AU2012361041B2 - Antiperspirant aerosol preparations with reduced textile staining - Google Patents

Antiperspirant aerosol preparations with reduced textile staining Download PDF

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AU2012361041B2
AU2012361041B2 AU2012361041A AU2012361041A AU2012361041B2 AU 2012361041 B2 AU2012361041 B2 AU 2012361041B2 AU 2012361041 A AU2012361041 A AU 2012361041A AU 2012361041 A AU2012361041 A AU 2012361041A AU 2012361041 B2 AU2012361041 B2 AU 2012361041B2
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dimethicone
antiperspirant
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preparations
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Torsten Bluschke
Anette Burger
Annika Scholz
Michael Urban
Bjorna Windisch
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Beiersdorf AG
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/046Aerosols; Foams
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/26Aluminium; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • A61K8/342Alcohols having more than seven atoms in an unbroken chain
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36Carboxylic acids; Salts or anhydrides thereof
    • A61K8/361Carboxylic acids having more than seven carbon atoms in an unbroken chain; Salts or anhydrides thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37Esters of carboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41Amines
    • A61K8/416Quaternary ammonium compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/892Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a hydroxy group, e.g. dimethiconol
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/92Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A61K8/922Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00Anti-perspirants or body deodorants

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
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  • Birds (AREA)
  • Epidemiology (AREA)
  • Chemical & Material Sciences (AREA)
  • Emergency Medicine (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Cosmetics (AREA)
  • Detergent Compositions (AREA)

Abstract

The invention relates to the use of Si gums in antiperspirant preparations in order to reduce stain formation in or on clothing and to improve the ability to wash stains out of clothing.

Description

2012361041 06 Mar 2017 1
Antiperspirant Aerosol Preparations With Reduced Staining of Textiles
The invention relates to the use of silicone gums in antiperspirant preparations to reduce staining in or on clothing and to improve the extent to which spots can be washed out of clothing.
Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field.
Antiperspirants and/or deodorants are used to eliminate or prevent the body odor that occurs when perspiration, which is essentially odorless when fresh, is decomposed by microorganisms. The usual cosmetic deodorants are based on various active principles. In general linguistic usage, there is not always a clear separation between the terms "deodorant" and "antiperspirant." Instead, products for use in the underarm area are referred to in general as deodorants, in particular in German-speaking areas, regardless of whether or not there is an antiperspirant effect.
Antiperspirants (AP) are agents that prevent perspiration - in contrast with deodorants, which in general prevent microbial decomposition of perspiration that has already formed - which should prevent perspiration from being secreted at all.
In contrast with antiperspirants, pure deodorants do not have any active influence on perspiration secretion but instead merely control and/or influence the natural odor of the body and/or the axillary region (odor-improving agents). Conventional mechanisms of action for this purpose include antibacterial effects, such as those also manifested by non-colloidal silver, neutralization of odors (masking), influencing bacterial metabolism, simple perfuming as well as the use of precursors of certain perfume components, which are converted into pleasant smelling substances by enzymatic reaction.
It is an object of the present invention to overcome or ameliorate at least one of the disadvantages of the prior art, or to provide a useful alternative. 506585520 1\ 2012361041 06 Mar 2017 1a
According to an embodiment of the invention, no antiperspirant is present when the secretion of perspiration is not affected due to the use of an agent, i.e., no antiperspirant effect is manifested. Active antiperspirant ingredients according to the invention include substances, which have an influence on the secretion of perspiration.
The desired minimization of perspiration secretion may be achieved by various mechanisms, which traditionally include the use of astringents which cause coagulation and protein 506585520 1\ 2 precipitation and thus cause a narrowing or occlusion of the perspiration glands. Novel antiperspirant active ingredients are based on the principle of anticholinergics, for example, which interrupt the neural stimuli that lead to an increase in secretion by the sweat glands. Another principle of novel antiperspirant active ingredients is based on influencing membrane transport processes in the cell. Specific aquaporin inhibitors thus inhibit the proteins which form channels in the cell membrane to facilitate the passage of water and additional molecules. Ion channel inhibitors have an influence on membrane transport processes and/or osmosis processes. Another novel active antiperspirant mechanism can be implemented by the use of short-chain vicinal diols such that this mechanism can be attributed to their osmotic activity.
Antiperspirants and deodorants are usually available in a multitude of product forms, with rollers, pump atomizers and aerosols being predominant in Europe, while the stick form is more common in the United States, Central and South America. Anhydrous products (suspension) and water-based products (hydro-alcoholic formulations, emulsions) are known.
Preferred forms of application for antiperspirant formulations are anhydrous aerosols, which are marketed in aluminum cans or tin cans. This form of application is the most common form in the field of deodorants and antiperspirants throughout the world. "Anhydrous" means that the amount of water in the aerosol preparations is almost 0 wt%, apart from any contaminants that might have been entrained or water of crystallization.
An aerosol is a disperse system in which a solid and/or a liquid is/are distributed in a gas in an extremely fine form. The aerosol is usually created only when applied with the help of a suitable spray system by spraying solutions, emulsions or suspensions, for which purpose spray cans can be used, with a liquefied compressed gas serving as the gaseous propellant. When the pressure valve is opened, the gas mixture of propellant and active ingredient solution escapes through a fine nozzle, the propellant evaporates leaving behind the finely divided sprayed substance as an aerosol. In common usage in application technology, the term "aerosol" is often also used by those skilled in the art in the sense of aerosol sprays, i.e., an "aerosol" is understood here to refer not only to the plain spray mist but also to a packaged compressed gas plus the dispensing or metering device and the filling material. The filling material includes the active ingredient solution and the propellant. The active ingredient solution is the sum of all preparation ingredients, not including the propellant. The term "active ingredient solution" is also used when the preparation is in the form of a suspension or emulsion, for example. A 3 suspension is to be understood as a dispersion in which the continuous phase is in the liquid state and the dispersed phase is in the solid state.
An aerosol preparation and/or aerosol product is understood to refer to any container made of metal, glass or plastic, and includes the gas, which has been compressed or liquefied or dissolved under pressure and contained therein, with or without a liquid, paste or powder, and this container is equipped with a dispensing mechanism that makes it possible to dispense its contents in the form of solid or liquid particles suspended in gas and dispensed in the form of a foam, paste, powder or liquid.
Many consumers have complained about unwanted stains in the underarm area of the clothing after using antiperspirants or deodorants. These are often yellowish spots, which may also have a tendency to form encrustations. These deposits and stains are formed mainly by a complex interaction between the product, skin oil, perspiration and detergents and are very difficult to remove by traditional cleaning methods.
These spots are to be differentiated from the residues on skin or clothing that are referred to as a "white stain."
These stains and spots may vary, depending on the person. One cause is the aluminum salts that are used in most deodorant and antiperspirant products and function as active antiperspirant ingredients. This stubborn discoloration is difficult or impossible to remove completely by washing, even after pretreating with a stain remover.
There is extensive literature and numerous patents relating to the formation of stains and spots on the skin and clothing and howto prevent them when using antiperspirants. EP 973492 A1 describes the use of surface-active substances, mainly nonionic emulsifiers in antiperspirants. The antiperspirant formulations include nonvolatile emollients, a vehicle such as cyclomethicone, a fatty alcohol such as stearyl alcohol, an antiperspirant material and a surfactant. The problems associated with the formation of white residues on the skin and clothing, which may be formed when using antiperspirants that contain aluminum, are discussed. In this patent, the problem of the white stains caused by the formulation is approached by adjusting the refractive index of the ingredients. 4 EP 1178775 A1 describes the use of water-soluble surfactants to improve the wash-off of residues from the skin and clothing. This patent describes combinations of astringent salts with water-soluble nonionic surfactants that have a rapid onset of antiperspirant effect and a high efficacy. EP 858317 A1 describes preparations with surface-active substances having an HLB > 10 for removing fatty residues from the skin. EP 696188 A1 describes the use of a wash-off agent for removing the lipid components from the skin, preferably using ethoxylates for this purpose. DE 102008052748 A1 is an earlier patent application from the present patent applicant, describing how emulsifiers are used in waterless suspensions for improved wash-off results in washing the formulation off the skin. The structurizers, which are advantageously present in the anhydrous formulation, may leave perceptible waxy residues on skin. Due to the presence of polar groups in the emulsifiers used, the affinity for water is increased when the formulation is washed off and the residues disappear. Therefore, nonionic emulsifiers are preferred. WO 2011050044 A1 describes preparations for reducing or eliminating yellow staining with an antiperspirant agent and at least one antioxidant. WO 2010097205 A2 describes the use of charged surfactants to reduce staining of textiles.
One disadvantage is the obligatory use of surfactants, which may cause or contribute to problems in pharmaceutical formulations.
It is desirable to make available cosmetic antiperspirants, which cause reduced staining of clothing and in particular help to improve the subsequent wash-off results without requiring the use of surfactants.
In addition, these cosmetic preparations should not have any instabilities and should be simple to formulate.
One important aspect in the formulation of cosmetic antiperspirants is how well they are tolerated on skin, so that in addition to the task of removing spots or improving wash-off results, the skin tolerance should also be taken into account. 5
In the field of antiperspirant aerosol sprays, the use of various silicone oils is widespread. Oils containing silicone also include the high-molecular polydiorganosiloxanes known as silicone gums. Silicone gums are described in US Patent 4,152,416, for example. "High molecular" means having a molecular weight of approx. 100,000 to 2,000,000 g/mol. Known silicone gums include polymeric polydimethylsiloxanes (INCI designation: dimethicone), for example, the products distributed under the brand name DC 1411 Fluid and DC 1413 Fluid by Dow Corning and dimethylsiloxanes with hydroxyl end groups (INCI designation: dimethiconol), for example, the commercial products DC 1501. Other known silicone gums for cosmetic applications include, for example, SF 1236, SF 1276, CF 1251 by Momentive Performance Materials.
In addition, the silicone gums from Dow Corning with the brand names Dow Corning® 1501 Fluid (cyclopentasiloxane, dimethiconol), Dow Corning® 1503 Fluid (dimethicone, dimethiconol), Dow Corning® CB 1556 Fluid (phenyl trimethicone, dimethiconol) and Dow Corning® BY 25-320 (C 13-16 isoparaffin, dimethicone). Mixture of silicone fluids and volatile silicone oils such as cyclomethicone and silicone gums are also known in cosmetic preparations. Dimethicone, which is present in the commercial product DC 1503 in the amount of 88%, has a molecular weight of less than 100,000 g/mol and therefore is not a silicone gum according to the invention. WO 9804236 A1 describes antiperspirants (AP) containing silicone latex and other thickeners, such as silicone gum, for example. EP 452762 A2 describes antiperspirant aerosols comprising silicone gum and silica, solvents, antiperspirant salt and a propellant, where a combination of silica and silicone gum is used as a suspension aid. WO 2005074877 A1 describes aerosol antiperspirants with silicones that are inert with respect to antiperspirant agents. WO 2005063188 A1 describes silicone-free antiperspirant sprays. DE 102005047370 A1 discloses W/O emulsions (sprays) that contain antiperspirant with the antiperspirant agent dissolved in the internal phase. DE 69823490 T2 describes anhydrous antiperspirant aerosols containing 5-25% pentane and silicone gum, which is used to increase the cooling properties. 2012361041 06 Mar 2017 6 US Patent 4,152,416 A discloses antiperspirant aerosols with little formation of a mist and dust using antiperspirant salt, propellant gas, suspension aid and a synthetic polymer gum (500,000 to 100 million cSt). EP 343843 B1 describes antiperspirant aerosols with a spray rate of no more than 0.5 g/s with an antiperspirant salt, propellant gas and a combination of silicone polymer and a volatile low viscosity fluid. EP 1803660 A1 discloses a cosmetic product comprising a water-in-oil emulsion with at least one cosmetic or dermatologic active ingredient, at least one propellant and an aerosol dispensing device, wherein the parts of the valve of the dispensing device that come in contact with the emulsion are made of nonmetallic materials and the emulsion is discharged at a spray rate of 0.05-0.5 g/s, preferably 0.1 -0.35 g/s, especially preferably 0.15-0.2 g/s. WO 2010/054921 A1 discloses an aerosol-formulation that contains a silicone gum.
It has now surprisingly been found that silicone gums, such as dimethiconol or dimethicone in particular lead to aerosol preparations, which have an antiperspirant effect and have significantly reduced spotting, which would otherwise have been formed on clothing due to the cosmetic aerosol product without silicone gums.
Therefore, according to the invention, silicone gums are used in cosmetic or dermatologic preparations comprising one or more active antiperspirant agents, to reduce or prevent staining and spots in or on clothing.
According to the invention, high-molecular polydiorganosiloxanes, dimethicone and dimethiconol are considered to be silicone gums. High-molecular indicates a molecular weight of approx. 100,000 to 2,000,000 g/mol.
In a first aspect of the present invention there is provided use of one or more silicone gums in cosmetic or dermatological preparations comprising one or more antiperspirant active agents to reduce or prevent staining or spots in or on clothing, wherein silicone gums are high-molecular polydiorganosiloxanes, dimethicone and dimethiconol with a molecular weight of approx. 100,000 to 2,000,000 g/mol 506585520 _1\ 2012361041 06 Mar 2017 6a
In a second aspect of the present invention there is provided use of one or more silicone gums in cosmetic or dermatological preparations comprising one or more antiperspirant active agents to improve the wash-off results with spots caused by the preparation in or on the clothing, wherein silicone gums are high-molecular polydiorganosiloxanes, dimethicone and dimethiconol with a molecular weight of approx. 100,000 to 2,000,000 g/mol.
Unless the context clearly requires otherwise, throughout the description and the claims, the words “comprise”, “comprising”, and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of “including, but not limited to”.
The following products are preferably selected as the silicone gums according to the invention: - DC 1501 Fluid (INCI: cyclopentasiloxane (and) dimethiconol) 15% dimethiconol (active content), 85% cyclopentasiloxane - DC 1411 Fluid (INCI: cyclopentasiloxane (and) dimethicone) 15% dimethicone (active content), 85% cyclopentasiloxane 506585520_1\ 2012361041 06 Mar 2017 7 - DC 1503 Fluid (INCI: dimethicone (and) dimethiconol) 12% dimethiconol (active content), 88% dimethicone - DC BY 25-320 (INCI: C13.16 isoparaffin (and) dimethicone (and) C10-13 isoparaffin) 20% dimethicone gum (active content), 80% isoparaffin - DC 1413 Fluid (INCI: dimethicone) 14% active content dimethicone gum
According to the invention, the problem is the known yellowish staining by antiperspirants in or on clothing after the clothing item has been washed. The approach according to an embodiment of the invention is also aimed at improving wash-off results. The yellow value of a stain is therefore defined in particular as being above the b* value, which can be determined photometrically by means of the colorimetric values in the CIE L*a*b color space.
In addition, the purpose of reducing the yellow staining according to an embodiment of the invention can of course also be detected by simple inspection and comparison.
The use of the prevention of spots and/or improved wash-off effect according to an embodiment of the invention preferably relates to textiles containing cotton or made of cotton.
The use of silicone gums can also be combined with other approaches described in the technology for reducing textile staining in a manner that is preferred according to the invention. This can then contribute toward further reducing the staining effect.
However, merely the use of silicone gums is responsible according to the invention for reducing spotting and improving the wash-off results with spots, as proven by tests that have been conducted.
According to the invention, the reduction in the b* value, which is determined photometrically by means of the colorimetry values in the CIE L*a*b color space, and/or prevention of spotting on textiles before and in particular after washing should be understood to refer to the value determined in this way, and as measured in comparison with the b* values of textiles stained with a preparation containing an antiperspirant agent without the silicone gums according to the invention.
One disadvantage of the use of antiperspirants, in particular aluminum salt, is the formation of residues in or on the clothing, which can discolor the clothing in an unattractive manner, as already explained above. 506585520_1\ 2012361041 06 Mar 2017 8
Textile stains are understood to be stains in the underarm area in particular. These are stains that remain in clothing after being worn and/or washed and may become more intense as the age of the clothing item increases. These stains are not the residues on the skin or clothing that are referred to as white specks.
The invention does not refer to spots formed as white specks in the case of direct contact of a deodorant or antiperspirant with the fabric. These tend to be whitish deposits of the ingredients of the formulation, e.g., aluminum salts. These spots can be prevented easily if the product is allowed to dry if possible before putting on one's clothing. These white residues can usually be removed mechanically (brushing) or by washing. These problems of "white stain" have been described in detail in the prior art, where approaches toward solving these problems are proposed.
The present invention instead relates to stains that are mostly yellowish and are formed when the cosmetic product or ingredients thereof reach the fabrics together with the body's underarm secretions from perspiration. When these textiles are washed, some of the deposits are washed off, while some remain as a residue on the textile.
According to the invention the preparation is unable to prevent or reduce the formation of such spots which may be formed on a clothing item due to a variety of causes. However, the preparation according to an embodiment of the invention can reduce or prevent the formation of stains that are caused in part by the preparation itself, in particular those caused by antiperspirants and to improve their wash-off results.
The difference in comparison with the formation of spots and/or their wash-off in use of the preparation according to the invention and the preparation without silicone gum is defined as a measure of this improvement and/or reduction in spotting.
However, independent observers (panel) have also fundamentally evaluated the result as being that the preparations according to the present invention do not cause stains to appear on clothing at all or the stains are at least not as yellow. This therefore amounts to a fundamental reduction in spotting.
One method of testing the spots which are caused in part by the antiperspirant substances contained in the cosmetic or dermatological preparations in or on clothing is described in WO 2010097205 A1. 506585520 1\ 9
For application of the product-sebum mixture, it may be advantageous to apply the sample to the test textile by screen printing.
The comparison tests should relate to the active ingredient solution containing the antiperspirant active ingredient and should not be based on the sprayed preparation. Various factors are known to have an influence on the spray pattern of the aerosol preparation. However, outlet openings, valve dimensions as well as the ingredients of the preparation can also influence the spray pattern, i.e., the spray cone. Therefore, if the spray cone is very narrow, more ingredients that cause spotting can be found in the test area on the textiles than is the case with spray cones having a wider spray distribution, a high degree of atomization, spray formation, etc.
As evidence of the improved wash-off results and reduced spotting achieved with the preparations according to the invention, in vitro tests were performed, yielding the results depicted in Figure 1 and Table 1.
Various active ingredient solutions of antiperspirant spray formulations were tested with regard to the formation of yellow staining over three in vitro applications/washing cycles. Standard white cotton (CO) fabric was used. The antiperspirant formulations were mixed homogeneously with sebum in a 5:1 ratio according to Bey and applied to five test strips using screen printing methods (TW24 according to the Hohenstein Institute, two squeegee application processes) and then incubated immediately thereafter in a climate cabinet overnight (temperature 38 ± 1 °C, relative atmospheric humidity: 80 ± 2%). After the incubation process, which served to simulate wearing conditions, the test strips were washed in a household washing machine (60°C, cotton program, powdered all-purpose detergent, approx. 3 kg clean additional load), followed by drying in a drum dryer. After the third cycle, a colorimetric characterization of the resulting spotting was performed by measuring the color differences in the spot location in comparison with a free spot on the test strip using the Spectral Flash 600 colorimeter (Datacolor International), Datacolor Tools, version 1.1.1 as the color measurement software, measurement geometry d/8°, gloss component excluded, type of light D65 (corresponding to average daylight), calibration standard DCI Kachel 10848 (secondary standard attributable to NRC (NRC Report No. PAR-2007-2573 of November 27, 2007)), measurement opening 30 mm diameter, sample position two-layer, sample background: 10 layers of backing paper, test climate 21°C (± 1°C), 41% (± 4%) relative humidity. 2012361041 06 Mar 2017 10
The change in the b value from the CIE lab system was used for the analysis. The B axis in the CIE lab system characterizes the yellow-blue color impression, where B values indicate an increase in the yellow content. The higher the B value, the greater the yellow impression.
The CIE lab system or L*a*b* color space is a measurement space, which contains all perceptible colors. The color space is constructed on the basis of the opposing color theory.
One of the most important properties of the L*a*b* color model is that it is not dependent on the specific equipment used, i.e., the colors are defined independently of how they are created and the reproduction technology. The corresponding German standard is DIN 6174: "Colorimetric determination of color standard values and color intervals in the approximately uniform CIELAB color space." The coordinates of the CIELAB plane are formed form the red/green value a and the yellow/blue value b. The lightness axis L is perpendicular to this plane.
According to DIN 6174, L, a and b are to be written with an asterisk (*) to provide a differentiation from other systems, e.g., the "Hunter Lab" system.
These tests have shown that in the case of 0.5 wt% (0.07% active content) of a silicone gum, for example, based on the total mass of the preparation, the spotting (b*, yellow value) on white cotton can be reduced significantly in the case of a conventional commercial antiperspirant spray.
Table 1. Tested preparations and their yellow value of spots; b* value INCI A Standard antiperspirant spray B C D Aluminum chlorohydrate (activated) 5.25 5.25 2.5 5.25 Cyclomethicone to 100 to 100 to 100 to 100 Dimethicone (86% M < 100,000) + dimethicone (14%) 0.5 (0.07% active content silicone gum) 0.8(0.112) 0.5 (0.07% active content silicone gum) Octyldodecanol 0.1 0.1 0.1 0.1 Dimethicone 0.45 0.45 ___ 0.45 Isopropyl palmitate --- 1.5 1.5 — 506585520_1\ 11 C12-15 alkyl benzoate ___ ___ 1.5 ___ Perfume 1.0 1.0 1.0 1.0 Propylene carbonate ___ 0.075 0.1 0.075 Disteardimonium hectorite 0.6 0.53 0.3 0.53 Butane + isobutane + propane 85 85 85 85 Staining (Db*) 6.1 4.9 3.9 4.9
The results show a definite reduction in spotting due to the use of silicone gum.
The active silicone gum content is therefore chosen according to the invention to be in the range of 0.02-0.5 wt%, based on the total mass of the preparation, especially preferably in the range of 0.035 to 0.2 wt%, in particular in the range of 0.04 to 0.1 wt%, based on the total mass of the preparation including propellant. DC 1413 fluid was used as the preferred silicone gum. DC 1413 comprises 14% silicone gum according to the invention (dimethicone; M > 100,000 g/mol). This DC 1413 mixture can be used advantageously in the amount of 5 wt%, resulting in an active content of silicone gum of 0.7 wt% in the active solution not including the propellant gas. This yields an advantageous proportional range of approx. 0.105 wt% silicone gum based on the total mass of the preparation including propellant gas at a propellant gas content of approx. 85%. In the preparation in the examples, 0.5 wt% (or 0.8 wt%) DC 1413 was used, each based on the total mass of the preparation including propellant.
Thus, the amount of silicone gum in the total preparation (active content) is 0.07 wt% (or 0.112 wt%).
In addition to the tests presented here for determining the yellow value b*, it was found by visual inspection in the various washing tests that the yellow staining had disappeared or was reduced with the preparations according to the invention.
In these tests that were performed as well as in additional tests it was also found that a special lipid combination also has a surprising influence on the reduction in and/or prevention of yellow textile stains which are caused in part by the antiperspirant active ingredients. 12
Examples B and C also include isopropyl palmitate or C12-is alkyl benzoate in addition to the silicone gum according to the invention. These two lipids result in a further reduction in yellow staining. This supportive effect was also observed with other specific lipids.
According to the invention, the aerosol preparations therefore advantageously comprise one or more silicone gums and one or more lipids selected from the group of isopropyl esters preferably isopropyl palmitate, alkyl benzoate preferably C12-is alkyl benzoate, triglycerides, preferably caprylic/capric triglyceride, dimethicone and/or hydrocarbon mixtures with a predominant chain length >C16.
Predominantly according to the invention means that the amount of ingredients in the hydrocarbon mixture with chain length >C16 is at least 50% preferably at least 60%.
Hydrocarbon mixtures consisting exclusively of ingredients with a chain length of C16 are therefore not covered by the present invention. This would also include Cu-22 alkanes.
Also preferred is a hydrocarbon mixture with a carbon number Cx of x = 16 + 4*a, where a is selected from the natural numbers N = {0, 1,2,3, ...}. The amount of hydrocarbons, in which a = 0 is at least 50 wt%, preferably at least 55 wt%, in particular at least 60 wt%, based on the total mass of the hydrocarbon mixture.
The hydrocarbon mixture Cx is formed from oligomers of butene and/or butadiene.
The amount of hydrocarbons Cx, in which a > 1, is preferably at least 0.5 wt% according to the invention; when a > 4 (i.e., hydrocarbon > C28) it is less than 0.5 wt%, each based on the total mass of the hydrocarbon mixture.
In other words, the hydrocarbon content amounts to at least 0.5 wt% C20, C24, C28 or C30. The amount of C32, C36, etc., is less than 0.5 wt%.
The amount of ingredients in the hydrocarbon mixture Cxwith chain lengths equal to C16 is at least 50%, preferably at least 55%. Hydrocarbon mixtures consisting only of ingredients with C16 as chain lengths are not preferred according to the invention.
These lipids are suitable for reducing or preventing the yellow staining in or on clothing in particular cotton clothing caused by the preparation in combined use with silicone gum in antiperspirant preparations. 13
However, those skilled in the art would expect a limited solubility of silicone gums in the preferred nonvolatile oils isopropyl palmitate, alkyl benzoate, caprylic/capric triglyceride and/or linear/branched hydrocarbon oils with a predominant chain length of >C16. However, it has surprisingly been possible to incorporate the silicone gums in such a way that they could be stable and effective. According to the invention, hydrocarbons, e.g., Cu-22 alkanes with a predominant chain length of >C16 or the preferred hydrocarbon mixtures Cx are also inexpensive alternatives.
The term "lipids" refers to fats, fat-like substances and oils. For cosmetics they are important primarily as softening ("emollient") ingredients and as natural lipids of the stratum comeum, which are situated between the horny cells. They enable the skin to store moisture. In addition to the skin care aspect, lipids are added to cosmetic preparations to ensure a better distribution on the skin and to improve the sensory properties of the preparations.
Due to the use of these lipids, an additional skin care feel is imparted, the yellow staining in or on clothing is reduced, and also the white residues of aluminum chlorohydrate are masked. This means that plain yellow staining is apparent and also there is less visible residue on the skin and black clothing.
The preparations according to the invention include at least one antiperspirant active ingredient. In addition to the actual antiperspirant active ingredients, these preparations may also contain substances that inhibit the microbial degradation of perspiration, for example, butyl octanoic acid. However, butyl octanoic acid has only a deodorant action but does not have an antiperspirant effect since no influence on perspiration secretion is derived from the influence on the bacterial flora of the skin.
In the case of antiperspirants based on aluminum salts in particular, it may be possible to omit the further addition of substances with a strictly deodorant effect, since these have an antimicrobial potential perse. Furthermore, bacterial growth is also inhibited due to the reduced availability of water due to the diminished perspiration secretion.
Antiperspirant active ingredients in the sense of the present patent application are to be selected in particular from the following groups.
Some of the main antiperspirant active ingredients are astringents, mainly aluminum compounds. The aluminum sulfate and aluminum chloride salts, which have a strongly acidic 14 effect and were used in the past, and agaric acid have been largely replaced by aluminum hydroxychloride and aluminum alcoholates. The list of advantageous antiperspirant active ingredients to be used given below should not be understood to be restrictive in any sense: aluminum salts: • aluminum salts, such as aluminum chloride AICI3, aluminum sulfate (AI2(S04)3 • aluminum chlorides of the empirical formula [AI2(OH)mCln], wherein m + n = 6 • aluminum chlorohydrate [AI2(OH)5CI] x H20 • standard Al complexes: Locron P (Clariant), Micro-Dry 323 (Summit Reheis),
Aloxicoll PF 40 (BK Giulini) • activated Al complexes: Reach 103 (Summit Reheis), AACH-7171/AACH-7172 (Summit Reheis), Aloxicoll P (BK Giulini), Zloxicoll SD 100 (BK Giulini) • aluminum sesquichlorohydrate [ΑΙ2(ΟΗ)4.5θΙ1.5] x H20 • standard Al complexes: Aloxicoll 31P (BK Giulini) • aluminum dichlorohydrate [AI2(OH)4CI2] χ H20
These aluminum salts may be used in a powdered form or as hollow beads or a mixture of these. The density of these particles is advantageously in the range of 0.7 to 2.0 g/cm3.
The antiperspirant active ingredients from the groups described above are preferably used in the inventive formulations in an amount of 0.5 to 10 wt%, preferably 2 to 6 wt%, based on the total mass of the preparation, i.e., including the propellant gases that are present.
When using approx. 35 wt% AACH (activated aluminum chlorohydrate) in the active ingredient solution for an aerosol spray (not including propellant gas) and a filling ratio of approx. 15:85 (active ingredient solution to propellant gas), an amount of approx. 5.25 wt% AACH is present in the end product.
The amount of aluminum salts is advantageously chosen to be in the range of 1.0 to 6 wt%, preferably 1.0 to 3.0 wt%, based on the total mass of the preparation.
To reduce the spotting of textiles that can be attributed to the antiperspirant agent, it may be advantageous according to the invention to reduce the use concentration of the antiperspirant active ingredient in comparison with that of a standard product. The lower limit of the advantageous use concentration according to the invention is determined by the provision that an antiperspirant effect must be achieved with the product. 15
The addition of silicone gums according to the invention surprisingly makes it possible to reduce the amount of aluminum salts. By reducing the amount of antiperspirant, the ratio between silicone gum and antiperspirant is influenced in an advantageous manner according to the invention. A reduction in the yellow spotting has been detected at a ratio of silicone gum (active content) to antiperspirant of less than 1:100. An advantageous ratio between silicone gum and antiperspirant is approx. 1:75, but definite effects have been observed even at a ratio of approx. 1:20.
It is thus advantageous according to the invention to select the weight ratio of silicone gum to antiperspirant agent, in particular aluminum salts, in particular aluminum chlorohydrates, to be in the range of 1:100 to 1:10, in particular 1:75 to 1:15, in particular 1:20.
Aluminum chlorohydrates, in particular activated aluminum chlorohydrates (AACH) are preferably used as antiperspirant active ingredients in antiperspirant aerosol preparations. The preferred propellant for use in the inventive aerosol is propane, propene, n-butane, isobutane, isobutene, n-pentane, n-pentene, isopentane, isopentene, methane and ethane individual or in combination. Hydrophilic propellant gases, for example, carbon dioxide may advantageously be used in the sense of the present invention when the amount of hydrophilic gases is selected to be low, and a lipophilic propellant gas (e.g., propane/butane) is present in excess.
Especially preferred propellant gases include propane, butane, isobutane and/or mixtures thereof. The aforementioned gases may each be used individually or in any mixtures in the sense of the present invention. Mixtures with a pressure level of 1.0 to 3.5 bar are preferred. Pressure levels of 2.5 to 3.0 bar are preferred, most especially preferably 2.7 bar.
Preferred filling ratios of active ingredient solution to propellant gas are 40:60 to 5:95, preferably 25:75 to 10:90, most especially preferably 15:85.
The preparations according to the invention are advantageously free of surfactants, emulsifiers, antioxidants and/or complexing agents. The preparations are advantageously free of surfactants, free of emulsifiers, free of antioxidants and free of complexing agents.
In particular the preparations according to the invention are free of butylhydroxytoluene (BHT), pentaerythrityl tetra-di-tert-butyl hydroxyhydrocinnamate (TTHP, BHPM), caffeine, abies picea [spruce] extract and citric acid. 16 "Free of here means that the amount of these substances in the preparation is 0 wt%, based on the total mass of the preparation, apart from impurities or other substances that are entrained unintentionally, for example, due to contaminated raw materials or during production.
It is also advantageous that the preparations according to the invention are free of certain masking agents, such as phenyl trimethicone and/or trimethyl citrate in particular.
Phenyl trimethicones are known, for example, for masking white residues. In addition, phenyl trimethicone should have the ability to reduce yellow staining caused by antiperspirants. These properties have been described in the prior art and have been disclosed for non-aerosol applications. However, the use of phenyl trimethicone for aerosol products cannot be recommended to an unlimited extent in view of the toxicological aspects.
The present invention for the use of silicone gums therefore takes another route to reduce and/or prevent unwanted yellow staining.
Triethyl citrate has been described as an antioxidant, a deodorant, a masking oil and a solvent. Because of its polarity, it is used as the solvent in perfume oils in particular. However a formulation containing large amounts of triethyl citrate may encounter pharmaceutical problems in the case of vehicle systems containing primarily apolar vehicle oils.
Because of this, the addition of triethyl citrate is preferably to be avoided according to the present invention.
The aerosol preparations according to the invention may contain cosmetic additives and additional active ingredients such as those typically used in antiperspirant preparations, for example, preservatives, preservative additives, bactericides, perfumes, substances for preventing film, coloring agents and colored pigments, thickeners, moistening and/or humectant substances, fats, oils, waxes or other conventional ingredients of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, film stabilizers, electrolytes, organic solvents or silicone derivatives if the additive does not impair the required properties or is ruled out according to the invention.
Preferred application forms for the inventive formulations include anhydrous aerosols which are marketed in aluminum cans. This application form is preferred because it is the most common form in the field of deodorants/antiperspirants throughout the world. Because of the very good 2012361041 06 Mar 2017 17 compatibility with the package material, use in anhydrous formulations is recommended since there are hardly any changes in the packaging materials over a period of 6 months of storage at +40°C.
The following examples are presented to illustrate the preparations according to the invention. The amounts given are amounts by weight based on the total mass of the respective preparations including the propellant gas.
Examples: INCI 1 2 Aluminum chlorohydrate (activated) 5.25 2.5 Cyclomethicone to 100 to 100 Dimethicone (86% M < 100,000) + dimethicone (14%) 0.5 (0.07% active content silicone gum) 0.8(0.112) Octyldodecanol 0.1 0.1 Dimethicone 0.45 — Isopropyl palmitate 1.5 1.5 C12-15 alkyl benzoate ___ 1.5 Perfume 1.0 1.0 Propylene carbonate 0.075 0.1 Disteardimonium hectorite 0.53 0.3 Butane + isobutane + propane 85 85 Staining (Db*) 4.9 3.9
The following list shows the raw materials used and their commercial designations: INCI Brand name Manufacturer/Supplier Aluminum chlorohydrate Aloxicoll PF 40 BK Giulini Chemie Butyl octanoic acid Isocarb 12 Sasol Aluminum chlorohydrate (activated) Activated Aloxicoll P BK Giulini Chemie Cyclomethicone Baysilone SF 1202 Momentive Performance Materials Inc. Persea gratissima oil Avocado oil, refined, DAC Henry Lamotte Isopropyl palmitate Isopropyl palmitate Cognis 506585520_1\ 18
Cyclomethicone + dimethiconol DC 1501 Fluid Dow Corning Cyclomethicone + dimethicone DC 1411 Fluid Dow Corning Dimethicone + dimethiconol DC 1503 Fluid Dow Corning Ci3-i6 isoparaffin + dimethicone + C10-13 isoparaffin DC BY 25-320 Dow Corning Dimethicone + dimethicone DC 1413 Fluid Dow Coming C12-15 alkyl benzoate TegosoftTN 2 Evonik Goldschmidt Octyldodecanol Isofol 20 Sasol Dimethicone (M < 100,000 g/mol) BRB silicone oil DM 100 BRB International Propylene carbonate 807051 propylene carbonate for synthesis Merck Disteardimonium hectorite Bentone 38V CG Elementis Butane + isobutane + propane Drivosol 27 D60 Evonik Oxeno
These examples show that preparations according to the invention comprise only the silicone gums according to the invention, antiperspirant active ingredients, in particular aluminum salts, the lipids that have been mentioned as advantageous, propellants and volatile silicone oils and only layered silicates, propylene carbonate and optionally skin care agents (emollients) and/or deodorant substances such as perfume.
The cosmetic aerosol preparations according to the invention therefore advantageously consist of only one or more silicone gums, one or more antiperspirant active ingredients in particular aluminum salts, one or more lipids selected from the group of isopropyl esters, preferably isopropyl palmitate, alkyl benzoate, preferably C12-is alkyl benzoate, triglycerides, preferably caprylic/capric triglyceride, dimethicones and/or hydrocarbon mixtures with a predominant chain length of >C16, one or more propellants, one or more silicone oils that are volatile at room temperature, in particular cyclomethicones, one or more layered silicates, in particular disteardimonium hectorite, propylene carbonate, optional skin care agents and perfume.
These preparations according to the invention have an excellent antiperspirant efficacy, are tolerated well on the skin and in particular prevent or reduce yellow staining in or on clothing.

Claims (18)

  1. Patent Claims
    1. Use of one or more silicone gums in cosmetic or dermatological preparations comprising one or more antiperspirant active agents to reduce or prevent staining or spots in or on clothing, wherein silicone gums are high-molecular polydiorganosiloxanes, dimethicone and dimethiconol with a molecular weight of approx. 100,000 to 2,000,000 g/mol.
  2. 2. Use of one or more silicone gums in cosmetic or dermatological preparations comprising one or more antiperspirant active agents to improve the wash-off results with spots caused by the preparation in or on the clothing, wherein silicone gums are high-molecular polydiorganosiloxanes, dimethicone and dimethiconol with a molecular weight of approx. 100,000 to 2,000,000 g/mol.
  3. 3. Use according to claim 1 or claim 2, wherein the amount of silicone gum is selected to be in the range of 0.02 to 0.5 wt%, based on the total mass of the preparation.
  4. 4. Use according to claim 3, wherein the amount of silicone gum is selected to be in the range of 0.035% to 0.2 wt%, based on the total mass of the preparation.
  5. 5. Use according to any one of the preceding claims, wherein the preparations are anhydrous.
  6. 6. Use according to any one of the preceding claims, wherein the preparation comprises one or more lipids selected from the group of isopropyl esters, alkyl benzoate, triglycerides, dimethicone and/or hydrocarbon mixtures with a predominant chain length of >Ci6.
  7. 7. Use according to any one of the preceding claims, wherein the preparation comprises one or more lipids selected from the group of isopropyl palmitate, alkyl benzoate, triglycerides, dimethicone and/or hydrocarbon mixtures with a predominant chain length of >Ci6.
  8. 8. Use according to any one of the preceding claims, wherein the preparation comprises one or more lipids selected from the group of isopropyl esters, C12-15 alkyl benzoate, triglycerides, dimethicone and/or hydrocarbon mixtures with a predominant chain length of >Ci6.
  9. 9. Use according to any one of the preceding claims, wherein the preparation comprises one or more lipids selected from the group of isopropyl esters, alkyl benzoate, caprylic/capric triglyceride, dimethicone and/or hydrocarbon mixtures with a predominant chain length of >Ci6.
  10. 10. Use according to any one of the preceding claims, wherein the preparation comprises one or more lipids selected from the group of isopropyl palmitate, C12-15 alkyl benzoate, caprylic/capric triglyceride, dimethicone and/or hydrocarbon mixtures with a predominant chain length of >Ci6.
  11. 11. Use according to any one of the preceding claims, wherein one or more aluminum salts, are selected as the antiperspirant active ingredients.
  12. 12. Use according to claim 11, wherein the one or more aluminum salts are aluminum chlorohyd rates.
  13. 13. Use according to claim 11 or claim 12, wherein the amount of aluminum salts is selected to be in the range of 1.0 to 6 wt%, based on the total mass of the preparation.
  14. 14. Use according to claim 13, wherein the amount of aluminum salts is selected to be in the range of 1.0 to 3.0 wt%, based on the total mass of the preparation.
  15. 15. Use according to any one of the preceding claims, wherein the preparations are free of surfactants, emulsifiers, antioxidants and/or complexing agents.
  16. 16. Use according to any one of the preceding claims, wherein the preparations are free of butylhydroxytoluene (BHT), pentaerythrityl tetra-di-tert-butyl hydroxyhydrocinnamate (TTHP, BHPM), caffeine, abies picea extract, citric acid, phenyl trimethicone and/or trimethyl citrate.
  17. 17. Use according to any one of the preceding claims, wherein the weight ratio of silicone gums to antiperspirant active ingredients is selected to be in the range of 1:100 to 1:10,
  18. 18. Use according to claim 17, wherein the weight ratio of silicone gums to antiperspirant active ingredients is selected to be in the range of 1:75 to 1:15.
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