AKYPO Optimizing Coacervate Formation

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

concentration), which represents the minimum and maximum surfactant concentration at

which coacervate formation occurs. Finally, in the rinsing step coacervate separates from the
Solubilization

Coacervation
WASHING

Micelle + + + +

RINSING

*cac

Coacervate Surfactant C-Polymer

Cationic polymer

cmc Shampoo Concentration

*cac

Figure 1. Mechanism of coacervate formation.

1

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 &

Toiletries. Vol 116, No. 11/November 2001.

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

Presence of electrolyte, pH, etc.

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)

Active Matter (%)

Trademark

Laureth-6 Carboxylic Acid

C12-14

4.5

Liquid

92

AKYPO RLM 45 CA

Sodium Laureth-6 Carboxylate

C12-14

4.5

Na

Paste

82

AKYPO RLM 45 N

Sodium Laureth-6 Carboxylate

C12-14

4.5

Na

Liquid

22

AKYPO SOFT 45 HP

Sodium Laureth-5 Carboxylate

C12

Na

Paste

60

AKYPO FOAM RL 40

Laureth-11 Carboxylic Acid

C12-14

10

Liquid

90

AKYPO RLM 100

Sodium Laureth-11 Carboxylate

4

C12-14

10

Na

Liquid

70

AKYPO SOFT 100 BVC

Polyquartenium-74: An Advanced Hair Conditioning Polymer. Eric Leroy. Rhodia Research, Aubervilliers, France. Cosmetics & Toiletries.
L L L L L

Vol. 123, No. 3/March 2008

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

Coacervation Benefits Excellent Combability AKYPO

shows a significant combing force

reduction. Figure 4 illustrates the combing force of two test compositions with 0.3% of polymer. The percentage reduction of

Transmittance (%)

90

combing force versus composition without AKYPO

a ) n on e b ) mai n su rfa c tant c ) c o- su rf act an t

80

for

polyquartenium-10

and

70

polyquartenium-7 are 21% and 17%.

1000
Wet Combability Force, gf
SLES-2EO/CAPB at 3:1 ratio

60

50 1 10 Dilution r atio 100 1000

800 600

765

AKYPO RLM 45CA/CAPB at 3:1 ratio

603 424
400 200 0 PQ-10 PQ-7

Figure 3. Coacervation profiles of PQ-10 with AKYPO

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

779 560 524

0.10% PQ-10

0.30% PQ-10

541 422

Figure 5. Combing Force profile at different % of PQ-10

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

Superior Polymer deposition

Avg. Tress Diameter (cm)

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

SLES-2EO/AKYPO RLM 45CA/CAPB + 0.3%PQ-10

Figure 8. Volume measurement of PQ-10 with AKYPO

24.7 18.5 16.7

E (CIE L*a*b*)

30

Sensorial Benefits Sensorial consumer with benefits a basic have been

20

demonstrated
10

shampoo

6.4

formulation and on a final shower cream formula (C-141).

0 without silicone 0,5% silicone

SLES/CAPB at 3:1 ratio, 0.3% PQ-10

Figure 6. Polymer deposition profile Hair Conditioning without Build-Up

SLES/AKYPO RLM 45CA/CAPB at 2:1:1 ratio, 0.3% PQ-10

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

Smoothness during rinse-off

Dry Feel

Detangling Wet Combability

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

Figure 7. Build-up of PQ-10 with AKYPO

Contact Kao Chemicals Europe

Market product Foam speed
5

AKYPO

For more information, complete literature, and product

Moisturising

samples, Europe

you

can

reach

a at

Kao the

Foam volume

4 3 2 1

Chemicals

representative

following numbers or visit our web site at

Dry Smoothness

Foam size

www.kaochemicals-eu.com:

Foam creaminess

Smoothness during rinse-off

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.

AKYPO range, a new approach to coacervation technology