Elementis Specialties

Pure in Cosmetics

April 26th , 2016

1
"Modificadores reolgicos - aliados
importantes para la mejora del
performance en Personal Care

April 26th , 2016

2
 Rheology
Is the study of how materials deform and flow

Why use rheological agents ?

Viscosity Ease of pouring
Suspension and emulsion stability
Leveling
Flow and ease of application
Aesthetics
Texture and skin feel
Processing and filling


Much more than THICKENING...

3
 Shear Stress
A= Area [m] F [N]

= Shear Stress = F/A [N/m] or [Pa]

Consider a fluid between 2 parallel plates
Consider an external force (1 Newton) acting laterally on an area (1 m2)

The pulling action is defined as shear stress.

4
 Shear Rate
v = Velocity [m/s]

.
= Shear Rate = v/d [1/s] d [m]

Consider the liquid to be composed of thin layers. As the top layer moves under the
shear stress it pulls the underlying layer with it. This action is transmitted through all
the layers.

The velocity gradient is defined as shear rate.
5
 Definition of Viscosity

Shear Stress ()
Viscosity () = . [Pas]
(Resistance to flow) Shear Rate ()

6
 Rheological Measurements
Rheograms / flow curves

Depict viscosity versus shear rate

Measuring devices
Rheometers
Viscometers (Brookfield)

7
Brookfield Viscometer Spindle /
Rotating Disk

Measures multi point

viscosity.
Shear rate varies from zero to
upper limit defined by
rotational speed & disk
diameter.

8
 Brookfield Measurement

Sample 1
Viscosity (Pa.s)

Sample 2

9
Shear Rate (1/s)
Rheometer

50 m gap

Cone / Plate Plate / Plate

10
Din Cylinder
 Flow Curve Measurement

Sample 1
Viscosity (Pas)

Sample 2

Shear Rate (1/s)

11
Viscosity Profiles

12
Thixotropy

13
 Thixotropic vs Pseudoplastic
Viscosity recovery after force
0,1 s-1 0,1 s-1 Quick Recovery
(Pseudoplastic)
Viscosity (Pa s)

Slow Recovery
(Thixotropic)

1000 s-1

Time (s)
14
Thixotropy: Properties

15
Oscillation

Rotation

Viscosity vs Shear Rate

Viscosity profile 16
Oscillation

Rotation Oscillation

17
Viscoelasticity
 Viscoelasticity
Ideal vs Real Materials

ideal-viscous Ideal-elastic
Mineral Oil Steel
- Deform irreversibly - Deform elastically
- They do not go back, - They spring back
they flow and exhibit unchanged
viscosity

18
 Viscoelasticity
Ideal vs Real Materials

Viscoelastic
Gum
Real materials show a
viscous (G) and an
elastic (G) component that
can be measured with
oscillation function of
G rheometer G

Visco-elastic continuum 19
 Practical Meaning
The determination and the value/relation of G and G allow
a characterisation of a cosmetic formula:

if G > G (more elastic, reversible flow) :

a good storage stability can be expected

if G > G (more viscous, irreversible flow):

a good levelling, spreadability and flow can be expected

20
 Viscoelasticity / Stability
Salad dressing Olive oil Salad dressing Olive oil

direct after 5 minutes

Stable unstable
G > G G < G
21
 Measuring G and G
2
10

Pa
Stable G and G very close and G dominates
0
10
Gives insights
10
-1 into the structure
-2
of cosmetic
G'
10 formulations
-3
10 The large disparity between G & G,
with a low G, indicates poor structure
G''
10
-4
Data is useful to
-5 optimize a
10
formulation
-6
10

-7
Unstable much lower G
10

-8
10
0.1 1 10 1/s 100
Angular Frequency

G' Salad dressing G' Olive oil G'' Salad dressing G'' Olive oil
Factors effecting settling
velocity
Particle Suspending Medium
count density
size charge
shape yield point
density viscosity
charge

23
Yield Point

24
 Exceed yield point . . .

Product begins
to flow
Yield Point =
Minimum Shear Stress needed to induce flow 25
 Yield Point

Minimum Shear Stress needed to induce flow

Yield Point
Viscosity Pas
Pa

Honey 0 11.0

Ketchup 14 0.1

Mayonnaise 85 0.6

26
 Summary

Viscosity ( or ) Aesthetics
Emulsion stability

Viscosity profile
(Thixotropy) Suspension

Easy application
Viscoelasiticity
Flow

Yield point Levelling

FORMULATION PROPERTIES
27
 Summary

Viscosity ( or ) Aesthetics
Emulsion stability

Viscosity profile
(Thixotropy) Suspension

Easy application
Viscoelasiticity
Flow

Yield point Levelling

FORMULATION PROPERTIES
28
 Summary

Viscosity ( or ) Aesthetics
Emulsion stability

Viscosity profile
(Thixotropy) Suspension

Easy application
Viscoelasiticity
Flow

Yield point Levelling

FORMULATION PROPERTIES
29
 Summary

Viscosity ( or ) Aesthetics
Emulsion stability

Viscosity profile
(Thixotropy) Suspension

Easy application
Viscoelasiticity
Flow

Yield point Levelling

FORMULATION PROPERTIES
30
 Summary

Viscosity ( or ) Aesthetics
Emulsion stability

Viscosity profile
(Thixotropy) Suspension

Easy application
Viscoelasiticity
Flow

Yield point Levelling

BENTONE / BENTONE GEL FORMULATION PROPERTIES

RHEOLUXE / THIXCIN R 31
 RHEOLOGY MODIFIERS ELEMENTIS
SPECIALTIES

Rheological agents for HPC systems

aqueous anhydrous

RHEOLUXE
BENTONE BENTONE GEL THIXCIN R
Associative
Hydrophilic clays Organophilic clays
thickeners

32
 BENTONE / BENTONE GEL
Rheology modifiers derived from hectorite
Aqueous system = BENTONE EW, BENTONE MA
Anhydrous systems = BENTONE GEL - ready to use mastergels
BENTONE GEL VS-5 PC V HV in Cyclopentasiloxane
BENTONE GEL TN V in C12-C15 Alkyl Benzoate
BENTONE GEL ISD V in Isododecane

Thixotropic Flow
Shear thinning for easy application

Enhanced Emulsion Stability

Thermal Stability

Better suspension capacity

Electrolyte tolerance gel-structure

Silky skin feel Equilibrium between Van der Waals attraction and
electrostatic repulsion
33

33
 BENTONE Rheology of Hectorite Clays
1000

100
Viscosity [Pas]

10

0.1

0.01
0.001 0.01 0.1 1 10 100 1000 10000 100000
Shear Rate [s-1]
34
 THIXCIN R

Rheology for anhydrous phase

High thixotropic value

Increased Yield Point in emulsions

Flow control

Acts as a binder for pressed powders

Water-repellency in Lipsticks

Ecocert approved

Positive wax effect

Formulation becomes thick/stiff, but applies smoothly

35
 RHEOLUXE
associative thickeners derived from polyurethane or polyether polyol

tolerates pH 2 to 11 and eletrolytes outstanding sensory profile

No tackiness
easy to use added at most convenient stage
Easy application

RHEOLUXE 812 RHEOLUXE 880 RHEOLUXE 8015 RHEOLUXE 811

- High viscosity - Moderate to high - Moderate viscosity - Effective viscosity to
- Thixotropic flow viscosity - Newtonian flow sulfate-free systems
- cationic, non-ionic and anionic - Thixotropic flow - Rich after-feel - Richier, creamier foam
emulsions - Transfer resistance film - Improved transparency
- Allows reduction of fatty
alcohols/waxes improving
sensorial profile

36
RHEOLOGY CONTRIBUTING TO STABILITY

37
 Mascara - Temperature Stability

Mascara Mascara
no Organoclay + BENTONE GEL PTIS V

After a few days at room temperature the sample with no organoclay showed dramatic
phase separation, whereas the sample with BENTONE GEL PTIS V remained stable
38
 Mascara - Temperature Rotation

1,000,000
Mascara
+ BENTONE GEL PTIS V
Viscosity cps

100,000

10, 000

Mascara with no Organoclay

1
0 10 20 30 40 50 60 70 80
Temperature C

The sample with BENTONE GEL PTIS V gave a constant viscosity throughout
the temperature range 10 - 80 C
39
 W/O Inorganic Sunscream - Stability

After 1 month at 40oC

Phase separation without
BENTONE GEL
Stable formulation by adding
organoclay
(BENTONE GEL IHD V, OP V, or TN V)

Organoclay improves stability of sunscreen emulsions

40
 W/O Inorganic Sunscream - Oscillation (10-80C)

Temperature Curve - Oscillation

300
Pa
280

260

240

220

200

180
G
160

140
G
120

100

80

60

40

20

0
10 15 20 25 30 35 40 45 50 55 60 65 70 75 C 80
Temperature
W/O Suncream no BENTONE GEL W/O Suncream BENTONE GEL OP V
W/O Suncream BENTONE GEL IHD V W/O Suncream BENTONE GEL TN V

G > G constantly over the temperature range with use of BENTONE GEL products, indicating sun creams
stronger elastic behaviour than viscous behaviour, and good stability
Organoclay improves internal structure and formulation thermostability
41
 W/O Inorganic Sunscream Frequency sweep

Frequency Sweep
1,200
Pa
1,100

1,000

900

800

700
G
600
G
500

400

300

200

100

0
0.1 1 10 1/s 100
Angular Frequency w
O/W Suncream no BENTONE GEL O/W Suncream BENTONE GEL OP V
O/W Suncream BENTONE GEL IHD V O/W Suncream BENTONE GEL TN V

Formulations with BENTONE GEL show higher G, as well as G and G difference, indicating system is
relatively undisturbed under gravity, shipping/handling, thus better suspending capability
Rheological data indicate good suspending offered by organoclay
42
RHEOLOGY CONTRIBUTING TO ENHANCED
PERFORMANCE

43
 Cream layer right after application

Cream layer
Skin Surface

44
 Cream layer after Sagging or Slumping

Reduced Protection
on Hill Tops

Cream layer
Skin Surface

Excessive Protection
in Valleys 45
UV
Cream layer containing
BENTONE GEL

Skin Surface

BENTONE GEL provides more uniform layer on the skin surface

for an even spread and protection
46
 Enhanced SPF values
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
Organic W/O Inorganic O/W Inorganic W/O Inorganic Organic Organic
Suncream Suncream Suncream Sunscream Sunscreen Suncream Suncream
BENTONE BENTONE BENTONE BENTONE BENTONE BENTONE BENTONE
GEL EUG V GEL TN V GEL IHD V GEL IPM V GEL TN V GEL TN V GEL HSO V

In-Vitro SPF
Formula with 38.9 23.3 15.5 44.7 13.2 30.4 14.2
organoclay
(BENTONE
GEL)

In-Vitro SPF
Formula 32.5 17.9 9.4 41.9 12.2 26.6 12.8
without
organoclay

- BENTONE GEL enhances sunscreen SPF values (In-Vitro)

- Increase of SPF value may vary with formulation

47
 Enhanced coverage

Foundation Foundation with

no Organoclay BENTONE GEL PTIS V

BENTONE GEL PTIS V improved the coverage due to better

particle dispersion and more uniform layer on the skin

48
Anti-perspirant - suspension

No additive BENTONE GEL VS-5PC V

49
RHEOLOGY CONTRIBUTING TO AFTER-FEEL,
SENSORY PERCEPTION

50
 By adjusting the rheology of a system, working with its
texture, the sensorial experience can change

 Perception of key attributes is related to systems flow, for

example:
Moisturization

Skin protection

Anti-aging effect

51
 Understanding impact in sensory
perception
Protocol: Basic formula was prepared using 04 types of rheology modifiers

A Deionized Water Water 75.50

Glycerin Glycerin 3.00
B Blandol Mineral Oil 5.00
Liponate GC (Lipo) Caprylic/Capric Triglyceride 5.00
KR-96L-CS Dimethicone 3.00
Cremophor A 20 (BASF) Ceteareth-20 3.00
Tego Alkanol 16 (Evonik) Cetyl Alcohol 2.00
Tego Alkanol 1618 (Evonik) Cetearyl Alcohol 2.00
Stearic Acid Stearic Acid 0.50
Spectrastat (Inolex) Caprylhydroxamic Acid (and) Caprylyl Glycol (and) 1.00
Glycerin
C Citric Acid, 25% aq.sol Citric Acid qs
Rheology modifier Rheology Modifier* qs
*Rheology Modifier
Formula A 1% Bentone EW (Hectorite)
Formula B 1% Rheoluxe 812 (Bis-Lauryl Cocaminopropylamine/HDI/PEG-100 Copolymer (and) Butylene Glycol)
Formula C 1% Rheoluxe 8015 (PEG/PPG-450/50 Trimethylolpropane Dodecyl Ether)
Formula D 1% Thixcin R (Trihydroxystearin)

52
 Understanding impact in sensory perception

Viscosities:

Control 10,400 cps NO rheology additive

Formula A 41,600 cps 1% Bentone EW (Hectorite)

Formula B 84,000 cps 1% Rheoluxe 812 (Bis-Lauryl Cocaminopropylamine/HDI/PEG-100 Copolymer

(and) Butylene Glycol)

Formula C 32,800 cps 1% Rheoluxe 8015 (PEG/PPG-450/50 Trimethylolpropane Dodecyl Ether)

Formula D 30,400 cps 1% Thixcin R (Trihydroxystearin)

53
 Understanding impact in sensory perception

Linear Flowcurve
800000
cP
700000
650000
600000
550000
500000
450000
400000
350000
300000
250000
200000
150000
100000
50000
0
0.1 1 10 100 1/s 1000
Shear Rate

Daily Skin Hydrator + 1% BENTONE EW Daily Skin Hydrator + 1% RHEOLUXE 8015

Daily Skin Hydrator + 1% RHEOLUXE 812 Daily Skin Hydrator + 1% THIXCIN R

54
 Understanding impact in sensory perception

Protocol: 21 panelists evaluating the products before applying

cream to the skin, during application and upon drying.

- Initial Perception based on appearance (before applying it

to the skin)
- During application how does it affect your skin?
- Final perception based on entire experience

55
 Understanding impact in sensory perception

Initial perception - appearance

Most Moisturising
18
16
14
12

Richest 10 Most Oily

8 A= 1% BENTONE EW
6 B= 1% RHEOLUXE 812
4
2
C=1% RHEOLUXE 8015
0 D=1% THIXCIN R

Lightest Most Dry

Most Soothing

56
 Understanding impact in sensory perception

During application During application During application

- More Moisture - - Lighter after-feel - - Richer after-feel -

8%
17% 14%
22%

24% 10%
44%
13%

9%

67%

48% 24%

57
 Understanding impact in sensory perception

Final Perception Final Perception Final Perception

- Better for sensitive skin - - Prevent wrinckles - - Better for dry skin -

17% 14%
18%
22%

41%
45%
13%
27%

29%

48% 12% 14%

58
 Understanding influence of rheological
characteristics in sensory perception, stability
and performance is important to develop
successful products.

59
 SUMMARY

Rheological agents for HPC systems

aqueous anhydrous

BENTONE RHEOLUXE BENTONE GEL THIXCINR

hydrophilic clays Associative thickeners Organophilic clays

Tixotropic flow Tolerates extreme pH and Uniform coverage

eletrolytes Consistency with improved
Suspension Thermo-stability pay-off
Thermo-stability Versatility Improved dispersion of
Shear thinning or Newtonian particles

60
ELEMENTIS SPECIALTIES
Rheology leadership plus so much more
ELEMENTIS SPECIALTIES

Specialty Products supplies high technology additives and

technical service for high performance, high growth markets

Rheology and other functional additives for Coatings

Oilfield rheology for drilling

Personal Care rheology and other functional additives

62
Global Footprint

Headquarters Plants Research Technical Service

63
Consumer BU
Rheology modifiers:
BENTONE Clays for aqueous systems
BENTONE GEL Mastergels for anhydrous systems SPECIALTIES

THIXCIN Hydrogenated Castor Oil

NANOX Nanosized ZnO
RHEOLUXE Associative thickeners

 Vegetable Oils and derivatives

FANCOR ABYSSINIAN OIL
FANCOR MEADOWFOAM SEED OIL
FANCORSIL LIM
MEADOWQUAT
MEADOWESTOLIDE
BETAFAN-M

64
TRIALS IN LABORATORY

65
ACONDICIONADOR CAPILAR POST
TRATAMIENTO

66
CREMA FACIAL ANTIAGE

67
TRATAMIENTO CAPILAR NUTRITIVO

68
HAIR MIST

69
SHAMPOO SULFATE-FREE HIDRATANTE

70