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 2
3 Origins of Sulfate-Free and Current Market Status
4 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.
Alkyl Sulfates and Alkyl Ether Sulfates R O O S O O - Alkyl Sulfate Advantages M + R O O O S n O - O Alkyl Ether Sulfate Excellent foaming properties in soft and hard water Relatively inexpensive Excellent detergency Rinse easily Easy to use - Good water solubility - Can be thickened effectively with salt 5 M + Disadvantages 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 They are sulfates and these have a negative connotation for a growing number of consumers.
Sulfate-Free Launches - Shampoo and Skin Cleansers 1,600 Middle East & Africa Number 1,400 1,200 1,000 800 Latin America North America Europe Asia Pacific 600 400 200 6 0 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 Year
7 Sulfate-Free Personal Cleansers Market Continuing growing trend
8 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
9 Options and challenges to formulating away from sulfates
10 Sulfate Vs Sulfate Free Shampoos higher cost with lower performance Commercial Sulfate Shampoos Typical non-iselux Commercial Sulfate-Free Shampoos
11 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.
Sulfate-Free Surfactant options for formulators 12 PRODUCT Acyl Isethionates Pureact SCI Acyl Methyl Isethionates Iselux Innospec supplies Polar Head Class EO Origin Inorganic Sulfate Hydrophobe Origin Yes 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 Foam Optimum ph Irritantancy Ease of Formulation Thickening Alkyl Ether Carboxylates Pureact Carboxylates Acyl Glycinates Pureact SLG Alkylamphoacetates Pureact LAA Yes COO Anionic Y N Nat Moderate >5.5 Mild Easy External Yes COO Anionic N N Nat Excellent >7 Mild Easy External 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 Yes SO3 Anionic N Trace/Low Nat Moderate 3-11 Moderate Mod External Pureact WS 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
13 Sulfate Free what if you want it all? Primary, Highly Foaming, Mild, EO-Free, Naturally Derived and Thickens With Salt 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 -
14 Innospec s Iselux Solutions to Convenient Sulfate-free Formulating
Sulfate-Free Surfactant Solutions From Innospec Iselux Sodium Lauroyl Methyl Isethionate 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. 15
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 16 Shampoo bars
Iselux Features and Benefits Feature Benefit Structured systems achievable Dense creamy lather Elegant after-feel Ultra mild surfactant Excellent water solubility Sulfate-free 1,4-Dioxane-free Nitrosamine-free EO / PEG-free Dramatic formulation flexibility enhanced creativity Creates a luxurious bath / shower experience Ideal for sensitive skin Can be used in clear systems Safe at all use levels Readily biodegradable Derived from renewable resources Formulates like an ether sulfate Broad ph stability Friendly to the environment Formulating flexibility 17
Background Why move from SCI to 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: SLMI Iselux 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
19 Regional Annual Introductions featuring Iselux 140 120 100 Number 80 60 40 Middle East & Africa Latin America Asia Pacific North America Europe 20 0 2009 2010 2011 2012 2013 2014 2015 Year
20 Recent launches featuring Iselux
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 21
Considerations When Formulating with Iselux : ph 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 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: 23 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
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 10% Active Iselux + Cocamidopropyl Betaine Viscosity @ 25 C 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) % NaCl 24
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 14000 12000 10000 8000 6000 4000 2000 No co-surfactant (Control) Sodium Methyl Oleyl Taurate (Pureact MS-CG) Disodium Oleamido MIPA Sulfosuccinate (Pureact MD-318) Sodium Methyl Cocoyl Taurate (Pureact WS Conc) 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 10000 Viscosity / cps @ 25 C 8000 6000 4000 Lauryl Glucoside (Pureact Gluco L) Coco Glucoside (Pureact Gluco C) No co-surfactant 2000 0 Decyl Glucoside (Pureact Gluco D) 0 0.5 1 1.5 2 2.5 Salt %w/w Brookfield RVT @ 20rpm, #5 spindle ph 5.8 26
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 27 Neat shampoo (Coacervate is Solubilised) 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
29 Salon Testing an Iselux Sulfate-Free Shampoo Prototype Versus Market Benchmarks
Innospec Sulfate-Free Shampoo Prototype Formula Ref. DV-12-251F 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 30
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 Appearance @ 25 C Innospec Premium Sulfate-Free Shampoo DV-12-251F * Opaque, Pearlescent Liquid Pantene Pro-V Classic Care Daily Shampoo 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 Innospec Premium Sulfate-Free Shampoo DV-12-251F * Opaque, Pearlescent Liquid EverPure TM/MC volume Shampoo 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 33 * NOTE: PEG Free % Inorganic Sulfate < 350 ppm
Half Head Salon Trial - Innospec sulfate-free shampoo vs Everpure Volume Shampoo Innospec - 21% solids Everpure - 35% solids 34 * significant at 10% ** significant at 5%
35 Iselux blend options
Innospec Surfactant Blends Products Ingredients % naturally derived Iselux SFS-SB Iselux SLC Iselux Ultra Mild Water, Sodium lauroyl methyl isethionate, Cocamidopropyl betaine, Sodium cocoyl isethionate (and) Sodium methyl oleoyl taurate, Sodium benzoate Water, Sodium lauroyl methyl isethionate, Sodium lauroamphoacetate, Cocamide MIPA, Sodium benzoate Water, Sodium Lauroyl Methyl Isethionate, Cocamidropyl Betaine, Sodium Methyl Oleoyl Taurate, Lauryl Glucoside, Coco Glucoside, Sodium benzoate 80 77 84 36
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. 37
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 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. 39
40 Iselux Ultra Mild Viscosity (30% Dilution, no additives) NB: Viscosity can be influenced by fragrance and other additives
41 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
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? tony.gough@innospecinc.com