Formulating High

Performance, SulfateFree Cleansing

Products
Dr. Tony Gough

Content
Origins of sulfate free and current market status
Chemistry options to formulate away from sulfates
Iselux as the solution
Formulating high performing sulfate free systems
Summary

Origins of Sulfate-Free and Current

Market Status

Why go sulfate-free?
Concerns over alkyl sulfates and alkyl ether sulfates in
personal cleansers started >10 years ago as a small fringe and
an internet blog.
Over the past c. 7 years consumer concern over the use of alkyl
sulfates and alkyl ether sulfates has grown significantly.

The debate for replacing sulfates in personal care products

continues to gain momentum globally.

Market leaders are bringing an ever increasing number of

sulfate-free formulas to the mass and professional markets.

But, economics will never be the driver for elimination of sulfates

in personal cleansers.

Alkyl Sulfates and Alkyl Ether Sulfates

R

O
S - +
O M
O

Alkyl Sulfate

O
S - +
nO O M

Alkyl Ether Sulfate

Advantages

Disadvantages

Excellent foaming properties in soft and hard

water

Skin and eye irritants

- require irritation mollifying agents

Relatively inexpensive

Strip the skin and hair

- require conditioning agents

Excellent detergency

Lauryl Ether Sulfates contain EO moieties - 1,4

dioxane

Rinse easily

They are sulfates and these have a negative

connotation for a growing number of
consumers.

Easy to use
- Good water solubility
- Can be thickened effectively with salt
5

Sulfate-Free Launches - Shampoo and Skin Cleansers

1,600

Middle East & Africa

Latin America

1,400

North America

Number

1,200

Europe
Asia Pacific

1,000
800
600
400
200
0
2003

2004

2005

2006

2007

2008

2009

Year

2010

2011

2012

2013

2014

2015

Sulfate-Free Personal Cleansers Market

Continuing growing trend

Sulfate-Free and Innospec

Innospec identified this emerging trend in 2007

We have dedicated the majority of our R&D expansion since then to support
our customers in sulfate-free formulating
A significant percentage of our applications / formulation effort is in the
segment
We have expanded our claim support competency to support sulfate free
product claims

A significant percentage of our new product introductions are in sulfate free

surfactants

Innospec is now recognised by many of our key customers as the go

to supplier partner in this segment

Options and challenges to formulating

away from sulfates

Sulfate Vs Sulfate Free Shampoos

higher cost with lower performance

Commercial
Sulfate
Shampoos

10

Typical non-Iselux
Commercial Sulfate-Free
Shampoos

Technical Challenges and Options

Sulfate-free typical considerations: Cost sulfate-free surfactants and thus formulations of them are
invariably more expensive versus Sulfate ones.
Solids/actives levels can be much higher in sulfate-free surfactant
systems since higher levels are needed for foam volume, etc.
Thickening Sulfate-free surfactants can be difficult to thicken with salt
need rheology modifiers.
Performance Often the need for acceptance of deficiencies versus
Sulfates. Formulators often compromise on performance to achieve
sulfate-free systems.

Current approaches: Replace with other anionics

levels of inorganic sulfate.

Possible irritancy issues and/or high

Increase the levels of secondary surfactants and use mixtures of different

types
can add complexity to the formulation and manufacture.
11

EO Origin

Inorganic
Sulfate

Hydrophobe
Origin

Foam

Optimum pH

Irritantancy

Ease of
Formulation

Thickening

SO3

Anionic

Trace/Low

Nat

Excellent

5.5-8.5

Moderate

Dif

External

Yes

SO3

Anionic

Trace/Low

Nat

Excellent

5.-9

Moderate

Easy

Betaine/Salt

Alkyl Benzene Sulfonates

No

SO3

Anionic

Syn

Excellent

3-11

Harsh

Easy

External

Alkyl Ether Carboxylates

Pureact Carboxylates

Yes

COO

Anionic

Nat

Moderate

>5.5

Mild

Easy

External

Acyl Glycinates
Pureact SLG

Yes

COO

Anionic

Nat

Excellent

>7

Mild

Easy

External

Alkylamphoacetates
Pureact LAA

Yes

COO

Amphoteric

Nat

Moderate

>5

Moderate

Easy

External

Alpha Olefin Suflonates

No

SO3

Anionic

Syn

Excellent

3-11

Harsh

Easy

Betaine/Salt

APG's
Pureact Gluco

Yes

NA

Nonionic

Nat

Low

4.5-8.5

Mild

Easy

External

Betaines
Fatty Acid Soaps

No
No

COO
COO

Amphoteric
Anionic

N
N

N
N

Nat
Nat

Moderate
Moderate

>5
>6

Moderate
Harsh

Easy
Easy

External
External

Yes

COO

Anionic

Nat

Moderate

>6.0

Moderate

Easy

External

Yes

SO3

Anionic

Trace/Low

Nat

Moderate

3-11

Moderate

Mod

External

No
Pending
No

SO3
SO3
SO3

Anionic
Anionic
Amphoteric

N
TBD
N

Y
Y
Trace/Low

Nat
Nat
Nat

Moderate
Moderate
Moderate

3-11
5.5-8.5
3-11

Moderate
Mild
Moderate

Dif
Easy
Easy

Betaine/Salt
External
External

Acyl Isethionates
Pureact SCI
Acyl Methyl Isethionates
Iselux

Sarcosinates
Pureact LSR
Sodium Methyl Acyl
Taurates
Pureact WS
Sulfoacetates
Sulfosuccinates
Sultaines

12

Polar

Head

Yes

PRODUCT

Innospec
supplies

Class

Sulfate-Free Surfactant options for formulators

Sulfate Free what if you want it all?

Primary, Highly Foaming, Mild, EO-Free, Naturally Derived and
Thickens With Salt

13

Type

Innospec Trade Name

Alkyl ether carboxylates

Pureact TA; WLL

Alpha olefin sulfonates

Alkyl benzene sulfonates

Primary

Secondary

Fits all Criteria?

Sulfosuccinates

Pureact MD-318

Alkylamphoacetates

Pureact LAA

Betaines

Sultaines

Acyl isethionates

Pureact I Series; SLI

Acyl methyl isethionates

Iselux

Acyl methyl taurates

Pureact WS Conc, MS

Acyl sarcosinates

Pureact SLR

Acyl glycinates

Pureact SCG

APGs

Pureact Gluco range

Alcohol ethoxylates

Sulfoacetates

Fatty acid soaps

Innospecs Iselux Solutions to

Convenient Sulfate-free Formulating

14

Sulfate-Free Surfactant Solutions From Innospec

Iselux
Sodium Lauroyl Methyl Isethionate

15

Key choice as primary surfactant for sulfate-free formulas

unique technology to Innospec.
Dense creamy foam and elegant foam feel.
Salt thickens with betaine and other amphoterics.
Makes clear or opaque formulations.
Mild on the skin.
Cost effective lower active formulations possible.
Can be used for sulfate-free hair shampoo bars.

Iselux
Applications as primary or secondary surfactant

Body wash or shower gels

Hair shampoos
Facial cleansers
Body scrubs
Liquid hand soaps
Shaving preparations
Wipes and towelettes
Baby baths
Beauty bars
Shampoo bars
16

Iselux Features and Benefits

Feature
Structured systems achievable

Dramatic formulation flexibility

enhanced creativity

Dense creamy lather

Elegant after-feel

Creates a luxurious bath / shower

experience

Ultra mild surfactant

Ideal for sensitive skin

Excellent water solubility

Can be used in clear systems

Sulfate-free
1,4-Dioxane-free
Nitrosamine-free
EO / PEG-free

17

Benefit

Safe at all use levels

Readily biodegradable
Derived from renewable resources

Friendly to the environment

Formulates like an ether sulfate

Broad pH stability

Formulating flexibility

Background Why move from SCI to Iselux?

SLMI
Iselux

SCI

Replacing a hydrogen with a methyl group has the effect of:

- Dramatically increasing the solubility in water.
- Markedly increasing the hydrolytic stability.
- Increasing the performance - foam quality, etc.
Iselux is available in flake or liquid form:
10% solutions
in water

Iselux Flake
(80-85% Active)

Iselux Liquid
(32-34% Active (in water))

Iselux has the same foam height as SLES but has a denser,
creamier foam and is a considerably milder surfactant .
18

Regional Annual Introductions featuring Iselux

140

120

Number

100

Middle East & Africa

80

Latin America
Asia Pacific

60

North America
Europe

40

20

0
2009

2010

2011

2012

Year
19

2013

2014

2015

Recent launches
featuring Iselux

20

Innospec Formulating Approach

Primary Surfactants: Isethionates

Iselux
Sodium Acyl Isethionates

Secondary/Co-Surfactants

Cocamidopropyl Betaine
Sodium Lauroamphoacetate
Sodium Lauroyl Sarcosinate
Sodium Methyl Acyl Taurates (Coco and Oleic Acid)
Glycinates
Akyl Glucosides

Thickening
Electrolytes
PEG Esters
Natural/Synthetic Polymers

Conditioning

21

Cationic Guars
Cationic Cellulosics (PQ-10)
Synthetic Polymers
Silicones/Silicone Derivatives

Considerations When Formulating with Iselux: pH

Popular Sulfate-Free Anionic Surfactants

pH Stability Range
5.0 9.0

Sodium Lauroyl Methyl Isethionate (Iselux )

6.0 8.0
Sodium Cocoyl Isethionate (Pureact I-series)

6.0 8.0
Sodium Lauryl Sulfoacetate

6.0 8.0
Sodium Laureth Sulfosuccinate

Due to its greater hydrolytic stability, Iselux can be

formulated stably at pHs at which common organic acid
preservatives are effective (pH 5.0 5.8).
22

Considerations When Formulating with Iselux: Choice of Co-surfactants

Viscosity building options:
Electrolyte (eg, NaCl): Include Cocamidopropyl Betaine. Addition of tertiary
surfactants such as Taurates and APGs, etc can further enhance the viscosity
profile.
Rheology modifiers: Used when fragrance, pH or lack of suitable co-surfactants
means that the system cant be thickened with electrolyte. Iselux systems are
compatible with all of the common polymeric thickeners.
Foam characteristics: Can be diverse, and modified as desired, depends on the
types of secondary/tertiary co-surfactants used.
Need to balance versus desired viscosity.
Fragrance: Iselux systems can be sensitive to fragrance
reduction in viscosity
and/or clarity when attempting to thicken with electrolyte. Three options here:
i) Reformulate the system with alternative co-surfactants or ratios.
ii) Work with your fragrance supplier.
iii) Use polymeric thickeners.
Preservatives:
No issues with preservatives effective in the range pH 6.0 7.0
Careful formulating needed for pH 5.0 6.0
23

Electrolyte Thickening of Iselux/CAPB Systems

A binary system using Iselux + betaine increased formulation viscosity
Topped fatty acids provide increased viscosities at lower concentrations vs. oil based betaines

Viscosity @ 25C

10% Active Iselux + Cocamidopropyl Betaine

6% Active Betaine (oil based made from triglyceride oil)

4% Active Betaine (topped fatty acid reduced C8 and C10 fatty acid)

4% Active Betaine (oil based)

2% Active Betaine (topped fatty acid)
2% Active Betaine (oil based)
0% Betaine

(pH 6.0)

24

% NaCl

Electrolyte Thickening of Iselux/CAPB/Tertiary Surfactant Systems

6% Active Iselux, 2.5% Active CAPB (Topped), 3% Active Co-Surfactant

18000

Viscosity / cps @25C

16000

Sodium Methyl Oleyl Taurate (Pureact MS-CG)

14000
Disodium Oleamido MIPA
Sulfosuccinate
(Pureact MD-318)

12000
10000
8000
6000
4000

No co-surfactant
(Control)

Sodium Methyl Cocoyl Taurate

(Pureact WS Conc)

2000
0
0

0.5

1.5

2.5

3.5

% NaCl
Brookfield RVT @ 20rpm, 25C, #5 spindle pH 5.8

25

Sodium Lauroyl Sarcosinate

(Pureact LSR)

Electrolyte Thickening of Iselux/CAPB/Alkyl Polyglucoside

6% Active Iselux, 2.5% Active CAPB (Topped), 3% Active Co-Surfactant
12000

Viscosity / cps @ 25C

10000

Lauryl Glucoside (Pureact Gluco L)

8000

Coco Glucoside (Pureact Gluco C)

6000

No co-surfactant
4000

2000

Decyl Glucoside
(Pureact Gluco D)
0
0

0.5

1.5
Salt %w/w

Brookfield RVT @ 20rpm, #5 spindle pH 5.8

26

2.5

Demonstration that Iselux Can Form Coacervates When Used at Typical

Shampoo Formulation Concentrations
12 % SLMI, 2.5 % CAPB, 0.4 % Cationic Guar
Gum (Jaguar Excel)

Left to stand for several hours

Coacervate

Neat shampoo
(Coacervate is
Solubilised)
27

1 : 10 dilution
(average dilution for
application on head)
(Coacervate precipitates)

Sedimentation
of coacervate

Turbidity (Coacervate Formation) Profiles of Iselux/CAPB Versus SLES/CAPB with PQ-10

and Cationic Guar

12 % Surfactant, 2.5 % CAPB, 0.4% Polyquaternium-10

28

12 % Surfactant, 2.5 % CAPB, 0.4 % Cationic guar

Salon Testing an Iselux Sulfate-Free

Shampoo Prototype Versus Market
Benchmarks

29

Innospec Sulfate-Free Shampoo Prototype

Formula
Ref. DV-12-251F
INCI Name
Sodium Lauroyl Methyl Isethionate
Sodium Cocoyl Isethionate
Sodium Methyl Cocoyl Taurate
Sodium Lauroyl Glycinate
Cocamidopropyl Betaine
Ethylene Glycol Monostearate
Polyquaternium-7
Guar Hydroxypropyltrimonium Chloride
Cyanopsis Tetragonoloba (Gaur Gum)
Citric Acid, EDTA, NaCl
Preservative, fragrance
*NOTE:
PEG-Free
% Inorganic Sulfate < 350 ppm

30

Innospec Trade Amount / %

Name
wt/wt
Iselux
Pureact I-85EC
Pureact WS Conc
Pureact SLG-C
Condicare PQ-7
Activsoft C-17
Activsoft S
-

5.00
3.00
5.00
10.00
7.00
2.25
1.00
0.20
0.50

Innospec Premium Sulfate-Free Shampoo

Prototype vs Pantene Pro-V
Pantene Pro-V
Ingredients: Water, Sodium Laureth Sulfate, Sodium Lauryl Sulfate, Glycol
Distearate, Dimethicone, Cocamidopropyl Betaine, Sodium Citrate, Cocamide
MEA, Sodium Xylenesulfonate, Fragrance, Citric Acid, Sodium Benzoate, Guar
Hydroxypropyltrimonium Chloride, Sodium Chloride, Tetrasodium EDTA, Trisodium
Ethylenediamine Disuccinate, Panthenol, Panthenyl Ethyl Ether, Methylchloroisothiazolinone, Methylisothiazolinone

Innospec Premium
Pantene Pro-V Classic
Sulfate-Free Shampoo
Care Daily Shampoo
DV-12-251F *
Appearance @
25C

Opaque, Pearlescent
Liquid

Opaque, Pearlescent
Liquid

pH (As Is)

5.8

6.4

Viscosity @ 25C

11,780 cps

9,760 cps

% Non Volatiles

20.8

23.3

* NOTE:
PEG Free
% Inorganic Sulfate < 350 ppm

31

Half Head Salon Trial - Innospec sulfate-free

shampoo vs market leading sulfate shampoo

Innospec formula
has ~11% lower
solids

32

* significant at 10%
** significant at 5%
*** significant at 1%

Innospec Premium Sulfate-Free Shampoo Prototype

vs EverPure Volume Shampoo (Sulfate-free)
EverPure TM/MC volume Shampoo
Ingredients: Aqua/Water/Eau, Sodium Cocoyl Isethionate, Sodium Lauryl Sulfoacetate, Disodium Laureth
Sulfosuccinate, Cocamidopropyl Betaine, Sodium Lauroyl Sarcosinate, Glycol Distearate, Glycereth-26,
Decyl Glucoside, Parfum/Fragrance, PPG-5-Ceteth-20, Amodimethicone, Polyquaternium-7, Methylparaben,
PEG-55 Propylene Glycol Oleate, Propylene Glycol, Carbomer, C11-15 Pareth-7, Benzophenone-3, Benzyl
Salicylate, Hexyl Cinnamal, Glycerin, Trideceth-12, Laureth-9, Linalool, Tocopherol, Limonene, Benzyl Alcohol,
Juniperus Communis Oil / Juniperus Communis Fruit Oil, Leaf Oil Methylchloroisothia-zolinone, Rosmarinus
Officinalis / Rosemary leaf Oil, Methylisothiazolinone, Sodium Hydroxide, Citric Acid, F.I.L.#D43591/4

Appearance @
25C
pH (as is)
Viscosity @ 25C
% Non Volatiles
* NOTE:
PEG Free
% Inorganic Sulfate < 350 ppm

33

Innospec Premium
Sulfate-Free
Shampoo
DV-12-251F *
Opaque, Pearlescent
Liquid
5.8
11,780 cps
20.8

EverPureTM/MC volume
Shampoo
Opaque, Pearlescent
Liquid
6.19
11,860 cps
34.7

Half Head Salon Trial -

Innospec sulfate-free
shampoo vs Everpure Volume Shampoo

Innospec - 21% solids

Everpure - 35% solids
* significant at 10%
** significant at 5%

34

Iselux blend options

35

Innospec Surfactant Blends

36

Products

Ingredients

% naturally
derived

Iselux SFS-SB

Water, Sodium lauroyl methyl isethionate,

Cocamidopropyl betaine, Sodium cocoyl isethionate
(and) Sodium methyl oleoyl taurate, Sodium
benzoate

80

Iselux SLC

Water, Sodium lauroyl methyl isethionate, Sodium

lauroamphoacetate, Cocamide MIPA, Sodium
benzoate

77

Iselux Ultra Mild

Water, Sodium Lauroyl Methyl Isethionate,

Cocamidropyl Betaine, Sodium Methyl Oleoyl
Taurate, Lauryl Glucoside, Coco Glucoside, Sodium
benzoate

84

ISELUX SFS
Formulated, Sulfate-Free Concentrate

37

Excellent foaming properties dense, creamy

lather suitable for shampoos, shower
gels/creams, etc.
Sulfate-free, formaldehyde-free, PEG-free and
1,4-dioxane-free.
Cold processing - dilutes readily in RT water to
yield crystal clear, formulated cleanser systems.
Economical.
Derived from natural, renewable resources.
Readily bio-degradable.
Conveniently builds viscosity with electrolyte
addition.

Iselux SLC (Structured Liquid Concentrate)

Structured liquids are materials in a unique physical state capable

of suspending incompatible performance additives
Eg oils, silicone, beads

Easy to use, optimised blend designed to produce structured

liquid formulations - takes the complexity out of manufacturing
stable structured liquids

Sulfate-free, formaldehyde-free, PEG-free, EO-free

and 1,4-dioxane-free
Spherulite

Simple, cost effective cold mix process

Enhanced consumer appeal:

Suspended
material

- Appealing lotion-like texture

- Luxuriously creamy foam
- High oil component loading contributing to elegant foam
texture and exceptionally pleasant skin after-feel

38

Iselux Ultra Mild

39

Breakthrough high-foaming ultra mild blend for baby

cleansers, sensitive-skin facial wash, intimate
cleansers, etc

No tears and no eye irritation blend which is also mild on

the skin.

Sulfate-free, formaldehyde-free, PEG-free, EO-free and

1,4-dioxane-free.

Can achieve excellent viscosity.

Iselux Ultra Mild Viscosity

(30% Dilution, no additives)

NB: Viscosity can be influenced by

fragrance and other additives

40

Iselux Ultra Mild

Effect of Sodium Chloride on Viscosity
(30% Dilution, no additives, at pH 6.0)

Viscosity, cps

RVT spindle 5, 20
rpm @ 20C

% NaCl

41

Sulfate Free Summary

Sulfate-free personal cleansing products continue to be a

growing, global trend.

Formulating high performance, cost effective sulfate-free

products is a challenge to even the most skilled
formulators but use of Iselux can alleviate the pain
of this!

Iselux is becoming ever popular as the choice ingredient

to replace sulfates - this is driven by its outstanding
performance.

Our applications team is available and keen to help our

customers create stable, high performing sulfate free
cleansers

42

Thank you for listening!

Any questions?

tony.gough@innospecinc.com