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
►
2
Origins of Sulfate-Free and Current
Market Status
3
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.
4
Alkyl Sulfates and Alkyl Ether Sulfates
R
O
S - +
O M
O
O
Alkyl Sulfate
R
O
O
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
6
2004
2005
2006
2007
2008
2009
Year
2010
2011
2012
2013
2014
2015
Sulfate-Free Personal Cleansers Market
Continuing growing trend
7
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
8
Options and challenges to formulating
away from sulfates
9
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
Y
Trace/Low
Nat
Excellent
5.5-8.5
Moderate
Dif
External
Yes
SO3
Anionic
N
Trace/Low
Nat
Excellent
5.-9
Moderate
Easy
Betaine/Salt
Alkyl Benzene Sulfonates
No
SO3
Anionic
N
Y
Syn
Excellent
3-11
Harsh
Easy
External
Alkyl Ether Carboxylates
Pureact Carboxylates
Yes
COO
Anionic
Y
N
Nat
Moderate
>5.5
Mild
Easy
External
Acyl Glycinates
Pureact SLG
Yes
COO
Anionic
N
N
Nat
Excellent
>7
Mild
Easy
External
Alkylamphoacetates
Pureact LAA
Yes
COO
Amphoteric
N
N
Nat
Moderate
>5
Moderate
Easy
External
Alpha Olefin Suflonates
No
SO3
Anionic
N
Y
Syn
Excellent
3-11
Harsh
Easy
Betaine/Salt
APG's
Pureact Gluco
Yes
NA
Nonionic
N
N
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
N
N
Nat
Moderate
>6.0
Moderate
Easy
External
Yes
SO3
Anionic
N
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
-



Innospec’s 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 pH’s 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 can’t 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 @ 25°C
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
1.5
2
2.5
3
3.5
4
% NaCl
Brookfield RVT @ 20rpm, 25°C, #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 @ 25°C
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
1.5
Salt %w/w
Brookfield RVT @ 20rpm, #5 spindle pH 5.8
26
2
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 @
25°C
Opaque, Pearlescent
Liquid
Opaque, Pearlescent
Liquid
pH (As Is)
5.8
6.4
Viscosity @ 25°C
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 @
25°C
pH (as is)
Viscosity @ 25°C
% 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 @ 20°C
% 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?
[email protected]