WO2006046945A1 - Activated aluminum/depolymerized zirconium antiperspirant compositions - Google Patents
Activated aluminum/depolymerized zirconium antiperspirant compositions Download PDFInfo
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- WO2006046945A1 WO2006046945A1 PCT/US2004/035006 US2004035006W WO2006046945A1 WO 2006046945 A1 WO2006046945 A1 WO 2006046945A1 US 2004035006 W US2004035006 W US 2004035006W WO 2006046945 A1 WO2006046945 A1 WO 2006046945A1
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- zirconium
- aluminum
- sec
- solution
- hplc
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
- C09C1/407—Aluminium oxides or hydroxides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/28—Zirconium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q15/00—Anti-perspirants or body deodorants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/87—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by chromatography data, e.g. HPLC, gas chromatography
Definitions
- This invention relates to aluminum-zirconium antiperspirant compositions of enhanced efficacy comprising activated aluminum and depolymerized zirconium species and the methods of making said compositions.
- Antiperspirants of enhanced efficacy usually have high SEC-HPLC Band III, with Band III to Band II area ratio of at least 0.5.
- the activation of aluminum is achieved by the dilution and heat treatment of aluminum chlorohydrate (ACH) solution. Heating the more diluted ACH solution for a longer period of time produces an activated aluminum antiperspirant with higher Band III/II ratio.
- the Band III aluminum species are generally very reactive and quickly revert back to Band II aluminum species.
- the activated aluminum solutions are dried to powders in order to preserve their enhanced efficacy.
- GB2048229A describes an activated aluminum salt made by aging or heating from 5% to 40% by weight ACH from 50 0 C to 100 0 C.
- the patent does not disclose any preferred SEC-HPLC profile.
- U.S. Patent No. 4,944,933 discloses a direct process of making activated basic aluminum chlorohydrate solution at 7.5% to 13% by weight having an aluminum to chloride ratio of 1.7:1 to 2.2:1 and a Band III fraction of at least 20%.
- U.S. Patent No. 5,356,609 describes a process of making basic aluminum chloride solution with high Band III of at least 25% by the direct reaction of AlCl 3 solution with Al powder at 50 0 C to 100 0 C and at a concentration of about 8% to about 25% by weight.
- the product has a large amount of Al b species.
- U.S. Patent Publication No. 2004/0101500 Al provides a method of making an activated aluminum salt solution having a ratio of aluminum to chloride ranging from 1.5:1 to 2.0:1 and an aluminum concentration ranging from 0.5% to 3.8% by weight. Heat treatment of the solution is involved.
- the aluminum salt has a ratio of SEC-HPLC Band III to Band II of greater than 3:1.
- Activated aluminum-zirconium antiperspirant salts are produced by the addition of zirconium compounds to the activated aluminum solutions, which are dried to powders due to the fast change of Band III into Band II in solution forms that result in the loss of efficacy of the corresponding salts.
- the introduction of zirconium species into these aluminum salt solutions further depolymerize the aluminum species, which results in a change in the distribution of aluminum species and an increase in efficacy is observed.
- the zirconium species on the other hand, become further polymerized during the process and the effect is more pronounced when activated aluminum solutions are involved.
- Patents describing the preparation of such activated aluminum-zirconium antiperspirant salts include:
- U.S. Patent No. 4,775,528 which discloses an aluminum-zirconium solid composition of enhanced efficacy.
- the process of making includes firstly, heating a 2% to 18% by weight ACH solution at a temperature of at least 50 0 C for a certain period of time, secondly mixing zirconium hydroxy chloride with the solution before, during or after the heat treatment of the diluted ACH solution and thirdly drying the solution to a powder. No differences in the final compositions were observed between addition of the zirconium species to the aluminum solution before, during or after the heat treatment. The sequence of the addition however, has a substantial effect on the degree of polymerization of the zirconium species.
- the aluminum- zirconium salts prepared according to U.S. Patent No. 4,775,528 show a large SEC-HPLC peak 1, which is an indication that the zirconium species are greatly polymerized.
- U.S. Patent No. 4,871,525 teaches a process of making an aluminum-zirconium hydroxy chloride glycinate complex having a peak 4 to peak 3 peak height ratio of 0.5 to 1.8 and peaks (1+2) contain less than 4% of the total distribution by weight.
- the process involves mixing an aqueous zirconyl hydroxychloride solution with an 8% to 35% by weight basic aluminum chloride solution at a temperature of from 50 0 C to 100 0 C for a period of time of less than 2 hours to form a combined solution.
- Zirconium species are further polymerized during the heating process, which can not always be demonstrated by SEC-HPLC profile depending on the types of size exclusion columns involved and the experimental conditions employed.
- U.S. Patent No. 4,900,534 discloses a direct process of making aluminum-zirconium salt by dissolving aluminum metal in an aqueous solution comprising zirconium oxychloride and aluminum chloride at about 50 0 C to 105 0 C.
- the solution of the final aluminum- zirconium chlorohydrate has a concentration of metal of 0.5 to 2.3 moles/Kg and a SEC- HPLC Band III of at least 20%.
- the high temperature treatment polymerizes the zirconium species substantially, which results in the loss of effectiveness of the antiperspirant.
- EU0653203 Al teaches an improved process for making novel zirconium salts which involves mixing zirconium starting material and glycine at ambient temperature and combining said zirconium/glycine aqueous mixture with an aluminum chlorohydrate starting material then rapidly drying the resultant aluminum chlorohydrate/glycine/zirconium mixture.
- U.S. Patent No. 6,375,937 Bl describes an aluminum-zirconium chlorohydrate composition with low metals to chloride ratio of from 0.9 to 1.2 and a glycine to zirconium molar ratio greater than 1.3.
- the active salt can be prepared by three different methods; the mixing of zirconyl chloride with activated ACH salt is one of the disclosed methods.
- the ratio of glycine to zirconium of the said composition is greater than 1.30.
- U.S. Patent No. 6,436,381 Bl discloses enhanced efficacy aluminum-zirconium antiperspirant compositions having SEC-HPLC peak 5 of about 33% or more and an SEC- HPLC peak 4 to peak 3 area ratio of at least 0.4.
- the salt compositions have a low metal to chloride ratio of about 0.9 to about 1.0, which when applied can give rise to skin irritation.
- the enhanced efficacy of aluminum-zirconium antiperspirant salts is generally achieved through the activation of aluminum species and the extent of the activation is characterized by different methods such as SEC-HPLC, 27 Al NMR and Ferron analysis. These methods mostly characterize the aluminum species. There is very little information generally available about the nature and extent of polymerization of the zirconium species in antiperspirant salts. There are limited methods available for the characterization of zirconium species that restricts the understanding of the zirconium chemistry that contributes to the enhanced efficacy of aluminum-zirconium antiperspirant salts.
- aluminum-zirconium antiperspirant salts having increased efficacy comprising both activated aluminum species and depolymerized zirconium complexes.
- Such aluminum-zirconium antiperspirant compositions will provide higher efficacy than the conventional prior art salts heretofore described under the same conditions, such as Al to Zr ratio and metal to chloride ratio content.
- an Inductively Coupled Plasma (ICP) instrument is applied to characterize the extent of the polymerization of zirconium species of activated aluminum-zirconium antiperspirant salts.
- the zirconium species are first separated by Size Exclusion Chromatography (SEC) operated via a High Performance Liquid Chromatograh (HPLC). It was discovered that after SEC-HPLC separation, analysis by ICP revealed a good correlation between the intensity of the zirconium peak at retention time of about 4.3 minutes to 4.9 minutes and the extent of the polymerization of the zirconium species, i.e., the higher the intensity of the zirconium species, the greater their degree of polymerization.
- SEC Size Exclusion Chromatography
- HPLC High Performance Liquid Chromatograh
- the extent of polymerization of the zirconium species in an activated aluminum- zirconium salt is affected by several factors such as (a) the ratio of chloride to zirconium in a zirconium hydroxy chloride (ZHC) solution; (b) the heat treatment of ZHC glycinate solution; and (c) the concentration of the activated basic aluminum chloride (BAC) solution.
- ZHC zirconium hydroxy chloride
- BAC activated basic aluminum chloride
- the activated aluminum-zirconium salt of this invention is prepared by (1) heating a solution of about 15% to 25%, preferably 18% to 22%, by weight, BAC solution having an aluminum to chloride ratio of about 1.5 to about 2.1, preferably from about 1.8 to about 2.0, at a temperature of at least 50 0 C, preferably higher, for a period of time sufficient to yield the desired activation; (2) blending a concentrated ZHC glycinate solution that has been heated at a temperature of greater than 50 0 C with the heated BAC solution at RT, and (3) drying the blended final solution to a powder.
- Fig. 1 is the SEC-HPLC of ZHC solution with Cl/Zr ratio of 1.05.
- Fig. 2 is the SEC-HPLC of ZHC solution with Cl/Zr ratio of 1.27.
- Fig. 3 is the SEC-HPLC of ZHC solution with Cl/Zr ratio of 1.53.
- Fig. 4 is the ICP-SEC-HPLC of ZHC solution with Cl/Zr ratio of 1.05.
- Fig. 5 is the ICP-SEC-HPLC of ZHC solution with Cl/Zr ratio of 1.27 .
- Fig. 6 is the ICP-SEC-HPLC of ZHC solution with Cl/Zr ratio of 1.53.
- Fig. 7 is the SEC-HPLC of ZHC glycinate solution with Cl/Zr ratio of 1.05 at RT.
- Fig. 8 is the SEC-HPLC of ZHC glycinate solution with Cl/Zr ratio of 1.05 at 8O 0 C.
- Fig. 9 is the SEC-HPLC of ZHC glycinate solution with Cl/Zr ratio of 1.05 at reflux.
- Fig. 10 is the SEC-HPLC of ZHC glycinate solution with Cl/Zr ratio of 1.53 at RT.
- Fig. 11 is the SEC-HPLC of ZHC glycinate solution with Cl/Zr ratio of 1.53 at 8O 0 C.
- Fig. 12 is the SEC-HPLC of ZHC glycinate solution with Cl/Zr ratio of 1.53 at reflux.
- Fig. 10 is the SEC-HPLC of ZHC glycinate solution with Cl/Zr ratio of 1.53 at RT.
- Fig. 11 is the SEC-HPLC of ZHC glycinate solution with Cl/Zr ratio of 1.53 at 8O 0 C.
- Fig. 13 is the ICP-SEC-HPLC of ZHC glycinate solution with Cl/Zr ratio of 1.05 at RT.
- Fig. 14 is the ICP-SEC-HPLC of ZHC glycinate solution with ClIZx ratio of 1.05 at RT.
- Fig. 15 is the ICP-SEC-HPLC of ZHC glycinate solution with Cl/Zr ratio of 1.05 at reflux.
- Fig. 16 is the ICP-SEC-HPLC of ZHC glycinate solution with Cl/Zr ratio of 1.53 at RT.
- Fig. 17 is the ICP-SEC-HPLC of ZHC glycinate solution with Cl/Zr ratio of 1.53 at 80 0 C.
- Fig. 18 is the ICP-SEC-HPLC of ZHC glycinate solution with Cl/Zr ratio of 1.53 at reflux.
- Fig. 19 is the ICP-SEC-HPLC of activated Al-Zr powder with M/Cl ratio of 1.13 and with ZHC glycinate solution made at RT .
- Fig. 20 is the ICP-SEC-HPLC of activated Al-Zr powder with M/Cl ratio of 1.25 where ZHC glycinate solution was formed at RT.
- Fig. 21 is the ICP-SEC-HPLC of activated Al-Zr powder with M/Cl ratio of 1.25 where ZHC glycinate solution was formed at 80 0 C.
- Fig. 22 is the SEC-HPLC of activated Al-Zr powder with M/Cl ratio of 1.25 where ZHC glycinate solution was formed at RT.
- Fig. 23 is the SEC-HPLC of activated Al-Zr powder with M/Cl ratio of 1.25 where ZHC glycinate solution was formed at 80 0 C.
- Fig. 24 is the Al NMR of activated Al-Zr powder according to Experiment 8 in Example 2 (Table II).
- the present invention describes enhanced efficacy aluminum-zirconium antiperspirant salt compositions comprising activated aluminum and depolymerized zirconium species.
- the compositions have a SEC-HPLC Band III to II area ratio of at least 0.5, preferably at least 0.7 and most preferably at least 0.9, which are achieved by the heating of 15% to 25% by weight basic aluminum salts having the formula
- BAC solution with aluminum to chloride ratio of about 1.3 to about 2.1 and most preferably from about 1.6 to about 2.0.
- the time of the heating depends on the temperatures, as longer times are usually required at lower temperatures and shorter times at higher temperatures. It is preferred to heat the diluted BAC solutions at 50 0 C, preferably at 80 0 C and most preferably at reflux for at least 2 hours.
- concentration of the BAC solutions has a large effect on the extent of the polymerization of the zirconium species in the activated aluminum-zirconium antiperspirant salt.
- BAC solutions In order to achieve the increased efficacy of the combined salt, it is preferable to have about 15% to about 25% by weight BAC solutions and most preferably about 18% to about 22% by weight of BAC solutions.
- the zirconium hydroxychloride solution can be prepared by the reaction of basic zirconium carbonate with hydrochloric acid or zirconyl chloride at elevated temperature for a certain period of time. It has been found that there is not a substantial difference in the polymerization of the zirconium species in ZHC solution prepared by the above two different methods, especially at higher chloride to zirconium ratio. The conditions of the preparation such as the preparation temperature, heating time and the concentration of the ZHC solutions have greater effects on the polymerization of zirconium species.
- the polymerization of the zirconium species is largely controlled by the chloride to zirconium (Cl/Zr) ratio of the ZHC solutions, i.e., the higher the Cl/Zr ratio the more the depolymerized the zirconium species. It is desirable to have ZHC solutions with Cl/Zr ratio of at least 1, preferably of at least 1.4, and more preferably of at least 1.6.
- the ZHC solutions are further mixed with an amino acid, preferably glycine, at a temperature of about 50 0 C, preferably at about 80 0 C to reflux, for a period of about 1 hour to about 4 hours.
- heating of the ZHC glycinate solutions has a very substantial effect on the degree of polymerization of the zirconium species in the final aluminum-zirconium antiperspirant salt, especially at higher Cl/Zr ratio.
- Heating the ZHC glycinate solution at 80 0 C for 1 hour for example greatly depolymerized the zirconium species, sometimes to a greater extent, even at lower Cl/Zr ratios, than mixing the higher Cl/Zr ratio ZHC glycinate solution at RT.
- the amino acids that may be used include glycine, alanine, lysine, ornithine, citrulline, hydroxyproline, cysteine, threonine, valine, serine, methionine, glutamic acid and the mixtures thereof.
- Glycine is the most preferred amino acid.
- the quantity of glycine is controlled such that the glycine to zirconium molar ratio is of about 1.
- the aluminum-zirconium solution is prepared by mixing the activated BAC solution with heat treated ZHC glycinate solution at RT for a certain period of time generally no more than 1 hour and the final solution is dried to a powder by any appropriate means, including freeze-drying and vacuum drying. Spray drying is the most preferred method.
- the aluminum-zirconium salts thus prepared have a M/Cl ratio of more than 1, and most preferably at least 1.2.
- Aluminum-zirconium antiperspirant salts with very low M/Cl ratios of 1 or less generally have increased efficacy. However, these salts are very difficult to formulate. The difficulties include fragrance stability, yellow color and softness of the stick when these salts are used. They can also be irritating to skin.
- the aluminum-zirconium salts according to the present patent having a M/Cl ratio of 1.2 or above demonstrate increased efficacy from both activated aluminum and depolymerized zirconium species, are easy to formulate and generally more mild to the skin.
- the degree of the polymerization of aluminum complexes is determined by Size Exclusion Chromatography (SEC) operated via a High Performance Liquid Chromatograph (HPLC) instrument.
- SEC Size Exclusion Chromatography
- HPLC High Performance Liquid Chromatograph
- the highest molecular weight Al species are eluted first and are designated as Band I or otherwise called peaks 1 and 2.
- Band II (or peak 3) and Band III (or peak 4) are due to intermediate molecular weight Al complexes.
- Band IV or peak 5 is due to the lowest molecular weight Al complexes, including monomers and dimmers.
- the relative area of one or more peaks is determined in order to characterize the distribution of polymeric species in aluminum complexes formed.
- the aluminum-zirconium antiperspirant salts of the present invention have SEC-HPLC Band III to Band II area ratio of at least 0.5, preferably at least 0.7, and most preferably at least 0.9.
- NMR Nuclear Magnetic Resonance
- a sharp peak at chemical shift of about 0 ppm by 27 Al NMR indicates the presence of monomeric octahedral Al species.
- a sharp peak at about 63 ppm from a tetrahedral aluminum species indicates the presence Al 13 species which contains one tetrahedral Al center. The other 12 octahedral Al centers in this compound have peaks that are too broad to be detected.
- a broad chemical shift at about 72 ppm is also from tetrahedral aluminum species and indicates the presence of Al 41 species. Larger aluminum species usually show chemical shifts that are too broad to be detected.
- the aluminum-zirconium antiperspirant salts of enhanced efficacy comprising activated aluminum and depolymerized zirconium species according to the present invention do not show sharp peaks at about 63 ppm.
- ICP Inductively Coupled Plasma Spectroscopy
- the present invention employs ICP-SEC-HPLC analysis to study the polymerization of zirconium species and the distribution of the aluminum polymers.
- the size exclusion column operated by HPLC has been used to separate the aluminum and zirconium polymers by size.
- the separated species are sent to the ICP instead of a refractive index (RI) detector as in regular HPLC.
- RI refractive index
- the column was conditioned by repeated injections of a 10% aluminum-zirconium tetrachlorohydrex glycine solution until the area of Band I is constant.
- the SEC-HPLC data for aluminum-zirconium salt obtained by using RI detector are sometimes found to be misleading with respect to the distribution of zirconium species as can be seen from Figs. 20 to 23.
- the RI detector is not very sensitive to the zirconium species of aluminum-zirconium antiperspirant salts and secondly the zirconium pealc(s) at retention times between 4.3 minutes to 4.9 minutes overlap with the aluminum peaks Band I and Band II, especially when activated aluminum-zirconium salts are involved.
- the separated species from the SEC column are detected by ICP, discrete zirconium and aluminum peaks are observed.
- the intensity of the zirconium peak(s) at retention times of 4.3 to 4.9 minutes changes with the apparent extent of polymerization of the zirconium species.
- Example 1 Comparison of Basic Aluminum Chloride Solutions Prepared by both Direct and Indirect Methods
- the first is a direct process, which includes the direct reaction of aluminum powder with aluminum chloride solution at elevated temperature.
- the second is an indirect process, which involves heating a diluted BAC solution at above 50 0 C for a certain period of time, preferably at reflux for about 4 hours.
- the following solutions are made by both the direct and indirect processes and their properties are listed in Table I.
- the data indicate that there is a different distribution of aluminum species in the diluted BAC solutions when made by either the direct and indirect process.
- the activated BAC solution made from the direct process contains more Al b species that is not considered to be efficacious as an antiperspirant. It is preferable to make a solution having a concentration of about 15% to 25% by weight solution of activated BAC through the indirect process.
- Three ZHC solutions were made by dissolving basic zirconium carbonate paste in aqueous zirconyl chloride solutions at about 60 0 C until clear.
- the ZHC solutions have zirconium contents of about 20% with ClIZx ratio of 1.53, 1.27 and 1.05, respectively.
- the SEC-HPLC profiles of the three ZHC solutions are illustrated in Figs.l, 2 and 3 with zirconium species eluted at retention time(s) of about 4.5-4.9 minutes and chloride at about 7.5 minutes.
- the solutions were also analyzed by ICP-SEC-HPLC and the chromatograms are shown in Figs. 4, 5 and 6.
- the ZHC solutions with Cl/Zr ratios of 1.53, 1.27 and 1.05 prepared above were mixed with glycine at glycine to zirconium molar ratio of about 1.
- the ZHC glycinate solutions were then mixed at RT for 2 hours, 80 0 C for an hour and refluxed for 2 hours, respectively.
- the solutions were subjected to both SEC-HPLC and ICP-SEC-HPLC.
- Example 5 Effects of MJCl Ratio and Heat Treatment of ZHC Glycinate Solutions on the Polymerization of Zirconium Species of the Activated Al-Zr Antiperspirant Salts
- Four activated Al-Zr antiperspirant powders were prepared with M/Cl ratios of 1.13,
- ICP-SEC-HPLC and SEC-HPLC profiles of the activated Al-Zr AP powders at M/Cl ratios of 1.13 and 1.25 from ZHC glycinate solutions formed at both RT and 80 0 C are illustrated in Figs. 19 through 23.
- the data further support that zirconium species depolymerize at lower M/Cl ratios such as 1.13 and that a similar extent of depolymerization of the zirconium species can be achieved at higher M/Cl ratios such as 1.25 by the heat treatment of ZHC glycinate solutions.
- the ICP-SEC-HPLC data also indicate that the SEC- HPLC Bands I, II and III can be misleading with respect to the concentration of aluminum species.
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2004324474A AU2004324474A1 (en) | 2004-10-22 | 2004-10-22 | Activated aluminum/depolymerized zirconium antiperspirant compositions |
CN200480044685.4A CN101087582A (zh) | 2004-10-22 | 2004-10-22 | 活化的铝/解聚的锆止汗剂组合物 |
EP04796066A EP1814508A1 (en) | 2004-10-22 | 2004-10-22 | Activated aluminum/depolymerized zirconium antiperspirant compositions |
PCT/US2004/035006 WO2006046945A1 (en) | 2004-10-22 | 2004-10-22 | Activated aluminum/depolymerized zirconium antiperspirant compositions |
CA002586725A CA2586725A1 (en) | 2004-10-22 | 2004-10-22 | Activated aluminum/depolymerized zirconium antiperspirant compositions |
MX2007006141A MX2007006141A (es) | 2004-10-22 | 2004-10-22 | Composiciones antitranspirantes de aluminio activado-zirconio despolimerizado. |
Applications Claiming Priority (1)
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PCT/US2004/035006 WO2006046945A1 (en) | 2004-10-22 | 2004-10-22 | Activated aluminum/depolymerized zirconium antiperspirant compositions |
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WO2006046945A1 true WO2006046945A1 (en) | 2006-05-04 |
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PCT/US2004/035006 WO2006046945A1 (en) | 2004-10-22 | 2004-10-22 | Activated aluminum/depolymerized zirconium antiperspirant compositions |
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EP (1) | EP1814508A1 (zh) |
CN (1) | CN101087582A (zh) |
AU (1) | AU2004324474A1 (zh) |
CA (1) | CA2586725A1 (zh) |
MX (1) | MX2007006141A (zh) |
WO (1) | WO2006046945A1 (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9174851B2 (en) | 2011-04-26 | 2015-11-03 | Colgate-Palmolive Company | Compositions containing polyhydroxyoxoaluminum cations and manufacture thereof |
US9408789B2 (en) | 2011-04-26 | 2016-08-09 | Colgate-Palmolive Company | Antiperspirant active compositions and manufacture thereof |
US9463985B2 (en) | 2010-11-02 | 2016-10-11 | Colgate-Palmolive Company | Aluminum salt containing high percentage of Al30 |
US9539188B2 (en) | 2010-11-02 | 2017-01-10 | Colgate-Palmolive Company | Antiperspirant active compositions and manufacture thereof |
EP2361078B1 (de) * | 2008-12-22 | 2019-01-30 | Henkel AG & Co. KGaA | TRANSPARENTE SCHWEIßHEMMENDE GELE |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6375937B1 (en) * | 2000-10-20 | 2002-04-23 | Colgate-Palmolive Company | Antiperspirant salts for enhanced cosmetic products |
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2004
- 2004-10-22 AU AU2004324474A patent/AU2004324474A1/en not_active Abandoned
- 2004-10-22 CA CA002586725A patent/CA2586725A1/en not_active Abandoned
- 2004-10-22 WO PCT/US2004/035006 patent/WO2006046945A1/en active Application Filing
- 2004-10-22 MX MX2007006141A patent/MX2007006141A/es unknown
- 2004-10-22 EP EP04796066A patent/EP1814508A1/en not_active Withdrawn
- 2004-10-22 CN CN200480044685.4A patent/CN101087582A/zh active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6375937B1 (en) * | 2000-10-20 | 2002-04-23 | Colgate-Palmolive Company | Antiperspirant salts for enhanced cosmetic products |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2361078B1 (de) * | 2008-12-22 | 2019-01-30 | Henkel AG & Co. KGaA | TRANSPARENTE SCHWEIßHEMMENDE GELE |
US9463985B2 (en) | 2010-11-02 | 2016-10-11 | Colgate-Palmolive Company | Aluminum salt containing high percentage of Al30 |
US9539188B2 (en) | 2010-11-02 | 2017-01-10 | Colgate-Palmolive Company | Antiperspirant active compositions and manufacture thereof |
US10118832B2 (en) | 2010-11-02 | 2018-11-06 | Colgate-Palmolive Company | Aluminum salt containing high percentage of Al30 |
US9174851B2 (en) | 2011-04-26 | 2015-11-03 | Colgate-Palmolive Company | Compositions containing polyhydroxyoxoaluminum cations and manufacture thereof |
US9408789B2 (en) | 2011-04-26 | 2016-08-09 | Colgate-Palmolive Company | Antiperspirant active compositions and manufacture thereof |
US9717663B2 (en) | 2011-04-26 | 2017-08-01 | Colgate-Palmolive Company | Antiperspirant active compositions and manufacture thereof |
Also Published As
Publication number | Publication date |
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CN101087582A (zh) | 2007-12-12 |
AU2004324474A1 (en) | 2006-05-04 |
MX2007006141A (es) | 2007-07-19 |
EP1814508A1 (en) | 2007-08-08 |
CA2586725A1 (en) | 2006-05-04 |
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