Drug – bio-affecting and body treating compositions – Preparations characterized by special physical form – Cosmetic – antiperspirant – dentifrice
Reexamination Certificate
2000-09-15
2003-03-04
Dees, Jose′ G. (Department: 1616)
Drug, bio-affecting and body treating compositions
Preparations characterized by special physical form
Cosmetic, antiperspirant, dentifrice
C424S059000, C514S937000, C514S938000
Reexamination Certificate
active
06528070
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to emulsions comprising an emulsification system comprising a mixture of at least one cationic surfactant, at least one anionic surfactant, at least one “bridging surfactant”, an oil and water, along with methods for preparing such emulsions. More specifically, the invention relates to stable, synergistic emulsions of various oils, water, cationic, anionic, and bridging surfactants that are useful in preparing a variety of finished personal care, laundry, and cleaning products. The emulsification system of the instant invention, even when utilized in low levels, is capable allowing for the emulsification of very high levels of oils in water, whereby such emulsions are storage stable over extended periods of time at various temperatures. Additionally, concentrated emulsions of the invention are readily dilutable to very low concentrations, and yet, are also extremely stable phase systems. The instant invention further provides sunscreen emulsions, solid particulate matter suspensions and methods of producing the same. The emulsions of the instant invention are preferably oil-in-water emulsions, but may also be in the form of water-in-oil emulsions.
BACKGROUND OF THE INVENTION
Water-in-oil and oil-in-water emulsions have been employed in a wide variety of applications. Among these are polishes and waxes for hard surfaces of, for example, automobiles, shoes, and furniture. Emulsions are also used as antiperspirants, sunscreens, skin creams and lotions, and hair treatment compositions such as hair conditioners.
Incorporation of increased amounts of oil, and especially silicone oil, leads to difficulty in preparing stable formulations. It is particularly difficult to formulate stable emulsions having in excess of 50% by weight silicone oil. Thus, formulations of systems with oils such as silicones requires the use of an emulsification system capable of providing the requisite emulsion stability.
U.S. Pat. No. 5,188,823 discloses water-in-oil antiperspirant formulations comprising silicone oils, copolyols, phthalamic acids and/or ammonium phthalamates, and aluminum and zirconium antiperspirant salts. Water-in-oil formulations containing at most about 33% cyclomethiones are disclosed having viscosities ranging from about 2,700 to 14,000 cps. The pH of these water-in-oil formulations is from about 3.5 to 4.5. U.S. Pat. No. 5,015,415 teaches conditioning shampoos comprising phthalamic acids and/or ammonium phthalamates and silicone oils. Shampoo formulations are disclosed with no more than 0.50% silicone oil. These formulations are taught to be stable at pH values between 3 and 9.
Canadian Patent Application 2,056,859 discloses hair treatment compositions comprising a water-in-oil emulsion, wherein the water phase constitutes 40-95% by weight of the composition and the oil phase 5-60% by weight of the composition, wherein the oil phase comprises a silicone material having a viscosity of 10
4
to 10
9
mPas at 25° C.
Surfactant mixtures related or used in combination with emulsions are somewhat known. U.S. Pat. No. 5,441,541 (to Colgate-Palmolive) describes the use of anionic and cationic complexes to remove oily soils from fabrics. U.S. Pat. No. 5,607,980 (to Procter & Gamble) describes topical anionic and cationic compositions for application to skin. U.S. Pat. No. 5,622,925 (to Procter & Gamble) discloses heavy duty detergent compositions comprising cationic fabric softeners, fatty acids and anionic surfactants, with optional nonionics, enzymes and detergent builders. U.S. Pat. No. 6,007,802 (to Procter & Gamble) discloses mixed surfactant systems for hair care applications. U.S. Pat. No. 5,939,059 (to Akzo Nobel) discloses 2-in-1 anionic/cationic conditioning shampoos. U.S. Pat. No. 5,997,854 (to Henkel) discloses hair conditioning shampoos comprising a wide variety of components, including emulsification components. U.S. Pat. No. 6,024,952. U.S. Pat. No. 4,931,216 (to Kao) discloses anionic/cationic detergents.
For other mixed surfactant systems related to emulsions, see generally, WO 97/12022 (to Procter & Gamble); WO 97/033164 (to Procter & Gamble); WO 99/58106 (to Witco); JP 62126113; JP 6293620; and JP 2558704.
Generally, anionic-cationic surfactant mixtures are very well known to the art. See generally, U.S. Pat. Nos. 5,441,541, 5,472,455, 5,204,010, 4,790,856, 4,298,480, 3,730,912 (all to The Colgate-Palmolive Company), U.S. Pat. Nos. 5,622,925, 5,607,980, 5,565,145, 4,913,828, 4,659,802, 4,436,653, 4,338,204, 4,333,862, 4,132,680 (all to The Procter & Gamble Co.); also see WO 97/03164, WO 97/12022 and WO 96/37591 (all to The Procter & Gamble Co.), and WO 97/28238 and WO 97/15647 (both to Reckit & Colman, Inc.). See also, U.S. Pat. Nos. 5,610,187 and 4,247,538 (both to Witco Corp.), U.S. Pat. No. 5,344,949 (to Th. Goldschmidt AG), U.S. Pat. Nos. 5,332,854 and 5,324,862 (both to Dai-lchi Kogoyo Seiyaku Co., Ltd.), U.S. Pat. No. 4,273,760 (to National Starch and Chemical), and U.S. Pat. No. 4,264,457 (to DeSoto, Inc.). Mixed surfactant systems have also been disclosed in “
Mixed Surfactant Systems”,
ACS Symposium Series 501, P. M. Holland and D. N. Rubingh (Jun. 17-19, 1991).
Additionally, there have been many studies and symposia on mixed surfactant systems. See, for example, Scamehorn, J. F., ed., “Phenomena in Mixed Surfactant Systems”, ACS Symposium Series 311, Washington, D.C. (1986). The effects of alkyl groups and oxyethylene groups in nonionic surfactants on the surface tension of anionic-nonionic systems have been described. See Abe et al., J. Colloid Interface Sci., 107, p. 503 (1985); Ogino et al., J. Colloid Interface Sci., 107, p. 509 (1985); and Rosen et al., J. Colloid Interface Sci., 95, 443 (1983). Interaction between betaines and cationic surfactants has also been studied. See Zhu et al., J. Colloid Interface Sci., 108, 423 (1985).
Mixed surfactant systems have shown synergistic improvements in surfactant properties compared to the properties of their individual surfactant components. Synergism increases with the degree of charge difference. Thus, the greatest synergistic surfactant property improvements are realized when mixing anionic and cationic surfactants. See Rosen et al. in “Phenomena in Mixed Surfactant Systems” (Scamehorn, J. F., ed.), ACS Symposium Series 311, Washington, D.C. (1986), pp. 144-162; Zhao et al. in “Phenomena in Mixed Surfactant Systems” (Scamehorn, J. F., ed.) ACS Symposium Series 311, Washington, D.C. (1986) pp. 184-198.
In detergent applications, although in principle any surfactant is suitable, in practice only anionic and nonionic surfactants typically are used. Cationic surfactants, especially quaternary ammonium salts, can decrease detergency and enhance soil redeposition when used in heavy-duty liquid detergents. Consequently, there is a general notion that anionic and cationic surfactants cannot be used in the same formula without loss of efficacy. Similar worries regarding potential loss of efficacy exist when contemplating use of cationic surfactants in hair and skin conditioning applications. Thus, anionic-cationic surfactant mixtures have been used only sparingly in the production of consumer cleaning products and personal care products.
Studises on anionic-cationic systems are recent and few compared to studies on other mixed surfactant systems. However, strong synergism has been exhibited by these systems. Surface activity properties, particularly the critical micelle concentration (cmc), surface tension, and microemulsion behavior (Bourrel et al., Tenside Detergents, 21, 311 (1984)), were the most studied properties. For example, the surface activities of mixed aqueous solutions of sodium dihexylsulfosuccinate with dioctyl(hydroxyethyl)methylammonium chloride and sodium dihexylsulfosuccinate with octyl(hydroxyethyl)dimethylammonium chloride were much higher than those of the single surfactants. See Zao, G., Huoxue Xuebo, 43, 705 (1985) (Ch. Chem. Abstracts 103:184033n). The strong synergistic effect on surface pressure for mixed solutions of cationic and anionic sur
Bernhardt Randal J.
Bratescu Daniela T.
Dees Jose′ G.
George Konata M.
McDonnell & Boehnen Hulbert & Berghoff
Stepan Company
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