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What is a COACERVATE? A coacervate is a thermodynamically stable aggregate of colloidal droplets held together by electrostatic attractive forces that measures few tens of microns. This aggregate is formed by a polymer-surfactant complex which polymer and the air-water interface become saturated with surfactant and normal
micelles first appear2,3. During the washing step the surfactant concentration falls below the critical level required for solubilisation (CMC), and insoluble polymer/surfactant
separates from the solution as it is diluted1. What is COACERVATION? Coacervation is a physicochemical mechanism that occurs while a composition based on a cationic polymer and surfactant base is diluted. Figure 1 illustrates this phenomenon. Cationic polymers are compatible with anionic surfactant systems, where they are soluble in the final product (i.e. shampoo) because the
Deposition
Surfactant Decrease Leads to Aggregation Surface Tension (mN/m)
complex, called coacervate, is formed. Figure 1 depicts the normal surface tension curve in presence of a cationic polymer that shows two breakpoints, *cac (critical aggregation
which coacervate formation occurs. Finally, in the rinsing step coacervate separates from the
Solubilization
Coacervation
WASHING
Micelle + + + +
RINSING
*cac
Cationic polymer
*cac
Synergistic effects of high molecular weight polyethylene oxide (PEO) and cationic cellulosic polymers on conditioning properties of hair and
skin care products. Wing Li, Susan L.P. Jordan, et.al. Cosmetics & Toiletries manufacture World wide. 31-35. 2004.
2
A Brief Review of Polymer/Surfactant Interaction. Robert Y. Lochhead and Lisa R. Huisinga. The Institute for Formulation Science, The
University of Southern Mississippi, Hattiesburg, Mississippi USA. Cosmetics & Toiletries. Vol. 119, No. 2/February 2004.
3
Formulating Conditioning Shampoos. Robert Y. Lochhead. The University of Southern Mississippi, Hattiesburg, MS, USA. Cosmetics &
bulk solution and deposits on the hair or the skin. Once deposited, cationic polymer
other inorganic as well organic cations. The carboxyl group enables Alkyl Ether Carboxylic acids to perform a double function as non-ionic and anionic surfactant. Figure 2 shows the water soluble ring complex formation and the complexation with a cationic polymer. Because of this structure, AKYPO enhances coacervate formation. Therefore, a higher level of polymer deposition or insoluble actives on hair and skin occurs.
provides soft feel, conditioning effect, easy to comb and pleasing in appearance. In addition, coacervate aids in the deposition of insoluble actives, such as silicone. Many factors can modify the nature of the coacervate: Polymer molecular weight & charge density distribution Chemical surfactant structure Type and ratio of surfactant used
The amount of polymer deposition can be controlled by selecting the appropriate grade of polymer or by changing the surfactant used in the system. Fine Deposition Control using AKYPO Alkyl Ether Carboxylates are represented by the following structure: R-O-(CH2CH2O)n-CH2COOM R is derived from fatty alcohols and is
Figure 2. Water soluble ring complex formation and complexation with a cationic polymer. How is Coacervate Formation Measured? The most common way to determine the coacervate formation is by transmittance
measurement with a UV spectrophotometer at 600nm4, for different dilution ratios of test composition. Figure 3 depicts the coacervation behaviour of different systems with
generally between C4H9 and C18H37. EO-degree is represented by n and can be between 2 and 20. M may be hydrogen or a cation such as sodium, ammonium, magnesium or calcium. AKYPO forms a water soluble ring complex with a cation which can be easily exchanged by
polyquartenium-10 (PQ-10).
Test composition at 12% total active matter, 0.3% polymer and pH 6.5:
a) SLES-2EO/CAPB at 3:1 ratio
Table I: Alkyl Ether Carboxylic acids and derivatives for Personal Care applications
INCI Name
Alkyl Chain
Appearance (20C)
Trademark
C12-14
4.5
Liquid
92
AKYPO RLM 45 CA
C12-14
4.5
Na
Paste
82
AKYPO RLM 45 N
C12-14
4.5
Na
Liquid
22
AKYPO SOFT 45 HP
C12
Na
Paste
60
AKYPO FOAM RL 40
C12-14
10
Liquid
90
C12-14
10
Na
Liquid
70
Polyquartenium-74: An Advanced Hair Conditioning Polymer. Eric Leroy. Rhodia Research, Aubervilliers, France. Cosmetics & Toiletries.
L L L L L
b) AKYPO RLM 45CA/CAPB at 3:1 ratio c) SLES-2EO/AKYPO RLM 45CA/CAPB at 2:1:1 ratio Abbreviations: SLES-2EO: Sodium Laureth Sulfate CAPB: Cocamidopropyl Betaine
100
reduction. Figure 4 illustrates the combing force of two test compositions with 0.3% of polymer. The percentage reduction of
Transmittance (%)
90
80
for
polyquartenium-10
and
70
60
800 600
765
603 424
400 200 0 PQ-10 PQ-7
353
Haze region is linked to the quantity of coacervates. Test compositions with AKYPO show higher haze region. Therefore, AKYPO enhances coacervate formation providing
Figure 4. Combing force profile Cost/Performance Balance AKYPO improves combing force independently of % polymer but achieving lower value at 0.3% polymer. Using AKYPO, polymer
better conditioning effect. The minimum of transmission for the test composition based on AKYPO as main
surfactant (figure 3) is obtained at low dilution ratio, which is a sign that more substantivity will be achieved. Therefore, better combability and conditioning effect is expected. On the
concentration can be reduced maintaining the performance and optimizing the cost, as it can be seen in Figure 5.
Wet Combability Force, gf
1000 800 600 400 200 0 SLES-2EO/CAPB SLES-2EO/AKYPO RLM 45CA/CAPB
0.05% PQ-10
other hand, test composition based on AKYPO as co-surfactant shows the minimum of
transmission at a high dilution ratio, which provides a soft feel and volume enhancement of the hair5.
723
0.10% PQ-10
0.30% PQ-10
541 422
5 Cationic cellulosic polymers with multifunctional and oustanding performance for personal care. Wing L i, Susan L .P. Jordan. Amenchol Corporation, Cosmetics & Toiletries manufacture World wide. 157 160. 2003.
L L L L L L L L L L L L L L L
7 6 5 4 3 2 1 0
AKYPO deposits significantly more polymer and, additionally, when silicone is added, better assistance deposition is obtained. Figure 6 illustrates polymer deposition which is
6.3 5.3
measured indirectly by detecting the amount of anionic Red 80 dye bounded by the cationic polymer deposition on wool. Higher E value means superior polymer
SLES-2EO/CAPB + 0.3%PQ-10
deposition.
40
SLES-2EO/CAPB + 0,3%PQ-10 SLES-2EO/AKYPO RLM 45CA/CAPB + 0,3%PQ-10
E (CIE L*a*b*)
30
20
demonstrated
10
shampoo
6.4
Foam performance
If too much polymer is deposited onto the hair surface, polymer build-up can occur after many shampoo treatments. It will cause the hair to be weighted down and appear limp, resulting in a loss of volume. Composition with AKYPO does not build-up after several applications; on the contrary it increases the volumizing ability, as seen in Figure 7 and 8.
40
SLES-2EO/CAPB + 0.3% PQ-10 SLES-2EO/AKYPO RLM 45CA/CAPB + 0.3% PQ-10
Wet Smoothness
4 3
Shine
Rinse-off
2 1
Loose hair
Dry Feel
Dry Combability
Scores: 1 = very bad; 5 = very good. Significant differences. Figure 9.Sensorial test profile of basic shampoo formula
E (CIE L*a*b*)
30
20
18.5 8.8
18.7
10
6.4
0 1 wash 3 washes
AKYPO
samples, Europe
you
can
reach
a at
Kao the
Foam volume
4 3 2 1
Chemicals
representative
Foam size
www.kaochemicals-eu.com:
Foam creaminess
Kao Corporation, S.A. Puig dels Tudons, 10 E-08210 Barber del Vall Tel: +34 93 7399-300 Fax: +34 93 7399-377 e-mail: sales@kao.es
Wet Smoothness
Rinse-off
Scores: 1 = very bad; 5 = very good. Significant differences. Figure 10. Sensorial test profile of a final shower cream (C-141). Formulations with AKYPO offer truly
Kao Chemicals GmbH Kupferstrasse 1 D-46446 Emmerich, Germany Tel: +49(0)2822 711-0 Fax: +49(0)2822 711-201 e-mail: sales@kaochemicals.de
noticeable consumer benefits. AKYPO in a basic shampoo formula provides excellent wet hair detangling & combing rinse-off. and In imparts addition
smoothness
during
AKYPO offers creamy foam and a rinses out well, with a soft skin feel in shower gel cream products with high oil content.
The capacity of AKYPO surfactants to promote coacervate formation allows optimizing polymers performance with the best cost/effectiveness ratio.