New Formulating Options with Silicone Emulsifiers

Isabelle Van Reeth

Marilena Morè
Dow Corning Europe

Robin Hickerson
Dow Corning USA

In today’s highly competitive skin care
and underarm markets, multifunctional,
high performance products have the
best chance of success. Consumers ex-
pect convenience and superior aesthet-
ics. They want long-lasting, highly
efficient moisturizers; effective anti-
aging and anti-wrinkle creams; durable,
wash-off resistant, protective color cos-
metics; and underarm products that go
on smoothly, without tackiness or resi-
due. Formulators strive for all that and
more: cost-effectiveness, formulating
flexibility and easy processing.
In many cases, the solution to fulfilling
this broad range of requirements points
to evolving emulsion technologies. More
than 80 percent of emulsions in today’s
personal care market are oil-in-water
systems. Emulsions of this type are fa-
vored for their stability, flexibility, high
water content (and hence, lower cost),
their nongreasy and nonoily feel, and their
ability to form an extensive array of prov-
en systems with predictable stability.
Compared to oil-in-water emulsions,
water-in-oil systems are recognized for
a different range of benefits. The external
oil phase typically spreads more easily
on skin, formulations generally are longer
lasting with improved emolliency and
wash-off resistance, and they exhibit
enhanced film barrier properties. Despite
these characteristics, conventional water-
in-oil systems can be perceived as im-
parting a greasy, oily feel, and lacking
in formulation flexibility. In addition,
they tend to be less cost effective and
more difficult to produce, typically re-
quiring a high shear finishing step.
Silicone Emulsifiers for the Best
All-Around
Silicone emulsifiers can help bridge the
gap between the two systems, providing
the best characteristics of both: they
can aid in the formulation of stable,
aesthetically pleasing cosmetic emul-
sions with high water levels, while re-
quiring no heat during processing to
provide a positive impact on overall
cost. Some silicone emulsifiers such
as cyclopentasiloxane (and) PEG/PPG-
18/18 dimethiconea already have earned
aDow Corning® 5225C Formulation Aid
bDow Corning® 5200 Formulation Aid
a reputation in personal care by making
possible new product forms, particularly
clear gels for antiperspirant applications.
These materials belong to the dimethi-
cone copolyol family of silicones, which
is broadly used in personal care prod-
ucts. Combined U.S. and West European
consumption of dimethicone copolyols
for skin care applications was estimated
at between 2,500 metric tons and 3,000
metric tons in 2002. The U.S. accounts
for around 65 percent of this total,
driven by the large consumption of
dimethicone copolyols in antiperspirants
and deodorants, estimated at more than
85 percent of total U.S. dimethicone
copolyol consumption for skin care
applications. In contrast, antiperspirant
and deodorant applications account
for only 55 percent of West European
dimethicone copolyol consumption
for skin care applications (1).
Silicone emulsifier technology is based
on the ability of these materials to func-
tion differently from organic emulsifi-
ers. To perform properly, a silicone
emulsifier must satisfy three require-
ments: it must be able to migrate to the
interface between the two phases, stay
at that interface, and stabilize the repul-
sion forces of the two phases. While
typical organic emulsifiers are am-
phiphilic molecules of type AB, the
action of the silicone emulsifier is the
50
40
Interfacial Tension (mN/m)
30
20
10
0
-5 -4
Figure 1. Comparison of the difference in interfacial tension at the water-oil
boundary as a function of the log emulsifier concentration.
result of functional groups alongside
the silicone backbone, which result in
lower interfacial tension and a more
robust, flexible film at the interface.
This characteristic is exemplified by
dimethicone copolyol emulsifiers such
as the previously mentioned material,
cyclomethicone (and) PEG/PPG-18/18
dimethicone, and also by lauryl
PEG/PPG-18/18 methicone.b
The graph in Figure 1 compares the
difference in interfacial tension at the
water and oil boundary for two organic
emulsifiers and a silicone emulsifier.
Notice that a lower concentration of
lauryl PEG/PPG-18/18 methicone is
required to reduce interfacial tension
compared to the organic materials.
Finally, because of their branched struc-
tures and high molecular weights, each
silicone molecule packs very tightly at
the oil and water interface. Hydrophilic
and lipophilic portions of the molecule
are tightly aligned by the flexible sili-
cone backbone to provide highly effec-
tive steric repulsion.
A New Option: Low Shear
Processing
In general, most silicone water-in-oil
emulsifiers require high shear to make
emulsions with optimized stability.
Recent developments in silicone emul-
sifier technology have resulted in still
Polyglycerin-3
Diisostearate
Sorbitan Oleate
Lauryl PEG/
PPG-18/18
Methicone
-3 -2 -1 0 1 2 3 4
Log Emulsifier Concentration ( µ mol/1)
newer materials that offer expanded sifier is outside current clear antiperspi- The Solution for Novel Product
performance along with cost effective- rant patents and therefore allows free- Forms
ness and formulating ease. For next- dom to practice.
generation water-in-oil emulsions, a For formulators seeking ways to create
new silicone emulsifier based on sili- Formulation 1 illustrates the use of the highly differentiated product forms, lauryl
cone elastomer technology has been new silicone emulsifier in a clear antiper- PEG/PPG-18/18 methicone, a dimethi-
developed. This material allows formu- spirant gel made with a low shear process. cone copolyol emulsifier previously men-
lators to develop stable water-in-silicone tioned, offers unique potential in skin
emulsions without the need for high Formulation 2 demonstrates the use of care applications.
shear processing equipment. Given the the silicone emulsifier in a water-in-
INCI designation cyclopentasiloxane silicone foundation.
(and) PEG-12 dimethicone crosspoly- Formulation 1
merc, the emulsifier provides: Clear Antiperspirant Gel
• A broad variety of sensory profiles
Ingredient Wt. % Trade Name/Supplier
and textures to offer a sensory ex-
Phase A
perience ranging from very light to
1. Cyclopentasiloxane (and) PEG-12 10.0 Dow Corning® 9011 Silicone Elastomer Blend
rich, depending on the oil used. dimethicone crosspolymer
Enhanced aesthetics over dimethi- 2. Dimethicone 3.5 XIAMETER® PMX-200 Silicone Fluid 10 cSt
cone copolyol emulsifiers. 3. Phenyl trimethicone 0.5 Dow Corning® 556 Cosmetic Grade Fluid
• Formulation flexibility for forming 4. Cyclopentasiloxane 6.0 XIAMETER® PMX-0245 Cyclopentasiloxane
clear emulsions with stability at low Phase B
to high viscosities, and accommo- 5. Aluminum sesquichlorohydrate 42.0 Reach 301 Solution/Reheis Inc.
dating a wide range of oil-phase 6. Deionized water 17.5
ingredients. 7. Propylene glycol 12.5 Propylene glycol/The Dow Chemical Company
8. Glycerin 6.5 Glycerin/Fisher Chemical Company
• Processing flexibility for low- to
9. Ethyl alcohol, 200 proof 1.5 Alcohol/Equistar
high-shear processing and the option
for cold mixing. Procedure
• Cost effectiveness, with the option Combine Phase A ingredients. In a separate container, combine Phase B ingredients. Match the refractive
index of Phase A to that of Phase B. If the refractive index of Phase A is higher than that of Phase B, add
for using high water content (up to water to the aqueous phase to match. If lower, add glycerin to match. With rapid mixing, add Phase B to
82 percent water in the internal Phase A very slowly, using a separatory funnel. (Use a 1000 ml tall beaker and 1376 rpm.)
phase), low emulsifier levels and
cold processing.
Formulation 2
• Stability for long shelf life and con- Water-in-Silicone Foundation
sistent performance. Improved active
suspension in underarm products.
Ingredient Wt. % Trade Name/Supplier
Using the new emulsion, it is also pos- Phase A
sible to create novel product forms such 1. Dextrin palmitate 2.10 Rheopearl KL/Miyoshi Kasel
as anhydrous systems or multiple emul- 2. PEG-12 dimethicone 1.90 XIAMETER® OFX-0193 Fluid
sions with two distinct aqueous phases 3. Tricaprylin 5.00 Trivent OC-G/Trivent
(water-in-oil-in-water). The latter ap- 4. Cyclopentasiloxane (and) PEG-12 10.00 Dow Corning® 9011 Silicone Elastomer Blend
proach results in aesthetics that are dimethicone crosspolymer
different from those associated with Phase B
typical water-in-silicone emulsions; the 5. Cyclopentasiloxane & Cyclohexasiloxane 20.00 XIAMETER® PMX-0345 Cyclosiloxane Blend
external phase is now aqueous, making Phase C
the first impression on the skin very 6. C.I. 77891, Dimethicone 2.75 SAT-T-47-051/US Cosmetics
light. This method also suggests poten- 7. C.I. 77492, Dimethicone 0.43 SAT-Y-338073/US Cosmetics
tial use for delivery of active ingredients 8. C.I. 77491, Dimethicone 0.32 SAT-R-33-128/US Cosmetics
such as emollients, moisturizers, sun- 9. C.I. 77499, Dimethicone 0.01 SAT-B-33134/US Cosmetics
screens, pigments, vitamins and anti- Phase D
perspirant salts. The ability of this 10. Deionized water to 100.00
emulsifier to make stable anhydrous 11.Sodium chloride 1.00 Sodium chloride/Merck
propylene glycol-in-silicone emulsions
Procedure
allows formulators to develop systems Heat Phase A to 80˚C, ensuring that ingredient 1 is fully dissolved. Cool to 50˚C. Combine ingredients of Phase
where vitamin C is not degraded during C. Add Phase C to Phase B and mix. Add Phase B to Phase A with mixing. Combine ingredients of Phase D.
the shelf life of the product. This emul- Add Phase D to Phase A with high shear mixing. (Formulation developed by S Black Ltd. UK)

cDow Corning® 9011 Silicone Elastomer Blend

This material allows:
• Very stable water-in-oil systems with-
out the addition of waxes and up to
approximately 80 percent water phase.
• The ability to accommodate a low
to medium polarity oil phase includ-
ing a high level of silicone oils.
• Long-lasting moisturizing, wash-off
resistance and superior aesthetics.
• A flexible sensory profile from light
and nongreasy to nourishing and
richly emollient.
• The option for cold processing.
• Novel product forms such as water-
in-wax emulsions for potential use
in foundation sticks and lipsticks.
For example, a prototype water-in-
wax base stick containing 60 percent
water imparts a feel of freshness to
skin compared to the expected feel
from an anhydrous stick. In addition
to a surprising feel, the presence of
water offers the possibility of adding
water-soluble actives to the stick, as
well as reducing the overall cost of
the formulation.
Figure 2 illustrates the moisturizing per-
formance of a water-in-oil emulsion
based on lauryl PEG/PPG-18/18 methi-
cone. These data show that an increase
of 40 percent in the hydration level of
the skin can be maintained for longer
than six hours. Although this formulation
contains 10 percent glycerin, the cream
has a silky, nongreasy and nontacky feel
as shown in Figure 3, where it is com-
pared to an oil-in-water emulsion.
Based on paired comparisons, the spider
diagram of Figure 3 compares the sen-
sory profiles of an oil-in-water formula-
tion and a water-in-oil formulation made
with the lauryl PEG/PPG-18/18 methi-
cone emulsifier. Except for the wetness
and spreadability parameters, the water-
in-oil formulation demonstrates either
equivalent or improved sensory perfor-
mance over the oil-in-water system. For
an equivalent performance on greasiness
(a parameter that is usually a disadvan-
tage of water-in-oil systems), the water-
in-oil formulation with the silicone emul-
sifier has a silky, nontacky and slippery
feel on the skin.
Moisturization with Corneometer.
Percentage increase moisturization
70
60
50
versus neat skin.
40
30
20
10
0
0 min 30 min 1 hour 2 hours 3 hours 4 hours 5 hours 6 hours
T ime
Figure 2. Corneometer measurements of moisturization effect from a water-in-
oil formulation containing lauryl PEG/PPG-18/18 methicone emulsifier.
An Added Advantage: Durability Figure 4 illustrates the wash-off resis-
tance of a water-soluble sunscreen ac-
and Resistance to Wash-Off
tive in an oil-in-water formulation con-
With their external oil phase, water-in-
oil systems can form an immediate con- taining an organic emulsifier (cetyl
phosphate) and a water-in-oil system
tinuous and homogeneous film on the
skin to optimize the film-barrier prop- formulated with lauryl PEG/PPG-18/18
methicone. The formulation containing
O/W
Wetness 99.9%
W/O
8.00
Slipperiness 99.9%
7.00 Spreadability 99.9%
6.00
5.00
4.00
Tackiness after absorption 99.9%
3.00
2.00
Tackiness before absorption
1.00
0.00
Silkiness 99.9% Absorbancy
Greasiness Gloss
Film residue
Figure 3. Sensory profiles of oil-in-water and water-in-oil formulations, based
on paired comparisons.
erties. In addition, since the emulsifier the silicone emulsifier resists wash-off,
is water insoluble, wash-off resistance while 53 percent of the sunscreen in the
will be improved because the oil phase formulation containing the organic
cannot be re-emulsified by water. The emulsifier is washed away.
degree of film forming properties and
wash-off resistance will be dependent Forming Stable Emulsions
on the types of ingredients present in
the oil phase. Another benefit of water- Stable emulsions can exist only when
in-oil emulsions is the protection of the internal phase “droplets” remain
hydrosoluble actives such as vitamin separated from one another over a peri-
C, which are sensitive to oxidation. od of time. Several factors affect this
state, such as particle size, distribution
of particle sizes, formulation compo-
nents and phase ratio. A homogeneous
particle size is key to developing a stable
emulsion. A bi- or multi-modal particle
size distribution can significantly reduce
stability by increasing coalescence
through the collisions of the particles
among themselves. Uniformity is more
critical to stability than size because
large particles have a greater mass, and
when collisions with smaller particles
occur, large particles will incorporate
the smaller particles. Drop in viscosity
is often the first sign that coalescence is
occurring. When a multi-modal particle
size distribution occurs, both formulation
and process should be investigated.
Emulsifier level. Too much emulsifier
can result in as much difficulty as too
53 %
% sunscreen washed away
the use of waxes, bentonite gels or sil-
icone elastomers.
Aqueous phase. In the formulation of
underarm products, small changes in
active ingredients (e.g., switching from
ACH to AlZr salts) should have little
impact on the system. However, any
element in either phase that changes
the solubility of the emulsifier will have
an impact on the system. Some fra-
grance components may have this effect,
as can high levels of antiperspirant salts
in combination with lauryl PEG/PPG-
18/18 methicone.
Oil Phase. Some emulsifiers are more
effective in certain types of oil systems,
such as cyclic versus linear siloxanes
or low viscosity versus high viscosity.
humectancy properties decreases the
water loss; however, high levels might
destabilize the emulsion.
Co-emulsifiers. The use of co-emulsifiers
(e.g., polysorbate-20, C12-15 pareth-9,
laureth-7) should be limited. These in-
gredients should be used at levels lower
than their critical micelle concentration
to avoid depletion flocculation.
Table 1 compares the levels of formu-
lation components for forming stable
water-in-oil or water-in silicone systems
with silicone emulsifiers.
Processing. The following general pro-
cessing guidelines are recommended for
formulating with silicone emulsifiers:
Combine the ingredients of Phase A and
Phase B in separate containers and mix
each until uniform. Add the water Phase
B to the silicone or oil Phase A very
slowly, using a high turbulence mechan-

60
50
40
30
20
<1%
10
0
O/W W/O
O/W: Cetyl phosphate + 3 % Phenylbenzimidazole sulfonic acid*
W/O: Laurylmethicone copolyol + 3 % Phenylbenzimidazole sulfonic acid
*Parsol HS
Figure 4. Comparison of wash-off resistance between a water-soluble sunscreen
active in a water-in-oil formulation containing a silicone emulsifier, versus an
oil-in-water formulation containing an organic emulsifier.
In addition, the resulting polarity of the
little. Excess emulsifier may surround
itself or attract other droplets. For that oil phase should be considered. Lauryl
PEG/PPG-18/18 methicone is most ef-
reason, the recommended approach is
to formulate with the minimum and ficient with low to medium polarity. It
is important to thoroughly investigate
maximum amount of emulsifier until
instability is noted. the formulation on a laboratory scale
prior to production.
Phase ratio. A phase ratio of 80:20
(water to oil) can be achieved with the Inorganic electrolytes and polyols. The
use of an inorganic electrolyte (e.g.,
three silicone emulsifiers discussed in
this article. Increasing the internal phase sodium citrate, magnesium sulfate, so-
dium chloride or sodium tetraborate) at
increases viscosity. Phase ratios signif-
icantly below 65 percent internal phase approximately 1-2 percent by weight
may require either additional emulsifier, has been shown to reduce even further
thickener or a reduced particle size to the interfacial tension as well as improve
avoid settling. For example, the oil freeze-thaw stability. The addition of
(external) phase can be thickened by small quantities of polyols with their
ical blade mixer set at high speed (900
ft/min tip speed). This addition should
take from 10 to 30 minutes. Because
the aqueous phase typically has a higher
density than the oil phase, it gravitates
to the bottom of the mixing container.
Adding the aqueous phase from the top
enhances mixing efficiency.
After addition is complete continue mixing
for another 10 to 30 minutes. This step
narrows the particle size distribution. To
finish the emulsion, homogenize the sys-
tem with a high shear mixing device. This
step reduces the mean particle size and
increases emulsion viscosity. The final
high shear step is optional when using
cyclopentasiloxane (and) PEG-12 dime-
thicone crosspolymer. Without the final
shear step, particle diameters will typically
be in the 1 to 3 micron range. With a final
high shear pass, diameters will be less
than 1 micron. Additional details related
to processing and stability assessments
are available in separate publications (2,3).
Table 2 compares some of the physical
and formulating characteristics that
distinguish three silicone emulsifiers.
By comparing the requirements and prop-
erties of various formulation types, it is
possible to determine which silicone
emulsifier is most appropriate for a par-
ticular application. Table 3 provides some
 Table 1. Critical Factors for Stable Emulsions general guidelines. Additional details are
available in a separate publication (4).
Water-in-Silicone Emulsions Water-in-Oil Emulsions
Level (%) Conclusions
(Dow Corning® 5225C* and 9011) (Dow Corning® 5200*)
New developments in silicone emulsifier
technology provide expanded options
Emulsifier 7 - 20 1-3 for creating stable water-in-oil and water-
in-silicone emulsions with a broad range
Oil phase 20 - 50 20 - 35 of sensory characteristics. In skin and
Water phase 50 - 82 65 - 80 underarm products, these ingredients
give formulators flexibility for develop-
Electrolyte ing clear products with superior aesthetics
1-2 1-2
(NaCl preferred) and novel forms such as anhydrous sys-
tems, multiple emulsions or water-in-
Co-emulsifier 0.5 0.5
wax sticks. In addition, benefits of water-
* Dispersion of approximately 10% active emulsifier in-oil systems such as good sensory
Table 2. Overview of Silicone Emulsifier Characteristics profiles, improved wash-off resistance
and excellent moisturization have been
demonstrated. Silicone emulsifiers offer
Cyclopentasiloxane versatility for low or high shear options
Cyclopentasiloxane Lauryl PEG/PPG-
INCI Name and PEG-12 as well as cold processing, presenting
and PEG/PPG-18/18 18/18 Methicone
Dimethicone new opportunities for cost-effective and
Dimethicone Crosspolymer (Dow Corning® highly innovative skin care and underarm
(Dow Corning® 5225C) 5200) products.
(Dow Corning® 9011)
References
Water-in-silicone,
Water-in-silicone, Water-in-oil, 1. Personal Communication, Gillian
Emulsion Type multiple emulsions,
multiple emulsions Water-in-wax Morris, Group Director, Chemicals,
anhydrous emulsions
Minerals, Polymers, Kline & Com-
pany (2003).
% Actives 10% 12.5% 100%
2. Kasprzak, K., “A guide to formulating
Water-in-Silicone emulsions with
Shear / Dow Corning® 3225C formulation
Processing High shear Low to high shear High shear aid,” Dow Corning Internal Docu-
requirements
ment, Form no. 25-713-01 (1995).
Use Levels 7-15% 6-14% 2-3% 3. Dahms, G., and Zombeck, A., “New
formulation possibilities offered by
silicone copolyols,” Cosmetics &
Table 3. Selection Criteria for Silicone Emulsifiers Toiletries, Vol 110 number 3, p 91+
(1995). Also available as Dow Corning
Dow Corning® Dow Corning® Dow Corning®
System Type Internal Document, Form no.
5225C 9011 5200
25-710-01 (1995).
W/Si Systems X X
4. Hickerson, R. and Van Reeth, I.,
W/O Systems X “Silicone Emulsifiers Guide,”
Anhydrous Systems (PPG/S) X Dow Corning Internal Document,
Form no. 27-1063-01 (2002).
Clear systems X X
Moisturizing, wash-off
X
resistant, long lasting creams
Multiple emulsions W/Si/W X X
Multiple emulsions W/O/W X
Water-in-wax (W/W) systems X
Emulsions containing AP salts X X
New product forms / new sensory X X
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