Meeting the Challenge Formulating High Performance Sulfate Free Products Chemistry & Formulation Science
Agenda Origins of sulfate free and current market status Formulation challenges Chemistry options Formulating high performing sulfate free systems
Origins of Sulfate Free and Current Market Status
Alkyl Sulfates and Alkyl Ether Sulfates R O O S O O - M + Alkyl Sulfate R O O O S n O - O Alkyl Ether Sulfate M + 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
Why consider eliminating sulfate? Concerns over sulfates and ether sulfates in personal cleansers started > 10 years ago as a small fringe and an internet blog Over the past 4-5 years the momentum has grown into a global phenomenon in salon, prestige, and mass market brands The trend will likely to continue to grow in the coming years as more companies including the majors embrace the concept
Sulfate Free Consumer Image Milder to skin (and hair) than ordinary shampoo, body washes, or personal 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 Marketing Claims 279 209 447 Natural Beauty enhancing Ethical & environmental Improved performance Free from unwanted chemicals 302 331
Sulfate Free Market Growing Global Trend
Sulfate Free Global Introductions* Shampoo and Skin Cleansers 1400 1200 North America Middle East & Africa Latin America Europe Asia Pacific 1000 800 600 400 200 0 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015
Formulation Challenges
Formulation Challenges Benchmarked Against Sulfate Formulas Performance Foaming/Lathering Mildness (Skin & Eyes) Harshness/Detergency Conditioning Aesthetics Viscosity Clear/Opaque Ease of Formulation Cost in the Bottle
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 Increase the levels of secondary surfactant combinations Replace with other anionics
Sulfate Free Shampoos water (aqua), cocamidopropyl betaine, disodium laureth sulfosuccinate, sodium lauroyl sarcosinate, cocamide MEA, parfum (fragrance), glycerin, PEG-120 methyl glucose dioleate, divinyldimethicone/dimethicone copolymer, glycol distearate, phenoxyethanol, acrylates/vinyl neodecanoate crosspolymer, disodium cocoamphodiacetate, 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, hexyl cinnamal, linalool, citronellol, butylphenyl methylpropional
Sulfate vs Sulfate Free Shampoos Higher Cost with Lower Performance Commercial Sulfate Shampoos Commercial Sulfate Free Shampoos
Formulation Considerations Establishing the Pallet INCI Name (Perception Vs Chemistry) Inorganic Salts Sodium Sulfate/Inorganic Sulfates Sodium Chloride Feedstocks (Synthetic, Animal, Plant Origins) Amide Free? PEG Free? Free of Ethylene Oxide Origins? Dioxane Free? Preservatives? Others?
Sulfate Free Chemistries Sulfates and Ether Sulfates R OH R O O H x Fatty Alcohol and Alcohol Ethoxylates Olefin Sulfonates and LAS R CH 2 Alpha Olefin Amino Acid Surfactants and Isethionates O R OH Fatty Acids
Sulfate Free Alternatives Carboxylates ph Performance Sensitive Moderate to Low Foamers O R S O O - Sulfonates Inorganic Sulfate INCI Name RO(CH 2 CH 2 O) n H Ethoxylates/Nonionics EO/Dioxane Concerns Low Foam
Sulfate Free Surfactant options for formulators PRODUCT Polar Head Class EO Origin Inorganic Sulfate Hydrophobe Origin Foam Optimum ph Irritantancy Ease of Formulation Thickening Acyl Isethionates SO3 Anionic Y Trace/Low Nat Excellent 5.5-8.5 Moderate Dif External Acyl Methyl Isethionates SO3 Anionic N Trace/Low Nat Excellent 5.-9 Moderate Easy Betaine/Salt Alkyl Benzene Sulfonates SO3 Anionic N Y Syn Excellent 3-11 Harsh Easy External Alkyl Ether Carboxylates COO Anionic Y N Nat Moderate >5.5 Mild Easy External Acyl Glycinates COO Anionic N N Nat Excellent >7 Mild Easy External Alkylamphoacetates COO Amphoteric N N Nat Moderate >5 Moderate Easy External Alpha Olefin Suflonates SO3 Anionic N Y Syn Excellent 3-11 Harsh Easy Betaine/Salt APG's NA Nonionic N N Nat Low 4.5-8.5 Mild Easy External Betaines COO Amphoteric N N Nat Moderate >5 Moderate Easy External Fatty Acid Soaps COO Anionic N N Nat Moderate >6 Harsh Easy External Sarcosinates COO Anionic N N Nat Moderate >6.0 Moderate Easy External Sodium Methyl Acyl Taurates SO3 Anionic N Trace/Low Nat Moderate 3-11 Moderate Mod External Sulfoacetates SO3 Anionic N Y Nat Moderate 3-11 Moderate Dif Betaine/Salt Sulfosuccinates SO3 Anionic TBD Y Nat Moderate 5.5-8.5 Mild Easy External Sultaines SO3 Amphoteric N Trace/Low Nat Moderate 3-11 Moderate Easy External
Sulfate Free Formulations Thickening Agents & Rheology Modifiers Ingredient Examples Benefits Drawbacks Electrolytes Sodium Chloride Ammonium Chloride Sodium Sulfate Economical; Easy to use Limited impact on most Sulfate Free Surfactants Fatty Alkanolamides Cocamide MEA Cocamide MIPA Foam stabilizers; Easy to use Inefficient; Irritation PEG Esters PEG 150 Distearate PEG 120 Methyl Glucose Dioleate Efficient; Easy to Use EO source; Poor rheology Natural Polymers Guar Cellulosics Carrageenan Natural sources; Foam boosters; Yield Micro concerns; Grainy, Stringy Rheology Synthetic Polymers Acrylates; Carbomers Acrylate/Alkyl Acrylate Crosspolymers Efficient; Yield; Particle suspension Ingredient & ph sensitive; Salt Sensitive Bio-polymers Xanthan Gum Succinoglycan Natural ; Yield; Particulate suspension Difficult to use; Clarity; Ingredient incompatibilities
Sodium Cocoyl Isethionate (SCI) Sodium Lauroyl Isethionate (SLI) O R O S O O O- M + Recognized chemistry widely used today in Beauty Bars, Baby Bars, and Niche personal cleansing formulations Benefits Dense Rich Lather Mild Smooth, Clean After-feel Rinseability Biodegradable Limitations Poor Water Solubility Difficult to Formulate ph Stability (ph 6-8)
14 Day Cumulative Skin Irritation 0.50% Active Mean Cumulative Score 35 30 25 20 15 10 5 0
Sodium Cocoyl Isethionate % Active Anionic @ 45 C
Phase Diagram Profile M-Phase 2 Phases Anionic surfactant Lamellar Phase Micellar Phase Electrolyte Amphoteric Surfactant
Surfactant Phase Transition Transition Transition Micellar state M-phase, gel Sheer thinning Lamellar state Foaming Dilution upon use in shower Cleansing Spherulite Structured system Micellar state Deposition
Structured Liquid Systems Formulation Properties/Advantages Yield value rheology High temperature stability Opaque, lotion-like appearance Excellent stability over wide temperature ranges Excellent particulate suspension properties Fragrance tolerant Electrolyte tolerant Active delivery
Key Application Areas Shower gels Where enhanced (24 hour) moisturization is the goal Visual effects are desired To deliver Incompatible ingredient for performance benefits Skin cleansers The need to suspend objects for either visual or performance is required Incompatible ingredients are required to deliver performance Shampoos Incompatible ingredients are required to deliver performance Visual effects are desired
Sulfate Free Summary 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 Thank you! QUESTIONS