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Title: High efficacy gel with
low glycol content
United States Patent: 7,204,976
Issued: April 17, 2007
Inventors: Popoff;
Christine (Morganville, NJ), Chopra; Suman (Dayton, NJ), Bustos; Mardoqueo
(Hillsboro, NJ), Tang; Xiaozhong (Bridgewater, NJ), Fei; Lin (Kendall
Park, NJ)
Assignee: Colgate-Palmolive
Company (New York, NY)
Appl. No.: 10/448,514
Filed: May 30, 2003
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Outsourcing Guide
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Abstract
The invention is a clear, elastomer-free,
gel composition comprising: (a) 14 30 weight % of an antiperspirant active
having a low metal to chloride ratio; (b) 7 23.3 weight % of one or more
cyclomethicones having a flash point of 100 degrees C. or less; (c) 0.6
0.9 weight % of a silicone surfactant having an HLB value.ltoreq.8; (d) 30
70 weight % water; (e) 3.85 10 weight % of a water soluble glycol or
polyglycol and (f) 0.1 3.0 weight % of a non-siliconized organic fragrance
solubilizer; wherein the composition is a gel having a viscosity greater
than 150,000 centipoise and a ratio of oil phase to water phase in the
range of 10:90 to 24:76.
SUMMARY OF THE
INVENTION
The invention is a clear (50 250 NTU at
21.0 degrees C.), high efficacy gel composition which is a high viscosity
(>150,000 centipoise) water-in-oil, elastomer-free emulsion. These gels
comprise a glycine containing antiperspirant active with a low metal to
chloride ratio in a high water content (>30 weight % of the formula)
internal (aqueous) phase, a copolyol, and a fragrance solubilizer in the
external phase. The external (oil) phase of the composition is free of
silicone emollients that have a high refractive index (R.I.>1.4200). The
gel compositions of this invention can include increased amounts of the
cosmetically active ingredient (which must be added in an amount of at
least 14 weight %). These cosmetic gels are quick drying due to the
combination of low levels of nonvolatile materials in the oil phase and
low levels (3.85 10 weight %) of glycols but provided that the amount of
propylene glycol should not exceed 7.5 weight %. The overall level of
silicone emollients is also controlled and is limited to .ltoreq.1 weight
%. Monovalent or divalent salt are used as refractive index modifying
agents in the aqueous phase so as to match the refractive index of the oil
phase, thus rendering a clear gel.
The invention is a clear water-in-oil emulsion having an external oil
phase and internal water phase wherein:
(I) The Oil Phase Comprises:
(a) 7.0 23.3 weight % (more particularly 9 20 weight %) of one or more
cyclomethicones having a flash point of 100 degrees C. or less;
(b) 0.6 0.9 weight % on an active basis (particularly 0.6 0.8% ) of a
silicone surfactant having an HLB value (hydrophilic lipophilic
balance).ltoreq.8);
(c) 0.1 3.0 weight % of an non-siliconized organic fragrance solubilizer
(particularly 0.5 2%) consisting of silicone compatible straight or
branched hydrocarbons with a molecular weight less than 1000, alkyl
substituted phenyl esters with an alkyl carbon chain length between C-1 to
C-20, and ethoxylated and or propoxylated ethers with a carbon chain
length from C-1 to C-25 and ethoxylation and or propoxylation from 1 10
(for example, a member of the group consisting of hydrogenated
polyisobutene (Polyiso 250), C12 15 alkyl benzoate (FINSOLV TN), and PPG-3
myristyl ether (particularly PPG-3 myristyl ether) which can help to
solubilize the fragrance oils in the otherwise all silicone based oil
phase and which does not negatively affect the skin feel and dry down
characteristics of the composition. Aesthetic skin feel attributes such as
wetness, stickiness, and residue have been evaluated by a 10 member
trained panel both on the forearm and underarm by rating some of the
antiperspirant gels described in this invention along with a commercial
gel. Significant differences in performance between some of the formulas
described herein and a commercial gel were noted at the 95% confidence
level.
(d) 0 1 weight % (particularly 0 0.25 weight % or 0.1 1.0 weight %) of a
low refractive index (R.I.<1.4200 at 21 degrees C.) silicone emollients
(by definition excluding (a) and (b) of this section) selected from the
group consisting of (i) volatile linear polydialkylsiloxanes with a flash
point is .ltoreq.100 degrees C. (particularly low viscosity dimethicones);
(ii) nonvolatile linear polydialkylsiloxanes with a flash point >100
degrees C.; and (iii) silanols (for example dimethiconols such as DC 9023
and DC 1501 from Dow Corning) in which one or two of the alkyl groups of
the foregoing materials (i) or (ii) are replaced with a hydroxyl group;
(note that combinations of these low refractive index silicone emollients
may also be used, however, the maximum level of silicone emollients must
still be .ltoreq.1 weight % (note that one particular embodiment of the
invention is free of volatile linear silicones (e.g. volatile dimethicones)
and/or free of non-volatile silicones).
(e) 0 5 weight % fragrance or odor masking component; and
(II) The Aqueous Phase Comprises:
(a) 14 30 weight % on an anhydrous basis (particularly 17 30 weight % and,
more particularly, 17 25 weight %) of a glycine containing antiperspirant
active salt comprising either aluminum or aluminum and zirconium metals
such that (i) if aluminum and zirconium salt is used then the metal/Cl
ratio of the salt should be low, such as 0.9 1.3:1 (more particularly in
the range of 0.9 1.05:1); the glycine/Zr ratio should be >1.2, and
Peak-5/Peak-3 should be >1.0; (ii) if aluminum salt is used then the
aluminum to chloride molar ratio should be in the range of 0.5 2.5:1; the
glycine/Al molar ratio should be in the range of 0.05 0.26:1 (preferably
in the range of 0.05 0.16:1);
wherein the glycine containing antiperspirant active salt has a pH in the
range of 2 4 (when measured in water at a concentration of 15%), is free
of any other halide scavenging material, and has a value of at least 0.50
for the ratio calculated as:
.times..times..times..times..times..times..times..times..times..times..tim-
es..times..times..times..times..times..times..times..times..times.
##EQU00001## -- see Original Patent.
(b) 30 70 weight % water (particularly 45 65% and, more particularly, 50
60%);
(c) 3.85 10 weight % (particularly 4 8 weight %) of a water soluble glycol
system which comprises at least 0.2% propylene glycol and an additional
glycol component selected from the group consisting of ethylene glycol;
diethylene glycol; triethylene glycol; tetraethylene glycol; propylene
glycol; dipropylene glycol; tripropylene glycol; 1,3 propanediol; 2-methyl
propanediol; methyl propanediol; 1,6-hexanediol; 1,3 butanediol; 1,4
butanediol; PEG-4 through PEG-600; PPG-9 through PPG-34; neopentyl glycol;
trimethylpropanediol; 2,2 dimethyl-1,3propandiol;
2,2,4,4-tetramethyl-1,3-cyclobutane-diol; and mixtures thereof in which
the amount of propylene glycol does not exceed 7.5% (particularly not
exceeding 5%). (More particular examples of the glycol component include
one or more members of the group consisting of propylene glycol,
dipropylene glycol, 2-methyl-1, 3 propanediol, methyl propylene glycol,
low molecular weight (less than 600) polyethylene glycol and mixtures of
any of the foregoing.)
(d) 0.2 4 weight % of a monovalent or divalent ionizable, water-soluble
inorganic or organic salts to help increase the refractive index of the
active phase and optimize the glycol level. These salts are of the form
M.sub.aX.sub.b where a=1, or 2 and b=1 or 2; M is a member selected from
the group consisting of Na.sup.+1, Li.sup.+1, K.sup.+1, Mg.sup.+2, Ca.sup.+2,
Sr.sup.+2 and Zn.sup.+2 and X is a member selected from the group
consisting of chloride, bromide, iodide, citrate, gluconate, lactate,
glycinate, glutamate, ascorbate, aspartate, nitrate, phosphate,
hydrogenphosphate, dihydrogenphosphate, formate, maloneate, maleate,
succinate, carbonate, bicarbonate, sulfate, hydrogensulfate. Salts of
particular utility are NaCl and ZnCl.sub.2.
(e) 0 5% of a water soluble carbon based high refractive index
(R.I.>1.4200) agent selected from the group consisting of additional
glycine (which is not part of the original salt), glycerin,
trimethylglycine ("Betaine,"), alanine, diglycereth-7, triglycereth-7
citrate, glycereth-7 glycolate, glycereth-5 lactate, lauramidopropyl
glycerin, glycereth-5 lactate, glycereth-7 glycolate, and glycereth-20
benzoate (Ethox GB-2) (for example, 0.5 3 weight % of a high refractive
index agent selected from the group consisting of diglycereth-7 citrate,
glycereth-7 glycolate, glycereth-5 lactate, lauramidopropyl glycerin,
glycereth-5 lactate, glycereth-7 glycolate and glycereth-20 benzoate; or,
as a second example, 0.5 3 weight % of a high refractive index agent
selected from the group consisting of additional glycine (which is not
part of the original salt), glycerin, trimethylglycine, and alanine;
(f) 0 10 weight % (particularly 0 4%) of an alcohol having 2 4 carbons
(for example, 1 5% ethanol);
wherein (i) all amounts are based on the weight of the entire composition,
(ii) the composition is an emulsion having a viscosity greater than
150,000 centipoise (for example, in the range of 150,000 600,000
centipoise, more specifically, 200,000 350,000 centipoise), and (iii) the
composition has a ratio of oil phase to water phase in the range of 10:90
to 24:76, and (iv) the composition is free of elastomers, borate
crosslinkers soap gelling agents, secondary water-soluble surfactants
having an HLB value.gtoreq.9.
Compositions of the invention according to a first aspect of the present
invention, various of the foregoing objects are achieved through a high
viscosity emulsion having (1) an aqueous phase containing water (or water
and a water soluble organic solvent as defined above); the antiperspirant
active containing aluminum and zirconium metals having a low M:Cl ratio
(0.9 to 1.3:1; and at least one monovalent or divalent salt, a combination
of propylene glycol and another glycol containing two hydroxy groups or
polymeric glycol in which the total level of glycol species does not
exceed 10 weight percent; and (2) an oil phase containing a volatile
organic or silicone material, and the composition further including (3) a
suitable silicone based surfactant such as an alkoxylated, alkyl
substituted siloxane surface active agent in an amount of 0.6 0.9 weight %
(on an actives basis) which suitable to form a high viscosity (>150,000
cps) gel as described above and (4) a suitable fragrance solublizer such
as myristyl ether which helps to solubilize the fragrance oils in the
predominantly silicone based oil phase.
The refractive index of the active phase is matched to the oil phase
(comprised of fragrance, surfactants, fragrance solubilizers silicones) by
adding glycols, monovalent and/or divalent salts and optionally monohydric
alcohols such that the refractive index of the active phase differs from
the refractive index of the oil phase by an amount of about 0.000 to
0.0040 units. This renders a clear product have an NTU (Nephelometric
Turbidity Units) value in the range of between 50 and 250 and an R.I. in
the range of 1.4025 to 1.4150. Most preferably the refractive index of the
active phase is lower than that of the fragranced oil phase thereby
minimizing the level of glycols. If added to the composition, the
fragrance oils typically have refractive indices ranging from 1.4450
1.4850 and are used typically at levels ranging from 0.50 2.0 weight
percent. Ionizable monovalent and divalent inorganic salts, antiperspirant
salts, water and optional ingredients such as alcohol are optimized to
provide a quick drying gel composition.
Refractive index measurements are made at a temperature of about 20 25
degrees C. using a Bausch and Lomb Abbe 3L Refractometer. Turbidity
measurements as described herein are made with an Orbeco-Hellige #965
Direct-Reading Turbidimeter.
One embodiment of the invention is comprised of an oil phase composition
such that the addition of the fragrance component (if fragrance is added
to the composition) provides a refractive index in the range from about
1.4015 to about 1.4150; especially from about 1.4025 to about 1.4090.
One of the benefits of adding a non-siliconized organic fragrance
solubilizer is to improve the solubility of the fragrance within the
silicone (primarily cyclomethicones) based oil phase of the gel emulsion.
The limited solubility of some fragrances in the cyclomethicone and linear
polydialkylorganosiloxanes (if present) is easily determined by the
turbidity of the aforementioned silicone(s) when approximately 10 30
weight % of fragrance is added to the silicone. To those skilled in the
art, it is known that the addition of as little as 5 10 weight % (the
amount depending on the fragrance) of the fragrance solubilizers
previously described (e.g PPG-3 myristyl ether) to the silicone/fragrance
mixture results in a clear solution.
The high viscosity gel compositions of the present invention include an
antiperspirant active agent in an amount sufficient to have a deodorizing
effect and/or in an amount sufficient to reduce the flow of perspiration
when the composition is applied to a human. For the antiperspirant active
used in the internal (also called "active") phase various antiperspirant
active materials that can be utilized according to the present invention
provided that they are soluble at a suitable concentration in the active
phase.
Antiperspirant actives can be incorporated into compositions according to
the present invention in amounts in the range of 14 30 weight % (on an
anhydrous solids basis), particularly 17 25 weight % of the total weight
of the composition. Mixtures of actives can also be used. The amount used
will depend on the formulation of the composition. At amounts at the
higher end of the range a good antiperspirant effect can be expected. As
noted above, the active is preferably included in the compositions of the
invention by premixing the active with water and possibly small amount of
propylene glycol.
Antiperspirant actives can be incorporated into compositions according to
the present invention in amounts as described above. At lower levels the
antiperspirant active material may not completely reduce the flow of
perspiration, but will reduce malodor, for example, by acting as an
antimicrobial material. At amounts of 15 25% by weight of the total weight
of the composition (on an actives basis), an antiperspirant effect may be
observed.
Particularly preferred are antiperspirant actives having the specific low
metal to chloride ratio specified above and those described in U.S. Pat.
No. 6,375,937 and patent application assigned to the same owners as this
case (U.S. Ser. No. 10/314,712 filed Dec. 9, 2002).
In one particular type of salt of interest, an aluminum zirconium
tetrasalt with glycine is used wherein aluminum zirconium
tetrachlorohydrex glycine salt having a metal to chloride ratio in the
range of 0.9 to 1.2:1 (especially in the range of 0.9 to 1.1:1 and, more
particularly in the range of 0.9 to 1.0:1); and a glycine:zirconium mole
ratio greater than 1.2:1, particularly greater than 1.4:1. This type of
salt may be made in a variety of ways as described in U.S. Pat. No.
6,375,937 as referenced above.
Another particular type of salt of interest is an aluminum chloride salt
buffered by glycine, wherein the salt has a metal to chloride ratio in the
range of 0.9 to 1.2:1 (especially in the range of 0.9 to 1.1:1 and, more
particularly in the range of 0.9 to 1.0:1). Also of interest are salts
which include Betaine, additional glycine, or another amino acid such as
alanine to further increase the refractive index of the glycine-containing
active complex.
Examples of salts include those made as follows: Method A: An aluminum
chlorohydrate (ACH) solution of ACH salt in water of suitable
concentration is mixed with an aqueous solution of zirconyl chloride
(ZrOCl.sub.2) of suitable concentration and powdered glycine. The mixture
is stirred at room temperature to obtain the salt. Method B: A suitable
commercially available aluminum zirconium tetrachlorohydrex glycine salt
is obtained and mixed with a sufficient amount of an aqueous aluminum
chloride (AlCl.sub.3) solution and powdered glycine. The mixture is
stirred at room temperature to obtain the salt. When Method B is used, a
suitable salt to use as a starting material includes various types of
tetra salts such as aluminum zirconium tetrachlorohydrex gly, aluminum
zirconium tetrachlorohydrex gly propylene glycol complex, aluminum
zirconium tetrachlorohydrex gly dipropylene glycol complex, and mixtures
of any of the foregoing. These salts may be referred to hereinafter as
experimental salts or carry an "exp" suffix in their designation. It is
preferred that the experimental salt be used in the form of a 28 50% water
solution when added to form the compositions of the invention.
The cyclomethicones used in this invention are one or more members
selected from the group consisting of cyclic polydimethylsiloxanes such as
those represented by Formula III -- see Original Patent.
Suitable silicone surfactants include silicone polyglucosides (for
example, octyl dimethicone ethoxy glucoside) and silicone copolyols having
an HLB value (hydrophilic lipophilic balance).ltoreq.8. The HLB value may
be measured in a variety of ways such as described in conventional
references or found listed in tables of data recording such values. It is
intended that any type of HLB measurement technique may be used.
A silicone copolyol (especially dimethicone copolyol) may be used in an
amount of 0.6 0.9 weight % (actives basis), particularly 0.6 0.8.
In general, silicone copolyols useful in the present invention include
copolyols of the following Formulae I and II -- see Original Patent.
Formula I materials may be represented by: (R.sup.10).sub.3--SiO--[(R.sup.11).sub.2--SiO].sub.x--[Si(R.sup.12)(R.sup-
.b--O--(C.sub.2H.sub.4O).sub.p--(C.sub.3H.sub.6O).sub.s--R.sup.c)O].sub.y--
-Si--(R.sup.13).sub.3 Formula I wherein each of R.sup.10, R.sup.11,
R.sup.12 and R.sup.13 may be the same or different and each is selected
from the group consisting of C1 C6 alkyl; R.sup.b is the radical
--C.sub.mH.sub.2m--; R.sup.c is a terminating radical which can be
hydrogen, an alkyl group of one to six carbon atoms, an acyl group such as
an ester with a terminating alkyl group of 1 4 carbons, or an aryl group
such as phenyl; m has a value of two to eight; p and s have values such
that the oxyalkylene segment --(C.sub.2H.sub.4O).sub.p--(C.sub.3H.sub.6O).sub.s--
has a molecular weight in the range of 200 to 5,000; the segment
preferably having fifty to one hundred mole percent of oxyethylene units
--(C.sub.2H.sub.4O).sub.p-- and one to fifty mole percent of oxypropylene
units --(C.sub.3H.sub.6O).sub.s--; x has a value of 8 to 400; and y has a
value of 2 to 40. Preferably each of R.sup.10, R.sup.11, R.sup.12 and
R.sup.13 is a methyl group; R.sup.c is H; m is preferably three or four
whereby the group R.sup.b is most preferably the radical
--(CH.sub.2).sub.3--; and the values of p and s are such as to provide a
molecular weight of the oxyalkylene segment
--(C.sub.2H.sub.4O).sub.p--(C.sub.3H.sub.6O).sub.s-- of between about
1,000 to 3,000. Most preferably p and s should each have a value of about
18 to 28.
A second siloxane polyether (copolyol) has the Formula II:
(R.sup.10).sub.3--SiO--[(R.sup.11).sub.2--SiO].sub.x--[Si(R.sup.12)(R.sup-
.b--O--(C.sub.2H.sub.4O).sub.p--R.sup.c)O].sub.y--Si--(R.sup.13).sub.3
Formula II wherein p has a value of 6 to 16; x has a value of 6 to 100;
and y has a value of 1 to 20 and the other moieties have the same
definition as defined in Formula I.
It should be understood that in both Formulas I and II shown above, that
the siloxane-oxyalkylene copolymers of the present invention may, in
alternate embodiments, take the form of endblocked polyethers in which the
linking group R.sup.b, the oxyalkylene segments, and the terminating
radical R.sup.c occupy positions bonded to the ends of the siloxane chain,
rather than being bonded to a silicon atom in the siloxane chain. Thus,
one or more of the R.sup.10, R.sup.11, R.sup.12 and R.sup.13 substituents
which are attached to the two terminal silicon atoms at the end of the
siloxane chain can be substituted with the segment --R.sup.b--O--(C.sub.2H.sub.4O).sub.p--(C.sub.3H.sub.6O).sub.s--R.sup.c
or with the segment --R.sup.b--O--(C.sub.2H.sub.4O).sub.p--R.sup.c. In
some instances, it may be desirable to provide the segment --R.sup.b--O--(C.sub.2H.sub.4O).sub.p--(C.sub.3H.sub.6O).sub.s--R.sup.c
or the segment --R.sup.b--O--(C.sub.2H.sub.4O).sub.p--R.sup.c at locations
which are in the siloxane chain as well as at locations at one or both of
the siloxane chain ends.
Particular examples of suitable dimethicone copolyols are available either
commercially or experimentally from a variety of suppliers including Dow
Coming Corporation, Midland, Mich.; General Electric Company, Waterford,
N.Y.; Witco Corp., Greenwich, Conn.; and Goldschmidt Chemical Corporation,
Hopewell, Va. Examples of specific products include DOW CORNING.RTM. 5225C
from Dow Corning which is a 10% dimethicone copolyol in cyclomethicone;
DOW CORNING.RTM. 2-5185C which is a 45 49% dimethicone copolyol in
cyclomethicone; SILWET L-7622 from Witco; ABIL EM97 from Goldschmidt which
is a 85% dimethicone copolyol in D5 cyclomethicone; and various
dimethicone copolyols available either commercially or in the literature.
It should also be noted that various concentrations of the dimethicone
copolyols in cyclomethicone can be used. While a concentration of 10% in
cyclomethicone is frequently seen commercially, other concentrations can
be made by stripping off the cyclomethicone or adding additional
cyclomethicone. The higher concentration materials such as DOW CORNING.RTM.
2-5185 material is of particular interest.
In one particular embodiment 3 9 weight % (particularly 5 8%) of a 10%
silicone copolyol such as dimethicone copolyol in cyclomethicone mixture
may be used, wherein the amount of mixture added is selected so that the
level of silicone copolyol in the cosmetic composition is in the range of
0.6 0.9% (particularly 0.6 0.8%) (for example, 6.5% of a 10% dimethicone
copolyol in cyclomethicone mixture).
Emollient selection is limited to those which have a relatively low
refractive index (R.I.<1.4200) in order to reduce the refractive index of
the oil phase thereby making it easier to match the refractive index of
the internal active phase. Emollients are a known class of materials in
this art, imparting a soothing effect to the skin. They are ingredients
which help to maintain the soft, smooth and pliable appearance of the
skin. Emollients are also known to reduce whitening on the skin and/or
improve aesthetics. Examples of suitable emollients which meet the low
refractive index requirement are limited to silicone-based structures
which are absent of phenyl groups.
Preferably linear silicones, are selected from the group consisting of
polydialkylsiloxanes represented by the formulae: (1)
(R.sup.10).sub.3SiO(Si(R.sup.11).sub.2O).sub.xSi(R.sup.12).sub.3 where
R.sup.10, R.sup.11 and R.sup.12 can be the same or different and are each
independently selected from the group consisting of C1 C10 alkyl (with
particular examples being polydimethylsiloxanes (dimethicones), especially
low viscosity dimethicones (viscosity <100 cps) (with the R groups and x
values being selected to maintain the RI limits); (2) silanols and/or
dimethiconols in which one or two of the alkyl (such as methyl) groups of
the foregoing formula may be replaced with a hydroxyl group and is
represented by formulae:
HO(R.sup.14).sub.2SiO(Si(R.sup.15).sub.2O).sub.xSi(R.sup.16).sub.2OH and
R17(R.sup.14).sub.2SiO(Si(R.sup.15).sub.2O).sub.xSi(R.sup.16).sub.2OH
where R.sup.14, R.sup.15 and R.sup.16 and R.sup.17 can be the same or
different and are each independently selected from the group consisting of
C1 C10 alkyl (with a particular example being methyl) (with the R groups
and x values being selected to maintain the RI limits);
Particular examples of suitable silicone emollients include, but are not
limited to, members of the group consisting of dimethicones having a
viscosity in the range of 0.5 5.0 centistokes (e.g. Dow Corning.RTM. DC
200), dimethiconol (Dow Corning.RTM. DC1501), Dow Corning 2501 cosmetic
wax (dimethicone copolyol) dimethiconol behenate, C.sub.30-45 alkyl
methicone, stearoxytrimethylsilane, and stearyl dimethicone) as well as
silanol DC 9023 also from Dow Corning).
The low refractive index emollient or emollient mixture or blend thereof
incorporated in compositions according to the present invention can,
illustratively, be included in amounts of 0 1 weight % inclusive,
preferably 0.5 1%.
The oil phase according to the present invention is, desirably, a silicone
oil phase, so as to provide a water-in-silicone oil emulsion. The total of
oil phase and siloxane surface-active agent preferably makes up from about
10% to about 24% by weight, of the total weight of the composition. This
surface-active agent is an emulsifier which, when properly mixed with the
aqueous phase components, and oil phase components, yields a water-in-oil
emulsion. The oil phase is desirably a blend of liquids, but does not
contain any significant amount of non-volatiles (that is, less than 1.0
weight % of any material having a flash point greater than 100 degrees
C.). Moreover, the nonvolatile silicone based emollients described in this
composition all have a refractive index lower than 1.420.
The refractive index of the oil phase (including fragrance) is determined,
and, if necessary, adjusted to be in the range of 1.4015 to about 1.4150;
especially from about 1.4025 to about 1.4090 and the refractive index of
the aqueous phase is determined and adjusted (if necessary) to differ from
the refractive index of the oil phase by less than 0.0050, preferable less
than 0.0030 units. The aqueous phase is then mixed with the oil phase (for
example, the aqueous phase is slowly added to the oil phase with turbulent
agitation), and then additional additives, or other active ingredients,
are added with mixing. Alternatively the fragrance can be added after the
active phase is added to the oil phase. In this instance the refractive
index of the oil phase (absent of fragrance) and aqueous phase should
differ less than 0.0020. The resulting emulsion is then passed through,
for example, a colloid mill or other high shear emulsifier so as to
provide a viscous gel, the gel then being transferred to a suitable
applicator or container for use by the consumer. Desirably, according to
the present invention the aqueous phase further includes a glycol mixture
consisting of propylene glycol and 2-methyl propanediol and/or dipropylene
glycol providing advantages in the final product as discussed previously.
A particular example of an alkoxylated, alkyl substituted siloxane surface
active agent is preferably, but not limited to, a dimethicone copolyol. An
illustrative alkoxylated silicone-containing surfactant utilizable
according to the present invention is cetyl dimethicone copolyol, referred
to in U.S. Pat. No. 5,162,378 to Guthauser. Illustratively, the
alkoxylated, alkyl substituted siloxane surface active agent is included
in the composition in an amount of 6.0% to 9.0% by weight, of the total
weight of the composition. Another example of a suitable surfactant is
octyl dimethicone ethoxy glucoside (from Wacker-Belsil, Adrian, Mich.).
A specific cyclomethicone-dimethicone copolyol fluid which can be utilized
to provide the alkoxylated silicone-containing surface-active agent is a
mixture of cyclomethicone and dimethicone copolyol designated as DC 5225C
from Dow Corning Corporation. This is a polyether substituted silicone of
cyclomethicone and dimethicone copolyol (refractive index (RI)=1.3994) at
about 20 25 degrees C. This DC 5225C, which is an emulsifying agent, is
useful for preparing stable water-in-oil emulsions where a silicone makes
up a large portion of the oil phase, and is a dispersion of a silicone
surfactant (dimethicone copolyol) (10% by wt.) in cyclomethicone (Dow
Corning 245) (90% by weight).
The mixture of cyclomethicone and dimethicone copolyol fluid is present in
the composition, illustratively, in an amount of from about 7.0% to about
23.3% by weight, of the total weight of the composition.
According to another aspect of the present invention, the aqueous phase of
the clear cosmetic gel composition further includes a glycol system in low
amount (3.85 10 weight % preferably 4 8%) comprising propylene glycol and,
preferably, at least one other glycol or polyglycol to help increase the
refractive index of the active phase so as to match it within 0.0000
0.0040 units (preferably 0.0010 0.0030 units) of the fragranced oil phase.
Illustratively, tripropylene glycol can be utilized as the additional
polypropylene glycol. According to this aspect of the present invention,
propylene glycol can be used in combination with the glycols up to a
limited amount. Incorporation of glycols, particularly MP-diol (2-methyl
1,3 propanediol) and dipropylene glycol in the gel composition also
improves cosmetic properties, including a reduction of tack and a decrease
in the whitening and in the residue after application of the composition.
Moreover, compositions incorporating polypropylene glycol, particularly,
tripropylene glycol, have improved mildness (that is, reduced skin
irritation potential) relative to commercially available products. The
glycol or polyglycol is selected from the group consisting of ethylene
glycol, propylene glycol, 1,2 propanediol, 2-methyl propanediol,
diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene
glycol, tripropylene glycol, methyl propanediol, 1,6-hexanediol, 1,3
butanediol, 1,4 butanediol, PEG-4 through PEG-600, PPG-9 through PPG-34,
neopentyl glycol, trimethylpropanediol, 2,2 dimethyl-1,3 propanediol,
2,2,4,4-tetramethyl-1,3-cyclobutane-diol and mixtures thereof. More
particular examples of the glycols which can be used with the propylene
glycol are one or more members of the group consisting of dipropylene
glycol, 2-methyl-1, 3 propanediol, methyl propylene glycol, low molecular
weight (less than 600) polyethylene glycol and mixtures of any of the
foregoing in which the amount of propylene glycol does not exceed 7.5%.
Clear gel compositions of the invention further include at least one
ionizable inorganic salt which helps to increase the refractive index of
the active phase and optimize the glycol level. Higher levels of glycols,
although good for reducing tackiness tend to increase dry-down time. These
ionizable salts are of the form M.sub.aX.sub.b where a=1, or 2 and b=1 or
2; M is a member selected from the group consisting of Na.sup.+1, Li.sup.+1,
K.sup.+1, Mg.sup.+2, Ca.sup.+2, Sr.sup.+2 and Zn.sup.+2 and X is a member
selected from the group consisting of chloride, bromide, iodide, citrate,
gluconate, lactate, glycinate, glutamate, ascorbate, aspartate, nitrate,
phosphate, hydrogenphosphate, dihydrogenphosphate, formate, maloneate,
maleate, succinate, carbonate, bicarbonate, sulfate, hydrogensulfate.
Salts of particular utility are NaCl and ZnCl.sub.2. As will be
appreciated by those skilled in the art, while it may be possible under
certain circumstances to add a salt directly to a portion of the mixture
during manufacturing, it is preferred to add the salt as a mixture or
solution of the salt in a carrier or solvent, particularly water. Of
course various concentrations of the salt premix can be made such as in
the range of 1 40%.
The present invention also includes methods of forming high viscosity
cosmetic gel compositions described herein. In such methods an aqueous
phase comprising water and the antiperspirant active is formed separately
from the oil phase containing an alkoxylated, alkyl substituted siloxane
surface active agent, an organic fragrance solubilizer and cyclomethicone
and optional fragrance. The two phases are then combined and homogenized
to achieve the desired viscosity.
For one embodiment the active phase is a water phase containing 17 30
weight % (anhydrous) of the low metal:chloride glycine-containing
antiperspirant active, 4.05 14 weight % of the water-soluble glycol system
with the monovalent or divalent ionizable water-soluble salt.
Illustratively, free water is included in the composition in the range of
30 70 weight % based on the total weight of the composition. The water
phase can also include, for example, (along with the antiperspirant
active, water-soluble glycol system and ionizable divalent or monovalent
salt) 1 5 weight % of a water-soluble carbon-based, high refractive index
agent (particularly additional glycine (an additional amount that is not
part of the original salt), glycerin, alanine and/or Betaine (as defined
above, trimethylglycine).
These compositions of the present invention may be prepared by a batch
process, or a continuous or semi-continuous process, and the processes
yield compositions which are stable, highly efficacious and possess
excellent aesthetic qualities.
The compositions according to the present invention are used as
conventional cosmetic gel compositions. For example, where the composition
according to the present invention is a clear antiperspirant soft gel
composition, packaged in a dispensing container having a top surface with
slots or pores, the gel is extruded from the dispensing container through
the slots or pores and applied to the skin (for example, in axillary
regions of the human body) by rubbing the soft gel material extruded
through the top surface of the container on the skin in the axillary
region.
As a further aspect of the present invention, the dispensing container can
be clear and can be tinted so as to for example, fit to the fragrance
hedonics. The composition has reduced tack, quick dry down, a cool
sensation, and a silky feel and imparts much less or no white residue on
dry down compared to commercially available products. Moreover,
compositions of the present invention incorporating a polypropylene glycol
component have improved mildness (have reduced skin irritation potential)
as compared to commercially available products, and have improved cosmetic
properties (including reduced tackiness) and reduced white residue upon
application. The gel emulsions according to the present invention are
stable and optically clear are cosmetically elegant, and are capable of
being delivered from a suitable applicator package.
Throughout the present specification, the antiperspirant active materials,
when utilized in an antiperspirant effective amount in the composition,
act to reduce body malodor by reducing production of perspiration;
however, these antiperspirant active materials can also have a deodorant
function, e.g., as an antimicrobial agent. The deodorant active materials
do not substantially reduce the production of perspiration, but reduce
malodor in other ways, e.g., as fragrances masking the malodor or reducing
the malodor intensity, as odor absorbents, as antimicrobial agents, as
agents chemically reacted with malodorous materials, etc.
The amount of active component that can be used will vary with the
particular active ingredient incorporate. The product comprises
antiperspirant active materials in amounts sufficient to combat body
malodor either as a deodorant or as an antiperspirant when applied to the
axillary regions of the body. As a general rule, an antiperspirant product
should contain an active antiperspirant material in an amount anywhere
from about 9% to about 25% by weight, of the total weight of the
composition. However, for the present invention it has been found that a
minimum of at least 14 weight % of antiperspirant salt must be used to
obtain the clarity desired. The active antiperspirant material utilized in
the compositions of the present invention can be pre-dissolved in water or
in another solvent (for example, in propylene glycol), and may be buffered
or unbuffered. Preferably, the antiperspirant materials are present in
solution in a solvent.
Where a deodorant active material is utilized other than lower amounts of
an antiperspirant active, any deodorant active material, which can be
dissolved in the oil phase, can be utilized in an amount sufficient to
have a deodorant effect. Illustratively, the deodorant active material can
be 2,4,4'-trichloro-2'-hydroxy diphenyl ether (triclosan), and/or
benzethonium chloride and/or octoxyglycerin (Sensiva.RTM. SC 50). Where
the deodorant ingredient is used in place of the antiperspirant active
ingredient, a deodorant gel composition (rather than an antiperspirant gel
composition) would be provided.
Throughout the present specification, where compositions are described as
including or comprising specific components or materials, it is
contemplated by the inventors that the compositions of the present
invention also consist essentially of, or consist of, the recited
components or materials. Accordingly, throughout the present disclosure
any described composition of the present invention can consist essentially
of, or consist of, the recited components or materials.
A desired feature of the present invention is that a clear cosmetic gel
composition (e.g., clear deodorant or antiperspirant gel composition) can
be provided. The term clear (that is clarity), according to the present
invention, is intended to connote its usual dictionary definition; thus, a
clear, e.g., cosmetic gel composition of the present invention allows
ready viewing of objects behind it. By contrast, a translucent composition
allows light to pass through, but causes the light to be so scattered that
it will be impossible to see objects behind the translucent composition.
Optical clarity of compositions of the present invention can be measured
using a turbidmeter as described above, and desirably lies between 50 and
250 NTU measured at room temperature (20.degree. 25.degree. C.).
Moreover, the clear cosmetic gel composition of the present invention,
which is in the form of a macro-emulsion as contrasted to a
micro-emulsion, does not need to contain wax or gelling agents such as
soaps, cellulosic materials or alginates. Furthermore, the composition
according to the present invention does not require
polydimethylcyclosiloxane, although the present compositions may contain
this material. comprising 3 7 weight % of propylene glycol in combination
with either 2-methyl propane diol or dipropylene glycol.
Several particular embodiments include those comprising one or more of the
following: 1 4 weight % of ethanol or propanol; 9 20 weight % of the one
or more cyclomethicones; 0.6 0.8 weight % of the silicone surfactant; 0.5
2 weight % of the fragrance solubilizer; and 45 65 weight % water.
Various materials incorporated in the water-based phase and in the
oil-based phase, and their refractive indices (as measured using the
Bausch and Lomb Abbe 3L Refractometer) are set forth in the following
particular formulations: 6.0 9.0 weight % dimethicone copolyol/cyclomethicone
(10%) (for example, Dow Corning 5225C); 7 23.3 weight % preferably 8 15
weight percent cyclomethicone (D4, D5, D6 or mixtures thereof); 0.1 3.0
weight % PPG-3 myristyl ether; 17 25 weight % antiperspirant active (for
example, Al--Zr tetrachlorohydrex gly (such as Z-522, 27.5% from Summit
Research Labs, Huguenot, N.Y.) and aluminum dichlorohydrate (such as
Westchlor 100, 36.1% to which glycine has been added so that the molar
ratio of gly/Al is in the range of 0.05 0.26:1) such as, for example,
described in U.S. Pat. No. 6,375,937 and patent application assigned to
the same owners as this case U.S. Ser. No. 10/314,712 filed Dec. 9, 2002);
30 70 weight % water; 0.2 to 4.0 weight % of an ionizable salt or
combinations of ionizable salts of the form M.sub.aX.sub.b where a=1 or 2;
b=1 or 2; M is a member selected form the group consisting of Na.sup.+1,
Li.sup.+1, K.sup.+1, Mg.sup.+2, Sr.sup.+2 and Zn.sup.+2, Ca.sup.+2 and X
is a member selected from the group consisting of chloride, bromide,
iodide, citrate, gluconate, lactate, glycinate, glutamate, ascorbate,
aspartate, nitrate, phosphate, hydrogenphosphate, dihydrogenphosphate,
formate, malonate, maleate, succinate, carbonate, bicarbonate, sulfate and
hydrogensulfate (preferred salts are ZnCl.sub.2 and NaCl or combinations
thereof); 4 8 weight % of the glycol system as described above in the
definition of the invention; 0 1 weight % of a low refractive index
emollients (RI<1.4200) such as dimethiconol, dimethicones, silanol and
combinations thereof; 0 1.0 weight % sage oil (any type such as Clary or
Dalmation); 0 5 weight % fragrance or odor masking component; 0 10% of a
water soluble non-glycol organic solvent selected from the group
consisting of 2 4 carbon chain alcohols (for example ethanol), 0 5 weight
% of a water-soluble carbon based high refractive index agent such as
additional glycine which is not part of the original salt,
trimethylglycine, alanine, glycerin, Diglycereth-7, Triglycereth-7
citrate, glycereth-7 glycolate, glycereth-5 lactate, lauramidopropyl
glycerin, glycereth-5 lactate, Glycereth-7 glycolate, and glycereth-20
benzoate; wherein the composition has a phase ratio in the range of 10:90
25:75 of oil to water and a viscosity is in the range of 150,000 600-000
centipoise.
Claim 1 of 26 Claims
1. A composition comprising a
water-in-oil emulsion having an external oil phase and internal water
phase wherein: (I) the oil phase comprises: (a) 7.0 23.3 weight % of one
or more cyclomethicones having a flash point of 100 degrees C. or less;
(b) 0.6 0.9 weight % of a silicone surfactant having a hydrophilic
lipophilic balance .ltoreq.8; and (c) 0.1 3.0 weight % of a non-siliconized
organic fragrance solubilizer; and (II) the aqueous phase comprises: (a)
14 30 weight % on an anhydrous basis of a glycine containing
antiperspirant active salt comprising either aluminum or aluminum and
zirconium metals provided that (i) if an aluminum and zirconium salt is
used then the metal/Cl ratio of the salt is in the range of 0.9 1.3:1, the
glycine/Zr ratio is >1.2, and Peak-5/Peak-3 is >1.0; and (ii) if an
aluminum salt is used then the aluminum to chloride molar ratio is in the
range of 0.5 2.5:1, and the glycine/Al molar ratio is in the range of 0.05
0.26:1; wherein the glycine containing antiperspirant active salt has a pH
in the range of 2 4 when measured in water at a concentration of 15%, is
free of any other halide scavenging material, and has a value of at least
0.50 for a ratio calculated as: .times..times..times..times..times..times..times..times..times..times..ti-
mes..times..times..times..times..times..times..times..times..times.
##EQU00002## -- see Original Patent. (b) 30 70 weight % water; (c) 0.3 10
weight % of a water soluble glycol system which comprises at least 0.2%
propylene glycol and an additional glycol component, in which the amount
of propylene glycol does not exceed 7.5%; and (d) 0.2 4 weight % of a
monovalent or divalent ionizable, water soluble inorganic or organic salt
of formula M.sub.aX.sub.b where a=1, or 2 and b=1 or 2; M is a member
selected from the group consisting of Na.sup.+1, Li.sup.+1, K.sup.+1,
Mg.sup.+2, Ca.sup.+2, Sr.sup.+2 and Zn.sup.+2 and X is a member selected
from the group consisting of chloride, bromide, iodide, citrate, gluconate,
lactate, glycinate, glutamate, ascorbate, aspartate, nitrate, phosphate,
hydrogenphosphate, dihydrogenphosphate, formate, maloneate, maleate,
succinate, carbonate, bicarbonate, sulfate, hydrogensulfate; wherein the
composition is a clear emulsion; wherein the composition has a ratio of
oil phase to water phase in the range of 10:90 to 24:76; wherein the
composition has a viscosity fo greater than 150,000; and wherein the
composition is free of elastomers, borate crosslinkers soap gelling
agents, and seccondary water-soluble surfactants having an HLB value
.gtoreq.9.
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