredients.
(c) Emulsifier for dispersin_ the aqueous phase
The water-in-silicone emulsions of the present invention preferably comprise
an
emulsifier. In a preferred embodiment, the composition contains from about
0.1% to about 10%
emulsifier, more preferably from about 0.5% to about 7.5%, most preferably
from about 1% to
about 5%, by weight of the composition formed, of an emulsifier. The
emulsifier helps disperse
and suspend the aqueous phase within the continuous silicone phase.
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A wide variety of emulsifying agents can be employed herein to form the
preferred water-
in-silicone emulsion. Known or conventional emulsifying agents can be used in
the composition,
provided that the selected emulsifying agent is chemically and physically
compatible with
essential components of the composition, and provides the desired dispersion
characteristics.
Suitable emulsifiers include silicone emulsifiers, non-silicon-containing
emulsifiers, and mixtures
thereof, known by those skilled in the art for use in topical personal care
products. Preferably
these emulsifiers have an HLB value of or less than about 14, more preferably
from about 2 to
about 14, and most preferably from about 4 to about 14. Emulsifiers having an
HLB value
outside of these ranges can be used in combination with other emulsifiers to
achieve an effective
weighted average HLB for the combination that falls within these ranges.
Emulsifying silicone elastomers are preferred for use herein and are discussed
more fully
above. Other silicone emulsifiers are also preferred. A combination of
emulsifying silicone
elastomer and silicone emulsifier is also useful herein.
A wide variety of silicone emulsifiers are useful herein. These silicone
emulsifiers are
typically organically modified organopolysiloxanes, also known to those
skilled in the art as
silicone surfactants. Useful silicone emulsifiers include dimethicone
copolyols. These materials
are polydimethyl siloxanes which have been modified to include polyether side
chains such as
polyethylene oxide chains, polypropylene oxide chains, mixtures of these
chains, and polyether
chains containing moieties derived from both ethylene oxide and propylene
oxide. Other
examples include alkyl-modified dimethicone copolyols, i.e., compounds which
contain C2-C30
pendant side chains. Still other useful dimethicone copolyols include
materials having various
cationic, anionic, amphoteric, and zwitterionic pendant moieties.
The dimethicone copolyol emulsifiers useful herein can be described by the
following
general structure:
i Hs i H3 i H3 i Hs i Hs
CH3 Si-O i i O i i O i i O i i-CH3
CH3 CH3 ~ R ~ R2 CH3
x y z
wherein R is C1-C30 straight, branched, or cyclic alkyl and R2 is selected
from the group
consisting of
__(CH2)ri -O__(CH~CHR30)m -H,
and
--(CH~)ri -O__(CH2CHR30)m -(CH~CHR40)o--H,
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wherein n is an integer from 3 to about 10; R3 and R4 are selected from the
group consisting of H
and C1-C6 straight or branched chain alkyl such that R3 and R4 are not
simultaneously the same;
and m, o, x, and y are selected such that the molecule has an overall
molecular weight from about
200 to about 10,000,000, with m, o, x, and y being independently selected from
integers of zero or
greater such that m and o are not both simultaneously zero, and z being
independently selected
from integers of 1 or greater. It is recognized that positional isomers of
these copolyols can be
achieved. The chemical representations depicted above for the R2 moieties
containing the R3 and
R4 groups are not meant to be limiting but are shown as such for convenience.
Also useful herein, although not strictly classified as dimethicone copolyols,
are silicone
surfactants as depicted in the structures in the previous paragraph wherein R2
is:
__(CH2)ri -O__R5
wherein RS is a cationic, anionic, amphoteric, or zwitterionic moiety.
Nonlimiting examples of dimethicone copolyols and other silicone surfactants
useful as
emulsifiers herein include polydimethylsiloxane polyether copolymers with
pendant polyethylene
oxide sidechains, polydimethylsiloxane polyether copolymers with pendant
polypropylene oxide
sidechains, polydimethylsiloxane polyether copolymers with pendant mixed
polyethylene oxide
and polypropylene oxide sidechains, polydimethylsiloxane polyether copolymers
with pendant
mixed poly(ethylene)(propylene)oxide sidechains, polydimethylsiloxane
polyether copolymers
with pendant organobetaine sidechains, polydimethylsiloxane polyether
copolymers with pendant
carboxylate sidechains, polydimethylsiloxane polyether copolymers with pendant
quaternary
ammonium sidechains; and also further modifications of the preceding
copolymers containing
pendant C2-C30 straight, branched, or cyclic alkyl moieties. Examples of
commercially available
dimethicone copolyols useful herein sold by Dow Corning Corporation are Dow
Corning 190,
193, Q2-5220, 2501 Wax, 2-5324 fluid, and 3225C (this later material being
sold as a mixture
with cyclomethicone). Cetyl dimethicone copolyol is commercially available as
a mixture with
polyglyceryl-4 isostearate (and) hexyl laurate and is sold under the tradename
ABIL~ WE-09
(available from Goldschmidt). Cetyl dimethicone copolyol is also commercially
available as a
mixture with hexyl laurate (and) polyglyceryl-3 oleate (and) cetyl dimethicone
and is sold under
the tradename ABIL~ WS-08 (also available from Goldschmidt). Other nonlimiting
examples of
dimethicone copolyols also include lauryl dimethicone copolyol, dimethicone
copolyol acetate,
diemethicone copolyol adipate, dimethicone copolyolamine, dimethicone copolyol
behenate,
dimethicone copolyol butyl ether, dimethicone copolyol hydroxy stearate,
dimethicone copolyol
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isostearate, dimethicone copolyol laurate, dimethicone copolyol methyl ether,
dimethicone
copolyol phosphate, and dimethicone copolyol stearate. See International
Cosmetic In edient
Dictionary, Fifth Edition, 1993.
Among the non-silicone-containing emulsifiers useful herein are various non-
ionic and
anionic emulsifying agents such as sugar esters and polyesters, alkoxylated
sugar esters and
polyesters, C1-C30 fatty acid esters of C1-C30 fatty alcohols, alkoxylated
derivatives of C1-C30
fatty acid esters of C1-C30 fatty alcohols, alkoxylated ethers of C1-C30 fatty
alcohols,
polyglyceryl esters of C1-C30 fatty acids, C1-C30 esters of polyols, C1-C30
ethers of polyols,
alkyl phosphates, polyoxyalkylene fatty ether phosphates, fatty acid amides,
acyl lactylates, soaps,
and mixtures thereof.
Nonlimiting examples of suitable non-silicone-containing emulsifiers for use
herein
include: polyethylene glycol 20 sorbitan monolaurate (Polysorbate 20),
polyethylene glycol 5
Soya sterol, Steareth-20, Ceteareth-20, PPG-2 methyl glucose ether distearate,
Ceteth-10,
Polysorbate 80, cetyl phosphate, potassium cetyl phosphate,~diethanolamine
cetyl phosphate,
Polysorbate 60, glyceryl stearate, PEG-100 stearate, polyoxyethylene 20
sorbitan trioleate
(Polysorbate 85), sorbitan monolaurate, polyoxyethylene 4 lauryl ether sodium
stearate,
polyglyceryl-4 isostearate, hexyl laurate, steareth-20, ceteareth-20, PPG-2
methyl glucose ether
distearate, ceteth-10, diethanolamine cetyl phosphate, glyceryl stearate, PEG-
100 stearate, and
mixtures thereof.
Optional Components
The compositions of the present invention may contain a variety of other
ingredients such
as are conventionally used in a given product type provided that they do not
unacceptably alter the
benefits of the invention.
In a preferred embodiment, where the composition is to be in contact with
human
keratinous tissue, the optional components should be suitable for application
to keratinous tissue,
that is, when incorporated into the composition they are suitable for use in
contact with human
keratinous tissue without undue toxicity, incompatibility, instability,
allergic response, and the
like within the scope of sound medical judgment. The CTFA Cosmetic
Ifzgf~ediefzt Handbook,
Second Edition (1992) describes a wide variety of nonlimiting cosmetic and
pharmaceutical
ingredients commonly used in the skin care industry, which are suitable for
use in the
compositions of the present invention. Examples of these ingredient classes
include: abrasives,
absorbents, aesthetic components such as fragrances, pigments,
coloringslcolorants, essential oils,
skin sensates, astringents, etc. (e.g., clove oil, menthol, camphor,
eucalyptus oil, eugenol, menthyl
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lactate, witch hazel distillate), anti-acne agents, anti-caking agents,
antifoaming agents,
antimicrobial agents (e.g., iodopropyl butylcarbamate), antioxidants (e.g.
BHT, BHA,
tocopherol), binders, biological additives, buffering agents, bulking agents,
chelating agents,
chemical additives, colorants, cosmetic astringents, cosmetic biocides,
denaturants, drug
astringents, external analgesics, film formers or materials, e.g., polymers,
for aiding the film-
forming properties and substantivity of the composition (e.g., copolymer of
eicosene and vinyl
pyrrolidone), opacifying agents, pH adjusters, propellants, reducing agents,
sequestrants, skin
bleaching and lightening agents (e.g., hydroquinone, kojic acid, ascorbic
acid, magnesium
ascorbyl phosphate, ascorbyl glucosamine, pyridoxine), skin-conditioning
agents (e.g.,
humectants, including miscellaneous, and occlusive), skin soothing and/or
healing agents (e.g.,
panthenol and derivatives such as ethyl panthenol, aloe vera, pantothenic acid
and its derivatives,
allantoin, bisabolol, and dipotassium glycyrrhizinate), skin treating agents
(e.g., vitamin D
compounds, mono-, di-, and tri-terpenoids, beta-ionol, cedrol), thickeners,
and vitamins and
vitamin derivatives.
Desquamation Actives
A safe and effective amount of a desquamation active may be added to the
compositions
of the present invention, preferably from about 0.1 % to about 10%, more
preferably from about
0.2% to about 5%, even more preferably from about 0.5% to about 4%, by weight
of the
composition. Desquamation actives enhance the skin appearance benefits of the
present
invention. For example, the desquamation actives tend to improve the texture
of the skin (e.g.,
smoothness). One desquamation system that is suitable for use herein contains
sulfhydryl
compounds and zwitterionic surfactants and is described in U.S. Patent No.
5,681,852, to Bissett,
incorporated herein by reference. Another desquamation system that is suitable
for use herein
contains salicylic acid and zwitterionic surfactants and is described in U.S.
Patent No. 5,652,228
to Bissett, incorporated herein by reference. Zwitterionic surfactants such as
described in these
applications are also useful as desquamatory agents herein, with cetyl betaine
being particularly
preferred.
Anti-Wrinkle Actives/Anti-Atrophy Actives
The compositions of the present invention may contain a safe and effective
amount of one
or more anti-wrinkle actives or anti-atrophy actives. Exemplary anti-
wrinklelanti-atrophy actives
suitable for use in the compositions of the present invention include sulfur-
containing D and L
amino acids and their derivatives and salts, particularly the N-acetyl
derivatives, a preferred
example of which is N-acetyl-L-cysteine; thiols, e.g. ethane thiol; hydroxy
acids (e.g., alpha-
hydroxy acids such as lactic acid and glycolic acid or beta-hydroxy acids),
phytic acid, lipoic acid;
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lysophosphatidic acid, skin peel agents (e.g., phenol and the like) which
enhance the keratinous
tissue appearance benefits of the present invention, especially in regulating
keratinous tissue
condition, e.g., skin condition.
Water-Soluble Vitamins
The compositions of the present invention may contain a safe and effective
amount of one
or more water-soluble vitamins. Examples of water-soluble vitamins include,
but are not limited
to, water-soluble versions of vitamin B, vitamin B derivatives, vitamin C,
vitamin C derivatives,
vitamin K, vitamin K derivatives, vitamin D, vitamin D derivatives, vitamin E,
vitamin E
derivatives, and mixtures thereof.
Vitamin B3 Compounds
The compositions of the present invention may contain a safe and effective
amount of a
vitamin, B3 compound. When vitamin B3 compounds are present in the
compositions of the
instant invention, the compositions preferably contain from about 0.01% to
about 50%, more
preferably from about 0.1% to about 10%, still more preferably from about 1%
to about 5%, and
still more preferably from about 2% to about 5%, by weight of the composition,
of the vitamin B3
compound.
As used herein, "vitamin B3 compound" means a compound having the formula:
~a
wherein R is - CONH2 (i.e., niacinamide), - COOH (i.e., nicotinic acid) or -
CH20H (i.e.,
nicotinyl alcohol); derivatives thereof; and salts of any of the foregoing.
Exemplary derivatives of the foregoing vitamin B3 compounds include nicotinic
acid
esters, including non-vasodilating esters of nicotinic acid (e.g.,
niacinamide), nicotinyl amino
acids, nicotinic acid N-oxide and niacinamide N-oxide.
Hydroxy Acids
The compositions of the present invention may contain a safe and effective
amount of a
Hydroxy Acid. Preferred hydroxy acids for use in the compositions of the
present invention
include alpha hydroxy acids such as lactic acid and glycolic acid. When
present in the
compositions of the present invention, the hydroxy acid is preferably used in
an amount of from
about 0.01% to about 50%, more preferably from about 0.1% to about 10%, and
still more
preferably from about 0.5% to about 2%.
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Pe-ptides
Peptides, including but not limited to, di-, tri-, tetra-, and pentapeptides
and derivatives
thereof, may be included in the compositions of the present invention in
amounts that are safe and
effective. As used herein, "peptides" refers to both the naturally occurring
peptides and
synthesized peptides. Also useful herein are naturally occurring and
commercially available
compositions that contain peptides.
Suitable dipeptides for use herein include Carnosine (beta-ala-his). Suitable
tripeptides
for use herein include, gly-his-lys, arg-lys-arg, his-gly-gly. Preferred
tripeptides and derivatives
thereof include palmitoyl-gly-his-lys, which may be purchased as Biopeptide
CL~ (100ppm of
palmitoyl-gly-his-lys commercially available from Sederma, France); Peptide CK
(arg-lys-arg);
Peptide CK+ (ac-arg-lys-arg-NH2); and a copper derivative of his-gly-gly sold
commercially as
Iamin, from Sigma (St.Louis, Missouri). Suitable tetrapeptides for use herein
include Peptide E,
arg-ser-arg-lys (SEQ m NO:1). Suitable pentapeptides for use herein include
lys-thr-thr-lys-ser.
A preferred commercially available pentapeptide derivative composition is
Matrixyl~, which
contains 100 ppm palmitoyl-lys-thr-thr-lys-ser (SEQ ID N0:2, commercially
available from
Sederma, France).
Preferably, the peptide is selected from palmitoyl-lys-thr-thr-lys-ser,
palmitoyl-gly-his-
lys, their derivatives, and combinations thereof.
When included in the present compositions, peptides are preferably included in
amounts
of from about 1x10-~% to about 10%, more preferably from about 0.001% to about
10%, even
more preferably from about 0.1% to about 10%, by weight of the composition.
Anti-Oxidants/Radical Scavengers
The compositions of the present invention may include a safe and effective
amount of an
anti-oxidanbradical scavenger, preferably from about 0.1% to about 10%, more
preferably from
about 1% to about 5%, of the composition. The anti-oxidant/radical scavenger
is especially useful
for providing protection against LTV radiation which can cause increased
scaling or texture
changes in the stratum corneum and against other environmental agents which
can cause skin
damage.
Anti-oxidants/radical scavengers such as ascorbic acid (vitamin C) and its
salts, ascorbic
acid derivatives (e.g., magnesium ascorbyl phosphate, sodium ascorbyl
phosphate), tocotrienols,
butylated hydroxy benzoic acid salts, uric acid salts, sorbic acid salts,
dihydroxy fumaric acid
salts, lysine; methionine, proline, superoxide dismutase, silymarin, tea
extracts, grape skin/seed
extracts, melanin, and rosemary extracts may be used. A preferred anti-
oxidants/radical
scavenger is vitamin C.
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Water-Soluble Flavonoids
The compositions of the present invention may contain a safe and effective
amount of a
water-soluble flavonoid. A preferred example is o-glycoside.
Anti-Cellulite Agents
The compositions of the present invention may contain a safe and effective
amount of an
anti-cellulite agent. Suitable agents may include, but are not limited to,
xanthine compounds
(e.g., theophylline, theobromine, and aminophylline).
Tanning Actives
The compositions of the present invention may contain a safe and effective
amount of a
tanning active, preferably from about 0.1 % to about 20% of dihydroxyacetone
as an artificial
tanning active.
Dihydroxyacetone, which is also known as DHA or 1,3-dihydroxy-2-propanone, is
a
white to off white, crystalline powder.
Skin Li hte~ning Agents
The compositions of the present invention may contain a skin lightening agent.
When
used, the compositions preferably contain from about 0.1% to about 10%, more
preferably from
about 0.2% to about 5%, also preferably from about 0.5% to about 2%, by weight
of the
composition, of a skin lightening agent. Suitable skin lightening agents
include those known in
the art, including kojic acid, arbutin, ascorbic acid and derivatives thereof
(e.g., magnesium
ascorbyl phosphate or sodium ascorbyl phosphate), and extracts (e.g., mulberry
extract, placental
extract).
Skin Soothing and Skin Healing Actives
A safe and effective amount of a skin soothing or skin healing active may be
added to the
present composition, preferably, from about 0.1% to about 30%, more preferably
from about
0.5% to about 20%, still more preferably from about 0.5% to about 10 %, by
weight of the
composition formed. Skin soothing or skin healing actives suitable for use
herein include
panthenoic acid derivatives (including panthenol, dexpanthenol, ethyl
panthenol), aloe vera,
allantoin, and dipotassium glycyrrhizinate.
Antimicrobial and Antifun~al Actives
The compositions of the present invention may contain an antimicrobial or
antifungal
active. A safe and effective amount of an antimicrobial or antifungal active
may be added to the
present compositions, preferably, from about 0.001% to about 10%, more
preferably from about
0.01 % to about 5 %, and still more preferably from about 0.05 % to about 2%.
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WO 02/03930 PCT/USO1/21602
Preferred examples of actives useful herein include those selected from
glycolic acid,
lactic acid, phytic acid, N-acetyl-L-cysteine, phenoxyethanol,
phenoxypropanol,
phenoxyisopropanol, and mixtures thereof.
Sunscreen Actives
Exposure to ultraviolet light can result in excessive scaling and texture
changes of the
stratum corneum. Therefore, the compositions of the subject invention may
optionally contain a
sunscreen active. As used herein, "sunscreen active" includes both sunscreen
agents and physical
sunblocks. Suitable sunscreen actives may be organic or inorganic.
Non-limiting examples of inorganic sunscreens useful herein include the
following
metallic oxides; titanium dioxide having an average primary particle size of
from about 15 nm to
about 100 nm, zinc oxide having an average primary particle size of from about
15 nm to about
150 nm, zirconium oxide having an average primary particle size of from about
15 nm to about
150 nm, iron oxide having an average primary particle size of from about 15 nm
to about 500nm,
and mixtures thereof. When used herein, the inorganic sunscreens are present
in the amount of
from about 0.1% to about 20%, preferably from about 0.5% to about 10%, more
preferably from
about 1% to about 5%, by weight of the composition.
A wide variety of conventional sunscreen actives are suitable for use herein.
Sagarin, et
al., at Chapter VIII, pages 189 et seq., of Cosmetics Science and Technology
(1972), discloses
numerous suitable actives. Specific suitable sunscreen actives include, for
example: p-
aminobenzoic acid, its salts and its derivatives (ethyl, isobutyl, glyceryl
esters; p-
dimethylaminobenzoic acid); anthranilates (i.e., o-amino-benzoates; methyl,
menthyl, phenyl,
benzyl, phenylethyl, linalyl, terpinyl, and cyclohexenyl esters); salicylates
(amyl, phenyl, octyl,
benzyl, menthyl, glyceryl, and di-pro-pyleneglycol esters); cinnamic acid
derivatives (menthyl
and benzyl esters, a-phenyl cinnamonitrile; butyl cinnamoyl pyruvate);
dihydroxycinnamic acid
derivatives (umbelliferone, methylumbelliferone, methylaceto-umbelliferone);
trihydroxy-
cinnamic acid derivatives (esculetin, methylesculetin, daphnetin, and the
glucosides, esculin and
daphnin); hydrocarbons (diphenylbutadiene, stilbene); dibenzalacetone and
benzalacetophenone;
naphtholsulfonates (sodium salts of 2-naphthol-3,6-disulfonic and of 2-
naphthol-6,8-disulfonic
acids); di-hydroxynaphthoic acid and its salts; o- and p-
hydroxybiphenyldisulfonates; coumarin
derivatives (7-hydroxy, 7-methyl, 3-phenyl); diazoles (2-acetyl-3-
bromoindazole, phenyl
benzoxazole, methyl naphthoxazole, various aryl benzothiazoles); quinine salts
(bisulfate, sulfate,
chloride, oleate, and tannate); quinoline derivatives (8-hydroxyquinoline
salts, 2-
phenylquinoline); hydroxy- or methoxy-substituted benzophenones; uric and
violuric acids; tannic
acid and its derivatives (e.g., hexaethylether); (butyl carbotol) (6-propyl
piperonyl) ether;
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WO 02/03930 PCT/USO1/21602
hydroquinone; benzophenones (oxybenzene, sulisobenzone, dioxybenzone,
benzoresorcinol,
2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone,
octabenzone;
4-isopropyldibenzoylmethane; butylmethoxydibenzoylmethane; etocrylene;
octocrylene; [3-(4'-
methylbenzylidene bornan-2-one) and 4-isopropyl-di-benzoylmethane.
Of these, 2-ethylhexyl-p-methoxycinnamate (commercially available as PARSOL
MCX),
4,4'-t-butyl methoxydibenzoyl-methane (comnnercially available as PARSOL
1789), 2-hydroxy-4-
methoxybenzophenone, octyldimethyl-p-aminobenzoic acid, digalloyltrioleate,
2,2-dihydroxy-4-
methoxybenzophenone, ethyl-4-(bis(hydroxy-propyl))aminobenzoate, 2-ethylhexyl-
2-cyano-3,3-
diphenylacrylate, 2-ethylhexyl-salicylate, glyceryl-p-aminobenzoate, 3,3,5-tri-
methylcyclohexylsalicylate, methylanthranilate, p-dimethyl-aminobenzoic acid
or aminobenzoate,
2-ethylhexyl-p-dimethyl-amino-benzoate, 2-phenylbenzimidazole-5-sulfonic acid,
2-(p-
dimethylaminophenyl)-5-sulfonicbenzoxazoic acid, octocrylene and mixtures of
these
compounds, are preferred.
Also useful in the compositions are sunscreen actives having, in a single
molecule, two
distinct chromophore moieties which exhibit different ultra-violet radiation
absorption spectra.
One of the chromophore moieties absorbs predominantly in the UVB radiation
range and the
other absorbs strongly in the UVA radiation range.
When present in the composition, a safe and effective amount of the sunscreen
active is
used, typically from about 1% to about 20%, more typically from about 2% to
about 10% by
weight of the composition. Exact amounts will vary depending upon the
sunscreen chosen and
the desired Sun Protection Factor (SPF).
Particulate Material
The compositions of the present invention may, in some embodiments, contain a
particulate material, preferably a metallic oxide. These particulates can be
coated or uncoated,
charged or uncharged. Charged particulate materials are disclosed in U.S.
Patent No. 5,997,887,
to Ha, et al., incorporated herein by reference. Particulate materials useful
herein include;
bismuth oxychloride, iron oxide, mica, mica treated with barium sulfate,
titanium dioxide (Ti02),
zinc oxide, zirconium oxide, silica, nylon, polyethylene, talc, styrene,
polypropylene,
ethylene/acrylic acid copolymer, sericite, aluminum oxide, silicone resin,
barium sulfate, calcium
carbonate, cellulose acetate, polymethyl methacrylate, and mixtures thereof.
Inorganic particulate materials, e.g., Ti02, ZnO, or Zr02 are commercially
available
from a number of sources. One example of a suitable particulate material
contains the material
available from U.S. Cosmetics (TRONOX Ti02 series, SAT-T CR837, a rutile
Ti02).
Preferably, particulate materials are present in the composition in levels of
from about 0.01 % to
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WO 02/03930 PCT/USO1/21602
about 2%, more preferably from about 0.05% to about 1.5%, still more
preferably from about
0.1 % to about 1 %, by weight of the composition. There are no specific
limitations as to the
pigment, colorant or filler powders used in the composition.
Preferred organic powders/fillers include, but are not limited, to polymeric
particles
chosen from the methylsilsesquioxane resin microspheres such as for example
those sold by
Toshiba silicone under the name Tospearl 145A; microspheres of
polymethylmethacrylates such
as those sold by Seppic under the name Micropearl M 100; the spherical
particles of crosslinked
polydimethylsiloxanes, especially such as those sold by Dow Corning Toray
Silicone under the
name Trefil E 506C or Trefil E SOSC, sphericle particles of polyamide and more
specifically
Nylon 12, especially such as those sold by Atochem under the name Orgasol
2002D Nat COS,
polystyerene microspheres such as for example those sold by Dyno Particles
under the name
Dynospheres, ethylene acrylate copolymer sold by Kobo under the name FloBead
EA209 and
mixtures thereof.
Also useful herein are pigment andlor dye encapsulates such nanocolorants from
BASF
and multi-layer interference pigments such as Sicopearls from BASF. '
It is preferred that the pigments/powders are surface treated to provide added
stability of
color and ease of formulation. Hydrophobically treated pigments are more
preferred, because
they may be more easily dispersed in the delivery vehicle. In addition, it may
be useful to treat
the pigments with a material that is compatible with a silicone phase.
Particularly useful
hydrophobic pigment treatments for use in water-in-silicone emulsions include
polysiloxane
treatments such as those disclosed in U.S. Patent 5,143,722, incorporated
herein by reference in
its entirety. Also preferred are pigment/powders having a primary average
particle size of from
about 10 nm to about 100,000 nm, more preferably from about SOnm to about
S,OOOnm, most
preferably from about 100nm to about 1000nm. Mixtures of the same or different
pigment/powder having different particle sizes are also useful herein (e.g.,
incorporating a Ti02
having a primary particle size of from about 100 nm to about 400 nm with a
TiO2 having a
primary particle size of from about 10 nm to about 50 nm).
Conditioning A
The compositions of the present invention may comprise a conditioning agent
selected
from the group consisting of humectants, moisturizers, or skin conditioners. A
variety of these
materials can be employed and each can be present at a level of from about
0.01% to about 40%,
more preferably from about 0.1% to about 30%, and most preferably from about
0.5% to about
10%, by weight of the composition. Non-limiting examples of conditioning
agents include
guanidine; urea; glycolic acid and glycolate salts (e.g. ammonium and
quaternary alkyl
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WO 02/03930 PCT/USO1/21602
ammonium); salicylic acid; lactic acid and lactate salts (e.g., ammonium and
quaternary alkyl
ammonium); aloe vera in any of its variety of forms (e.g., aloe vera gel);
polyhydroxy alcohols
such as sorbitol, mannitol, xylitol, erythritol, glycerol, hexanetriol,
butanetriol, propylene glycol,
butylene glycol, hexylene glycol and the like; polyethylene glycols; sugars
(e.g., melibiose) and
starches; sugar and starch derivatives (e.g., alkoxylated glucose, fucose,
glucosamine); hyaluronic
acid; lactamide monoethanolamine; acetamide monoethanolamine; panthenol;
allantoin; and
mixtures thereof. Also useful herein are the propoxylated glycerols described
in U. S. Patent No.
4,976,953, to Orr et al, issued December 11, 1990, incorporated herein by
reference.
Also useful are various Cl-C3o monoesters and polyesters of sugars and related
materials.
These esters are derived from a sugar or polyol moiety and one or more
carboxylic acid moieties.
Preferably, the conditioning agent is selected from the group consisting of
urea,
guanidine, sucrose polyester, panthenol, allantoin, and combinations thereof.
Thickening Agent (including thickeners and egg a a
The compositions of the present invention can comprise one or more thickening
agents,
preferably from about 0.1% to about 5%, more preferably from about 0.1% to
about 3%, and most
preferably from about 0.25% to about 2%, by weight of the composition. The
compositions of the
present invention may also contain mixtures of thickening agents.
Nonlimiting classes of thickening agents include those selected from the group
consisting
of:
a) Carboxylic Acid Pol.
Non-limiting examples of commercially available carboxylic acid polymers
useful herein
include the carbomers, which are homopolymers of acrylic acid crosslinked with
allyl ethers of
sucrose or pentaerytritol. The carbomers are available as the Carbopol~ 900
series from B.F.
Goodrich (e.g., Carbopol~ 954). In addition, other suitable carboxylic acid
polymeric agents
include copolymers of C10-30 alkyl acrylates with one or more monomers of
acrylic acid,
methacrylic acid, or one of their short chain (i.e., C1_4 alcohol) esters,
wherein the crosslinking
agent is an allyl ether of sucrose or pentaerytritol. These copolymers are
known as acrylates/Clo-
3o alkyl acrylate crosspolymers and are commercially available as Carbopol~
1342, Carbopol~
1382, Pemulen TR-1, and Pemulen TR-2, from B.F. Goodrich
b) Crosslinked Pol,~rylate Pol, mers
Non-limiting examples of useful crosslinked nonionic polyacrylate polymers and
crosslinked cationic polyacrylate polymers are those described in U. S. Patent
No. 5,100,660, to
Hawe et al, issued March 31, 1992; U. S. Patent No. 4,849,484, to Heard,
issued July 18, 1989; U.
CA 02413276 2002-12-16
WO 02/03930 PCT/USO1/21602
S. Patent No. 4,835,206, to Farrar et al, issued May 30, 1989; U.S. Patent No.
4,628,078 to Glover
et al issued December 9, 1986; U.S. Patent No. 4,599,379 to Flesher et al
issued July 8, 1986; and
EP 228,868, to Farrar et al, published July 15, 1987, all of which are
incorporated herein.
c) Polyacrylamide Polymers
A non-limiting example of a polyacrylamide nonionic polymer useful herein is
one given
the CTFA designation polyacrylamide and isoparaffm and laureth-7, available
under the
Tradename Sepigel 305 from Seppic Corporation (Fairfield, NJ).
Other polyacrylamide polymers useful herein include mufti-block copolymers of
acrylamides and substituted acrylamides with acrylic acids and substituted
acrylic acids.
Commercially available examples of these mufti-block copolymers include Hypan
SR150H,
SS500V, SS500W, SSSA100H, from Lipo Chemicals, Inc., (Patterson, NJ).
d) Polysaccharides
Nonlimiting examples of polysaccharide gelling agents include those selected
from the
group consisting of cellulose, carboxymethyl hydroxyethylcellulose, cellulose
acetate propionate
carboxylate, hydroxyethylcellulose, hydroxyethyl ethylcellulose,
hydroxypropylcellulose,
hydroxypropyl methylcellulose, methyl hydroxyethylcellulose, microcrystalline
cellulose, sodium
cellulose sulfate, and mixtures thereof. Also useful herein are the alkyl
substituted celluloses. In
these polymers, the hydroxy groups of the cellulose polymer is
hydroxyalkylated (preferably
hydroxyethylated or hydroxypropylated) to form a hydroxyalkylated cellulose
which is then
further modified with a Clo-Cso straight chain or branched chain alkyl group
through an ether
linkage. Typically these polymers are ethers of Cio-C3o straight or branched
chain alcohols with
hydroxyalkylcelluloses. Examples of alkyl groups useful herein include those
selected from the
group consisting of stearyl, isostearyl, lauryl, myristyl, cetyl, isocetyl,
cocoyl (i.e. alkyl groups
derived from the alcohols of coconut oil), palmityl, oleyl, linoleyl,
linolenyl, ricinoleyl, behenyl,
and mixtures thereof. Preferred among the alkyl hydroxyalkyl cellulose ethers
is the material
given the CTFA designation cetyl hydroxyethylcellulose, which is the ether of
cetyl alcohol and
hydroxyethylcellulose. This material is sold under the tradename Natrosol~ CS
Plus from
Aqualon Corporation (Wilmington, DE).
Other useful polysaccharides include scleroglucans comprising a linear chain
of (1-3)
linked glucose units with a (1-6) linked glucose every three units, a
commercially available
example of which is ClearogelTM CS 11 from Michel Mercier Products Inc.
(Mountainside, NJ).
e) Gums
Nonlimiting examples of gelling agent gums include materials selected from the
group
consisting of acacia, agar, algin, alginic acid, ammonium alginate,
amylopectin, calcium alginate,
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WO 02/03930 PCT/USO1/21602
calcium carrageenan, carnitine, carrageenan, dextrin, gelatin, gellan gum,
guar gum, guar
hydroxypropyltrimonium chloride, hectorite, hyaluroinic acid, hydrated silica,
hydroxypropyl
chitosan, hydroxypropyl guar, karaya gum, kelp, locust bean gum, natto gum,
potassium alginate,
potassium carrageenan, propylene glycol alginate, sclerotium gum, sodium
carboyxmethyl
dextran, sodium carrageenan, tragacanth gum, xanthan gum, and mixtures
thereof.
Composition Preparation
The compositions useful for the methods of the present invention are generally
prepared
by conventional methods such as are known in the art of making topical
compositions. Such
methods typically involve mixing of the ingredients in one or more steps to a
relatively uniform
state, with or without heating, cooling, application of vacuum, and the like.
Methods of Use
The compositions of the present invention are useful for enhancing the
delivery of oil-
soluble skin care actives into the skin. The percentage of oil-soluble active
delivered to the skin
dermis by the compositions of the present invention is greater than the
percentage delivered by a
single application of a conventional oil-in-water or water-in-oil emulsion
wherein the active is in
the oil phase. Measurement of such delivery enhancement may be completed by
any conventional
means of comparing the delivery of actives in standard topical skin care
compositions. For
example, ex-vivo skin penetration through cadaver skin using Franz cells is a
standard
methodology for measuring skin penetration of skin care actives.933
The compositions of the present invention are also useful for regulating the
condition of
skin and/or hair while having good aesthetics and improved delivery of oil-
soluble skin care
actives. Regulating the condition of skin includes reducing the appearance of
fine lines and/or
wrinkles on the skin, reducing the appearance of eye bags and dark circles
under the eys, sagging
skin, scars/marks, dimples, pores, stretch marks, roughness, skin surface
blemishes, frown lines,
expression lines, rhytides, blemishes, photodamage, crevices, and/or
unevenness.
Regulation of the keratinous tissue conditions of the skin with such actives
in
combination with the tacky solvent soluble active, and improved delivery
system can include
prophylactic and therapeutic regulation. For example, such regulating methods
are directed to
thickening keratinous tissue (i.e., building the epidermis and/or dermis
layers of the skin and
where applicable the keratinous layers of the nail and hair shaft) and
preventing andlor retarding
atrophy of mammalian skin, preventing and/or retarding the appearance of
spider vessels and/or
red blotchiness on mammalian skin, preventing and/or retarding the appearance
of dark circles
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WO 02/03930 PCT/USO1/21602
under the eye of a mammal, preventing and/or retarding sallowness of mammalian
skin,
preventing and/or retarding sagging of mammalian skin, softening and/or
smoothing lips, hair and
nails of a mammal, preventing and/or relieving itch of mammalian skin,
regulating skin texture
(e.g. wrinkles and fine lines), and improving skin color (e.g. redness,
freckles).
In a preferred embodiment the composition is chronically applied to the skin.
By
"chronic topical application" is meant continued topical application of the
composition over an
extended period during the subject's lifetime, preferably for a period of at
least about one week,
more preferably for a period of at least about one month, even more preferably
for at least about
three months, even more preferably for at least about six months, and more
preferably still for at
least about one year. While benefits are obtainable after various maximum
periods of use (e.g.,
five, ten or twenty years), it is preferred that the chronic application
continues throughout the
subject's ,lifetime. Typically applications would be on the order of about
once per day over such
extended periods, however application rates can vary from about once per week
up to about three
times per day or more.
A wide range of quantities of the compositions of the present invention can be
employed
to provide a skin appearance and/or feel benefit. Quantities of the present
compositions which are
typically applied per application are, in mg composition/cm2 skin, from about
0.1 mg/cm2 to
about 10 mg/cm2. A particularly useful application amount is about 1 mg/cm2 to
about 2
mg/cm2.
Modifying and/or regulating skin appearance, feel, and/or condition is
preferably
practiced by applying a composition in the form of a skin lotion, cream, gel,
foam, ointment,
paste, emulsion, spray, conditioner, tonic, cosmetic, lipstick, foundation,
nail polish, after-shave,
or the like which is preferably intended to be left on the skin or other
keratin structure for some
esthetic, prophylactic, therapeutic or other benefit (i.e., a "leave-on"
composition). After applying
the composition to the skin, it is preferably left on the skin for a period of
at least about 15
minutes, more preferably at least about 30 minutes, even more preferably at
least about 1 hour,
still more preferably for at least several hours, e.g., up to about 12 hours.
Any part of the external
portion of the face, hair, and/or nails can be treated, e.g., face, lips,
under-eye area, eyelids, scalp,
neck, torso, arms, hands, legs, feet, fingernails, toenails, scalp hair,
eyelashes, eyebrows, etc. The
composition can be applied with the fingers or with an implement or device
(e.g., pad, cotton ball,
applicator pen, spray applicator, and the like).
Another approach to ensure a continuous exposure of the skin to at least a
minimum level
of the composition is to apply the compound by use of a patch applied, e.g.,
to the face. Such an
approach is particularly useful for problem skin areas needing more intensive
treatment (e.g.,
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WO 02/03930 PCT/USO1/21602
facial crows feet area, frown lines, under eye area, age spots, and the like).
The patch can be
occlusive, semi-occlusive or non-occlusive and can be adhesive or non-
adhesive. The
composition can be contained within the patch or be applied to the skin prior
to application of the
patch. The patch can also include additional actives such as chemical
initiators for exothermic
reactions such as those described in U.S. Patents numbered 5,821,250,
5,981,547, and 5,972,957
to Wu, et al. The patch is preferably left on the skin for a period of at
least about 5 minutes, more
preferably at least about 15 minutes, more preferably still at least about 30
minutes, even more
preferably at least about 1 hour, still more preferably at night as a form of
night therapy.
Examples
The following examples further describe and demonstrate embodiments within the
scope
of the present invention. 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.
Examples 1- 7
Water-in-Silicone Skin Cream
Water-in-silicone skin creams are prepared by conventional methods from the
following
components. Amounts of ingredients are listed in percent by weight of the
composition.
Ingredient 1 2 3 4 5 6 7
PHASE Water qs qs qs qs qs qs qs
A:
Disodium EDTA 0.100.10 0.10 0.10 0.10 0.10 0.10
Methyl Paraben 0.100.10 0.10 0.10 0.10 0.10 0.10
Propyl Paraben 0.100.10 0.10 0.10 0.10 0.10 0.10
Niacinamide 2.00 7.5 5.0 3.50 10.005.0
Dexpanthenol 0.50 1.0 1.0 0.50 1.0 0.50
Allantoin 0.2 0.2 0.2 0.2
Benzyl Alcohol 0.250.25 0.25 0.25 0.25 0.25 0.25
Green Tea Extract1.001.00 1.00 1.00 1.00 1.00
Glycerin 6.00 20.0010.007.00 15.0015
Terephthalylidene 5.0
dicamphor sulfonic
acid 1
Palmitoyl Lys 0.0003 0.0003
Thr Thr Lys
Ser Z
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WO 02/03930 PCT/USO1/21602
PHASE Dow Coming 9040'11.0015.00 20.0010.007.50 10
B:
KSG -21 4 4.00 5.50 15.00 7.00 0.50 10
Cyclomethicone 12.0017.0020.00 25.0020.003.00 20
Dimethicone 3.00 5.00 2.50 2.00
Copolyol
(Dow Corning
5225C)
Vitamin E Acetate 0.50 0.5 0.50 0.50
Titanium Dioxide 0.50 0.50
GLW75CAP-MP
5
Fragrance 0.20 0.20 0.20 0.20
Famesol 3.00 5.00 1.00
(-)-alpha Bisabolol 0.50 1.00
Parsol 1789 3.00 2.00
6
Fytosterol-85' 1.00
Octyl Salicylate 5.00
Isopropyl Palinitate 7.00 6.00
Tospearl 145 1.00 1.00
PHASE Finsolv TN 2.00 2.00 2.00
C
Retinol 0.10
~~ Retinyl Propionate 0.20 0.20
~
t Can be obtained from Chimex as Mexoryl SX
2 Peptide can be obtained from Sederma
3 12% Dimethicone/Vinyl Dimethicone crosspolymer in cyclomethicone from Dow
Corning
4 Available from Shin-Etsu; 25% Dimethicone/Copolyol Crosspolymer in
dimethicone
5 Titanium Dioxide GLW75CAP-MP can be obtained from KOBO
~ Parsol 1789 can be obtained from Roche
~ Fytosterol-85 can be obtained from Dragoco
The ingredients of Phase A are mixed together in a suitable container and the
ingredients
of Phase B are mixed together in a separate suitable container, both using a
suitable mixer (e.g.,
Tekmar model RW20DZM) equipped with a propeller blade. If Phase C ingredients
are present,
such ingredients are mixed together in a separate suitable container (where
necessary) and are
added to Phase B. When both Phases are homogenous, Phase A is slowly added to
Phase B while
mixing Phase B with propeller blade. Mixing is maintained until the batch is
uniform. The
resulting emulsion is then milled using a suitable mill (e.g. Tekmar T25) for
several minutes to
insure uniformity. The product is then poured into suitable containers. The
resulting product
exhibits enhanced penetration of the oil-soluble skin care actives and good
aesthetics.
