662 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS EXPERIMENTAL AND RESULTS Deodorant Sprays The three propellant/alcohol systems studied were: System I, 55%* anhydrons ethyl alcohol and 45% Propellant* 12/114 (50:50). System II, 75% anhydrous ethyl alcohol and 25% Propellant 12. System III, 62% anhydrous ethyl alcohol and 38% Propellant 12. Three different valves were used. Each valve had a nylon body with a stem orifice of 0.018 in. and a vapor tap orifice of 0.020 in. The size of the body orifice was varied. The three valves had body orifices of 0.016, 0.020, and 0.025 in., respectively. This yielded body orifice-to- vapor tap orifice ratios of 0.8: 1, 1: 1, and 1.25:1, respectively. All containers were filled to 85% liquid full, by volume, providing the recommended nominal 15% head space. Each container was dis- charged, each day, in two 4-second sprays, separated by a 30-second in- terval, to simulate the application of a personal deodorant. The compo- sition of the liquid phase was analyzed after 25, 50, and 75% of the con- tents were discharged. Procedures similar to those previously described were used (1). The most significant changes occurred after 75% of the prodnct was discharged. These results are shown in Table I for System I. All percentages are by weight, unless otherwise noted. Genetron© ttuorocarbon Propellants 12 and 114, Allied Chemical Corp., Morristown, N.J. Table I Composition of Liquid Phase after Discharging 75% of Product (System I•--Propellant 12/114/Ethyl Alcohol) Valve: Stem: 0.018 in. Vapor tap: 0.020 in. Body orifice: As indicated Body orifice, in. 0. 016 0. 020 0. 025 Wt % Liquid Component Propellant 12 4.5 7.9 11.7 Propellant 114 16.4 18.4 21.0 Ethyl alcohol 79.1 73.7 67.3 Propellant ratio Propellant 12 22 30 37 Propellant 114 78 70 63 "55 %, by wt, anhydrous ethyl alcohol 45 %, by wt, Propellant 12/114 (50' 50).

ORIFICE SIZE AND PROPELLANT/CONCENTRATE RATIO 663 The propellant composition underwent the greatest change with the smallest valve body orifice and the least change with the largest body orifice. As can be seen in the table, the Propellant 12/114 composition went from the original 50:50 ratio to 22:78 with the 0.016-in. body ori- fice, to 30:70 with the 0.020-in. valve body orifice, and to 37:63 with the 0.025-in. body orifice. In other words, propellant fractionation was least when the ratio of valve body orifice to vapor tap orifice was greatest. Similarly, the alcohol content in the total product increased the most with the smallest valve body orifice and least with the largest body orifice. In Systems II and III, where Propellant 12 is used alone with ethyl alcohol, considerable fractionation occurred because of the large differ- ence in boiling points. Propellant 12 boils at --21.6øC, while ethyl alcohol boils at 78øC. In System II, which originally contained 25% Propellant 12, the propellant concentration dropped to 1% with the smallest body orifice, after 75% of the product had been discharged. Changing the ratio of valve body orifice to vapor tap orifice from 0.8:1 to 1:1 netted only a 1% gain in propellant concentration after dispensing 75% of the prod- uct. However, 12% of the propellant remained at 75% empty with the 0.025-in. body valve orifice. Thus, less change occurs in the propel- lant/concentrate ratio with a larger valve body orifice and a larger ratio of valve body orifice to vapor tap orifice. The results of the tests with Systems II and III are shown in Table II Similar results were obtained with System III which contained 38% Propellant 12 in the original product. While the propellant loss was Table II Composition of Liquid Phase after Discharging 75% of Product (Systems II a and IIIb--Propellant 12/Ethyl Alcohol) Valve: Stem: 0.018 in. Vapor tap: 0.020 in. Body orifice: As indicated Body orifice, in. 0. 016 0. 020 0. 025 Wt % Liquid System II Components Propellant 12 1 2 12 Ethyl alcohol 99 98 88 System III Components Propellant 12 16 20 27 Ethyl alcohol 84 80 73 75%, by wt, anhydrous ethyl alcohol 25%, by wt, Propellant 12. 62 %, by wt, anhydrous ethyl alcohol 38 %, by wt, Propellant 12.