Hair 101

Shampoo Introduction
Vicki Li
Sep 2014

AGENDA
Shampoo Composition
Ingredients & Function
AD Technology

What is a Shampoo ?
Getting to know more about technology in shampoo
Perfume

Shampoo

Emotive

Silicone

Aesthetic & emotive

ingredients:
Perfumes, dyes,
pearliser/opacifiers, viscosity
modifiers, emotives to support
product story.

Active ingredients:
Conditioning Polymers, silicones, AD
actives, other benefit agents,
System
suspending agents.

Polymer

SLES/
CAPB

Surfactant
System

Surfactant base:
Delivers the primary function of
shampoo - effective cleansing.

Shampoo Composition
Ingredients & Function
AD Technology

WHAT IS SURFACTANT?
A SURFACTANT or SURFACE ACTIVE AGENT is a molecule
which consists of a polar (hydrophilic) head group and a
non-polar (hydrophobic) tail.
non-polar tail

polar head group

Amphiphile:
A molecule that likes and hates water at the same time.

Surfactant types
- determined by nature of the polar head group
NONIONIC

-(-O-CH -CH2-)2
n

Good cleaning, poor foaming

NO CHARGE

ANIONIC

-O.SO
3

NEGATIVE CHARGE

Good foaming & cleaning, cheap

Used in shampoo

CATIONIC

+
-N(CH 3)
3

POSITIVE CHARGE

Inferior cleaning and foaming,

anti-static, used in conditioner

AMPHOTERIC

+
-N(CH )-CH -CO
32
2
2

BOTH POSITIVE &

NEGATIVE CHARGE

Effective cleaning & foaming,

mild, relatively expensive

Solution properties
Critical Micelle Concentration, cmc
air

monomer
water

micelle

The cmc is the concentration in water at which

surfactant monomers aggregate to form micelles.
This is known as the HYDROPHOBIC EFFECT.

SOLUTION PROPERTIES
Micelle shape and packing constraints
Disc

Sphere
Rod

3v
a=
r

2v
a=
r

a = area of molecule at micelle surface

a=

v
r

v = volume of surfactant molecule

r = micelle radius

SOLUTION PROPERTIES
Micelle shape and packing constraints
With surface/volume ratio now at a minimum, increases in
intermicellar forces through increases in surfactant concentration
can only be reduced by formation of larger aggregates.
This leads to the formation of liquid crystalline phases.
Hexagonal

Lamellar

Solution properties
Micellar aggregation and flow

Viscosity
rods
discs

hexagonal
phase

spheres

cmc

Concentration

lamellar
phase

Hydrophobic head

Hydrophilic head

How surfactant works?

Shampoo contains
between 6- 20%
surfactant
Surfactant molecules
are attracted to fatty
deposits...

removing
sebum and dirt
in surfactant
micelles

Key shampoo surfactants

Primary Surfactant -
CH3 CH2
CH2

- Na+

OCH2CH 2 OSO3

Sodium Lauryl Ether Sulphate - SLES 1EO

Secondary Surfactant -
CH3
CH2

CH3

+
CH2 CH2 N
2 CO2
CH
N
CO.NH CH2
CH3

Coco Amido Propyl Betaine - CAPB

Foam Characteristics
Foaming is a key consumer attribute.
Consumers judge lather based on:
volume (rate of foam generation)
creaminess / feel of lather

Creaminess is related to bubble size. Smaller bubbles

increase perception of creaminess as will volume as
lather will appear thicker and richer

Cationic polymer

Jaguar
Cheaper
Higher level of functionality
CAN NOT be used for formulating transparent shampoos to be
marketed in transparent packaging

Polyquaternium 10 10
Expensive
Volume benefit
Used to formulate opaque and transparent shampoos

What is silicone?
Dimethicone

Dimethiconol

Shampoo Active - Silicones

B
A
S
I
C
A
L
L
Y
P
O
L
Y
D
I
M
E
T
H
Y
L
S
I
L
O
X
A
N
E
S
:
-

Cationic

Polymers provide
good wet combing BUT
only small benefits on dry
hair.

3 C
3 C
3
C
H
H
H
3
3
C
H
S
i
O
S
i
O
S
i
C
H
3 C
3 C
3
C
H
H
H

Silicones

act as lubricants
delivering easy dry
combing & making hair feel
soft & smooth.

n
=
1
8
0
n
=
1
5
0
0
n
=
4
5
0
0

3
5
0
C
s
f
l
u
i
d
6
0
,
0
0
0
C
s
f
l
u
i
d
H
i
g
h
m
o
l
e
c
u
l
a
r
w
e
i
g
h
t
g
u
m

U
S
E
D
A
S
E
M
U
L
S
I
O
N
:
-M
e
c
h
a
n
i
c
a
l
(
p
s
>
0
.
5
u
m
)
-E
m
u
l
s
i
o
n
P
o
l
y
m
e
r
i
s
e
d
(
p
s
)

UL Deposition Technology
Jaguar + Sub-micron silicone emulsion + Carbomer
Jaguar (High mwt cationic polymer):

High mw cationic polymer - Jaguar is particularly efficacious

as a deposition aid from shampoo.

Sub-micron silicone emulsion:

Small droplet size is very important - smaller is generally

better in Jaguar containing shampoos

Carbomer (cross-linked polyacrylate):

There are many possible suspending agents but, unlike most

others, Carbopol does not attenuate silicone deposition.

Unilever Deposition Technology

1. Jaguar adsorbs onto shampoo

ingredients in the bottle
2. dilution at point of use
causes flocculation...
Lift-off

Flow

3. flocs deposit onto hair.

Loss

Spreading
Retention
(Hague & Rennie LPPS 92 6507).

Competitor Technology
Our competitors use an alternative mechanism- big blobs or direct
transfer deposition - which has a different set of rules...

forced wetting

Key factors thought to be

deformability, adhesion
(chemistry of oil and hair)
and cohesion (oil viscosity).
Less efficient than polymeraided deposition. Better
control of selectivity.

Determined by droplet
deformability (size and
viscosity) and by
hydrodynamics.

detergency

retention
Large droplets subject to high
removal forces. Retention
through rinse generally poor.

Attainment of equilibrium
contact angle occurs rapidly.
Removal of oil depends on
adhesion to hair and
cohesion within droplet.

Different Deposition Mechanism

Flocculation (Unilever)

Filtration (P&G)

SHAMPOO ATTRIBUTES - FRAGRANCE

THE ADDITION OF FRAGRANCE SOUNDS EASY BUT PROBLEMS
CAN OCCUR: Shampoo Base Odour
Discolouration

Off Odours Forming with Time

PROPER BRIEFING TO FRAGRANCE HOUSES AND STORAGE

TESTING IS IMPORTANT

SHAMPOO PRESERVATION
VITAL TO PREVENT THE GROWTH OF YEASTS, MOULDS AND BACTERIA WHICH
CAN SPOIL THE PRODUCT APPEARANCE AND POTENTIALLY HARM THE

CONSUMER
Product
Technology

Primary

% Active
in
Formula

Secondary

% Active in
Formula

Shampoo

CIT/MIT
DMDM H

0.0009
0.055

A. CIT/MIT
B. DMDM H

0.0009
0.11 - 0.22

Anti-Dandruff
Shampoos
(Zinc
Pyrithione
Formulations)

DMDM H

0.22

MIT

0.0095

Comments

Ideally incorporate EDTA at 0.05-0.1%.

Secondary B: If DMDM H is the sole preservative,
EDTA is strongly recommended.
Secondary A/B: Add MEP if mould activity is too low.

Methyl Paraben (MEP) may be added, at 0.2% 0.4%, if challenge test data against yeast and mould
indicates insufficient antifungal activity.
MIT is not currently approved in LATAM and Korea.
CIT/MIT and EDTA are incompatible with Zinc
Pyrithione and can not be used in these formulations.

Preservative Abbreviations
CIT/MIT Chloro-Methylisothiazolinone/Methylisothiazolinone
DMDM H Dimethylol Dimethyl Hydantoin

Other Ingredients
Pearlizing Agents examples; Ethylene glycol monostearate, ethylene
glycol distearate, polyethylene glycol distearates, Mica particles
These are present as platelets that reflect light & can also help suspend other
insoluble elements of the formulation.

Dyes: for colorful appearance

Sunscreens: preservation of product color
Emotives Ingredients: support claims

Example: Commercial shampoo

Lux Dry Shampoo
SLES-1 surfactants
CAPB

14.0%
1.6%

Surfactants

Silicone emulsion
Carbopol 980
Jaguar C13S
Jaguar C17

2%
0.4%
0.15%
0.05%

Active ingredient

EGDS
Emotives
Fragrance
Preservative (DMDM H/Kathon CG)
Citric acid/NaOH /PPG-9/salt

7%
0.11%
0.55%
0.16%
to spec.

Aesthetics / Emotives

Shampoo Composition
Ingredients & Function
AD Technology

AGENDA

ANTI-DANDRUFF ACTIVE

UNILEVER AD TECHNOLOGY

Scalp barrier

The top layers of the scalp are made of cells and lipids and acts as
a barrier to prevent external irritants from penetrating into the
scalp. The barrier also helps to keep water within the skin.

Scalp barrier damage

It also allows the waste products of the fungus, Malassezia to

penetrate into the scalp.

Anti Dandruff Active Introduction

Key Anti-dandruff Actives

How it works in the Shampoo

Current AD agents in market

ADActive

Efficacy

Users

Zinc
Pyrithione

High-Broad
specturm

UL, P&G

Octopirox

High

Loreal

Forml
Ease
High

Regulatory

Chem Structure

Max 1.5% in
China

Zn
S

Cl

High

O
O

Climbazole

High but not

for all
ethnicity

Colgate,
Wella

Ketoconazole

High

J&J

Selenium
sulphide

High

Salicylic Acid

High

Poor, Under
review by EU

P&G

Low

Poor

J&J,
colgate

low

SeS2

Top 3 commercialized anti-fungi actives

ZnPTO
Insoluble particulates
0.5um in Unilever, 2.5um in P&G
MIC of Malassezia Furfur: 4 ppm
P&G, Unilever
Climbazole
Water insoluble, soluble in surfactant
micelle
Crystalline powder (mp 94-99C)
MIC of Malassezia Furfur: 0.3 ppm
Colgate, Unilever
Octopirox
Slight soluble in water (0.05%)
Soluble in surfactant micelle
Crystalline powder (mp 133-136)
MIC of Malassezia Furfur: 16 ppm
Loreal, Kao

Zn
S

N
Cl
N

CH3
CH3

CH3
O

ZnPTO Shampoo

0.5% ZnPTO Shampoo Before Wash Vs. After Wash

(After 3 weeks cultivation)

Malassezia
Clone

ZnPTO shampoo in clinical test

ZnPTO deposition
5.3

5.0
4.0
3.0
2.0

1.0

1.0

Microorganism level

6.0

Microorganism reduction

3 times better

0.0
Unilever Clear

H&S

Week 0 Week 1 Week 2 Week 3 Week 4

Clear ZnPTO
H&S

Old clear vs. old HNS before 2007

AGENDA

ANTI-DANDRUFF ACTIVE
UNILEVER AD TECHNOLOGY

1.Technical Routes of Anti-dandruff

Less damage
Mild shampoo
Anti-Fungi
ZnPTO, Climbazole and Octopriox

Scalp moisturization
Glycerine
Sunflower seed oil

Patented Silicone Technology

2500

Deposition, ppm

More hydrophilic Silicone surface

Better deposition on Hair tip
( damaged parts )

2000
1500

Root
Tip

1000
500
0
Standard silicone

Small particle size silicone

For better surface coverage
and hair softness

Big particle size silicone

To provide smoothness with
good clean feel

Deposition
+Co deposition

Deposition

Patented silicone

Scalp nourishment

SSO and glycerin restores

integrity of scalp barrier
Damaged barrier

Repaired barrier

+
Nourishment

Reducing Malassezia on scalp

and scalp nourishment
allow scalp barrier to recover.
This helps scalp to retain
moisture/lipids and reduces
dandruff & itch.

NEW CLEAR--COSMO SUPERIORITY IN 2011

50

Confirmatory Test (BKK Sep09)

99%

TWHS Dryness

40

95%

30

99%

20

10

Active phase
0

H&S

CURREN
T
CLEAR

Day 0

Wk 1

Wk 2

CLEAR
DUALACTIVE

Wk 3

Dual Active Clear

Wk 4

Wk 5

Wk 6

N=69

H&S

Dual active technical and clinical superiority

NUTRIUM 10
60000

Restore Lipid level

PAN SS

H&S SS
50000

FATTY ACID
Increase NMF
Biosynthesis

CERAMIDES

Dry friction force[g.mm]

Bioconversion

Clinical hair switch smoothness measurement (n=30 per cell)

Clear DA
40000

Clear DA

30000
20000

P<0.001

P<0.001

10000
0

Upgrade proteins

Scalp nourishment claims

Superior Fibre Care/Clinical Benefits

Q&A
What are the main types of surfactants?
What are the key surfactants used in our
shampoo?
What are the anti-dandruff agent used in our
shampoo?

THANKS