Note: Descriptions are shown in the official language in which they were submitted.
wo gs/04s37 2 1 6 8 4 2 5 PCT/US94/08838
COSMETIC COMPOSITIONS
- Field of the Invention
The present invention relates to cosmetic compositions and more
particularly, to pigmented foundation make-up compositions and
concealers having anti-acne activity and formulation and colour
stability.
Back~round of the Invention
A foundation composition can be applied to the face and other parts of
- the body to even skin tone and te~ture and to hide pores,
imperfections, fine lines and the like. A foundation composition is
also applied to moisturize the skin, to balance the oil level of the skin
and to provide protection against the adverse effects of sunlight, wind
and the harsh environment.
Make-up compositions are generally available in the form of liquid or
cream suspensions, emulsions, gels, pressed powders or anhydrous oil
and wa~ compositions.
US Patent No. 3,444,291 discloses a method of filling and
camo~fl~in~ skin cavities by applying a composition which includes
65 to 75 parts by weight of a microcrystalline wax and about 25 to 35
parts of a mineral oil. The composition includes a colourant,
preferably a coal tar dye, for e~cample, D &C Red No. 17, which
matches the colour of the user's skin.
A spreadable, flowable and greaseless cosmetic cover-up composition
is taught in US Patent No 4,486,405. That composition is
characterized by the presence of a first and a second alko~ylated
surfactant present in subst~nti~lly the same concentration.
WO 95/04537 2 1 6 8 4 2 5 PCT/USg4/08838
US Patent No. 4,804,532 recites a facial cosmetic powder which
utilizes crystalline silica in much lower concentration than that
employed in the then prior art compositions. This powder, used as a
blush or a facial coating, is said to be effective in hiding skin wrinkles,
lines and pores. The composition is a mi~ture of a colour phase and a
diluent phase. The colour phase is formed by blending crystalline
silica with colourants. The resultant colour phase is mi~ed with the
diluent phase, essentially formed from nacreous materials such as talc
and mica, to form the composition.
The use of a foundation composition which has a significantly high
concentration of nacreous material is taught in US Patent No.
3,978,207. This foundation, a pressed powder composition, is
characterized by the presence of a nacreous material such as mica and
a binder oil which provides a frosted pearl effect, that is, a lustrous
look. The colour of this foundation is provided by the nacreous
material.
US Patent No. 4,659,562 discloses a cosmetic make-up composition
which includes, as a binding agent therefore, an intim~te mi~ture of
from S to 95 weight percent of a mi~ture of finely divided silica and
about 5 to 95 weight percent of finely divided polyethylene fibres. The
composition is recited to m~int~in its uniformity over the areas of the
skin to which it is applied. That is, it is said to be "creaseproof". The
composition of the '562 patent includes colourant in admixture with
nacreous agents.
Nakamura et al., ~ hlls of the XIVth I.F.S.C.C. Congress,
Barcelona, 1986, Vol. I, 51-63 (1986) describes a novel make-up
composition ~ltili7in~ spherical silica and polydimethyl silo~ane. This
combination is recited to provide a foundation which reduces wrinkle
visibility to a greater e~ctent than make-up foundations with which it
was co~ ,ared. This reduction in wrinkle visibility is caused by optical
blurring enhanced by the novel use of spherical silica and polydimethyl
silo~ane.
W0 95/04537 2 1 6 8 4 2 5 ~usg4~08838
-
US Patent No. 5,143,722 discloses a cosmetic make-up composition
comprising water-in-oil emulsions comprising pigment coated with
polysilo~ane, a silicone phase, a water phase and a
polydiorganosilo~ane-polyoxyalkylene copolymeric surfactant.
Foundations in the form of water-in-oil emulsions are well known and
provide good coverage and good skin feel, wear and appearance. At
the same time, it would be desirable to provide a foundation
composition having topical anti-acne activity. There are many
compounds which are known to e~hibit anti-acne properties when
applied topically to the skin. A commonly used keratolytic agent
having anti-acne activity is salicylic acid. As salicylic acid is virtually
insoluble in water it is difficult to incorporate into the aqueous phase of
an emulsion composition. Delivery of salicylic acid from the pigment-
conf~ining oil phase of an emulsion foundation composition can,
however, lead to discolouration of the composition due to interaction
between the salicylic acid and pigments, especially of the iron o~ide
type. It would therefore be desirable to deliver the salicylic acid in
soluble form from the aqueous phase.
Polyvinylpyrrolidone is known for use as a solubilizing/comple~ing
agent in a variety of compositions.
GB-A-2,041,963 discloses an aqueous detergent composition for
cle~n~in~ oily skin comprising a water-soluble salt of an N-acyl ester
of sarcosine, a polyvinylpyrrolidone cosolubilizer and a protein and/or
protein hydrolysate. The composition can also contain salicylic acid as
a keratolytic agent and a buffer such as citric acid/citrate. There is no
disclosure, however, of cosmetic compositions cont~inin~ solubilized
acidic anti-acne actives in fully protonated form as specified herein.
Since acidic anti-acne agents are most active at low pH (when a high
concentration of free acid is present in solution) it would be desirable
to deliver the agent from an aqueous phase at a pH at which it exists
significantly in protonated form. It is accordingly a primary object of
this invention to provide a cosmetic composition comprising a low pH
aqueous solution of an anti-acne active.
wo gs/W537 2 1 6 8 4 2 5 ~CTfUS94/08838
It is also an object of the invention to provide a cosmetic compositionhaving improved anti-acne activity and stability.
It is a further object of the invention to provide a cosmetic composition
in the form of an oil-in-water or water-in-oil emulsion having
improved colour stability and pigment/anti-acne active compatibility.
Sllmm~ry of the invention
In accordance with one aspect of the present invention, there is
provided a cosmetic composition in the form of an emulsion, gel or
lotion comprising an aqueous/alcoholic solution of an acidic anti-acne
active and a pyrrolidone-based comple~cing agent therefor, and wherein
the aqueous/alcoholic solution has a pH of less than about pKa + 1,
where pKa is the logarithmic acidity constant for the fully protonated
anti-acne active.
The cosmetic compositions of the present invention provide anti-acne
efficacy together with improved product and colour stability.
According to another aspect of the present invention there is provided
a make-up composition in the form of a water-in-oil or oil-in-water
emulsion comprising an acidic anti-acne active dissolved in the
aqueous phase and a pigment or mi~ture of pigments dispersed in the
oil phase.
All levels and ratios are by weight of total composition, unless
otherwise indicated. Chain length and degrees of alko~ylation are also
specified on a weight average basis.
Detailed Description of the Invention
The cosmetic composition according to one aspect of the present
invention comprises an aqueous/alcoholic solution of an acidic anti-
WO 95/04537 2 1 6 8 4 2 5 PCT/US94/08838
acne active and a pyrrolidone-based complexing agent. The
composition is in the form of an emulsion, gel or lotion.
According to this first aspect of the present invention a first essential
component is an aqueous/alcoholic solution of an anti-acne active.
Suitable anti-acne actives for use herein include salicylic acid, retinoic
acid and its derivatives, azelaic acid and its derivatives, lactic acid,
glycolic acid, pyruvic acid, flavonoids, and mixtures thereof.
The anti-acne active used in the composition herein is preferably
selected from salicylic acid and azelaic acid, and mi~tures thereof,
more preferably salicyclic acid. The anti-acne active is present at a
level of from about 0.1 % to about 10%, preferably from about 0. 1 %
to about 5%, more preferably from about 0.5% to about 3%, by
weight of composition.
The anti-acne active is solubilized in water or an alcoholic solution, for
e~ample, solutions based upon C2-C6 alcohols, diols and polyols,
preferled alcohols being selected from ethanol, dipropylene glycol,
butylene glycol, he~ylene glycol, and mi~ctures thereof. Alcohol is
preferably present in the compositions herein at a level of from about
1% to about 20%. The final aqueous/alcoholic anti-acne active
solution preferably has a pH at ambient temperature (25C) of less
than about PKa + 1, where PKa is the logarithmic acidity constant for
the fully protonated anti-acne active. In preferred embodiments, the
pH of the final solution is less than about pKa.
The logarithmic acidity constant is thus defined by reference to the
equilibrium
H+ + Hn-lA = HnA
where HnA is the fully protonated acid, n is the number of protons in
the fully protonated acid and Hn 1 A is the conjugate base of the acid
corresponding to loss of one proton.
WO 95/04537 2 1 6 8 4 2 5 PCT/US94/08838
The acidity constant for this equilibrium is therefore
Kn = [HnA]
rH+] [Hn lA]
and PKa = 1 og 1 oKn
For the purposes of this specification, acidity constants are defined at
25C and at zero ionic strength. Literature values are taken where
possible (see Stability Constants of Metal-Ion Complexes, Special
Publication No. 25, The Chemical Society, London); where doubt
arises they are determined by potentiometric titration using a glass
electrode.
The PKa f the acidic anti-acne active used herein is preferably in the
range of from about 1 to about 6, more preferably from about 1 to
about 4.5, especially from about 1.5 to about 4Ø
The pH of the final aqueous/alcoholic anti-acne active solution is
preferably in the range of from about 1 to about 7, more preferably
from about 2 to about 5, especially from about 2 to about 4. At pH
values of less than about 5 the aqueous phase is preferably free of acid
labile species such as acrylic acid/ethyl acrylate copolymers and
polyglycerylmethacrylate .
A second essential component of the compositions of the first aspect of
the present invention is a pyrrolidone-based comple~ing agent.
The pyrrolidone-based complexing agent is useful herein from the
viewpoint of aiding solubilization of the anti-acne active. The
pyrrolidone-based comple~cing agent used herein is preferably selected
from polyvinylpyrrolidone comple~ing agents or Cl-C4 alkyl
polyvinylpyrrolidone comple~ing agents having a molecular weight
(viscosity average) in the range from about 1500 to about 1,500,000,
preferably from about 3000 to about 700,000, more preferably from
about 5000 to about 100,000. Suitable examples of pyrrolidone-based
wo 95/04537 2 1 6 8 4 2 5 PCTIUS94/08838
comple~ing agents are polyvinylpyrrolidone (PVP) (or povidone) and
butylated polyvinylpyrrolidone. The most preferred pyrrolidone-based
comple~ing agent herein is a polyvinylpyrrolidone complexing agent.
PVP is commercially available under the trade name Luviskol (RTM)
from BASF. A preferred PVP complexing agent herein is Luviskol
K17 which has a viscosity-average molecular weight of about 9,000.
Other pyrrolidone-based comple~ing agents for use herein include C I -
Clg alkyl or hydroxyalkyl pyrrolidones such as lauryl pyrrolidone.
The pyrrolidone-based comple~ing agent is present in the composition
herein in a level of from about 0.1% to about 10%, preferably from
about 0.1 % to about 5 % by weight of composition. The weight ratio
of anti-acne active: pyrrolidone-based comple~ing agent is in the
range from about 10:1 to about 1:10, preferably from about 5:1 to
about 1 :5.
Preferred embodiments of the invention additionally comprise from
about 0.01 % to about 5 % by weight of an acid or salt thereof which is
soluble in water at pH values of less than or equal to the pKa of the
corresponding acid, for e~ample, an acid selected from citric acid,
boric acid, and salts, and mi~tures thereof. These materials are
valuable herein in combination with the pyrrolidone-based comple~ing
agent from the viewpoint of aiding solubilization of the anti-acne
active. Particularly prefelred herein from this viewpoint is a sodium
salt of citric acid. In preferred embodiments, the acid or salt thereof is
soluble to a level of at least 5% w/w at 25C.
The composition of the present invention can be in emulsion (w/o or
o/w), gel or lotion form but is preferably in the form of a water-in-oil
emulsion, wherein in prefe1red embodiments the oil phase comprises a
mi~ture of volatile silicones and non-volatile silicones. The silicone oil
is present in an amount of from about 1% to about 50% by weight.
Suitable volatile silicone oils include cyclic and linear volatile
polyorganosilo~anes (as used herein, "volatile" refers to those
materials which have a measurable vapour pressure at ambient
conditions).
wo 95/W~7 2 1 6 8 4 2 5 PCT/US94108838
A description of various volatile silicones is found in Todd, et al..
"Volatile Silicone Fluids for Cosmetics", 91 Cosmetics and Toiletries
27-32 (1976).
Preferred cyclic silicones include polydimethylsilo~anes containing
from about 3 to about 9 silicon atoms, preferably cont~ining from
about 4 to about 5 silicon atoms. Preferred linear silicone oils in~lud~
the polydimethylsilo~anes cont~inin~ from about 3 to about 9 silicon
atoms. The linear volatile silicones generally have viscosities of less
than about 5 centistokes at 25C, while the cyclic materials have
viscosities of less than about 10 centistokes. E~amples of silicone oils
useful in the present invention include: Dow Corning 344, Dow
Corning 21330, Dow Corning 345, and Dow Corning 200
(manufactured by the Dow Corning Corporation): Silicone 7207 and
Silicone 7158 (manufactured by the Union Carbide Corporation).
SF:202 (m~nllf~ctured by General Electric) and SWS-03314
(manufactured by Stauffer Chemical).
Suitable non-volatile silicones preferably have an average viscosity of
from about 1,000 to about 2,000,000 mm2.s~1 at 25C. more
preferably from about 10,000 to about 1,800,000 mm2.s~l, even more
~referably from about 100,000 to about 1,500,000 mm2.s~l. Lower
viscosity non-volatile silicone conditioning agents, however, can also
be used. Viscosity can be measured by means of a glass capillary
viscometer as set forth in Dow Corning Corporate Test Method
CTM0004, July 20, 1970. Suitable non-volatile silicone fluids for use
herein include polyalkyl silo~anes, polyaryl silo~anes, polyalkylaryl
silo~canes, polysilo~anes with amino functional substitutions, polyether
siloxane copolymers, and mi~tures thereof. The silo~anes useful in the
present invention may be endcapped with any number of moieties,
including, for e~ample, methyl, hydro~yl, ethylene o~cide, propylene
o~ide, amino and carbo~yl. However, other silicone fluids having skin
conditioning properties may be used. The non-volatile polyalkyl
silo~ane fluids that may be used include, for e~cample,
polydimethylsilo~anes. These silo~anes are available, for example,
from the General Electric Company as a Viscasil (RTM) series and
from Dow Corning as the Dow Corning 200 series. Preferably, the
wo gstw537 2 1 ~ 8 4 2 5 PCT/US94/08838
_
viscosity ranges from about 10 mm2.s~1 to about 100,000 mm2.s~1 at
25C. The polyalkylaryl siloxane fluids that may be used, also
include, for e~ample, polymethylphenylsiloxanes. These silo~anes are
available, for example, from the General Electric Company as SF 1075
methyl phenyl fluid or from Dow Corning as 556 Cosmetic Grade
Fluid. The polyether silo~cane copolymer that may be used includes,
for e~ample, a polypropylene oxide modified dimethylpolysiloxane
(e.g., Dow Corning DC-1248) although ethylene oxide or mixtures of
ethylene o~ide and propylene o~ide may also be used.
References disclosing suitable silicone fluids include US-A-2,826,551,
Green; US-A-3,964,500, Drakoff, issued June 22nd, 1976; US-A-
4,364,837, Pader; and GB-A-849,433, Woolston. In addition, Silicone
Compounds distributed by Petrarch Systems Inc., 1984 provides an
e~tensive (though not e~clusive) listing of suitable silicone fluids.
Preferred non-volatile silicones for use herein include
polydiorganosilo~ane-polyo~yalkylene copolymers cont~inin~ at least
one polydiorganosilo~ane segment and at least one polyoxyalkylene
segment, said polydiorganosilo~ane segment consisting essentially of
Rbsio(4-b)l2
siloxane units wherein b has a value of from about 0 to about 3,
inclusive, there being an average value of appro~imately 2 R radicals
per-silicon for all silo~cane units in the ccpolymer, and R denotes a
radical selected from methyl, ethyl, vinyl, phenyl and a divalent
radical bonding said polyo~yalkylene segment to the
polydiorganosilo~ane segment, at least about 95 % of all R radicals
being methyl; and said polyo~yalkylene segment having an average
molecular weight of at least about 1000 and consisting of from about 0
to about 50 mol percent polyo~ypropylene units and from about 50 to
about 100 mol percent polyo~yethylene units, at least one terminal
portion of said polyo~yalkylene segment being bonded to said
W09~/W~37 2 1 6 8 4 2 5 PCT~S94/08838
polydiorganosilo~ane segment, any terminal portion of said
polyoxyalkylene segment not bonded to said polydiorganosiloxane
segment being satisfied by a termin~ting radical; the weight ratio of
polydiorganosiloxane segments to polyoxyalkylene segments in said
copolymer having a value of from about 2 to about 8. Such polymers
are described in US-A-4,268,499.
More preferred for use herein are polydiorganosiloxane-
polyoxyalkylene copolymers having the general formula:
CH3 CH3 CH3 CH3
H3C Si 0 - (Si )x (Si 0) Si CH3
CH3 CH3 C3H6 CH3
o (~ H40)a(C3H6)bR
wherein ~ and y are selected such that the weight ratio of
polydiorganosilo~ane segments to polyoxalkylene segments is from
about 2 to about 8, the mol ratio of a:(a+b) is from about 0.5 to about
1, and R is a chain termin~ting group, especially selected frorll
hydrogen; hydroxyl; alkyl, such as methyl, ethyl, propyl, butyl,
benzyl; aryl, such as phenyl; alkoxy such as methoxy, ethoxy,
propo~y, buto~y; benzyloxy; aryloxy, such as phenoxy; alkenyloxy,
such as vinylo~y and allylo~y; acyloxy, such as acetoxy, acryloxy and
propiono~cy and amino, such as dimethylamino.
The number of and average molecular weights of the segments in the
copolymer are such that the weight ratio of polydiorganosiloxane
segments to polyoxyalkylene segments in the copolymer is preferably
from about 2.5 to about 4Ø
WO 95/04537 2 1 6 8 4 2 5 PCT/US94/08838
. _
Il
Suitable copolymers are available commercially under the tradenames
Belsil (RTM) from Wacker-Chemie GmbH, Geschaftsbereich S,
Postfach D-8000 Munich 22 and Abil (RTM) from Th. Goldsehmidt
Ltd,. Tego House, Victoria Road, Ruislip, Middlesex, HA4 OYL.
Particularly preferred for use herein are Belsil (RTM) 6031, Abil
(RTM) B88183 and DC3225C. A preferred silicone herein is known
by its CTFA designation as dimethicone copolyol.
The silicone oil phase preferably comprises from about 2% to about
25 %, more preferably from about 5 ~3Zo to about 15 % by weight of
composition of non-volatile silicones.
A highly preferred component of the compositions herein is a
humectant or mi~cture of humectants. The humectant or mi~ture of
humectants herein is present in an amount of from about 0.1 % to about
30% preferably from about 5% to about 25%, and more preferably
from about 10% to about 20% by weight of composition. Suitable
humectants are selected from glycerine and polyglycerylmethacrylate
lubricant having a viscosity at 25C of 300,000 to l,lOO,OOO cps; a
specific gravity at 25C of 1 to 1.2g/ml, a pH of 5.0 to 5.5; a bound
water content of 33 to 58%; and, a free water content from 5 to 20%.
The humectant can be incorporated at least partly into the oil phase of
the water-in-oil emulsion so as to form a multiphase humectant-in-oil-
in-water dispersion. The oil phase preferably comprises from about
0.1% to about 10%, more prefe-~bly from about O.l % to about 3% hy
weight of hl)mectant on a composition basis. The humectant can be
introduced into the oil phase in the form of a mi~ture with or
incorporated within a particulate lipophilic or hydrophobic carrier
material.
Polyglycerylmethacrylate lubricants having the desired properties are
marketed by Guardian Chemical Corporation under the trademark
"Lubrajel". The "Lubrajels" identified as "Lubrajel DV", "Lubrajel
MS", and "Lubrajel CG" are preferred in the present invention. The
gelling agents sold under these trademarks contain about I % propylene
glycol.
WO 95/W537 2 1 6 8 4 2 5 PCT/US94/08838
Other suitable humectants include sorbitol, panthenols, propylene
glycol, butylene glycol, hexylene glycol, alko~ylated glucose
derivatives, such as Glucam (RTM) E-20, hexanetriol, and glucose
ethers, and mi~tures thereof. Urea is also suitably added as a
humectant in the internal aqueous phase.
The panthenol moisturiser can be selected from D-panthenol ([R]-2,4-
dihydro~y-N-[3-hydro~ypropyl)]-3,3-dimethylbutamide), DL-
panthenol, calcium pantothenate, royal jelly, panthetine, pantotheine,
panthenyl ethyl ether, p~n~mic acid, pyrido~in, pantoyl lactose and
Vitamin B comple~.
The preferred humectant herein is glycerine. Chemically, glycerine is
1,2,3-propanetriol and is a product of commerce.
Preferred embodiments herein comprise a pigment or mi~ture of
pigments. Suitable pigments for use herein can be inorganic and/or
organic. Also included within the term pigment are materials having a
low colour or lustre such as matte fini~hin~ agents, and also light
scattering agents. E~amples of suitable pigments are iron oxides,
acylgll~t~m~te iron o~ides, ultramarine blue, D&C dyes, carmine, and
mi~tures thereof. Depending upon the type of make-up composition,
eg. foundation or blusher, a mi~ture of pigments will normally be
used.
It is a feature of the composition herein that the pigment and anti-acne
active have e~ccellent overall compatability and colour stability. Thu~
according to another aspect of the present invention there is provided a
make-up composition in the form of a water-in-oil or oil-in-water
emulsion comprising an acidic anti-acne active dissolved in the
aqueous phase and a pigment or mi~ture of pigments dispersed in the
oil phase.
The foundation composition can also include at least one matte
fini~hin~ agent. The function of the matte finishing agent is to hide
skin defects and reduce shine. Such cosmetically acceptable inorganic
WO 95/04537 2 1 6 8 4 2 5 PCT/US94/08838
. _
13
agents, i.e., those included in the CTFA Cosmetic Ingredient
Dictionary, Third Ed., as silica, hydrated silica, silicone-treated silica
beads, mica, talc, polyethylene, titanium dio~ide, bentonite, hectorite,
kaolin, chalk, diatomaceous earth, attapulgite zinc oxide and the like
may be utilized. Of particular usefulness as a matte finishing agent is
low lustre pigment such as tit~n~te~l mica (mica coated with titanium
dio~ide) coated with barium sulfate. Of the inorganic components
useful as a matte fini~hin~ agent low lustre pigment, talc, polyethylene,
hydrated silica, kaolin, titanium dio~ide and mi~tures thereof are
particularly preferred. Materials suitable for use herein as light-
scattering agents can be generally described as spherical shaped
inorganic materials having a particle size of up to about 100 microns,
preferably from about 5 to about 50 microns, for example spherical
silica particles.
The total concentration of the pigment may be from about 0.1 to about
25% by weight and is preferably from about 1 to about 10% by weight
of the total composition, the e~act concentration being dependent to
some e~ctent upon the specific mi~ture of pigments selected for use in a
foundation make-up or blusher to achieve the desired shades. The
preferred compositions contain from about 2% to about 20% by weight
of titanium dio~ide and most preferably from about 5% to about 10%
by weight of titanium dio~cide.
The preferred pigments for use herein from the viewpoint of
moisturisation, skin feel, skin appearance and emulsion compatibility
are treated pigments. The pigments can be treated with compounds
such as amino acids such as Iysine, silicones, lauroyl, collagen,
polyethylene, lecithin and ester oils. The more preferred pigments are
the silicone (polysilo~ane) treated pigments.
The balance of the composition of the present invention is deionized
water. The composition preferably comprises from about 30% to
about 95%, more preferably from about 40% to about 80% by weight
of the oil phase, and from about 5% to about 70%, more preferably
from about 20% to about 60% by weight of the water phase.
wo ss/04s37 2 1 6 8 4 2 5 PCT/USg4/08838
The make-up compositions of the present invention can also comprise a
particulate cross-linked hydrophobic acrylate or methacrylate
copolymer. This copolymer is particularly valuable for reducing shine
arld controlling oil while helping to provide effective moisturization
benefits. The cross-linked hydrophobic polymer is preferably in the
form of a copolymer lattice with at least one active ingredient
dispersed uniformly throughout and entrapped within the copolymer
lattice. Alternatively, the hydrophobic polymer can take the form of
porous particle having a surface area (N2-BET) in the range from
about 50 to S00, preferably lO0 to 300m2/g and having the active
ingredient absorbed therein.
The cross-linked hydrophobic polymer when used herein is in an
amount of from about 0.1% `to about 10% by weight and is preferably
incorporated in the e~ternal silicone-cont~inin~ oil phase. The active
ingredient can be one or more or a mixture of skin compatible oils,
skin compatible humectants, emollients, moisturizing agents and
sunscreens. The polymer material is in the form of a powder, the
powder being a combined system of particles. The system of powder
particles forms a lattice which includes unit particles of less than about
one micron in average diameter, agglomerates of fused unit particles of
sized in the range of about 20 to 100 microns in average diameter and
aggregates of clusters of fused agglomerates of sizes in the range of
about 200 to 1,200 microns in average diameter.
The powder material of the present invention which can be employed
as the carrier for the active ingredient can be broadly described as a
cross-linked "post absorbed" hydrophobic polymer lattice. The
powder l~rcferably has ent-apped and dispersed therein, an active
which may be in the form of a solid, liquid or gas. The lattice is in
particulate form and constitutes free flowing discrete solid particles
when loaded with the active material. The lattice may contain a
predetermined quantity of the active material. The polymer has the
structural formula:
WO 95/04537 PCT/US94/08838
21 68425
~s
CH3 CH3
CH2 C C --CH2
C=O C=O
O O
I
R' R' '
o
C=O
CH C
CH3 X
where the ratio of ~ to y is 80:20, R' is -CH2CH2- and R" is -
(CH2)1 1CH3-
The hydrophobic polymer is a highly crosslinked polymer, more
particularly a highly cross-linked polymethacrylate copolymer. The
material is manufactured by the Dow Corning Corporation, Midland.
Michigan, USA, and sold under the trademark POLYTRAP (RTM) .
It is an ultralight free-flowing white powder and the particles are
capable of absorbing high levels of lipophilic liquids and some
hydrophilic liquids while at the same time maint~ining a free-flowing
powder character. The powder structure consists of a lattice of unit
particles less than one micron that are fused into agglomerates of 20 to
100 microns and the agglomerates are loosely clustered into macro-
particles or aggregates of about 200 to about 1200 micron size. The
polymer powder is capable of cont~ininp as much as four times its
weight of fluids, emulsions, dispersions or melted solids.
WO 95/04537 2 1 6 8 4 2 5 PCT/US94/08838
Adsorption of actives onto the polymer powder can be accomplished
using a stainless steel mixing bowl and a spoon, wherein the active is
added to the powder and the spoon is used to gently fold the active into
the polymer powder. Low viscosity fluids may be adsorbed by
addition of the fluids to a sealable vessel containing the polymer and
then tumbling the materials until a consistency is achieved. More
elaborate blending equipment such as ribbon or twin cone blenders can
also be employed. The preferred active ingredient for use herein is
glycerine. Preferably, the weight ratio of humectant: carrier is from
about 1:4 to about 3:1.
Also suitable as a highly cross-linked polymethacrylate copolymer is
Microsponges 5647. This takes the form of generally spherical
particles of cross-linked hydrophobic polymer having a pore size of
from about 0.01 to about O.O51lm and a surface area of 200-300m2/g.
Again, it is preferably loaded with humectant in the levels described
above.
The compositions of the invention can also contain a hydrophilic
gelling agent at a level preferably from about 0.01% to about 10%,
more preferably from about 0.02~o to about 2%, and especially from
about 0.02% to about 0.5%. The gelling agent preferably has a
viscosity (1% aqueous solution, 20C, Brookfield RVT) of at least
about 4000 mPa.s, more preferably at least about 10,000 mPa.s and
especially at least 50,000 mPa.s.
Suitable hydrophilic gelling agents can generally be described as
water-soluble or colloidally water-soluble polymers, and include
cellulose ethers (e.g. hydro~yethyl cellulose, methyl cellulose,
hydro~ypropylmethyl cellulose), polyvinylalcohol, polyquaternium-10,
guar gum, hydro~ypropyl guar gum and ~nth~n gum.
Among suitable hydrophilic gelling agents are acrylic acid/ethyl
acrylate copolymers and the carbo~yvinyl polymers sold by the B.F.
Goodrich Company under the trade mark of Carbopol resins. These
resins consist essentially of a colloidally water-soluble polyalkenyl
polyether crosslinked polymer of acrylic acid crosslinked with from
wo ss/04s37 2 1 6 8 4 2 5 PCT/USg4/08838
17
0.75% to 2.00% of a crosslinking agent such as for e~ample polyallyl
sucrose or polyallyl pentaerythritol. Examples include Carbopol 934,
Carbopol 940, Carbopol 950, Carbopol 980, Carbopol 951 and
Carbopol 981. Carbopol 934 is a water-soluble polymer of acrylic
acid crosslinked with about 1% of a polyallyl ether of sucrose having
an average of about 5.8 allyl groups for each sucrose molecule. Also
suitable for use herein are hydrophobically-modified cross-linked
polymers of acrylic acid having amphipathic properties available under
the Trade Name Carbopol 1382, Carbopol 1342 and Pemulen TR-I
(CTFA Designation: Acrylates/10-30 Alkyl Acrylate Crosspolymer).
A combination of the polyalkenyl polyether cross-linked acrylic acid
polymer and the hydrophobically modified cross-linked acrylic acid
polymer is also suitable for use herein. Other suitable gelling agents
suitable for use herein are oleogels such as trihydro~ystearin and
aluminium magnesium hydro~y stearate. The gelling agents herein are
particularly valuable for providing e~cellent stability characteristics
over both normal and elevated temperatures.
Neutr~1i7in~ agents suitable for use in neutralizing acidic group ~ontainin~
hydrophilic gelling agents herein include sodium hydroxide, potassium
hydro~cide, ammonium hydro~cide, monoethanolamine, diethanolamine and
triethanol~mine.
The make-up compositions herein can additionally comprise an
emollient. Emollients suitable for the compositions of the present
invention include natural and synthetic oils selected from mineral,
vegetable, and ~nim~l oils, fats and wa~es, fatty acid esters, fatty
alcohols, alkylene glycol and polyalkylene glycol ethers and esters,
fatty acids and mi~tures thereof.
Suitable emollients for use herein include, for e~ample, optionally
hydro~y-substituted Cg-Cso I-n~ rated fatty acids and esters thereof,
C1-C24 esters of Cg-C30 saturated fatty acids such as isopropyl
myristate, cetyl palmitate and octyldodecylmyristate (Wickenol 142),
beeswa~, saturated and l~n~ rated fatty alcohols such as behenyl
alcohol and cetyl alcohol, hydrocarbons such as mineral oils,
petrolatum and squalane, fatty sorbitan esters (see US-A-3988255,
WO 95/W537 2 1 6 8 4 2 5 PCT/US94/08838
18
Seiden, issued October 26 1976), lanolin and lanolin derivativ~ u~h
as lanolin alcohol ethoxylated, hydro~ylated and acetylated lanolins,
cholesterol and derivatives thereof, ~nim~l and vegetable triglycerides
such as almond oil, peanut oil, wheat germ oil, linseed oil, jojoba oil,
oil of apricot pits, walnuts, palm nuts, pistachio nuts, sesame seeds,
rapeseed, cade oil, corn oil, peach pit oil, poppyseed oil, pine oil,
castor oil, soybean oil, avocado oil, saMower oil, coconut oil, hazelnut
oil, olive oil, grapeseed oil, and sunflower seed oil and Cl C24 esters
of dimer and trimer acids such as diisopropyl dimerate,
diisostearylm~l~te, diisostearyldimerate and triisostearyltrimerate.
r~efeifed emollients are selected from hydrocarbons such as
isohe~ ec~ne, mineral oils, petrolatum and squalane, lanolin alcohol,
and stearyl alcohol. These emollients may be used independently or in
mi~tures and may be present in the composition of the present
invention in an amount from about 1% to about 305'o by weight, and
preferably are present in an amount from about 5 % to about 15 % by
weight of the total composition.
The composition may also contain additional materials su~h as, for
e~ample, fragrances, fillers such as nylon, sun-screens, preservatives,
electrolytes such as sodium chloride, proteins, antio~idants, chelating
agents and water-in-oil emulsifiers as appropriate.
Another optional component of the make-up composition is one or
more ultraviolet absorbing agents. Ultraviolet absorbing agents, often
described as sunscreening agents, can be present in a concentration in
the range of between about 1% and about 12% by weight, based on the
total weight of composition. Preferably, the UV absorbing agents
constitute between about 2% and 8% by weight. More preferably, the
UV absorbing agents can be present in the composition in a
concentration range of between about 4% and about 6% by weight. Of
the ultraviolet absorbing agents suitable for use herein, benzophenone-
3, octyl dimethyl PABA (P~dim~te O) and mi~tures thereof are
particularly preferred.
WO 95tO4537 2 1 6 8 4 2 5 PCT/US94/08838
19
Another optional but preferred component herein is one or more
additional chelating agents, preferably in the range of from about
0.02% to about 0.10% by weight, based on the total weight of the
composition. Preferably, the chelating agent is present in a
concentration in the range of between about 0.03% and about 0.07~c
by weight, based on the total weight of the composition. Among the
chelating agents that may be included in the composition is tetrasodium
EDTA.
Another optional but preferred component of the foundation
composition is one or more preservatives. The preservative
concentration in the foundation composition, based on the total weight
of that composition, is in the range of between about 0.05 % and about
0.8% by weight, preferably between about 0.1% and about 0.3% by
weight. Suitable preservatives for use herein include sodium benzoate
and propyl paraben, and mi~tures thereof.
The make-up compositions of the present invention can be in the form
of foundations, blushers, concealers, compact powders, and the like,
preferably as foundations and concealers.
WO 95/~537 PCT~S94/08838
2 1 68425 --
The following Table is provided to illustrate compositions of the make-
up of the present invention:
Example I II III IV V VI V~l
Wt Wt Wt Wt Wt Wt Wt
% % % % % % %
A.
Cetyloctanoate 2.00 0.0 0.0 0.0 0.0 0.0 2.0
Cyclomethicone 8.57 12.25 12.25 15.0 12.0 8.57 8.57
Cyclomethicone/
dimethicone
cOpOIyOI (90:10) 17.16 20.0 20.0 5.0 8.0 10.0 17.16
Propylparaben 0.75 0.75 0.0 0.75 0.0 0.75 0.75
(33 %) in
laureth-7
Dimethicone 2.0 0.0 2.0 3.0 5.0 10.0 0.0
Fluid
Benzophenene-3 0.0 0.0 0.0 0.0 0.0 2.0 0.0
Propylene glycol
Dicaprylate/
Dicaprate 0.0 0.0 0.0 5.0 0.0 10.0 0.0
Titanium Dio~ide 8.25 6.0 1.5 6.0 8.0 20.0 8.25
Titanium Dio~ide
treated
(Aluminium
hydrate, stearic
acid) 0.25 0.5 3.0 0.25 0.25 0.0 0.25
Titanated Micas 0.1 0.1 0.1 0.25 1.0 0.0 0.1
Talc 3.38 4.5 6.0 0.7 0.7 0.7 3.38
Silica 0.6 4.25 6.0 4.25 0.6 0.6 0.6
Nylon 0.0 0.0 0.0 0.0 0-5
WO 95/04537 2 1 6 8 4 2 5 PCT/US94/08838
Example I II III IV V VI VII
Wt Wt Wt Wt Wt Wt Wt
% % % % % % %
C.
Cyclomethicone/
dimethicone
copolyol (90:10) 1.85 1.5 1.85 5.0 1.0 l.0 1.85
Yellow Iron
O~ide 1.2 1.2 0.6 0.4 1.2 1.2 1.2
Red Iron O~ide 0.49 0.6 0.6 0.49 0.49 0.2 0.6
Black Iron O~ide 0.16 0.1 0.24 0.1 0.1 0.24 0.24
Ultramarine Blue 0.0 0.0 0.0 0.1 0.0 0.0 0.0
Cyclomethicone 0.0 0.0 0.0 0.0 0.68 0.0 0.0
Synthetic Wa~ 0.1 0.5 0.5 0.1 0.0 0.0 0.0
Arachidyl
behenate 0.3 0.0 0.0 0.3 0.5 0.3 0 3
Stearic Acid 0.0 0.0 0.0 0.0 0.0 0.0 2.5
Palmitic Acid 0.0 0.0 0.0 0.0 0.0 2.5 0.0
Silica (spheron 6.0 0.0 6.0 0.0 0.0 0.0 0.0
P1500)
Trihydro~y- 0.3 0.3 1.5 1.5 0.0 0.0 0.0
stearin
Cyclomethicone 1.0 4.0 0.0 0.0 4.0 4.0 4.0
Beeswa~ 1.5 1.2 0.0 0.0 1.3 0.0 0.0
Abil WED9 0.0 3.0 0.0 0.0 0.0 0.0 0.0
wo ss/04s37 2 1 6 8 4 2 5 PCTNS94108838
Example I II III IV V VI VII
Wt Wt Wt Wt Wt Wt Wt
% % % 5'o % %
G.
Ethylene 0.05 0.0 0.0 0.0 0.0 0.05 0.05
brassylate
BHT 0.05 0.0 0.0 0.0 0.0 0.05 0.05
Deionized water ------- ------- -----to 100-- ------- ------- -------
Ethanol 6 5.5 4.0 7 6.0 8.0 6.0
Salicylic acid 1 1 1 2 2 2 0.0
Azeleicacid 0.0 0.0 0.0 0.0 0.0 0.0 5
Propylene glycol 2.37 2.37 1.37 2.37 0.0 2.37 0.0
Dipropylene 6.0 5.0 6.5 7.00 8.0 6.0 5.0
glycol
Sodium chloride 0.5 0.5 0.5 0.5 0.5 0.5 1.0
Glycerine 4.5 5.0 10.0 5.0 5.0 10.0 15.0
Tetrasodium 0.05 0.05 0.05 0.1 0.1 0.1 0.01
EDTA
Triethanol~mine 0.0 0.0 0.0 0 0 0 0 0 0 0 75
Allantoin 0.0 0.0 0.1 0.0 0.0 0.0 0.0
sunscreen 0.0 0.0 0.0 0.2 0.2 0.0 0.0
polyvinylpyrrolid- 1 2 1.5 1 1 1 2
-one (Luviskol
K17)
Sodiumcitrate 0.3 0.3 0.0 0.2 0.4 0.3 0.4
Sodium 0.0 0.0 0.1 0.4 0.0 0.2 0.0
Tetraborate
pH of aqueous 2.9 2.8 2.9 3.2 3.0 2.9 3.1
phase
Deionized Water 0.0 0.0 0.0 0.0 10.0 0.0 0.0
WO 95tO4537 2 1 6 8 4 2 5 PCT/US94/08838
23
E~ample I II III IV V VI V~I
Wt Wt Wt Wt Wt Wt Wt
% % % % % % %
J.
Propylene Glycol 0.0 0.0 0.0 2.0 0.0 0.0 0.0
X~nth~n Gum 0.0 0.0 0.0 0.08 0.0 0.0 0.0
Essential Oils 0.0 0.0 0.0 0.20 0.0 0.0 0.0
PerfumeOil 0.0 0.25 0.0 0.20 0.0 0.0 0.0
Vitamin A
Palmitate 0.0 0.05 0.0 0.0 0.0 0.0 0.0
AloeVeraGel 0.0 0.0 3.0 0.0 0.0 0.0 0.0
Chamomile
E~tract 0.0 0.0 0.1 0.0 0.0 0.0 0.0
* Contains about 1% propylene glycol.
The various components listed in the Table have been segregated into
groups, the constituents of each group being mi~ed together before
being added to members of the rem~inin~ groups in accordance with
the procedures set forth below.
In the first step, the mi~cture of components of phase A is stirred forappro~imately 5 minlltes with sheer mi~ing until homogeneous. With
high speed sheer mi~cing, the materials of phase B are added gradually
to A and the batch is mi~ed for 20 minutes until dispersed.
The components of phase C and then phase D are slowly added to the
mi~ture of phases A and B with high shear mi~ing until dispersed.
Silica is added at this point and dispersed through the mi~ture.
WO 95/04537 2 1 68 4 25 PCT/US94/08838
24
The resulting batch heated to 90C before the addition of the
components of phase E. The vessel is cooled to 55C and the
premixed phase F is added. The batch is mixed untiJ homogeneous.
The mi~ture is cooled to 30C and phase G is added.
A premi~ of phase H is made by mi~ing all the components until
completely dissolved. At 30C the premi~ of phase H is added to the
batch mi~ture with high shear, ensuring that there is no excess water
on the surface. The mi~ture is then milled for 15 minutes.
Finally phases I, J, K, and L are added as diluent.
The resulting make-up composition is ready for packaging.
The make-up compositions of the E~amples e~hibit anti-acne activity
and improved formulation and colour stability.
