Formulating High Performance, Sulfate-Free 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

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Origins of Sulfate-Free and Current Market Status

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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.

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Alkyl Sulfates and Alkyl Ether Sulfates

M+

RO

O-

O

OS

O

nM+R

O-

O

OS

O

Alkyl Sulfate 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

0

200

400

600

800

1,000

1,200

1,400

1,600

2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015

Middle East & Africa

Latin America

North America

Europe

Asia Pacific

Year

Num

ber

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Sulfate-Free Personal Cleansers Market Continuing growing trend

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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

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Options and challenges to formulating away from sulfates

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Sulfate Vs Sulfate Free Shampoos – higher cost with lower performance

Commercial Sulfate Shampoos

Typical non-Iselux Commercial Sulfate-Free Shampoos

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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 Possible irritancy issues and/or high

levels of inorganic sulfate.

• Increase the levels of secondary surfactants and use mixtures of different types can add complexity to the formulation and manufacture.

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Sulfate-Free Surfactant options for formulators

PRODUCT

Inno

spec

su

pplie

s

Pola

r H

ead

Cla

ss

EO O

rigin

Inor

gani

c Su

lfate

Hyd

roph

obe

O

rigin

Foam

Opt

imum

pH

Irrita

ntan

cy

Ease

of

Form

ulat

ion

Thic

keni

ng

Acyl Isethionates Pureact SCI Yes SO3 Anionic Y Trace/Low Nat Excellent 5.5-8.5 Moderate Dif External

Acyl Methyl Isethionates Iselux® 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 No COO Amphoteric N N Nat Moderate >5 Moderate Easy External Fatty Acid Soaps No COO Anionic N N Nat Moderate >6 Harsh Easy External

Sarcosinates Pureact LSR Yes COO Anionic N N Nat Moderate >6.0 Moderate Easy External

Sodium Methyl Acyl Taurates

Pureact WS Yes SO3 Anionic N Trace/Low Nat Moderate 3-11 Moderate Mod External

Sulfoacetates No SO3 Anionic N Y Nat Moderate 3-11 Moderate Dif Betaine/Salt Sulfosuccinates Pending SO3 Anionic TBD Y Nat Moderate 5.5-8.5 Mild Easy External

Sultaines No SO3 Amphoteric N Trace/Low Nat Moderate 3-11 Moderate Easy External

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Type Innospec Trade Name Primary Secondary Fits all Criteria? Alkyl ether carboxylates Pureact TA; WLL Alpha olefin sulfonates - Alkyl benzene sulfonates -

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 -

Sulfate Free – what if you want it all? Primary, Highly Foaming, Mild, EO-Free, Naturally Derived and Thickens With Salt

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Innospec’s Iselux Solutions to Convenient Sulfate-free Formulating

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Iselux®

► 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.

Sulfate-Free Surfactant Solutions From Innospec

Sodium Lauroyl Methyl Isethionate

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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 Benefit

Structured systems achievable Dramatic formulation flexibility enhanced creativity

Dense creamy lather Elegant after-feel

Ultra mild surfactant Ideal for sensitive skin

Excellent water solubility Can be used in clear systems

Sulfate-free 1,4-Dioxane-free Nitrosamine-free

Readily biodegradable Derived from renewable resources

Formulates like an ether sulfate Broad pH stability

Friendly to the environment

Safe at all use levels

Creates a luxurious bath / shower experience

Formulating flexibility

EO / PEG-free

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Background – Why move from SCI to Iselux®?

SCI SLMI Iselux®

• 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:

Iselux® Flake (80-85% Active)

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

10% solutions in water

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

0

20

40

60

80

100

120

140

2009 2010 2011 2012 2013 2014 2015

Middle East & Africa

Latin America

Asia Pacific

North America

Europe

Regional Annual Introductions featuring Iselux®

Year

Num

ber

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Recent launches featuring Iselux®

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

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Popular Sulfate-Free Anionic Surfactants pH Stability Range

Sodium Lauroyl Methyl Isethionate (Iselux ®)

5.0 – 9.0

Sodium Cocoyl Isethionate (Pureact ® I-series)

6.0 – 8.0

Sodium Lauryl Sulfoacetate

6.0 – 8.0

Sodium Laureth Sulfosuccinate

6.0 – 8.0

• 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).

Considerations When Formulating with Iselux®: pH

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Considerations When Formulating with Iselux®: Choice of Co-surfactants

• Electrolyte (eg, NaCl): Include Cocamidopropyl Betaine. Addition of tertiary surfactants such as Taurates and APGs, etc can further enhance the viscosity profile.

Viscosity building options:

• 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

10% Active Iselux® + Cocamidopropyl Betaine

% NaCl

Visc

osity

@ 2

5°C

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

4% Active Betaine (oil based)

2% Active Betaine (oil based)

0% Betaine

2% Active Betaine (topped fatty acid)

(pH 6.0)

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

Electrolyte Thickening of Iselux/CAPB Systems

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

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

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

0 0.5 1 1.5 2 2.5 3 3.5 4

Vis

cosi

ty / c

ps @

25C

% NaCl

Electrolyte Thickening of Iselux/CAPB/Tertiary Surfactant Systems

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

Sodium Methyl Oleyl Taurate (Pureact® MS-CG)

Disodium Oleamido MIPA Sulfosuccinate (Pureact® MD-318)

Sodium Methyl Cocoyl Taurate (Pureact® WS Conc)

No co-surfactant (Control)

25 Sodium Lauroyl Sarcosinate

(Pureact LSR)

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

0

2000

4000

6000

8000

10000

12000

0 0.5 1 1.5 2 2.5

Visc

osity

/ cps

@ 2

5°C

Salt %w/w

Brookfield RVT @ 20rpm, #5 spindle pH 5.8

Electrolyte Thickening of Iselux/CAPB/Alkyl Polyglucoside

Lauryl Glucoside (Pureact® Gluco L)

Coco Glucoside (Pureact® Gluco C)

No co-surfactant

Decyl Glucoside (Pureact® Gluco D)

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

Neat shampoo (Coacervate is Solubilised)

Sedimentation of coacervate

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

Coacervate

Demonstration that Iselux Can Form Coacervates When Used at Typical Shampoo Formulation Concentrations

Left to stand for several hours

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

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

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

Salon Testing an Iselux® Sulfate-Free Shampoo Prototype Versus Market

Benchmarks

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Innospec Sulfate-Free Shampoo Prototype Formula

INCI Name Innospec Trade Name

Amount / % wt/wt

Sodium Lauroyl Methyl Isethionate Iselux® 5.00 Sodium Cocoyl Isethionate Pureact I-85EC 3.00 Sodium Methyl Cocoyl Taurate Pureact WS Conc 5.00 Sodium Lauroyl Glycinate Pureact SLG-C 10.00 Cocamidopropyl Betaine - 7.00 Ethylene Glycol Monostearate - 2.25 Polyquaternium-7 Condicare PQ-7 1.00 Guar Hydroxypropyltrimonium Chloride Activsoft C-17 0.20 Cyanopsis Tetragonoloba (Gaur Gum) Activsoft S 0.50 Citric Acid, EDTA, NaCl - Preservative, fragrance -

*NOTE: • PEG-Free • % Inorganic Sulfate < 350 ppm

Ref. DV-12-251F

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Innospec Premium

Sulfate-Free Shampoo DV-12-251F *

Pantene Pro-V Classic Care Daily Shampoo

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

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, Methylchloroiso- thiazolinone, Methylisothiazolinone

Pantene Pro-V

Innospec Premium Sulfate-Free Shampoo Prototype vs Pantene Pro-V

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Half Head Salon Trial - Innospec sulfate-free shampoo vs market leading sulfate shampoo

Innospec formula has ~11% lower solids

* significant at 10% ** significant at 5% *** significant at 1% 32

Innospec Premium Sulfate-Free

Shampoo DV-12-251F *

EverPureTM/MC volume Shampoo

Appearance @ 25°C

Opaque, Pearlescent Liquid

Opaque, Pearlescent Liquid

pH (as is) 5.8 6.19 Viscosity @ 25°C 11,780 cps 11,860 cps

% Non Volatiles 20.8 34.7

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

Innospec Premium Sulfate-Free Shampoo Prototype vs EverPure Volume Shampoo (Sulfate-free)

* NOTE: • PEG Free • % Inorganic Sulfate < 350 ppm

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Half Head Salon Trial - Innospec sulfate-free shampoo vs Everpure Volume Shampoo

Innospec - 21% solids Everpure - 35% solids

* significant at 10% ** significant at 5%

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Iselux® blend options

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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

Innospec Surfactant Blends

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ISELUX® SFS Formulated, Sulfate-Free Concentrate

► 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.

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Iselux® SLC (Structured Liquid Concentrate) ► Structured liquids are materials in a unique physical state capable

of suspending incompatible performance additives

Eg oils, silicone, beads…

- Appealing lotion-like texture - Luxuriously creamy foam - High oil component loading contributing to elegant foam

texture and exceptionally pleasant skin after-feel

Spherulite

Suspended material

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► Easy to use, optimised blend designed to produce structured liquid formulations - takes the complexity out of manufacturing stable structured liquids

► Simple, cost effective cold mix process

► Sulfate-free, formaldehyde-free, PEG-free, EO-free and 1,4-dioxane-free

► Enhanced consumer appeal:

Iselux® Ultra Mild

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► 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

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

RVT spindle 5, 20 rpm @ 20°C

Visc

osity

, cps

% NaCl

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► 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

Sulfate Free Summary

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Thank you for listening!

Any questions?

tony.gough@innospecinc.com