(19)
(11)EP 3 380 065 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
13.05.2020 Bulletin 2020/20

(21)Application number: 16826653.4

(22)Date of filing:  28.12.2016
(51)Int. Cl.: 
A61K 8/24  (2006.01)
A61K 8/19  (2006.01)
A61K 8/21  (2006.01)
A61Q 15/00  (2006.01)
A61K 8/20  (2006.01)
(86)International application number:
PCT/US2016/069035
(87)International publication number:
WO 2017/117301 (06.07.2017 Gazette  2017/27)

(54)

PERSONAL CARE COMPOSITIONS

KOSMETISCHE FORMULIERUNGEN

COMPOSITIONS COSMÉTIQUES


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 30.12.2015 US 201562273306 P

(43)Date of publication of application:
03.10.2018 Bulletin 2018/40

(73)Proprietor: Colgate-Palmolive Company
New York, NY 10022 (US)

(72)Inventors:
  • NAWROCKI, Shiri
    Tenafly New Jersey 07670 (US)
  • DUBOVOY, Viktor
    Cresskill New Jersey 07626 (US)
  • PAN, Long
    Somerset New Jersey 08873 (US)

(74)Representative: Wichmann, Hendrik 
Wuesthoff & Wuesthoff Patentanwälte PartG mbB Schweigerstraße 2
81541 München
81541 München (DE)


(56)References cited: : 
WO-A1-2015/028096
WO-A1-2016/178652
US-A- 2 145 583
US-A- 3 934 004
US-A1- 2004 042 978
WO-A1-2016/105438
WO-A2-2007/062365
US-A- 2 236 387
US-A- 5 487 906
US-A1- 2012 207 686
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description


    [0001] This application claims priority to U.S. Provisional Application No. 62/273,306 filed December 30, 2015.

    BACKGROUND



    [0002] 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.

    [0003] 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



    [0004] 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).

    [0005] 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.

    [0006] The invention is defined in the appended claims.

    [0007] 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 (K5R3O10) or sodium tripolyphosphate (Na5P3O10), e.g., sodium tripolyphosphate (Na5P3O10)

    [0008] Also provided are external personal care compositions, e.g., antiperspirants and/or deodorants, comprising the aqueous soluble tin phosphate complexes.

    [0009] Further provided are antiperspirants and/or deodorants comprising the aqueous soluble tin phosphate complexes that form a precipitate when contacted with sweat.

    [0010] 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.

    [0011] 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.

    [0012] 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.

    [0013] 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.

    [0014] 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



    [0015] The present invention will become more fully understood from the detailed description and the accompanying drawings, wherein:

    Figure 1 depicts Fourier transform infrared spectra.

    Figure 2 depicts Fourier transform infrared spectra.

    Figure 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).

    Figures 4a, 4b, and 4c depict 31P NMR spectra of solutions with P:Sn molar ratios of 10 (Figure 4a), 5 (Figure 4b), and 2 (Figure 4c).

    Figures 5a, 5b, and 5c depict 119Sn NMR spectra of solutions with P:Sn molar ratios of 10 (Figure 5a), 5 (Figure 5b), and 2 (Figure 5c).

    Figure 6 is a Fourier transform infrared spectrum of SnF2.

    Figure 7 depicts a 31PNMR spectrum of a solution of STPP.


    DETAILED DESCRIPTION



    [0016] 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.

    [0017] 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 the event of a conflict in a definition in the present disclosure and that of a cited reference, the present disclosure controls.

    [0018] 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.

    [0019] 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 (K5R3O10) 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 Figure 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 Figure 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 cm1.

    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 cm1, 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 Figure 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 Figure 4a, 4b, or 4c, 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, -62 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), -76 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% H5PO4 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 Figure 5a, 5b, or 5c, 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 (11) 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 : Sn, 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 : I Sn, 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 I P : 1Sn to less than 15P : 1Sn, e.g., greater than 1P : 1Sn to less than 15P : I Sn, 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: I Sn, 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 IOP : I Sn, 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.



    [0020] 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.

    [0021] 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 (H) 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 : I Sn, e.g., 2P : 1Sn to 10P : I Sn, 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 : I Sn, 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 l5P : 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 5 P : 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.



    [0022] Further provided is an aqueous soluble tin phosphate complex made by any of Method 2 et seq.

    [0023] 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.



    [0024] 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 : 1 Sn, 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 : 1 Sn, 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 : 1 Sn, 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 tripolyphopshate 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 tripolyphopshate 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.



    [0025] 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 : 1 Sn, 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 tripolyphosphte by weight of the mixture, e.g., 1-15 weight % sodium tripolyphosphte 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.



    [0026] 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.

    [0027] 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.

    [0028] 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 C2-8 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.

    [0029] 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.

    [0030] The complexes disclosed herein, e.g., any of Complex 1 et seq., can be formulated into body washes and soaps (e.g., hand soaps).

    [0031] 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.

    [0032] 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.

    [0033] 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.

    [0034] As used herein, "external" means suitable for application to the skin, including the scalp, and nails.

    [0035] As used herein, "aqueous solution" means a solution in which the solvent is water.

    [0036] 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



    [0037] 
    Table 1
    P:Sn Molar RatioAmount (g)Percent in SolutionpH Upon Preparation
    0.2 0.4 SnF2 2% SnF2 5.8
    0.4 15% STPP solution 2% STPP
    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 solution upon preparation
    1.8 STPP 24%
    5.8 H2O 74%


    [0038] 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.

    [0039] 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.

    [0040] 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.

    [0041] The solutions with a P:Sn molar ratio of 2 and 5 remain stable after aging for two weeks at room temperature.

    [0042] 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.

    [0043] A 2% stannous fluoride solution shows precipitate almost immediately after dissolution.

    Example 2



    [0044] 
    Table 2
    SampleAmount of BSA (g)Amount of Total Solution (g)
    1% BSA in 1Sn : 2P solution RT 0.05 5
    1% BSA in 1Sn : 5P solution RT 0.05 5
    1% BSA in 1Sn : 2P solution 37°C 0.05 5
    1% BSA in 1Sn : 5P solution 37°C 0.05 5
    Control: 1% BSA in DI water 0.02 2


    [0045] 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



    [0046] 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.

    [0047] 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.

    [0048] The solution with a P:Sn molar ratio of 2 with 1% BSA forms a precipitate after aging overnight at room temperature.

    [0049] 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.

    [0050] 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



    [0051] 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
    P:Sn Molar RatioAmount (g)Percent in Solution 
    2 0.2 SnF2 9% Solution remains clear
    1.6 STPP 15% STPP solution 14%
    - 78%
    2 0.2 SnF2 10% Solution is clear upon preparation but becomes turbid overnight
    0.2 STPP 16%
    1.2 H2O 74%
    2 0.2 SnF2 11% Does not form a clear solution
    0.2 STPP 18%
    1 H2O 71%


    [0052] 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



    [0053] 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 Cs1 beam splitter, DTGS detector, and single-bounce diamond KRS-5 ATR crystal. Sample is placed directly on the ATR diamond. See Figure 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
    WavenumberAbsorbance
    (cm-1) (A)
    512 0.9993
    733 0.3144
    883 0.6826
    969 0.536
    1081 0.4922


    [0054] 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 Figure 2. An FTIR-ATR for solid SnF2 is in Figure 6.

    [0055] FTIR-ATR analysis may be conducted on about 10-100 mg of solid.

    Example 5



    [0056] 
    Table 5
    P:Sn Molar RatioAmount (g) pH Upon Preparation
    1 0.2 SnCl2•2H2O Turbid 1.6
    0.1 STPP
    7.5 H2O
    2 0.2 SnCl2•2H2O Turbid 3.2
    1.6 1 5% STPP solution
    6.0 H2O
    3 0.2 SnCl2•2H2O Clear 4.4
    2.5 15% STPP solution
    5.2 H2O
    5 0.2 SnCl2•2H2O Clear 7.1
    4.1 1 5% STPP solution
    3.5 H2O
    10 0.2 SnCl2•2H2O Cloudy 7.7
    1.2 STPP
    6.4 H2O
    15 0.2 SnCl2•2H2O Turbid 7.4
    1.8 STPP
    5.8 H2O


    [0057] 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.

    [0058] 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



    [0059] Solutions of 2% SnF2 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 Figure 3 and peaks are listed in Table 6 (below).
    Table 6
    SampleRaman Shift
     (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



    [0060] Solutions of 2% SnF2 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. Figures 4a, 4b, and 4c depict 31P NMR spectra of solutions with P:Sn molar ratios of 10 (Figure 4a), 5 (Figure 4b), and 2 (Figure 4c). Figures 5a, 5b, and 5c depict 119Sn NMR spectra of solutions with P:Sn molar ratios of 10 (Figure 5a), 5 (Figure 5b), and 2 (Figure 5c). 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 Figure 7.
    Table 7
     P/Sn Molar Ratio31P 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 Ratio119Sn 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



    [0061] 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
    MaterialWeight Percent
    Aqueous soluble tin phosphate complex 5-30%
    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, 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.
     
    2. The composition of claim 1, wherein the tripolyphosphate salt is sodium tripolyphosphate (Na5P3O10).
     
    3. The composition of claim 1 or 2, wherein tin (II) fluoride or tin (II) chloride and the tripolyphosphate salt form an aqueous soluble tin phosphate complex.
     
    4. The composition of claim 3, wherein the complex is formed in the composition in situ.
     
    5. The composition of claim 3, wherein the complex is formed in situ in an aqueous solution and combined with the composition.
     
    6. The composition of claim 5, wherein the complex is isolated from the aqueous solution in solid form and combined with the composition.
     
    7. The composition of any one of claims 3, 5, or 6, wherein the complex is lyophilized and combined with the composition.
     
    8. The composition of any one of claims 3 or 5-7, wherein the complex is isolated with an anti-solvent and combined with the composition.
     
    9. The composition of any one of claims 3-8, wherein the complex is present in an amount of 5 to 30 weight % by weight of the composition.
     
    10. The composition of any one of the preceding claims, wherein the composition comprises 1 to 10 weight % tin (II) fluoride or tin (II) chloride by weight of the composition and 1 to 20 weight % tripolyphosphate salt by weight of the composition.
     
    11. The composition of any one of the preceding claims further comprising another antiperspirant salt comprising a polyvalent cation.
     
    12. The composition of any one of claims 1-10, wherein the composition is entirely or substantially free of aluminum and optionally zirconium.
     
    13. The composition of any one of the preceding claims further comprising 60 to 85 weight % water by weight of the composition.
     
    14. The composition of any one of the preceding claims, wherein the composition is an antiperspirant, a deodorant, for use to occlude pores, or for use to reduce sweat.
     
    15. A non-therapeutic 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 any one of claims 1-14 to the skin of the person.
     


    Ansprüche

    1. Externe Körperpflegezusammensetzung, umfassend Zinn-(II)-Fluorid oder Zinn-(II)-Chlorid und ein Tripolyphosphatsalz, wobei die Zusammensetzung Zinn-(II)-Fluorid oder Zinn-(II)-Chlorid und das Tripolyphosphatsalz in einem Molverhältnis von 3P:1Sn zu 5P:1Sn umfasst.
     
    2. Zusammensetzung nach Anspruch 1, wobei das Tripolyphosphatsalz Natriumtripolyphosphat (Na5P3O10) ist.
     
    3. Zusammensetzung nach Anspruch 1 oder 2, wobei Zinn-(II)-Fluorid oder Zinn-(II)-Chlorid und das Tripolyphosphatsalz einen wasserlöslichen Zinnphosphatkomplex bilden.
     
    4. Zusammensetzung nach Anspruch 3, wobei der Komplex in der Zusammensetzung in situ gebildet wird.
     
    5. Zusammensetzung nach Anspruch 3, wobei der Komplex in einer wässrigen Lösung in situ gebildet und mit der Zusammensetzung kombiniert wird.
     
    6. Zusammensetzung nach Anspruch 5, wobei der Komplex in fester Form aus der wässrigen Lösung isoliert und mit der Zusammensetzung kombiniert wird.
     
    7. Zusammensetzung nach einem der Ansprüche 3, 5 oder 6, wobei der Komplex gefriergetrocknet und mit der Zusammensetzung kombiniert wird.
     
    8. Zusammensetzung nach einem der Ansprüche 3 oder 5-7, wobei der Komplex mit einem Antilösungsmittel isoliert und mit der Zusammensetzung kombiniert wird.
     
    9. Zusammensetzung nach einem der Ansprüche 3-8, wobei der Komplex in einer Menge von 5 bis 30 Gew.-% bezogen auf das Gewicht der Zusammensetzung vorhanden ist.
     
    10. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei die Zusammensetzung 1 bis 10 Gew.-% Zinn-(II)-Fluorid oder Zinn-(II)-Chlorid der Zusammensetzung und 1 bis 20 Gew.-% Tripolyphosphatsalz bezogen auf das Gewicht der Zusammensetzung umfasst.
     
    11. Zusammensetzung nach einem der vorhergehenden Ansprüche, ferner umfassend ein anderes antihidrotisches Salz, das ein polyvalentes Kation umfasst.
     
    12. Zusammensetzung nach einem der Ansprüche 1-10, wobei die Zusammensetzung gänzlich oder im Wesentlichen frei von Aluminium und optional Zirkonium ist.
     
    13. Zusammensetzung nach einem der vorhergehenden Ansprüche, ferner umfassend 60 bis 85 Gew.-% Wasser bezogen auf das Gewicht der Zusammensetzung.
     
    14. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei die Zusammensetzung ein Antiperspirant, ein Deodorant zur Verwendung zum Verschließen von Poren oder zur Verwendung zum Reduzieren von Schweiß ist.
     
    15. Nicht therapeutisches Verfahren zum Verschließen von Poren und/oder Reduzieren von Schweiß bei einer Person, die dies benötigt, umfassend das Auftragen einer wirksamen Menge einer externen Körperpflegezusammensetzung nach einem der Ansprüche 1-14 auf die Haut der Person.
     


    Revendications

    1. Composition de soins personnels externes comprenant du fluorure stanneux ou du chlorure d'étain (II) et un sel de tripolyphosphate, la composition comprenant du fluorure stanneux ou du chlorure d'étain (II) et du sel de tripolyphosphate dans un rapport molaire de 3P:1Sn à 5P:1Sn.
     
    2. Composition selon la revendication 1, dans laquelle le sel de tripolyphosphate est le tripolyphosphate de sodium (Na5P3O10).
     
    3. Composition selon la revendication 1 ou 2, dans laquelle le fluorure stanneux ou le chlorure d'étain (II) et le sel de tripolyphosphate forment un complexe aqueux soluble de phosphate d'étain.
     
    4. Composition selon la revendication 3, dans laquelle le complexe est formé dans la composition in situ.
     
    5. Composition selon la revendication 3, dans laquelle le complexe est formé in situ dans une solution aqueuse et combiné avec la composition.
     
    6. Composition selon la revendication 5, dans laquelle le complexe est isolé de la solution aqueuse sous forme solide et combiné avec la composition.
     
    7. Composition selon l'une quelconque des revendications 3, 5 ou 6, dans laquelle le complexe est lyophilisé et combiné avec la composition.
     
    8. Composition selon l'une quelconque des revendications 3 ou 5 à 7, dans laquelle le complexe est isolé avec un anti-solvant et combiné avec la composition.
     
    9. Composition selon l'une quelconque des revendications 3 à 8, dans laquelle le complexe est présent en une quantité de 5 à 30 % en poids de la composition.
     
    10. Composition selon l'une quelconque des revendications précédentes, dans laquelle la composition comprend 1 à 10 % en poids de fluorure stanneux ou de chlorure d'étain (II) en poids de la composition et 1 à 20 % en poids de sel de tripolyphosphate en poids de la composition.
     
    11. Composition selon l'une quelconque des revendications précédentes, comprenant en outre un autre sel anti-transpirant comprenant un cation polyvalent.
     
    12. Composition selon l'une quelconque des revendications 1 à 10, dans laquelle la composition est entièrement ou sensiblement exempte d'aluminium et éventuellement de zirconium.
     
    13. Composition selon l'une quelconque des revendications précédentes, comprenant en outre 60 à 85 % en poids d'eau en poids de la composition.
     
    14. Composition selon l'une quelconque des revendications précédentes, dans laquelle la composition est un anti-transpirant, un déodorant, à utiliser pour obstruer les pores ou pour réduire la transpiration.
     
    15. Procédé non thérapeutique pour obstruer les pores et/ou réduire la transpiration chez une personne qui en a besoin, comprenant l'application d'une quantité efficace d'une composition de soins personnels externes selon l'une quelconque des revendications 1 à 14 sur la peau de la personne.
     




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    REFERENCES CITED IN THE DESCRIPTION



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    Patent documents cited in the description