U.S. patent application number 11/599171 was filed with the patent office on 2007-11-15 for use of hydrophilic-rich alkylmethylsiloxane-dimethylsiloxane-polyoxyalkylene copolymers as emulsifiers for the preparation of cosmetic o/w emulsions of improved aesthetic properties and mildness.
Invention is credited to Michael E. Silver.
Application Number | 20070264223 11/599171 |
Document ID | / |
Family ID | 38685368 |
Filed Date | 2007-11-15 |
United States Patent
Application |
20070264223 |
Kind Code |
A1 |
Silver; Michael E. |
November 15, 2007 |
Use of hydrophilic-rich
alkylmethylsiloxane-dimethylsiloxane-polyoxyalkylene copolymers as
emulsifiers for the preparation of cosmetic o/w emulsions of
improved aesthetic properties and mildness
Abstract
This invention relates to the use of hydrophilic-rich, rake-type
alkylmethylsiloxane-dimethylsiloxane-polyoxyalkylene copolymers.
##STR1##
Inventors: |
Silver; Michael E.;
(Holland, MI) |
Correspondence
Address: |
King & Partners, PLC
170 College Avenue
SUITE 230
HOLLAND
MI
49423
US
|
Family ID: |
38685368 |
Appl. No.: |
11/599171 |
Filed: |
November 13, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11107325 |
Apr 13, 2005 |
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11599171 |
Nov 13, 2006 |
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Current U.S.
Class: |
424/78.03 |
Current CPC
Class: |
A61Q 17/04 20130101;
A61K 8/06 20130101; A61K 8/894 20130101; A61K 31/74 20130101; C08G
77/50 20130101; A61Q 1/14 20130101; A61K 8/062 20130101; A61Q 19/00
20130101 |
Class at
Publication: |
424/078.03 |
International
Class: |
A61K 31/74 20060101
A61K031/74; A61Q 19/00 20060101 A61Q019/00 |
Claims
1. The use for the formation of stable o/w emuslsions of
hydrophilic-rich organo-functional silicone copolyols, that are
intermediate between the typically hydrophilic silicone copolyols
and typically hydrophobic organo-functional silicone copolyols.
2. The alkyl dimethicone copolyol emulsifiers of this invention
have additional benefits of providing lift from the surface,
creating an overall skin feel that is soft and extremely smooth.
This softening effect is important beyond aesthetics in that it
reduces the overall roughness of the surface of the skin, allowing
light to reflect more evenly. The skin appears more uniform in
color and texture, a benefit strongly desired in anti-aging skin
care products. This benefit is not observed using either the
aforementioned alkyl dimethicone copolyol w/o emulsifiers of the
prior art (such as Goldschmidt ABIL EM90) or o/w emulsifiers of the
dimethicone copolyol variety (such as Dow Corning DC 193) or o/w
emulsifiers of the non-silicone containing variety (such as
Glyceryl Stearate and PEG 100 Stearate). Additional benfits
provided by the emulsifiers of this invention over the
aforementioned emulsifiers are a reduction of greasy feeling for
emulsions that have high (15% or higher) oil and/or petrolatum
content, a brilliant white appearance and less dense, souffle-like
texture for said high oil and or petrolatum emulsions, a decreased
rub in time, a final rub out that is less greasy, and a markedly
decreased irritancy.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of co-pending U.S.
application Ser. No. 10/891,438, filed Jul. 14, 2004, which claims
the benefit of U.S. Provisional Application Ser. No. 60/487,179
filed Jul. 14, 2004, and U.S. Provisional Application Ser. No.
60/513,136 filed Oct. 21, 2003, all of which are hereby
incorporated herein by reference in their entirety.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The invention present invention relates to novel,
hydrophilic-rich
organomethylsiloxane-dimethylsiloxane-polyoxyalkylene copolymers
and to their use as emulsifiers for the preparation of cosmetic
emulsions of improved aesthetic properties and mildness.
[0004] 2. Background Art
[0005] An emulsion is a dispersion of droplets of one liquid in a
second, immiscible liquid.
[0006] The process of dispersing one liquid in a second immiscible
liquid is called emulsification.
[0007] An emulsifier is required to stabilize an emulsion.
Emulsifiers are surface-active agents, that is a soluble compound
that reduces the surface tension of liquids, or reduces the
interfacial tension between two liquids. Surface tension is the
force acting on the surface of a liquid, tending to minimize the
area of the surface. Surfactants and emulsifiers (all emulsifiers
are a class of surfactants) reduce the surface tension of a liquid.
The surface tension of water is 72 dyne/cm; a surfactant can reduce
this to a value in the range of 30-50 dyne/cm.
[0008] There are two basic types of emulsions: oil in water (o/w)
and water in oil (w/o). The substance named last indicates the
continuous or outer phase. Whether a particular oil and water blend
will form a w/o or o/w emulsion depends largely on the choice of
emulsifier. Emulsifiers that are more soluble in water than in the
oil generally produce o/w emulsions. Emulsifiers that are more
soluble in the oil produce w/o emulsions.
[0009] Choice of emulsifier type is dependant upon the final skin
feel desired. The continuous phase will be the most perceived phase
while applying the lotion and after dry down. Water in oil
emulsions (w/o) tend to be heavier, leave a more distinctive
after-feel and are considered warmer than emulsions with water as
the continuous phase (o/w). When water is the continuous or outer
phase, typically the formulation is lighter, easier to rub in to
the skin, and the after-feel is lighter. The overall skin
conditioning efficacy of both emulsion types o/w and w/o is
dependant on the relative concentrations of the ingredients
used.
[0010] A predominantly hydrophilic emulsifier, will best stabilize
o/w emulsions, while a predominantly lipophilic emulsifier, will
best stabilize w/o emulsions.
[0011] HLB, the hydrophile/lipophile balance of a surfactant, can
help determine the best surfactants to use as emulsifiers. As
expected, products with higher ethylene oxide content are more
suitable for o/w emulsification, while products with lower ethylene
oxide content are more suitable for w/o emulsification.
[0012] A review of predominant skin care products currently in the
market shows strong regional preferences for specific emulsion
types. Typically European markets sell heavier, more occlusive
formulations and as such have a strong preference for w/o
formulations. Outside of the European markets, the overwhelming
global preference of lotions is o/w. This preference is most
predominant in Asian markets. The o/w formulations provide
excellent skin treatment products without leaving excessively
coated heavy feeling. This is most preferable in hot humid
environments. Very few if any w/o formulations are even sold in
Asia. The United States and Latin American markets also have strong
preferences toward the lighter feeling o/w formulation, however
there are some brands sold using W/o technology.
[0013] The alkyl dimethicone copolyol emulsifiers of this invention
are unique in that they serve as o/w emulsifiers and provide stable
o/w emulsions. This is in contrast to alkyl dimethicone copolyol
emulsifiers of the prior art (see, for example, U.S. Pat. No.
4,698,178), which specifically serve as w/o emulsifiers and provide
stable w/o emulsions. The alkyl dimethicone copolyol emulsifiers of
this invention have an additional benefit of providing lift from
the surface, creating an overall skin feel that is soft and
extremely smooth. This softening effect is important beyond
aesthetics in that it reduces the overall roughness of the surface
of the skin, allowing light to reflect more evenly. The skin
appears more uniform in color and texture, a benefit strongly
desired in anti-aging skin care products. This benefit is not
observed using either the aforementioned alkyl dimethicone copolyol
w/o emulsifiers of the prior art (such as Goldschmidt ABIL EM90) or
o/w emulsifiers of the dimethicone copolyol variety (such as Dow
Corning DC 193) or o/w emulsifiers of the non-silicone containing
variety (such as Glyceryl Stearate and PEG 100 Stearate).
Additional benfits provided by the emulsifiers of this invention
over the aforementioned emulsifiers are a reduction of greasy
feeling for emulsions that have high (15% or higher) oil and/or
petrolatum content, a brilliant white appearance and less dense,
souffle-like texture for said high oil and or petrolatum emulsions,
a decreased rub in time, a final rub out that is less greasy, and a
markedly decreased irritancy.
[0014] There is considerable prior art relating to
polydimethylsiloxane-polyoxyalkylene copolymers (silicone
copolyols) and
organomethylsiloxane-dimethylsiloxane-polyoxyalkylene copolymers
(organo-functional silicone copolyols).
[0015] Organo-functional silicone copolyols related to those of
this invention have been prepared from silicon hydride containing
siloxanes of the general structure Me.sub.3
SiO(Me.sub.2SiO).sub.x(HMeSiO).sub.ySiMe.sub.3 wherein Me is
methyl, x is 0 to about 200, and y is about 1 to 100, via a
hydrosilation coupling reaction (that utilizes a platinum catalyst)
with terminally unsaturated pblyoxyalkylenes and terminally
unsaturated organic molecules. The synthesis of organo-functional
silicone copolyols is described in U.S. Pat. Nos. 3,234,252,
4,047,958, 3,427,271, 2,846,458, and 6,346,553, and yields products
of the general formulas Me.sub.3
SiO(Me.sub.2SiO).sub.x(MeRSiO).sub.y(MeQSiO).sub.zM
QMe.sub.2SiO(Me.sub.2SiO).sub.x(MeRSiO).sub.ySiOMeQ wherein R
denotes an alkyl radical and Q denotes a polyoxyalkylene radical
having the formula
--CH.sub.2CH.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.p(OCH.sub.2CHCH-
.sub.3).sub.qOR' wherein R'.dbd.H or Me and both p and q range
between 0-50. These preparations are similar to those for the
preparation of silicone copolyols. The preparation of such
copolymers by the platinum catalyzed hydrosilation of silicon
hydride containing siloxanes and a polyoxyalkylene that is allyl
terminated at one end and either OMe or O(CO)R terminated at the
other end is well known and straightforward. The similar
preparation of silicone copolyols that employ polyoxyalkylene but
that is allyl terminated at one end and OH terminated at the other
end is more problematic. In all reported cases prior to this
invention, steps are taken in an attempt to eliminate or minimize
competing crosslinking side reactions that involve the
polyoxyalkylene terminal OH function and are well know to those
practiced in the art. One such crosslinking side reaction is due to
reaction of the Si--H and COH groups. Another is conversion of
terminal allyl groups to propenyl groups followed by crosslinking
via acetal formation with a polyoxyalkylene OH terminus. These
crosslinking reactions are catalyzed by platinum catalysts such as
chloroplatininc acid (H.sub.2PtCl.sub.6.6H.sub.2O), and lead to a
generally undesired increase in viscosity of the final product
and/or eventual gellation.
[0016] Much of the prior art relating to the preparation of
silicone copolyols, embodied in U.S. Pat. Nos. 3,280,160,
3,401,192, 4,122,029, 3,518,288, 4,520,160, 5,958,448, 6,346,583,
and 6,346,595, discloses the use of one or more solvents, often a
small cyclic polydimethylsiloxane or an alcohol, to minimize the
aforementioned side reactions. A solventless process is disclosed
in U.S. Pat. Nos. 4,847,398 and 6,372,874 that employ catalyst
modifiers which also minimize the aforementioned crosslinking side
reactions. In U.S. Pat. No. 4,025,456, a solventless process for
the preparation of siloxane-polyoxyalkylene copolymers is revealed.
This reference, however, utilizes alkoxy endblocked polyethers in
the hydrosilation reaction and does not disclose the use of OH
terminal oxyalkylene polyethers.
[0017] Similarly, much of the prior art relating to the preparation
of organo-functional silicone copolyols discloses the use of one or
more solvents or endblocked (protected) polyethers to minimize the
aforementioned side reactions. In U.S. Pat. No. 6,346,553, a
solventless process for the preparation of organo-functional
silicone copolyols is revealed that utilizes alkoxy endblocked
polyethers. Another common method is to protect the polyoxyalkylene
OH termini via conversion to OSiMe.sub.3, followed by deprotection
after hydrosilation, as is the case in U.S. Pat. No. 2,846,458.
[0018] Silicone copolyols and organo-functional silicone copolyols
are commonly used as emulsifiers for the preparation of cosmetic
formulations, a fact well known to those practiced in the art.
Typical examples of silicone copolyols are
Me.sub.3SiO(Me.sub.2SiO).sub.22(MeQSiO).sub.4SiMe.sub.3 and
Me.sub.3SiO(Me.sub.2SiO).sub.8.7(MeQSiO).sub.3.7SiMe.sub.3 (where
Q=(CH.sub.2).sub.3(OCH.sub.2CH.sub.2).sub.12OH). These and similar
materials are "water soluble" (i.e., they are either truly soluble
or they form stable dispersions in water). According to U.S. Pat.
Nos. 4,381,241, and 4,698,178, rake-type organo-functional silicone
copolyols of the type
Me.sub.3SiO(Me.sub.2SiO).sub.x(MeRSiO).sub.y(MeQSiO).sub.2M can
also be used as emulsifiers for the preparation of cosmetic
emulsions. The ABA or end-blocked organo-functional silicone
copolymers QMe.sub.2SiO(Me.sub.2SiO).sub.x(MeRSiO).sub.ySiOMeQ of
U.S. Pat. No. 6,346,553 can be used as emulsifiers for the
preparation of combined oil-silicone O/W emulsions. In all of these
cases, the preferred formula is one in which the number of units
having alkyl (R) radicals is at least twice as large (and typically
much greater than twice as large) as the number of units with
polyoxyalkylene (Q) radicals. This preference, along with the
preferred length of the alkyl radical and the preferred composition
of the polyoxyalkylene radical (which generally includes water
insoluble propylene oxide units along with water soluble ethylene
oxide units) results in predominantly hydrophobic (water insoluble)
organo-functional silicone copolyols. One such example, a rake-type
alkylmethylsiloxane-dimethylsiloxane-polyoxyalkylene emulsifier of
the type described in U.S. Pat. No. 4,698,178, is available under
the name Goldschmidt ABIL EM90 and is insoluble in water. Thus,
whereas organo-functional silicone copolyols of the prior art are
insoluble in water, the organo-functional silicone-copolyol
emulsifiers of this invention are soluble in that they form stable
dispersions in water at .gtoreq.15% mass emulsifier.
[0019] Many modern cosmetic formulations that make use of
emulsifiers of the type described above and/or other emulsifiers
have a high oil content (>20% by mass oils). Desirable aesthetic
effects for such cosmetic formulations include a light texture, an
initial rub-in that possesses a light, slightly wet, cool feel (as
opposed to a heavy, greasy, warm feel), a short overall rub-in
time, and a final rub-out that is not heavy, greasy, or tacky, but
instead leaves a light occlusive barrier on the skin. Also
desirable is a minimization of skin irritancy (i.e., maximum
mildness). Emulsifiers that can bestow these properties to cosmetic
formulations would be desirable and valuable.
SUMMARY OF THE INVENTION
[0020] We have prepared a class of hydrophilic-rich
organo-functional silicone copolyols that are intermediate in
behavior between the well-known silicone copolyols and
organo-functional silicone copolyols. By hydrophilic-rich, it is
meant that the copolymer can be easily taken up by water at a
concentration of about .gtoreq.15% by mass copolymer with simple
stirring to yield a stable dispersion of micron and sub-micron
sized particles. Such behavior is typical for silicone copolyols
(which are typically hydrophilic to the point that they form the
aforementioned dispersions or they are completely water soluble),
but not for organo-functional silicone copolyols of the prior art
(which are preferably water insoluble and predominantly
hydrophobic). The organo-functional silicone copolyols of this
invention are thus intermediate in that they are organo-functional
but are intentionally designed to contain sufficient hydrophilic
character such that they form the aforementioned dispersions in
water at a concentration of about .gtoreq.15% by mass copolymer
with simple stirring. In addition, the hydrophilic-rich organo
functional silicone copolymers of this invention function as
emulsifiers for high oil content (>20% by mass) cosmetic o/w
formulations such that, when compared to similar cosmetic
formulations employing either (a) traditional non-silicone
emulsifiers such as glycerol stearate +PEG 100 stearate
emulsifiers, or (b) organo-functional silicone copolymer
emulsifiers such as Goldschmidt ABIL EM90, or (c), silicone
copolymer emulsifiers such as
Me.sub.3SiO(Me.sub.2SiO).sub.8.7(MeQSiO).sub.3.7SiMe.sub.3 (where
Q=(CH.sub.2).sub.3(OCH.sub.2CH.sub.2).sub.12OH), result in a much
improved set of aesthetic set of properties including (1) a lighter
texture, (2) an initial rub-in that has a lighter, wetter, and
cooler feel, (3) a shorter overall rub-in time, and (4) a final
rub-in that is less-tacky, less greasy, and leaves a lighter
feeling occlusive barrier on the skin] and increased mildness as
measured by cyto-toxicity tests.
DETAILED DESCRIPTION OF THE INVENTION
[0021] While this invention is susceptible of embodiment in many
different forms, there is described herein in detail several
specific embodiments with the understanding that the present
disclosure is to be considered as an exemplification of the
principles of the invention and is not intended to limit the
invention to the embodiments illustrated.
[0022] The present invention was accomplished by using, as an
emulsifier for the preparation of cosmetic emulsions (both W/O and
O/W) with high oil content, organo-functional silicone copolyols of
this invention, which have the following nominal formula: ##STR2##
Organo-functional silicone copolyols of the previous art (see for
example, U.S. Pat. No. 4,698,718) have a preferred formula in which
the number of units having alkyl radicals is at least twice as
large (y>2z) and typically much greater than twice as large as
the number of units with polyoxyalkylene radicals, rendering them
predominantly hydrophobic. The organo-functional silicone copolyols
of this invention have preferred formula such that y.ltoreq.2z (the
number of units having alkyl radicals is less than or equal to 2
times the number of units with polyoxyalkylene radicals), which
functions to render the copolymers hydrophilic-rich (i.e., they are
readily taken up by water and simple stirring to form stable
dispersions at 15% by mass copolymer). Secondly, the number of
dimethylsiloxane units is adjusted to be no more than three times
the sum of the number of alkylmethysiloxane and polyoxyalkylene
units [x.ltoreq.3(y+z+q)], which also functions to render the
copolymers of this invention hydrophilic rich. Thirdly, the
copolymers of this invention typically employ polyoxyethylene
copolymers, whereas the copolymers disclosed in U.S. Pat. No.
4,698,178 employ polyoxyalkylenes that are oxyethylene-oxypropylene
copolymers of the type
(C.sub.2H.sub.4O--).sub.x(C.sub.3H.sub.6O--).sub.yR with preferred
weight ratio of oxyethylene to oxypropylene groups from 40:60 to
70:30. Oxypropylene groups render the polyoxyalkylene less
hydrophilic. The preferred use for this invention of
polyoxyalkylenes with no oxypropylene component (only oxyethylene
component) further increases the hydrophilic content of the
copolymers of this invention.
[0023] The hydrophilic-rich organo-functional silicone copolyols of
this invention may be used as primary emulsifiers or may also be
used in combination with known emulsifiers such as glyceryl
stearate, PEG 100 stearate, oleth-3, etc. Those skilled in the art
know that emulsifier mixtures frequently enable stable emulsions to
be prepared.
[0024] The oil phase may contain silicone oils. Within the meaning
of the present invention, silicone oils are liquid to very viscous
gels, particularly linear or cyclic, organosilicon compounds, whose
silicon units are predominantly difunctional and correspond to the
formula ##STR3## The R.sup.1 and R.sup.2 radicals may be the same
or different and are hydrocarbon radicals, especially alkyl or aryl
radicals, with methyl or phenyl radicals being especially
preferred. A portion of the R.sup.1 and R.sup.2 radicals may be
hydrogen radicals; p is a number not less than 2. The silicone oils
may have an end group and especially may be groups having the
formula (R.sup.1, R.sup.2).sub.3SiO-- or hydroxyl groups.
Trifunctional silicon units of formula (R.sup.1,
R.sup.2)SiO.sub.1.5-- may also be contained in small amounts. The
viscosity of the silicones usually falls within the range of 0.5
mPa sec to 3.times.10.sup.5 mPa sec.
[0025] The oily phase of the emulsions may contain carbon based
oils, waxes, or petrolatum in addition to the silicone oil. An
example of these oils include isopropyl palmitate.
[0026] The preparation of the desired emulsion is accomplished in a
know manner. The emulsifier of this invention is used either as 15%
by mass aqueous dispersion or as the pure material. Advisably, the
aqueous dispersion is added to the aqueous phase, whereas the pure
material is added to the oil phase. The procedure is then as
follows: (1) Heat the aqueous phase and the oil phase separately to
70.degree. C. (2) When both phases are at 70.degree. C., add the
oil phase to the water phase with stirring. (3) Cool to 45.degree.
C. (4) Add the neutralizer and preservative phase. (5) Cool to room
temperature with mixing.
[0027] The following examples (as set forth in the Table below)
illustrate the composition of high-oil phase emulsions prepared
using emulsifiers of this invention as well as representative
commercially available emulsifiers. TABLE-US-00001 Control A* B C**
WATER PHASE Water 67.65 69.65 67.65 67.65 Carbomer 980 0.10 0.10
0.10 0.10 Glycerin 2.00 2.00 2.00 2.00 Glycereth-26 3.00 3.00 3.00
3.00 Methylparaben 0.25 0.25 0.25 0.25 Emulsifier of this invention
0.00 3.00 0.00 0.00 Glyceryl Stearate & PEG 100 Stearate 5.00
0.00 0.00 0.00 emulsifiers OIL PHASE Isopropyl Palmitate 7.00 7.00
7.00 7.00 Petrolatum 7.50 7.50 7.50 7.50 Behenyl Alcohol 2.50 2.50
2.50 2.50 Sorbitan Stearate 1.00 1.00 1.00 1.00 Dimethicone 0.50
0.50 0.50 0.50 Goldschmidt ABIL EM-90 emulsifier 0.00 0.00 5.00
Emulsifier of this invention 0.00 0.00 0.00 5.00 NEUTRALIZER AND
PRESERVATIVE PHASE Water 2.00 2.00 2.00 2.00 Triethanolamine 0.50
0.50 0.50 0.50 Benzyl Alcohol 1.00 1.00 1.00 1.00 TYPE OF EMULSION
FORMED O/W O/W W/O O/W *Emulsifier of this invention is a 15%
aqueous emulsion of the copolymer with R = dodecyl, R' = H, x = 18,
y = 6, z + q = 4, q .ltoreq. 0.8, p = 12. **Emulsifier of this
invention is the pure copolymer with R = dodecyl, R' = Me, x = 18,
y = 5, z + q = 4, q .ltoreq. 0.8, p = 12.
[0028] ##STR4##
[0029] The control emulsion and emulsion B that employed the
commercially available stearate and organo-functional silicone
copolyols emulsifiers, respectively, were similar in that they
produced a warm, greasy initial feel, possessed a long rub-in time,
and gave rise to a final rub-out that was heavy and oily and left a
heavy occlusive barrier on the skin. In addition, emulsion B
employing Goldschmidt ABIL EM90 had a slippery, silicone feel and
was off white in color. Emulsions A and C employing emulsifiers of
this invention were a brilliant white color, possessed a light,
souffle-like texture, applied with a light, cool, wet feel,
possessed a shorter rub-in time, and gave rise to a final rub-out
that was light, less oily, and left a light occlusive barrier on
the skin.
[0030] Emulsifiers of this invention also result in cosmetic
formulations that are milder (less irritating to the skin) relative
to similar formulations employing other emulsifiers as measured via
cell culture cell-survival tests (so called cyto-toxicity tests)
for eye-makeup remover formulations based on MTT data from cells
treated with test reagent for the indicated time (as set forth in
the following Table). TABLE-US-00002 % Control % Control % Control
t.sub.50 Sample viability 2 hrs viability 6 hrs viability 24 hr
(hrs) A 99.0 93.4 48.8 24 Negative Ctrl 100 100 100 na Positive
Ctrl 17.9 5.4 5.9 <1 B 90.5 67.4 4.5 .about.11 C 87.6 65.5 19.7
.about.12.5
Results are the averages of treatments divided by the average of
the negative control. t.sub.50 were estimated from the graphic
results. MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium
bromide) is a water-soluble chemical. Active mitochondrial
dehydrogenases of living cells convert the yellowish MTT to an
insoluble purple formazan. This conversion does not take place in
dead cells. This water-insoluble formazan can be solubilized using
isopropanol, and the dissolved material can be measured
spectrophotometrically. The t.sub.50 value is the time of exposure
to test reagent (samples A-C) that reduced MTT metabolism to 50% of
control levels.
[0031] The formulations A-C consisted of cyclomethicone (48%),
dimethicone (2%), butylene glycol (8%) and preservatives (1%).
Sample A employed 5% of Example 4 as the emulsifier and the
remainder was water. Sample B employed 5% Dow Corning DC 193 as the
emulsifier (a silicone polyethyleneglycol-copolyol) and the
remainder was water. Sample C employed oleth-3 as the emulsifier
and was anhydrous, employing petrolaturn instead of water. The
results clearly indicate significantly enhanced cell survivability
for sample A, supporting the claim of increased mildness.
[0032] The following examples (as set forth in the Table below)
illustrate the composition of various stable w/o emulsions prepared
using emulsifiers of this invention. TABLE-US-00003 Formula
Description INCI Name % High Oil Phase Make-Up Cyclomethicone 48.00
Remover Oil in Water Emulsion Dimethicone 2.00 Example 6 Emulsifier
(15% 5.00 aqueus dispersion) Deionized Water 39.25 Butylene Glycol
3.00 Glycein 2.00 Phenoxyethanol, Methylparaben, 0.75 Ethylparaben,
Propylparaben, Butylparaben 100.00
[0033] TABLE-US-00004 Sprayable Lotion Deionized Water 90.85 Oil in
Water Emulsion Example 8 Emulsifier (5% 5.00 aqueous dispersion)
Botanical Extracts 2.00 Propylene Glycol, Diazolidinyl 0.75 Urea,
Methylparaben, Propylparaben C12-15 Alkyl Benzoate 0.50 Polysorbate
20 0.75 Fragrance 0.15 FD&C Red No. 4 trace 100.00
[0034] TABLE-US-00005 TiO2 Sunscreen Lotion Deionized Water 63.55
Oil in Water Emulsion Carbomer 0.20 Glyceryl Polymethacrylate 10.00
Glycerin 1.50 Butylene Glycol 4.50 Methylparaben 0.25 Disodium EDTA
0.05 Polysorbate 20 0.50 Squalane 3.00 Dimethicone 2.00 Petrolatum
3.00 Example 8 Emulsifier (5% 4.00 aqueous dispersion) Polyethylene
0.50 40% TiO2 in C12-15 Alkyl 6.00 Benzoate Triethanolamine 0.30
Phenoxyethanol, Methylparaben, 0.50 Ethylparaben, Propylparaben,
Butylparaben Fragrance 0.15 100.00
[0035] TABLE-US-00006 High Petrolatum Cream Water 52.750 Oil in
Water Emulsion Carbomer 980 0.100 Glycerin 2.000 Glycereth-26 3.000
Methylparaben 0.250 Example 6 Emulsifer (15% 20.000 aqueous
dispersion) Isopropyl Palmitate 7.000 Petrolatum 7.500 Behenyl
Alcohol 2.500 Sorbitan Stearate 1.000 Dimethicone 0.500 Water 2.000
Triethanolamine 0.150 Benzyl Alcohol 1.000 Fragrance 0.250
100.000
[0036] TABLE-US-00007 Emollient Lotion Water 67.65 Oil in Water
Emulsion Carbomer 980 0.10 Glycerin 2.00 Glycereth-26 3.00
Methylparaben 0.25 Example 6 Emulsifier (15% 5.00 aqueous
dispersion) Isopropyl Palmitate 7.00 Petrolatum 7.50 Behenyl
Alcohol 2.50 Sorbitan Stearate 1.00 Dimethicone 0.50 Water 2.00
Triethanolamine 0.50 Benzyl Alcohol 1.00 100.00
Preparation of Hydrophylic-Rich
Alkylmehtylsiloxane-dimethylsiloxane-polyoxyalkylene Copolymer
Emulsifiers
[0037] Experimental Procedure
[0038] Raw Materials
[0039] 1. Preparation of Silanic Hydrogen Containing
Intermediates
[0040] Silicone intermediates of the type used to make the
compounds of this invention are well known to those skilled in the
art. They conform to the following structure (the hydrogen
containing units are randomly distributed): ##STR5##
[0041] These compounds were prepared from equilibration of
octamethylcyclotetrasiloxane, hexamethyldisiloxane, and either
tetramethylcyclotetrasiloxane or
Me.sub.3SiO--(MeHSiO).sub.50--SiMe.sub.3, with tonsil acid clay (1
g per 100 g of reaction mixture) at 80.degree. C. for a minimum of
eight hours, filtered, and stripped of volatiles to 175.degree. C.
at 0.01 mm Hg. The structures were confirmed using proton NMR
spectroscopy. GPC analysis resulted in average molecular weights
close to the calculated molecular weights listed below.
TABLE-US-00008 Calculated Molecular Example a b Weight (g/mole) 1
18 9 2038 2 18 10 2098 3 27 9 2706
[0042] 2. OH/Allyl and OMe/Allyl Terminal Polyoxyalkylenes
[0043] The Allyl/OH terminal polyoxyalkylene (polyether) used in
this invention conforms to the following structure and is
abbreviated in the examples below as Allyl/OH-PEO- 12: ##STR6##
This compound was obtained from the Dow Corporation of Midland
Mich. (DOW AE501) and from Goldschmidt AG of Essen Germany. These
materials typically are wet, containing from 0.05% to 0.3% by mass
water, and were used as is or were dried via azeotropic
distillation of the water using toluene. The toluene was then
removed via distillation. Drying made no significant change in the
reaction or in the properties of the materials afterwards. One of
the Allyl/OMe terminal polyoxyalkylenes used in this invention
conforms to the following structure and is also abbreviated in the
examples below as Allyl/OMe-PEO-12: ##STR7## This compound was
obtained from Goldschmidt AG of Essen Germany. This material
typically is wet, containing approximately 0.12% by mass water, and
was used as is or was dried via azeotropic distillation of the
water using toluene. The toluene was then removed via distillation.
Drying made no significant change in the reaction or in the
properties of the materials afterwards. Another of the Allyl/OMe
terminal polyoxyalkylenes used in this invention conforms to the
following structure and is also abbreviated in the examples below
as Allyl/OMe-PEO-10: ##STR8## This compound was obtained from the
Clariant Corporation and was used as is.
[0044] 3. Alpha Olefins
[0045] The Alpha olefins used were 1-dodecene and ethylene, both
available from a variety of sources.
[0046] Hydrosilation
[0047] All hydrosilation reactions were performed without solvent
in a one liter heated Parr Model 4511 pressurizeable steel reactor
equipped with two horizontally stacked pitched blade impellers and
sampling port. The hydrosilation reaction used to make the
compounds of this invention is well known to those skilled in the
art. One of the many references is International Publication
(Silicone Alkylene Oxide Copolymers As Foam Control Agents) WO
86/05411 by Paul Austin (Sep. 25, 1986) p.19. A freshly prepared
0.050 M solution of H.sub.2PtCl.sub.6.6H.sub.2O in 2-propanol was
the source of platinum catalyst used to achieve a platinum
concentration of 5 ppm for all reactions.
[0048] Preparation of Aqueous Dispersions and Determination of
Dispersion Particle Size
[0049] All of the copolymers of this invention form smooth, white
15% by mass dispersions in water. The dispersions were prepared as
follows: (1) 200 g of neat copolymer were weighed into a 3-L round
bottom flask followed by addition of sufficient room temperature RO
(reverse osmosis) water (1133 mL) such that the resulting
dispersion would be 15% by mass copolymer. (2) The water/copolymer
combination was mechanically stirred at room temperature
(mechanical stirrer employed a motor, and a glass shaft connected
to a 76 mm length.times.19 mm width Teflon stir blade-Ace Glass
Catalog item # 8085-11) at approximately 480-500 rpm. After about 1
hour the dispersion appeared white and smooth, however, stirring
was allowed to continue for a total duration of at least 8
hours.
[0050] Aqueous dispersion particle size was measured with the use
of a Honeywell Microtrac UPA Particle Size Analyzer, which
determines particle velocity distribution and size via measurement
of Doppler shifts to the incident laser frequency at a single angle
(dynamic light scattering technique). For this technique, aqueous
dispersions of 1% concentration were employed (via appropriate
dilution of the above 15% aqueous dispersion) and were filtered
through a 0.45 .mu.m filter to remove dust particles prior to
study.
[0051] Molecular Weight Determination
[0052] Molecular weight determinations were made using a Water's
System GPC with refractive index detection using a Phenomenex
Phenogel 5 50 mm.times.7.80 mm guard column followed by a
Phenomenex Phenogel 5 MXM 300 mm.times.7.8 mm 5 .mu.m particle size
5 K-500 K column followed by a Phenomenex Phenogel 5 MXL 300
mm.times.7.8 mm 5 .mu.m particle size OK-40 K column in THF
relative to polystyrene standards.
EXAMPLE 4
Copolymer where R Dodecyl, R'.dbd.H, x=18, y=5, z+q=4,
q.ltoreq.0.8, p=12
[0053] ##STR9##
[0054] Previously nitrogen saturated 1-dodecene (82.58 g, 0.491
mol), silanic hydrogen intermediate Example 1 (200.0 g, 0.0981
mol), and allyl/OH-PEO-12 (92.11 g, 0.157 mol) were combined in a
Parr Model 4511 reactor and the head space was purged with
nitrogen. The mixture was then stirred and heated to 85.degree. C.,
whereupon the reactor was opened to allow for the injection of Pt
catalyst (192.2 .mu.L of a freshly prepared 0.050 M solution of
H.sub.2PtCl.sub.6.6H.sub.2O in isopropyl alcohol). The reactor was
sealed and the head space again purged with nitrogen while stirring
was initiated, resulting in an exotherm leading to a rapid
approximate35.degree. C. increase in temperature. After 43 minutes,
the reactor was opened and nitrogen saturated allyl/OH-PEO-12
(138.17 g, 0.235 mol) and additional Pt catalyst (70.7 .mu.L) were
added. The reactor was resealed and the stirred reaction allowed
continued for an additional 67 minutes. By this time the reaction
temperature was at 124.degree. C. Next, the reactor was pressurized
with 40 psi of ethylene and allowed to stir for an additional 50
minutes, during which time residual unreacted Si--H was consumed
(monitored via IR spectroscopy). The maximum temperature reached
during this interval was 125.degree. C. The product, a clear,
colorless semi-viscous liquid, was removed from the reactor and
degassed of saturated ethylene in vacuo. Proton NMR spectra of the
product were consistent with the expected structure.
EXAMPLE 5
Copolymer where R=Dodecyl, R'.dbd.H, x=18, y=6, z+q=4,
q.ltoreq.0.8, p=12
[0055] ##STR10##
[0056] Previously nitrogen saturated 1-dodecene (111.08 g, 0.660
mol), silanic hydrogen intermediate Example 2 (230.82 g, 0.110
mol), and allyl/OH-PEO-12 (103.22 g, 0.176 mol) were combined in a
Parr Model 4511 reactor and the head space was purged with
nitrogen. The mixture was then stirred and heated to 85.degree. C.,
whereupon the reactor was opened to allow for the injection of Pt
catalyst (215.3 .mu.L of a freshly prepared 0.050 M solution of
H.sub.2PtCl.sub.6.6H.sub.2O in isopropyl alcohol). The reactor was
sealed and the head space again purged with nitrogen while stirring
was initiated, resulting in an exotherm leading to a rapid
approximate 50.degree. C. increase in temperature. After 30
minutes, the reactor was opened and nitrogen saturated
allyl/OH-PEO-12 (154.88 g, 0.264 mol) and additional Pt catalyst
(92.3 .mu.L) were added. The reactor was resealed and the stirred
reaction allowed continued for an additional 30 minutes. By this
time the reaction temperature was at 106.degree. C. Next, the
reactor was pressurized with 40 psi of ethylene and allowed to stir
for an additional 60 minutes, during which time residual unreacted
Si--H was consumed (monitored via IR spectroscopy). The maximum
temperature reached during this interval was 123.degree. C. The
product, a clear, colorless semi-viscous liquid, was removed from
the reactor and degassed of saturated ethylene in vacuo. Proton NMR
spectra of the product were consistent with the expected
structure.
EXAMPLE 6
Copolymer where R Dodecyl, R'=Me, x=18, y=5, z+q 4, q.ltoreq.0.8,
p=12
[0057] ##STR11##
[0058] Previously nitrogen saturated 1-dodecene (82.58 g, 0.491
mol), silanic hydrogen intermediate Example 1 (200.0 g, 0.0981
mol), and allyl/OMe-PEO-12 (94.31 g, 0.157 mol) were combined in a
Parr Model 4511 reactor and the head space was purged with
nitrogen. The mixture was then stirred and heated to 85.degree. C.,
whereupon the reactor was opened to allow for the injection of Pt
catalyst (186.1 .mu.L of a freshly prepared 0.050 M solution of
H.sub.2PtCl.sub.6.6H.sub.2O in isopropyl alcohol). The reactor was
sealed and the head space again purged with nitrogen while stirring
was initiated, resulting in an exotherm leading to a rapid
approximate 42.degree. C. increase in temperature. After 30
minutes, the reactor was opened and nitrogen saturated
allyl/OMe-PEO-12 (141.50 g, 0.235 mol) and additional Pt catalyst
(79.7 .mu.L) were added. The reactor was resealed and the stirred
reaction allowed continued for an additional 60 minutes. By this
time the reaction temperature was at 115.degree. C. Next, the
reactor was pressurized with 40 psi of ethylene and allowed to stir
for an additional 60 minutes, during which time residual unreacted
Si--H was consumed (monitored via IR spectroscopy). The maximum
temperature reached during this interval was 119.degree. C. The
product, a clear, pale amber, not particularly viscous liquid, was
removed from the reactor and degassed of saturated ethylene in
vacuo. Proton NMR spectra of the product were consistent with the
expected structure. GPC (8 mg/ml THF), shown below for this
example, revealed an expected and acceptable molecular weight
distribution and a low level of low molecular weight fraction.
Particle size determination via dynamic laser light scattering for
a 1% dispersion, shown below for this example, revealed a particle
size distribution that was predominantly sub-micron. The GPC and
light scattering result shown below for this example are typical of
the other examples. TABLE-US-00009 Peak Results Ret Time Area
Height # Name (min) (uV * sec) (uV) 1 14.883 290091 _694 2 17.917
15460 282 3 19.083 29814 573 4 20.983 4571 120
[0059]
EXAMPLE 7
Copolymer where R=Dodecyl, R'.dbd.Me, x=27, y=5, z+q=4,
q.ltoreq.0.8, p=12
[0060] ##STR12##
[0061] Previously nitrogen saturated 1-dodecene (62.44 g, 0.371
mol), silanic hydrogen intermediate Example 3 (200.1 g, 0.0739
mol), and allyl/OMe-PEO-12 (71.23 g, 0.118 mol) were combined in a
Parr Model 4511 reactor and the head space was purged with
nitrogen. The mixture was then stirred and heated to 85.degree. C.,
whereupon the reactor was opened to allow for the injection of Pt
catalyst (225.7 .mu.L of a freshly prepared 0.050 M solution of
H.sub.2PtCl.sub.6.6H.sub.2O in isopropyl alcohol). The reactor was
sealed and the head space again purged with nitrogen while stirring
was initiated, resulting in an exotherm leading to a rapid
approximate 31.degree. C. increase in temperature. After 30
minutes, the reactor was opened and nitrogen saturated
allyl/OMe-PEO-12 (144.15 g, 0.240 mol) were added. The reactor was
resealed and the stirred reaction allowed continued for an
additional 2 hours. By this time the reaction temperature was at
125.degree. C. Next, the reactor was pressurized with 40 psi of
ethylene and allowed to stir for an additional 1.5 hours, during
which time residual unreacted Si--H was consumed (monitored via IR
spectroscopy). The maximum temperature reached during this interval
was 124.degree. C. The product, a clear, pale amber, not
particularly viscous liquid, was removed from the reactor and
degassed of saturated ethylene in vacuo. Proton NMR spectra of the
product were consistent with the expected structure.
EXAMPLE 8
Copolymer where R=dodecyl, R'.dbd.Me, x=18, y=4.25, z+q=4.75,
q.ltoreq.0.8, p=10
[0062] Previously nitrogen saturated 1-dodecene (103.40 g), silanic
hydrogen intermediate Example 1 (294.62 g), and allyl/OMe-PEO-10
(140.79) were combined in a Parr Model 4511 reactor and the head
space was purged with nitrogen. The mixture was then stirred and
heated to 85.degree. C., whereupon the reactor was opened to allow
for the injection of Pt catalyst (384.4 .mu.L of a freshly prepared
0.050 M solution of H.sub.2PtCl.sub.6.6H.sub.2O in isopropyl
alcohol). A strong exotherm was noted. After 30 minutes, the
reactor was opened and nitrogen saturated allyl/OMe-PEO-10 (211.18)
were added. The reactor was resealed and the stirred reaction
allowed continued for an additional 2 hours. By this time the
reaction temperature was at 125.degree. C. Next, the reactor was
pressurized with 40 psi of ethylene and allowed to stir for an
additional 1.5 hours, during which time residual unreacted Si--H
was consumed (monitored via IR spectroscopy). The maximum
temperature reached during this interval was 125.degree. C. The
product, a clear, pale amber, not particularly viscous liquid, was
removed from the reactor and degassed of saturated ethylene in
vacuo. Proton NMR spectra of the product were consistent with the
expected structure.
[0063] The above description is considered that of the preferred
embodiments only. Modifications of the invention will occur to
those skilled in the art and to those who make or use the
invention. Therefore, it is understood that the embodiments shown
in the drawings and described above are merely for illustrative
purposes and not intended to limit the scope of the invention,
which is defined by the following claims as interpreted according
to the principles of patent law, including the Doctrine of
Equivalents.
* * * * *