WO2012148481A1 - Compositions containing polyhydroxyoxoaluminum cations and manufacture thereof - Google Patents
Compositions containing polyhydroxyoxoaluminum cations and manufacture thereof Download PDFInfo
- Publication number
- WO2012148481A1 WO2012148481A1 PCT/US2011/066018 US2011066018W WO2012148481A1 WO 2012148481 A1 WO2012148481 A1 WO 2012148481A1 US 2011066018 W US2011066018 W US 2011066018W WO 2012148481 A1 WO2012148481 A1 WO 2012148481A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- aluminum
- nmr
- buffer
- ppm
- molar ratio
- Prior art date
Links
- 150000001768 cations Chemical class 0.000 title claims abstract description 71
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 54
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 48
- 239000000872 buffer Substances 0.000 claims description 48
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 23
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 20
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 150000001413 amino acids Chemical class 0.000 claims description 16
- 239000004471 Glycine Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 15
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 13
- 150000007529 inorganic bases Chemical class 0.000 claims description 11
- 229960003237 betaine Drugs 0.000 claims description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000920 calcium hydroxide Substances 0.000 claims description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 10
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 claims description 9
- -1 aluminum monochlorohydrate Chemical compound 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 4
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- XILPPDQAWPSZIL-UHFFFAOYSA-H dialuminum;dichloride;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Cl-].[Cl-] XILPPDQAWPSZIL-UHFFFAOYSA-H 0.000 claims description 4
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 4
- CJGYQECZUAUFSN-UHFFFAOYSA-N oxygen(2-);tin(2+) Chemical compound [O-2].[Sn+2] CJGYQECZUAUFSN-UHFFFAOYSA-N 0.000 claims description 4
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 4
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 4
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 4
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 claims description 4
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 4
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 claims description 4
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- 150000003841 chloride salts Chemical class 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 3
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 3
- 150000003755 zirconium compounds Chemical class 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 238000004910 27Al NMR spectroscopy Methods 0.000 abstract 3
- 238000005481 NMR spectroscopy Methods 0.000 description 50
- 239000000463 material Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000001166 anti-perspirative effect Effects 0.000 description 8
- 239000003213 antiperspirant Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical compound [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- YXZZLAMCXFHTTE-UHFFFAOYSA-N aluminum;propane-1,2-diol;trihypochlorite;hydrate Chemical compound O.[Al+3].Cl[O-].Cl[O-].Cl[O-].CC(O)CO YXZZLAMCXFHTTE-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000003754 zirconium Chemical class 0.000 description 2
- HRSYWPMGIIAQIW-UHFFFAOYSA-N 5-bromo-2,3-dihydro-1,4-benzodioxine-7-carbaldehyde Chemical compound O1CCOC2=C1C=C(C=O)C=C2Br HRSYWPMGIIAQIW-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZGUQGPFMMTZGBQ-UHFFFAOYSA-N [Al].[Al].[Zr] Chemical compound [Al].[Al].[Zr] ZGUQGPFMMTZGBQ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003212 astringent agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/021—After-treatment of oxides or hydroxides
- C01F7/026—Making or stabilising dispersions
-
- 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
- A61K8/26—Aluminium; 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
- A61K8/19—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
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/58—Metal complex; Coordination compounds
-
- 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
- C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
-
- 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
- the present invention is directed to compositions containing polyhydroxyoxoaluminum cations and manufacture thereof. These aluminum materials can be used for antiperspirant salts, water treatment, wastewater treatment, dye mordants, taste astringents, and clay pillaring.
- ZAG ZAG complexes
- AZG ZAG complexes
- AI13 is composed of 12 octahedrally coordinated Al atoms surrounded by one centrally-cited Al atom which is tetrahedrally coordinated.
- the AI30 polyhydroxyoxoaluminum cation is essentially a dimer of the AI13 polyhydroxyoxoaluminum cation and contains 2 tetrahedrally coordinated Al atoms which resonate at 70 ppm.
- Al NMR spectroscopy may not fully elucidate the chemical composition of a partially neutralized Al salt solution, since there may be a variety of Al species that do not give rise to sharp and unambiguous resonance peaks. These species can be considered
- Figure 1 is a 27 Al NMR spectrograph of material 1 from the examples before heating.
- composition comprising a
- polyhydroxyoxoaluminum cation 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
- the buffer is glycine.
- the inorganic salt is at least one chloride salt chosen from calcium chloride, magnesium chloride, strontium chloride, barium chloride, stannous chloride, and yttrium chloride.
- the inorganic base includes at least one member chosen from calcium hydroxide, magnesium hydroxide, strontium hydroxide, barium hydroxide, stannous hydroxide, yttrium hydroxide, calcium oxide, magnesium oxide, strontium oxide, barium oxide, stannous oxide, yttrium oxide, calcium carbonate, magnesium carbonate, strontium carbonate, barium carbonate, stannous carbonate, and yttrium carbonate.
- the inorganic base is calcium hydroxide.
- the inorganic base is calcium hydroxide.
- the first aluminum salt is an aluminum chloride compound chosen from aluminum trichloride, aluminum chlorohexahydrate, aluminum dichlorohydrate, and aluminum monochlorohydrate.
- the composition further comprises zirconium.
- the zirconium compound may be ZrOCl 2 -8H 2 0 or Oxo-Hexameric Zirconium-Octaamino Acid.
- the present invention further provides a composition produced by the method of the invention or the use of the invention.
- Al NMR visible species that have known structures, such as AI13 and AI30
- the inorganic salt and buffer help to stabilize the species of polyhydroxyoxoaluminum
- the inorganic salt is at least one chloride salt chosen from calcium chloride, strontium chloride, barium chloride, magnesium chloride, stannous chloride, and yttrium chloride.
- the salt is calcium chloride.
- the buffer is glycine. In certain embodiments, the inorganic salt is calcium chloride and the buffer is glycine.
- the Al 30 containing compositions may be made in a variety of ways involving a stepwise procedure to neutralize aluminum chloride in solution (optionally buffered) using inorganic basic salts.
- the procedure generally includes the step of heating an aqueous solution containing an aluminum chloride compound (optionally with a buffer agent) at a temperature of 50°C to 100°C, optionally 50°C to 95°C, for a period of time of 1 hour to 6 hours.
- the heating may be under stirring, such as vigorous stirring, or under reflux.
- an aqueous solution containing an aluminum chloride compound and a buffer agent is heated at a temperature of 75°C to 95°C to reflux for a period of time of 2 hours to 4 hours.
- the temperature is 95°C under vigorous stirring for a period of time of 2.5 hours.
- an aqueous solution of an inorganic base is added to the heated solution to thereby obtain a pH adjusted aluminum salt solution having a hydroxide to aluminum molar ratio of 1 : 1 to 4 : 1 , and a pH of 2 to 5.
- the hydroxide to aluminum molar ratio of 2: 1 to 3 1.
- the hydroxide to aluminum molar ratio is 2.1 : 1 to 2.6: 1.
- the inorganic base can be at least one base chosen from metal hydroxides, calcium hydroxide, magnesium hydroxide, strontium hydroxide, barium hydroxide, stannous hydroxide, yttrium hydroxide, calcium oxide, magnesium oxide, strontium oxide, barium oxide, stannous oxide, yttrium oxide, calcium carbonate, magnesium carbonate, strontium carbonate, barium carbonate, stannous carbonate, and yttrium carbonate.
- metal hydroxides calcium hydroxide, magnesium hydroxide, strontium hydroxide, barium hydroxide, stannous hydroxide, yttrium hydroxide, calcium oxide, magnesium oxide, strontium oxide, barium oxide, stannous oxide, yttrium oxide, calcium carbonate, magnesium carbonate, strontium carbonate, barium carbonate, stannous carbonate, and yttrium carbonate.
- the inorganic base is calcium hydroxide.
- the addition of calcium hydroxide provides an aqueous solution having a Ca(OH) 2 : glycine molar ratio of at least 0.1 : 1.
- the present invention provides for aluminum compositions and/or aluminum-zirconium compositions having high levels of low molecular weight Al and Zr species.
- the high levels of low molecular weight Al and Zr species is reflected in a SEC trace that has an intense Peak 4 and low Peaks 1, 2, 3 and 5.
- the polymerization of the aluminum species in aqueous solutions and the correspondent gelation process are followed by monitoring the molecular weight profile of the polyoxohalides in time by SEC.
- the relative retention time (“Kd”) for each of these peaks varies depending on the experimental conditions, but the peaks remain relative to each other.
- fpi is the fraction of peak i
- Pi or Pj are the intensity of peaks Pi or Pj, respectively.
- the amount of low molecular weight Al species will be correlated with the fraction, f P4 , or percentage, f P4 xlOO, of SEC-Peak 4.
- a preferred aluminum species would have a very low fpi , fp2, fp3, and/or f P5 , and a high f P4 .
- the ratio of Peak 4 to Peak 3 is at least 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, or any number up to infinity.
- Peak 3 is so low as to be undetectable.
- an aluminum salt and/or aluminum-zirconium salt, in aqueous solution exhibit a SEC profile wherein the SEC Peak 4 to Peak 3 intensity ratio is even as high as infinity, because the Peak 3 is undetectable.
- the percentage of SEC Peak 4 of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram is: at least at least 90%; at least 95%, or 95 to 100%. In another such embodiment, the SEC Peak 4 area is 100%.
- the aluminum salt and/or the aluminum-zirconium salt, in aqueous solution exhibits a SEC profile which exhibits a low percentage of SEC Peak 1 and a low percentage of SEC Peak 2.
- the percentage of SEC Peak 1 area of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram is less than 5 %; less than 2 %; or less than 1 %, or the salt has no SEC Peak 1 area.
- the percentage of SEC Peak 2 area of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram is less than 5 %; less than 2 % or less than 1 %; or the salt has no SEC Peak 2 area.
- compositions of this invention may be used to formulate many different aluminum containing materials. Examples include, but are not limited to, antiperspirant salts, water treatment, wastewater treatment, and clay pillaring.
- Two materials prepared in accordance with PCT/US2010/55030 are provided.
- the materials are aqueous systems that contain the glycine buffer and the calcium chloride byproduct of the manufacturing process.
- Material 1 is held at reflux for 30 days at 100°C.
- Material 2 is subjected to 100°C for 5 days in an isochoric reaction vessel.
- the following discussion relates only with the relative integrations instead of raw data.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Geology (AREA)
- Dispersion Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
- Steroid Compounds (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MX2013012371A MX361821B (en) | 2011-04-26 | 2011-12-20 | Compositions containing polyhydroxyoxoaluminum cations and manufacture thereof. |
ES11810736.6T ES2569856T3 (en) | 2011-04-26 | 2011-12-20 | Compositions containing polyhydroxyoxuminium cations and manufacturing thereof |
BR112013024919A BR112013024919A2 (en) | 2011-04-26 | 2011-12-20 | compositions containing polyhydroxy oxoaluminum cations and manufacture thereof |
US14/110,723 US9174851B2 (en) | 2011-04-26 | 2011-12-20 | Compositions containing polyhydroxyoxoaluminum cations and manufacture thereof |
CA2834129A CA2834129A1 (en) | 2011-04-26 | 2011-12-20 | Compositions containing polyhydroxyoxoaluminum cations and manufacture thereof |
EP11810736.6A EP2702008B1 (en) | 2011-04-26 | 2011-12-20 | Compositions containing polyhydroxyoxoaluminum cations and manufacture thereof |
AU2011366871A AU2011366871B2 (en) | 2011-04-26 | 2011-12-20 | Compositions containing polyhydroxyoxoaluminum cations and manufacture thereof |
RU2013152256/05A RU2013152256A (en) | 2011-04-26 | 2011-12-20 | COMPOSITIONS CONTAINING POLYHYDROXYOXOALUMINUM CATION, AND THEIR PRODUCTION |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161479081P | 2011-04-26 | 2011-04-26 | |
US61/479,081 | 2011-04-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012148481A1 true WO2012148481A1 (en) | 2012-11-01 |
Family
ID=45498118
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2011/066018 WO2012148481A1 (en) | 2011-04-26 | 2011-12-20 | Compositions containing polyhydroxyoxoaluminum cations and manufacture thereof |
Country Status (12)
Country | Link |
---|---|
US (1) | US9174851B2 (en) |
EP (1) | EP2702008B1 (en) |
AR (1) | AR086120A1 (en) |
AU (1) | AU2011366871B2 (en) |
BR (1) | BR112013024919A2 (en) |
CA (1) | CA2834129A1 (en) |
CL (1) | CL2013003093A1 (en) |
CO (1) | CO6801753A2 (en) |
ES (1) | ES2569856T3 (en) |
MX (1) | MX361821B (en) |
RU (1) | RU2013152256A (en) |
WO (1) | WO2012148481A1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016066527A1 (en) | 2014-10-27 | 2016-05-06 | Unilever Plc | Anhydrous antiperspirant compositions |
WO2017076562A1 (en) | 2015-11-06 | 2017-05-11 | Unilever Plc | Antiperspirant compositions |
US9775791B2 (en) | 2013-05-20 | 2017-10-03 | Conopco, Inc. | Method of manufacture of antiperspirant salts |
EP2999452B1 (en) | 2013-05-20 | 2017-12-13 | Unilever PLC | Antiperspirant compositions |
US9867765B2 (en) | 2014-11-19 | 2018-01-16 | Conopco, Inc. | Antiperspirant compositions |
US10098821B2 (en) | 2014-11-19 | 2018-10-16 | Conopco, Inc. | Process of manufacture of an antiperspirant composition |
US10117814B2 (en) | 2014-10-27 | 2018-11-06 | Conopco, Inc. | Anhydrous antiperspirant aerosol compositions |
US10682293B2 (en) | 2015-11-06 | 2020-06-16 | Conopco, Inc. | Aerosol antiperspirant product |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006103092A1 (en) | 2005-03-31 | 2006-10-05 | Unilever Plc | Process of preparing aluminium species |
US20100055030A1 (en) | 2006-11-27 | 2010-03-04 | Naohiko Matsuda | Reforming apparatus and method of operating the same |
Family Cites Families (50)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3991176A (en) | 1973-11-23 | 1976-11-09 | Armour Pharmaceutical Company | Aluminum-zirconium anti-perspirant systems with hydroxy carboxylic compounds |
US3979510A (en) | 1973-11-23 | 1976-09-07 | Armour Pharmaceutical Company | Aluminum-zirconium anti-perspirant systems with complex aluminum buffers |
GB2144992A (en) | 1983-08-16 | 1985-03-20 | Gillette Co | Antiperspirants |
US5358694A (en) | 1986-01-08 | 1994-10-25 | Westwood Chemical Corporation | Method for preparing basic aluminum halides and product produced therefrom |
US4871525A (en) | 1986-10-24 | 1989-10-03 | Westwood Chemical Corporation | Antiperspirant composition and method of preparation |
GB8619553D0 (en) | 1986-08-11 | 1986-09-24 | Unilever Plc | Antiperspirants |
AU597822B2 (en) | 1987-05-15 | 1990-06-07 | Unilever Plc | Transparent antiperspirant stick compositions |
US5330751A (en) | 1988-04-14 | 1994-07-19 | The Gilette Company | Antiperspirant and method of making same |
US5348720A (en) | 1988-08-17 | 1994-09-20 | The Mennen Company | Basic aluminum antiperspirant active material having enhanced activity, antiperspirant active composition containing such material, and methods for preparation of such material and composition |
US5643558A (en) | 1994-11-02 | 1997-07-01 | The Gillette Company | Method of making polyhydric alcohol solutions of enhanced efficacy antiperspirant actives |
US5725846A (en) | 1995-03-02 | 1998-03-10 | The Gillette Company | Clear antiperspirant stick containing dibenzylidene alditol and hydroxyalkyl cellulose |
US6010688A (en) | 1997-06-25 | 2000-01-04 | The Gillette Company | Polyhydric alcohol stabilized antiperspirant salt solutions |
US5997850C1 (en) | 1997-10-29 | 2001-11-27 | Colgate Palmolive Co | Antiperspirant actives and formulations made therefrom |
US6682749B1 (en) | 1998-04-03 | 2004-01-27 | Colgate-Palmolive Company | Low Residue cosmetic composition |
US6042816A (en) | 1998-08-19 | 2000-03-28 | The Gillette Company | Enhanced antiperspirant salts stabilized with calcium and concentrated aqueous solutions of such salts |
US5955065A (en) | 1998-08-19 | 1999-09-21 | The Gillette Company | Antiperspirant compositions containing calcium salts |
US6136302A (en) | 1999-02-18 | 2000-10-24 | The Procter & Gamble Company | Process of making zirconium-aluminum antiperspirant active |
ATE221766T1 (en) | 1999-05-29 | 2002-08-15 | Bk Giulini Chem Gmbh & Co Ohg | METHOD FOR PRODUCING FINE PARTICULAR ANTIPERSPIRANT ACTIVE SUSPENSIONS |
US6149897A (en) | 1999-08-24 | 2000-11-21 | The Procter & Gamble Company | Process for making anhydrous compositions containing solubilized, enhanced antiperspirant active |
US6451296B1 (en) | 2000-02-01 | 2002-09-17 | Zijun Li | Enhanced efficacy aluminum-zirconium antiperspirants and methods for making |
GB0012267D0 (en) | 2000-05-19 | 2000-07-12 | Unilever Plc | Method pf prepatationof an antiperspirant salt |
US6375937B1 (en) | 2000-10-20 | 2002-04-23 | Colgate-Palmolive Company | Antiperspirant salts for enhanced cosmetic products |
US6436381B1 (en) | 2000-10-25 | 2002-08-20 | The Gillette Company | Aluminum-zirconium antiperspirant salts with high peak 5 al content |
GB0100549D0 (en) | 2001-01-09 | 2001-02-21 | Unilever Plc | Antiperspirant or deodorant compositions |
US6342210B1 (en) | 2001-04-20 | 2002-01-29 | Colgate-Palmolive Company | Antiperspirant actives from a glass form and products made therewith |
US6765668B2 (en) | 2002-01-10 | 2004-07-20 | Chemimage, Inc. | Method for detection of pathogenic microorganisms |
US6726901B2 (en) | 2002-05-09 | 2004-04-27 | The Gillette Company | Stabilized antiperspirant compositions containing aluminum-zirconium salts with low M:Cl ratio |
US6835373B2 (en) | 2002-07-12 | 2004-12-28 | The Procter & Gamble Company | Non-irritating antiperspirant compositions containing acidic antiperspirant active |
MXPA05001299A (en) | 2002-08-02 | 2005-04-28 | Gillette Co | Clear personal care compositions containing visible capsules. |
US20040091436A1 (en) | 2002-11-12 | 2004-05-13 | Zijun Li | Antiperspirant compositions of enhanced efficacy containing strontium |
US6936242B2 (en) | 2002-11-15 | 2005-08-30 | The Gillette Company | Multi-portion antiperspirant composition |
US20040198998A1 (en) | 2003-04-04 | 2004-10-07 | Marian Holerca | Glycine-free antiperspirant salts with betaine for enhanced cosmetic products |
US7105691B2 (en) | 2003-06-26 | 2006-09-12 | Colgate-Palmolive Company | Aluminum / zirconium / glycine antiperspirant actives stabilized with Betaine |
US6942850B2 (en) | 2003-08-15 | 2005-09-13 | The Gillette Company | Aqueous alcoholic antiperspirant composition containing calcium enhanced antiperspirant salt |
US6902724B1 (en) | 2004-03-24 | 2005-06-07 | Reheis, Inc. | Enhanced efficacy basic aluminum halides, antiperspirant active compositions and methods for making |
US7087220B2 (en) | 2004-05-28 | 2006-08-08 | Reheis, Inc. | High pH antiperspirant compositions of enhanced efficacy |
AU2004324474A1 (en) | 2004-10-22 | 2006-05-04 | Zijun Li | Activated aluminum/depolymerized zirconium antiperspirant compositions |
US8883129B2 (en) | 2005-01-13 | 2014-11-11 | The Procter & Gamble Company | Enhanced efficacy antiperspirant active |
US7704531B2 (en) | 2005-02-18 | 2010-04-27 | Colgate-Palmolive Company | Enhanced efficacy aluminum or aluminum-zirconium antiperspirant salt compositions containing calcium salt(s) and betaine |
US20060292098A1 (en) | 2005-05-19 | 2006-12-28 | Scavone Timothy A | Consumer noticeable improvement in wetness protection |
US20070003499A1 (en) | 2005-06-30 | 2007-01-04 | The Gillette Company | Particulate enhanced efficacy antiperspirant salt with raised pH |
US20070020211A1 (en) | 2005-07-22 | 2007-01-25 | Reheis, Inc. | Betaine with Calcium and/or Strontium Antiperspirants |
CL2006003116A1 (en) | 2005-11-16 | 2008-02-29 | Colgate Palmolive Co | ANTI-TRANSPIRING COMPOSITION THAT INCLUDES AT LEAST ONE CHOSEN ALUMINUM SALT, ZIRCONY ALUMINUM, A COMPLEX ALUMINUM SALT OR A COMPLEX ALUMINUM-ZIRCONY SALT, A HYDROXIACIDE AND AN ACID COMPOUND OF QUATERNARY AMMONIUM; PROCESS TO PREPARE |
US8801909B2 (en) | 2006-01-06 | 2014-08-12 | Nextchem, Llc | Polymetal hydroxychloride processes and compositions: enhanced efficacy antiperspirant salt compositions |
US20070196303A1 (en) | 2006-02-17 | 2007-08-23 | Reheis, Inc. | Stable buffered aluminum compositions having high hplc bands iii and iv containing calcium/strontium |
WO2008063188A2 (en) | 2006-11-03 | 2008-05-29 | Reheis, Inc. | Betaine with calcium and/or strontium antiperspirants |
US20080131354A1 (en) | 2006-12-05 | 2008-06-05 | Reheis, Inc. | Polyaluminum calcium hydroxychlorides and methods of making the same |
US20090016979A1 (en) | 2007-07-09 | 2009-01-15 | Zijun Li | Aluminum and aluminum-zirconium compositions of enhanced efficacy containing reduced buffer and/or reduced zirconium |
US20100202993A1 (en) | 2007-12-12 | 2010-08-12 | Long Pan | Antiperspirant Active Compositions Having SEC Chromatogram Exhibiting High SEC Peak 4 Intensity |
US20130209387A1 (en) | 2010-11-02 | 2013-08-15 | Colgate-Palmolive Company | Antiperspirant Active Compositions and Manufacture Thereof |
-
2011
- 2011-12-20 US US14/110,723 patent/US9174851B2/en active Active
- 2011-12-20 EP EP11810736.6A patent/EP2702008B1/en active Active
- 2011-12-20 AU AU2011366871A patent/AU2011366871B2/en not_active Ceased
- 2011-12-20 CA CA2834129A patent/CA2834129A1/en not_active Abandoned
- 2011-12-20 WO PCT/US2011/066018 patent/WO2012148481A1/en active Application Filing
- 2011-12-20 BR BR112013024919A patent/BR112013024919A2/en not_active IP Right Cessation
- 2011-12-20 ES ES11810736.6T patent/ES2569856T3/en active Active
- 2011-12-20 RU RU2013152256/05A patent/RU2013152256A/en not_active Application Discontinuation
- 2011-12-20 MX MX2013012371A patent/MX361821B/en active IP Right Grant
-
2012
- 2012-04-26 AR ARP120101460A patent/AR086120A1/en not_active Application Discontinuation
-
2013
- 2013-10-21 CO CO13248917A patent/CO6801753A2/en not_active Application Discontinuation
- 2013-10-25 CL CL2013003093A patent/CL2013003093A1/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006103092A1 (en) | 2005-03-31 | 2006-10-05 | Unilever Plc | Process of preparing aluminium species |
US20100055030A1 (en) | 2006-11-27 | 2010-03-04 | Naohiko Matsuda | Reforming apparatus and method of operating the same |
Non-Patent Citations (8)
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4321147A2 (en) | 2013-05-20 | 2024-02-14 | Unilever IP Holdings B.V. | Antiperspirant compositions |
US9775791B2 (en) | 2013-05-20 | 2017-10-03 | Conopco, Inc. | Method of manufacture of antiperspirant salts |
EP2999452B1 (en) | 2013-05-20 | 2017-12-13 | Unilever PLC | Antiperspirant compositions |
EP3295922A1 (en) | 2013-05-20 | 2018-03-21 | Unilever PLC | Antiperspirant compositions |
US10398633B2 (en) | 2014-10-27 | 2019-09-03 | Conopco, Inc. | Anhydrous antiperspirant compositions |
US10729627B2 (en) | 2014-10-27 | 2020-08-04 | Conopco, Inc. | Anhydrous antiperspirant compositions |
WO2016066527A1 (en) | 2014-10-27 | 2016-05-06 | Unilever Plc | Anhydrous antiperspirant compositions |
US10117814B2 (en) | 2014-10-27 | 2018-11-06 | Conopco, Inc. | Anhydrous antiperspirant aerosol compositions |
US10098821B2 (en) | 2014-11-19 | 2018-10-16 | Conopco, Inc. | Process of manufacture of an antiperspirant composition |
US9867765B2 (en) | 2014-11-19 | 2018-01-16 | Conopco, Inc. | Antiperspirant compositions |
US10632052B2 (en) | 2015-11-06 | 2020-04-28 | Conopco, Inc. | Antiperspirant compositions |
US10682293B2 (en) | 2015-11-06 | 2020-06-16 | Conopco, Inc. | Aerosol antiperspirant product |
WO2017076562A1 (en) | 2015-11-06 | 2017-05-11 | Unilever Plc | Antiperspirant compositions |
Also Published As
Publication number | Publication date |
---|---|
RU2013152256A (en) | 2015-06-10 |
MX2013012371A (en) | 2014-02-03 |
US9174851B2 (en) | 2015-11-03 |
AU2011366871B2 (en) | 2014-10-30 |
BR112013024919A2 (en) | 2016-12-20 |
EP2702008A1 (en) | 2014-03-05 |
CA2834129A1 (en) | 2012-11-01 |
AR086120A1 (en) | 2013-11-20 |
US20140147405A1 (en) | 2014-05-29 |
CO6801753A2 (en) | 2013-11-29 |
EP2702008B1 (en) | 2016-03-09 |
ES2569856T3 (en) | 2016-05-12 |
CL2013003093A1 (en) | 2014-02-21 |
AU2011366871A1 (en) | 2013-05-02 |
MX361821B (en) | 2018-12-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU2011366871B2 (en) | Compositions containing polyhydroxyoxoaluminum cations and manufacture thereof | |
US9717663B2 (en) | Antiperspirant active compositions and manufacture thereof | |
EP2635353B1 (en) | Aluminum salt containing high percentage of AL30 | |
US9463985B2 (en) | Aluminum salt containing high percentage of Al30 | |
JP2007522260A (en) | Highly effective aluminum-zirconium antiperspirant | |
Pappas et al. | Aluminum salt containing high percentage of Al 30 | |
WO2001089994A1 (en) | Method of preparation of an antiperspirant salt |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11810736 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2011366871 Country of ref document: AU Date of ref document: 20111220 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13248917 Country of ref document: CO Ref document number: 2011810736 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2834129 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/A/2013/012371 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2013003093 Country of ref document: CL |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2013152256 Country of ref document: RU Kind code of ref document: A |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112013024919 Country of ref document: BR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14110723 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 112013024919 Country of ref document: BR Kind code of ref document: A2 Effective date: 20130927 |