Document QgQ83e8v9B0gmnkbVGGk4bdv8

K At) 05 Sol "FREON" products laboratory E. I. da Pont de Nemours & Company TECHNICAL REPORT | Report Number: t i ii | Subject: KSS-4966 Reformulation of "Right Guard" Deodorant j Company: i j i ! B^.: The Gillette Company Boston, Massachusetts R. P* Ayer Date: September 10, 1964 i k f Object: To reformulate "Right Guard Deodorant with a less expensive propellent than the presently used 45# "Freon-12"/ "Freon-114" (57/43)without unfavorably altering the vapor pressure, flammability, spray characteristics and nonchilling (tingling) sensation on the stein according to the following criteria: Vapor pressure 40 psig or less at 70F Flammability Flash point over 100F; flame extension and flashback no longer than "Right Guard" with present valve/actuator combination Spray characteristics - Virtually unchanged Nonchilling (tingling)on skin Determined by placing shaving lather formulated with propellent in question on the upper lip and comparing tingling sensation to that of shaving lather formulated with "Freon-12"/ "Freon-114" (57/43) EID10479 KA005301 2 Conclusions: The submitted concentrate can be formulated with either 45^ "Freon-12 V"Freon-ll4"Ainyl chloride (49/39/12) or 45^ "Freon-12"/" Freon-114"/" Freon-11" SAsobutane (57/27/10/6) and packaged with the presently used valve and actuator at pro pellent cost savings of approximately 3.5^/1b and 7.1tf/lb, respectively, compared to t'Freon-12"/1,Freon-ll4" (57/43), without unfavorably altering the above mentioned criteria. Additional propellent cost savings, might be achieved by one or more of the following: decrease propellent/ concentrate ratio to 40/60, use 5 more "Freon-11" S and 5& less "Freon-114" in the quaternary blend, replace some of the r,Freon-ll4" of the ternary blend with "Freon-ll" S. Further cost reduction will mean forfeiting one or more of the desirable characteristics of the present commercial product (at least with the present valve/actuator combination). Neither the over-all shelf life nor the odor was evaluated for any length of time on these less expensive propellent/present concentrate combinations; however, the odor does not appear objectionable on casual observation and it is known the shelf life is satisfactory with both "Freon-12"/,'Freon-lln S and "Freon-12"/"Freon-114". Therefore, any trouble can be pin pointed quickly to vinyl chloride and isobutane, respectively, and an appropriate "Freon-12"/"Freon-ll4"/"Freon-ll" S blend can still effect some cost reduction. Resul ts: Experimental work included a quick evaluation of "Freon-12", "Freon-121'/vinyl chloride (85/15) and "Freon-12"/ isobutane (95/5) propellents with the submitted concentrate. None are acceptable, because with sufficient propellent to raise the flash point of the aerosol formulation ever 100F, the pressure is higher than 40 pslg and the spray characteristics are not desirable. Considerable evaluation and testing were carried out or. "Freon-12"/"Freon-ll4"/"Freon-ll" S/isobutane .mixtures in order to have a3 much "Freon-11" as possible without Introducing what, in our opinion, would be an undesirable tingling sensation and to have as much lsobutane as possible without adversely affecting the flammability. This was accomplished by choosing the "Freon-12"/'lFreon-ll4r`/leobutane (56/34/10) mixture having a vapor pressure of approximately 50 psig at 70F and introducing E1D10480 3 ^g0053 01 Results: (Continued) "Freon-ll" S at 5> 10 and 15# of the total mixture. Every blend was used to prepare aerosol samples for checkins the vapor pressure at 70F, the flammability, spray characteristics, and the tingling sensation. Once the latter reached an upper limit (greater than 10#), in our opinion, for the particular tingling test.used, the amount of isobutane was reduced until the flash point, within experimental error, reached 100F. All the samples contained 45# propellent with the exception of the shaving lather which contained 10#. The tingling sensation and the flash point are the two criteria with most variance among the various blends tested. For extra certainty In keeping the flash point over 100F, It is recommended the amount of Isobutane In. the blend be at 6 rather than 7#. It is also recommended "Freon-ll" S be used to inhibit the free radical reaction between "Freon-ll" and alcohol. The results are summarized in Table I. Similar experiments, the results of which are summarized in Table II, were carried out with "Freon-12"/ "Freon-ll4"/vinyl chloride mixtures having vapor pressures of approximately 50 pslg at 70F. The amount of vinyl chloride was reduced from 20# of the mixture until the flash point reached 100F. It Is recommended the vinyl chloride be reduced from 13 to 12# of the total to be absolutely certain the flash point is greater than 100F. Comments: Samples for measuring the vapor pressure and determining the flammability were prepared by loading 55.0 g of "Right Guard" concentrate (or anhydrous SDA-40 ethanol) In three-ounce, sideseam funlined) containers and very carefully purging with "Freon-12" before capping with the submitted vapor tap valves and pressure filling 45.0gof the respective propellents. Vapor pressures-were determined on samples thermostatted at 70F for 30 minutes with a prepressurized gage. Because of the change in composition during spraying with a vapor tap valve, separate samples were used for determining the flash point and flame extension/ flashback. Flash point determinations were started when the contents of the aerosols were at -50F. The shaving lathers were prepared by loading 90.0gof shaving lather concentrate In four-ounce, plastic-coated glass bottles before purging, capping with a standard Precision valve and pressure filling lO.Ogof the respective propellents. EID10481 K&005301 4 Results: (Continued) The tingling tests were carried out on samples less than one day old by placing foam from a "Freon-12M/''Freon-ll4" (57/43) sample on one side of the upper lip and foam from the other propellent mixture samples (one at a time) on the other side of the lip and waiting from 2-3 minutes or until some difference or tingling sensation was noticeable. Of the foams tested, only those containing propellent with 15& "Freon-ll" were considered unacceptable and those with 1C$ "Freon-ll" were borderline. Assuming this test is extremely sensitive, blend3 with 15# "Freon-lln S may be satisfactory for the intended end-use. The propellents used in the preparation of the aerosol samples were first prepared, in two-pound cylinders with the exception of "Freon-12"/1'Freon-114" (57/43). In order to conserve concentrate, some of the samples were prepared with anhydrous ethanol. As would be expected, the results of vapor pressure measurements and flammability determinations with either concentrate or alcohol are within experi mental error of one another. The vapor pressures were consistently 40 psig or less, and with commercially cold-filled samples, pressures of 1-2 psig less can be expected. The results of the flammability tests are quite consistent and straightforward. With the exception of flashback in the side position, the propellents suggested for replacement of "Freon-12"/"Freon-114" (57/43) will, when used with a 45/55 propellent to concentrate ratio, give a product which would have a Combustible classification according to the NYCFD flammability regulations for pressurized products Just as the present "Right Guard". This Is assuming the transitory flashback In the Inverted position would be Ignored. Unfortunately, the side-position flashback is not short-lived with any of the pro pellents, including "Freon-12"/"Freon-114" (57/43). Flashback can be eliminated with another vapor tap valve/actuator combination, but it i3 our experience that those which do this have more power ful, less desirable spray characteristics than does "Right Guard" or the experimental samples with which we were comparing it. Worthy of future ccn sideratlon Is the fact that the proposed changes to the ICC pressure regulations would allow formulations with pressures up to 160 psig at 130F to be packaged in sideseam containers. This would Include formulations with straight "Freon-12" and with enough of it (40^-50^) to give flash points over 100F. The spray characteristics would be esthetlcally less desirable but the flame extension/flashbackproblem could doubtlessly be balanced to give a Combustible NYCFD classification for the resulting more powerful sprays. EID10482 :esults: (Continued) r-- D KA005S01 Should odor or some other unforeseen.problem ender either or both Isobutane and vinyl chloride unsuitable for .se with your present concentrate, further effort can -be - directed oward a straight nFreon-12" formulation or a "Freon-1211/"Freon-11411 / Freon-11v: 3 formulation. The latter blend would be the one having pproximately 50 psig vapor pressure at 70F.(so that aerosols ould be 40 or under) and the .maximum amount of r,Preon-ll" S which ill not give an underarm tingling sensation (probably 10$-15$ ased on lip test). Additional effort at reducing the propellent/ oncentrat: ratio to 40/60 vjould also be worthwhile, regardless of he propellent blend, based on the favorable flash.point result one experiment) with ,IFrecn-12,,/nI?reon-ll4n (57/43). The fish oint Is the limiting factor here and with these nonflammable lends the flash point is essentially a function of the alcohol on cent ration,. It should be remembered that although the uaternary blend may sound rather ominous, especially to our lant, the "Freon-ll" S can be added with the concentrate and he propellent supplied as a ternary mixture of "Freon-12M/"?'reon-ll4 sobutane, i.. EID10483 EID10484 zns%*jz?` 7 KA0 05 3 01 Notes for Table I: (l) Phillips Petroleum Company (A-3l) (?) Lip test with 10 propellent in shaving lather* Compared to " Freon-12"/1'Freon-ll4" (57/43) (3) Fall to zero as soon as standpipe liquid exhausted (4) SDA-40 anhydrous alcohol substituted for "Right Guar^" concentrate ((5) Sample consisted of 60$o concentrate, 4o propellent * Stearic acid Coconut fatty acid Triethanolamine Glycerine Water 7.06 Wt 1.72 4.40 2.00 84.82 EID10485 l- EID10486