11/18/2020
Selecting and Evaluating Emulsifiers for Cosmetics
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Selecting and Evaluating Emulsifiers for Cosmetics
It takes a lot to develop complex cosme c formula ons that come up to our expecta ons. Today, we are lucky to have a wide range of different ‘drop-in-and-go’ technologies to help us balance
crea vity with emulsifiers under ght deadlines.
Get detailed informa on about emulsions, types of emulsifiers used to create emulsions for cosme cs, factors to be considered in their selec on and evalua ng them before using in your personal
care formula ons. Review:
Emulsifiers: Benefits & Limita ons
Emulsifiers Based on Ingredient's Chemistry
Chemistry of the Water Phase
Types of Emulsifiers: O/W, W/O, Natural, Silicone, Co-emulsifiers
Emulsifiers: Selec on Factors
HLB System: Selec on & Calcula on
Evalua ng Emulsifiers for Cosme cs
(Let’s start by understanding role of emulsifiers or click to go on specific sec on of the page)
We would like to acknowledge Amanda Foxon-Hill and Nick Morante for providing technical informa on needed to develop this guide.
By SpecialChem
Emulsifiers: Types, Selec on
Factors & HLB Calcula on
Role of Emulsifiers
Channel Alerts
Emulsions are systems composed of two or more immiscible materials, in which one
material (the discon nuous or internal phase) is suspended or dispersed throughout
another material (the con nuous or external phase) in separate droplets. The
immiscible phases can be water, oil or silicone.
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When emulsions are made surfactants called emulsifiers are used to slow the process
of separa on of the immiscible phases. All emulsions are inherently unstable with the
excep on of some spontaneously forming microemulsions.
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Selecting and Evaluating Emulsifiers for Cosmetics
Simply put, any combina on of unlike phases that
are put together can be considered a type of
emulsion. Emulsions are classified by:
The con nuous phase (external)
The discon nuous phase (internal)
The use of homogenizers and other equipment to
minimize droplet size will improve the stability of an
emulsion.
When naming the emulsion type, the first le er is
the discon nuous phase.
O/W stands for oil-in-water and is classified as an
emulsion.
W/O stands for water-in-oil and is classified as an invert emulsion.
These types of emulsions are much more difficult to stabilize than oil-in-water systems.
They also must have much smaller droplets to help them stay together longer.
Making emulsions can some mes be fun, and some mes not. When things go well, it certainly is a lot
of fun. In all cases, emulsions vary in the size and type of each of the phases and this phase ra o is
cri cal in determining the characteris cs and performance of the resul ng product.
Changing the phase ra o alters the physical proper es of the emulsion. It is the emulsifiers that help
keep them together.
» View All the Commercially Available Emulsifiers in Market Today!
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The cosme cs ingredients database is available to all, free of charge. You can filter down your op ons
by INCI, origin, applica ons, end consumer benefits and many more dimensions.
Benefits & Limitations of Emulsifiers
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Crea ng cosme c formula ons could be a task without having comprehensive knowledge about the
ingredients involved in it. Before adding any ingredient, it becomes necessary for a formulator to know
about the strengths and weaknesses it imparts.
Considering these aspects beforehand, a formulator could decide if the addi ve is actually required or
not. If added, would it give an extra edge to the end product? Also, it could help the formulator to
engineer his formula on to achieve desired end-use requirements.
Similarly, it is wise to look upon emulsifier benefits and limita ons to stumble upon the right emulsifier.
The table below discusses emulsifier benefits in cosme cs and some limita ons associated with them.
55
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Emulsifiers
Benefits
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Limita ons
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Correct use of emulsifiers creates
homogenous mixtures, dispersions or
emulsions of oily or waxy substances with
water.
Being physically unstable they get separated into
dis nc ve phases.
Addi on of emulsifiers helps solids to be
dispersed in liquids or insoluble liquids with
other liquids.
The dispersed oil droplets can fuse together and rise
in o/w emulsion or may get se led down in w/o
emulsions.
Greasy anhydrous creams can be modified to
washable ones.
Permanently irreversible separa on and fusion of the
dispersed phase may occur. Conversion of w/o to o/w
(or vice versa) can be observed.
Emulsifiers can be anionic, ca onic or non-ionic depending on the ingredient's chemistry. Let's discuss
their chemistry in detail...
Emulsifiers Based on Ingredient's Chemistry
Anionic Emulsifiers
Anionic emulsifiers are, in some ways, the old-fashioned cousins when it comes to emulsifier
technology. Soap-based emulsifiers can be extremely useful in cleansing formula ons but can also form
part of a very elegant high-end an -aging formula on just as long as your selec on of ac ves is chosen
carefully.
Anionic emulsifiers carry a net nega ve charge in solu on and because of that they, like the
ca onics, are sensi ve to electrolytes.
Anionics benefit from the presence of a li le monovalent salt or acid up to a point (as the increased
sal ness/ acidity increases the cri cal micelle concentra on and ac vity of the water phase).
Above that, the formula can cri cally fail in a similar way like over-salted surfactant blends. Salt content
can creep up on you in an ac ve formula as ingredients such as:
Aloe
Sodium PCA
Seaweed Extracts
Sodium Hyaluronate, and even some herbal ac ves can push the limits
As such, freeze/ thaw stability is an essen al part of early anionic emulsion stability tes ng
In terms of skin irrita on poten al, the old pharmacopeia driven Sodium Lauryl Sulfate and its ‘harshon-skin’ reputa on has largely been replaced. Anionic emulsifiers, especially elegant phosphate esters
renowned for their skin compa bility or gentler surfactants such as the lactylates or glutamates making
it en rely possible to make an anionic emulsion that is skin-kind and gentle.
Anionic emulsifiers are the most common used in emulsions. For example, Sodium Laureth Sulfate and
PEG-100 Stearate.
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The PEG-100 part of the emulsifier is a func on of adding Polyethylene Glycol, or PEG. This process is
called ethoxyla on. This common a ribute of anionic emulsifiers is that they are also compounds that
have been ethoxylated. This process creates ingredients that have varied amounts of water solubility.
The higher the amount of ethylene oxide (or EtO for short),
the more water solubility the emulsifier has.
The one major issue with ethoxylates is that they can be irrita ng at high levels. The molecular formula
for Polyethylene Glycol is given below, where "n" is the number of moles of ethylene oxide in the
molecule.
OH–(CH2–CH2–O)n–H
Structure of Polyethylene Glycol
Ca onic Emulsifiers
Ca onic technology for skin care arose from the wool industry and then transferred to hair care. As hair
and skin are both kera n-derived it didn’t take long for the benefits of ca onics to be harnessed in
moisturizer technology.
Ca onics func on very well in formula ons that are desired to stay on the skin for a long me such as
sunscreens, long-wear make-up and barrier creams. This is because they are posi ve, ca onic charge
adheres these products strongly to the surface of the skin, resis ng wash-off and wear.
A prac cal example of where ca onic emulsifiers has proved very helpful, is in preven ng sand from
s cking to a freshly-sun-screened body. Thanks to its an -sta c capacity.
Like anionics, ca onics are also sensi ve to what is going on in the water phase and cope best with a
rela vely quiet external phase rather than one loaded with addi ves. Due to their natural capacity for
skin adhesion, ca onic emulsifiers can be more likely to irritate than other chemical families, but that
said, in many cases the formulator can work around this – formula ng to an acidic pH is advisable.
The new genera on of ca onic emulsifiers tend to favor long hydrophobic tail(s) as these have the
effect of reducing the charge density of the head group and thus minimizing irrita on poten al. This,
of course, must be balanced by the ingredients capacity to form and hold an emulsion.
As with anionic emulsifiers, ca onics do benefit from a li le monovalent salt as this can boost the CMC
and as a consequence of that, the viscosity, but beyond a certain point, the salt becomes detrimental to
stability.
It is important to note that, in using a ca onic emulsifier system the formulator does rule out the use of
pre y much all grades of Carbomer, and even anionic thickening agents such as xanthan, unmodified
guar and tragacanth.
Ca onic emulsifiers are those that are mostly used in hair care products. These are commonly called
quaternium ammonium compounds or "quats". An example is Distearyldimonium Chloride.
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Apart from having excellent emulsifica on capabili es, they act as hair condi oners because of their
natural electrical charge in associa on with that of the hair.
They also have very good preserva ve ac vity such as Quaternium-15 (Hexamethylenetetramine
Chloroallyl Chloride or Dowicil™ 100). These ingredients are very substan ve and quite func onal.
The one downside of ca onic emulsifiers is that they can be somewhat irrita ng at high levels, more so
than the anionic emulsifiers with higher levels of ethoxyla on.
Ca onic emulsifiers exhibit a charge on the molecule with the use of a halogen ion, such as a chloride
or bromide. Below is an example of Quaternium-70 (Stearamidopropyl Dimethyl Myristyl Acetate
Ammonium Chloride), another ingredient that can act as a ca onic emulsifier and an -sta c
condi oning agent in hair care.
Structure of Quaternium-70
No ce the ammonium groups [-NH-] and the chloride ion, which gives the molecule its nega ve charge.
Non-ionic Emulsifiers
Non-ionics remain the first choice go-to emulsifiers for most applica ons due to their flexibility and low
poten al for chemical interac on. Non-ionic emulsifiers are those that are free from any external
electrical charge caused by free ions. Examples of these are:
Polysorbate 80
Polysorbate 20
These are familiarly known as Tweens, a common trade name.
It is o en a non-ionic emulsifier blend that is chosen first when crea ng creams with high ac vity levels
or hard-to-stabilize ingredients such as:
Salicylic acid
AHA’s
Zinc Oxide or high strength vitamin C
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There were ingredients such as Seppic’s MONTANOV™ 68 MB that first got us hooked on the selfemulsifying blend of non-ionic and freed us from the trials of calcula ng HLB in a complex oil-phase
world.
The key benefit of a non-ionic emulsifier is its robust salt tolerance.
In fact, the addi on of a li le non-ionic is recommended in ionic emulsions as the mixed micelles that
will form tend to display a drama cally enhanced salt tolerance over the ionic alone.
While the presence of self-emulsifying blends has made things easier, it doesn’t for a moment mean
we shouldn’t consider what is going on inside of our product.
The HLB system is alive and well in the non-ionic world and gives us a great insight into where the
emulsifier will orient itself and whether it is able to bring any other features to the product. That said, it
is also important to men on the existence of more than one HLB system so that one can compare like
with like.
Liquid Crystal Emulsifiers
Liquid Crystal Emulsifiers work on the principle of forming a lamella network in the cream, which most
closely mimics the skin barrier, thus facilita ng the effec ve delivery of ac ves. Lecithin naturally works
this way, as does Olivem 100 and various other combina ons available to purchase today.
Because of their skin-like structure, liquid crystal emulsifiers are o en desired for their beau ful
aesthe cs.
While it is possible to create a range of textures using almost any emulsifier, depending on what goes
into the rest of the formula, it would be reasonable to say that the liquid crystal genera ng emulsifier is
the most foolproof way of crea ng a beau ful texture without too much addi onal work.
Polymeric Emulsifiers
Polymeric emulsifiers are a good op on for those looking for elegant and quick cold-process solu ons.
O en sold as liquid polymer suspensions, these emulsifiers can create anything from lightweight
sprayable milks through to thicker, richer creams depending on what they are paired with.
While not for the natural market, these can be quite a sustainable op on, due to:
Their low addi on rate
The speed with which they can form an emulsion, and
Their cold processing capabili es
Polymeric emulsifiers won’t work in every situa on. O en these emulsifiers are acrylic acid polymers
that tend to form complexes with ca onic species.
In addi on, the general salt tolerance of acrylates is low (reflec ng the overall intolerance of ionic
substances).
But one large advantage over ionic and, to a certain point the non-ionic emulsifiers is their ability to
form highly stable emulsions with a very low level of polymer (with a non-polar or very slightly polar oil
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phase). This makes them the perfect emulsifier for a silicone-based emulsion, even those containing
cyclomethicone.
A few destabilizing and stabilizing factors are men oned below. Let's understand how cri cal it is to
study the phases before making the right selec on of emulsifier(s)…
Chemistry of the Water Phase
As men oned in the beginning, an emulsion is a combina on of two immiscible phases held together
by what to many looks and feels like magic! What is really going on is a physical rearrangement of
components, all trying to get themselves into a posi on that means they are exer ng the lowest
possible amount of energy – those dispersed phase droplets are lazy!
The dispersed and con nuous phases are influenced by everything that comes into the formula, and
some things are more disrup ve than others.
Impact of Surface Tension in Water Phase
The surface tension between oil and water is so high that they don’t mix unless you add a surfactant
(emulsifier in this situa on). We understand that and have discussed the different types of emulsifiers
that we could add, but do we understand what other ingredients do to the product’s surface tension?
Preserva ves and solvents can drama cally alter the surface tension between the oil and water
droplets. As we see with our emulsifier, some reduc on in surface tension is required to facilitate the
development of an emulsion, but in other cases, the changes are catastrophic and can result in viscosity
and emulsion collapse.
Glycerin, Propylene Glycol and Ethanol are common addi ves in a cosme c product and can all impact
on surface tension. All of these ingredients decrease the polarity of the water phase, and the influence
of that decrease changes depending on the quan ty of addi ve present, although the rela onship
between dose and effect is not strictly linear.
Reducing water phase polarity loosens the grip the water has on the dispersed phase somewhat by
toning down the intramolecular forces that make water behave as it does – Van Der Waals, DipoleDipole and hydrogen bonding.
While all emulsifiers depend on these forces to some degree to stabilize the product, the Ionic
emulsifiers depend on them more strongly and are therefore most likely to be influenced by their
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presence.
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Cosme cs 102: Tailoring Formulas to Your Needs
Impact of Ions in Water Phase
We o en talk about salt and sal ness in formula ng, but what we really talk about much of the me is
the ionic strength of con nuous phase.
The swapping of demineralized water for sea water, might cause formulary issues, we are less likely to
accept that the ac ves we carefully measure into our water phase are doing the same. Be they acids,
bases or salts, an ion-rich water phase, can cause havoc, for the stability of a product.
Ionic charge in the water phase can help increase intramolecular bonding and can also help in the
forma on of an electric double layer around the dispersed phase, which increases stability but things
can go too far, especially with:
Divalent salts such as zinc
Strong acids, and
Oxidizing agents such as glycolic and peroxide
In general, the cosme c chemist is looking to minimize chemical reac ons in their formula, and so any
addi on of ions should be thought of as fueling the fire of chemical rebellion. Every emulsion has its
limits, plus adding too many ions into the con nuous phase will give the product a s cky/ tacky/ salty
feel when applied.
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Tricky Oil Phases
Silicone Oils
When compared to vegetable oils, silicones demonstrate prac cally no polarity as well as a very
different chemical structure – flexible chains vs bulky triglycerides. Because of these differences,
silicone fluids such as dimethicone and cyclomethicone tend to mix poorly or not at all with vegetable
oils in the same formula.
If the formulator wishes to create a silicone rich emulsion, the influence of this low polarity should
be considered.
Steps to reduce the polarity of the con nuous phase would increase stability and take some of the
pressure off the emulsifier as the surface tension between the two phases would be lessened.
Silicone emulsifiers are available from the major silicone manufacturers should be the first port of call
for all those looking to create a silicone-dominant emulsion, especially where the silicone phase will be
large or even dominant. Having said that, with careful considera on it is also possible to create a
silicone-rich emulsion with non-silicone emulsifiers if the chemistry of the whole product is considered
and accounted for.
Solvent
Water
Polarity
Solubility Parameter
(A difference of <2 indicates
mutual structural solubility)
Based on the theory of ‘like
dissolving like’
23.40
Glycerin
16.26
Lac c Acid
14.81
Propylene Glycol
14.00
Ethanol
12.55
Isopropyl Alcohol
Cetyl Alcohol / Stearyl Alcohol
11.24
8.94 – 8.90
Castor Oil
8.90
Isopropyl Myristate
8.02
Olive Oil
7.87
Isopropyl Palmitate
7.78
White Mineral Oil
7.09
Squalene
6.19
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Squalane
6.03
Cyclomethicone D5
5.77
Dimethicone
5.92
Is your emulsion going to be salty, acidic, basic, or contains a high propor on of solvents that are less
polar than water, or does it contain Hydrogen Peroxide? If so, the best star ng point is non-ionic.
Types of Emulsifiers
As water and oil do not mix, emulsifiers in cosme cs assist in forming homogenous mixtures of both.
Emulsifiers in cosme cs stabilize the emulsion and influence the consistency of the formula on. Most
of the cosme c products make good use of emulsifiers in their formula ons like:
Creams
Lo ons
Sprays, and
Foams
Some common emulsifiers in cosme cs are:
Oil-in-water
Water-in-oil
Natural emulsifiers
Silicone emulsifiers, and
Co-emulsifiers
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Key Features of Various Types of Emulsifiers
Oil-in-water (O/W)
Water-in-oil (W/O)
Can be synthe c
Can be synthe c
Keeps oil drops
packed in water
Keeps water
droplets packed in
oil
Used for moisturizing
effects
Natural
Silicone
Derived from
natural resource
Used for a fa y feel
They are much into
being due to a
global emphasis on
going green
Reduce the cost of
the overall
formula on
Water-in-silicone
(W/S) emulsifiers last
longer
Oil-in-water Emulsifiers
Oil-in-water emulsifiers create oil-in-water emulsions. In oil-in-water (o/w) emulsion systems, oil
droplets are dispersed in water.
Oil is the internal/ dispersed phase whereas water is the
external/con nuous phase.
O/W emulsifiers are more soluble in water than in oil.
O/W emulsifiers have an HLB greater than 15.
The emulsions produced with the help of oil-in-water emulsifiers have
certain advantages, disadvantages and applica ons which are discussed
below.
Oil-in-water Emulsifiers
Advantages
Applica ons
Disadvantages
Oil-in-water emulsions have
a good spreadability on skin.
They are economical and can
be easily manufactured.
They have good physical
stability.
Are stable at temperatures
even below 0°C.
Oil-in-water emulsions
provide a cooling effect to
the skin as water cons tutes
the external phase of these
emulsions.
Used in personal care
products like:
Cleansing milks
Hair condi oning
formula ons
Shaving creams
Moisturizing lo ons, and
Sprayable emulsions
More vulnerable to microbial
a ack and bacterial
contamina on.
Do not prove to be cost
effec ve as addi on of
preserva ves is required to
prevent degrada on of the
formula on.
Listed below are few oil-in-water emulsifiers along with their main proper es and applica ons.
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Product
name
Emulsynt™
1055
(Liquid)
HallStar®
EGAS
(Flakes)
HallStar®
GMS SE
(Flakes)
HallStar®
GMS
SE/AS
(Flakes)
INCI
PEG-8
PROPYLENE
GLYCOL
COCOATE
POLYGLYCERYL-4
OLEATE
STEARAMIDE
AMP
GLYCOL
STEARATE
GLYCERYL
STEARATE SE
PEG-100
STEARATE
GLYCERYL
STEARATE
CAS
Applica ons
9007-48-1,
977061-81-6
and
126645-98-5
Skin / Sun
care
Hair care
Fragrances
Toiletries/
Make-up
111-60-4
and
68951-62-2
or
36284-86-3
Skin / Sun
care
Hair care
Fragrances
Toiletries/
Make-up
11099-07-3
and
593-29-3
Skin / Sun
care
Hair care
Toiletries/
Make-up
123-94-4,
9004-99-3
Skin / Sun
care
Hair care
Toiletries/
Make-up
Main Proper es
Acts as a water-in-oil, water-insilicone emulsifier as well as
auxiliary stabilizer for oil-inwater prepara ons.
Acts as a bodying agent, coemulsifying agent, emulsifying
agent (o/w), emulsion stabilizing
agent and viscosity stabilizer.
Is plant derived / vegetal-based
and biodegradable.
Provides good electrolyte
stability for both hair and skin
condi oning emulsions.
Acts as bodying agent, co
emulsifying agent, emulsifying
agent (o/w) and emulsion
stabilizing agent.
Is biodegradable, plant derived /
vegetal-based.
Acts as a bodying agent, coemulsifying agent, emulsifying
agent (o/w), emulsion stabilizing
agent and viscosity stabilizer.
Is plant derived / vegetal-based
and biodegradable.
Provides good electrolyte
stability for both hair and skin
condi oning emulsions.
Water-in-oil Emulsifiers
Water-in-oil emulsifiers help in producing water-in-oil (w/o) emulsions. In W/O emulsions, water
droplets are dispersed in oil (oil encases water).
The oil comes in contact with skin first providing more greasiness.
These emulsifiers are more soluble in oil than in water.
They have HLB between 2.5-6 are non-ionic or polymeric.
Emulsions produced by W/O emulsifiers aid in protec ng and nurturing dry and dehydrated skin
(moisturizing effect). Thus, these are brought to use in moisturizers, dry skin care, skin-nourishing
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lo ons, etc.
The benefits of water-in-oil emulsifiers are given below along with their
disadvantages and applica ons.
Water-in-oil Emulsifiers
Benefits
Applica ons
Water resistant
Limita ons
W/O emulsions are used in
manufacturing skin care
products like:
Lustrous and glossy
Opaque and
When applied , these may
give a heavy and greasy
feeling on the skin
Lo ons
Great skin feel
Sunscreens
Smooth applica on
Cold creams, as they are
more water resistant than
O/W emulsions
Milder than o/w and do not
harm the lipid bilayers in the
skin
Make up products, with all
types of oil
Less suscep ble to
microbiological a ack
O en difficult to obtain
stable W/O systems,
addi on of stabilizers may
be required
Some water-in-oil emulsifiers are listed below along with their proper es and applica ons.
Product
name
Capmul®
MCM C10
(Powder)
INCI
GLYCERYL
CAPRATE
CAS
Applica ons
Skin care
Fragrances
Toiletries/
Make-up
26402-22-2
Main Proper es
Glyceryl caprylate.
Acts as water / oil emulsifier.
Recommended for creams,
lo ons, ointments and
lips cks.
Highly efficient emulsifier for
water-in-oil systems.
Elfacos® E
200
(Paste)
Cremophor®
WO 7
(Liquid)
METHOXY PEG22/DODECYL
GLYCOL
COPOLYMER
PEG-7
HYDROGENATED
CASTOR OIL
88507-00-0
Skin care
61788-85-0
Skin care
Has a high water reten on
capacity that allows the
formula on of light creams
with a very high water content
that do not leave the skin
feeling greasy.
Used in W/O emulsions,
par cularly suitable for liquid
and modern, so prepara ons
that are known as so creams.
Acts as a non-ionic emulsifier.
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Does not leave a no ceable
fa y sheen on the skin but
produce a visible cosme c
effect.
Dehymuls®
PGPH
(Liquid)
Acts as a W/O emulsifier.
POLYGLYCERYL-2
DIPOLYHYDROXY
STEARATE
144470-58-6
Skin care
Used in W/O creams
containing greater frac ons of
high molecular oils, like
vegetable oils.
Co-emulsifiers in Cosme cs
Co-emulsifiers are added to improve the viscosity and stability of the resultant emulsion. Borax, cetyl
alcohol, cetearyl alcohol, etc. are some examples of co-emulsifiers in cosme cs.
Product
name
Cerasynt®
PA ester
(Flakes)
Natrosol®
PLUS 330CS
Pluracare®
F127
(Solid)
Hostacerin®
DGMS
(Pellets)
INCI
CAS
PROPYLENE
GLYCOL
STEARATE
1323-36-3
Skin care
Hair care
Toiletries
80455-45-4
Skin care
Hair care
Sun care
Decora ves/
Make-up
Toiletries
CETYL
HYDROXYETHYL
CELLULOSE
Applica ons
POLOXAMER
407
9003-11-6
Skin care
Hair care
Sun care
Decora ves/
Make-up
Toiletries
POLYGLYCERYL-2
STEARATE
61725-93-7
Skin care
Main Proper es
Acts as an opacifier, pearlizer and
co-emulsifier.
Cetyl hydroxyethylcellulose, coemulsifier, lubricant and
thickener.
Stabilizes O/W emulsions.
Used in shampoos, cosme cs,
shower gels, foam bath and facial
wash.
Acts as a non ionic surfactant.
Possesses solubilizing, bodying
and gelling proper es.
Acts as an EO free thickener and
co-emulsifier for O/W emulsions.
Used in liquid and creamy oil-inwater emulsions.
Silicone Emulsifiers in Cosme cs
Silicone-based emulsifiers are generally liquid at room temperature. There are two general structures
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Selecting and Evaluating Emulsifiers for Cosmetics
for this class of emulsifiers.
The first one being a rake silicone polyether in which the polyether segments are a ached to a
silicone backbone, which allows for the addi on of alkyl chains in order to increase their
compa bility with organic oils.
The other structure is an (AB)n silicone polyether, where the polyether segments are added within
the silicone backbone.
These emulsifiers have an affinity for silicone and organic oils which makes the oil phase flexible
enough for the addi on of other specialty silicones. Silicone emulsifiers help to reduce the cost of the
overall formula on by emulsifying up to 80 percent water.
Moreover, water in silicone (W/Si) emulsifiers last longer and are wash resistant when compared to
O/W emulsifiers. Silicone emulsifiers find uses in almost all skin care products.
Natural Emulsifiers in Cosme cs
Natural emulsifiers, as their name says, are naturally sourced. Since their introduc on to the cosme c
industry, they have received an overwhelming response. Thanks to the "global go-green" emphasis.
Natural emulsifiers in cosme cs are more suscep ble to microbial a ack, and the formula on needs
the addi on of a preserva ve. They are not too effec ve as emulsifiers which calls for their addi on in
large quan es. Though a natural emulsifier containing formula on has an extra edge over others, it
can have some serious repercussions on the skin of the end-user.
Being naturally sourced, natural emulsifiers in cosme cs can prove poten al allergens to some
individuals.
Lanolin - sheep's water-free wool fat is a natural emulsifier that serves as a bond between water
and oil. It is added to skin care creams.
Lecithin is a natural emulsifier that can be used alone or in combina on with other emulsifiers. They
are usually based on chemicals called phospholipids and can be both plant an animal derived.
Depending upon the quan ty of lecithin added, a formulator can achieve the desired consistency
in a lo on.
It is majorly used in skin care formula ons due to its emollience/ moisturiza on effect.
For hair care applica ons, in addi on to lecithin, pec n and glycerin is also used.
Beeswax, another natural emulsifier finds good use in lip balms, lips cks, ointments, etc.
Product
name
ALKOLAN® CD
80
INCI
CAS
PALM
KERNELAMIDE DEA
68155-07-7
(Liquid)
Applica ons
Skin care
Hair care
Sun care
Fragrances
Toiletries
Main Proper es
Acts as a thickener, foam
stabilizer, re-fa ng agent,
detergent, emulsifier and
solubilizer for fragrances
and essen al oils in the
formula on of personal care
products.
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Selecting and Evaluating Emulsifiers for Cosmetics
Exhibits emolliency and
neutralizing proper es.
Phoenotaine®
C-35
(Liquid)
SODIUM
COCAMIDOPROPYL
PG-DIMONIUM
CHLORIDE
PHOSPHATE
83682-78-4
Skin care
Hair care
Toiletries
Used as extremely mild
surfactants, especially in
baby products such as
shampoos, bath and shower
gels, body wash, bath beads,
and products used in
personal care.
Acts as a natural emulsifier.
Phytocompo™
-PP
(Powder)
Lecinol S-PIE
(Powder)
GLYCINE SOJA
STEROLS
HYDROGENATED
LECITHIN
HYDROGENATED
LECITHIN
92128-87-5, Skin care
68555-08-8 Hair care
Enhances barrier proper es,
moisturizes skin and
provides a unique skin
feeling.
It can be used in synthe c
surfactant-free products.
92128-87-5
Skin care
Hair care
Sun care
Fragrances
Toiletries
Decora ve/
Make-up
Used in cosme cs.
Possesses good heat and
oxida on stability compared
to natural lecithin.
Factors for Selecting Emulsifiers
There are four main factors that deserve considera on:
1. Marke ng/ Product Posi oning
2. Performance
3. Physical Character
4. Chemistry
As Cosme c Chemistry is an applied science, it is appropriate to start with the marke ng as this is the
main reason for us embarking on this formula on work.
Marke ng
Emulsifier-Free Claim
An emerging niche of ‘emulsifier-free’ creams designed around the philosophy that the emulsifier,
being a surface-ac ve ingredient, may be a source of irrita on for very sensi ve skins and that avoiding
the use of an emulsifier may make the product more suitable for this demographic.
Now, this may or may not work out to be true, but nevertheless, the concept is of interest as there is
some truth in the idea that surface-ac ve ingredients (of which emulsifiers are a part) can contribute to
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a product’s irrita on poten al.
So, if you don’t use an emulsifier to hold the oil and water together, what
do you use?
Small amounts of oil can be held in suspension with the use of thickeners/
stabilizers such as Carbomer, and even xanthan and sclero um gums to a
lesser degree. These aren’t emulsifiers and neither are they forming an
emulsion, more of a suspension, but if the oil phase is light and dispersed
well enough, these products can be made stable through steric hindrance –
the oil droplets are caught up, as if in a fishing net!
Some mes bentonite clays can also be used in this way to bring opacity to
the formula and to provide an electrical repulsion layer into the structure to
help repel agglomera on of the dispersed phase.
Another op on in this space is a modified acrylate copolymer such as Acrylates/Beheneth-25
Methacrylate Copolymer.
Although this polymer is best suited to surfactant formula ons, it does have a role to play in leaveon skin care.
As it has the benefit of being tolerant to rela vely high level of salt and other water-phase
destabilizers making it a versa le choice for the ‘emulsifier-free’ concept developer.
The fact that the polymer can stabilize a reasonably sized oil phase while remaining ‘emulsifier-free’
paired with its low use levels, add to the cost efficiency of this solu on. Another interes ng feature of
these polymeric ‘emulsifier-free’ ingredients is their ability to be sprayed which opens up new doors
for the formulator and marke ng department.
What if you are looking to create something a bit richer and with an oil phase more typical of a
tradi onal moisturizer?
Modified lecithin chemistry has become the accepted technology in the ‘no emulsifier’ space,
especially because these lecithin frac ons o en have lipid enhancing proper es and can be sold on
their ‘skin compa bility’ and moisture binding powers.
In addi on, the phospholipid structure also lends itself to ac ve delivery given how similar in
structure they are to human cell membranes (well at least in terms of their chemical cons tuents).
Lecithin chemistry tends towards forming a liquid crystal network in the con nuous phase, which
both traps and interacts with the dispersed phase in an ultra-stable and skin compa ble threedimensional structure.
A number of companies are now offering a range of modified lecithins suitable for everything from light
hypoallergenic milk formula ons through to super-rich balms which should please marke ng
departments over the world over, but from a chemist's perspec ve it is hard to see how these
ingredients have managed to escape the ‘emulsifier’ tag.
Ingredient Origin and Ethics
Another important considera on for the general public and formulators alike is ingredient sustainability
and/or ethics. There is a steady yet growing interest in ‘palm oil-free or sustainable palm’ concepts,
the achieving of which is surprisingly difficult. That said, making an emulsion without adding any palm
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Selecting and Evaluating Emulsifiers for Cosmetics
derived ingredients used to be easy – just use petroleum derived chemicals – but these days that is just
as unacceptable for a growing number of brands.
The reality is, our enthusiasm for embracing the natural revolu on has increased demand for
vegetable-based feedstock and those of us who have been in the industry for a while know that means
either palm (orang-u-tan habitat) or Rapeseed/ canola (pes cides and bees).
So today while it is s ll not easy to create palm free emulsion it is not impossible too, given that our
previous ‘emulsifier free’ examples are predominantly palm free (lecithin phospholipids are frequently
made from Rapeseed, Egg, Soybean and/or Sunflower).
In fact, it would be fair to say that the hardest thing about making a palm free emulsion today is not
over which emulsifier to choose, but which suppor ng ingredients can be used to increase stability,
viscosity (without gumminess) and overall skin feel.
INCI Name – It Has To Look Good On The Label!
S ll under the guise of marke ng issues, the issue of
INCI names also comes up here. While ingredient
manufacturers do have to abide by a ‘truth in
marke ng’ legisla on when they apply for their INCI
names (they can’t just make them up). The reality is
that a natural sounding INCI will sell more and have
be er shelf appeal than a more chemical sounding
ingredient.
This reality has really hit home and that can be both good and bad. In some cases, we have very
average ingredients (in terms of performance) becoming popular because they have a nice name while
outstanding ingredients (that are s ll natural in many cases) are overlooked.
» Click Here to Get Informa on on Cosme c Ingredients from SpecialChem's INCI Database
Directory!
Show Me The Money!
Another important factor in the marke ng basket is price. Emulsifiers can make quite a dent in the
formula budget. When comparing something natural to a stock-standard petroleum-based emulsifier
you can be looking at anything from three to five mes the price which of course has to be jus fied.
In many ways this is the acid test – will customers put their money where their ethical mouths are or do
we have to sell them another benefit? Blending different technologies together can be a good way to
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increase performance while managing price. This philosophy has kept many of the older emulsifier’s
op ons such as glyceryl stearate SE alive and selling well.
Performance
Performance benefits of different technology have been looked at more in the chemistry sec on but as
we are star ng to see from some of the claims rela ng to emulsifier free formula ons, the ingredient
that holds the oil and water together is, in many cases expected to do so much more besides.
When the Olive derived emulsifier Olivem 1000 first came onto the market there was a great deal of
interest in its ability to act as an ac ve delivery system as well as the ingredient that just happened to
make an emulsion possible. That benefit contributed to the ‘emulsifier-free’ marke ng tagline (it isn’t
an emulsifier; it is an ac ve delivery system) while also helping the cosme c chemist deliver oil soluble
ac ves deep into the skin (theore cally).
This important dual func onality contributed to the immediate success of this technology, success that
con nues today in spite of the ingredients rela vely high price point compared with older technology
or ingredients like cetearyl alcohol which also form liquid crystal structures for a frac on of the price!
In terms of integra ng new emulsifier technology into the laboratory these days the real ques on
isn’t the price but how many benefits one gets for that price? The following benefits are possible
thanks to the combina on of science and nature:
Water resistance
Barrier protec on
Long-wear characteris cs
Increased dispersion of ac ves
Viscosity boos ng, and
Rheological benefits
Physical Character
Something that we may overlook when considering price is the emulsifier’s physical form and this is
because we o en just think of emulsions as hot-process items and so the form of the emulsifier is not
really a talking point. But it doesn’t have to be that way.
Electricity prices are rising in many countries and even those with cheap power aren’t in the habit of
was ng it so liquid emulsifiers that can be used in cold-process applica ons can help the formulator to
ck a few boxes from sustainability through to the economic benefits of saving me and money.
The range of liquid emulsifiers is steadily growing and is worth a look, especially for markets that
demand an ultra-light touch finished product with li le to no wax or bu er content.
Chemistry
Of course, we couldn’t talk about emulsifier selec on without talking about the chemistry. The
emulsifier is the heart of the formula and while it may o en seem like, today the chemistry has all been
done for you, as men oned in the beginning, there are some very challenging problems that await the
professional cosme c chemist that only an apprecia on of the underlying chemistry will help solve!
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Selecting and Evaluating Emulsifiers for Cosmetics
Select Emulsifiers & Surfactants Faster!
Avoid stability issues in your emulsions by efficiently selec ng and adap ng your surfactant / emulsifier
system. Join the course: Emulsifiers & Surfactant Selec on for Stable Cosme cs today.
HLB System in Selecting Emulsifiers
While preparing an emulsion choosing an emulsifier can be cumbersome. HLB system was introduced
to save me and stumble upon the right emulsifier/ emulsifiers for an applica on. HLB stands for
Hydrophile-Lipophile Balance (balance between the hydrophilic por on to the lipophilic por on of the
non-ionic surfactant).
Between 1949-1954 Griffin developed a pre y robust yet simple HLB system and that is the
standard upon which the Span and Tween pairings from ICI were arranged.
The method produced a scale ranging from 0-20 indica ng what percentage of the emulsifier was
hydrophilic. The number given was the percentage hydrophilicity / 5 (so the maximum number 20
related to a molecule being 100% hydrophilic).
This simple system was expanded upon by Davie’s in 1957, who thought that some weight should be
given to the func onality of the chemical groups on the molecule.
This makes sense given the variety of structures available to give a hydrophilic character.
This method is widely used today and is one of the reasons that ionic emulsifiers can be assigned an
HLB value.
It is also the reason that HLB numbers in 30’s is found (the maximum HLB in this system is 40).
While formula ng both the emulsifier and the oils to be emulsified have an HLB a ached to them –
the emulsifiers have a real HLB whereas the oils have a required HLB.
It is widely accepted that the best emulsifier pairings are formed when a high HLB emulsifier is
combined with an emulsifier with a low HLB rather than just selec ng the emulsifier with the exact HLB
you want to achieve. This combina on effect serves to best fill the interface surrounding the
con nuous and dispersed phase, leaving less room for gaps and therefore increasing stability.
Calcula ng HLB Number of a System
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In the HLB system, an ingredient or combina ons of ingredients that need to be emulsified are assigned
a number and then an emulsifier having the same number is chosen to create an emulsion.
A lipophilic/oil loving/ non-polar emulsifier is assigned a low HLB number (below 9) and a
hydrophilic/water loving/ polar emulsifier is assigned a high HLB (above 11.0). The ones that fall in the
range of 9-11 are intermediates.
Let's say for example we have a blend of emulsifiers to create an emulsion. To find out the HLB of the
blend the following calcula ons can be carried out:
Values: 70% Emulsifier 1 having an HLB number 15, 30% Emulsifier 2 having HLB number 4.3
HLB Calcula on
+
Emulsifier 1
70% X 15
Emulsifier 2
30% X 4.3
10.5
1.3
HLB of Blend
11.8
Evaluating Emulsifiers
How do Emulsifiers feel?
A very simple formula based on a common non-ionic
emulsifier – Cetearyl Alcohol and Cetearyl Glucoside has
been developed. This formula was then replicated with
different emulsifiers, one from each different class (except
silicone). The products were evaluated by an expert panel of
five people as well as having their viscosity checked before
being evaluated under the microscope.
The formula and feedback is not presented to help sway a
decision towards or away from a par cular type of
emulsifier, merely it is to illustrate a point, that the emulsifier can impact everything from viscosity to
feel, efficacy to stability. It also demonstrates the importance of op mizing the whole formula so as to
get the most out of the emulsifier of choice. Plus there is always room for pairing up on technologies or
trying something new!
So the only difference between these formula ons is the emulsifier except for the ca onic version
which was incompa ble with the thickener Acacia and Xanthan gum blend. In the ca onic, a ca onic
guar has been used at the same level. This could be seen from the table below:
Viscosity @ 3.0
Spindle
Formula
Skin Feel
Ca onic (Brassicyl Isoleucinate Esylate
(and) Brassica Glycerides (and) Brassica
Alcohol)
Anionic (Potassium Cetyl Phosphate)
Thin, high spreading, slightly tacky to
touch at first drying to
powdery
Silky, takes a while to absorb, feels
19,380
90,630
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Selecting and Evaluating Emulsifiers for Cosmetics
substan ve a er drying.
Non-Ionic (Cetearyl Alcohol, Cetearyl
Glucoside)
Mixed Anionic/ Non-ionic. (Glyceryl
Stearate (and) Cetearyl Alcohol (and)
Sodium Stearoyl Lactylate)
Non-Ionic Synthe c (Cetearyl Alcohol,
Ceteareth-20)
Polymeric (Acrylates/C10-30 Alkyl
Acrylate Crosspolymer)
Liquid Crystal Emulsifier (Cetearyl
Olivate, Sorbitan Olivate)
HLB balance (Sorbitan Monooleate,
PET-20 Sorbitan Monostearate)
Easy to rub in
56,250
Easily absorbed
74,690
Very thick and creamy, light a er feel
160,600
Ultra-light, quick break and high
spreading. Tacky on drying.
15,310
Rich waxy texture, slow spreading
82,190
Very light and spreadable
13,440
Base formula on used could be observed from the table shown below:
Phase
Water Phase
Oil Phase
Finishing Touches
Ingredient
%
200g
Func on
Deionized Water
71.95
143.9
Solvent
Acacia and Xanthan
Gum
0.4
0.8
Thickener/
Stabilizer
Glycerin
3
6
Humectant
EDTA
0.1
0.2
Chela ng Agent
Jojoba Oil
8
16
Emollient
Shea Bu er
8
16
Barrier Protec on
Squalane
2.5
5
Emollient
Emulsifier of
choice
3
6
Emulsifier
Cetearyl Alcohol
1.25
1.25
Emulsion Stabilizer
Natural Vitamin E
0.5
1
An oxidant
Perfume
0.3
0.6
Aroma
Preserva ve
(Phenoxyethanol
Ethylhexylglycerin)
1
2
Broad Spectrum
Preserva ve
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Selecting and Evaluating Emulsifiers for Cosmetics
TOTAL
100
200
Suitable Emulsifiers Used in Cosme c Formula ons
Eastman Tenox™ 20A Food Grade An oxidant, Kosher
Eastman
Canola oil glyceride, Zea mays oil, TBHQ (20%), propylene glycol and citric acid (3%). Eastman
Tenox™ 20A Food Grade An oxidant, Kosher by Eastman acts as an an oxidant and emulsifier.
Eastman... view more
Beeswax Care 144
Paramelt
Cera alba. Beeswax Care 144 by Paramelt acts as a consistency factor, emulsifier and stabilizer. It
also acts as an emollient and oil binder in s ck products. It is a 100% pure, bleached beeswax...
view more
Beeswax Care 146
Paramelt
Cera alba. Beeswax Care 146 by Paramelt acts as a consistency factor, emulsifier and stabilizer. It
also acts as an emollient and oil binder in s ck products. It is a 100% pure and refined beeswax...
view more
Paracera® C 44
Paramelt
Paraffin (and) Synthe c Wax (and) Copernicia Cerifera Cera. Paracera® C 44 is a consistency factor,
oil binder and co-emulsifier by Paramelt. It is a blend of carnauba and other waxes. Offers... view
more
Silsurf® Q25315-O
Siltech
PEG/PPG-12/12 Dimethylsiloxysilicate. Silsurf® Q25315-O by Siltech is an ultra-highly branched
silicone polyether func onal MQ resin-based, oil-in-water emulsifier. It provides excellent pigment...
view more
View All Products
Check Latest News on Emulsifiers for Cosme cs
Explore the Formula ons Containing Emulsifiers
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Selecting and Evaluating Emulsifiers for Cosmetics
About Amanda Foxon-Hill
Amanda Foxon-Hill is a consultant Chemist and Science Communicator with over 14
years of experience in the global cosme cs industry. She is a writer, a er dinner
speaker, strategist and lecturer in all aspects of cosme c science and runs a successful
consultancy prac ce under the name of Realize Beauty.
Amanda’s key skills are in networking and communica ng ideas and opportuni es both
on a business to business and business to market level. She is an advocate for green
science and through her team funds research into the development of more sustainable manufacturing
prac ces.
About Nick Morante
Nick Morante is currently a Senior Chemist at IFC Solu ons (formerly Interna onal
Foodcra ) in New Jersey where he works with many types of colors and addi ves for
both the food and cosme cs industries.
He has over 40 years of experience in the formula on of cosme cs, personal care
products and makeup products. Prior to joining IFC, Nick was a consultant to the
cosme cs industry for over 10 years providing custom formula ons for clients as well
as giving presenta ons and seminars to various companies and organiza ons within
the cosme cs industry providing guidance in the prac cal use of color in consumer products.
He is current an adjunct faculty member at Fairleigh Dickinson University’s School of Natural Sciences in
Hackensack, NJ where he is an instructor in the Master of Science Program in Cosme c Science.
Nick also spent over 30 years in Research and Development at The Estée Lauder Companies where he
was both a formulator and laboratory manager in the corporate makeup and hair care departments. He
was also in charge of the Color Science Laboratory where he was responsible for color measurement
and spectrophotometric analysis of finished products, ingredients and human skin as it relates to color
that is used in various cosme c products, as well as developing tes ng protocols and methodologies for
many color applica ons.
Nick holds a Bachelor of Science degree from The New York Ins tute of Technology. He has taken
numerous con nuing educa on courses in the area of cosme c science. He is a long me member of
U.S. The Society of Cosme c Chemists and has been ac ve both on the local and na onal levels having
served on the execu ve commi ee for the Long Island Chapter and on the Na onal Board, serving as
Area Director and Na onal Secretary. He has been elected a Fellow of the Society and is an instructor
for the Society’s Con nuing Educa on Program (CEP) Program in the area of color and makeup
formula on problem solving and troubleshoo ng.
He has given many seminars and presenta ons worldwide as well as to the SCC, CTFA and HBA. He has
been awarded numerous patents and has contributed many ar cles and papers and authored chapters
in numerous cosme c, technical and beauty publica ons and texts.
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