Personal care compositions

Abstract

Described herein, are aqueous soluble tin phosphate complexes formed from a mixture comprising tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt, e.g., sodium tripolyphosphate (Na5P3O10), and external personal care compositions comprising the complexes, and uses thereof.

Description

BACKGROUND

There have been many antiperspirants designed to help people reduce sweat. Examples of these can be found in U.S. Code of Regulation 21 C.F.R. § 350. The majority of the active agents used in antiperspirants are aluminum and zirconium halide compounds and complexes and their derivatives. While these active agents are generally effective, there is still a need for alternative antiperspirant actives.

Tin (II) fluoride (also known as stannous fluoride, SnF₂) is soluble in water; however, it oxidizes to form insoluble precipitates of tin. In addition, tin can form insoluble compounds with phosphates. Thus, there is still a need for methods to stabilize tin (II) compounds, for instance tin (II) fluoride and tin (II) chloride, to make them effective in personal care products. Embodiments of the present invention are designed to meet these, and other, needs.

BRIEF SUMMARY

It has now been discovered that tin (II) fluoride and tin (II) chloride form aqueous soluble tin phosphate complexes upon mixture with a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., potassium tripolyphosphate (K₅P₃O₁₀) or sodium tripolyphosphate (Na₅P₃O₁₀) (STPP).

Without being bound by theory, it is believed that when the complexes are contacted with proteins to simulate sweat, the aqueous soluble tin phosphate complexes form a white precipitate, which may be an appropriate occlusive active for wetness control because it forms plugs that can physically inhibit sweat from skin.

Provided are aqueous soluble tin phosphate complexes, e.g., formed from a mixture comprising tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., potassium tripolyphosphate (K₅P₃O₁₀) or sodium tripolyphosphate (Na₅P₃O₁₀), e.g., sodium tripolyphosphate (Na₅P₃O₁₀).

Also provided are external personal care compositions, e.g., antiperspirants and/or deodorants, comprising the aqueous soluble tin phosphate complexes.

Further provided are antiperspirants and/or deodorants comprising the aqueous soluble tin phosphate complexes that form a precipitate when contacted with sweat.

Further provided are external personal care compositions, e.g., antiperspirants and/or deodorants, comprising tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., potassium tripolyphosphate (K₅P₃O₁₀) or sodium tripolyphosphate (Na₅P₃O₁₀), e.g., sodium tripolyphosphate (Na₅P₃O₁₀), e.g., wherein the tin (II) fluoride or tin (II) chloride and tripolyphosphate salt form an aqueous soluble tin phosphate complex.

Further provided are methods of using the external personal care compositions, e.g., antiperspirants, to occlude pores and/or reduce sweat in a person in need thereof comprising applying the composition to the skin of the person.

Further provided are methods of making the aqueous soluble tin phosphate complexes comprising combining tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., sodium tripolyphosphate, in aqueous solution, e.g., at a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn; optionally isolating the complexes thus formed as a solid.

Further provided are methods of making the external personal care compositions, e.g., antiperspirants, comprising admixing the aqueous soluble tin phosphate complexes with a personal care carrier.

Further areas of applicability of the present invention will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will become more fully understood from the detailed description and the accompanying drawings, wherein:

FIG. 1 depicts Fourier transform infrared spectra.

FIG. 2 depicts Fourier transform infrared spectra.

FIG. 3 depicts Raman spectra of water, STPP, and solutions with P:Sn molar ratios of 2, 5, and 10 (from top to bottom: STPP, P:Sn molar ratio 10, P:Sn molar ratio 5, P:Sn molar ratio 2, and water).

FIG. 4 depicts ³¹P NMR spectra of solutions with P:Sn molar ratios of 10 (A), 5 (B), and 2 (C).

FIG. 5 depicts ¹¹⁹Sn NMR spectra of solutions with P:Sn molar ratios of 10 (A), 5 (B), and 2 (C).

FIG. 6 is a Fourier transform infrared spectrum of SnF₂.

FIG. 7 depicts a ³¹P NMR spectrum of a solution of STPP.

DETAILED DESCRIPTION

The following description of the preferred embodiment(s) is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.

As used throughout, ranges are used as shorthand for describing each and every value that is within the range. Any value within the range can be selected as the terminus of the range. In addition, all references cited herein are hereby incorporated by reference in their entireties. In the event of a conflict in a definition in the present disclosure and that of a cited reference, the present disclosure controls.

Unless otherwise specified, all percentages and amounts expressed herein and elsewhere in the specification should be understood to refer to percentages by weight. The amounts given are based on the active weight of the material.

Provided is an aqueous soluble tin phosphate complex (Complex 1), e.g.,

• • 1.1 Complex 1, wherein the complex is formed from a mixture comprising tin (II) fluoride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., potassium tripolyphosphate (K₅P₃O₁₀) or sodium tripolyphosphate (Na₅P₃O₁₀).
  • 1.2 Complex 1, wherein the complex is formed from a mixture comprising tin (II) chloride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., potassium tripolyphosphate (K₅P₃O₁₀) or sodium tripolyphosphate (Na₅P₃O₁₀).
  • 1.3 Complex 1 or 1.1, wherein the complex is formed from a mixture comprising tin (II) fluoride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., potassium tripolyphosphate (K₅P₃O₁₀) or sodium tripolyphosphate (Na₅P₃O₁₀), in an aqueous solution.
  • 1.4 Complex 1 or 1.2 wherein the complex is formed from a mixture comprising tin (II) chloride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., potassium tripolyphosphate (K₅P₃O₁₀) or sodium tripolyphosphate (Na₅P₃O₁₀), in an aqueous solution.
  • 1.5 Complex 1.3, wherein the aqueous solution has a pH from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from 6-8, e.g., from 6-7, e.g., from 7-8.
  • 1.6 Complex 1.4, wherein the aqueous solution has a pH from 4-9, e.g., from 4-8, e.g., from 4-7, e.g., from 5-8, e.g., from 6-8, e.g., from 5-7, e.g., from 4-6, e.g., from 4-5, e.g., from 5-6, e.g., from 6-7, e.g., from 7-8.
  • 1.7 Any of Complexes 1, 1.1, 1.3, or 1.5, wherein the complex is formed from a mixture comprising tin (II) fluoride and sodium tripolyphosphate (Na₅P₃O₁₀).
  • 1.8 Any of Complexes 1, 1.2, 1.4, or 1.6, wherein the complex is formed from a mixture comprising tin (II) chloride and sodium tripolyphosphate (Na₅P₃O₁₀).
  • 1.9 Any of the foregoing complexes, wherein the complex exhibits a Fourier transform infrared spectrum substantially as shown in the Sn-STPP spectrum in FIG. 1.
  • 1.10 Any of the foregoing complexes, wherein the complex exhibits a Fourier transform infrared spectrum substantially as shown in the Sn-STPP spectrum in FIG. 2.
  • 1.11 Any of the foregoing complexes, wherein the complex exhibits a Fourier transform infrared spectrum comprising one or more peaks selected from the group consisting of: 1077 cm⁻¹, 963 cm⁻¹, 881 cm⁻¹, and 704 cm⁻¹.
  • 1.12 Any of the foregoing complexes, wherein the complex exhibits a Fourier transform infrared spectrum comprising one or more peaks selected from the group consisting of: 2233 cm⁻¹, 1077 cm⁻¹, 963 cm⁻¹, 881 cm⁻¹ and 704 cm⁻¹.
  • 1.13 Any of the foregoing complexes, wherein the complex exhibits a Fourier transform infrared spectrum comprising one or more peaks selected from the group consisting of: 3257 cm⁻¹, 2233 cm⁻¹, 1648 cm⁻¹, 1077 cm⁻¹, 963 cm⁻¹, 881 cm⁻¹, and 704 cm⁻¹.
  • 1.14 Any of the foregoing complexes, wherein the complex exhibits a Fourier transform infrared spectrum comprising the following peaks: 1077 cm⁻¹, 963 cm⁻¹, 881 cm⁻¹, and 704 cm⁻¹.
  • 1.15 Any of the foregoing complexes, wherein the complex exhibits a Fourier transform infrared spectrum comprising the following peaks: 3257 cm⁻¹, 1648 cm⁻¹, 1077 cm⁻¹, 963 cm⁻¹, 881 cm⁻¹, and 704 cm⁻¹.
  • 1.16 Any of the foregoing complexes, wherein the complex exhibits a Fourier transform infrared spectrum comprising the following peaks: 2233 cm⁻¹, 1077 cm⁻¹, 963 cm⁻¹, 881 cm⁻¹, and 704 cm⁻¹.
  • 1.17 Any of the foregoing complexes, wherein the complex exhibits a Fourier transform infrared spectrum comprising the following peaks: 3257 cm⁻¹, 2233 cm⁻¹, 1648 cm⁻¹, 1077 cm⁻¹, 963 cm⁻¹, 881 cm⁻¹, and 704 cm⁻¹.
  • 1.18 Any of the foregoing complexes, wherein the complex exhibits a Fourier transform infrared spectrum comprising one or more peaks selected from the group consisting of: 1081 cm⁻¹, 969 cm⁻¹, 883 cm⁻¹, 733 cm⁻¹, and 512 cm⁻¹.
  • 1.19 Any of the foregoing complexes, wherein the complex exhibits a Fourier transform infrared spectrum comprising the following peaks: 1081 cm⁻¹, 969 cm⁻¹, 883 cm⁻¹, 733 cm⁻¹, and 512 cm⁻¹.
  • 1.20 Any of the foregoing complexes, wherein the complex exhibits a Raman spectrum substantially as shown in any of the P/Sn Raman spectra of FIG. 3.
  • 1.21 Any of the foregoing complexes, wherein the complex exhibits a Raman spectrum comprising one or more peaks selected from the group consisting of: 719 cm⁻¹ and 1084 cm⁻¹.
  • 1.22 Any of the foregoing complexes, wherein the complex exhibits a Raman spectrum comprising the following peaks: 719 cm⁻¹ and 1084 cm⁻¹.
  • 1.23 Any of the foregoing complexes, wherein the complex exhibits a Raman spectrum comprising one or more peaks selected from the group consisting of: 719 cm⁻¹, 978 cm⁻¹, and 1084 cm⁻¹.
  • 1.24 Any of the foregoing complexes, wherein the complex exhibits a Raman spectrum comprising the following peaks: 719 cm⁻¹, 978 cm⁻¹, and 1084 cm⁻¹.
  • 1.25 Any of the foregoing complexes, wherein the complex exhibits a Raman spectrum comprising one or more peaks selected from the group consisting of: 712 cm⁻¹, 978 cm⁻¹, and 1094 cm⁻¹.
  • 1.26 Any of the foregoing complexes, wherein the complex exhibits a Raman spectrum comprising the following peaks: 712 cm⁻¹, 978 cm⁻¹, and 1094 cm⁻¹.
  • 1.27 Any of the foregoing complexes, wherein the complex exhibits a ³¹P NMR spectrum as shown in any of the NMR spectra of FIG. 4, wherein the NMR spectrum is obtained on an aqueous solution with 5 weight % D₂O added and is externally referenced to 85% H₃PO₄ set to 0 ppm.
  • 1.28 Any of the foregoing complexes, wherein the complex exhibits a ³¹P NMR spectrum comprising one or more peaks selected from the group consisting of: −6 ppm (doublet) and −19 ppm (triplet), e.g., −6.2 ppm (doublet), −6.3 ppm (doublet), −19.1 ppm (triplet), −19.2 ppm (triplet), and −19.3 ppm (triplet), e.g., −6.24 ppm (doublet), −6.33 ppm (doublet), −19.08 ppm (triplet), −19.17 ppm (triplet), and −19.27 ppm (triplet), wherein the NMR spectrum is obtained on an aqueous solution with 5 weight % D₂O added and is externally referenced to 85% H₃PO₄ set to 0 ppm.
  • 1.29 Any of the foregoing complexes, wherein the complex exhibits a ³¹P NMR spectrum comprising the following peaks: −6 ppm (doublet) and −19 ppm (triplet), e.g., −6.2 ppm (doublet), −6.3 ppm (doublet), −19.1 ppm (triplet), −19.2 ppm (triplet), and −19.3 ppm (triplet), e.g., −6.24 ppm (doublet), −6.33 ppm (doublet), −19.08 ppm (triplet), −19.17 ppm (triplet), and −19.27 ppm (triplet), wherein the NMR spectrum is obtained on an aqueous solution with 5 weight % D₂O added and is externally referenced to 85% H₃PO₄ set to 0 ppm.
  • 1.30 Any of the foregoing complexes, wherein the complex exhibits a ³¹P NMR spectrum comprising one or more peaks selected from the group consisting of: 2 ppm, −6 ppm (doublet), −7 ppm, and −19 ppm (triplet), e.g., 2.2 ppm, −6.2 ppm (doublet), −6.3 ppm (doublet), −6.7 ppm, −19.1 ppm (triplet), −19.2 ppm (triplet), and −19.3 ppm (triplet), e.g., 2.21 ppm, −6.24 ppm (doublet), −6.33 ppm (doublet), −6.68 ppm, −19.08 ppm (triplet), −19.17 ppm (triplet), and −19.27 ppm (triplet), wherein the NMR spectrum is obtained on an aqueous solution with 5 weight % D₂O added and is externally referenced to 85% H₃PO₄ set to 0 ppm.
  • 1.31 Any of the foregoing complexes, wherein the complex exhibits a ³¹P NMR spectrum comprising the following peaks: 2 ppm, −6 ppm (doublet), −7 ppm, and −19 ppm (triplet), e.g., 2.2 ppm, −6.2 ppm (doublet), −6.3 ppm (doublet), −6.7 ppm, −19.1 ppm (triplet), −19.2 ppm (triplet), and −19.3 ppm (triplet), e.g., 2.21 ppm, −6.24 ppm (doublet), −6.33 ppm (doublet), −6.68 ppm, −19.08 ppm (triplet), −19.17 ppm (triplet), and −19.27 ppm (triplet), wherein the NMR spectrum is obtained on an aqueous solution with 5 weight % D₂O added and is externally referenced to 85% H₃PO₄ set to 0 ppm.
  • 1.32 Any of the foregoing complexes, wherein the complex exhibits a ³¹P NMR spectrum comprising one or more peaks selected from the group consisting of: −8 ppm (doublet) and −19 ppm (triplet), e.g., −7.5 ppm (doublet), −7.6 ppm (doublet), −19.1 ppm (triplet), −19.2 ppm (triplet), and −19.3 ppm (triplet), e.g., −7.52 ppm (doublet), −7.62 ppm (doublet), −19.09 ppm (triplet), −19.19 ppm (triplet), and −19.29 ppm (triplet), wherein the NMR spectrum is obtained on an aqueous solution with 5 weight % D₂O added and is externally referenced to 85% H₃PO₄ set to 0 ppm.
  • 1.33 Any of the foregoing complexes, wherein the complex exhibits a ³¹P NMR spectrum comprising the following peaks: −8 ppm (doublet) and −19 ppm (triplet), e.g., −7.5 ppm (doublet), −7.6 ppm (doublet), −19.1 ppm (triplet), −19.2 ppm (triplet), and −19.3 ppm (triplet), e.g., −7.52 ppm (doublet), −7.62 ppm (doublet), −19.09 ppm (triplet), −19.19 ppm (triplet), and −19.29 ppm (triplet), wherein the NMR spectrum is obtained on an aqueous solution with 5 weight % D₂O added and is externally referenced to 85% H₃PO₄ set to 0 ppm.
  • 1.34 Any of the foregoing complexes, wherein the complex exhibits a ³¹P NMR spectrum comprising one or more peaks selected from the group consisting of: 2 ppm, −7 ppm, −8 ppm (doublet), −10 ppm, −11 ppm, −12 ppm, and −19 ppm (triplet), e.g., 1.7 ppm, −7.3 ppm, −7.5 ppm (doublet), −7.6 ppm (doublet), −9.9 ppm, −10.4 ppm, −10.8 ppm, −11.6 ppm, −19.1 ppm (triplet), −19.2 ppm (triplet), and −19.3 ppm (triplet), e.g., 1.73 ppm, −7.27 ppm, −7.52 ppm (doublet), −7.62 ppm (doublet), −9.89 ppm, −10.37 ppm, −10.83 ppm, −11.62 ppm, −19.09 ppm (triplet), −19.19 ppm (triplet), and −19.29 ppm (triplet), wherein the NMR spectrum is obtained on an aqueous solution with 5 weight % D₂O added and is externally referenced to 85% H₃PO₄ set to 0 ppm.
  • 1.35 Any of the foregoing complexes, wherein the complex exhibits a ³¹P NMR spectrum comprising the following peaks: 2 ppm, −7 ppm, −8 ppm (doublet), −10 ppm, −11 ppm, −12 ppm, and −19 ppm (triplet), e.g., 1.7 ppm, −7.3 ppm, −7.5 ppm (doublet), −7.6 ppm (doublet), −9.9 ppm, −10.4 ppm, −10.8 ppm, −11.6 ppm, −19.1 ppm (triplet), −19.2 ppm (triplet), and −19.3 ppm (triplet), e.g., 1.73 ppm, −7.27 ppm, −7.52 ppm (doublet), −7.62 ppm (doublet), −9.89 ppm, −10.37 ppm, −10.83 ppm, −11.62 ppm, −19.09 ppm (triplet), −19.19 ppm (triplet), and −19.29 ppm (triplet), wherein the NMR spectrum is obtained on an aqueous solution with 5 weight % D₂O added and is externally referenced to 85% H₃PO₄ set to 0 ppm.
  • 1.36 Any of the foregoing complexes, wherein the complex exhibits a ³¹P NMR spectrum comprising one or more peaks selected from the group consisting of: −8 ppm (doublet) and −18 ppm (triplet), e.g., −8.3 ppm (doublet), −8.4 ppm (doublet), −17.7 ppm (triplet), −17.8 ppm (triplet), and −17.9 ppm (triplet), e.g., −8.27 ppm (doublet), −8.37 ppm (doublet), −17.69 ppm (triplet), −17.79 ppm (triplet), and −17.89 ppm (triplet), wherein the NMR spectrum is obtained on an aqueous solution with 5 weight % D₂O added and is externally referenced to 85% H₃PO₄ set to 0 ppm.
  • 1.37 Any of the foregoing complexes, wherein the complex exhibits a ³¹P NMR spectrum comprising the following peaks: −8 ppm (doublet) and −18 ppm (triplet), e.g., −8.3 ppm (doublet), −8.4 ppm (doublet), −17.7 ppm (triplet), −17.8 ppm (triplet), and −17.9 ppm (triplet), e.g., −8.27 ppm (doublet), −8.37 ppm (doublet), −17.69 ppm (triplet), −17.79 ppm (triplet), and −17.89 ppm (triplet), wherein the NMR spectrum is obtained on an aqueous solution with 5 weight % D₂O added and is externally referenced to 85% H₃PO₄ set to 0 ppm.
  • 1.38 Any of the foregoing complexes, wherein the complex exhibits a ³¹P NMR spectrum comprising one or more peaks selected from the group consisting of: −8 ppm (doublet), −9 ppm, and −18 ppm (triplet), e.g., −8.3 ppm (doublet), −8.4 ppm (doublet), −9.1 ppm, −17.7 ppm (triplet), −17.8 ppm (triplet), and −17.9 ppm (triplet), e.g., −8.27 ppm (doublet), −8.37 ppm (doublet), −9.07 ppm, −17.69 ppm (triplet), −17.79 ppm (triplet), and −17.89 ppm (triplet), wherein the NMR spectrum is obtained on an aqueous solution with 5 weight % D₂O added and is externally referenced to 85% H₃PO₄ set to 0 ppm.
  • 1.39 Any of the foregoing complexes, wherein the complex exhibits a ³¹P NMR spectrum comprising the following peaks: −8 ppm (doublet), −9 ppm, and −18 ppm (triplet), e.g., −8.3 ppm (doublet), −8.4 ppm (doublet), −9.1 ppm, −17.7 ppm (triplet), −17.8 ppm (triplet), and −17.9 ppm (triplet), e.g., −8.27 ppm (doublet), −8.37 ppm (doublet), −9.07 ppm, −17.69 ppm (triplet), −17.79 ppm (triplet), and −17.89 ppm (triplet), wherein the NMR spectrum is obtained on an aqueous solution with 5 weight % D₂O added and is externally referenced to 85% H₃PO₄ set to 0 ppm.
  • 1.40 Any of the foregoing complexes, wherein the complex exhibits a ¹¹⁹Sn NMR spectrum as shown in any of the NMR spectra of FIG. 5, wherein the NMR spectrum is obtained on an aqueous solution with 5 weight % D₂O added and is externally referenced to saturated SnF₂ in D₂O at −796 ppm.
  • 1.41 Any of the foregoing complexes, wherein the complex exhibits a ¹¹⁹Sn NMR spectrum comprising the following peak: −688 ppm, e.g., −687.9 ppm, e.g., −687.87 ppm, wherein the NMR spectrum is obtained on an aqueous solution with 5 weight % D₂O added and is externally referenced to saturated SnF₂ in D₂O at −796 ppm.
  • 1.42 Any of the foregoing complexes, wherein the complex exhibits a ¹¹⁹Sn NMR spectrum comprising the following peak: −700 ppm, e.g., −699.5 ppm, e.g., −699.51 ppm, wherein the NMR is obtained on an aqueous solution with 5 weight % D₂O added and is externally referenced to saturated SnF₂ in D₂O at −796 ppm.
  • 1.43 Any of the foregoing complexes, wherein the complex exhibits a ¹¹⁹Sn NMR spectrum comprising one or more peaks selected from the group consisting of: −685 ppm, −692 ppm, −700 ppm, −714 ppm, −717 ppm, −723 ppm, −725 ppm, and −733 ppm, e.g., −684.6 ppm, −691.7 ppm, −699.5 ppm, −714.3 ppm, −717.3 ppm, −723.0 ppm, −725.3 ppm, and −732.6 ppm, e.g., −684.61 ppm, −691.73 ppm, −699.51 ppm, −714.30 ppm, −717.32 ppm, −723.01 ppm, −725.28 ppm, and −732.59 ppm, wherein the NMR spectrum is obtained on an aqueous solution with 5 weight % D₂O added and is externally referenced to saturated SnF₂ in D₂O at −796 ppm.
  • 1.44 Any of the foregoing complexes, wherein the complex exhibits a ¹¹⁹Sn NMR spectrum comprising the following peaks: −685 ppm, −692 ppm, −700 ppm, −714 ppm, −717 ppm, −723 ppm, −725 ppm, and −733 ppm, e.g., −684.6 ppm, −691.7 ppm, −699.5 ppm, −714.3 ppm, −717.3 ppm, −723.0 ppm, −725.3 ppm, and −732.6 ppm, e.g., −684.61 ppm, −691.73 ppm, −699.51 ppm, −714.30 ppm, −717.32 ppm, −723.01 ppm, −725.28 ppm, and −732.59 ppm, wherein the NMR spectrum is obtained on an aqueous solution with 5 weight % D₂O added and is externally referenced to saturated SnF₂ in D₂O at −796 ppm.
  • 1.45 Any of the foregoing complexes, wherein the complex exhibits a ¹¹⁹Sn NMR spectrum comprising the following peak: −715 ppm, e.g., −715.0 ppm, e.g., −714.97 ppm, wherein the NMR spectrum is obtained on an aqueous solution with 5 weight % D₂O added and is externally referenced to saturated SnF₂ in D₂O at −796 ppm.
  • 1.46 Any of the foregoing complexes, wherein the complex is formed from a mixture comprising tin (II) fluoride or tin (II) chloride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn. For instance, wherein the complex is formed from a mixture comprising tin (II) fluoride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn. For instance, wherein the complex is formed from a mixture comprising tin (II) chloride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a molar ratio of 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.
  • 1.47 Any of the foregoing complexes, wherein the complex is formed from a mixture comprising tin (II) fluoride or tin (II) chloride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a molar ratio of 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn. For instance, wherein the complex is formed from a mixture comprising tin (II) fluoride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a molar ratio of 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn. For instance, wherein the complex is formed from a mixture comprising tin (II) chloride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a molar ratio of greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.
  • 1.48 Any of the foregoing complexes, wherein the complex is formed from a mixture comprising tin (II) fluoride or tin (II) chloride and sodium tripolyphosphate in a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn. For instance, wherein the complex is formed from a mixture comprising tin (II) fluoride and sodium tripolyphosphate in a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn. For instance, wherein the complex is formed from a mixture comprising tin (II) chloride and sodium tripolyphosphate in a molar ratio of 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.
  • 1.49 Complex 1.48, wherein the complex is formed from a mixture comprising tin (II) fluoride and sodium tripolyphosphate in a molar ratio of 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn.
  • 1.50 Complex 1.48, wherein the complex is formed from a mixture comprising tin (II) chloride and sodium tripolyphosphate in a molar ratio of 2P:1Sn to less than 10P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.
  • 1.51 Any of the foregoing complexes, wherein the complex is formed from a mixture comprising 1-10 weight % tin (II) fluoride or tin (II) chloride by weight of the mixture, e.g., 1-9 weight % tin (II) fluoride or tin (II) chloride by weight of the mixture, e.g., 3 weight % tin (II) fluoride or tin (II) chloride by weight of the mixture, e.g., 2 weight % tin (II) fluoride or tin (II) chloride by weight of the mixture, and 1-20 weight % tripolyphosphate salt, e.g., alkali tripolyphosphate salt, by weight of the mixture, e.g., 1-15 weight % tripolyphosphate salt by weight of the mixture, e.g., more than 3 weight % tripolyphosphate salt to less than 16 weight % tripolyphosphate salt by weight of the mixture, e.g., 4-15 weight % tripolyphosphate salt by weight of the mixture, e.g., 1-10 weight % tripolyphosphate salt by weight of the mixture, e.g., 4-10 weight % tripolyphosphate salt by weight of the mixture, e.g., 3-4 weight % tripolyphosphate salt by weight of the mixture, e.g., 7-8 weight % tripolyphosphate salt by weight of the mixture. For instance, wherein the complex is formed from a mixture comprising 1-10 weight % tin (II) fluoride by weight of the mixture, e.g., 1-9 weight % tin (II) fluoride by weight of the mixture, e.g., 2 weight % tin (II) fluoride by weight of the mixture, and 1-10 weight % tripolyphosphate salt, e.g., alkali tripolyphosphate salt, by weight of the mixture, e.g., 3-4 weight % tripolyphosphate salt by weight of the mixture, e.g., 7-8 weight % tripolyphosphate salt by weight of the mixture. For instance, wherein the complex is formed from a mixture comprising 1-10 weight % tin (II) chloride by weight of the mixture, e.g., 1-9 weight % tin (II) chloride by weight of the mixture, e.g., 3 weight % tin (II) chloride by weight of the mixture, and 1-20 weight % tripolyphosphate salt, e.g., alkali tripolyphosphate salt, by weight of the mixture, e.g., 1-15 weight % tripolyphosphate salt by weight of the mixture, e.g., more than 3 weight % tripolyphosphate to less than 16 weight % tripolyphosphate salt by weight of the mixture, e.g., 4-15 weight % tripolyphosphate salt by weight of the mixture, e.g., 1-10 weight % tripolyphosphate salt by weight of the mixture, e.g., 4-10 weight % tripolyphosphate salt by weight of the mixture.
  • 1.52 Any of the foregoing complexes, wherein the complex is formed from a mixture comprising 1-10 weight % tin (II) fluoride or tin (II) chloride by weight of the mixture, e.g., 1-9 weight % tin (II) fluoride or tin (II) chloride by weight of the mixture, e.g., 3 weight % tin (II) fluoride or tin (II) chloride by weight of the mixture, e.g., 2 weight % tin (II) fluoride or tin (II) chloride by weight of the mixture, and 1-20 weight % sodium tripolyphosphate by weight of the mixture, e.g., 1-15 weight % sodium tripolyphosphate by weight of the mixture, e.g., more than 3 weight % sodium tripolyphosphate to less than 16 weight % sodium tripolyphosphate by weight of the mixture, e.g., 4-15 weight % sodium tripolyphosphate by weight of the mixture, e.g., 1-10 weight % sodium tripolyphosphate by weight of the mixture, e.g., 4-10 weight % sodium tripolyphosphate by weight of the mixture, e.g., 3-4 weight % sodium tripolyphosphate by weight of the mixture, e.g., 7-8 weight % sodium tripolyphosphate by weight of the mixture.
  • 1.53 Any of the foregoing complexes, wherein the complex is isolated.
  • 1.54 Any of the foregoing complexes, wherein the complex is lyophilized.
  • 1.55 Any of the foregoing complexes, wherein the complex is isolated with an anti-solvent, e.g., an organic solvent, e.g., ethanol.
  • 1.56 Any of the foregoing complexes for use in an external personal care composition, e.g., an antiperspirant, deodorant, body wash, shower gel, soap (e.g., bar soap, hand soap), shampoo, hair conditioner, or cosmetic, e.g., an antiperspirant and/or deodorant comprising the aqueous soluble tin phosphate complex as described in any of the foregoing, e.g., a body wash or soap (e.g., hand soap) comprising the aqueous soluble tin phosphate complex as described in any of the foregoing.
  • 1.57 Any of the foregoing complexes for use to occlude pores.
  • 1.58 Any of the foregoing complexes for use to reduce sweat.

Further provided is a method (Method 1) to occlude pores and/or reduce sweat, in a person in need thereof comprising applying an effective amount of any of Complex 1 et seq. to the skin of the person.

Further provided is a method (Method 2) of making an aqueous soluble tin phosphate complex, e.g., any of Complex 1 et seq., comprising combining tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., potassium tripolyphosphate or sodium tripolyphosphate, e.g.,

• • 2.1 Method 2 comprising combining tin (II) fluoride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, e.g., sodium tripolyphosphate, in an aqueous solution.
  • 2.2 Method 2 comprising combining tin (II) chloride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, e.g., sodium tripolyphosphate, in an aqueous solution.
  • 2.3 Method 2.1, wherein the aqueous solution has a pH from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from 6-8, e.g., from 6-7, e.g., from 7-8.
  • 2.4 Method 2.2, wherein the aqueous solution has a pH from 4-9, e.g., from 4-8, e.g., from 4-7, e.g., from 5-8, e.g., from 6-8, e.g., from 5-7, e.g., from 4-6, e.g., from 4-5, e.g., from 5-6, e.g., from 6-7, e.g., from 7-8.
  • 2.5 Any of the foregoing methods comprising combining tin (II) fluoride or tin (II) chloride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn. For instance, comprising combining tin (II) fluoride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn. For instance, comprising combining tin (II) chloride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a molar ratio of 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.
  • 2.6 Any of the foregoing methods, wherein the tripolyphosphate salt is sodium tripolyphosphate.
  • 2.7 Any of the foregoing methods comprising combining tin (II) fluoride or tin (II) chloride and sodium tripolyphosphate in a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn. For instance, comprising combining tin (II) fluoride and sodium tripolyphosphate in a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn. For instance, comprising combining tin (II) chloride and sodium tripolyphosphate in a molar ratio of 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.
  • 2.8 Method 2.7 comprising combining tin (II) fluoride and sodium tripolyphosphate in a molar ratio of 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn.
  • 2.9 Method 2.7 comprising combining tin (II) chloride and sodium tripolyphosphate in a molar ratio of greater than 2P:1Sn to less than 10P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.
  • 2.10 Any of the foregoing methods comprising combining 1-10 weight % tin (II) fluoride or tin (II) chloride by weight of the combination, e.g., 1-9 weight % tin (II) fluoride or tin (II) chloride by weight of the combination, e.g., 3 weight % tin (II) fluoride or tin (II) chloride by weight of the combination, e.g., 2 weight % tin (II) fluoride or tin (II) chloride by weight of the combination, and 1-20 weight % tripolyphosphate salt, e.g., alkali tripolyphosphate salt by weight of the combination, e.g., 1-15 weight % tripolyphosphate salt by weight of the combination, e.g., more than 3 weight % tripolyphosphate salt to less than 16 weight % tripolyphosphate salt by weight of the combination, e.g., 4-15 weight % tripolyphosphate salt by weight of the combination, e.g., 1-10 weight % tripolyphosphate salt by weight of the combination, e.g., 4-10 weight % tripolyphosphate salt by weight of the combination, e.g., 3-4 weight % tripolyphosphate salt by weight of the combination, e.g., 7-8 weight % tripolyphosphate salt by weight of the combination. For instance, comprising combining 1-10 weight % tin (II) fluoride by weight of the combination, e.g., 1-9 weight % tin (II) fluoride by weight of the combination, e.g., 2 weight % tin (II) fluoride by weight of the combination, and 1-10 weight % tripolyphosphate salt, e.g., alkali tripolyphosphate salt, by weight of the combination, e.g., 3-4 weight % tripolyphosphate salt by weight of the combination, e.g., 7-8 weight % tripolyphosphate salt by weight of the combination. For instance, comprising combining 1-10 weight % tin (II) chloride by weight of the combination, e.g., 1-9 weight % tin (II) chloride by weight of the combination, e.g., 3 weight % tin (II) chloride by weight of the combination, and 1-20 weight % tripolyphosphate salt, e.g., alkali tripolyphosphate salt, by weight of the combination, e.g., 1-15 weight % tripolyphosphate salt by weight of the combination, e.g., more than 3 weight % tripolyphosphate salt to less than 16 weight % tripolyphosphate salt by weight of the combination, e.g., 4-15 weight % tripolyphosphate salt by weight of the combination, e.g., 1-10 weight % tripolyphosphate salt by weight of the combination, e.g., 4-10 weight % tripolyphosphate salt by weight of the combination.
  • 2.11 Any of the foregoing methods comprising combining 1-10 weight % tin (II) fluoride or tin (II) chloride by weight of the combination, e.g., 1-9 weight % tin (II) fluoride or tin (II) chloride by weight of the combination, e.g., 3 weight % tin (II) fluoride or tin (II) chloride by weight of the combination, e.g., 2 weight % tin (II) fluoride or tin (II) chloride by weight of the combination, and 1-20 weight % sodium tripolyphosphate by weight of the combination, e.g., more than 3 weight % sodium tripolyphosphate to less than 16 weight % sodium tripolyphosphate by weight of the combination, e.g., 4-15 weight % sodium tripolyphosphate by weight of the combination, e.g., 1-10 weight % sodium tripolyphosphate by weight of the combination, e.g., 4-10 weight % sodium tripolyphosphate by weight of the combination, e.g., 3-4 weight % sodium tripolyphosphate by weight of the combination, e.g., 7-8 weight % sodium tripolyphosphate by weight of the combination. For instance, comprising combining 1-10 weight % tin (II) fluoride by weight of the combination, e.g., 1-9 weight % tin (II) fluoride by weight of the combination, e.g., 2 weight % tin (II) fluoride by weight of the combination, and 1-10 weight % sodium tripolyphosphate by weight of the combination, e.g., 3-4 weight % sodium tripolyphosphate by weight of the combination, e.g., 7-8 weight % sodium tripolyphosphate by weight of the combination. For instance, comprising combining 1-10 weight % tin (II) chloride by weight of the combination, e.g., 1-9 weight % tin (II) chloride by weight of the combination, e.g., 3 weight % tin (II) chloride by weight of the combination, and 1-20 weight % sodium tripolyphosphate by weight of the combination, e.g., 1-15 weight % sodium tripolyphosphate by weight of the combination, e.g., more than 3 weight % sodium tripolyphosphate to less than 16 weight % sodium tripolyphosphate by weight of the combination, e.g., 4-15 weight % sodium tripolyphosphate by weight of the combination, e.g., 1-10 weight % sodium tripolyphosphate by weight of the combination, e.g., 4-10 weight % sodium tripolyphosphate by weight of the combination.
  • 2.12 Any of the foregoing methods comprising isolating the complex in solid form.
  • 2.13 Any of the foregoing methods comprising lyophilizing the complex.
  • 2.14 Any of the foregoing methods comprising isolating the complex with an anti-solvent, e.g., an organic solvent, e.g., ethanol.
  • 2.15 An external personal care composition, e.g., an antiperspirant, deodorant, body wash, shower gel, soap (e.g., bar soap, hand soap), shampoo, hair conditioner, or cosmetic, e.g., an antiperspirant and/or deodorant, comprising an aqueous soluble tin phosphate complex made as described in any of the foregoing methods, e.g., a body wash or soap (e.g., hand soap) comprising an aqueous soluble tin phosphate complex made as described in any of the foregoing methods.

Further provided is an aqueous soluble tin phosphate complex made by any of Method 2 et seq.

Further provided is an external personal care composition (Composition 1), e.g., an antiperspirant, deodorant, body wash, shower gel, soap (e.g., bar soap, hand soap), shampoo, hair conditioner, or cosmetic, comprising tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., potassium tripolyphosphate (K₅P₃O₁₀) or sodium tripolyphosphate (Na₅P₃O₁₀) (STPP), e.g., any of Complex 1 et seq., e.g.,

• • 1.1 Composition 1, wherein the tripolyphosphate salt is sodium tripolyphosphate (Na₅P₃O₁₀).
  • 1.2 Composition 1 or 1.1, wherein the tin (II) fluoride or tin (II) chloride and tripolyphosphate salt, e.g., alkali tripolyphosphate salt, form an aqueous soluble tin phosphate complex, e.g., any of Complex 1 et seq.
  • 1.3 Composition 1.2, wherein the complex is formed in the composition in situ, e.g., wherein the composition has a pH from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from 6-8, e.g., from 6-7, e.g., from 7-8. For instance, wherein the complex is formed in situ in the composition from tin (II) fluoride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, e.g., wherein the composition has a pH from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from 6-8, e.g., from 6-7, e.g., from 7-8. For instance, wherein the complex is formed in situ in the composition from tin (II) chloride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, e.g., wherein the composition has a pH from 4-8, e.g., from 4-7, e.g., from 5-8, e.g., from 5-7, e.g., from 4-6, e.g., from 4-5, e.g., from 5-6, e.g., from 6-7, e.g., from 7-8.
  • 1.4 Composition 1.2, wherein the complex is formed in situ in an aqueous solution and combined with the composition, e.g., wherein the aqueous solution has a pH from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from 6-8, e.g., from 6-7, e.g., from 7-8. For instance, wherein the complex is formed in situ in an aqueous solution from tin (II) fluoride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, e.g., wherein the aqueous solution has a pH from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from 6-8, e.g., from 6-7, e.g., from 7-8. For instance, wherein the complex is formed in situ in an aqueous solution from tin (II) chloride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, e.g., wherein the aqueous solution has a pH from 4-9, e.g., from 4-8, e.g., from 4-7, e.g., from 5-8, e.g., from 6-8, e.g., from 5-7, e.g., from 4-6, e.g., from 4-5, e.g., from 5-6, e.g., from 6-7, e.g., from 7-8.
  • 1.5 Composition 1.2 or 1.4, wherein the complex is combined as a solid with the composition, e.g., wherein the complex is isolated from the aqueous solution in solid form and combined with the composition.
  • 1.6 Any of Composition 1.2, 1.4, or 1.5, wherein the complex is lyophilized and combined with the composition.
  • 1.7 Any of Composition 1.2 or 1.4-1.6, wherein the complex is isolated with an anti-solvent, e.g., an organic solvent, e.g., ethanol, and combined with the composition.
  • 1.8 Any of Composition 1.2-1.7, wherein the complex is made as described in any of Method 2 et seq.
  • 1.9 Any of Composition 1.2-1.8, wherein the complex is present in an amount of 5-30 weight % by weight of the composition.
  • 1.10 Any of the foregoing compositions, wherein the composition comprises or wherein the complex is formed from tin (II) fluoride or tin (II) chloride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn. For instance, wherein the composition comprises or wherein the complex is formed from tin (II) fluoride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn. For instance, wherein the composition comprises or wherein the complex is formed from tin (II) chloride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a molar ratio of 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.
  • 1.11 Any of the foregoing compositions, wherein the composition comprises or wherein the complex is formed from tin (II) fluoride or tin (II) chloride and sodium tripolyphosphate in a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn. For instance, wherein the composition comprises or wherein the complex is formed from tin (II) fluoride and sodium tripolyphosphate in a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn. For instance, wherein the composition comprises or wherein the complex is formed from tin (II) chloride and sodium tripolyphosphate in a molar ratio of 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.
  • 1.12 Composition 1.11, wherein the composition comprises or wherein the complex is formed from tin (II) fluoride and sodium tripolyphosphate in a molar ratio of 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn.
  • 1.13 Composition 1.11, wherein the composition comprises or wherein the complex is formed from tin (II) chloride and sodium tripolyphosphate in a molar ratio of greater than 2P:1Sn to less than 10P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.
  • 1.14 Any of the foregoing compositions, wherein the composition comprises or wherein the complex is formed from a mixture comprising 1-10 weight % tin (II) fluoride or tin (II) chloride by weight of the composition or the mixture, e.g., 1-9 weight % tin (II) fluoride or tin (II) chloride by weight of the composition or the mixture, e.g., 3 weight % tin (II) fluoride or tin (II) chloride by weight of the composition or the mixture, e.g., 2 weight % tin (II) fluoride or tin (II) chloride by weight of the composition or the mixture, and 1-20 weight % tripolyphosphate salt, e.g., alkali tripolyphosphate salt, by weight of the composition or the mixture, e.g., 1-15 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., more than 3 weight % tripolyphosphate salt to less than 16 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., 4-15 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., 1-10 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., 4-10 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., 3-4 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., 7-8 weight % tripolyphosphate salt by weight of the composition or the mixture. For instance, wherein the composition comprises or wherein the complex is formed from a mixture comprising 1-10 weight % tin (II) fluoride by weight of the composition or the mixture, e.g., 1-9 weight % tin (II) fluoride by weight of the composition or the mixture, e.g., 2 weight % tin (II) fluoride by weight of the composition or the mixture, and 1-10 weight % tripolyphosphate salt, e.g., alkali tripolyphosphate salt, by weight of the composition or the mixture, e.g., 3-4 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., 7-8 weight % tripolyphosphate salt by weight of the composition or the mixture. For instance, wherein the composition comprises or wherein the complex is formed from a mixture comprising 1-10 weight % tin (II) chloride by weight of the composition or the mixture, e.g., 1-9 weight % tin (II) chloride by weight of the composition or the mixture, e.g., 3 weight % tin (II) chloride by weight of the composition or the mixture, and 1-20 weight % tripolyphosphate salt, e.g., alkali tripolyphosphate salt, by weight of the composition or the mixture, e.g., 1-15 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., more than 3 weight % tripolyphosphate salt to less than 16 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., 4-15 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., 1-10 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., 4-10 weight % tripolyphosphate salt by weight of the composition or the mixture.
  • 1.15 Any of the foregoing compositions, wherein the composition comprises or wherein the complex is formed from a mixture comprising 1-10 weight % tin (II) fluoride or tin (II) chloride by weight of the composition or the mixture, e.g., 1-9 weight % tin (II) fluoride or tin (II) chloride by weight of the composition or the mixture, e.g., 3 weight % tin (II) fluoride or tin (II) chloride by weight of the composition or the mixture, e.g., 2 weight % tin (II) fluoride or tin (II) chloride by weight of the composition or the mixture, and 1-20 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., more than 3 weight % sodium tripolyphosphate to less than 16 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., 4-15 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., 1-10 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., 4-10 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., 3-4 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., 7-8 weight % sodium tripolyphosphate by weight of the composition or the mixture. For instance, wherein the composition comprises or wherein the complex is formed from a mixture comprising 1-10 weight % tin (II) fluoride by weight of the composition or the mixture, e.g., 1-9 weight % tin (II) fluoride by weight of the composition or the mixture, e.g., 2 weight % tin (II) fluoride by weight of the composition or the mixture, and 1-10 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., 3-4 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., 7-8 weight % sodium tripolyphosphate by weight of the composition or the mixture. For instance, wherein the composition comprises or wherein the complex is formed from a mixture comprising 1-10 weight % tin (II) chloride by weight of the composition or the mixture, e.g., 1-9 weight % tin (II) chloride by weight of the composition or the mixture, e.g., 3 weight % tin (II) chloride by weight of the composition or the mixture, and 1-20 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., 1-15 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., more than 3 weight % sodium tripolyphosphate to less than 16 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., 4-15 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., 1-10 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., 4-10 weight % tripolyphosphate salt by weight of the composition or the mixture.
  • 1.16 Any of the foregoing compositions further comprising another antiperspirant salt comprising a polyvalent cation, e.g., antiperspirant complexes of (i) aluminum and optionally zirconium, (ii) chlorohydrate, and (iii) optionally an amino acid and/or ammonium acid, for example glycine and/or trimethylglycine, e.g., aluminum zirconium tetrachlorohydrex glycine. The complex may enhance the efficacy of the other antiperspirant salt.
  • 1.17 Any of Composition 1 or 1.1-1.15, wherein the composition is entirely or substantially free of aluminum and optionally zirconium. For example, the composition may include less than 2 weight % by weight of the composition, or less than 0.5 weight % by weight of the composition, or less than 0.1 weight % by weight of the composition, or less than 0.01 weight % by weight of the composition, or less than 0.001 weight % by weight of the composition, or less than 0.0001 weight % by weight of the composition, aluminum or zirconium.
  • 1.18 Any of the foregoing compositions, wherein the composition comprises an aqueous solution.
  • 1.19 Any of the foregoing compositions further comprising 60-85 weight % water by weight of the composition.
  • 1.20 Any of the foregoing compositions, wherein the composition comprises tin (II) fluoride.
  • 1.21 Any of Composition 1 or 1.1-1.19, wherein the composition comprises tin (II) chloride.
  • 1.22 Composition 1.20, wherein the composition has a pH from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from 6-8, e.g., from 6-7, e.g., from 7-8.
  • 1.23 Composition 1.21, wherein the composition has a pH from 4-9, e.g., from 4-8, e.g., from 4-7, e.g., from 5-8, e.g., from 6-8, e.g., from 5-7, e.g., from 4-6, e.g., from 4-5, e.g., from 5-6, e.g., from 6-7, e.g., from 7-8.
  • 1.24 Any of the foregoing compositions, wherein the composition is an antiperspirant.
  • 1.25 Any of the foregoing compositions, wherein the composition is a deodorant.
  • 1.26 Any of the foregoing compositions, wherein the composition is a body wash or soap (e.g., hand soap).
  • 1.27 Any of the foregoing compositions for use to occlude pores.
  • 1.28 Any of the foregoing compositions for use to reduce sweat.

Further provided is a method (Method 3) to occlude pores and/or reduce sweat, in a person in need thereof comprising applying an effective amount of an external personal care composition comprising tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., potassium tripolyphosphate (K₅P₃O₁₀) or sodium tripolyphosphate (Na₅P₃O₁₀) (STPP), e.g., any of Composition 1 et seq., to the skin of the person, e.g.,

• • 3.1 Method 3, wherein the tin (II) fluoride or tin (II) chloride and tripolyphosphate salt, e.g., alkali tripolyphosphate salt, form an aqueous soluble tin phosphate complex, e.g., any of Complex 1 et seq.
  • 3.2 Method 3.1, wherein the complex is formed in situ in the composition, e.g., wherein the composition has a pH from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from 6-8, e.g., from 6-7, e.g., from 7-8. For instance, wherein the complex is formed in situ in the composition from tin (II) fluoride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, e.g., wherein the composition has a pH from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from 6-8, e.g., from 6-7, e.g., from 7-8. For instance, wherein the complex is formed in situ in the composition from tin (II) chloride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, e.g., wherein the composition has a pH from 4-9, e.g., from 4-8, e.g., from 4-7, e.g., from 5-8, e.g., from 6-8, e.g., from 5-7, e.g., from 4-6, e.g., from 4-5, e.g., from 5-6, e.g., from 6-7, e.g., from 7-8.
  • 3.3 Method 3.1, wherein the complex is formed in situ in an aqueous solution and combined with the composition, e.g., wherein the aqueous solution has a pH from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from 6-8, e.g., from 6-7, e.g., from 7-8. For instance, wherein the complex is formed in situ in an aqueous solution from tin (II) fluoride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, e.g., wherein the aqueous solution has a pH from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from 6-8, e.g., from 6-7, e.g., from 7-8. For instance, wherein the complex is formed in situ in an aqueous solution from tin (II) chloride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, e.g., wherein the aqueous solution has a pH from 4-9, e.g., from 4-8, e.g., from 4-7, e.g., from 5-8, e.g., from 6-8, e.g., from 5-7, e.g., from 4-6, e.g., from 4-5, e.g., from 5-6, e.g., from 6-7, e.g., from 7-8.
  • 3.4 Method 3.1 or 3.3, wherein the complex is combined as a solid with the composition, e.g., wherein the complex is isolated from the aqueous solution in solid form and combined with the composition.
  • 3.5 Any of Method 3.1, 3.3, or 3.4, wherein the complex is lyophilized and combined with the composition.
  • 3.6 Any of Method 3.1 or 3.3-3.5, wherein the complex is isolated with an anti-solvent, e.g., an organic solvent, e.g., ethanol, and combined with the composition.
  • 3.7 Any of Method 3.1-3.6, wherein the complex is made as described in any of Method 2 et seq.
  • 3.8 Any of Method 3.1-3.7, wherein the complex is present in an amount of 5-30 weight % by weight of the composition.
  • 3.9 Any of the foregoing methods, wherein the tripolyphosphate salt is sodium tripolyphosphate (Na₅P₃O₁₀).
  • 3.10 Any of the foregoing methods, wherein the composition comprises or wherein the complex is formed from tin (II) fluoride or tin (II) chloride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn. For instance, wherein the composition comprises or wherein the complex is formed from tin (II) fluoride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn. For instance, wherein the composition comprises or wherein the complex is formed from tin (II) chloride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a molar ratio of 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.
  • 3.11 Any of the foregoing methods, wherein the composition comprises or wherein the complex is formed from tin (II) fluoride or tin (II) chloride and sodium tripolyphosphate in a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn. For instance, wherein the composition comprises or wherein the complex is formed from tin (II) fluoride and sodium tripolyphosphate in a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn. For instance, wherein the composition comprises or wherein the complex is formed from tin (II) chloride and sodium tripolyphosphate in a molar ratio of 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.
  • 3.12 Method 3.11, wherein the composition comprises or wherein the complex is formed from tin (II) fluoride and sodium tripolyphosphate in a molar ratio of 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn.
  • 3.13 Method 3.11, wherein the composition comprises or wherein the complex is formed from tin (II) chloride and sodium tripolyphosphate in a molar ratio of greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.
  • 3.14 Any of the foregoing methods, wherein the composition comprises or wherein the complex is formed from a mixture comprising 1-10 weight % tin (II) fluoride or tin (II) chloride by weight of the composition or the mixture, e.g., 1-9 weight % tin (II) fluoride or tin (II) chloride by weight of the composition or the mixture, e.g., 3 weight % tin (II) fluoride or tin (II) chloride by weight of the composition or the mixture, e.g., 2 weight % tin (II) fluoride or tin (II) chloride by weight of the composition or the mixture, and 1-20 weight % tripolyphosphate salt, e.g., alkali tripolyphosphate salt, by weight of the composition or the mixture, e.g., 1-15 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., more than 3 weight % tripolyphosphate salt to less than 16 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., 4-15 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., 1-10 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., 4-10 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., 3-4 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., 7-8 weight % tripolyphosphate salt by weight of the composition or the mixture. For instance, wherein the composition comprises or wherein the complex is formed from a mixture comprising 1-10 weight % tin (II) fluoride by weight of the composition or the mixture, e.g., 1-9 weight % tin (II) fluoride by weight of the composition or the mixture, e.g., 2 weight % tin (II) fluoride by weight of the composition or the mixture, and 1-10 weight % tripolyphosphate salt, e.g., alkali tripolyphosphate salt, by weight of the composition or the mixture, e.g., 3-4 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., 7-8 weight % tripolyphosphate salt by weight of the composition or the mixture. For instance, wherein the composition comprises or wherein the complex is formed from a mixture comprising 1-10 weight % tin (II) chloride by weight of the composition or the mixture, e.g., 1-9 weight % tin (II) chloride by weight of the composition or the mixture, e.g., 3 weight % tin (II) chloride by weight of the composition or the mixture, and 1-20 weight % tripolyphosphate salt, e.g., alkali tripolyphosphate salt, by weight of the composition or the mixture, e.g., 1-15 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., more than 3 weight % tripolyphosphate salt to less than 16 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., 4-15 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., 1-10 weight % tripolyphosphate salt by weight of the composition or the mixture, e.g., 4-10 weight % tripolyphosphate salt by weight of the composition or the mixture.
  • 3.15 Any of the foregoing methods, wherein the composition comprises or wherein the complex is formed from a mixture comprising 1-10 weight % tin (II) fluoride or tin (II) chloride by weight of the composition or the mixture, e.g., 1-9 weight % tin (II) fluoride or tin (II) chloride by weight of the composition or the mixture, e.g., 3 weight % tin (II) fluoride or tin (II) chloride by weight of the composition or the mixture, e.g., 2 weight % tin (II) fluoride or tin (II) chloride by weight of the composition or the mixture, and 1-20 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., and 1-15 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., more than 3 weight % sodium tripolyphosphate to less than 16 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., 4-15 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., 1-10 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., 4-10 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., 3-4 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., 7-8 weight % sodium tripolyphosphate by weight of the composition or the mixture. For instance, wherein the composition comprises or wherein the complex is formed from a mixture comprising 1-10 weight % tin (II) fluoride by weight of the composition or the mixture, e.g., 1-9 weight % tin (II) fluoride by weight of the composition or the mixture, e.g., 2 weight % tin (II) fluoride by weight of the composition or the mixture, and 1-10 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., 3-4 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., 7-8 weight % sodium tripolyphosphate by weight of the composition or the mixture. For instance, wherein the composition comprises or wherein the complex is formed from a mixture comprising 1-10 weight % tin (II) chloride by weight of the composition or the mixture, e.g., 1-9 weight % tin (II) chloride by weight of the composition or the mixture, e.g., 3 weight % tin (II) chloride by weight of the composition or the mixture, and 1-20 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., 1-15 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., more than 3 weight % sodium tripolyphosphate to less than 16 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., 4-15 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., 1-10 weight % sodium tripolyphosphate by weight of the composition or the mixture, e.g., 4-10 weight % sodium tripolyphosphate by weight of the composition or the mixture.
  • 3.16 Any of the foregoing methods, wherein the composition further comprises another antiperspirant salt comprising a polyvalent cation, e.g., antiperspirant complexes of (i) aluminum and optionally zirconium, (ii) chlorohydrate, and (iii) optionally an amino acid and/or ammonium acid, for example glycine and/or trimethylglycine, e.g., aluminum zirconium tetrachlorohydrex glycine. The complex may enhance the efficacy of the other antiperspirant salt.
  • 3.17 Any of Method 3 or 3.1-3.15, wherein the composition is entirely or substantially free of aluminum and optionally zirconium. For example, the composition may include less than 2 weight % by weight of the composition, or less than 0.5 weight % by weight of the composition, or less than 0.1 weight % by weight of the composition, or less than 0.01 weight % by weight of the composition, or less than 0.001 weight % by weight of the composition, or less than 0.0001 weight % by weight of the composition, aluminum or zirconium.
  • 3.18 Any of the foregoing methods, wherein the composition comprises an aqueous solution.
  • 3.19 Any of the foregoing methods, wherein the composition further comprises 60-85 weight % water by weight of the composition.
  • 3.20 Any of the foregoing methods, wherein the composition comprises tin (II) fluoride.
  • 3.21 Any of Method 3 or 3.1-3.19, wherein the composition comprises tin (II) chloride.
  • 3.22 Method 3.20, wherein the composition has a pH from 4-9, e.g. from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from 6-8, e.g., from 6-7, e.g., from 7-8.
  • 3.23 Method 3.21, wherein the composition has a pH from 4-9, e.g., from 4-8, e.g., from 4-7, e.g., from 5-8, e.g., from 6-8, e.g., from 5-7, e.g., from 4-6, e.g., from 4-5, e.g., from 5-6, e.g., from 6-7, e.g., from 7-8.
  • 3.24 Any of the foregoing methods, wherein the method is to occlude pores.
  • 3.25 Any of the foregoing methods, wherein the method is to reduce sweat.
  • 3.26 Any of the foregoing methods, wherein the composition is any of Composition 1 et seq.
  • 3.27 Any of the foregoing methods, wherein the composition is an antiperspirant.
  • 3.28 Any of the foregoing methods, wherein the composition is a deodorant.

Further provided is a method (Method 4) of making an external personal care composition comprising tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., sodium tripolyphosphate, e.g., any of Composition 1 et seq., comprising mixing tin (II) fluoride or tin (II) chloride and the tripolyphosphate salt with a personal care carrier, e.g.,

• • 4.1 Method 4, wherein tin (II) fluoride or tin (II) chloride and the tripolyphosphate salt, e.g., sodium tripolyphosphate, form an aqueous soluble tin phosphate complex, e.g., any of Complex 1 et seq.
  • 4.2 Method 4.1, wherein the complex is formed in situ in the composition, e.g., wherein the composition has a pH from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from 6-8, e.g., from 6-7, e.g., from 7-8. For instance, wherein the complex is formed in situ in the composition from tin (II) fluoride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, e.g., wherein the composition has a pH from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from 6-8, e.g., from 6-7, e.g., from 7-8. For instance, wherein the complex is formed in situ in the composition from tin (II) chloride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, e.g., wherein the composition has a pH from 4-9, e.g., from 4-8, e.g., from 4-7, e.g., from 5-8, e.g., from 6-8, e.g., from 5-7, e.g., from 4-6, e.g., from 4-5, e.g., from 5-6, e.g., from 6-7, e.g., from 7-8.
  • 4.3 Method 4.1, wherein the complex is formed in situ in an aqueous solution and combined with the personal care carrier, e.g., wherein the aqueous solution has a pH from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from 6-8, e.g., from 6-7, e.g., from 7-8. For instance, wherein the complex is formed in situ in an aqueous solution from tin (II) fluoride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, e.g., wherein the aqueous solution has a pH from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from 6-8, e.g., from 6-7, e.g., from 7-8. For instance, wherein the complex is formed in situ in an aqueous solution from tin (II) chloride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, e.g., wherein the aqueous solution has a pH from 4-9, e.g., from 4-8, e.g., from 4-7, e.g., from 5-8, e.g., from 6-8, e.g., from 5-7, e.g., from 4-6, e.g., from 4-5, e.g., from 5-6, e.g., from 6-7, e.g., from 7-8.
  • 4.4 Method 4.1 or 4.3, wherein the complex is combined as a solid with the personal care carrier, e.g., wherein the complex is isolated from the aqueous solution in solid form and combined with the personal care carrier, e.g., an antiperspirant and/or deodorant carrier, e.g., an antiperspirant carrier, e.g., a deodorant carrier.
  • 4.5 Any of Method 4.1, 4.3, or 4.4, wherein the complex is lyophilized and combined with the personal care carrier, e.g., an antiperspirant and/or deodorant carrier, e.g., an antiperspirant carrier, e.g., a deodorant carrier.
  • 4.6 Any of Method 4.1 or 4.3-4.5, wherein the complex is isolated with an anti-solvent, e.g., an organic solvent, e.g., ethanol, and combined with the personal care carrier, e.g., an antiperspirant and/or deodorant carrier, e.g., an antiperspirant carrier, e.g., a deodorant carrier.
  • 4.7 Any of Method 4.1-4.6, wherein the complex is made as described in any of Method 2 et seq.
  • 4.8 Any of Method 4.1-4.7, wherein the complex is present in an amount of 5-30 weight % by weight of the composition.
  • 4.9 Any of the foregoing methods, wherein the tripolyphosphate salt is sodium tripolyphosphate (Na₅P₃O₁₀).
  • 4.10 Any of the foregoing methods comprising mixing tin (II) fluoride or tin (II) chloride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn. For instance, comprising mixing tin (II) fluoride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn. For instance, comprising mixing tin (II) chloride and the tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a molar ratio of 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.
  • 4.11 Any of the foregoing methods comprising mixing tin (II) fluoride or tin (II) chloride and sodium tripolyphosphate in a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn. For instance, comprising mixing tin (II) fluoride and sodium tripolyphosphate in a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn. For instance, comprising mixing tin (II) chloride and sodium tripolyphosphate in a molar ratio of 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.
  • 4.12 Method 4.11 comprising mixing tin (II) fluoride and sodium tripolyphosphate in a molar ratio of 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn.
  • 4.13 Method 4.11 comprising mixing tin (II) chloride and sodium tripolyphosphate in a molar ratio of greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.
  • 4.14 Any of the foregoing methods comprising mixing 1-10 weight % tin (II) fluoride or tin (II) chloride by weight of the mixture, e.g., 1-9 weight % tin (II) fluoride or tin (II) chloride by weight of the mixture, e.g., 3 weight % tin (II) fluoride or tin (II) chloride by weight of the mixture, e.g., 2 weight % tin (II) fluoride or tin (II) chloride by weight of the mixture, and 1-20 weight % tripolyphosphate salt, e.g., alkali tripolyphosphate salt, by weight of the mixture, e.g., 1-15 weight % tripolyphosphate salt by weight of the mixture, e.g., more than 3 weight % tripolyphosphate salt to less than 16 weight % tripolyphosphate salt by weight of the mixture, e.g., 4-15 weight % tripolyphosphate salt by weight of the mixture, e.g., 1-10 weight % tripolyphosphate salt by weight of the mixture, e.g., 4-10 weight % tripolyphosphate salt by weight of the mixture, e.g., 3-4 weight % tripolyphosphate salt by weight of the mixture, e.g., 7-8 weight % tripolyphosphate salt by weight of the mixture. For instance, comprising mixing 1-10 weight % tin (II) fluoride by weight of the mixture, e.g., 1-9 weight % tin (II) fluoride by weight of the mixture, e.g., 2 weight % tin (II) fluoride by weight of the mixture, and 1-10 weight % tripolyphosphate salt, e.g., alkali tripolyphosphate salt, by weight of the mixture, e.g., 3-4 weight % tripolyphosphate salt by weight of the mixture, e.g., 7-8 weight % tripolyphosphate salt by weight of the mixture. For instance, comprising mixing 1-10 weight % tin (II) chloride by weight of the mixture, e.g., 1-9 weight % tin (II) chloride by weight of the mixture, e.g., 3 weight % tin (II) chloride by weight of the mixture, and 1-20 weight % tripolyphosphate salt, e.g., alkali tripolyphosphate salt, by weight of the mixture, e.g., 1-15 weight % tripolyphosphate salt by weight of the mixture, e.g., more than 3 weight % tripolyphosphate salt to less than 16 weight % tripolyphosphate salt by weight of the mixture, e.g., 4-15 weight % tripolyphosphate salt by weight of the mixture, e.g., 1-10 weight % tripolyphosphate salt by weight of the mixture, e.g., 4-10 weight % tripolyphosphate salt by weight of the mixture.
  • 4.15 Any of the foregoing methods comprising mixing 1-10 weight % tin (II) fluoride or tin (II) chloride by weight of the mixture, e.g., 1-9 weight % tin (II) fluoride or tin (II) chloride by weight of the mixture, e.g., 3 weight % tin (II) fluoride or tin (II) chloride by weight of the mixture, e.g., 2 weight % tin (II) fluoride or tin (II) chloride by weight of the mixture, and 1-20 weight % sodium tripolyphosphate by weight of the mixture, e.g., 1-15 weight % sodium tripolyphosphate by weight of the mixture, e.g., more than 3 weight % sodium tripolyphosphate to less than 16 weight % sodium tripolyphosphate by weight of the mixture, e.g., 4-15 weight % sodium tripolyphosphate by weight of the mixture, e.g., 1-10 weight % sodium tripolyphosphate by weight of the mixture, e.g., 4-10 weight % sodium tripolyphosphate by weight of the mixture, e.g., 3-4 weight % sodium tripolyphosphate by weight of the mixture, e.g., 7-8 weight % sodium tripolyphosphate by weight of the mixture. For instance, comprising mixing 1-10 weight % tin (II) fluoride by weight of the mixture, e.g., 1-9 weight % tin (II) fluoride by weight of the mixture, e.g., 2 weight % tin (II) fluoride by weight of the mixture, and 1-10 weight % sodium tripolyphosphate by weight of the mixture, e.g., 3-4 weight % sodium tripolyphosphate by weight of the mixture, e.g., 7-8 weight % sodium tripolyphosphate by weight of the mixture. For instance, comprising mixing 1-10 weight % tin (II) chloride by weight of the mixture, e.g., 1-9 weight % tin (II) chloride by weight of the mixture, e.g., 3 weight % tin (II) chloride by weight of the mixture, and 1-20 weight % sodium tripolyphosphate by weight of the mixture, e.g., 1-15 weight % sodium tripolyphosphate by weight of the mixture, e.g., more than 3 weight % sodium tripolyphosphate to less than 16 weight % sodium tripolyphosphate by weight of the mixture, e.g., 4-15 weight % sodium tripolyphosphate salt by weight of the mixture, e.g., 1-10 weight % sodium tripolyphosphate by weight of the mixture, e.g., 4-10 weight % sodium tripolyphosphate salt by weight of the mixture.
  • 4.16 Any of the foregoing methods, wherein the personal care carrier is an antiperspirant carrier.
  • 4.17 Any of the foregoing methods, wherein the personal care carrier is a deodorant carrier.

Tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., sodium tripolyphosphate, may be combined to form a pre-formed aqueous soluble tin phosphate complex, e.g., any of Complex 1 et seq., which may be prepared in bulk, and then incorporated into the external personal care compositions disclosed herein, e.g., any of Composition 1 et seq. Alternatively, tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., sodium tripolyphosphate, may be combined during the manufacture of the external personal care compositions disclosed herein, e.g., any of Composition 1 et seq., to form the complex in situ in the composition.

For antiperspirant and/or deodorants, the carrier can be any carrier that is used for antiperspirants and/or deodorants. The carrier can be in the form of a stick, a gel, a roll-on, or an aerosol (e.g. spray). For stick compositions, the carrier may include oils and/or silicones and gelling agents.

Optional ingredients that may be included in an antiperspirant and/or deodorant disclosed herein, e.g., any of Composition 1 et seq., include solvents; water-soluble alcohols such as C_2-8 alcohols; glycols; glycerides including mono-, di- and triglycerides; medium to long chain organic acids, alcohols, and esters; surfactants including emulsifying and dispersing agents; amino acids; structurants including thickeners and gelling agents, for example polymers, silicates, and silicon dioxide; emollients; fragrances; and colorants including dyes and pigments.

The complexes disclosed herein, e.g., any of Complex 1 et seq., can be formulated into topical antiperspirants and/or deodorants suitable for application to skin, illustratively a stick, a gel, a cream, a roll-on, a soft solid, a powder, a liquid, an emulsion, a suspension, a dispersion, or a spray. The compositions disclosed herein, e.g., any of Composition 1 et seq., can comprise a single phase or can be a multi-phase system, for example a system comprising a polar phase and an oil phase, optionally in the form of a stable emulsion. The compositions disclosed herein, e.g., any of Composition 1 et seq., can be liquid, semi-solid, or solid. Antiperspirants and/or deodorants may be provided in any suitable container such as an aerosol can, tube, or container with a porous cap, roll-on container, bottle, container with an open end, etc.

The complexes disclosed herein, e.g., any of Complex 1 et seq., can be formulated into body washes and soaps (e.g., hand soaps).

The complexes and compositions disclosed herein, e.g., any of Complex 1 et seq., e.g., any of Composition 1 et seq., may be destructive to or inhibit the growth of bacteria. For instance, the complexes disclosed herein, e.g., any of Complex 1 et seq., may act as a preservative system. In addition, the formation of precipitate of the complexes and compositions disclosed herein, e.g., any of Complex 1 et seq., e.g., any of Composition 1 et seq., may provide a residual antibacterial effect.

The complexes and compositions disclosed herein, e.g., any of Complex 1 et seq., e.g., any of Composition 1 et seq., may be used in a method to reduce sweating by applying the complex and/or composition to skin. In certain embodiments, the application is to axilla. Thus, provided is a method for controlling perspiration comprising applying to skin an antiperspirant effective amount of a complex or a composition disclosed herein, e.g., any of Complex 1 et seq., e.g., any of Composition 1 et seq.

A complex disclosed herein may be described by reference to a spectrum as “substantially” shown or depicted in a figure or by one or more data points. It will be appreciated that a Fourier transform infrared, Raman, or NMR spectrum of a given sample may vary depending on factors known to those of skill in the art, e.g., instrument used, etc. Therefore, the Fourier transform infrared, Raman, and NMR spectrum peaks set forth herein will have an acceptable level of deviation. For example, for Fourier transform infrared spectra, the peaks may have an acceptable deviation of, e.g., ±20 cm⁻¹ or ±16 cm⁻¹ or ±4 cm⁻¹ or ±2 cm⁻¹ or ±1 cm⁻¹ or ±0.5 cm⁻¹. For example, for Raman spectra, the peaks may have an acceptable deviation of, e.g., ±1-2 cm⁻¹, e.g., ±1 cm⁻¹, e.g., ±2 cm⁻¹. For example, for NMR spectra, the peaks may have an acceptable deviation of, e.g., ±1 ppm.

As used herein, “external” means suitable for application to the skin, including the scalp, and nails.

As used herein, “aqueous solution” means a solution in which the solvent is water.

As used herein, “aqueous soluble tin phosphate complex” includes a complex in which 1 gram of the complex is soluble in 1 or 10 to 100 ml water, e.g., 1 or 10 to 90 ml water, e.g., 1 or 10 to 80 ml water, e.g., 1 or 10 to 70 ml water, e.g., 1 or 10 to 60 ml water, e.g., 1 or 10 to 50 ml water, e.g., 1 or 10 to 40 ml water, e.g., 1 or 10 to 30 ml water, e.g., 1 or 10 to 20 ml water, e.g., 1-10 ml water, e.g., less than 1 ml water.

EXAMPLES

Example 1

TABLE 1
		Percent	pH Upon
P:Sn Molar Ratio	Amount (g)	in Solution	Preparation
0.2	0.4 SnF2	2% SnF2	5.8
	0.4 15% STPP	2% STPP
	solution
	18.8 H2O	96% H2O
1	0.2 SnF2	2%	4.9
	0.1 STPP	2%
	7.6 H2O	96%
2	0.5 SnF2	2%	5.6
	0.7 STPP	3%
	22.3 H2O	95%
5	0.3 SnF2	2%	7.8
	1.2 STPP	8%
	14.1 H2O	90%
10	0.3 SnF2	2%	8.0
	2.5 STPP	16%
	12.9 H2O	82%
15	0.2 SnF2	2%	Does not form a clear
	1.8 STPP	24%	solution upon
	5.8 H2O	74%	preparation

Solutions are prepared by first dissolving sodium tripolyphosphate (STPP) in water (mixing under high heat if necessary) and then adding stannous fluoride (SnF₂) to the clear solution. The solutions are then further mixed at room temperature until a clear solution forms. All of the solutions contain 2% SnF₂. A clear solution forms for all of the solutions except for P:Sn=15 molar ratio.

The solutions with a P:Sn molar ratio spanning from 1 to 15 containing 2% SnF2 are aged overnight at room temperature. After overnight aging, only the solutions with a P:Sn molar ratio spanning from 2 to 10 remain clear.

After aging for two days, the solution with a P:Sn molar ratio of 10 contains a little precipitate on the bottom of the vial.

The solutions with a P:Sn molar ratio of 2 and 5 remain stable after aging for two weeks at room temperature.

A different set of solutions with a P:Sn molar ratio of 2 and 5 are placed in a 50° C. oven for eight weeks. After the aging period, the solutions appear clear.

A 2% stannous fluoride solution shows precipitate almost immediately after dissolution.

Example 2

TABLE 2
		Amount of Total
Sample	Amount of BSA (g)	Solution (g)
1% BSA in 1Sn:2P solution	0.05	5
RT
1% BSA in 1Sn:5P solution	0.05	5
RT
1% BSA in 1Sn:2P solution	0.05	5
37° C.
1% BSA in 1Sn:5P solution	0.05	5
37° C.
Control: 1% BSA in DI water	0.02	2

Bovine serum albumin (BSA) simulates sweat proteins and may reveal the benefit of the complex in antiperspirants, as the formation of precipitate may block sweat ducts.

Aging of the BSA Solutions

The solutions with a P:Sn molar ratio of 2 and 5 containing 1% bovine serum albumin (BSA) are aged at 37° C. and at room temperature overnight.

Both solutions of stannous fluoride (SnF₂) and sodium tripolyphosphate (STPP) with 1% BSA form a precipitate after aging overnight at 37° C. The solution with a P:Sn molar ratio of 5 forms clumps of precipitates. The solution with a P:Sn molar ratio of 2 appears turbid throughout.

The solution with a P:Sn molar ratio of 2 with 1% BSA forms a precipitate after aging overnight at room temperature.

The solution with a P:Sn molar ratio of 5 with 1% BSA has a little precipitate after aging overnight at room temperature but still remains relatively clear.

A 1% BSA control after aging overnight at room temperature shows no precipitate. A 1% BSA control after aging overnight at 37° C. shows no precipitate.

Example 3

Compositions comprising elevated concentrations of a complex comprising tin (II) fluoride and a polyphosphate, having a P:Sn molar ratio of 2, are evaluated.

TABLE 3
		Percent
P:Sn Molar Ratio	Amount (g)	in Solution
2	0.2 SnF2	9%	Solution remains clear
	1.6 STPP 15%	14%
	STPP solution
	—	78%
2	0.2 SnF2	10%	Solution is clear upon
	0.2 STPP	16%	preparation but
	1.2 H2O	74%	becomes turbid
			overnight
2	0.2 SnF2	11%	Does not form a clear
	0.2 STPP	18%	solution
	1 H2O	71%

As illustrated by the data described in Table 3 (above), only the solution containing 9% SnF₂ remains clear after 1 week at room temperature.

Example 4

A clear solution comprising 2% stannous fluoride (SnF₂) and sodium tripolyphosphate (STPP) with a P:Sn molar ratio of 5 is lyophilized using a Labconco FreeZone 2.5 Freeze Dryer. FTIR-ATR analysis is conducted on freeze dried powder on an extended range Spectrum One Perkin Elmer system featuring a CsI beam splitter, DTGS detector, and single-bounce diamond KRS-5 ATR crystal. Sample is placed directly on the ATR diamond. See FIG. 1. Peaks observed for the Sn-STPP complex are listed in Table 4 (broad peaks from water/ethanol at about 1640 and 3200 cm⁻¹ are omitted from peak table).

TABLE 4
Wavenumber Absorbance
(cm−1)     (A)
512        0.9993
733        0.3144
883        0.6826
969        0.536
1081       0.4922

Ethanol is added dropwise to a clear solution comprising 2% stannous fluoride (SnF₂) and sodium tripolyphosphate (STPP) with a P:Sn molar ratio of 5 until precipitate forms. Solid is filtered and air dried. FTIR-ATR analysis is conducted on solid on an extended range Spectrum One Perkin Elmer system featuring a CsI beam splitter, DTGS detector, and single-bounce diamond KRS-5 ATR crystal. Sample is placed directly on the ATR diamond. See FIG. 2. An FTIR-ATR for solid SnF₂ is in FIG. 6.

FTIR-ATR analysis may be conducted on about 10-100 mg of solid.

Example 5

TABLE 5
P:Sn Molar Ratio	Amount (g)	pH Upon Preparation
1	0.2 SnCl2•2H2O	Turbid
	0.1 STPP	1.6
	7.5 H2O
2	0.2 SnCl2•2H2O	Turbid
	1.6 15% STPP solution	3.2
	6.0 H2O
3	0.2 SnCl2•2H2O	Clear
	2.5 15% STPP solution	4.4
	5.2 H2O
5	0.2 SnCl2•2H2O	Clear
	4.1 15% STPP solution	7.1
	3.5 H2O
10	0.2 SnCl2•2H2O	Cloudy
	1.2 STPP	7.7
	6.4 H2O
15	0.2 SnCl2•2H2O	Turbid
	1.8 STPP	7.4
	5.8 H2O

Upon preparation, the solutions with P/Sn molar ratios of 1, 2, and 15 appear turbid and the solution with a P/Sn molar ratio of 10 appears slightly cloudy. Only the solutions with P/Sn molar ratios of 3 and 5 are clear.

The solutions are aged overnight at room temperature. After 24 hours, the solutions containing a P/Sn molar ratio of 3 and 5 remain clear. The solutions with P/Sn molar ratios of 1, 2, and 15 are turbid and the solution with a P/Sn molar ratio of 10 appears slightly cloudy.

Example 6

Solutions of 2% SnE₂ and STPP in water with P/Sn molar ratios of 2, 5, and 10 are prepared. The solutions are analyzed as-prepared on an Agiltron PeakSeeker Raman System equipped with a fiber optic probe designed for liquid samples. The spectra, obtained in 30 second integration times, is compared to that of scintillation vials containing deionized water as a blank using RSIQ software. Raman spectra for the solutions are shown in FIG. 3 and peaks are listed in Table 6 (below).

TABLE 6
        Raman Shift
Sample  (cm−1)
STPP    705
        978
        1022
        1094
P/Sn 2  719
        1084
P/Sn 5  719
        978
        1094
P/Sn 10 712
        978
        1094

Example 7

Solutions of 2% SnE₂ and STPP in water with P/Sn molar ratios of 2, 5, and 10 are prepared. 5 weight % D₂O is added to the solutions. ³¹P and ¹¹⁹Sn NMR are acquired on a Bruker AVANCE 500 spectrometer working at 202.4 MHz for ³¹P NMR and 163.5 MHz for ¹¹⁹Sn NMR at room temperature. ³¹P NMR are externally referenced to 85% H₃PO₄ set to 0 ppm. ¹¹⁹Sn NMR are externally referenced to saturated SnF₂ in D₂O at −796 ppm prepared right before measurement. FIG. 4, depicts ³¹P NMR spectra of solutions with P:Sn molar ratios of 10 (A), 5 (B), and 2 (C). FIG. 5 depicts ¹¹⁹Sn NMR spectra of solutions with P:Sn molar ratios of 10 (A), 5 (B), and 2 (C). ³¹P NMR peaks are listed in Table 7 and ¹¹⁹Sn NMR peaks are listed in Table 8. A ³¹P NMR spectrum of a solution of STPP in water with 5 weight % D₂O added and externally referenced to 85% H₃PO₄ set to 0 ppm is in FIG. 7.

	TABLE 7
	P/Sn Molar Ratio	31P Chemical Shift (ppm)
	SnF2-STPP	10	2.21
			−6.24 (doublet)
			−6.33 (doublet)
			−6.68
			−19.08 (triplet)
			−19.17 (triplet)
			−19.27 (triplet)
	SnF2-STPP	5	1.73
			−7.27
			−7.52 (doublet)
			−7.62 (doublet)
			−9.89
			−10.37
			−10.83
			−11.62
			−19.09 (triplet)
			−19.19 (triplet)
			−19.29 (triplet)
	SnF2-STPP	2	−8.27 (doublet)
			−8.37 (doublet)
			−9.07
			−17.69 (triplet)
			−17.79 (triplet)
			−17.89 (triplet)

	TABLE 8
	P/Sn Molar Ratio	119Sn Chemical Shift (ppm)
	SnF2-STPP	10	−687.87
	SnF2-STPP	5	−684.61
			−691.73
			−699.51
			−714.30
			−717.32
			−723.01
			−725.28
			−732.59
	SnF2-STPP	2	−714.97

Example 8

A roll-on antiperspirant comprising the aqueous soluble tin phosphate complex as disclosed herein can be formulated as described in Table 9 (below).

TABLE 9
Material        Weight Percent
Aqueous soluble 5-30%
tin phosphate
complex
Surfactant(s)   1-30%, e.g., 5%
Emollient(s)    1-10%, e.g., 2%
Silicone(s)     1-10%, e.g., 2%
Fragrance(s)    0.5-5%, e.g., 1%
Water           Q.S.

Claims

1. An external personal care composition comprising tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt in a molar ratio of greater than 2P:1Sn to less than 10P:1Sn, wherein tin (II) fluoride or tin (II) chloride and the tripolyphosphate salt form an aqueous soluble tin phosphate complex.

2. The composition of claim 1, wherein the tripolyphosphate salt is sodium tripolyphosphate (Na5P3O10).

3. The composition of claim 1, wherein the complex is formed in the composition in situ.

4. The composition of claim 1, wherein the complex is formed in situ in an aqueous solution and combined with the composition.

5. The composition of claim 4, wherein the complex is isolated from the aqueous solution in solid form and combined with the composition.

6. The composition of claim 1, wherein the complex is lyophilized and combined with the composition.

7. The composition of claim 1, wherein the complex is isolated with an anti-solvent and combined with the composition.

8. The composition of claim 1, wherein the complex is present in an amount of 5 to 30 weight % by weight of the composition.

9. The composition of claim 1, wherein the composition comprises tin (II) fluoride or tin (II) chloride and the tripolyphosphate salt in a molar ratio of 2P:1Sn to 5P:1Sn.

10. The composition of claim 1, wherein the composition comprises tin (II) fluoride or tin (II) chloride and the tripolyphosphate salt in a molar ratio of 3P:1Sn to 5P:1Sn.

11. The composition of claim 1, wherein the composition comprises tin (II) fluoride or tin (II) chloride and the tripolyphosphate salt in a molar ratio of 5P:1Sn.

12. The composition of claim 1, wherein the composition comprises tin (II) fluoride or tin (II) chloride and sodium tripolyphosphate in a molar ratio of 2P:1Sn to 5P:1Sn.

13. The composition of claim 1, wherein the composition comprises tin (II) fluoride or tin (II) chloride and sodium tripolyphosphate in a molar ratio of 3P:1Sn to 5P:1Sn.

14. The composition of claim 1, wherein the composition comprises tin (II) fluoride or tin (II) chloride and sodium tripolyphosphate in a molar ratio of 5P:1Sn.

15. The composition of claim 1, wherein the composition comprises tin (II) fluoride.

16. The composition of claim 1, wherein the composition comprises tin (II) chloride.

17. The composition of claim 1 further comprising another antiperspirant salt comprising a polyvalent cation.

18. The composition of claim 1, wherein the composition is entirely or substantially free of aluminum and optionally zirconium.

19. The composition of claim 1, wherein the composition comprises an aqueous solution.

20. The composition of claim 1 further comprising 60 to 85 weight % water by weight of the composition.

21. The composition of claim 1, wherein the composition is an antiperspirant.

22. The composition of claim 1, wherein the composition is a deodorant.

23. The composition of claim 1 for use to occlude pores.

24. The composition of claim 1 for use to reduce sweat.

25. A method to occlude pores and/or reduce sweat in a person in need thereof comprising applying an effective amount of an external personal care composition as claimed in claim 1 to the skin of the person.