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New Formulating Options with Silicone Emulsifiers

Isabelle Van Reeth


Marilena Mor
Dow Corning Europe
Robin Hickerson
Dow Corning USA

and underarm markets, multifunctional,


high performance products have the
best chance of success. Consumers expect convenience and superior aesthetics. They want long-lasting, highly
efficient moisturizers; effective antiaging and anti-wrinkle creams; durable,
wash-off resistant, protective color cosmetics; and underarm products that go
on smoothly, without tackiness or residue. 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 todays
personal care market are oil-in-water
systems. Emulsions of this type are favored 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 proven 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 waterin-oil systems can be perceived as imparting a greasy, oily feel, and lacking
in formulation flexibility. In addition,
they tend to be less cost effective and
more difficult to produce, typically requiring 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 emulsions with high water levels, while requiring no heat during processing to
provide a positive impact on overall
cost. Some silicone emulsifiers such
as cyclopentasiloxane (and) PEG/PPG18/18 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 dimethicone copolyol family of silicones, which
is broadly used in personal care products. 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 function differently from organic emulsifiers. To perform properly, a silicone
emulsifier must satisfy three requirements: it must be able to migrate to the
interface between the two phases, stay
at that interface, and stabilize the repulsion forces of the two phases. While
typical organic emulsifiers are amphiphilic molecules of type AB, the
action of the silicone emulsifier is the

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 structures 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 silicone backbone to provide highly effective 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 emulsifier technology have resulted in still

50
Polyglycerin-3
Diisostearate

40
Interfacial Tension (mN/m)

In todays highly competitive skin care

Sorbitan Oleate

30

Lauryl PEG/
PPG-18/18
Methicone

20
10
0

-5

-4

-3

-2

-1

Log Emulsifier Concentration ( mol/1)

Figure 1. Comparison of the difference in interfacial tension at the water-oil


boundary as a function of the log emulsifier concentration.

newer materials that offer expanded


performance along with cost effectiveness and formulating ease. For nextgeneration water-in-oil emulsions, a
new silicone emulsifier based on silicone elastomer technology has been
developed. This material allows formulators to develop stable water-in-silicone
emulsions without the need for high
shear processing equipment. Given the
INCI designation cyclopentasiloxane
(and) PEG-12 dimethicone crosspolymerc, the emulsifier provides:
A broad variety of sensory profiles
and textures to offer a sensory experience ranging from very light to
rich, depending on the oil used.
Enhanced aesthetics over dimethicone copolyol emulsifiers.
Formulation flexibility for forming
clear emulsions with stability at low
to high viscosities, and accommodating a wide range of oil-phase
ingredients.
Processing flexibility for low- to
high-shear processing and the option
for cold mixing.
Cost effectiveness, with the option
for using high water content (up to
82 percent water in the internal
phase), low emulsifier levels and
cold processing.
Stability for long shelf life and consistent performance. Improved active
suspension in underarm products.
Using the new emulsion, it is also possible to create novel product forms such
as anhydrous systems or multiple emulsions with two distinct aqueous phases
(water-in-oil-in-water). The latter approach results in aesthetics that are
different from those associated with
typical water-in-silicone emulsions; the
external phase is now aqueous, making
the first impression on the skin very
light. This method also suggests potential use for delivery of active ingredients
such as emollients, moisturizers, sunscreens, pigments, vitamins and antiperspirant salts. The ability of this
emulsifier to make stable anhydrous
propylene glycol-in-silicone emulsions
allows formulators to develop systems
where vitamin C is not degraded during
the shelf life of the product. This emulcDow Corning 9011 Silicone Elastomer Blend

sifier is outside current clear antiperspirant patents and therefore allows freedom to practice.
Formulation 1 illustrates the use of the
new silicone emulsifier in a clear antiperspirant gel made with a low shear process.
Formulation 2 demonstrates the use of
the silicone emulsifier in a water-insilicone foundation.

The Solution for Novel Product


Forms
For formulators seeking ways to create
highly differentiated product forms, lauryl
PEG/PPG-18/18 methicone, a dimethicone copolyol emulsifier previously mentioned, offers unique potential in skin
care applications.

Formulation 1
Clear Antiperspirant Gel
Ingredient
Phase A
1. Cyclopentasiloxane (and) PEG-12
dimethicone crosspolymer
2. Dimethicone
3. Phenyl trimethicone
4. Cyclopentasiloxane
Phase B
5. Aluminum sesquichlorohydrate
6. Deionized water
7. Propylene glycol
8. Glycerin
9. Ethyl alcohol, 200 proof

Wt. %

Trade Name/Supplier

10.0

Dow Corning 9011 Silicone Elastomer Blend

3.5
0.5
6.0

XIAMETER PMX-200 Silicone Fluid 10 cSt


Dow Corning 556 Cosmetic Grade Fluid
XIAMETER PMX-0245 Cyclopentasiloxane

42.0
17.5
12.5
6.5
1.5

Reach 301 Solution/Reheis Inc.


Propylene glycol/The Dow Chemical Company
Glycerin/Fisher Chemical Company
Alcohol/Equistar

Procedure
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
water to the aqueous phase to match. If lower, add glycerin to match. With rapid mixing, add Phase B to
Phase A very slowly, using a separatory funnel. (Use a 1000 ml tall beaker and 1376 rpm.)

Formulation 2
Water-in-Silicone Foundation
Ingredient
Wt. %
Phase A
1. Dextrin palmitate
2.10
2. PEG-12 dimethicone
1.90
3. Tricaprylin
5.00
4. Cyclopentasiloxane (and) PEG-12
10.00
dimethicone crosspolymer
Phase B
5. Cyclopentasiloxane & Cyclohexasiloxane 20.00
Phase C
6. C.I. 77891, Dimethicone
2.75
7. C.I. 77492, Dimethicone
0.43
8. C.I. 77491, Dimethicone
0.32
9. C.I. 77499, Dimethicone
0.01
Phase D
10. Deionized water
to 100.00
11.Sodium chloride
1.00

Trade Name/Supplier
Rheopearl KL/Miyoshi Kasel
XIAMETER OFX-0193 Fluid
Trivent OC-G/Trivent
Dow Corning 9011 Silicone Elastomer Blend
XIAMETER PMX-0345 Cyclosiloxane Blend
SAT-T-47-051/US Cosmetics
SAT-Y-338073/US Cosmetics
SAT-R-33-128/US Cosmetics
SAT-B-33134/US Cosmetics

Sodium chloride/Merck

Procedure
Heat Phase A to 80C, ensuring that ingredient 1 is fully dissolved. Cool to 50C. Combine ingredients of Phase
C. Add Phase C to Phase B and mix. Add Phase B to Phase A with mixing. Combine ingredients of Phase D.
Add Phase D to Phase A with high shear mixing. (Formulation developed by S Black Ltd. UK)

Very stable water-in-oil systems without the addition of waxes and up to


approximately 80 percent water phase.
The ability to accommodate a low
to medium polarity oil phase including 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 waterin-wax emulsions for potential use
in foundation sticks and lipsticks.
For example, a prototype water-inwax 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 performance of a water-in-oil emulsion
based on lauryl PEG/PPG-18/18 methicone. 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 compared to an oil-in-water emulsion.
Based on paired comparisons, the spider
diagram of Figure 3 compares the sensory profiles of an oil-in-water formulation and a water-in-oil formulation made
with the lauryl PEG/PPG-18/18 methicone emulsifier. Except for the wetness
and spreadability parameters, the waterin-oil formulation demonstrates either
equivalent or improved sensory performance over the oil-in-water system. For
an equivalent performance on greasiness
(a parameter that is usually a disadvantage of water-in-oil systems), the waterin-oil formulation with the silicone emulsifier has a silky, nontacky and slippery
feel on the skin.

Percentage increase moisturization


versus neat skin.

This material allows:

Moisturization with Corneometer.


70
60
50
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-inoil formulation containing lauryl PEG/PPG-18/18 methicone emulsifier.

An Added Advantage: Durability


and Resistance to Wash-Off
With their external oil phase, water-inoil systems can form an immediate continuous and homogeneous film on the
skin to optimize the film-barrier prop-

Figure 4 illustrates the wash-off resistance of a water-soluble sunscreen active in an oil-in-water formulation containing an organic emulsifier (cetyl
phosphate) and a water-in-oil system
formulated with lauryl PEG/PPG-18/18
methicone. The formulation containing
O/W
W/O

Wetness 99.9%
8.00

Slipperiness 99.9%

Spreadability 99.9%

7.00
6.00
5.00
4.00
3.00

Tackiness after absorption 99.9%

Tackiness before absorption

2.00
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
is water insoluble, wash-off resistance
will be improved because the oil phase
cannot be re-emulsified by water. The
degree of film forming properties and
wash-off resistance will be dependent
on the types of ingredients present in
the oil phase. Another benefit of waterin-oil emulsions is the protection of
hydrosoluble actives such as vitamin
C, which are sensitive to oxidation.

the silicone emulsifier resists wash-off,


while 53 percent of the sunscreen in the
formulation containing the organic
emulsifier is washed away.

Forming Stable Emulsions


Stable emulsions can exist only when
the internal phase droplets remain
separated from one another over a period of time. Several factors affect this
state, such as particle size, distribution

of particle sizes, formulation components 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.

% sunscreen washed away

Emulsifier level. Too much emulsifier


can result in as much difficulty as too

60

the use of waxes, bentonite gels or silicone 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 fragrance components may have this effect,
as can high levels of antiperspirant salts
in combination with lauryl PEG/PPG18/18 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.

53 %

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
oil phase should be considered. Lauryl
itself or attract other droplets. For that
PEG/PPG-18/18 methicone is most efreason, the recommended approach is
ficient with low to medium polarity. It
to formulate with the minimum and
is important to thoroughly investigate
maximum amount of emulsifier until
the formulation on a laboratory scale
instability is noted.
prior to production.
Phase ratio. A phase ratio of 80:20
Inorganic electrolytes and polyols. The
(water to oil) can be achieved with the
use of an inorganic electrolyte (e.g.,
three silicone emulsifiers discussed in
sodium citrate, magnesium sulfate, sothis article. Increasing the internal phase
dium chloride or sodium tetraborate) at
increases viscosity. Phase ratios signifapproximately 1-2 percent by weight
icantly below 65 percent internal phase
has been shown to reduce even further
may require either additional emulsifier,
the interfacial tension as well as improve
thickener or a reduced particle size to
freeze-thaw stability. The addition of
avoid settling. For example, the oil
small quantities of polyols with their
(external) phase can be thickened by

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 ingredients should be used at levels lower
than their critical micelle concentration
to avoid depletion flocculation.
Table 1 compares the levels of formulation components for forming stable
water-in-oil or water-in silicone systems
with silicone emulsifiers.
Processing. The following general processing 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 mechanical 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 system 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 dimethicone 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 properties of various formulation types, it is
possible to determine which silicone
emulsifier is most appropriate for a particular application. Table 3 provides some

Table 1. Critical Factors for Stable Emulsions


Water-in-Silicone Emulsions

Level (%)

(Dow

Corning 5225C*

Emulsifier
Oil phase
Water phase

and 9011)

Water-in-Oil Emulsions
(Dow Corning 5200*)

7 - 20

1-3

20 - 50

20 - 35

1-2

1-2

0.5

0.5

50 - 82

Electrolyte

(NaCl preferred)

Co-emulsifier

general guidelines. Additional details are


available in a separate publication (4).

65 - 80

* Dispersion of approximately 10% active emulsifier

Table 2. Overview of Silicone Emulsifier Characteristics

INCI Name

Cyclopentasiloxane
and PEG/PPG-18/18
Dimethicone
(Dow Corning 5225C)

Cyclopentasiloxane
and PEG-12
Dimethicone
Crosspolymer
(Dow Corning 9011)

Lauryl PEG/PPG18/18 Methicone


(Dow Corning
5200)

Conclusions
New developments in silicone emulsifier
technology provide expanded options
for creating stable water-in-oil and waterin-silicone emulsions with a broad range
of sensory characteristics. In skin and
underarm products, these ingredients
give formulators flexibility for developing clear products with superior aesthetics
and novel forms such as anhydrous systems, multiple emulsions or water-inwax sticks. In addition, benefits of waterin-oil systems such as good sensory
profiles, improved wash-off resistance
and excellent moisturization have been
demonstrated. Silicone emulsifiers offer
versatility for low or high shear options
as well as cold processing, presenting
new opportunities for cost-effective and
highly innovative skin care and underarm
products.

References
Emulsion Type

Water-in-silicone,
multiple emulsions,

Water-in-silicone,
multiple emulsions

anhydrous emulsions

Water-in-oil,
Water-in-wax

% Actives

10%

12.5%

100%

Shear /
Processing
requirements

High shear

Low to high shear

High shear

Use Levels

7-15%

6-14%

2-3%

Table 3. Selection Criteria for Silicone Emulsifiers


System Type

Dow Corning
5225C

Dow Corning
9011

W/Si Systems

W/O Systems

Anhydrous Systems (PPG/S)


Clear systems

X
X

Moisturizing, wash-off
resistant, long lasting creams
Multiple emulsions W/Si/W

Dow Corning
5200

X
X

Multiple emulsions W/O/W

Water-in-wax (W/W) systems

Emulsions containing AP salts


New product forms / new sensory

X
X

1. Personal Communication, Gillian


Morris, Group Director, Chemicals,
Minerals, Polymers, Kline & Company (2003).
2. Kasprzak, K., A guide to formulating
Water-in-Silicone emulsions with
Dow Corning 3225C formulation
aid, Dow Corning Internal Document, Form no. 25-713-01 (1995).
3. Dahms, G., and Zombeck, A., New
formulation possibilities offered by
silicone copolyols, Cosmetics &
Toiletries, Vol 110 number 3, p 91+
(1995). Also available as Dow Corning
Internal Document, Form no.
25-710-01 (1995).
4. Hickerson, R. and Van Reeth, I.,
Silicone Emulsifiers Guide,
Dow Corning Internal Document,
Form no. 27-1063-01 (2002).

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