CA2144662C - Homogeneous cosmetic stick products - Google Patents
Homogeneous cosmetic stick products Download PDFInfo
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- CA2144662C CA2144662C CA002144662A CA2144662A CA2144662C CA 2144662 C CA2144662 C CA 2144662C CA 002144662 A CA002144662 A CA 002144662A CA 2144662 A CA2144662 A CA 2144662A CA 2144662 C CA2144662 C CA 2144662C
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- deodorant
- cosmetic stick
- antiperspirant
- stick product
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- 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
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0216—Solid or semisolid forms
- A61K8/0229—Sticks
-
- 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
-
- 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
- A61K8/18—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
- A61K8/37—Esters of carboxylic acids
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S424/00—Drug, bio-affecting and body treating compositions
- Y10S424/05—Stick
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- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
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- Chemical & Material Sciences (AREA)
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Abstract
This invention provides an antiperspirant-deodorant cosmetic stick product consisting of a solid organic matrix which contains a omogeneous dispersion of particulate antiperspirant and deodorant ingredients.
A deodorant cosmetic stick product is also provided which oes not contain an antiperspirant ingredient. The solid organic matrix and dispersed particles phases have densities which are sufficiently patched to prevent setting of the dispersed particles during manufacture, and to provide a cosmetic stick product with dimensional stability.
A deodorant cosmetic stick product is also provided which oes not contain an antiperspirant ingredient. The solid organic matrix and dispersed particles phases have densities which are sufficiently patched to prevent setting of the dispersed particles during manufacture, and to provide a cosmetic stick product with dimensional stability.
Description
HOMOGENEOUS COSMETIC STICK PRODUCTS
BACKGROUND OF THE INVENTION
Antiperspirants combat axillary odors by inhibiting perspiration through the action of astringent salt such as aluminum and zinc salts, but may be irritating to a large number of users. Deodorants function by neutralizing the objectionable odors resulting from the degradation of several components of perspiration by chemical and microbial action into malodorous fatty aids.
Numerous solid antiperspirant and/or deodorant compositions have been described in the chemical and cosmetic literature. These compositions generally are emulsion sticks or suspensoid sticks. Emulsion sticks contain a solution of the antiperspirant ingredient incorporated into the stick via emulsion. Although emulsion sticks are desirable in certain respects, they tend to be unstable, exhibit tackiness, and leave a visible residue on the skin after use. Suspensoid sticks contain the powdered WO 94/13256 PCT/US93/0908~
BACKGROUND OF THE INVENTION
Antiperspirants combat axillary odors by inhibiting perspiration through the action of astringent salt such as aluminum and zinc salts, but may be irritating to a large number of users. Deodorants function by neutralizing the objectionable odors resulting from the degradation of several components of perspiration by chemical and microbial action into malodorous fatty aids.
Numerous solid antiperspirant and/or deodorant compositions have been described in the chemical and cosmetic literature. These compositions generally are emulsion sticks or suspensoid sticks. Emulsion sticks contain a solution of the antiperspirant ingredient incorporated into the stick via emulsion. Although emulsion sticks are desirable in certain respects, they tend to be unstable, exhibit tackiness, and leave a visible residue on the skin after use. Suspensoid sticks contain the powdered WO 94/13256 PCT/US93/0908~
antiperspirant ingredient suspended in the stick without the use of water or an emulsion. While suspensoids have stability, they tend to leave a white chalky residue on the skin after application.
Manufacturers have found that anhydrous antiperspirant stick systems are more marketable and have good consumer acceptance primarily due to the ease of application to the skin, good cosmetic esthetics and an acceptable degree of effectiveness.
Previous to the development of anhydrous stick systems, numerous water based systems were developed in which the active astringent salts were solubilized in a thickened or gelled composition.
This is exemplified in United States Patent Numbers 2,732,327; 2,857,315; 3,255,082; and 3,928,557. The water based systems are difficult to apply to the skin, and their consistency and effectiveness are variable.
Many anhydrous stick compositions have been described in the literature which attempt to improve the delivery and the effectiveness of their antiperspirant and deodorant characteristics.
Antiperspirant stick systems consisting of low molecular weight monohydric alcohols in conjunction with polyhydric alcohols are described in U.S. 4,137,306. These sticks have the advantage of quicker drying rates, but the residue of the polyhydric alcohols in combination with the ~O 94/13256 PCT/US93/09080 2~.4~fifi~
Manufacturers have found that anhydrous antiperspirant stick systems are more marketable and have good consumer acceptance primarily due to the ease of application to the skin, good cosmetic esthetics and an acceptable degree of effectiveness.
Previous to the development of anhydrous stick systems, numerous water based systems were developed in which the active astringent salts were solubilized in a thickened or gelled composition.
This is exemplified in United States Patent Numbers 2,732,327; 2,857,315; 3,255,082; and 3,928,557. The water based systems are difficult to apply to the skin, and their consistency and effectiveness are variable.
Many anhydrous stick compositions have been described in the literature which attempt to improve the delivery and the effectiveness of their antiperspirant and deodorant characteristics.
Antiperspirant stick systems consisting of low molecular weight monohydric alcohols in conjunction with polyhydric alcohols are described in U.S. 4,137,306. These sticks have the advantage of quicker drying rates, but the residue of the polyhydric alcohols in combination with the ~O 94/13256 PCT/US93/09080 2~.4~fifi~
astringent salts produces a high degree of tack, and their effectiveness is limited to the type and amount of astringent salts that could be incorporated in the stick matrix.
Anhydrous stick compositions that suspend the aluminum salt in a hydrophobic matrix are described in U.S. 4,049,792. These compositions employ waxy materials and long chain fatty esters to form a stick that delivers the active astringent salts to the skin.
Cosmetic stick compositions made in accordance with these embodiments are greasy, and the active astringent salt is enveloped in a manner that prevents maximum performance. To alleviate this inherent negative characteristic, volatile silicone fluids replacement of the less volatile long chain fatty esters is described in U.S. 4,126,679. This disclosure teaches the advantage of utilizing a volatile non-staining liquid such as cyclic dimethylpolysiloxanes (referred to as volatile silicones), in combination with various types of waxes, as a carrier for the active astringent salts in an antiperspirant stick composition. Similar antiperspirant stick compositions containing volatile silicones are described in United States Patent Numbers 4,511,554;
Anhydrous stick compositions that suspend the aluminum salt in a hydrophobic matrix are described in U.S. 4,049,792. These compositions employ waxy materials and long chain fatty esters to form a stick that delivers the active astringent salts to the skin.
Cosmetic stick compositions made in accordance with these embodiments are greasy, and the active astringent salt is enveloped in a manner that prevents maximum performance. To alleviate this inherent negative characteristic, volatile silicone fluids replacement of the less volatile long chain fatty esters is described in U.S. 4,126,679. This disclosure teaches the advantage of utilizing a volatile non-staining liquid such as cyclic dimethylpolysiloxanes (referred to as volatile silicones), in combination with various types of waxes, as a carrier for the active astringent salts in an antiperspirant stick composition. Similar antiperspirant stick compositions containing volatile silicones are described in United States Patent Numbers 4,511,554;
4,980,156; and 4,985,238.
With respect to deodorant activity, sodium bicarbonate has long been recognized for its deodorant properties, and has commonly been used as WO 94/13256 PCT/US93/0908C~
a household deodorant. Plain powdered sodium bicarbonate, or sodium bicarbonate diluted with talc , or other filler, has been used as an underarm deodorant as disclosed in U.S. 4,382,079. Other publications which describe cosmetic stick compositions containing a bicarbonate deodorant include U.S. 4,822,602 and U.S. 4,832,945.
However, the development of a practical and effective antiperspirant composition in cosmetic stick form which is also capable of deodorization, and which is capable of consumer acceptability, presents many factors which are unique. Because sodium and potassium bicarbonate have only limited solubility in water, alcohol and other solvents, the preparation of a composition suitable for dispensing in cosmetic stick form has involved many processing obstacles. In addition to the problem of limited solubility, sodium bicarbonate is incompatible with the active astringent salts and with other ingredients of conventional stick compositions.
Also, the dimensional stability of the cosmetic stick containing sodium bicarbonate, and the esthetic appearance and the "feel" on the skin, are just a few of the additional difficulties encountered in the preparation of a low residue antiperspirant-deodorant cosmetic stick product.
Another significant problem associated with the incorporation of a bicarbonate deodorant ingredient in a cosmetic stick formulation is the ~O 94/13256 PCTlUS93109080 tendency for the high density bicarbonate salt particles to settle in the fluid medium during processing. Also, under the elevated temperature conditions required for the admixing and blending of 5 ingredients, bicarbonate degradation and evolution of carbon dioxide occur.
There is continuing interest in the development of improved cosmetic stick products which exhibit antiperspirant and/or deodorant 1o activity, and in processes for their preparation.
Accordingly, it is an object of this invention to provide a process for the manufacture of a cosmetic stick product which exhibits deodorant properties, and is characterized by excellent esthetics and cosmetic properties.
It is another object of this invention to provide a homogeneous antiperspirant-deodorant cosmetic stick product which contains a dispersed phase of particulate antiperspirant and deodorant ingredients in a solid organic matrix phase, and which phases are density matched to prevent settling of the dispersed particles.
Other objects and advantages of the present invention shall become apparent from the accompanying description and examples.
With respect to deodorant activity, sodium bicarbonate has long been recognized for its deodorant properties, and has commonly been used as WO 94/13256 PCT/US93/0908C~
a household deodorant. Plain powdered sodium bicarbonate, or sodium bicarbonate diluted with talc , or other filler, has been used as an underarm deodorant as disclosed in U.S. 4,382,079. Other publications which describe cosmetic stick compositions containing a bicarbonate deodorant include U.S. 4,822,602 and U.S. 4,832,945.
However, the development of a practical and effective antiperspirant composition in cosmetic stick form which is also capable of deodorization, and which is capable of consumer acceptability, presents many factors which are unique. Because sodium and potassium bicarbonate have only limited solubility in water, alcohol and other solvents, the preparation of a composition suitable for dispensing in cosmetic stick form has involved many processing obstacles. In addition to the problem of limited solubility, sodium bicarbonate is incompatible with the active astringent salts and with other ingredients of conventional stick compositions.
Also, the dimensional stability of the cosmetic stick containing sodium bicarbonate, and the esthetic appearance and the "feel" on the skin, are just a few of the additional difficulties encountered in the preparation of a low residue antiperspirant-deodorant cosmetic stick product.
Another significant problem associated with the incorporation of a bicarbonate deodorant ingredient in a cosmetic stick formulation is the ~O 94/13256 PCTlUS93109080 tendency for the high density bicarbonate salt particles to settle in the fluid medium during processing. Also, under the elevated temperature conditions required for the admixing and blending of 5 ingredients, bicarbonate degradation and evolution of carbon dioxide occur.
There is continuing interest in the development of improved cosmetic stick products which exhibit antiperspirant and/or deodorant 1o activity, and in processes for their preparation.
Accordingly, it is an object of this invention to provide a process for the manufacture of a cosmetic stick product which exhibits deodorant properties, and is characterized by excellent esthetics and cosmetic properties.
It is another object of this invention to provide a homogeneous antiperspirant-deodorant cosmetic stick product which contains a dispersed phase of particulate antiperspirant and deodorant ingredients in a solid organic matrix phase, and which phases are density matched to prevent settling of the dispersed particles.
Other objects and advantages of the present invention shall become apparent from the accompanying description and examples.
6 PCT/US93/0908~
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,DESCRIPTION OF THE INVENTION
One or more objects of the present invention are accomplished by the provision of an antiperspirant-deodorant cosmetic stack product consisting of a solid organic matrix comprising the following parts by weight of ingredients:
volatile silicone oil 10-50 liquid emollient 1-30 low melting point wax 12-24 and the solid organic matrix has homogeneously dispersed therein between about 18-35 parts by weight of particulate antiperspirant and between about 0.05-30 parts by weight of particulate water-soluble inorganic salt deodorant ingredients;
wherein the dispersed particles have a density which is less than about one gram per cubic centimeter higher than the density of the solid organic matrix.
The particulate antiperspirant and deodorant ingredients typically have an average particle size between about 5-200 microns.
The density of the solid organic matrix is between about 0.8-1.6 grams per cubic centimeter, and the density of the antiperspirant and deodorant particles is between about 0.9-2 grams per cubic centimeter.
~O 94/13256 PCT/US93/09080 '.°~z~4~~sz In another embodiment this invention provides a process for preparing an antiperspirant-deodorant cosmetic stick product which comprises (i) heating and forming a liquid organic matrix of ingredients comprising between about 10-50 parts by weight of a volatile silicone oil; between about 1-30 parts by weight of a liquid emollient, and between about 12-24 parts by weight of a low melting point wax; (2) adding and dispersing in the heated liquid organic matrix between about 18-35 parts by weight of particulate antiperspirant and between about 0.05-30 parts by weight of particulate water-soluble inorganic salt deodorant to form a homogeneous fluid suspension medium; and (3) dispensing the heated fluid suspension medium into cosmetic stick containers, and cooling the container contents to form solid sticks at room temperature; wherein the dispersed particles have a density which is less than about one gram per cubic centimeter higher than the density of the organic matrix in the cosmetic stick product.
In a preferred embodiment between about 0.5-5 parts by weight of a surfactant ingredient is included in the step(2) formation of the liquid organic matrix.
An invention antiperspirant-deodorant cosmetic stick product typically contains the following weight proportions of main ingredients:
WO 94/13256 PC'd'/US93/0908C~
~> i ,.
~nqredient ' Wei t volatile silicone oil ~ 25-50 , liquid emollient 2-20 wax (MP 95-180F) 15-20 antiperspirant 20-30 bicarbonate deodorant 0.1-25 surfactant 1-3 In another embodiment this invention provides a cosmetic stick product as described above which contains a deodorant ingredient but does not contain an antiperspirant ingredient.
An invention deodorant cosmetic stick product can contain the following weight proportions of main ingredients:
Ingredient Wei volatile silicone oil 10-55 liquid emollient 1-35 wax (MP 95-180F) 12-30 bicarbonate deodorant 1-40 surfactant 0.5-5 The volatile silicone oil ingredient in an antiperspirant-deodorant cosmetic stick product of the present invention preferably is a cyclic or linear polydimethylsiloxane containing between about 3-9 silicon atoms. A suitable cyclic volatile .
polydimethylsiloxane compound is illustrated by the f ormula ~O 94/13256 PCTIUS93109080 ~: ~.
(Si-O]~
where n is an integer with a value of about 3-7.
A suitable linear polydimethylsiloxane is illustrated by the formula:
( CH3 ) 3S i-O [ S i ( CH3 ) 2-O ] n-S i ( CH3 ) 3 where n is an integer with a value of about 1-7.
Linear volatile silicone compounds generally have viscosities of less than about 5 centistokes at 25°C, while the cyclic type compounds have viscosities of less than about 10 centistokes.
Typical of the volatile silicone compounds that can be employed for purposes of the present invention is cyclomethicone, which is a cyclic dimethylpolysiloxane conforming to the above formula where n averages between 3-6. Dow Corning 245 Fluid (Dow Corning) is a cyclic volatile silicone which is commercially available. CTFA Cosmetic Ingredient Dictionary, Third Edition, (Estrin et al., Editors;
The Cosmetic, Toiletry and Fragrance Association, Inc.; 1982) lists cyclic silicones on page 60, under the entry "Cyclomethicone".
WO 94/13256 PCTILTS93/09080~
F v' The liquid emollient ingredient of an invention cosmetic stick product is selected from one or more water-insoluble organic compounds which are liquid at 25°C and which contribute a combination of properties that are advantageous in an invention antiperspirant-deodorant cosmetic stick product.
The term "water-insoluble" as employed herein refers to an emollient ingredient which has a water-solubility of less than about vne weight percent at 25°C.
A present invention emollient ingredient exhibits a low degree of irritation and toxicity in topical applications, and provides a softening or soothing effect on surface skin tissue.
Preferred water-insoluble liquid emollients include fatty acids such as oleic and ricinoleic; fatty alcohols such as oleyl, lauryl and hexadecyl; esters such as diisopropyl adipate, benzoic acid esters of C9-C~5 alcohols, and isononyl isononanoate; alkanes such as mineral oil; silicones such as dimethylpolysiloxane and cyclic dimethyl-polysiloxane; and ethers such as polyoxypropylene butyl ether and polyoxypropylene cetyl ether.
Preferred water-insoluble liquid emollients include diisopropyl adipate, 2-ethylhexyl palmitate, dimethylpolysiloxane (50 cst.), and polyoxypropylene (14) butyl ether.
~O 94/13256 PCT/LTS93/09080 ~~~4~~~
The low melting point wax ingredient of a present invention cosmetic stick product comprises one or more organic compounds which have a melting point in the range between about 95°-180°F.
Suitable types of wax-like compounds include fatty acids, fatty alcohols, fatty acid esters, fatty acid amides, and the like, which have an aliphatic chain length between about 8-30 carbon atoms. Illustrative of wax-like compounds are cetyl l0 alcohol, palmitic acid, myristyl alcohol, stearyl alcohol, paraffin, and the like, and mixtures thereof .
The low melting point wax ingredient can include up to about 30 weight percent, based on the weight of wax ingredient, of a wax which has a melting point between about 180°-220°F.
Illustrative of these higher melting waxes are beeswax, spermaceti, carnauba, bayberry, candelilla " montan, ozokerite, ceresin, paraffin, castor wax, Fischer-Tropsch waxes, and the like.
The antiperspirant ingredient of a present invention cosmetic stick product typically is a particulate astringent compound which has an average particle size between about 5-200 microns. Superior cosmetic stick properties are obtained if part yr all of the antiperspirant ingredient is in the form of particles which have a diameter less than about one micron.
WO 94113256 PCT/US93/0908(~
~~~1~~
Suitable astringent compounds include aluminum chloride, aluminum chlorohydrate, aluminum , sulfocarbolate, aluminum sulfate, aluminum-zirconium chlorohydrate, zinc sulfate, zinc sulfocarbolate, and zirconium chlorohydrate. Preferred types of astringent compounds are aluminum chlorohydrates and aluminum-zirconium chlorohydrates, such as aluminum zirconium tetrachlorohydrex glycine which is commercially available as Rezal 36 GP Superultrafine (Reheis), and Reach AZP 908 (Reheis). The organometallic astringent compounds tend to have lower densities which are advantageous for purposes of density matching of the organic matrix phase and dispersed particle phase in an invention cosmetic stick product.
The water-soluble inorganic salt deodorant ingredient of an invention cosmetic stick product preferably is selected from alkali metal and ammonium bicarbonates, such as sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate and mixtures thereof. The bicarbonate deodorant ingredient can contain up to about 30 weight percent, based on the weight of deodorant ingredient, of an alkali metal or ammonium carbonate compound.
The average particle size of the water-soluble inorganic salt deodorant ingredient can be in the range between about 5-200 microns. Improved cosmetic stick properties are obtained if part or ~O 94/13256 PCT/US93/09080 2 ~ ~Y4 fi~~ ~ ._ all of the inorganic salt ingredient has a particle size diameter less than about one micron. Colloidal size particles facilitate incorporation into the cosmetic stick matrix, and the resultant stick composition has a smoother non-gritty feel when applied to the skin.
The term "water-soluble" as employed herein refers to an inorganic salt which has a solubility of at least about one gram.per one hundred grams of water at 25°C.
The optional surfactant ingredient of an invention cosmetic stick product can be selected from nonionic, cationic and anionic polymers.
Suitable surfactant polymers include cetyltrimethylammonium bromide; sodium lauryl sulfate; sodium dodecylbenzenesulfonate; ammonium . lignosulfonate; condensation products of ethylene oxide with fatty alcohols, amines or alkylphenols;
partial esters of fatty acids and hexitol anhydrides; polyalkylene glycol esters; and the like. Illustrative of a preferred type of surfactant polymer is polyethylene glycol (PEG) stearate, which is commercially available as PEG 600 distearate.
Other optional ingredients also may be included in an invention cosmetic stick formulation, such as bacteriostats, fungistats, fillers, stabilizing agents, antioxidants, pigments, coloring agents, perfumes, hardeners, chelating agents, and the like.
WO 94/13256 PCT/LTS93/0908(~
A bacteriostat such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether (Triclosan) typically is added in a quantity between about 0.08-3 weight percent, based on the weight of the cosmetic stick product.
An optional ingredient such as colloidal silica suspending agent is added in a quantity between about 1-3 weight percent, based on the weight of the cosmetic stick product.
An important aspect of the present invention is the provision of an antiperspirant-deodorant cosmetic stick product which is composed of a solid organic matrix containing a homogeneous dispersion of particulate antiperspirant and deodorant ingredients.
The solid organic matrix and dispersed particle phases have densities which are sufficiently matched to prevent settling of the dispersed particles during manufacture, and to provide a cosmetic stick product with dimensional stability.
Antiperspirant and inorganic salt deodorant compounds nominally have a density above about two grams per cubic centimeter. If high density particulate ingredients are suspended in an organic matrix having a density of about one gram per cubic centimeter, the particles have a tendency to settle out of the organic matrix, and the resultant cosmetic stick product is inhomogeneous and dimensionally unstable.
- .~ ~z~4~~vi~
In the present invention, separation of organic matrix and suspended particle phases is prevented by providing particulate antiperspirant and deodorant ingredients having densities which 5 more closely match the density of the organic matrix of a cosmetic stick product.
One means of density matching is by the utilization of organic polymer pre-coated particles of antiperspirant and inorganic salt deodorant 10 ingredients in the manufacture of the antiperspirant-deodorant cosmetic stick product.
Pre-coating of ingredient particles has the beneficial effect of improving the suspension properties of the particles in the fluid formulation 15 admixture during processing. Less particle settling occurs in the organic matrix because the density of . the coated particles and the organic matrix density are more closely matched than is the case with uncoated particles. There is a tendency for uncoated particles to settle out during the manufacturing process when the organic matrix is in a fluid state, and also in the cosmetic stick product when the organic matrix is in a solid form.
The organic polymer coating on the dispersed antiperspirant and inorganic salt deodorant particles~also has the benefit of minimizing any reaction between acidic antiperspirant and basic deodorant compounds, and preventing loss of antiperspirant-deodorant activities.
WO 94/13256 PC'T/US93/0908~
..
The application of the coating to the particles is accomplished by conventional means such as pan coating, fluidized coating, centrifugal fluidized coating, and the like. The coating polymer usually is dissolved in a suitable solvent such as water, methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethylformamide, and the like, as appropriate for a selected polymer species. A coating polymer also can be applied in the form of an emulsion or suspension. After the coating medium is applied to the particles, the solvent medium is removed by evaporation, thereby forming a continuous film coating which encapsulates the individual particles.
The coating thickness on the particle surfaces typically will vary in the range between about 0.1-20 microns. The coating can consist of a single layer or multiple layers. The polymer coating can constitute between about 5-30 weight percent of the total dry weight of the coated particles. The average size of the inner core particle typically is in the range between about 5-80 microns.
The polymer employed for coating the ingredient particles is selected from hydrophilic water-soluble and water-dispersible organic polymers. A mixture of polymers can be employed, and a content of between about 0.5-40 weight percent of a hydrophobic water-insoluble polymer, based on the coating weight, can be included.
D 94/13256 PCTlUS93109080 The term "hydrophilic°° as employed herein refers to an organic polymer which has a water-solubility of at least about 0.5 gram per 100 grams of water at 25°C.
Suitable hydrophilic polymers for coating particles include gum arabic, gum karaya, gum tragacanth, guar gum, locust bean gum, xanthan gum, carrageenan, alginate salt, casein, dextran, pectin, agar, sorbitol, 2-hydroxyethyl starch, 2-aminoethyl l0 starch, maltodextrin, polydextrose, 2-hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose salt, cellulose sulfate salt, polyvinylpyrrolidone, polyethylene glycol, polypropylene glycol, polyethylene oxide, polyvinyl alcohol/acetate, polyacrylamide, and the like. Polyvinyl acetate is illustrative of a water-insoluble polymer which can be included as an additional coating component to moderate the hydrophilicity of the coating.
The rate of particle matrix compound release from the particle core under moisture conditions can be controlled by the quantity and type of hydrophilic polymer coating on the particle surfaces.
Low molecular weight hydrophilic polymers will release the particle matrix compound at a relatively fast rate in the presence of moisture.
High molecular weight polymers which are less hydrophilic will release at a relatively slow rate.
Additional rate control is obtained by employing mixtures of polymer components of varied hydrophilicity.
- ~~4~s~z Polyethylene glycol (M.W. of 4000) or polyvinyl alcohol will release particle matrix compound at a relatively fast rate. Polyethylene oxide (M. W. of 4,000,000) or partially hydrolyzed polyvinyl acetate will release at a relatively slow rate. Polyvinylpyrrolidone will release particle matrix compound at an immediate rate when in contact with underarm type of moisture.
Another means of achieving density matching of organic matrix and suspended particle phases is by the utilization of antiperspirant and inorganic salt particles which have a microporous structure. Microporosity in crystalline compounds can be achieved by various methods developed in chemical practice.
In one method, particles of the desired compound are prepared in admixture with a second compound, such as by coprecipitation from a solvent medium. The second compound is selected so that it can be removed from the particle mass by selective solvent extraction, or by heat treatment to convert the second compound into a volatile fraction.
Illustrative of this method is a coprecipitated mixture of sodium bicarbonate and ammonium bicarbonate. Heat treatment of the coprecipitate above 100°C decomposes the ammonium bicarbonate to volatile components, and the residual sodium bicarbonate can have a lowered density in the range of 1-2 grams per cm3.
~O 94/13256 PCTILTS93/09080 i :.. .
~ P
~1~~~~6~~
In another method of preparing microporous particles, an aqueous solution of alkali metal bicarbonate can be diluted with an organic solvent such as methanol, and the resultant precipitate is in the form of particles composed of agglomerated monoclinic needles of alkali metal bicarbonate. The needles have a crystal length between about 0.5-2 microns, and the agglomerated particles have an average size between about 4-12 microns in the l0 largest dimension. The particles are characterized by a network of microporous voids between the agglomerated needles.
Another means of achieving density matching of organic matrix and suspended particle phases is by the utilization of antiperspirant and inorganic salt particles which are coordinated with an organic complexing compound.
Alkali metal bicarbonate can form molecular complexes with organic compounds such as 2o I3-cyclodextrin, mannitol, sorbitol, crown ether, trioxane, and the like. The density of the alkali metal bicarbonate: organic compound complex is less than the density of the free alkali metal bicarbonate. A molecular complex can be obtained by evaporating an aqueous solution of the alkali metal bicarbonate and water-soluble organic complexing compound.
In general, the ingredients of the cosmetic stick formulation can be blended in any order during manufacture. However, in the practice of the invention process there is advantage in WO 94/13256 PCT/US93/0908(~
~.1 ~f ~f t' employing a phased order of ingredient addition and blending under controlled temperature conditions. _ Additional advantage is obtained in the invention process if there is a short time lapse between an 5 alkali metal bicarbonate deodorant ingredient addition step and the cosmetic stick container filling and solidifying step. Alkali metal bicarbonate can convert to alkali metal carbonate, carbon dioxide and water at elevated temperatures.
1o Adding a bicarbonate deodorant as the last ingredient of the blended formulation, and processing the formulation to the solid cosmetic stick formation stage within a short time period, are factors which minimize the degradation of the 15 bicarbonate ingredient, and the undesirable formation of water and carbon dioxide vapor byproducts. The addition and mixing of a bicarbonate deodorant ingredient into the formulation, and the dispensing of the formulation 20 into cosmetic stick containers, can be accomplished as an essentially instantaneous procedure by utilizing an integrated mixing valve nozzle device, such as the type described in United States Patent Numbers 2,816,518; 3,454,198; 3,949,904; 4,318,429;
4,549,813; 5,046,538; 5,094,276; arid the like.
The practice of the invention process for the production of a cosmetic stick product can be conducted in conventional equipment, and is readily , adaptable to a commercial-scale manufacturing operation.
!O 94/13256 PCT/US93/09080 ~~~4~y&G~
A present invention cosmetic stick product preferably has a hardness penetration value between about 4-12 millimeters, as determined by American Society For Testing Materials (ASTMj Method D5.
A present invention antiperspirant-deodorant cosmetic stick product has exceptional properties for treating or preventing perspiration and malodor associated with human underarm perspiration. A present invention cosmetic stick product can be applied effectively with safety and comfort for reduction of underarm perspiration and offensive odors.
A present invention deodorant cosmetic stick product provides particular advantage for users who wish to avoid the risk of skin irritation caused by the presence of an antiperspirant ingredient.
Because of the density matching of organic matrix and dispersed particle phases, an invention cosmetic stick product has improved dimensional stability, and better esthetic appearance and "feel"
when applied to human skin. The density matching of ingredients also has application in roll-on cosmetic products.
The following Examples are further illustrative of the present invention. The components and specific ingredients are presented as being typical and various modifications can be derived in view of the foregoing disclosure within the scope of the invention.
WO 94/13256 PCT/US93/09080~
y149~~~~
EXAMPLE I
This Example illustrates-a procedure for coating a particulate bicarbonate deodorant compound with a water-soluble organic polymer in accordance with the present invention.
Guar gum (15 g, Supercol, Aqualon Co.) is dissolved in 150 ml of 50% aqueous ethanol solvent.
Sodium bicarbonate (100 g, 50-80 microns, Church & Dwight) is suspended in the solution medium l0 with stirring.
The solvent medium is removed by evaporation under vacuum. A dry free-flowing powder is obtained. The particles are coated with a guar film having an average thickness of 2-5 microns.
~O 94/13256 PCT/US93/09080 EXAMPLE II
This Example illustrates a fluidized bed procedure for coating an antiperspirant compound with a water-soluble polymer in accordance with the present invention.
A fluidized bed vessel is utilized which is equipped with a Wurster air-suspension coater system (WARF) as described in U.S. 4,568,559 and U.S. 4,877,621.
A coating solution is prepared by dissolving polyethylene glycol (45 g, Poly-G 2000, Olin Corp.), and propylene glycol butyl ether (10 g, PPG 14, Americol) in ethanol (600 g).
Particulate aluminum zirconium tetrachlorohydrex glycine (600 g, 60-100 microns, Reheis) is charged into the coating chamber.
Compressed air is introduced into the coating chamber, and the polymeric coating solution is sprayed on the air-suspended antiperspirant core matrix particles, until the coating weight is about 20% of the total dry weight of the coated particles.
The procedure is repeated, except that Hydroxypropylmethylcellulose (Methocel 60 HG, Dow Chemical Co.) is employed as the water-soluble polymer.
WO 94/13256 PCT/LJS93/0908(~
EXAMPLE III
This Example illustrates a pilot-plant procedure for the preparation of an antiperspirant-deodorant cosmetic stick product in accordance With the present invention.
A stainless steel tank is provided which is equipped with turbine agitation.
Silicone oil DC 245 (600 lbs, Dow Corning) is charged to the mixing tank. Agitation (55-65 RPM) is initiated, and heating the liquid medium to 176°F is commenced.
During the heating period, the following order of ingredients are added to the stirred liquid medium:
lbs.
diisopropyl adipate 60 PPG 14 butyl ether (Americol) 40 stearyl alcohol 340 castor wax (MP-70) 60 2o eicosanol l0 PEG 600 distearate (Mater) 40 The mixture is stirred at 176°F for about 30 minutes until the ingredients are melted and the liquid medium is homogeneous. The stirring speed is reduced to about 35 RPM, then Cab-o-sil M-5 (15 lbs, Cabot) and aluminum zirconium tetrachlorohydrex ~O 94/13256 PCT/US93/09080 - ~ - ~~~~.44iC 6~
glycine (480 lbs, Reheis) are added. The temperature is maintained at 176°F~for about 40 minutes until the fluid medium is uniform, and then the temperature is lowered to 124°F.
5 Polymer-coated sodium bicarbonate 3 DF
(140 lbs, Church & Dwight) and a fragrance (6 lbs, 1FF 567-AT) respectively are added with stirring to Silicone oil DC 245 (245 lbs, Dow Corning) in a second mixing tank at a temperature of 124°F to form 10 a homogeneous suspension medium. The sodium bicarbonate particles are pre-coated with guar gum as described in Example I.
The contents of the two mixing tanks which contain heated fluid medium are transferred to 15 separate fill tanks through a Greer mill, and the fill tanks are connected to a mixing and dispensing . nozzle device, of the type described in U.S. 5,094,276. The nozzle device is adapted for homogeneously blending the two separate streams of 20 fluid media, and dispensing a predetermined quantity of the blended fluid.
Plastek 2 oz. bottom-fill stick containers are filled with the blended fluid. The container contents are cooled to a room temperature solid 25 stick over a period of about 45 minutes. The average hardness value of the solid sticks is 7 (ASTM Method D5).
Similar results are obtained when microporous sodium bicarbonate is employed in place of the polymer-coated sodium bicarbonate ingredient.
WO 94/13256 PCT/US93/0908(~
A deodorant cosmetic stick product is prepared by eliminating the antiperspirant ingredient, and increasing the quantity of sodium bicarbonate ingredient from 140 lbs to 180 lbs in the above described manufacturing process.
,.
,v ~. s ~y446~~
,DESCRIPTION OF THE INVENTION
One or more objects of the present invention are accomplished by the provision of an antiperspirant-deodorant cosmetic stack product consisting of a solid organic matrix comprising the following parts by weight of ingredients:
volatile silicone oil 10-50 liquid emollient 1-30 low melting point wax 12-24 and the solid organic matrix has homogeneously dispersed therein between about 18-35 parts by weight of particulate antiperspirant and between about 0.05-30 parts by weight of particulate water-soluble inorganic salt deodorant ingredients;
wherein the dispersed particles have a density which is less than about one gram per cubic centimeter higher than the density of the solid organic matrix.
The particulate antiperspirant and deodorant ingredients typically have an average particle size between about 5-200 microns.
The density of the solid organic matrix is between about 0.8-1.6 grams per cubic centimeter, and the density of the antiperspirant and deodorant particles is between about 0.9-2 grams per cubic centimeter.
~O 94/13256 PCT/US93/09080 '.°~z~4~~sz In another embodiment this invention provides a process for preparing an antiperspirant-deodorant cosmetic stick product which comprises (i) heating and forming a liquid organic matrix of ingredients comprising between about 10-50 parts by weight of a volatile silicone oil; between about 1-30 parts by weight of a liquid emollient, and between about 12-24 parts by weight of a low melting point wax; (2) adding and dispersing in the heated liquid organic matrix between about 18-35 parts by weight of particulate antiperspirant and between about 0.05-30 parts by weight of particulate water-soluble inorganic salt deodorant to form a homogeneous fluid suspension medium; and (3) dispensing the heated fluid suspension medium into cosmetic stick containers, and cooling the container contents to form solid sticks at room temperature; wherein the dispersed particles have a density which is less than about one gram per cubic centimeter higher than the density of the organic matrix in the cosmetic stick product.
In a preferred embodiment between about 0.5-5 parts by weight of a surfactant ingredient is included in the step(2) formation of the liquid organic matrix.
An invention antiperspirant-deodorant cosmetic stick product typically contains the following weight proportions of main ingredients:
WO 94/13256 PC'd'/US93/0908C~
~> i ,.
~nqredient ' Wei t volatile silicone oil ~ 25-50 , liquid emollient 2-20 wax (MP 95-180F) 15-20 antiperspirant 20-30 bicarbonate deodorant 0.1-25 surfactant 1-3 In another embodiment this invention provides a cosmetic stick product as described above which contains a deodorant ingredient but does not contain an antiperspirant ingredient.
An invention deodorant cosmetic stick product can contain the following weight proportions of main ingredients:
Ingredient Wei volatile silicone oil 10-55 liquid emollient 1-35 wax (MP 95-180F) 12-30 bicarbonate deodorant 1-40 surfactant 0.5-5 The volatile silicone oil ingredient in an antiperspirant-deodorant cosmetic stick product of the present invention preferably is a cyclic or linear polydimethylsiloxane containing between about 3-9 silicon atoms. A suitable cyclic volatile .
polydimethylsiloxane compound is illustrated by the f ormula ~O 94/13256 PCTIUS93109080 ~: ~.
(Si-O]~
where n is an integer with a value of about 3-7.
A suitable linear polydimethylsiloxane is illustrated by the formula:
( CH3 ) 3S i-O [ S i ( CH3 ) 2-O ] n-S i ( CH3 ) 3 where n is an integer with a value of about 1-7.
Linear volatile silicone compounds generally have viscosities of less than about 5 centistokes at 25°C, while the cyclic type compounds have viscosities of less than about 10 centistokes.
Typical of the volatile silicone compounds that can be employed for purposes of the present invention is cyclomethicone, which is a cyclic dimethylpolysiloxane conforming to the above formula where n averages between 3-6. Dow Corning 245 Fluid (Dow Corning) is a cyclic volatile silicone which is commercially available. CTFA Cosmetic Ingredient Dictionary, Third Edition, (Estrin et al., Editors;
The Cosmetic, Toiletry and Fragrance Association, Inc.; 1982) lists cyclic silicones on page 60, under the entry "Cyclomethicone".
WO 94/13256 PCTILTS93/09080~
F v' The liquid emollient ingredient of an invention cosmetic stick product is selected from one or more water-insoluble organic compounds which are liquid at 25°C and which contribute a combination of properties that are advantageous in an invention antiperspirant-deodorant cosmetic stick product.
The term "water-insoluble" as employed herein refers to an emollient ingredient which has a water-solubility of less than about vne weight percent at 25°C.
A present invention emollient ingredient exhibits a low degree of irritation and toxicity in topical applications, and provides a softening or soothing effect on surface skin tissue.
Preferred water-insoluble liquid emollients include fatty acids such as oleic and ricinoleic; fatty alcohols such as oleyl, lauryl and hexadecyl; esters such as diisopropyl adipate, benzoic acid esters of C9-C~5 alcohols, and isononyl isononanoate; alkanes such as mineral oil; silicones such as dimethylpolysiloxane and cyclic dimethyl-polysiloxane; and ethers such as polyoxypropylene butyl ether and polyoxypropylene cetyl ether.
Preferred water-insoluble liquid emollients include diisopropyl adipate, 2-ethylhexyl palmitate, dimethylpolysiloxane (50 cst.), and polyoxypropylene (14) butyl ether.
~O 94/13256 PCT/LTS93/09080 ~~~4~~~
The low melting point wax ingredient of a present invention cosmetic stick product comprises one or more organic compounds which have a melting point in the range between about 95°-180°F.
Suitable types of wax-like compounds include fatty acids, fatty alcohols, fatty acid esters, fatty acid amides, and the like, which have an aliphatic chain length between about 8-30 carbon atoms. Illustrative of wax-like compounds are cetyl l0 alcohol, palmitic acid, myristyl alcohol, stearyl alcohol, paraffin, and the like, and mixtures thereof .
The low melting point wax ingredient can include up to about 30 weight percent, based on the weight of wax ingredient, of a wax which has a melting point between about 180°-220°F.
Illustrative of these higher melting waxes are beeswax, spermaceti, carnauba, bayberry, candelilla " montan, ozokerite, ceresin, paraffin, castor wax, Fischer-Tropsch waxes, and the like.
The antiperspirant ingredient of a present invention cosmetic stick product typically is a particulate astringent compound which has an average particle size between about 5-200 microns. Superior cosmetic stick properties are obtained if part yr all of the antiperspirant ingredient is in the form of particles which have a diameter less than about one micron.
WO 94113256 PCT/US93/0908(~
~~~1~~
Suitable astringent compounds include aluminum chloride, aluminum chlorohydrate, aluminum , sulfocarbolate, aluminum sulfate, aluminum-zirconium chlorohydrate, zinc sulfate, zinc sulfocarbolate, and zirconium chlorohydrate. Preferred types of astringent compounds are aluminum chlorohydrates and aluminum-zirconium chlorohydrates, such as aluminum zirconium tetrachlorohydrex glycine which is commercially available as Rezal 36 GP Superultrafine (Reheis), and Reach AZP 908 (Reheis). The organometallic astringent compounds tend to have lower densities which are advantageous for purposes of density matching of the organic matrix phase and dispersed particle phase in an invention cosmetic stick product.
The water-soluble inorganic salt deodorant ingredient of an invention cosmetic stick product preferably is selected from alkali metal and ammonium bicarbonates, such as sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate and mixtures thereof. The bicarbonate deodorant ingredient can contain up to about 30 weight percent, based on the weight of deodorant ingredient, of an alkali metal or ammonium carbonate compound.
The average particle size of the water-soluble inorganic salt deodorant ingredient can be in the range between about 5-200 microns. Improved cosmetic stick properties are obtained if part or ~O 94/13256 PCT/US93/09080 2 ~ ~Y4 fi~~ ~ ._ all of the inorganic salt ingredient has a particle size diameter less than about one micron. Colloidal size particles facilitate incorporation into the cosmetic stick matrix, and the resultant stick composition has a smoother non-gritty feel when applied to the skin.
The term "water-soluble" as employed herein refers to an inorganic salt which has a solubility of at least about one gram.per one hundred grams of water at 25°C.
The optional surfactant ingredient of an invention cosmetic stick product can be selected from nonionic, cationic and anionic polymers.
Suitable surfactant polymers include cetyltrimethylammonium bromide; sodium lauryl sulfate; sodium dodecylbenzenesulfonate; ammonium . lignosulfonate; condensation products of ethylene oxide with fatty alcohols, amines or alkylphenols;
partial esters of fatty acids and hexitol anhydrides; polyalkylene glycol esters; and the like. Illustrative of a preferred type of surfactant polymer is polyethylene glycol (PEG) stearate, which is commercially available as PEG 600 distearate.
Other optional ingredients also may be included in an invention cosmetic stick formulation, such as bacteriostats, fungistats, fillers, stabilizing agents, antioxidants, pigments, coloring agents, perfumes, hardeners, chelating agents, and the like.
WO 94/13256 PCT/LTS93/0908(~
A bacteriostat such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether (Triclosan) typically is added in a quantity between about 0.08-3 weight percent, based on the weight of the cosmetic stick product.
An optional ingredient such as colloidal silica suspending agent is added in a quantity between about 1-3 weight percent, based on the weight of the cosmetic stick product.
An important aspect of the present invention is the provision of an antiperspirant-deodorant cosmetic stick product which is composed of a solid organic matrix containing a homogeneous dispersion of particulate antiperspirant and deodorant ingredients.
The solid organic matrix and dispersed particle phases have densities which are sufficiently matched to prevent settling of the dispersed particles during manufacture, and to provide a cosmetic stick product with dimensional stability.
Antiperspirant and inorganic salt deodorant compounds nominally have a density above about two grams per cubic centimeter. If high density particulate ingredients are suspended in an organic matrix having a density of about one gram per cubic centimeter, the particles have a tendency to settle out of the organic matrix, and the resultant cosmetic stick product is inhomogeneous and dimensionally unstable.
- .~ ~z~4~~vi~
In the present invention, separation of organic matrix and suspended particle phases is prevented by providing particulate antiperspirant and deodorant ingredients having densities which 5 more closely match the density of the organic matrix of a cosmetic stick product.
One means of density matching is by the utilization of organic polymer pre-coated particles of antiperspirant and inorganic salt deodorant 10 ingredients in the manufacture of the antiperspirant-deodorant cosmetic stick product.
Pre-coating of ingredient particles has the beneficial effect of improving the suspension properties of the particles in the fluid formulation 15 admixture during processing. Less particle settling occurs in the organic matrix because the density of . the coated particles and the organic matrix density are more closely matched than is the case with uncoated particles. There is a tendency for uncoated particles to settle out during the manufacturing process when the organic matrix is in a fluid state, and also in the cosmetic stick product when the organic matrix is in a solid form.
The organic polymer coating on the dispersed antiperspirant and inorganic salt deodorant particles~also has the benefit of minimizing any reaction between acidic antiperspirant and basic deodorant compounds, and preventing loss of antiperspirant-deodorant activities.
WO 94/13256 PC'T/US93/0908~
..
The application of the coating to the particles is accomplished by conventional means such as pan coating, fluidized coating, centrifugal fluidized coating, and the like. The coating polymer usually is dissolved in a suitable solvent such as water, methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethylformamide, and the like, as appropriate for a selected polymer species. A coating polymer also can be applied in the form of an emulsion or suspension. After the coating medium is applied to the particles, the solvent medium is removed by evaporation, thereby forming a continuous film coating which encapsulates the individual particles.
The coating thickness on the particle surfaces typically will vary in the range between about 0.1-20 microns. The coating can consist of a single layer or multiple layers. The polymer coating can constitute between about 5-30 weight percent of the total dry weight of the coated particles. The average size of the inner core particle typically is in the range between about 5-80 microns.
The polymer employed for coating the ingredient particles is selected from hydrophilic water-soluble and water-dispersible organic polymers. A mixture of polymers can be employed, and a content of between about 0.5-40 weight percent of a hydrophobic water-insoluble polymer, based on the coating weight, can be included.
D 94/13256 PCTlUS93109080 The term "hydrophilic°° as employed herein refers to an organic polymer which has a water-solubility of at least about 0.5 gram per 100 grams of water at 25°C.
Suitable hydrophilic polymers for coating particles include gum arabic, gum karaya, gum tragacanth, guar gum, locust bean gum, xanthan gum, carrageenan, alginate salt, casein, dextran, pectin, agar, sorbitol, 2-hydroxyethyl starch, 2-aminoethyl l0 starch, maltodextrin, polydextrose, 2-hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose salt, cellulose sulfate salt, polyvinylpyrrolidone, polyethylene glycol, polypropylene glycol, polyethylene oxide, polyvinyl alcohol/acetate, polyacrylamide, and the like. Polyvinyl acetate is illustrative of a water-insoluble polymer which can be included as an additional coating component to moderate the hydrophilicity of the coating.
The rate of particle matrix compound release from the particle core under moisture conditions can be controlled by the quantity and type of hydrophilic polymer coating on the particle surfaces.
Low molecular weight hydrophilic polymers will release the particle matrix compound at a relatively fast rate in the presence of moisture.
High molecular weight polymers which are less hydrophilic will release at a relatively slow rate.
Additional rate control is obtained by employing mixtures of polymer components of varied hydrophilicity.
- ~~4~s~z Polyethylene glycol (M.W. of 4000) or polyvinyl alcohol will release particle matrix compound at a relatively fast rate. Polyethylene oxide (M. W. of 4,000,000) or partially hydrolyzed polyvinyl acetate will release at a relatively slow rate. Polyvinylpyrrolidone will release particle matrix compound at an immediate rate when in contact with underarm type of moisture.
Another means of achieving density matching of organic matrix and suspended particle phases is by the utilization of antiperspirant and inorganic salt particles which have a microporous structure. Microporosity in crystalline compounds can be achieved by various methods developed in chemical practice.
In one method, particles of the desired compound are prepared in admixture with a second compound, such as by coprecipitation from a solvent medium. The second compound is selected so that it can be removed from the particle mass by selective solvent extraction, or by heat treatment to convert the second compound into a volatile fraction.
Illustrative of this method is a coprecipitated mixture of sodium bicarbonate and ammonium bicarbonate. Heat treatment of the coprecipitate above 100°C decomposes the ammonium bicarbonate to volatile components, and the residual sodium bicarbonate can have a lowered density in the range of 1-2 grams per cm3.
~O 94/13256 PCTILTS93/09080 i :.. .
~ P
~1~~~~6~~
In another method of preparing microporous particles, an aqueous solution of alkali metal bicarbonate can be diluted with an organic solvent such as methanol, and the resultant precipitate is in the form of particles composed of agglomerated monoclinic needles of alkali metal bicarbonate. The needles have a crystal length between about 0.5-2 microns, and the agglomerated particles have an average size between about 4-12 microns in the l0 largest dimension. The particles are characterized by a network of microporous voids between the agglomerated needles.
Another means of achieving density matching of organic matrix and suspended particle phases is by the utilization of antiperspirant and inorganic salt particles which are coordinated with an organic complexing compound.
Alkali metal bicarbonate can form molecular complexes with organic compounds such as 2o I3-cyclodextrin, mannitol, sorbitol, crown ether, trioxane, and the like. The density of the alkali metal bicarbonate: organic compound complex is less than the density of the free alkali metal bicarbonate. A molecular complex can be obtained by evaporating an aqueous solution of the alkali metal bicarbonate and water-soluble organic complexing compound.
In general, the ingredients of the cosmetic stick formulation can be blended in any order during manufacture. However, in the practice of the invention process there is advantage in WO 94/13256 PCT/US93/0908(~
~.1 ~f ~f t' employing a phased order of ingredient addition and blending under controlled temperature conditions. _ Additional advantage is obtained in the invention process if there is a short time lapse between an 5 alkali metal bicarbonate deodorant ingredient addition step and the cosmetic stick container filling and solidifying step. Alkali metal bicarbonate can convert to alkali metal carbonate, carbon dioxide and water at elevated temperatures.
1o Adding a bicarbonate deodorant as the last ingredient of the blended formulation, and processing the formulation to the solid cosmetic stick formation stage within a short time period, are factors which minimize the degradation of the 15 bicarbonate ingredient, and the undesirable formation of water and carbon dioxide vapor byproducts. The addition and mixing of a bicarbonate deodorant ingredient into the formulation, and the dispensing of the formulation 20 into cosmetic stick containers, can be accomplished as an essentially instantaneous procedure by utilizing an integrated mixing valve nozzle device, such as the type described in United States Patent Numbers 2,816,518; 3,454,198; 3,949,904; 4,318,429;
4,549,813; 5,046,538; 5,094,276; arid the like.
The practice of the invention process for the production of a cosmetic stick product can be conducted in conventional equipment, and is readily , adaptable to a commercial-scale manufacturing operation.
!O 94/13256 PCT/US93/09080 ~~~4~y&G~
A present invention cosmetic stick product preferably has a hardness penetration value between about 4-12 millimeters, as determined by American Society For Testing Materials (ASTMj Method D5.
A present invention antiperspirant-deodorant cosmetic stick product has exceptional properties for treating or preventing perspiration and malodor associated with human underarm perspiration. A present invention cosmetic stick product can be applied effectively with safety and comfort for reduction of underarm perspiration and offensive odors.
A present invention deodorant cosmetic stick product provides particular advantage for users who wish to avoid the risk of skin irritation caused by the presence of an antiperspirant ingredient.
Because of the density matching of organic matrix and dispersed particle phases, an invention cosmetic stick product has improved dimensional stability, and better esthetic appearance and "feel"
when applied to human skin. The density matching of ingredients also has application in roll-on cosmetic products.
The following Examples are further illustrative of the present invention. The components and specific ingredients are presented as being typical and various modifications can be derived in view of the foregoing disclosure within the scope of the invention.
WO 94/13256 PCT/US93/09080~
y149~~~~
EXAMPLE I
This Example illustrates-a procedure for coating a particulate bicarbonate deodorant compound with a water-soluble organic polymer in accordance with the present invention.
Guar gum (15 g, Supercol, Aqualon Co.) is dissolved in 150 ml of 50% aqueous ethanol solvent.
Sodium bicarbonate (100 g, 50-80 microns, Church & Dwight) is suspended in the solution medium l0 with stirring.
The solvent medium is removed by evaporation under vacuum. A dry free-flowing powder is obtained. The particles are coated with a guar film having an average thickness of 2-5 microns.
~O 94/13256 PCT/US93/09080 EXAMPLE II
This Example illustrates a fluidized bed procedure for coating an antiperspirant compound with a water-soluble polymer in accordance with the present invention.
A fluidized bed vessel is utilized which is equipped with a Wurster air-suspension coater system (WARF) as described in U.S. 4,568,559 and U.S. 4,877,621.
A coating solution is prepared by dissolving polyethylene glycol (45 g, Poly-G 2000, Olin Corp.), and propylene glycol butyl ether (10 g, PPG 14, Americol) in ethanol (600 g).
Particulate aluminum zirconium tetrachlorohydrex glycine (600 g, 60-100 microns, Reheis) is charged into the coating chamber.
Compressed air is introduced into the coating chamber, and the polymeric coating solution is sprayed on the air-suspended antiperspirant core matrix particles, until the coating weight is about 20% of the total dry weight of the coated particles.
The procedure is repeated, except that Hydroxypropylmethylcellulose (Methocel 60 HG, Dow Chemical Co.) is employed as the water-soluble polymer.
WO 94/13256 PCT/LJS93/0908(~
EXAMPLE III
This Example illustrates a pilot-plant procedure for the preparation of an antiperspirant-deodorant cosmetic stick product in accordance With the present invention.
A stainless steel tank is provided which is equipped with turbine agitation.
Silicone oil DC 245 (600 lbs, Dow Corning) is charged to the mixing tank. Agitation (55-65 RPM) is initiated, and heating the liquid medium to 176°F is commenced.
During the heating period, the following order of ingredients are added to the stirred liquid medium:
lbs.
diisopropyl adipate 60 PPG 14 butyl ether (Americol) 40 stearyl alcohol 340 castor wax (MP-70) 60 2o eicosanol l0 PEG 600 distearate (Mater) 40 The mixture is stirred at 176°F for about 30 minutes until the ingredients are melted and the liquid medium is homogeneous. The stirring speed is reduced to about 35 RPM, then Cab-o-sil M-5 (15 lbs, Cabot) and aluminum zirconium tetrachlorohydrex ~O 94/13256 PCT/US93/09080 - ~ - ~~~~.44iC 6~
glycine (480 lbs, Reheis) are added. The temperature is maintained at 176°F~for about 40 minutes until the fluid medium is uniform, and then the temperature is lowered to 124°F.
5 Polymer-coated sodium bicarbonate 3 DF
(140 lbs, Church & Dwight) and a fragrance (6 lbs, 1FF 567-AT) respectively are added with stirring to Silicone oil DC 245 (245 lbs, Dow Corning) in a second mixing tank at a temperature of 124°F to form 10 a homogeneous suspension medium. The sodium bicarbonate particles are pre-coated with guar gum as described in Example I.
The contents of the two mixing tanks which contain heated fluid medium are transferred to 15 separate fill tanks through a Greer mill, and the fill tanks are connected to a mixing and dispensing . nozzle device, of the type described in U.S. 5,094,276. The nozzle device is adapted for homogeneously blending the two separate streams of 20 fluid media, and dispensing a predetermined quantity of the blended fluid.
Plastek 2 oz. bottom-fill stick containers are filled with the blended fluid. The container contents are cooled to a room temperature solid 25 stick over a period of about 45 minutes. The average hardness value of the solid sticks is 7 (ASTM Method D5).
Similar results are obtained when microporous sodium bicarbonate is employed in place of the polymer-coated sodium bicarbonate ingredient.
WO 94/13256 PCT/US93/0908(~
A deodorant cosmetic stick product is prepared by eliminating the antiperspirant ingredient, and increasing the quantity of sodium bicarbonate ingredient from 140 lbs to 180 lbs in the above described manufacturing process.
Claims (47)
1. An antiperspirant-deodorant cosmetic stick product consisting of a solid organic matrix comprising the following parts by weight of ingredients:
volatile silicone oil 10-50 liquid emollient 1-30 low melting point wax 12-24 and the solid organic matrix has homogeneously dispersed therein between about 18-35 parts by weight of particulate antiperspirant and between about 0.05-30 parts by weight of particulate water-soluble inorganic salt deodorant ingredients;
wherein the dispersed particles have a density which is less than about one gram per cubic centimeter higher than the density of the solid organic matrix.
volatile silicone oil 10-50 liquid emollient 1-30 low melting point wax 12-24 and the solid organic matrix has homogeneously dispersed therein between about 18-35 parts by weight of particulate antiperspirant and between about 0.05-30 parts by weight of particulate water-soluble inorganic salt deodorant ingredients;
wherein the dispersed particles have a density which is less than about one gram per cubic centimeter higher than the density of the solid organic matrix.
2. A cosmetic stick product in accordance with claim 1 wherein the particulate antiperspirant and deodorant ingredients having an average particle size between about 5-200 microns.
3. A cosmetic stick product in accordance with claim 1 or 2 wherein the density of the solid organic matrix is between about 0.8-1.6 grams per cubic centimeter, and the density of the antiperspirant and deodorant particles is between about 0.9-2 grams per cubic centimeter.
4. A cosmetic stick product in accordance with any one of claims 1 to 3 wherein the antiperspirant ingredient is selected from astringent aluminum and zirconium compounds, and complexes or mixtures thereof.
5. A cosmetic stick product in accordance with any one of claims 1 to 4 wherein the antiperspirant ingredient is an aluminum-zirconium tetrachlorohydrate compound.
6. A cosmetic stick product in accordance with any one of claims 1 to 5 wherein the deodorant ingredient particles are microporous.
7. A cosmetic stick product in accordance with any one of claims 1 to 6 wherein the deodorant ingredient particles comprise a molecular complex of inorganic salt and organic complexing compounds.
8. A cosmetic stick product in accordance with any one of claims 1 to 7 wherein the deodorant ingredient is sodium, potassium or ammonium bicarbonate or a mixture thereof.
9. An antiperspirant-deodorant cosmetic stick product consisting of a solid organic matrix comprising the following parts by weight of ingredients:
volatile silicone oil 10-50 liquid emollient 1-30 low melting point wax 12-24 and the solid organic matrix has homogeneously dispersed therein between about 18-35 parts by weight of particulate antiperspirant and between about 0.05-30 parts by weight of particulate water-soluble inorganic salt deodorant ingredients;
wherein the dispersed particles have a density which is less than about one gram per cubic centimeter higher than the density of the solid organic matrix, and an average particle size between about 5-200 microns, and wherein the surfaces of the deodorant particles are coated with a hydrophilic polymer coating having a thickness in the range between about 0.1-20 microns.
volatile silicone oil 10-50 liquid emollient 1-30 low melting point wax 12-24 and the solid organic matrix has homogeneously dispersed therein between about 18-35 parts by weight of particulate antiperspirant and between about 0.05-30 parts by weight of particulate water-soluble inorganic salt deodorant ingredients;
wherein the dispersed particles have a density which is less than about one gram per cubic centimeter higher than the density of the solid organic matrix, and an average particle size between about 5-200 microns, and wherein the surfaces of the deodorant particles are coated with a hydrophilic polymer coating having a thickness in the range between about 0.1-20 microns.
10. A cosmetic stick product in accordance with claim 9 wherein the antiperspirant ingredient is selected from astringent aluminum and zirconium compounds, and complexes or mixtures thereof.
11. A cosmetic stick product in accordance with claim 9 or 10 wherein the antiperspirant ingredient is an aluminum-zirconium tetrachlorohydrate compound.
12. A cosmetic stick product in accordance with any one of claims 9 to 11 wherein the deodorant ingredient is sodium, potassium or ammonium bicarbonate or a mixture thereof.
13. A cosmetic stick product in accordance with any one of claims 9 to 12 wherein the polymer coating on the deodorant particles has a polysaccharidic, oxyalkylene or polyvinyl structure.
14. A cosmetic stick product in accordance with any one of claims 9 to 13 wherein the polymer coating on the deodorant particles includes a water-insoluble polymer component.
15. An antiperspirant-deodorant cosmetic stick product consisting of a solid organic matrix comprising the following parts by weight of ingredients:
volatile silicone oil 10-50 liquid emollient 1-30 low melting point wax 12-24 and the solid organic matrix has homogeneously dispersed therein between about 18-35 parts by weight of particulate antiperspirant and between about 0.05-30 parts by weight of particulate water-soluble inorganic salt deodorant ingredients;
wherein the dispersed particles have a density which is less than about one gram per cubic centimeter higher than the density of the solid organic matrix, and an average particle size between about 5-200 microns, and wherein the surfaces of the antiperspirant particles are coated with a hydrophilic polymer coating having a thickness in the range between about 0.1-20 microns.
volatile silicone oil 10-50 liquid emollient 1-30 low melting point wax 12-24 and the solid organic matrix has homogeneously dispersed therein between about 18-35 parts by weight of particulate antiperspirant and between about 0.05-30 parts by weight of particulate water-soluble inorganic salt deodorant ingredients;
wherein the dispersed particles have a density which is less than about one gram per cubic centimeter higher than the density of the solid organic matrix, and an average particle size between about 5-200 microns, and wherein the surfaces of the antiperspirant particles are coated with a hydrophilic polymer coating having a thickness in the range between about 0.1-20 microns.
16. A cosmetic stick product in accordance with claim 15 wherein the antiperspirant ingredient is selected from astringent aluminum and zirconium compounds, and complexes or mixtures thereof.
17. A cosmetic stick product in accordance with claim 15 or 16 wherein the antiperspirant ingredient is an aluminum-zirconium tetrachlorohydrate compound.
18. A cosmetic stick product in accordance with any one of claims 15 to 17 wherein the deodorant ingredient is sodium, potassium or ammonium bicarbonate or a mixture thereof.
19. A cosmetic stick product in accordance with any one of claims 15 to 18 wherein the polymer coating on the antiperspirant particles has a polysaccharidic, oxyalkylene or polyvinyl structure.
20. A cosmetic stick product in accordance with any one of claims 15 to 19 wherein the polymer coating on the antiperspirant particles includes a water-insoluble polymer component.
21. An antiperspirant-deodorant cosmetic stick product consisting of a solid organic matrix comprising the following parts by weight of ingredients:
volatile silicone oil 10-50 liquid emollient 1-30 low melting point wax 12-24 and the solid organic matrix has homogeneously dispersed therein between about 18-35 parts by weight of particulate antiperspirant and between about 0.05-30 parts by weight of particulate water-soluble inorganic salt deodorant ingredients;
wherein the dispersed particles have a density which is less than about one gram per cubic centimeter higher than the density of the solid organic matrix, and an average particle size between about 5-200 microns, and wherein the surfaces of the antiperspirant and deodorant particles are coated with a hydrophilic polymer coating having a thickness in the range between about 0.1-20 microns.
volatile silicone oil 10-50 liquid emollient 1-30 low melting point wax 12-24 and the solid organic matrix has homogeneously dispersed therein between about 18-35 parts by weight of particulate antiperspirant and between about 0.05-30 parts by weight of particulate water-soluble inorganic salt deodorant ingredients;
wherein the dispersed particles have a density which is less than about one gram per cubic centimeter higher than the density of the solid organic matrix, and an average particle size between about 5-200 microns, and wherein the surfaces of the antiperspirant and deodorant particles are coated with a hydrophilic polymer coating having a thickness in the range between about 0.1-20 microns.
22. A cosmetic stick product in accordance with claim 21 wherein the antiperspirant ingredient is selected from astringent aluminum and zirconium compounds, and complexes or mixtures thereof.
23. A cosmetic stick product in accordance with claim 21 or 22 wherein the antiperspirant ingredient is an aluminum-zirconium tetrachlorohydrate compound.
24. A cosmetic stick product in accordance with any one of claims 21 to 23 wherein the deodorant ingredient is sodium, potassium or ammonium bicarbonate or a mixture thereof.
25. A cosmetic stick product in accordance with any one of claims 21 to 24 wherein the polymer coating on the antiperspirant and deodorant particles has a polysaccharadic, oxyalkylene or polyvinyl structure.
26. A cosmetic stick product in accordance with any one of claims 21 to 25 wherein the polymer coating on the antiperspirant and deodorant particles includes a water-insoluble polymer component.
27. A process for preparing an antiperspirant-deodorant cosmetic stick product which comprises (1) heating and forming a liquid organic matrix of ingredients comprising between about 10-50 parts by weight of a volatile silicone oil, between about 1-30 parts by weight of a liquid emollient, and between about 12-24 parts by weight of a low melting point wax; (2) adding and dispersing in the heated liquid organic matrix between about 18-35 parts by weight of particulate antiperspirant and between about 0.05-30 parts by weight of particulate water-soluble inorganic salt deodorant to form a homogeneous fluid suspension medium; and (3) dispensing the heated fluid suspension medium into cosmetic stick containers, and cooling the container contents to form solid sticks at room temperature; wherein the dispersed particles have a density which is less than about one gram per cubic centimeter higher than the density of the organic matrix in the cosmetic stick product.
28. A process in accordance with claim 27 wherein between about 0.5-5 parts by weight of a surfactant ingredient is included in the step(2) formation of the liquid organic matrix, and wherein the surfactant ingredient is selected from nonionic cationic and anionic polymers.
29. A process in accordance with claim 27 wherein between about 0.08-3 parts by weight of a bacteriostat ingredient is included in the step(2) formation of the liquid organic matrix.
30. A process in accordance with claim 27 wherein the particulate antiperspirant and deodorant ingredients have an average particle size between about 5-200 microns.
31. A process in accordance with claim 27 wherein the density of the solid organic matrix is between about 0.8-1.6 grams per cubic centimeter, and the density of the antiperspirant and deodorant particles is between about 0.9-2 grams per cubic centimeter.
32. A process in accordance with claim 27 wherein the heating in step(1) is at a temperature between about 120°-220°F.
33. A process in accordance with claim 27 wherein the volatile silicone oil ingredient comprises between about 25-50 weight percent of the cosmetic stick product, and is a cyclic or linear polydimethylsiloxane containing 3-9 silicon atoms.
34. A process in accordance with claim 27 wherein the liquid emollient ingredient comprises between about 2-20 weight percent of the cosmetic stick product, and is a water-insoluble organic acid, ester or ether compound.
35. A process in accordance with claim 27 wherein the wax ingredient has a melting point in the range of about 95°-180°F and comprises between about 15-20 weight percent of the cosmetic stick product, and is selected from C8-C30 alcohol, acid, ester and amide compounds.
36. A process in accordance with claim 27 wherein the antiperspirant ingredient comprises between about 20-30 weight percent of the cosmetic stick product, and is selected from astringent aluminum and zirconium compounds, and complexes or mixtures thereof.
37. A process in accordance with claim 27 wherein the deodorant ingredient comprises between about 0.1-25 weight percent of the cosmetic stick product, and is selected from alkali metal and ammonium bicarbonates.
38. A process in accordance with claim 27 wherein the deodorant ingredient is alkali metal or ammonium bicarbonate containing up to about 30 weight percent of alkali metal or ammonium carbonate, based on the weight of deodorant ingredient.
39. A process in accordance with claim 27 wherein at least one of the antiperspirant or deodorant ingredients has particle surfaces which are pre-coated with a hydrophilic polymer coating.
40. A process in accordance with claim 27 wherein the deodorant ingredient particles are microporous.
41. A process in accordance with claim 27 wherein the deodorant ingredient particles comprise a molecular complex of inorganic salt and organic complexing compound.
42. A deodorant cosmetic stick product consisting of a solid organic matrix comprising the following parts by weight of ingredients:
volatile silicone oil 10-55 liquid emollient 1-35 low melting point wax 12-30 and the solid organic matrix has homogeneously dispersed therein between about 1-40 parts by weight water-soluble inorganic salt deodorant ingredient; wherein the dispersed particles have a density which is less than about one gram per cubic centimeter higher than the density of the solid organic matrix.
volatile silicone oil 10-55 liquid emollient 1-35 low melting point wax 12-30 and the solid organic matrix has homogeneously dispersed therein between about 1-40 parts by weight water-soluble inorganic salt deodorant ingredient; wherein the dispersed particles have a density which is less than about one gram per cubic centimeter higher than the density of the solid organic matrix.
43. A cosmetic stick product in accordance with claim 42 wherein the deodorant ingredient is sodium, potassium or ammonium bicarbonate or a mixture thereof.
44. A cosmetic stick product in accordance with any one of claims 1 to 26, wherein the liquid emollient is selected from one or more water-insoluble organic compounds which are liquid at 25°C.
45. The cosmetic stick product in accordance with claim 44, wherein the water-insoluble organic compounds are selected from the group consisting of fatty acids, fatty alcohols, esters, alkanes, silicones and ethers.
46. The cosmetic stick product in accordance with any one of claims 1 to 26 or claim 44 or 45, wherein the low melting point wax has a melting point in the range between about 95°-180°F, and is selected from the group consisting of fatty acids, fatty alcohols, fatty acid esters and fatty acid amides, each having an aliphatic chain length between about 8-30 carbon atoms.
47. The cosmetic stick product in accordance with claim 46, wherein the low melting point wax includes up to about 30 weight percent based on the weight of wax ingredient, of a wax which has a melting point between about 180°-220°F and is selected from the group consisting of beewax, spermaceti, carnauba, bayberry, candelilla, montan, ozokerite, ceresin, paraffin, castor wax and Fischer-Tropsch wax.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US986,810 | 1992-12-08 | ||
| US07/986,810 US5486355A (en) | 1992-12-08 | 1992-12-08 | Homogeneous cosmetic stick products |
| PCT/US1993/009080 WO1994013256A1 (en) | 1992-12-08 | 1993-09-28 | Homogeneous cosmetic stick products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2144662A1 CA2144662A1 (en) | 1994-06-23 |
| CA2144662C true CA2144662C (en) | 2001-04-17 |
Family
ID=25532765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002144662A Expired - Fee Related CA2144662C (en) | 1992-12-08 | 1993-09-28 | Homogeneous cosmetic stick products |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US5486355A (en) |
| AU (1) | AU5536494A (en) |
| CA (1) | CA2144662C (en) |
| WO (1) | WO1994013256A1 (en) |
Families Citing this family (38)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5631013A (en) * | 1995-08-07 | 1997-05-20 | Church & Dwight Co., Inc. | Cosmetic deodorant products containing encapsulated co-micronized bicarbonate ingredient |
| US5837223A (en) * | 1996-08-12 | 1998-11-17 | Revlon Consumer Products Corporation | Transfer resistant high lustre cosmetic stick compositions |
| US5897856A (en) * | 1996-10-24 | 1999-04-27 | The Procter & Gamble Company | Methods and compositions for reducing body odor |
| US5874067A (en) * | 1996-10-24 | 1999-02-23 | The Procter & Gamble Company | Methods for controlling environmental odors on the body |
| US5897855A (en) * | 1996-10-24 | 1999-04-27 | The Procter & Gamble Company | Methods and compositions for reducing body odor |
| US5879666A (en) * | 1996-10-24 | 1999-03-09 | The Procter & Gamble Company | Methods and compositions for reducing body odor |
| US5911976A (en) * | 1996-10-24 | 1999-06-15 | The Procter & Gamble Company | Compositions for reducing body odor |
| US5882638A (en) * | 1996-10-24 | 1999-03-16 | The Proctor & Gamble Company | Methods using uncomplexed cyclodextrin solutions for controlling environmental odors |
| US5885599A (en) * | 1996-10-28 | 1999-03-23 | The Procter & Gamble Company | Methods and compositions for reducing body odors and excess moisture |
| US5780020A (en) * | 1996-10-28 | 1998-07-14 | The Proctor & Gamble Company | Methods and compositions for reducing body odor |
| US5863524A (en) * | 1997-03-26 | 1999-01-26 | Church & Dwight Co., Inc. | Transparent bicarbonate salt containing deodorant cosmetic stick product |
| US5972319A (en) * | 1997-03-31 | 1999-10-26 | The Colgate-Palmolive Company | Antiperspirant stick with improved characteristics |
| US5861144A (en) * | 1997-06-09 | 1999-01-19 | The Procter & Gamble Company | Perfumed compositions for reducing body odors and excess moisture |
| US5871718A (en) * | 1997-06-09 | 1999-02-16 | The Procter & Gamble Company | Perfumed two phase compositions for reducing body odor |
| US6001343A (en) * | 1997-06-09 | 1999-12-14 | The Procter & Gamble Company | Uncomplexed cyclodextrin compositions for odor and wrinkle control |
| US5861145A (en) * | 1997-06-09 | 1999-01-19 | The Procter & Gamble Company | Method of reducing body odor using perfumed, odor absorbing, two phase compositions |
| US5928631A (en) * | 1997-06-09 | 1999-07-27 | The Procter & Gamble Company | Methods for controlling environmental odors on the body using compositions comprising uncomplexed cyclodextrins |
| US5874070A (en) * | 1997-06-09 | 1999-02-23 | The Procter & Gamble Company | Compositions for reducing body odor |
| US5942214A (en) * | 1997-06-09 | 1999-08-24 | The Procter & Gamble Company | Methods for controlling environmental odors on the body using compositions comprising uncomplexed cyclodextrins and perfume |
| WO1998056337A1 (en) * | 1997-06-09 | 1998-12-17 | The Procter & Gamble Company | Malodor reducing composition containing amber and musk materials |
| US6656923B1 (en) | 1997-06-09 | 2003-12-02 | The Procter & Gamble Company | Uncomplexed cyclodextrin compositions for odor and wrinkle control |
| US5858335A (en) * | 1997-06-09 | 1999-01-12 | The Procter & Gamble Company | Method of reducing body odor using perfume-free two phase compositions |
| US5897854A (en) * | 1997-06-09 | 1999-04-27 | The Procter & Gamble Company | Methods for reducing body odor |
| US5871719A (en) * | 1997-06-09 | 1999-02-16 | The Procter & Gamble Company | Perfume-free two phase compositions for reducing body odor |
| US5861143A (en) * | 1997-06-09 | 1999-01-19 | The Procter & Gamble Company | Methods for reducing body odors and excess moisture |
| US5861146A (en) * | 1997-06-09 | 1999-01-19 | The Procter & Gamble Company | Method for reducing body odor |
| US5955093A (en) * | 1997-06-09 | 1999-09-21 | The Procter & Gamble Company | Uncomplexed cyclodextrin compositions for odor control |
| US5861147A (en) * | 1997-06-09 | 1999-01-19 | The Procter & Gamble Company | Methods for controlling environmental odors on the body using compositions comprising uncomplexed cyclodextrins and perfume |
| AR017716A1 (en) | 1998-04-27 | 2001-09-12 | Procter & Gamble | ARTICLE OF MANUFACTURE IN THE FORM OF A NON-MANUALLY OPERATED ATOMIZING EXPENDER |
| DE19921184A1 (en) * | 1999-05-07 | 2000-11-09 | Henkel Kgaa | Antiperspirant active ingredients |
| US6749841B2 (en) * | 2001-07-26 | 2004-06-15 | Revlon Consumer Products Corporation | Stabilized aqueous acidic antiperspirant compositions and related methods |
| GB0304508D0 (en) * | 2003-02-27 | 2003-04-02 | Unilever Plc | Antiperspirant actives and compositions |
| US20050152858A1 (en) * | 2003-07-11 | 2005-07-14 | Isp Investments Inc. | Solubilizing agents for active or functional organic compounds |
| AU2009353312B2 (en) * | 2009-09-30 | 2013-04-04 | Colgate-Palmolive Company | Antiperspirant/deodorant composition |
| US20140037566A1 (en) | 2012-08-02 | 2014-02-06 | The Procter & Gamble Company | Antiperspirant Compositions and Methods |
| RU2016102713A (en) * | 2013-07-29 | 2017-09-01 | Колгейт-Палмолив Компани | Antiperspirant / Deodorant Compositions |
| DE102013214843A1 (en) * | 2013-07-30 | 2015-02-05 | Henkel Ag & Co. Kgaa | Anhydrous compositions of light texture |
| ITUA20161622A1 (en) * | 2016-03-14 | 2017-09-14 | Chromavis Spa | A cosmetic element and a method for making this cosmetic element |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4944937A (en) * | 1984-12-19 | 1990-07-31 | The Procter & Gamble Company | Cosmetic sticks |
| US4822602A (en) * | 1987-04-29 | 1989-04-18 | The Procter & Gamble Company | Cosmetic sticks |
| US4919934A (en) * | 1989-03-02 | 1990-04-24 | Richardson-Vicks Inc. | Cosmetic sticks |
| US5019375A (en) * | 1989-03-14 | 1991-05-28 | The Procter & Gamble Company | Low residue antiperspirant creams |
| US5254332A (en) * | 1992-03-20 | 1993-10-19 | Church & Dwight Co., Inc. | Low residue antiperspirant sticks |
-
1992
- 1992-12-08 US US07/986,810 patent/US5486355A/en not_active Expired - Lifetime
-
1993
- 1993-09-22 US US08/124,549 patent/US5508028A/en not_active Expired - Fee Related
- 1993-09-28 CA CA002144662A patent/CA2144662C/en not_active Expired - Fee Related
- 1993-09-28 WO PCT/US1993/009080 patent/WO1994013256A1/en active Application Filing
- 1993-09-28 AU AU55364/94A patent/AU5536494A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| AU5536494A (en) | 1994-07-04 |
| CA2144662A1 (en) | 1994-06-23 |
| WO1994013256A1 (en) | 1994-06-23 |
| US5486355A (en) | 1996-01-23 |
| US5508028A (en) | 1996-04-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |