2005 ANNUAL SCIENTIFIC SEMINAR 343 it is expelled from the can to produce the foam. The polymer and emulsifier provide the foam stability. Most commercial mousse foams vary in density, strength, and bloom, but must break down quickly when worked into the hair. The polymers that are typically used in mousse formulas are cationic and provide fixative and conditioning benefits. The cationic resins are substantive to hair, yield good hold, and offer excellent combing and feel in the wet and dry stages. Examples of cationic mousse polymers are Polyquatemium-4, I 0, 11, and 16. Nonionic polymers, including PVP and PVP/V A, can be included for enhanced holding power. In addition, acrylic resins (Acrylates Copolymer) can be blended with the cationic polymers to provide improved hold and humidity resistance. There are a variety of surfactants to choose from when formulating a mousse system, however nonionic emulsifiers will have the widest compatibility range with the other ingredients. Nonionic emulsifier blends of low HLB with high HLB tend to provide the best foam density and foam strength. Hydrocarbon propellants, typically combinations ofisobutane and propane, are used in aerosol mousses to force the concentrate out of the can to form a foam. The hydrocarbon or DME propellants and ethanol total cannot exceed more than 6% VOC in a US mousse formula, which can result in thick, rich foams that are difficult to work with. To combat this issue, Hydrofluorocarbon 152A (non-VOC propellant) may be added with the hydrocarbon propellant to reduce foam density and improve foam breakdown. Styling Gel Gels also provide hold, control, and a textured look to the hair style. These formulations are higher in viscosity and typically contain a thickener to create body, prevent dnpping, and provide texture to the gel product. The current CARB and OTC regulations are 6% VOC for styling gels. A typical gel formulation is listed below in Table I. When formulating a gel product, it is important that the polymer and thickening agent are compatible with each other. There are many thickeners to choose from, with each having specific requirements for pH, viscosity build, clarity, and compatibility with salts, polymers, additives, and alcohol. Different thickeners will also provide different rheology and texture. Anionic polycarboxylate thickeners (i.e., Carbomer) are popular choices due to their shear thinning rheology and buttery texture however, they ca!lnot tolerate high levels of salt and may experience incompatibilities with anionic and cationic ingredients. Therefore, nonionic polymers such as PVP or PVP/V A are typically used as the fixing agents in Carbomer-based gels. Cellulose derivatives (hydroxyethylcellulose), gums (xanthan, hydroxypropyl guar), nonionic synthetics, and acrylic associative thickeners are other examples of thickening agents that can be used in a styling gel formula. These gelling ingredients may need to be neutralized to create the viscosity build. Although PVP copolymers are still commonly used in gel products, newer styling gel fixatives are being offered to provide improved hold and high humidity curl retention performance while still maintaining acceptable gel clarity. These new polymers are based on polyacrylate, methacrylamide, modified xanthan gum, and polyamide chemistries. Since gels are primarily aqueous, they require a preservative to prevent microbial growth. Most gel formulations also need an ultraviolet sunscreen to prevent color, clarity, or viscosity degradation when exposed to light. In addition, a chelating agent is recommended to tie up the salts from other ingredients, which will protect the color, fragrance, and gel integrity of the formula. Table 1: T ical 55% voe Hain ra , 6% VOe Mousse, and 6'1/o voe Gel Formulations Ingredient Aerosol HS Non-Aerosol HS Aero Mousse N/A Mousse Gel Polymer 2-8% 2-12% 0.5-5% 0.5-5% 0.5-5% Neutralizer (if needed) calculated based on polymer, level calculated based on polymer, level Additives 0.1-2% 0.1-2% 0.2-2% 0.2-2% 0.1-1% Ethanol 10-35% :s_55% 0-6% 0-6% Water q.s. q.s. q.s. q.s. q.s. Fragrance 0.1-0.5% 0.1-0.5% 0.1-0.5% 0.1-0.5% 0.1-0.5% Corrosion Inhibitor 0.1-1% Nonionic Surfactant 0.3-2% 0.3-2% 0.5-1% Preservative 0.2-1% 0.2-1% 0.2-1% Thickener 0.25-1% UV Screen 0.1% 0.1% 0.1% Chelating Agent 0.1% Propellant 20-45% 6-10% Total 100% 100% 100% 100% 100%
344 JOURNAL OF COSMETIC SCIENCE PROPERTY AND PERFORMANCE COMPARISON OF HAIR FIXATIVE POLYMERS FOR 55% voe HAIRSPRAY Terry A. Oldfield, Suzanne W. Dobbs and Kab S. Seo Eastman Chemical Company, Kingsport, TN INTRODUCTION New state VOC (volatile organic compound) regulations went into effect January 1, 2005, in states that adopted the Ozone Transport Commission's model rule for consumer products. Delaware, Maryland, New Jersey, New York, Pennsylvania, and the District of Columbia, as well as California, now limit VOCs in hairspray to 55%. A similar rule in Maine takes effect in May 2005. One approach to reducing voes in hairspray is to replace a portion of the ethanol with water. However, if this is done without also changing the hair fixatiye polymer, the result can be larger spray droplets, greater initial curl droop, and slower drying compared to 80% VOC formulations. Typical polymers used in 80% VOC hairsprays are vinyl polymers such as V Ncrotonates/vinyl neodecanoatc copolymer, octylacrylamide/acrylates/butylaminoethyl methacl}fate copolymer, and esters of PYM/MA copolymer. Suppliers of hair fixative polymers ha\'e either modified these existing polymers or developed new ones to accommodate the higher water content of 55% voe formulations. For example, the Yiscosity of ethanol/water solutions of vinyl pol:ymers can be reduced by decreasing the molecular weight of the polymer. In the case of the water-dispersible polyester used in an alcohol-free hairspray, the monomer content was adjusted to accommodate 55% ethanol. When selecting a hair fixative polymer for a 55o/o VOC hairspray, the formulator needs to consider the properties of the polymer and how those properties relate to the desired performance characteristics on the hair. MATERIALS AND METHODS The hair fixative polymers listed in Table 1 were evaluated in ethanol/water aerosol concentrates at 7 7 \\1% (without propellant) or at a concentration of 5.0 \\1% in aerosols with dimethyl ether propellant. The total concentration of VOCs, ethanol (SDA 40-B) plus dimetl1yl ether, in tl1e aerosol was 55%. The polymers requiring neutralization were neutralized with aminomethyl propanol (Af..11'). The purpose of this study was to compare polymer properties without the influence of other ingredients. Therefore, no other additiyes were used in tl1e formulations. The test metl10ds used are as follows. Po(rmer Particle Size and Concentration - Particle size and the concentration of polymer particles in dispersion/solution were determined using the Polymer Laboratories PL-PSDA particle size distribution analyzer. The PL-PSDA operates on the principle of packed column hydrodynamic chromatography (HDe), a technique for separating particles based on their size, eluting in order largest to smallest. Vi. cosity - The Yiscosity of the aerosol concentrates was measured using the Brookfield viscometer. model LVDV-1+. Dry Time -The aerosol formulations were sprayed in a controlled manner on hair tresses and dl}· time was assessed by feeling tl1c tresses as they dried. Dry time was also determined by dynamic mechanical analysis (OMA). The test developed at Eastman Chemical Company monitors changes in the ,iscoclastic properties of a polymer film during dl}·ing in real time. 1 About 0.1 ml of the polymer solution is transferred to a circular trough (0.2 mm deep) and the surface is smoothed with a straight edge. AT-bar mounted on a dynamic rheomcter is lm,ered into the liquid film. The T-bar oscillates at 10 rad/sec while the film dries, measuring complex ,·iscosity (ri*), viscous modulus (G"), and elastic modulus (f f ). T"ck - The tackiness of the aerosol formulations sprayed on hair tresses was assessed at the same time as the tactual assessment of dry time. DMA and other metJ10ds for determining tack arc being evaluated and will be discussed in tl1is presentation. Gloss -The aerosol formulations were sprayed on lacquer-coated Leneta chart paper to form a continuous film and allowed to dl}' overnight. The BYK-Gardner micro-TRI-gloss reflectometer was used to measure gloss of the polymer films at a 60° reflection angle. Curl Retention - Hair tresses of equal weight were washed, dried, hung on a pegboard, and cut to equal length (L)_ The pegboard is marked with graduations to facilitate length measurements. Tresses were tJ1en rewet and curled on 1 /2-in diameter Teflon rods. After drying overnight, each curl was carefully removed from its curling rod and hung back on the pegboard. The original curl length (Lo) of each curl was recorded. Each curl was rotated while being sprayed for 4 seconds, tl1en immediately re-hung on the pegboard. After 10 minutes, curl length (L1) was measured. This length is a measure of the initial curl
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