US3095356A - Dentifrice comprising insoluble sodium metaphosphate and a cadmium, tin, zinc, manganese or iron compound to inhibit calcium ion sequestering - Google Patents
Dentifrice comprising insoluble sodium metaphosphate and a cadmium, tin, zinc, manganese or iron compound to inhibit calcium ion sequestering Download PDFInfo
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- US3095356A US3095356A US566353A US56635356A US3095356A US 3095356 A US3095356 A US 3095356A US 566353 A US566353 A US 566353A US 56635356 A US56635356 A US 56635356A US 3095356 A US3095356 A US 3095356A
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- Prior art keywords
- zinc
- tin
- phosphates
- cadmium
- manganese
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- 239000000551 dentifrice Substances 0.000 title claims description 32
- AQMNWCRSESPIJM-UHFFFAOYSA-M sodium metaphosphate Chemical compound [Na+].[O-]P(=O)=O AQMNWCRSESPIJM-UHFFFAOYSA-M 0.000 title claims description 26
- 230000014759 maintenance of location Effects 0.000 title claims description 20
- 239000011701 zinc Substances 0.000 title claims description 19
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 title claims description 17
- 229910001424 calcium ion Inorganic materials 0.000 title claims description 17
- 229910052725 zinc Inorganic materials 0.000 title claims description 17
- 229910052718 tin Inorganic materials 0.000 title claims description 14
- 229910052793 cadmium Inorganic materials 0.000 title claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims description 10
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims description 8
- 229910052748 manganese Inorganic materials 0.000 title claims description 7
- 239000011572 manganese Substances 0.000 title claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 3
- 239000011135 tin Substances 0.000 title description 6
- 150000002506 iron compounds Chemical class 0.000 title 1
- 239000000203 mixture Substances 0.000 claims description 25
- -1 CADMIUM HALIDES Chemical class 0.000 claims description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 238000005498 polishing Methods 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 11
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000013980 iron oxide Nutrition 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 6
- 150000004820 halides Chemical class 0.000 claims 1
- 150000002222 fluorine compounds Chemical class 0.000 description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 235000010210 aluminium Nutrition 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 8
- 235000019983 sodium metaphosphate Nutrition 0.000 description 8
- 235000021317 phosphate Nutrition 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 6
- 239000001488 sodium phosphate Substances 0.000 description 6
- 235000011008 sodium phosphates Nutrition 0.000 description 6
- 239000000606 toothpaste Substances 0.000 description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 6
- 235000014692 zinc oxide Nutrition 0.000 description 6
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 5
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 5
- 229920000388 Polyphosphate Polymers 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 5
- 150000002736 metal compounds Chemical class 0.000 description 5
- 239000001205 polyphosphate Substances 0.000 description 5
- 235000011176 polyphosphates Nutrition 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 4
- 235000013024 sodium fluoride Nutrition 0.000 description 4
- 239000011775 sodium fluoride Substances 0.000 description 4
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 4
- 229960002799 stannous fluoride Drugs 0.000 description 4
- 229940034610 toothpaste Drugs 0.000 description 4
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 4
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical class [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- 235000009529 zinc sulphate Nutrition 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical class [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 3
- NRGIRRZWCDKDMV-UHFFFAOYSA-H cadmium(2+);diphosphate Chemical class [Cd+2].[Cd+2].[Cd+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O NRGIRRZWCDKDMV-UHFFFAOYSA-H 0.000 description 3
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical class [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical class [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical class [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- 235000002908 manganese Nutrition 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 3
- BECVLEVEVXAFSH-UHFFFAOYSA-K manganese(3+);phosphate Chemical class [Mn+3].[O-]P([O-])([O-])=O BECVLEVEVXAFSH-UHFFFAOYSA-K 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical class [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 229940081974 saccharin Drugs 0.000 description 3
- 235000019204 saccharin Nutrition 0.000 description 3
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical class [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 3
- QUBMWJKTLKIJNN-UHFFFAOYSA-B tin(4+);tetraphosphate Chemical class [Sn+4].[Sn+4].[Sn+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QUBMWJKTLKIJNN-UHFFFAOYSA-B 0.000 description 3
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- 241000416162 Astragalus gummifer Species 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229920000569 Gum karaya Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- LVEULQCPJDDSLD-UHFFFAOYSA-L cadmium fluoride Chemical compound F[Cd]F LVEULQCPJDDSLD-UHFFFAOYSA-L 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940077441 fluorapatite Drugs 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- 235000010494 karaya gum Nutrition 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- RLBIQVVOMOPOHC-UHFFFAOYSA-N parathion-methyl Chemical compound COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C=C1 RLBIQVVOMOPOHC-UHFFFAOYSA-N 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
-
- 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
-
- 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
- A61K8/24—Phosphorous; Compounds thereof
Definitions
- This invention relates to polishing compositions suitable for use as a dentifrice base and particularly to those compositions which contain the insoluble form of sodium metaphosphate as an ingredient thereof.
- An object of the present invention is the provision of an improved dentifrice.
- 'Ilhe specific metal compounds which I mayadd to the insoluble sodium metaphosphate may either be soluble or insoluble in water or related aqueous solutions.
- suitable salts representative of all of the above class, but exemplified specifically with respect to the aluminum' and zinc compounds are the oxides A1 0 or ZnO, or hydrated oxides Al O -3H O, the chlorides AlCl or ZnCl the sulfates Al (SO or ZnSO the citrates A1C6H5O7, or Zn (C H O the phosphates such as the orthophosp-hates A1PO or Zn (PO etc. Other molec ular forms and various hydrated compounds may also be employed.
- additive materials may be incorporated in the proportion of 0.05% to 50% by weight as a slurry or dry powder with the insoluble metaphosphate for incorporation into a tooth powder or tooth pastel
- proportion of such metal salts is not critical, and hence, may be varied in order to furnish the desired inhibiting action.
- Particularly useful salts in this relationship are the fluorides of cadmium, tin, zinc, manganese, aluminum and iron, a preferred group being aluminum fluoride, AlF or zinc fluoride, ZnF These fluorides concomitantly provide an agent elfective in reducing the sequestering action of the soluble portion of the sodium metaphosphate, while also providing fluoride in a form which is useful in formulated dentifrices. All of the fluoride compounds described above are effective in reducing the sequestering action of insoluble sodium meta-phosphate.
- a soluble fluoride salt maybe used, for example stannous fluoride employed at about 0.1 weight percent, calculated as fluoride.
- the weight percentage of the fluoride, including the preferred group of aluminum fluoride, stannous fluoride and sodium fluoride, present as the salt, is in the range of 0.5% to 1%.
- An advantage of the present use of fluorides with the above-described group of metal salts is the improvement United States Patent 0 3,095,356 Patented June 25, 1963 of fluoride uptake by the teeth. Soluble fluorides are found to be taken up to a greater extent when these metal salts are also present with the fluoride.
- the proportion of the fluorides, such as aluminum, tin, or sodium fluoride employed in the practice of the present invention is in the range of 0.05 to 1% by weight of the dentifrice composition.
- the total proportion of metal compounds of the group of cadmium, tin, zinc, manganese, aluminum and iron which are present in the dentifrice is within the broader range of 0.05 to 50 weight percent.
- the insoluble sodium metaphosphate containing the usual impurities may exist as a chain-type of molecular structure, and also in the form of relatively short-chain polyphosphates.
- the presently employed metal compounds control the sequestering action of polyphosphates, thereby controlling the type of molecular structures present in an aqueous solution or dispersion in which the said insoluble sodium metaphosphate may "be present.
- the above discussion is not necessarily a complete explanation of the mode of action of the presently employed metal compounds, for example, and the present invention is not restricted thereto.
- the invention in general contemplates the use of finely divided insoluble sodium inetaphosphate as a component of a dentifrice base.
- the combination also includes a suflicient amount of the above compound of a metal selected from the group consisting of cadmium, tin, zinc, manganese, aluminum, and iron to inhibit the calcium ion sequestering effect, characteristic of the said sodium met-aphosphate.
- a preferred group of compounds utilized for such inhibition are the compounds of aluminum and zinc, a still vmore preferred embodiment being aluminum hydrate, i.e., Al(OH)
- This compound which is also known as aluminum hydroxide is employed in the present dentifrice composition. It is also found that this compound provides a secondary advantage in dentifrice compositions, inasmuch as the aluminum hydrate provides a highly desirable whitening effect which improves the tinctorial power and opacity of the toothpaste.
- the combination of the sodium metaphosphate and aluminum hydrate provides a highly eflicacious dentifrice base which may be formulated with conventional fluoride compounds.
- fluorides exhibit substantial solubility in a precipitating system such as a toothpaste, .so that precipitation and consequent loss of the fluorideis avoided: cadmium fluoride, stannous fluoride, zinc fluoride, manganous fluoride, aluminum fluoride, ferrous fluoride, and ferric fluoride.
- Soluble calcium salts and insoluble calcium orthophosphates are undesirable in fluoride dentifrices because of reaction with the fluoride to produce insoluble calcium fluoride or fluorapatite which renders the fluoride content unavailable to the teeth. Similar disadvantages are found to arise in the use of magnesium compounds. Furthermore, the use of magnesium compounds in the presence of insoluble sodium metaphosphate has the disadvantage that the magnesium salts cause a setting up or solidification in the toothpaste tube.
- Example 1 One hundred g. of insoluble sodium metaphosphate were extracted with distilled water in order to remove the soluble portion. The water extract (after separation from the insoluble metaphosphate) was then treated with about 50 ml. of a 10% solution of zinc acetate at room temperature. It was found that a filterable precipitate formed almost immediately, representing the zinc salts of short-chain polyphosphates. The insoluble sodium metaphosphate was thus reduced in sequestration ability.
- Example 2 One hundred g. of insoluble sodium metaphosphate was treated with 100 ml. of distilled water in order to extract the minor proportion of soluble components representative of shortchain polyphosphates. The water extract (after separation from the insoluble metaphosphate) was then treated with a 50 ml. portion of aluminum sulfate (10% solution) at room temperature. It was found that a gel was formed which could be precipitated on heating to 60 C. for 10 minutes. This gel, corresponding to the alumi num salt of the polyphosphate components present, rendered the insoluble sodium metaphosphate free from a solubilizing effect on insoluble calcium salts dispersed or present in the solution.
- Example 3 A toothpowder was prepared utilizing the following formulations by weight, and also indicating the range of variation of the components:
- the detergents employed, in general, are of the alkyl sulfate type.
- non-soap synthetic detergents are of utility in this relationship in the present invention to provide a non-soap wetting and foaming agent in the dentifrice.
- the toothpaste was prepared by combining 450 parts by weight of powder prepared according to the above formulation with 550 parts of an elixir prepared utilizing the formulation below:
- the two formulations are found to yield satisfactory V dentifrices which possess a long shelf life without setting up in the tube.
- the proportion of the powder components is from to by weight in order to obtain smooth paste.
- a soluble fluoride salt for example aluminum fluoride, is used at about 0.1%, calculated as fluoride (e.g., 0.939 in the above formulation).
- the weight percentage of the fluoride as a salt is preferred to be in the range of 0.05 to 1%.
- a dentifrice polishing composition comprising finely divided insoluble sodium metaphosphate normally containing calcium ion sequestering soluble phosphates and a sufiicient amount of a compound selected from the group consisting of cadmium halides, cadmium phosphates, cadmium sulphates, cadmium oxides, zinc halides, zinc phosphates, zinc sulphates, zinc oxides, manganese halides, manganese phosphates, manganese sulphates,
- a dentifrice polishing composition according to claim 1 additionally containing from about 0.05% to about 1% by Weight of a soluble fluoride selected from the group consisting of aluminum fluoride, stannous fluoride and sodium fluoride.
- a dentifrice polishing composition comprising finely divided insoluble sodium metaphosphate containing water-soluble polymeric sodium phosphates, which soluble phosphates possess a calcium ion sequestering effect, and an amount of a zinc halide suflicient to inhibit the said calcium ion sequestering effect.
- a dentifrice polishing composition comprising finely divided insoluble sodium metaphosphate containing water-soluble polymeric sodium phosphates, which soluble phosphates possess a calcium ion sequestering effect, and an amount of a zinc phosphate sufficient to inhibit the said calcium ion sequestering effect.
- a dentifrice polishing composition as in claim 4 containing from 0.05 to 50% of said zinc phosphate.
- a dentifrice polishing composition comprising finely divided insoluble sodium metaphosphate containing- Water-soluble polymeric sodium phosphates, which soluble phosphates possess a calcium ion sequestering effect, and an amount of zinc sulphate sufficient to inhibit the said calcium ion sequestering effect.
- a dentifrice polishing composition comprising finely divided insoluble sodium metaphosphate containing water-soluble polymeric sodium phosphates, which soluble phosphates possess a calcium ion sequestering effect, and an amount of zinc oxide sufficient to inhibit said calcium ion sequestering effect.
- a dentifrice polishing composition comprising finely divided insoluble sodium metaphosphate containing water-soluble polymeric sodium phosphates, which soluble phosphates possess a calcium ion sequestering effect, and an amount of zinc oxide in the range of from 0.05% to 50.0% by weight relative to the said sodium metaphosphate.
- a dentifrice polishing composition containing the followmg components by weight:
- Percent Insoluble sodium metaphos hate containing water soluble polymeric sodium p osphates which possess a calcium ion sequestering effect
- Organic detergent 28 Saccharin 0.052 Flavoring other than saiccharin 0.05'2
- a dentifrice polishing composition containing the :following components by weight:
- Percent Insoluble sodium metaphosphate containin water sol- 'uble polymeric sodium phosphates whic possess a calcium ion sequestering efl'fect
- a dentifrice polishing composition containing about in combination with an elixir comprising the following components by weight
- Bodying agents selected from the group consisting of gum karaya and gum tragacanth 0.5-4
Description
Delaware N Drawing. Filed Feb. 20, 1956, Ser. No. 566,333
11 Claims. (Cl. 167-93) This invention relates to polishing compositions suitable for use as a dentifrice base and particularly to those compositions which contain the insoluble form of sodium metaphosphate as an ingredient thereof.
An object of the present invention is the provision of an improved dentifrice.
The use of the so-called insoluble form of sodium metaphosphate in finely divided form has been proposed as a dentifrice. This material, however, has a definite, though small, solubility in water or other aqueous liquids. Further, it has been found that the soluble part of the so-oalled insoluble metaphosphate has a definite solubilizing action on certain lime salts.
I have now found that by incorporating small amounts of compounds of cadmium, tin, zinc, manganese, aluminum and iron, particularly those of aluminum and zinc, which furnish available dissolved aluminum or zinc ions, it becomes possible to inhibit the dissolving action of the soluble portion of the insoluble form of sodium metaphosphate.
'Ilhe specific metal compounds which I mayadd to the insoluble sodium metaphosphate may either be soluble or insoluble in water or related aqueous solutions. Exam ples of suitable salts, representative of all of the above class, but exemplified specifically with respect to the aluminum' and zinc compounds are the oxides A1 0 or ZnO, or hydrated oxides Al O -3H O, the chlorides AlCl or ZnCl the sulfates Al (SO or ZnSO the citrates A1C6H5O7, or Zn (C H O the phosphates such as the orthophosp-hates A1PO or Zn (PO etc. Other molec ular forms and various hydrated compounds may also be employed. These additive materials may be incorporated in the proportion of 0.05% to 50% by weight as a slurry or dry powder with the insoluble metaphosphate for incorporation into a tooth powder or tooth pastel The proportion of such metal salts is not critical, and hence, may be varied in order to furnish the desired inhibiting action.
Particularly useful salts in this relationship are the fluorides of cadmium, tin, zinc, manganese, aluminum and iron, a preferred group being aluminum fluoride, AlF or zinc fluoride, ZnF These fluorides concomitantly provide an agent elfective in reducing the sequestering action of the soluble portion of the sodium metaphosphate, while also providing fluoride in a form which is useful in formulated dentifrices. All of the fluoride compounds described above are effective in reducing the sequestering action of insoluble sodium meta-phosphate.
If a fluoride type dentifrice is desired, a soluble fluoride salt maybe used, for example stannous fluoride employed at about 0.1 weight percent, calculated as fluoride. In general the weight percentage of the fluoride, including the preferred group of aluminum fluoride, stannous fluoride and sodium fluoride, present as the salt, is in the range of 0.5% to 1%.
An advantage of the present use of fluorides with the above-described group of metal salts is the improvement United States Patent 0 3,095,356 Patented June 25, 1963 of fluoride uptake by the teeth. Soluble fluorides are found to be taken up to a greater extent when these metal salts are also present with the fluoride. The proportion of the fluorides, such as aluminum, tin, or sodium fluoride employed in the practice of the present invention is in the range of 0.05 to 1% by weight of the dentifrice composition. However, the total proportion of metal compounds of the group of cadmium, tin, zinc, manganese, aluminum and iron which are present in the dentifrice is within the broader range of 0.05 to 50 weight percent.
According to one of the present theories as to the molecular aggregation of phosphate salts, the insoluble sodium metaphosphate containing the usual impurities, may exist as a chain-type of molecular structure, and also in the form of relatively short-chain polyphosphates. According to this theory, the presently employed metal compounds control the sequestering action of polyphosphates, thereby controlling the type of molecular structures present in an aqueous solution or dispersion in which the said insoluble sodium metaphosphate may "be present. However, the above discussion is not necessarily a complete explanation of the mode of action of the presently employed metal compounds, for example, and the present invention is not restricted thereto.
The invention in general contemplates the use of finely divided insoluble sodium inetaphosphate as a component of a dentifrice base. The combination also includes a suflicient amount of the above compound of a metal selected from the group consisting of cadmium, tin, zinc, manganese, aluminum, and iron to inhibit the calcium ion sequestering effect, characteristic of the said sodium met-aphosphate. A preferred group of compounds utilized for such inhibition are the compounds of aluminum and zinc, a still vmore preferred embodiment being aluminum hydrate, i.e., Al(OH) This compound which is also known as aluminum hydroxide is employed in the present dentifrice composition. It is also found that this compound provides a secondary advantage in dentifrice compositions, inasmuch as the aluminum hydrate provides a highly desirable whitening effect which improves the tinctorial power and opacity of the toothpaste.
The above-described inhibiting compositions utilized together with the insoluble sodium metaphosphate are also of great utility in combination with various fluorides which are employed in many dentifrice compositions. it has been a disadvantage of many polishing agents conventionally employed in dentifrices that certain polishing agents are incompatible with fluorides. For example, calcium compounds readily'precipitate the highly insoluble calcium fluoride which thus prevents the fluoride ion from being eflective in the use of such toothpowders and toothpastes containing the same. The use of the presently described metal compounds, for example aluminum hydrate as described above, in combination with insoluble sodium metaphosphate, completely eliminates the possibility of precipitating fluoride ions which may be present in combination with these two components. Accordingly, the combination of the sodium metaphosphate and aluminum hydrate provides a highly eflicacious dentifrice base which may be formulated with conventional fluoride compounds. With regard to the other compounds described above, the following fluorides exhibit substantial solubility in a precipitating system such as a toothpaste, .so that precipitation and consequent loss of the fluorideis avoided: cadmium fluoride, stannous fluoride, zinc fluoride, manganous fluoride, aluminum fluoride, ferrous fluoride, and ferric fluoride.
Soluble calcium salts and insoluble calcium orthophosphates, as set forth above, are undesirable in fluoride dentifrices because of reaction with the fluoride to produce insoluble calcium fluoride or fluorapatite which renders the fluoride content unavailable to the teeth. Similar disadvantages are found to arise in the use of magnesium compounds. Furthermore, the use of magnesium compounds in the presence of insoluble sodium metaphosphate has the disadvantage that the magnesium salts cause a setting up or solidification in the toothpaste tube.
Another advantage resulting from the use of the abovedescribed compounds of cadmium, tin, zinc, manganese, aluminum, and iron in combination with sodium metaphosphate in fluoride dentifrices is the reduced corrosivity towards metal containers. Prior art fluoride dentifrices may be corrosive towards metal containers such as tin cans utilized to contain toothpowders, or tin, aluminum, or lead tubes provided for the dispensing of toothpastes. Aluminum hydrate, for example, when used in the present combination compositions containing the said metal salts together with the insoluble sodium metaphosphate and a specific fluoride exhibit less corrosivity towards the above-described metal containers than do the same fluoride compounds such as sodium fluoride utilized alone.
Specific examples illustrative of the present invention are set forth below.
Example 1 One hundred g. of insoluble sodium metaphosphate were extracted with distilled water in order to remove the soluble portion. The water extract (after separation from the insoluble metaphosphate) was then treated with about 50 ml. of a 10% solution of zinc acetate at room temperature. It was found that a filterable precipitate formed almost immediately, representing the zinc salts of short-chain polyphosphates. The insoluble sodium metaphosphate was thus reduced in sequestration ability.
Example 2 One hundred g. of insoluble sodium metaphosphate was treated with 100 ml. of distilled water in order to extract the minor proportion of soluble components representative of shortchain polyphosphates. The water extract (after separation from the insoluble metaphosphate) was then treated with a 50 ml. portion of aluminum sulfate (10% solution) at room temperature. It was found that a gel was formed which could be precipitated on heating to 60 C. for 10 minutes. This gel, corresponding to the alumi num salt of the polyphosphate components present, rendered the insoluble sodium metaphosphate free from a solubilizing effect on insoluble calcium salts dispersed or present in the solution.
Example 3 Example 4 A toothpowder was prepared utilizing the following formulations by weight, and also indicating the range of variation of the components:
Range, percent (1) Insoluble sodium metaphosphate, 400 grams 36-97 (2) Hydrated aluminum oxide (Reynolds C-33 grade), 21 grams 1-50 (3) Detergent (sodium lauryl sulfate), 20 grams 2-8 (4) Saccharine, 1 gram 0.05-2
(5) Flavoring (essential oil), 4 grams .05-2
The detergents employed, in general, are of the alkyl sulfate type. However non-soap synthetic detergents are of utility in this relationship in the present invention to provide a non-soap wetting and foaming agent in the dentifrice.
The toothpaste was prepared by combining 450 parts by weight of powder prepared according to the above formulation with 550 parts of an elixir prepared utilizing the formulation below:
Range, percent The two formulations are found to yield satisfactory V dentifrices which possess a long shelf life without setting up in the tube. In general, the proportion of the powder components is from to by weight in order to obtain smooth paste.
'If a fluoride dentifrice is desired, a soluble fluoride salt, for example aluminum fluoride, is used at about 0.1%, calculated as fluoride (e.g., 0.939 in the above formulation). In general the weight percentage of the fluoride as a salt is preferred to be in the range of 0.05 to 1%.
What I claim is:
1. A dentifrice polishing composition comprising finely divided insoluble sodium metaphosphate normally containing calcium ion sequestering soluble phosphates and a sufiicient amount of a compound selected from the group consisting of cadmium halides, cadmium phosphates, cadmium sulphates, cadmium oxides, zinc halides, zinc phosphates, zinc sulphates, zinc oxides, manganese halides, manganese phosphates, manganese sulphates,
manganese oxides, iron halides, iron phosphates, iron sulphates, iron oxides, tin oxides, tin sulphates, tin phosphates and tin halides other than fluorides, to inhibit said calcium ion sequestering effect.
2. A dentifrice polishing composition according to claim 1 additionally containing from about 0.05% to about 1% by Weight of a soluble fluoride selected from the group consisting of aluminum fluoride, stannous fluoride and sodium fluoride.
3. A dentifrice polishing composition comprising finely divided insoluble sodium metaphosphate containing water-soluble polymeric sodium phosphates, which soluble phosphates possess a calcium ion sequestering effect, and an amount of a zinc halide suflicient to inhibit the said calcium ion sequestering effect.
4. A dentifrice polishing composition comprising finely divided insoluble sodium metaphosphate containing water-soluble polymeric sodium phosphates, which soluble phosphates possess a calcium ion sequestering effect, and an amount of a zinc phosphate sufficient to inhibit the said calcium ion sequestering effect.
5. A dentifrice polishing composition as in claim 4 containing from 0.05 to 50% of said zinc phosphate.
6. A dentifrice polishing composition comprising finely divided insoluble sodium metaphosphate containing- Water-soluble polymeric sodium phosphates, which soluble phosphates possess a calcium ion sequestering effect, and an amount of zinc sulphate sufficient to inhibit the said calcium ion sequestering effect.
7. A dentifrice polishing composition comprising finely divided insoluble sodium metaphosphate containing water-soluble polymeric sodium phosphates, which soluble phosphates possess a calcium ion sequestering effect, and an amount of zinc oxide sufficient to inhibit said calcium ion sequestering effect.
8. A dentifrice polishing composition comprising finely divided insoluble sodium metaphosphate containing water-soluble polymeric sodium phosphates, which soluble phosphates possess a calcium ion sequestering effect, and an amount of zinc oxide in the range of from 0.05% to 50.0% by weight relative to the said sodium metaphosphate.
9. A dentifrice polishing composition containing the followmg components by weight:
Percent Insoluble sodium metaphos hate containing water soluble polymeric sodium p osphates which possess a calcium ion sequestering effect A compound selected from the group consisting of cadmium halides, cadmium phosphates, cadmium sulphates, cadmium oxides, zinc halides, zinc phosphates, zinc sulphates, zinc oxides, manganese halides, manganese phosphates, manganese sulphates, manganese oxides, iron halides, iron phosphates, iron sulphates, iron oxides, tin oxides, tin sulphates, tin phosphates, and tin halides other than fluorides 1-5 Organic detergent 28 Saccharin 0.052 Flavoring other than saiccharin 0.05'2
10. A dentifrice polishing composition containing the :following components by weight:
Percent Insoluble sodium metaphosphate containin water sol- 'uble polymeric sodium phosphates whic possess a calcium ion sequestering efl'fect A compound selected from the group consisting of cadmium halides, cadmium phosphates, cadmium sulphates, cadmium oxides, zinc halides, zinc phos Ehates, zinc sulphates, zinc oxides, manganese alides, manganese phosphates, manganese sulphates, manganese oxides, iron halides, iron phosphates, iron sulphates, iron oxides, tin oxides, tin sulphates, tin phosphates, and tin halides other than fluorides 1-50 Organic detergent 28 Saccharin 0.052 Flavoring other than saccharin 0052 Soluble fluoride 0205-1 11. A dentifrice polishing composition containing about in combination with an elixir comprising the following components by weight:
Percent Glycerine 29-59 Water 59-38 Bodying agents selected from the group consisting of gum karaya and gum tragacanth 0.5-4
References Cited in the file of this patent UNITED STATES PATENTS 1,529,486 Kaemmerling et a1. Mar. 10, 1925 2,086,867 Hall July '13, 1937 2,216,821 Long Oct. 8, 1940 FOREIGN PATENTS 158,717 Australia Sept. 9', 1954 OTHER REFERENCES
Claims (1)
1. A DENTIFRICE POLISHING COMPOSITION COMPRISING FINELY DIVIDED INSOLUBLE SODIUM METAPHOSPHATE NORMALLY CONTAINING CALCIUM ION SEQUESTERING SOLUBLE PHOSPHATES AND A SUFFICIENT AMOUNT OF A COMPOUND SELECTED FROM YHE GROUP CONSISTING OF CADMIUM HALIDES, CADMIUM PHOSPHATES, CADMIUM SIULPHATES, CADMIUM OXIDES, ZINC HALIDES, ZINC PHOSPHATES, ZINC SULPHATES, ZINC OXIDES, MANGANESE HALIDES, MANGANESE PHOSPHATES, MANGANESE SULPHATES, MANGANESE OXIDES, IRON HALIDES, IRON PHOSPHATES, IRON SULPHATES, IRON OXIDES, TIN OXIDES, TIN SULPHATES, TIN PHOSPHATES AND TIN HALIDES OTHER THAN FLUORIDES, TO INHIBIT SAID CALCIUM ION SEQUESTERING EFFECT.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US566353A US3095356A (en) | 1956-02-20 | 1956-02-20 | Dentifrice comprising insoluble sodium metaphosphate and a cadmium, tin, zinc, manganese or iron compound to inhibit calcium ion sequestering |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US566353A US3095356A (en) | 1956-02-20 | 1956-02-20 | Dentifrice comprising insoluble sodium metaphosphate and a cadmium, tin, zinc, manganese or iron compound to inhibit calcium ion sequestering |
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| Publication Number | Publication Date |
|---|---|
| US3095356A true US3095356A (en) | 1963-06-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US566353A Expired - Lifetime US3095356A (en) | 1956-02-20 | 1956-02-20 | Dentifrice comprising insoluble sodium metaphosphate and a cadmium, tin, zinc, manganese or iron compound to inhibit calcium ion sequestering |
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Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1953944A1 (en) * | 1968-10-29 | 1970-05-06 | Unilever Nv | Toothpastes |
| US3622662A (en) * | 1969-04-21 | 1971-11-23 | Colgate Palmolive Co | Stable dental cream |
| US3624199A (en) * | 1969-04-21 | 1971-11-30 | James Norfleet | Dental cream |
| US3864471A (en) * | 1968-12-20 | 1975-02-04 | Colgate Palmolive Co | Stable dentifrices containing a monofluorophosphate, an insoluble metaphosphate, and calcium carbonate |
| US4022880A (en) * | 1973-09-26 | 1977-05-10 | Lever Brothers Company | Anticalculus composition |
| US4100269A (en) * | 1973-06-28 | 1978-07-11 | Lever Brothers Company | Anticalculus dentifrice |
| US4108981A (en) * | 1976-08-02 | 1978-08-22 | Indiana University Foundation | Alkaline oral compositions comprising aluminum and a carboxylic acid |
| US4108979A (en) * | 1976-08-02 | 1978-08-22 | Indiana University Foundation | Dentifrice preparations comprising aluminum and a compatible abrasive |
| US4159280A (en) * | 1976-09-15 | 1979-06-26 | J. M. Huber Corporation | Therapeutic dentifrices in unlined container and methods |
| US4170634A (en) * | 1975-01-28 | 1979-10-09 | Colgate Palmolive Company | Modified abrasive system for dentifrices |
| US4187288A (en) * | 1975-01-28 | 1980-02-05 | Colgate Palmolive Company | Modified abrasive system for dentifrices |
| US4309409A (en) * | 1975-12-22 | 1982-01-05 | Stauffer Chemical Company | Anti-corrosion formulation for toothpastes |
| EP0049830A2 (en) * | 1980-10-10 | 1982-04-21 | Unilever N.V. | Mouthwash compositions comprising hexetidine and zinc salts for the synergistic inhibition of dental plaque |
| US4421527A (en) * | 1977-12-20 | 1983-12-20 | J. M. Huber Corporation | High fluoride compatibility dentifrice abrasives and compositions |
| EP0316079A1 (en) * | 1987-10-20 | 1989-05-17 | Unilever Plc | Oral compositions |
| US4976954A (en) * | 1986-12-02 | 1990-12-11 | Purdue Research Foundation | Anticariogenic compositions |
| US5000944A (en) * | 1989-06-09 | 1991-03-19 | Colgate-Palmolive Company | Zinc-containing oral products with reduced astringency |
| US5064640A (en) * | 1986-12-02 | 1991-11-12 | Purdue Research Foundation | Anticariogenic compositions |
| US5188819A (en) * | 1992-02-21 | 1993-02-23 | Purdue Research Foundation | Manufacture of aluminum-based anticariogenic compositions |
| US6667027B2 (en) * | 1996-11-21 | 2003-12-23 | The Procter & Gamble Company | Method of reducing staining of stannous in dentifrice compositions |
| US6821507B2 (en) * | 1999-11-12 | 2004-11-23 | The Procter & Gamble Co. | Stannous oral compositions |
| US9656102B2 (en) | 2013-04-23 | 2017-05-23 | Rita Vaccaro | Thin film toothpaste strip |
| WO2017223292A1 (en) | 2016-06-24 | 2017-12-28 | Colgate-Palmolive Company | Oral care compositions and methods of using the compositions |
| US10105296B2 (en) | 2013-04-23 | 2018-10-23 | Rita Vaccaro | Thin film toothpaste strip |
| US10555883B2 (en) | 2015-07-01 | 2020-02-11 | Colgate-Palmolive Company | Oral care compositions and methods of use |
| US10588840B2 (en) | 2016-06-24 | 2020-03-17 | Colgate-Palmolive Company | Oral care compositions and methods of use |
| US10908099B2 (en) | 2017-12-18 | 2021-02-02 | Colgate-Palmolive Company | Analytical methods using x-ray absorption spectroscopy for quantifying or evaluating metal ions in a dentifrice |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1529486A (en) * | 1923-11-26 | 1925-03-10 | Kaemmerling Gerhard | Tooth paste |
| US2086867A (en) * | 1936-06-19 | 1937-07-13 | Hall Lab Inc | Laundering composition and process |
| US2216821A (en) * | 1938-11-04 | 1940-10-08 | Pepsodent Co | Dentifrice |
-
1956
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1529486A (en) * | 1923-11-26 | 1925-03-10 | Kaemmerling Gerhard | Tooth paste |
| US2086867A (en) * | 1936-06-19 | 1937-07-13 | Hall Lab Inc | Laundering composition and process |
| US2216821A (en) * | 1938-11-04 | 1940-10-08 | Pepsodent Co | Dentifrice |
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1953944A1 (en) * | 1968-10-29 | 1970-05-06 | Unilever Nv | Toothpastes |
| US3864471A (en) * | 1968-12-20 | 1975-02-04 | Colgate Palmolive Co | Stable dentifrices containing a monofluorophosphate, an insoluble metaphosphate, and calcium carbonate |
| US3622662A (en) * | 1969-04-21 | 1971-11-23 | Colgate Palmolive Co | Stable dental cream |
| US3624199A (en) * | 1969-04-21 | 1971-11-30 | James Norfleet | Dental cream |
| US4100269A (en) * | 1973-06-28 | 1978-07-11 | Lever Brothers Company | Anticalculus dentifrice |
| US4022880A (en) * | 1973-09-26 | 1977-05-10 | Lever Brothers Company | Anticalculus composition |
| US4170634A (en) * | 1975-01-28 | 1979-10-09 | Colgate Palmolive Company | Modified abrasive system for dentifrices |
| US4187288A (en) * | 1975-01-28 | 1980-02-05 | Colgate Palmolive Company | Modified abrasive system for dentifrices |
| US4309409A (en) * | 1975-12-22 | 1982-01-05 | Stauffer Chemical Company | Anti-corrosion formulation for toothpastes |
| US4108981A (en) * | 1976-08-02 | 1978-08-22 | Indiana University Foundation | Alkaline oral compositions comprising aluminum and a carboxylic acid |
| US4108979A (en) * | 1976-08-02 | 1978-08-22 | Indiana University Foundation | Dentifrice preparations comprising aluminum and a compatible abrasive |
| US4159280A (en) * | 1976-09-15 | 1979-06-26 | J. M. Huber Corporation | Therapeutic dentifrices in unlined container and methods |
| US4421527A (en) * | 1977-12-20 | 1983-12-20 | J. M. Huber Corporation | High fluoride compatibility dentifrice abrasives and compositions |
| EP0049830A2 (en) * | 1980-10-10 | 1982-04-21 | Unilever N.V. | Mouthwash compositions comprising hexetidine and zinc salts for the synergistic inhibition of dental plaque |
| EP0049830A3 (en) * | 1980-10-10 | 1983-02-02 | Unilever Nv | Oral composition inhibiting dental plaque |
| US4522806A (en) * | 1980-10-10 | 1985-06-11 | Lever Brothers Company | Oral compositions for hexetidine and zinc salts for the synergistic inhibition of dental plaque |
| US5064640A (en) * | 1986-12-02 | 1991-11-12 | Purdue Research Foundation | Anticariogenic compositions |
| US4976954A (en) * | 1986-12-02 | 1990-12-11 | Purdue Research Foundation | Anticariogenic compositions |
| EP0316079A1 (en) * | 1987-10-20 | 1989-05-17 | Unilever Plc | Oral compositions |
| US5000944A (en) * | 1989-06-09 | 1991-03-19 | Colgate-Palmolive Company | Zinc-containing oral products with reduced astringency |
| US5188819A (en) * | 1992-02-21 | 1993-02-23 | Purdue Research Foundation | Manufacture of aluminum-based anticariogenic compositions |
| US6667027B2 (en) * | 1996-11-21 | 2003-12-23 | The Procter & Gamble Company | Method of reducing staining of stannous in dentifrice compositions |
| US6821507B2 (en) * | 1999-11-12 | 2004-11-23 | The Procter & Gamble Co. | Stannous oral compositions |
| US10105296B2 (en) | 2013-04-23 | 2018-10-23 | Rita Vaccaro | Thin film toothpaste strip |
| US9656102B2 (en) | 2013-04-23 | 2017-05-23 | Rita Vaccaro | Thin film toothpaste strip |
| US10555883B2 (en) | 2015-07-01 | 2020-02-11 | Colgate-Palmolive Company | Oral care compositions and methods of use |
| WO2017223292A1 (en) | 2016-06-24 | 2017-12-28 | Colgate-Palmolive Company | Oral care compositions and methods of using the compositions |
| US10588840B2 (en) | 2016-06-24 | 2020-03-17 | Colgate-Palmolive Company | Oral care compositions and methods of use |
| US10617620B2 (en) | 2016-06-24 | 2020-04-14 | Colgate-Palmolive Company | Oral care compositions and methods of use |
| US11207254B2 (en) | 2016-06-24 | 2021-12-28 | Colgate-Palmolive Company | Oral care compositions and methods of use |
| US11234915B2 (en) | 2016-06-24 | 2022-02-01 | Colgate-Palmolive Company | Oral care compositions and methods of use |
| US10908099B2 (en) | 2017-12-18 | 2021-02-02 | Colgate-Palmolive Company | Analytical methods using x-ray absorption spectroscopy for quantifying or evaluating metal ions in a dentifrice |
| US11378529B2 (en) | 2017-12-18 | 2022-07-05 | Colgate-Palmolive Company | Analytical methods using X-ray absorption spectroscopy for quantifying or evaluating metal ions in a dentifrice |
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