WO2001028502A1 - Stable multiple emulsion composition - Google Patents

Stable multiple emulsion composition Download PDF

Info

Publication number
WO2001028502A1
WO2001028502A1 PCT/EP2000/010378 EP0010378W WO0128502A1 WO 2001028502 A1 WO2001028502 A1 WO 2001028502A1 EP 0010378 W EP0010378 W EP 0010378W WO 0128502 A1 WO0128502 A1 WO 0128502A1
Authority
WO
WIPO (PCT)
Prior art keywords
surfactant
phase
emulsion
oil
aqueous phase
Prior art date
Application number
PCT/EP2000/010378
Other languages
French (fr)
Inventor
Mark Stephen Naser
Tirucherai Varahan Vasudevan
Henri Louis Rosano
Francois Gerard Gandolfo
Kanouni Mouncine
Original Assignee
Unilever Plc
Unilever Nv
Hindustan Lever Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US09/425,717 external-priority patent/US6235298B1/en
Priority claimed from US09/425,366 external-priority patent/US6290943B1/en
Application filed by Unilever Plc, Unilever Nv, Hindustan Lever Limited filed Critical Unilever Plc
Priority to AU77898/00A priority Critical patent/AU7789800A/en
Priority to CA002388161A priority patent/CA2388161A1/en
Priority to JP2001531098A priority patent/JP2003511235A/en
Publication of WO2001028502A1 publication Critical patent/WO2001028502A1/en

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • A61K8/066Multiple emulsions, e.g. water-in-oil-in-water
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/31Hydrocarbons
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • A61K8/345Alcohols containing more than one hydroxy group
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A61K8/442Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof substituted by amido group(s)
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/463Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/892Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a hydroxy group, e.g. dimethiconol
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/10Washing or bathing preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/02Preparations for cleaning the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/06Preparations for styling the hair, e.g. by temporary shaping or colouring
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/30Characterized by the absence of a particular group of ingredients
    • A61K2800/31Anhydrous

Definitions

  • the present invention relates to liquid surfactant compositions, e.g., liquid shower gels or liquid shampoos, comprising multiple emulsions.
  • the invention relates to multiple emulsion compositions which may comprise high levels of surfactants but are nonetheless stable (e.g., microscopically stable) .
  • the compositions microscopically maintain multiple emulsion droplet integrity while, macroscopically, there is little or no phase separation.
  • the invention also relates to methods of stabilizing the multiple emulsion compositions.
  • emulsion systems (broadly defined as systems in which water/oil and oil/water emulsion co-exist) are very valuable because they permit incorporation and enhanced delivery of benefit agents.
  • multiple emulsions have been used for many years, for example, in cosmetic and pharmaceutical areas to deliver cosmetic or pharmacological benefit agents (see for Example, U.S. Patent No. 5,306,498 to Vesperini; or U.S. Patent No. 5,567,426 to Nadaud et al . ) .
  • the level of cleansing surfactant m almost all of the cosmetic and pharmaceutical compositions referred to in the prior art is below 5% by wt . of the compositions. Greater amounts lead to less stability and phase separation.
  • U.S. Patent Nos. 5,656,280 and 5,589,177 (Herb et al . ) and their European equivalents EP 717,978 and EP 715,842 describe the stabilization of multiple emulsions m compositions containing high levels of conditioning surfactant.
  • the stable multiple emulsion composition disclosed therein comprise surfactants (i.e., conditioning surfactants) which must form stabilizing liquid crystals, i.e., lamellar liquid crystals.
  • the compositions described wherein the surfactants formed an isotropic phase (for example, Example 29 at column 29 of U.S. Patent No. 5,589,177 at lines 30-44) were unstable (see column 34, where stability of Example 29 is only 5 minutes) .
  • the surfactant phase of compositions of the present invention is an isotropic surfactant phase, yet the multiple emulsion does not break into a simple emulsion when evaluated at room temperature for at least 2 weeks, preferably greater than 4 weeks, more preferably greater than 8 weeks, when measured at a temperature of about 25°C.
  • compositions comprising isotropic surfactant phases are advantageous over compositions comprising lamellar liquid crystal phase in that they can be formed using a much wider range of surfactants and provide improved foam/lather properties . Accordingly, it is an object of the invention to provide compositions with a surfactant phase which is not limited to lamellar phase.
  • compositions may be stabilised over time (in addition to being microscopically stable as noted) by using specific selection of an external surfactant system in combination with a stabilizing natural gum polymer which forms a gelled external aqueous phase with a relatively high concentration of surfactant.
  • compositions which employ similar technology
  • Patent No. 5,306,498 to Vesperini U.S. Patent No.
  • the surfactant system comprises mixtures of anionic and amphoteric surfactants and levels of surfactant are greater than about 10.5% by wt . of the total composition.
  • the invention further relates to methods of stabilizing the multiple emulsion systems described above.
  • the invention comprises a water-in-oil- in-water ( 1 -O- 2 ) multiple emulsion wherein the water-in- oil (Wi/O) emulsion itself comprises an internal aqueous phase ( i) which contains a solute and optional surfactant; an oil phase 0 (an oil combined with a low HLB emulsifier, e.g., emulsifier with HLB less than 10) surrounding the internal aqueous phase; and a topically active compound which may be in either the aqueous i or in 0.
  • the water-in- oil (Wi/O) emulsion itself comprises an internal aqueous phase ( i) which contains a solute and optional surfactant; an oil phase 0 (an oil combined with a low HLB emulsifier, e.g., emulsifier with HLB less than 10) surrounding the internal aqueous phase; and a topically active compound which may be in either the aqueous i or in
  • the W ⁇ O phase is surrounded by an external aqueous isotropic phase ( 2 ) containing cleansing surfactant, optional topically active compound (which may be the same or different as the first optional topically active compound), and optional solute.
  • cleansing surfactant optional topically active compound (which may be the same or different as the first optional topically active compound)
  • optional solute optional solute will almost always be present in the surfactant or will be formed when adjusting pH. It is critical that the surfactant phase W 2 must not contain an anionic surfactant with an amido group.
  • the oil in the O phase should not comprise more than 50% unsaturated compounds; or should not be a volatile silicone (e.g., a silicone having a viscosity of 10 centistokes or less) .
  • a volatile silicone e.g., a silicone having a viscosity of 10 centistokes or less
  • the invention may be distinguished from the prior art (for example U.S. Patent No. 5,656,280) which requires that the aqueous phase 2 (e.g., external aqueous phase) comprises a surfactant system capable of forming stabilizing liquid crystals.
  • the present application requires that the external aqueous phase be an isotropic phase.
  • the isotropic phase in turn is formed by selection of a specific surfactant system which must not contain an anionic surfactant with an amido group.
  • a lamellar phase is a liquid crystalline phase whereas an isotropic phase is micellar; optically a lamellar phase would show birefringence under a polarized light source while a micellar phase does not exhibit this feature .
  • the invention comprises a W 1 -O-W 2 multiple emulsion composition
  • a W 1 -O-W 2 multiple emulsion composition comprising: (1) about 1% to 99% by wt . of the composition, preferably 2% to 90% by wt . , more preferably 5% to 80% of a i/O emulsion comprising; (a) about 1% to 99% of the emulsion of an internal aqueous phase comprising (i) water; (ii) 0.01 to 30% solute; and (iii) 0 to 30% optional surfactant ; (b) about 0.1% to about 99%, preferably 0.5 to 95%, more preferably 1 to 80% of the emulsion of an oil phase surrounding the internal aqueous phase comprising a non-volatile silicone compound, a volatile hydrocarbon compound, a non-volatile hydrocarbon compound or a mixture thereof; (c) about 0.1 to 20%, preferably 1 to 15%, more preferably 1.5 to 15% by wt
  • a surfactant emulsifier selected from a silicon-free surfactant or surfactant blend having an HLB value of about ten or less, an oil soluble silicon based surfactant, an oil -soluble polymeric surfactant and mixtures thereof;
  • a topically effective amount e.g., 0.01 to 40%, preferably 0.05 to 15% by wt .
  • a first topically active compound which may be found in either aqueous phase (a) and/or oil phase (b) ;
  • composition (2) about 1 to 99% by wt . , preferably 20 to 95% by wt . of an external isotropic aqueous phase 2 comprising non-amido anionic and/or other surfactants.
  • the composition contains non-amido anionic and amphoteric surfactants, wherein the ratio of first surfactant (preferably anionic) to amphoteric is 100:1 to 1:100.
  • the composition optionally contains a second topically effective compound, typically 0-40% by wt . of the external phase to perform a function identical to, similar to or different from the first topically active compound, and optional solute.
  • the surfactant will typically comprise about 2-80% of the aqueous phase .
  • the W 1 -O-W 2 multiple emulsion compositions are stable (e.g., typically they will not break down into a simple emulsion at room temperature for at least two weeks) and they exhibit exceptional aesthetic and functional properties.
  • the W ⁇ -0- 2 multiple emulsion compositions are liquids or creams, and are capable of effectively delivering one or more topically active compounds to the skin or hair from a single composition.
  • this embodiment relates to the selection of natural gum polymers and surfactant (s) or combinations of surfactants which form a gelled external phase for the multiple emulsions described above.
  • the invention therefore, further comprises a W 1 -O-W 2 multiple emulsion wherein the ⁇ O phase, in addition to being surrounded by an external aqueous isotropic phase 2 , an optional topically active compound and an optional solute, is also surrounded by a stabilizing natural gum polymer.
  • the natural gum stabilizer and the selected surfactant (s) form a gel.
  • the surfactant phase 2 must not contain an anionic surfactant with an amido group.
  • the 2 surfactant phase must be isotropic. The isotropic phase in turn is formed by selection of a specific surfactant system which must not contain an anionic sufactant with an amido group.
  • the oil in the 0 phase (e.g., light mineral oil, hexadecane, octyl palmitate) should preferably not comprise (1) more than 50% unsaturated compounds; or (2) should not be a volatile silicone (e.g., a silicone having viscosity of 10 centistokes or less) .
  • a volatile silicone e.g., a silicone having viscosity of 10 centistokes or less
  • the invention further comprises a 1 -O- 2 multiple emulsion composition comprising:
  • the composition contains all non-amido anionic or all amphoteric surfactant, or combinations of the two in which 60% by weight or greater is the anionic surfactant.
  • the surfactant typically comprises about 2-80% of the aqueous phase and 0.01 to 10% of a stabilizing natural gum polymer.
  • the composition optionally contains a second topically effective compound, typically 0-40% by wt . of the external phase to perform a function identical to, similar to or different from the first topically active compound and optional solute. It is preferred that in systems where the external surfactant W2 is comprised entirely of, or contains a majority of, anionic surfactant, that a nonionic gum polymer is used. Conversely, in systems where the external surfactant 2 is comprised entirely of or contains a majority of amphoteric surfactant, it is preferred that an anionic gum polymer is used.
  • the W 1 -O-W 2 multiple emulsion compositions are physically stable (e.g., typically they will not phase separate at room temperature for at least 45 days and exhibit exceptional aesthetic and functional properties.
  • the W 1 -O-W 2 multiple emulsion compositions are liquids or creams, and are capable of effectively delivering one or more topically active compounds to the skin or hair from a single composition.
  • Figure 1 relating to a first embodiment of invention is a schematic drawing wherein Figure 1A shows a stable multiple emulsion in which the W ⁇ /0 phase is surrounded by the W 2 phase and Figure IB shows a multiple emulsion which has broken down into a simple 0/( ⁇ + 2 ) emulsion.
  • Figures 2 and 3 relating to a second embodiment of the invention both show a plot of viscosity vs Haake RV06 spindle speed.
  • an anionic natural gum example carrageenan
  • an amphoteric surfactant example cocamidopropyl betaine
  • Figure 3 it is clear that the addition of 1% by weight of a nonionic natural gum (example locust bean) to an anionic surfactant (example sodium laureth sulfate) yields a gelled external 2 phase.
  • the present invention relates to ⁇ O- 2 multiple emulsion compositions comprising:
  • a topically active agent may be present in W phase, 0 phase or both;
  • phase preferably comprises anionic, amphoteric, optional second topically effective compound, and solute.
  • the external aqueous phase W2 (1 to 99% of total emulsion) differs from the art in that it is an isotropic, aqueous surfactant phase rather than a lamellar phase.
  • These compositions are able to comprise relatively large amounts of surfactants (i.e., 10.5% by wt . or greater, preferably 11% -75%, more preferably 12% to 60%, more preferably 13% to 60%, more preferably 15% to 60%, more preferably 16% to 55%, more preferably 17 to 50% by wt . of the composition) while the integrity of the multiple emulsion still remains.
  • surfactant system and oil are specifically selected as described herein, such multiple emulsion compositions will generally break very rapidly into simple emulsion (see Figure 1) .
  • the invention relates to W -0-W 2 multiple emulsions where the integrity of the multiple emulsion droplet is maintained and the composition does not phase separate.
  • These formulations comprise:
  • Wi/O emulsion comprising about 1% to 99% of (containing water, solute and optional surfactant), and 0.5 to 99% of 0 phase (containing oil compound and low HLB emulsifier) .
  • a topically active agent may be present in W-* . phase, 0 phase or both;
  • an external aqueous phase comprising non-amido anionic and/or amphoteric surfactant, a stabilizing natural gum polymer, an optional second topically effective compound, and solute .
  • the external aqueous phase W2 contains a high concentration (i.e., 15% by wt . or greater, preferably 16% or greater, preferably 17 to 75%, more preferably 20 to 70%, more preferably 22% to 60%, more preferably 25 to 50% by wt . of the composition) of surfactant which is isotropic. It is essential that the natural gum stabilizer and the selected surfactant (s) form a gel.
  • the W ⁇ /0 emulsion comprises an internal aqueous phase with water, solute and optional surfactant, and an oil phase 0.
  • the water, solute and first topically-active compound comprise the internal aqueous phase of the W ⁇ /0 emulsion although the active compound may also be in the oil phase if oil compatible. That is, the i phase comprises droplets containing water, solute and possibly a first topically-active compound.
  • droplets containing water, solute and a first topically-active compound (Wx) may have a diameter ranging from about 0.01 to about 75 and may be enveloped by a membrane or film comprising the oil phase.
  • the contents of the internal aqueous phase (Wx) therefore do not contact the external aqueous phase (W 2 ) of the W ⁇ -0- 2 multiple emulsion.
  • the primary W ⁇ /0 emulsion is present in a W ⁇ -0-W 2 multiple emulsion composition in an amount of about 1% to about 99%, preferably 2% to 90%, more preferably about 5% to about 80%, by weight of the multiple emulsion composition.
  • the primary W ⁇ /0 emulsion is present in an amount of about 10% to about 80%.
  • the (WI) internal aqueous phase comprises about 1% to about 99% by weight of the emulsion, an oil phase separates the internal aqueous phase (Wx) of the emulsion from the external aqueous phase (W 2 ) .
  • the internal aqueous phase (Wx) of the present W ⁇ -0-W 2 multiple emulsion compositions generally comprises water, solute and an optional first topically-active compound (which may also be found in the oil phase alone or in both) .
  • the internal aqueous phase may further comprise additional topically-active compounds and/or optional water soluble compounds capable of providing a desired aesthetic or functional effect, such as a fragrance.
  • the aqueous phase (Wx) comprises about 1% to about 99%, and preferably about 10% to about 95%, more preferably abut 25% to about 95% by weight of the W ⁇ /0 emulsion.
  • topically active compounds may be incorporated into the W ⁇ /0 emulsion as the first topically active compound. If found in the Wx phase, the topically active compounds are water soluble or water dispersible and include both cosmetic and other compounds that act upon contact with the skin or hair.
  • the first topically active compound is present in a sufficient amount to perform its intended function, typically in an amount of about 0.01% to about 40% by weight, preferably 0.05 to 15% of the W ⁇ O emulsion.
  • the first topically active compound typically remains on the skin or hair after application, as opposed to being rinsed from the skin or hair. However, in some cases the first topically active compounds are designed to be rinsed from the skin or hair after the compound has performed its intended function.
  • the first topically active compound may be incorporated into the aqueous phase or into the oil phase of the primary emulsion, or both. Whether a particular first topically active compound is incorporated into the aqueous phase or the oil phase of the primary emulsion is related to the solubility of the topically active composition in water.
  • the first topically active compound is water soluble and is incorporated into the internal W x aqueous phase. However, a more hydrophobic agent may be used in the oil phase.
  • water soluble means water soluble or water dispersible.
  • a water soluble compound has a water solubility of at least 0.1 g (grams) per 100 ml (milliliters) of water and forms a true solution.
  • a water soluble compound can be inherently water soluble or can be made water soluble by the addition of a solubilizing compound, such as a coupling agent, a co-surfactant, or a solvent.
  • a water dispersible compound remains dispersed in water for at least the time period necessary to manufacture the primary W ⁇ /0 emulsion, i.e., at least about one hour.
  • topically active compound may be incorporated into the external aqueous phase W 2 to achieve enhanced efficacy.
  • the topically active compound therefore can be one of, or a combination of, a cosmetic compound, a medicinally active compound or any other compound that is useful upon topical application to the skin or hair.
  • Such topically active compounds include, but are not limited to, hair and skin conditioners, hair and skin cleansers, hair fixatives, hair dyes, hair growth promoters, deodorants, skin care compounds, permanent wave compounds, hair relaxers, hair straighteners, antibacterial compounds, antifungal compounds, anti-inflammatory compounds, topical anaesthetics, sunscreens and other cosmetic and medicinal topically effective compounds.
  • the topically active compound comprises a water soluble hair conditioner, such as a quaternary ammonium compound.
  • a water soluble hair conditioner such as a quaternary ammonium compound.
  • Quaternary ammonium compounds are substantive to the hair and are excellent hair conditioners, but are well known to be incompatible with anionic surfactants and anionic dyes. Therefore, quaternary ammonium compounds are generally not a component of shampoo conditioner compositions or anionic dye-based compositions, but are applied to the hair from a separate conditioning composition.
  • Water soluble quaternary ammonium compounds suitable for the purposes of the present application have the general structural formula:
  • Rx is an alkyl group containing from about 8 to about 18 carbon atoms
  • R 2 is selected from an alkyl group containing from about 8 to about 18 carbon atoms, a hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group and a hydroxyethyl group
  • R 3 is selected from a benzyl group, a hydrogen atom, an ethyl group, a methyl group, a hydroxymethyl group and a hydroxyethyl group
  • R 4 is selected from a hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group and a hydroxyethyl group
  • X is an anion.
  • the quaternary nitrogen of the water soluble quaternary ammonium compound also can be a component of a heterocyclic nitrogen containing moiety, such as morpholine or pyridine .
  • the anion of the quaternary ammonium compound can be any common anion, such as chloride, methosulfate, ethosulfate, nitrate, bromide tosylate, acetate, or phosphate .
  • the water soluble quaternary ammonium compounds may have one or two long chain alkyl groups containing from about 8 to about 18 carbon atoms.
  • the long chain alkyl groups can also include, in addition to, or in replacement of, carbon and hydrogen atoms, either linkages or similar water solubilizing linkages.
  • the remaining two or three substituents of the quaternary nitrogen of the quaternary ammonium compound can be hydrogen; or benzyl, or short chain alkyl or hydroxyalkyl groups, such as methyl, ethyl, hydroxymethyl or hydroxyethyl groups; or combinations thereof, either of the same or different identity.
  • Exemplary water soluble quaternary ammonium compounds include, but are not limited to lautrimonium chloride Quaternium-16 ; lauralkonium chloride; olealkonium chloride dilauryldimonium chloride; cetalkonium chloride dicetyldimonium chloride; laurylpyridinium chloride; cetylpyridinium chloride; soyatrimonium chloride; Polyquaternium-6 ; Polyquaternium-7 ; guarhydroxypropyltrimonium chloride; Polyquaternium-11 ; Polyquaternium-5; Polyquaternium-10 ; Polyquaternium-24 ; cetrimonium chloride; Quaternium-24 ; mytrimonium chloride; PEG-2 cocomonium chloride; PEG-2 cocoyl quaternium-4; PEG-15 cocoyl quaternium-4; PEG-2 stearyl quaternium-4; PEG-2 oleyl quaternium-4; and PEG 15 olelyl quaternium-4
  • CTFA Cosmetic Ingredient Dictionary 4th Ed., 1991, hereinafter referred to as the CTFA Dictionary.
  • CTFA Dictionary Other water soluble quaternary ammonium compounds are listed in the CTFA Cosmetic Ingredient Handbook, 1st Ed. , 1988 (hereinafter the CTFA Handbook) at pages 40-42, incorporated herein by reference.
  • water soluble hair conditioners are also suitable as the first topically active compound.
  • Such hair conditioners include, but. are not limited to, fatty amine salts, ethoxylated fatty amine salts, dimethicone copolyols, protonated polyethylenimines, protonated ethoxylated polyethylenimines, soluble animal collagen, lauramine oxide, cationic polymers, numerous other water soluble hair conditioners listed in the CTFA Handbook at page 71-73,
  • a skin conditioner can be used as the first topically active compound.
  • Skin conditioning agents include, but are not limited to, humectants, such as fructose, glucose, glycerin, propylene glycol, glycereth-26, mannitol and urea; pyrrolidone carboxylic acid; hydrolyzed lecithin; coco-betaine; cysteing hydrochloride; glutamine; PPG-15; sodium gluconate; potassium aspartate; olelyl betaine, thiamine hydroxychloride; sodium laureth sulfate; sodium hyaluronate; hydrolyzed proteins; hydrolyzed keratin; amino acids; amine oxides; water soluble derivatives of vitamins A, E and D; amino functional silicones; ethoxylated glycerin; alpha- hydroxy acids and salts thereof; water soluble fatty oil derivatives, such as PEG-24 hydrogenated lanolin, almond oil, grape
  • the first topically active compound may also be a hair fixative or film former that imparts style retention properties to hair, i.e., sets the hair.
  • the hair fixative typically is a homopolymer, a copolymer, or a terpolymer.
  • the polymers can be nonionic, amphoteric, anionic or cationic.
  • hair fixatives include, but are not limited to, an acrylamide copolymer; an acrylamide/sodium acrylate copolymer; a polystyrene sulfonate; a polyethylene oxide; a water dispersible polyester; a cationic cellulose; an acrylate/ammoniummethacrylate copolymer; an aminoethylacrylate phosphate/acrylate copolymer; a polyacrylamide; Polyquaternium-1 ; Polyquaternium-2 Polyquaternium-4; Polyquaternium-4 ; Polyquaternium-5 Polyquaternium-7 ; Polyquaternium-8 ; Polyquaternium-9 Polyquaternium-10 Polyquaternium-11 ; Polyquaternium-12 ; Polyquaternium-13 Polyquaternium-14 ; Polyquaternium-15 ; Polyquaternium-16 Polyquaternium-28 ; a PVP
  • polyvinylpyrrolidone polyvinylpyrrolidone
  • a PVP/ dimethylaminoethylmethacrylate copolymer a PVP/ethyl methacrylate/methacrylic acid copolymer
  • a carboxylated polyvinyl acetate vinyl/caprolactam/PVP/dimethylaminoethyl methacrylate copolymer (GAFFIX VC713)
  • GFFIX VC713 a PVP/vinyl acetate copolymer
  • a sodium acrylate/ vinyl alcohol copolymer sodium carrageenan
  • a vinyl acetate/crotonic acid copolymer numerous other water soluble hair fixatives listed in the
  • the first topically active compound may also be a water soluble hair dye, such as, but not limited to, m-aminophenol hydrochloride, p-aminophenol sulfate, 2 , 3-diaminophenol hydrochloride, 1 , 5-naphthalenediol , phenylenediamine hydrochloride, sodium picramate, water soluble cationic dyes, water soluble anionic dyes, water soluble FD&C dyes, such as Blue No. 1, Blue No. 2, Red No. 3, Red No. 4, or Red No. 40, water soluble D&C dyes, such as Yellow No. 10, Red No. 22 or Red No. 28, and pyrogallol . Numerous other hair dyes are listed in the CTFA Handbook, pages 70-71, incorporated herein by reference.
  • the first topically active compound may also be an antioxidant, such as ascorbic acid or erythorbic acid; or a fluorescent whitening agent or optical brightener, such as a distyrylbiphenyl derivative, stilbene or a stilbene derivative, a pyralozine derivative or a coumarin derivative.
  • a self-tanning compound such as dihydroxy acetone, or a hair growth promoter, or a hair bleaching agent, such as perborate or a persulfate salt, can be the first topically active compound.
  • the first topically active compound can also be a deodorant compound, such as an astringent salt or a bioactive compound.
  • the astringent salts include organic and inorganic salts of aluminum, zirconium, zinc, and mixtures thereof.
  • the anion of the astringent salt can be, for example, sulfate, chloride, chlorohydroxide, alum, formate, lactate, benzyl sulfonate orphenyl sulfonate.
  • Exemplary classes of antiperspirant astringent salts include aluminum halides, aluminum hydroxyhalides, zirconyl oxyhalides, zirconyl hydroxyhalides, and mixtures thereof.
  • Exemplary aluminum salts include aluminum chloride and the aluminum hydroxyhalides having the general formula
  • AI 2 (OH) x Q y XH 2 ⁇ wherein Q is chlorine, bromine or iodine; x is about 2 to about 5; x+y is about 6, wherein x and y are not necessarily integers; and X is about 1 to about 6.
  • Exemplary zirconium compounds include zirconium oxy salts and zirconium hydroxy salts, also referred to as zirconyl salts and zirconyl hydroxy salts, and represented by the general empirical formula ZrO (OH) 2 -nz ⁇ z wherein z varies from about 0.9 to about 2 and is not necessarily an integer; n is the valence of L; 2-nz is greater than or equal to 0 ; and L is selected from halides, nitrate, sulfamate, sulfate, and mixtures thereof.
  • Exemplary deodorant compounds therefore include, but are not limited to, aluminum bromohydrate, potassium alum, sodium aluminum chlorihydroxy lactate, aluminum sulfate, aluminum chlorohydrate, aluminum-zirconium tetrachlorohydrate, an aluminum-zirconium polychlorohydrate complexed with glycine, aluminum-zirconium trichlorohydrate, aluminum-zirconium octachlorohydrate, aluminum sesquichlorohydrate, aluminum sesquichlorohydrex PG, aluminum chlorohydrex PEG, aluminum zirconium octachlorohydrex glycine complex, aluminum zirconium pentachlorohydrex glycine complex, aluminum zirconium tetrachlorohydrex glycine complex, aluminum zirconium trichlorohydrex glycine complex, aluminum chlorohydrex PG, zirconium chlorohydrate, aluminum dichlorohydrate, aluminum dichlorohydrex PEG, aluminum dichlorohydrex PG, aluminum
  • the deodorant compound can be a bacteriostatic quaternary ammonium compound, such as, for example, cetyl trimethyl ammonium bromide, cetyl pyridinium chloride, benzethonium chloride, diisobutylbenzoxyethoxyethyl-dimethylbenzyl ammonium chloride, sodium N-lauryl sarcosine, sodium N-polymethyl sarcosine, lauroyl sarcosine, N-myristolyl glycine, potassium N-lauroyl sarcosine, and stearyl trimethyl ammonium chloride; or a bioactive compound; or a carbonate or bicarbonate salt, such as, for example, the alkali metal carbonates and bicarbonates, and the ammonium and tetraalkylammonium carbonates and bicarbonates .
  • a bioactive compound or a carbonate or bicarbonate salt, such as, for example, the alkali metal carbonates
  • compositions can be included in the primary emulsion as the first topically active compound in an amount sufficient to perform their intended function.
  • sunscreen compounds such as benzophenone-4, trihydroxycinnamic acid and salts, tannic acid, uric acid, quinine salts dihydroxy naphtholic acid; an anthranilate, diethanolamine methoxycinnamate, p- aminobenzoic acid, phenylbenzimidazole sulfonic acid, PEG-25 p-aminobenzoic acid or triethanolamine salicylate may be incorporated into the internal aqueous phase.
  • sunscreen compounds such as dioxybenzone , ethyl 4-
  • topically active drugs such as antifungal compounds, antibacterial compounds; anti-inflammatory compounds; topical anaesthetics; skin rash, skin disease and dermatitis medications; and anti-itch and irritation reducing compounds may be included in the compositions of the present invention.
  • analgesics such as benzocaine, dyclonine hydrochloride, aloe vera and the like; anaesthetics such as butamben picrate, lidocaine hydrochloride, xylocaine and the like; antibacterials and antiseptics, such as povidone-iodine, polymyxin sulfate- bacitracin, zinc-neomycin sulfate-hydrocortisone, chloramphenicol, methylbenzethonium chloride, and erythromycin and the like; antiparastitics, such as lindane; deodorants, such as chlorophyllin copper complex, aluminum chloride, aluminum chloride hexahydrate, and methylbenzethonium chloride; essentially all dermatologicals, such as acne preparations, such as benzoyl peroxide, erythromycinbenzoyl peroxide, clindamycin phosphate, 5, 7-dichloro-8-hydroxyquinoline,
  • Remington ' s (hereinafter Remington ' s) , incorporated herein by reference.
  • first topically active compound is designed to remain on the skin or hair to perform its intended function.
  • a first topically active compound that is rinsed from the skin or hair can be incorporated into the internal aqueous W x phase of the primary emulsion.
  • a W ⁇ -0-W 2 multiple emulsion composition designed as a permanent wave composition can incorporate a reducing agent into the external aqueous phase as the second topically active compound.
  • the external aqueous phase is rinsed from the hair leaving droplets of the primary emulsion on the hair.
  • the primary emulsion has incorporated therein an oxidizing agent as the first topically active compound.
  • the oil phase and preferably a volatile oil phase, evaporates from the primary emulsion, the oxidizing agent is released to neutralize the hair and any reducing agent remaining on the hair. Excess oxidizing agent can then be rinsed from the hair in a second rinsing step.
  • Exemplary, but non-limiting, oxidizing agents used as the first topically active compound are ammonium persulfate, hydrogen peroxide, potassium bromate, potassium chromate, potassium persulfate, sodium bromate, sodium carbonate, peroxide, sodium iodate, sodium perborate, sodium persulfate, urea peroxide, and mixtures thereof.
  • An oxidizing agent may also be the second topically active compound when the first topically active compound is a hair conditioner.
  • the second topically active compound may be a bleaching agent (i.e., an oxidizing agent) and the first topically active compound may be a hair dye.
  • the topically active compound should not be cationic in nature, particularly if anionic surfactants are used.
  • Sufficient water is present in the aqueous phase such that the aqueous phase comprises about 1% to about 99% by weight of the W ⁇ O.
  • Total water present in the W ⁇ -0- 2 multiple emulsion composition is about 30% to about 99.9%, and typically about 40% to about 95%, by weight of the composition.
  • the internal aqueous phase must also include oil -insoluble solute (s) .
  • the solutes are introduced to balance osmotic pressure.
  • solutes which may be added are organic or inorganic salts such as alkali metal chlorides, sulfates, nitrates, benzoates and acetates and sugars and sugar derivatives, for example glucose and sucrose.
  • Solute when added to the internal aqueous phase, comprises 0.01 to 30% by wt . , preferably 0.1 to 20%, most preferably 0.5 to 15%.
  • surfactant may be any of the surfactants discussed in connection with the W 2 phase below.
  • the internal aqueous phase can also include optional ingredients traditionally included in topically applied compositions. These optional ingredients include, but are not limited to, dyes, fragrances, preservatives, antioxidants, detackifying agents, and similar types of compounds. The optional ingredients are included in the internal aqueous phase of the primary emulsion in an amount sufficient to perform their intended function. 0 Phase
  • the primary W x /0 emulsion also comprises about 0.5% to about 99%, preferably about 0.75% to about 80%, and most preferably about 1% to about 70%, by weight of the emulsion of an oil phase.
  • the oil phase is comprised of an oil and a low HLB surfactant.
  • the oil phase encapsulates the internal aqueous Wi phase of the primary emulsion to form droplets of about 0.1 to about l,000 ⁇ , preferably about 1 to about 500 ⁇ , in diameter.
  • the oil phase therefore provides a barrier between the internal aqueous phase of the primary emulsion and the external aqueous phase of the W -0- 2 multiple emulsion composition.
  • the oil phase provides a sufficient barrier even though the oil phase constitutes as little as 0.5% by weight of the W ⁇ O emulsion.
  • the oil may be volatile (except for silicone) or nonvolatile.
  • a volatile oil may comprise a volatile hydrocarbon oil which evaporates during the process of drying skin or hair, and thereby releases the internal aqueous x phase, which includes the first topically active compound to contact the skin or hair.
  • This oil preferably should contain no volatile silicone since volatile silicones tend to destabilize the multiple emulsion.
  • the oil may comprise a combination of a volatile oil (except for silicone) and a nonvolatile oil.
  • an oil can be designed to evaporate at a pre-selected temperature and provide a controlled release of the first topically active compound at the pre-selected temperature. Pre-selected temperatures are those encountered during normal hair drying, provided by a hair dryer, or provided by a curling iron.
  • the oil may also include a water insoluble topically active compound in a sufficient amount to impart a particular functional or aesthetic effect (e.g., emolliency) , as long as the topically active compound does not adversely affect the W ⁇ -0- 2 multiple emulsion composition (e.g., does not impart emulsion instability).
  • a particular functional or aesthetic effect e.g., emolliency
  • the topically active compound does not adversely affect the W ⁇ -0- 2 multiple emulsion composition (e.g., does not impart emulsion instability).
  • the oil can incorporate a topically active compound
  • the topically active compound preferably is incorporated into the internal aqueous phase .
  • the volatile oil preferably comprises a volatile hydrocarbon compound, such as a hydrocarbon having about 10 to about 30 carbon atoms, that has sufficient volatility to slowly volatilize from the skin or hair after application of the W ⁇ -0-W 2 multiple emulsion composition to the skin or hair and subsequent rinsing.
  • a volatile hydrocarbon compound is an aliphatic hydrocarbon having about 12 to about 24 carbon atoms, and having a boiling point of about 100°C to about 250°C.
  • the volatile hydrocarbon compounds perform the same function and provide essentially the same benefits as the volatile silicone compounds.
  • Volatile hydrocarbon compounds incorporated into the primary emulsion include, for example, isododecane and isohexadecane, i.e., PERMETHYL 99A, PERMETHYL 101A and PERMETHYL 102A, available from Presperse, Inc., South Plainfield, N.J.
  • Other exemplary volatile hydrocarbon compounds are depicted in general structural formula (I) , wherein m ranges from 2 to 5.
  • ISOPAR M a C ⁇ 3 -C ⁇ 4 isoparaffin available from Exxon Chemical Co.
  • the volatile hydrocarbon is less than 50% unsaturated.
  • the oil may also be a nonvolatile oil.
  • the nonvolatile oil comprises a nonvolatile silicone compound, a nonvolatile hydrocarbon, or mixtures thereof.
  • the nonvolatile oil comprises compounds which contain less than 50% unsaturation.
  • the nonvolatile oil phase does not evaporate from the skin or hair.
  • the first topically active compound therefore is released by rubbing the skin or hair to rupture the W ⁇ /0 emulsion.
  • a nonvolatile oil has a boiling point at atmospheric pressure of greater than about 250°C.
  • Exemplary nonvolatile silicone compounds include a polyalkyl siloxane, a polyaryl siloxane or a polyalkylaryl siloxane. Mixtures of these nonvolatile silicone compounds are also useful.
  • the nonvolatile silicones are nonfunctional siloxanes or siloxane mixtures having a viscosity of about 10 to about 600,000 cs, and typically about 350 to about 10,000 cs, at 25°C.
  • the so-called "rigid silicones", as described in U.S. Patent No. 4,902,499, (herein incorporated by reference), having a viscosity above 600,000 cs at 20°C, and a weight average molecular weight of at least about 500,000, are also useful in compositions of the present invention.
  • a phenyltrimethicone is also useful as a nonvolatile silicone compound.
  • the nonvolatile silicone compound is a nonvolatile polydimethylsiloxane compound, such as a mixture, in about a 2:1 weight ratio, of a low molecular weight polydimethylsiloxane fluid and a higher molecular weight polydimethylsiloxane gum.
  • Preferred silicone gums include linear and branched polydimethylsiloxanes of the general formula:
  • n is a number from about 2,000 to about 15,000, and preferably from about 2,000 to about 7,000.
  • Silicone gums useful in compositions of the present invention are available from a variety of commercial sources, including General Electric Company, Waterford, N.Y. and Dow Corning Corp., Midland, Michigan.
  • the nonvolatile oil may also comprise a nonvolatile hydrocarbon compound, such as mineral oil.
  • Other exemplary nonvolatile hydrocarbon compounds that may be used include, but are not limited to, a branched 1-decene oligomer, such as 1-decene dimer or a polydecene.
  • the oil may also further optionally comprise (1) an oil, such as jojoba oil, wheat germ oil or purcellin oil; or (2) a water insoluble emollient, such as, for example, an ester having at least about 10 carbon atoms, preferably about 10 to about 32 carbon atoms.
  • an oil such as jojoba oil, wheat germ oil or purcellin oil
  • a water insoluble emollient such as, for example, an ester having at least about 10 carbon atoms, preferably about 10 to about 32 carbon atoms.
  • Suitable esters include those comprising an aliphatic alcohol having about eight to about twenty carbon atoms and an aliphatic or aromatic carboxylic acid including from two to about twelve carbon atoms, or conversely, an aliphatic alcohol having two to about twelve carbon atoms with an aliphatic or aromatic carboxylic acid including about eight to about twenty carbon atoms.
  • the ester is either straight chained or branched.
  • the ester has a molecular wt . of less than about 500.
  • Suitable esters therefore include, for example, but are not limited to:
  • aliphatic monohydric alcohol esters for example: myristyl propionate, isopropyl isostearate, isopropyl myristate, isopropyl palmitate, cetyl acetate, cetyl propionate, cetyl stearate, isodecyl neopentanotate, cetyl octanoate, isocetyl stearate;
  • aliphatic polyhydric alcohol esters for example: propylene glycol dipelargonate;
  • aliphatic esters of aromatic acids for example: 12 -C 15 alcohol esters of benzoic acid, octyl salicylate, sucrose benzoate, and dioctyl phthalate.
  • the 0 phase of the present invention also includes about 0.1% to about 30%, and preferably about 1% to about 15% of the weight of the oil of a low HLB emulsifier.
  • the low HLB emulsifier may comprise a silicon-free surfactant, or a blend of silicon- free surfactants, having an HLB value of about less than 10 (i.e., an HLB value of about 0.1 to about less than 10), an oil-soluble silicon- based surfactant, an oil-soluble polymeric surfactant, or mixtures thereof.
  • the silicon-free surfactant or surfactant blend has an HLB value of about 1 to about 7, more preferably about 3 to about 6.
  • oil-soluble as used herein means a compound having a solubility of at least 0.1 g per 100 ml of oil phase to form a true solution.
  • the HLB value of a particular surfactant can be estimated by dividing the weight percent of oxyethylene in the surfactant by five (for surfactants including only ethoxy moieties) .
  • the HLB value of a surfactant blend can be estimated by the following formula:
  • HLB (wt.% A) (HLB A ) + (wt . % B) (HLB B ) ,
  • wt . % A and wt . % B are the weight percent of surfactants A and B in the silicon-free surfactant blend
  • HLB A and HLB ⁇ are the HLB values for surfactants A and B, respectively.
  • Suitable Low HLB surfactants may be a silicone-based surfactant or a silicone free surfactant.
  • Suitable classes of silicon-free nonionic surfactants include, but are not limited to, polyoxyethylene ethers of fatty (C 6 -C 22 ) alcohols, polyoxyethylene/polyoxypropylene ethers of fatty (C 6 -C 22 ) alcohols, ethoxylated alkylphenols, polyethylene glycol ethers of methyl glucose, polyethylene glycol ethers of sorbitol, and mixtures thereof.
  • Suitable silicon-free nonionic surfactants are the ethoxylated alcohols having an HLB value of about 0.1 to about 10.
  • An especially preferred ethoxylated alcohol is laureth-1, i.e., lauryl alcohol ethoxylated with an average of one mole of ethylene oxide.
  • Other suitable ethoxylated alcohols include laureth-2, laureth-3 and laureth-4.
  • Numerous other suitable nonionic surfactants having an HLB of about 0.1 to about 10 are listed in McCutcheon s at pages 229-236, (incorporated herein by reference) .
  • exemplary silicon-free nonionic surfactants having an HLB value of about 0.1 to about 10 include, but are not limited to, the ethoxylated nonylphenols, ethoxylated octylphenols , ethoxylated dodecylphenols , ethoxylated fatty (C6-C22) alcohols having four or fewer ethylene oxide moieties, oleth-2, steareth-3, steareth-2, ceteth-2, oleth-3,and mixtures thereof .
  • the emulsifier may also comprise a silicon-free surfactant blend having an HLB value of about 1 to about 10.
  • the blend is a mixture of a sufficient amount of a surfactant having an allowable HLB value, i.e., about 0.1 to about 10, and a sufficient amount of a surfactant having a higher HLB value, i.e., about 1 to greater than about 10, such that the surfactant blend has an overall HLB value of about 1 to about 10.
  • exemplary, but non-limiting, nonionic surfactants having a high HLB value are listed in McCutcheon ' s at pages 236-246, (incorporated herein by reference) .
  • a preferred silicone free surfactant is PEG 30 dipolyhydroxystearate .
  • An exemplary oil-soluble silicon-based surfactant is a dimethicone copolyol , which is a dimethylsiloxane polymer having polyoxyethylene and/or polyoxypropylene side chains, such as DOW CORNING 3225C and 5225C FORMULATION AID, available from Dow Corning Co., Midland, Mich.
  • the dimethicone copolyol has about 15 or fewer ethylene oxide and/or propylene oxide monomer units, in total, in the side chains.
  • Dimethicone copolyols are conventionally used in conjunction with silicones because the silicon-containing surfactants are extremely soluble in a volatile or a nonvolatile silicone compound, are extremely insoluble in water, and have a low skin irritancy potential.
  • alkyl dimethicone copolyol such as cetyl dimethicone copolyol available commercially as ABIL (R> EM 90 from Goldschmidt Chemical Corporation, Hopewell, Va.
  • ABIL R> EM 90 from Goldschmidt Chemical Corporation, Hopewell, Va.
  • the alkyl dimethicone copolyols have the structure: - ?SSii H - O
  • p is a numeral from 7 to 17; q is a numeral from 1 to 100; m is a numeral from 1 to 40; n is a numeral from 0 to 200; and
  • PE is (C 2 H 4 O) a (C 3 HgO) -H having a molecular weight of about 250 to about 2000, wherein a and b are selected such that the weight ratio of C 2 H 4 0/C 3 H 6 0 is from 100/0 to 20/80.
  • the surfactant phase may also comprise an oil-soluble polymeric surfactant.
  • Polymeric surfactants capable of forming water-in-oil emulsions have the advantages that they completely cover the surface of the water droplet, are firmly anchored at the oil -water interface, the external oil phase is a good solvent for the stabilizing portion of the polymeric surfactant, and the thickness of the polymer layer on the oil side of the interface is sufficient to ensure stability.
  • These surfactants may include ethoxy, propoxy and/or similar alkylene oxide monomer units, e.g., butoxy.
  • the oil-soluble polymeric surfactants act as surfactants and are not physically or chemically cross-linked in solution.
  • the oil -soluble polymeric surfactants are therefore differentiated from polymeric gelling agents such as polyacrylic acid or polymethacrylic acid.
  • oil-soluble polymeric surfactants include, but are not limited to, polyoxyethylene- polyoxypropylene block copolymers, and similar polyoxyalkylene block copolymers.
  • the oil-soluble block copolymers typically have less than about 20% by weight of ethylene oxide.
  • oil -soluble polymeric surfactants include Poloxamer 101 , Poloxamer 105, PPG-2- Buteth-3, PPG-3-Butech-5, PPG-5-Butech-7 , PPG-7-Butech-10 , PPG-9-Buteth-12, PPG-12-Buteth-16 , PPG-15-Buteth-20 , PPG-20- Buteth-30, PPG-24-Buteth-27, PPG-28-Buteth-35 , and PEG-15 Butanediol .
  • Other useful oil-soluble polymeric surfactants are polyamines, i.e., polyoxyethylene-polyoxypropylene block copolymers of ethylene diamine, having less than about 40% by weight ethylene oxide.
  • the hydrophobic moiety of a silicon- free surfactant, silicon-containing surfactant or a polymeric surfactant is sufficiently soluble in the oil phase such that a sufficient amount of the surfactant is present in the oil phase to stabilize the primary W ⁇ /0 emulsion.
  • the surfactant phase comprises either a silicon-based surfactant, a silicon-free surfactant having a hydrophobic moiety preferably containing about ten to about fourteen carbon atoms, an oil -soluble polymeric surfactant, or a mixture thereof.
  • the hydrophobic moiety of the silicon-free surfactant is saturated and includes more than about 14 carbon atoms, the silicon-free surfactant is insoluble in the silicone phase and the primary W ⁇ /0 emulsion is unstable. If the hydrophobic moiety includes less than about 10 carbon atoms, the primary W ⁇ /0 emulsion has a tendency to coalesce i.e., the emulsion droplets fuse to form large droplets.
  • the amount of surfactant phase necessary to provide a primary emulsion of desired W ⁇ /0 droplet diameter varies with the amount of aqueous phase in the primary emulsion and is easily determined by those skilled in the art.
  • a particularly preferred emulsifier is cetyl dimethicone copolyol .
  • the external aqueous phase ( 2) of the W ⁇ -0-W 2 multiple emulsion comprises an isotropic mixture of surfactants phase (as opposed to lamellar phase of U.S. Patent No. 5,656,280).
  • this external phase comprises a non-amido anionic surfactant and/or other surfactant.
  • it comprises anionic in combination with amphoteric surfactants wherein the nonamido group anionic comprises 1 to 99% of the surfactant system and amphoteric comprises 1 to 99% of the surfactant system.
  • the key to the invention is that much greater levels of surfactants may be used than previously believed possible while maintaining a stable multiple emulsion.
  • the external aqueous phase (W 2 ) of the ⁇ -0-W 2 multiple emulsion comprises a relatively high level of surfactant (s) that form an isotropic phase, a second topically effective compound, typically 0-40% by wt . of the external phase to perform a function identical to, similar to or different from the first topically active compound, solute, and 0.01 to 10% by wt . of a stabilizing natural gum polymer.
  • the composition contains all non-amido anionic or all amphoteric surfactant, or combinations of the two.
  • the surfactant typically comprises about 2-80% of the aqueous phase .
  • the anionic surfactant in either of the above embodiment may be, for example, an aliphatic sulfonate, such as a primary alkane (e.g., C 8 -C 22 ) sulfonate, primary alkane (e.g., Cs-
  • C 22 disulfonate, C 8 -C 22 alkene sulfonate, C 8 -C22 hydroxyalkane sulfonate or alkyl glyceryl ether sulfonate
  • AVS aromatic sulfonate
  • alkyl benzene sulfonate an aromatic sulfonate
  • the anionic may also be an alkyl sulfate (e.g., C ⁇ 2 ⁇ C ⁇ s alkyl sulfate) or alkyl ether sulfate (including alkyl glyceryl ether sulfates) .
  • alkyl ether sulfates are those having the general formula:
  • R is an alkyl or alkenyl group having about 8 to 18 carbons, preferably 12 to 18 carbons, n has an average value of greater than 1.0, preferably between 2 and 3; and M is a solubilizing cation such as sodium, potassium, ammonium or substituted ammonium. Ammonium and sodium lauryl ether sulfates are preferred.
  • the anionic may also be alkyl sulfosuccinates (including mono- and dialkyl, e.g., C 6 -C 22 sulfosuccinates); alkyl and acyl taurates, alkyl and acyl sarcosinates, sulfoacetates,
  • Sulfosuccinates may be monoalkyl sulfosuccinates having the formula:
  • R ranges from C 8 -C 22 alkyl and M is a solubilizing cation defined above;
  • alkoxylated citrate sulfosuccinates alkoxylated citrate sulfosuccinates
  • alkoxylated sulfosuccinates such as the following:
  • Taurates are generally identified by the formula
  • R ranges from C 8 -C 20 alkyl
  • R ranges from C -C 4 alkyl
  • M is a solubilizing cation
  • carboxylates such as follows:
  • R is Cs to C 20 alkyl; n is 0 to 20; and M is as defined above.
  • amido alkyl polypeptide carboxylates such as, for example, Monteine
  • Cs-C ⁇ 8 acyl isethionates are the Cs-C ⁇ 8 acyl isethionates . These esters are prepared by reaction between alkali metal isethionate with mixed aliphatic fatty acids having from 6 to 18 carbon atoms and an iodine value of less than 20. At least 75% of the mixed fatty acids have from 12 to 18 carbon atoms and up to 25% have from 6 to 10 carbon atoms .
  • Acyl isethionates when present, will generally range from about 0.5-15% by weight of the total composition, preferably, from about 1 to about 10%.
  • the acyl isethionate may be an alkoxylated isethionate such as is described in Ilardi et al . , U.S. Patent No. 5,393,466, (hereby incorporated by reference) .
  • This compound has the general formula:
  • R is an alkyl group having 8 to 18 carbons
  • m is an integer from 1 to 4
  • X and Y are hydrogen or an alkyl group having 1 to 4 carbons
  • M is a monovalent cation such as, for example, sodium, potassium or ammonium.
  • the anionic component will comprise from about 1 to 30% by weight of the composition, preferably 2 to 25%, most preferably 5 to 20% by weight of the composition.
  • Zwitterionic surfactants are exemplified by those which can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals may be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • a general formula for these compounds is:
  • R contains an alkyl, alkenyl , or hydroxy alkyl radical containing about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety;
  • Y is selected from nitrogen, phosphorus, and sulfur atoms;
  • R is an alkyl or monohydroxyalkyl group containing about 1 to about 3 carbon atoms;
  • X is 1 when Y is a sulfur atom, and 2 when Y is a nitrogen or phosphorus
  • R is an alkylene or hydroxyalkylene of from about 1 to about 4 carbon atoms and Z is a radical selected from carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups .
  • surfactants examples include:
  • Amphoteric detergents which may be used in this invention include at least one acid group. This may be a carboxylic or a sulphonic acid group. They should generally include an alkyl or alkenyl group containing 7 to 18 carbon atoms.
  • Suitable amphoteric detergents within the above general formula include simple betaines of formula:
  • R is alkyl or alkenyl of 7 to 18 carbons; R and R are each independently alkyl, hydroxyalkyl or carboxyalkyl containing 2 to 3 carbon atoms .
  • R may in particular be a mixture of C ⁇ 2 and C 14 alkyl groups derived from coconut so that at least half, preferably at least three quarters of the groups R have 10 to 14 carbon
  • R and R are preferably methyl .
  • amphoteric detergent is a sulphobetaine of formula:
  • the amphoteric/zwitterionic surfactant generally comprises about 1 to 30% by weight, preferably 2 to 25% of the composition, more preferably 5 to 20%.
  • the surfactant system may optionally comprise a nonionic surfactant .
  • the nonionic which may be used includes in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic detergent compounds are alkyl (C 6 -C 22 ) phenols-ethylene oxide condensates, the condensation products of aliphatic (C ⁇ -CX ⁇ ) primary or secondary linear or branched alcohols with ethylene oxide, and products produced by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine .
  • Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides .
  • the nonionic may also be a sugar amide, such as a polysaccharide amide.
  • the surfactant may be one of the lactobionamides described in U.S. Patent No. 5,389,279 to Au et al . which is hereby incorporated by reference or it may be one of the sugar amides described in Patent No. 5,009,814 to Kelkenberg, hereby incorporated into the subject application by reference.
  • Other surfactants which may be used are described in U.S. Patent No. 3,723,325 to Parran Jr. and alkyl polysaccharide nonionic surfactants as disclosed in U.S. Patent No. 4,565,647 to Llenado, both of which are also incorporated into the subject application by reference.
  • alkyl polysaccharides are alkylpolyglycosides of the formula:
  • R is selected from alkyl, alkylphenyl , hydroxyalkyl, hydroxyalkylphenyl , and mixtures thereof in which alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 0 to 3, preferably 2; t is from 0 to about 10, preferably 0 ; and x is from 1.3 to about 10, preferably from 1.3 to about 2.7.
  • the glycosyl is preferably derived from glucose. To prepare these compounds , the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position) . The additional glycosyl units may then be attached between the 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.
  • Nonionic comprises 0 to 10% by wt . of the composition.
  • the external aqueous phase must also comprise about 0.01 to 10% by wt of a stabilizing natural gum polymer. It is preferred that in systems where the external surfactant W2 is comprised entirely of or contains a majority of (60% or higher) anionic surfactant that a nonionic gum polymer is used.
  • Nonionic seed polysaccharides are particularly soluble and dispersible in anionic surfactants and anionic rich surfactant systems.
  • One such stabilizer is guar gum, which is structurally composed of a straight chain of D-mannose with a D-galactose side chain on approximately every other mannose unit. The usual ratio of mannose to galactose is approximately 2:1 and molecular weights are usually on the order of 100,000 to 1,000,000.
  • locust bean gum a galactomannan consisting of a main chain of D-mannose units with single galactose side chains on approximately every fourth unit. As with guar gum, approximate molecular weights are between 100,000 and 1, 000, 000.
  • an anionic gum polymer is preferred. These may be seaweed polysaccharides , exudate polysaccharides, or microbial polysaccharides.
  • a preferred anionic seaweed polysaccharide is carrageenan, or Irish moss, a complex mixture of sulfated polysaccharides.
  • Carrageenan is a mixture of galactans that carry varying proportions of half-ester sulfate groups linked to one or more of the hydroxyl groups of the galactose units, which are joined by alternating -1,3 and ⁇ -1,4 glycosidic linkages.
  • the molecular weight usually ranges from 100,000 to 1,000,000.
  • a preferred anionic exudate polysaccharide is gum tragacanth, a complex mixture of acidic polysaccharides containing galacturonic acid, galactose, fucose, xylose, and arabinose .
  • Another preferred anionic exudate polysaccharide is gum karaya, a partially acetylated high molecular weight polysaccharide which contains L-rhamnose, D-galactose, D- galacturonic acid, and D-glucuronic acid residues.
  • amphoteric or amphoteric rich surfactant systems are microbial anionic hetero polysaccharide gums, most preferably Xanthan gum.
  • the primary structure of these microbial gums contains two glucose units, two mannose units, and one glucuronic acid unit.
  • Sodium ISE To measure multiple emulsion stability, a sodium ion sensitive electrode (Corning 476138) was attached to an Orion EA 920 expandable ion analyzer.
  • the multiple emulsion samples were intentionally prepared with a too low internal NaCl concentration.
  • the Na ion concentration of the separated bottom phase served as a rapid indicator of multiple emulsion stability.
  • Standards were prepared by taking 1,2, 3, 4 and 5 g samples of the original external phase and diluting them with 49, 48, 47, 46, and 45 g of milli-Q water, respectively, to 50 g. 50 g of 0.5 M TEA was added to each sample, as above.
  • Each of the standard samples and the separated emulsion sample were measured for sodium ion activity (concentration) using the sodium ion sensitive electrode.
  • Oil Phase The oil and the oil soluble surfactant (low HLB emulsifier) were mixed together at room temperature using overhead stirring.
  • W ⁇ /0 preparation the oil phase (0) was charged into the vessel.
  • the salt/topically active compound solution (Wx) was added to the oil phase steadily through the addition funnel over the course of 10-12 minutes while mixing with the side scraper (60-80 rpm) .
  • Slow addition of aqueous phase under low shear mixing is essential to obtain a stable primary emulsion.
  • the mixing speed of the side scraper was reduced to
  • External aqueous phase (W 2 ) : External aqueous phases were prepared in a jacketed vessel by mixing the minority surfactant into the majority surfactant at 60°C with intense mixing. The pH of each surfactant solution was pre-adjusted to 7.0. Surfactant solutions which had a gel like consistency were centrifuged at 7000 rpm for 20 minutes to remove the entrapped air.
  • 1 /O/W 2 preparation The primary emulsion (W ⁇ /0) was charged into the smaller scale vessel followed by addition of the external aqueous phase ( 2) . The mixture was hand- mixed gently for 15 seconds using a spatula. This was followed by mixing with the side-scraper for 8 minutes at 70-105 rpm (higher speed was used when mixing at lower speed was found to be inadequate) . A small spatula was inserted into the vessel as a baffle to ensure good mixing around the center spindle of the side scraper. The resulting multiple emulsions were transferred into 250 ml separatory funnels to await separation of the aqueous phase for emulsion stability analysis .
  • Examples 1-37 relate to the first embodiment and 38-59 relate to the second.
  • compositions 2 and 34-37 were prepared. Table 8. Effect of incorporating benefit agent (lactic acid) into WI phase on multiple emulsion stability
  • Examples 34 and 35 demonstrate the criticality that if a cationic hair styling polymer is used in systems containing an anionic surfactant, multiple emulsion stability will be adversely affected.
  • Example 38 the control, has a Newtonian anionic external W2 phase (SLES) and it phase separates 40% over 45 days.
  • SLES Newtonian anionic external W2 phase
  • Examples 2 and 3 show that by gelling the external phase with a nonionic natural gum stabilizer, phase separation is prevented by incorporating locust bean gum or retarded by incorporating guar gum.
  • Example 41 shows that Locust bean gum also gels another anionic surfactant, sodium lauryl sulfate.
  • Example 42 shows that octyl palmitate can be substituted for light mineral oil.
  • Example 43 we attempted to incorporate an anionic gum into an anionic surfactant but the 2 phase was not homogeneous.
  • Examples 39-42 show the criticality that the gum must be nonionic when the surfactant is anionic.
  • Example 44 the control , has a Newtonian amphoteric external 2 phase (betaine) and it phase separates 50% over 45 days.
  • Examples 45 through 49 show that by gelling the external phase with an anionic natural gum stabilizer, phase separation is prevented by incorporating xanthan gum or retarded by incorporating gum tragacanth, gum karaya, or carrageenan.
  • Example 49 shows that xanthan gum also gels another amphoteric surfactant, cocoamphoglycinate .
  • Example 50 shows that octyl palmitate can be substituted for light mineral oil.
  • Example 52 is a control with anionic as the majority surfactant.
  • Examples 53 and 54 show that when nonionic gum stabilizer (locust bean) is used, phase separation is prevented whereas when an anionic gum stabilizer (xanthan) is used, phase separation is still close to the control.
  • Example 56 shows that the anionic ratio can be changed from 13:2 to 9:6 without phase separation.
  • Example 56 is a control with amphoteric as the majority surfactant.
  • Examples 57 and 58 show that when an anionic gum stabilizer (xanthan) is used, phase separation is prevented whereas when a nonionic gum stabilizer (locust bean) is used, phase separation is still close to the control.
  • Example 59 shows that the amphoteric ratio can be changed from 11:4 to 7.5:7.5 without phase separation.

Abstract

W1-O-W2 emulsions are disclosed in which the W1/O emulsion comprises an internal aqueous phase comprising a benefit agent and an oil phase surrounding it, and, around this is found an external isotropic aqueous phase wherein the external surfactant phase does not comprise an amido containing anionic. Methods of stabilizing the multiple oil compositions are also disclosed.

Description

STABLE MULTIPLE EMULSION COMPOSITION
FIELD OF THE INVENTION
The present invention relates to liquid surfactant compositions, e.g., liquid shower gels or liquid shampoos, comprising multiple emulsions. In particular, the invention relates to multiple emulsion compositions which may comprise high levels of surfactants but are nonetheless stable (e.g., microscopically stable) . In another embodiment, the compositions microscopically maintain multiple emulsion droplet integrity while, macroscopically, there is little or no phase separation. The invention also relates to methods of stabilizing the multiple emulsion compositions.
BACKGROUND OF THE INVENTION
Multiple emulsion systems (broadly defined as systems in which water/oil and oil/water emulsion co-exist) are very valuable because they permit incorporation and enhanced delivery of benefit agents. Thus, multiple emulsions have been used for many years, for example, in cosmetic and pharmaceutical areas to deliver cosmetic or pharmacological benefit agents (see for Example, U.S. Patent No. 5,306,498 to Vesperini; or U.S. Patent No. 5,567,426 to Nadaud et al . ) .
In general, however, as the level of cleansing surfactant
(e.g., having high HLB, e.g., HLB greater than 10, preferably greater than 12) in such multiple emulsion systems is increased, the emulsions become less and less stable. Thus, for example, the level of cleansing surfactant m almost all of the cosmetic and pharmaceutical compositions referred to in the prior art is below 5% by wt . of the compositions. Greater amounts lead to less stability and phase separation.
U.S. Patent Nos. 5,656,280 and 5,589,177 (Herb et al . ) and their European equivalents EP 717,978 and EP 715,842 describe the stabilization of multiple emulsions m compositions containing high levels of conditioning surfactant. However, the stable multiple emulsion composition disclosed therein comprise surfactants (i.e., conditioning surfactants) which must form stabilizing liquid crystals, i.e., lamellar liquid crystals. The compositions described wherein the surfactants formed an isotropic phase (for example, Example 29 at column 29 of U.S. Patent No. 5,589,177 at lines 30-44) were unstable (see column 34, where stability of Example 29 is only 5 minutes) . The applicants have now surprisingly found that the surfactant phase of compositions of the present invention is an isotropic surfactant phase, yet the multiple emulsion does not break into a simple emulsion when evaluated at room temperature for at least 2 weeks, preferably greater than 4 weeks, more preferably greater than 8 weeks, when measured at a temperature of about 25°C.
Compositions comprising isotropic surfactant phases are advantageous over compositions comprising lamellar liquid crystal phase in that they can be formed using a much wider range of surfactants and provide improved foam/lather properties . Accordingly, it is an object of the invention to provide compositions with a surfactant phase which is not limited to lamellar phase.
It is another object of the invention to provide a surfactant phase (which is an isotropic phase) which contains high levels of surfactant and yet does not destabilize the multiple emulsion.
In a second embodiment, it has been further found that compositions may be stabilised over time (in addition to being microscopically stable as noted) by using specific selection of an external surfactant system in combination with a stabilizing natural gum polymer which forms a gelled external aqueous phase with a relatively high concentration of surfactant. Compositions which employ similar technology
(i.e. gelled external aqueous phase) are described in U.S.
Patent No. 5,306,498 to Vesperini, U.S. Patent No.
4,083,798 to Versteeg, U.S. Patent No. 5,332,595 to Gaonkar, U.S. Patent Nos. 5,576,064 and 5,656,263 both to Fructus, and U.S. Patent No. 5,567,426 to Nadaud. In the prior art compositions disclosed, however, the level of high HLB external surfactant was in one case only 5% and in most cases zero.
It is thus yet another object of this invention to provide a gelled isotropic external surfactant phase which contains high levels of surfactant where the integrity of the multiple emulsion droplet is maintained and the composition does not phase separate. BRIEF SUMMARY OF THE INVENTION
In one embodiment, applicants have now found that it is possible to obtain multiple emulsion systems which comprise high levels of surfactant forming an isotropic phase whereby the multiple emulsion can deliver desirable benefit agent (e.g., in the internal oil phase) while simultaneously maintaining the stability of the multiple emulsion. Previously it has been difficult or impossible to make stable multiple emulsions in the presence of high levels of surfactant which form an isotropic phase. In preferred embodiments, the surfactant system comprises mixtures of anionic and amphoteric surfactants and levels of surfactant are greater than about 10.5% by wt . of the total composition.
The invention further relates to methods of stabilizing the multiple emulsion systems described above.
More specifically, the invention comprises a water-in-oil- in-water ( 1-O- 2) multiple emulsion wherein the water-in- oil (Wi/O) emulsion itself comprises an internal aqueous phase ( i) which contains a solute and optional surfactant; an oil phase 0 (an oil combined with a low HLB emulsifier, e.g., emulsifier with HLB less than 10) surrounding the internal aqueous phase; and a topically active compound which may be in either the aqueous i or in 0. The WχO phase is surrounded by an external aqueous isotropic phase ( 2) containing cleansing surfactant, optional topically active compound (which may be the same or different as the first optional topically active compound), and optional solute. (It should be understood that some solute will almost always be present in the surfactant or will be formed when adjusting pH) . It is critical that the surfactant phase W2 must not contain an anionic surfactant with an amido group.
Another essential feature is that the oil in the O phase should not comprise more than 50% unsaturated compounds; or should not be a volatile silicone (e.g., a silicone having a viscosity of 10 centistokes or less) .
As noted above, the invention may be distinguished from the prior art (for example U.S. Patent No. 5,656,280) which requires that the aqueous phase 2 (e.g., external aqueous phase) comprises a surfactant system capable of forming stabilizing liquid crystals. In contrast, the present application requires that the external aqueous phase be an isotropic phase. The isotropic phase in turn is formed by selection of a specific surfactant system which must not contain an anionic surfactant with an amido group.
By definition, a lamellar phase is a liquid crystalline phase whereas an isotropic phase is micellar; optically a lamellar phase would show birefringence under a polarized light source while a micellar phase does not exhibit this feature .
In particular, the invention comprises a W1-O-W2 multiple emulsion composition comprising: (1) about 1% to 99% by wt . of the composition, preferably 2% to 90% by wt . , more preferably 5% to 80% of a i/O emulsion comprising; (a) about 1% to 99% of the emulsion of an internal aqueous phase comprising (i) water; (ii) 0.01 to 30% solute; and (iii) 0 to 30% optional surfactant ; (b) about 0.1% to about 99%, preferably 0.5 to 95%, more preferably 1 to 80% of the emulsion of an oil phase surrounding the internal aqueous phase comprising a non-volatile silicone compound, a volatile hydrocarbon compound, a non-volatile hydrocarbon compound or a mixture thereof; (c) about 0.1 to 20%, preferably 1 to 15%, more preferably 1.5 to 15% by wt . emulsion of a surfactant emulsifier selected from a silicon-free surfactant or surfactant blend having an HLB value of about ten or less, an oil soluble silicon based surfactant, an oil -soluble polymeric surfactant and mixtures thereof; and
(d) a topically effective amount (e.g., 0.01 to 40%, preferably 0.05 to 15% by wt . ) of a first topically active compound which may be found in either aqueous phase (a) and/or oil phase (b) ; and
(2) about 1 to 99% by wt . , preferably 20 to 95% by wt . of an external isotropic aqueous phase 2 comprising non-amido anionic and/or other surfactants. Preferably the composition contains non-amido anionic and amphoteric surfactants, wherein the ratio of first surfactant (preferably anionic) to amphoteric is 100:1 to 1:100. The composition optionally contains a second topically effective compound, typically 0-40% by wt . of the external phase to perform a function identical to, similar to or different from the first topically active compound, and optional solute. The surfactant will typically comprise about 2-80% of the aqueous phase .
The W1-O-W2 multiple emulsion compositions are stable (e.g., typically they will not break down into a simple emulsion at room temperature for at least two weeks) and they exhibit exceptional aesthetic and functional properties. The Wχ-0- 2 multiple emulsion compositions are liquids or creams, and are capable of effectively delivering one or more topically active compounds to the skin or hair from a single composition.
In a second embodiment, applicants have now found that specific selection of an external surfactant system in combination with a stabilizing natural gum polymer which forms a gelled external aqueous phase with a relatively high concentration of surfactant, results in the formation of a multiple emulsion system which enables delivery of desirable benefit agent (s) while simultaneously maintaining both the integrity of the multiple emulsion droplets and physical stability of the composition (i.e. the bottom clear layer formed due to phase separation should be less than 20 volume percent of the total volume of the sample for a period of at least 45 days at room temperature.)
Specifically, this embodiment relates to the selection of natural gum polymers and surfactant (s) or combinations of surfactants which form a gelled external phase for the multiple emulsions described above.
The invention, therefore, further comprises a W1-O-W2 multiple emulsion wherein the χO phase, in addition to being surrounded by an external aqueous isotropic phase 2, an optional topically active compound and an optional solute, is also surrounded by a stabilizing natural gum polymer.
It is essential that the natural gum stabilizer and the selected surfactant (s) form a gel. As in the first embodiment, it is also essential that the surfactant phase 2 must not contain an anionic surfactant with an amido group. Furthermore, the 2 surfactant phase must be isotropic. The isotropic phase in turn is formed by selection of a specific surfactant system which must not contain an anionic sufactant with an amido group.
The oil in the 0 phase (e.g., light mineral oil, hexadecane, octyl palmitate) should preferably not comprise (1) more than 50% unsaturated compounds; or (2) should not be a volatile silicone (e.g., a silicone having viscosity of 10 centistokes or less) . As noted above, the invention can be distinguished from prior art U.S. Patent Nos. 5,306,498 (Vesperini) 4,083,798 (Versteeg) 5,332,595 (Gaonkar) , 5,576,064 and 5,656,263 (Fructus), and 5,567,426 (Nadaud) because our invention uses surfactant levels of 10.5% or greater whereas the aforementioned compositions use levels of only 0-5% external surfactant .
In particular, the invention further comprises a 1-O- 2 multiple emulsion composition comprising:
(1) about 1% to 99% by wt . of the composition, preferably 2% to 90% by wt . , more preferably 5% to 80%, more preferably 5 to 50% of a W--./0 emulsion comprising;
(a) about 1% to 99% of the emulsion of an internal aqueous phase comprising (i) water; (ii) 0.01 to 30% solute; and (iii) optional 0 to 30% surfactant;
(b) about 0.5% to about 99%, preferably 1 to 80% of the emulsion of an oil phase surrounding the internal aqueous phase comprising a non-volatile silicone compound, a volatile hydrocarbon compound, a non-volatile hydrocarbon compound or a mixture thereof ;
(c) about 0.1 to 20%, preferably 1 to 15%, more preferably 1.5 to 15% 1.5 to 15% by wt . emulsion of a surfactant emulsifier selected from a silicon-free surfactant or surfactant blend having an HLB value of about ten or less, an oil soluble silicon based surfactant, an oil-soluble polymeric surfactant and mixtures thereof; and (d) a topically effective amount (e.g., 0.01 to 40%, preferably 0.05 to 15% by wt . ) of a first topically active compound which may be found in either aqueous phase (a) and/or oil phase (b) ; and
(2) about 1 to 99% by wt . , preferably 20 to 95% by wt . of an external isotropic aqueous phase W2 comprising non-amido anionic and/or other surfactants .
The composition contains all non-amido anionic or all amphoteric surfactant, or combinations of the two in which 60% by weight or greater is the anionic surfactant. The surfactant typically comprises about 2-80% of the aqueous phase and 0.01 to 10% of a stabilizing natural gum polymer.
The composition optionally contains a second topically effective compound, typically 0-40% by wt . of the external phase to perform a function identical to, similar to or different from the first topically active compound and optional solute. It is preferred that in systems where the external surfactant W2 is comprised entirely of, or contains a majority of, anionic surfactant, that a nonionic gum polymer is used. Conversely, in systems where the external surfactant 2 is comprised entirely of or contains a majority of amphoteric surfactant, it is preferred that an anionic gum polymer is used. The W1-O-W2 multiple emulsion compositions are physically stable (e.g., typically they will not phase separate at room temperature for at least 45 days and exhibit exceptional aesthetic and functional properties. The W1-O-W2 multiple emulsion compositions are liquids or creams, and are capable of effectively delivering one or more topically active compounds to the skin or hair from a single composition.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 relating to a first embodiment of invention is a schematic drawing wherein Figure 1A shows a stable multiple emulsion in which the Wχ/0 phase is surrounded by the W2 phase and Figure IB shows a multiple emulsion which has broken down into a simple 0/( ι+ 2) emulsion.
Figures 2 and 3 relating to a second embodiment of the invention both show a plot of viscosity vs Haake RV06 spindle speed. In Figure 2, it is clear that the addition of 3% by weight of an anionic natural gum (example carrageenan) to an amphoteric surfactant (example cocamidopropyl betaine) yields a gelled external 2 phase i.e. a viscoelastic solution that exhibits shear thinning behavior. In Figure 3, it is clear that the addition of 1% by weight of a nonionic natural gum (example locust bean) to an anionic surfactant (example sodium laureth sulfate) yields a gelled external 2 phase. In each of these cases, addition of the gum to the surfactant has transformed the rheology of the 2 phase from a Newtonian low viscosity to a shear thinning, high viscosity gel. This gelled external ( 2) phase, resulting from proper surfactant and stabilizer selection, helps keep the multiple emulsion from phase separating while still rendering the composition pourable. A viscosity of at least 6000 cps at a spindle speed of 5 rpm and a viscosity of no more than 9000 cps at 50 rpm are preferred to render the composition phase both stable and pourable .
DETAILED DESCRIPTION OF THE INVENTION
In a first embodiment, the present invention relates to χ~ O- 2 multiple emulsion compositions comprising:
(1) 1 to 99% χ/0 emulsion comprising about 1% to 99% of (containing water, solute and optional surfactant), and 0.1 to 99% of 0 phase (containing oil compound and low HLB emulsifier) . A topically active agent may be present in W phase, 0 phase or both; and
(2) about 1% to 99% by wt . of an external aqueous phase comprising non-amido anionic and/or other surfactants. The phase preferably comprises anionic, amphoteric, optional second topically effective compound, and solute.
The external aqueous phase W2 (1 to 99% of total emulsion) differs from the art in that it is an isotropic, aqueous surfactant phase rather than a lamellar phase. These compositions are able to comprise relatively large amounts of surfactants (i.e., 10.5% by wt . or greater, preferably 11% -75%, more preferably 12% to 60%, more preferably 13% to 60%, more preferably 15% to 60%, more preferably 16% to 55%, more preferably 17 to 50% by wt . of the composition) while the integrity of the multiple emulsion still remains. Unless the surfactant system and oil are specifically selected as described herein, such multiple emulsion compositions will generally break very rapidly into simple emulsion (see Figure 1) .
In a second embodiment, the invention relates to W -0-W2 multiple emulsions where the integrity of the multiple emulsion droplet is maintained and the composition does not phase separate. These formulations comprise:
(1) 1 to 99% Wi/O emulsion comprising about 1% to 99% of (containing water, solute and optional surfactant), and 0.5 to 99% of 0 phase (containing oil compound and low HLB emulsifier) . A topically active agent may be present in W-*. phase, 0 phase or both; and
(2) about 1% to 99% by wt . of an external aqueous phase comprising non-amido anionic and/or amphoteric surfactant, a stabilizing natural gum polymer, an optional second topically effective compound, and solute . The external aqueous phase W2 contains a high concentration (i.e., 15% by wt . or greater, preferably 16% or greater, preferably 17 to 75%, more preferably 20 to 70%, more preferably 22% to 60%, more preferably 25 to 50% by wt . of the composition) of surfactant which is isotropic. It is essential that the natural gum stabilizer and the selected surfactant (s) form a gel. Applicants have unexpectedly found that in systems where the external surfactant W2 is comprised entirely of or contains a majority of anionic surfactant, that a nonionic gum polymer should be used. Conversely, in systems where the external surfactant W2 is comprised entirely of or contains a majority of amphoteric surfactant, that an anionic gum polymer should be used. This differs from prior art in that the external phase now contains high levels of cleansing surfactant and the choice of stabilizing polymer is subject to the above criticalities.
The invention will now be described in greater detail
The Water-in-Oil (Wχ/0) Emulsion
The Wχ/0 emulsion comprises an internal aqueous phase with water, solute and optional surfactant, and an oil phase 0.
Generally the water, solute and first topically-active compound comprise the internal aqueous phase of the Wχ/0 emulsion although the active compound may also be in the oil phase if oil compatible. That is, the i phase comprises droplets containing water, solute and possibly a first topically-active compound. For example, droplets containing water, solute and a first topically-active compound (Wx) may have a diameter ranging from about 0.01 to about 75 and may be enveloped by a membrane or film comprising the oil phase.
The contents of the internal aqueous phase (Wx) therefore do not contact the external aqueous phase (W2) of the Wχ-0- 2 multiple emulsion.
The primary Wχ/0 emulsion is present in a Wχ-0-W2 multiple emulsion composition in an amount of about 1% to about 99%, preferably 2% to 90%, more preferably about 5% to about 80%, by weight of the multiple emulsion composition. Suitably, the primary Wχ/0 emulsion is present in an amount of about 10% to about 80%.
The Internal Aqueous Phase
The (WI) internal aqueous phase comprises about 1% to about 99% by weight of the emulsion, an oil phase separates the internal aqueous phase (Wx) of the emulsion from the external aqueous phase (W2) .
The internal aqueous phase (Wx) of the present Wχ-0-W2 multiple emulsion compositions generally comprises water, solute and an optional first topically-active compound (which may also be found in the oil phase alone or in both) . The internal aqueous phase may further comprise additional topically-active compounds and/or optional water soluble compounds capable of providing a desired aesthetic or functional effect, such as a fragrance.
The aqueous phase (Wx) comprises about 1% to about 99%, and preferably about 10% to about 95%, more preferably abut 25% to about 95% by weight of the Wχ/0 emulsion.
Topically-Active Compounds
A wide variety of topically active compounds may be incorporated into the Wχ/0 emulsion as the first topically active compound. If found in the Wx phase, the topically active compounds are water soluble or water dispersible and include both cosmetic and other compounds that act upon contact with the skin or hair. The first topically active compound is present in a sufficient amount to perform its intended function, typically in an amount of about 0.01% to about 40% by weight, preferably 0.05 to 15% of the WχO emulsion.
The first topically active compound typically remains on the skin or hair after application, as opposed to being rinsed from the skin or hair. However, in some cases the first topically active compounds are designed to be rinsed from the skin or hair after the compound has performed its intended function. The first topically active compound may be incorporated into the aqueous phase or into the oil phase of the primary emulsion, or both. Whether a particular first topically active compound is incorporated into the aqueous phase or the oil phase of the primary emulsion is related to the solubility of the topically active composition in water. In preferred embodiments, the first topically active compound is water soluble and is incorporated into the internal Wx aqueous phase. However, a more hydrophobic agent may be used in the oil phase.
As used herein, the term "water soluble" means water soluble or water dispersible. A water soluble compound has a water solubility of at least 0.1 g (grams) per 100 ml (milliliters) of water and forms a true solution. A water soluble compound can be inherently water soluble or can be made water soluble by the addition of a solubilizing compound, such as a coupling agent, a co-surfactant, or a solvent. A water dispersible compound remains dispersed in water for at least the time period necessary to manufacture the primary Wχ/0 emulsion, i.e., at least about one hour.
In addition, the topically active compound may be incorporated into the external aqueous phase W2 to achieve enhanced efficacy.
The topically active compound therefore can be one of, or a combination of, a cosmetic compound, a medicinally active compound or any other compound that is useful upon topical application to the skin or hair. Such topically active compounds include, but are not limited to, hair and skin conditioners, hair and skin cleansers, hair fixatives, hair dyes, hair growth promoters, deodorants, skin care compounds, permanent wave compounds, hair relaxers, hair straighteners, antibacterial compounds, antifungal compounds, anti-inflammatory compounds, topical anaesthetics, sunscreens and other cosmetic and medicinal topically effective compounds.
In accordance with one aspect of the present invention, the topically active compound comprises a water soluble hair conditioner, such as a quaternary ammonium compound. Quaternary ammonium compounds are substantive to the hair and are excellent hair conditioners, but are well known to be incompatible with anionic surfactants and anionic dyes. Therefore, quaternary ammonium compounds are generally not a component of shampoo conditioner compositions or anionic dye-based compositions, but are applied to the hair from a separate conditioning composition.
Water soluble quaternary ammonium compounds suitable for the purposes of the present application have the general structural formula:
Figure imgf000019_0001
wherein Rx is an alkyl group containing from about 8 to about 18 carbon atoms; R2 is selected from an alkyl group containing from about 8 to about 18 carbon atoms, a hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group and a hydroxyethyl group; R3 is selected from a benzyl group, a hydrogen atom, an ethyl group, a methyl group, a hydroxymethyl group and a hydroxyethyl group; R4 is selected from a hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group and a hydroxyethyl group; and X is an anion. The quaternary nitrogen of the water soluble quaternary ammonium compound also can be a component of a heterocyclic nitrogen containing moiety, such as morpholine or pyridine . The anion of the quaternary ammonium compound can be any common anion, such as chloride, methosulfate, ethosulfate, nitrate, bromide tosylate, acetate, or phosphate .
The water soluble quaternary ammonium compounds may have one or two long chain alkyl groups containing from about 8 to about 18 carbon atoms. The long chain alkyl groups can also include, in addition to, or in replacement of, carbon and hydrogen atoms, either linkages or similar water solubilizing linkages. The remaining two or three substituents of the quaternary nitrogen of the quaternary ammonium compound can be hydrogen; or benzyl, or short chain alkyl or hydroxyalkyl groups, such as methyl, ethyl, hydroxymethyl or hydroxyethyl groups; or combinations thereof, either of the same or different identity.
Exemplary water soluble quaternary ammonium compounds include, but are not limited to lautrimonium chloride Quaternium-16 ; lauralkonium chloride; olealkonium chloride dilauryldimonium chloride; cetalkonium chloride dicetyldimonium chloride; laurylpyridinium chloride; cetylpyridinium chloride; soyatrimonium chloride; Polyquaternium-6 ; Polyquaternium-7 ; guarhydroxypropyltrimonium chloride; Polyquaternium-11 ; Polyquaternium-5; Polyquaternium-10 ; Polyquaternium-24 ; cetrimonium chloride; Quaternium-24 ; mytrimonium chloride; PEG-2 cocomonium chloride; PEG-2 cocoyl quaternium-4; PEG-15 cocoyl quaternium-4; PEG-2 stearyl quaternium-4; PEG-2 oleyl quaternium-4; and PEG 15 olelyl quaternium-4, and mixtures thereof, wherein the compound designation is provided by the Cosmetic, Toiletry and Fragrance Association, Inc. in the CTFA Cosmetic Ingredient Dictionary, 4th Ed., 1991, hereinafter referred to as the CTFA Dictionary. Other water soluble quaternary ammonium compounds are listed in the CTFA Cosmetic Ingredient Handbook, 1st Ed. , 1988 (hereinafter the CTFA Handbook) at pages 40-42, incorporated herein by reference.
Other water soluble hair conditioners are also suitable as the first topically active compound. Such hair conditioners include, but. are not limited to, fatty amine salts, ethoxylated fatty amine salts, dimethicone copolyols, protonated polyethylenimines, protonated ethoxylated polyethylenimines, soluble animal collagen, lauramine oxide, cationic polymers, numerous other water soluble hair conditioners listed in the CTFA Handbook at page 71-73,
(incorporated herein by reference) and mixtures thereof.
In addition to hair conditioners, a skin conditioner can be used as the first topically active compound. Skin conditioning agents include, but are not limited to, humectants, such as fructose, glucose, glycerin, propylene glycol, glycereth-26, mannitol and urea; pyrrolidone carboxylic acid; hydrolyzed lecithin; coco-betaine; cysteing hydrochloride; glutamine; PPG-15; sodium gluconate; potassium aspartate; olelyl betaine, thiamine hydroxychloride; sodium laureth sulfate; sodium hyaluronate; hydrolyzed proteins; hydrolyzed keratin; amino acids; amine oxides; water soluble derivatives of vitamins A, E and D; amino functional silicones; ethoxylated glycerin; alpha- hydroxy acids and salts thereof; water soluble fatty oil derivatives, such as PEG-24 hydrogenated lanolin, almond oil, grape seed oil and castor oil; numerous other water soluble skin conditioners listed in the CTFA Handbook, pages 79-84, (incorporated herein by reference); and mixtures thereof. Other conditioners include alpha hydroxy acids such as lactic acid, glycolic acid or their salts thereof.
The first topically active compound may also be a hair fixative or film former that imparts style retention properties to hair, i.e., sets the hair. The hair fixative typically is a homopolymer, a copolymer, or a terpolymer. The polymers can be nonionic, amphoteric, anionic or cationic. Examples of hair fixatives include, but are not limited to, an acrylamide copolymer; an acrylamide/sodium acrylate copolymer; a polystyrene sulfonate; a polyethylene oxide; a water dispersible polyester; a cationic cellulose; an acrylate/ammoniummethacrylate copolymer; an aminoethylacrylate phosphate/acrylate copolymer; a polyacrylamide; Polyquaternium-1 ; Polyquaternium-2 Polyquaternium-4; Polyquaternium-4 ; Polyquaternium-5 Polyquaternium-7 ; Polyquaternium-8 ; Polyquaternium-9 Polyquaternium-10 Polyquaternium-11 ; Polyquaternium-12 ; Polyquaternium-13 Polyquaternium-14 ; Polyquaternium-15 ; Polyquaternium-16 Polyquaternium-28 ; a PVP
(polyvinylpyrrolidone) ; a PVP/ dimethylaminoethylmethacrylate copolymer; a PVP/ethyl methacrylate/methacrylic acid copolymer; a carboxylated polyvinyl acetate; vinyl/caprolactam/PVP/dimethylaminoethyl methacrylate copolymer (GAFFIX VC713) ; a PVP/vinyl acetate copolymer; a sodium acrylate/ vinyl alcohol copolymer; sodium carrageenan; a vinyl acetate/crotonic acid copolymer; numerous other water soluble hair fixatives listed in the
CTFA Handbook at pages 73-74, incorporated herein by reference; and mixtures thereof. Numerous hair fixatives also are disclosed in U.S. Patent No. 5,277,899, incorporated herein by reference.
The first topically active compound may also be a water soluble hair dye, such as, but not limited to, m-aminophenol hydrochloride, p-aminophenol sulfate, 2 , 3-diaminophenol hydrochloride, 1 , 5-naphthalenediol , phenylenediamine hydrochloride, sodium picramate, water soluble cationic dyes, water soluble anionic dyes, water soluble FD&C dyes, such as Blue No. 1, Blue No. 2, Red No. 3, Red No. 4, or Red No. 40, water soluble D&C dyes, such as Yellow No. 10, Red No. 22 or Red No. 28, and pyrogallol . Numerous other hair dyes are listed in the CTFA Handbook, pages 70-71, incorporated herein by reference.
The first topically active compound may also be an antioxidant, such as ascorbic acid or erythorbic acid; or a fluorescent whitening agent or optical brightener, such as a distyrylbiphenyl derivative, stilbene or a stilbene derivative, a pyralozine derivative or a coumarin derivative. In addition, a self-tanning compound, such as dihydroxy acetone, or a hair growth promoter, or a hair bleaching agent, such as perborate or a persulfate salt, can be the first topically active compound.
The first topically active compound can also be a deodorant compound, such as an astringent salt or a bioactive compound. The astringent salts include organic and inorganic salts of aluminum, zirconium, zinc, and mixtures thereof. The anion of the astringent salt can be, for example, sulfate, chloride, chlorohydroxide, alum, formate, lactate, benzyl sulfonate orphenyl sulfonate. Exemplary classes of antiperspirant astringent salts include aluminum halides, aluminum hydroxyhalides, zirconyl oxyhalides, zirconyl hydroxyhalides, and mixtures thereof.
Exemplary aluminum salts include aluminum chloride and the aluminum hydroxyhalides having the general formula
AI2 (OH) xQyXH2θ, wherein Q is chlorine, bromine or iodine; x is about 2 to about 5; x+y is about 6, wherein x and y are not necessarily integers; and X is about 1 to about 6. Exemplary zirconium compounds include zirconium oxy salts and zirconium hydroxy salts, also referred to as zirconyl salts and zirconyl hydroxy salts, and represented by the general empirical formula ZrO (OH) 2-nzϊz wherein z varies from about 0.9 to about 2 and is not necessarily an integer; n is the valence of L; 2-nz is greater than or equal to 0 ; and L is selected from halides, nitrate, sulfamate, sulfate, and mixtures thereof.
Exemplary deodorant compounds therefore include, but are not limited to, aluminum bromohydrate, potassium alum, sodium aluminum chlorihydroxy lactate, aluminum sulfate, aluminum chlorohydrate, aluminum-zirconium tetrachlorohydrate, an aluminum-zirconium polychlorohydrate complexed with glycine, aluminum-zirconium trichlorohydrate, aluminum-zirconium octachlorohydrate, aluminum sesquichlorohydrate, aluminum sesquichlorohydrex PG, aluminum chlorohydrex PEG, aluminum zirconium octachlorohydrex glycine complex, aluminum zirconium pentachlorohydrex glycine complex, aluminum zirconium tetrachlorohydrex glycine complex, aluminum zirconium trichlorohydrex glycine complex, aluminum chlorohydrex PG, zirconium chlorohydrate, aluminum dichlorohydrate, aluminum dichlorohydrex PEG, aluminum dichlorohydrex PG, aluminum sesquichlorohydrex PG, aluminum chloride, aluminum zirconium pentachlorohydrate, numerous other useful antiperspirant compounds listed in the CTFA
Handbook at p. 56, (incorporated herein by reference), and mixtures thereof .
In addition to the astringent salts, the deodorant compound can be a bacteriostatic quaternary ammonium compound, such as, for example, cetyl trimethyl ammonium bromide, cetyl pyridinium chloride, benzethonium chloride, diisobutylbenzoxyethoxyethyl-dimethylbenzyl ammonium chloride, sodium N-lauryl sarcosine, sodium N-polymethyl sarcosine, lauroyl sarcosine, N-myristolyl glycine, potassium N-lauroyl sarcosine, and stearyl trimethyl ammonium chloride; or a bioactive compound; or a carbonate or bicarbonate salt, such as, for example, the alkali metal carbonates and bicarbonates, and the ammonium and tetraalkylammonium carbonates and bicarbonates .
In addition, other compounds can be included in the primary emulsion as the first topically active compound in an amount sufficient to perform their intended function. For example, if the composition is intended to be a sunscreen, compounds such as benzophenone-4, trihydroxycinnamic acid and salts, tannic acid, uric acid, quinine salts dihydroxy naphtholic acid; an anthranilate, diethanolamine methoxycinnamate, p- aminobenzoic acid, phenylbenzimidazole sulfonic acid, PEG-25 p-aminobenzoic acid or triethanolamine salicylate may be incorporated into the internal aqueous phase.
Further, sunscreen compounds such as dioxybenzone , ethyl 4-
[bis (hydroxypropyl) ] aminobenzoate, glyceryl aminobenzoate, homosalate, menthyl anthranilate, octocrylene, octyl methoxycinnamate, octyl salicylate, oxybenzone, padimate 0, red petrolatum, titanium dioxide, 4-menthylbenzylidene camphor, benzophenone-1, benzophenone-2 , benzophenone-7, benzophenone-12, isopropyl dibenzoyl methane, butyl methoxydibenzoylmethane , zotocrylene, or zinc oxide can be incorporated into the oil phase of the primary emulsion. Other sunscreen compounds soluble in either the aqueous or organic phase are listed in CTFA Handbook, pages 87 and 87, (incorporated herein by reference) .
Similarly, topically active drugs, such as antifungal compounds, antibacterial compounds; anti-inflammatory compounds; topical anaesthetics; skin rash, skin disease and dermatitis medications; and anti-itch and irritation reducing compounds may be included in the compositions of the present invention. For example, analgesics such as benzocaine, dyclonine hydrochloride, aloe vera and the like; anaesthetics such as butamben picrate, lidocaine hydrochloride, xylocaine and the like; antibacterials and antiseptics, such as povidone-iodine, polymyxin sulfate- bacitracin, zinc-neomycin sulfate-hydrocortisone, chloramphenicol, methylbenzethonium chloride, and erythromycin and the like; antiparastitics, such as lindane; deodorants, such as chlorophyllin copper complex, aluminum chloride, aluminum chloride hexahydrate, and methylbenzethonium chloride; essentially all dermatologicals, such as acne preparations, such as benzoyl peroxide, erythromycinbenzoyl peroxide, clindamycin phosphate, 5, 7-dichloro-8-hydroxyquinoline, and the like; anti-inflammatory agents, such as alcometasone dipropionate, betamethasone velerate, and the like; burn relief ointments, such as o-amine-p-toluene sulfonamide monoacetate and the like; depigmenting agents, such as monobenzone; dermatitis relief agents, such as the active steroid acinonide, diflorasone diacetate, hydrocortisone, and the like; diaper rash relief agents, such as methylbenzethonium chloride and the like; emollients and moisturizers, such as mineral oil, PEG-4 dilaurate, lanolin oil, petrolatum, mineral wax and the like; fungicides, such as butocouazole nitrate, haloprogen, clotrimazole, and the like; herpes treatment drugs, such as 0- [ (2-hydroxyethoxy) -methyl] guanine; pruritic medications, such as alcometasone dipropionate, betamethasone valerate, isopropyl myristate MSD, and the like; psoriasis, seborrhea ad scabicide agents, such as anthralin, methoxsalen, coal tar and the like; steroids, such as 2- (acetyloxy) -9-fluoro-1' , 2' , 3' , 4' -tetrahydro-11- hydroxypregna-1, 4-dieno [16, 17-b] naphthalene-3 , 20-dione and 21-chloro-9-fluoro-1' , 2 ' , 3 ' , 4 ' -tetrahydro-llb-hydroxypregna-
1,4-dienol [16z, 17-b] naphthalene-3 , 20-dione. Any other medication capable of topical administration also can be incorporated in a composition of the present invention in an amount sufficient to perform its intended function. Other topically active compounds are listed in Remington ' s
Pharmaceutical Sciences, 17th Ed . , Merck Publishing Co,
Easton, Pa. (1985) , pages 773-791 and pages 1054-1048
(hereinafter Remington ' s) , incorporated herein by reference.
An above-described first topically active compound is designed to remain on the skin or hair to perform its intended function. However, in particular situations, a first topically active compound that is rinsed from the skin or hair can be incorporated into the internal aqueous Wx phase of the primary emulsion.
For example, a Wχ-0-W2 multiple emulsion composition designed as a permanent wave composition can incorporate a reducing agent into the external aqueous phase as the second topically active compound. After applying the Wχ-0-W2 composition to the hair and allowing the composition to contact the hair for a sufficient time to reduce the hair, the external aqueous phase is rinsed from the hair leaving droplets of the primary emulsion on the hair. The primary emulsion has incorporated therein an oxidizing agent as the first topically active compound. After the oil phase, and preferably a volatile oil phase, evaporates from the primary emulsion, the oxidizing agent is released to neutralize the hair and any reducing agent remaining on the hair. Excess oxidizing agent can then be rinsed from the hair in a second rinsing step.
Exemplary, but non-limiting, oxidizing agents used as the first topically active compound are ammonium persulfate, hydrogen peroxide, potassium bromate, potassium chromate, potassium persulfate, sodium bromate, sodium carbonate, peroxide, sodium iodate, sodium perborate, sodium persulfate, urea peroxide, and mixtures thereof. An oxidizing agent may also be the second topically active compound when the first topically active compound is a hair conditioner. In addition, the second topically active compound may be a bleaching agent (i.e., an oxidizing agent) and the first topically active compound may be a hair dye.
In preferred embodiments of the invention, the topically active compound should not be cationic in nature, particularly if anionic surfactants are used.
Water
Sufficient water is present in the aqueous phase such that the aqueous phase comprises about 1% to about 99% by weight of the WχO. Total water present in the Wχ-0- 2 multiple emulsion composition is about 30% to about 99.9%, and typically about 40% to about 95%, by weight of the composition.
Solutes
The internal aqueous phase must also include oil -insoluble solute (s) . The solutes are introduced to balance osmotic pressure. Among solutes which may be added are organic or inorganic salts such as alkali metal chlorides, sulfates, nitrates, benzoates and acetates and sugars and sugar derivatives, for example glucose and sucrose. Solute, when added to the internal aqueous phase, comprises 0.01 to 30% by wt . , preferably 0.1 to 20%, most preferably 0.5 to 15%.
Optional Components
It is also possible to add surfactant to the internal aqueous phase though this is generally added to the external W2 phase. The surfactant may be any of the surfactants discussed in connection with the W2 phase below.
The internal aqueous phase can also include optional ingredients traditionally included in topically applied compositions. These optional ingredients include, but are not limited to, dyes, fragrances, preservatives, antioxidants, detackifying agents, and similar types of compounds. The optional ingredients are included in the internal aqueous phase of the primary emulsion in an amount sufficient to perform their intended function. 0 Phase
The primary Wx/0 emulsion also comprises about 0.5% to about 99%, preferably about 0.75% to about 80%, and most preferably about 1% to about 70%, by weight of the emulsion of an oil phase. The oil phase is comprised of an oil and a low HLB surfactant. The oil phase encapsulates the internal aqueous Wi phase of the primary emulsion to form droplets of about 0.1 to about l,000μ, preferably about 1 to about 500μ, in diameter. The oil phase therefore provides a barrier between the internal aqueous phase of the primary emulsion and the external aqueous phase of the W -0- 2 multiple emulsion composition. The oil phase provides a sufficient barrier even though the oil phase constitutes as little as 0.5% by weight of the WχO emulsion.
Oil
The oil may be volatile (except for silicone) or nonvolatile.
A volatile oil may comprise a volatile hydrocarbon oil which evaporates during the process of drying skin or hair, and thereby releases the internal aqueous x phase, which includes the first topically active compound to contact the skin or hair. This oil preferably should contain no volatile silicone since volatile silicones tend to destabilize the multiple emulsion. In one embodiment, the oil may comprise a combination of a volatile oil (except for silicone) and a nonvolatile oil. In this embodiment, an oil can be designed to evaporate at a pre-selected temperature and provide a controlled release of the first topically active compound at the pre-selected temperature. Pre-selected temperatures are those encountered during normal hair drying, provided by a hair dryer, or provided by a curling iron.
As previously stated, the oil may also include a water insoluble topically active compound in a sufficient amount to impart a particular functional or aesthetic effect (e.g., emolliency) , as long as the topically active compound does not adversely affect the Wχ-0- 2 multiple emulsion composition (e.g., does not impart emulsion instability).
Although the oil can incorporate a topically active compound, the topically active compound preferably is incorporated into the internal aqueous phase .
The volatile oil preferably comprises a volatile hydrocarbon compound, such as a hydrocarbon having about 10 to about 30 carbon atoms, that has sufficient volatility to slowly volatilize from the skin or hair after application of the Wχ-0-W2 multiple emulsion composition to the skin or hair and subsequent rinsing. A preferred volatile hydrocarbon compound is an aliphatic hydrocarbon having about 12 to about 24 carbon atoms, and having a boiling point of about 100°C to about 250°C. The volatile hydrocarbon compounds perform the same function and provide essentially the same benefits as the volatile silicone compounds.
Volatile hydrocarbon compounds incorporated into the primary emulsion include, for example, isododecane and isohexadecane, i.e., PERMETHYL 99A, PERMETHYL 101A and PERMETHYL 102A, available from Presperse, Inc., South Plainfield, N.J. Other exemplary volatile hydrocarbon compounds are depicted in general structural formula (I) , wherein m ranges from 2 to 5.
Figure imgf000033_0001
Another exemplary volatile hydrocarbon compound is ISOPAR M (a Cχ3-Cχ4 isoparaffin available from Exxon Chemical Co.,
Baytown, Tex) . Preferably, the volatile hydrocarbon is less than 50% unsaturated.
As previously stated, the oil may also be a nonvolatile oil. The nonvolatile oil comprises a nonvolatile silicone compound, a nonvolatile hydrocarbon, or mixtures thereof. Preferably, the nonvolatile oil comprises compounds which contain less than 50% unsaturation. The nonvolatile oil phase does not evaporate from the skin or hair. The first topically active compound therefore is released by rubbing the skin or hair to rupture the Wχ/0 emulsion. A nonvolatile oil has a boiling point at atmospheric pressure of greater than about 250°C. Exemplary nonvolatile silicone compounds include a polyalkyl siloxane, a polyaryl siloxane or a polyalkylaryl siloxane. Mixtures of these nonvolatile silicone compounds are also useful. The nonvolatile silicones are nonfunctional siloxanes or siloxane mixtures having a viscosity of about 10 to about 600,000 cs, and typically about 350 to about 10,000 cs, at 25°C. The so-called "rigid silicones", as described in U.S. Patent No. 4,902,499, (herein incorporated by reference), having a viscosity above 600,000 cs at 20°C, and a weight average molecular weight of at least about 500,000, are also useful in compositions of the present invention. A phenyltrimethicone is also useful as a nonvolatile silicone compound.
Preferably the nonvolatile silicone compound is a nonvolatile polydimethylsiloxane compound, such as a mixture, in about a 2:1 weight ratio, of a low molecular weight polydimethylsiloxane fluid and a higher molecular weight polydimethylsiloxane gum. Preferred silicone gums include linear and branched polydimethylsiloxanes of the general formula:
(CH3) 3SiO— [Si (CH3) 20] n—Si (CH3) 3 ,
wherein n is a number from about 2,000 to about 15,000, and preferably from about 2,000 to about 7,000. Silicone gums useful in compositions of the present invention are available from a variety of commercial sources, including General Electric Company, Waterford, N.Y. and Dow Corning Corp., Midland, Michigan. The nonvolatile oil may also comprise a nonvolatile hydrocarbon compound, such as mineral oil. Other exemplary nonvolatile hydrocarbon compounds that may be used include, but are not limited to, a branched 1-decene oligomer, such as 1-decene dimer or a polydecene.
The oil may also further optionally comprise (1) an oil, such as jojoba oil, wheat germ oil or purcellin oil; or (2) a water insoluble emollient, such as, for example, an ester having at least about 10 carbon atoms, preferably about 10 to about 32 carbon atoms.
Suitable esters include those comprising an aliphatic alcohol having about eight to about twenty carbon atoms and an aliphatic or aromatic carboxylic acid including from two to about twelve carbon atoms, or conversely, an aliphatic alcohol having two to about twelve carbon atoms with an aliphatic or aromatic carboxylic acid including about eight to about twenty carbon atoms. The ester is either straight chained or branched. Preferably, the ester has a molecular wt . of less than about 500. Suitable esters therefore include, for example, but are not limited to:
(a) aliphatic monohydric alcohol esters, for example: myristyl propionate, isopropyl isostearate, isopropyl myristate, isopropyl palmitate, cetyl acetate, cetyl propionate, cetyl stearate, isodecyl neopentanotate, cetyl octanoate, isocetyl stearate;
(b) aliphatic di- and tri-esters of polycarboxylic acids, or example: diisopropy1 adipate , diisotstearyl fumarate, dioctyl adipate, and triisostearyl citrate;
(c) aliphatic polyhydric alcohol esters, for example: propylene glycol dipelargonate;
(d) aliphatic esters of aromatic acids, for example: 12-C15 alcohol esters of benzoic acid, octyl salicylate, sucrose benzoate, and dioctyl phthalate.
Numerous other esters are listed in the CTFA Handbook at pages 24 through 26, (incorporated herein by reference) .
Low HLB Emulsifier
The 0 phase of the present invention also includes about 0.1% to about 30%, and preferably about 1% to about 15% of the weight of the oil of a low HLB emulsifier.
The low HLB emulsifier may comprise a silicon-free surfactant, or a blend of silicon- free surfactants, having an HLB value of about less than 10 (i.e., an HLB value of about 0.1 to about less than 10), an oil-soluble silicon- based surfactant, an oil-soluble polymeric surfactant, or mixtures thereof. Preferably, the silicon-free surfactant or surfactant blend has an HLB value of about 1 to about 7, more preferably about 3 to about 6. The term oil-soluble as used herein means a compound having a solubility of at least 0.1 g per 100 ml of oil phase to form a true solution.
The HLB value of a particular surfactant can be found in
McCutcheon ' s Emulsifiers and Detergents, North American and
International Edi tions , MC Publishing , Glen Rock, NJ (1993)
(hereinafter McCutcheon ' s) . Alternatively, the HLB value of a particular surfactant can be estimated by dividing the weight percent of oxyethylene in the surfactant by five (for surfactants including only ethoxy moieties) . In addition, the HLB value of a surfactant blend can be estimated by the following formula:
HLB = (wt.% A) (HLBA) + (wt . % B) (HLBB) ,
wherein wt . % A and wt . % B are the weight percent of surfactants A and B in the silicon-free surfactant blend, and HLBA and HLBβ are the HLB values for surfactants A and B, respectively.
Suitable Low HLB surfactants may be a silicone-based surfactant or a silicone free surfactant. Suitable classes of silicon-free nonionic surfactants include, but are not limited to, polyoxyethylene ethers of fatty (C6-C22) alcohols, polyoxyethylene/polyoxypropylene ethers of fatty (C6-C22) alcohols, ethoxylated alkylphenols, polyethylene glycol ethers of methyl glucose, polyethylene glycol ethers of sorbitol, and mixtures thereof.
Suitable silicon-free nonionic surfactants are the ethoxylated alcohols having an HLB value of about 0.1 to about 10. An especially preferred ethoxylated alcohol is laureth-1, i.e., lauryl alcohol ethoxylated with an average of one mole of ethylene oxide. Other suitable ethoxylated alcohols include laureth-2, laureth-3 and laureth-4. Numerous other suitable nonionic surfactants having an HLB of about 0.1 to about 10 are listed in McCutcheon s at pages 229-236, (incorporated herein by reference) . Other exemplary silicon-free nonionic surfactants having an HLB value of about 0.1 to about 10 include, but are not limited to, the ethoxylated nonylphenols, ethoxylated octylphenols , ethoxylated dodecylphenols , ethoxylated fatty (C6-C22) alcohols having four or fewer ethylene oxide moieties, oleth-2, steareth-3, steareth-2, ceteth-2, oleth-3,and mixtures thereof .
The emulsifier may also comprise a silicon-free surfactant blend having an HLB value of about 1 to about 10. The blend is a mixture of a sufficient amount of a surfactant having an allowable HLB value, i.e., about 0.1 to about 10, and a sufficient amount of a surfactant having a higher HLB value, i.e., about 1 to greater than about 10, such that the surfactant blend has an overall HLB value of about 1 to about 10. Exemplary, but non-limiting, nonionic surfactants having a high HLB value are listed in McCutcheon ' s at pages 236-246, (incorporated herein by reference) .
A preferred silicone free surfactant is PEG 30 dipolyhydroxystearate .
An exemplary oil-soluble silicon-based surfactant is a dimethicone copolyol , which is a dimethylsiloxane polymer having polyoxyethylene and/or polyoxypropylene side chains, such as DOW CORNING 3225C and 5225C FORMULATION AID, available from Dow Corning Co., Midland, Mich. The dimethicone copolyol has about 15 or fewer ethylene oxide and/or propylene oxide monomer units, in total, in the side chains. Dimethicone copolyols are conventionally used in conjunction with silicones because the silicon-containing surfactants are extremely soluble in a volatile or a nonvolatile silicone compound, are extremely insoluble in water, and have a low skin irritancy potential.
Another exemplary, but non-limiting, oil-soluble, silicon- based surfactant is an alkyl dimethicone copolyol, such as cetyl dimethicone copolyol available commercially as ABIL(R> EM 90 from Goldschmidt Chemical Corporation, Hopewell, Va. The alkyl dimethicone copolyols have the structure: - ?SSiiH- O
Figure imgf000040_0001
Figure imgf000040_0002
wherein: p is a numeral from 7 to 17; q is a numeral from 1 to 100; m is a numeral from 1 to 40; n is a numeral from 0 to 200; and
PE is (C2H4O) a (C3HgO) -H having a molecular weight of about 250 to about 2000, wherein a and b are selected such that the weight ratio of C2H40/C3H60 is from 100/0 to 20/80.
The surfactant phase may also comprise an oil-soluble polymeric surfactant. Polymeric surfactants capable of forming water-in-oil emulsions have the advantages that they completely cover the surface of the water droplet, are firmly anchored at the oil -water interface, the external oil phase is a good solvent for the stabilizing portion of the polymeric surfactant, and the thickness of the polymer layer on the oil side of the interface is sufficient to ensure stability. These surfactants may include ethoxy, propoxy and/or similar alkylene oxide monomer units, e.g., butoxy.
The oil-soluble polymeric surfactants act as surfactants and are not physically or chemically cross-linked in solution. The oil -soluble polymeric surfactants are therefore differentiated from polymeric gelling agents such as polyacrylic acid or polymethacrylic acid.
Accordingly, exemplary oil-soluble polymeric surfactants include, but are not limited to, polyoxyethylene- polyoxypropylene block copolymers, and similar polyoxyalkylene block copolymers. The oil-soluble block copolymers typically have less than about 20% by weight of ethylene oxide. Specific non- limiting oil -soluble polymeric surfactants include Poloxamer 101 , Poloxamer 105, PPG-2- Buteth-3, PPG-3-Butech-5, PPG-5-Butech-7 , PPG-7-Butech-10 , PPG-9-Buteth-12, PPG-12-Buteth-16 , PPG-15-Buteth-20 , PPG-20- Buteth-30, PPG-24-Buteth-27, PPG-28-Buteth-35 , and PEG-15 Butanediol . Other useful oil-soluble polymeric surfactants are polyamines, i.e., polyoxyethylene-polyoxypropylene block copolymers of ethylene diamine, having less than about 40% by weight ethylene oxide.
The hydrophobic moiety of a silicon- free surfactant, silicon-containing surfactant or a polymeric surfactant is sufficiently soluble in the oil phase such that a sufficient amount of the surfactant is present in the oil phase to stabilize the primary Wχ/0 emulsion. In one embodiment when the oil phase comprises a silicone compound, the surfactant phase comprises either a silicon-based surfactant, a silicon-free surfactant having a hydrophobic moiety preferably containing about ten to about fourteen carbon atoms, an oil -soluble polymeric surfactant, or a mixture thereof. If the hydrophobic moiety of the silicon-free surfactant is saturated and includes more than about 14 carbon atoms, the silicon-free surfactant is insoluble in the silicone phase and the primary Wχ/0 emulsion is unstable. If the hydrophobic moiety includes less than about 10 carbon atoms, the primary Wχ/0 emulsion has a tendency to coalesce i.e., the emulsion droplets fuse to form large droplets. The amount of surfactant phase necessary to provide a primary emulsion of desired Wχ/0 droplet diameter varies with the amount of aqueous phase in the primary emulsion and is easily determined by those skilled in the art.
A particularly preferred emulsifier is cetyl dimethicone copolyol .
The External Aqueous Phase
In the first embodiment, the external aqueous phase ( 2) of the Wχ-0-W2 multiple emulsion comprises an isotropic mixture of surfactants phase (as opposed to lamellar phase of U.S. Patent No. 5,656,280). As noted, this external phase comprises a non-amido anionic surfactant and/or other surfactant. Preferably, it comprises anionic in combination with amphoteric surfactants wherein the nonamido group anionic comprises 1 to 99% of the surfactant system and amphoteric comprises 1 to 99% of the surfactant system. The key to the invention is that much greater levels of surfactants may be used than previously believed possible while maintaining a stable multiple emulsion. In the second embodiment the external aqueous phase (W2) of the χ-0-W2 multiple emulsion comprises a relatively high level of surfactant (s) that form an isotropic phase, a second topically effective compound, typically 0-40% by wt . of the external phase to perform a function identical to, similar to or different from the first topically active compound, solute, and 0.01 to 10% by wt . of a stabilizing natural gum polymer. The composition contains all non-amido anionic or all amphoteric surfactant, or combinations of the two. The surfactant typically comprises about 2-80% of the aqueous phase .
The anionic surfactant in either of the above embodiment may be, for example, an aliphatic sulfonate, such as a primary alkane (e.g., C8-C22) sulfonate, primary alkane (e.g., Cs-
C22) disulfonate, C8-C22 alkene sulfonate, C8-C22 hydroxyalkane sulfonate or alkyl glyceryl ether sulfonate
(AGS) ; or an aromatic sulfonate such as alkyl benzene sulfonate.
The anionic may also be an alkyl sulfate (e.g., Cχ2~Cχs alkyl sulfate) or alkyl ether sulfate (including alkyl glyceryl ether sulfates) . Among suitable alkyl ether sulfates are those having the general formula:
RO(CH2CH20)nS03M
wherein R is an alkyl or alkenyl group having about 8 to 18 carbons, preferably 12 to 18 carbons, n has an average value of greater than 1.0, preferably between 2 and 3; and M is a solubilizing cation such as sodium, potassium, ammonium or substituted ammonium. Ammonium and sodium lauryl ether sulfates are preferred.
The anionic may also be alkyl sulfosuccinates (including mono- and dialkyl, e.g., C6-C22 sulfosuccinates); alkyl and acyl taurates, alkyl and acyl sarcosinates, sulfoacetates,
C8-C22 alkyl phosphates and phosphates, alkyl phosphate esters and alkoxyl alkyl phosphate esters, acyl lactates,
C8-C22 monoalkyl succinates and maleates, sulphoacetates , and acyl isethionates .
Sulfosuccinates may be monoalkyl sulfosuccinates having the formula:
R402CCH2CH (S03M) C02M;
4 wherein R ranges from C8-C22 alkyl and M is a solubilizing cation defined above;
Also included are the alkoxylated citrate sulfosuccinates; and alkoxylated sulfosuccinates such as the following:
0
II R-O- (CH2CH20) nCCH2CH (S03M) C02M wherein n = 1 to 20; and M is as defined above. Sarcosinates are generally indicated by the formula RCON(CH3)CH22M, wherein R ranges from C8 to C2o alkyl and M is a solubilizing cation.
Taurates are generally identified by the formula
R2CONR3CH2CH2S03M
2 3 wherein R ranges from C8-C20 alkyl, R ranges from C -C4 alkyl and M is a solubilizing cation.
Another class of anionics are carboxylates such as follows:
R- (CH2CH2θ)nC02M
wherein R is Cs to C20 alkyl; n is 0 to 20; and M is as defined above.
Another carboxylate which can be used is amido alkyl polypeptide carboxylates such as, for example, Monteine
(R) LCQ by Seppic.
Other surfactants which may be used are the Cs-Cχ8 acyl isethionates . These esters are prepared by reaction between alkali metal isethionate with mixed aliphatic fatty acids having from 6 to 18 carbon atoms and an iodine value of less than 20. At least 75% of the mixed fatty acids have from 12 to 18 carbon atoms and up to 25% have from 6 to 10 carbon atoms . Acyl isethionates, when present, will generally range from about 0.5-15% by weight of the total composition, preferably, from about 1 to about 10%.
The acyl isethionate may be an alkoxylated isethionate such as is described in Ilardi et al . , U.S. Patent No. 5,393,466, (hereby incorporated by reference) . This compound has the general formula:
O X Y
II I I
R C-O-CH-CH2- (OCH-CH2)m-Sθ" 3M+
wherein R is an alkyl group having 8 to 18 carbons, m is an integer from 1 to 4 , X and Y are hydrogen or an alkyl group having 1 to 4 carbons and M is a monovalent cation such as, for example, sodium, potassium or ammonium.
In general the anionic component will comprise from about 1 to 30% by weight of the composition, preferably 2 to 25%, most preferably 5 to 20% by weight of the composition.
Zwitterionic and Amphoteric Surfactants
Zwitterionic surfactants are exemplified by those which can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals may be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. A general formula for these compounds is:
( 3)x
R2-Y( + )-CH2-R4Z(-)
2 wherein R contains an alkyl, alkenyl , or hydroxy alkyl radical containing about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety; Y is selected from nitrogen, phosphorus, and sulfur atoms; R is an alkyl or monohydroxyalkyl group containing about 1 to about 3 carbon atoms; X is 1 when Y is a sulfur atom, and 2 when Y is a nitrogen or phosphorus
4 atom; R is an alkylene or hydroxyalkylene of from about 1 to about 4 carbon atoms and Z is a radical selected from carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups .
Examples of such surfactants include:
4- [N,N-di (2 -hydroxyethyl) -N-octadecylammonio] -butane-1- carboxylate;
5- [S-3 -hydroxypropyl -S-hexadecylsulfonio] -3- hydroxypentane-1-sulfate ; 3- [P, P-diethyl-P-3 , 6, 9-trioxatetradexocylphosphonio] -2- hydroxypropane-1-phosphate ;
3- [N,N-dipropyl-N-3-dodecoxy-2-hydroxypropylammonio] - propane- 1 -phosphonate ;
3- (N,N-dimethyl-N-hexadecylammonic) propane- 1-sulfonate; 3- (N,N-dimethyl-N-hexadecylammonio) -2-hydroxypropane-l- sulfonate;
4- [N,N-di (2 -hydroxyethyl) -N- (2-hydroxydodecyl) ammonio] - butane-1-carboxylate ; 3- [S-ethyl-S- (3 -dodecoxy- 2 -hydroxypropyl) sulfonio] - propane- 1 -phosphate;
3- [P, P-dimethyl-P-dodecylphosphonio] -propane-1- phosphonate ; and
5- [N,N-di (3 -hydroxypropyl) -N-hexadecylammonio] -2- hydroxy-pentane-1-sulfate .
Amphoteric detergents which may be used in this invention include at least one acid group. This may be a carboxylic or a sulphonic acid group. They should generally include an alkyl or alkenyl group containing 7 to 18 carbon atoms.
Suitable amphoteric detergents within the above general formula include simple betaines of formula:
R2
R1—N+—CH2C02 '
R3
1 2 3 where R is alkyl or alkenyl of 7 to 18 carbons; R and R are each independently alkyl, hydroxyalkyl or carboxyalkyl containing 2 to 3 carbon atoms .
R may in particular be a mixture of Cχ2 and C14 alkyl groups derived from coconut so that at least half, preferably at least three quarters of the groups R have 10 to 14 carbon
2 3 atoms . R and R are preferably methyl .
A further possibility is that the amphoteric detergent is a sulphobetaine of formula:
R
R -N -(CH2)3S03
R" or
R
R1 - CONH (CH2)m-N+-(CH2)3S03 '
R"
where m is 2 or 3, or variants of these in which -(CH2)3SO 3 is replaced by
OH
-CH2CHCH2 SO3 "
1 2 3 wherein R , R and R are as def ined previously . The amphoteric/zwitterionic surfactant generally comprises about 1 to 30% by weight, preferably 2 to 25% of the composition, more preferably 5 to 20%.
In addition to one or more anionic and amphoteric and/or zwitterionic, the surfactant system may optionally comprise a nonionic surfactant .
The nonionic which may be used includes in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are alkyl (C6-C22) phenols-ethylene oxide condensates, the condensation products of aliphatic (CΘ-CXΘ) primary or secondary linear or branched alcohols with ethylene oxide, and products produced by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine . Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides .
The nonionic may also be a sugar amide, such as a polysaccharide amide. Specifically, the surfactant may be one of the lactobionamides described in U.S. Patent No. 5,389,279 to Au et al . which is hereby incorporated by reference or it may be one of the sugar amides described in Patent No. 5,009,814 to Kelkenberg, hereby incorporated into the subject application by reference. Other surfactants which may be used are described in U.S. Patent No. 3,723,325 to Parran Jr. and alkyl polysaccharide nonionic surfactants as disclosed in U.S. Patent No. 4,565,647 to Llenado, both of which are also incorporated into the subject application by reference.
Preferred alkyl polysaccharides are alkylpolyglycosides of the formula:
R 0(CnH2nO)t(glycosyl)x
2 wherein R is selected from alkyl, alkylphenyl , hydroxyalkyl, hydroxyalkylphenyl , and mixtures thereof in which alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 0 to 3, preferably 2; t is from 0 to about 10, preferably 0 ; and x is from 1.3 to about 10, preferably from 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds , the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position) . The additional glycosyl units may then be attached between the 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.
Nonionic comprises 0 to 10% by wt . of the composition.
According to a second embodiment , the external aqueous phase must also comprise about 0.01 to 10% by wt of a stabilizing natural gum polymer. It is preferred that in systems where the external surfactant W2 is comprised entirely of or contains a majority of (60% or higher) anionic surfactant that a nonionic gum polymer is used.
Nonionic seed polysaccharides are particularly soluble and dispersible in anionic surfactants and anionic rich surfactant systems. One such stabilizer is guar gum, which is structurally composed of a straight chain of D-mannose with a D-galactose side chain on approximately every other mannose unit. The usual ratio of mannose to galactose is approximately 2:1 and molecular weights are usually on the order of 100,000 to 1,000,000. Another useful stabilizer is locust bean gum, a galactomannan consisting of a main chain of D-mannose units with single galactose side chains on approximately every fourth unit. As with guar gum, approximate molecular weights are between 100,000 and 1, 000, 000.
In systems where the external surfactant W2 is comprised entirely of or contains a majority (50% or higher) , of amphoteric surfactant, an anionic gum polymer is preferred. These may be seaweed polysaccharides , exudate polysaccharides, or microbial polysaccharides.
A preferred anionic seaweed polysaccharide is carrageenan, or Irish moss, a complex mixture of sulfated polysaccharides. Carrageenan is a mixture of galactans that carry varying proportions of half-ester sulfate groups linked to one or more of the hydroxyl groups of the galactose units, which are joined by alternating -1,3 and β-1,4 glycosidic linkages. The molecular weight usually ranges from 100,000 to 1,000,000.
A preferred anionic exudate polysaccharide is gum tragacanth, a complex mixture of acidic polysaccharides containing galacturonic acid, galactose, fucose, xylose, and arabinose . Another preferred anionic exudate polysaccharide is gum karaya, a partially acetylated high molecular weight polysaccharide which contains L-rhamnose, D-galactose, D- galacturonic acid, and D-glucuronic acid residues.
The most preferred amphoteric or amphoteric rich surfactant systems are microbial anionic hetero polysaccharide gums, most preferably Xanthan gum. The primary structure of these microbial gums contains two glucose units, two mannose units, and one glucuronic acid unit.
Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts or ratios of materials or conditions or reaction, physical properties of materials and/or use are to be understood as modified by the word "about" .
Where used in the specification, the term "comprising" is intended to include the presence of stated features, integers, steps, components but not to preclude the presence or addition of one or more features, integers, steps, components or groups thereof. All percentages used, unless indicated otherwise, are intended to be percentages by weight .
Definition and Measurement of Stability (for purposes of first embodiment)
Sodium ISE: To measure multiple emulsion stability, a sodium ion sensitive electrode (Corning 476138) was attached to an Orion EA 920 expandable ion analyzer.
The multiple emulsion samples were intentionally prepared with a too low internal NaCl concentration. Thus, the Na ion concentration of the separated bottom phase served as a rapid indicator of multiple emulsion stability.
In the case of multiple emulsion breakage, the NaCl from the internal phase is released and the NaCl concentration in the external aqueous phase increases because the initial salt concentration is greater m the internal phase. A plot of separated phase sodium ion concentration versus storage time shows a positive slope (increasing Na ion concentration over time) .
In the case of a stable multiple emulsion, the NaCl is held m the internal phase and only water is released to the external phase. A plot of separated phase sodium ion concentration versus storage time shows a negative slope
(gradual Na ion dilution over time) or virtually no slope
(water was released at an early stage) . 5g of the separated external aqueous (bottom) phase was taken from the separatory funnel and diluted to 50 g with 45 g of milli-Q water. To this was added 50 g of 0.5 M triethanolamine (TEA) to maintain ionic strength and equalize activity coefficients.
Standards were prepared by taking 1,2, 3, 4 and 5 g samples of the original external phase and diluting them with 49, 48, 47, 46, and 45 g of milli-Q water, respectively, to 50 g. 50 g of 0.5 M TEA was added to each sample, as above.
Each of the standard samples and the separated emulsion sample were measured for sodium ion activity (concentration) using the sodium ion sensitive electrode.
Those multiple emulsions which showed a zero or negative slope over the course of 30 days at room temperature (20- 25°C) storage were deemed stable . Conversely, those which displayed a positive slope over the same amount of time were deemed unstable .
Definition and Measurement of Stability (for second embodiment)
Multiple emulsion stability was measured after 45 days by collecting the amount of separated water phase (if any) and measuring the weight of collected material. This weight is then divided by the total weight of product in the separatory funnel to obtain % separation. Multiple Emulsion Preparation (for both embodiments)
Primary (Wχ/0) Emulsions
Oil Phase: The oil and the oil soluble surfactant (low HLB emulsifier) were mixed together at room temperature using overhead stirring.
Internal aqueous phase (Wx) : Sodium chloride solutions with or without topically active compounds of appropriate concentrations were prepared and the pH was adjusted to 7.0.
Wχ/0 preparation: the oil phase (0) was charged into the vessel. The salt/topically active compound solution (Wx) was added to the oil phase steadily through the addition funnel over the course of 10-12 minutes while mixing with the side scraper (60-80 rpm) . Slow addition of aqueous phase under low shear mixing is essential to obtain a stable primary emulsion. Upon complete addition of the aqueous phase, the mixing speed of the side scraper was reduced to
40 rpm and the homogenizer was turned on. Homogenization was carried out for 3 minutes each at 8000, 9500 and 13,500 rpm at room temperature . The heat generated during the homogenization process raised the temperature of the batch to ~35°C.
Multiple Emulsion
External aqueous phase (W2) : External aqueous phases were prepared in a jacketed vessel by mixing the minority surfactant into the majority surfactant at 60°C with intense mixing. The pH of each surfactant solution was pre-adjusted to 7.0. Surfactant solutions which had a gel like consistency were centrifuged at 7000 rpm for 20 minutes to remove the entrapped air.
1/O/W2 preparation: The primary emulsion (Wχ/0) was charged into the smaller scale vessel followed by addition of the external aqueous phase ( 2) . The mixture was hand- mixed gently for 15 seconds using a spatula. This was followed by mixing with the side-scraper for 8 minutes at 70-105 rpm (higher speed was used when mixing at lower speed was found to be inadequate) . A small spatula was inserted into the vessel as a baffle to ensure good mixing around the center spindle of the side scraper. The resulting multiple emulsions were transferred into 250 ml separatory funnels to await separation of the aqueous phase for emulsion stability analysis .
Examples 1-37 relate to the first embodiment and 38-59 relate to the second.
EXAMPLES
The following components were used in the experiment as follows ;
Figure imgf000058_0001
EXAMPLES 1 - 14
In order to show the effect of varying anionics in mixture with amphoterics (e.g., betaine) on multiple emulsion stability, the following examples were prepared:
Table 1. Effect of different anionics in mixture with betaine on multiple emulsion stability
Figure imgf000060_0001
Figure imgf000060_0002
s c ear y seen, an on c sur actants with amido group render the multiple emulsion unstable (Examples 8 to 14 compared to 1 to 7) .
EXAMPLES 15-21
In order to determine effect, if any, of amphoteric/anionic ratio on stability, the following examples were prepared:
Table 2. Effect of amphoteric/anionic ratio on multiple emulsion stability
Figure imgf000061_0001
As noted, regardless of amphoteric/anionic ratio, emulsion was stable.
EXAMPLES 1 and 22 From the following examples, it can be seen that multiple emulsion may be stable over various types of amphoterics. Table 3. Effect of different amphoterics with anionic on multiple emulsion stability
Figure imgf000062_0001
EXAMPLES 23 and 24 The following compositions were prepared to show that nonionics and amphoterics also form stable multiple emulsions
Table 4. Effect of nonionics with amphoteric on multiple emulsion stability
Figure imgf000063_0001
EXAMPLES 1 AND 25-28
From the following table, it can be seen that stable multiple emulsions are formed when the composition of the oil phase is less than 50% unsaturated hydrocarbon compounds, i.e. sunflower oil has a composition which is greater than 50% unsaturated hydrocarbon compounds. Table 5. Effect of different oils on multiple emulsion stability
Figure imgf000064_0001
EXAMPLES 29-31
In order to show the effect of low HLB emulsifier concentration, the following examples were prepared. Table 6. Effect of emulsifier concentration on multiple emulsion stability
Figure imgf000065_0001
EXAMPLES 2, 32 AND 33
To show whether multiple emulsions are stable over broad composition of surfactant/oil ratios, the following examples were prepared:
Table 7. Effect of total surfactant/oil ratio on multiple emulsion stability
Figure imgf000066_0001
As clearly seen, the stability remained over a broad range of surfactant/oil ratios.
EXAMPLES 2, 34-37
In order to show the stability of the multiple emulsion when a skin benefit agent or hair styling polymer is incorporated into the WI phase, Compositions 2 and 34-37 were prepared. Table 8. Effect of incorporating benefit agent (lactic acid) into WI phase on multiple emulsion stability
Figure imgf000067_0001
As clearly seen, in Examples 34 and 35, incorporation of benefit agent had no effect on multiple emulsion stability. Examples 36 and 37 demonstrate the criticality that if a cationic hair styling polymer is used in systems containing an anionic surfactant, multiple emulsion stability will be adversely affected.
Materials (for second embodiment) and Examples 38-59
The following components were used in the experiments as follows :
Figure imgf000068_0001
EXAMPLES 38-43
Figure imgf000069_0001
Example 38, the control, has a Newtonian anionic external W2 phase (SLES) and it phase separates 40% over 45 days. Examples 2 and 3 show that by gelling the external phase with a nonionic natural gum stabilizer, phase separation is prevented by incorporating locust bean gum or retarded by incorporating guar gum. Example 41 shows that Locust bean gum also gels another anionic surfactant, sodium lauryl sulfate. Example 42 shows that octyl palmitate can be substituted for light mineral oil. In Example 43, we attempted to incorporate an anionic gum into an anionic surfactant but the 2 phase was not homogeneous. Examples 39-42 show the criticality that the gum must be nonionic when the surfactant is anionic.
EXAMPLES 44-51
CO c on ω
cn x m q
30
C r- m o )
Figure imgf000071_0001
Example 44 , the control , has a Newtonian amphoteric external 2 phase (betaine) and it phase separates 50% over 45 days. Examples 45 through 49 show that by gelling the external phase with an anionic natural gum stabilizer, phase separation is prevented by incorporating xanthan gum or retarded by incorporating gum tragacanth, gum karaya, or carrageenan. Example 49 shows that xanthan gum also gels another amphoteric surfactant, cocoamphoglycinate . Example 50 shows that octyl palmitate can be substituted for light mineral oil. In Example 51, we attempted to incorporate a nonionic gum into an amphoteric surfactant but the W2 phase was not homogeneous. Examples 45-50 thus show that the gum must be anionic when the surfactant is amphoteric.
EXAMPLES 52-59
Figure imgf000073_0001
ts_
)
Figure imgf000073_0002
Example 52, is a control with anionic as the majority surfactant. Examples 53 and 54 show that when nonionic gum stabilizer (locust bean) is used, phase separation is prevented whereas when an anionic gum stabilizer (xanthan) is used, phase separation is still close to the control. Example 56 shows that the anionic ratio can be changed from 13:2 to 9:6 without phase separation. Conversely, Example 56 is a control with amphoteric as the majority surfactant. Examples 57 and 58 show that when an anionic gum stabilizer (xanthan) is used, phase separation is prevented whereas when a nonionic gum stabilizer (locust bean) is used, phase separation is still close to the control. Example 59 shows that the amphoteric ratio can be changed from 11:4 to 7.5:7.5 without phase separation.
These examples demonstrate the criticality that when the majority surfactant is anionic, that a nonionic gum stabilizer must be used. Furthermore, when the surfactant mixture is half or greater amphoteric, an anionic gum stabilizer must be used.

Claims

1. A W1-O-W2 multiple emulsion comprising:
(1) 1% to 99% by wt. of the composition of a χ/0 emulsion comprising;
(a) 1% to 99% by wt .0 of the emulsion of an internal aqueous phase comprising (i) water; (ii) 0.01 to 30% by wt . emulsion solute; and (iii) 0-30% optional surfactant; (b) 0.1% to 99% by wt . of the emulsion of an oil phase surrounding the internal aqueous phase wherein the oil is selected from volatile hydrocarbon, nonvolatile hydrocarbons, nonvolatile silicones and mixtures thereof; (c) 0.1 to 20% by wt . of the emulsion of a surfactant emulsifier selected from silicon- free surfactant or surfactant blend having an HLB value of about 10 or less, an oil soluble silicon based surfactant, an oil-soluble polymeric surfactant and mixtures thereof; and (d) a topically effective amount of a first topically active compound, which may be found in either the aqueous phase (a) , oil phase (b) or both; and
(2) 1 to 99% by wt. of an external isotropic aqueous phase 2 comprising:
(a) 2 to 80% by wt . aqueous phase of a surfactant phase which comprises a non-amido anionic or nonionic or mixtures thereof in combination with at least one amphoteric; wherein the ratio of anionic and/or nonionic to amphoteric is 100:1 to 1:100 (b) optionally 0 to 60% by wt . of external phase of a second topically active compound; and (c) optional solute.
2. A 1-O-W2 multiple emulsion comprising: (1) 1% to 99% by wt . of the composition of a /0 emulsion comprising;
(a) 1% to 99% by wt . of the emulsion of an internal aqueous phase comprising (i) water; (ii) 0.01 to 30% by wt . emulsion solute; and (iii) optional surfactant;
(b) 0.1% to 99% by wt . of the emulsion of an oil phase surrounding the internal aqueous phase wherein the oil is selected from volatile hydrocarbon, nonvolatile hydrocarbons, nonvolatile silicones and mixtures thereof;
(c) 0.1 to 20% by wt. of the emulsion of a surfactant emulsifier selected from silicon- free surfactant or surfactant blend having an HLB value of about 10 or less, an oil soluble silicon based surfactant, an oil -soluble polymeric surfactant and mixtures thereof; and
(d) a topically effective amount of a first topically active compound, which may be found in either the aqueous phase (a) , oil phase (b) or both; and
(2) 1 to 99% by wt . of an external isotropic aqueous phase 2 comprising:
(a) 2 to 80% by wt . aqueous phase of a surfactant phase which comprises a non-amido anionic, or an amphoteric or a mixture of the two in which either (i) 60% by weight or greater is the anionic surfactant or (ii) 50% by weight or greater is the amphoteric surfactant;
(b) 0 to 60% by wt . of external phase of a second topically active compound;
(c) optional solute; and (d) 0.01 to 10% of a nonionic natural gum stabilizer when 60% or greater of the surfactant phase in (2) (a) (i) above is anionic, or 0.01 to 10% of an anionic natural gum stabilizer when 50% or greater of the surfactant phase in (2) (a) (ii) above is amphoteric, wherein in both instances the multiple emulsion droplets maintain their integrity and the multiple emulsion composition does not phase separate.
3. An emulsion according to claim 1 or claim 2 comprising
2 to 90% by wt. ι/0 emulsion.
4. An emulsion according to claim 3, comprising 5 to 80% by wt. Wι/0 emulsion.
5. An emulsion according to any of the preceding claims, wherein the solute in the internal aqueous phase is alkali metal chloride, sucrose or glucose.
6. An emulsion according to any of the preceding claims wherein the oil phase comprises 1 to 80% of the internal Wχ/0 phase.
7. An emulsion according to any of the preceding claims wherein the hydrocarbon is a saturated vegetable based oil .
8. An emulsion according to claim 7, wherein oil is > 50% saturated.
9. An emulsion according to claim 8, wherein oil is > 85% saturated.
10. An emulsion according to any of the preceding claims wherein the emulsifier (c) is cetyl dimethicone copolyol .
11. An emulsion according to any of the preceding claims wherein the topically active compound (1) (d) is lactic acid.
12. An emulsion according to claim 10, wherein the second topically active compound (2) (b) is also lactic acid.
13. An emulsion according to any of the preceding claims wherein topically active compound is a nonionic hair styling polymer.
14. An emulsion according to any of the preceding claims wherein topically active compound is PVP.
15. An emulsion according to any of the preceding claims, which is stable at a temperature of 25°C after 2 weeks.
16. An emulsion according to claim 15, which is stable after 30 days.
(e) 17. An emulsion according to any of the preceding claims, wherein the natural gum stabilizing polymer is locust bean gum or guar gum.
PCT/EP2000/010378 1999-10-22 2000-10-19 Stable multiple emulsion composition WO2001028502A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU77898/00A AU7789800A (en) 1999-10-22 2000-10-19 Stable multiple emulsion composition
CA002388161A CA2388161A1 (en) 1999-10-22 2000-10-19 Stable multiple emulsion cosmetic composition comprising high levels of surfactant
JP2001531098A JP2003511235A (en) 1999-10-22 2000-10-19 Stable multiple emulsion composition

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US09/425,717 US6235298B1 (en) 1999-10-22 1999-10-22 Phase stable multiple emulsion compositions
US09/425,366 1999-10-22
US09/425,366 US6290943B1 (en) 1999-10-22 1999-10-22 Stable multiple emulsion composition
US09/425,717 1999-10-22

Publications (1)

Publication Number Publication Date
WO2001028502A1 true WO2001028502A1 (en) 2001-04-26

Family

ID=27026655

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/010378 WO2001028502A1 (en) 1999-10-22 2000-10-19 Stable multiple emulsion composition

Country Status (4)

Country Link
JP (1) JP2003511235A (en)
AU (1) AU7789800A (en)
CA (1) CA2388161A1 (en)
WO (1) WO2001028502A1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10206796A1 (en) * 2002-02-19 2003-08-28 Beiersdorf Ag Sunscreen composition, comprises separate water-in-oil emulsion and lipophilic or aqueous phases, at least one of which is not transparent or translucent
GB2400609A (en) * 2003-04-16 2004-10-20 Reckitt Benckiser Multiple-emulsion cleaner
US7476394B2 (en) 2004-08-04 2009-01-13 Conopco, Inc. Detergent composition with benefit agents
CN102014852B (en) * 2008-03-11 2013-12-11 玫琳凯有限公司 Stable three-phased emulsions
EP2797423B1 (en) 2011-11-15 2016-04-20 Starck's Food GmbH & Co. KG Vegan emulsion
WO2020200979A1 (en) * 2019-04-01 2020-10-08 Unilever Plc Multiple emulsion comprising an oil continuous nanoemulsion and a method for using the same
US11540984B2 (en) 2018-05-23 2023-01-03 Conopco, Inc. Nanoemulsions and a method for making the same

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4659510B2 (en) * 2005-04-28 2011-03-30 サンスター株式会社 W / O / W type emulsion composition
EP2821057B1 (en) * 2012-02-28 2019-09-11 Suntory Holdings Limited W/o/w emulsion having temporal stability and method for producing the same
DE102020214353A1 (en) * 2020-11-16 2022-05-19 Beiersdorf Aktiengesellschaft Emulsion containing Ceratonia Siliqua Gum and Aluminum Chlorohydrate

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4083798A (en) * 1976-06-17 1978-04-11 Exxon Research & Engineering Co. Stabilized static liquid membrane compositions
US4254105A (en) * 1975-10-11 1981-03-03 The Lion Dentifrice Co., Ltd. Multiple emulsion having a form of water/oil/water phase and process for preparation thereof, and multiple emulsion type cosmetics
US5306498A (en) * 1991-04-05 1994-04-26 L'oreal Cosmetic composition in the form of a triple emulsion
US5332595A (en) * 1991-03-18 1994-07-26 Kraft General Foods, Inc. Stable multiple emulsions comprising interfacial gelatinous layer, flavor-encapsulating multiple emulsions and low/no-fat food products comprising the same
US5656263A (en) * 1993-03-11 1997-08-12 The Boots Company Plc Multiple emulsions
EP0908170A1 (en) * 1997-10-03 1999-04-14 L'oreal Stable water-in-oil-in-water emulsion and its use as cosmetic and/or dermatological composition

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58183611A (en) * 1982-04-19 1983-10-26 Kanebo Ltd Cosmetic of polyphase emulsification type
DE4322174A1 (en) * 1993-07-03 1995-01-12 Goldschmidt Ag Th Liquid or pasty, storage-stable, multiple emulsion of the type W · 1 · / O / W · 2 ·
JPH08245364A (en) * 1995-03-15 1996-09-24 Kose Corp W/o/w-type emulsion cosmetic

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4254105A (en) * 1975-10-11 1981-03-03 The Lion Dentifrice Co., Ltd. Multiple emulsion having a form of water/oil/water phase and process for preparation thereof, and multiple emulsion type cosmetics
US4083798A (en) * 1976-06-17 1978-04-11 Exxon Research & Engineering Co. Stabilized static liquid membrane compositions
US5332595A (en) * 1991-03-18 1994-07-26 Kraft General Foods, Inc. Stable multiple emulsions comprising interfacial gelatinous layer, flavor-encapsulating multiple emulsions and low/no-fat food products comprising the same
US5306498A (en) * 1991-04-05 1994-04-26 L'oreal Cosmetic composition in the form of a triple emulsion
US5656263A (en) * 1993-03-11 1997-08-12 The Boots Company Plc Multiple emulsions
EP0908170A1 (en) * 1997-10-03 1999-04-14 L'oreal Stable water-in-oil-in-water emulsion and its use as cosmetic and/or dermatological composition

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10206796A1 (en) * 2002-02-19 2003-08-28 Beiersdorf Ag Sunscreen composition, comprises separate water-in-oil emulsion and lipophilic or aqueous phases, at least one of which is not transparent or translucent
GB2400609A (en) * 2003-04-16 2004-10-20 Reckitt Benckiser Multiple-emulsion cleaner
US7776812B2 (en) 2003-04-16 2010-08-17 Reckitt Benckiser (Uk) Limited Multiple emulsion hard surface cleaning compositions
US7476394B2 (en) 2004-08-04 2009-01-13 Conopco, Inc. Detergent composition with benefit agents
CN102014852B (en) * 2008-03-11 2013-12-11 玫琳凯有限公司 Stable three-phased emulsions
EP2797423B1 (en) 2011-11-15 2016-04-20 Starck's Food GmbH & Co. KG Vegan emulsion
US11540984B2 (en) 2018-05-23 2023-01-03 Conopco, Inc. Nanoemulsions and a method for making the same
WO2020200979A1 (en) * 2019-04-01 2020-10-08 Unilever Plc Multiple emulsion comprising an oil continuous nanoemulsion and a method for using the same

Also Published As

Publication number Publication date
CA2388161A1 (en) 2001-04-26
AU7789800A (en) 2001-04-30
JP2003511235A (en) 2003-03-25

Similar Documents

Publication Publication Date Title
US6235298B1 (en) Phase stable multiple emulsion compositions
US5656280A (en) Water-in-oil-in-water compositions
AU688632B2 (en) Water-in-oil-in-water compositions
US6290943B1 (en) Stable multiple emulsion composition
EP1282681B1 (en) Dual chamber cleansing system
US6268322B1 (en) Dual chamber cleansing system, comprising multiple emulsion
AU709578B2 (en) Topically-effective antiperspirant compositions
US8263058B2 (en) Personal care compositions that deposit hydrophilic benefit agents
US20060078524A1 (en) Multi phase personal care composition comprising a conditioning phase and an oil continuous benefit phase
ES2257456T3 (en) TRANSPARENT EMULSION WITH HIGH CONTENT IN OIL THAT INCLUDES A DIENIC ELASTOMERO.
JP4355034B2 (en) Two-phase cosmetic composition
WO2005065630A1 (en) Monophase microemulsion composition, o/w ultrafine emulsion external formulation and process for producing the same
JP2004520418A (en) Delivery of reactive drugs via multiple emulsions for use in storage-stable products
JP4072296B2 (en) Use of silicone rubber to stabilize ascorbic acid and novel compositions containing these components
KR20160008548A (en) Cosmetic composition comprising a silicone oil and polymethylmethacrylate particles
WO2001028502A1 (en) Stable multiple emulsion composition
US20040234478A1 (en) Personal care compositions containing a silicone elastomer
AU2004238310A1 (en) Personal care compositions containing a silicone elastomer and a dispersed oil phase
KR20120023576A (en) Compositions comprising a silicone water-in-oil emulsifier and a low nitrogen containing amino-functional silicone gum
CN100408022C (en) Personal care compositions containing a silicone elastomer and a dispersed oil phase
JPH10218726A (en) Skin cosmetic

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
ENP Entry into the national phase

Ref country code: JP

Ref document number: 2001 531098

Kind code of ref document: A

Format of ref document f/p: F

WWE Wipo information: entry into national phase

Ref document number: 2388161

Country of ref document: CA

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase