US20040109833A1 - High efficacy, low irritation aluminum salts and related products - Google Patents
High efficacy, low irritation aluminum salts and related products Download PDFInfo
- Publication number
- US20040109833A1 US20040109833A1 US10/314,712 US31471202A US2004109833A1 US 20040109833 A1 US20040109833 A1 US 20040109833A1 US 31471202 A US31471202 A US 31471202A US 2004109833 A1 US2004109833 A1 US 2004109833A1
- Authority
- US
- United States
- Prior art keywords
- aluminum
- antiperspirant
- cyclomethicone
- peak
- nitrogen containing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 230000007794 irritation Effects 0.000 title description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 25
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 8
- 230000003139 buffering effect Effects 0.000 claims abstract description 8
- 150000004820 halides Chemical class 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 230000002000 scavenging effect Effects 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 90
- 230000001166 anti-perspirative effect Effects 0.000 claims description 64
- 239000003213 antiperspirant Substances 0.000 claims description 64
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 claims description 39
- 239000003205 fragrance Substances 0.000 claims description 34
- 229940086555 cyclomethicone Drugs 0.000 claims description 32
- 229920001971 elastomer Polymers 0.000 claims description 26
- 239000000806 elastomer Substances 0.000 claims description 26
- 239000004471 Glycine Substances 0.000 claims description 23
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 23
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 23
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 23
- 229940008099 dimethicone Drugs 0.000 claims description 22
- DLAHAXOYRFRPFQ-UHFFFAOYSA-N dodecyl benzoate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1 DLAHAXOYRFRPFQ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 15
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 14
- -1 polyethylene Polymers 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 8
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 7
- 229920006007 hydrogenated polyisobutylene Polymers 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 229960003237 betaine Drugs 0.000 claims description 4
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 claims description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 claims description 2
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 claims description 2
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 claims description 2
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 claims description 2
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 2
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004473 Threonine Substances 0.000 claims description 2
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- 229940087101 dibenzylidene sorbitol Drugs 0.000 claims description 2
- 239000003349 gelling agent Substances 0.000 claims description 2
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000004474 valine Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 description 32
- 239000000243 solution Substances 0.000 description 32
- 239000004615 ingredient Substances 0.000 description 24
- 238000009472 formulation Methods 0.000 description 23
- 238000000034 method Methods 0.000 description 21
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 13
- XXBAQTDVRLRXEV-UHFFFAOYSA-N 3-tetradecoxypropan-1-ol Chemical compound CCCCCCCCCCCCCCOCCCO XXBAQTDVRLRXEV-UHFFFAOYSA-N 0.000 description 12
- 229920001296 polysiloxane Polymers 0.000 description 12
- 229940116987 ppg-3 myristyl ether Drugs 0.000 description 12
- XILPPDQAWPSZIL-UHFFFAOYSA-H dialuminum;dichloride;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Cl-].[Cl-] XILPPDQAWPSZIL-UHFFFAOYSA-H 0.000 description 11
- 239000000499 gel Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 210000004243 sweat Anatomy 0.000 description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- 229910052726 zirconium Inorganic materials 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000443 aerosol Substances 0.000 description 8
- 235000001014 amino acid Nutrition 0.000 description 8
- 150000001413 amino acids Chemical class 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- 241000894007 species Species 0.000 description 8
- 210000000245 forearm Anatomy 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 229920000582 polyisocyanurate Polymers 0.000 description 6
- 239000011495 polyisocyanurate Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002537 cosmetic Substances 0.000 description 5
- 239000006071 cream Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002781 deodorant agent Substances 0.000 description 4
- 238000000265 homogenisation Methods 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 0 [1*][N+]([2*])([3*])C Chemical compound [1*][N+]([2*])([3*])C 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000012875 nonionic emulsifier Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- 239000007762 w/o emulsion Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- ZGUQGPFMMTZGBQ-UHFFFAOYSA-N [Al].[Al].[Zr] Chemical compound [Al].[Al].[Zr] ZGUQGPFMMTZGBQ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229940032051 peg-8 distearate Drugs 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 238000001542 size-exclusion chromatography Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 210000000106 sweat gland Anatomy 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- HBXWUCXDUUJDRB-UHFFFAOYSA-N 1-octadecoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCCCC HBXWUCXDUUJDRB-UHFFFAOYSA-N 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 description 1
- 241000952610 Aphis glycines Species 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical class [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 description 1
- YCLAMANSVUJYPT-UHFFFAOYSA-L aluminum chloride hydroxide hydrate Chemical compound O.[OH-].[Al+3].[Cl-] YCLAMANSVUJYPT-UHFFFAOYSA-L 0.000 description 1
- 229940053431 aluminum sesquichlorohydrate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- UFVWHIGSVGIZRQ-UHFFFAOYSA-N bis(2-ethylhexyl) naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OCC(CC)CCCC)C=CC2=CC(C(=O)OCC(CC)CCCC)=CC=C21 UFVWHIGSVGIZRQ-UHFFFAOYSA-N 0.000 description 1
- 239000007957 coemulsifier Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 239000008406 cosmetic ingredient Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229940049657 cyclomethicone 5 Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002363 hafnium compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000003319 supportive effect Effects 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- 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
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/895—Polysiloxanes containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0216—Solid or semisolid forms
- A61K8/0229—Sticks
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/046—Aerosols; Foams
-
- 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
- A61K8/30—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
- 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
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
-
- 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
Definitions
- This invention relates to a class of high efficacy, low irritation aluminum salts that may be used to formulate non-aerosol, propellant-free antiperspirants and/or deodorants.
- U.S. Pat. No. 4,331,609 to Orr teaches an antiperspirant active comprising aluminum and zirconium made with separate aluminum and zirconium compounds as well as a neutral amino acid wherein the molar ratio of neutral amino acid to total metal is from about 0.90 to about 0.24.
- the total metal:chlorine ratio in the complex that is formed is less than 1.30.
- U.S. Pat. No. 4,499,069 to Krafton describes a stable antiperspirant emulsion comprising an aluminum salt, volatile cyclic silicone, water, and a low pH-stable emulsifier mixture of polyethylene glycol (21) stearyl ether and a lipophilic co-emulsifier such that the HLB of the emulsifier mixture is greater than 7.5 and less than 9.9.
- U.S. Pat. No. 4,871,525 to Giovanniello et al describes a solid powder of aluminum zirconium hydroxyl halide glycinate complex having improved antiperspirant activity wherein the glycine is used to prevent gel formation.
- the ratio of Zr to glycine is less than 1:1.
- U.S. Pat. No. 5,384,117 to Vu et al teaches a substantially clear anhydrous antiperspirant compositions that can me made with an aluminum chlorohydrate salt in solid particulate form suspended in an essentially anhydrous vehicle, wherein the salt is free of opacifying contaminants and the salt and vehicle have refractive indices in selective ranges.
- U.S. Pat. No. 5,356,612 to Curtin, et al describes an antiperspirant comprising a basic aluminum salt mixed with monosilicic acid in aqueous solution.
- U.S. Pat. No. 5,599,533 to Stepniewski et al describes a stable water-in-oil emulsion system formed of an organopolysiloxane elastomer, a vehicle in which the elastomer is dispersed or dispersible, a stabilizing agent (such as a selected electrolyte), a surfactant and an aqueous component and a process for forming the stable water-in-oil emulsion.
- electrolytes are alkali metal salts and alkaline earth salts, as well as aluminum chlorohydrate, and polyelectrolytes.
- the stabilizing agent is, or includes, an electrolyte, it amounts to about 0.1 to 5 wt.-% and more preferably 0.5 to 3 wt. % of the total composition.
- U.S. Pat. No. 6,024,945 to Parekh describes aerosol products comprising an aluminum salt, 1,1-difluoroethane in combinations with selected additives to prevent the formation of toxic compounds.
- additives include, for example, and an amino acid (such as glycine) selected salts thereof, or metal glycinates.
- U.S. Pat. No. 6,066,314 to Tang describes the use of post added glycine to aluminum zirconium salts in an amount in the range of 1:1.2-1:5 of zirconium:amino acid on a weight:weight basis.
- U.S. Pat. No. 6,126,928 to Swaile describes antiperspirant compositions wherein the molar ratio of neutral amino acid to total metal (aluminum+zirconium) is from about 0.90 to about 0.24, and the mole ratio of (aluminum+zirconium):chlorine is less than about 1.30:1.
- EP publication number 0 047 650 describes aqueous solution-stable antiperspirant complexes comprising an aluminum compound, a zirconium or hafnium compound, a water soluble neutral amino acid and an inorganic acid.
- the molar ratio of neutral amino acid to total metal is from about 0.90 to about 0.24 in an aqueous system, and the molar ratio of neutral amino acid to total metal is from about 0.90 to about 0.75 in a non-aqueous system.
- the total metal:chlorine ratio in the complex that is formed is less than 1.30.
- United Kingdom Patent Application GB 2,076,289 describes an antiperspirant compositions comprising a combination of an aluminum chloride and an aluminum zirconium hydroxychloride in a synergistic mixture.
- the metal:chloride ratio is less than 0.9.
- Canadian Patent 1,153,313 describes an antiperspirant composition which contains a buffering agent such as glycine with a synergistic mixture of aluminum chlorohydrate, aluminum chloride or aluminum zirconium polychlorohydrate complex.
- a buffering agent such as glycine
- the molar ratio of aluminum to chloride is in the range of 0.78:1 to abut 1.95:1.
- Various salts are described which have a metal:halide ratio of 2.1:1-0.9:1.
- the glycine:zirconium ratio is much less than 1:1.
- This invention comprises zirconium-free aluminum salts which:
- (b) comprises a nitrogen containing buffering material (particularly glycine) in an amount such that the ratio of nitrogen containing material to aluminum is the range of 0.05-0.26:1 and preferably in the range of 0.05-0.16:1 and which nitrogen containing material is selected from the group consisting of a nitrogen containing a buffering material of formula
- n is a number in the range of 1-20, and each of R 1 , R 2 , and R 3 is independently selected from the group consisting of hydrogen, methyl and ethyl (preferably methyl); and
- the salt has a pH in the range of 2-4 (when measured in water at a concentration of 15%);
- the salt is free of any other halide scavenging material and has a value of at least 0.50 for the ratio calculated as: area ⁇ ⁇ of ⁇ ⁇ Peak ⁇ ⁇ 5 total ⁇ ⁇ area ⁇ ⁇ under ⁇ ⁇ Peak ⁇ ⁇ 2 + Peak ⁇ ⁇ 3 + Peak ⁇ ⁇ 4 + Peak ⁇ ⁇ 5
- the salts of the invention may be made as spray dried powders or made as solutions of up to 50 weight % based on the weight of the final product.
- the invention also includes antiperspirant and/or deodorant products made with these salts.
- Such formulations may be made as sticks, soft solids or creams, roll-ons or non-aerosol sprays.
- the formulations are free of propellants.
- This invention is limited to aluminum antiperspirant salts that do not contain zirconium.
- the amount of nitrogen buffering material must be kept below 5 weight % ( and preferably less than 3%) to achieve a stability of 2 weeks at room temperature for an anhydrous aluminum dichlorohydrate in a water solution at an anhydrous level of 25% active salt without water.
- Another way of describing the amount of nitrogen containing material that may be used is by specifying a ratio range.
- the molar ratio of the nitrogen containing material (particularly glycine) to aluminum should be in the range of 0.05-0.26:1 and preferably in the range of 0.05-0.16:1.
- the lower concentrations may be used for longer stability times such as 3 weight % for 4 weeks and 2 weight % for several months.
- the salt may be spray dried to create a material with much longer stability such as on the order of years. The dried salt material may then be added to the formulation during the manufacturing process. Thus, efficacy may be maintained in aluminum only systems.
- Method A An aluminum dichlorohydrate (ADCH) solution of ADCH salt in water of suitable concentration is mixed with a suitable concentration of a powdered form of the nitrogen containing material such as glycine. The mixture is stirred at room temperature to obtain the product.
- Aluminum sesquichlorohydrate (ASCH) may be substituted for ADCH.
- Method B Method A is repeated and the product is then spray dried to obtain the salt in powder form.
- the size of the particles of antiperspirant active of the invention currently does not appear to be critical and may include conventional sizes such as greater than 2 to 100 microns, with selected grades having an average particle size of 30-40 microns; finer sized grades having an average particle size distribution from 2-10 microns with average size of about 7 microns as made by a dry-grinding method; and micronized grades of the type described in a co-pending patent application PCT case WO 01/97,768 having an average particle size of less than or equal to 2 microns, particularly less than or equal to 1.5 microns.
- the enhanced salts of this invention may be used to formulate antiperspirants having improved efficacy.
- antiperspirants include solids such as sticks and creams (creams sometimes being included in the term “soft solid”), gels, liquids (such as are suitable for roll-on products), and aerosols.
- the forms of these products may be suspensions or emulsions.
- glycol content of the formulations be kept to a minimum, preferably not exceeding 1.0 weight %.
- Suitable formulations include the following.
- Sticks—Stick products may be made with conventional gelling agents such as stearyl alcohol and dibenzylidene sorbitol.
- a sample formulation is as follows:
- Soft solids may be made with formulations described in co-pending patent application (U.S. Ser. No. 9/273152 and PCT Publication number WO 99/51192
- a sample formulation is as follows:
- polyethylene for example, beads having a density in the range of 0.91-0.98 g/cm 3 and an average particle size in the range of 5-40 microns
- Gels may be made with a variety of formulations such as
- the refractive indices of the external and internal phases are matched within 0.005 to obtain a clear product.
- compositions of interest include:
- dimethicone copolyol for example, Dow Corning 2-5185C (48%)
- cyclomethicone for example, DC-9040 from Dow Corning Corporation (Midland, Mich.) or KSG-15 from Shin-Etsu Silicones of America (Akron, Ohio)
- dimethicone copolyol for example, Dow Corning 2-5185C (48%)
- elastomer in cyclomethicone for example, DC-9040 from Dow Corning Corporation (Midland, Mich.) or KSG-15 from Shin-Etsu Silicones of America (Akron, Ohio)
- dimethicone copolyol for example, Dow Corning 2-5185C (48%)
- cyclomethicone for example, DC-9040 from Dow Corning Corporation (Midland, Mich.) or KSG-15 from Shin-Etsu Silicones of America (Akron, Ohio)
- dimethicone copolyol for example, Dow Corning 2-5185C (48%)
- elastomer in cyclomethicone for example, DC-9040 from Dow Corning Corporation (Midland, Mich.) or KSG-15 from Shin-Etsu Silicones of America (Akron, Ohio)
- dimethicone copolyol for example, Dow Corning 2-5185C (48%)
- elastomer in cyclomethicone for example, DC-9040 from Dow Corning Corporation (Midland, Mich.) or KSG-15 from Shin-Etsu Silicones of America (Akron, Ohio)
- dimethicone copolyol for example, Dow Corning 2-5185C (48%)
- elastomer in cyclomethicone for example, DC-9040 from Dow Corning Corporation (Midland, Mich.) or KSG-15 from Shin-Etsu Silicones of America (Akron, Ohio)
- the cosmetic composition according to the present invention can be packaged in conventional containers, using conventional techniques.
- a gel, cream or soft-solid cosmetic composition is produced, the composition can be introduced into a dispensing package (for example, conventional packages for gels with glide on applicators, jars where the gel or cream is applied by hand, and newer style packages having a top surface with pores) as conventionally done in the art.
- the product can be dispensed from the dispensing package as conventionally done in the art, to deposit the active material, for example, on the skin.
- sprays, aerosols and roll-ons the compositions can be placed in a conventional types of container (with the inclusion of propellants in aerosols). This provides good deposition of the active material on the skin.
- compositions of the present invention can be formulated as clear, translucent or opaque products, although clear products are preferred.
- a desired feature of the present invention is that a clear, or transparent, cosmetic composition, (for example, a clear or transparent deodorant or antiperspirant composition) can be provided.
- the term clear or transparent according to the present invention is intended to connote its usual dictionary definition; thus, a clear liquid or gel antiperspirant composition of the present invention allows ready viewing of objects behind it.
- a translucent composition although allowing light to pass through, causes the light to be scattered so that it will be impossible to see clearly objects behind the translucent composition.
- An opaque composition does not allow light to pass therethrough.
- a gel or stick is deemed to be transparent or clear if the maximum transmittance of light of any wavelength in the range 400-800 nm through a sample 1 cm thick is at least 35%, preferably at least 50%.
- the gel or liquid is deemed translucent if the maximum transmittance of such light through the sample is between 2% and less than 35%.
- a gel or liquid is deemed opaque if the maximum transmittance of light is less than 2%.
- the transmittance can be measured by placing a sample of the aforementioned thickness into a light beam of a spectrophotometer whose working range includes the visible spectrum, such as a Bausch & Lomb Spectronic 88 Spectrophotometer. As to this definition of clear, see European Patent Application Publication No. 291,334 A2.
- compositions are described as including or comprising specific components or materials, or where methods are described as including or comprising specific steps, it is contemplated by the inventors that the compositions of the present invention also consist essentially of, or consist of, the recited components or materials, and also consist essentially of, or consist of, the recited steps. Accordingly, throughout the present disclosure any described composition of the present invention can consist essentially of, or consist of, the recited components or materials, and any described method of the present invention can consist essentially of, or consist of, the recited steps.
- the amounts of the components are in weight percents based on the standard described; if no other standard is described then the total weight of the composition is to be inferred.
- Various names of chemical components include those listed in the CTFA International Cosmetic Ingredient Dictionary (Cosmetics, Toiletry and Fragrance Association, Inc., 7 th ed. 1997). While specific amounts of particular elastomers have been described, there are chemical differences in the variety of elastomers that are available. The use of different elastomers may result in the need to increase or decrease the amount of elastomer used in a particular formulation, especially if a clear product is desired.
- the antiperspirant active either as a powder or in some type of solution such as dissolved in water at a concentration or 25-45% actives on an anhydrous basis.
- Improved aluminum di-chlorohydrate salts (10.0% anhydrous) can be made with glycine as follows using the amounts of ingredients listed in Table A. Glycine powder (at the level listed in Table A) and distilled water are added into an aluminum dichlorohydrate solution (Westchlor 100, 38% anhydrous excluding waters of hydration) and stirred for 5 minutes to make six Examples as shown in Table A. The concentration for all the Examples 1-6 is 10% by weight. Table A also contains the pH values as measured with a Corning pH meter 430. Finally, a profile was run on each of the solutions listed in Table A and the areas under each peak were calculated. The method used is the same one described in U.S. Pat. No. 6,066,314.
- the Size exclusion chromatography (“SEC”) column separates the species by molecular size, using a refractive index (RI) detector connected to the column outlet.
- RI refractive index
- the % of each peak of the whole was also calculated and the values are listed in Table A. All concentrations are in % by weight based on the entire weight of the solution. The increase in Peak 5 species is supportive of improved efficacy. (Also see U.S. Pat. No. 6,375,937.)
- Size exclusion chromatography method is frequently used for obtaining information on polymer distribution in antiperspirant salt solutions. With appropriate chromatographic columns, at least 5 distinctive groups of polymer species can be detected in an aluminum salt, appearing in a chromatogram as peaks 1, 2, 3, 4, and a peak referred to here as “5”. Peaks 2 and 3 are larger aluminum species. Peak 4 is smaller aluminum species (aluminum oligomers) and has been correlated with enhanced efficacy for ACH salts. Peak 5 is the smallest aluminum species. The relative retention time (“Kd”) for each of these peaks varies depending on the experimental conditions. Data for Table A was obtained using the SEC method described in an issued patent owned by the same company as this case, U.S. Pat. No.
- Each of the Examples 1-18 can be formed into a powder using conventional spray drying or freeze drying techniques known to those skilled in the art. Examples of such methods may be found in U.S. Pat. No. 5,589,196. Note that in spray drying the material, the maximum amount of water left in the spray dried product should not exceed 25 weight %.
- the external and internal phases are formed separately either at room temperature or with heating as described below.
- the internal phase is added to the external phase very slowly while stirring at to form an emulsion. After the addition has been completed, the mixture is stirred at higher speed to achieve a homogeneous mixture.
- the final formula viscosity is then achieved by homogenizing the emulsion under either batch or continuous process conditions as described below.
- the fragrance may be added at any time during the process prior to final homogenization.
- the ingredients to be used in the external phase are weighed out at room temperature and combined in a suitable vessel such as a 2 liter glass beaker.
- the mixture is stirred at about 500 rpm for 15-20 minutes using an overhead mixer such as a Lightnin Mixer Model L1003.
- an overhead mixer such as a Lightnin Mixer Model L1003.
- the mixture may be heated to facilitate dissolution while stirring then cooled to room temperature prior to combination with the internal phase as described below.
- the elastomer component is obtained as a suspension of elastomer in cyclomethicone (for example at a concentration of 6% active in D5 cyclomethicone).
- the elastomer component is added to the external phase with stirring at high speed (500-700 rpm for a 0.5 kilogram batch) until no particles of elastomer are visible to the eye.
- the internal dispersed phase is prepared as described below. Ingredients are mixed for a time sufficient to achieve homogeneity. The antiperspirant active used is weighed into a large beaker equipped with an overhead stirrer. Other internal phase ingredients are then added while stirring.
- the fragrance (if any is used) is added last and may be added either to the internal phase or the external phase or the final formula prior to homogenization. For many of the examples described here, one could add the fragrance to the internal phase.
- the emulsifier and propylene glycol are combined in a separate beaker and heated to 40 degrees C. with stirring until the non-ionic emulsifier completely dissolved. The heat is turned off and the remaining ingredients to be used in the internal phase, including the antiperspirant active are weighed out and added to the mixture of propylene glycol and non-ionic emulsifier.
- the internal phase is prepared as follows.
- the solution containing antiperspirant active salt as received from supplier is weighed into a large beaker equipped with a magnetic stirrer. Additional ingredients such as propylene glycol, ethanol and water are added while stirring.
- a salt water solution such as for NaCl, etc.
- the salt water solution is prepared by dissolving the crystalline salt in water in a separate beaker and stirring until dissolved. The salt water solution is then added to the rest of the internal phase and the mixture is stirred until homogeneous.
- the internal phase made as described above is then added to the external phase over the course of 15-30 minutes while stirring at a speed of 500-700 rpm. After the addition is complete, the mixture is stirred at 500-700 rpm for 20 minutes using a Lightnin Mixer Model L1003. The mixture is then homogenized for 2-4 minutes (especially 3 minutes) using a homogenizer from Greerco Corp., Hudson, N.H. at a reading of about 60 on a Powerstat Variable Autotransformer from Superior Electric Co., Bristol, Conn.
- the product is then further processed by homogenization to achieve the desired final viscosity.
- This can be done by using a Gilford-Wood Model 1-L (Greerco Corp., Hudson, N.H.) homogenizer.
- the homogenizer speed is controlled by a Powerstat Variable Autotransformer Type 3PN116B (Superior Electronic. Co., Bristol, Conn.). Typical voltage setting and processing time are chosen to give a desired final formula viscosity.
- An other method of homogenization of the final product is to pass the emulsion through a colloid mill such as a Sonic Tri-Homo Colloid Mill or a process sonolator such Sonic Production Sonolator 200-30 both available from Sonic Corporation of Stratford, Conn. Process conditions are chosen to give the desired final product viscosity.
- a colloid mill such as a Sonic Tri-Homo Colloid Mill or a process sonolator such Sonic Production Sonolator 200-30 both available from Sonic Corporation of Stratford, Conn. Process conditions are chosen to give the desired final product viscosity.
- Example 37 The method described in Example 37 may be used to make the compositions listed in Tables D and E with the types and amounts of ingredients listed in the Tables. Amounts are in percent by weight based on the total weight of the composition.
- antiperspirant active any of the solutions of actives described in Examples 1-18 may be used. TABLE D Ingredient Ex. 38 Ex. 39 Ex. 40 Ex. 41 Ex. 42 Ex. 43 Ex. 44 Ex. 45 Ex. 46 Ex.
- a forearm starch/iodine test may be used as a rapid screening tool for underarm formulations prior to underarm clinical testing. The following procedure may be used for all tests discussed in this patent document. Panelists should be chosen who had not placed any antiperspirant products on their interior forearms for at least 14 days prior to the start of the test. Test formulations are applied on the inner forearms in preselected amounts. A control product such as a commercial product (Lady Speed Stick AP) is applied to one site on the panelists' arms as a positive control. After application of the formulations, the sites are occluded with covering chambers for one hour under conditions of about 40 degrees C. and 30% relative humidity. Panelists then remove the covering chambers.
- the forearms are each washed with a mild soap. This is repeated for the first two days of the study. On the third day of product application, the sites are occluded for one (1) hour, but are not washed with soap.
- the panelists perform their normal cleansing regimen using a mild soap during the course of the study. Approximately 20 hours after the last application of the products, the panelists are equilibrated in a room at 40 degrees C. (105° F.) and 40% relative humidity for 15 minutes. The panelists arms are then patted dry with a paper towel followed by application of paper strips impregnated with iodine to the test sites.
- Exposure to sweat causes the paper to turn purple at sites of hydration, generating a spatial map of the firing sweat glands.
- the papers are removed once the purple spots begin to appear on the backside or after five minutes, whichever comes first. Images of the papers may be digitized to quantify the amount of purple spot coverage. Once images are digitized, the area for measurement is identified using the same area as occluded by the chambers. A comparison of the total area of hydration for treated skin versus untreated sites is used to calculate a % Sweat Reduction (Eq:1).
- the area of sweat from untreated sites used in Equation 1 is calculated as the mean sweat areas of all the untreated sites directly adjacent to the treated site of interest. Since the number of firing sweat glands varies along the surface of the volar forearm, the mean sweat area of the adjacent untreated sites is used to approximate the area of sweat which would have been produced if a formula had not been applied to the treatment site.
- An antiperspirant product can be made using the following ingredients:
- An antiperspirant product can be made using the following ingredients:
- An antiperspirant product can be made using the following ingredients:
- An antiperspirant product can be made using the following ingredients:
- Phase inversion temperature concentrate such as Emulgade® CM from (from Cognis Co., Ambler, Pa.)
- fragrance 1%
- nonionic surfactant Emgen L from Cognis Co., Ambler, Pa.
- An antiperspirant product can be made using the following ingredients:
- An antiperspirant product can be made using the following ingredients:
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Cosmetics (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Catalysts (AREA)
Abstract
A zirconium-free aluminum salt which: (a) has an aluminum to chloride molar ratio in the range of 0.5-2.5:1; (b) comprises a nitrogen containing buffering material in an amount such that the ratio of nitrogen containing material to aluminum is the range of 0.05-0.26:1, and which nitrogen containing material is selected from the group consisting of a nitrogen containing buffering material of formula
where n is a number in the range of 1-20, and each of R1, R2, and R3 is independently selected from the group consisting of hydrogen, methyl and ethyl; and (c) the salt has a pH in the range of 2-4 at a concentration of 15%; wherein the salt is free of any other halide scavenging material and has a value of at least 0.50 for the ratio calculated as: area of Peak 5/total area under Peak 2+Peak 3+Peak 4+Peak 5.
Description
- This invention relates to a class of high efficacy, low irritation aluminum salts that may be used to formulate non-aerosol, propellant-free antiperspirants and/or deodorants.
- A variety of art is available that describes various salts and methods of making them.
- U.S. Pat. No. 4,331,609 to Orr teaches an antiperspirant active comprising aluminum and zirconium made with separate aluminum and zirconium compounds as well as a neutral amino acid wherein the molar ratio of neutral amino acid to total metal is from about 0.90 to about 0.24. The total metal:chlorine ratio in the complex that is formed is less than 1.30.
- U.S. Pat. No. 4,499,069 to Krafton describes a stable antiperspirant emulsion comprising an aluminum salt, volatile cyclic silicone, water, and a low pH-stable emulsifier mixture of polyethylene glycol (21) stearyl ether and a lipophilic co-emulsifier such that the HLB of the emulsifier mixture is greater than 7.5 and less than 9.9.
- U.S. Pat. No. 4,675,177 to Geary teaches aluminum salts comprising particular lactate, citrate, tartrate or adipate esters for enhanced efficacy.
- U.S. Pat. No. 4,871,525 to Giovanniello et al describes a solid powder of aluminum zirconium hydroxyl halide glycinate complex having improved antiperspirant activity wherein the glycine is used to prevent gel formation. The ratio of Zr to glycine is less than 1:1.
- U.S. Pat. No. 5,234,677 to Murray et al teaches a method for making enhanced aluminum chlorides with increased efficacy.
- U.S. Pat. No. 5,384,117 to Vu et al teaches a substantially clear anhydrous antiperspirant compositions that can me made with an aluminum chlorohydrate salt in solid particulate form suspended in an essentially anhydrous vehicle, wherein the salt is free of opacifying contaminants and the salt and vehicle have refractive indices in selective ranges.
- U.S. Pat. No. 5,393,518 to Kwass teaches a stable and substantially clear antiperspirant composition comprising a stable water-in-oil emulsion, wherein the oil phase is at lest 30% of ht e product.
- U.S. Pat. No. 5,356,612 to Curtin, et al describes an antiperspirant comprising a basic aluminum salt mixed with monosilicic acid in aqueous solution.
- U.S. Pat. Nos. 5,718,876 and 5,908,616 to Parekh describes a method for making enhanced aluminum halides with increased efficacy.
- U.S. Pat. No. 5,599,533 to Stepniewski et al describes a stable water-in-oil emulsion system formed of an organopolysiloxane elastomer, a vehicle in which the elastomer is dispersed or dispersible, a stabilizing agent (such as a selected electrolyte), a surfactant and an aqueous component and a process for forming the stable water-in-oil emulsion. Possible choices for electrolytes are alkali metal salts and alkaline earth salts, as well as aluminum chlorohydrate, and polyelectrolytes. When the stabilizing agent is, or includes, an electrolyte, it amounts to about 0.1 to 5 wt.-% and more preferably 0.5 to 3 wt. % of the total composition.
- U.S. Pat. No. 6,024,945 to Parekh describes aerosol products comprising an aluminum salt, 1,1-difluoroethane in combinations with selected additives to prevent the formation of toxic compounds. These additives include, for example, and an amino acid (such as glycine) selected salts thereof, or metal glycinates.
- U.S. Pat. No. 6,066,314 to Tang describes the use of post added glycine to aluminum zirconium salts in an amount in the range of 1:1.2-1:5 of zirconium:amino acid on a weight:weight basis.
- U.S. Pat. No. 6,126,928 to Swaile describes antiperspirant compositions wherein the molar ratio of neutral amino acid to total metal (aluminum+zirconium) is from about 0.90 to about 0.24, and the mole ratio of (aluminum+zirconium):chlorine is less than about 1.30:1.
- EP publication number 0 047 650 describes aqueous solution-stable antiperspirant complexes comprising an aluminum compound, a zirconium or hafnium compound, a water soluble neutral amino acid and an inorganic acid. The molar ratio of neutral amino acid to total metal is from about 0.90 to about 0.24 in an aqueous system, and the molar ratio of neutral amino acid to total metal is from about 0.90 to about 0.75 in a non-aqueous system. The total metal:chlorine ratio in the complex that is formed is less than 1.30.
- United Kingdom Patent Application GB 2,076,289 describes an antiperspirant compositions comprising a combination of an aluminum chloride and an aluminum zirconium hydroxychloride in a synergistic mixture. The metal:chloride ratio is less than 0.9.
- Canadian Patent 1,153,313 describes an antiperspirant composition which contains a buffering agent such as glycine with a synergistic mixture of aluminum chlorohydrate, aluminum chloride or aluminum zirconium polychlorohydrate complex. The molar ratio of aluminum to chloride is in the range of 0.78:1 to abut 1.95:1. Various salts are described which have a metal:halide ratio of 2.1:1-0.9:1. The glycine:zirconium ratio is much less than 1:1.
- None of the above cases described the combination of metal to chloride in combination with the glycine to zirconium ratio as found in the instant invention. Thus, it is surprising that the antiperspirant actives described in this invention provide more efficacious cosmetic products.
- While a great deal of work has been done on Al/Zr salts, there is still a need to have aluminum salts to use in a variety of products (including non-aerosol sprays for antiperspirants and/or deodorants where zirconium cannot be used) that are capable of being formulated into products with reduced irritation and better fragrance stability.
- This invention comprises zirconium-free aluminum salts which:
- (a) have an aluminum to chloride molar ratio in the range of 0.5-2.5:1;
- (b) comprises a nitrogen containing buffering material (particularly glycine) in an amount such that the ratio of nitrogen containing material to aluminum is the range of 0.05-0.26:1 and preferably in the range of 0.05-0.16:1 and which nitrogen containing material is selected from the group consisting of a nitrogen containing a buffering material of formula
- where n is a number in the range of 1-20, and each of R1, R2, and R3 is independently selected from the group consisting of hydrogen, methyl and ethyl (preferably methyl); and
- (c) the salt has a pH in the range of 2-4 (when measured in water at a concentration of 15%);
-
- The salts of the invention may be made as spray dried powders or made as solutions of up to 50 weight % based on the weight of the final product.
- The invention also includes antiperspirant and/or deodorant products made with these salts. Such formulations may be made as sticks, soft solids or creams, roll-ons or non-aerosol sprays. The formulations are free of propellants.
- This invention is limited to aluminum antiperspirant salts that do not contain zirconium.
- It has been found that by adding a selected amount of a nitrogen containing buffering agent (for example, glycine, alanine, serine, glutamine, threonine, valine, leucine, betaine) and lowering the aluminum:chloride ratio in aluminum chlorohydroxide salts, the amount of smaller aluminum species is increased with an appropriate increase in efficacy. Since the pH of such salts with lowered aluminum:chloride ratio is low, the problems of irritancy, fragrance compatibility, color changes, etc. must be addressed. It has been found that by adding a nitrogen containing compound as described above, the pH may be elevated to an acceptable range while still maintaining or increasing the relative amount of the smallest Peak 5 aluminum species in solution. It is also critical to note, however, that the use of too high an amount of the nitrogen buffering material may cause new problems such as unwanted gellation of the active (with corresponding decrease in efficacy). Thus, it has been found that in solutions of the salts, the amount of nitrogen buffering material must be kept below 5 weight % ( and preferably less than 3%) to achieve a stability of 2 weeks at room temperature for an anhydrous aluminum dichlorohydrate in a water solution at an anhydrous level of 25% active salt without water. Another way of describing the amount of nitrogen containing material that may be used is by specifying a ratio range.
- In particular, the molar ratio of the nitrogen containing material (particularly glycine) to aluminum should be in the range of 0.05-0.26:1 and preferably in the range of 0.05-0.16:1. The lower concentrations may be used for longer stability times such as 3 weight % for 4 weeks and 2 weight % for several months. Of course the salt may be spray dried to create a material with much longer stability such as on the order of years. The dried salt material may then be added to the formulation during the manufacturing process. Thus, efficacy may be maintained in aluminum only systems.
- The salts of this invention may be made in a variety of ways:
- Method A: An aluminum dichlorohydrate (ADCH) solution of ADCH salt in water of suitable concentration is mixed with a suitable concentration of a powdered form of the nitrogen containing material such as glycine. The mixture is stirred at room temperature to obtain the product. Aluminum sesquichlorohydrate (ASCH may be substituted for ADCH.
- Method B: Method A is repeated and the product is then spray dried to obtain the salt in powder form.
- If the product is used as a solid powder, the size of the particles of antiperspirant active of the invention currently does not appear to be critical and may include conventional sizes such as greater than 2 to 100 microns, with selected grades having an average particle size of 30-40 microns; finer sized grades having an average particle size distribution from 2-10 microns with average size of about 7 microns as made by a dry-grinding method; and micronized grades of the type described in a co-pending patent application PCT case WO 01/97,768 having an average particle size of less than or equal to 2 microns, particularly less than or equal to 1.5 microns.
- The enhanced salts of this invention may be used to formulate antiperspirants having improved efficacy. Such antiperspirants include solids such as sticks and creams (creams sometimes being included in the term “soft solid”), gels, liquids (such as are suitable for roll-on products), and aerosols. The forms of these products may be suspensions or emulsions.
- It is preferred that the glycol content of the formulations be kept to a minimum, preferably not exceeding 1.0 weight %.
- Examples of suitable formulations include the following.
- Sticks—Stick products may be made with conventional gelling agents such as stearyl alcohol and dibenzylidene sorbitol. A sample formulation is as follows:
- 40-55% (particularly 45%) cyclomethicone (particularly D4-D6 and especially D5 cyclomethicone)
- 20-30% (particularly 21%) stearyl alcohol
- 7-15% (particularly 10%) talc
- 15-22% (particularly 22%) aluminum antiperspirant active in powder form
- 1-3% (particularly 2%) fragrance (optional)
- Roll-Ons—
- 45-65% (particularly 55%) cyclomethicone (particularly D4-D6 and especially D5 cyclomethicone)
- 0.1-10% (particularly 3%) cyclomethicone/dimethicone copolyol (such as Dow Corning 2-5185 C)
- 10-25% (particularly 20%) antiperspirant active in solution form (25-45% actives on an anhydrous basis in water)
- 5-30% (particularly 20%) water
- 1-3% (particularly 2%) fragrance (optional)
- Soft solids—Soft solids may be made with formulations described in co-pending patent application (U.S. Ser. No. 9/273152 and PCT Publication number WO 99/51192
- A sample formulation is as follows:
- 40-70% (particularly 50%) elastomer in cyclomethicone (KSG-15 from Shin-Etsu)
- 5-15% (particularly 6%) polyethylene (for example, beads having a density in the range of 0.91-0.98 g/cm3 and an average particle size in the range of 5-40 microns)
- 10-20% (particularly 15%) C12-15 alkylbenzoate (FINSOLV TN from Finetex)
- 0.1-25%% (particularly 22%) antiperspirant active in powder form
- 1-15% (particularly 5%) dimethicone (100 centistokes)
- 1-3% (particularly 2%) fragrance (optional)
- Gels—Gels may be made with a variety of formulations such as
- 5-50% (particularly 29%) cyclomethicone (particularly D4-D6 and particularly D5)
- 0.1-10% (particularly 3%) cyclomethicone/dimethicone copolyol (such as Dow Corning 2-5185 C)
- 0-10% (particularly 5%) hydrogenated polyisobutene 250
- 0-10% (particularly 5%) C12-15 alkylbenzoate (FINSOLV TN from Finetex)
- 0-10% (particularly 5%) dimethicone (100 centistokes)
- 0.1-25% (particularly 20%) antiperspirant active in powder form or 10-25% (particularly 20%) of active in solution (25-45% actives on an anhydrous basis)
- 5-50% (particularly 30%) water
- 1-3% (particularly 2%) fragrance (optional)
- Note that in the explanation of the invention, where water is listed it is intended to count the contribution of the water present in the antiperspirant solution as part of the overall water content. Thus, water is sometimes listed as part of the actives solution or sometimes listed separately.
- In a preferred embodiment the refractive indices of the external and internal phases are matched within 0.005 to obtain a clear product.
- Particular formulations of interest include:
- Formulation A:
- 0.5-2.5% dimethicone copolyol (for example, Dow Corning 2-5185C (48%))
- 55-65% elastomer in cyclomethicone (for example, DC-9040 from Dow Corning Corporation (Midland, Mich.) or KSG-15 from Shin-Etsu Silicones of America (Akron, Ohio))
- 1-10% PPG-3 myristyl ether
- 10-25% antiperspirant active of the invention
- 10-25% water
- 0.5-1.5% fragrance
- Formulation B
- 1.0-3.0% dimethicone copolyol (for example, Dow Corning 2-5185C (48%))
- 40-60% elastomer in cyclomethicone (for example, DC-9040 from Dow Corning Corporation (Midland, Mich.) or KSG-15 from Shin-Etsu Silicones of America (Akron, Ohio))
- 1-5% cyclomethicone (in addition to that found in the elastomer)
- 4-12% PPG-3 myristyl ether
- 15-30% antiperspirant active of the invention
- 15-35% water
- 0.5-1.5% fragrance
- Formulation C
- 1.0-3.0% dimethicone copolyol (for example, Dow Corning 2-5185C (48%))
- 1-10% hydrogenated polyisobutene (for example, Fancol™ Polyiso 250)
- 40-55% elastomer in cyclomethicone (for example, DC-9040 from Dow Corning Corporation (Midland, Mich.) or KSG-15 from Shin-Etsu Silicones of America (Akron, Ohio))
- 3-8% PPG-3 myristyl ether
- 15-20% antiperspirant active of the invention 20-30% water
- 1.0-3.0% fragrance
- Formulation D
- 1.0-3.0% dimethicone copolyol (for example, Dow Corning 2-5185C (48%))
- 40-60% elastomer in cyclomethicone (for example, DC-9040 from Dow Corning Corporation (Midland, Mich.) or KSG-15 from Shin-Etsu Silicones of America (Akron, Ohio))
- 3-8% PPG-3 myristyl ether
- 15-30% antiperspirant active of the invention
- 15-30% water
- 0.5-1.5% fragrance
- 1-10% diethylhexyl naphthalate
- Formulation E
- 0.5-2.5% dimethicone copolyol (for example, Dow Corning 2-5185C (48%))
- 60-70% elastomer in cyclomethicone (for example, DC-9040 from Dow Corning Corporation (Midland, Mich.) or KSG-15 from Shin-Etsu Silicones of America (Akron, Ohio))
- 7-10% antiperspirant active of the invention
- 25-35% water
- 1-10% methylpropylene diol (MP Diol)
- 0.5-1.5% fragrance
- Formulation F
- 1.0-3.0% dimethicone copolyol (for example, Dow Corning 2-5185C (48%))
- 6-10% hydrogenated polyisobutene (for example, Fancol™ Polyiso 250)
- 35-45% elastomer in cyclomethicone (for example, DC-9040 from Dow Corning Corporation (Midland, Mich.) or KSG-15 from Shin-Etsu Silicones of America (Akron, Ohio))
- 6-10% PPG-3 myristyl ether
- 40-50% antiperspirant active of the invention as 43% active in water
- no additional water
- 0.5-1.0% fragrance
- Formulation G
- 0.1-0.6% dimethicone copolyol (for example, Dow Corning 2-5185C (48%))
- 4-7% hydrogenated polyisobutene (for example, Fancol™ Polyiso 250)
- 40-50% elastomer in cyclomethicone (for example, DC-9040 from Dow Corning Corporation (Midland, Mich.) or KSG-15 from Shin-Etsu Silicones of America (Akron, Ohio))
- 4-7% PPG-3 myristyl ether
- 40-50% antiperspirant active of the invention as 43% active in water
- no additional water
- 0.5-1.0% fragrance
- Formulation H
- 0.5-2.0% dimethicone copolyol (for example, Dow Corning 2-5185C (48%))
- 1-7% hydrogenated polyisobutene (for example, Fancol™ Polyiso 250)
- 40-50% elastomer in cyclomethicone (for example, DC-9040 from Dow Corning Corporation (Midland, Mich.) or KSG-15 from Shin-Etsu Silicones of America (Akron, Ohio))
- 45-55% antiperspirant active as 43% active of the invention in water
- no additional water
- 0.5-1.5% fragrance
- Formulation I
- 2-7% dimethicone copolyol (for example, Dow Corning 2-5185C (48%))
- 0.1-1% Oleath-20
- 1-5% C12-15 alkyl benzoate (FINSOLV TN)
- 15-25% elastomer in cyclomethicone (for example, DC-9040 from Dow Corning Corporation (Midland, Mich.) or KSG-15 from Shin-Etsu Silicones of America (Akron, Ohio))
- 15-25% antiperspirant active
- 15-30% water
- 0.5-1.5% fragrance
- The cosmetic composition according to the present invention can be packaged in conventional containers, using conventional techniques. Where a gel, cream or soft-solid cosmetic composition is produced, the composition can be introduced into a dispensing package (for example, conventional packages for gels with glide on applicators, jars where the gel or cream is applied by hand, and newer style packages having a top surface with pores) as conventionally done in the art. Thereafter, the product can be dispensed from the dispensing package as conventionally done in the art, to deposit the active material, for example, on the skin. For sticks, sprays, aerosols and roll-ons the compositions can be placed in a conventional types of container (with the inclusion of propellants in aerosols). This provides good deposition of the active material on the skin.
- Compositions of the present invention can be formulated as clear, translucent or opaque products, although clear products are preferred. A desired feature of the present invention is that a clear, or transparent, cosmetic composition, (for example, a clear or transparent deodorant or antiperspirant composition) can be provided. The term clear or transparent according to the present invention is intended to connote its usual dictionary definition; thus, a clear liquid or gel antiperspirant composition of the present invention allows ready viewing of objects behind it. By contrast, a translucent composition, although allowing light to pass through, causes the light to be scattered so that it will be impossible to see clearly objects behind the translucent composition. An opaque composition does not allow light to pass therethrough. Within the context of the present invention, a gel or stick is deemed to be transparent or clear if the maximum transmittance of light of any wavelength in the range 400-800 nm through a sample 1 cm thick is at least 35%, preferably at least 50%. The gel or liquid is deemed translucent if the maximum transmittance of such light through the sample is between 2% and less than 35%. A gel or liquid is deemed opaque if the maximum transmittance of light is less than 2%. The transmittance can be measured by placing a sample of the aforementioned thickness into a light beam of a spectrophotometer whose working range includes the visible spectrum, such as a Bausch & Lomb Spectronic 88 Spectrophotometer. As to this definition of clear, see European Patent Application Publication No. 291,334 A2. Thus, according to the present invention, there are differences between transparent (clear), translucent and opaque compositions.
- It is believed that the more homogeneous the composition is and the more uniform the particle size, the better properties of the composition.
- Throughout the present specification, where compositions are described as including or comprising specific components or materials, or where methods are described as including or comprising specific steps, it is contemplated by the inventors that the compositions of the present invention also consist essentially of, or consist of, the recited components or materials, and also consist essentially of, or consist of, the recited steps. Accordingly, throughout the present disclosure any described composition of the present invention can consist essentially of, or consist of, the recited components or materials, and any described method of the present invention can consist essentially of, or consist of, the recited steps.
- The following Examples are offered as illustrative of the invention and are not to be construed as limitations thereon. In the Examples and elsewhere in the description of the invention, chemical symbols and terminology have their usual and customary meanings. In the Examples as elsewhere in this application values for n, m, etc. in formulas, molecular weights and degree of ethoxylation or propoxylation are averages. Temperatures are in degrees C. unless otherwise indicated. If alcohol is used, it is 95% unless otherwise indicated. Unless otherwise indicated, “water” or “D.I. water” means deionized water. As is true throughout the application, the amounts of the components are in weight percents based on the standard described; if no other standard is described then the total weight of the composition is to be inferred. Various names of chemical components include those listed in theCTFA International Cosmetic Ingredient Dictionary (Cosmetics, Toiletry and Fragrance Association, Inc., 7th ed. 1997). While specific amounts of particular elastomers have been described, there are chemical differences in the variety of elastomers that are available. The use of different elastomers may result in the need to increase or decrease the amount of elastomer used in a particular formulation, especially if a clear product is desired.
- In the Examples, as elsewhere in the description of the invention, reference is made to using the antiperspirant active either as a powder or in some type of solution such as dissolved in water at a concentration or 25-45% actives on an anhydrous basis.
- Improved aluminum di-chlorohydrate salts (10.0% anhydrous) can be made with glycine as follows using the amounts of ingredients listed in Table A. Glycine powder (at the level listed in Table A) and distilled water are added into an aluminum dichlorohydrate solution (Westchlor 100, 38% anhydrous excluding waters of hydration) and stirred for 5 minutes to make six Examples as shown in Table A. The concentration for all the Examples 1-6 is 10% by weight. Table A also contains the pH values as measured with a Corning pH meter 430. Finally, a profile was run on each of the solutions listed in Table A and the areas under each peak were calculated. The method used is the same one described in U.S. Pat. No. 6,066,314. The Size exclusion chromatography (“SEC”) column separates the species by molecular size, using a refractive index (RI) detector connected to the column outlet. The % of each peak of the whole was also calculated and the values are listed in Table A. All concentrations are in % by weight based on the entire weight of the solution. The increase in Peak 5 species is supportive of improved efficacy. (Also see U.S. Pat. No. 6,375,937.)
- Size exclusion chromatography method is frequently used for obtaining information on polymer distribution in antiperspirant salt solutions. With appropriate chromatographic columns, at least 5 distinctive groups of polymer species can be detected in an aluminum salt, appearing in a chromatogram as peaks 1, 2, 3, 4, and a peak referred to here as “5”. Peaks 2 and 3 are larger aluminum species. Peak 4 is smaller aluminum species (aluminum oligomers) and has been correlated with enhanced efficacy for ACH salts. Peak 5 is the smallest aluminum species. The relative retention time (“Kd”) for each of these peaks varies depending on the experimental conditions. Data for Table A was obtained using the SEC method described in an issued patent owned by the same company as this case, U.S. Pat. No. 6,066,314, incorporated by reference as to the test method described therein.
TABLE A Concentration of % Example glycine (anhydrous) pH Peak 3 % Peak 4 % Peak 5 1 0 2.67 24.58 25.61 49.81 2 1 2.79 19.93 17.15 62.92 3 2 2.84 18.85 13.85 67.30 4 3 2.94 18.75 13.92 67.34 5 4 3.10 17.87 14.31 67.81 6 5 3.50 18.01 14.63 67.36 - Using the concentration listed in Table B, betaine powder and distilled water are added into an aluminum di chlorohydrate solution (Westchlor 100, 48% anhydrous) and stirred for five minutes to make Examples 7-12 with a concentration of 10 weight % ADCH. The same analytical method described for Examples 1-6 was used to obtain the data listed in Table B.
TABLE B Concentration of % Example betaine (anhydrous) pH Peak 3 % Peak 4 % Peak 5 7 0 2.67 24.58 25.61 49.81 8 1 2.72 24.10 23.63 52.27 9 2 2.80 22.76 22.7 54.54 10 3 2.82 20.83 21.37 57.80 11 4 2.90 20.83 21.37 57.80 12 5 3.03 18.20 18.33 63.47 - A clinical evaluation with forearm screening using the procedure described below was done with liquid gel formulae containing antiperspirant salt solution made with aluminum dichlorohydrate, water and glycine so that the concentration of the antiperspirant on an anhydrous basis is 25 weight % and the concentration of glycine is the amount listed in Table C. It will be noted that the % sweat reduction of the salt in stored solution (8 days at about 40 degrees C. (105 degrees F.) decreases after the amount of glycine exceeds 3%. The sweat reduction for the Examples with 1% and 2% glycine is similar to the one without glycine. This means that the use of glycine does not negatively impact efficacy. The drop in efficacy at the addition levels of 3% and 5% glycine is due to the gellation of the aluminum salt in the internal phase. Thus, if a solution of the salt is to be used, the concentration should be kept less than 3%. Table C shows that the use of a 1% or 2% salt material of the invention as a solution to achieve the low irritancy and fragrance favorable properties in a clear, non-yellowing solution can be done without sacrificing efficacy. Note that spray drying the salt product can keep this gellation from happening and allow the use of higher concentrations of glycine.
TABLE C Concentration Forearm rating Example of glycine (% sweat reduction) 13 0% 60% 14 1% 70% 15 2% 60% 16 3% 25% 17 4% NA 18 5% 15% - Each of the Examples 1-18 can be formed into a powder using conventional spray drying or freeze drying techniques known to those skilled in the art. Examples of such methods may be found in U.S. Pat. No. 5,589,196. Note that in spray drying the material, the maximum amount of water left in the spray dried product should not exceed 25 weight %.
- In general, the external and internal phases are formed separately either at room temperature or with heating as described below. The internal phase is added to the external phase very slowly while stirring at to form an emulsion. After the addition has been completed, the mixture is stirred at higher speed to achieve a homogeneous mixture. The final formula viscosity is then achieved by homogenizing the emulsion under either batch or continuous process conditions as described below. The fragrance may be added at any time during the process prior to final homogenization.
- Preparation of the External Phase:
- The ingredients to be used in the external phase (including the elastomer) are weighed out at room temperature and combined in a suitable vessel such as a 2 liter glass beaker. The mixture is stirred at about 500 rpm for 15-20 minutes using an overhead mixer such as a Lightnin Mixer Model L1003. If a waxy or solid emollient is to be added to the external (also called “continuous”) phase, the mixture may be heated to facilitate dissolution while stirring then cooled to room temperature prior to combination with the internal phase as described below. The elastomer component is obtained as a suspension of elastomer in cyclomethicone (for example at a concentration of 6% active in D5 cyclomethicone). The elastomer component is added to the external phase with stirring at high speed (500-700 rpm for a 0.5 kilogram batch) until no particles of elastomer are visible to the eye.
- Preparation of the Internal Phase:
- The internal dispersed phase is prepared as described below. Ingredients are mixed for a time sufficient to achieve homogeneity. The antiperspirant active used is weighed into a large beaker equipped with an overhead stirrer. Other internal phase ingredients are then added while stirring.
- The fragrance (if any is used) is added last and may be added either to the internal phase or the external phase or the final formula prior to homogenization. For many of the examples described here, one could add the fragrance to the internal phase.
- If an optional non-ionic emulsifier such as Oleath-20 is used, the emulsifier and propylene glycol are combined in a separate beaker and heated to 40 degrees C. with stirring until the non-ionic emulsifier completely dissolved. The heat is turned off and the remaining ingredients to be used in the internal phase, including the antiperspirant active are weighed out and added to the mixture of propylene glycol and non-ionic emulsifier.
- If water or a salt solution are used, the internal phase is prepared as follows. The solution containing antiperspirant active salt as received from supplier is weighed into a large beaker equipped with a magnetic stirrer. Additional ingredients such as propylene glycol, ethanol and water are added while stirring. If a salt water solution is used (such as for NaCl, etc.), the salt water solution is prepared by dissolving the crystalline salt in water in a separate beaker and stirring until dissolved. The salt water solution is then added to the rest of the internal phase and the mixture is stirred until homogeneous.
- Preparation of the Emulsion:
- The internal phase made as described above is then added to the external phase over the course of 15-30 minutes while stirring at a speed of 500-700 rpm. After the addition is complete, the mixture is stirred at 500-700 rpm for 20 minutes using a Lightnin Mixer Model L1003. The mixture is then homogenized for 2-4 minutes (especially 3 minutes) using a homogenizer from Greerco Corp., Hudson, N.H. at a reading of about 60 on a Powerstat Variable Autotransformer from Superior Electric Co., Bristol, Conn.
- Further Processing:
- The product is then further processed by homogenization to achieve the desired final viscosity. This can be done by using a Gilford-Wood Model 1-L (Greerco Corp., Hudson, N.H.) homogenizer. The homogenizer speed is controlled by a Powerstat Variable Autotransformer Type 3PN116B (Superior Electronic. Co., Bristol, Conn.). Typical voltage setting and processing time are chosen to give a desired final formula viscosity.
- An other method of homogenization of the final product is to pass the emulsion through a colloid mill such as a Sonic Tri-Homo Colloid Mill or a process sonolator such Sonic Production Sonolator 200-30 both available from Sonic Corporation of Stratford, Conn. Process conditions are chosen to give the desired final product viscosity.
- The method described in Example 37 may be used to make the compositions listed in Tables D and E with the types and amounts of ingredients listed in the Tables. Amounts are in percent by weight based on the total weight of the composition. For the antiperspirant active, any of the solutions of actives described in Examples 1-18 may be used.
TABLE D Ingredient Ex. 38 Ex. 39 Ex. 40 Ex. 41 Ex. 42 Ex. 43 Ex. 44 Ex. 45 Ex. 46 Ex. 47 External Phase Elastomer (KSG-15, 6% active) 62 50 48 40 41.5 42.0 46.5 35 32.17 25 Dimethicone copolyol 2 2 1.5 4 1.5 0.5 1.0 1.0 2.48 1.0 (Dow Corning 2-5185, 48% active in cyclomethicone) Hydrogenated 0 0 5 8 5 5 5 5 4.95 0 polyisobutene (Polyiso 250) PPG-3 Myristyl Ether 5 5 4.5 0 4.5 5.0 0 0 0 5 C12-l5 alkyl benzoate 0 0 0 2.0 0 0 0 0 0 0 (FINSOLV TN) Cyclomethicone (Dow Corning 245) 0 2 0 0 0 0 0 0 0 0 Fragrance 1 1 1 1 1 1 1 1 1 0 Internal Phase 0 Antiperspirant Activea 15 20 17.5 19.5 46.5 46.5 46.5 58 59.40 48.45 Water (deionized)b 15 20 22.5 25 0 0 0 0 0 0 Oleath-20 (HLB > 8) 0 0 0 0.5 0 0 0 0 0 19.55 Total 100 100 100 100 100 100 100 100 100 100 -
TABLE E Ingredient Ex. 48 Ex. 49 Ex. 50 Ex. 51 Ex. 52 Ex. 53 Ex. 54 Ex. 55 Ex. 56 Ex. 57 Ex. 58 External Phase Elastomer (DC 9040) 12% 55 62 62 40 41.5 25 31.5 21 17 17 50 active) Dimethicone copolyol 1 2 2 4 1 1 2.5 1 1 1 2 (Dow Corning 2-5185, 48% active in cyclomethicone) Hydrogenated 5 — — 8 5 — 5 1.5 1.5 1.5 — polyisobutene (Polyiso 250) PPG-3 Myristyl Ether 3 4.5 5 — 5 5 — 0.5 0.5 0.5 5.0 C12-15 alkyl benzoate — — — 2 — — — — — — — (FINSOLV TN) Cyclomethicone — — — — — — — 5 9.0 9.0 2.0 (Dow Corning 245) Fragrance 1 1 1 1 1 1 1 1 1 1 1 Internal Phase Antiperspirant Activea 15 15.5 30 19.5 46.5 48.45 60.0 60.5 63.68 60.13 20 Water (deionized)b 20 15 25 19.55 9.5 6.32 9.87 20 Oleath-20 (HLB > 8) — — — 0.5 — — — — — — — Total 100 100 100 100 100 100 100 100 100 100 100 - A forearm starch/iodine test may be used as a rapid screening tool for underarm formulations prior to underarm clinical testing. The following procedure may be used for all tests discussed in this patent document. Panelists should be chosen who had not placed any antiperspirant products on their interior forearms for at least 14 days prior to the start of the test. Test formulations are applied on the inner forearms in preselected amounts. A control product such as a commercial product (Lady Speed Stick AP) is applied to one site on the panelists' arms as a positive control. After application of the formulations, the sites are occluded with covering chambers for one hour under conditions of about 40 degrees C. and 30% relative humidity. Panelists then remove the covering chambers. One hour after removal of the covering chambers, the forearms are each washed with a mild soap. This is repeated for the first two days of the study. On the third day of product application, the sites are occluded for one (1) hour, but are not washed with soap. The panelists perform their normal cleansing regimen using a mild soap during the course of the study. Approximately 20 hours after the last application of the products, the panelists are equilibrated in a room at 40 degrees C. (105° F.) and 40% relative humidity for 15 minutes. The panelists arms are then patted dry with a paper towel followed by application of paper strips impregnated with iodine to the test sites. Exposure to sweat causes the paper to turn purple at sites of hydration, generating a spatial map of the firing sweat glands. The papers are removed once the purple spots begin to appear on the backside or after five minutes, whichever comes first. Images of the papers may be digitized to quantify the amount of purple spot coverage. Once images are digitized, the area for measurement is identified using the same area as occluded by the chambers. A comparison of the total area of hydration for treated skin versus untreated sites is used to calculate a % Sweat Reduction (Eq:1). The area of sweat from untreated sites used in Equation 1 is calculated as the mean sweat areas of all the untreated sites directly adjacent to the treated site of interest. Since the number of firing sweat glands varies along the surface of the volar forearm, the mean sweat area of the adjacent untreated sites is used to approximate the area of sweat which would have been produced if a formula had not been applied to the treatment site.
- % Sweat Reduction=100[1−(Area-Treated/Mean(Area-Untreated))] Eq:1
- An antiperspirant product can be made using the following ingredients:
- Part 1
- 51% Cyclomethicone (D5); 3% PPG-3 myristyl ether; 6% C12-15 alkyl benzoate (FINSOLV TN from Finetex Inc., Elmwood Park, N.J.); 1% fragrance; 10% vinyl polydimethyl siloxane elastomer 10% in D5 cyclomethicone (USG-103 from Shin-Etsu Silicones of America, Inc., Akron, Ohio);
- Part 2
- 5% fumed silica (Cab-O-Sil from Cabot Corp.); 24% of an active made as for Example 32
- All ingredients in Part 1 are added into a beaker, and stirred at about 400 rpm using an overhead mixer such as a Lightnin' Mixer Model L1003 until it becomes visually homogeneous. The mixture is then transferred into the container of a Hobart Mixer (Model N-50), where the ingredients in Part 2 have been placed. The Hobart Mixer is then turned on and running at “low” speed for 30 minutes or until a uniform creamy product is formed.
- An antiperspirant product can be made using the following ingredients:
- Part 1
- 10% Cyclomethicone (DC 345 from Dow Corning); 20% stearyl alcohol; 12% C12-15 alkyl benzoate (FINSOLV TN); 4% hydrogenated castor oil (MP80); 4% PEG-8 distearate
- Part 2
- 20.80% Cyclomethicone (DC 345); 3% dimethicone copolyol (DC 5225C from Dow Corning, 10%); 25% of an active as described in Example 33
- Part 3
- 1% fragrance
- Formation of Part 1
- Mix cyclomethicone and FINSOLV TN at 300 rpm using an overhead mixer such as a Lightnin' Mixer Model L1003. Heat the mixture to 70° C. and add stearyl alcohol with continuous stirring. After stearyl alcohol is melted, the temperature is increased to 75° C. Melt PEG-8 distearate by adding it to the mixture. Increase temperature further to 80° C. Add hydrogenated castor oil. Stir it in the solution until it is dissolved.
- Formation of Part 2
- Put all ingredients in Part 2 in a separate beaker. Heat it to 70° C. with stirring.
- Formation of Stick
- Add Part 2 to Part 1 at 70-75° C., and mix at 450 rpm for 15 min. Turn the heater off and let it cool to 65° C., and add fragrance. Pour the sample out into barrels at 58° C. Form sticks by placing the barrels into refrigerator for 15 minutes.
- An antiperspirant product can be made using the following ingredients:
- Part 1
- 3% dimethicone copolyol (DC 5225C); 13.5% dimethicone (2 cst viscosity, DC 200 from Dow Corning); 2.5% PPG-3 myristyl ether; 0.80% fragrance
- Part 2
- 72% of the composition described in Example 14; 8.2% propylene glycol
- Mix the ingredients in Part 1 to form a clear solution with an overhead mixture. Mix the ingredients in Part 2 in a separate beaker to form an aqueous solution. Add Part 2 to Part 1 slowly with continuous mixing at 600 rpm using a Lightnin' Mixer (Model L1003). Keep stirring for another 20 minutes after addition of Part 2 is finished or until a visually uniform emulsion is formed. Homogenize the emulsion for 2-4 minutes using a homogenizer (Greerco Corp., Hudson, N.H.) at a reading of about 30 on a Powerstat Variable Autotransformer (Superior Electric Co., Bristol, Conn.).
- An antiperspirant product can be made using the following ingredients:
- Part 1:
- 36% Phase inversion temperature concentrate (“PIT Concentrate” such as Emulgade® CM from (from Cognis Co., Ambler, Pa.)
- Part 2:
- 1% fragrance; 1% nonionic surfactant (Emulgen L from Cognis Co., Ambler, Pa.)
- Part 3:
- 62% of a composition as described in Example 15
- Mix the fragrance and surfactant in a separate beaker to form a clear solution. Add Part 3 and the above solution into Part 1 one after the other at room temperature with continuous stirring until a uniform translucent liquid is formed.
- An antiperspirant product can be made using the following ingredients:
- Part 1:
- 16.30% Cyclomethicone (DC 245 from Dow Corning); 2.80% PPG-3 myristyl ether; 0.80% fragrance
- Part 2:
- 69.99% of a composition from Example 14; 9.70% propylene glycol; 0.40% Polyquaternium-10 (Polymer JR, from Amerchol, Edison, N.J.); 0.010% Oleath-10 (Volpo 10 from Croda, Inc., New Jersey)
- All of the ingredients for Part 1 are combined in a beaker and the mixture is stirred at 300-400 rpm using a Lightnin' Mixer Model L 1003 until a homogeneous solution is obtained.
- Add all the ingredients in Part 2 in a separate beaker together and heat it to 40-50° C. with agitation until a clear solution is obtained.
- Add Part 2 to Part 1.
- An antiperspirant product can be made using the following ingredients:
- Part 1:
- 24.00% Cyclomethicone (D5); 5.00% PPG-3 myristyl ether; 1.00% fragrance
- Part 2:
- 65.00% of a composition of Example 15; 5.00% ethanol (Alcohol SD-200 proof (100%))
- Mix the ingredients in Part 1 to form a clear solution by using an overhead mixer. Mix the ingredients in Part 2 to form an aqueous solution. Add Part 2 to Part 1.
Claims (11)
1. A zirconium-free aluminum salt which:
(a) has an aluminum to chloride molar ratio in the range of 0.5-2.5:1;
(b) comprises a nitrogen containing buffering material in an amount such that the ratio of nitrogen containing material to aluminum is the range of 0.05-0.26:1 and which nitrogen containing material is selected from the group consisting of a nitrogen containing buffering material of formula
where n is a number in the range of 1-20, and each of R1, R2, and R3 is independently selected from the group consisting of hydrogen, methyl and ethyl; and
(c) the salt has a pH in the range of 2-4 at a concentration of 15%; wherein the salt is free of any other halide scavenging material and has a value of at least 0.50 for the ratio calculated as:
2. A zirconium-free aluminum salt according to claim 1 wherein the ratio of nitrogen containing material to aluminum is in the range of 0.05-0.16:1.
3. A zirconium-free aluminum salt according to claim 1 wherein each of R1, R2, and R3 is methyl.
4. A zirconium-free aluminum salt according to claim 1 wherein the nitrogen containing material is selected from the group consisting of glycine, alanine, serine, glutamine, threonine, valine, leucine and betaine.
5. An antiperspirant composition made with the composition of claim 1 .
6. An antiperspirant composition according to claim 5 wherein the composition is a stick comprising a gelling agent which is stearyl alcohol or dibenzylidene sorbitol.
7. An antiperspirant composition according to claim 6 comprising:
40-55% cyclomethicone; 20-30% stearyl alcohol; 7-15% talc; 15-22% aluminum antiperspirant active added as a powder; optionally 1-3% fragrance.
8. An antiperspirant composition according to claim 5 wherein the composition is a roll-on comprising 45-65% cyclomethicone; 0.1-10% cyclomethicone/dimethicone copolyol; 10-25% in a solution form as 25-45% actives on an anhydrous basis in water; 5-30% water; and optionally 1-3% fragrance.
9. An antiperspirant composition according to claim 5 wherein the composition is a soft solid comprising 40-70% elastomer in cyclomethicone; 5-15% polyethylene; 10-20% C12-15 alkylbenzoate; 0.1-25% antiperspirant active added in powder form 1-15% dimethicone (100 centistokes); and optionally 1-3% fragrance.
10. An antiperspirant composition according to claim 5 wherein the composition is a gel comprising 5-50% cyclomethicone; 0.1-10% cyclomethicone/dimethicone copolyol; 0-10% hydrogenated polyisobutene 250; 0-10% C12-15 alkylbenzoate; 0-10% dimethicone (100 centistokes); 0.1-25% antiperspirant active added in powder form or 10-25% of antiperspirant active added as a solution of 25-45% actives on an anhydrous basis; 5-50% water; and optionally 1-3% fragrance.
11. An antiperspirant composition according to any one of claims 5-10 wherein the glycol content is less than 1.0 weight %.
Priority Applications (15)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/314,712 US20040109833A1 (en) | 2002-12-09 | 2002-12-09 | High efficacy, low irritation aluminum salts and related products |
AU2003293362A AU2003293362A1 (en) | 2002-12-09 | 2003-12-04 | High efficacy, low irritation aluminum salts and antiperspirant products |
PCT/US2003/038486 WO2004052325A1 (en) | 2002-12-09 | 2003-12-04 | High efficacy, low irritation aluminum salts and antiperspirant products |
BR0317094-2A BR0317094A (en) | 2002-12-09 | 2003-12-04 | Zirconium-free aluminum salt and antiperspirant composition |
RU2005121556/15A RU2005121556A (en) | 2002-12-09 | 2003-12-04 | HIGH-PERFORMANCE ALUMINUM SALTS WITH A LOW IRRITANT EFFECT AND ANTI-PERSPECTIVE PRODUCTS |
CA002511831A CA2511831A1 (en) | 2002-12-09 | 2003-12-04 | High efficacy, low irritation aluminum salts and antiperspirant products |
PL377343A PL377343A1 (en) | 2002-12-09 | 2003-12-04 | High efficacy, low irritation aluminum salts and antiperspirant products |
MXPA05006068A MXPA05006068A (en) | 2002-12-09 | 2003-12-04 | High efficacy, low irritation aluminum salts and antiperspirant products. |
EP03790308A EP1572144A1 (en) | 2002-12-09 | 2003-12-04 | High efficacy, low irritation aluminum salts and antiperspirant products |
GT200300272A GT200300272A (en) | 2002-12-09 | 2003-12-08 | LITTLE IRRITANT AND HIGH-EFFICIENT ALUMINUM SALTS AND RELATED PRODUCTS |
PA20038591301A PA8591301A1 (en) | 2002-12-09 | 2003-12-09 | ALUMINUM SALTS OF HIGH EFFECTIVENESS AND LOW IRRITATION AND RELATED PRODUCTS |
ARP030104531A AR042346A1 (en) | 2002-12-09 | 2003-12-09 | LOW IRRITANT AND HIGH EFFECTIVE ALUMINUM SALTS AND THE ANTI-TRANSPIRING COMPOSITIONS CONTAINING THEM |
CL200302555A CL2003002555A1 (en) | 2002-12-09 | 2003-12-09 | ZIRCONIO FREE ALUMINUM SALT THAT IS RELATED TO AL: CHLORIDE OF 0.5 -2.5: 1, A SHOCK ABSORBER THAT HAS NITROGEN IN A REASON REGARDING ALUMINUM OF 0.05 - 0.25: 1, HIS PH IS FOUND UNDERSTANDED BETWEEN 2 - 4 AT A CONCENTRATION OF 15% AND IS A |
US11/080,913 US7311898B2 (en) | 2002-12-09 | 2005-03-15 | High efficacy, low irritation aluminum salts and related products |
ZA200504623A ZA200504623B (en) | 2002-12-09 | 2005-06-06 | High efficacy, low irritation aluminium salts and anti-perspirant products |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/314,712 US20040109833A1 (en) | 2002-12-09 | 2002-12-09 | High efficacy, low irritation aluminum salts and related products |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/080,913 Continuation US7311898B2 (en) | 2002-12-09 | 2005-03-15 | High efficacy, low irritation aluminum salts and related products |
Publications (1)
Publication Number | Publication Date |
---|---|
US20040109833A1 true US20040109833A1 (en) | 2004-06-10 |
Family
ID=32468544
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/314,712 Abandoned US20040109833A1 (en) | 2002-12-09 | 2002-12-09 | High efficacy, low irritation aluminum salts and related products |
US11/080,913 Expired - Fee Related US7311898B2 (en) | 2002-12-09 | 2005-03-15 | High efficacy, low irritation aluminum salts and related products |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/080,913 Expired - Fee Related US7311898B2 (en) | 2002-12-09 | 2005-03-15 | High efficacy, low irritation aluminum salts and related products |
Country Status (14)
Country | Link |
---|---|
US (2) | US20040109833A1 (en) |
EP (1) | EP1572144A1 (en) |
AR (1) | AR042346A1 (en) |
AU (1) | AU2003293362A1 (en) |
BR (1) | BR0317094A (en) |
CA (1) | CA2511831A1 (en) |
CL (1) | CL2003002555A1 (en) |
GT (1) | GT200300272A (en) |
MX (1) | MXPA05006068A (en) |
PA (1) | PA8591301A1 (en) |
PL (1) | PL377343A1 (en) |
RU (1) | RU2005121556A (en) |
WO (1) | WO2004052325A1 (en) |
ZA (1) | ZA200504623B (en) |
Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040241123A1 (en) * | 2003-05-30 | 2004-12-02 | Christine Popoff | Suspension free and elastomer free antiperspirant cream |
US20040241122A1 (en) * | 2003-05-30 | 2004-12-02 | Christine Popoff | High efficacy gel with low glycol content |
US20040265255A1 (en) * | 2003-06-26 | 2004-12-30 | Marian Holerca | Aluminum / zirconium / glycine antiperspirant actives stabilized with betaine |
US20060263312A1 (en) * | 2005-05-19 | 2006-11-23 | Scavone Timothy A | Consumer noticeable improvement in wetness protection using solid antiperspirant compositions |
US20060292098A1 (en) * | 2005-05-19 | 2006-12-28 | Scavone Timothy A | Consumer noticeable improvement in wetness protection |
US20070020211A1 (en) * | 2005-07-22 | 2007-01-25 | Reheis, Inc. | Betaine with Calcium and/or Strontium Antiperspirants |
US20070196303A1 (en) * | 2006-02-17 | 2007-08-23 | Reheis, Inc. | Stable buffered aluminum compositions having high hplc bands iii and iv containing calcium/strontium |
US20070248553A1 (en) * | 2005-05-19 | 2007-10-25 | Scavone Timothy A | Consumer noticeable improvement in wetness protection |
US20070248552A1 (en) * | 2005-05-19 | 2007-10-25 | Scavone Timothy A | Consumer noticeable improvement in wetness protection using solid antiperspirant compositions |
US20070286829A1 (en) * | 2004-05-13 | 2007-12-13 | Batista Andrea P | Antiperspirant Or Deodorant Compositions |
WO2008097716A2 (en) | 2007-02-02 | 2008-08-14 | Colgate-Palmolive Company | Antiperspirant/deodorant composition |
US20080213191A1 (en) * | 2007-03-01 | 2008-09-04 | Timothy Alan Scavone | Composition and/or articles comprising cyclodextrin complexing material |
WO2008144079A1 (en) | 2007-02-02 | 2008-11-27 | Colgate-Palmolive Company | Antiperspirant / deodorant compositions |
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 |
US20110014144A1 (en) * | 2005-11-16 | 2011-01-20 | Colgate-Palmolive Company | Antiperspirant compositions |
US20110076309A1 (en) * | 2009-09-30 | 2011-03-31 | Misner H Steven | Antiperspirant/Deodorant Composition |
US20110076310A1 (en) * | 2009-09-30 | 2011-03-31 | Colgate-Palmolive Company | Antiperspirant/Deodorant Composition |
WO2011050044A1 (en) | 2009-10-20 | 2011-04-28 | Colgate-Palmolive Company | Antiperspirant that reduces/eliminates yellowing on clothing |
WO2011079001A2 (en) | 2009-12-23 | 2011-06-30 | Colgate-Palmolive Company | Anhydrous liquid antiperspirant/deodorant composition |
WO2012005720A1 (en) | 2010-07-06 | 2012-01-12 | Colgate-Palmolive Company | Personal care product and manufacture thereof |
WO2014092688A1 (en) | 2012-12-11 | 2014-06-19 | Colgate-Palmolive Company | Antiperspirant/deodorant with alkylated polyvinylpyrrolidone |
WO2014171948A1 (en) | 2013-04-19 | 2014-10-23 | Colgate-Palmolive Company | Aerosol antiperspirants |
US8895041B2 (en) | 2012-03-23 | 2014-11-25 | The Procter & Gamble Company | Compositions for delivering perfume to the skin |
US9896645B2 (en) | 2013-03-15 | 2018-02-20 | The Procter & Gamble Company | Personal care compositions |
WO2018125030A1 (en) | 2016-12-27 | 2018-07-05 | Colgate-Palmolive Company | Extruded antiperspirant composition for improved efficacy |
US10111817B2 (en) | 2014-07-21 | 2018-10-30 | Colgate-Palmolive Company | Antiperspirant compositions containing ethylenediamine disuccinate |
WO2019117903A1 (en) | 2017-12-14 | 2019-06-20 | Colgate-Palmolive Company | Antiperspirant/deodorant compositions including biodegradable amino carboxylates and methods for the same |
US11000468B2 (en) | 2016-09-06 | 2021-05-11 | The Procter & Gamble Company | Aerosol compositions |
WO2021096518A1 (en) | 2019-11-14 | 2021-05-20 | Colgate-Palmolive Company | Personal care compositions for treating odor causing bacteria and methods for the same |
US11090250B2 (en) | 2007-03-01 | 2021-08-17 | The Procter & Gamble Company | Compositions and/or articles comprising cyclodextrin complexing material |
US11491099B2 (en) | 2016-09-06 | 2022-11-08 | The Procter & Gamble Company | Antiperspirant and deodorant compositions |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2149907A3 (en) * | 2002-08-29 | 2014-05-07 | Seoul Semiconductor Co., Ltd. | Light-emitting device having light-emitting diodes |
US8883129B2 (en) | 2005-01-13 | 2014-11-11 | The Procter & Gamble Company | Enhanced efficacy antiperspirant active |
Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4331609A (en) * | 1980-09-08 | 1982-05-25 | The Procter & Gamble Company | Antiperspirant composition |
US4499069A (en) * | 1983-02-07 | 1985-02-12 | The Gillette Company | Antiperspirant emulsion |
US4606915A (en) * | 1981-04-23 | 1986-08-19 | Bristol-Myers Company | Antiperspirant combination containing an aluminum halohydrate and a stannic halide |
US4675177A (en) * | 1980-10-09 | 1987-06-23 | American Cyanamid Company | Antiperspirant compositions |
US4871525A (en) * | 1986-10-24 | 1989-10-03 | Westwood Chemical Corporation | Antiperspirant composition and method of preparation |
US5234677A (en) * | 1984-11-21 | 1993-08-10 | Reheis Inc. | Enhanced efficacy aluminum chlorhydrate antiperspirant and method of making same |
US5356612A (en) * | 1988-04-14 | 1994-10-18 | The Gillette Company | Antiperspirant and method of making same |
US5384117A (en) * | 1989-05-03 | 1995-01-24 | The Gillette Company | Antiperspirant |
US5393518A (en) * | 1989-12-08 | 1995-02-28 | The Gillette Company | Clear roll-on antiperspirant composition |
US5518714A (en) * | 1984-04-24 | 1996-05-21 | Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. | Method for inhibiting the dissolution of antiperspirant compounds in alcohols |
US5599533A (en) * | 1994-12-15 | 1997-02-04 | Estee Lauder, Inc. | Stable water-in-oil emulsion system |
US5718876A (en) * | 1990-09-07 | 1998-02-17 | Reheis Inc. | Basic aluminum and aluminum/zirconium antiperspirants and method of making the same |
US6024945A (en) * | 1999-07-29 | 2000-02-15 | Reheis, Inc. | Antiperspirant compositions for aerosol formulations |
US6066314A (en) * | 1997-10-29 | 2000-05-23 | Colgate-Palmolive Company | Antiperspirant actives and formulations made therefrom |
US6126928A (en) * | 1999-08-24 | 2000-10-03 | The Procter & Gamble Company | Compositions containing solubilized, acid-enhanced antiperspirant active |
US6375937B1 (en) * | 2000-10-20 | 2002-04-23 | Colgate-Palmolive Company | Antiperspirant salts for enhanced cosmetic products |
Family Cites Families (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1025615A (en) * | 1911-10-19 | 1912-05-07 | Hoffmann La Roche Chemical Works | Process of separating meta- and para-cresols. |
US4025615A (en) | 1975-02-25 | 1977-05-24 | Armour Pharmaceutical Company | Antiperspirant complexes formed with alkali metal and ammonium zirconyl carbonates |
FR2303536A1 (en) * | 1975-03-11 | 1976-10-08 | Rhone Poulenc Ind | NEW ALUMINUM SALTS, THEIR PREPARATION AND THE COMPOSITIONS CONTAINING THEM |
US4359456A (en) * | 1976-01-14 | 1982-11-16 | Lever Brothers Company | Antiperspirant activity of basic aluminum compounds |
FR2407713A1 (en) * | 1977-11-03 | 1979-06-01 | Warner Lambert Co | ANTI-PERSPIRANT COMPOSITIONS AND THEIR PREPARATION |
CA1140470A (en) | 1980-05-27 | 1983-02-01 | Leonard Mackles | Aluminum chloride and aluminum zirconium hydroxychloride as antiperspirant |
US4435382A (en) * | 1980-07-14 | 1984-03-06 | Bristol-Myers Company | Anhydrous alcoholic antiperspirant suspension composition containing certain aluminum or aluminum/zirconium salt glycine complexes |
CA1153313A (en) | 1980-12-15 | 1983-09-06 | Chung T. Shin | Antiperspirant composition containing aluminum chlorohydrate, aluminum chloride and an aluminum zirconium polychlorohydrate complex and method of use |
US4775528A (en) * | 1983-08-16 | 1988-10-04 | The Gillette Company | Antiperspirant composition |
US5589196A (en) * | 1983-08-16 | 1996-12-31 | The Gillette Company | Antiperspirant composition |
CA2046170A1 (en) * | 1990-07-10 | 1992-01-11 | Morton Lawrence Barr | Basic aluminum antiperspirant active materials having enhanced activity, antiperspirant active compositions containing such materials, and methods for preparation of such materials and compositions |
NZ241567A (en) | 1991-02-13 | 1994-08-26 | Bristol Myers Squibb Co | Zirconium-aluminium-amino acid salts, and antiperspirant compositions thereof |
US5225187A (en) * | 1991-02-15 | 1993-07-06 | Somerville Technology Group, Inc. | Process for preparing concentrated aluminum-zirconium solutions |
ZA945542B (en) | 1993-08-10 | 1995-05-26 | Bristol Myers Squibb Co | Novel zirconium salts and their synthesis |
US5516511A (en) * | 1994-05-06 | 1996-05-14 | The Procter & Gamble Company | Antiperspirant gel compositions comprising chelators |
US5643558A (en) * | 1994-11-02 | 1997-07-01 | The Gillette Company | Method of making polyhydric alcohol solutions of enhanced efficacy antiperspirant actives |
HUP0101738A3 (en) | 1998-04-03 | 2003-04-28 | Colgate Palmolive Co New York | Improved low residue cosmetic composition |
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 |
DE19855935A1 (en) | 1998-12-04 | 2000-06-08 | Beiersdorf Ag | Use of functionally substituted betaines as antiperspirants |
DE19855934A1 (en) | 1998-12-04 | 2000-06-08 | Beiersdorf Ag | Use of betaines as antiperspirants |
US6265364B1 (en) | 1999-12-28 | 2001-07-24 | Colgate-Palmolive Company | Solid cleansing composition comprising a choline salt |
AR031108A1 (en) | 2000-06-19 | 2003-09-10 | Colgate Palmolive Co | A METHOD FOR IMPROVING THE ACTIVITY OF AN ALUMINUM OR ALUMINUM / CIRCONIUM SALT CONTAINING SMALL AND LARGE ALUMINUM SPECIES, SALES SO OBTAINED AND ANTI-TRANSPIRING AND / OR DEODORANT PRODUCTS PREPARED WITH SUCH IMPROVED SALTS |
US6436381B1 (en) | 2000-10-25 | 2002-08-20 | The Gillette Company | Aluminum-zirconium antiperspirant salts with high peak 5 al content |
US6726901B2 (en) | 2002-05-09 | 2004-04-27 | The Gillette Company | Stabilized antiperspirant compositions containing aluminum-zirconium salts with low M:Cl ratio |
US20040091436A1 (en) | 2002-11-12 | 2004-05-13 | Zijun Li | Antiperspirant compositions of enhanced efficacy containing strontium |
US6911195B2 (en) | 2002-12-16 | 2005-06-28 | The Gillette Company | Gel antiperspirant composition containing volatile linear silicone and calcium enhanced antiperspirant salt |
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 |
US6902724B1 (en) * | 2004-03-24 | 2005-06-07 | Reheis, Inc. | Enhanced efficacy basic aluminum halides, antiperspirant active compositions and methods for making |
US7014843B2 (en) * | 2004-03-24 | 2006-03-21 | Reheis, Inc. | Enhanced efficacy basic aluminum halides/metal cation salt, antiperspirants actives and compositions containing such materials and methods for making |
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 |
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 |
-
2002
- 2002-12-09 US US10/314,712 patent/US20040109833A1/en not_active Abandoned
-
2003
- 2003-12-04 EP EP03790308A patent/EP1572144A1/en not_active Withdrawn
- 2003-12-04 CA CA002511831A patent/CA2511831A1/en not_active Abandoned
- 2003-12-04 WO PCT/US2003/038486 patent/WO2004052325A1/en not_active Application Discontinuation
- 2003-12-04 RU RU2005121556/15A patent/RU2005121556A/en not_active Application Discontinuation
- 2003-12-04 MX MXPA05006068A patent/MXPA05006068A/en not_active Application Discontinuation
- 2003-12-04 AU AU2003293362A patent/AU2003293362A1/en not_active Abandoned
- 2003-12-04 PL PL377343A patent/PL377343A1/en not_active Application Discontinuation
- 2003-12-04 BR BR0317094-2A patent/BR0317094A/en not_active IP Right Cessation
- 2003-12-08 GT GT200300272A patent/GT200300272A/en unknown
- 2003-12-09 CL CL200302555A patent/CL2003002555A1/en unknown
- 2003-12-09 PA PA20038591301A patent/PA8591301A1/en unknown
- 2003-12-09 AR ARP030104531A patent/AR042346A1/en not_active Application Discontinuation
-
2005
- 2005-03-15 US US11/080,913 patent/US7311898B2/en not_active Expired - Fee Related
- 2005-06-06 ZA ZA200504623A patent/ZA200504623B/en unknown
Patent Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4331609A (en) * | 1980-09-08 | 1982-05-25 | The Procter & Gamble Company | Antiperspirant composition |
US4675177A (en) * | 1980-10-09 | 1987-06-23 | American Cyanamid Company | Antiperspirant compositions |
US4606915A (en) * | 1981-04-23 | 1986-08-19 | Bristol-Myers Company | Antiperspirant combination containing an aluminum halohydrate and a stannic halide |
US4499069A (en) * | 1983-02-07 | 1985-02-12 | The Gillette Company | Antiperspirant emulsion |
US5518714A (en) * | 1984-04-24 | 1996-05-21 | Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. | Method for inhibiting the dissolution of antiperspirant compounds in alcohols |
US5234677A (en) * | 1984-11-21 | 1993-08-10 | Reheis Inc. | Enhanced efficacy aluminum chlorhydrate antiperspirant and method of making same |
US4871525A (en) * | 1986-10-24 | 1989-10-03 | Westwood Chemical Corporation | Antiperspirant composition and method of preparation |
US5356612A (en) * | 1988-04-14 | 1994-10-18 | The Gillette Company | Antiperspirant and method of making same |
US5384117A (en) * | 1989-05-03 | 1995-01-24 | The Gillette Company | Antiperspirant |
US5393518A (en) * | 1989-12-08 | 1995-02-28 | The Gillette Company | Clear roll-on antiperspirant composition |
US5718876A (en) * | 1990-09-07 | 1998-02-17 | Reheis Inc. | Basic aluminum and aluminum/zirconium antiperspirants and method of making the same |
US5908616A (en) * | 1990-09-07 | 1999-06-01 | Reheis Inc. | Method of inhibiting perspiration with basic aluminum and aluminum/zirconium antiperspirants |
US5599533A (en) * | 1994-12-15 | 1997-02-04 | Estee Lauder, Inc. | Stable water-in-oil emulsion system |
US6066314A (en) * | 1997-10-29 | 2000-05-23 | Colgate-Palmolive Company | Antiperspirant actives and formulations made therefrom |
US6024945A (en) * | 1999-07-29 | 2000-02-15 | Reheis, Inc. | Antiperspirant compositions for aerosol formulations |
US6126928A (en) * | 1999-08-24 | 2000-10-03 | The Procter & Gamble Company | Compositions containing solubilized, acid-enhanced antiperspirant active |
US6375937B1 (en) * | 2000-10-20 | 2002-04-23 | Colgate-Palmolive Company | Antiperspirant salts for enhanced cosmetic products |
Cited By (58)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7204976B2 (en) | 2003-05-30 | 2007-04-17 | Colgate-Palmolive Company | High efficacy gel with low glycol content |
US20040241122A1 (en) * | 2003-05-30 | 2004-12-02 | Christine Popoff | High efficacy gel with low glycol content |
US20040241123A1 (en) * | 2003-05-30 | 2004-12-02 | Christine Popoff | Suspension free and elastomer free antiperspirant cream |
US20040265255A1 (en) * | 2003-06-26 | 2004-12-30 | Marian Holerca | Aluminum / zirconium / glycine antiperspirant actives stabilized with betaine |
US7105691B2 (en) * | 2003-06-26 | 2006-09-12 | Colgate-Palmolive Company | Aluminum / zirconium / glycine antiperspirant actives stabilized with Betaine |
US20070286829A1 (en) * | 2004-05-13 | 2007-12-13 | Batista Andrea P | Antiperspirant Or Deodorant Compositions |
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 |
US20060263312A1 (en) * | 2005-05-19 | 2006-11-23 | Scavone Timothy A | Consumer noticeable improvement in wetness protection using solid antiperspirant compositions |
US20060263311A1 (en) * | 2005-05-19 | 2006-11-23 | Scavone Timothy A | Consumer noticeable improvement in wetness protection using solid antiperspirant compositions |
US20070248553A1 (en) * | 2005-05-19 | 2007-10-25 | Scavone Timothy A | Consumer noticeable improvement in wetness protection |
US20070248552A1 (en) * | 2005-05-19 | 2007-10-25 | Scavone Timothy A | Consumer noticeable improvement in wetness protection using solid antiperspirant compositions |
US20060292098A1 (en) * | 2005-05-19 | 2006-12-28 | Scavone Timothy A | Consumer noticeable improvement in wetness protection |
US8632755B2 (en) | 2005-05-19 | 2014-01-21 | The Procter & Gamble Company | Consumer noticeable improvement in wetness protection |
US8147808B2 (en) | 2005-05-19 | 2012-04-03 | The Procter & Gamble Company | Consumer noticeable improvement in wetness protection using solid antiperspirant compositions |
US20070020211A1 (en) * | 2005-07-22 | 2007-01-25 | Reheis, Inc. | Betaine with Calcium and/or Strontium Antiperspirants |
EP2324815A1 (en) * | 2005-11-16 | 2011-05-25 | Colgate-Palmolive Company | Antiperspirant compositions |
EP1948317B1 (en) * | 2005-11-16 | 2013-10-16 | Colgate-Palmolive Company | Antiperspirant compositions |
US20110014144A1 (en) * | 2005-11-16 | 2011-01-20 | Colgate-Palmolive Company | Antiperspirant 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 |
EP2559457A1 (en) | 2007-02-02 | 2013-02-20 | Colgate-Palmolive Company | Antiperspirant/deodorant compositions |
EP2149366A2 (en) | 2007-02-02 | 2010-02-03 | Colgate-Palmolive Company | Antiperspirant/deodorant composition |
WO2008097716A2 (en) | 2007-02-02 | 2008-08-14 | Colgate-Palmolive Company | Antiperspirant/deodorant composition |
WO2008144079A1 (en) | 2007-02-02 | 2008-11-27 | Colgate-Palmolive Company | Antiperspirant / deodorant compositions |
US10149910B2 (en) | 2007-03-01 | 2018-12-11 | The Procter & Gamble Plaza | Compositions and/or articles comprising cyclodextrin complexing material |
US9649387B2 (en) | 2007-03-01 | 2017-05-16 | The Procter & Gamble Company | Compositions and/or articles comprising cyclodextrin complexing material |
US9649386B2 (en) | 2007-03-01 | 2017-05-16 | The Procter & Gamble Company | Compositions and/or articles comprising cyclodextrin complexing material |
US11090250B2 (en) | 2007-03-01 | 2021-08-17 | The Procter & Gamble Company | Compositions and/or articles comprising cyclodextrin complexing material |
US20080213191A1 (en) * | 2007-03-01 | 2008-09-04 | Timothy Alan Scavone | Composition and/or articles comprising cyclodextrin complexing material |
US20110076309A1 (en) * | 2009-09-30 | 2011-03-31 | Misner H Steven | Antiperspirant/Deodorant Composition |
US20110076310A1 (en) * | 2009-09-30 | 2011-03-31 | Colgate-Palmolive Company | Antiperspirant/Deodorant Composition |
US11058904B2 (en) | 2009-09-30 | 2021-07-13 | Colgate-Palmolive Company | Antiperspirant/deodorant composition |
WO2011040909A1 (en) | 2009-09-30 | 2011-04-07 | Colgate-Palmolive Company | Antiperspirant/deodorant composition |
EP3653197A1 (en) | 2009-10-20 | 2020-05-20 | Colgate-Palmolive Company | Antiperspirant that reduces/eliminates yellowing on clothing |
WO2011050044A1 (en) | 2009-10-20 | 2011-04-28 | Colgate-Palmolive Company | Antiperspirant that reduces/eliminates yellowing on clothing |
WO2011087702A2 (en) | 2009-12-23 | 2011-07-21 | Colgate-Palmolive Company | Aqueous antiperspirant/deodorant composition |
US8663610B2 (en) | 2009-12-23 | 2014-03-04 | Colgate-Palmolive Company | Method of making an anhydrous liquid antiperspirant composition |
US8815222B2 (en) | 2009-12-23 | 2014-08-26 | Colgate—Palmolive Company | Anhydrous liquid antiperspirant composition |
US8557228B2 (en) | 2009-12-23 | 2013-10-15 | Colgate-Palmolive Company | Aqueous antiperspirant composition |
WO2011087701A2 (en) | 2009-12-23 | 2011-07-21 | Colgate-Palmolive Company | Method of making an anhydrous liquid antiperspirant composition |
WO2011079001A2 (en) | 2009-12-23 | 2011-06-30 | Colgate-Palmolive Company | Anhydrous liquid antiperspirant/deodorant composition |
US9585825B2 (en) | 2009-12-23 | 2017-03-07 | Colgate-Palmolive Company | Method of making an anhydrous liquid antiperspirant composition |
US8529919B2 (en) | 2010-07-06 | 2013-09-10 | Colgate-Palmolive Company | Personal care product and manufacture thereof |
WO2012005720A1 (en) | 2010-07-06 | 2012-01-12 | Colgate-Palmolive Company | Personal care product and manufacture thereof |
US8895041B2 (en) | 2012-03-23 | 2014-11-25 | The Procter & Gamble Company | Compositions for delivering perfume to the skin |
US9364417B2 (en) | 2012-03-23 | 2016-06-14 | The Procter & Gamble Company | Compositions for delivering perfume to the skin |
US9161899B2 (en) | 2012-03-23 | 2015-10-20 | The Procter & Gamble Company | Compositions for delivering perfume to the skin |
US9707171B2 (en) | 2012-12-11 | 2017-07-18 | Colgate-Palmolive Company | Antiperspirant/deodorant with alkylated polyvinylpyrrolidone |
WO2014092688A1 (en) | 2012-12-11 | 2014-06-19 | Colgate-Palmolive Company | Antiperspirant/deodorant with alkylated polyvinylpyrrolidone |
US9896645B2 (en) | 2013-03-15 | 2018-02-20 | The Procter & Gamble Company | Personal care compositions |
US10316269B2 (en) | 2013-03-15 | 2019-06-11 | The Procter & Gamble Company | Personal care compositions |
US9408799B2 (en) | 2013-04-19 | 2016-08-09 | Colgate-Palmolvie Company | Aerosol antiperspirants |
WO2014171948A1 (en) | 2013-04-19 | 2014-10-23 | Colgate-Palmolive Company | Aerosol antiperspirants |
US10111817B2 (en) | 2014-07-21 | 2018-10-30 | Colgate-Palmolive Company | Antiperspirant compositions containing ethylenediamine disuccinate |
US11000468B2 (en) | 2016-09-06 | 2021-05-11 | The Procter & Gamble Company | Aerosol compositions |
US11491099B2 (en) | 2016-09-06 | 2022-11-08 | The Procter & Gamble Company | Antiperspirant and deodorant compositions |
WO2018125030A1 (en) | 2016-12-27 | 2018-07-05 | Colgate-Palmolive Company | Extruded antiperspirant composition for improved efficacy |
WO2019117903A1 (en) | 2017-12-14 | 2019-06-20 | Colgate-Palmolive Company | Antiperspirant/deodorant compositions including biodegradable amino carboxylates and methods for the same |
WO2021096518A1 (en) | 2019-11-14 | 2021-05-20 | Colgate-Palmolive Company | Personal care compositions for treating odor causing bacteria and methods for the same |
Also Published As
Publication number | Publication date |
---|---|
PA8591301A1 (en) | 2004-12-16 |
ZA200504623B (en) | 2006-08-30 |
BR0317094A (en) | 2005-10-25 |
CA2511831A1 (en) | 2004-06-24 |
AR042346A1 (en) | 2005-06-15 |
CL2003002555A1 (en) | 2005-02-04 |
GT200300272A (en) | 2004-08-18 |
PL377343A1 (en) | 2006-01-23 |
MXPA05006068A (en) | 2005-08-16 |
US20050158261A1 (en) | 2005-07-21 |
WO2004052325A1 (en) | 2004-06-24 |
US7311898B2 (en) | 2007-12-25 |
RU2005121556A (en) | 2006-01-20 |
AU2003293362A1 (en) | 2004-06-30 |
EP1572144A1 (en) | 2005-09-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7311898B2 (en) | High efficacy, low irritation aluminum salts and related products | |
US6969510B2 (en) | Glycine-free antiperspirant salts with Betaine for enhanced cosmetic products | |
US6375937B1 (en) | Antiperspirant salts for enhanced cosmetic products | |
US6403067B1 (en) | Stable emulsions for cosmetic products | |
US6468511B1 (en) | Emulsions with naphthalate esters | |
MXPA03003487A (en) | High oil clear emulsion with elastomer. | |
US20030103921A1 (en) | Antiperspirant compositions comprising microemulsions | |
AU2001263255A1 (en) | Emulsions with naphthalate esters | |
US20050191256A1 (en) | Glycine-free antiperspirant salts with betaine for enhanced cosmetic products | |
JPH05201827A (en) | Powder-containing water-in-oil type emulsion cosmetic |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: COLGATE-PALMOLIVE COMPANY, NEW YORK Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:TANG, XIAOZHONG;FEI, LIN;CHOPRA, SUMAN;AND OTHERS;REEL/FRAME:013729/0581 Effective date: 20030128 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO PAY ISSUE FEE |