Chapter 14

Secondary Surfactants for Personal Care Applications

Minh Tong and Thomas Giese
Stepan Company, Northfield, Illinois, USA

Introduction
Primary surfactants, most commonly anionic in nature, carry a negative charge on
the surface active or hydrophobic portion of the molecule (RCOO– Na+, where R
is a fatty hydrophobe). “Surfactant” denotes an organic molecule having surface-
active properties. The term surfactant is a convenient contraction of “surface active
agent,” that originated in one of the industry’s leading laboratories and is now
widely accepted.
Secondary surfactants can be loosely defined as any surface-active agent that
is used in conjunction with a primary surfactant to enhance foaming characteris-
tics, modify formulated viscosity responses, or improve the overall mildness of the
formulation. It can also be employed as a wetting agent, a solubilizer of essential
oils and fragrances, or a conditioner for hair and skin.
In the personal care world, primary surfactants are generally anionic in nature.
Thus, for the purpose of this discussion, amphoterics, and non-ionics will be treat-
ed as secondary surfactants. The main focus of this chapter is the application of
these surfactants in the personal care arena, with some emphasis on the synthesis
process as well as chemical and physical properties.

Amphoterics
The term “amphoteric” was most likely coined by Hans S. Mannheimer in the mid-
1940s to describe a class of molecules that contain both ionic charges (1).
Amphoterics exist as anions in alkaline systems, as cations in acidic systems, and as
zwitterions at their isoelectric point. This class of molecules became significant in the
1950s due to their mildness characteristics. For those consumer product formulations
intended to contact the human body, irritation to the skin and eyes is often mitigated
by use of mild amphoterics. Such mildness characteristics were well documented by
J.H. Draize in a study conducted in 1959 (2). In the personal care market, amphoterics
are considered a “detoxifier” of primary surfactants. Synergistic mildness achieved by
the use of mixed surfactant systems, coupled with improved end-use performance
properties, such as foam generation, make amphoterics an integral part of today’s
cleansing formulations (3). The amphoterics examined in this chapter are amphoac-
etates, amphoproprionates, and ampholytes.

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 Fig. 14.1. Sodium cocoam-
phoacetate (CAA).

Amphoacetate is an amphoteric derived from a fatty imidazoline reacted with

sodium chloroacetate (4). Frequently used amphoacetates are shown in Figures
14.1–14.3. Amphoacetates are efficient viscosity builders (Fig. 14.4).
Amphopropionates are formed by reacting acrylic acid or its derivatives with
aminoethylethanol amine and coco fatty acid. Amphopropionates are salt (sodium
chloride) free materials (5). Two commonly used amphopropionates are shown in
Figures 14.5 and 14.6. Amphoacetates and amphoproprionates do not have the same
foam response compared to cocoamidopropyl betaines or cocamidopropyl hydroxy-
sultaines (Fig. 14.7), but they are less irritating to the eyes and skin than ampholytes.

Ampholytes
Ampholytes are compounds that can exist as cationics in acidic conditions, or as
zwitterionics at the isoelectric point. The most commonly used group of ampholyt-
ic surfactant is betaine (6). Commonly used classes of betaines include those
shown in Figures 14.8–14.10.
Due to their documented mildness to skin and eyes, betaine use as secondary
surfactants in shampoo formulations became prevalent in the late 1960s (7). Betaine
mildness is a function of the mixed micelle systems that betaines form with primary
(typically anionic) surfactants (8). In shampoo applications, betaines help reduce
the buildup of electrostatic charge on hair follicles caused by frictional forces in
“fly-away” hair. Additionally, cocamidopropyl betaines can increase the color
intensity of direct dye shampoos by increasing deposition (9). Sulfo-betaines have

Fig. 14.2. Disodium

cocoamphodiacetate
(CADA).

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 Fig. 14.3. Sodium laury-
lamphoacetate (LAA).

been found to be especially effective suspending agents for cellulose ether car-
boxylic acids in milky white cleansing systems (10).
Carbon chain length has a direct effect on the viscosity of betaines. High car-
bon chain betaines produce higher viscosity and are thus more difficult to handle
(11). Additionally, C12 and C14 cuts produce the most efficacious cleansers.
Accordingly, in the personal care industry, use of betaines with a coconut or pure
lauryl distribution is most prevalent. Major global suppliers of betaines include
Goldschmidt, Stepan, McIntyre, Lonza, Uniqema, and Rhodia (12).

Non-ionics
Alkoxylation Technology
Alcohol Ethoxylates. The reactions of alcohols or other active hydrogen com-
pounds with alkylene oxides (i.e., ethylene oxide, propylene oxide) are the basis of
alkoxylation processes (Fig. 14.11) (13). Alkoxylation is arguably the most impor-
tant synthesis route in the production of non-ionics. Reactions with ethylene oxide
Viscosity (cps)

Fig. 14.4. Viscosity building properties of amphoacetates with SLES-2.

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 Fig. 14.5. Sodium cocoamphopropionate.

Fig. 14.6. Disodium cocoamphodipropionate.

Units

Fig. 14.7. Foam response of coconut-based amphoterics. Abbreviations: Sodium cocoam-

phoacetate, 1C; disodium cocoamphodiacetate, 2C; sodium cocoamphopro-pionate,
CSF; disodium cocoamphodipropionate, 2CSF; cocoamidopropyl hydroxysul-taine, CS50;
and cocoamidopropyl betaine, HCA. Note: AMPHOSOL® is a Stepan trademark.

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 Fig. 14.8. ADMA betaines R = C8–C18.

increase the hydrophilicity and water solubility of an alcohol. This is generally

accomplished via a batch process, where the alcohol is treated with a catalyst and
subsequently reacted with an alkoxide to generate non-ionic ethoxylates.
Alkoxylated products catalyzed by standard catalysts (KOH, NaOMe) deliver
a broad range ethoxylate (BRE) distribution of oligomers or polymers with a mean
degree of polymerization. Special catalysts are employed to deliver a narrow range
ethoxylate (NRE) (14) distribution of oligomers but at additional cost and little
functional differentiation over broad range alkoxylates. NRE are typically used in
systems where enhanced viscosity response, improved cloud point, better odor, or
improved solubility is required.

Hydrophile-Lipophile Balance (HLB). Hydrophile-lipophile balance (HLB) is a

measure of “balance” between the hydrophilic EO headgroup and the lipophilic hydro-
carbon tail used to better describe how an alcohol ethoxylate will perform. The system
was developed by chemist William C. Griffin in 1949 at the Atlas Powder Company.
The HLB system should be employed to identify which surfactant to use to emulsify
any given oil or wax. This can be expressed as shown in Equation 14.1.

HLB = EO (wt%)/5 [1]

The HLB of an alcohol ethoxylate can be used as a guide to their application (Table
14.1).
As indicated in Table 14.1 , the lower the HLB value, the more lipophilic the sur-
factant. Conversely, the higher the HLB value, the more hydrophilic the surfactant will

Fig. 14.9. DMAPA betaines R = C8–C18.

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 Fig. 14.10. Sulfobetaines.

act. Lipophilic surfactants are used to emulsify those materials that are soluble in a
non-aqueous medium. Likewise, hydrophobic surfactants are used to help solubilize
materials that will readily dilute in water. By matching the HLB number of the surfac-
tant with the HLB number of the oil, the formulator can obtain an efficacious emulsifi-
cation (12).
The cloud point of an anionic surfactant increases with temperature. This is
because alcohol ethoxylates usually become insoluble at high temperatures due to
hydrogen-bonding instability. It is important to note that the detergency of an alcohol
ethoxylate is optimal near its cloud point. This correlation is of obvious importance
when selecting an appropriate alcohol ethoxylate for a given cleansing application.
In emulsification technologies, phase inversion temperature (PIT) can be used as a
metric by which one may identify the most appropriate alcohol ethoxylate to serve as
an emulsifier. The PIT is the temperature at which phase inversion from o/w to w/o in
a ternary system of oil, water, and surfactant is observed. For purposes of emulsifica-
tion, the formulator should choose an alcohol ethoxylate with a PIT similar to the melt
point of the oil or wax to be solubilized (16).
Alcohol ethoxylates have utility in numerous applications including detergents,
cleansers, emulsifiers, textiles, agricultural products, paper chemistries, as intermedi-
ates for sulfation, and in emulsion polymerization. Alcohol ethoxylates are considered
environmentally safe; much supporting biodegradation data have been published.

Alkanolamides. Alkanolamides are generated by reacting fatty acids, triglycerides, or

methyl esters with amine. Alkanolamide chemistry was first developed by a Stepan
chemist by the name of Kritchevsky. To this day, alkanolamides are sold under the
trade name Ninol, a name coined by Kritchevsky because he had a daughter Nina.
Today’s most commonly used alkanoalmides are monoethanolamides (MEA), (Fig.

Fig. 14.11. Ethoxylation reaction.

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 TABLE 14.1
Hydrophile-Lipophile Balance Guide to Applications

HLB Application
4–6 Without emulsifier
7–15 Wetting agents
8–18 Without emulsifier
10–15 Typical detergents
10–18 Solubilizers

14.12), monoispropanolamides (MIPA), and diethanolamides (DEA). It is important to

note that alkanolamides generated from triglycerides will typically have 6–10% glyc-
erine as a by-product. Glycerine will typically act to reduce the viscosity of the fin-
ished product. Such amides can also act as a humectant, promoting moisture retention.
Alkanolamides are water dispersible, not water soluble. This is sometimes misstat-
ed as formulators often add alkanolamide to a system already containing a surfactant. In
this case, the surfactant acts to solubilize the alkanolamide. Accordingly, the alka-
nolamide works to align itself on the inside of the existing surfactant micelles causing an
increase in micelle size and an increase in viscosity. Alkanolamides are often employed
to improve foam stability and morphology. Although often thought to be thickeners and
foam boosters, neither is entirely true. Alkanolamides work to stabilize foam, but unless
a 2:1 amide derived from the Kritchevsky reaction (Stepan’s Ninol 201) which also con-
tains one mole of amine soap, the 1:1 amides will not boost foam. Instead, they stabilize
the foam by reducing the ability of water to leave the surfactant bubble over time. The
1:1 amides are more commonly used in personal care applications.
Like all surfactants, the size of the carbon chain has significant impact on the per-
formances of the amides. The C12 to C18 distribution will typically increase the prod-
uct viscosity, whereas the C12 to C14 chain amides will enhance foam elasticity and
stability. General guidelines that can be used in the selection of an alkanolamide are
water solubility, DEA > MIPA > MEA; viscosity building, MEA = MIPA > DEA;
foam morphology, MEA = MIPA > DEA; and ease of handling, DEA > MEA >
MIPA (Figs. 14.13–14.15).
Alkanolamides are used to solubilize oils and fragrances, conditioning agents,
wetting agents, and cleansing agents. These products provide anti-static as well as anti-
corrosion properties. For anti-corrosion applications, a 2:1 Kritchevsky amide should
be used. Major producers of alkanolamides include Stepan Company and Uniqema.

Fig. 14.12. Monoethanolamide reaction where R = C8–C18.

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 Fig. 14.13. Effect of amides on building viscosity with SLES-2. Viscosity response of
10% active STEOL® CS-230 with 2% active amide, pH 6.5.

Amine Oxides
Amine oxides are non-ionics in alkaline and neutral conditions. However, in an
acid medium, they act as weak cationics (17). Amine oxides are unique secondary
surfactants in that a formulator can achieve some charge-induced deposition on the
negatively charged hair follicle. As such, it behooves the formulator to evaluate
surfactant systems that contain amine oxides under slightly acidic pH conditions.
Amine oxides are synthesized by reacting tertiary amines with hydrogen per-
oxides (Fig. 14.16). This reaction is conducted in an oxidizing environment. A
well-controlled process is required to minimize the side reaction that can generate
nitroso amines. Nitroso amines are on the carcinogenic suspect list.
Like other non-ionic surfactants, an amine oxide’s critical micelle concentra-
tion (CMC) decreases with increasing temperature (Table 14.2). CMC is the
threshold below which micelle formation does not take place, and thus the cleans-
ing mechanism is compromised (18). The major U.S. producers of amine oxides
are Procter & Gamble, Stepan Company, Sherex Chemical, and Akzo Chemicals
Inc. Aliphatic amine oxides are used as foam boosters and stabilizers in liquid

Fig. 14.14. Effect of amides on building viscosity with SLS. Viscosity response of 10%
active sodium lauryl sulfate with 3% active amide, pH 6.5.

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 Foam height (mL)

Fig. 14.15. Effect of amides on foaming capacity with SLS and SLES-2. Foaming
response of 10% active sodium lauryl sulfate, 2% active amide, pH 6.5.

cleansing systems. Additionally, amine oxides impart viscosity response, emollien-

cy, detergency, and antistatic properties in personal care formulations.

Conclusion
Although anionic surfactants have dominated the surfactant market to date, sec-
ondary surfactants play a vital role in personal cleansing formulations. Secondary
surfactants improve the overall mildness of personal care products, play an integral
part in boosting foam, improve foam stability, and improve the viscosity response
of personal care formulations. By optimizing the use of primary and secondary sur-
factants, today’s formulator has tools at his or her disposal of which earlier formu-
lators would be envious.

Fig. 14.16. Amine oxide reaction.

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 TABLE 14.2
CMC versus Temperature

Temperature (ºC) CMC (mole/L)

1 0.0028
27 0.0021
40 0.0018
50 0.0017
Abbreviation: Critical micelle concentration, CMC.

References
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Cosmetics, Association of Food and Drug Officials of the U.S., Austin, Texas, 1959.
3. Ernst, R., U.S. Patent 3,280,179 (1966).
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17. Herrmann, K.W., Non-Ionic-Cationic Micellar Properties of Dimethyldodecylamine
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