High pH antiperspirant compositions of enhanced efficacy
View Patent ↗Aluminum and aluminum-zirconium antiperspirant compositions of enhanced efficacy and a pH value of at least 3.5 are provided that are made by reaction with insoluble, strongly alkaline strontium or calcium salts. The aluminum and aluminum-zirconium strontium or calcium compositions show high pH values with characteristic HPLC Band III to Band II ratios of at least 0.5. The basic aluminum halohydrate (or nitrate) solutions typically have aluminum to anion ratio of less that 1.9. The solution compositions are stable with respect to both HPLC Band III to Band II ratio and viscosity at concentrations of about 20% to about 40% by weight of anhydrous solid. The solid state compositions form hard sticks with low irritation, at low metal to chloride ratios of about 0.9 to about 1.2.
1. A method of making an antiperspirant liquid composition having improved efficacy and a pH value of at least 3.5 when dissolved as 15% by weight aqueous solution and wherein the composition comprises an antiperspirant active selected from
(i) basic aluminum salts having the formula
Al 2 (OH) 6-a X a
wherein X is Cl, Br, I or NO 3 , a is from about 1.1 to about 6, at a concentration of about 20% to about 40% by weight of anhydrous solid and having an aluminum to anion mole ratio of about 1.0 to about 1.8 and
(ii) aluminum-zirconium salts having an Al:Zr ratio of from about 2:1 to about 10:1 that are obtained by adding to the salts of formula (i) a zirconium compound selected from those having the formula
ZrO(OH) b X 2-b
wherein b is a number from 0 to 1.2, and X is Cl, Br, I or NO 3 ,
the steps comprising:
(1) treating the aqueous reaction mixture of said antiperspirant active with from about 0.1% to about 2% by weight of an additive selected from the group consisting of strongly alkaline water insoluble calcium and strontium compounds and mixtures thereof, and
(2) mixing and reacting said mixture, wherein said additive is activated by contact with said antiperspirant active, until a stable solution with respect to HPLC Band III and Band II area ratio of at least 0.5 is obtained.
2. The method of claim 1 wherein the reacting step (2) is maintained until an HPLC Band III and Band II area ratio of at least 0.7 is obtained.
3. The method of claim 1 wherein the antiperspirant comprises the basic aluminum salts of formula (i).
4. The method of claim 1 wherein the antiperspirant composition comprises the aluminum-zirconium salts of formula (ii).
5. The method of claim 4 wherein the reaction of step (2) is maintained until an HPLC Band III and Band II area ration of at least 0.9 is obtained.
6. The method of claim 3 wherein the reacted liquid composition contains from about 25% to about 35% by weight of the salt.
7. The method of claim 3 wherein the reacted liquid composition contains from about 25% to about 35% by weight salt and up to about 8% by weight of an amino acid.
8. The method of claim 4 wherein the reacted liquid composition contains from about 25% to about 35% by weight salt and up to about 8% by weight of an amino acid.
9. The method of claim 4 wherein the reacted liquid composition contains from about 25% to about 35% by weight salt and from about 3% to about 6% by weight of an amino acid.
10. The method of claim 1 wherein the insoluble, strongly alkaline compound is selected from strontium hydroxide, strontium oxide, calcium oxide, calcium hydroxide and mixtures thereof.
11. The method of claim 7 wherein the amino acid is glycine.
12. The method of claim 8 wherein the amino acid is glycine.
13. The method of claim 4 wherein a basic aluminum halohydrate (or nitrate) is reacted with calcium oxide and a zirconium compound in the presence of glycine.
14. The method of claim 4 including reacting a basic aluminum halohydrate (or nitrate) solution with calcium oxide and a zirconium hydroxyhalohydrate (or nitrate) glycinate solution at a temperature of from about room temperature to about reflux temperature.
15. The method of claim 4 wherein the zirconium compound (ii) is reacted with calcium oxide at a temperature of from about room temperature to about reflux temperature, adding a polyhydric alcohol to the solution and mixing the solution with basic aluminum halohydrate (or nitrate) for a period of time sufficient to provide the enhanced efficacy salt.
16. The method of claim 1 wherein the resultant stable solution from step (2) is dried to a powder form.
17. The method of claim 3 wherein the resultant stable solution form step (2) is spray dried.
18. The method of claim 4 wherein the resultant stable solution from step (2) is spray dried.
19. The method of claim 17 wherein from about 5% to about 25% of the spray dried product is admixed with a silicone oil and an aliphatic alcohol; heated until a homogenous blend is obtained, poured into a stick-antiperspirant mold form and solidified.
20. The method of claim 18 wherein from about 5% to about 25% of the spray dried product is admixed with a silicone oil and an aliphatic alcohol; heated until a homogenous blend is obtained, poured into a stick-antiperspirant mold form and solidified.
21. A product obtained by the method of claim 1 .
22. A product obtained by the method of claim 3 .
23. A product obtained by the method of claim 4 .
24. A product obtained by the method of claim 6 .
25. A product obtained by the method of claim 7 .
26. A product obtained by the method of claim 8 .
27. A product obtained by the method of claim 9 .
28. A product obtained by the method of claim 10 .
29. A product obtained by the method of claim 11 .
30. A product obtained by the method of claim 12 .
31. A product obtained by the method of claim 13 .
32. An aluminum-zirconium antiperspirant composition prepared with calcium oxide according to claim 4 wherein the reaction of step (2) is maintained until a product having a metal to chloride ratio of from about 1.0 to about 1.2 and a pH of at least 3.5 is obtained.