Sulfate Free

Personal Cleansing Products

Chemistry & Formulation Science

Alkyl Sulfates and Alkyl Ether Sulfates

• The most widely used primary surfactants for personal cleansing applications

• Excellent foaming properties in soft and hard water

• Relatively inexpensive

• Rinse easily

• Excellent detergency

• Easy to use

– Show good water solubility

– Can be thickened with salt

• Skin and eye irritants – require irritation mollifying agents

• Strip the skin and hair – require conditioning agents

• Lauryl Ether Sulfates contain EO moieties - 1,4 dioxane

M+

RO

O-

O

O

SO

nM+R

O-

O

O

SO

Alkyl Sulfate Alkyl Ether Sulfate

Sulfate Free Market

• Concern over sulfates started about 8 years ago

• Over past 3 – 4 years the trend has greatly expanded

• The number of sulfate-free products is increasing

0

50

100

150

200

250

2004 2005 2006 2007 2008 2009

Middle East & Africa

Latin America

Asia Pacific

Europe

North America

Regional Annual Introductions

Sulfate Free MarketGrowing Global Trend

Sulfate Free “Consumer Image”

• Milder to skin (and hair) than ordinary shampoo, body washes, orpersonal cleansers

• Pure which equates to “safer” for the consumer

• Non Stripping- Gentle Cleansing

• Natural/Organic - Environmentally Friendly

• Less impact on sensitive skin

• Improves color retention in color treated hair

• Lengthens the effectiveness of chemically treated hair

447

331302

279

209Natural

Beauty enhancing

Ethical & environmental

Improved performance

Free from unwanted chemicals

Marketing Claims

Sulfate Free Personal Care Products

• Science Vs Perception

• Formulation Challenges

• Formulation Alternatives (Chemistry & Performance)

• Creating Cost Effective Formulations

Formulation ChallengesBenchmarked Against Sulfate Formulas

• Performance

– Foaming/Lathering

– Mildness (Skin & Eyes)

– Harshness/Detergency

– Conditioning

• Aesthetics

– Viscosity

– Clear/Opaque

• Ease of Formulation

• Cost in the Bottle

RO(CH2CH2O)nH

R S

O

O

O-

CarboxylatespH Performance SensitiveModerate to Low Foamers

SulfonatesInorganic Sulfate

INCI Name

Ethoxylates/NonionicsEO/Dioxane Concerns

Low Foam

Sulfate Free Alternatives

Technical Challenges and Options

• Sulfate free options are typically more expensive –formulas are therefore more expensive

• Sulfate free alternatives typically have performance deficiencies

• Sulfate free formulas have higher solids/actives

• Formulators typically compromise performance for sulfate free

Typical Approaches

– Replace with other anionics

– Increase the levels of secondary surfactants

– Combinations of co-surfactants

Sulfate Vs Sulfate Free Shampoos

0

5

10

15

20

25

30

35

40

So

lid

s, %

Commercial Sulfate

Shampoos

Commercial Sulfate Free Shampoos

Conventional Sulfate Free

Primary Surfactant(s)

Ether Sulfate/Sulfate 10-18

Non-Sulfate Anionics 0-5 0-20

Secondary Surfactants

Betaine/Sultaine 0-5 0-20

Amphoterics 0-5 0-10

Sulfosuccinates 0-5 0-10

Taurates 0-5 0-10

Sarcosinates 0-3 0-5

APG's 5 0-15

Conditioning Agents 0.1-0.5 0.1-0.5

Viscosity Building Agents

Electrolytes 0-2 0-2

Polymers 0-2 0-2

Preservatives, Mis. 0.1-3 0.1-3

Total 13-21 18-37

Active Ingredient Composition

Sulfate Vs Sulfate Free Shampoos

Sulfate Free Surfactant Summary Sheet

PRODUCTPolar

HeadClass

EO

Origin

Inorganic

Sulfate

Hydrophobe

Origin

Detergency/

IrritationFoam

Alkyl Ether

CarboxylatesCOO Anionic Y N Nat/Syn Mild Moderate

Alpha Olefin

SuflonatesSO3 Anionic N Y Syn Harsh Excellent

Alkyl Benzene

SulfonatesSO3 Anionic N Y Syn Harsh Excellent

Sulfosuccinates SO3 Anionic TBD Y Nat Mild Moderate

Alkylamphoacetates COO Amphoteric N N Nat Moderate Moderate

Betaines COO Amphoteric N N Nat Moderate Moderate

Sultaines SO3 Amphoteric N Trace/Low Nat Moderate Moderate

Acyl Isethionates SO3 Anionic N Trace/Low Nat Moderate Excellent

Acyl Methyl

IsethionatesSO3 Anionic N Trace/Low Nat Moderate Excellent

Sodium Methyl Acyl

TauratesSO3 Anionic N Trace/Low Nat Moderate Moderate

Sarcosinates COO Anionic N N Nat Moderate low/Mod

APG's NA Nonionic N N Nat Mild Low

Acohol Ethoxylates NA Nonionic Y N Syn/Nat Moderate Low

Sulfoacetates SO3 Anionic N Y Nat Moderate Excellent

Fatty Acid Soaps COO Anionic N N Nat Harsh Low/Mod

Product Innospec Trade Name

Alkyl Ether Carboxylates Pureact T-A; WLL

Alkylamphoacetates Pureact LAA

Acyl Isethionates Pureact I-85; SLI

Acyl Methyl Isethionates Iselux™

Sodium Methyl Acyl Taurates Pureact WS Conc.

Sarcosinates Pureact LSR

aqua (water), sodium cocoyl isethionate, sodium lauryl sulfoacetate, disodium laureth sulfosuccinate, cocamidopropyl betaine, sodium lauroyl sarcosinate, glycol distearate, PPG-5-ceteth-20, PEG-55 propylene glycol oleate, C11-15 pareth-7, C12-13 pareth-23, C12-13 pareth-3, linalool, carbomer, glycereth-26, glycerin, amodimethicone, trideceth-12, methylparaben, methylchloroisothiazolinone, methylisothiazolinone, divinyldimethicone/dimethicone copolymer, sodium isethionate, sodium chloride, juniperus communis oil, juniperus communis fruit oil, sodium hydroxide, rosmarinus officinalis leaf oil, rosemary leaf oil, phenoxyethanol, coconut acid, tocopherol, limonene, propylene glycol, laureth-9, citric acid, decyl glucoside, polyquaternium-7, polyquaternium-10, hexyl cinnamal, benzoic acid, benzyl salicylate, benzyl alcohol, parfum (fragrance),

Sulfate Free Shampoos

water (aqua), cocamidopropyl betaine, disodium laureth sulfosuccinate, sodium lauroyl sarcosinate, cocamideMEA, parfum (fragrance), glycerin, PEG-120 methyl glucose dioleate, divinyldimethicone/dimethiconecopolymer, glycol distearate, phenoxyethanol, acrylates/vinyl neodecanoate crosspolymer, disodiumcocoamphodiacetate, laureth-4, polyquaternium-7, amodimethicone, quaternium-95, sodium chloride, sodium glycolate, polyquaternium-55, sodium benzoate, polyquaternium-44, polyquaternium-10, C11-15 pareth-7,….

water (aqua), sodium lauroyl methyl isethionate, cocamidopropyl betaine, sodium methyl cocoyl taurate, lactamide MEA, PEG-7 glyceryl cocoate, glycol distearate, PEG-150 pentaerythrityl tetrastearate, fragrance (parfum), polyfluoroester, laureth-23, PEG-6 caprylic/capric glyceride, tetrasodium EDTA, hydrolyzed wheat protein, behenyl alcohol, polyquaternium-47, laureth-4, methylchloroisothiazolinone, limonene, hexylcinnamal, linalool, citronellol, butylphenyl methylpropional

OII

RC-OCH CH SO Na

PUREACTSodium Cocoyl Isethionate (SCI)

Benefits

• Dense Rich Lather

• Mild

• Smooth, Clean After-feel

• Rinseability

• Biodegradable

Limitations

• Poor Water Solubility

• Difficult to Formulate

• pH Stability (pH 6-8)

Recognized Chemistry Widely Used Today in Beauty Bars, Baby Bars, and Niche Personal Cleansing Formulations

2 2 3

Iselux™ Sodium Acyl Methyl Isethionate

• By modifying the SCI structure

OII

RC-OCH CH SO Na

PUREACT I-85 Sodium Cocoyl Isethionate

• It is possible to improve

– Solubility in water

– Hydrolytic stability

– Performance

– Alkyl-substituted acylethylisethionate esters have the following general formula

O R1II I

RC-OCHCH SO Na

ISELUX™ Sodium Lauroyl Methyl Isethionate

2 2 3

2 3

ISELUX™

ISELUX Flake

80-85% Active

ISELUX LQ-CLR

32-34% Active Liquid

Iselux™

SCI Iselux

10% Solids in Water

0.5% Sodium

Lauryl Ether Sulfate

Time: 0 Min

0.5% Sodium

Lauryl Ether Sulfate Time: 10 Min

0.5% Sodium

LauroylMethyl Isethionate

Time: 0 Min

0.5% Sodium

LauroylMethyl Isethionate

Time: 10 Min

Foam Quality IseluxTM Vs SLES

IseluxTM Biodegradation Profile*Modified Sturm Test

0

10

20

30

40

50

60

70

80

90

100

2 4 6 8 10 12 14 16 18 20 22 24 26 28

Day of Study

% D

egra

dation

*Courtesy Of the Huntsman Corp.

14 Day Cumulative Skin Irritation

0.50% ActiveMean Cumulative Score

0

5

10

15

20

25

30

35S

LS

SLES

-2

CA

PB

ISELU

X

PU

RE

AC

TS

CI

PU

RE

AC

T

WS

Conc

PU

RE

AC

TLA

A

SL

ES

-2/

LA

A

(1:1

)

ISE

LU

XI/

LA

A (1:1

)

Dis

t.

Wate

r

IseluxTM Activity @ 120º F

8

9

10

11

Day 0 Day 6 Day 13 Day 22 Day 30

pH 4.5

pH 5.5

pH 6.5

pH 7.5

pH 8.5

pH 9.5

% A

cti

ve

Outstanding stability over a broad pH range

0

2000

4000

6000

8000

10000

12000

14000

16000

0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 2.8 3

10% Active Iselux + 3% Active CAPB

10% Active Iselux

Effect of Sodium Chloride on Thickening Iselux™

Typical Viscosity Profile

pH 5.5 / 25ºC

Vis

co

sit

y c

ps

% NaCl

Iselux™ Viscosity Profiles10% Active ISELUX™

0

10000

20000

30000

40000

50000

60000

70000

80000

0 6.67% 13.33% 20% 26.67% 33.33%

(30% Active) Cocamidopropyl Betaine

Vis

co

sit

y (

cp

s)

@ 2

0°C

No

5 S

p. @

5 r

pm

0.5% NaCl Added

Iselux™ Viscosity Profiles12% Active ISELUX™

(30% Active) Cocamidopropyl Betaine

Vis

co

sit

y (

cp

s)

@ 2

0°C

No

5 S

p. @

5 r

pm

0

20000

40000

60000

80000

100000

120000

0 6.67% 13.33% 20% 26.67% 33.33%

ISELUX

ISELUX + 0.5% NaCl

ISELUX + 2% Act.Taurate

ISELUX + 2% Act.Taurate + 0.5% NaCl

IseluxTM (82% Active) 6 – 15%

Cocamidopropyl Betaine 1-25%

(or Sodium Lauroamphoacetate)

Other Secondary Surfactants 0- 5%

Conditioning Agent(s) 0.1-0.5%

Chelant (Natrlquest E-30) Q.S.

Citric Acid (to pH 4.5-6.0) Q.S.

Electrolyte (e.g. NaCl) Q.S to Desired Viscosity

Iselux™

Sulfate / Amide Free Formulas

Sulfate FreeFormulating Cost Effective Products

AC-172 AC-156 AC-171 AC-173

ISELUX™ 10 12 10 6

PUREACT I-78 FLAKE 2.5 5

PUREACT WS Conc 3

Cocamidopropyl Betaine (30% Act.) 15.6 20 15 20

Polyquaternium-10 0.1 0.1

ACTIVSOFT C-17 0.2

CONDICARE PQ-7 1

Glycol Distearate 2

NATRLQUEST E-30 0.85 0.9 0.75 0.45

Sodium Chloride 0.2-0.4 0.0-0.5 0.05-0.4 0.1-0.4

D.I. Water QS QS QS QS

Citric Acid pH 6 pH 5.5-6.0 pH 6 pH 5-6

Appearance Clear & Brilliant Clear & Brilliant Opaque Clear & Brilliant

Viscosity (cps) @ 24°C 5,000-10,000 18,000-25,000 10,000-15,000 5,000-10,000

% Solids 18.5-19.5 20-21 24-25 13.2-14.2

Shampoo ShampooBody Wash Body Wash

• Derived From Natural / Renewable Feedstocks (Palm Kernel Oil)

• Readily Bio-Degradable

• No EO Origins & 1,4 Dioxane Free

• Mild Surfactant with Dense Creamy Lather and Long-Lasting Foam

• Excellent Water Solubility – Can Be Used in Clear Systems

• Provides Good Slip, Elegant After-Feel and Reduced Tack on Drying

IseluxTM

Features & Properties

• Sulfate Free, Personal Cleansing Products Continue to be a Growing, Global Trend in the Industry

• Formulating High Performance/Cost Effective Sulfate Free Products is a Challenge to Even the Most Skilled Formulators

• Isethionate Chemistries, Especially Sodium LauroylMethyl Isethionate (ISELUX™), are Fast Becoming the Choice Ingredients as Replacements for Sulfates Because of their Outstanding Performance Benefits

Sulfate Free Summary