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Formulating “Sulfate-Free”, Super Mild and Luxurious Personal Cleansing

Products with Amino Acid-Based Surfactants

Evelyn G. Su, Ph.D., Xue Hongyu, Wang Zhiqian & Wei Yi

Abstract:
A major trend driven by consumers calling for “sulfate-free”, super mild and luxurious personal
cleansing products is sweeping the personal care industry at an awakening speed. Formulators are
increasingly facing the challenges this trend has presented, yet only with limited choices of
“sulfate-free” surfactants to formulate various personal cleansing products. This paper will evaluate a
number of “sulfate free” alternatives for personal cleansing formulations with a focus on amino
acid-based surfactants, especially the glycinates. The various attributes of amino acid-based surfactants
will be elaborated and compared with other “sulfate-free” alternatives. The formulating techniques
using glycinates will be discussed in detail and exemplified with typical cleansing systems, such as facial
cleansers, body shampoos and from-head-to-toe baby shampoos.

Keywords: Amino Acid-based Surfactants, Glycinates, Sulfate-Free, Personal Cleansing;

Facial Cleansers, Body Shampoos, Baby Shampoos, Super Mild Surfactants; Luxurious
User Experience

Introduction
Fatty acid salts are the earliest surfactants used in soap; it is derived from natural oil or
fats. It has the advantages of abundant sources and strong cleansing performance. On
the other hand, it also has many disadvantages, such as cleansing power reduction in hard
water, drying skin after long period of use, and sting after-feel. Consequently, safer and
more effective surfactants have been sought. Alkyl ether sulfate (AES) is the
representative of them. AES has the characteristics of excellent foaming power, good
cleaning performance in hard water. But impurities in AES tend to be absorbed and
accumulated in the skin, which is unfavorable to health. As the consumers are more and
more concerned with product safety, it is desired that cleansing products should not only
have excellent cleansing power but also excellent safety and biodegradability. For these
reasons, researchers have developed many surfactants derived from natural materials to
improve attributes of irritation, safety, foaming power, biodegradability and etc. Amino
acid-based surfactants, as a unique category of anionic surfactants, have many unique
properties and have attracted much attention. And their advantages of very low irritation,
non-toxic, rapid biodegradation, and safety have made them very desirable in many
personal cleansing products. Furthermore, they do not only provide excellent cleansing
performance equivalent to fatty acid soaps, but also impart skin super mild, smooth, soft
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and luxurious after-feel. As a result, they are becoming an excellent choice in personal
cleansing systems.

Amino acid-based surfactants can be used as substitutes of fatty acid salts, alkyl ether
sulfates as well as all other surfactants as a “Sulfate-free”, “Phosphorus-Free” , super-mild
surfactants in various cleansing products for better performance, more luxurious user
experience and better environmental care. Amino acid based surfactants produce
substantial foam even in hard water. They leave smooth, soft, and luxurious after feel on
the skin, which suits for all kinds of consumers. They also make hair supple, silky smooth,
easy to comb. At the same time some of them have mild antimicrobial activity.
Three series of amino acid-based surfactants will be discussed in the following
paragraphs, namely, glycinate series, sarcosinate series and glutamate series.

1. Properties and Features:

1.1 Physicochemical Properties
1.1.1 Glycinate series
Some basic physicochemical properties of glycinate series are given in Table 1 below:
Table 1. Physicochemical Properties of Glycinate series
Products Solubility (5%) pH value
(30%, 25 oC)
25oC 40oC
Potassium Cocoyl Glycinate (YCK) S S 7.0-9.0
Sodium Cocoyl Glycinate (YCS) S S 9.0-10.0
S- indicates “soluble in water”; NS- indicates “not soluble in water”

1.1.2 Sarcosinate series

The physicochemical properties of Sodium Lauroyl Sarcosinate are in Table 2.
Table2. Physicochemical Properties of Sarcosinate
Products Solubility pH value (30%, 25 oC)
(5%)
25 C 40oC
o

Sodium Lauroyl Sarcosinate (S-12) S S 7.0-8.0

S- indicates “soluble in water”; NS- indicates “not soluble in water”

1.1.3 Glutamate series

Table 3 below shows the physicochemical properties of Glutamate series.
Table 3 Physicochemical Properties of Glutamate Series
Products Solubility (5%) pH value (1%, 40 oC)
25oC 40oC
Potassium Cocoyl Glutamate S S 5.0-6.5
Sodium Cocoyl Glutamate S S 5.0-6.5
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Sodium Lauroyl Glutamate S S 5.0-6.5

TEA Cocoyl Glutamate S S 5.0-6.5
S- indicates “soluble in water”; NS- indicates “not soluble in water”

1.2 Foaming Power

1.2.1 Foaming Power of different amino acid –based surfactants
Fig.1 Foam Power of different surfactants

250

200

150 YCS
YCK
100
S-12
50

0
6 7 8 9

Figure 1 shows that different amino acid-based surfactants have different foaming power at
different pH. The foam power of glycinate series (YCK, YCS is excellent within a pH
range of 7.0-9.0; while that of the sarcosinate (S-12) is excellent within a pH range of
6.0-7.0.

1.2.2 Synergistic Effect with Fatty Acid Salts

Glycinate series have excellent synergistic effect with fatty acid soaps and salts, and
increase the amount of foam and foam retention, as demonstrated in the example of YCK of
the glycinate series shown here in Fig. 2.
Fig. 2 Synergistic Effect with Fatty Acid Salts

400
Foam Height/mL

300

200

100

0 0 m in
0 20 40 60 80 100 5 m in

E v e r s o f t T M Y C K /%

Where YCK%= YCK/ (YCK+ Potassium Laurate) (%w/w)

1.3 Wide compatibility with other surfactants

Glycinate series have wide compatibility with other surfactants, such as
Cocamidopropyl Sultaine (CAB), Sodium Lauroyl Amphohydroxypropyl Sulfonate (SLAS),
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Alkyl poly-glucosides (APG), Lauryl Hydrooxyethyl Imidazoline (LG-30), Alkyl Ether

Sulfate (AES), Potassium Cetyl Phosphate (MAP 160K) and so on.
When 10% (active) Glycinate series (such as YCK, YCS) were mixed up with 1%
Surfactants such as CAB, SLAS, APG, LG-30 and AES, the clear liquid could come into
being. This suggested the favorable compatibility between Glycinate series with familiar
surfactants.

1.4 The Effect of Foam of Common Surfactants

The foam properties of Glycinate series are impacted to various extents by other
common surfactants. A mixed system of Glycinate and other common surfactants is used
to evaluate these effects. In particular, the test system used consists of 15% YCK and
1.5% surfactant (active), the system pH is about 8.0. Table 4 shows the effect of foam of a
number of common surfactants on Glycinate series.

Table 4. Foam Effect with Different Surfactant Systems

Surfactant Foam Properties/Wash After-Feel

SLAS The most rapid and rich foam form with compact and substantial
foam
Easy to flush with smooth and fresh after-feel
LG-30 Rapid and rich foam form, compact and substantial foam
Easy to flush with smooth and fresh after-feel
APG Slowly and more poor foam form , empty foam
Easy to flush with smooth and fresh after-feel
CAB Rapid and rich foam form, not obvious compact and substantial
foam
Easy to flush with smooth and fresh after-feel
Na-AES Rapid and poor foam form
Easy to flush with smooth and fresh after-feel
MAP-160K Rapid and poor foam form
Easy to flush with smooth and fresh after-feel

1.5 Biodegradable Property

All Amino acid-based surfactants should be 75-95% degraded in 28-day
biodegradation study.

2. Application--Thickening the Amino Acid Based Surfactant System

According to their properties, these amino acid-based surfactants can be widely used in
various personnel cleansing products. They can be used in super mild and naturally
derived hair shampoos, bath lotions, facial cleaners, from head-to-toe baby products,
toothpastes, etc. They have excellent foaming power; and are completely compatible to
hair and skin. They can improve hair combability and reduce static. For skin care
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cleansing products, they leave skin a natural, refreshing, clean, silky soft and luxurious
after-feel. They have strong tolerance to hard water, and thus they are well-suited for use
in hard water areas. In addition, due to their mildness, they can also be used in silk and
wool detergents without causing any damage. These excellent application attributes for
amino acid-based surfactants are well-known in the personal care industry, nevertheless, the
difficulty to thicken the amino acid-based surfactant systems are equally well-known.
This technical difficulty in combination with their relatively high pricing has hindered
significantly its applications, until now.
In the next a few paragraphs, we will discuss in detail how to use these amino
acid-based surfactants in formulation in order to get excellent application attributes in
typical cleansing systems. Especially, we will discuss how to thicken the amino acid
based surfactant system, in particular, the Glycinate system. A high level of difficulty
exists for the thickening of the amino acid based surfactant systems, and we have
conquered this difficulty via a number of methods and these have been exemplified in the
following prototype formulas.

F1: Facial cleanser (ZS-SX-080086)

Ingredient/INCI Name %W/W

A: Sodium Cocoyl Glycinate （Eversoft™ YCS-30） 50.0

Glycerin 20.0
Lauric Acid 0.3
Myristic Acid 0.9
Stearic Acid 0.3
B: Citric Acid 1.2
Deionized Water 14.8
C: Glycol Distearate 1.0
Sodium Lauroyl-methyl Taurate 3.0
Cocamidopropyl Sultaine 4.0
Acrylate Copolymer (30%) 4.0
D: Preservative 0.3
Fragrance 0.2

Procedure
1. Add Eversoft YCS-30 and Glycerin, mix and heat to 85℃.

2. Add Lauric Acid and Myristic Acid and Stearic Acid, mix at 85℃, stir for 1 hr.

3. Mix ingredients of phase B, slowly add it into phase A under agitation.

4. Add phase C ingredients under thorough agitation.

5. Cool to 40℃ to form cream, add phase D ingredients.

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6. Cool to 30℃ under agitation.

Formulation Analysis & Guideline

The above formulation sample is white pearlescent cream with a pH of 6.5-7.0.
Sodium Cocoyl Glycinate has rich foam when pH≥7.0. When the pH is 6.5-7.0, the foam
became poor if Sodium Cocoyl Glycinate was used alone. The problem is solved
perfectly by adding some co-surfactants, such as Sodium Lauroylmethyl Taurate and
Sodium Cocoyl Isethionate.

The key thickening method in this example is to use the Glycinate surfactant with a
relatively large quantity of glycerin, which forms a paste with the Glycinate surfactant.
The purpose of adding Acrylates Copolymer in the system is to improve the stability of the
system at high temperature. The cost of this formulation may be further reduced through
reducing the use levels of Sodium Cocoyl Glycinate and Glycerin and optimizing the use
levels of other ingredients while maintaining the application attributes.

F2: Facial cleanser (ZS-SX-080085)

Ingredient/INCI Name %W/W

A: Potassium Cocyl Glycinate （Eversoft™ YCK, 30%） 30.0

Lauric Acid 0.3
Myristic Acid 0.6
Deionized Water 34.6
B: Cocamide MEA 2.0
Sodium Cocoyl Isethionate (65%) 3.0
Glycol Distearate 2.0
Sodium Lauroylmethyl Taurate 3.0
Sodium Lauroyl Amphohydroxypropyl Sulfonate (30%) 15.0
C: Glycerin 8.0
Polyquaternium -7 1.0
Preservative 0.3
Fragrance 0.2

Procedure
1. Mix phase A and heat to 85℃, stir for 30 min .

2. Add phase B, mix at 85℃ to dissolve.

3. Cool down with string to form pearl cream, add phase C ingredients.

4. Cool to 25℃ under agitation.

Formulation Analysis & Guideline

The above prototype formulation has an appearance of white cream with a pH of 6.5-7.0
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and viscosity of 25,000 mpa.s (25℃). This example represents the second thickening
method, that is, by using synergistic secondary surfactant(s) such as Sodium Lauroyl
Amphohydroxypropyl Sulfonate together with Potassium Cocoyl Glycinate to increase the
viscosity of the Glycinate system with a much reduced level of glycerin. Sodium
Lauroylmethyl Taurate is used here to provide richer foam.

F3: Soap-Based Body Wash (ZS-SX-080030)

Ingredient %W/W

A: Lauric Acid 12.0

B: KOH (91%) 3.7
Deionized Water 36.8
C: Cocoyl Monoethanolamide 2.0
Glycol Distearate 1.5
Sodium Lauroyl Amphohydroxypropyl Sulfonate (30%) 15.0
EDTA-2Na 0.1
Potassium Cocoyl Glycinate （Eversoft™ YCK, 30%） 10.0
D: PEG-14M (5%) 2.0
Preservative 0.3
Fragrance 0.5

Procedure
1.Heat phase A and B ingredients to 85℃ separately.

2.Mix thoroughly, stir 30 min at 85℃.

2. Add phase C ingredients, stir to dissolve thoroughly.

3. Cool to 40℃ with stirring, add phase D ingredients.

5. Cool to room temperature under agitation.

Formulation Analysis & Guideline

This is a typical application for Glycinate to provide an excellent synergistic effect with
fatty acid soaps. The system delivers creamy and resilient foam and leaves a fresh feeling
on the skin after washing without feeling taut. It also reduces irritation to skin.

F4: Body Wash (ZS-SX-080019)

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Ingredient %W/W

Sodium Cocyl Glycinate ( Eversoft™ YCS-30S) 30.0

Lauric Acid 0.3
Myristic Acid 0.6
Deionized Water 36.8
Cocoyl Monoethanolamide 2.0
Glycol Distearate 1.5
Sodium Lauroyl Amphohydroxypropyl Sulfonate (30%) 15.0
Acrylates Copolymer (30%) 4.0
Deionized Water 8.0
PEG-14M (5%) 1.0
Preservative 0.3
Fragrance 0.5

Procedure
1. Mix and heat phase A ingredients to 85℃, mix for 30 min.

2. Add phase B ingredients at 85℃ stir to dissolve thoroughly.

3. Cool to form pearlescent, add phase C ingredients.

5. Cool to room temperature under agitation.

Formulation Analysis & Guideline

The sample is a pearlescent white viscous liquid with a pH of 6.5-7.0, and the viscosity
is about 2000~3000 mpa.s (25°C).
In this example, Sodium Cocoyl Glycinate works synergistically with Sodium Lauroyl
Amphohydroxypropyl Sulfonate and Acrylates Copolymer to get a stable system.
This formula delivers creamy and resilient foam and leaves a fresh feeling on the skin
after washing without feeling taut.

F5: From Head-to-Toe Baby Shampoo (ZS-HX-080025)

Ingredient % w/w
A Sodium Lauroyl Sarcosinate (Eversoft™ S-12，30% 20.00

Citric acid 0.25

Deionized Water 54.55

B PEG-150 Pentaerythrityl Tetrasterate 1.00

Sodium Lauroyl Amphohydroxy propyl Sulfonate,30% 20.00

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C PEG-20 Methyl Glucoside 2.00

Cis-1-(chloroallyl)-3,5,7-triaza-1-azoniaadamantanechloride 0.10

Fragrance 0.10

Procedure
1. Mix Phase A ingredients and heat to 85℃，stir to homogenous;
2. Add Phase B to Phase A under agitation, keep temperature at 85℃;
3. Cool to 45℃, add Phase C , stir to homogenous.

Formulation Analysis & Guideline

The above example is a clear, viscous liquid with a pH of 6.0～6.5 and a viscosity of
4000-6000 mPa.s. It is very mild and non-irritating. It has rich foam and imparts a silky
after-feel to baby’s skin.
The Structure of formulation 5 is chiefly based on synergistic effect of Sodium Lauroyl
Sarcosinate with Sodium Lauroyl Amphohydroxy propyl Sulfonate and PEG-150
Pentaerythrityl Tetrasterate to get the suitable viscosity for the system.
The viscosity can be adjusted with different use levels of PEG-150 Pentaerythrityl
Tetrasterate.
The pH of the system is controlled in a range of 6.0～6.5 in order to deliver super mildness.

F6: Facial Cleanser (ZS-SX-080086)

Ingredient/INCI Name %W/W

A Deionized Water a.q.

PEG 14M 0.05
B Sodium Cocoyl Glycinate （Eversoft™ YCS-30） 50.0
Laryl Hydrooxyethyl Imidazoline (30%) 10.0
Sodium Lauroyl Amphohydroxypropyl Sulfonate 6.67
C NaOH (10%) 2.5
D Glycol Distearate 2.0
Everthek™ MT 1819 4.0
E Preservative 0.2
Fragrance 0.2
F Acrylate Copolymer (30%) 5.0
Deionized Water 10.0

Procedure
1. Add PEG 14M into water in Phase A with stirring till mixed well.
2. Add Phase B ingredients slowly with stirring , heat to 75-80℃.
3. Add Phase C.
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4. Add Phase D ingredients with stirring, mix at 75-80℃ about 20 minutes, dissolve ingredients fully.
5. Cool to 45℃, add phase E ingredients.
6. Mix phase F advanced; add into the fifth system with agitation.

Formulation Analysis & Guideline

The above formulation sample is white pearl cream with pH about 8.0.
The viscosity of system can get 30-50 Pa.s by adding a special thickening agent Everthek™
MT 1819 with Acrylate Copolymer.

Conclusion
As “sulfate free” and super mild surfactants, amino acid-based surfactants can be used in
various cleansing systems and deliver a number of excellent attributes, such as creamy and
elastic foam, silky and invigorating skin after-feel, reducing irritancy and improving
sensory attributes as co-surfactant, environmentally friendly and so on. They are the best
alternative to lauryl ether sulfates and they are setting new standards for personal cleansing
in terms of sensory attributes as well as in the aspects of naturally derived and
environmentally friendliness. They are a natural choice for the “sulfate-free”and super
mild personal cleansing products.