Note: Descriptions are shown in the official language in which they were submitted.
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
CLEANSING ARTICLES FOR SKIN AND/OR HAIR
WHICH ALSO DEPOSITS SKIN CARE ACTIVES
TECHNICAL FIELD
The present invention relates to a substantially dry, disposable, personal
cleansing article useful for both cleansing the skin or hair and delivering
skin care
actives to the skin or hair. These articles are used by the consumer by
wetting the
dry article with water, producing lather from the article, and contacting the
skin with
the lathered article in the normal use of cleansing the skin. These articles
comprise a
to water insoluble substrate, at least one lathering surfactant, and at least
one skin care
active.
Use of the substrate enhances lathering at low surfactant levels, increases
cleansing and exfoliation, optimizes delivery and deposition of the skin care
active
ingredients, and provides desirable characteristics such as texture, thickness
and
bulk. As a result, this invention provides effective cleansing using low, and
hence
less irritating, levels of surfactant while providing superior delivery of
skin care
actives to the skin or hair.
The invention also encompasses articles comprising various skin
conditioning agents for delivery to the skin or hair.
The invention also encompasses a method for consistent deposition of skin
care actives to the skin or hair.
The invention also encompasses a method for simultaneously cleansing the
skin or hair and delivering skin care actives onto the skin or hair using the
articles of
the present invention and also to methods for manufacturing these articles.
BACKGROUND OF THE INVENTION
Personal cleansing articles have traditionally been marketed in a variety of
forms such as bar soaps, creams, lotions, and gels. These cleansing
formulations
have attempted to satisfy a number of criteria to be acceptable to consumers.
These
criteria include cleansing effectiveness, skin feel, mildness to skin, hair,
and ocular
3o mucosae, and lather volume. Ideal personal cleansers should gently cleanse
the skin
or hair, cause little or no irritation, and not leave the skin or hair overly
dry after
frequent use.
However, these traditional forms of personal cleansing articles have the
inherent problem of balancing cleansing efficacy against delivering a skin
care
benefit. One solution to this problem is to use separate cleansing and skin
care
articles. However, this is not always convenient or practical and many
consumers
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
2
would prefer to use a single article which can both cleanse and deliver skin
care
benefits. In a typical cleansing composition the skin care ingredients are
difficult to
formulate because many skin care actives are incompatible with the
surfactants,
resulting in an undesirable non-homogenous mixture. To obtain a homogeneous
s mixture with skin care ingredients, and to prevent the loss of skin care
ingredients
before deposition, additional ingredients, e.g. emulsifiers, thickeners, and
gellants
are often added to suspend the skin care ingredients within the surfactant
mixture.
This results in an aesthetically pleasing homogenous mixture, but often
results in
poor deposition of skin care ingredients, because the skin care ingredients
are
l0 emulsified and not efficiently released during cleansing. Also, many skin
care
agents have the disadvantage of suppressing lather generation. Lather
suppression is
a problem because many consumers seek cleansing articles that provide a rich,
creamy, and generous lather.
Therefore, it is seen that conventional cleansing articles which attempt to
1 s combine surfactants and skin care ingredients suffer from disadvantages
inherently
resulting from the incompatibilities of surfactants and skin care ingredients.
A need
clearly exists to develop cleansing systems which provide effective cleansing
and yet
consistently provide sufficient skin care benefits in a single article.
It is also highly desirable to deliver cleansing and skin care benefits from a
2o disposable, single use article. Disposable articles are convenient because
they
obviate the need to carry cumbersome bottles, bars, jars, tubes, and other
forms of
personal care products. Disposable articles are also a more sanitary
alternative to the
use of a sponge, washcloth, or other cleansing implement intended for multiple
reuse, because such implements develop bacterial growth, unpleasant odors, and
25 other undesirable characteristics related to repeated use.
It has been surprisingly found in the present invention that articles can be
developed to provide effective cleansing and consistent delivery of skin care
actives
in a convenient, inexpensive, and sanitary disposable personal cleansing
article
having the desirable properties of a washcloth. The present invention provides
the
3o convenience of not needing to use both a separate cleansing and skin
benefit article.
The present invention is highly convenient to use because it is in the form of
a
substantially dry article that is wetted before use.
The present invention relates to a dry, disposable, personal cleansing article
useful for both cleansing the skin or hair and delivering skin care actives to
the skin
3s or hair. These articles are used by the consumer by wetting the dry article
with
water. The articles of the present invention consist of a water insoluble
substrate, at
least one lathering surfactant, and at least one skin care active. In some
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
3
embodiments, these articles further contain a deposition aid. Without being
limited
by theory, it is believed that the substrate enhances lathering at low
surfactant levels,
increases cleansing and exfoliation, and optimizes delivery and consistent
deposition
of the skin care ingredients. As a result, this invention provides effective
cleansing
using low, and hence less irritating, levels of surfactant while providing
superior
skin care benefits in a consistent and efficient manner. It has also been
found that
these articles are useful for delivering a wide range of conditioning
ingredients to the
skin or hair during the cleansing process.
Accordingly, it is an object of the present invention to provide substantially
1 o dry washcloth-like articles for both cleansing the skin or hair and
delivering a skin
care active to the skin or hair, wherein the articles are used in combination
with
water.
It is another object of the present inventian to provide articles which are
disposable and intended for single use.
It is another object of the present invention to provide articles which are
mild
to the skin or hair.
It is another object of the present invention to provide articles useful for
delivering conditioning agents to the skin or hair during the cleansing
process.
It is another object of the present invention to provide articles which
2o consistently deposit skin care actives and other conditioning agents onto
the skin or
hair.
It is another object of the present invention to provide methods of cleansing
the skin or hair and consistently delivering skin care actives onto the skin
or hair.
It is another object of the present invention to provide methods of
manufacturing the articles of the present invention.
These and other objects of this invention will become apparent in light of the
following disclosure.
SUMMARY OF THE INVENTION
The present invention relates to disposable, single use personal care
3o cleansing and conditioning articles comprising (A) a water insoluble
substrate, (B) at
least one lathering surfactant added onto or impregnated into said substrate,
and (C)
a skin care component comprising at least one skin care active selected from
the
group consisting of water soluble skin care actives, oil soluble skin care
actives and
mixtures thereof. The skin care active component is also added onto or
impregnated
into said substrate. These articles are substantially dry before wetting. Upon
wetting, however, these articles are capable of generating an Average Lather
Volume of greater than or equal to about 30 ml.
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
4
In further embodiments, the articles of the present invention further comprise
at least one deposition aid added onto or impregnated into said substrate.
In still further embodiments, the present invention relates to methods of
manufacturing these disposable, single use personal care cleansing articles.
The
method comprises the steps of (A) separately or simultaneously adding onto or
impregnating into a water insoluble substrate (i) a lathering surfactant, and
(ii) a skin
care active component; and (B) substantially drying the treated substrate. The
resulting article generates an Average Lather Volume of greater than or equal
to
about 30 ml.
to In still further embodiments, the present invention relates to methods for
simultaneously cleansing the skin or hair and delivering skin care actives
onto the
skin or hair with the personal cleansing articles described herein.
In even further embodiments, the present invention relates to methods of
consistently depositing skin care active onto the skin or hair.
1 s All percentages and ratios used herein, unless otherwise indicated, are by
weight and all measurements made are at 25°C, unless otherwise
designated. The
invention hereof can comprise, consist of, or consist essentially of, the
essential as
well as optional ingredients and components described therein.
DETAILED DESCRIPTION OF THE INVENTION
2o The personal cleansing articles of the present invention are highly
efficacious
for cleansing the skin or hair while at the same time providing effective
deposition
of skin care actives onto the skin or hair. The articles can also contain
conditioning
agents to be deposited onto the skin or hair.
Without being limited by theory it is believed that the substrate
significantly
2s contributes to generation of lather and deposition of skin care actives and
any other
conditioning agents onto the skin or hair. It is believed that this increase
in lather
and deposition is the result of the surface interaction of the substrate with
the skin or
hair. As a result, milder and significantly lower amounts of surfactants may
be
employed. The decreased amount of required surfactant is believed to relate to
a
30 decrease in the drying effect of the skin or hair by the surfactants.
Furthermore, the
diminished amount of surfactant dramatically decreases the surfactant
inhibitory
action (e.g., via emulsification or direct removal by the surfactants) on the
deposition of skin care active ingredients onto the skin or hair.
Without being limited by theory, the substrate also enhances deposition of
35 skin care active ingredients and conditioning agents. Since the invention
is in dry
form, the invention does not require emulsifiers, which can inhibit deposition
of skin
care active ingredients and conditioning agents. Furthermore, because the skin
care
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
active ingredients and skin conditioners are dried onto or impregnated into
the
substrate, they are transferred directly to the skin or hair by surface
contact of the
wetted article to the skin.
The substrate also enhances cleansing. The substrate can have differing
5 textures on each side, e.g. a rough side and a smooth side. The substrate
acts as an
efficient lathering and exfoliating implement. By physically coming into
contact
with the skin or hair, the substrate significantly aids in cleansing and
removal of dirt,
makeup, dead skin, and other debris.
By a "lathering surfactant" is meant a surfactant, which when combined with
to water and mechanically agitated generates a foam or lather. Preferably,
these
surfactants should be mild, which means that these surfactants provide
sufficient
cleansing or detersive benefits but do not overly dry the skin or hair (e.g.,
removing
too much natural oil and/or moisture), and yet meet the lathering criteria
described
above.
The terms "disposable" or "single use", are used herein in their ordinary
sense to mean a article that is disposed or discarded after one usage event.
The terms "lathering article" or "lathered article," as used herein, means
that
the articles of the present invention contain enough of the surfactants
described
herein to generate >_ 30 ml of Lather Volume, as described herein in the
Lather
2o Volume Test. These Lather Volume measurements are conducted with a medium
hardness water (8-10 grains per gallon) at 95 °C.
The term "water-activated," as used herein, means that the present invention
is presented to the consumer in dry form to be used after it is wetted with
water. It is
found that these articles produce a lather or are "activated" by contacting
them with
water and then further subjecting the article to mechanical forces, such as
rubbing.
The term "substantially dry," as used herein, means that prior to use the
article is substantially free of water and generally feels dry to the touch.
Thus, the
articles of the present invention will generally comprise less than about 10%
by
weight of water, preferably less than about 5% by weight of water, and more
3o preferably less than about 1% by weight of water, the forgoing measured in
a dry
environment, e.g., low humidity. One of ordinary skill in the art would
recognize
that the water content of a article such as in the present invention can vary
with the
relative humidity of the environment.
The term "mild" as used herein in reference to the lathering surfactants and
articles of the present invention means that the articles of the present
invention
demonstrate skin mildness comparable to a mild alkyl glyceryl ether sulfonate
(AGS) surfactant based synthetic bar, i.e. synbar. Methods for measuring
mildness,
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
6
or inversely the irritancy, of surfactant containing articles, are based on a
skin barrier
destruction test. In this test, the milder the surfactant, the lesser the skin
barrier is
destroyed. Skin barrier destruction is measured by the relative amount of
radio-
labeled (tritium labeled) water (3H-H20) which passes from the test solution
through the skin epidermis into the physiological buffer contained in the
diffusate
chamber. This test is described by T.J. Franz in the J. Invest. Dermatol.,
1975, 64,
pp. 190-195; and in U.S. Patent No. 4,673,525, to Small et al., issued June
16, 1987,
which are both incorporated by reference herein in their entirety. Other
testing
methodologies for determining surfactant mildness well known to one skilled in
the
1o art can also be used.
The term "deposition consistency," as used herein, means that deposition of
the skin care actives will be relatively unvarying no matter how the consumer
prepares to use, and actually uses, the cleansing article (e.g., lathering the
side of the
substrate carrying the skin care actives versus lathering the substrate side
with the
surfactant). The articles of the present invention will have a deposition
consistency
of greater than about 60%, preferably greater than about 65%, more preferably
greater than about 70%, and most preferably greater than about 75%. The
deposition
consistency measurement is the quotient obtained by dividing the amount of
deposition of skin care actives that occurs via "nan-ideal lathering and use"
by the
2o amount of deposition of skin care actives that occurs via "ideal lathering
and use."
Non-ideal lathering, as used herein, means that lathering is achieved by
rubbing
together or against itself the surface of the article containing the skin care
actives
and then contacting the skin or hair with the same surface. This causes
inefficient
deposition of the skin care actives because some of the skin care actives
become
emulsified by the surfactant. Ideal lathering, as used herein, means that
lathering is
achieved by rubbing together or against itself the surface of the article
containing
surfactant, but not containing skin care actives, and then contacting the skin
or hair
with the surface containing the skin care actives. The same reference points
would
apply if both surfaces of the substrate are treated with the skin care actives
(e.g.
3o deposition obtained from lathering and contacting the skin with the same
lathered
surface containing emulsified skin care actives versus contacting the skin
with the
non-lathered surface which contains non-emulsified skin care actives).
Deposition
consistency is maximized when the hardness value of the skin care active
component
is greater than about 0.02 kg.
The personal care articles of the present invention comprise the following
essential components: (A) a water insoluble substrate, (B) at least one
lathering
surfactant added onto or impregnated into the substrate, and (C) at least one
skin
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
7
care active. The articles of the present invention can further comprise of at
least one
deposition aid.
WATER INSOLUBLE SUBSTRATE
The articles of the present invention comprise a water insoluble substrate.
By "water insoluble" is meant that the substrate does not dissolve in or
readily break
apart upon immersion in water. The water insoluble substrate is the implement
or
vehicle for delivering the lathering surfactant and the skin care actives of
the present
invention to the skin and/or hair. Without being limited by theory, it is
believed that
the substrate, as the means for transmitting mechanical forces and providing
1o agitation, provides a lather generating effect and also aids in the
deposition of the
skin care actives onto the skin and/or hair.
A wide variety of materials can be used as the substrate. The following
nonlimiting characteristics are desirable: (i) sufficient wet strength for
use, (ii)
sufficient abrasivity, (iii) sufficient loft and porosity, (iv) sufficient
thickness, and
~ 5 (v) appropriate size.
Nonlimiting examples of suitable insoluble substrates which meet the above
criteria include nonwoven substrates, woven substrates, hydroentangled
substrates,
air entangled substrates, natural sponges, synthetic sponges, polymeric netted
meshes, and the like. Preferred embodiments employ nonwoven substrates since
20 they are economical and readily available in a variety of materials. By
nonwoven is
meant that the layer is comprised of fibers which are not woven into a fabric
but
rather are formed into a sheet, mat, or pad layer. The fibers can either be
random
(i.e., randomly aligned) or they can be carded (i.e. combed to be oriented in
primarily one direction). Furthermore, the nonwoven substrate can be composed
of
2s a combination of layers of random and carded fibers.
Nonwoven substrates may be comprised of a variety of materials both natural
and synthetic. By natural is meant that the materials are derived from plants,
animals, insects or byproducts of plants, animals, and insects. By synthetic
is meant
that the materials are obtained primarily from various man-made materials or
from
3o natural materials which have been further altered. The conventional base
starting
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
8
material is usually a fibrous web comprising any of the common synthetic or
natural
textile-length fibers, or mixtures thereof.
Nonlimiting examples of natural materials useful in the present invention are
silk fibers, keratin fibers and cellulosic fibers. Nonlimiting examples of
keratin
fibers include those selected from the group consisting of wool i'ibers, camel
hair
fibers, and the like. Nonlimiting examples of cellulosic fibers include those
selected
from the group consisting of wood pulp fibers, cotton fibers, hemp fibers,
jute fibers,
flax fibers, and mixtures thereof.
Nonlimiting examples of synthetic materials useful in the present invention
include those selected from the group consisting of acetate fibers, acrylic
fibers,
cellulose ester fibers, modacrylic fibers, polyamide fibers, polyester fibers,
polyolefin fibers, polyvinyl alcohol fibers, rayon fibers, polyurethane foam,
and
mixtures thereof. Examples of some of these synthetic materials include
acrylics
such as acrilan, creslan, and the acrylonitrile-based fiber, orlon; cellulose
ester fibers
l5 such as cellulose acetate, arnel, and acele; polyamides such as nylons
(e.g., nylon 6,
nylon 66, nylon 610, and the like); polyesters such as fortrel, kodel, and the
polyethylene terephthalate fiber, dacron; polyolefins such as polypropylene,
polyethylene; polyvinyl acetate fibers; polyurethane foams and mixtures
thereof.
These and other suitable fibers and the nonwoven materials prepared therefrom
are
2o generally described in Riedel, "Nonwoven Bonding Methods and Materials,"
Nonwoven World (1987); The Enc~lopedia Americana, vol. 11, pp. 147-153, and
vol. 26, pp. 566-581 (1984); U.S. Patent No. 4,891,227, to Thaman et al.,
issued
January 2, 1990; and U.S. Patent No. 4,891,228 which are all incorporated by
reference herein in their entirety.
25 Nonwoven substrates made from natural materials consist of webs or sheets
most commonly formed on a fine wire screen from a liquid suspension of the
fibers.
See C.A. Hampel et al., The Encyclopedia of Chemistry, third edition, 1973,
pp.
793-795 (1973); The Enc~pedia Americana, vol. 21, pp. 376-383 (I984); and
G.A. Smook, Handbook of Pulp and Paper Technolo~~ies, Technical Association
for
3o the Pulp and Paper Industry (1986); which are incorporated by reference
herein in
their entirety.
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
9
Substrates made from natural materials useful in the present invention can be
obtained from a wide variety of commercial sources. Nonlimiting examples of
suitable commercially available paper layers useful herein include AirtexR, an
embossed airlaid cellulosic layer having a base weight of about 71 gsy,
available
from James River, Green Bay, WI; and WalkisoftR, an embossed airlaid
cellulosic
having a base weight of about 75 gsy, available from Walkisoft U.S.A., Mount
Holly, NC.
Methods of making nonwoven substrates are well known in the art.
Generally, these nonwoven substrates can be made by air-laying, water-laying,
1o meltblowing, coforming, spinbonding, or carding processes in which the
fibers or
filaments are first cut to desired lengths from long strands, passed into a
water or air
stream, and then deposited onto a screen through which the fiber-laden air or
water
is passed. The resulting layer, regardless of its method of production or
composition, is then subjected to at least one of several types of bonding
operations
~ 5 to anchor the individual fibers together to form a self sustaining web. In
the present
invention the nonwoven layer can be prepared by a variety of processes
including
hydroentanglement, thermally bonding or thermo-bonding, and combinations of
these processes. Moreover, the substrates of the present invention can consist
of a
single layer or multiple layers. In addition, a multilayered substrate can
include
2o films and other nonfibrous materials.
Nonwoven substrates made from synthetic materials useful in the present
invention can also be obtained from a wide variety of commercial sources.
Nonlimiting examples of suitable nonwoven layer materials useful herein
include
HEF 40-047, an apertured hydroentangled material containing about 50% rayon
and
25 50% polyester, and having a basis weight of about 43 grams per square yard
(gsy),
available from Veratec, Inc., Walpole, MA; HEF 140-102, an apertured
hydroentangled material containing about 50% rayon and 50% polyester, and
having
a basis weight of about 56 gsy, available from Veratec, Inc., Walpole, MA;
NovonetR 149-616, a therma-bonded grid patterned material containing about
100%
3o polypropylene, and having a basis weight of about 50 gsy, available from
Veratec,
Inc., Walpole, MA; NovonetR 149-801, a thermo-bonded grid patterned material
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
containing about 69% rayon, about 25% polypropylene, and about 6% cotton, and
having a basis weight of about 75 gsy, available from Veratec, Inc. Walpole,
MA;
NovonetR 149-191, a thenmo-bonded grid patterned material containing about 69%
rayon, about 25% polypropylene, and about 6% cotton, and having a basis weight
of
5 about 100 gsy, available from Veratec, Inc. Waipole, MA; HEF NubtexR 149-
801, a
nubbed, apertured hydroentangled material, containing about 100% polyester,
and
having a basis weight of about 70 gsy, available from Veratec, Inc. Walpole,
MA;
KeybakR 951 V, a dry formed apertured material, containing about 75% rayon,
about
25% acrylic fibers, and having a basis weight of about 43 gsy, available from
1o Chicopee, New Brunswick, NJ; KeybakR 1368, an apertured material,
containing
about 75% rayon, about 25% polyester, and having a basis weight of about 39
gsy,
available from Chicopee, New Brunswick, NJ; DuralaceR 1236, an apertured,
hydroentangled material, containing about 100% rayon, and having a basis
weight
from about 40 gsy to about 115 gsy, available from Chicopee, New Brunswick,
NJ;
DuralaceR 5904, an apertured, hydroentangled material, containing about 100%
polyester, and having a basis weight from about 40 gsy to about 115 gsy,
available
from Chicopee, New Brunswick, NJ; ChicopeeR 5763, a carded hydroapertured
material (8x6 apertures per inch), containing about 70% rayon, about 30%
polyester,
and a optionally a latex binder (EVA) of up to about 5% w/w, and having a
basis
weight from about 75 gsy to about 63 gsy, available form Chicopee, New
Brunswick, NJ; ChicopeeR 9900 series (e.g., Chicopee 9931 - 52 gsy, 50/50
rayon/polyester, and Chicopee 9950 - 42 gsy, 50/50 rayon/poIyester), a carded,
hydroentangled material, containing a fiber composition of from 50% rayon and
50% polyester to 100% polyester, and having a basis weight of from about 30
gsy to
about 70 gsy, available form Chicopee, New Brunswick, NJ; Sontara 8868, a
hydroentangled material, containing about SO% cellulose and about 50%
polyester,
and having a basis weight of about 60 gsy, available from Dupont Chemical
Corp.
Alternatively, the water insoluble substrate can be a polymeric mesh sponge
as described in European Patent No. EP 702550 A1 published March 27, 1996,
incorporated by reference herein in its entirety. The polymeric sponge
comprises a
plurality of plies of an extruded tubular netting mesh prepared from a strong
flexible
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
polymer, such as addition polymers of olefin monomers and poIyamides of
polycarboxylic acids. Although these polymeric sponges are designed to be used
in
conjunction with a liquid cleanser, these types of sponges can be used as the
water
insoluble substrate in the present invention.
The substrate can be made into a wide variety of shapes and forms including
flat pads, thick pads, thin sheets, ball-shaped implements, irregularly shaped
implements, and having sizes ranging from a surface area of about a square
inch to
about hundreds of square inches. The exact size will depend upon the desired
use
and product characteristics. Especially convenient are square, circular,
rectangular,
or oval pads having a surface area of from about 1 in2 to about 144 in2,
preferably
from about 10 in2 to about 120 in2, and more preferably from about 30 in2 to
about
80 in2, and a thickness of from about I mil to about 500 mil, preferably from
about
5 mil to about 250 mil, and more preferably from about 10 mil to about 100
mil.
The water insoluble substrates of the present invention can comprise two or
more layers, each having different textures, abrasiveness, and
extensibilities. The
differing textures can result from the use of different combinations of
materials or
from the use of different manufacturing processes or a combination thereof. A
dual
textured substrate can be made to provide the advantage of having a more
abrasive
side for exfoliation and a softer, absorbent side for gentle cleansing.
Furthermore,
2o the substrate can be a laminate of two layers having differing wet
extensibilities.
Such laminate substrates are exemplified in copending U.S. Application Ser.
No.
09/013,640, filed January 26, 1998, which application is herein incorporated
by
reference in its entirety. In addition, separate layers of the substrate can
be
manufactured to have different colors, thereby helping the user to further
distinguish
the surfaces. Furthermore, it is desirable for the substrates of the present
invention
to have rounded corners. This feature prevents the tendency of water to
accumulate
at the corners of an unrounded square substrate.
LATHERING SURFACTANT
The articles of the present invention comprise enough of a lathering
3o surfactant to generate >_ 30 ml of Lather Volume (medium hardness water at
95 °C)
according to the Lather Volume Test described herein. Preferably, the articles
of the
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
12
present invention comprise from about 0.5% to about 40%, more preferably from
about 0.75% to about 12.5%, and most preferably from about 1 % to about 11 %,
based on the weight of the water insoluble substrate, of a lathering
surfactant.
By a lathering surfactant is meant a surfactant, which when combined with
water and mechanically agitated generates a foam or lather sufficient to cause
the
article, as a whole, to lather. Preferably, these surfactants or combinations
of
surfactants should be mild, which means that these surfactants provide
sufficient
cleansing or detersive benefits but do not overly dry the skin or hair, and
yet meet
the lathering criteria described above.
A wide variety of lathering surfactants are useful herein and include those
selected from the group consisting of anionic lathering surfactants, nonionic
lather
surfactants, amphotheric lathering surfactants, and mixtures thereof.
Generally, the
lathering surfactants do not strongly interfere with deposition of the
conditioning
agents, e.g., are fairly water soluble, and usually have an HLB value of above
10.
Cationic surfactants can also be used as optional components, provided they do
not
negatively impact the overall lathering characteristics of the required,
lathering
surfactants.
Anionic Lathering Surfactants
Nonlimiting examples of anionic lathering surfactants useful in the
2o compositions of the present invention are disclosed in McCutcheon's, Deter
ents
and Emulsifiers, North American edition (1986), published by allured
Publishing
Corporation; McCutcheon's, Functional Materials, North American Edition
(1992);
and U.S. Patent No. 3,929,678, to Laughlin et al., issued December 30, 1975
all of
which are incorporated by reference herein in their entirety.
A wide variety of anionic lathering surfactants are useful herein.
Nonlimiting examples of anionic lathering surfactants include those selected
from
the group consisting of sarcosinates, sulfates, isethionates, taurates,
phosphates,
lactylates, glutamates, and mixtures thereof. Amongst the isethionates, the
alkoyl
isethionates are preferred, and amongst the sulfates, the alkyl and alkyl
ether sulfates
3o are preferred. The alkoyl isethionates typically have the formula
RCO-OCH2CH2S03M wherein R is alkyl or alkenyl of from about 10 to about 30
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
13
carbon atoms, and M is a water-soluble canon such as ammonium, sodium,
potassium and triethanolamine. Nonlimiting examples of these isethionates
include
those alkoyl isethionates selected from the group consisting of ammonium
cocoyl
isethionate, sodium cocoyI isethionate, sodium lauroyl isethionate, and
mixtures
thereof.
The alkyl and alkyl ether sulfates typically have the respective formulae
ROS03M and RO(C2H40)xS03M, wherein R is alkyl or alkenyl of from about 10
to about 30 carbon atoms, x is from about 1 to about 10, and M is a water-
soluble
cation such as ammonium, sodium, potassium and triethanolamine. Another
1 o suitable class of anionic surfactants are the water-soluble salts of the
organic,
sulfuric acid reaction products of the general formula:
R1 __S03__M
wherein R1 is chosen from the group consisting of a straight or branched
chain,
saturated aliphatic hydrocarbon radical having from about 8 to about 24,
preferably
about 10 to about 16, carbon atoms; and M is a cation. Still other anionic
synthetic
surfactants include the class designated as succinamates, olefin sulfonates
having
about 12 to about 24 carbon atoms, and b-alkyloxy alkane sulfonates. Examples
of
these materials are sodium lauryl sulfate and ammonium lauryl sulfate.
Other anionic materials useful herein are soaps (i.e. alkali metal salts,
e.g.,
2o sodium or potassium salts) of fatty acids, typically having from about 8 to
about 24
carbon atoms, preferably from about 10 to about 2U carbon atoms. The fatty
acids
used in making the soaps can be obtained from natural sources such as, for
instance,
plant or animal-derived glycerides (e.g., palm oil, coconut oil, soybean oil,
castor
oil, tallow, lard, etc.) The fatty acids can also be synthetically prepared.
Soaps are
described in more detail in U.S. Patent No. 4,557,853, cited above.
Other useful anionic materials include phosphates such as monoalkyl,
dialkyl, and trialkylphosphate salts.
Other anionic materials include alkanoyl sarcosinates corresponding to the
formula RCON(CH3)CH2CH2C02M wherein R is alkyl or alkenyl of about 10 to
3o about 20 carbon atoms, and M is a water-soluble cation such as ammonium,
sodium,
potassium and alkanolamine {e.g., triethanolamine), a preferred examples of
which
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
14
are sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, ammonium lauroyl
sarcosinate, and sodium myristoyl sarcosinate. TEA salts of sarcasinates are
also
useful.
Also useful are taurates which are based on taurine, which is also known as
2-aminoethanesulfonic acid. Especially useful are taurates having carbon
chains
between Cg and C 16. Examples of taurates include N-alkyltaurines such as the
one
prepared by reacting dodecylamine with sodium isethionate according to the
teaching of U.S. Patent 2,658,072 which is incorporated herein by reference in
its
entirety. Further nonlimiting examples include ammonium, sodium, potassium and
alkanolamine (e.g., triethanolamine) salts of lauroyl methyl taurate,
myristoyl
methyl taurate, and cocoyl methyl taurate.
Also useful are lactylates, especially those having carbon chains
between Cg and C 16. Nonlimiting examples of lactylates include ammonium,
sodium, potassium and alkanolamine (e.g., triethanolamine) salts of lauroyl
lactylate,
cocoyl lactylate, lauroyl lactylate, and caproyl lactylate.
Also useful herein as anionic surfactants are glutamates, especially those
having carbon chains between Cg and C16. Nonlimiting examples of glutamates
include ammonium, sodium, potassium and alkanolamine (e.g., triethanolamine)
salts of lauroyl glutamate, myristoyl glutamate, and cocoyl glutamate.
Nonlimiting examples of preferred anionic lathering surfactants useful herein
include those selected from the group consisting of sodium lauryl sulfate,
ammonium lauryl sulfate, ammonium laureth sulfate, sodium laureth sulfate,
sodium
trideceth sulfate, ammonium cetyl sulfate, sodium cetyl sulfate, ammonium
cocoyl
isethionate, sodium lauroyl isethionate, sodium lauroyl lactylate,
triethanolamine
lauroyl lactylate, sodium caproyl lactylate, sodium lauroyl sarcosinate,
sodium
myristoyl sarcosinate, sodium cocoyl sarcosinate, sodium lauroyl methyl
taurate,
sodium cocoyl methyl taurate, sodium lauroyl glutamate, sodium myristoyl
glutamate, and sodium cocoyl glutamate and mixtures thereof.
Especially preferred for use herein is ammonium lauryl sulfate, ammonium
laureth sulfate, sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, sodium
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
myristoyl sarcosinate, sodium lauroyl lactylate, and triethanolamine lauroyl
lactylate.
Nonionic Latherine Surfactants
Nonlimiting examples of nonionic lathering surfactants for use in the
5 compositions of the present invention are disclosed in McCutcheon's,
Detergents
and Emulsifiers, North American edition (1986), published by allured
Publishing
Corporation; and McCutcheon's, Functional Materials, North American Edition
( 1992}; both of which are incorporated by reference herein in their entirety.
Nonionic lathering surfactants useful herein include those selected from the
10 group consisting of alkyl glucosides, alkyl polyglucosides, polyhydroxy
fatty acid
amides, alkoxylated fatty acid esters, lathering sucrose esters, amine oxides,
and
mixtures thereof.
Alkyl glucosides and alkyl polyglucosides are useful herein, and can be
broadly defined as condensation articles of long chain alcohols, e.g. C8-30
alcohols,
15 with sugars or starches or sugar or starch polymers, i.e., glycosides or
polyglycosides. These compounds can be represented by the formula (S)n-O-R
wherein S is a sugar moiety such as glucose, fructose, mannose, and galactose;
n is
an integer of from about 1 to about 1000, and R is a C8-30 alkyl group.
Examples
of long chain alcohols from which the alkyl group can be derived include decyl
alcohol, cetyl alcohol, stearyl alcohol, iauryl alcohol, myristyl alcohol,
oleyl
alcohol, and the like. Preferred examples of these surfactants include those
wherein
S is a glucose moiety, R is a C8-20 alkyl group, and n is an integer of from
about 1
to about 9. Commercially available examples of these surfactants include decyl
polyglucoside (available as APG 325 CS from Henkel) and lauryl polyglucoside
(available as APG 600CS and 625 CS from Henkel). Also useful are sucrose ester
surfactants such as sucrose cocoate and sucrose laurate.
Other useful nonionic surfactants include polyhydroxy fatty acid amide
surfactants, more specific examples of which include glucosamides,
corresponding
to the structural formula:
O ~I
~-C-
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
16
wherein: R1 is H, C 1-C4 alkyl, 2-hydroxyethyl, 2-hydroxy- propyl, preferably
C 1-C4 alkyl, more preferably methyl or ethyl, most preferably methyl; R2 is
CS-C31 alkyl or alkenyl, preferably C7-C19 alkyl or alkenyl, more preferably
Cg-C 17 alkyl or alkenyl, most preferably C 11-C 15 alkyl or alkenyl; and Z is
a
polhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with a least 3
hydroxyls directly connected to the chain, or an alkoxylated derivative
(preferably
ethoxylated or propoxylated) thereof. Z preferably is a sugar moiety selected
from
the group consisting of glucose, fructose, maltose, lactose, galactose,
mannose,
xylose, and mixtures thereof. An especially preferred surfactant corresponding
to
1 o the above structure is coconut alkyl N-methyl glucoside amide (i.e.,
wherein the
R2C0- moiety is derived from coconut oil fatty acids). Processes for making
compositions containing polyhydroxy fatty acid amides are disclosed, for
example,
in G.B. Patent Specification 809,060, published February 18, 1959, by Thomas
Hedley & Co., Ltd.; U.S. Patent No. 2,965,576, to E.R. Wilson, issued December
20, 1960; U.S. Patent No. 2,703,798, to A.M. Schwartz, issued March 8, 1955;
and
U.S. Patent No. 1,985,424, to Piggott, issued December 25, 1934; which are
incorporated herein by reference in their entirety.
Other examples of nonionic surfactants include amine oxides. Amine oxides
correspond to the general formula RIR2R3N0, wherein R1 contains an alkyl,
2o alkenyl or monohydroxy alkyl radical of from about 8 to about 18 carbon
atoms,
from 0 to about 10 ethylene oxide moieties, and from 0 to about 1 glyceryl
moiety,
and R2 and R3 contain from about 1 to about 3 carbon atoms and from 0 to about
1
hydroxy group, e.g., methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl
radicals.
The arrow in the formula is a conventional representation of a semipolar bond.
2s Examples of amine oxides suitable for use in this invention include
dimethyl-
dodecylamine oxide, oleyldi(2-hydroxyethyl) amine oxide, dimethyloctylamine
oxide, dimethyl-decylamine oxide, dimethyl-tetradecylamine oxide, 3,6,9-
trioxaheptadecyldiethylamine oxide, di{2-hydroxyethyl)-tetradecylamine oxide,
2-
dodecoxyethyldimethylamine oxide, 3-dodecoxy-2-hydroxypropyldi(3-
3o hydroxypropyl)amine oxide, dimethylhexadecylamine oxide.
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
17
Nonlimiting examples of preferred nonionic surfactants for use herein are
those selected form the group consisting of C8-C 14 glucose amides, C8-C 14
alkyl
polyglucosides, sucrose cocoate, sucrose laurate, lauramine oxide, cocoamine
oxide,
and mixtures thereof.
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
18
Amphoteric Latherine Surfactants
The term "amphoteric lathering surfactant," as used herein, is also intended
to encompass zwitterionic surfactants, which are well known to formulators
skilled
in the art as a subset of amphoteric surfactants.
A wide variety of amphoteric lathering surfactants can be used in the
compositions of the present invention. Particularly useful are those which are
broadly described as derivatives of aliphatic secondary and tertiary amines,
preferably wherein the nitrogen is in a cationic state, in which the aliphatic
radicals
can be straight or branched chain and wherein one of the radicals contains an
ionizable water solubilizing group, e.g., carboxy, sulfonate, sulfate,
phosphate, or
phosphonate.
Nonlimiting examples of amphoteric surfactants useful in the compositions
of the present invention are disclosed in McCutcheon's, Detergents and
Emulsifiers,
North American edition (1986), published by allured Publishing Corporation;
and
McCutcheon's, Functional Materials, North American Edition (1992); both of
which
are incorporated by reference herein in their entirety.
Nonlimiting examples of amphoteric or zwitterionic surfactants are those
selected from the group consisting of betaines, sultaines, hydroxysultaines,
alkyliminoacetates, iminodialkanoates, aminoalkanoates, and mixtures thereof.
Examples of betaines include the higher alkyl betaines, such as coco
dimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl
dimethyl alphacarboxyethyl betaine, cetyl dimethyl carboxymethyl betaine,
cetyl
dimethyl betaine (available as Lonzaine 16SP from Lonza Corp.), lauryl
bis-{2-hydroxyethyl} carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl
betaine, lauryl bis-(2-hydroxypropyl)alpha-carboxyethyl betaine, coco dimethyl
sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-
hydroxyethyl)
sulfopropyl betaine, amidobetaines and amidosulfobetaines (wherein the
RCONH(CH2)3 radical is attached to the nitrogen atom of the betaine), oleyl
betaine (available as amphoteric Velvetex OLB-50 from Henkel), and
3o cocamidopropyl betaine (available as Velvetex BK-35 and BA-35 from Henkel).
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
19
Examples of sultaines and hydroxysultaines include materials such as
cocamidopropyl hydroxysultaine (available as Mirataine CBS from
Rhone-Poulenc).
Preferred for use herein are ampf~oteric surfactants having the following
structure:
O R2
R'~-(~-NH-(CH~rr~n +N-R4--X
~3
wherein R1 is unsubstituted, saturated or unsaturated, straight or branched
chain
alkyl having from about 9 to about 22 carbon atoms. Preferred R1 has from
about
11 to about 18 carbon atoms; more preferably from about 12 to about 18 carbon
1 o atoms; mare preferably still from about 14 to about 18 carbon atoms; m is
an integer
from 1 to about 3, more preferably from about 2 to about 3, and more
preferably
about 3; n is either 0 or 1, preferably 1; R2 and R3 are independently
selected from
the group consisting of alkyl having from 1 to about 3 carbon atoms,
unsubstituted
or mono-substituted with hydroxy, preferred R2 and R3 are CH3; X is selected
from
the group consisting of C02, S03 and 504; R4 is selected from the group
consisting of saturated or unsaturated, straight or branched chain alkyl,
unsubstituted or monosubstituted with hydroxy, having from 1 to about 5 carbon
atoms. When X is C02, R4 preferably has 1 or 3 carbon atoms, more preferably 1
carbon atom. When X is S03 or S04, R4 preferably has from about 2 to about 4
carbon atoms, more preferably 3 carbon atoms.
Examples of amphoteric surfactants of the present invention include the
following compounds:
Cetyl dimethyl betaine (this material also has the CTFA designation cetyl
betaine)
C1~"C~~2
Cocamidopropylbetaine
R-C N+-(CH~g ~ N-CHz-COi
wherein R has from about 9 to about 13 carbon atoms
Cocamidopropyl hydroxy sultaine
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
F~-~ NH-(CI-hy3 ~N--CH2--~ CI-i~-S03
wherein R has from about 9 to about 13 carbon atoms,
Examples of other useful amphoteric surfactants are alkyliminoacetates, and
iminodialkanoates and aminoalkanoates of the formulas RN[CH2)mC02M]2 and
5 RNH(CH2)mC02M wherein m is from 1 to 4, R is a Cg-C22 alkyl or alkenyl, and
M is H, alkali metal, alkaline earth metal ammonium, or alkanolammonium. Also
included are imidazolinium and ammonium derivatives. Specific examples of
suitable amphoteric surfactants include sodium 3-dodecyl-aminopropionate,
sodium
3-dodecylaminopropane sulfonate, N-higher alkyl aspartic acids such as those
1o produced according to the teaching of U.S. Patent 2,438,091 which is
incorporated
herein by reference in its entirety; and the products sold under the trade
name
"Miranol" and described in U.S. Patent 2,528,378, which is incorporated herein
by
reference in its entirety. Other examples of useful amphoterics include
amphoteric
phosphates, such as coamidopropyl PG-dimonium chloride phosphate
15 (commercially available as Monaquat PTC, from Mona Corp.). Also useful are
amphoacetates such as disodium lauroamphodiacetate, sodium lauroamphoacetate,
and mixtures thereof.
Preferred lathering surfactants for use herein are the following, wherein the
anionic lathering surfactant is selected from the group consisting of ammonium
20 lauroyl sarcosinate, sodium trideceth sulfate, sodium lauroyl sarcosinate,
ammonium
laureth sulfate, sodium laureth sulfate, ammonium lauryl sulfate, sodium
lauryl
sulfate, ammonium cocoyl isethionate, sodium cocoyl isethionate, sodium
lauroyl
isethionate, sodium cetyl sulfate, sodium lauroyl lactylate, triethanolamine
lauroyl
lactylate, and mixtures thereof; wherein the nonionic lathering surfactant is
selected
from the group consisting of lauramine oxide, cocoamine oxide, decyl
polyglucose,
lauryl polyglucose, sucrose cocoate, C12-14 glucosamides, sucrose laurate, and
mixtures thereof; and wherein the amphoteric lathering surfactant is selected
from
the group consisting of disodium lauroamphodiacetate, sodium
lauroamphoacetate,
cetyl dimethyl betaine, cocoamidopropyl betaine, cocoamidopropyl hydroxy
3o sultaine, and mixtures thereof.
Lather Volume Test
The articles of the present invention comprise enough of the lathering
surfactant to generate greater than about 30 ml, preferably greater than about
50 ml,
more preferably greater than about 75 ml, and most preferably greater than
about
150 ml of Average Lather Volume. The Average Lather Volume is a measurement
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
21
determined by the Lather Volume Test. This test provides a consistent volume
measurement of the lather/foam generated by the articles described herein. The
Lather Volume Test protocol is described as follows:
( 1 ) Hands are washed with Ivory bar before conducting the test. This step
removes any soils which may affect the accuracy of the measurement.
(2) The test article is held open in the non-dominant hand with the edges
turned up.
(3) 10 m. of water (medium hardness of about 8-10 grains per gallon) at 95
°C
is added onto the test article via a l Occ syringe or a Brinkmann repipetter.
(4) The lather is then generated by rubbing the test article with the dominant
hand in a circular motion between the palms for 6 seconds (~2 rotations
per second), using moderate pressure (e.g., 4 oz.), and allowing the article
to ball-up between the palms of the hand.
(5) The test article is then held open in the non-dominant hand and an
additional 10 ml of water (medium hardness of about 8-10 grains per
gallon) at 95 °C is added onto the test article via a lOcc syringe or a
Brinkmann repipetter. The wetted article is again rubbed with the
dominant had (3 rotations) using moderate force {e.g, 4 oz.) so that the test
article becomes balled-up between the palms.
(6) The test article is then opened and rubbed 5 times by holding one edge of
the article in one hand and rotating the hand holding the other side to
further activate lather.
f7) The test article is then flipped over and Step #6 is repeated using the
other
hand.
(s) The lather is gathered by holding the test article in a cupped hand and
scraping the lather off the test article with the other hand, being careful to
only scrape lather form the test article. The lather from the test article is
placed into a graduated cylinder or beaker big enough to hold the
generated lather. This procedure is repeated S times on the same test
3o article, and the lather from each iteration is accumulated in the same
graduated cylinder or beaker. The total accumulated lather from these
iterations is designated as the Lather Volume.
(9) To achieve consistent results, the Average Lather Volume is reported as
the average of three test sample replications of Steps 1-8.
SKIN CARE ACTIVE COMPONENT
The personal cleansing articles of the present invention essentially comprise
a safe and effective amount of a skin care active component which comprises at
least
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
22
one skin care active selected from the group consisting of water soluble skin
care
actives, oil soluble skin care actives, pharmaceutically-acceptable salts and
mixtures
thereof. The term "skin care active," as used herein, means personal care
actives
which can be used to deliver a benefit to the skin and/or hair and which
generally are
not used to confer a conditioning benefit, as hereinafter defined. The term
"safe and
effective amount" as used herein, means an amount of a skin care active
ingredient
high enough to modify the condition to be treated or to deliver the desired
skin care
benefit, but low enough to avoid serious side effects, at a reasonable benefit
to risk
ratio within the scope of sound medical judgment. The term "skin care
benefit," as
to used herein, means the therapeutic, prophylactic, and/or chronic benefits
associated
with treating a particular condition with one or more of the skin care actives
described herein. What is a safe and effective amount of the skin care active
ingredient will vary with the specific skin care active, the ability of the
active to
penetrate through the skin, the age, health condition, and skin condition of
the user,
I5 and other like factors. Preferably the articles of the present invention
comprise from
about 0.001 % to about 50%, more preferably from about 0.01 % to about 25%,
even
more preferably 0.05% to about 10%, and most preferably 0.1 % to about S%, by
weight of the water insoluble substrate, of the skin care active component.
The skin care active component of the present invention can comprise: a
2o water soluble skin care active, an oil soluble skin care active, a skin
care emulsion,
or any combination or permutation of the three. The oil soluble skin care
active is
selected from one or more oil soluble skin care actives such that the weighted
arithmetic mean solubility parameter of the oil soluble skin care active is
less than or
equal to 10.5. The water soluble skin care active is selected from one or more
water
25 soluble skin care active such that the weighted arithmetic mean solubility
parameter
of the water soluble conditioning agent is greater than 10.5. It is
recognized, based
on this mathematical definition of solubility parameters, that it is possible,
for
example, to achieve the required weighted arithmetic mean solubility
parameter, i.e.
less than or equal to 10.5, for an oil soluble skin care active comprising two
or more
30 compounds if one of the compounds has an individual solubility parameter
greater
than 10.5. Conversely, it is possible to achieve the appropriate weighted
arithmetic
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
23
mean solubility parameter, i.e. greater than 10.5, for a water soluble skin
care active
comprising two or more compounds if one of the compounds has an individual
solubility parameter less than or equal to 10.5.
Solubility parameters are well known to the formulation chemist of ordinary
skill in the art and are routinely used as a guide for determining
compatibilities and
solubilities of materials in the formulation process. The solubility parameter
of a
chemical compound, b, is defined as the square root of the cohesive energy
density
for that compound. Typically, a solubility parameter for a compound is
calculated
from tabulated values of the additive group contributions for the heat of
vaporization
and molar volume of the components of that compound, using the following
equation:
~Ej
i
Emj
i
1/2
wherein Ei Ei = the sum of the heat of vaporization additive group
contributions, and
~, m, = the sum of the molar volume additive group contributions
i i
Standard tabulations of heat of vaporization and molar volume additive group
contributions for a wide variety of atoms and groups of atoms are collected in
Barton, A.F.M. Handbook of Solubility Parameters, CRC Press, Chapter 6, Table
3,
2o pp. 64-66 (1985), which is incorporated by reference herein in its
entirety. The
above solubility parameter equation is described in Fedors, R.F., "A Method
for
Estimating Both the Solubility Parameters and Molar Volumes of Liquids",
Polymer
En ineeringr and Science, vol. 14, no. 2, pp. 147-154 (February 1974), which
is
incorporated by reference herein in its entirety.
Solubility parameters obey the law of mixtures such that the solubility
parameter for a mixture of materials is given by the weighted arithmetic mean
(i.e.
the weighted average) of the solubility parameters for each component of that
mixture. See, Handbook of Chemistry and Physics, 57th edition, CRC Press, p. C-
726 (1976-1977), which is incorporated by reference herein in its entirety.
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
24
Formulation chemists typically report and use solubility parameters in units
of
(cal/cm3 ) 1 /2. The tabulated values of additive group contributions for heat
of
vaporization in the Handbook of Solubility Parameters are reported in units of
kJ/mol. However, these tabulated heat of vaporization values are readily
converted
to cal/mol using the following well-known relationships:
1 J/mol = 0.239006 cal/mol and 1000 J = 1 kJ.
See Gordon, A.J. et al., The Chemist's Companion, John Wiley & Sons, pp. 456-
463, (1972), which is incorporated by reference herein in its entirety.
Solubility
parameters have also been tabulated for a wide variety of chemical materials.
I o Tabulations of solubility parameters are found in the above-cited Handbook
of
Solubilitv Parameters. Also, see "Solubility Effects In Product, Package,
Penetration, And Preservation", C.D. Vaughan, Cosmetics and Toiletries, vol.
103,
October 1988, pp. 47-69, which is incorporated by reference herein in its
entirety.
Using the information hereinbefore described, the formulation chemist of
ordinary skill in the art can determine the solubility parameters of the skin
care
active ingredients hereinafter described.
The skin care active ingredients useful herein can be categorized by their
therapeutic benefit or their postulated mode of action. However, it is to be
understood that the active ingredients useful herein can in some instances
provide
2o more than one therapeutic 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 ingredient to that particular application or
applications
listed. Furthermore, pharmaceutically-acceptable salts of these active
ingredients are
also useful herein. The following active ingredients are useful in the
compositions
of the present invention.
A wide variety of skin care active ingredients are useful herein and include
those selected from the group consisting of anti-acne actives, anti-wrinkle
and anti-
skin atrophy actives, skin barrier repair aids, cosmetic soothing aids,
topical
anesthetics, artificial tanning agents and accelerators, skin lightening
actives,
antimicrobial and antifungal actives, sunscreen actives, sebum stimulators,
sebum
inhibitors, and mixtures thereof.
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
Anti-Acne Actives:
Anti-acne actives can be effective in treating acne vulgaris, a chronic
disorder of the pilosebaceous follicles. The condition involves inflammation
of the
pilosebaceous apparatus thereby resulting in lesions, which may include
papules,
5 pustules, cysts, comedomes, and severe scarnng. The bacteria
~Corynebacterium
acnes and Staphylococcus epidermidis are usually present in the pustular
contents.
Nonlimiting examples of useful anti-acne actives include the keratolytics
such as salicylic acid (o-hydroxybenzoic acid), derivatives of salicylic acid
such as
5-octanoyl salicylic acid and 4 methoxysalicylic acid, and resorcinal;
retinoids such
l0 as retinoic acid and its derivatives (e.g., cis and trans); sulfur-
containing D and L
amino acids and their derivatives and salts, particularly their N-acetyl
derivatives, a
preferred example of which is N-acetyl-L-cysteine; lipoic acid; antibiotics
and
antimicrobials such as benzoyl peroxide, octopirox, tetracycline, 2,4,4'-
trichloro-2'-
hydroxy diphenyl ether, 3,4,4'-trichlorobanilide, azelaic acid and its
derivatives,
15 phenoxyethanol, phenoxypropanol, phenoxyisopropanol, ethyl acetate,
clindamycin
and meclocycline; sebostats such as flavonoids and bioflavonoids; bile salts
such as
scymnol sulfate and its derivatives, deoxycholate, and cholate; abietic acid;
adapalene; allantoin; aloe extracts; arbietic acid and its salts; ASEBIOL
(available
from Laboratories Serobiologiques, located in Somervilie, N.J); azaleic acid;
20 barbeny extracts; bearberry extracts; belamcanda chinensis;
benzoquinolinones;
berberine; BIODERMINE (available from Sederma, located in Brooklyn, NY);
bisabolol; S-carboxymethyl cysteine; carrot extracts; cassin oil; clove
extracts; citral;
citronellal; CREMOGEN M82 (available from Dragoco, located in Totowa, NJ);
cucumber extracts; dehydroacetic acid and its salts; dehydroeplandersterone
25 salicylate; dichlorophenyl imidazoldioxolan which is commercially available
as
COMPLETECH MBAC-OS ( from Lipo, located in Paterson, NJ); DL valine and its
esters; DMDM hydantoin; erythromycin; escinol; ethyl hexyl monoglyceryl ether;
ethyl 2-hydroxy undecanoate; farnesol; farnesol acetate; geranoil; glabridin;
gluconic acid; gluconolactone; glyceryl monocaprate; glycolic acid; grapefruit
seed
extract; gugu lipid; hesperitin; hinokitol; hops extract; hydrogenated rosin;
10
hydroxy decanoic acid; ichtyhol; interleukin 1 alpha antagonists;
ketoconazole;
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
26
lactic acid; lemon grass oil; linoleic acid; LIPACIDE C8C0 (available from
Seppic,
located in Paris, France); lovastatin; metronidazole; minocycline; mukurossi;
neem
seed oil; vitamin B3 compounds (such as niaincamide and nicotinic acid);
nisin;
octopirox; panthenol; 1-pentadecanol; peonia extract; peppermint extract;
phelladendron extract; 2-phenyl-benzothiophene derivatives; phloretin;
PHLOROGINE (available from Secma); phosphatidyl choline; proteolytic enzymes;
quercetin; red sandalwood extract; rosemary extract; rutin; sage extract;
skull cap
extract; siber hegner extract; Siberian saxifrage extract; silicol; sodium
lauryl sulfate;
sodium sulfoacetamide; sorbic acid; sulfur; sunder vati extract; tea tree oil;
to tetracyline; tetra hydroabietic acid; thyme extract; tioxolone; tocopherol;
trehalose 6-
undecylenoate; 3 tridecene-2-ol; tropolone; UNITRIENOL T27 (available from
Unichem, located in Gouda, Netherlands); vitamin D3 and its analogs; white
thyme
oil; wogonin; Ylang Ylang; zinc glycerolate; zinc linoleate; zinc oxide; zinc
pyrithione; zinc sulfate and mixtures thereof.
Antimicrobial and Antifung_al Actives:
Antimicrobial and antifungal actives can be effective to prevent the
proliferation and growth of bacteria and fungi. Nonlimiting examples of
antimicrobial and antifungal actives include !3-lactam drugs, quinolone drugs,
ciprofloxacin, norfloxacin, tetracycline, erythromycin, amikacin, 2,4,4'-
trichloro-2'-
2o hydroxy diphenyl ether, 3,4,4'-trichlorobanilide, phenoxyethanol, phenoxy
propanol,
phenoxyisopropanol, doxycycline, capreomycin, chlorhexidine,
chlortetracycline,
oxytetracycline, clindamycin, ethambutol, hexamidine isethionate,
metronidazole,
pentamidine, gentamicin, kanamycin, lineomycin, methacycline, methenamine,
minocycline, neomycin, netilmicin, paromomycin, streptomycin, tobramycin,
miconazole, tetracycline hydrochloride, erythromycin, zinc erythromycin,
erythromycin estolate, erythromycin stearate, amikacin sulfate, doxycycline
hydrochloride, capreomycin sulfate, chlorhexidine gluconate, chlorhexidine
hydrochloride, chlortetracycline hydrochloride, oxytetracycline hydrochloride,
clindamycin hydrochloride, ethambutol hydrochloride, metronidazole
hydrochloride,
3o pentamidine hydrochloride, gentamicin sulfate, kanamycin sulfate,
lineomycin
hydrochloride, methacycline hydrochloride, methenamine hippurate, methenamine
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
27
mandelate, minocycline hydrochloride, neomycin sulfate, netilmicin sulfate,
paromomycin sulfate, streptomycin sulfate, tobramycin sulfate, miconazole
hydrochloride, amanfadine hydrochloride, amanfadine sulfate, octopirox,
parachlorometa xylenol, nystatin, tolnaftate, zinc pyrithione; clotrimazole;
alantolactone; isoalantolactone; alkanet extract (alaninin); anise; arnica
extract
(helenalin acetate and 11, 13 dihydrohelenalin); Aspidium extract (phloro,
lucinol
containing extract); barberry extract (berberine chloride); bay sweet extract;
bayberry bark extract (myricitrin); benzalkonium chloride; benzethonium
chloride;
benzoic acid and its salts; benzoin; benzyl alcohol; blessed thistle; bletilla
tuber;
1 o bloodroot; boas de rose oil; burdock; butyl paraben; cade oil; CAE
(available from
Ajinomoto, located in Teaneck, NJ); cajeput oil; Cangzhu; caraway oil;
cascarilla
bark (sold under the tradename ESSENTIAL OIL); cedarleaf oil; chamomille;
chaparral; chlorhexidine gluconate; chlorophenesin; chlorxylenol; cinnamon
oil;
citronella oil; clove oil; dehydroacetic acid and its salts; dill seed oil;
DOWICIL 200
~ 5 (available from Dow Chemical, located in Midland, MI); echinacea; elenolic
acid;
epimedium; ethyl paraben; Fo-Ti; galbanum; garden burnet; GERMALL 115 and
GERMALL II (available from ISP-Sutton Labs, located in Wayne, NJ); German
chamomile oil; giant knotweed; GLYDANT (available from Lonza, located in
Fairlawn, NJ); GLYDANT PLUS (available from Lonza); grapefruit seed oil;
2o hexamidine diisethionate; hinokitiol; honey; honeysuckle flower; hops;
immortelle;
iodopropynl butyl carbamide (available from Lonza); isobutyl paraben;
isopropyl
paraben; JM ACTICARE (available from Microbial Systems International, located
in Nottingham, NG); juniper berries; KATHON CG (available from Rohm and
Haas, located in Philadelphia, PA); labdanum; lavender; lemon balm oil; lemon
25 grass; methyl paraben; mint; mume; mustard; myrrh; neem seed oil; ortho
phenyl
phenol; olive leaf; parsley; patchouly oil; peony root; PHENONIP (available
from
Napa Labs, located in Wilmington, DE); phenoxyethanol; pine needle oil;
PLANSERVATIVE (available from Campo Research); propyl paraben; purslane;
quillaira; rhubarb; rose geranium oil; rosemary; sage; salicylic acid;
sassafras;
3o savory; Sichuan lovage; sodium meta bisulfate; sodium sulfite; SOPHOLIANCE
(available from Soliance, located in Compiegne, France); sorbic acid and its
salts;
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99100635
28
stevia; storax; tannic acid; tea; tea tree oil (cajeput oil); thyme;
triclosan;
triclocarban; tropolone; turpentine; umbelliferone (antifungal); yucca; zinc
pyrithione; and mixtures thereof.
Anti-Wrinkle and Anti-Skin Atrophy Actives'
Anti-wrinkle and anti-skin atrophy actives can be effective in replenishing or
rejuvenating the epidermal layer. These actives generally provide these
desirable
skin care benefits by promoting or maintaining the natural process of
desquamation.
Nonlimiting examples of antiwrinkle and anti-skin atrophy actives include
retinoic
acid and its derivatives (e.g., cis and trans); retinal; retinol; retinyl
esters such as
to retinyl acetate, retinyl palmitate, and retinyl propionate; vitamin B3
compounds
(such as niacinamide and nicotinic acid), salicylic acid and derivatives
thereof (such
as 5-octanoyl salicylic acid, heptyloxy 4 salicylic acid, 4-methoxy salicylic
acid, and
5 - octanoyl salicylic acid); sulfur-containing D and L amino acids and their
derivatives and salts, particularly the N-acetyl derivatives, a preferred
example of
1 s which is N-acetyl-L-cysteine; thiols, e.g. ethane thiol; hydroxy acids,
phytic acid,
lipoic acid; lysophosphatidic acid; skin peel agents (e.g., phenol and the
like);
adapalene; ademethionine; adenosine; aletris extract; aloe derived lectins; 3-
aminopropyl dihydrogen phosphate; anise extracts; AOSINE (available from
Secma); ASC III (available from E. Merck, located in Darmstadt, Germany);
2o ascorbic acid; ascorbyl palmitate; asiatic acid; asiaticosides; ARLAMOL
GEOT""
(available from ICI, located in Wilmington, DE); azaleic acid; benzoic acid
derivatives; bertholletia extracts; betulinic acid; BIOCHANIN A AND
BIOPEPTIDE CL (available from Sederma, located in Brooklyn, NY);
BIOPEPTIDE EL (available from Sederma); blackberry bark extract; blackberry
lily
2s extracts; black cohosh extract; butanoyl betulinic acid; citric acid
esters; chaste tree
extract; clover extracts; daidzein; debromo laurinterol; 1-decanoyl-glycero-
phosphonic acid; dehydrocholesterol; dehydrodicreosol; dehydrodieugenol;
dehydroepiandersterone; DERMOLECTINE (available from Sederma);
dehydroascorbic acid; dehydroepiandersterone sulfate; dianethole; 2, 4
3o dihydroxybenzoic acid; diosgenin; disodium ascorbyl phosphate;
dodecanedioic
acid; estrogen and its derivatives; ethocyn; ELESERYL SH (available from
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
29
Laboratories Serobiologiques, located in Somerviile, N.J); ENDONUCLEINE
(available from Laboratories SerobioIogiques); ergosterol; eythrobic acid;
fennel
extract; fenugreek seed extract; FIBRASTII. (available from Sederma);
FIBROSTIMULINES S and P (available from Sederma); FIRMOGEN LS 8445
s (available from Laboratories Serobiologiques); formononetin; forsythia fruit
extract;
gallic acid esters; gamma butyric acid; GATULINE RC (available from
Gattlefosse,
located in Priest, France); genistein; genisteine; genistic acid; gingko
bilboa extracts;
ginseng extracts; ginsenoside (RO, R~_,, Rb_z,Rb_3, Rc, RD, RE, RF, RF_z,
R~_,, Re_2);
gluco pyranosyl-1-ascorbate; glutathione and its esters; hexahydro curcumin;
HMG-
1 o coenzyme A reductase inhibitors; hops extracts; I 1 hydroxy undecanoic
acid; 10
hydroxy decanoic acid; 25-hydroxycholesterol; kinetin; L-2-OXO-thiazolidine-4-
carboxylic acid esters; lactate dehydrogenase inhibitors; 1-lauryl; -Iyso-
phosphatidyl
choline; licorice extracts; lumisterol; luteolin; magnesium ascorbyl
phosphate;
melatonin; metalloproteinase inhibitors; methoprene; methoprenic acid; MPC
15 COMPLEX (available from CLR); N methyl serine; N methyl taurine; N, N'-bis
(lactyl) cysteamine; naringenin; neotigogenin; oleanolic acid; photoanethone;
placental extracts; pratensein; pregnenolone; pregnenolone acetate;
pregnenolone
succinate; premarin; raloxifene; REPAIR FACTOR 1 and REPAIR FACTOR FCP
both available from Sederma); retinoates (esters of Cz-Czo alcohols); retinyl
2o glucuronate; retinyl linoleate; S-carboxymethyl cysteine; SEANAMINE FP
(available from Laboratories Serobiologiques); soya extracts; spleen extracts;
tachysterol; tazarotene; thymulen; thymus extracts; tigogenin; tocopheryl
retinoate;
traumatic acid; tricholine citrate; trifoside; ursolic acid; vitamin D3 and
its analogs;
yam extract; yamogenin; zeatin; and mixtures thereof.
25 Skin Barrier Repair Actives:
Skin barrier repair actives are those skin care actives which can help repair
and replenish the natural moisture barrier function of the epidermis.
Nonlimiting
examples of skin barner repair actives include brassicasterol; caffeine;
campesterol;
canola derived sterols; CERAMAX (available from Quest, located in Ashford,
3o England); CERAMIDE 2 and CERAMIDE H03T"" (both available from Sederma);
CERAMIDE II and CERAMIDE III (both available from Quest); IIIB (available
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
from Cosmoferm, located in Deft, Netherlands); CERAMIDE LS 3773 (available
from Laboratories Serobiologiques); CERAMINOL (available from Inocosm);
cholesterol; cholesterol hydroxystearate; cholesterol isostearate; 7
dehydrocholesterol; DERMATEIN BRC and DERMATEIN GSL (both available
5 from Hormel); ELDEW CL 301 AND ELDEW PS 203 (both available from
Ajinomoto); glyceryl serine amide; lactic acid; lanolin alcohols; lanosterol;
lauric
acid N laurylglucamide; lipoic acid; N-acetyl cysteine; N-acetyl-L-serine; N
methyl-
L-Serine; vitamin B3 compounds (such as niacinamide and nicotinic acid);
palmitic
acid; panthenol; panthetine; phosphodiesterase inhibitors; PHYTO/CER
(available
l0 from Intergen); phytoglycolipid millet extract (available from Barnet
Products
Distributer, located in Englewood, NJ); PHYTOSPHINGOSINE (available from
Gist Brocades, located in King of Prussia, PA); PSENDOFILAGGRIN (available
from Brooks Industries, located in South Plainfield, NJ); QUESTAMIDE H
(available from Quest); serine; sigmasterol; sitosterol; soybean derived
sterols;
15 sphingosine; S-lactoyl glutathione; stearic acid; SUPER STEROL ESTERS
(available from Croda); thioctic acid; THSC CERAMIDE OIL (available from
Campo Research); trimethyl glycine; tocopheryl nicotinate; vitamin D3; Y2
(available from Ocean Pharmaceutical); and mixtures thereof.
Non-steroidal Cosmetic Soothing Actives:
20 Cosmetic soothing actives can be effective in preventing or treating
inflammation of the skin. The soothing active enhances the skin appearance
benefits
of the present invention, e.g., such agents contribute to a more uniform and
acceptable skin tone or color. The exact amount of anti-inflammatory agent to
be
used in the compositions will depend on the particular anti-inflammatory agent
25 utilized since such agents vary widely in potency. Nonlimiting examples of
cosmetic soothing agents include the following categories: propionic acid
derivatives; acetic acid derivatives; fenamic acid derivatives;
biphenylcarboxylic
acid derivatives; and oxicams. All of these cosmetic soothing actives are
fully
described in U.S. Patent 4,985,459 to Sunshine et al., issued January 15,
1991,
3o incorporated by reference herein in its entirety. Nonlimiting examples of
useful
cosmetic soothing actives include acetyl salicylic acid, ibuprofen, naproxen,
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
31
benoxaprofen, flurbiprofen, fenoprofen, fenbufen, ketoprofen, indoprofen,
pirprofen,
carprofen, oxaprozin, pranoprofen, miroprofen, tioxaprofen, suprofen,
alminoprofen,
tiaprofenic acid, fluprofen, bucloxic acid, absinthium, acacia, aescin, alder
buckthorn
extract, allantoin, aloe, aloe, APT (avaiable from Centerchem), arnica,
astragalus,
astragalus root extract, azulene, baikal skullcap, baizhu, balsam Canada, bee
pollen,
BIOPHYTEX (avaiable from Laboratories Serobiologiques), bisabolol, black
cohosh, black cohosh extract, blue cohosh, blue cohosh extract, boneset,
borage,
borage oil, bromelain, calendula, calendula extract, candelilla wax, Cangzhu,
canola
phytosterols, capsicum, carboxypeptidase, celery seed, celery stem extract,
1 o CENTAURIUM (avaiable from Sederma), centaury extract, chamazulene,
chamomile, chamomile extract, chaparral, chaste tree, chaste tree extract,
chickweed,
chicory root, chicory root extract, chirata, chishao, collodial oatmeal,
comfrey,
comfrey extract, CROMOIST CM GLUCAN (avaiable from Croda), dehurian
angelica, devil's claw, divalent metals (such as, magnesium, strontium, and
manganese), doggrass, dogwood, eleuthero, ELHIBIN (avaiable from Pentapharm),
ENTELINE 2 (avaiable from Secma), ephedra, epimedium, evening primrose,
eyebright, Fangfeng, feverfew, ficin, forsythia fruit, ganoderma, gaoben,
gentian,
germanium extract, gingko bilboa, ginkgo, ginseng extract, goldenseal,
gorgonian
extract, gotu kola, grape fruit extract, guaiac wood oil, guggal extract,
helenalin
2o esters, henna, honeysuckle flower, horehound extract, horsechestnut,
horsetail,
huzhang, hypericum, ichthyol, immortelle, ipecac, job's tears, jujube, kola
extract,
LANACHRYS 28 (avaiable from Lana Tech), lemon oil, lianqiao, licorice root,
ligusticum, ligustrum, lovage root, luffa, mace, magnolia flower, manjistha
extract,
margaspidin, margaspidin, matricin, MICROAT IRC (avaiable from Nurture),
mints,
mistletoe, musk, oat extract, orange, panthenol, papain, peony bark, peony
root,
purslane, QUENCH T (avaiable from Centerchem), quillaia, red sage, rehmaniiia,
rhubarb, rosemary, rosmarinic acid, royal jelly, rue, rutin, sandlewood,
sanqi,
sarsaparilla, saw palmetto, SENSILINE (avaiable from Silab), SIEGESBECKIA
(avaiable from Sederma), stearyl glycyrrhetinate, storax, sweet birch oil,
sweet
3o woodruff, tagetes, tea extract, thyme extract, tienchi ginseng, tocopherol,
tocopheryl
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
32
acetate, turmeric, urimei, ursolic acid, white pine bark, witch hazel, xinyi,
yarrow,
yeast extract, yucca, and mixtures thereof.
Artificial Tanning Actives and Accelerators
Artif cial tanning actives can help in simulating a natural suntan by
increasing melanin in the skin or by producing the appearance of increased
melanin
in the skin. Nonlimiting examples of artificial tanning agents and
accelerators
include dihydroxyacetaone; tyrosine; tyrosine esters such as ethyl tyrosinate
and
glucose tyrosinate; acetyl tyrosine; phospho-DOPA; brazilin; caffeine; coffee
extracts; dihydroxyacetone; DNA fragments; isobutyl methyl xanthine; methyl
xanthine; prostaglandins; tea extracts; theophylline; UNIPERTAN P2002 and
UNIPERTAN P27 (both avaiable from Unichem); and mixtures thereof.
Skin Li htening Actives:
Skin lightening actives can actual decrease in the amount of melanin in the
skin or provide an such an effect by other mechanisms. Skin li~htenin~ actives
suitable for use herein are described in copending patent application Serial
No.
08/479,935, filed on June 7, 1995 in the name of Hillebrand, corresponding to
PCT
Application No. U.S. 95/07432, filed 6/12/95; and copending patent application
Serial No.08/390,152, filed on February 24, 1995 in the names of Kalla L.
Kvalnes,
Mitchell A. DeLong, Barton J. Bradbury, Curtis B. Motley, and John D. Carter,
2o corresponding to PCT Application No. U.S. 95/02809, filed 3/1/95, published
9/8/95; all incorporated herein by reference. Nonlimiting examples of skin
lightening actives useful herein include adapalene, aloe extract, ammonium
lactate,
anethole derivatives, apple extract, arbutin, ascorbic acid, ascorbyl
palmitate, azelaic
acid, bamboo extract, bearberry extract, bletilla tuber, bupleurum falcatum
extract,
burnet extract, butyl hydroxy anisole, butyl hydroxy toluene, Chuanxiong, Dang-
Gui, deoxyarbutin, I, 3 diphenyl propane derivatives, 2, 5 dihydroxybenzoic
acid
and its derivatives, 2-(4-acetoxyphenyl)-1,3 dithane, 2-(4-hydroxyphenyl)-1,3
dithane, ellagic acid, escinol, estragole derivatives, FADEOUT (available from
Pentapharm), Fangfeng, fennel extract, ganodenma extract, gaoben, GATULINE
3o WHITENING (available from Gattlefosse), genistic acid and its derivatives,
glabridin and its derivatives, gluco pyranosyl-I-ascorbate, gluconic acid,
glycolic
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
33
acid, green tea extract, 4-Hydroxy-5-methyl-3 [2H]-furanone, hydroquinone, 4
hydroxyanisole and its derivatives, 4-hydroxy benzoic acid derivatives,
hydroxycaprylic acid, inositol ascorbate, kojic acid, lactic acid, lemon
extract,
linoleic acid, magnesium ascorbyl phosphate, MELAWHITE (available from
Pentapharm), morus alba extract, mulberry root extract, niacinamide, 5-
octanoyl
salicylic acid, parsley extract, phellinus linteus extract, pyrogallol
derivatives,
retinoic acid, retinol, retinyl esters (acetate, propionate, palmitate,
linoleate), 2, 4
resorcinol derivatives, 3, 5 resorcinol derivatives, rose fruit extract,
salicylic acid,
Song-Yi extract, 3, 4, 5 trihydroxybenzyl derivatives, tranexamic acid,
vitamin D3
1 o and its anaologs, and mixtures thereof.
Sunscreen Actives:
Also useful herein are sunscreening actives. A wide variety of sunscreening
agents are described in U.S. Patent No. 5,087,445, to Haffey et al., issued
February
11, 1992; U.S. Patent No. 5,073,372, to Turner et al., issued December 17,
1991;
U.S. Patent No. 5,073,371, to Turner et al. issued December 17, 1991; and
Segarin,
et al., at Chapter VIII, pages 189 et seq., of Cosmetics Science and
Technolo~y, all
of which are incorporated herein by reference in their entirety. Nonlimiting
examples of sunscreens which are useful in the compositions of the present
invention are those selected from the group consisting of 2-ethylhexyl p-
2o methoxycinnamate, 2-ethylhexyl N,N-dimethyl p-aminobenzoate, p-aminobenzoic
acid, 2-phenylbenzimidazole-5-sulfonic acid, octocrylene, oxybenzone,
homomenthyl salicylate, octyl salicylate, 4,4'-methoxy-t-
butyldibenzoylmethane, 4-
isopropyl dibenzoylmethane, 3-benzylidene camphor, 3-(4-methylbenzylidene)
camphor, titanium dioxide, zinc oxide, silica, iron oxide, and mixtures
thereof. Still
other useful sunscreens are those disclosed in U.S. Patent No. 4,937,370, to
Sabatelli, issued June 26, 1990; and U.S. Patent No. 4,999,186, to Sabatelli
et al.,
issued March 12, 1991; these two references are incorporated by reference
herein in
their entirety. Still other useful sunscreens include aminobenzoic acid
(PABA),
butyl methoxy dibenzoyl methane, diethanolamine p-methoxycinnamate,
3o dioxybenzone, ethyl dihydroxypropyl (PABA), glyceryl aminobenzoate,
homomenthyl saiicylate, isopropyl dibenzoyl methane, lawsone and
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
34
dihydroxyacetone, menthyl anthranilate, methyl anthranilate, octocrylene,
octyl
dimethyl (PABA), octyl methoxycinnamate, 2-phenylbenzimidazole-5-sulfonic
acid,
red petrolatum, sulisobenzone, triethanolamine salicylate, and mixtures
thereof.
Especially preferred examples of these sunscreens include those selected from
the
group consisting of 4-N,N-(2-ethylhexyl)methylaminobenzoic acid ester of 2,4-
dihydroxybenzophenone, 4-N,N-(2-ethylhexyl)methylaminobenzoic acid ester with
4-hydroxydibenzoylmethane, 4-N,N- (2-ethylhexyl)-methylaminobenzoic acid ester
of 2-hydroxy-4-(2-hydroxyethoxy)benzophenone, 4-N,N-(2-ethylhexyl)-
methylaminobenzoic acid ester of 4-(2-hydroxyethoxy)dibenzoylmethane, and
1 o mixtures thereof.
Exact amounts of sunscreens which can be employed will vary depending
upon the sunscreen chosen and the desired Sun Protection Factor (SPF) to be
achieved. SPF is a commonly used measure of photoprotection of a sunscreen
against erythema. See Federal Register, Vol. 43, No. 166, pp. 38206-38269,
August
25, 1978, which is incorporated herein by reference in its entirety.
Sebum Stimulators
Sebum stimulators can increase the production of sebum by the sebaceous
glands. These skin care actives are especially useful for post menopausal
women
who are sebum deficient. Nonlimiting examples of sebum stimulating actives
2o include bryonolic acid, dehydroetiandrosterone (also known as DHEA),
orizanol and
mixtures thereof.
Sebum Inhibitors
Sebum inhibitors can decrease the production of sebum by the sebaceous
glands. Nonlimiting examples of sebum inhibiting actives include ASEBIOL
(available from Laboratories Serobiologiques), BIODERMINE (available from
Sederma), COMPLETECH MBAC-OS (available from Lipo), cucumber extracts,
dehydroacetic acid and its salts, dichlorophenyl imidazoldioxolan,
niacinamide,
phloretin, PHLOROGINE (available from Secma), S-carboxylmethyl cysteine,
tioxolone, tocopherol, UNITRIENOL T27 (available from Unichem), and mixtures
3o thereof.
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
Preferred examples of actives useful herein include those selected from the
group consisting of salicylic acid, benzoyl peroxide, 3-hydroxy benzoic acid,
glycolic acid, lactic acid, 4-hydroxy benzoic acid, acetyl salicylic acid,
niacinamide,
cis-retinoic acid, trans-retinoic acid, retinol, retinyl palmitate, 2-
hydroxybutanoic
5 acid, 2-hydroxypentanoic acid, 2-hydroxyhexanoic acid, cis-retinoic acid,
trans-
retinoic acid, retinol, phytic acid, N-acetyl-L-cysteine, lipoic acid, azelaic
acid,
arachidonic acid, benzoylperoxide, tetracycline, ibuprofen, naproxen,
hydrocortisone, acetominophen, resorcinol, phenoxyethanol, phenoxypropanol,
phenoxyisopropanol, 2,4,4'-trichloro-2'-hydroxy diphenyl ether, 3,4,4'-
10 trichlorocarbanilide, octopirox, lidocaine hydrochloride, clotrimazole,
miconazole,
neocycin sulfate, 2-ethylhexyl p-methoxycinnamic acid, oxybenzone, 2-
phenylbenzimidozole-5-sulfonic acid, dihydroxyacetone, panthenol, lactic acid,
arbutin, kojic acid, allantoin, cholesterol, C,o-C3o cholesterol/lanosterol
esters,
tocopherol, tocopheryl acetate, and mixtures thereof.
15 The skin care active component of the present invention can also comprise a
skin care emulsion which is useful for providing a skin care benefit to the
skin or
hair. The term "skin care emulsion" as used herein means the combination of a
discontinuous phase comprising an aqueous component that is enveloped by a
continuous phase comprising an oil soluble component. The water soluble
2o component comprises compounds selected from the group consisting of water,
water
soluble skin care actives, water soluble skin conditioning agents, as
hereinafter
described, and mixtures thereof. The oil soluble component comprises compounds
selected from the group consisting of oil soluble skin care actives, oil
soluble skin
conditioning agents, as hereinafter described, and mixtures thereof. In
preferred
25 embodiments, the skin care emulsion would further comprise an emulsifier.
The
skin care emulsion comprises from about 0.25% to about 150%, preferably from
about 0.5% to about 100%, and more preferably from about 1 % to about 50% by
weight of said water insoluble substrate.
Although an emulsifier capable of forming an emulsion of the discontinuous
3o and continuous phases is preferred in the present invention, it is
recognized in the art
of skin care formulations that a water soluble skin care active can be
enveloped by
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
36
an oil soluble skin care active without an emulsifier. As long as the water
soluble
skin care active is enveloped by the oil soluble agent, thereby protected from
being
rinsed away during the cleansing process, the composition would be within the
scope of the present invention.
The discontinuous phase can optionally comprise other water-soluble or
dispersible materials that do not adversely affect the stability of the skin
care
emulsion. One such material is a water-soluble electrolyte. The dissolved
electrolyte minimizes the tendency of materials present in the lipid phase to
also
dissolve in the water phase. Any electrolyte capable of imparting ionic
strength to
the internal phase can be used. Suitable electrolytes include the water
soluble mono-
di- or trivalent inorganic salts such as water-soluble halides, e.g.,
chlorides, nitrates
and sulfates of alkali metals and alkaline earth metals. Examples of such
electrolytes include sodium chloride, calcium chloride, sodium sulfate,
magnesium
sulfate, and sodium bicarbonate. The electrolyte will typically be included in
a
concentration in the range of from about 1 to about 20% of the discontinuous
phase.
Other water-soluble or dispersible materials that can be present in the
discontinuous phase include thickeners and viscosity modifiers. Suitable
thickeners
and viscosity modifiers include water-soluble polyacrylic and hydrophobically
modified polyacrylic resins such as Carbopol and Pemulen, starches such as
corn
2o starch, potato starch, tapioca, gums such as guar gum, gum arabic,
cellulose ethers
such as hydroxypropyl cellulose, hydroxyethyl cellulose, carboxymethyl
cellulose,
and the like. These thickeners and viscosity modifiers will typically be
included in a
concentration in the range of from about 0.05 to about 0.5% of the
discontinuous
phase.
Other water soluble or dispersible materials that can be present in the
discontinuous water phase include polycationic polymers to provide steric
stabilization at the water-lipid interface and nonionic polymers that also
stabilize the
water-in-lipid-emulsion. Suitable polycationic polymers include RETEN 201,
KYMENE 557H~ and ACCO 7112. Suitable nonionic polymers include
polyethylene glycols (PEG) such as CARBOWAX. These polycationic and
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
37
nonionic polymers will typically be included in a concentration in the range
of from
about 0.1 to about 1.0% of the discontinuous phase.
Preferred embodiments of the present invention which contain skin care
emulsions comprise an emulsifier capable of forming an emulsion of the
discontinuous and continuous phases. In the emulsions of the present
invention, the
emulsifier is included in an effective amount. What constitutes an "effective
amount" will depend on a number of factors including the respective amounts of
the
oil soluble agents, the type of emulsifier used, the level of impurities
present in the
emulsifier, and like factors. Typically, the emulsifier comprises from 0% to
about
1 o 20%, preferably from about 0.01 % to about 10%, and more preferably from
about
0.1 % to about 6% by weight of the skin care emulsion.
The emulsifiers useful in the present invention typically are oil soluble or
miscible with the continuous phase materials, especially at the temperature at
which
the oil soluble material melts. It also should have a relatively low HLB
value.
Emulsifiers suitable for use in the present invention have HLB values
typically in
the range of from about 1 to about 7 and can include mixtures of different
emulsifiers. Preferably, these emulsifiers will have HLB values from about 1.5
to
about 6, and more preferably from about 2 to about 5.
A wide variety of emulsifiers are useful herein and include, but not limited
to, those selected from the group consisting of sorbitan esters, glyceryl
esters,
polyglyceryl esters, methyl glucose esters, sucrose esters, ethoxylated fatty
alcohols,
hydrogenated castor oil ethoxylates, sorbitan ester ethoxylates, polymeric
emulsifiers, and silicone emulsifiers.
Sorbitan esters are useful in the present invention. Preferable are sorbitan
esters of C16-C22 saturated, unsaturated and branched chain fatty acids.
Because of
the manner in which they are typically manufactured, these sorbitan esters
usually
comprise mixtures of mono-, di-, tri-, etc. esters. Representative examples of
suitable sorbitan esters include sorbitan monooleate (e.g., SPANC~ 80),
sorbitan
sesquioleate (e.g., ARLACEL~ 83), sorbitan monoisostearate (e.g., CRILL~ 6
made by Croda), sorbitan stearates (e.g., SPANO 60), sorbitan triooleate
(e.g.,
SPAN~ 85), sorbitan tristearate (e.g., SPAN~ 65), sorbitan dipalmitates (e.g.,
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
38
SPAN~ 40), and sorbitan isostearate. Sorbitan monoisostearate and sorbitan
sesquioleate are particularly preferred emulsifiers for use in the present
invention.
Other suitable emulsifiers for use in the present invention include, but is
not
limited to, glyceryl monoesters, preferably glyceryl monoesters of C 16-C22
saturated, unsaturated and branched chain fatty acids such as glyceryl oleate,
glyceryl monostearate, glyceryl monopalmitate, glyceryl monobehenate, and
mixtures thereof; polyglyceryl esters of C 16-C:22 saturated, unsaturated and
branched chain fatty acids, such as polyglyceryl-4 isostearate, polyglyceryl-3
oleate,
diglycerol monooleate, tetraglycerol monooleate and mixtures thereof; methyl
1 o glucose esters, preferably methyl glucose esters of C 16-C22 saturated,
unsaturated
and branched chain fatty acids such as methyl glucose dioleate, methyl glucose
sesquiisostearate, and mixtures thereof; sucrose fatty acid esters, preferably
sucrose
esters of C 12-C22 saturated, unsaturated and branched chain fatty acids such
as
sucrose stearate, sucrose trilaurate, sucrose distearate (e.g., CRODESTA~
F10), and
mixtures thereof; C 12-C22 ethoxylated fatty alcohols such as oleth-2, oleth-
3,
steareth-2, and mixtures thereof; hydrogenated castor oil ethoxylates such as
PEG-7
hydrogenated castor oil; sorbitan ester ethoxylates such as PEG-40 sorbitan
peroleate, Polysorbate-80, and mixtures thereof; polymeric emulsifiers such as
ethoxylated dodecyl glycol copolymer; and silicone emulsifiers such as
Iaurylmethicone copolyol, cetyldimethicone, dimethicone copolyol, and mixtures
thereof.
In addition to these primary emulsifiers, the compositions of the present
invention can optionally contain a coemulsifier ,ta provide additional water-
lipid
emulsion stability. Suitable coemulsifiers include, but is not limited to,
phosphatidyl
cholines and phosphatidyl choline-containing compositions such as lecithins;
long
chain C 16-C22 fatty acid salts such as sodium stearate; long chain C 16-C22
dialiphatic, short chain C1-C4 dialiphatic quaternary ammonium salts such as
ditallow dimethyl ammonium chloride and ditallow dimethvl ammonium
methylsulfate; long chain C 16-C22 dialkoyl(alkenoyl)-2-hydroxyethyl, short
chain
3o C 1-C4 dialiphatic quaternary ammonium salts such as ditallowoyl-2-
hydroxyethyl
dimethyl ammonium chloride; the long chain C 16-C22 dialiphatic imidazolinium
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
39
quaternary ammonium salts such as methyl-1-tallow amido ethyl-2-tallow
imidazolinium methylsulfate and methyl-1-oleyl amido ethyl-2-oleyl
imidazolinium
methylsulfate; short chain C 1-C4 dialiphatic, long chain C 16-C22
monoaliphatic
benzyl quaternary ammonium salts such as dimethyl stearyl benzyl ammonium
chloride, and synthetic phospholipids such as stearamidopropyl PG-dimonium
chloride (PHOSPHOLIPID PTS from Mona Industries).
DEPOSITION AID
The articles of the present invention can further comprise from about 0.01
to about 10%, preferably from about 0.05% to about 7%, more preferably from
1 o about 0.10% to about 5%, and most preferably from about 0. I 5% to about
2%, based
on the weight of the water insoluble substrate, of a deposition aid.
Preferably, the
deposition aid is water dispersable. By "water dispersible" is meant that the
deposition aid is soluble in water at a concentration of 0.1% in water
(distilled or
equivalent) at 25 °C, preferably at 0.5% concentration, more preferably
at 1.0%
concentration. Although optional, preferred embodiments of the present
invention
contain a deposition aid, especially if a water soluble skin care active is
used.
Without being limited by theory, the deposition aid is believed to enhance
deposition of the water soluble conditioning agents onto the skin or hair
during the
cleansing process, and also help the water soluble conditioning agent to
adhere onto
the surface of the skin and hair during the rinsing process. Generally, it is
also
believed that these deposition aids function, in part or in whole, via the
following
mechanisms: electrostatic attraction (mammalian skin is negatively charged);
hydrophobic attraction because skin is more hydrophobic than water; and
materials
which are water dispersible in the presence of a surfactant but become water
insoluble during the rinse process. One or more of the deposition aids useful
herein
can be added onto or impregnated into the substrate separately, or in
combination
with either the surfactant or the water soluble conditioning agents. The
deposition
aid can be cationic, nonionic, anionic, or zwitterionic, preferably cationic
or
nonionic, and more preferably cationic. Suitable deposition aids for use
herein are
3o described in U.S. Pat. Nos. 5,588,752, issued Nov. 18, 1997 to Turner et
al., U.S.
Pat. No. 5,624,666, issued April 29, 1997 to Coffindaffer et al., U.S. Pat.
No.
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
5,635,469, issued June 3, 1997 to Fowler et al., U.S. Pat. No. 5,672,576,
issued Sept.
30, 1997 to Behrens et al., U.S. Pat. No. 5,716,920, issued Feb. 10, 1998 to
Glenn,
Jr. et al., U.S. Pat. No. 5,720,964, issued Feb. 24, 1998 to Murray, and U.S.
Pat. No.
5,714,446, issued Feb. 3, 1998 to Bartz et al., all of which references are
s incorporated herein in their entirety.
The CTFA Cosmetic Ingredient Handbook, Second Edition, 1992, which is
incorporated by reference herein in its entirety, describes a wide variety of
deposition aids which are suitable for use herein. Nonlimiting examples of
useful
deposition aids include cationic polymers, nonionic polymers, zeolites, clays
and
10 mixtures thereof. Cationic polymers are especially useful as deposition
aids in the
articles of the present invention, because they are believed to have the
ability to
associate with the negatively charged skin surface, thereby helping to keep
the
various components of the formulation upon the surface of the skin.
Furthermore,
cationic polymers are believed to form coascervates (e.g., water insoluble
1s complexes) with the anionic surfactant.
The cationic polymers hereof will generally have a weight average molecular
weight which is at least about 5,000, typically at least about 10,000, and is
less than
about 10 million. Preferably, the weight average molecular weight is from
about
100,000 to about S million, more preferably about 200,000 to about 2 million.
The
20 cationic polymers will have cationic nitrogen-containing moieties such as
quaternary
ammonium or cationic amino moieties, or a mixture thereof. Suitable cationic
polymers are described in U.S. Pat. Nos. 5,672,576, Behrens et al., issued
Sept. 30,
1997, and 5,720,964, Murray, issued Feb. 24, 1998, both of which references
are
being incorporated herein be reference in their entirety.
2s The cationic nitrogen-containing moiety will be present generally as a
substituent, on a fraction of the total monomer units of the cationic hair
conditioning
polymers. Thus, the cationic polymer can comprise copolymers, terpolymers,
etc. of
quaternary ammonium or cationic amine-substituted monomer units and other non-
cationic units referred to herein as spacer monomer units. Such polymers are
known
30 in the art, and a variety can be found in the CTFA Cosmetic Ingredient
Dictionary,
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
41
3rd edition, edited by Estrin, Crosley, and Haynes, (The Cosmetic, Toiletry,
and
Fragrance Association, Inc., Washington, D.C., 1982).
The cationic charge density is preferably at least about 0.3 meq/gram, more
preferably at least about 0.6 meq/gram, even more preferably at least about
1.0
meq/gram, 1.2, most preferably at least about 1.2 meq/gram. The cationic
charge
density in general will be about 4 meq/gram or less, more generally about 3.0
meq/gram or less. Cationic charge density of the cationic polymer can be
determined according to the Kjeldahl Method. Those skilled in the art will
recognize that the charge density of amino-containing polymers in the final
product
1o may vary depending upon pH and the isoelectric point of the amino groups.
The
charge density should be within the above limits at the pH of intended use.
Any anionic counterions can be utilized for the cationic polymers so long as
the water solubility criteria is met. Suitable counterions include halides
(e.g., CI, Br,
I, or F, preferably CI, Br, or I), sulfate, and methylsulfate. Others can also
be used,
as this list is not intended to be exhaustive.
As discussed above, the cationic polymer hereof is water dispersible. This
does not mean, however, that it must become soluble when the articles of the
present
invention are wetted and agitated to produce lather. Preferably, however, the
cationic polymer is either dispersible when the articles described herein are
wetted
2o and agitated to produce lather, or treat the water insoluble substrate with
a pre-
complexed coacervate phase formed by the cationic polymer and the anionic
material. This complex coacervate phase can be added onto or impregnated into
the
substrate independently or in combination with either the lathering surfactant
or the
water soluble conditioning agent. Complex coacervates of the cationic polymer
can
be formed with anionic surfactants or with anionic polymers that can
optionally be
added to the compositions hereof (e.g., sodium polystyrene sulfonate). Complex
coacervates are believed to more readily deposit water soluble conditioning
agents
onto the skin or hair. Thus, in general, it is preferred that the cationic
polymer exist
in/on the articles of the present invention as a complexed coacervate phase or
form a
3o coacervate phase upon dilution of the lather produced after wetting and
agitating
these articles. If not already a coacervate in/on the articles of the present
invention,
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
42
the cationic polymer will preferably exist in a complex coacervate form upon
dilution.
Coacervate formation is dependent upon a variety of criteria such as
molecular weight, concentration, and ratio of interacting ionic materials,
ionic
strength (including modification of ionic strength, for example, by addition
of salts),
charge density of the cationic and anionic species, pH, and temperature.
Coacervate
systems and the effect of these parameters has previously been studied. See,
for
example, J. Caelles, et al., "Anionic and Cationic Compounds in Mixed System",
Cosmetics Toiletries, Vol, 106, April 1991, pp 49-54; Van Oss, "Coacervation,
to Complex-Coacervation and Flocculation", J. Dispersion Science and
Technology,
Vol. 9 (5,6), 1988-89, pp 561-573; D. J. Burgess, "Practical Analysis of
Complex
Coacervate Systems", J. of Colloid and Interface Science, Vol. 140, No. l,
November 1990, pp 227-238; and U.S. Pat. No. 5,716,920, Glenn Jr. et al.,
issued
Feb. 10, 1998; all of which references being incorporated by reference herein.
Techniques for analysis of formation of complex coacervates are known in
the art. For example, microscopic analyses of the lather, at any chosen stage
of
dilution, can be utilized to identify whether a coacervate phase has formed.
Such
coacervate phase will be identifiable as an additional emulsified phase. The
use of
dyes can aid in distinguishing the coacervate phase from other insoluble
phases
2o dispersed in the lather.
The nonionic and cationic polymers useful herein include those derived from
both natural sources and synthetic sources. Among the polymers derived from
natural sources, those that are derived from cellulose and proteins are highly
preferred. Among the synthetic polymers, those that are polyethylenimines and
polyacrylamides are preferred. General classes of suitable deposition aids for
use in
the articles described herein include gums, hydraphilic colloids and
derivatives
thereof, biological polymers and derivatives thereof, synthetic polymers,
polymeric
ethers, proteins and derivatives thereof, quaternary ammonium compounds,
coacervates, and mixtures thereof. The following are nonlimiting examples of
cationic and nonionic deposition aids for use herein.
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
43
Gums, hvdronhilic colloids biolo ig ca_polymers and proteins and mixtures
thereof are useful herein as deposition aids. Nonlimiting examples of these
materials
include carboxymethyl hydroxyethylcellulose, carboxymethyl hydroxypropyl guar,
carrageenan, cellulose gum, gelatin, guar gum, guar hydroxypropyltrimonium
chloride, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropyl
methylcellulose, methylcellulose, xanthan gum, chitin, chitosan, hydroxypropyl
chitosan, potato starch, oat protein, milk protein, cocoyl hydrolyzed
collagen, cocoyl
hydrolyzed keratin, hydroxypropyltrimonium gelatin, and mixtures thereof.
Cellulose derived polymers are also useful herein as deposition aids. By
1o cellulose derived polymers, as used herein, is meant to describe those
polymers
containing a cellulose backbone, i.e. a polysaccharide backbone of repeating
glucose
units. In these cellulose derived polymers, the hydroxy groups of the
cellulose
polymer have been hydroxyalkylated (preferably hydroxyethylated or
hydroxypropylated) to form a hydroxyalkylated cellulose which is then further
modified with a cationic quaternary ammonium or protonated ammonium group.
Preferred cationic modifying groups are those having at least one C,o_zo alkyl
chain
and two shorter alkyl chains (i.e. C, or Cz) on the nitrogen. The substituent
on the
cellulose polymer can thus be depicted as -(X)NRR'R" wherein X is hydroxyalkyl
(preferably-OCHZCHz- or -OCHZCHOHCHz-), R and R' are methyl or ethyl, and R"
2o is C,o_zo alkyl (preferably lauryl, stearyl, or cocoyl (i.e. a mixture of
alkyl groups
derived from coconut oil)]. In other alternative structures it has been found
that
when R, R', and R" are all methyl (i.e. the trimonium group) that useful
cellulose
polymers are also obtained. In yet other alternative structures the cationic
substituent on the cellulose contains both a hydroxyethyl and a hydroxypropyl
group
such that the moiety can be depicted as -(OCHzCHzO)-CHZCHOHCHzNRR'R"
wherein R, R', and R" are methyl or ethyl, and R" is C,o_zo alkyl [preferably
lauryl,
stearyl, or cocoyl (i.e. a mixture of alkyl groups derived from coconut oil)],
or
alternatively wherein R, R', and R" are all methyl (i.e. the trimonium group).
Commercially available cationic modified celluloses include: laurdimonium
3o hydroxethyl cellulose (wherein in the above formula X is -OCHZCHz-, R and
R' are
methyl, and R" is lauryl), steardimonium hydroxyethyl cellulose (wherein in
the
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
44
above formula X is -OCHZCHz , R and R' are methyl, and R" is stearyl), and
cocodimonium hydroxyethyl cellulose (wherein in the above formula X is -
OCH,CHZ-, R and R' are methyl, and R" is cocoyl). These three materials are
known
by the trade names Crodacel QL, Crodacel QS, and Crodacel QM, respectively,
s which are all commercially available from Croda Corp. Another highly useful
cationic cellulose is laurdimmonium hydroxypropyl oxyethyl cellulose (wherein
the
modifying group on the cellulose is -(OCHZCH20)-CHZCHOHCHzNRR'R", wherein
R R' are methyl and R" is lauryl), which is commercially available as CRODACEL
QL SPECIAL, from Croda Corp. Other useful cationic celluloses are available
from
1o Amerchol Corp. (Edison, N.J., USA) in their POLYMER JR~"'', LR'~''',and
LK~"''
series of polymers, as salts of hydroxyethyl cellulose reacted with trimethyl
ammonium substituted epoxide, referred to in the industry (CTFA) as
Polyquaternium 10; cationic cellulose ethers described in U.S. Pat. Nos.
3,816,616
4,272,515, which are commercially available from Union Carbide Corp. under the
15 trademark POLYMER JR.; and the polymeric quaternary ammonium salts of
hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted
epoxide,
referred to in the industry (CTFA) as Polyquaternium 24 which are available
from
Amerchol Corp. (Edison, N.J., USA) under the tradename POLYMER LM-200.
Other suitable cationic polymers that can be used herein include cationic guar
20 gum derivatives, such as the cationic polygalactomannan gum derivative
described
in U.S. Pat. No. 4,298,494 which are commercially available under the
trademark
JAGUAR; the hydroxypropyltrimethylammonium derivative of guar gum which is
commercially available under the trademark JAGUAR C-13-S and JAGUAR C-17
(CTFA designation guar hydroxypropyltrimonium chloride); and the
25 hydroxypropylated cationic guar derivative known as JAGUAR C-16
(commercially
available from Celanese Corp. in their JAGUAR~ series). Other materials
include
quaternary nitrogen-containing cellulose ethers (e.g., as described in U.S.
Pat. No.
3,962,418, incorporated by reference herein), and copolymers of etherified
cellulose
and starch (e.g., as described in U.S. Pat. No. 3,958,581, incorporated by
reference
3o herein). Especially preferred cationic polymers include Polyquaternium 10.
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
Related to these cellulose polymers are ones having backbones that are
derived from other sugars (or their related acids, alcohols, amines, etc.),
e.g.
galactose, mannose, arabinose, xylose, fucose, fructose, glucosamine,
galactosamine,
glucuronic acid, galacturonic acid, 5 or 6 membered ring polyalcohols, and
mixtures
s thereof.
Protein derived~olymers are another type of useful derivative of a naturally
occurnng polymer. The protein derived polymers useful herein are derived from
a
wide variety of protein sources. However, those that are derived from
hydrolyzed
proteins (i.e. proteins which are broken down into lower molecular weight
segments
10 of from about 1000 MW to about 5000 MW) are preferred. Hydrolyzed proteins
are
well known to the cosmetic chemist of ordinary skill in the art and can be
derived
using standard synthetic techniques such as the acid, alkaline, or enzymatic
hydrolysis of various protein sources. The protein source used will determine
the
ultimate amino acid composition of the hydrolyzed protein obtained.
Nonlimiting
i s examples of hydrolyzed proteins which are useful as polymers herein
include those
selected from the group consisting of hydrolyzed casein, hydrolyzed collagen,
hydrolyzed conchiorin protein, hydrolyzed corn protein, hydrolyzed elastin,
hydrolyzed fibronectin, hydrolyzed hair keratin, hydrolyzed human placental
protein, hydrozlyed keratin, hydrolyzed potato protein, hydrolyzed rice
protein,
2o hydrolyzed silk, hydrolyzed soy protein, hydrolyzed vegetable protein,
hydrolyzed
wool protein, hydrolyzed wheat protein, and mixtures thereof. These hydrolyzed
proteins are described in the CTFA International Cosmetic Ingredient
Dictionary,
1991, pp. 246-249, which are incorporated by reference herein in their
entirety.
It has been found that cationically modified hydrolyzed proteins are
25 especially useful polymers in the present invention. Using a variety of
synthetic
techniques known to the artisan of ordinary skill in the chemical arts, the
nitrogen
atoms of the amino acids comprising these hydrolyzed proteins can be
hydroxyalkylated (preferably hydroxyethylated or hydroxypropylated) to form a
hydroxyalkylated protein hydrolyzate which is then further modified with a
cationic
3o quaternary ammonium or protonated ammonium group. Preferred cationic
modifying groups are those having at least one C,o.2o alkyl chain and two
shorter
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
46
alkyl chains (i.e. C, or Cz) on the nitrogen. The substituent on the
hydrolyzed
protein can be depicted as -(X)NRR'R" wherein X is hydroxyalkyl (preferably-
OCHzCHz- or-OCHZCHOHCHz-), R and R' are methyl or ethyl, and R" is C,o_zo
alkyl
[(preferably lauryl, stearyl, or cocoyl (i.e. a mixture of alkyl groups
derived from
coconut fats}). In other alternative structures it has been found that when R,
R', and
R" are all methyl (i.e. the trimonium group) that useful cationic hydrolyzed
proteins
are also obtained. Commercially available cationic modified protein
hydrolyzates
include: hydroxypropyltrimonium hydrolyzed casein, hydroxypropyltrimonium
hydrozlyed collagen, hydoxypropyltrimonium hydrolyzed keratin,
1o hydroxypropyltrimonium hydrolyzed silk, hydroxypropyl trimonium hydrolyzed
soy
protein, hydroxypropyl trimonium hydrolyzed vegetable protein, and
hydroxypropyltrimonium hydrolyzed wheat protein, wherein the -(X)NRR'R"
substituent on each of these protein hydrolyzates is such that X is -
OCHzCHOHCHz-
and R, R', and R" are methyl. These hydrolyzed proteins are described in the
CTFA International Cosmetic Ingredient Dictionary, 1991, pp. 254-255, which
are
incorporated by reference herein in their entirety. Other commercially
available
cationic modified protein hydrolyzates include lauryldimonium hydroxypropyl
hydrolyzed collagen, lauryldimonium hydroxypropyl hydrolyzed keratin,
lauryldimonium hydroxypropyl hydrolyzed silk, lauryldimonium hydroxypropyl
2o hydrolyzed soy protein, stearyldimonium hydroxypropyl hydrolyzed casein,
stearyldimonium hydroxypropyl hydrolyzed collagen, stearyldimonium
hydroxypropyl hydrolyzed keratin, stearyldimonium hydroxypropyl hydrolyzed
rice
protein, stearyldimonium hydorxypropyl hydrolyzed silk, stearyldimonium
hydroxypropyl hydrolyzed vegetable protein, stearyldimonium hydroxypropyl
hydrolyzed wheat protein, cocodimonium hydroxypropyl hydrolyzed casein,
cocodimonium hydroxypropyl hydrolyzed collagen, cocodimonium hydroxypropyl
hydrolyzed keratin, cocodimonium hydroxypropyl hydrolyzed rice protein,
cocodimonium hydroxypropyl hydrolyzed silk, cocodimonium hydroxypropyl
hydrolyzed soy protein, cocodimnoium hydroxypropyl hydrolyzed wheat protein,
wherein in each of these protein hydrolyzates the -(X)NRR'R" substituent is
such
that X is -OCH2CHOHCH2-, R and R' are methyl, and R" is lauryl or stearyl or
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
47
cocoyl. These hydrolyzed proteins are described in the CTFA International
Cosmetic Ingredient Dictionary, 1991, pp. 112-113, 293-294, 586, which are
incorporated by reference herein in their entirety. Preferred among these
cationic
hydrolyzed proteins are lauryldimmonium hydroxypropyl hydrolyzed collagen,
lauryldimmonium hydroxypropyl hydrolyzed keratin, lauryldimmonium
hydroxypropyl hydrolyzed keratin, lauryldimmonium hydroxypropyl hydrolyzed
silk, lauryldimmonium hydroxypropyl hydrolyzed soy protein, and mixtures
thereof.
Polyrneric ethers are also useful as deposition aids herein as long as the
number of repeating units is greater than 50. These materials are also known
ac
polyethylene glycols and polypropylene glycols (designated as PEG and PPG in
the
CTFA, respectively). Nonlimiting examples of these materials include PEG 25M,
PEG 75, PEG 90, PEG 100, PEG 2M, PEG 7M, PEG 14M, and mixtures thereof.
Synthetic polymers and copolymers are also useful as deposition aids herein.
Suitable cationic polymers include, for example, copolymers of vinyl monomers
having cationic amine or quaternary ammonium functionalities with water
soluble
spacer monomers such as acrylamide, methacrylamide, alkyl and dialkyl
acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylate, alkyl
methacrylate,
vinyl caprolactone, and vinyl pyrrolidone. The alkyl and dialkyl substituted
monomers preferably have C,-C, alkyl groups, more preferably C,-C3 alkyl
groups.
2o Other suitable spacer monomers include vinyl esters, vinyl alcohol (made by
hydrolysis of polyvinyl acetate), malefic anhydride, propylene glycol, and
ethylene
glycol.
The cationic amines can be primary, secondary, or tertiary amines, depending
upon the particular species and the pH of the shampoo. In general, secondary
and
tertiary amines, especially tertiary amines, are preferred.
Amine-substituted vinyl monomers can be polymerized in the amine form,
and then optionally can be converted to ammonium by a quaternization reaction.
Amines can also be similarly quaternized subsequent to formation of the
polymer.
For example, tertiary amine functionalities can be quaternized by reaction
with a salt
of the formula R'X wherein R' is a short chain alkyl, preferably a C,-C,
alkyl, more
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
48
preferably a C,-C3 alkyl, and X is an anion which forms a water soluble salt
with the
quaternized ammonium.
Suitable cationic amino and quaternary ammonium monomers include, for
example, vinyl compounds substituted with dialkylaminoalkyl acrylate,
dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate,
monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammonium salt,
trialkyl acryloxyalkyl ammonium salt, diallyl quaternary ammonium salts, and
vinyl
quaternary ammonium monomers having cyclic cationic nitrogen-containing rings
such as pyridinium, imidazolium, and quaternized pyrrolidone, e.g., alkyl
vinyl
I0 imidazolium, alkyl vinyl pyridinium, alkyl vinyl pyn olidone salts. The
alkyl
portions of these monomers are preferably lower alkyls such as the C,-C;
alkyls,
more preferably C, and C, alkyls.
Suitable amine-substituted vinyl monomers for use herein include
dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, dialkylaminoalkyl
acrylamide, and dialkylaminoalkyl methacrylamide, wherein the alkyl groups are
preferably C,-C, hydrocarbyls, more preferably C,-C:3, alkyls.
The cationic polymers hereof can comprise mixtures of monomer units
derived from amine- and/or quaternary ammonium-substituted monomer and/or
compatible spacer monomers.
Suitable synthetic cationic polymers include, for example: copolymers of 1-
vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salt (e.g., chloride salt)
(referred to in the industry by the Cosmetic, Toiletry, and Fragrance
Association,
"CTFA", as Polyquaternium-16), such as those commercially available from BASF
Wyandotte Corp. (Parsippany, N.J., USA) under the LUVIQUAT tradename (e.g.,
LUVIQUAT FC 370); copolymers of 1-vinyl-2-pyrrolidone and dimethylaminoethyl
methacrylate (referred to in the industry by CTFA as Polyquaternium-11) such
as
those described in U.S. Pat. No. 4,080,310 and commercially available from ISP
Corporation (Wayne, N.J., USA) under the GAFQUAT tradename (e.g., GAFQUAT
755 and 755N); cationic diallyl quaternary ammonium-containing polymers,
including, for example, dimethyldiallylammonium chloride homopolymer and
copolymers of acrylamide and dimethyldiallylammonium chloride, referred to in
the
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
49
industry (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively; the
mineral acid salts of amino-alkyl esters of homo- and co-polymers of
unsaturated
carboxylic acids having from 3 to 5 carbon atoms, as described in U.S. Pat.
No.
4,009,256; the graft cationic copolymer containing N-vinylpyrrolidone,
dimethylaminoethyl methacrylate and polyethylene glycol described in U.S. Pat.
No.
4,048,301; the polymers of etherified starch described in U.S. Pat. No.
3,186,911;
cationic polyacrylamides of the type described in British Pat. App.
94031565.4; the
high molecular weight cationic polymers designated in the CTFA as Quaternium-
40
(a highly charged cationic dimethyldiallylammonium chloride homopolymer) and
Quaternium-41 (a highly charged cationic copolymer prepared with
dimethyldiallylammonium chloride and acrylamide), which are commercially
available under the trademarks MERQUAT 100 and MERQUAT 550 from Merck &
Com., Inc.; and mixtures thereof. Further nonlimiting examples of other
suitable
synthetic polymers include acrylylates/C 10-30 alkyl acrylate crosspolymer,
acrylates
copolymer, acrylates/PVP copolymer, acrylates/VA copolymer, butylated
polyoxymethylene urea, butylated PVP, carbomer, hydroxyethyl PEI-1000, methyl
methacrylate crosspolymer, PEI-1000, PEI-1500, PEI-2500, polybutene,
polyacrylamide, polyacrylic acid, polyethylene, polyisobutene, polymethyl
methacrylate, polystyrene, polyvinly alcohol, PVP, PVP/Eicosene copolymer,
2o PVP/VA copolymer, sodium acrylates copolymer, sodium carbomer, sodium
polyacrylate, sodium polymethacrylate, styrene/PVP copolymer, TEA carbomer,
and
mixtures thereof.
Other polymers: Other useful polymers include polyvinylpyrrolidone and
copolymers of vinylpyrrolidone such as those containing vinyl acetate,
dimethylaminoethylmethacrylate and quaternary versions of the same with methyl
sulfates, and polymers and copolymers of vinyl alcohol and vinyl acetate.
Another
highly useful polymer is the protonated form of polyethyleneimine.
Polyethylenimine is a polymer which is produced from the polymerization of
ethylenimine. The protonated polyethylenimine polymers preferred herein are
those
3o having a molecular weight of from about 500,000 to about 750,000, branching
such
that the ratio of primary to secondary to tertiary nitrogen is about 1:2:1, a
tertiary
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
s0
nitrogen site on average at about every 3 to about 3.5 atoms, a charge density
of
about 20 mini-equivalents per gram at pH 4.5, a density of about 1070 kg/m3,
and a
viscosity of about 17,000 to about 28,000 mini-Pascals. A protonated
polyethylenimine polymer meeting this description is commercially available as
s POLYMIN P from BASF Corp.
Cationic surfactants (nonpolymeri~ are also useful herein as deposition aids
herein, provided that these materials are selected so as to not interfere with
the
overall lathering characteristics of the required lathering surfactants.
Cationic
surfactants useful herein contain amino or quaternary ammonium hydrophilic
moieties which are positively charged when dissolved in the aqueous
composition of
the present invention. Cationic surfactants suitable for use are disclosed in
the
following documents, all incorporated by reference herein: M.C. Publishing
Co.,
McCutcheon's, Detergents & Emulsifrers, (North American edition 1979);
Schwartz,
et al., Surface Active Agents, Their Chemistry and Technology, New York:
1s Interscience Publishers, 1949; U.S. Pat. No. 3,155,591, Hilfer, issued Nov.
3, 1964;
U.S. Pat. No. 3,929,678, Laughlin, et al., issued Dec. 30, 1975; U.S. Pat. No.
3,959,461, Bailey, et al., issued May 25, 1976; U.S. Pat. No. 4,275,055,
Nachtigal,
et al., issued June 23, 1981; U.S. Pat. No. 4,387,090, Bolich, Jr., issued
Jun. 7, 1983;
U.S. Pat. No. 4,704,272, Oh et al, issued Nov. 3, 1987; U.S. Pat. No.
5,034,218,
2o Duvel, issued July 23, 1991;U.S. Pat. No. 5,393,452, Raleigh et al, issued
Sept. 14,
1993; U.S. Pat. No. 5,672,576, Behrens et al., issued Sept. 30, 1997; U.S.
Pat. No.
5,714,446, Bartz et al., issued Feb. 3, 1998.
Among the quaternary ammonium-containing cationic surfactant materials
useful herein are those of the general formula:
R, ~ R3 +
N~ X
Rz~ . RQ
2s
wherein R,-R4 are independently selected from hydrogen, an aliphatic group
of from about 1 to about 22 carbon atoms, or aromatic, aryl, an alkoxy,
polyoxyaIkylene, alkylamido, hydroxyalkyl, or alkylaryl group having from
about 1
to about 22 carbon atoms; and X is an anion selected from halogen, acetate,
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
51
phosphate, nitrate, sulfate, alkylsulfate radicals (e.g., methyl sulfate and
ethyl
sulfate), tosylate, lactate, citrate, and glycolate. The aliphatic groups may
contain, in
addition to carbon and hydrogen atoms, ether linkages, and other groups such
as
hydroxy or amino group substituents (e.g., the alkyl groups can contain
polyethylene
glycol and polypropylene glycol moieties). The longer chain aliphatic groups,
e.g.,
those of about 12 carbons, or higher, can be saturated or unsaturated.
More preferably, R~ is an alkyl group having from about 12 to about 18
carbon atoms; Rz is selected from H or an alkyl group having from about 1 to
about
18 carbon atoms; R3 and R4 are independently selected from H or an alkyl group
to having from about 1 to about 3 carbon atoms; and X is as described in the
previous
paragraph.
Most preferably, R~ is an alkyl group having from about 12 to about 18
carbon atoms; RZ, R3, and R4 are selected from H or an alkyl group having from
about 1 to about 3 carbon atoms; and X is as described previously.
Alternatively, other useful cationic surfactants include amino-amides,
wherein in the above structure R1 is alternatively RSCO-(CHZ)n -, wherein RS
is an
alkyl group having from about 12 to about 22 carbon atoms, and n is an integer
from
about 2 to about 6, more preferably from about 2 to about 4, and most
preferably
from about 2 to about 3. Nonlimiting examples of these cationic emulsifiers
include
2o stearamidopropyl PG-dimonium chloride phosphate, stearamidopropyl
ethyldimonium ethosulfate, stearamidopropyl dimethyl (myristyl acetate)
ammonium chloride, stearamidopropyl dimethyl cetearyl ammonium tosylate,
stearamidopropyl dimethyl ammonium chloride, stearamidopropyl dimethyl
ammonium lactate, and mixtures thereof.
Nonlimiting examples of quaternary ammonium salt cationic surfactants
include those selected from the group consisting of cetyl ammonium chloride,
cetyl
ammonium bromide, lauryl ammonium chloride, lauryl ammonium bromide, stearyl
ammonium chloride, stearyl ammonium bromide, cetyl dimethyl ammonium
chloride, cetyl dimethyl ammonium bromide, lauryl dimethyl ammonium chloride,
lauryl dimethyl ammonium bromide, stearyl dimethyl ammonium chloride, stearyl
dimethyl ammonium bromide, cetyl trimethyl ammonium chloride, cetyl trimethyl
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
52
ammonium bromide, lauryl trimethyl ammonium chloride, lauryl trimethyl
ammonium bromide, stearyl trimethyl ammonium chloride, stearyl trimethyl
ammonium bromide, lauryl dimethyl ammonium chloride, stearyl dimethyl cetyl
ditallow dimethyl ammonium chloride, dicetyl ammonium chloride, dicetyl
ammonium bromide, dilauryl ammonium chloride, dilauryl ammonium bromide,
distearyl ammonium chloride, distearyl ammonium bromide, dicetyl methyl
ammonium chloride, dicetyl methyl ammonium bromide, dilauryl methyl
ammonium chloride, dilauryl methyl ammonium bromide, distearyl methyl
ammonium chloride, distearyl dimethyl ammonium chloride, distearyl methyl
to ammonium bromide, and mixtures thereof. Additional quaternary ammonium
salts
include those wherein the C 12 to C22 alkyl carbon chain is derived from a
tallow
fatty acid or from a coconut fatty acid. The term "tallow" refers to an alkyl
group
derived from tallow fatty acids (usually hydrogenated tallow fatty acids),
which
generally have mixtures of alkyl chains in the C 16 to C 18 range. The term
"coconut" refers to an alkyl group derived from a coconut fatty acid, which
generally have mixtures of alkyl chains in the C 12 to C 14 range. Examples of
quaternary ammonium salts derived from these tallow and coconut sources
include
ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl
sulfate, di(hydrogenated tallow) dimethyl ammonium chloride, di(hydrogenated
2o tallow) dimethyl ammonium acetate, ditallow dipropyl ammonium phosphate,
ditallow dimethyl ammonium nitrate, di(coconutalkyl)dimethyl ammonium
chloride, di(coconutalkyl)dimethyl ammonium bromide, tallow ammonium
chloride, coconut ammonium chloride, stearamidopropyl PG-dimonium chloride
phosphate, stearamidopropyl ethyldimonium ethosulfate, stearamidopropyl
dimethyl
(myristyl acetate) ammonium chloride, stearamidopropyl dimethyl cetearyl
ammonium tosylate, stearamidopropyl dimethyl ammonium chloride,
stearamidopropyl dimethyl ammonium lactate, and mixtures thereof.
Preferred cationic surfactants useful herein include those selected from the
group consisting of dilauryl dimethyl ammonium chloride, distearyl dimethyl
ammonium chloride, dimyristyl dimethyl ammonium chloride, dipalmityl dimethyl
ammonium chloride, distearyl dimethyl ammonium chloride, and mixtures thereof.
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
53
Among the cationic polymers useful herein, preferred are those selected from
the group consisting of hydroxyethyl cellulose, hydroxypropyl cellulose,
lauryldimmonium hydroxypropyl oxyethyl cellulose, laurdimonium hydroxyethyl
cellulose, steardimonium hydroxyethyl cellullose, cocodimonium hydroxyethyl
cellulose, hydroxypropyl hydrolyzed collagen, lauryldimmonium hydroxypropyl
hydrolyzed keratin, lauryldimmonium hydroxypropyl hydrolyzed keratin,
lauryldimmonium hydroxypropyl hydrolyzed silk, lauryldimmonium hydroxypropyl
hydrolyzed soy protein, protonated polyethylenimine, Polyquaternium 10, and
mixtures thereof. More preferred are lauryldimonium hydroxypropyl hydrolyzed
1o collagen, laurdimonium hydroxypropyl oxyethyl cellulose, and mixtures
thereof.
Preferably the deposition aid is selected from the group comprising
hydroxyalkyl
cellulose ethers and cationic guar derivatives. Particularly preferred
deposition aids
are JAGUAR C13S with a cationic charge density of 0.8meq/g. Other particularly
preferred materials include JAGUAR C 15, JAGUAR C 17, JAGUAR C 16, JAGUAR
C 162, Polyquaternium 10, and mixtures thereof. Most preferred is
Polyquaternium
10 (e.g., POLYMER JR400 and POLYMER JR30M).
Among the nonionic polymers useful herein, preferred are those selected
from the group consisting of hydrolyzed casein, hydrolyzed collagen,
hydrolyzed
vegetable protein, guar gum, polyvinylpyrrolidone, PEG 14M, and mixtures
thereof.
2o More preferred is PEG 14M and hydrolyzed casein.
WEIGHT RATIOS AND WEIGHT PERCENTAGES
In the present invention, the weight ratio of the lathering surfactant to the
skin care active is from about 1000:1 to about 1:1, preferably from about
800:1 to
about 2:1, and more preferably from about 500:1 to :3:1.
ADDITIONAL INGREDIENTS
The articles of the present invention can comprise a wide range of optional
ingredients. Some of these ingredients are listed in more detail herein.
Particularly
useful are various active ingredients useful for delivering various
conditioning
benefits during the cleansing process. In these compositions, the article is
useful for
3o also delivering these conditioning ingredients to the skin or hair.
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
54
Conditioning Component
The articles of the present invention can optionally comprise a conditioning
component which is useful for providing a conditioning benefit to the skin or
hair
during the use of the article. By "conditioning benefit," as used herein,
describes the
ability of a material (e.g., compound or composition), in whole or in part, to
improve
the appearance and/or feel of mammalian skin upon/after topical application
(e.g.,
after rinsing and pat drying) via one or more of the following mechanisms:
moisturization, hydration, plasticization, lubrication, and occlusion.
Nonlimiting
examples of materials which suitably perform these mechanisms are described in
the
CTFA Cosmetic Ingredient Handbook, Second Edition, 1992, which is incorporated
by reference herein in its entirety. The articles of the present invention
comprise
from about 0.05% to about 99%, preferably from about 0.1% to about 50%, and
more preferably from about 1 % to about 25% of a conditioning component, by
weight of said water insoluble substrate.
The conditioning component of the present invention can comprise: a water
soluble conditioning agent; an oil soluble conditioning agent; a conditioning
emulsion; or any combination or permutation of the three. By conditioning
emulsion is meant that conditioning agents are present in the skin care
emulsions
described hereinbefore, e.g., in either the water soluble discontinuous phase
or the
oil soluble continuous phase. The oil soluble conditioning agent is selected
from
one or more oil soluble conditioning agents such that the weighted arithmetic
mean
solubility parameter of the oil soluble conditioning agent is less than or
equal to
10.5. The water soluble conditioning agent is selected from one or more water
soluble conditioning agents such that the weighted arithmetic mean solubility
parameter of the water soluble conditioning agent is greater than 10.5. It is
recognized, based on this mathematical definition of solubility parameters,
that it is
possible, for example, to achieve the required weighted arithmetic mean
solubility
parameter, i.e. less than or equal to 10.5, for an oil soluble conditioning
agent
comprising two or more compounds if one of the compounds has an individual
3o solubility parameter greater than 10.5. Conversely, it is possible to
achieve the
appropriate weighted arithmetic mean solubility parameter, i.e. greater than
10.5, for
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
a water soluble conditioning agent comprising two or more compounds if one of
the
compounds has an individual solubility parameter less than or equal to 10.5.
The
solubility parameters of conditioning agents can be determined as described
hereinbefore in the Skin Care Active Component Section.
5 Nonlimiting examples of conditioning agents useful ~ as oil soluble
conditioning agents include those selected from the group consisting of
mineral oil,
petrolatum, C7-C40 branched chain hydrocarbons, CI-C30 alcohol esters of CI-
C30
carboxylic acids, CI-C30 alcohol esters of C2-C30 dicarboxylic acids,
monoglycerides of C1-C30 carboxylic acids, diglycerides of C1-C30 carboxylic
1 o acids, triglycerides of C 1-C30 carboxylic acids, ethylene glycol
monoesters of C I-
C30 carboxylic acids, ethylene glycol diesters of C1-C30 carboxylic acids,
propylene glycol monoesters of C1-C30 carboxylic acids, propylene glycol
diesters
of C 1-C30 carboxylic acids, C I -C30 carboxylic acid monoesters and
polyesters of
sugars, polydialkylsiloxanes, polydiarylsiloxanes, polyalkarylsiloxanes,
~5 cylcomethicones having 3 to 9 silicon atoms, vegetable oils, hydrogenated
vegetable
oils, polypropylene glycol C4-C20 alkyl ethers, di C8-C30 alkyl ethers, and
mixtures thereof.
Mineral oil, which is also known as petrolatum liquid, is a mixture of liquid
hydrocarbons obtained from petroleum. See The Merck Index, Tenth Edition,
Entry
20 7048, p. 1033 (1983) and International Cosmetic Ingredient Dictionary,
Fifth
Edition, vol. 1, p.415-417 (1993), which are incorporated by reference herein
in their
entirety.
Petrolatum, which is also known as petroleum jelly, is a colloidal system of
nonstraight-chain solid hydrocarbons and high-boiling liquid hydrocarbons, in
which
25 most of the liquid hydrocarbons are held inside the micelles. See The Merck
Index,
Tenth Edition, Entry 7047, p. 1033 (1983); Schindler, Drug. Cosmet. Ind., 89,
36-
37, 76, 78-80, 82 (1961); and International Cosmetic Ingredient Dictionary,
Fifth
Edition, vol. I, p. 537 (1993), which are incorporated by reference herein in
their
entirety.
30 Straight and branched chain hydrocarbons having from about 7 to about 40
carbon atoms are useful herein. Nonlimiting examples of these hydrocarbon
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
56
materials include dodecane, isododecane, squalane, cholesterol, hydrogenated
polyisobutylene, docosane (i.e. a C22 hydrocarbon), hexadecane, isohexadecane
(a
commercially available hydrocarbon sold as Permethyl~ lOIA by Presperse, South
Plainfield, NJ). Also useful are the C7-C40 isoparaffins, which are C7-C40
s branched hydrocarbons.
Also useful are C1-C30 alcohol esters of C1-C30 carboxylic acids and of C2-
C30 dicarboxylic acids, including straight and branched chain materials as
well as
aromatic derivatives. Also useful are esters such as monoglycerides of C1-C30
carboxylic acids, diglycerides of C1-C30 carboxylic acids, triglycerides of C1-
C30
1o carboxylic acids, ethylene glycol monoesters of C1-C30 carboxylic acids,
ethylene
glycol diesters of C1-C30 carboxylic acids, propylene glycol monoesters of C1-
C30
carboxylic acids, and propylene glycol diesters of C1-C30 carboxylic acids.
Straight
chain, branched chain and aryl carboxylic acids are included herein. Also
useful are
propoxylated and ethoxylated derivatives of these materials. Nonlimiting
examples
15 include diisopropyl sebacate, diisopropyl adipate, isopropyl myristate,
isopropyl
palmitate, myristyl propionate, ethylene glycol distearate, 2-ethylhexyl
palmitate,
isodecyl neopentanoate, di-2-ethylhexyl maleate, cetyl palmitate, myristyl
myristate,
stearyl stearate, cetyl stearate, behenyl behenrate, dioctyl maleate, dioctyl
sebacate,
diisopropyl adipate, cetyl octanoate, diisopropyl dilinoleate, caprilic/capric
20 triglyceride, PEG-6 caprylic/capric triglyceride, PEG-8 caprylic/capric
triglyceride,
cetyl ricinoleate, cholesterol hydroxystearate, cholesterol isostearate, and
mixtures
thereof.
Also useful are various C1-C30 monoesters and polyesters of glycerin and
related materials. These esters are derived from glycerin and one or more
carboxylic
25 acid moieties. Depending on the constituent acid and glycerin, these esters
can be in
either liquid or solid form at room temperature. Nonlimiting examples of solid
esters include: glyceryl tribehenate, glyceryl stearate, glyceryl palmitate,
glyceryl
distearate, glyceryl dipalmitate.
Also useful are various Cl-C30 monoesters and polyesters of sugars and
3o related materials. These esters are derived from a sugar or polyol moiety
and one or
more carboxylic acid moieties. Depending on the constituent acid and sugar,
these
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
57
esters can be in either liquid or solid form at room temperature. Examples of
liquid
esters include: glucose tetraoleate, the glucose tetraesters of soybean oil
fatty acids
(unsaturated), the mannose tetraesters of mixed soybean oil fatty acids, the
galactose
tetraesters of oleic acid, the arabinose tetraesters of linoleic acid, xylose
tetralinoleate, galactose pentaoleate, sorbitol tetraoleate, the~sorbitol
hexaesters of
unsaturated soybean oil fatty acids, xylitol pentaoleate, sucrose tetraoleate,
sucrose
pentaoletate, sucrose hexaoleate, sucrose hepatoleate, sucrose octaoleate, and
mixtures thereof. Examples of solid esters include: sorbitol hexaester in
which the
carboxylic acid ester moieties are palmitoleate and arachidate in a 1:2 molar
ratio;
the octaester of raffinose in which the carboxylic acid ester moieties are
linoleate
and behenate in a 1:3 molar ratio; the heptaester of maltose wherein the
esterifying
carboxylic acid moieties are sunflower seed oil fatty acids and lignocerate in
a 3:4
molar ratio; the octaester of sucrose wherein the esterifying carboxylic acid
moieties
are oleate and behenate in a 2:6 molar ratio; and the octaester of sucrose
wherein the
esterifying carboxylic acid moieties are laurate, linoleate and behenate in a
1:3:4
molar ratio. A preferred solid material is sucrose polyester in which the
degree of
esterification is 7-8, and in which the fatty acid moieties are C 18 mono-
and/or di-
unsaturated and behenic, in a molar ratio of unsaturates:behenic of 1:7 to
3:5. A
particularly preferred solid sugar polyester is the octaester of sucrose in
which there
2o are about 7 behenic fatty acid moieties and about 1 oleic acid moiety in
the
molecule. Other materials include cottonseed oil or soybean oil fatty acid
esters of
sucrose. The ester materials are further described in, U.S. Patent No.
2,831,854,
U.S. Patent No. 4,005,196, to Jandacek, issued January 25, 1977; U.S. Patent
No.
4,005,195, to Jandacek, issued January 25, 1977, U.S. Patent No. 5,306,516, to
Letton et al., issued April 26, 1994; U.S. Patent No. 5,306,515, to Lettan et
al.,
issued April 26, 1994; U.S. Patent No. 5,305,514, to Letton et al., issued
April 26,
1994; U.S. Patent No. 4,797,300, to Jandacek et al., issued January 10, 1989;
U.S.
Patent No. 3,963,699, to Rizzi et al, issued June 15, 1976; U.S. Patent No.
4,518,772, to Volpenhein, issued May 21, 1985; and U.S. Patent No. 4,517,360,
to
3o Volpenhein, issued May 21, 1985; all of which are incorporated by reference
herein
in their entirety.
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
58
Nonvolatile silicones such as polydialkylsiloxanes, polydiarylsiloxanes, and
polyalkarylsiloxanes are also useful oils. These silicones are disclosed in
U.S.
Patent No. 5,069,897, to Orr, issued December 3, 1991, which is incorporated
by
reference herein in its entirety. The polyalkylsiloxanes correspond to the
general
chemical formula R3Si0[R2Si0]xSiR3 wherein R is an alkyl group (preferably R
is
methyl or ethyl, more preferably methyl) and x is an integer up to about 500,
chosen
to achieve the desired molecular weight. Commercially available
polyalkylsiloxanes
include the polydimethylsiloxanes, which are also known as dimethicones,
nonlimiting examples of which include the VICASIL~ series sold by General
l0 Electric Company and the DOW CORNING~ 200 series sold by Dow Corning
Corporation. Specific examples of polydimethylsiloxanes useful herein include
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
200°C.
Also useful are materials such as trimethylsiloxysilicate, which is a
polymeric
material corresponding to the general chemical farmula [(CH2)3Si01/2]x[Si02]y,
wherein x is an integer from about I 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. Also useful herein are
2o dimethiconols, which are hydroxy terminated dimethyl silicones. These
materials
can be represented by the general chemical formulas R3Si0[R2Si0]xSiR20H and
HOR2SiOjR2Si0]xSiR20H wherein R is an alkyl group (preferably R is methyl or
ethyl, more preferably methyl) and x is an integer up 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). Also useful herein are polyalkylaryl siloxanes,
with
polymethylphenyl siloxanes having viscosities from about I5 to about 65
centistokes
at 25°C being preferred. These materials are available, for example, as
SF 1075
METHYLPHENYL FLUID (sold by General Electric Company) and 556
COSMETIC GRADE PHENYL TRIMETHICONE FLUID (sold by Dow Corning
Corporation).
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
59
Vegetable oils and hydrogenated vegetable oils are also useful herein.
Examples of vegetable oils and hydrogenated vegetable oils include safflower
oil,
castor oil, coconut oil, cottonseed oil, menhaden oil, palm kernel oil, palm
oil,
peanut oil, soybean oil, rapeseed oil, linseed oil, rice bran oil, pine oil,
sesame oil,
sunflower seed oil, hydrogenated safflower oil, hydrogenated castor oil,
hydrogenated coconut oil, hydrogenated cottonseed oil, hydrogenated menhaden
oil,
hydrogenated palm kernel oil, hydrogenated palm oil, hydrogenated peanut oil,
hydrogenated soybean oil, hydrogenated rapeseed oil, hydrogenated linseed oil,
hydrogenated rice bran oil, hydrogenated sesame oil, hydrogenated sunflower
seed
oil, and mixtures thereof.
Also useful are C4-C20 alkyl ethers of polypropylene glycols, C1-C20
carboxylic acid esters of polypropylene glycols, and di-C8-C30 alkyl ethers.
Nonlimiting examples of these materials include PPG-14 butyl ether, PPG-15
stearyl
ether, dioctyl ether, dodecyl octyl ether, and mixtures thereof.
Other useful oil soluble conditioning agents include CREMEROL (available
from Amerchol), ELDEW CL301 (available from Ajinomoto), MODULAN (an
acetylated lanolin which is commercially available from Croda), OHLAN (a
hydroxylated lanolin which is commercially available from Amerchol),
phytantriol,
super sterol esters, such as C,-C,o cholesterol/lanosterol esters, (available
from
Croda), and mixtures thereof.
Nonlimiting examples of conditioning agents useful as water soluble
conditioning agents include those selected from the group consisting of
polyhydric
alcohols, polypropylene glycols, polyethylene glycols, areas, pyrolidone
carboxylic
acids, ethoxylated and/or propoxylated C3-C6 diols and triols, alpha-hydroxy
C2-C6
carboxylic acids, ethoxylated and/or propoxylated sugars, polyacrylic acid
copolymers, sugars having up to about 12 carbons atoms, sugar alcohols having
up
to about 12 carbon atoms, and mixtures thereof. Specific examples of useful
water
soluble conditioning agents include materials such as urea; guanidine;
glycolic acid
and glycolate salts (e.g. ammonium and quaternary alkyl ammonium); lactic acid
and lactate salts (e.g. ammonium and quaternary alkyl ammonium); sucrose,
fructose, glucose, eruthrose, erythritol, sorbitol, mannitol, glycerol,
hexanetriol,
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
propylene glycol, butylene glycol, hexylene glycol, and the like; polyethylene
glycols such as PEG-2, PEG-3, PEG-4, PEG-5, PEG-6, PEG-8, PEG-9, PEG-10,
PEG-15 PEG-30, PEG-S0, polypropylene glycols such as PPG-9, PPG-12, PPG-15,
PPG-17, PPG-20, PPG-26, PPG-30, PPG-34; alkoxylated glucose; hyaluronic acid;
s and mixtures thereof. Also useful are materials such as aloe vera imany of
its variety
of forms (e.g., aloe vera gel), chitin, starch-grafted sodium polyacrylates
such as
SANWET (RTM) IM-1000, IM-1500, and IM-2500 (available from Celanese
Superabsorbent Materials, Portsmouth, VA); lactamide monoethanolamine;
acetamide monoethanolamine; and mixtures thereof. Also useful are propoxylated
to glycerols as described in propoxylated glycerols described in U.S. Patent
No.
4,976,953, to Orr et al., issued December 11, 1990, which is incorporated by
reference herein in its entirety. Other useful water soluble conditioning
agents
include arginine, arginine asparate (available from Ajinomoto), ARGININE PCA
(available from Argidone-UCIB), 1,3 butylene glycol, CHITOLAM NB/101
i s (available from Lamberti), chitosan salts, COLLAGEN AMINO ACID (available
from Crotein CAA-Croda), creatine, dextran, dextrin, diglycerol, dipropylane
glycol,
erythritol, FUCOGEL (available from Solabia), fructose, glucamine salts,
glucose
glutamate (commercially available as WICKENOL 545 from Caschem), glucuronic
acid salts, glutamic acid salts, glycereth 12, glycereth 20, gIycereth 7,
glycerin,
2o glyceryl PCA, glycogen, hexylene glycol, honey, hydrogenated honey,
hydrogenated
starch hydrolysates, hydrolyzed mucopolysaccharides, hydroxy proline,
inositol,
keratin amino acids {commercially available as CROTEIN HKP from Croda),
LYSINE PLA (commercially available as LYSIDONE from UCIB), maltitol,
maltose, mannitol, mannose, methoxy, methyl gluceth 10 (commercially available
as
25 GLUCAM E10 from Amerchol), methyl gluceth 20 (commercially available as
GLUCAM E20 from Amerchol), methyl glucose, 3 methyl 1, 3 butandiol, N acetyl
glucosamine salts, panthenol, butanediol, pentaerythitol pentaerythitol, 1,2
pentanediol, polyglycerol sorbitol, PPG 1 glyceryl ether, proline, propylene
glycol, 2
pyrrolidone-5-carboxylic acid and its salts, saccharide isomerate
(commercially
3o available as PENTAVITIN from Pentapharm), serine, silk amino acids
(commercially available as CROSLIK LIQL1ID from Croda), sodium
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
61
acetylhyaluronate, sodium hyaluronate, sodium polyaspartate (commercially
available as AQUADEW SPA-30 from Ajinomoto), sodium polyglutamate
(commercially available as AJICOAT SPG from Ajinomoto), sorbeth 20, sorbeth 6,
sorbitol, trehalose, triglycerol, trimethyolpropane, tris (hydroxymethyl)
amino
methane salts, xylitol, xylose, and mixtures thereof:
HARDNESS VALUE
In embodiments further comprising a conditioning component comprising an
oil soluble conditioning agent, the skin care active component will preferably
have a
minimum hardness value about 0.02 kg. The hardness value is a physical
hardness
measurement of the combination of all ingredients (e.g., water soluble skin
care
actives, oil soluble skin care actives, and conditioning agents) within the
skin care
active component. It is believed that increasing the hardness value increases
deposition consistency of the skin care actives and conditioning agents
despite
variations in lathering techniques employed by the consumer. It is believed
that
increasing skin care active component hardness decreases transfer within the
substrate and also decreases emulsification of the skin care active component
by the
surfactants during the lathering step. As a result, more of the skin care
active
component remain available for mechanical transfer via contact with the skin
or hair.
The skin care active component of the present invention has a hardness value
of greater than about 0.02 kg, preferably greater than about 0.05, and more
preferably greater than about 0.10. Preferably, the hardness value of the skin
care
active component should not be greater than about 5.00 kg., more preferably
about
4.00 kg, most preferably 3.00, because hardness levels beyond this point can
negatively affect deposition of the ingredients in the skin care active
component to
the skin or hair.
Hardness Test
The hardness value is measured by a test traditionally used to measure bar
soap hardness. A Chatillon force gauge is employed to measure the hardness
value
of a 5-8 oz. sample of the skin care active component. Several readings are
taken,
3o each on a fresh sample, to obtain an average value. The Chatillon force
gauge model
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
62
no. DFIS 100 is manufactured by Chatillon Corporation which is located in
Greensboro, North Carolina.
Materials Used to Increase Hardness Value
The cleansing articles of the present invention may comprise a hardening
material used in combination with the skin care actives comprising the skin
care
active component described hereinbefore. Many materials can be used as both a
conditioning agent and as a lipid hardening material. In fact, any solid
conditioning
agent, described hereinbefore, may be used as a hardening material. The amount
of
the hardening material needed to achieve the minimum hardness value of 0.02
kg. is
dependent upon the particular material used and can be easily determined by
one of
ordinary skill in the art. The hardening material can be used as an individual
hardening material or a combination of hardening materials, and is included at
concentrations ranging from about 0.1 % to about 99.9%, preferably from about
0.5%
to about 75%, more preferably from about 1 % to about 50%, even more
preferably
from about 2% to about 25%, by weight of the skin care active component.
As used herein the term "hardening materials" refers to those materials which
have a melting point above about 30°C, preferably above about
30°C to about 250°
C, more preferably from about 37°C to about 100°C, even more
preferably from
about 37°C to about 80°C.
Any material may be used to increase the hardness value of the skin care
active component provided that the following criteria are met: (i) the
material must
be soluble in the skin care actives of the skin care active component and (ii)
the
material must have a melting point of greater than 20° C (e.g., be a
solid at room
temperature). Examples of suitable hardening materials include, but are not
limited
to, petrolatum, highly branched hydrocarbons, fatty alcohols, fatty acid
esters,
vegetable oils, hydrogenated vegetable oils, polypropylene glycols, alpha-
hydroxy
fatty acids, fatty acids having from about 10 to about 40 carbon atoms, alkyl
amides
of di and/or tri-basic carboxylic acids, n-acyl amino acid derivatives, and
mixtures
thereof. Hardening materials useful in the present invention are further
described in
U.S. Patent No. 4,919,934, to Deckner et al., issued April 24 1990, which is
incorporated herein by reference in its entirety.
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
63
Suitable highly branched hydrocarbons for use herein include hydrocarbon
compounds having from about 17 to about 40 carbon atoms. Nonlimiting examples
of these hydrocarbon compounds include squalane, cholesterol, lanolin,
docosane
(i.e. a C22 hydrocarbon), and isoparaffins.
Suitable fatty alcohols for use herein include monohydric alcohols,
ethoxylated fatty alcohols, and fatty alcohol esters, excluding the
,ethoxylated fatty
alcohols and fatty alcohol esters useful as emulsifiers herein. Specific
examples of
commercially available fatty alcohols include, but are not limited to, UNILIN
550,
L1NILIN 700, UNILIN 425, tJNILIN 400, L1NILIN 350, AND UNILIN 325, all of
to which are available from Petrolite. Suitable ethoxylated fatty alcohols
include, but
are not limited, UNITHOX 325, UNITHOX 400, AND I1NITHOX 450,
UNITHOX 480, UNITHOX 520, UNITHOX 550, UNITHOX 720, UNITHOX
750, all of which are available from Petrolite. Non-limiting examples of
suitable
esters of fatty alcohols include tri-isostearyl citrate, ethyleneglycol di-12-
hydroxystearate, tristearylcitrate, stearyl octanoate, stearyl heptanoate,
trilaurylcitrate.
Suitable fatty acid esters for use herein include ester waxes, monoglycerides,
diglycerides, triglycerides and mixtures thereof. Non-limiting examples of
suitable
ester waxes include stearyl stearate, stearyl behenate, palmityl stearate,
stearyl
octyldodecanol, cetyl esters, cetearyl behenate, behenyl behenate, ethylene
glycol
distearate, ethylene glycol dipalmitate, and beeswax. Examples of commercial
ester
waxes include KESTER waxes from Koster Keunen, CRODAMOL SS from Croda
and DEMALCARE SPS from Rhone Poulenc.
Vegetable oils and hydrogenated vegetable oils which are solid or semi-solid
at ambient temperatures of from about 20°C to about 25°C are
also useful herein as
hardening materials. Examples of suitable vegetable oils and hydrogenated
vegetable oils include butterfat, chicken fat, goose fat, horse fat, lard
(fatty tissue)
oil, rabbit fat, sardine oil, tallow (beef), tallow (mutton), Chinese
vegetable tallow,
babassu oil, cocoa butter, coconut oil; palm oil, palm kernal oil,
hydrogenated
3o safflower oil, hydrogenated castor oil, hydrogenated coconut oil,
hydrogenated
cottonseed oil, hydrogenated menhaden oil, hydrogenated palm kernel oil,
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99100635
64
hydrogenated palm oil, hydrogenated peanut oil, hydrogenated soybean oil,
hydrogenated rapeseed oil, hydrogenated linseed oil, hydrogenated rice bran
oil,
hydrogenated sesame oil, hydrogenated sunflower seed oil, derivatives thereof
and
mixtures thereof.
Examples of suitable alpha-hydroxy fatty acids and fatty acids having from
about 10 to about 40 carbon atoms include 12-hydroxystearic acid, 12-
hydroxylauric
acid, 16-hydroxyhexadecanoic acid, behenic acid, eurcic acid, stearic acid,
caprylic
acid, lauric acid, isostearic acid, and mixtures thereof. Examples of some
suitable
fatty acids are further described in U.S. Patent 5,429,816, issued to
Hofrichter et al.
l0 on July 4, 1995; and U.S. Patent 5,552,136, issued to Motley on September
3, 1996,
which descriptions are incorporated herein by reference.
Suitable alkyl amides of di and/or tri-basic carboxylic acids for use herein
include disubstituted or branched monoamides, monosubstituted or branched
diamides, triamides, and mixtures thereof. Some specific examples of alkyl
amides
of di- and tri-basic carboxylic acids include, but are not limited to, alkyl
amides of
citric acid, tricarballylic acid, aconitic acid, nitrilotriacetic acid and
itaconic acid
such as 1,2,3-propane tributylamide, 2-hydroxy-1,2,3-propane tributylamide, 1-
propene-1,2,3-trioctylamide, N,N',N"-tri(methyldecylamide)amine, 2 docecyl-
N,N'-
dibutylsuccinamide, and mixtures thereof. Other suitable amides include the n-
acyl
2o amino acid derivatives described in U.S. Patent 5,429,816, issued to
Hofrichter et al.
on July 4, 1995.
Also suitable for use in the present invention are waxes having a HLB of
from about 1 to about 10, preferably from about 6 and most preferably from
about 5.
The HLB (short for "Hydrophile-Lipophile Balance") value system is fully
described, and values for various materials are provided, in the publication
The
Time-Saving Guide to Emulsifier Selection (published by ICI Americas Inc.,
Wilmington, Del.; 1984), the disclosure of which are incorporated herein by
reference in their entirety.
Useful ester waxes include C 10-C40 fatty acid, diesters, of C 10-C40 fatty
3o acids where the alcohol is propylene glycol, ethylene glycol, polyethylene
glycol,
polypropylene glycol, polyglycerin, or glycerin, triglycerides or diglycerides
of C10
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99100635
6s
C4p fatty acids, pentaerythritol tri- ortetra- esters of C 10-C40 fatty acids,
C 10-C40
fatty acids of sorbitan triesters, C 10-C40 fatty acids of sucrose polyesters
having 3-8
moles of substitution, myristyl myristate, paraffin, synthetic waxes such as
Fischer-
Tropsche waxes, microcrystalline waxes, castor wax, partially hydrogenated
s vegetable oils, behenyl behenrate and myristyl propionate and mixtures
thereof.
Useful diester waxes include SYNCHROWAX ERL-C (C18-36 acid
glycolester) (available from Croda) and propylene glycol diester waxes
including
ethylene glycol distearate and glycol distearate. Useful triglyceride waxes
include
shea butter, cocoa butter, SYNCHROWAX HGL-C (C18-36 acid triglyceride),
t o SYNCHROWAX HRC (tribehenin), SYNCHROWAX HRS-C [tribehenin (and)
calcium behenate) (all available from Croda Inc.), tristearin, trimyristate
and fully
hydrogenated vegetable oils and mixtures thereof. Preferred is a mixture of
diester
and triglyceride waxes in a ratio of from about 5:1 to about l :l and more
preferably
from about 4:1 to about 1:1.
1s Waxes useful in the compositions of this invention are disclosed in the
following, all of which are incorporated by reference herein in their
entirety: U.S.
Pat No. 5,219,558 to Woodin, Jr. et al., issued June 15, 1993; U.S. Pat. No.
4,049,792, to Elsnau, issued Sept. 20, 1977; U.S. Pat. No.4,1 s 1,272, to
Geary et al.,
issued Apr. 24, 197s; U.S. Pat. No. 4,229,432, to Geria, issued Oct. 21, 1980;
U.S.
2o Pat No. 4,280,994, to Turney, issued Jul. 28, 1981; U.S. Pat. No.
4,126,679, to Davy
et al., issued Nov. 21, 1978; and European Patent Application Publication
Number
117,070 to May, published Aug. 29, 1984, "The Chemistry and Technology of
Waxes", A. H. Warth, 2nd Edition, reprinted in 1960, Reinhold Publishing
Corporation, pp. 391-393 and 421; "The Petroleum Chemicals Industry", R. F.
2s Goldstein and A. L. Waddeam, 3rd Edition ( 1967), E &F.N. Span Ltd., pp. 33-
40;
"The Chemistry and Manufacture of Cosmetics", M. G. DeNavarre, 2nd Edition
(1970), Van Nostrand & Company, pp. 354-376; and in "Encyclopedia of Chemical
Technology:, Vol. 24, Kirk-Othmer, 3rd Edition (1979) pp. 466-481.
Additional non-limiting examples of useful hardening materials are those
30 selected from the group consisting of sorbitan esters, glyceryl esters,
polyglyceryl
esters, methyl glucose esters, sucrose esters, ethoxylated fatty alcohols,
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
66
hydrogenated castor oil ethoxylates, sorbitan ester ethoxylates, polymeric
emulsifiers, and silicone emulsifiers.
Sorbitan esters are useful in the present invention. Preferable are sorbitan
esters of C 16-C22 saturated, unsaturated and branched chain fatty acids.
Because of
the manner in which they are typically manufactured, these sorbitan esters
usually
comprise mixtures of mono-, di-, tri-, etc. esters. Representative examples of
suitable sorbitan esters include sorbitan monooleate (e.g., SPAN~ 80),
sorbitan
sesquioleate (e.g., ARLACEL~ 83), sorbitan monoisostearate (e.g., CRILL~ 6
made by Croda), sorbitan stearates (e.g., SPAN~ 60), sorbitan triooleate
(e.g.,
SPAN~ 85), sorbitan tristearate (e.g., SPAN~ 65), sorbitan dipalmitates (e.g.,
SPAN~ 40}, and sorbitan isostearate. Sorbitan monoisostearate and sorbitan
sesquioleate are particularly preferred emulsif ers for use in the present
invention.
Other suitable hardeners for use in the present invention include, but is not
limited to, glyceryl monoesters, preferably glyceryl monoesters of C 16-C22
saturated, unsaturated and branched chain fatty acids such as glyceryl oleate,
glyceryl monostearate, glyceryl monopalmitate, glyceryl monobehenate, and
mixtures thereof; polyglyceryl esters of C 16-C22 saturated, unsaturated and
branched chain fatty acids, such as polyglyceryl-4 isostearate, polyglyceryl-3
oleate,
diglycerol monooleate, tetraglycerol monooleate and mixtures thereof; methyl
2o glucose esters, preferably methyl glucose esters of C 16-C22 saturated,
unsaturated
and branched chain fatty acids such as methyl glucose dioleate, methyl glucose
sesquiisostearate, and mixtures thereof; sucrose fatty acid esters, preferably
sucrose
esters of C 12-C22 saturated, unsaturated and branched chain fatty acids such
as
sucrose stearate, sucrose trilaurate, sucrose distearate (e.g., CRODESTA~ F
10), and
mixtures thereof; C12-C22 ethoxylated fatty alcohols such as oleth-2, oleth-3,
steareth-2, and mixtures thereof; hydrogenated castor oil ethoxylates such as
PEG-7
hydrogenated castor oil; sorbitan ester ethoxylates such as PEG-40 sorbitan
peroleate, polysorbate-80, and mixtures thereof; polymeric emulsifiers such as
ethoxylated dodecyl glycol copolymer; and silicone emulsifiers such as
laurylmethicone copolyol, cetyldimethicone, dimethicone copolyol, and mixtures
thereof.
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
67
Other useful hardeners include, but are not limited to, phosphatidyl cholines
and phosphatidyl choline-containing compositions such as lecithins; long chain
C16-
C22 fatty acid salts such as sodium stearate; long chain C 16-C22 dialiphatic,
short
chain C1-C4 dialiphatic quaternary ammonium salts such as ditallow dimethyl
ammonium chloride and ditallow dimethyl ammonium methylsulfate; long chain
C 16-C22 dialkoyl(alkenoyl)-2-hydroxyethyl, short chain C 1-C4 dialiphatic
quaternary ammonium salts such as ditallowoyl-2-hydroxyethyl dimethyl
ammonium chloride; the long chain C 16-C22 dialiphatic imidazolinium
quaternary
ammonium salts such as methyl-I-tallow amido ethyl-2-tallow imidazolinium
methylsulfate and methyl-I-oleyl amido ethyl-2-oleyl imidazoIinium
methylsulfate;
short chain C I -C4 dialiphatic, long chain C 16-C22 monoaliphatic benzyl
quaternary
ammonium salts such as dimethyl stearyl benzyl ammonium chloride, and
synthetic
phospholipids such as stearamidopropyl PG-dimonium chloride (PHOSPHOLIPID
PTS from Mona industries).
Other Optional Ingredients
The compositions of the present invention can comprise a wide range of
other optional components. These additional components should be
pharmaceutically acceptable. The CTFA Cosmetic Ingredient Handbook, Second
Edition, 1992, which is incorporated by reference herein in its entirety,
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. Nonlimiting examples of functional classes of ingredients
are
described at page 537 of this reference. Examples of these and other
functional
classes include: abrasives, absorbents, anticaking agents, antioxidants,
vitamins,
2s binders, biological additives, buffering agents, bulking agents, chelating
agents,
chemical additives, colorants, cosmetic astringents, denaturants, drug
astringents,
film formers, fragrance components, opacifying agents, pH adjusters,
preservatives,
propellants, and reducing agents.
Also useful herein are aesthetic components such as fragrances, pigments,
colorings, essential oils, skin sensates, and astringents.
METHODS OF MANUFACTURE
CA 02332948 2000-11-21
WO 99/55303 PCT/1B99/00635
68
The disposable, single use personal care cleansing articles of the present
invention are manufactured by separately or simultaneously adding onto or
impregnating into the water insoluble substrate (e.g., in any permutation) a
lathering
surfactant, a skin care active component, and preferably a deposition aid. The
optional conditioning component can also be separately or simultaneously added
onto or impregnated into the substrate with the other three components. By
"separately" is meant that the surfactants and the skin care active component
can be
added sequentially, in any order without first being combined together. By
"simultaneously" is meant that the surfactants and conditioning agents can be
added
at the same time, with or without first being combined together.
Preferably, the lathering surfactant and the skin care active component are
added separately to prevent emulsification of the skin care actives. This
separate
treatment of the substrate also applies to the optional conditioning
component. In
this preferred embodiment, the optional deposition aid can be (i) mixed with
the
lathering surfactant before treating the substrate with such a mixture, (ii)
mixed with
the skin care active component before treating the substrate with such a
mixture, or
(iii) separately added onto or impregnated into the substrate. However, if the
surfactant is added via a dip/nip process, it is preferred to added the skin
care active
component and any optional components to the substrate after application of
the
2o surfactant. Despite the order of treatment, excess surfactant, skin care
active
component, and/or deposition aid should be removed (e.g., by a nipping
process).
Thereafter, the treated substrate should be dried by conventional means. The
surfactant, skin care component, deposition aid, and any optional ingredients
can be
added onto or impregnated into the substrate by any means known to those
skilled in
the art: for example, by spraying, laser printing, splashing, dipping,
soaking, or
coating (e.g., extrusion coating and slot coating).
When water or moisture is used or present in the manufacturing process, the
resulting treated substrate is then dried so that it is substantially free of
water. The
treated substrate can be dried by any means known to those skilled in the art.
3o Nonlimiting examples of known drying means include the use of convection
ovens,
radiant heat sources, microwave ovens, forced air ovens, and heated rollers or
cans.
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
69
Drying also includes air drying without the addition of heat energy, other
than that
present in the ambient environment. Also, a combination of various drying
methods
can be used.
METHODS OF MAINTAINING THE SKIN CARE ACTIVES SUBSTANTIALLY
ON THE SURFACE OF THE SUBSTRATE
The products of the present invention effectively and efficiently deliver skin
care actives to the skin and hair by maintaining the skin care actives
substantially on
the surface of the substrate. The following subsections discuss in further
detail the
processes and compositional improvements which allow a Surface to Saturation
1o Ratio of greater than or equal to about 1.25. All of the following
processing and
compositional improvements can be used individually or in combination to
maintain
the skin care actives substantially on the surface. The term "chemical
component,"
as used herein, means the skin care active or a combination of the
conditioning agent
and the skin care active.
Chemical Treatment of the Substrate
One method of substantially maintaining the chemical component on the
surface of the substrate is by chemically treating the substrate or the fibers
of the
substrate with either a hydrophobic or hydrophilic substance. Choosing the
appropriate substance (hydrophobic or hydrophilic) is dependent on the
chemical
component that is meant to be deposited. For example, if a oil soluble
conditioning
agent is to be deposited onto the skin or hair, the substrate or its fibers
would
typically be treated with a hydrophilic substance, and vice versa. Because
most
substrates are hydrophobic by their nature, e.g., usually derived from
polyolefins,
this section will concentrate on hydrophilic chemical treatment of the
substrate.
Any of a wide variety of surfactants, including ionic and nonionic
surfactants, may be employed to hydrophilically modify the substrate. Suitable
surfactants may be internal modifiers, e.g., the modifying compounds are added
to
the polymer composition prior to spinning or forming fibers, or topical
modifiers,
e.g., the modifying compounds are topically applied during or subsequent to
the
formation of fibers or nonwoven webs. An internal m(lClifc'.atinn nrnracc ;c
disclosed in U.S. Patent No. 4,578,414 to Sawyer et al, and a topical
modification
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
process is disclosed in U.S. Patent No. 5,057,361 to Sayovitz et al., both
references
incorporated herein in their entirety.
Nonlimiting examples of suitable surfactants include silicone based
surfactants, e.g., polyalkelene-oxide modified polydimethyl siloxane;
fluoroaliphatic
5 surfactants, e.g., perfluoroalkyl polyalkylene oxides; and other ~
surfactants, e.g.,
actyl-phenoxypolyethoxy ethanol nonionic surfactants, alkylaryl polyether
alcohols,
and polyethylene oxides. Commercially available surfactants suitable for the
present
invention include various polyethylene oxide) based surfactants available
under the
tradename TRITON, e.g., grade X-102, from Rohm and Haas Corp.; various
1 o polyethylene glycol based surfactants available under the tradename
EMEREST,
e.g., grades 2620 and 2650, from Emery Indust.; various polyalkylene oxide
modified polydimethylsiloxane based surfactants available under the tradename
SILWET, e.g., grade Y12488, from OSI Specialty Chemicals; and alkenyl
succinamide surfactants available under the tradename LUBRIZOL, e.g., grade
15 OS85870, from Lubrizol Corp.; and polyoxyalkylene modified fluoroaliphatic
surfactants available from Minnesota Mining and Manufacturing Co. The amount
of
surfactants required and the hydrophilicity of the modified substrate or
fibers of the
substrate for each application will vary depending on the type of surfactant
selected
and the component polymers used. In general, the surfactant may be added,
2o topically or internally, in the range of from about 0.1 to about 5%,
preferably from
about 0.3% to about 4%, by weight of the substrate or the fibers of the
substrate.
Increasin~~ ViscositX
Another method of substantially maintaining the chemical component on the
surface of the substrate is by increasing the viscosity before application
onto the
2s substrate. This prevents the saturation of the substrate with the chemical
component.
Generally there are two methods for increasing the viscosity of the chemical
component: (i) application onto the substrate at the transition temperature of
the
chemical component; and (ii) introducing a thickener to the chemical component
mixture before application onto the substrate. A combination of these methods
is
3o preferable.
Phase transition temperature application to the substrate
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
71
One method of maintaining the chemical component on the surface of the
substrate is to apply the chemical component to the substrate at the phase
transition
temperature of the chemical component. This method can be employed with any
chemical component wherein the phase transition temperature of the chemical
component is above about 35oC (e.g., viscous at room temperature). Phase
transition temperature is defined, as used herein, as the temperature at which
the
chemical component transforms from a fluid, liquid state to a viscous state.
In
essence, this method applies the chemical component at the temperature at
which the
chemical component becomes viscous from a fluid liquid state during the
cooling
to process.
Typically, the chemical component is applied onto the substrate by melting
or heating. Alternatively, the chemical component can be heated and dissolved
into
a solvent before application to the substrate. However, some chemical
components
may be viscous yet fluid enough to be applied without heating. If a chemical
component has a transition temperature at about room temperature or slightly
above
room temperature the other methods within this section must be employed to
maintain the chemical component on the surface of the substrate. The
transition
temperatures (also known as melting point) of most chemicals may be easily
obtained from the Merck Index, Tenth Edition (1983) and the CTFA Cosmetic
2o Ingredient Handbook, Second Edition, (1992), which are incorporated by
reference
herein in their entirety.
A corollary to transition temperature application to the substrate is
supercooling the chemical component upon application to the substrate. By
supercooling is meant that the cooling rate is artificially increase above the
normal
ambient temperature cooling rate. This provides the dual benefit of having
fluidity
of the chemical component during processing yet reaching the phase transition
temperature before the substrate is saturated by the chemical component. This
method would be used when a chemical component is viscous and plastic at room
temperature.
3o Thickening Agent: If the chemical component is a liquid at room
temperature (e.g., not viscous), the chemical component will not remain
primarily on
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99J00635
72
the surface of the substrate. Instead, the chemical component will tend to
migrate
and flow into the void volume of the substrate. The present method provides a
solution by introducing a thickening agent into the chemical component. This
increases the viscosity of the chemical component thereby achieving an
equivalent
result as phase transition temperature application to the substrate. Because
the
viscosity of the chemical component is effectively increased, it remains
substantially
on the surface of the substrate without saturating the substrate. Generally,
the
thickening agent must be viscous at room temperature, and it must be miscible
in the
chemical component. Phase transition temperatures and suitable viscosities of
to thickening agent will vary drastically upon the particular thickener.
However,
typically, the phase transition temperature of the thickening agent must be
greater
than about 35oC, preferably greater than about 40oC.
Generally, anything that is viscous at room temperature can be a thickener.
The CTFA Cosmetic Ingredient Handbook, Second Edition, (1992), which is
incorporated by reference herein in its entirety, discloses many appropriate
thickeners. In fact, any conditioning agent, disclosed above, that is more
viscous
than the chemical component and is miscible in the chemical component can be
an
appropriate thickener.
Nonlimiting examples of useful thickening agents of the present invention
2o are selected from the group consisting of fatty alcohols, fatty acids,
fatty alcohol
ethoxylates having an average degree of ethoxylation ranging from 2 to about
30,
sorbitan esters, glyceryl esters, polygIyceryl esters, methyl glucose esters,
sucrose
esters, sorbitan ester ethoxylates, natural and synthetic waxes, polyacrylic
and
hydrophobically modified polyacrylic resins, starches, gums, cellulose ethers,
polycationic polymers, nonionic polymers, polyethylene glycols (PEG), and
mixtures thereof.
Nonlimiting examples of useful thickening agents in the present invention
include stearic acid, behenic acid, stearyl alcohol, cetyl alcohol, sorbitan
monooleate, sorbitan sesquioleate, sorbitan monoisostearate, sorbitan
stearates,
3o sorbitan triooleate, sorbitan tristearate, sorbitan dipalmitates, sorbitan
isostearate,
glyceryl oleate, glyceryl monostearate, glyceryl monopalmitate, glyceryl
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
73
monobehenate, polyglyceryl-4 isostearate, polyglyceryl-3 oleate, diglycerol
monooleate, tetraglycerol monooleate, methyl glucose dioleate, methyl glucose
sesquiisostearate, sucrose stearate, sucrose trilaurate, sucrose distearate
oleth-2,
oleth-3, steareth-2, PEG-40 sorbitan peroleate, Polysorbate-80, beeswax,
polyethylene wax, CARBOPOL, PEMULEN, corn starch, potato starch, tapioca,
guar gum, gum arabic, hydroxypropyl cellulose, hydroxyethyl cellulose,
carboxymethyl cellulose, RETEN 201, KYMENE 557H~, ACCO 7112,
CARB O WAX.
Nonuniform Application to the Substrate
to Another method of substantially maintaining the chemical component on the
surface of the substrate is by applying the chemical component nonuniformly to
the
surface of the substrate. By "nonuniform" is meant that the amount, pattern of
distribution, etc. of the chemical component can vary over the surface of the
substrate. For example, some portions of the surface of the substrate can have
greater or lesser amounts of the chemical component, including portions of the
surface that do not have any chemical component.
Order of At~plication of Ingredients to the Substrate
Another method of substantially maintaining the chemical component on the
surface of the substrate is by determining the order of application of
ingredients to
2o the substrate. Generally, the best results are obtained when the chemical
component
is added onto a dry substrate. Thus, applying the lathering surfactant first,
and then
drying the surfactant treated substrate before application of the chemical
component
will greatly enhance the delivery of the chemical component.
METHODS OF CLEANSING AND TREATING THE SKIN OR HAIR
The present invention also relates to a method of cleansing and treating the
skin or hair with a personal cleansing article of the present invention. These
methods comprise the steps of wetting with water a substantially dry,
disposable,
single use personal cleansing article comprising a water insoluble substrate,
a
lathering surfactant, and a skin care active component, and contacting the
skin or
3o hair with such wetted article. In further embodiments, the present
invention is also
useful for delivering various conditioning agents to the skin or hair.
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
74
The articles of the present invention are substantially dry and are intended
to
be wetted with water prior to use. The article is wetted by immersion in water
or by
placing it under a stream of water. Lather is generated from the article by
mechanically agitating and/or deforming the article either prior to or during
contact
of the article with the skin or hair. The resulting lather is useful for
cleansing and
treating the skin or hair. During the cleansing process and subsequent rinsing
with
water, the skin care actives and optional ingredients are deposited onto the
skin or
hair. Deposition of skin care actives and conditioning ingredients are
enhanced by
the physical contact of the substrate with the skin or hair.
METHOD OF CONSISTENTLY DEPOSITING SKIN CARE ACTIVES AND
ANY CONDITIONING INGREDIENTS ONTO THE SKIN OR HAIR
The articles of the present invention are useful for consistently depositing
the
skin care actives of the present invention to the skin or hair. In further
embodiments
where a conditioning agent is present, the compositions are also useful for
consistently depositing the conditioning agent to the skin or hair.
The articles of the present invention have a deposition consistency of greater
than about 60%, preferably greater than about 65%, more preferably greater
than
about 70%, and most preferably greater than about 75%.
The deposition consistency measurement is the quotient obtained from
2o dividing the deposition of skin care actives via "non-ideal lathering and
use" by
deposition of skin care actives via "ideal lathering and use." Non-ideal
lathering, as
used herein, means that lathering is achieved by rubbing the surface of the
article
containing the skin care actives and then contacting the skin or hair with the
same
surface. This causes inefficient deposition of the skin care actives because
some of
the skin care actives become emulsified by the surfactant. Ideal lathering, as
used
herein, means that lathering is achieved by rubbing the surface of the article
not
containing skin care actives and then contacting the skin or hair with the
surface
containing the skin care actives. The same reference points would apply if
both
surfaces of the substrate are treated with the skin care actives (e.g.
deposition
3o obtained from lathering and contacting the skin with the same lathered
surface
containing emulsified skin care actives versus contacting the skin with the
non-
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
lathered surface which contains non-emulsified skin care actives). Deposition
consistency is maximized when the hardness value of the skin care active
component
is greater than about 0.02 kg.
Quantification of the skin care actives deposited on the skin or hair can be
5 measured using a variety of standard analytical techniques well known to the
chemist of ordinary skill in the art. Such methods include for instance
extraction of
an area of the skin or hair with a suitable solvent followed by analysis by
chromatography (i.e. gas chromatography, liquid chromatography, supercritical
fluid
chromatography, etc.), IR spectroscopy, UVNIS spectroscopy, mass spectrometry,
1 o etc. Direct measurements can also be made on the skin or hair by
techniques such as
IR spectroscopy, UVNIS spectroscopy, opacity measurements, fluoresce
spectroscopy, ESCA spectroscopy, and the like.
In a typical method for measuring deposition, a article of the present
invention is wetted with water and squeezed and agitated to generate a lather.
The
15 article is then rubbed for approximately 15 seconds on a site,
approximately about
25 cm2 to about 300 cm2, preferably about 50 cm2 to about 100 cm2, on the skin
or
head which has been demarcated using an appropriate indelible marker. The site
is
then rinsed for approximately 10 seconds and then allowed to air dry for
approximately 10 minutes. The site is then either extracted and the extracts
2o analyzed, or analyzed directly using any techniques such as those
exemplified above.
EXAMPLES
The following examples further describe and demonstrate embodiments within
the scope of the present invention. In the following examples, all ingredients
are
listed at an active Level. The examples are given solely for the purpose of
illustration
25 and are not to be construed as limitations of the present invention, as
many
variations thereof are possible without departing from the spirit and scope of
the
invention.
Ingredients are identified by chemical or CTFA name, and all weights are in
percent actives.
3o Examples (1-5~
I. The Surfactant Phase
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
76
In a suitable vessel, the following ingredients are mixed at room temperature.
Apply heat if necessary to disperse completely.
In;~redients Wei,~ht
Percent
ExampleExample Example ExampleExample
1 2 3 4 . 5
Water QS 100 QS 100 QS 100
QS 100 QS 100
Polyquaternium-10 0.25 -- -- __ __
PEG 14M 0.5 -- -- 0.5 --
Hydroxypropyltrimonium-- -- -- -- 0.5
Chloride
Hydroxyelthylcellulose-- 0.25 -- -_ __
Guar Gum -- 0.25 -- -_ __
While the above mixture is being mixed the following ingredients are added
to the mixture.
Disodium EDTA 0.10 0.10 0.10 0.10 0.10
Sodium Lauroyl 3.33 3.33 3.33 3.33 3.33
Sarcosinate
Sodium -- -- -- -- 3.33
Lauroamphoacetate
Cocamidopropyl Betaine3.33 3.33 3.33 3.33 --
Decyl Polyglucoside3.33 3.33 3.33 3.33 3.33
Methyl Paraben 0.25 0.25 0.25 0.25 0.25
Phenoxyethanol 0.3 0.3 0.3 0.3 0.3
Benzyl Alcohol 0.3 0.3 0.3 0.3 0.3
s In a separate mixing vessel add the following. Mix (with heat to 40C if
necessary) until propyl paraben is dissolved.
Water 2.0 2.0 2.0 2.0 2.0
Butylene Glycol 2.0 2.0 2.0 2.0 2.0
Propyl Paraben 0.15 0.15 0.1 0.15 0.1 S
S
Add this mixture to the first mixing vessel. Apply 1.5 - 2.5 g of the
resultant
mixture to a substrate, as described herein, and then dry.
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
77
II. The Skin Care Active phase
In a suitable vessel, the following ingredients are mixed at room temperature.
Apply heat if necessary to disperse completely.
Water QS 100 QS 100 QS I QS I QS 100
00 00
Glycerin 60.0 40.0 U.0 50.0 30.0
Dex Panthenol 1.0 4.0 2.0 4.0 4.0
Urea __ __ __ 2.0 __
PEG-30 -- 20.0 25.0 -- 5.0
Lactic Acid __ 4,0 __ --
Dihydroxyacetone 4.0 -- __ __
Niacinamide -- 5.0 10.0
Arbutin -- 3.0 _ -- __
kojic acid -- 3.0 -- -_
allantoin -- 2.0 2.0
Propylene glycol -- 5.0 30.0 -- --
Polyquaternium-10 -- 3.0 _.. __ __
PEG 14M 5.0 3.0 3.0 3.0 5.0
Hydroxyelthylcellulose-- -- 2.0 2.0 --
Guar Gum -- -- -- 1.0 --
Apply 0.10 to I .0 grams of this phase to the dry substrate already containing
the materials from the Surfactant Phase. Allow anv added water rr, ~,-.. The
resulting cleansing and article is used by wetting with water and is useful
for
cleansing the skin or hair and for depositing the skin care active component
onto the
skin or hair. Alternatively, the Skin Care Active Phase can be added onto or
impregnated into the insoluble substrate before the Surfactant Phase, as long
as the
I o surfactant is not added via dip/nip process. This alternative process is
possible when
using extrusion or gravure printing application methods.
Examples 6-10
I. Surfactant Phase
In a suitable vessel, the following ingredients are mixed at room temperature.
Apply heat if necessary to disperse completely.
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
78
Example ExampleExample ExampleExample
6 7 8 9 10
Water QS 100 QS 100 QS 100 QS 100 QS 100
Polyquaternium-10 -- -- -- 0.25 --
PEG 14M 0.5 -- -- 0.5 --
Hydroxypropyltrimonium-- -- -- -- ~ 0.5
Chloride
Hydroxyelthylcellulose-- 0.25 -- __ __
Guar Gum -- 0.25 -- -- _-
While the above mixture is being mixed the following ingredients are added
to the mixture.
Disodium EDTA 0.10 0.10 0.10 0.10 0.10
Sodium Lauroyl 3.33 3.33 3.33 3.33 3.33
Sarcosinate
Sodium -- -- -- -- 3.33
Lauroamphoacetate
Cocamidopropyl Betaine3.33 3.33 3.33 3.33 --
Decyl Polyglucoside3.33 3.33 3.33 3.33 3.33
Methyl Paraben 0.25 0.25 0.25 0.25 0.25
Phenoxyethanol 0.3 0.3 0.3 0.3 0.3
Benzyl Alcohol 0.3 0.3 0.3 0.3 0.3
In a separate mixing vessel add the following. Mix (with heat to 40C if
necessary) until propyl paraben is dissolved.
Water 2.0 2.0 2.0 2.0 2.0
Butylene Glycol 2.0 2.0 2.0 2.0 2.0
Propyl Paraben 0.15 0.15 0.15 0.1 0.15
S
Add this mixture to the first mixing vessel. Apply 1.5 - 2.5 g of the
resultant
mixture to a substrate, as described herein, and then dry.
II: Skin Care Active Phase
In a suitable vessel, the following ingredients are mixed with heat until
molten (between 75-115oC.
SEFA* Cottonate 48.00 43.00 46.00 48.00 48.00
~
SEFA* Behenate 12.00 -- _- __ __
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
79
Petrolatum 10.00 10.00 10.00 10.00 10.00
Tribehenin 5.00 5.0 5.0 5.0 5.0
Polyethylene Wax -- 9.0 9.0 9.0 -
Paraffin -- -- -- -- 12.00
Synthetic Beeswax -- 3.0 3.0 3.0 --
C10-C30 18.00 23.00 23.00 23.00 20.00
Cholesterol/Lanosterol
Esters
Vitamin E Acetate -- 2.0 2.0 2.0 2.0
~' ~~;rA 1s an acronym for sucrose esters of fatty acids
Add the following ingredients to the above mnltPn mitt"rP nn..P "";f",..r,
Retinyl Palmitate -- -- 2.0 -- 1.0
PPG-15 Stearyl Ether5.0 -- -- _-
*
Salicylic Acid 2.0 -- -- __
*
Titanium Dioxide -- 5.0 -- -- 2.0
~ w .r__ m_
....~ um~c uymcm~ umu 5a11Cy11C aCIQ 1S Q1SSOIVed.
Apply 0.05 - 0.75 grams of this phase to the substrate already containing the
materials from the Surfactant phase. This Skin Care Active Phase should be
applied
in a Iiquid/molten state and then cooled. The resulting cleansing article is
used by
wetting with water and is useful for cleansing the skin or hair and for
depositing the
1 o skin care active component onto the skin or hair in a consistent manner.
Alternatively, the Skin Care Active Phase can be added onto or impregnated
into the
insoluble substrate before the Surfactant Phase, as Lang as the surfactant is
not added
via dip/nip process. This alternative process is possible when using extrusion
or
gravure printing application methods.
Examples 11-15
I. Surfactant Phase
In a suitable vessel, the following ingredients are mixed at room temperature.
Apply heat if necessary to disperse completely.
In redients Weight
Percent
ExampleExample Example ExampleExample
1 2 3 4 5
Water QS 100 QS 100 QS 100 QS 100 QS 100
Polyquaternium-10 0.25 -- -- __ -_
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
PEG 14M 0.5 -- -- 0.5 --
Hydroxypropyltrimonium- -- -- -- 0.5
Chloride
Hydroxyelthylcellulose-- 0.25 ..- __ __
Guar Gum __ 0.25 -- __ __
While the above mixture is being mixed the following ingredients are added
to the mixture.
Disodium EDTA 0.10 0.10 0.10 0.10 0.10
Sodium Lauroyl 3.33 3.33 3.33 3.33 3.33
Sarcosinate
Sodium -- -- -- -- 3.33
Lauroamphoacetate
Cocamidopropyl Betaine3.33 3.33 3.33 3.33 --
Decyl Polyglucoside3.33 3.33 3.33 3.33 3.33
Methyl Paraben 0.25 0.25 0.25 0.25 0.25
Phenoxyethanol 0.3 0.3 0.3 0.3 0.3
Benzyl Alcohol 0.3 0.3 0.3 0.3 0.3
In a separate mixing vessel add the following. Mix (with heat to 40
°C if
necessary) until the propyl paraben is dissolved.
Water 2.0 2.0 2.0 2.0 2.0
Butylene Glycol 2.0 2.0 2.0 2.0 2.0
Propyl Paraben 0.15 0.15 0.15 0.15 0.15
Add
this
mixture
to
the
first
mixing
vessel.
Apply
1.5
-
2.5
g
of
the
resultant
mixture to a substrate, as described herein, and then dry.
II. The Skin Care Emulsion Phase
In a suitable vessel, the following ingredients are mixed at with heat until
to uniform (75-115 °C).
SEFA* Cottonate 27.36 25.36 46.00 48.00 48.00
SEFA* Behenate __ __ -_ __ --
Petrolatum 5.7 5.7 10.00 10.00 10.00
Tribehenin 2.85 2.85 5.0 5.0 5.0
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
81
Polyethylene Wax 5.13 5.13 9.0 9.0 __
Paraffin -- -- - -- 12.00
Synthetic Beeswax 1.7I 1.71 3.0 3.0 --
C 10-C30 13. 13.1 23.00 23.00 20.00
Cholesterol/LanosterolI
Esters
Vitamin E Acetate 1.1 1.15 2.0 2.0 2.0
S
Decaglyceryl Dipalmitate0,3 0.3 0.3
Triglyceryl Monostearate2.7 0.3 2.7 2.7 0.3
Decaglyceryl Stearate__ 2,7 ___ ___ 2.7
Polyglyceryl Tristearate-_ --- --_
~Retinyl Palmitate -- I 2.0 I 2 0 -- 1 0
f I
Mix the following ingredients at room temperature. Add slowly with
agitation to the above mixture once it is uniform.
Water 5.0 2.0 11.0 10.0 0.0
Glycerin 30.0 9.0 5.0 5.0 10.0
Dex Panthenol 1.0 1.0 2.0 4.0 3.0
Urea -- -- -- 2.0 --
PEG-30 -- 20.0 1.5.0 12.0 10.0
Lactic Acid -- 4.0 -- __
Dihydroxyacetone 4.0 -- __ __ __
Niacinamide -- 5.0 10.0
Arbutin -- 3.0 __ __
kojic acid -- 3.0 -- __
allantoin -- ~ 2.0 --
Propylene glycol -- 5.0 -- I -- 7.0~
Apply 0.05 - I .5 grams of this phase to the dry substrate already containing
the materials from the Surfactant Phase and allow to cool. The resulting
cleansing
and article is used by wetting with water and is useful for cleansing the skin
or hair
and for depositing the skin care active component onto the skin or hair.
Alternatively, the Skin Care Emulsion Phase can be added onto or impregnated
into
the insoluble substrate before the Surfactant Phase, as long as the surfactant
is not
CA 02332948 2000-11-21
WO 99/55303 PCT/IB99/00635
82
added via dip/nip process. This alternative process is possible when using
extrusion
or gravure printing application methods.
The following alternative manufacturing procedures can be applied to any of
the examples described hereinbefore. For treating a substrate having two
layers, the
lathering surfactants, skin care active component, and optional ingredients
are
separately or simultaneously added onto or impregnated into either surface of
(i)
either or both layers prior to combining the layers into a laminate, or (ii)
after the
layers are combined into a Laminate. The process of adding onto or
impregnating
into the substrate the surfactant and/or conditioning component is achieved by
1 o spraying, printing, splashing, dipping, or coating.
Similarly, the lathering surfactant and the skin care active component can be
added to the substrate in any order. Nonlimiting examples of the process
sequences
include (i) first adding surfactant to the second layer, then joining the
substrate, then
treating with the skin care active component; (ii) first combining surfactant
with skin
care active component then treating the second layer, then joining the two
layers;
(iii) prior to joining the two layers, treating the second layer with the
surfactant first
and then the skin care active component second, then joining the two layers.
In alternative embodiments, other substrates such as woven substrates,
hydroentangled substrates, natural sponges, synthetic sponges, or polymeric
netted
meshes are substituted for the present substrate.
