2005 ANNUAL SCIENTIFIC SEMINAR 339 ► Good Hair Gloss/Shine ► Stiffness or No Excessive Stiffness ► Easy Application on Wet Hair/ No Clumping ► More flexibility or movement of styled hair ► No Sticky Feel ► Quiek Drying ► Good Stability ► Smoothness ► To Control Frizz ► To Define the Curl Polymer Requirements for Styling & Fixing:7 Typically the polymer provides many of the attributes during styling, as well as the holding and texture characteristics. However the total formulation determines the functionality such as ease of application, distribution of polymer, absence from flaking, shine, longevity of hold, restylability, and removability. This will be discussed further in the program by several of the other speakers today. In designing a new styling product there are speci fie polymer attributes that are desired. You may require a product with a particular spreading or distribution characteristic (rheology), in order for it to distribute it through the hair. The degree of tackiness or wetness needs to be optimized so that it is not too tacky or wet. The stiffness, crispness, or slip can also be tailored by choosing a polymer with a specific molecular weight. Typically 500M- l .5MM) MW is a good starting point. Sprayability will also need to be controlled especially for low VOC products where a low MW polymer in the range of (I 0M-200M) may need to be utilized. Or a host of other effects that will require the addition of other additives for the required feel, shine or hold specified by the consumer's need. As stated previously, the product performance and efficacy is rarely a function of only one active ingredient. Polymer Properties That Affect Hold ► Molecular Weight ► Glass Transition Temperature, Tg ► Particle Size of Spray ► Spreadability ► Cohesive/Adhesive Balance ► Hydrophobicity ► Ability to Form Strong "Spot Welds" ► Concentration of Active Polymer There are many polymers to choose from in developing your formulation. The key is to understand the polymer profile characteristics and use conditions to achieve a successful styling and fixative product. Polymer Offerings Prior to voe Reformulation:• NON IONICS (PYP) (VP/VA Copolymers) ANIONICS (Esters of PYM/MA) (Acetates) POL YQUATERNIUMS (Polyquatemium-4, 10, and 11) CATIONICS (Cationic VP Copolymers and terpo\ymers) AMPHOTERICS (Acrylate Copolymers) Polymer Offerings After voe Reformulation' ANIONICS (Low MW Esters of PVM/MA) (Low MW Acetates) (Maleimide Copolymers) CATIONICS (Cationic VP Copolymers and Terpolymers) AMPHOTERICS (Low MW Acrylate Copolymers) POLYESTERS POLYURETHANES ACRYLAMIDE COPOLYMERS POLYVINYLCAPROLACTAMS POL YQU A TERNIUMS (PQ-4, -10, -1 l, -16, -28, -39, - 44, -55) POLYAMIDES RHEOLOGY MODIFIERS: New Product forms have changed the whole styling segment category with respect to thickening agents. Besides thickening the product, rheology modifiers create body, prevent dripping, and provide texture to the gel/cream product. Crystal clear, water white gels are still sought but new products are requiring the need for new thickeners to achieve the desired results i.e. sheer thinning, suspension. Traditional Thickeners: Anionic Polycarboxylates Carbomer Cellulose Derivatives Hydroxyethyl Cellulose Gums Hydroxypropyl Guar Expanded Product Range to Address New Rheology Market Needs: Carbomer Hydroxyethyl Cellulose Hydroxypropyl Guar Acrylates Copolymers Anionic Liquid Dispersion Polymers (LDP's) Sodium Polyacrylates and various carriers Cationic Liquid Dispersion Polymers (LDP's) Polyquatemium -32 (and) Mineral Oil (and) PPG-I Trideceth-6 Polyquatemium-37 (and) Mineral Oil (and) PPG-! Trideceth-6 Polyquatemium-37 (and) Propylene Glycol Dicaprylate/ Dicaprate (and) PPG-l Trideceth-6 Acknowledgement: The author acknowledges Ellen Werner for identifying new product trends for 2004 based on a market search of new styling products introduced in 2004. Rererences 1 2005 Euromonitor International, Styling Agents Segment- Company Data 2 Claire Briney, Hair Care Stays on Too. GCI, December 2004 3 GNPD Mintel International Data Base, Jan 2005 4 Ciba Specialty Chemicals Brochure, Asian Hair Care, 2003 5 2005 Euromonitor International, Styling Agents Segment- Brand Data 6 C. Rocafort and J. Dalla], National SCC CEP Course: Hair Styling & Fixatives, (2005) 7 C. Rocafort and J. Dalla!, Hair and Hair Care, edited by Dale H. Johnson, Marcel Dekker, Inc. NY, l 997, chapter 5. 8 Lochhead, Robert and Fron, William, 1993 "Encyclopedia of Polymers and Thickeners for Cosmetics", Cosmetics & Toiletries, !08:95-!38. '2002 "Encyclopedia of Polymers and Thickeners", Cosmetics & Toiletries, Vol I I 7, No. 12/December 2002.

340 JOURNAL OF COSMETIC SCIENCE KEY PROPERTIES OF HAIR FIXATIVES NECESSARY TO MAKE AND EDUCATED CHOICE Vittoria Signori, Ph.D. BASF Corporation, Ledgewood, NJ In order to formulate an cffecti,·e hair st)·Iing product it is very important to understand the properties of the ingredients used in the formulation, in particular of the fixative ingredients, that, for the most part arc polymers. The following is an outline of some of the properties that should be considered in the choice of the fixative polymer. Basic technical ph,·sical chemical properties of poh·mers: l) Chemical nature, ionic, non-ionic, cationic, anionic arnphotcric. 2) % solids, or acti\-es. Note that for pre-neutralized polymers the weight of the neutralizer is usually included in the \'alue for% solids. 3) Acid rnlue and suggested neutralization level: relevant only to acid containing monomers (e.g.: acrylic copolymers). The following are the neutralization equations provided by different polymer suppliers, slightJy different forms to calculate the amount of ncutraliicr needed in the formulation: N = (X y z :\) / IOON = quantity of neutralizing agent (g) x = quantity of polymer raw material (Kg) y = acid \'alue for the polymer ( mg / g) z = degree of neutralization (no units, 0 z 100) A= factor for each specific neutralizer (no units). A is the ratio between the molecular weight of the neutralizer and the molecular weight of potassium hydroxide (KOH = 56.l) X =(.-\DC D)/E 1000 X = neutralizing agent (g) .\ = acidity of the polymer (millimolcs) B - g of polymer us.:d in the formulation (g) C = molecular weight of neutralizing agent (g/mole) IJ = % of neutralization required hy the polymer (no units, 0 D 1110) E = •• concentration of the neutralization agent used (no units. 0 E 100) (W x Ax 1" 1 Ex sytooo = g ofntulraJizer required W = Weight of polymer in grams (g) A = Acidity of polymer in (meq/g) N = Percentage of desired neutralization (no units, 0 :"/ I 00) E = Equivalent weight ofneulralizer (meq/g) S = Solids content ofpol�mer (no units, 0 S 100) NOTE: The level of neutralization of the polymer will ha\'e an influence on \'arious properties of the polymer, among which water solubility, and ability to be removed from the hair (wash out), .:ompatihility with the formulation medium, particularly in the case of aerosol sprays. In standard hair spray formulations the acidity of the polymer and it's le\':I of neutralization ddermine the pH of the formulations. ➔) Cationic charge, tJ1is property id of importance for cationic polymers, depending on the chemistl')' of the polymer there are preferred methods to report the results, for instance, when the cationic charge is being measured by titration, the result will be reported as equiYalent or milliequi\'alents of titration agent per gram of polymer (or raw material), when the cationic charge is being measured by chemical analysis it may be reported by% nitrogen 5) Certificate of Analysis, it is an excellent idea to always check the Co A of each new raw material that one is thinking of using, this will also alert you to many other information, like, expiration date, level of residual monomers, etc. Succific ,,hnical chemical properties of poh·mers: I) Glass transition temperature (Tg): is the temperature (different for each polymer) below which the polymer becomes hard and brittle, like glass. This property is linked to the effect that temperature and humidity may Jm·e on the style retention ability of the polymer (or the formulation). In a finished formula or in simply a diluted solution of the polymer, curl retention is a very commonly tested property, this test involves styling the hair, usually in curls, exposing it to controlled humidity and temperature, and monitoring the hold, with time, of the initial size and shape of the curL The results are often expressed in tenns of% curl retention and it is a function of the polymer in combination with all the other ingredients of the formulation,