Antiperspirant active compositions and manufacture thereof

Abstract

An antiperspirant active composition comprising an aluminum salt, the aluminum salt (i) having an aluminum to chloride molar ratio of 0.3:1 to 3:1; and (ii) having a species of polyhydroxyoxoaluminum cation detectable at 76 ppm by 27 Al NMR that is present in a relative abundance on a 27 Al NMR spectrograph that is greater than any other polyhydroxyoxoaluminum cation detectable by 27 Al NMR. Also, disclosed are methods of making the antiperspirant active.

What is claimed is: 
     
         1 . An antiperspirant active composition comprising an aluminum salt, the aluminum salt (i) having an aluminum to chloride molar ratio of 0.3:1 to 3:1; and (ii) having a species of polyhydroxyoxoaluminum cation detectable at 76 ppm by  27 Al NMR that is present in a relative abundance on a  27 Al NMR spectrograph that is greater than any other polyhydroxyoxoaluminum cation detectable by  27 Al NMR. 
     
     
         2 . The antiperspirant active composition of  claim 1 , wherein the species of polyhydroxyoxoaluminum cation detectable at 76 ppm by  27 Al NMR is present in an amount that is at least 50% of a total amount of all species of polyhydroxyoxoaluminum cation detectable by  27 Al NMR. 
     
     
         3 . The antiperspirant active composition of  claim 1 , wherein the species of polyhydroxyoxoaluminum cation detectable at 76 ppm by  27 Al NMR is present in an amount that is a majority of a total amount of all species of polyhydroxyoxoaluminum cations detectable by  27 Al NMR. 
     
     
         4 . The antiperspirant active composition of  claim 1 , wherein the aluminum salt exhibits a SEC chromatogram having a SEC Peak 4 area of at least 90% of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram 
     
     
         5 . The antiperspirant active composition of  claim 1 , wherein the  27 Al NMR spectrum has a species distribution including at most 5% Al 13  polyhydroxyoxoaluminum cation in the species detectable by  27 Al NMR within the aluminum salt. 
     
     
         6 . The antiperspirant active composition of  claim 1 , wherein the  27 Al NMR spectrum has a species distribution including no Al 13  polyhydroxyoxoaluminum cation in the species detectable by  27 Al NMR within the aluminum salt. 
     
     
         7 . The antiperspirant active composition of  claim 1 , wherein the aluminum salt has an OH to Al ratio of at most 2.6:1. 
     
     
         8 . The antiperspirant active composition of  claim 1 , wherein the aluminum salt has an OH to Al ratio of 2:1 to 2.5:1. 
     
     
         9 . The antiperspirant active composition of  claim 1 , further comprising a buffer, wherein a molar ratio of buffer to aluminum is at least 0.1:1. 
     
     
         10 . The antiperspirant active composition of  claim 9 , wherein the buffer is at least one buffer chosen from an amino acid, betaine, and quat. 
     
     
         11 . The antiperspirant active composition of  claim 10 , wherein the buffer is an amino acid and a molar ratio of amino acid to aluminum is at least 0.1. 
     
     
         12 . The antiperspirant active composition of  claim 1 , wherein the composition has a SEC Peak 4 area of at least 95% of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram. 
     
     
         13 . The antiperspirant active composition of  claim 1 , wherein the composition has a SEC Peak 3 area of less than 5% of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram. 
     
     
         14 . The antiperspirant active composition of  claim 1 , wherein the composition has a SEC Peak 5 area of less than 5% of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram. 
     
     
         15 . The antiperspirant active composition of  claim 1 , wherein the composition has a SEC Peak 4 area of 95 to 100%, no SEC Peak 3 area, and a SEC Peak 5 area of from 0 to 5% of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram. 
     
     
         16 . The antiperspirant active composition of  claim 1 , wherein the composition further comprises zirconium. 
     
     
         17 . The antiperspirant active composition of  claim 16 , wherein a molar ratio of aluminum to zirconium is 5:1 to 10:1. 
     
     
         18 . A method of making an antiperspirant active composition comprising:
 I) heating an aqueous solution containing i) a first aluminum salt containing an Al 30  polyhydroxyoxoaluminum cation and having an aluminum to chloride molar ratio of 0.3:1 to 3:1, ii) an inorganic salt, and iii) a buffer, wherein the buffer is at least one of an amino acid, betaine, and quat, and a molar ratio of buffer to aluminum is at least 0.1:1, wherein the heating is one of
 a) at a temperature of 100° C. to 250° C. in an isochoric reactor or under hydrothermal reaction for a time sufficient to form a species of polyhydroxyoxoaluminum cation detectable at 76 ppm by  27 Al NMR; or 
 b) at 100° C. at reflux for about 0 days or greater, optionally for about 30 days or greater, 
 to form a fourth aluminum salt. 
   
     
     
         19 . A method of making an antiperspirant active composition comprising:
 I) heating an aqueous solution containing a first aluminum salt having an aluminum to chloride molar ratio of 0.3:1 to 3:1 and a buffer, wherein the buffer is at least one of an amino acid, betaine, and quat, and a molar ratio of buffer to aluminum is at least 0.1:1, at a temperature of 50° C. to 100° C. for a period of time of 1 hour to 6 hours to obtain a first aluminum salt solution;   II) adding to the first aluminum salt solution an aqueous solution of an inorganic base to obtain a second pH adjusted aluminum salt solution having an OH:Al molar ratio of at most 2.6:1 and a pH of 2 to 5;   III) heating the second pH adjusted aluminum salt solution at a temperature of 50° C. to 100° C. for a period of time of at least 6 hours to obtain a third aluminum salt solution containing an Al 30  polyhydroxyoxoaluminum cation;   IV) heating the third aluminum salt solution at one of
 a) at a temperature of 100° C. to 250° C. in an isochoric reactor for a time sufficient to form a species of polyhydroxyoxoaluminum cation detectable at 76 ppm by  27 Al NMR; or 
 b) at 100° C. at reflux for about 30 days or greater; 
 to form a fourth aluminum salt; and 
   V) optionally adding an aqueous solution containing a zirconium compound to the second pH adjusted aluminum salt solution to thereby obtain a second pH adjusted aluminum-zirconium salt solution having a molar ratio of aluminum to zirconium of 5:1 to 10:1.   
     
     
         20 . The method of  claim 18 , wherein the inorganic salt is at least one chloride salt chosen from calcium chloride, strontium chloride, barium chloride, and yttrium chloride. 
     
     
         21 . The method of  claim 18 , wherein the buffer is glycine. 
     
     
         22 . The method of  claim 18 , wherein the inorganic salt is calcium chloride and the buffer is glycine. 
     
     
         23 . The method of  claim 18 , wherein heating in the isochoric reactor or under hydrothermal reaction is one of
 i) at 100° C. for about 5 days,   ii) at 120° C. for about 12 hours, or   iii) at 150° C. for about 20 minutes.   
     
     
         24 . The method of  claim 18 , wherein the aluminum salt exhibits a SEC chromatogram having a SEC Peak 4 area of at least 90% of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram. 
     
     
         25 . The method of  claim 19 , wherein the buffer is glycine. 
     
     
         26 . The method of  claim 19 , wherein the inorganic base includes at least one member chosen from calcium hydroxide, strontium hydroxide, barium hydroxide, calcium oxide, strontium oxide, barium oxide, calcium carbonate, barium carbonate, strontium carbonate, yttrium hydroxide, yttrium oxide, and yttrium carbonate. 
     
     
         27 . The method of  claim 26 , wherein the inorganic base is calcium hydroxide. 
     
     
         28 . The method of  claim 19 , wherein the second pH adjusted aluminum salt solution has an OH to Al molar ratio of 2:1 to 2.5:1. 
     
     
         29 . The method of  claim 19 , wherein the first aluminum salt is an aluminum chloride compound chosen from aluminum trichloride, aluminum chlorohexahydrate, and aluminum dichlorohydrate. 
     
     
         30 . The method of  claim 19 , wherein the composition further comprises zirconium and step V) is present in the method. 
     
     
         31 . The method of  claim 30 , wherein the zirconium compound is ZrOCl 2 .8H 2 O. 
     
     
         32 . The method of  claim 18 , wherein the  27 Al NMR spectrum has a species distribution including at most 5% Al 13  polyhydroxyoxoaluminum cation in the species detectable by  27 Al NMR within the fourth aluminum salt. 
     
     
         33 . The method of  claim 18 , wherein the fourth aluminum salt has a SEC Peak 4 area of at least 95% of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram. 
     
     
         34 . The method of  claim 18 , wherein the fourth aluminum salt has a SEC Peak 3 area of less than 5% of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram, optionally no SEC Peak 3 area in the SEC chromatogram. 
     
     
         35 . The method of  claim 19 , wherein the third aluminum salt has a SEC Peak 5 area of less than 5% of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram. 
     
     
         36 . The method according to  claim 19 , wherein in step III) the period of time is at least 12 hours. 
     
     
         37 . A method of making a polyhydroxyoxoaluminum cation detectable at 76 ppm by  27 Al NMR comprising storing an aqueous solution containing i) the aluminum salt containing an Al 30  polyhydroxyoxoaluminum cation and having an aluminum to chloride molar ratio of 0.3:1 to 3:1, ii) an inorganic salt, and iii) a buffer, wherein the buffer is at least one of an amino acid, betaine, and quat, and a molar ratio of buffer to aluminum is at least 0.1:1 at a temperature of 15° C. to 60° C. for a period of time until the polyhydroxyoxoaluminum cation detectable at 76 ppm by  27 Al NMR that is present in a relative abundance on a  27 Al NMR spectrograph that is greater than any other polyhydroxyoxoaluminum cation detectable by  27 Al NMR. 
     
     
         38 - 44 . (canceled)