Post on 02-Feb-2021
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 SLES Vs Iselux®
Iselux® 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
X®
/
LA
A (1:1
)
Dis
t.
Wate
r
Iselux® 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 0.2CONDICARE 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
Iselux®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