Hair Shampoo Laundry Detergent “Cleaning Your Hair vs Cleaning Your Clothes” Jeff Easley – Sr. Global Performance Improvement Specialist Stepan Company Midwest SCC Meeting March 11, 2014

Objectives… Cleaning technology Ingredient types Ingredient functions Formulations Performance testing Regulatory environment Compare and Contrast:

Cleaning Technology

Cleaning Hair vs Cleaning Fabric Different substrates Many more fabric types than hair types Soils to be removed differ Surfactant interfacial phenomena similar Differences in washing processes In General…

Detersive Systems SystemSoilMechanical Action Detergent Household Laundry Mixed & Variable ModerateUnbuilt or Built Surfactant Hair Shampoo OilyVigorous Rubbing in Rinse cycle Organic Surfactant

Progression of Laundry Detergent Forms BarsPowders Liquids Heavy Duty Powders (HDP) Heavy Duty Liquids (HDL) Also known as:

Product Trends Increasing Concentration – 2X, 4X and greater Cold Water Cleaning Eco-friendly Products – Using “Green” or natural based Ingredients Recyclable Packaging High Efficiency – Low foaming variants

Comparison of Claims Hair Shampoo Rapid-Drying Fragrance Free Dermotologist Recommended Volumizing Clarifying Hypoallergenic pH Balanced No Animal Testing Mild Moisturizing Free From… Laundry Detergent Botanical/Herbal Kosher No Additives/Preservatives Fragrance Free Hypoallergenic Economy Convenient Packaging All Natural Product Ease of Use pH Neutral Dermatologically Tested

Interesting Laundry Fact…

Ingredient Types

Ingredient Comparison…. Hair Shampoo Laundry Detergent Surfactants Water pH adjusters Fragrance Dye Preservative Vitamins Protein derivatives Inorganic salts Humectants Emollients Silicones Thickening agents Chelants/Sequestrants Suncreen agents Surfactants Builders Buffering Agents Enzymes Optical Brightener Polymers Hydrotropes Enzyme Stabilizer Preservative Colorant Fragrance Softening Agent Bleach Anti-redepostion Agent Filler Water Key

Typical Physical Properties pHViscosity% Actives Hair ShampooSlightly acidic (5.5 – 6.5) 3,500– 7,000 cps at 25C 10-12% (mid-tier) Household Laundry Detergent (Liquid) Alkaline ( ) 300 – 700 cps at 25C 5-30% (bargain to premium)

Anionic & Nonionic Surfactants Anionic Surfactant Nonionic Surfactant, Solvents Enzymes Surfactants, Bleaching Agents Soils Types and Ingredients to Address Them

Surfactant Comparison Hair Shampoo Sulfonates – Alpha Olefin Sulfonate Sulfates – Alkyl ether sulfates – Alkyl sulfates Alkanolamides Amphoterics Methyl Esters Sulfoacetates Sulfosuccinates Laundry Detergent Sulfonates – Acids – Neutralized forms Sulfates – Alkyl ether sulfates – Alkyl sulfates Alkoxylates Alkanolamides Methyl esters Hydrotropes

Common Primary Anionic Surfactant Linear Alkylbenzene Sulfonic Acid (LABSA) – – Good foamer – Good detergency – Neutralization necessary – Best carbon chain C linear – Corrosive in acidic state

Common Primary Anionic Surfactant Alkyl Ether Sulfates (AES) – – Foam enhancer – Good hard water tolerance – Carbon chain C with 2-3 moles EO Preferred – Due to gel phase formation, add other ingredients first – Stable at 4<pH<10 C (O-CH 2 -CH 2 ) n OSO 3 - Na + n = 2 or 3

Other Primary Anionic Surfactant Alpha Olefin Sulfonate – Good foaming – Good detergency – Stable over a broad pH range – Synergism with LAS CH 3 (CH 2 ) m CH (CH 2 ) n SO 3 - Na + + CH 3 (CH 2 ) m CH (CH 2 ) n SO 3 - Na + Where m = 8 – 14; n = 1-3; and m + n = 9-15 OH

Common Primary Nonionic Surfactant Alcohol Ethoxylates – Mid to high HLB preferred – Good grease cleaner – Low foam generation – Stable in alkaline solutions – Compatible with anionics/cationics C (O-CH 2 -CH 2 ) n OH n = 7-9

Common Secondary Surfactant Amine Oxides (AO) Alcohol Ethoxylates (low HLB) Alkanolamides Soap (defoamer) C (O-CH 2 -CH 2 ) n OH n = 2-4

Ingredient Functions

Surfactant Attributes for Laundry Detergents Role of Surfactants The Ideal Surfactant Other Considerations Hydration of fabrics and soils Solubilization of greases/oils Suspension of hydrophobic soils Generation of suds

Surfactant Attributes for Laundry Detergents Role of Surfactants The Ideal Surfactant Other Considerations Low CMC Low Krafft temperature High solubility in hard/cold water Lowest air/water surface tension Low oil interfacial tension Fast kinetics

Surfactant Attributes for Laundry Detergents Role of Surfactants The Ideal Surfactant Other Considerations Low cost to performance ratio Excellent environmental profile Excellent human safety profile

Surfactant Function in HDL Formulas Primary Surfactants Provide: – Good foaming – Good detergency (removing soils from clothes) – Emulsification and solubilization of soils or dirt

Surfactants Function in HDL Formulas Secondary Surfactants Provide: –Foam enhancement –Cleaning enhancement –High viscosity formulas –Solubilization of other ingredients

Functions of Some Commonly Used Laundry Additives Builders Antiredeposition Agents Dye transfer inhibitors Soil release polymers Optical brighteners Enzymes Control additives for pH, viscosity, foam Preservatives, Perfume, Dye

Formulation Comparison

Primary Surfactants (5-40%)Hydrotropes (0-5%) Secondary Surfactant (0.5-3%)Enzyme Stabilizer (0-5%) Buffering Agents (1-8%)Preservative (0-0.05%) Builders (1-7%)Colorant (0-0.1%) Enzymes (0-1.5%)Fragrance (0-1%) Optical Brightener (0.02-2%)Softening Agent (0-7%) Polymers (0-1%) Formulation Ingredients HDLs

Primary Surfactants (5-15%) Polymers (0-1%) Builders (10-30%) Anti-caking Agent Bleach (0-5%) Filler (30-60%) Anti-redeposition Agent (0-1.5%) Colorant (0-0.1%) Enzymes (0-1.5%) Fragrance (0-1%) Optical Brightener (0.02-2%) Softening Agent (0-7%) Formulation Ingredients HDPs

Premium Laundry Formula INGREDIENTS% Wt. RANGEFUNCTIONALITY DODECYL BENZENE SULFONIC ACID10-15Primary Anionic Surfactant SODIUM ALKYL ETHER SULFATE7-10Primary Anionic Surfactant LINEAR ALCOHOL ETHOXYLATE12-18Primary Nonionic Surfactant SODIUM XYLENE SULFONATE2-4Hydrotrope HARDENED COCONUT FATTY ACID0.5-2Foam Modifier SODIUM HYDROXIDE (50% solution)3-5Neutralizer BORAX PENTAHYDRATE0.5-3Stabilizer PROPYLENE GLYCOL1-3Stabilizer CITRIC ACID (50% solution)2-4Builder TRIETHANOLAMINE0.25-1pH Buffer MONOETHANOLAMINE0.25-1pH Buffer FLUORESCENT WHITENING AGENT Brightener PROTEASE0.5-2Enzyme AMYLASE0.2-1Enzyme DI WATER, FRAGRANCE, COLORANT AND PRESERVATIVEq.s..to 100Additives

Economy Laundry Formula INGREDIENTS% Wt. RANGEFUNCTIONALITY DODECYL BENZENE SULFONIC ACID3-7Primary Anionic Surfactant SODIUM LAURETH SULFATE4-9Primary Anionic Surfactant LINEAR ALCOHOL ETHOXYLATE5-8Primary Nonionic Surfactant SODIUM CARBONATE (100% powder)2-4pH Buffer/Builder SODIUM HYDROXIDE (50% solution)0.5-2Neutralizer FLUORESCENT WHITENING AGENT Brightener DI WATER, FRAGRANCE, COLORANT AND PRESERVATIVEq.s.to 100Additives

Performance Testing

Cleaning Performance ASTM Methods D (stains) and D (artificial soils) Washing: – HE (High Efficiency) and top loading machines – Temperature controlled wash and rinse – 6-lb ballast – Purchased standard stained/soiled fabrics with dust sebum, clay, grass, red wine, cocoa, coffee, blueberry, blood/ink/milk, make-up among others – Duplicate washes Data Analysis: –Hunter Spectrophotometer Software and LabScan XE sensor SRI = 100 -L clean ( - L washed ) 2 +(a clean -a washed ) 2 + (b clean - b washed ) 2  SRI = SRI experimental - SRI control

Regulatory Environment

Some Regulatory Matters… ItemAt Issue…Hair Shampoo Laundry Detergent 1,4-DioxaneCarcinogenYesNo DiethanolamideCarcinogenYesNo Alkyl Phenol Ethoxylates Reproductive, Developmental effects NoYes NitrosamineCarcinogenYesNo PhosphatesEutrophicationYes

Summary Surfactants are the key to both laundry detergent and hair shampoo formulations There are several similarities and differences between laundry detergent and hair shampoo formulations Personal Care formulators can formulate laundry detergents too with a little know how Never use a laundry detergent as a substitute for hair shampoo !!

References Available Upon Request Contact information: Jeff Easley Sr. Global Performance Improvement Specialist Stepan Company Direct Dial: Fax: