Betaine with Calcium and/or Strontium Antiperspirants
Aluminum and aluminum-zirconium antiperspirant compositions comprising basic aluminum chlorides that have a particular molecular size distribution defined by having an SEC-HPLC Band III/II ratio of at least 0.5, having SEC-HPLC Band III plus Band II area of at least 70% of the total area and having SEC-HPLC Band I content no more than 5% and containing betaine (trimethylglycine), calcium and/or strontium are disclosed. Also disclosed are the methods of making these compositions and the use thereof in consumer acceptable antiperspirant vehicles such as aerosols, gels, roll-on, sticks and soft solids.
1 . An aqueous antiperspirant active solution comprising the reaction product of:
i. a basic aluminum chloride (BAC), having the empirical formula
Al 2 (OH) 6−a Cl a
where a is a number from about 1.2 to 2.0, in amounts of from about 10 to 50% by weight;
ii. betaine (trimethylglycine) in amounts of from about 2% to 15% by weight; and
iii. a metal ion selected from calcium, strontium and mixtures thereof in amounts of from about of 0.2% to 6% by weight; and
having an SEC-HPLC Band III to Band II area ratio of at least 0.5, having SEC-HPLC Band III plus Band II area of at least 70% of the total area and having SEC-HPLC Band I content of no more than 5%.
2 . The antiperspirant active solution of claim 1 wherein a is from 1.4 to 1.8.
3 . The antiperspirant active solution of claim 1 wherein the BAC is from about 30 to 50% by weight.
4 . The antiperspirant active solution of claim 1 wherein the SEC-HPLC Band III to Band II area ratio is at least 0.7.
5 . The antiperspirant active solution of claim 1 wherein betaine is present in amounts of from about 4% to 10% by weight.
6 . The antiperspirant active solution of claim 1 wherein a calcium is present in amounts of from about 1% to 2.5% by weight.
7 . The antiperspirant active solution of claim 1 wherein the calcium is selected from the group consisting of calcium chloride, calcium nitrate, calcium bromide, calcium citrate, calcium formate, calcium acetate, calcium ascorbate, calcium lactate, calcium carbonate, calcium sulfate, calcium hydroxide, calcium oxide and the mixture thereof.
8 . The antiperspirant active solution of claim 1 wherein a strontium is present in amounts of from about 1.5% to 3% by weight.
9 . The antiperspirant active solution of claim 1 wherein the strontium is selected from the group consisting of strontium chloride, strontium nitrate, strontium bromide, strontium citrate, strontium formate, strontium acetate, strontium ascorbate, strontium lactate, strontium carbonate, strontium sulfate, strontium hydroxide, strontium oxide and the mixture thereof.
10 . An antiperspirant powder obtained by spray drying the solution of claim 1 .
11 . A method of making the antiperspirant active solution of claim 1 comprising reacting a basic aluminum salt, betaine and a salt selected from those of calcium, strontium and mixtures thereof by a process selected from
(1) heating a solution from about 10% to about 50% by weight of a basic aluminum salt of the empirical formula
Al 2 (OH) 6−a Cl a
wherein a is from about 1.2 to 2.0, from about 2% to 15% by weight of betaine, and salts selected from those of calcium, strontium and mixtures thereof from about of 0.5% to 15% by weight at a temperature of from 40° C. to about reflux for a period of time from about 1 hour to about 7 days;
(2) reacting Sr(OH) 2 with AlCl 3 or HCl aqueous solution, adding betaine, then reacting with Al powder from about 50° C. to about reflux for a period of time from about 1 hour to about 24 hours to afford a final solution from about 10% to about 50% by weight of a basic aluminum salt of the empirical formula
Al 2 (OH) 6−a Cl a
wherein a is from about 1.2 to 2.0, from about 2% to 10% by weight of betaine, and 0.5-2.5% by weight of strontium;
(3) reacting CaO with AlCl 3 or HCl aqueous solution, adding betaine, then reacting with Al powder from about 50° C. to about reflux for a period of time from about 1 hour to about 24 hours to afford a final solution from about 10% to about 50% by weight of a basic aluminum salt of the empirical formula
Al 2 (OH) 6−a Cl a
wherein a is from about 1.2 to 2.0, from about 2% to 10% by weight of betaine, and 0.2-1.5% by weight of calcium; and
(4) reacting Al powder with AlCl 3 or HCl aqueous solution in the presence of from about 2% to 15% by weight of betaine, and a calcium and/or strontium salt from about of 0.2% to 15% by weight from about 50° C. to about reflux for a period of time from about 1 hour to about 24 hours to afford a solution from about 10% to about 50% by weight of a basic aluminum salt of the empirical formula
Al 2 (OH) 6−a Cl a
wherein a is from about 1.2 to 2.0;
resulting in the said solution having an SEC-HPLC Band III to Band II area ratio of at least 0.5, having SEC-HPLC Band III plus Band II area of at least 70% of the total area and having SEC-HPLC Band I content no more than 5%.
12 . The method of claim 11 wherein the aluminum to chloride atomic ratio of the resulting BAC solution is from 1.4 to 1.8.
13 . The method of claim 11 wherein the resulting solution comprises from about 30% to 50% by weight BAC.
14 . The method of claim 11 wherein the SEC-HPLC Band III to Band II area ratio is at least 0.7.
15 . The method of claim 11 wherein betaine is present in amounts of about 4% to 10% by weight.
16 . The method of claim 11 wherein the heating, in the process (1) is conducted at reflux for at least 2 hours.
17 . The method of claim 11 wherein calcium in the solution of processes (1) and (4) is present in amounts of from about 1% to 2.5% by weight.
18 . The method of claim 11 wherein in the processes of (1) and (4) the source of calcium is selected from the group consisting of calcium chloride, calcium nitrate, calcium bromide, calcium citrate, calcium formate, calcium acetate, calcium ascorbate, calcium lactate, calcium sulfate and the mixture thereof.
19 . The method of claim 11 wherein in the solutions of (1) and (4), the strontium is present in amounts of about 1.5% to 3% by weight.
20 . The method of claim 11 wherein the source of strontium in process (1) and process (4) is selected from the group consisting of strontium chloride, strontium nitrate, strontium bromide, strontium citrate, strontium formate, strontium acetate, strontium ascorbate, strontium lactate, strontium sulfate and the mixture thereof.
21 . The method of claim 11 wherein 1% to 2% by weight of strontium is present in the resulting solution of process (2).
22 . The method of claim 11 wherein the source of strontium in process (2) is selected from strontium carbonate, strontium hydroxide and the mixture thereof.
23 . The method of claim 11 wherein 0.4% to 1% by weight of calcium is present in the resulting solution of process (3).
24 . The method of claim 11 wherein the source of calcium in process (3) is selected from calcium hydroxide, calcium carbonate, calcium oxide and the mixture thereof.
25 . The method of claim 11 wherein the final solution is dried to a powder.
26 . An aqueous aluminum-zirconium antiperspirant active solution comprising the reaction product of:
(A) i. a basic aluminum chloride (BAC), having the empirical formula
Al 2 (OH) 6−a Cl a
where a is a number from about 1.2 to 2.0, in amounts of from about 10 to 50% by weight;
ii. betaine (trimethylglycine) in amounts of from about 2% to 15% by weight; and
iii. a metal ion selected from calcium, strontium and mixtures thereof in amounts of from about of 0.2% to 6% by weight;
having an SEC-HPLC Band III to Band II area ratio of at least 0.5, having SEC-HPLC Band III plus Band II area of at least 70% of the total area and having SEC-HPLC Band I content of no more than 5%;
(B) from about 15% to about 40% by weight a zirconium compound of the formula
ZrO(OH) b Cl c
wherein b is a numerical number from 0 to 1 and c is at least 1; and
the resulting solution having from about 1% to 10% by weight betaine (trimethylglycine) and from about of 0.2% to 5% by weight of a metal selected from calcium, strontium and mixtures thereof.
27 . The antiperspirant active solution of claim 26 wherein the c for the zirconium compound is at least 1.4.
28 . The antiperspirant active solution of claim 26 wherein the betaine to zirconium molar ratio is between about 0.5 and 2.
29 . The antiperspirant active solution of claim 26 wherein the betaine to zirconium molar ratio is about 1.
30 . The antiperspirant active solution of claim 26 wherein the M/Cl ratio is from about 0.9 to about 1.7 where M=Al+Zr.
31 . The antiperspirant active solution of claim 26 wherein the M/Cl ratio is between about 1 to 1.4.
32 . The antiperspirant active solution of claim 26 wherein the Al/Zr ratio is between about 2 to about 10.
33 . The antiperspirant active solution of claim 26 wherein the Al—Zr composition is a tetra-salt.
34 . The antiperspirant active solution of claim 26 wherein the Al—Zr composition is an octa-salt.
35 . The antiperspirant active solution of claim 26 having an SEC-HPLC Band III to Band II area ratio of at least 0.7.
36 . The antiperspirant active solution of claim 26 wherein the final solution is dried to a powder.
37 . A method of making an aqueous aluminum—zirconium antiperspirant active solution comprising reacting:
(A) the reaction product of:
i. a basic aluminum chloride (BAC), having the empirical formula
Al 2 (OH) 6−a Cl a
where a is a number from about 1.2 to 2.0, in amounts of from about 10 to 50% by weight;
ii. betaine (trimethylglycine) in amounts of from about 2% to 15% by weight; and
iii. a metal calcium, ion selected from strontium and mixtures thereof in amounts of from about of 0.2% to 6% by weight;
having an SEC-HPLC Band III to Band II area ratio of at least 0.5, having SEC-HPLC Band III plus Band II area of at least 70% of the total area and having SEC-HPLC Band I content of no more than 5%;
(B) from about 15% to about 40% by weight a zirconium compound of the formula
ZrO(OH) b Cl c
wherein b is a numerical number from 0 to 1 and c is at least 1; and
the resulting solution having from about 1% to 10% by weight betaine (trimethylglycine) and from about of 0.2% to 5% by weight of a metal selected from calcium, strontium and mixtures thereof.
38 . A topical antiperspirant composition in the form of a pump spray, roll-on, lotion, cream, or gel comprising an antiperspirant compositions according to claim 1 .
39 . A topical antiperspirant composition in the form of a pump spray, roll-on, lotion, cream, or gel comprising an antiperspirant compositions according to claim 26 .
40 . A topical antiperspirant composition in the form of an aerosol, roll-on or stick comprising an antiperspirant compositions according to claim 10 .
41 . A topical antiperspirant composition in the form of a stick or roll-on comprising an antiperspirant compositions according to claim 36.