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APPLICATION

y S. Herrwerth, H. Leidreiter, H. H. Wenk, M. Farwick, I. Ulrich-Brehm and B. Grüning

Highly Concentrated Cocamidopropyl


Betaine – The Latest Developments
for Improved Sustainability
and Enhanced Skin Care
Today Cocamidopropyl Betaine (CAPB) is the most important Out of the large number of different surfactant types, the
secondary surfactant used in personal care and household pro- so called primary surfactants are consumed in the largest vol-
ducts. Even the most modern CAPB-types still contain more umes. These surfactants are highly effective in terms of cost
water than active matter. Water which needs to be heated in performance and foaming power and are therefore the foun-
the manufacturing process, which needs to be transported, and dation of most liquid soaps, shampoos, and shower gels. Typi-
needs to be stored in storage tanks. The high water content not cal examples of commercially important primary surfactants
only contributes to the cost of production and logistics, but is are the anionic alkyl sulfates and alkyl ether sulfates.
also not favorable with respect to sustainability. Continuous re- Due to the irritating potential of most primary surfac-
search in the field of betaines has lead to another break-through tants, they are almost exclusively formulated in combination
in CAPB quality with a product containing approximately 47 % with secondary surfactants in order to improve their skin
active matter and less than 43 % water. Thus, savings in energy compatibility and to optimize their overall performance.
consumption and shipping volume of more than 36 % can be Probably the most important class of secondary surfac-
achieved as compared to the common 30 % CAPB quality. The tants are the amidopropyl betaines, in particular, Cocamido-
typically desired surfactant properties, the positive effects on propyl Betaine (CAPB), which is derived from coconut fatty
foam and rheology could be maintained. Moreover, further im- acid [1]. Since its introduction into the market in the 1960s
provements in quality and even additional skin care effects such CAPB has eclipsed the success of other secondary surfac-
as enhanced skin moisturization could be achieved. tants. Due to its excellent toxicological profile, superior
mildness and many other beneficial performance attributes,
Key words: Cocamidopropyl betaine, secondary surfactant, sus- Cocamidopropyl Betaine has become an indispensable com-
tainability, personal care ponent in shower gels, shampoos and even oral care pro-
ducts. Furthermore a large number of household cleaners
Hoch konzentriertes Cocoamidopropylbetain – Neueste Ent- and mild dishwashing liquids, as well as industrial and tech-
wicklungen für gesteigerte Nachhaltigkeit und verbesserte nical cleaners benefit from its performance. In all of these
Hautpflege. Cocoamidopropylbetain (CAPB) ist das zur Zeit applications, CAPB absolutely complies with the legal obli-
wichtigste Sekundärtensid in Körperpflege- und Haushaltspro- gations regarding biodegradability and ecotoxicity.
dukten. Jedoch enthalten auch die modernsten CAPB-Typen The addition of CAPB to primary surfactants like sodium
noch immer mehr Wasser als Aktivsubstanz. Wasser, das im Her- laureth sulfate (SLES) reduces the irritation of skin and mu-
stellungsprozess erhitzt, transportiert und in Vorratsbehältern cous membranes and leads to a pleasant, smooth and soft
gelagert werden muss. Der hohe Wassergehalt erhöht aber nicht skin feel [2, 3, 4]. Additionally, these formulations are easier
nur die Produktions- und Logistikkosten, sondern ist außerdem to thicken and they develop a richer and denser foam. Coc-
im Sinne der Nachhaltigkeit nicht wünschenswert. Kontinuierli- amidopropyl Betaine is also known to work synergistically
che Forschung auf dem Gebiet der Betaine hat einen neuen with primary surfactants, resulting in superior cleansing
Durchbruch bezüglich der CAPB-Qualität ermöglicht und zu ei- performance [5] while improving the conditioning proper-
nem Produkt geführt, das circa 47 % Aktivsubstanz und weniger ties of hair shampoos [6, 7].
als 43 % Wasser enthält. Dadurch lassen sich Einsparungen im In summary, Cocamidopropyl Betaine is the first choice
Energieverbrauch und im Transportvolumen von mehr als 36 % for secondary surfactants, combining good cost-performance
verglichen mit der üblichen 30 %igen CAPB-Qualität erreichen. ratio with a favorable toxicological and eco-toxicological pro-
Die typischen erwünschten Eigenschaften eines Tensids, der po- file as well as outstanding application properties.
sitive Einfluss auf Schaum und Rheologie konnten beibehalten
werden. Darüber hinaus wurden weitere Verbesserungen der 2 Production methods
Produktqualität und sogar zusätzliche Effekte im Bereich der
Hautpflege erzielt, wie z. B. eine gesteigerte Hautfeuchtigkeit. Alkylamidopropyl Betaines are produced in a two-step pro-
cess: In the first step, fatty acids, triglycerides, or fatty acid
Stichwörter: Cocoamidopropylbetain, Sekundärtenside, Nach- methyl esters are reacted with dimethylaminopropyl amine
haltigkeit, Kosmetik (DMAPA) to yield the amidoamine intermediate (3). Al-
though a number of fatty acid compositions are used in
1 Introduction & background commercial products (e. g. C8/10, C8 – 18, C12 – 18, C12, ricino-
leic acid), we will focus on Cocamidopropyl Betaine here,
Surfactants are the indispensable basis of the majority of which is by far the most broadly used amidopropyl betaine.
personal care and household cleaners, detergents and Coconut oil or hardened coconut oil (coconut fat) is the fatty
cleansing products. Their consumption is continuously in- acid source used in most cases but palm kernel oil is a suit-
creasing worldwide. able option as well. Differences in application properties be-

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S. Herrwerth et al.: Highly concentrated cocamidopropyl betaine

tween coconut oil and coconut fat derived betaines are mar- are generally known as concentrated betaines (tradename:
ginal. However, products made from hardened coconut fat TEGO1 Betain F 50), are now the “golden standard” for
generally have better quality regarding color and odor. CAPB products. However, even concentrated betaines con-
tain more water than active matter. Water, which has to be
heated in the manufacturing process, transported, and
stored in tanks before use in the final formulation.
Increased energy cost and the impact of greenhouse gas
emissions on global climate have recently triggered efforts
to reduce the consumption of fossil fuels in production,
transport and use of raw materials. One method is the re-
The process is typically carried out at about 120 – 160 8C. If duction of non-functional ingredients (e. g. solvents) result-
fatty acids or methyl esters are used as the fatty acid source, ing in more concentrated products, thereby reducing energy
the liberated water or methanol is continuously distilled consumption in production and transportation.
from the reaction mixture. Typically, the glycerol formed The culmination of this development is a highly concen-
during the reaction remains in the product if coconut fat is trated betaine (tradename: TEGO1 Betain C 60) with a sol-
used. DMAPA can be added in slight excess to drive the re- ids content of approximately 56 % (corresponding to ap-
action towards complete conversion of the fatty acid source proximately 47 % active matter) and a water content as low
and is then removed from the reaction mixture by distilla- as 44 %.
tion. Residual DMAPA, color, and odor are the most impor- This breakthrough was made possible through a pa-
tant quality factors of the intermediate amidoamine, and tented technology which employs a proprietary catalyst sys-
modern processes have been optimized to these parameters. tem as a process aid, thereby avoiding the formation of a gel
In the second process step, amidoamine (3) is reacted during manufacture. Additionally, refinements of process
with chloroacetic acid and sodium hydroxide (or directly parameters and careful selection of raw materials have re-
with sodium monochloroacetate) in aqueous solution to pro- sulted in an unprecedented purity, and low odor and color
duce Cocamidopropyl Betaine (4). value.

3 Product properties

3.1 Cost effectiveness and sustainability

The most obvious advantage of using this new, highly con-


Sodium chloride is formed as a by-product during the reac-
centrated CAPB is the reduction of transportation costs and
tion and usually remains in the final product. Careful con-
required storage capacity. Compared to a standard betaine,
trol of process parameters (in particular, temperature and
the volume needed for an equivalent amount of active mat-
pH) is necessary to avoid side reactions resulting in hydroly-
ter can be decreased by approximately 36 %, translating into
sis of chloroacetic acid to glycolic acid. The delicate balance
less energy consumption for manufacture and transport. Ex-
of the ratio of amidoamine and monochloroacetate is opti-
penses for analysis of incoming goods, the number of orders
mized to achieve the maximum consumption of both reac-
and booking procedures and the number of deliveries can be
tants. Neither residual chloroacetic acid, nor significant lev-
reduced by an equal amount.
els of remaining amidoamine are acceptable in modern
Consequently the increased content of active matter en-
betaine products.
hances efficiency along the entire supply chain and is con-
While a high content of active matter is highly desirable
sistent with the industry’s commitment to sustainability
in terms of transport and logistics cost as well as formula-
and sustainable development.
tion flexibility, it is limited by the intrinsic tendency of
CAPB solutions to form non-flowable gel phases above ap-
proximately 35 % solids content. Standard Cocamidopropyl 3.2 Application properties
Betaines are characterized by an active matter content of ap-
proximately 30 %. Continual, gradual improvements have Due to its high content of active matter, the new, highly con-
pushed this limit to about 38 %, and these products, which centrated betaine offers great formulation flexibility. The
light color is particularly beneficial for clear personal cleans-
ing products. An additional advantage of the low content of
Coconut oil Coconut fat by-products is the low odor, which allows formulations with
decreased amounts of perfume, even at pH values above 7.
C8 5–9 5–9 While standard betaines require the addition of a preser-
C10 5–8 5–8 vative to ensure microbiological stability, concentrated
CAPBs are self-preserving due to the low water content,
C12 45 – 49 45 – 49
which allows greater flexibility during formula development
C14 15 – 20 15 – 20 and throughout the production of final products. The for-
C16 8 – 11 8 – 11 mulator is enabled to select independently the most suitable
stabilizing system for the final formulation.
C18 2–4 10 – 14 The technical properties of the highly concentrated
C18:1 6–9 0–2 CAPB relevant to the application characteristics are essen-
tially identical with the common 30 % market quality CAPB.
C18:2 1–3 0
The most important application properties are listed in Ta-
Table 1 Typical composition of coconut derived fatty acids ble 2.

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S. Herrwerth et al.: Highly concentrated cocamidopropyl betaine

Highly concentrated CAPB 30 % market quality


Active level approx. 47 % approx. 30 %
Preservative free necessary
Odor very low typical
Color nearly colorless light to yellow
Foam better flash foaming standard foam
Mildness slightly irritant moderately irritant
Impurities very low regular
Added value moisturizing properties none
(MapDG)

Table 2 Comparison of the new highly concentrated Cocamidopropyl Be-


taine with the 30 % market quality CAPB Figure 2 Viscosity/salt response curve of two CAPB-types in a 9 %
SLES/3 % CAPB formulation

Figure 1 Foaming dynamics of a formulation containing 3 % SLES, 1 %


CAPB and 0.2 % NaCl, adjusted to pH 6, measured with a Sita Foam Tester
Figure 3 Mitigating effect of CAPB with SLES as primary surfactant deter-
mined via RBC-tests
3.3 Foam
Improvement of foam quality is a crucial point for the appli- availability of the Red-Blood-Cell test, a reliable in-vitro
cation of secondary surfactants in general and especially of method for the determination of mucous membrane irrita-
Cocamidopropyl Betaine. tion, allows the determination of the mildness of surfactants
The foam properties are evaluated by the Sita method [8], and surfactant blends without animal testing. Using photo-
which is based on a stirring procedure. This method allows metry the lysis of erythrocytes (L) and the denaturation of
the monitoring of the kinetics of foam formation as well as hemoglobin (D) are measured. The ratio L/D is a commonly
foam quantity in a fast and reproducible manner. accepted measure of the dermatological compatibility. Low
The new highly concentrated Cocamidopropyl Betaine L/D ratios indicate a certain irritation potential, while high
provides good lather properties. The foam forms rapidly dur- L/D ratios are an indication of mildness [9].
ing application. As shown in Figure 1 the flash foam is The data (Figure 3) illustrate the well known mitigating
further enhanced relative to the standard 30 % market qual- effect of CAPB. An increasing content of CAPB in blends
ity. The generated foam is creamy, dense and stable. with SLES correlates with a reduction of the irritating poten-
tial. The curves show a maximum for the L/D ratio at about
80 % secondary surfactant, a synergistic effect, which is
3.4 Rheology
characteristic for CAPB. Herein the L/D value is higher than
The new highly concentrated Cocamidopropyl Betaine pro- for both surfactants alone. The results indicate that the new
vides robust thickening properties in surfactant solutions. highly concentrated Cocamidopropyl Betaine is even milder
Figure 2 shows the response of viscosity to the increasing than the 30 % standard quality. The new highly concentrated
sodium chloride level in a system containing 3 % CAPB Cocamidopropyl Betaine with a L/D-ratio of 17 is therefore
and 9 % SLES. In the graph, the levels of NaCl necessary to only slightly irritant. The 30 % market quality CAPB in com-
obtain a viscosity of 3000 mPas are indicated. The formula- parison has a L/D-ratio of 7 and is moderately irritant. The
tion with the highly concentrated CAPB requires 1.9 % NaCl ‘synergistic’ maximum is shifted towards “basically non irri-
instead of the 1.3 % NaCl when using a 30 % market quality tant”. Below a ratio of 70 % CAPB small differences are ob-
CAPB. The viscosity of the formulation with the highly con- served between the new and common CAPB qualities.
centrated Cocamidopropyl Betaine can be easily adjusted by
choosing the appropriate level of NaCl. 3.6 Additional benefit: Moisturizing effect

3.5 Mildness As a result of the new manufacturing process, the active


matter of the new highly concentrated Cocamidopropyl Be-
The mildness to skin and mucous membranes of Cocamido- taine includes approximately 6 % MapDG (applied INCI:
propyl Betaine is one of its most outstanding properties. The Methanoylamidopropyl Dimethyl Glycine), a component

306 Tenside Surf. Det. 45 (2008) 6


S. Herrwerth et al.: Highly concentrated cocamidopropyl betaine

which provides additional benefits with regard to skin With the new, highly concentrated CAPB a 46 % reduc-
moisturization. tion of moisture loss compared with the 30 % market quality
CAPB and even a 61 % reduction of moisture loss compared
with SLES can be achieved (Figure 5). All these distinctions
are proven to be significant and the results are quite im-
pressive for a rinse-off application.

This effect was proven by in-vivo corneometer measure- 4 Summary


ments of a body cleansing application containing the new,
highly concentrated CAPB and for a leave-on formulation Continuous research in the field of betaines has lead to an-
containing MapDG as an ingredient. other break-through in Cocamidopropyl Betaine quality re-
Short term skin moisturization efficacy from a leave-on sulting in a product containing more than 46 % active mat-
emulsion was assessed by corneometer measurements (Fig- ter and less than 44 % water. With such a highly concen-
ure 4). The corneometer readings were taken from 12 subjects, trated CAPB (tradename: TEGO1 Betain C 60) savings in
each before and two hours after application of a body lotion energy consumption, transportation costs, and shipping vo-
with 4 % active matter on the inner forearm. A strong moistur- lume of more than 36 % can thus be achieved in comparison
izing effect comparable to glycerol was observed. to common 30 % CAPB qualities. The higher concentration
In order to demonstrate the activity of the new, highly of the CAPB increases efficiency along the entire supply
concentrated CAPB, an additional test out of a rinse-off for- chain, including reduced fuel consumption by transporta-
mulation was conducted by an independent test institute tion.
[10]. Skin moisture was measured before and after applica- This extraordinary step has been achieved by a combina-
tion of various rinse-off formulations containing 12 % sur- tion of specifically selected raw materials and a patented
factant active matter and adjusted to pH 6: technology capable of preventing the formation of gel
phases.
a) sodium lauryl ether sulfate (SLES), In addition, a product with an excellent impurity profile,
b) standard 30 % market quality CAPB, lower odor and color values could be achieved. The typically
c) the new, highly concentrated CAPB. desired surfactant properties, the positive effects on foam
The corneometer readings were taken from 30 subjects. 11 and rheology could be maintained.
treatments were applied on the inner forearm within 5 days. Finally, the moisturizing component MapDG, which is
While SLES leaves the skin with highly reduced moist- formed as a result of the novel process, offers an additional
ure content, both CAPB types show an increased moisture caring effect which can be claimed on final products.
content relative to the SLES formulation.

Figure 4 Moisturizing Efficacy of MapDG determined by Corneometer


measurements for a leave-on skin care formulation. (* p < 0.05 t-test)

Figure 5 Corneometer measurements of the skin hydration after rinse-off


treatment. (* p < 0.05 t-test)

Tenside Surf. Det. 45 (2008) 6 307


S. Herrwerth et al.: Highly concentrated cocamidopropyl betaine APPARATUS INFORMATION

Consequently, the new highly concentrated CAPB sets a Dr. rer. nat. Holger I. Leidreiter, born 1960, studied Physical Chemistry at University
of Göttingen, Germany. Since finalization of his PhD thesis in 1978, he worked at
new standard for high quality betaines for personal and Evonik Goldschmidt in technical service and in the development of raw material
household care applications. compounds and evaluation of product profiles for personal care applications. Since
1994 he is member of the task group “Hair Care” within DGK, the German Society
of Scientific and Applied Cosmetics).
References
Dr. rer. nat. Hans Henning Wenk was born in 1973 in Munich. He studied chemistry
until 1997 and finished his Ph. D. thesis at the Ruhr-Universität Bochum in 2002. In
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2002 he joined R&D of Degussa's Food Ingredients unit in Freising. Since 2005 he
(1973).
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Dr. rer. nat. Mike Farwick graduated in Biology from University of Düsseldorf, Ger-
D. A. and Barratt, M. D.: Proc. 4th CESIO Int. Surfactant Congress Vol. 3 (1996)
many. He earned his Ph. D. degree in Molecular Biology. After this Mike joined Evo-
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4. Hodgson, J. E., Martin, C. G. and Nicholson, S. H.: Parf. Kosm. 73 (1992) 260. nik Industries, formerly known as Degussa AG. He has started in the field of fermen-
5. Chevalier, Y.: Langmuir 7 (1991) 848. tative amino acid production for the Business Unit “Feed Additives”. There he was
6. Grüning, B.: Proc. 3rd CESIO Int. Surfactant Congress, (1992) 221. responsible for functional genome analysis including DNA-Chips, proteomics and
bioinformatics. From there he moved to a position as R&D Manager for Active Ingre-
7. Leidreiter, H. I., Jenni, K. and Jorbandt, C.: SÖFW-Journal 120 (1994) 852.
dients in the business line Personal Care. Since 2006 Mike is the Head of the R&D
8. Sita Messtechnik GmbH, Dresden, Germany.
9. Pape, W. J. W. and Hoppe, U.: Drug Res. 40 (1990) 498. department “Active Ingredients”.
10. Skin Investigation and Technology Hamburg GmbH, Hamburg, Germany.
Dr. rer. nat. Isabella Ulrich-Brehm, born 1973, studied chemistry at the University of
Mainz, Germany and the Cornell University, USA. After concluding her studies in
Received: 14. 07. 2008 2002 she joined the former Degussa, now Evonik Industries, as R&D Manager and
addressed the synthesis and exploration of organomodified silicones. In March
Revised: 26. 08. 2008 2006 she started to be engaged in Release Coating Systems and since May 2008
she has been working as Technical Manager in the Personal Care Department of
y Correspondence to Evonik Industries.

Dr. rer. nat. Burghard Grüning studied Organic Chemistry at the TU Braunschweig.
Dr. Sascha Herrwerth
After an engagement at the TU Berlin he joined Th. Goldschmidt, nowadays a part
Evonik Goldschmidt GmbH
of Evonik Industries AG, in 1980. In his career he took positions in the research and
Essen, Germany
development areas of silicones, inorganic and organic interfacially active derivatives.
Phone: +49(0)2 01-1732374
Since 2006 Burghard Grüning is directing the department Applied Technology Per-
E-mail: sascha.herrwerth@evonik.com
sonal Care within the Evonik Business Unit Consumer Specialties. His work resulted
in numerous publications and patents predominantly in the fields of organo-modi-
fied silicones, emulsifiers, betaines, biotechnology, and cosmetic formulations.

The authors of this paper

Dr. rer. nat. Sascha Herrwerth was born in 1972 in Hamburg, Germany. He studied
chemistry at the Ruprecht-Karls-Universität Heidelberg, Germany and at the Univer-
sity of Bristol, UK. He obtained his Ph. D. in Heidelberg under the supervision of Prof.
Dr. Michael Grunze in 2002 for working on “Oligoether terminated self-assembled
monolayers on gold and silver”. In 2003 he joined Evonik Goldschmidt GmbH (for- You will find the article and additional material by enter-
merly Degussa Goldschmidt GmbH), Essen, Germany where he was leading syn-
thetic groups in the research and the development department. Since 2007 he is
ing the document number TS100387 on our website at
heading the Applied Technology Rinse-Off group in the Business Line “Personal www.tsdjournal.com
Care”.

308 ª Carl Hanser Publisher, Munich Tenside Surf. Det. 45 (2008) 6