EMULSIONS CONTAINING POLYLYSINE AND POLAR MODIFIED POLYMER
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of priority from U.S.
Provisional Application Serial No. 61/541 ,310, filed September 30, 201 1, the
entire contents of which is hereby incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to emulsions comprising a
water-in-oil (W/O) emulsion comprising at least one oil-soluble polar modified
polymer and at least one polylysine. Such compositions can possess
improved properties and characteristics such as, for example, stability,
increased long wear and anti-smudging properties.
DISCUSSION OF THE BACKGROUND
[0003] A key trait of cosmetic compositions, such as for example
makeup and sunscreens, are long wear and low cost. In particular,
consumers are looking for affordable make up products that offers transfer
resistance, water resistance, wear comfort; the products should maintain of a
fresh look throughout the day. These properties are generally dependent on
the properties of silicone resins and silicone elastomers that are typically used
but have negative drawbacks such as high costs and formulation difficulties,
particularly with water. High water content make up products with a
possibility to encapsulate actives is beneficial and can provide additional skin
hydration.
[0004] The state of the art technology in makeup for texture and
non-transfer/long wear has been silicone chemistry. In the texture category,
silicone elastomers have superior cushioning and rheology profiles, with the
main drawback of having a high amount of transfer. In the long wear
category, silicone resins have been the primary film former in the cosmetics
field, with the main drawback of being sticky and tacky on the skin. In
addition, the use of silicone resins and elastomers with high amounts of water
in the cosmetic formulations give problematic issues in term of stability.
[0005] Water-insoluble reaction product of a polyamine
(polyethylemeimine (PEI)) and an oil-soluble polar modified polymer were
previously described, for example, in US 2010/0330024. Experience
demonstrated that emulsions containing such reaction products has a
maximum water content of up to 45%. Increased water-content resulted in
emulsion separation.
[0006] It remains desirable to provide cosmetic compositions,
particularly makeup compositions, which employ emulsions that having
excellent stability, high water content, and long-wear properties without
silicone resins.
SUMMARY OF THE INVENTION
[0007] The present invention relates to emulsions comprising a
water-in-oil (W/O) emulsion comprising at least one oil-soluble polar modified
polymer and at least one polylysine. Preferably, the emulsions are
substantially free of silicone resins.
[0008] The present invention also relates to colored emulsions
comprising a water-in-oil emulsion comprising at least one coloring agent, at
least one oil-soluble polar modified polymer, and at least one polylysine.
Preferably, the emulsions are substantially free of silicone resins. Such
colored emulsions can be in the form of cosmetic compositions such as, for
example, lip compositions (for example, lipstick or liquid lip colors),
foundations or mascaras.
[0009] The present invention also relates to methods of treating,
caring for and/or making up keratinous material (for example, skin, eyes,
eyelashes or lips) by applying compositions/emulsions of the present
invention to the keratinous material in an amount sufficient to treat, care for
and/or make up the keratinous material.
[0010] The present invention further relates to covering or hiding
skin defects associated with keratinous material (for example, skin or lips) by
applying compositions/emulsions of the present invention to the keratinous
material in an amount sufficient to cover or hide such skin defects.
[00 ] The present invention also relates to methods of enhancing
the appearance of keratinous material (for example, skin, eyelashes, or lips)
by applying compositions/emulsions of the present invention to the keratinous
material in an amount sufficient to enhance the appearance of the keratinous
material.
[0012] The present invention further relates to
compositions/emulsions having improved cosmetic properties such as, for
example, stability, increased anti-smudging properties, increased long wear
properties and/or better texture or feel upon application.
[0013] The present invention also relates to methods of increasing
both the anti-smudging properties and long wear properties of a
composition/emulsion comprising adding to a composition/emulsion at least
one oil-soluble polar modified polymer and at least one polylysine.
Preferably, the composition/emulsion is substantially free of silicone resin.
[0014] The present invention also relates to methods of making a
composition/emulsion comprising adding at least one oil-soluble polar
modified polymer, at least one polylysine and water to a
composition/emulsion. Preferably, the composition/emulsion is substantially
free of silicone resin.
[0015] The present invention further relates to methods of making a
composition/emulsion comprising mixing at least one oil-soluble polar
modified polymer, at least one surfactant and water to form a first emulsion;
and mixing the first emulsion with polylysine and water to yield a water-in-oil
emulsion.
[0016] It has been surprisingly discovered that the above-described
compositions/emulsions are stable over time (little or no separation and/or
creaming), even if a high amount of water is present. By using a polylysine
instead of PEI, W/O emulsions with a high water content can be achieved.
The emulsions are stable over time, with little or no separation and/or
creaming. Moreover, the films produced by application of these emulsions to
keratinous materials are water- and oil-resistant, and have nice texture and
pleasant feel.
[0017] It is to be understood that both the foregoing general
description and the following detailed description are exemplary and
explanatory only, and are not restrictive of the invention.
[0018] DETAILED DESCRIPTION OF THE INVENTION
[0019] Other than in the operating examples, or where otherwise
indicated, all numbers expressing quantities of ingredients and/or reaction
conditions are to be understood as being modified in all instances by the term
"about."
[0020] "Film former" or "film forming agent" or "film forming resin" as
used herein means a polymer which, after dissolution in at least one solvent
(such as, for example, water and organic solvents), leaves a film on the
substrate to which it is applied, for example, once the at least one solvent
evaporates, absorbs and/or dissipates on the substrate.
[0021] "Keratinous substrates", as used herein, include but are not
limited to, skin, hair, eyelashes, lips and nails.
[0022] "Substituted" as used herein, means comprising at least one
substituent. Non-limiting examples of substituents include atoms, such as
oxygen atoms and nitrogen atoms, as well as functional groups, such as
hydroxyl groups, ether groups, alkoxy groups, acyloxyalky groups,
oxyalkylene groups, polyoxyalkylene groups, carboxylic acid groups, amine
groups, acylamino groups, amide groups, halogen containing groups, ester
groups, thiol groups, sulphonate groups, thiosulphate groups, siloxane
groups, and polysiloxane groups. The substituent(s) may be further
substituted.
[0023] As defined herein, stability is tested by placing the
composition in a controlled environment chamber for 8 weeks at 25°C. In this
test, the physical condition of the sample is inspected as it is placed in the
chamber. The sample is then inspected again at 24 hours, 3 days, 1 week, 2
weeks, 4 weeks and 8 weeks. At each inspection, the sample is examined for
abnormalities in the composition such as phase separation if the composition
is in the form of an emulsion, bending or leaning if the composition is in stick
form, melting, or syneresis (or sweating). The stability is further tested by
repeating the 8-week test at 37°C, 40°C, 45°C, 50°C, and under freeze-thaw
conditions. A composition is considered to lack stability if in any of these
tests an abnormality that impedes functioning of the composition is observed.
The skilled artisan will readily recognize an abnormality that impedes
functioning of a composition based on the intended application.
[0024] "Substantially free" as used herein means that the emulsion
compositions described herein contain less than about 1% by weight of the
composition of the identified compound such as, for example, silicone resins
and/or surfactants. The emulsion compositions can also contain less than
about 0.5 % by weight of the composition, more preferably less than about
0.01 % by weight of the composition, and preferably 0% of identified
compounds such as silicone resins and/or surfactants (all of which are
compassed within the meaning of "substantially free").
[0025] "Volatile", as used herein, means having a flash point of less
than about 100°C. "Non-volatile", as used herein, means having a flash point
of greater than about 100°C.
[0026] As used herein, the expression "at least one" means one or
more and thus includes individual components as well as
mixtures/combinations.
[0027] Other than in the operating examples, or where otherwise
indicated, all numbers expressing quantities of ingredients and/or reaction
conditions are to be understood as being modified in all instances by the term
"about," meaning within 10% to 15% of the indicated number.
[0028] "Waterproof as used herein refers to the ability to repel
water and permanence with respect to water. Waterproof properties may be
evaluated by any method known in the art for evaluating such properties. For
example, a mascara composition may be applied to false eyelashes, which
may then be placed in water for a certain amount of time, such as, for
example, 20 minutes. Upon expiration of the pre-ascertained amount of time,
the false eyelashes may be removed from the water and passed over a
material, such as, for example, a sheet of paper. The extent of residue left on
the material may then be evaluated and compared with other compositions,
such as, for example, commercially available compositions. Similarly, for
example, a composition may be applied to skin, and the skin may be
submerged in water for a certain amount of time. The amount of composition
remaining on the skin after the pre-ascertained amount of time may then be
evaluated and compared. For example, a composition may be waterproof if a
majority of the product is left on the wearer, e.g., eyelashes, skin, etc. In a
preferred embodiment of the present invention, little or no composition is
transferred from the wearer.
[0029] "Long wear" compositions as used herein, refers to
compositions where color remains the same or substantially the same as at
the time of application, as viewed by the naked eye, after an extended period
of time. Long wear properties may be evaluated by any method known in the
art for evaluating such properties. For example, long wear may be evaluated
by a test involving the application of a composition to human hair, skin or lips
and evaluating the color of the composition after an extended period of time.
For example, the color of a composition may be evaluated immediately
following application to hair, skin or lips and these characteristics may then be
re-evaluated and compared after a certain amount of time. Further, these
characteristics may be evaluated with respect to other compositions, such as
commercially available compositions.
[0030] "Emulsions comprising a water-in-oil emulsion" include
emulsions such as, for example, a water-in-oil emulsion, a water-in-oil-inwater
emulsion, etc.
[0031] OIL-SOLUBLE POLAR MODIFIED POLYMER
[0032] According to the present invention, emulsions comprising at
least one oil-soluble polar modified polymer are provided. "Oil-soluble polar
modified polymer" as used herein refers to "oil-soluble low carbon polar
modified polymers" and/or "oil-soluble high carbon polar modified polymers.
[0033] OIL-SOLUBLE LOW CARBON POLAR MODIFIED
POLYMER
[0034] According to the present invention, compositions comprising
at least one oil-soluble low carbon polar modified polymer are provided. "Low
carbon polar modified polymer" as used herein refers to a hydrophobic
homopolymer or copolymer which has been modified with hydrophilic unit(s).
"Oil-soluble" as used herein means that the polar modified polymer is soluble
in oil.
[0035] Suitable monomers for the hydrophobic homopolymers
and/or copolymers include, but are not limited to, cyclic, linear or branched,
substituted or unsubstituted, C2-C20 compounds such as, for example,
styrene, ethylene, propylene, isopropylene, butylene, isobutylene, pentene,
isopentene, isoprene, hexene, isohexene, decane, isodecane, and
octadecane, including all ranges and subranges therebetween. Preferably,
the monomers are C2-C8 compounds, more preferably C2-C6 compounds,
and most preferably C2-C4 compounds such as ethylene, propylene and
butylene.
[0036] Suitable hydrophilic unit(s) include, but are not limited to,
maleic anhydride, acrylates, alkyl acrylates such as, for example, methyl
acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, and
polyvinylpyrrolidone (PVP).
[0037] According to the present invention, the low carbon polar
modified polymer is oil-soluble: that is, the polymer does not contain a
sufficient amount of hydrophilic unit(s) to render the entire polymer watersoluble
or oil-insoluble. According to preferred embodiments, the low carbon
polar modified polymer contains the same amount of hydrophobic monomer
as hydrophilic unit ( 1: 1 ratio) or more hydrophobic monomer than hydrophilic
unit. According to particularly preferred embodiments, the low carbon polar
modified polymer contains 50% or less hydrophilic unit(s) (based on weight of
the polymer), 40% or less hydrophilic unit(s), 30% or less hydrophilic unit(s),
20% or less hydrophilic unit(s), 10% or less hydrophilic unit(s), 5% or less
hydrophilic unit(s), 4% or less hydrophilic unit(s), or 3% or less hydrophilic
unit(s).
[0038] Preferably, the low carbon polar modified polymer has from
about 0.5% to about 10% hydrophilic units, more preferably from about 1% to
about 8% hydrophilic units by weight with respect to the weight of the
polymer, including all ranges and subranges therebetween. Particularly
preferred hydrophilically modified polymers are ethylene and/or propylene
homopolymers and copolymers which have been modified with maleic
anhydride units.
[0039] According to preferred embodiments of the present
invention, the low carbon polar modified polymer is a wax. According to
particularly preferred embodiments, the low carbon polar modified wax is
made via metallocene catalysis, and includes polar groups or units as well as
a hydrophobic backbone. Suitable modified waxes include those disclosed in
U.S. patent application publication no. 20070031361 , the entire contents of
which is hereby incorporated by reference. Particularly preferred polar
modified waxes are C2-C3 polar modified waxes.
[0040] In accordance with preferred embodiments of the present
invention, the low carbon polar modified wax is based upon a homopolymer
and/or copolymer wax of hydrophobic monomers and has a weight-average
molecular weight Mw of less than or equal to 25 000 g/mol, preferably of 1000
to 22 000 g/mol and particularly preferably of 4000 to 20,000 g/mol, a
number-average molecular weight Mn of less than or equal to 15 000 g/mol,
preferably of 500 to 2 000 g/mol and particularly preferably of 1000 to 5000
g/mol, a molar mass distribution Mw/Mn in the range from 1.5 to 10,
preferably from 1.5 to 5, particularly preferably from 1.5 to 3 and especially
preferably from 2 to 2.5, which have been obtained by metallocene catalysis.
Also, the low carbon polar modified wax preferably has a melting point above
75°C, more preferably above 90°C such as, for example, a melting point
between 90°C and 160°C, preferably between 100°C and 150°C, including all
ranges and subranges therebetween.
[0041] In the case of a copolymer wax, it is preferable to have,
based on the total weight of the copolymer backbone, 0.1 to 30% by weight of
structural units originating from the one monomer and 70.0 to 99.9% by
weight of structural units originating from the other monomer. Such
homopolymer and copolymer waxes can be made, for example, by the
process described in EP 571 882, the entire contents of which is hereby
incorporated by reference, using the metallocene catalysts specified therein.
Suitable preparation processes include, for example, suspension
polymerization, solution polymerization and gas-phase polymerization of
olefins in the presence of metallocene catalysts, with polymerization in the
monomers also being possible.
[0042] Low carbon polar modified waxes can be produced in a
known manner from the homopolymers and copolymers described above by
oxidation with oxygen-containing gases, for example air, or by graft reaction
with polar monomers, for example maleic acid or acrylic acid or derivatives of
these acids. The polar modification of metallocene polyolefin waxes by
oxidation with air is described, for example, in EP 0 890 583 A 1, and the
modification by grafting is described, for example, in U.S. Pat. No. 5,998,547,
the entire contents of both of which are hereby incorporated by reference in
their entirety.
[0043] Acceptable low carbon polar modified waxes include, but are
not limited to, homopolymers and/or copolymers of ethylene and/or propylene
groups which have been modified with hydrophilic units such as, for example,
maleic anhydride, acrylate, methacrylate, polyvinylpyrrolidone (PVP), etc.
Preferably, the C2-C3 wax has from about 0.5% to about 10% hydrophilic
units, more preferably from about 1% to about 8% hydrophilic units by weight
with respect to the weight of the wax, including all ranges and subranges
therebetween. Particularly preferred hydrophilically modified waxes are
ethylene and/or propylene homopolymers and copolymers which have been
modified with maleic anhydride units.
[0044] Particularly preferred C2-C3 polar modified waxes for use in
the present invention are polypropylene and/or polyethylene-maleic anhydride
modified waxes ("PEMA," "PPMA." "PEPPMA") commercially available from
Clariant under the trade name LICOCARE or LICOCENE, Specific examples
of such waxes include products marketed by Clariant under the LicoCare
name having designations such as PP207.
[0045] Other suitable polar modified polymers include, but are not
limited to A-C 573 A (ETHYLENE-MALEIC ANHYDRIDE COPOLYMER; Drop
Point, Mettler : 106°C) from Honeywell, A-C 596 A (PROPYLENE-MALEIC
ANHYDRIDE COPOLYMER; Drop Point, Mettler : 143°C) from Honeywell, AC
597 (PROPYLENE-MALEIC ANHYDRIDE COPOLYMER; Drop Point,
Mettler : 141 °C) from Honeywell, ZeMac® copolymers (from VERTELLUS)
which are 1:1 copolymers of ethylene and maleic anhydride, polyisobutylenemaleic
anhydride sold under the trade name ISOBAM (from Kuraray),
polyisoprene-graft-maleic anhydride sold by Sigma Aldrich, poly(maleic
anhydride-octadecene) sold by Chevron Philips Chemcial Co., poly (ethyleneco-
butyl acrylate-co-maleic anhydride) sold under the trade name of Lotader
(e.g. 2210, 3210, 4210, and 3410 grades) by Arkema, copolymers in which
the butyl acrylate is replaced by other alkyl acrylates (including methyl
acrylate [grades 3430, 4404, and 4503] and ethyl acrylate [grades 6200,
8200, 3300, TX 8030, 7500, 5500, 4700, and 4720) also sold by Arkema
under the Lotader name, and isobutylene maleic anhydride copolymer sold
under the name ACO-501 3 by ISP.
[0046] According to other embodiments of the present invention,
the low carbon polar modified polymer is not a wax. In accordance with these
embodiments of the present invention, the low carbon polar modified polymer
is based upon a homopolymer and/or copolymer of hydrophobic monomer(s)
and has a weight-average molecular weight Mw of less than or equal to
1,000,000 g/mol, preferably of 1000 to 250,000 g/mol and particularly
preferably of 5,000 to 50,000 g/mol, including all ranges and subranges
therebetween.
[0047] In accordance with these embodiments, the low carbon polar
modified polymer can be of any form typically associated with polymers such
as, for example, block copolymer, a grafted copolymer or an alternating
copolymer. For example, the low carbon polar modified polymer can contain
a hydrophobic backbone (such as polypropylene and/or polyethylene) onto
which hydrophilic groups (such as maleic anhydride) have been attached by
any means including, for example, grafting. The attached groups can have
any orientation (for example, atactic, isotactic or syndiotactic along the
backbone).
[0048] Preferably, the oil soluble low carbon polar modified
polymer(s) represent from about 0.5% to about 30% of the total weight of the
composition, more preferably from about 1% to about 20% of the total weight
of the composition, and most preferably from about 2% to about 10%,
including all ranges and subranges therebetween such as, for example, about
3% to about 9% and about 4% to about 8%.
[0049] OIL-SOLUBLE HIGH CARBON POLAR MODIFIED
POLYMER
[0050] According to the present invention, compositions comprising
at least one oil-soluble high carbon polar modified polymer are provided.
"Polar modified polymer" as used herein refers to a hydrophobic
homopolymer or copolymer which has been modified with hydrophilic unit(s).
"Oil-soluble" as used herein means that the polar modified polymer is soluble
in oil. "High carbon" means more than 20 carbon atoms.
[0051] Suitable monomers for the hydrophobic homopolymers
and/or copolymers include, but are not limited to, cyclic, linear or branched,
substituted or unsubstituted, C22-C40 compounds such as, C22-C28
compounds, C24-C26 compounds, C26-C28 compounds, and C30-C38
compounds, including all ranges and subranges therebetween. Preferably,
the monomers are C24-26 compounds, C26-C28 compounds or C30-C38
compounds.
[0052] Suitable hydrophilic unit(s) include, but are not limited to,
maleic anhydride, acrylates, alkyl acrylates such as, for example, methyl
acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, and
polyvinylpyrrolidone (PVP).
[0053] According to preferred embodiments, the oil-soluble high
carbon polar modified polymer is a wax. Also preferably, the oil-soluble high
carbon polar modified polymer wax has one or more of the following
properties:
[0054] a weight-average molecular weight Mw of less than or equal
to 30 000 g/mol, preferably of 500 to 10 000 g/mol and particularly preferably
of 1000 to 5,000 g/mol, including all ranges and subranges therebetween;
[0055] a number-average molecular weight Mn of less than or equal
to 15 000 g/mol, preferably of 500 to 12 000 g/mol and particularly preferably
of 1000 to 5000 g/mol, including all ranges and subranges therebetween;
[0056] a molar mass distribution Mw/Mn in the range from 1.5 to 10,
preferably from 1.5 to 5, particularly preferably from 1.5 to 3 and especially
preferably from 2 to 2.5, including all ranges and subranges therebetween;
and/or
[0057] a crystallinity of 8% to 60%, preferably 9% to 40%, and more
preferably 10% to 30%, including all ranges and subranges therebetween, as
determined by differential scanning calorimetry.
[0058] According to preferred embodiments relating to a copolymer
wax, it is preferable to have, based on the total weight of the copolymer
backbone, 0.1 to 30% by weight of structural units originating from the one
monomer and 70.0 to 99.9% by weight of structural units originating from the
other monomer.
[0059] Waxes of the present invention can be based upon
homopolymers or copolymers made, for example, by the process described in
EP 571 882, the entire contents of which is hereby incorporated by reference.
Suitable preparation processes include, for example, suspension
polymerization, solution polymerization and gas-phase polymerization of
olefins in the presence of catalysts, with polymerization in the monomers also
being possible.
[0060] Oil-soluble high carbon polar modified polymer wax can be
produced in a known manner from the hompopolymers and copolymers
described above by oxidation with oxygen-containing gases, for example air,
or by graft reaction with polar monomers, for example maleic acid or acrylic
acid or derivatives of these acids. The polar modification of polyolefin waxes
by oxidation with air is described, for example, in EP 0 890 583 A 1, and the
modification by grafting is described, for example, in U.S. Pat. No. 5,998,547,
the entire contents of both of which are hereby incorporated by reference in
their entirety.
[0061] Acceptable oil-soluble high carbon polar modified polymer
waxes include, but are not limited to, homopolymers and/or copolymers of
C24, C25 and/or C26 groups, copolymers C26, C27 and/or C28 groups, or
copolymers of C30-C38 groups, which have been modified with hydrophilic
units such as, for example, maleic anhydride, acrylate, methacrylate,
polyvinylpyrrolidone (PVP), etc. Preferably, the oil-soluble high carbon polar
modified polymer wax has from about 5% to about 30% hydrophilic units,
more preferably from about 10% to about 25% hydrophilic units by weight
with respect to the weight of the wax, including all ranges and subranges
therebetween. Particularly preferred hydrophilically modified waxes are C26,
C27 and/or C28 homopolymers and copolymers which have been modified
with maleic anhydride units.
[0062] Particularly preferred oil-soluble high carbon polar modified
polymer waxes for use in the present invention are C26-C28 alpha olefin
maleic acid anhydride copolymer waxes commercially available from Clariant
under the trade name LICOCARE or LICOCENE. Specific examples of such
waxes include products marketed by Clariant under the LicoCare name
having designations such as CM 401, which is a maleic anhydride modified
wax having a Mw of 2025 and a crystallinilty of 1 %, C30-C38
olefin/isopropylmaleate/maleic anhydride copolymer sold by Baker Hughes
under the name Performa® V 1608, and C24-C26 alpha olefin acrylate
copolymer wax commercially available from Clariant under the trade name
LICOCARE CA301 LP3346 based on a polar backbone with C24-26 side
chains with alternating ester and carboxylic acid groups.
[0063] According to other embodiments of the present invention,
the polar modified polymer is not a wax. In accordance with these
embodiments of the present invention, the polar modified polymer is based
upon a homopolymer and/or copolymer of hydrophobic monomer(s) and has
a weight-average molecular weight Mw of less than or equal to 1,000,000
g/mol, preferably of 1000 to 250,000 g/mol and particularly preferably of 5,000
to 50,000 g/mol, including all ranges and subranges therebetween.
[0064] In accordance with these embodiments, the polar modified
polymer can be of any form typically associated with polymers such as, for
example, block copolymer, a grafted copolymer or an alternating copolymer.
For example, the polar modified polymer can contain a hydrophobic backbone
(such as polypropylene and/or polyethylene) onto which hydrophilic groups
(such as maleic anhydride) have been attached by any means including, for
example, grafting. The attached groups can have any orienation (for
example, atactic, isotactic or syndiotactic along the backbone).
[0065] Preferably, the oil soluble high carbon polar modified
polymer(s) represent from about 0.5% to about 30% of the total weight of the
composition, more preferably from about 1% to about 20% of the total weight
of the composition, and most preferably from about 2% to about 10%,
including all ranges and subranges therebetween such as, for example, about
3% to about 9% and about 4% to about 8%.
[0066] POLYLYSINE
[0067] According to the present invention, emulsions further
comprising polylysine are provided. Polylysine is well known. Polylysine can
be a natural homopolymer of L-lysine that can be produced by bacterial
fermentation For example, polylysine can be e-Poly-L-lysine, typically used
as a natural preservative in food products. Polylysine is a polyelectrolyte
which is soluble in polar solvents such as water, propylene glycol and
glycerol. Polylysine is commercially available in various forms, such as poly
D-lysine and poly L-lysine. Polylysine can be in salt and/or solution form.
[0068] Preferably, the polylysine is present in an amount of 0.01 to
10% of the total weight of the emulsion composition, including 0.05 to 8% and
0.1 to 5% by weight, including all ranges and subranges therebetween.
[0069] REACTION PRODUCT
[0070] According to preferred embodiments of the present
invention, the oil-soluble polar modified polymer is reacted with the polylysine
compound, in the presence of water in, at minimum, an amount sufficient to
solubilize the polylysine, to form a reaction product. In accordance with the
preferred embodiments, the reaction product is water-insoluble.
[0071] Although not wanting to be bound by any particular theory, it
is believed that at a temperature below 100°C, the reaction of the oil-soluble
polar modified polymer with the polylysine opens the anhydride ring to form a
half acid and half amide crosslinked product. However, at a temperature
above 100°C, the reaction of the oil-soluble polar modified polymer with the
polylysine opens the anhydride ring to form an imide crosslinked product.
The former product is preferred over the latter product. It is not necessary for
all amine groups and all hydrophilic groups to react with each other to form
the reaction product. Rather, it is possible that the composition may contain
free polylysine and/or free oil-soluble polar modified polymer in addition to the
reaction product.
[0072] Although not wanting to be bound by any particular theory, it
is also believed that the polylysine(s) can be non-covalently assembled with
the polar modified polymer(s) by electrostatic interaction between an amine
group of the polylysine and a hydrophilic group (for example, carboxylic acid
group associated with maleic anhydride groups) of the oil-soluble polar
modified polymer to form a supramolecule. For example, with specific
reference to maleic anhydride groups, in the presence of water these groups
can open to form dicarboxylic acid groups which can interact with protonated
primary amines of the polylysine through ionic interaction to form a polymerpolymer
complex with hydrophilic core crosslinkers and a hydrophobic
network that act as supramolecular capsule. If a large amount of maleic
anhydride groups are present, further primary amine groups of polylysine are
also protonated and interact with alkyl carboxylates.
[0073] According to preferred embodiments, the oil-soluble polar
modified polymer is in an oil carrier, and the polylsyine compound is in an
aqueous carrier, and the reaction occurs by combining the oil carrier and the
aqueous carrier. Because the oil-soluble polar modified polymer is typically
solid at room temperature, the oil carrier is preferably heated to liquefy the
polymer prior to combination with the aqueous carrier. Preferably, the oil
carrier is heated beyond the melting point of the oil-soluble polar modified
polymer, typically up to about 80°C, 90°C or 100°C.
[0074] Without intending to be bound by any particular theory, it is
believed that the reason for this is that due to the chemical and physical
reactions which take place when the oil-soluble polar modified polymer is
combined with the polylysine, the subsequent reaction product that is formed
is surprisingly and unexpectedly able to entrap large amounts of water
molecules within its hydrophobic matrix. The resultant product is eminently
capable of forming a film, is self-emulsifying, waterproof. Moreover, the
product is both stable and capable of carrying various types of ingredients.
[0075] WATER
[0076] The emulsions of the present invention also contains of
water. The water can be present in an amount of from about 3% to about
90% by weight, preferably 5% to about 80% by weight, preferably about 10%
to about 75% by weight, including all ranges and subranges therebetween
such as, for example, 45%-90%, all weights being based on the total weight
of the composition.
[0077] SURFACTANT
[0078] According to the present invention, emulsions optionally
further comprising at least one surfactant are provided. In accordance with
such embodiments of the present invention, any suitable surfactant for use in
water-in-oil emulsions can be used. Such surfactants are well-known in the
field.
[0079] According to preferred embodiments, at least one surfactant
having an HLB value greater than or equal to 10 is present in the emulsion.
Preferably, the at least one surfactant has an HLB value of 10-17, preferably
11- 7, including all ranges and subranges therebetween. Examples of
suitable surfactants include, but are not limited to, PEG-40-stearate and PEG-
8-stearate. Any suitable surfactants for forming emulsions, including a waterin-
oil-in-water emulsion, can be used in accordance with the present invention.
In addition to alkoxlated/fatty acid surfactants discussed above such as the
PEG/fatty acid surfactants (which would include, but not be limited to, PEG
amounts ranging from 1 to about 100, 3 to about 75, and 8 to about 40,
including all ranges and subranges therebetween, and would also include but
not be limited to fatty acid components having from 8 to about 32 carbons,
from 10 to about 24 carbons, and from 12 to about 18 carbons, including all
ranges and subranges therebetween such as, e.g., stearate, oleate, myristate,
palmitate, etc.).
[0080] If present, the at least one surfactant may be present in
amounts from 0 to 20% of the total weight of the composition, preferably 0.05
to 10%, and preferably 0.1 to 5%, including all ranges and subranges
therebetween.
[0081] VOLATILE OIL
[0082] According to particularly preferred embodiments of the
present invention, compositions optionally further comprising at least one
volatile oil are provided. Preferably, the at least one volatile oil is a silicone
volatile oil, a hydrocarbon volatile oil, or a mixture thereof.
[0083] According to preferred embodiments, the composition may
contain one or more volatile silicone oils. Examples of such volatile silicone
oils include linear or cyclic silicone oils having a viscosity at room temperature
less than or equal to 6cSt and having from 2 to 7 silicon atoms, these
silicones being optionally substituted with alkyl or alkoxy groups of 1 to 10
carbon atoms. Specific oils that may be used in the invention include
octamethyltetrasiloxane, decamethylcyclopentasiloxane,
dodecamethylcyclohexasiloxane, heptamethyloctyltrisiloxane,
hexamethyldisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane
and their mixtures. Other volatile oils which may be used include KF 96A of
6 cSt viscosity, a commercial product from Shin Etsu having a flash point of
94°C. Preferably, the volatile silicone oils have a flash point of at least 40°C.
[0084] Non-limiting examples of volatile silicone oils are listed in
Table 1 below.
[0085] Table 1
[0086] Further, a volatile linear silicone oil may be employed in the
compositions of the present invention. Suitable volatile linear silicone oils
include those described in U.S. patent no. 6,338,839 and WO03/042221 , the
contents of which are incorporated herein by reference. In one embodiment
the volatile linear silicone oil is decamethyltetrasiloxane. In another
embodiment, the decamethyltetrasiloxane is further combined with another
solvent that is more volatile than decamethyltetrasiloxane.
[0087] According to other preferred embodiments, the composition
may contain one or more non-silicone volatile oils and may be selected from
volatile hydrocarbon oils, volatile esters and volatile ethers. Examples of
such volatile non-silicone oils include, but are not limited to, volatile
hydrocarbon oils having from 8 to 16 carbon atoms and their mixtures and in
particular branched Cs to C 6 alkanes such as Ca to C 6 isoalkanes (also
known as isoparaffins), isododecane, isodecane, isohexadecane, and for
example, the oils sold under the trade names of Isopar or Permethyl, the C to
Ci6 branched esters such as isohexyl or isodecyl neopentanoate and their
mixtures. Preferably, the volatile non-silicone oils have a flash point of at
least 40°C.
[0088] Non-limiting examples of volatile non-silicone volatile oils are
given in Table 2 below.
Table 2
[0089] The volatility of the solvents/oils can be determined using the
evaporation speed as set forth in U.S. patent no. 6,338,839.
[0090] Preferably, the volatile oil(s), when present, represent from
about 5% to about 90% of the total weight of the composition, more preferably
from about 10% to about 80% of the total weight of the composition, and most
preferably from about 20% to about 75%, including all ranges and subranges
therebetween.
[0091] Coloring Agents
[0092] According to particularly preferred embodiments of the
present invention, compositions optionally further comprising at least one at
least one coloring agent are provided. Preferably, such colored compositions
are cosmetic compositions such as, for example, lip compositions (for
example, lipstick or liquid lip colors), mascaras, nail polish or foundations.
[0093] According to this embodiment, the at least one coloring
agent is preferably chosen from pigments, dyes, such as liposoluble dyes,
nacreous pigments, and pearling agents.
[0094] Representative liposoluble dyes which may be used
according to the present invention include Sudan Red, DC Red 17, DC Green
6, b-carotene, soybean oil, Sudan Brown, DC Yellow 1, DC Violet 2, DC
Orange 5, annatto, and quinoline yellow. The liposoluble dyes, when present,
generally have a concentration ranging up to 20% by weight of the total
weight of the composition, such as from 0.0001% to 6%.
[0095] The nacreous pigments which may be used according to the
present invention may be chosen from white nacreous pigments such as mica
coated with titanium or with bismuth oxychloride, colored nacreous pigments
such as titanium mica with iron oxides, titanium mica with ferric blue or
chromium oxide, titanium mica with an organic pigment chosen from those
mentioned above, and nacreous pigments based on bismuth oxychloride. The
nacreous pigments, if present, be present in the composition in a
concentration ranging up to 50% by weight of the total weight of the
composition, such as from 0.1% to 20%, preferably from 0.1% to 15%,
including all ranges and subranges therebetween.
[0096] The pigments, which may be used according to the present
invention, may be chosen from white, colored, inorganic, organic, polymeric,
nonpolymeric, coated and uncoated pigments. Representative examples of
mineral pigments include titanium dioxide, optionally surface-treated,
zirconium oxide, zinc oxide, cerium oxide, iron oxides, chromium oxides,
manganese violet, ultramarine blue, chromium hydrate, and ferric blue.
Representative examples of organic pigments include carbon black, pigments
of D & C type, and lakes based on cochineal carmine, barium, strontium,
calcium, and aluminum.
[0097] If present, the pigments may be present in the composition
in a concentration ranging up to 50 % by weight of the total weight of the
composition, such as from 0.5% to 40%, and further such as from 2% to 30%,
including all ranges and subranges therebetween. In the case of certain
products, the pigments, including nacreous pigments, may, for example,
represent up to 50% by weight of the composition.
[0098] Film Forming Agents
[0099] According to particularly preferred embodiments of the
present invention, compositions optionally further comprising at least one at
least one film forming agent (film former) are provided. Acceptable film
forming agents are known in the art and include, but are not limited to, those
disclosed in U.S. patent application publication no. 2004/0170586, the entire
contents of which is hereby incorporated by reference. Non-limiting
representative examples of such film forming agents include silicone resins
such as, for example, MQ resins (for example, trimethylsiloxysilicates), Tpropyl
silsesquioxanes and MK resins (for example,
polymethylsilsesquioxanes), silicone esters such as those disclosed in U.S.
Pat. Nos. 6,045,782, 5,334,737, and 4,725,658, the disclosures of which are
hereby incorporated by reference, polymers comprising a backbone chosen
from vinyl polymers, methacrylic polymers, and acrylic polymers and at least
one chain chosen from pendant siloxane groups and pendant fluorochemical
groups such as those disclosed in U.S. Pat. Nos. 5,209,924, 4,693,935,
4,981 ,903, 4,981 ,902, and 4,972,037, and WO 01/32737, the disclosures of
which are hereby incorporated by reference, polymers such as those
described in U.S. Pat. No. 5,468,477, the disclosure of which is hereby
incorporated by reference (a non-limiting example of such polymers is
poly(dimethylsiloxane)-g-poly(isobutyl methacrylate), which is commercially
available from 3M Company under the tradename VS 70 IBM), .
[00100] According to preferred embodiments, the film former, when
present, is present in the composition in an amount ranging from 0.1 % to 30%
by weight relative to the total weight of the composition. Preferably, the film
former is present in an amount ranging from 0.5% to 20% by weight relative
to the total weight of the composition, and more preferably from 2% to 15%,
including all ranges and subranges therebetween. One of ordinary skill in the
art will recognize that the film former of the present invention may be
commercially available, and may come from suppliers in the form of a dilute
solution. The amounts of the film former disclosed herein therefore reflect the
weight percent of active material.
[00101] According to particularly preferred embodiments, when a film
forming agent is present, the combined amount of the amount of oil-soluble
polar modified polymer and the film forming agent is 30-50% by weight of the
entire weight of the composition.
[00102] However, in other preferred embodiments of the present
invention, the emulsion composition is substantially free of silicone resin (that
is, less than 1% of silicone resin) or essentially free of silicone resin (that is,
less than 0.5% silicone resin). According to a particularly preferred
embodiment, the emulsion contains no silicone resin.
[00103] Another particularly preferred embodiment of the present
invention is a composition for application to keratin materials (hair or
eyelashes) which is an emulsion but which is substantially free of
triethanolamine/stearate (TEA-stearate) (that is, less than 1% of TEAstearate)
or free of TEA Stearate (that is, less than 0.05% TEA-stearate).
[00104] Additional additives
[00105] The composition of the invention can also comprise any
additive usually used in the field under consideration. For example,
dispersants such as poly(12-hydroxystearic acid), antioxidants, essential oils,
sunscreens, preserving agents, fragrances, fillers, neutralizing agents,
cosmetic and dermatological active agents such as, for example, emollients,
moisturizers, vitamins, essential fatty acids, surfactants, pasty compounds
and mixtures thereof can be added. A non-exhaustive listing of such
ingredients can be found in U.S. patent application publication no.
2004/0170586, the entire contents of which is hereby incorporated by
reference. Further examples of suitable additional components can be found
in the other references which have been incorporated by reference in this
application. Still further examples of such additional ingredients may be
found in the International Cosmetic Ingredient Dictionary and Handbook (9th
ed. 2002).
[00106] A person skilled in the art will take care to select the optional
additional additives and/or the amount thereof such that the advantageous
properties of the composition according to the invention are not, or are not
substantially, adversely affected by the envisaged addition.
[00107] These substances may be selected variously by the person
skilled in the art in order to prepare a composition which has the desired
properties, for example, consistency or texture.
[00108] These additives may be present in the composition in a
proportion from 0% to 99% (such as from 0.01 % to 90%) relative to the total
weight of the composition and further such as from 0.1% to 50% (if present),
including all ranges and subranges therebetween.
[00109] Needless to say, the composition of the invention should be
cosmetically or dermatologically acceptable, i.e., it should contain a non-toxic
physiologically acceptable medium and should be able to be applied to the
eyelashes of human beings.
[00110] Non-limiting examples of such additional components
include non-volatile oils such as silicone oils (for example, dimethicone,
phenyl trimethicone, trimethyl pentaphenyl trisiloxane, etc) or hydrocarbon
oils (for example, esters). In one embodiment of the present invention, the
compositions of the present invention are substantially free of silicone oils
(i.e., contain less than about 1% silicone oils). In another embodiment, the
compositions are substantially free of non-silicone oils (i.e., contain less than
about 1% non-silicone oils). In another embodiment, the compositions are
substantially free of non-volatile oils (i.e., contain less than about 1% non¬
volatile oils).
[001 1] According to preferred embodiments of the present
invention, methods of treating, caring for and/or making up keratinous
material such as skin, lips, hair and mucous membranes by applying
compositions of the present invention to the keratinous material in an amount
sufficient to treat, care for and/or make up the keratinous material are
provided. Preferably, "making up" the keratin material includes applying at
least one coloring agent to the keratin material in an amount sufficient to
provide color to the keratin material.
[00112] According to other preferred embodiments, methods of
covering or hiding defects associated with keratinous material such as
imperfections or discolorations by applying compositions of the present
invention to the keratinous material in an amount sufficient to cover or hide
such defects are provided.
[00113] According to yet other preferred embodiments, methods of
enhancing the appearance of keratinous material by applying compositions of
the present invention to the keratinous material in an amount sufficient to
enhance the appearance of the keratinous material are provided.
[00114] In accordance with the three preceding preferred
embodiments, the compositions of the present invention comprising at least
one oil-soluble polar modified polymer and at least one polylysine are applied
topically to the desired area of the keratin material in an amount sufficient to
treat, care for and/or make up the keratinous material, to cover or hide
defects associated with keratinous material, skin imperfections or
discolorations, or to enhance the appearance of keratinous material. The
compositions may be applied to the desired area as needed, preferably once
or twice daily, more preferably once daily and then preferably allowed to dry
before subjecting to contact such as with clothing or other objects (for
example, a glass or a topcoat). Preferably, the composition is allowed to dry
for about 3 minute or less, more preferably for about 2 minutes or less. The
composition is preferably applied to the desired area that is dry or has been
dried prior to application, or to which a basecoat has been previously applied.
[00115] According to a preferred embodiment of the present
invention, compositions having improved cosmetic properties such as, for
example, improved stability, improved feel upon application (for example,
texture, reduced drag or tackiness), increased anti-smudging properties,
and/or increased long wear properties are provided.
[00116] According to other embodiments of the present invention,
methods of improving the anti-smudging, transfer-resistance and/or long wear
properties of a composition, comprising adding at least one oil-soluble polar
modified polymer and at least one polylysine to the composition are provided.
In accordance with this embodiment, the at least one oil-soluble polar
modified and the at least one polylysine are present in amounts sufficient to
achieve the desired result.
[00117] According to yet other embodiments of the present invention,
methods of making a composition comprising mixing together at least one
polylysine and at least one oil-soluble polar modified polymer to form a
composition are provided.
[00118] In accordance with preferred embodiments, W/O emulsions
are prepared in a process that includes reactive emulsion technology. The
technology is versatile in that allows producing W/O emulsions. Using such
reactive emulsion technology, it is believed that chemical crosslinking of the
at least one oil-soluble polar modified polymer and the at least one polylysine
occurs at the water-oil interface in the emulsion, allowing the emulsions with
various ranges of properties (e.g., rheology and water content) to be
achieved. Further, it is believed that such technology facilitates regulating the
size of the dispersed phase(s) as well as the water content in the water
phase.
[00119] According to preferred embodiments, an oil phase containing
the at least one oil-soluble polar modified polymer (e.g., Ethylene/maleic
Anhydride/propylene Copolymer) and a water-phase containing the at least
one polylysine are combined to form an W/O emulsion such that polylysine
reacts with the at least one oil-soluble polar modified polymer to form a
reaction product. It is believed that this reaction product is facilitated by
physical and/or chemical crosslinking discussed above, and occurs
depending on the processing conditions. It is believed, at least as a partial
result of such crosslinking, water is entrapped in the crosslinked oil-soluble
polar modified polymer polymer/polylysine reaction product, which is
surrounded by the oil phase.
[00120] Unless otherwise indicated, all numbers expressing
quantities of ingredients, reaction conditions, and so forth used in the
specification and claims are to be understood as being modified in all
instances by the term "about." Accordingly, unless indicated to the contrary,
the numerical parameters set forth in the following specification and attached
claims are approximations that may vary depending upon the desired
properties sought to be obtained by the present invention.
[00121] Notwithstanding that the numerical ranges and parameters
setting forth the broad scope of the invention are approximations, the
numerical values set forth in the specific examples are reported as precisely
as possible. Any numerical value, however, inherently contain certain errors
necessarily resulting from the standard deviation found in their respective
measurements. The following examples are intended to illustrate the
invention without limiting the scope as a result. The percentages are given on
a weight basis.
[00122] EXAMPLES
[00123] Example 1 - W/O emulsion
[001 24] Each of phase A-C are separately prepared.
[00125] Phases A and B are combined and mixed to form a
W/O emulsion.
[00126] This W/O emulsion is combined with phase C and
mixed at 80° for 30 minutes to form a W/O emulsion where the oil-soluble
polar modified polymer and polylysine are crosslinked at the water-oil
interface.
[001 27] Example 2 - W/O emulsion
c Millipore water 18.0
C Polylysine (PL) 1.0
Total 100
[00128] Each of phase A-B - C are separately prepared.
[00129] Phases A and B are mixed in a beaker with stirring at
80°C for 10 minutes until a stable emulsion is obtained followed by adding
phase C under stirring at 80°C for 30 min.
[00130] Example 3 - Liquid foundation
[00131] Each of phase A and phase B are separately
prepared and mixed in a beaker with stirring at 80°C for 10 minutes,
followed by adding of phase C with stirring at 80°C for 10 min, followed by
adding phase D and mixing for 30 min at 80°C. Ethanol is added under
stirring at room temperature.
CLAIMS
What is claimed is:
1. An emulsion comprising a water-in-oil emulsion comprising:
(a) water;
(b) at least one polylysine; and
(c) at least one polar modified polymer selected from the group consisting
of:
(1) a low carbon oil-soluble polar modified polymer comprising at
least one C2-C4 monomer and modified with at least one hydrophilic unit, and
having a weight-average molecular weight of less than or equal to 25 000 g/mol
and a melting point above 75°C;
(2) an high carbon oil-soluble polar modified polymer comprising at
least one C22-C40 monomer and modified with at least one hydrophilic unit,
and having a weight-average molecular weight of less than or equal to 30000
g/mol and a crystallinity of 8% to 60%; and
(3) mixtures thereof.
2. The emulsion of claim 1, wherein the emulsion comprises at least
one low carbon oil-soluble polar modified polymer comprising at least one C2-
C4 monomer and modified with at least one hydrophilic unit, and having a
weight-average molecular weight of less than or equal to 25 000 g/mol and a
melting point above 75°C.
3. The emulsion of claim 2, wherein the at least one low carbon oilsoluble
polar modified polymer consists essentially of polypropylene and
maleic anhydride units.
4. The emulsion of claim 1, wherein the composition comprises at least
one oil-soluble high carbon polar modified polymer comprising at least one
C26-C28 monomer and modified with at least one hydrophilic unit, and having
a weight-average molecular weight of less than or equal to 30000 g/mol and a
crystallinity of 8% to 60%.
5. The emulsion of claim 4 , wherein the at least one high carbon oilsoluble
polar modified polymer consists essentially of C26-C28 alpha olefin and
maleic acid anhydride units.
6. The emulsion of claim 1, further comprising at least one coloring agent.
7. The emulsion of claim 1, wherein the emulsion is made using from 0.01
to 10% by weight, based on the weight of the emulsion, of the polylysine.
8. The emulsion of claim 1, wherein the emulsion is made using from 0.05
to 8% by weight, based on the weight of the emulsion, of the polylysine.
9. The emulsion of claim 1, wherein the emulsion is made using from 0.5
to 30% by weight, based on the weight of the emulsion, of the oil-soluble polar
modified polymer.
10. The emulsion of claim , wherein water is present in an amount of
from 45 to 90% by weight, based on the weight of the emulsion.
1 . The emulsion of claim , further comprising at least one surfactant.
12. The emulsion of claim 1, in the form of a water-in-oil emulsion.
13. The emulsion of claim 1, in the form of a water-in-oil-in-water
emulsion.
14. A cosmetic composition comprising the emulsion of claim 1.
15. A method of making up skin comprising applying the composition of
claim 11 to the skin.
16. A method of making up lips comprising applying the composition of
claim 1 to the lips.
17. A method of making up eyelashes comprising applying the
composition of claim 1 to the eyelashes.