(12)
`
`[Translation from German]
`INTERNATIONAL APPLICATION PUBLISHED ACCORDING TO
`THE INTERNATIONAL PATENT COOPERATION TREATY (PCT)
`
`(19) World Intellectual Property Organization
`International Office
`WIPO I PCT
`
`[Bar Code]
`
`(43)
`
`International Publication Date
`
`26 July 2012 (26.07.2012)
`
`(10) International Publication Number
`WO 2012/098189 A2
`
`(51) International Patent Classification:
`
`A61K 8/26 (2006.01)
`
`(21)
`(22)
`
`International File No.: PCT/EP2012/050789
`International Application Date:
`19 January 2012 (19.01.2012)
`
`(25) Application Language:
`
`(26) Publication Language:
`
`German
`
`German
`
`(30) Priority Data: 10 2011 002 863.3
`
`19 January 2011 (19.01.2011) DE
`
`(71) Applicant (For all designated states except
`US): HENKEL AG & CO. KGAA [DE/DE];
`
`Henkelstr. 67, 40589 Dusseldorf (DE)
`
`(72) Inventor(s); and
`(75) Inventor(s)/Applicant(s) (for US only):
`ANDERHEGGEN, Bernd [DE/DE]; Am
`Bueschgen 1, 41189 Moenchengladbach
`(DE). CLAAS, Marcus [DE/DE];
`Schuetzenstr. 70b, 40723 Hilden (DE).
`BANOWSKI, Bernhard [DE/DE]; Benrode Str.
`6, 40597 Dusseldorf (DE).
`
`(81) Designated countries (unless indicated
`otherwise, for every available national
`registration): AE, AG, AL, AM, AO, AT, AU,
`AZ, BA, BB, BG, BH, BR, BW, BY, BZ, CA,
`CH, CL, CN, CO, CR, CU, CZ, DE, DK,
`DM, DO, DZ, EC, EE, EG, ES, FI, GB, GD,
`GE, GH, GM, GT, HN, HR, HU, ID, IL, IN,
`IS, JP, KE, KG, KM, KN, KP, KR, KZ, LA,
`LC, LK, LR, LS, LT, LU, LY, MA, MD, ME,
`MG, MK, MN, MW, MX, MY, MZ, NA, NG,
`NI, NO, NZ, OM, PE, PG, PH, PL, PT, QA,
`RO, RS, RU, RW, SC, SD, SE, SG, SK,
`SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR,
`TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM,
`ZW.
`
`(84) Designated countries (unless indicated
`otherwise, for every available regional
`registration): ARIPO (BW, GH, GM, KE, LR,
`LS, MW, MZ, NA, RW, SD, SL, SZ, TZ, UG,
`ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ,
`MD, RU, TJ, TM), European (AL, AT, BE,
`BG, CH, CY, CZ, DE, DK, EE, ES, Fl, FR,
`GB, GR, HR, HU, IE, IS, IT, LT, LU, LV, MC,
`MK, MT, NL, NO, PL, PT, RO, RS, SE, SI,
`SK, SM, TR), OAPI (BF, BJ, CF, CG, CI, CM,
`GA, GN, GQ, GW, ML, MR, NE, SN, TD, TG)
`
`Published:
`
`- Without International Search Report and to be
`republished if amendments are received (Rule
`48, Para. 2, Item g).
`
`(54) Title [In English and German]:
`
`ANTIPERSPIRANT STICKS WITH IMPROVED LONG-TERM STABILITY
`
`(57) Abstract [In English and German]
`
`Petitioner Dr. Squatch
` Ex. 1015
`
`

`

`WO 2012/098189
`
`PCT/EP2012/050789
`
`The present invention relates to water-free wax-based antiperspirant sticks that have improved
`
`long-term stability
`
`Water-free antiperspirant compositions that are manufactured as a wax-based stick generally
`
`contain, in addition to perspiration-reducing particulate active agents, at least one cosmetic oil
`
`as a carrier for the perspiration-reducing particulate active agent. Commercial sticks contain
`
`thickening agents such as aliphatic alcohols and/or waxes so that the antiperspirant active
`agent suspended in the oil does not precipitate during storage.
`
`In commercial antiperspirant sticks, the antiperspirant active agent suspended in the water-free
`
`oil-containing carrier is covered with an oil layer. However, this oil layer delays the release of an
`
`antiperspirant active agent in the effective water-soluble form. In order to avoid this, water-free
`wax-based antiperspirant sticks usually contain an oil-in-water emulsifier, which promotes the
`release of the antiperspirant active agent from the wax matrix on the skin under the influence of
`skin moisture and sweat.
`
`The basis for the present application was the observation that, in the case of such sticks from
`the prior art, the interaction between antiperspirant active agent, oil-in-water emulsifier and
`atmospheric humidity (during relatively long storage periods) or skin moisture and sweat
`(through contact with the skin during application) gives rise to adverse changes in the stick
`surface. The stick surface becomes hard, the product delivery when rubbed on the skin is
`reduced, and the cosmetic properties of the stick deteriorate. The perspiration-inhibiting effect of
`the product diminishes markedly after a period of regular use of as little as 2 to 3 weeks.
`
`The object of the present invention was therefore to provide water-free wax-based
`antiperspirant sticks that do not exhibit any deterioration of the delivery properties even after
`many use cycles under the influence of moisture (air/skin/sweat), wherein delivery properties
`should be understood to mean, in particular, the melting behavior and gliding ability of the stick
`when applied to the skin, but also the release of the antiperspirant active agent and thus the
`antiperspirant performance.
`
`Surprisingly, it was now found that the abovementioned disadvantages can be eliminated or at
`least significantly reduced, and the long-term stability of the delivery properties and the
`resistance to the influence of moisture can be significantly improved, for water-free wax-based
`antiperspirant sticks when the sticks contain, with respect to their total weight in each case,
`
`0)
`
`

`

`1 — 4% by weight, preferably 2 — 3.5% by weight, especially preferably 2.5 — 3% by weight, of at
`least one oil-in-water emulsifier, selected from ethoxylates of C,o-C22 alkanols with 8 to 16,
`preferably 10 — 14, especially preferably with 12, ethylene oxide units in the molecule.
`
`The subject matter of the present application is antiperspirant wax sticks, containing
`
`in total 3 — 27% by weight, with respect to the total weight of the anhydrous active substance
`
`(USP) in the total composition, of antiperspirant active agent(s),
`
`0 to maximum 8% by weight of free water,
`
`in total 30 — 70% by weight of at least one cosmetic oil that is liquid under normal conditions,
`
`therein 10— 50% by weight of at least one volatile oil that is selected from volatile cyclic
`
`silicones, volatile linear silicones and volatile aliphatic hydrocarbons, as well as mixtures
`
`thereof, and in addition to the at least one volatile oil
`
`in total 1 — 30% by weight of at least one nonvolatile oil,
`
`in total 15 — 25% by weight of at least one wax component that is solid under normal conditions,
`
`therein 12 — 22% by weight of at least one linear and saturated C14- C22 alkanol,
`
`0.5 — 5% by weight of at least one wax with a melting point from 65 — 150°C,
`
`0.5 — 8% by weight of at least one wax with a melting point from 25 to < 50°C,
`
`0.5 — 6% by weight of at least one water-insoluble particulate filler,
`
`1 — 4% by weight, preferably 2 — 3.5% by weight, especially preferably 2.5 — 3% by weight, of at
`
`least one oil-in-water emulsifier, selected from ethoxylates of C10- C22 alkanols with 8 to 16
`
`ethylene oxide units in the molecule,
`
`wherein all specifications of % by weight relate to the total weight of the antiperspirant wax stick
`unless otherwise noted.
`
`The subject matter of the present application is also antiperspirant wax sticks, containing
`in total 3 — 27% by weight, with respect to the total weight of the anhydrous active substance
`(USP) in the total composition, of antiperspirant active agent(s),
`
`0 to maximum 8% by weight of free water,
`
`in total 30 — 70% by weight of at least one cosmetic oil that is liquid under normal conditions,
`therein 10 — 50% by weight of at least one volatile oil that is selected from volatile cyclic
`silicones, volatile linear silicones and volatile aliphatic hydrocarbons, as well as mixtures
`thereof, and in addition to the at least one volatile oil
`in total 1 — 30% by weight of at least one nonvolatile oil,
`in total 15 — 25% by weight of at least one wax component that is solid under normal conditions,
`therein
`
`

`

`in total 12 — 22% by weight of at least one linear and saturated O14-C22 alkanol,
`in total 0.5 — 5% by weight of at least one wax with a melting point from 65 — 150°C,
`in total 0.5 — 8% by weight of at least one wax with a melting point from 25 to < 50°C,
`furthermore in total 0.5 — 6% by weight of at least one water-insoluble particulate filler,
`in total 1 — 4% by weight, preferably 2 — 3.5% by weight, especially preferably 2.5 — 3% by
`weight, of at least one oil-in-water emulsifier, selected from ethoxylates of O10- C22 alkanols with
`8 to 16 ethylene oxide units in the molecule,
`wherein all specifications of % by weight relate to the total weight of the antiperspirant wax stick
`
`unless otherwise noted.
`
`Within the meaning of the present application, "normal conditions" are a temperature of 20°C
`and a pressure of 1013 hPa. Melting point specifications likewise relate to a pressure of 1013
`
`hPa.
`
`The content of free water in the sticks according to the invention is 0 — 8% by weight, preferably
`0.1 — 6% by weight, especially preferably 0.2 — 4% by weight, extremely preferably 0.5-3% by
`
`weight, in each case with respect to the total weight of the antiperspirant wax stick
`
`Within the meaning of the present application, "free water" is water included in the antiperspirant
`
`composition that is not in the form of water of crystallization, water of hydration or similarly
`
`molecularly bound water. The content of water of crystallization, water of hydration or similarly
`
`molecularly bound water that is included in the constituents employed, in particular in the
`
`perspiration-inhibiting active agents, does not represent free water within the meaning of the
`
`present application. Free water is water that, for example, is added as a solvent, as a gel
`
`activator, or as a solvent constituent of other active agents, to the composition according to the
`
`invention.
`
`In the case of cosmetic oils, a distinction is drawn between volatile and nonvolatile oils.
`
`Nonvolatile oils are understood according to the invention to be oils that have a vapor pressure
`
`of less than 2.66 Pa (0.02 mm Hg) at 20°C and an ambient pressure of 1013 hPa. Volatile oils
`
`are understood according to the invention to be oils that have a vapor pressure of 2.66 Pa —
`
`40000 Pa (0.02 mm - 300 mm Hg), preferably 10 Pa — 12000 Pa (0.1 mm - 90 mm Hg),
`
`especially preferably 13 Pa — 3000 Pa, extremely preferably 15 — 500 Pa, at 20°C and an
`
`ambient pressure of 1013 hPa.
`
`4
`
`

`

`The terms, "antiperspirant wax stick," "antiperspirant stick," "wax-based antiperspirant stick,"
`"stick composition" and "composition according to the invention" are used synonymously with
`respect to the subject matter of the present application.
`
`The compositions according to the invention contain at least one perspiration-inhibiting active
`agent, which is also referred to as antiperspirant active agent, in a total amount of 3 — 27% by
`weight, preferably 5 — 22% by weight and especially preferably 10 - 20% by weight, in each
`case with respect to the total weight of the anhydrous active substance (USP) in the total
`
`composition.
`
`Preferred antiperspirant active agents are selected from the water-soluble astringent inorganic
`and organic salts of aluminum, zirconium and zinc, or any desired mixtures of these salts.
`
`According to the invention, water solubility is understood to be a solubility of at least 5% by
`weight at 20°C, which is to say that amounts of at least 5 g of the antiperspirant active agent are
`
`soluble in 95 g water at 20°C.
`
`The perspiration-inhibiting active agents are present in undissolved, suspended form. For
`reasons of product stability, it is preferred that the active agent particles have a number average
`particle size of 0.1 - 200 µm, preferably 1 — 50 µm, especially preferably 3 — 20 µm and
`extremely preferably 5— 10 µm.
`
`Especially preferred antiperspirant active agents are selected from aluminum chlorohydrate, in
`particular aluminum chlorohydrate with the general formula [Al2(OH)5CI - 1-6 H2O], preferably
`[AI2(OH)5CI - 2-3 H2O], which can be present in nonactivated or in activated (depolymerized)
`
`form, as well as aluminum chlorohydrate with the general formula [Al2(OH)4Cl2 - 1-6 H2O],
`preferably [Al2(OH)4Cl2 . 2-3 H2O], which can be present in nonactivated or in activated
`
`(depolymerized) form.
`
`The production of preferred antiperspirant active agents is disclosed in US 3,887,692, US
`3,904,741, US 4,359,456, GB 2,048,229 and GB 1,347,950, for example.
`
`Also preferred are aluminum sesquichlorohydrate, aluminum dichlorohydrate, aluminum
`
`chlorohydrex propylene glycol (PG) or aluminum chlorohydrex polyethylene glycol (PEG),
`
`aluminum or aluminum zirconium glycol complexes, e.g. aluminum or aluminum zirconium
`propylene glycol complexes, aluminum sesquichlorohydrex PG or aluminum sesquichlorohydrex
`
`PEG, aluminum PG dichlorohydrex or aluminum PEG dichlorohydrex, aluminum hydroxide,
`
`additionally selected from the aluminum zirconium chlorohydrates, such as aluminum zirconium
`
`trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium
`
`5
`
`

`

`pentachlorohydrate and aluminum zirconium octachlorohydrate, as well as the aluminum
`zirconium chlorohydrate glycine complexes, such as aluminum zirconium trichlorohydrex
`glycine, aluminum zirconium tetrachlorohydrex glycine, aluminum zirconium pentachlorohydrex
`glycine, and aluminum zirconium octachlorohydrex glycine, additionally from potassium
`aluminum sulfate (KAI(SO4)2 - 12 H2O, alum), aluminum undecylenoyl collagen amino acid,
`sodium aluminum lactate + aluminum sulfate, sodium aluminum chlorohydroxy lactate,
`aluminum bromohydrate, aluminum chloride, the complexes of zinc salts and sodium salts, the
`complexes of lanthanum and cerium, the aluminum salts of lipoamino acids, aluminum sulfate,
`aluminum lactate, aluminum chlorohydroxyallantoinate, sodium aluminum chlorohydroxy lactate,
`zinc chloride, zinc sulfocarbolate, zinc sulfate, zirconyl oxyhalides, in particular zirconyl
`oxychlorides, zirconyl hydroxyhalides, in particular zirconyl hydroxychlorides (zirconium
`chlorohydrate). Antiperspirant active agents that are especially preferred according to the
`invention are selected from aluminum chlorohydrate and aluminum zirconium chlorohydrates, in
`particular from aluminum zirconium tetrachlorohydrex glycine complexes.
`
`Antiperspirant active agents that are especially preferred according to the invention are selected
`from so-called "activated" aluminum and aluminum-zirconium salts, which are also referred to as
`"enhanced activity" antiperspirant active agents. Such active agents are known in the prior art
`and are also commercially available. Manufacture thereof is disclosed in GB 2,048,229, US
`
`4,775,528 and US 6,010,688, for example. Activated aluminum and aluminum-zirconium salts
`
`are generally made by heat treatment of a relatively dilute solution of the salt (e.g.,
`
`approximately 10% by weight of salt) in order to increase its HPLC peak 4 to peak 3 area ratio.
`The activated salt can then be dried, in particular spray dried, to a powder. Also suitable in
`addition to spray drying is, for example, drum drying.
`
`Activated aluminum and aluminum-zirconium salts typically have an HPLC peak 4 to peak 3
`
`area ratio of at least 0.4, preferably at least 0.7, especially preferably at least 0.9, wherein at
`
`least 70% of the aluminum is to be attributed to these peaks
`
`Additional preferred perspiration-inhibiting active agents are basic calcium-aluminum salts, such
`
`as are disclosed in US 2,571,030, for example. These salts are produced by reacting calcium
`
`carbonate with aluminum chlorhydroxide or aluminum chloride and aluminum powder, or by
`
`adding calcium chloride dihydrate to aluminum chlorhydroxide.
`
`Additional preferred perspiration-inhibiting active agents are aluminum zirconium complexes
`
`that are buffered with salts of amino acids, in particular with alkali and alkaline earth glycinates,
`
`such as are disclosed in US 4,017,599, for example.
`
`A
`
`

`

`Additional preferred perspiration-inhibiting active agents are activated aluminum or aluminum-
`zirconium salts such as are disclosed, for example, in US 6,245,325 or US 6,042,816,
`
`containing 5 — 78% by weight (USP) of an activated perspiration-inhibiting aluminum or
`
`aluminum-zirconium salt, an amino acid or hydroxyalkanoic acid in an amount so as to provide
`
`an (amino acid or hydroxyalkanoic acid) to (AI+Zr) weight ratio of 2:1 to 1:20, and preferably 1:1
`
`to 1:10, as well as a water-soluble calcium salt in an amount so as to provide a Ca:(AI+Zr)
`
`weight ratio of 1:1 to 1:28, and preferably 1:2 to 1:25.
`
`Especially preferred solid activated perspiration-inhibiting salt compositions, for example
`
`according to US 6,245,325 or US 6,042,816, contain 48 — 78% by weight (USP), preferably 66
`
`to 75% by weight, of an activated aluminum or aluminum-zirconium salt, and 1 — 16% by weight,
`
`preferably 4 — 13% by weight, of molecularly bound water (water of hydration), and also
`
`sufficient water-soluble calcium salt that the Ca:(AI+Zr) weight ratio is 1:1 to 1:28, preferably 1:2
`
`to 1:25, and sufficient amino acid that the amino acid to (AI+Zr) weight ratio is 2:1 to 1:20,
`
`preferably 1:1 to 1:10.
`
`Additional especially preferred solid perspiration-inhibiting activated salt compositions, for
`
`example according to US 6,245,325 or US 6,042,816, contain 48 — 78% by weight (USP),
`
`preferably 66 to 75% by weight, of an activated aluminum or aluminum-zirconium salt, and 1 —
`
`16% by weight, preferably 4 — 13% by weight, of molecularly bound water (water of hydration),
`
`and also sufficient water-soluble calcium salt that the Ca:(AI+Zr) weight ratio is 1:1 to 1:28,
`
`preferably 1:2 to 1:25, and sufficient glycine that the glycine to (AI+Zr) weight ratio is 2:1 to 1:20,
`
`preferably 1:1 to 1:10.
`
`Additional especially preferred solid perspiration-inhibiting activated salt compositions, for
`
`example according to US 6,245,325 or US 6,042,816, contain 48 — 78% by weight (USP),
`
`preferably 66 to 75% by weight, of an activated aluminum or aluminum-zirconium salt, and 1 —
`
`16% by weight, preferably 4 — 13% by weight, of molecularly bound water, and also sufficient
`
`water-soluble calcium salt that the Ca:(AI+Zr) weight ratio is 1:1 to 1:28, preferably 1:2 to 1:25,
`
`and sufficient hydroxyalkanoic acid that the hydroxyalkanoic acid to (AI+Zr) weight ratio is 2:1 to
`1:20, preferably 1:1 to 1:10.
`
`Preferred water-soluble calcium salts for stabilizing the perspiration-inhibiting salts are selected
`from calcium chloride, calcium bromide, calcium nitrate, calcium citrate, calcium formate,
`
`calcium acetate, calcium gluconate, calcium ascorbate, calcium lactate, calcium glycinate,
`calcium carbonate, calcium sulfate, calcium hydroxide and mixtures thereof.
`
`7
`
`

`

`Preferred amino acids for stabilizing the perspiration-inhibiting salts are selected from glycine,
`
`alanine, leucine, isoleucine, 13-alanine, valine, cysteine, serine, tryptophan, phenylalanine,
`
`methionine, 3-amino-n-butyric acid, and y-amino-n-butyric acid and the salts thereof, in each
`
`case in the D-form, the L-form and the DL-form; glycine is especially preferred.
`
`Preferred hydroxyalkanoic acids for stabilizing the perspiration-inhibiting salts are selected from
`
`glycolic acid and lactic acid.
`
`Additional preferred perspiration-inhibiting active agents are activated aluminum or aluminum-
`
`zirconium salts such as are disclosed, for example, in US 6,902,723, containing 5 — 78% by
`weight (USP) of an activated perspiration-inhibiting aluminum or aluminum-zirconium salt, an
`amino acid or hydroxyalkanoic acid in an amount so as to provide an (amino acid or
`
`hydroxyalkanoic acid) to (AI+Zr) weight ratio of 2:1 to 1:20, and preferably 1:1 to 1:10, as well as
`a water-soluble strontium salt in an amount so as to provide a Sr:(AI+Zr) weight ratio of 1:1 to
`
`1:28, and preferably 1:2 to 1:25.
`
`Especially preferred solid perspiration-inhibiting activated salt compositions, for example
`
`according to US 6,902,723, contain 48 — 78% by weight (USP), preferably 66 to 75% by weight,
`of an activated aluminum or aluminum-zirconium salt, and 1 — 16% by weight, preferably 4 —
`
`13% by weight, of molecularly bound water, and also sufficient water-soluble strontium salt that
`
`the Sr:(AI+Zr) weight ratio is 1:1 to 1:28, preferably 1:2 to 1:25, and sufficient amino acid that
`the amino acid to (AI+Zr) weight ratio is 2:1 to 1:20, preferably 1:1 to 1:10.
`
`Additional especially preferred solid perspiration-inhibiting activated salt compositions, for
`example according to US 6,902,723, contain 48 — 78% by weight (USP), preferably 66 to 75%
`by weight, of an activated aluminum or aluminum-zirconium salt, and 1 — 16% by weight,
`preferably 4 — 13% by weight, of molecularly bound water, and also sufficient water-soluble
`strontium salt that the Sr:(AI+Zr) weight ratio is 1:1 to 1:28, preferably 1:2 to 1:25, and sufficient
`glycine that the glycine to (AI+Zr) weight ratio is 2:1 to 1:20, preferably 1:1 to 1:10.
`
`Additional especially preferred solid perspiration-inhibiting activated salt compositions, for
`example according to US 6,902,723, contain 48 — 78% by weight (USP), preferably 66 to 75%
`by weight, of an activated aluminum or aluminum-zirconium salt, and 1 — 16% by weight,
`preferably 4 — 13% by weight, of molecularly bound water, and also sufficient water-soluble
`strontium salt that the Sr:(AI+Zr) weight ratio is 1:1 to 1:28, preferably 1:2 to 1:25, and sufficient
`hydroxyalkanoic acid that the hydroxyalkanoic acid to (AI+Zr) weight ratio is 2:1 to 1:20,
`preferably 1:1 to 1:10.
`
`0
`
`

`

`Additional preferred activated aluminum salts are those with the general formula Al2(OH)6_aXa,
`
`wherein X is Cl, Br, I, or NO3, and "a" is a value from 0.3 to 5, preferably from 0.8 to 2.5, and
`
`especially preferably from 1 to 2, so that the mole ratio of AI:X is 0.9:1 to 2.1:1, such as are
`disclosed in US 6,074,632, for example. In the case of these salts, there is generally some
`associatively bound water of hydration, typically 1 to 6 moles of water per mole of salt.
`
`Especially preferred is aluminum chlorohydrate (i.e., X is Cl in the aforementioned formula), and
`
`specifically 5/6 basic aluminum chlorohydrate, where "a" is 1, so that the mole ratio of aluminum
`
`to chlorine is 1.9:1 to 2.1:1.
`
`Preferred activated aluminum-zirconium salts are those that represent mixtures or complexes of
`the above-described aluminum salts with zirconium salts of the formula ZrO(OH)2_pbYb, wherein
`Y is Cl, Br, I, NO3, or SO4, b is a rational number from 0.8 to 2, and p is the valence of Y, such
`as are disclosed in US 6,074,632, for example. The zirconium salts likewise generally have
`
`some associatively bound water of hydration, typically 1 to 7 moles of water per mole of salt.
`Preferably, the zirconium salt is zirconyl hydroxychloride with the formula ZrO(OH)2_bClb,
`wherein b is a rational number from 0.8 to 2, preferably from 1.0 to 1.9. Preferred aluminum-
`zirconium salts have an AI:Zr mole ratio of 2 to 10 and a metal:(X+Y) ratio of 0.73 to 2.1,
`preferably 0.9 to 1.5. An especially preferred salt is aluminum-zirconium chlorohydrate (i.e, X
`and Y are Cl) that has an AI:Zr ratio of 2 to 10 and a molar metal:Cl ratio of 0.9 to 2.1. The term
`"aluminum-zirconium chlorohydrate" includes the tri-, tetra-, penta- and octa-chlorohydrate
`forms.
`
`Zirconium salts that are preferred according to the invention have the general formula ZrO(OH)2
`aCla - x H2O, where a = 1.5 — 1.87; x = 1 — 7, wherein a and x are rational numbers. These
`zirconium salts are disclosed, for example, in Belgian patent document BE 825,146.
`
`Additional preferred perspiration-inhibiting active agents are disclosed in US 6,663,854 and US
`2004/0009133.
`
`Preferred perspiration-inhibiting aluminum-zirconium salts have a metal to chloride molar ratio of
`0.9 — 1.5, preferably 0.9 — 1.3, especially preferably 0.9 — 1.1.
`
`Zirconium-free aluminum salts that are especially preferred according to the invention have a
`metal to chloride molar ratio of 1.9-2.1. Zirconium-free aluminum sesquichlorohydrates that
`are especially preferred according to the invention have a metal to chloride molar ratio of 1.5:1 —
`1.8:1.
`
`

`

`Preferred aluminum zirconium chlorohydrates generally have the empirical formula
`
`AInZr(OH)[3n+a-m(n+,)](Cl)[m(n+l)] where n = 2.0 - 10.0, preferably 3.0 - 8.0, m = 0.77 — 1.11
`(corresponding to a metal (AI+Zr) to chloride molar ratio of 1.3 — 0.9), preferably m = 0.91 — 1.11
`(corresponding to M:CI = 1.1 — 0.9), and especially preferably m = 1.00 — 1.11 (corresponding to
`M:CI = 1.0 - 0.9), further very preferred m = 1.02 — 1.11 (corresponding to M:CI = 0.98 - 0.9),
`as well as very preferred m = 1.04-1.11 (corresponding to M:CI = 0.96-0.9).
`
`In the case of these salts, there is generally some associatively bound water of hydration,
`typically 1 to 6 moles of water per mole of salt, corresponding to 1 — 16% by weight, preferably 4
`— 13% by weight, of water of hydration.
`
`Normally, the preferred aluminum zirconium chlorohydrates are associated with an amino acid
`in order to prevent polymerization of the zirconium species during production. Preferred
`stabilizing amino acids are selected from glycine, alanine, leucine, isoleucine, (3-alanine,
`cysteine, valine, serine, tryptophan, phenylalanine, methionine, 3-amino-n-butyric acid and y-
`amino-n-butyric acid, and the salts thereof, in each case in the D-form, the L-form and the DL-
`form; glycine is especially preferred. The amino acid is included in an amount from 1 — 3 moles,
`preferably 1.3 — 1.8 moles, in each case per mole of zirconium in the salt.
`
`Preferred perspiration-inhibiting salts are aluminum zirconium tetrachlorohydrate glycine
`complexes, in particular those with an AI:Zr atomic ratio of 2 — 6 and a metal to chloride molar
`ratio M:CI of 0.9 — 1.5, preferably aluminum zirconium tetrachlorohydrate glycine complexes
`with a metal to chloride molar ratio of 1.0 — 1.4, especially preferably 1.1 — 1.3.
`
`Also preferred according to the invention are aluminum zirconium chlorohydrate glycine
`complexes that are stabilized with betaine ((CH3)3N+—CH2—COO-). Especially preferred
`corresponding compounds have an overall (betaine+glycine)/Zr molar ratio of (0.1 - 3.0):1,
`preferably (0.7 — 1.5):1 and a molar ratio of betaine to glycine of at least 0.001:1. Corresponding
`compounds are disclosed in US 7,105,691, for example.
`
`In an especially preferred embodiment according to the invention, a so-called "activated" salt is
`included as an especially effective antiperspirant salt, in particular one having a high HPLC
`peak 5 aluminum content, in particular having a peak 5 area of at least 33%, especially
`preferably at least 45%, with respect to the total area under peaks 2 to 5, measured by HPLC in
`a 10% by weight aqueous solution of the active agent under conditions in which the aluminum
`species are resolved into at least four successive peaks (designated peaks 2 to 5). Preferred
`
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`aluminum-zirconium salts having a high HPLC peak 5 aluminum content (also referred to as
`
`"ESAZCH") are disclosed in US 6,436,381 and US 6,649,152, for example.
`
`Also preferred are those activated "ESAZCH" salts with HPLC peak 4 to peak 3 area ratio of at
`
`least 0.4, preferably at least 0.7, especially preferably at least 0.9.
`
`Additional especially preferred antiperspirant active agents are those aluminum-zirconium salts
`
`having a high HPLC peak 5 aluminum content that are additionally stabilized with a water-
`
`soluble strontium salt and/or with a water-soluble calcium salt. Corresponding salts are
`
`disclosed in US 6,923,952, for example.
`
`In an especially preferred embodiment, the composition contains an astringent aluminum salt, in
`
`particular aluminum chlorohydrate, which is marketed, for example, in powder form as Micro
`
`Dry® Ultrafine or Superultrafine by Reheis, as Micro-Dry 323 or Micro-Dry 3115 by Summit, as
`
`Chlorhydrol®, as well as in activated form as Reach® 501 by Reheis. Under the name Reach®
`
`301, an aluminum sesquichlorohydrate, which likewise is especially preferred, is offered by
`
`Reheis. Activated aluminum chlorohydrates are also especially preferred, which are available
`
`from Summit under the names Reach® 101 and Reach® 103, as well as AACH-7171. The use
`of aluminum zirconium tetrachlorohydrex glycine complexes can also be especially preferred
`
`according to the invention; these are on the market in powder form, for example, under the
`name Rezal® 36 GP from Reheis or AZG-364 or 369 from Summit, in activated quality, as
`Reach® AZP-908. Aluminum zirconium pentachlorohydrex glycine complexes (AAZG-3108 or
`AAZG-31 10 from Summit) are also preferred antiperspirant active agents.
`
`Especially preferred antiperspirant sticks according to the invention contain an astringent
`aluminum salt having a number average particle size of 1 — 50 µm, preferably 3 — 20 µm, and
`especially preferably 5— 10 pm, selected from aluminum chlorohydrate, aluminum
`sesquichlorohydrate, aluminum zirconium tetrachlorohydrex glycine complexes, aluminum
`zirconium pentachlorohydrex glycine complexes and aluminum zirconium octachlorohydrex
`glycine complexes, as well as mixtures thereof.
`
`The antiperspirant sticks according to the invention furthermore contain in total 30 — 70% by
`weight of at least one cosmetic oil that is liquid under normal conditions, therein 10 — 50% by
`weight of at least one volatile oil that is selected from volatile cyclic silicones, volatile linear
`silicones, and volatile aliphatic hydrocarbons, as well as mixtures thereof, and in addition to the
`at least one volatile oil, contain in total 1 — 30% by weight of at least one nonvolatile oil, wherein
`all specifications of% by weight relate to the total weight of the antiperspirant wax stick.
`
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`Such mixtures of volatile and nonvolatile oils provide for a pleasant, non-greasy feeling on the
`
`skin and good active substance release on the one hand and, on the other hand, good masking
`
`of visual residues that can arise owing to the powdered constituents of the stick.
`
`The total amount of cosmetic oils that are liquid under normal conditions is 30 - 70% by weight,
`
`preferably 39 — 60% by weight, especially preferably 42 — 54% by weight, extremely preferably
`
`45 — 49% by weight, in each case with respect to the total weight of the antiperspirant wax stick.
`
`Volatile Oils
`
`Preferred antiperspirant wax sticks according to the invention contain the at least one volatile oil
`
`that is selected from volatile cyclic silicones, volatile linear silicones and volatile aliphatic
`
`hydrocarbons, as well as mixtures thereof, in a total amount of 15 — 40% by weight, especially
`
`preferably 20 — 35% by weight, extremely preferably 25 — 30% by weight, in each case with
`
`respect to the total weight of the stick.
`
`Preferred volatile cyclic silicones are those with the INCI name cyclomethicones, in particular
`
`cyclotrisiloxane (hexamethylcyclotrisiloxane), cyclotetrasiloxane (octamethylcyclotetrasiloxane),
`
`cyclopentasiloxane (decamethylcyclopentasiloxane), and cyclohexasiloxane
`
`(dodecamethylcyclohexasiloxane), as well as mixtures thereof. These oils have a vapor
`
`pressure of approximately 13 to 15 Pa at 20° C. Preferred antiperspirant sticks contain 10 -
`
`50% by weight, preferably 15 — 40% by weight, especially preferably 20 — 35% by weight,
`
`extremely preferably 25 — 30% by weight, of cyclomethicones, in each case with respect to the
`total weight of the antiperspirant wax stick. Additional preferred antiperspirant sticks contain 10
`- 50% by weight, preferably 15 — 40% by weight, especially preferably 20 — 35% by weight,
`
`extremely preferably 25 — 30% by weight, of cyclopentasiloxane, in each case with respect to
`
`the total weight of the antiperspirant wax stick. Additional preferred antiperspirant sticks contain
`
`10 - 50% by weight, preferably 15 — 40% by weight, especially preferably 20 — 35% by weight,
`
`extremely preferably 25 — 30% by weight, of a cyclopentasiloxane / cyclohexasiloxane mixture,
`
`in each case with respect to the total weight of the antiperspirant wax stick. Additional preferred
`
`antiperspirant sticks according to the invention contain at least one volatile oil that is selected
`
`from volatile cyclic silicones, volatile linear silicones and volatile aliphatic hydrocarbons, as well
`
`as mixtures thereof, in a total amount of 15— 40% by weight, especially preferably 20 — 35% by
`weight, extremely preferably 25 — 30% by weight, in each case with respect to the total weight of
`
`the stick, wherein the at least one volatile oil is selected from cyclopentasiloxane.
`
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`Preferred volatile linear silicone oils are selected from linear silicone oils with 2 — 10, preferably
`
`3 — 6, siloxane units, such as hexamethyldisiloxane (L2), octamethyltrisi