WO2005025523A2 - Antiperspirant clear gel with low glycol content - Google Patents
Antiperspirant clear gel with low glycol content Download PDFInfo
- Publication number
- WO2005025523A2 WO2005025523A2 PCT/US2004/029116 US2004029116W WO2005025523A2 WO 2005025523 A2 WO2005025523 A2 WO 2005025523A2 US 2004029116 W US2004029116 W US 2004029116W WO 2005025523 A2 WO2005025523 A2 WO 2005025523A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- glycol
- group
- clear gel
- water
- Prior art date
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/26—Aluminium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/042—Gels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/28—Zirconium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
- A61K8/345—Alcohols containing more than one hydroxy group
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
- A61K8/585—Organosilicon compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/86—Polyethers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q15/00—Anti-perspirants or body deodorants
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/26—Optical properties
- A61K2800/262—Transparent; Translucent
Definitions
- the present invention is directed to a clear, high efficacy, high viscosity, elastomer- free, suspension-free gel composition
- a glycine free antiperspirant active preferably with a lower metal to chloride ratio
- Betaine trimethylglycine
- the active phase may additionally contain a monovalent or divalent ionizable water soluble salt.
- the gel is formulated as a clear product having reduced whitening and tack as well as reduced skin irritation.
- An odor neutralizing agent which provides improved odor protection is an additional optional ingredient which can easily be incorporated within the gel composition.
- U.S. Patent Application Number 10/406,856 filed April 4, 2003 comprises aluminum and/or zirconium salts with Betaine as a complexing agent and buffering agent and which do not contain glycine.
- Betaine can be used in its normal form or as Betaine hydrochloride.
- the enhanced salts of this invention may be used to formulate antiperspirants having improved efficacy.
- antiperspirants include solids such as sticks and creams (creams sometimes being included in the term "soft solid"), gels, liquids (such as are suitable for roll-on products), and aerosols.
- the forms of these products may be suspensions or emulsions.
- Patent Application Number 10/607,099 filed June 26, 2003 comprises aluminum/zirconium salts containing a complexation agent such as glycine and further stabilized with Betaine as complexation agent and buffer agent.
- the amount of Betaine that is used should be sufficient to have an overall Betaine+glycine to Zr ratio in the range of 0.1-3.0:1, and preferably in the range of 0.7-1.5:1, with a ratio of Betaine to glycine of at least 0.001:1.
- the enhanced salts of this invention may be used to formulate antiperspirants having improved efficacy.
- Antiperspirant products are well known in the art. Antiperspirants have appeared in the marketplace in varied dosage forms, such as sticks, soft solids, soft gels, roll-on, aerosols and creams.
- these dosage forms include a solution of the active ingredient in a suitable solvent, a suspension of the active ingredient in a non-solvent, or a multiphasic dispersion or emulsion in which a solution of the active ingredient is dispersed in some continuous phase or in which the solubilized active ingredient constitutes a continuous phase.
- the stick form is an example of a solid form
- the soft solid and soft gel are thickened forms which may or may not be solid (for example, under some circumstances, gels can flow).
- the stick form can be distinguished from a soft solid or soft gel in that, in a stick, the formulated product can retain its shape for extended time periods outside the package, the product not losing its shape significantly (allowing for some slirinkage due to solvent evaporation). Adjustment of amounts of gelling or thickening agents can be used in order to form a soft gel or stick.
- Soft gels or soft solids can be suitably packaged in containers which have the appearance of a stick, but which dispense through apertures (for example, slots or pores) on the top surface of the package.
- the soft solid products have also been called soft sticks or "smooth-ons", and hereinafter are generically called "soft solids". Reference is made to U.S. Patent Number 5,102,656 to Kasat, U.S.
- Patent Number 5,069,897 to Orr discloses such soft solids, including physical characteristics thereof such as viscosity and hardness.
- the contents of each of these three U.S. patents are incorporated herein by reference in their entirety for description of characteristics of soft solids and suitable packaging for such products.
- Patent Number 4,944,938 to Potini discloses clear, non-alcoholic, quick drying, antiperspirant and deodorant gels, which are stable both at room temperatures and at higher temperatures, are non-stinging and leave no white residue on the skin.
- the gel is free of gelling agents, waxes, clays, or monohydric alcohols having 2-8 carbon atoms.
- the gels use 3-5 carbon atom trihydric alcohols as coupling agents which act as solubilizers in the system and keep the system stable and clear.
- the gels can include an aluminum active salt; a volatile water-insoluble emollient, such as isostearyl benzoate: a soluble emollient such as cetyl ether; solubilizers such as propylene glycol and glycerin; volatile siloxanes; and water.
- a volatile water-insoluble emollient such as isostearyl benzoate: a soluble emollient such as cetyl ether
- solubilizers such as propylene glycol and glycerin; volatile siloxanes; and water.
- Some cellulosic materials such as hydroxypropylcellulose, among others, are compatible with polyvalent metal salts and have been used in the manufacture of clear lotions. These cellulosic materials, however, must be prepared with a high percentage of water or alcohol in order to insure solubilization of the active ingredient.
- the resulting formulations in addition to a high irritation potential, are tacky and low in efficacy, when alcohol-based; and exhibit tackiness and along drying time when water-based.
- Clear antiperspirant soft gels (which have been dispensed from containers having the appearance of stick) have recently been marketed, consisting of viscous, high-internal-phase emulsions. These soft gels exhibit some advantages over the aforementioned sticks, particularly acetal-based clear sticks, in that the selection of formulation ingredients is less restricted (for example, water can be used), and often tack can be reduced significantly. Concerning these emulsions, note U.S. Patent Number 4,673,570 to Soldati and U.S.
- These two U.S. patents disclose clear gelled antiperspirant compositions free of waxes and conventional gelling agents, containing a volatile silicone fluid, a silicone emulsifier, a destabilizing auxiliary emulsifier, water, nonvolatile emollient, a coupling agent, an active antiperspirant component and ancillary agents such as perfume, coloring agents, etc.
- the silicone emulsifiers a cyclomethicone- dimethicone copolyol silicone fluid marketed by Dow Corning Corporation under the trademark DOW CORNING 3225C formulation, hi particular, U.S.
- Patent Number 4,673,570 claim 1 is "from about 10-25% by weight of a cyclomethicone-dimethicone copolysilicone fluid (same as 1.0-2.5% on an actives basis).
- a cyclomethicone-dimethicone copolysilicone fluid (same as 1.0-2.5% on an actives basis).
- PCT International application
- WO 92/05767 This patent document discloses a clear gel-type cosmetic product having a viscosity of at least about 50,000 cps at 21 degrees C.
- the product being an emulsion with a water phase having an active ingredient incorporated therein and with an oil phase.
- the refractive indices (measured at 5893 Angstroms) of the water and oil phases match to within 0.0004.
- the oil phase includes an emulsifier which when properly mixed with the water phase component yields a water- in-oil emulsion, and the water phase includes one or a combination of various polar species such as water, propylene glycol, sorbitol and ethanol.
- the water phase includes the deodorant and or antiperspirant active ingredient.
- U.S. Patent Number 6,007,799 assigned to the same owner as this case, describes clear cosmetic gels that are water-in-oil emulsions and which comprise at least one coupling agent, silicone fluids and an alkoxylated, alkyl substituted silicone surface active agent.
- U.S. Patent Numbers 5,587,153 and 5,863,525 issued to Gillette also describe gel products that (1) contain silicone in the oil phase and (2) does not control the propylene glycol content.
- U.S. Patent Number 5,925,338 issued to Gillette describes a clear gel comprising selected amounts of various types of silicones.
- Patent Number 6,419,910 assigned to Unilever describes a clear emulsion and gel-type antiperspirant and deodorant composition which comprises a water in oil emulsion which is essentially free of glycols and low and middle chain alcohols.
- the composition comprises 25-35% of an oil phase comprising at least one non- volatile ester or at least one nonvolatile silicone wherein at least one oil phase soluble ingredients has a refractive index of about 1.40 to about 1.45.
- the active phase contains a water soluble, non-simple glycol component which raises the refractive index of the aqueous solution.
- Patent Application 2002/10051138 Al also assigned to Unilever, describes an essentially glycol free clear emulsion and gel-type antiperspirant and deodorant composition in which the water phase further differentiated by containing at least one polymeric ethylene oxide glycol and is essentially free of glycols and low and middle chain alcohols.
- U.S. Patent Application Publication Number 2004/0001795 Al Publication Date: Jan 1, 2004 filed by Reheis describes a glycine free high efficacy antiperspirant salt comprised of aluminum zirconium tetrasalt with a low M:C1 ratio.
- Patent Application Serial Number 10/625,038 filed by Reheis describes a glycine free high efficacy antiperspirant salt comprised of aluminum zirconium octasalt with a low M:C1 ratio. Further examples of making these types of salt complexes are described in U.S.
- U.S. Patent Number 6,042,816 describes enhanced efficacy antiperspirant salt compositions containing calcium and an amino acid or a hydroxy acid, methods of making such enhanced efficacy antiperspirant salt compositions, stabilized aqueous solutions of such enhanced efficacy antiperspirant salt compositions, and topical compositions containing such enhanced efficacy antiperspirant salt compositions.
- U.S. Patent Number 6,468,512 assigned to Avon describes a clear antiperspirant/deodorant gel composition.
- the composition is a water-in-oil emulsion having a viscosity about 7,000 cps to about 25,000 cps and a clarity from about 30 NTU or less.
- the composition further has an antiperspirant active, water, silicone gelling agent, and one or more silicone oils.
- Patent Number 6,485,716 assigned to the same owner as the present case describes a clear, elastomer-free, gel composition
- a clear, elastomer-free, gel composition comprising: (a) 0.1-25 weight % of an antiperspirant active having a low metal to chloride ratio in the range of 0.9-1.3: 1; (b) 9- 23.95 weight % of one or more volatile silicones having a flash point of 100 degrees C or less; (c) 0.05-0.5 weight % of a silicone surfactant having an HLB value less than or equal to 8; (d) 30-70 weight % water; (e) 0-50 weight % selected water soluble organic solvents; and (f) 0-10 weight % of an emollient; wherem the composition is a liquid gel having a viscosity in the range of 5-50,000 centipoise and a ratio of oil phase to water phase in the range of 10:90 to 24:76.
- U.S. Patent Number 6,500,412 assigned to the same owner as this case describes a non-sticky, clear water-in-oil emulsion comprising: (a) 65-90 weight % of an internal phase comprising 5-35 weight % of an antiperspirant salt (anhydrous basis) having a metalxhloride ratio in the range of 0.9-1.4:1; 5-15 weight % of tripropylene glycol; and 35- 70 weight % water; and (b) 10-35 weight % of an external phase comprismg 1-40 weight % of a volatile silicone which is not an elastomer; 0.1-5 weight % of a silicone copolyol surfactant; and 0-20 weight % of a nonvolatile silicone which is not an elastomer; wherein the composition is free of (1) Cl-5 saturated alcohols, (2) added propylene glycol, (3) elastomer gelling agents, (4) soap gelling agents (5) borate gelling agents, and (6) coupling agents, and wherein all amounts
- the Betaine (defined below) of this invention is not a surfactant and has been found to have properties important to the field of antiperspirant salts that contain zirconium.
- the Betaine used in this invention is a natural product found in a number of plants in the Chenopodiaceae family, and also in fish and selected- legumes. Extracted most often from sugar beets (Beta Vulgaris), it is reported as an extremely versatile molecule with a wide range of applications: food supplement, anti-irritant, skin moisturizer, skin-softening agent, skin-conditioning agent, promoter of wound healing and component in cosmetic compositions for skin aging and stressed skin.
- Betaine in ' IUPAC nomenclature is l-carboxy-N,N,N-trimethylmethanaminium hydroxide-inner salt, with alternative names including carboxymethyl-trimethyl-ammonium betaine or (carboxymethyl)trimethylarnmonium hydroxide-inner salt or glycine betaine or glycol betaine or glycyl betaine or trimethylglycine or trimethylglycol.
- German Patent DE 19725087 is related to cosmetic and dermatologic oil-in-water emulsion formulations for light protection containing hydrophobic inorganic micropigments and hydrophilic surfactants.
- PCT Publication WO 97/23594 describes skin cleansing compositions with enhanced antimicrobial activity comprising 0.1-30% of an amphoteric, zwitterionic, nonionic, anionic and/or cationic emulsifier, 0.00001-5% of an Ag compound (AgCl, Ag 2 C0 3 , etc.), deposited on a particulate inert support material (metal oxides, especially Ti0 2 ) as antimicrobial agent, and H 2 0.
- a typical composition contains cetyl betaine.
- Japanese Patent JP 2001163752 describes long-lasting cosmetic makeup compositions comprising plate-type glossy polymer powders and antiperspirants.
- European Patent EP 1005853 describes the use of betaines as antiperspirants.
- European Patent EP 1005852 describes the use of functionally substituted betaines as antiperspirants.
- Japanese Patent JP 11130652 discloses skin-conditioning and moisturizing cosmetics containing clay minerals and low-molecular-weight betaines to inhibit the release of pyrrolidonecarboxylic acid (a natural moisturizing factor) from human skin.
- German Patent DE 2610225 describes aluminum salts of Betaine chloride being useful as ulcer inhibitors, for treatment of gastritis, to promote wound healing, and as antiperspirants and deodorants.
- PCT Publication WO 01/62222 describes cosmetic compositions containing phospholipids and quaternary amines. The invention relates to a cosmetic composition, especially for use on aging and/or stressed skin, the composition comprising, in addition to water, at least one substance that forms lamellar structures with water.
- compositions including Betaine are described.
- PCT Publication WO 01/47479 assigned to the same owner as this case describes cosmetic moisturizing compositions containing quaternary ammonium compounds.
- Compositions with cocamidopropyl betaine are described.
- PCT Publication WO 01/39730 describes a cosmetic composition containing peat arid Betaine.
- PCT Publication WO 97/46246 is related to complex preparations for topical use containing Betaine to stimulate cellular and physiological processes.
- PCT Publication WO 91/18588 presents a method of reducing the irritating properties of a cosmetic composition by addition of Betaine derivatives.
- Japanese Patent JP 03033266 describes modified fabrics coated with a mixture of dodecyl betaine and other ingredients for controlling pH change in skin during sweating.
- cosmetic gel compositions including antiperspirant and deodorant compositions that are clear
- a cosmetic gel composition e.g., clear antiperspirant and/or deodorant gel composition
- Betaine is able to further stabilize the antiperspirant salts and thus maintain or boost their efficacy in time.
- odor masking and neutralizing technologies a number of materials have been reported to have malodor counteracting properties alone or in combination with fragrances.
- Patent Number 6,495,097, Streit et. al disclose a composition and a method of use for reducing malsensory agents comprising a component selected from the group consisting of fragrances, flavors, unfragranced carriers and mixtures thereof, with undecylenic acid and/or a derivative thereof, in an amount effective to reduce the malsensory agents and allow release of the component from the composition.
- fragrances may be designed to counteract malodors.
- the fragrance materials, which are most common to mask a malodor are those that contain a carbon- carbon double bond conjugated with one or more carbonyl groups.
- Aldehydes are the most commonly used materials of this class for counteracting malodors, with those most commonly used for deodorant properties being trimethyl hexanal, other alkyl aldehydes, benzaldehyde, and vanillin.
- European Patent Application 0404470 discloses the use of fragrance materials with good malodor reduction efficacy
- European Patent Application 0545556 discloses mixtures of fragrance materials that mask malodors.
- Other materials have also been shown to have malodor counteractant ("MOC”) properties. Schleppnik, U.S.
- Patent Number 4,622,221 discloses the use of cyclohexyl alcohols and ester derivatives in room fresheners.
- Kulka, U.S. Patent Number 3,074,891 discloses esters of alpha-, beta-unsaturated monocarboxylic acids as malodor counteractants.
- Kulka, U.S. Patent Number 3,077,457 discloses fumaric acid esters as malodor counteractants.
- Schleppnik, U.S. Patent Number 4,187,251 discloses alkyl cyclohexyl alkyl ketones as malodor counteractants. Schleppnik, U.S.
- Patent Number 4,310,512 discloses the use of derivatives of acetic and propionic acids, and Schleppnik et al.
- U.S. Patent Number 4,009,253 discloses the use of 4-cyclohexyl-4-methyl-2-pentanone as a malodor counteractant. These materials, however, are not capable of neutralizing all types of functional groups contained in malodor molecules. All of the U.S. patents discussed above are hereby incorporated by reference as if recited in full herein with respect to the teaching of substances that can counteract malodors.
- U.S. Patent Number 6,610,648 McGee et. al. disclose malodor counteracting compositions with low odor intensity that contain alpha, beta-unsaturated carbonyl compounds.
- malodor counteracting compositions reduce the perception of a variety of malodors it is not readily apparent that such compositions may also mask perceived fragrance intensity.
- the aforementioned patent application envisions the use of malodor counteracting accords in deodorant sprays, soft solids and solids, and antiperspirant sprays, soft solids, and solids and demonstrate inhibition of a synthetic sweat odor by applying an alcoholic solution of said malodor counteracting composition to a cotton pad impregnated with malodor.
- an in-vivo malodor counteracting effect is demonstrated by delivery on said malodor counteracting composition to the human axilla from a water-in-oil antiperspirant emulsion composition.
- a high viscosity emulsion having (1) an aqueous phase containing water (or water and a water soluble organic solvent as defined above); the antiperspirant active containing aluminum and zirconium metals having a low M:C1 ratio (0.9 to 1.3 : 1) and stabilized by Betaine; and (2) an oil phase containing a volatile organic or silicone material, and the composition further including (3) a suitable silicone based surfactant such as an alkoxylated, alkyl substituted siloxane surface active agent in an amount of 0.6-0.9 weight % (on an actives basis) which suitable to form a high viscosity (> 150,000 cps) gel as described above and (4) a suitable fragrance solublizer such as myristyl ether which helps to solubilize the fragrance oils in the predominantly silicone based oil phase.
- a suitable silicone based surfactant such as an alkoxylated, alkyl substituted siloxane surface active agent in an amount of 0.6-0.9 weight % (on
- This invention has an oil phase which has a relatively low refractive index when compared to other clear gels, thereby reducing the level of water soluble organic or silicone based refractive index matching agents (such as glycols and other monohydric or polyhydric alcohols, ionizable monovalent or divalent inorganic salts, sugars, esters and amino acids) used to match the refractive index of the water (internal) phase to the oil (external) phase to obtain a clear gel. It is a further object of this invention to provide antiperspirant and/or deodorant compositions which are not as sensitive to fragrance degradation as other products with low meta Cl ratios which might be expected to degrade fragrances.
- water soluble organic or silicone based refractive index matching agents such as glycols and other monohydric or polyhydric alcohols, ionizable monovalent or divalent inorganic salts, sugars, esters and amino acids
- compositions of this invention being free of buffering agents that contain nucleophihc amino groups such as glycine exhibit improved stability of (1) fragrances and (2) odor neutralizing alpha, beta unsaturated carbonyl ester compounds.
- the compositions of this invention may be used as antiperspirants and/or deodorants.
- the invention is a clear gel (50 - 250 NTU at 21.0 degrees C); high viscosity (> 150,000 centipoise); elastomer-free; suspension-free; water-in-oil emulsion having an overall level of silicone emollients ⁇ 3 weight % wherein the clear gel comprises:
- an internal (water) phase comprising: (i) 14-30 weight % of a glycine-free antiperspirant active with a low metal to chloride ratio in the range of 0.9-1.3:1 and stabilized by Betaine; (ii) a high water content such that the water level of the entire composition is > 30 weight % water based on the total gel composition; and (iii) 3.5 -10 weight % of a glycol system comprising propylene glycol and a second glycol selected from the group consisting of glycols and polyglycols in which the total amount of propylene glycol in the total gel composition is ⁇ 7.5 weight %; and
- an external (oil) phase comprising: (i) one or more cyclomethicones having a flash point of 100 degrees C or less (for example, one or more of D4, D5 and D6 cyclomethicones); (ii) a silicone copolyol; and (iii) a fragrance solubilizer; and (iv) 0-0.45 weight % (particularly 0.05 to about 0.45 weight %) of an alpha, beta- unsaturated ester (or mixtures thereof) malodor counteracting material; (v) 0-3 weight % of a silicone emollient; wherein: (1) all the amounts are based on the total formulation, (2) the maximum level of volatile linear silicones (if used) is ⁇ 1 weight %, and (3) the external phase is free of silicone emollients that have a refractive index > 1.4200.
- One particular embodiment is free of amino acids.
- Another embodiment contains amino acids provided the gel composition is still glycine-free.
- These cosmetic gels are quick drying due to the combination of low levels of nonvolatile materials in the oil phase.
- Monovalent or divalent salt can be optionally used as refractive index modifying agents in the aqueous phase so as to match the refractive index of the oil phase, thus rendering a clear gel.
- the present invention may also contain as an optional ingredient which is at least one malodor counteracting alpha, beta-unsaturated ester or mixtures of such materials.
- the level of malodor counteracting components in the finished formula composition falls within a narrowly defined effective window, the definition of which is not obvious without in-vivo deodorancy assessment.
- This invention identifies the optimal level of malodor counteracting composition to deliver a perceivable odor control benefit when delivered from an antiperspirant and/or deodorant gel as being in the range of about 0.05 to about 0.45 weight % based on the entire gel composition.
- the alpha, beta-unsaturated ester malodor counteracting materials are incorporated within the oil phase of the antiperspirant composition. Based on the chemical composition of these malodor counteracting components which include, but are not limited to, those discussed in U.S.
- Patent 6,610,648 (Givaudan) and U.S. Patent 6,495,097 (Shaw et al), it is not obvious that they should be stable in an antiperspirant and/or deodorant gel containing a higher acidity (low M:C1) antiperspirant active salt.
- the odor neutralizing alpha, beta unsaturated ester mixture demonstrates unexpected stability in the aforementioned antiperspirant compositions containing low metalxhloride (M:C1) ratio salts free of glycine.
- these malodor counteracting compositions are unstable when formulated within gel, cream and liquid gel compositions comprised of glycine containing antiperspirant active salts wherein the metal/Cl ratio of the salt is low (low being defined for aluminum zirconium terra or octasalts the wherein the metal/Cl ratio is in the range of 0.9 - 1.3:1; glycine/Zr ratio is > 1.2; for aluminum salts, the aluminum to chloride ratio being in the range of 0.5 - 2.5:1; the glycine/Al ratio being in the range of 0.05 - 0.26 :1).
- DETAILED DESCRIPTION OF THE INVENTION The invention is a clear gel (50 - 250 NTU at 21.0 degrees C); high viscosity
- the clear gel comprises, for example, an external phase comprising (in percentages are based on overall formula composition): (a) 6.5-23.4 weight % (more particularly 9-20 weight %) of one or more cyclomethicones having a flash point of 100 degrees C or less; (b) 0.6-0.9 weight % on an active basis (particularly 0.6-0.8 % ) of a silicone surfactant having an HLB value (hydrophilic lipophilic balance) ⁇ 8) such as a silicone copolyol (actives basis being the actual amount of the copolyol since the copolyol is frequently found with a carrier such as cyclornethicone is used, for example, as a 10% actives material); (c) 0.1-3.0 weight % of an non-siliconized organic fragrance solubilizer (particularly 0.5-2
- volatile dimethicones and/or free of non-volatile silicones.
- fragrance or odor masking component 0-5 weight %
- fragrance or odor masking component 0-5 weight %
- 0-0.45 weight % of an alpha, beta-unsaturated ester as a malodor counteracting material.
- This external phase may conveniently be combined with an internal phase, for example, an internal phase comprising: (a) 14-30 weight % on an anhydrous basis (particularly 17-30 weight % and, more particularly, 17-25 weight %) of a glycine-free antiperspirant active salt further stabilized by Betaine comprising either aluminum or aluminum and zirconium metals wherem the choice of components is such that (i) if aluminum and zirconium salt is used then the metal/Cl ratio of the salt should be low, such as 0.9 - 1.3:1 (more particularly in the range of 0.9-1.05 : 1); the Betaine/Zr ratio should be within the range of 0.2-3.0:1 (particularly 0.4- 1.5:1) and the Betaine:aluminum molar ratio in the range of 0.05-1.0:1 (particularly 0.05- 0.26:1 and, more particularly, 0.05-0.16:1); (ii) if only aluminum salt is used the aluminum/Cl ratio of the salt should be within the range of 0.5 - 2.5:
- glycol component include one or more members of the group consisting of propylene glycol, dipropylene glycol, 2-methyl- 1, 3 propanediol, methyl propylene glycol, low molecular weight (less than 600) polyethylene glycol and mixtures of any of the foregoing.)
- 0-4 weight % particularly 0.2-4 weight %) of a monovalent or divalent ionizable, water-soluble inorganic or organic salts to help increase the refractive index of the active phase and optimize the glycol level.
- agent selected from the group consisting of glycerin, alanine, choline, lysine, diglycereth-7, triglycereth-7 citrate, glycereth-7 glycolate, glycereth-5 lactate, lauramidopropyl glycerin, glycereth-5 lactate, glycereth-7 glycolate, and glycereth-20 benzoate (Ethox GB-2) (for example, 0.5-3 weight % of a high refractive index agent selected from the group consisting of diglycereth-7 citrate, glycereth-7 glycolate, glycereth-5 lactate, lauramidopropyl glycerin, glycereth-5 lactate, glycereth-7 glycolate and glycereth-20 benzoate; and (f) 0-10 weight % (particularly 0-4%) of an alcohol having 2-4 carbons (for example, 1-5 %
- the invention also includes combinations of the subranges and subgroups described above.
- the Betaine is incorporated during the synthesis of the salt so as to maximize the stabilizing effect this amino acid has on the zirconium salt species.
- it can be post added along with additional active phase ingredients to form a Betaine stabilized active.
- the refractive index of the active phase is matched to the oil phase (comprised of fragrance, surfactants, fragrance solubilizers silicones) by adding glycols, and optionally monovalent and/or divalent salts as well as monohydric alcohols such that the refractive index of the active phase differs from the refractive index of the oil phase by an amount of about 0.000 to 0.0040 units.
- NTU Nephelometric Turbidity Units
- R.I. refractive index of the active phase
- the fragrance oils typically have refractive indices ranging from 1.4450 - 1.4850 and are used typically at levels ranging from 0.50 -2.0 weight percent.
- Ionizable monovalent and divalent inorganic salts, antiperspirant salts, water and optional ingredients such as alcohol are optimized to provide a quick drying gel composition.
- Refractive index measurements are made at a temperature of about 20-25 degrees C using a Bausch and Lorrib Abbe 3L Refractometer. Turbidity measurements as described herein are made with an Orbeco-Hellige #965 Direct-Reading Turbidimeter.
- One particular embodiment is free of amino acids (Betaine hereby being excluded by definition from the class of amino acids.)
- One embodiment of the invention is comprised of an oil phase composition such that the addition of the fragrance component (if fragrance is added to the composition) provides a refractive index in the range from about 1.4015 to about 1.4150; especially from about 1.4025 to about 1.4090.
- One of the benefits of adding a non-siliconized organic fragrance solubilizer is to improve the solubility of the fragrance within the silicone (primarily cyclomethicones) based oil phase of the gel emulsion.
- the limited solubility of some fragrances in the cyclomethicone and linear polydialkylorganosiloxanes (if present) is easily determined by the turbidity of the aforementioned silicone(s) when approximately 10-30 weight % of fragrance is added to the silicone.
- the high viscosity gel compositions of the present invention include an antiperspirant active agent in an amount sufficient to have a deodorizing effect and/or in an amount sufficient to reduce the flow of perspiration when the composition is applied to a human.
- an antiperspirant active agent in an amount sufficient to have a deodorizing effect and/or in an amount sufficient to reduce the flow of perspiration when the composition is applied to a human.
- the antiperspirant active used in the internal (also called "active") phase various antiperspirant active materials that can be utilized according to the present invention provided that they are soluble at a suitable concentration in the active phase.
- Antiperspirant actives can be incorporated into compositions according to the present invention in amounts in the range of 14-30 weight % (on an anhydrous solids basis), particularly 17-25 weight % of the total weight of the composition. Mixtures of actives can also be used. The amount used will depend on the formulation of the composition. At amounts at the higher end of the range a good antiperspirant effect can be expected. As noted above, the active is preferably included in the compositions of the invention by premixing the active with water and possibly small amount of propylene glycol. Antiperspirant actives can be incorporated into compositions according to the present invention in amounts as described above.
- antiperspirant active material may not completely reduce the flow of perspiration, but will reduce malodor, for example, by acting as an antimicrobial material.
- an antiperspirant effect may be observed.
- antiperspirant actives having the specific low metal to chloride ratio specified above and those described in U.S. Patent Number 6,375,937 and patent application assigned to the same owners as this case (U.S. Patent Application Serial Number 10/314,712 filed 12/9/02).
- an aluminum zirconium tetrasalt or octasalt free of glycine wherein aluminum zirconium salt has a metal to chloride ratio in the range of 0.9 to 1.3:1 (especially in the range of 0.9 to 1.2:1 and, more particularly in the range of 0.9 to 1.1:1).
- the Al/Zr atomic ratio lies within the range of 3.2:1 to 4.1:1.0 and the Betaine:zirconium mole ratio lies within the range of 0.2-3.0:1 (particularly 0.4-1.5:1).
- One particular embodiment may be made with propylene glycol and an aluminum/zirconium tetrasalt so that the propylene glycol/Zr weight/weight ratio is in the range of 0.4- 2.5.
- One particular type of salt of interest is an aluminum chloride salt buffered by Betaine, wherein the salt has a metal to chloride ratio in the range of 0.9 to 1.3:1 (especially in the range of 0.9 to 1.2:1 and, more particularly in the range of 0.9 to 1.1:1).
- Examples of commercially available glycine-free, low M:C1 aluminum chloride salts include Westchlor 100 (from Westwood Chemicals).
- salts of interest include but are not limited to octasalts wherein the Al/Zr atomic ratio lies within the range of 6.2-10.0:1 and the Betaine:Zr mole ratio lies within the range of 0.2-3.0:1 (particularly 0.4-1.5:1).
- the Al/Zr atomic ratio lies within the range of 3.2 : 1.0 to 4.1 : 1.0 and the Betaine:Zr mole ratio lies within the range of 0.12 - 3.0 : 1.0 (particularly 0.4 : 1.5 : 1.0).
- the Betaine is incorporated during the synthesis of the salt so as to maximize the stabilizing effect this amino acid has (especially on the zirconium species).
- glycine free salt can be post added to a glycine free salt along with additional active phase ingredients to form a Betaine stabilized active.
- glycine free low M:C1 ratio tetrasalts and octasalts include (but are not limited to) Rezal AZP 955 CPG and Rezal AZP 885 respectively (both from Reheis Chemical Company, Berkeley Heights, NJ).
- Rezal AZP 955 CPG and Rezal AZP 885 both from Reheis Chemical Company, Berkeley Heights, NJ.
- a more detailed description of making such commercially available salts can be found for example, in U.S. Patent Application Publication US 2004/0001795 A 1 and U.S. Application Serial Number 10/625,038. Further examples of making this type of salt complexes are given in (but are not limited to) U.S.
- cyclomethicones used in this invention are one or more members selected from the group consisting of cyclic polydimethylsiloxanes such as those represented by Formula II:
- Fonnula II where n is an integer with a value of 4-6, particularly 5-6.
- n is an integer with a value of 4-6, particularly 5-6.
- D4 tetramer
- D5 pentamer
- D6 hexamer
- DC-245 fluid and DC-345 from Dow Coming Corporation (Midland, Michigan) are types of cyclomethicones which can be used. It is to be noted that for purposes of the present invention cyclomethicones are not considered as silicone emollients.
- Suitable silicone surfactants include silicone polyglucosides (for example, octyl dimethicone ethoxy glucoside) and silicone copolyols having an HLB value (hydrophilic lipophilic balance) ⁇ 8.
- the HLB value may be measured in a variety of ways such as described in conventional references or found listed in tables of data recording such values. HLB values are a concept well known in the art, for example, as described in U.S.
- R 10 ) 3 SiO-[(R 11 ) 2 -SiO] x - [Si(R 12 )(R b -0-(C 2 H 4 0)p-(C 3 H 6 0) s -R c )0] y — Si-(R 13 ) 3
- R 10 , R 11 , R 12 and R 13 may be the same or different and each is independently selected from the group consisting of C1-C6 alkyl
- R b is the radical -C m H m
- R° is a terminating radical which can be hydrogen, an alkyl group of one to six carbon atoms, an acyl group such as an ester with a terminating alkyl group of 1-4 carbons, or an aryl group such as phenyl
- m has a value of two to eight
- p and s have values such that the oxyalkylene segment -(C 2 H 4 0) p -(C 3
- each of R 10 , R 11 , R 12 and R 13 is a methyl group;
- R c is H;
- m is preferably three or four whereby the group R is most preferably the radical -(CH 2 ) 3 -; and the values of p and s are such as to provide a molecular weight of the oxyalkylene segment -(C 2 H 4 0) p -(C 3 H 6 ⁇ ) s - of between about 1,000 to 3,000.
- p and s should each have a value of about 18 to 28.
- a second siloxane polyether (copolyol) has the Formula IV:
- siloxane-oxyalkylene copolymers of the present invention may, in alternate embodiments, take the form of endblocked polyethers in which the linking group R b , the oxyalkylene segments, and the terminating radical R° occupy positions bonded to the ends of the siloxane chain, rather than being bonded to a silicon atom in the siloxane chain.
- one or more of the R 10 , R 11 , R 12 and R 13 substituents which are attached to the two terminal silicon atoms at the end of the siloxane chain can be substituted with the segment -R b -0- (C 2 H 4 0) p -(C 3 H 6 ⁇ ) s -R c or with the segment -R -0-(C 2 H 0) p -R c .
- suitable dimethicone copolyols are available either commercially or experimentally from a variety of suppliers including Dow Coming Corporation, Midland, MI; General Electric Company, Waterford, NY; Witco Corp., Greenwich, CT; and Goldschmidt Chemical Corporation, Hopewell, VA.
- Examples of specific products include DOW CORNING® 5225C from Dow Coming which is a 10% dimethicone copolyol in cyclomethicone; DOW CORNING® 2-5185C which is a 45-49% dimethicone copolyol in cyclomethicone; SILWET L-7622 from Witco; ABIL EM97 from Goldschmidt which is a 85% dimethicone copolyol in D5 cyclomethicone; and various dimethicone copolyols available either commercially or in the literature. It should also be noted that various concentrations of the dimethicone copolyols in cyclomethicone can be used.
- 3-9 weight % (particularly 5-8 %) of a 10 % silicone copolyol such as dimethicone copolyol in cyclomethicone rnixture may be used, wherein the amount of mixture added is selected so that the level of silicone copolyol in the cosmetic composition is in the range of 0.6-0.9 % (particularly 0.6-0.8%) (for example, 6.5 % of a 10 % dimethicone copolyol in cyclomethicone mixture).
- Emollient selection is limited to those which have a relatively low refractive index (R.I. ⁇ 1.4200) in order to reduce the refractive index of the oil phase thereby making it easier to match the refractive index of the internal active phase.
- Emollients are a known class of materials in this art, imparting a soothing effect to the skin. They are ingredients which help to maintain the soft, smooth and pliable appearance of the sldn. Emollients are also known to reduce whitening on the skin and/or improve aesthetics. Examples of suitable emollients which meet the low refractive index requirement are limited to silicone-based structures which are absent of phenyl groups.
- linear silicones are selected from the group consisting of polydialkylsiloxanes represented by the formulae: (1) (R 10 ) 3 SiO(Si (R u ) 2 0) x Si(R 12 ) 3 where R 10 , R 11 and R 12 can be the same or different and are each independently selected from the group consisting of Cl- C10 alkyl (with particular examples being polydimethylsiloxanes (dimethicones), especially low viscosity dimethicones (viscosity ⁇ 100 cps) (with the R groups and x values being selected to maintain the RI limits); (2) silanols and/or dimethiconols in which one or two of the alkyl (such as methyl) groups of the foregoing formula may be replaced with a hydroxyl group and is represented by formulae: HO(R 14 ) 2 SiO(Si(R 15 ) 2 0) x Si(R 16 ) 2 OH and R17(R 14 )
- suitable silicone emollients include members of the group consisting of linear silicones (both volatile and non-volatile) such as linear dimethicones, particularly dimethicones having a viscosity in the range of 0.5- 300,000 centistokes, indicated in Formula V, with t values being selected to maintain the viscosity limits.
- linear silicones both volatile and non-volatile
- dimethicones particularly dimethicones having a viscosity in the range of 0.5- 300,000 centistokes, indicated in Formula V, with t values being selected to maintain the viscosity limits.
- low viscosity dimethicones viscosity ⁇ 1,000 centistokes (e.g. DC 200) including hexamethyl disiloxane.
- silicone emollients include, dimethiconols (such as but not limited to Dow Corning® DC1501 ), Dow Corning 2501 cosmetic wax (dimethicone copolyol) dimethiconol behenate, C 3 o - 5 alkyl methicorie, stearoxytrimethylsilane, and stearyl dimethicone) as well as silanol DC 9023 also from Dow Coming).
- the low refractive index emollient or emollient mixture or blend thereof incorporated in compositions according to the present invention can, illustratively, be included in amounts of 0-1 weight % inclusive, preferably 0.5-1 %.
- the oil phase according to the present invention is, desirably, a silicone oil phase, so as to provide a water-in-silicone oil emulsion.
- the total of oil phase and siloxane surface- active agent preferably makes up from about 10% to about 24 % by weight, of the total weight of the composition.
- This surface-active agent is an emulsifier which, when properly mixed with the aqueous phase components, and oil phase components, yields a water-in-oil emulsion.
- the oil phase is desirably a blend of liquids, but does not contain any significant amount of non- volatiles (that is, less than 1.0 weight % of any material having a flash point greater than 100 degrees C).
- the nonvolatile silicone based emollients described in this composition all have a refractive index lower than 1.420.
- the refractive index of the oil phase (including fragrance) is determined, and, if necessary, adjusted to be in the range of 1.4015 to about 1.4150; especially from about 1.4025 to about 1.4090 and the refractive index of the aqueous phase is determined and adjusted (if necessary) to differ from the refractive index of the oil phase by less than 0.0050, preferable less than 0.0030 units.
- the aqueous phase is then mixed with the oil phase (for example, the aqueous phase is slowly added to the oil phase with turbulent agitation), and then additional additives, or other active ingredients, are added with mixing.
- additional additives, or other active ingredients are added with mixing.
- the fragrance can be added after the active phase is added to the oil phase.
- the refractive index of the oil phase (absent of fragrance) and aqueous phase should differ less than 0.0020.
- the resulting emulsion is then passed through, for example, a colloid mill or other high shear emulsifier so as to provide a viscous gel, the gel then being transferred to a suitable applicator or container for use by the consumer.
- the aqueous phase further includes a glycol mixture consisting of propylene glycol and 2-methyl propanediol and/or dipropylene glycol providing advantages in the final product as discussed previously.
- a glycol mixture consisting of propylene glycol and 2-methyl propanediol and/or dipropylene glycol providing advantages in the final product as discussed previously.
- a particular example of an alkoxylated, alkyl substituted siloxane surface active agent is preferably, but not limited to, a dimethicone copolyol.
- An illustrative alkoxylated silicone-containing surfactant utilizable according to the present invention is cetyl dimethicone copolyol, referred to in U.S. Patent No. 5,162,378 to Guthauser.
- the alkoxylated, alkyl substituted siloxane surface active agent is included in the composition in an amount of 6.0% to 9.0% by weight, of the total weight of the composition.
- a suitable surfactant is octyl dimethicone ethoxy glucoside (from Wacker-Belsil, Adrian, MI).
- a specific cyclomethicone-dimethicone copolyol fluid which can be utilized to provide the alkoxylated silicone-containing surface-active agent is a mixture of cyclomethicone and dimethicone copolyol designated as DC 5225C from Dow Corning Corporation.
- This is a polyether substituted silicone of cyclomethicone and dimethicone copolyol (refractive index (RI) 1.3994) at about 20-25 degrees C.
- This DC 5225C which is an emulsifying agent, is useful for preparing stable water-in-oil emulsions where a silicone makes up a large portion of the oil phase, and is a dispersion of a silicone surfactant (dimethicone copolyol) (10% by wt.) in cyclomethicone (Dow Corning 245) (90% by weight).
- the aqueous phase of the clear cosmetic gel composition further includes a glycol system in low amount (3.5-10 weight % preferably 4-8%) comprising propylene glycol and, preferably, at least one other glycol or polyglycol to help increase the refractive index of the active phase so as to match it within 0.0000 - 0.0040 units (preferably 0.0010-0.0030 units) of the fragranced oil phase.
- a glycol system in low amount (3.5-10 weight % preferably 4-8%) comprising propylene glycol and, preferably, at least one other glycol or polyglycol to help increase the refractive index of the active phase so as to match it within 0.0000 - 0.0040 units (preferably 0.0010-0.0030 units) of the fragranced oil phase.
- tripropylene glycol can be utilized as the additional polypropylene glycol.
- propylene glycol can be used in combination with the glycols up to a limited amount.
- Incorporation of glycols, particularly MP-diol (2-methyl 1,3 propanediol) and dipropylene glycol in the gel composition also improves cosmetic properties, including a reduction of tack and a decrease in the whitening and in the residue after application of the composition.
- compositions incorporating polypropylene glycol, particularly, tripropylene glycol have improved mildness (that is, reduced skin irritation potential) relative to commercially available products.
- the glycol or polyglycol is selected from the group consisting of ethylene glycol, propylene glycol, 1,2 propanediol, 2-methyl propanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, methyl propanediol, 1,6-hexanediol, 1,3 butanediol, 1,4 butanediol, PEG-4 through PEG-600, PPG-9 through PPG-34, neopentyl glycol, trimethylpropanediol, 2,2 dimethyl- 1,3 propanediol, 2,2,4,4- tetramethyl-l,3-cyclobutane-diol and mixtures thereof.
- the glycols which can be used with the propylene glycol are one or more members of the group consisting of dipropylene glycol, 2-methyl- 1, 3 propanediol, methyl propylene glycol, low molecular weight (less than 600) polyethylene glycol and mixtures of any of the foregoing in which the amount of propylene glycol does not exceed 7.5%.
- the aqueous phase further includes a glycol mixture consisting of propylene glycol and 2-methyl propanediol and/or dipropylene glycol providing advantages in the final product as discussed previously.
- Clear gel compositions of the invention may further include at least one ionizable inorganic salt which helps to increase the refractive index of the active phase and optimize the glycol level. Higher levels of glycols, although good for reducing tackiness tend to increase dry-down time.
- M is a member selected from the group consisting of Na , Li , K , Mg , Ca , Sr +2 and Zn +2
- X is a member selected from the group consisting of chloride, bromide, iodide, citrate, gluconate, lactate, glycinate, glutamate, ascorbate, aspartate, nitrate, phosphate, hydrogenphosphate, dihydrogenphosphate, formate, maloneate, maleate, succinate, carbonate, bicarbonate, sulfate, hydrogensulfate.
- Salts of particular utility are NaCI and ZnCl 2 .
- the present invention also includes methods of forming high viscosity cosmetic gel compositions described herein. In such methods an aqueous phase comprising water and the antiperspirant active is formed separately from the oil phase contaming an alkoxylated, alkyl substituted siloxane surface active agent, an organic fragrance solubilizer and cyclomethicone and optional fragrance. The two phases are then combined and homogenized to achieve the desired viscosity.
- the active phase is a water phase containing 17-30 weight % (anhydrous) of the low meta chloride Betaine-containing antiperspirant active, 3.5-10 weight % of the water-soluble glycol system and optionally 0-4% the monovalent or divalent ionizable water-soluble salt.
- free water is included in the composition in the range of 30-70 weight % based on the total weight of the composition.
- the water' phase can also include, for example, (along with the antiperspirant active, water- soluble glycol system and ionizable divalent or monovalent salt) 1-5 weight % of a water- soluble carbon-based, high refractive index agent such as glycerin
- a water- soluble carbon-based, high refractive index agent such as glycerin
- the composition according to the present invention is a clear antiperspirant soft gel composition, packaged in a dispensing container having a top surface with slots or pores appropriate for the viscosity range of this product
- the gel is extruded from the dispensing container through the slots or pores and applied to the skin (for example, in axillary regions of the human body) by rubbing the soft gel material extruded through the top surface of the container on the skin in the axillary region.
- the dispensing container can be clear and can be tinted so as to for example, fit to the fragrance hedonics.
- compositions of the present invention incorporating a polypropylene glycol component have improved mildness (have reduced skin irritation potential) as compared to commercially available products, and have improved cosmetic properties (including reduced tackiness) and reduced white residue upon application.
- the gel emulsions according to the present invention are stable and optically clear are cosmetically elegant, and are capable of being delivered from a suitable applicator package.
- the antiperspirant active materials when utilized in an antiperspirant effective amount in the composition, act to reduce body malodor by reducing production of perspiration; however, these antiperspirant active materials can also have a deodorant function, e.g., as an antimicrobial agent.
- the deodorant active materials do not substantially reduce the production of perspiration, but reduce malodor in other ways, e.g., as fragrances masking the malodor or reducing the malodor intensity, as odor absorbents, as antimicrobial agents, as agents chemically reacted with malodorous materials, etc.
- the amount of active component that can be used will vary with the particular active ingredient incorporate.
- the product comprises antiperspirant active materials in amounts sufficient to combat body malodor either as a deodorant or as an antiperspirant when applied to the axillary regions of the body.
- an antiperspirant product should contain an active antiperspirant material in an amount anywhere from about 9% to about 25% by weight, of the total weight of the composition.
- the active antiperspirant material utilized in the compositions of the present invention can be pre-dissolved in water or in another solvent (for example, in propylene glycol), and may be buffered or unbuffered.
- the antiperspirant materials are present in solution in a solvent.
- any deodorant active material which can be dissolved in the oil phase, can be utilized in an amount sufficient to have a deodorant effect.
- the deodorant active material can be 2, 4, 4'-trichloro-2'-hydroxy diphenyl ether (triclosan), and/or benzethonium chloride and/or octoxyglycerin (Sensiva® SC 50).
- a deodorant gel composition (rather than an antiperspirant gel composition) would be provided.
- an alpha, beta-unsaturated ester malodor counteracting material a number of examples can be described. These include clear gels wherein: (a) the fragrance level is less than 0.1 weight % and the alpha, beta-unsaturated ester malodor counteracting material is between 0.1 and 0.4 weight %; (b) the fragrance level is between 0.1 and 2.0% and the alpha, beta-unsaturated ester malodor counteracting material is between 0.1 and 0.4%; (c) the gel comprises an alpha, beta-unsaturated ester malodor counteracting material comprising a combination of two or more members selected from the following groups: (1) 3-phenyl-2-propenoic acid alkyl esters wherein R 1 is a substituent on the benzene ring and is an alkyl, an alkoxy, an aryl, or a substituted aryl, preferably R 1 is H, a CI to C8 alkyl, a CI to C8 alkoxy
- R 2 is a substituent group replacing the carboxylic acid hydrogen to form the ester where R 2 is a C6 to C12 alkyl or is a benzyl group; and (2) an ester of fumaric or maleic acid having linear ester carbon chains from 3-9 carbons, for example dihexyl fumarate; and (f) a gel wherein the alpha, beta-unsaturated ester malodor counteracting material is a mixture of: (1) an e-phenyl propenoic acid ester selected from the group consisting of octyl methoxy cinnamate, phenylethyl cinnamate, benzyl cinnamate; and (2) dihexyl fumarate.
- compositions of the present invention also consist essentially of, or consist of, the recited components or materials. Accordingly, throughout the present disclosure any described composition of the present invention can consist essentially of, or consist of, the recited components or materials.
- a desired feature of the present invention is that a clear cosmetic gel composition (e.g., clear deodorant or antiperspirant gel composition) can be provided.
- clear that is clarity
- a clear, e.g., cosmetic gel composition of the present invention allows ready viewing of objects behind it.
- a translucent composition allows light to pass through, but causes the light to be so scattered that it will be impossible to see objects behind the translucent composition.
- Optical clarity of compositions of the present invention can be measured using a turbidimeter as described above, and desirably lies between 50 and 250 NTU measured at room temperature (20°-25° C).
- the clear cosmetic gel composition of the present invention which is in the form of a macro-emulsion as contrasted to a micro-emulsion, does not need to contain wax or gelling agents such as soaps, cellulosic materials or alginates.
- the composition according to the present invention does not require polydimethylcyclosiloxane, although the present compositions may contain this material.
- Several particular embodiments include those comprising one or more of the following: 1-4 weight % of ethanol or propanol; 9-20 weight % of the one or more cyclomethicones; 0.6-0.8 weight % of the silicone surfactant; 0.5-2 weight % of the fragrance solubilizer; 45-65 weight % water; and a glycol system comprising 3-7 weight % of propylene glycol in combination with either 2-methyl propane diol or dipropylene glycol.
- antiperspirant active for example, Al-Zr tetrachlorohydrex such as Rezal AZP 955 CPG, or Al-Zr octasalt such as Rezal AZP 885 to which Betaine has been added so that the molar ratio of Betaine/Zr is in the range of 0.2 -2.0 or aluminum dichlorohydrate (such as Westchlor 100, 36.1% ) to which Betaine has been added so that the molar ratio of Betaine/Al is in the range of 0.05-1.0:1;
- Al-Zr tetrachlorohydrex such as Rezal AZP 955 CPG
- Al-Zr octasalt such as Rezal AZP 885
- a low refractive index emollients such as dimethiconol, dimethicones, silanol and combinations thereof;
- fragrance or odor masking component 0-5 weight % fragrance or odor masking component
- a water-soluble carbon based high refractive index agent such as additional Betaine which is not part of the original salt, alanine, choline, lysine, glycerin, Diglycereth- 7, Triglycereth-7 citrate, glycereth-7 glycolate, glycereth-5 lactate, lauramidopropyl glycerin, glycereth-5 lactate, Glycereth-7 glycolate, and glycereth-20 benzoate; wherein the composition has a phase ratio in the range of 10:90 - 24:76 of oil to water and a viscosity is in the range of 150,000-600-000 centipoise.
- additional Betaine which is not part of the original salt, alanine, choline, lysine, glycerin, Diglycereth- 7, Triglycereth-7 citrate, glycereth-7 glycolate, glycereth-5 lactate, lauramido
- RI Refractive Indices
- Example 1 A Betaine-stabilized antiperspirant salt solution may be made by dissolving 19.26 g of ZrOCl2-8H2 ⁇ in 49.6 g of water and then adding 8.39 g Betaine anhydrous. After everything is dissolved, an aluminum chlorohydrate (“ACH") powder (22.65 g of Chlorhydrol from Reheis Chemical Co., Berkeley Heights, NJ) into the solution with additional deionized (“DI”) water so that the total weight of the solution is 100 g. The solution is shaken or stirred to make sure the solution is clear. Optionally, the solution can be spray dried or freeze-dried to make a powder sample.
- Example 2 A Betaine-stabilized AP salt solution may be made by dissolving 18.15g of ZrOC0 3 x 8H 2 0 in 5.95 g of concentrated HC1 (37%) and 20 g of water (such as deionized (“DI”) water). After a clear solution is formed, 9.17 g of Betaine hydrochloride is added and stirred until dissolved.
- DI deionized
- this active is mixed with additional active phase components to render the active phase.
- the aluminum/zirconium terra salt can be made separately according to, for example, Patent Application Number 10/185,299.
- the Betaine along with the other active phase ingredients is then post added to the active solution by mixmg the components together at room temperature to render the active phase.
- This method of preparing the active phase results in a Betaine complexed active salt.
- Examples 3-28 Examples 3-28 shown in Tables A through C describe some illustrative methods which can be used (but do not limit) to prepare gel emulsions in which the sample sizes are about 500 grams.
- the oil phase is prepared by weighing and combining silicone copolyol, cyclomethicone, fragrance and fragrance solubilizer along with any optional oil phase components in a beaker.
- the mixture is stirred at 400-600 rpm using a Lightniri Mixer Model LI003.
- the active phase (see above description) are added to the oil phase while mixing.
- the entire mixture is mixed for 15 minutes.
- the mixture is then homogenized for 2-4 minutes at a reading of 50-70 on Powerstat Variable Transformer (Superior Electric Co., Bristol, CT) using a homogenizer from Greerco Corp. (Hudson, NH).
- Examples 8 and 9 are made with the same composition as Examples 6 and 7, respectively but additionally include an odor neutralizing alpha, beta- unsaturated ester as described above.
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MXPA06002612A MXPA06002612A (en) | 2003-09-08 | 2004-09-08 | Antiperspirant clear gel with low glycol content. |
EP04788610A EP1663136A2 (en) | 2003-09-08 | 2004-09-08 | Antiperspirant clear gel with low glycol content |
BRPI0414194-6A BRPI0414194A (en) | 2003-09-08 | 2004-09-08 | water-in-oil, suspension-free, elastomer-free emulsion |
CA002538017A CA2538017A1 (en) | 2003-09-08 | 2004-09-08 | Antiperspirant clear gel with low glycol content |
US10/571,488 US20070196308A1 (en) | 2003-09-08 | 2004-09-08 | Antiperspirant clear gel with low glycol content |
AU2004272034A AU2004272034B2 (en) | 2003-09-08 | 2004-09-08 | Antiperspirant clear gel with low glycol content |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US50112803P | 2003-09-08 | 2003-09-08 | |
US60/501,128 | 2003-09-08 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2005025523A2 true WO2005025523A2 (en) | 2005-03-24 |
WO2005025523A3 WO2005025523A3 (en) | 2005-06-09 |
Family
ID=34312251
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2004/029116 WO2005025523A2 (en) | 2003-09-08 | 2004-09-08 | Antiperspirant clear gel with low glycol content |
Country Status (11)
Country | Link |
---|---|
US (1) | US20070196308A1 (en) |
EP (1) | EP1663136A2 (en) |
AR (1) | AR045608A1 (en) |
AU (1) | AU2004272034B2 (en) |
BR (1) | BRPI0414194A (en) |
CA (1) | CA2538017A1 (en) |
GT (1) | GT200400178A (en) |
MX (1) | MXPA06002612A (en) |
RU (1) | RU2355381C2 (en) |
WO (1) | WO2005025523A2 (en) |
ZA (1) | ZA200602883B (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007048480A1 (en) * | 2005-10-28 | 2007-05-03 | Unilever Plc | Antiperspirant or deodorant compositions |
WO2008063188A2 (en) * | 2006-11-03 | 2008-05-29 | Reheis, Inc. | Betaine with calcium and/or strontium antiperspirants |
WO2008097716A2 (en) | 2007-02-02 | 2008-08-14 | Colgate-Palmolive Company | Antiperspirant/deodorant composition |
WO2008144079A1 (en) | 2007-02-02 | 2008-11-27 | Colgate-Palmolive Company | Antiperspirant / deodorant compositions |
WO2011040909A1 (en) | 2009-09-30 | 2011-04-07 | Colgate-Palmolive Company | Antiperspirant/deodorant composition |
WO2011050044A1 (en) | 2009-10-20 | 2011-04-28 | Colgate-Palmolive Company | Antiperspirant that reduces/eliminates yellowing on clothing |
WO2012005720A1 (en) | 2010-07-06 | 2012-01-12 | Colgate-Palmolive Company | Personal care product and manufacture thereof |
WO2015082380A1 (en) * | 2013-12-03 | 2015-06-11 | Unilever Plc | Deodorant compositions comprising hydrophilic cinnamic acid derivatives |
US9763509B1 (en) | 2016-06-17 | 2017-09-19 | Avon Products, Inc. | Applicator for personal care |
US10111817B2 (en) | 2014-07-21 | 2018-10-30 | Colgate-Palmolive Company | Antiperspirant compositions containing ethylenediamine disuccinate |
WO2021096518A1 (en) | 2019-11-14 | 2021-05-20 | Colgate-Palmolive Company | Personal care compositions for treating odor causing bacteria and methods for the same |
US11058904B2 (en) | 2009-09-30 | 2021-07-13 | Colgate-Palmolive Company | Antiperspirant/deodorant composition |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2785448C (en) | 2009-12-23 | 2014-10-14 | Colgate-Palmolive Company | Method of making an anhydrous liquid antiperspirant composition |
JP6639816B2 (en) * | 2015-06-29 | 2020-02-05 | 株式会社ファンケル | Cosmetics |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4058597A (en) * | 1975-03-11 | 1977-11-15 | Rhone-Poulenc Industries | Aluminium salts of betaine chloride and compositions containing the same |
US6007799A (en) * | 1995-08-18 | 1999-12-28 | Colgate Palmolive Company | Clear cosmetic gel composition |
EP1005853A1 (en) * | 1998-12-04 | 2000-06-07 | Beiersdorf Aktiengesellschaft | Use of betaines as antiperspirant |
US6485716B1 (en) * | 2001-10-05 | 2002-11-26 | Colgate-Palmolive Company | High efficacy liquid gel product |
US6500412B1 (en) * | 2002-04-08 | 2002-12-31 | Colgate-Palmolive Company | Clear antiperspirant with alcohol free active |
US20030008787A1 (en) * | 2000-12-22 | 2003-01-09 | Givaudan Sa | Malodor counteractant compositions |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6042816A (en) * | 1998-08-19 | 2000-03-28 | The Gillette Company | Enhanced antiperspirant salts stabilized with calcium and concentrated aqueous solutions of such salts |
-
2004
- 2004-09-07 AR ARP040103211A patent/AR045608A1/en unknown
- 2004-09-08 BR BRPI0414194-6A patent/BRPI0414194A/en not_active IP Right Cessation
- 2004-09-08 RU RU2006111453/15A patent/RU2355381C2/en not_active IP Right Cessation
- 2004-09-08 MX MXPA06002612A patent/MXPA06002612A/en unknown
- 2004-09-08 AU AU2004272034A patent/AU2004272034B2/en not_active Ceased
- 2004-09-08 GT GT200400178A patent/GT200400178A/en unknown
- 2004-09-08 US US10/571,488 patent/US20070196308A1/en not_active Abandoned
- 2004-09-08 EP EP04788610A patent/EP1663136A2/en not_active Withdrawn
- 2004-09-08 CA CA002538017A patent/CA2538017A1/en not_active Abandoned
- 2004-09-08 WO PCT/US2004/029116 patent/WO2005025523A2/en active Application Filing
-
2006
- 2006-04-07 ZA ZA200602883A patent/ZA200602883B/en unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4058597A (en) * | 1975-03-11 | 1977-11-15 | Rhone-Poulenc Industries | Aluminium salts of betaine chloride and compositions containing the same |
US6007799A (en) * | 1995-08-18 | 1999-12-28 | Colgate Palmolive Company | Clear cosmetic gel composition |
EP1005853A1 (en) * | 1998-12-04 | 2000-06-07 | Beiersdorf Aktiengesellschaft | Use of betaines as antiperspirant |
US20030008787A1 (en) * | 2000-12-22 | 2003-01-09 | Givaudan Sa | Malodor counteractant compositions |
US6485716B1 (en) * | 2001-10-05 | 2002-11-26 | Colgate-Palmolive Company | High efficacy liquid gel product |
US6500412B1 (en) * | 2002-04-08 | 2002-12-31 | Colgate-Palmolive Company | Clear antiperspirant with alcohol free active |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2006308228B2 (en) * | 2005-10-28 | 2010-05-20 | Unilever Global Ip Limited | Antiperspirant or deodorant compositions |
WO2007048480A1 (en) * | 2005-10-28 | 2007-05-03 | Unilever Plc | Antiperspirant or deodorant compositions |
CN101296682B (en) * | 2005-10-28 | 2011-03-09 | 荷兰联合利华有限公司 | Antiperspirant or deodorant compositions |
WO2008063188A2 (en) * | 2006-11-03 | 2008-05-29 | Reheis, Inc. | Betaine with calcium and/or strontium antiperspirants |
WO2008063188A3 (en) * | 2006-11-03 | 2010-09-16 | Reheis, Inc. | Betaine with calcium and/or strontium antiperspirants |
US7976828B2 (en) * | 2007-02-02 | 2011-07-12 | Colgate-Palmolive Company | Antiperspirant/deodorant composition |
WO2008144079A1 (en) | 2007-02-02 | 2008-11-27 | Colgate-Palmolive Company | Antiperspirant / deodorant compositions |
WO2008097716A2 (en) | 2007-02-02 | 2008-08-14 | Colgate-Palmolive Company | Antiperspirant/deodorant composition |
US7976829B2 (en) | 2007-02-02 | 2011-07-12 | Colgate-Palmolive Company | Antiperspirant/deodorant compositions |
EP2559457A1 (en) | 2007-02-02 | 2013-02-20 | Colgate-Palmolive Company | Antiperspirant/deodorant compositions |
EP2149366A2 (en) | 2007-02-02 | 2010-02-03 | Colgate-Palmolive Company | Antiperspirant/deodorant composition |
WO2011040909A1 (en) | 2009-09-30 | 2011-04-07 | Colgate-Palmolive Company | Antiperspirant/deodorant composition |
US11058904B2 (en) | 2009-09-30 | 2021-07-13 | Colgate-Palmolive Company | Antiperspirant/deodorant composition |
EP3653197A1 (en) | 2009-10-20 | 2020-05-20 | Colgate-Palmolive Company | Antiperspirant that reduces/eliminates yellowing on clothing |
WO2011050044A1 (en) | 2009-10-20 | 2011-04-28 | Colgate-Palmolive Company | Antiperspirant that reduces/eliminates yellowing on clothing |
US8529919B2 (en) | 2010-07-06 | 2013-09-10 | Colgate-Palmolive Company | Personal care product and manufacture thereof |
WO2012005720A1 (en) | 2010-07-06 | 2012-01-12 | Colgate-Palmolive Company | Personal care product and manufacture thereof |
WO2015082380A1 (en) * | 2013-12-03 | 2015-06-11 | Unilever Plc | Deodorant compositions comprising hydrophilic cinnamic acid derivatives |
US10111817B2 (en) | 2014-07-21 | 2018-10-30 | Colgate-Palmolive Company | Antiperspirant compositions containing ethylenediamine disuccinate |
US9763509B1 (en) | 2016-06-17 | 2017-09-19 | Avon Products, Inc. | Applicator for personal care |
WO2017218198A1 (en) * | 2016-06-17 | 2017-12-21 | Avon Products, Inc. | Applicator for personal care |
TWI750187B (en) * | 2016-06-17 | 2021-12-21 | 美商愛芳製品公司 | Product for personal use |
WO2021096518A1 (en) | 2019-11-14 | 2021-05-20 | Colgate-Palmolive Company | Personal care compositions for treating odor causing bacteria and methods for the same |
Also Published As
Publication number | Publication date |
---|---|
US20070196308A1 (en) | 2007-08-23 |
AR045608A1 (en) | 2005-11-02 |
RU2006111453A (en) | 2007-10-27 |
RU2355381C2 (en) | 2009-05-20 |
EP1663136A2 (en) | 2006-06-07 |
WO2005025523A3 (en) | 2005-06-09 |
AU2004272034A1 (en) | 2005-03-24 |
CA2538017A1 (en) | 2005-03-24 |
MXPA06002612A (en) | 2006-06-05 |
AU2004272034B2 (en) | 2009-11-05 |
GT200400178A (en) | 2005-05-02 |
ZA200602883B (en) | 2010-09-29 |
BRPI0414194A (en) | 2006-10-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0845977B1 (en) | Clear cosmetic gel composition | |
AU2004272034B2 (en) | Antiperspirant clear gel with low glycol content | |
US6447791B2 (en) | Use of isoparaffin extenders for clear gel cosmetic compositions | |
ZA200509493B (en) | A clear, low viscosity, water-in-oil emulsion antiperspirant gel composition | |
ZA200509494B (en) | Suspension free and elastomer free antiperspirant white cream | |
ZA200509492B (en) | A clear, low viscosity, water-in-oil emulsion antiperspirant gel composition | |
US6338841B1 (en) | Antiperspirant product with dibenzylidene sorbitol and elastomer in dimethicone | |
AU2001238372A1 (en) | Low tack cosmetic composition sticks | |
WO2001060329A1 (en) | Low tack cosmetic composition sticks | |
KR20010113955A (en) | Antiperspirant and deodorant compositions containing cyclohexasiloxane | |
US20020076385A1 (en) | Esters | |
AU2002354917A1 (en) | Antiperspirant product with dibenzylidene sorbitol and elastomer in dimethicone |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BW BY BZ CA CH CN CO CR CU CZ DK DM DZ EC EE EG ES FI GB GD GE GM HR HU ID IL IN IS JP KE KG KP KZ LC LK LR LS LT LU LV MA MD MK MN MW MX MZ NA NI NO NZ PG PH PL PT RO RU SC SD SE SG SK SY TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): BW GH GM KE LS MW MZ NA SD SZ TZ UG ZM ZW AM AZ BY KG MD RU TJ TM AT BE BG CH CY DE DK EE ES FI FR GB GR HU IE IT MC NL PL PT RO SE SI SK TR BF CF CG CI CM GA GN GQ GW ML MR SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2538017 Country of ref document: CA Ref document number: PA/a/2006/002612 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2004272034 Country of ref document: AU |
|
WWE | Wipo information: entry into national phase |
Ref document number: 06029589 Country of ref document: CO Ref document number: 2004788610 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2004272034 Country of ref document: AU Date of ref document: 20040908 Kind code of ref document: A |
|
WWP | Wipo information: published in national office |
Ref document number: 2004272034 Country of ref document: AU |
|
WWE | Wipo information: entry into national phase |
Ref document number: 200602883 Country of ref document: ZA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2006111453 Country of ref document: RU |
|
DPEN | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101) | ||
WWP | Wipo information: published in national office |
Ref document number: 2004788610 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: PI0414194 Country of ref document: BR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 10571488 Country of ref document: US Ref document number: 2007196308 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 10571488 Country of ref document: US |