US2191199A - Abrasive detergent composition - Google Patents
Abrasive detergent composition Download PDFInfo
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- US2191199A US2191199A US164371A US16437137A US2191199A US 2191199 A US2191199 A US 2191199A US 164371 A US164371 A US 164371A US 16437137 A US16437137 A US 16437137A US 2191199 A US2191199 A US 2191199A
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- Prior art keywords
- abrasive
- alkali
- soluble
- metal
- water
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- 239000000203 mixture Substances 0.000 title description 32
- 239000003599 detergent Substances 0.000 title description 18
- 229910052783 alkali metal Inorganic materials 0.000 description 32
- 235000019832 sodium triphosphate Nutrition 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- -1 alkali-metal tripolyphosphate Chemical class 0.000 description 14
- 150000001340 alkali metals Chemical class 0.000 description 12
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 12
- 239000000344 soap Substances 0.000 description 11
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 11
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 10
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 229940005740 hexametaphosphate Drugs 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 125000005341 metaphosphate group Chemical group 0.000 description 7
- 238000005498 polishing Methods 0.000 description 6
- 238000009991 scouring Methods 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 239000001506 calcium phosphate Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000551 dentifrice Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 235000019739 Dicalciumphosphate Nutrition 0.000 description 3
- 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003082 abrasive agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 description 3
- 229910000390 dicalcium phosphate Inorganic materials 0.000 description 3
- 229940038472 dicalcium phosphate Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 2
- ROPDWRCJTIRLTR-UHFFFAOYSA-L calcium metaphosphate Chemical compound [Ca+2].[O-]P(=O)=O.[O-]P(=O)=O ROPDWRCJTIRLTR-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- RHJYKEDKMHDZBL-UHFFFAOYSA-L metaphosphoric acid (hpo3), magnesium salt Chemical compound [Mg+2].[O-]P(=O)=O.[O-]P(=O)=O RHJYKEDKMHDZBL-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001236 detergent effect Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 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
- A61K8/24—Phosphorous; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
Definitions
- This invention relates to abrasive detergent compositions useful in cleaning, securing and polishing objects in general, for example, cleaning and polishing the teeth, polishing metallic objects such as silverware, or cleaning walls or other surfaces.
- Abrasive detergent compositions used for cleaning and polishing purposes contain an abrasive and also a detergent which may be soap or an alkali, or both, dependingupon the particular use of the composition.
- the type of abrasive which has been used in such compositions is one which is insoluble in water or other liquid used with the composition.
- a compositon may be produced in which the.
- solvent effect of a water solution of the detergent onthe abrasive is slow enough so that the abrasive is effective in performing its scouring function and yet is fast enough so that after the scouring function is performed, the abrasive has been dissolved so that it may be easily rinsed from the surface.
- the detergent present need not be in sufficient quantity to completely dissolve all of the abrasive since even the ability to dissolve a small quantity of the abrasive is of value in removing the abrasive from the surfaces to be cleansed.
- the partial dissolving effect prevents the adherence of the abrasive particles to the surface being cleaned and enables them to be washed away more readily.
- abrasives whichhave slow but definite solubility in water solutions of the detergent
- I may use dicalcium phosphate (CaHPO4), a tricalcic phosphate Cas(PO4)z, calcium carbonate (CaCOa), magnesium oxide (MgO), calcium metaphosphate or magnesium metaphosphate.
- alkali-metal metaphosphate As the detergent which in water solution exerts a solubilizing action on the abrasive, I may employ an alkali-metal metaphosphate or tripolyphosphate or mixtures thereof.
- the preferred alkali-metal metaphosphate is the soluble sodium hexametaphosphate sometimes. called Grahams salt".
- the sodium hexametaphosphate is assumed to be a complex of the general formula Naz(Na4PaO1a), although some authorities believe that salts of the formulas Na5(Na P8018) and NadNagPeOm) may also be present.
- Sodium hexametaphosphate in readily soluble form may be prepared by strongly heating monosodium dihydrogen orthophosphate and rapidly cooling the molten mass.
- the quick cooling is apparently essential to the formation of a readily soluble salt. If the monosodium dihydrpgen orthophosphate is not heated to fusion, ,or if the molten mass resulting from strong heating is not cooled with sufficient rapidity,- crystalline metaphosphates may be formed which are less readily soluble or even practically insoluble in water. These are less desirable, although even the sodium metaphosphates which are practically insoluble in water alone will dissolve to a limited extent in solutions of mineral acids, as described in Munter application Serial No. 68,442, and likewise in saliva to produce some of the effective sodium hexametaphosphate.
- the metaphosphate used in the detergent composition be formed in such a manner that it consists principally of the water-soluble hexametaphosphate
- the invention is intended to include the use of any alkali-metal metaphosphate which contains or yields under the conditions of use suflicient hexametaphosphate to produce the desired efiect.
- the alkali-metal tripolyphosphates act similarly to the alkali-metal metaphosphates in solubilizing the abrasives by combining with calcium and magnesium to form soluble complexes from which the calcium or magnesium is but extremely slightly ionized.
- the alkali-metal tripolyphosphates may therefore be used in place of or in combination with the alkali-metal hexametaphosphates.
- the preferred alkali-metal tripolyphosphate for use in accordance with the present invention is sodium tripolyphosphate.
- the alkali-metal tripolyphosphates are chemi cal compounds of the formula M5P3O1o in their anhydrous form, in which M represents an alkalimetal.
- Sodium tripolyphosphate is the most common and important of the alkali-metal tripolyphosphates. Chemical and X-ray analyses show that crystalline sodium tripolyphosphate is a definite chemical compound which is distinct from both sodium hexametapohsphate and sodium pyrophosphate and that it is not a mixture of the two.
- Sodium tripolyphosphate is fusible and the fused mass may be solidified by very rapidly cooling in a glassy amorphous mass. Under'slower cooling, the fused mass solidifies in the form of crystals. The glass may be converted into crystalline tripolyphosphate by annealing. Soditripolyphosphate is colorless, appearing white in the granulated crystalline form. When crushed,
- Tricalcium phosphate (CaaPOO- 40 Sodium hexametaphosphate or tripolyphosphate 10
- Example IV Per cent Trisodium phosphate 40 Finely divided calcium carbonate 30 Sodium hexametaphosphate or tripolyphosphate 30 it forms a free-flowing granular mass. By suitable precautions it may be produced in a mass which readily disintegrates into its constituent fine crystals. Sodium tripolyphosphate is not deliquescent and particularly in its hydrated form may be preserved indefinitely in ordinary atmospheres without caking or picking up moisture. Sodium tripolyphosphate is readilywatersoluble.
- the alkali-metal metaphosphates and tripolyphosphates are molecularly dehydrated phosphates as such term is employed in Hall and Jackson Patent No. 1,903,041.
- sodium metaphospl ate NaPOa
- sodium tripolyphosphate may be similarly considered as derived by molecular dehydration of a mixture of orthophosphates which is intermediate in acidity between the monosodium dihydrogen ortho phosphate and the disodium monohydrogen .orthophosphate.
- the metaphosphates and tripolyphosphates may be regarded as saltsof condensed or molecularly dehydrated phosphoric acids which have'been molecularly dehydrated to a greater extent than pyrophosphoric acid.
- the abrasive detergent composition may contain soap or an alkali, or both, in addition to the abrasive and the alkali-metal metaphosphate or tripolyphosphate.
- a composition for use as a powder in cleaning the teeth may be as follows:
- Example I v Per cent Impalpable dicalcium phosphate (CaHPO4) l0 Powdered sodium hexametaphosphate or so-
- the composition prepared in dry powdered form is used in the ordinary manner in cleaning teeth by applying the powder to the toothbrush.
- the composition may be made into a paste by the addition of Water.
- compositions for cleaning walls or polishing metallic objects are as follows:
- tral soap Other alkaline salts may be used iri place of the trisodium phosphate of Example IV, for example sodium carbonate, borax, sodium hydroxide, and sodium metaor other silicate.
- the powder may be supplied to a sponge or rag which has been previously moistened and the surface to be cleaned is rubbed.
- the alkali-metal hexametaphosphate and tripolyphosphate have a detergent and emulsifying effect on grease which may be present on the surfaces of metal objects or on the coating on walls or other surfaces.
- the hexametaphosphate and tripolyphosphate also have the property of preventing the precipitation of insoluble calcium and magnesium soaps and salts which otherwise would form when a composition containing soap or alkali is moistened with hard water.
- the prevention of the formation of insoluble calcium and magnesium soaps enables the soluble soap in the composition to act on the soil without hindrance by the formation of insoluble soaps.
- the alkali in the composition emulsifies grease and dirt, thereby increasing the efficiency of the soluble soap in the cleaning or polishing process.
- the scouring action of the abrasive is augmented by the emulsifying effect of the hexametaphosphate or tripolyphosphate on grease.
- the composition may be used as a powder, paste or other suitable form. While I prefer to use the sodium hexametaphosphate or tripolyphosphate, or mixtures thereof, other alkalimetal hexametaphosphates or tripolyphosphates may be used, such as the hexametaphosphates or tripolyphosphates of potassium,lithium and ammonium. Where mixtures of the alkali-metal metaphosphates and tripolyphosphates are employed, such mixtures may be made mechanically, or chemically by using the proper ratio of phosphorus pentoxide to alkali-metal oxide in the starting material.
- An abrasive detergent composition containing an alkali-metal salt of the group consisting of soluble metaphosphate and tripolyphosphate which is capable of sequestering calcium in a but slightly ionized condition, and an inorganic abrasivewhich is insoluble or only slightly soluble in water but which is soluble in water solutions of said alkali-metal salt.
- An abrasive detergent composition containing an alkali-metal hexametaphosphate and an inorganic abrasive which is insoluble or only slightly soluble in water but which is soluble in water solutions of said alkali-metal salt.
- An abrasive detergent composition containing sodium hexametaphosphate and an-inorganic abrasive which is insoluble or only slightly soluble in water but which is soluble in water solutions of said alkali-metal salt.
- An abrasive detergent composition containing an alkali-metal tripolyphosphate and an inorganicabrasive which is insoluble or only slightly soluble in water but which is soluble in water solutions of said alkali-metal salt.
- An abrasive detergent composition containing an alkali-metal salt of the group consisting of soluble metaphosphate and tripolyphosphate which is capable oi sequestering calcium in a but slightly ionized condition, and an inorganic abrasive oi the group consisting of dicalcium phosphate, tricalcic phosphate, calcium carbonate, magnesium oxide, calcium metaphosphate, and magnesium metaphosphate.
- a dentifrice containing a crystalline alkalirnetal metaphosphate which yields alkali-metal hexametaphosphate during'use in the mouth, and
- an inorganic abrasive which is insoluble or only slightly soluble in water but which is soluble in water solutions oi alkali-metal hexametaphos- Dhate.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Detergent Compositions (AREA)
Description
Patented Feb. 20, 1940 UNITED STATES PATENT OFFICE V I 2,191,199
ABRASIVE DETERGENT COMPOSITION Ralph E. Hall, Mount Lebanon, Pa., assignor to Hall Laboratories, Inc., Pittsburgh, Pa., 'a corporation of Pennsylvania ,No Drawing. Application September 17, 1937, Serial No. 164,371
10 Claims.
This invention relates to abrasive detergent compositions useful in cleaning, securing and polishing objects in general, for example, cleaning and polishing the teeth, polishing metallic objects such as silverware, or cleaning walls or other surfaces.
This application is a continuation-in-part of my copending application Serial No. 721,316, filed April 19, 1934.
Abrasive detergent compositions used for cleaning and polishing purposes contain an abrasive and also a detergent which may be soap or an alkali, or both, dependingupon the particular use of the composition. The type of abrasive which has been used in such compositions is one which is insoluble in water or other liquid used with the composition. These insoluble abrasives,
although necessary for imparting a scouring action to the composition, are objectionable in that it is difficult to wash them off from the surface after the cleaning operation. They tend to dry on the surfaces to which they have been applied, forming visible films of insoluble material.-
I have found that this objection may be overcome by employing a suitable type of abrasive whose solubility rate in water solutions of the composition is sufficiently low so as to permit effective scouring or polishing before it has dissolved. In addition to a certain type of abrasive, it is also necessary that the composition contain a material whose water solution has the effect of slowly dissolving the abrasive. I have found that by the proper selection of abrasive and detergent,
a compositon may be produced in which the.
solvent effect of a water solution of the detergent onthe abrasive is slow enough so that the abrasive is effective in performing its scouring function and yet is fast enough so that after the scouring function is performed, the abrasive has been dissolved so that it may be easily rinsed from the surface. The detergent present need not be in sufficient quantity to completely dissolve all of the abrasive since even the ability to dissolve a small quantity of the abrasive is of value in removing the abrasive from the surfaces to be cleansed. The partial dissolving effect prevents the adherence of the abrasive particles to the surface being cleaned and enables them to be washed away more readily.
As examples of abrasives whichhave slow but definite solubility in water solutions of the detergent, I may use dicalcium phosphate (CaHPO4), a tricalcic phosphate Cas(PO4)z, calcium carbonate (CaCOa), magnesium oxide (MgO), calcium metaphosphate or magnesium metaphosphate.
As the detergent which in water solution exerts a solubilizing action on the abrasive, I may employ an alkali-metal metaphosphate or tripolyphosphate or mixtures thereof. The preferred alkali-metal metaphosphate is the soluble sodium hexametaphosphate sometimes. called Grahams salt". The sodium hexametaphosphate is assumed to be a complex of the general formula Naz(Na4PaO1a), although some authorities believe that salts of the formulas Na5(Na P8018) and NadNagPeOm) may also be present. Sodium hexametaphosphate in readily soluble form may be prepared by strongly heating monosodium dihydrogen orthophosphate and rapidly cooling the molten mass. The quick cooling is apparently essential to the formation of a readily soluble salt. If the monosodium dihydrpgen orthophosphate is not heated to fusion, ,or if the molten mass resulting from strong heating is not cooled with sufficient rapidity,- crystalline metaphosphates may be formed which are less readily soluble or even practically insoluble in water. These are less desirable, although even the sodium metaphosphates which are practically insoluble in water alone will dissolve to a limited extent in solutions of mineral acids, as described in Munter application Serial No. 68,442, and likewise in saliva to produce some of the effective sodium hexametaphosphate. Although it is preferred that the metaphosphate used" in the detergent composition be formed in such a manner that it consists principally of the water-soluble hexametaphosphate, the invention is intended to include the use of any alkali-metal metaphosphate which contains or yields under the conditions of use suflicient hexametaphosphate to produce the desired efiect.
The alkali-metal tripolyphosphates act similarly to the alkali-metal metaphosphates in solubilizing the abrasives by combining with calcium and magnesium to form soluble complexes from which the calcium or magnesium is but extremely slightly ionized. The alkali-metal tripolyphosphates may therefore be used in place of or in combination with the alkali-metal hexametaphosphates. The preferred alkali-metal tripolyphosphate for use in accordance with the present invention is sodium tripolyphosphate.
The alkali-metal tripolyphosphates are chemi cal compounds of the formula M5P3O1o in their anhydrous form, in which M represents an alkalimetal. Sodium tripolyphosphate is the most common and important of the alkali-metal tripolyphosphates. Chemical and X-ray analyses show that crystalline sodium tripolyphosphate is a definite chemical compound which is distinct from both sodium hexametapohsphate and sodium pyrophosphate and that it is not a mixture of the two. Sodium tripolyphosphate is fusible and the fused mass may be solidified by very rapidly cooling in a glassy amorphous mass. Under'slower cooling, the fused mass solidifies in the form of crystals. The glass may be converted into crystalline tripolyphosphate by annealing. Soditripolyphosphate is colorless, appearing white in the granulated crystalline form. When crushed,
. Per cent Soap. 50
Tricalcium phosphate (CaaPOO- 40 Sodium hexametaphosphate or tripolyphosphate 10 Example IV Per cent Trisodium phosphate 40 Finely divided calcium carbonate 30 Sodium hexametaphosphate or tripolyphosphate 30 it forms a free-flowing granular mass. By suitable precautions it may be produced in a mass which readily disintegrates into its constituent fine crystals. Sodium tripolyphosphate is not deliquescent and particularly in its hydrated form may be preserved indefinitely in ordinary atmospheres without caking or picking up moisture. Sodium tripolyphosphate is readilywatersoluble.
The alkali-metal metaphosphates and tripolyphosphates are molecularly dehydrated phosphates as such term is employed in Hall and Jackson Patent No. 1,903,041. For example, sodium metaphospl ate (NaPOa) may be considered as derived from monosodlum dihydrogen orthophosphate by the removal of water 010011 stitution. Likewise, sodium tripolyphosphate may be similarly considered as derived by molecular dehydration of a mixture of orthophosphates which is intermediate in acidity between the monosodium dihydrogen ortho phosphate and the disodium monohydrogen .orthophosphate. The metaphosphates and tripolyphosphates may be regarded as saltsof condensed or molecularly dehydrated phosphoric acids which have'been molecularly dehydrated to a greater extent than pyrophosphoric acid.
The abrasive detergent composition may contain soap or an alkali, or both, in addition to the abrasive and the alkali-metal metaphosphate or tripolyphosphate.
A composition for use as a powder in cleaning the teeth may be as follows:
Example I v Per cent Impalpable dicalcium phosphate (CaHPO4) l0 Powdered sodium hexametaphosphate or so- The composition prepared in dry powdered form is used in the ordinary manner in cleaning teeth by applying the powder to the toothbrush. The composition may be made into a paste by the addition of Water.
Suitable compositions for cleaning walls or polishing metallic objects are as follows:
Example III 2,191,199 In Example III the soap is preferably a neu-,
tral soap. Other alkaline salts may be used iri place of the trisodium phosphate of Example IV, for example sodium carbonate, borax, sodium hydroxide, and sodium metaor other silicate. In cleaning walls and metal objects, the powder may be supplied to a sponge or rag which has been previously moistened and the surface to be cleaned is rubbed.
The alkali-metal hexametaphosphate and tripolyphosphate have a detergent and emulsifying effect on grease which may be present on the surfaces of metal objects or on the coating on walls or other surfaces. The hexametaphosphate and tripolyphosphate also have the property of preventing the precipitation of insoluble calcium and magnesium soaps and salts which otherwise would form when a composition containing soap or alkali is moistened with hard water. The prevention of the formation of insoluble calcium and magnesium soaps enables the soluble soap in the composition to act on the soil without hindrance by the formation of insoluble soaps. The alkali in the composition emulsifies grease and dirt, thereby increasing the efficiency of the soluble soap in the cleaning or polishing process. The scouring action of the abrasive is augmented by the emulsifying effect of the hexametaphosphate or tripolyphosphate on grease.
The composition may be used as a powder, paste or other suitable form. While I prefer to use the sodium hexametaphosphate or tripolyphosphate, or mixtures thereof, other alkalimetal hexametaphosphates or tripolyphosphates may be used, such as the hexametaphosphates or tripolyphosphates of potassium,lithium and ammonium. Where mixtures of the alkali-metal metaphosphates and tripolyphosphates are employed, such mixtures may be made mechanically, or chemically by using the proper ratio of phosphorus pentoxide to alkali-metal oxide in the starting material.
Although I have given certain preferred compositions by way of illustration only, it is to be understood that the invention may be otherwise embodied within the scope of a the following claims. a
I claim: 1. An abrasive detergent composition containing an alkali-metal salt of the group consisting of soluble metaphosphate and tripolyphosphate which is capable of sequestering calcium in a but slightly ionized condition, and an inorganic abrasivewhich is insoluble or only slightly soluble in water but which is soluble in water solutions of said alkali-metal salt.
2. An abrasive detergent composition containing an alkali-metal hexametaphosphate and an inorganic abrasive which is insoluble or only slightly soluble in water but which is soluble in water solutions of said alkali-metal salt.
3. An abrasive detergent composition containing sodium hexametaphosphate and an-inorganic abrasive which is insoluble or only slightly soluble in water but which is soluble in water solutions of said alkali-metal salt.
4. An abrasive detergent composition containing an alkali-metal tripolyphosphate and an inorganicabrasive which is insoluble or only slightly soluble in water but which is soluble in water solutions of said alkali-metal salt.
5. An abrasive detergent composition containing an alkali-metal salt of the group consisting of soluble metaphosphate and tripolyphosphate which is capable oi sequestering calcium in a but slightly ionized condition, and an inorganic abrasive oi the group consisting of dicalcium phosphate, tricalcic phosphate, calcium carbonate, magnesium oxide, calcium metaphosphate, and magnesium metaphosphate.
6. A dentrifrice containing an alkali-metalsalt or the group consisting of soluble metaphosphate and tripolyphosphate which is capable oi sequestering calcium in a but slightly ionized condition, and an inorganic abrasive which is insoluble or only slightly soluble in water but which is soluble in water solutions of said alkalimetal salt,
7. A dentifrice containing an alkali-metal hexametaphosphate and an inorganic abrasive which is insoluble or only slightly soluble in water but which is soluble in water solutions of said alkalimetal salt.
8. A dentifrice containing sodium hexametaphosphate and an inorganic abrasive which is insoluble or only slightly soluble in water but which is soluble in water solutions 01 said alkali-metal salt.
9. A dentifrice containing an alkali-metal tripolyphosphate and an inorganic abrasive which is insoluble or only slightly soluble in water but which is soluble in water solutions oi. said alkalimetal salt.
10. A dentifrice containing a crystalline alkalirnetal metaphosphate which yields alkali-metal hexametaphosphate during'use in the mouth, and
an inorganic abrasive which is insoluble or only slightly soluble in water but which is soluble in water solutions oi alkali-metal hexametaphos- Dhate.
. RALPH E. HALL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US164371A US2191199A (en) | 1937-09-17 | 1937-09-17 | Abrasive detergent composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US164371A US2191199A (en) | 1937-09-17 | 1937-09-17 | Abrasive detergent composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2191199A true US2191199A (en) | 1940-02-20 |
Family
ID=22594184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US164371A Expired - Lifetime US2191199A (en) | 1937-09-17 | 1937-09-17 | Abrasive detergent composition |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2191199A (en) |
Cited By (87)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2494827A (en) * | 1945-06-01 | 1950-01-17 | Hall Lab Inc | Abrasive detergent compositions |
| US2498344A (en) * | 1944-12-23 | 1950-02-21 | Lever Brothers Ltd | Denture cleansers |
| US2581278A (en) * | 1945-06-01 | 1952-01-01 | Hall Lab Inc | Abrasive detergent composition |
| DE840134C (en) * | 1949-08-25 | 1952-05-29 | Henkel & Cie Gmbh | Cleaning and care products for shiny surfaces |
| US2601238A (en) * | 1950-02-14 | 1952-06-24 | Victor Chemical Works | Dentifrice polishing composition |
| US2723217A (en) * | 1952-06-17 | 1955-11-08 | Lever Brothers Ltd | Dentifrice composition containing tyrothricin |
| US2739129A (en) * | 1948-10-02 | 1956-03-20 | Henkel & Cie Gmbh | Cleaning composition |
| US2772203A (en) * | 1952-04-03 | 1956-11-27 | Colgate Palmolive Co | Stable dental creams containing higher aliphatic acyl amide of aminocarboxxylic acid compound |
| US2876168A (en) * | 1956-08-20 | 1959-03-03 | Procter & Gamble | Calcium pyrophosphate abrasive and dentifrice containing the same |
| US2876166A (en) * | 1953-07-08 | 1959-03-03 | Indiana University Foundation | Dentifrice preparations |
| US2876167A (en) * | 1954-11-24 | 1959-03-03 | Colgate Palmolive Co | Fluoride dentifrice stabilized by a water-soluble acid phosphate compound |
| DE972089C (en) * | 1949-09-30 | 1959-05-21 | Hees G M B H Van | Process for increasing the fat content in sausage products |
| US2901400A (en) * | 1955-12-30 | 1959-08-25 | Monsanto Chemicals | Cryptocrystalline calcium pyrophosphate and dentifrice composition comprising the same |
| DE973267C (en) * | 1939-09-08 | 1960-01-07 | Benckiser Gmbh Joh A | Process to accelerate the conversion of high-percentage milk-fat-in-water-emulsion into high-percentage-water-in-milk-fat-emulsion |
| US2941926A (en) * | 1954-12-14 | 1960-06-21 | Colgate Palmolive Co | Chlorophyll dental powder |
| US2971818A (en) * | 1957-08-28 | 1961-02-14 | Bristol Myers Co | Production of ammonium hexametaphosphate by cation exchange resin |
| US3004897A (en) * | 1955-02-09 | 1961-10-17 | Shore Joseph | Dental preparation |
| US3032408A (en) * | 1957-08-05 | 1962-05-01 | Int Minerals & Chem Corp | Process of pelletizing phosphate rock |
| US3137632A (en) * | 1952-02-19 | 1964-06-16 | Colgate Palmolive Co | Chlorophyll dentifrice compositions |
| US3171787A (en) * | 1962-02-15 | 1965-03-02 | Lever Brothers Ltd | Dentifrice compositions containing surface-active n-(2-hydroxyalkyl)-n-methyltaurine-n-oxide |
| US3256155A (en) * | 1962-04-11 | 1966-06-14 | Lever Brothers Ltd | Dentifrice composition |
| US3488419A (en) * | 1965-12-08 | 1970-01-06 | Procter & Gamble | Oral compositions for calculus retardation |
| US3535420A (en) * | 1967-12-11 | 1970-10-20 | Procter & Gamble | Oral compositions for calculus retardation |
| US3666855A (en) * | 1968-01-29 | 1972-05-30 | Indiana University Foundation | Oral compositions and methods for retarding dental caries and calculus |
| US3678154A (en) * | 1968-07-01 | 1972-07-18 | Procter & Gamble | Oral compositions for calculus retardation |
| US3927202A (en) * | 1973-01-29 | 1975-12-16 | Colgate Palmolive Co | Dentifrices |
| US3927201A (en) * | 1973-01-29 | 1975-12-16 | Colgate Palmolive Co | Dentifrices |
| USRE29182E (en) * | 1965-12-08 | 1977-04-12 | The Procter & Gamble Company | Oral composition for calculus retardation |
| US4046872A (en) * | 1974-04-29 | 1977-09-06 | Colgate Palmolive Company | Dental cream |
| US4075317A (en) * | 1974-04-29 | 1978-02-21 | Colgate-Palmolive Company | Dental cream composition |
| US4122164A (en) * | 1975-10-02 | 1978-10-24 | Colgate-Palmolive Company | Dental cream composition |
| US4152417A (en) * | 1973-06-13 | 1979-05-01 | Colgate-Palmolive Company | Dental cream composition |
| EP0002184A1 (en) * | 1977-11-26 | 1979-06-13 | Giulini Chemie GmbH | Activity strengthener for dental cleaning products |
| EP0089136A3 (en) * | 1982-03-10 | 1984-05-30 | The Procter & Gamble Company | Oral hygiene products |
| US4460565A (en) * | 1981-07-03 | 1984-07-17 | Intradal N.V. | Anticariogenic remineralizing dentifrice |
| US4678662A (en) * | 1985-10-09 | 1987-07-07 | Monsanto Company | Pyrophosphate coating process for calcium carbonate dental abrasives |
| US5000944A (en) * | 1989-06-09 | 1991-03-19 | Colgate-Palmolive Company | Zinc-containing oral products with reduced astringency |
| US5200171A (en) * | 1990-11-20 | 1993-04-06 | Micropure, Inc. | Oral health preparation and method |
| US5296217A (en) * | 1992-06-15 | 1994-03-22 | Indiana University Foundation | Methods for preventing dental calculus in domestic animals |
| US5348734A (en) * | 1990-11-20 | 1994-09-20 | Micropure Inc. | Oral health preparation and method |
| US5977043A (en) * | 1997-04-17 | 1999-11-02 | Howie; Jane B. | Cleaning compound and method of use |
| US6190644B1 (en) * | 1996-11-21 | 2001-02-20 | The Procter & Gamble Company | Dentifrice compositions containing polyphosphate and monofluorophosphate |
| US6350436B1 (en) * | 1996-11-21 | 2002-02-26 | The Procter & Gamble Company | Method of reducing staining of stannous in dentifrice compositions |
| US6521216B1 (en) | 1999-11-12 | 2003-02-18 | The Procter & Gamble Company | Dual phase stannous oral compositions |
| US20030036980A1 (en) * | 2001-08-14 | 2003-02-20 | Wren Stephen C. | System for marketing goods and services utilizing computerized central and remote facilities |
| US6555094B1 (en) | 1999-11-12 | 2003-04-29 | The Procter & Gamble Company | Stannous oral compositions |
| US6610276B2 (en) * | 2001-01-12 | 2003-08-26 | Steven A. Melman | Multi-functional dental composition |
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Cited By (114)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE973267C (en) * | 1939-09-08 | 1960-01-07 | Benckiser Gmbh Joh A | Process to accelerate the conversion of high-percentage milk-fat-in-water-emulsion into high-percentage-water-in-milk-fat-emulsion |
| US2498344A (en) * | 1944-12-23 | 1950-02-21 | Lever Brothers Ltd | Denture cleansers |
| US2581278A (en) * | 1945-06-01 | 1952-01-01 | Hall Lab Inc | Abrasive detergent composition |
| US2494827A (en) * | 1945-06-01 | 1950-01-17 | Hall Lab Inc | Abrasive detergent compositions |
| US2739129A (en) * | 1948-10-02 | 1956-03-20 | Henkel & Cie Gmbh | Cleaning composition |
| DE840134C (en) * | 1949-08-25 | 1952-05-29 | Henkel & Cie Gmbh | Cleaning and care products for shiny surfaces |
| DE972089C (en) * | 1949-09-30 | 1959-05-21 | Hees G M B H Van | Process for increasing the fat content in sausage products |
| US2601238A (en) * | 1950-02-14 | 1952-06-24 | Victor Chemical Works | Dentifrice polishing composition |
| US3137632A (en) * | 1952-02-19 | 1964-06-16 | Colgate Palmolive Co | Chlorophyll dentifrice compositions |
| US2772203A (en) * | 1952-04-03 | 1956-11-27 | Colgate Palmolive Co | Stable dental creams containing higher aliphatic acyl amide of aminocarboxxylic acid compound |
| US2723217A (en) * | 1952-06-17 | 1955-11-08 | Lever Brothers Ltd | Dentifrice composition containing tyrothricin |
| US2876166A (en) * | 1953-07-08 | 1959-03-03 | Indiana University Foundation | Dentifrice preparations |
| US2876167A (en) * | 1954-11-24 | 1959-03-03 | Colgate Palmolive Co | Fluoride dentifrice stabilized by a water-soluble acid phosphate compound |
| US2941926A (en) * | 1954-12-14 | 1960-06-21 | Colgate Palmolive Co | Chlorophyll dental powder |
| US3004897A (en) * | 1955-02-09 | 1961-10-17 | Shore Joseph | Dental preparation |
| US2901400A (en) * | 1955-12-30 | 1959-08-25 | Monsanto Chemicals | Cryptocrystalline calcium pyrophosphate and dentifrice composition comprising the same |
| US2876168A (en) * | 1956-08-20 | 1959-03-03 | Procter & Gamble | Calcium pyrophosphate abrasive and dentifrice containing the same |
| US3032408A (en) * | 1957-08-05 | 1962-05-01 | Int Minerals & Chem Corp | Process of pelletizing phosphate rock |
| US2971818A (en) * | 1957-08-28 | 1961-02-14 | Bristol Myers Co | Production of ammonium hexametaphosphate by cation exchange resin |
| US3171787A (en) * | 1962-02-15 | 1965-03-02 | Lever Brothers Ltd | Dentifrice compositions containing surface-active n-(2-hydroxyalkyl)-n-methyltaurine-n-oxide |
| US3256155A (en) * | 1962-04-11 | 1966-06-14 | Lever Brothers Ltd | Dentifrice composition |
| US3488419A (en) * | 1965-12-08 | 1970-01-06 | Procter & Gamble | Oral compositions for calculus retardation |
| USRE29182E (en) * | 1965-12-08 | 1977-04-12 | The Procter & Gamble Company | Oral composition for calculus retardation |
| US3535420A (en) * | 1967-12-11 | 1970-10-20 | Procter & Gamble | Oral compositions for calculus retardation |
| US3666855A (en) * | 1968-01-29 | 1972-05-30 | Indiana University Foundation | Oral compositions and methods for retarding dental caries and calculus |
| US3678154A (en) * | 1968-07-01 | 1972-07-18 | Procter & Gamble | Oral compositions for calculus retardation |
| US3927202A (en) * | 1973-01-29 | 1975-12-16 | Colgate Palmolive Co | Dentifrices |
| US3927201A (en) * | 1973-01-29 | 1975-12-16 | Colgate Palmolive Co | Dentifrices |
| US4152417A (en) * | 1973-06-13 | 1979-05-01 | Colgate-Palmolive Company | Dental cream composition |
| US4075317A (en) * | 1974-04-29 | 1978-02-21 | Colgate-Palmolive Company | Dental cream composition |
| US4046872A (en) * | 1974-04-29 | 1977-09-06 | Colgate Palmolive Company | Dental cream |
| US4122164A (en) * | 1975-10-02 | 1978-10-24 | Colgate-Palmolive Company | Dental cream composition |
| EP0002184A1 (en) * | 1977-11-26 | 1979-06-13 | Giulini Chemie GmbH | Activity strengthener for dental cleaning products |
| US4460565A (en) * | 1981-07-03 | 1984-07-17 | Intradal N.V. | Anticariogenic remineralizing dentifrice |
| EP0089136A3 (en) * | 1982-03-10 | 1984-05-30 | The Procter & Gamble Company | Oral hygiene products |
| US4678662A (en) * | 1985-10-09 | 1987-07-07 | Monsanto Company | Pyrophosphate coating process for calcium carbonate dental abrasives |
| US5000944A (en) * | 1989-06-09 | 1991-03-19 | Colgate-Palmolive Company | Zinc-containing oral products with reduced astringency |
| US5200171A (en) * | 1990-11-20 | 1993-04-06 | Micropure, Inc. | Oral health preparation and method |
| US5348734A (en) * | 1990-11-20 | 1994-09-20 | Micropure Inc. | Oral health preparation and method |
| US5296217A (en) * | 1992-06-15 | 1994-03-22 | Indiana University Foundation | Methods for preventing dental calculus in domestic animals |
| US20060171907A1 (en) * | 1996-11-21 | 2006-08-03 | The Procter & Gamble Company | Oral care compositions providing enhanced whitening and stain prevention |
| US7063833B2 (en) | 1996-11-21 | 2006-06-20 | The Procter & Gamble Company | Method of reducing staining of stannous in dentifrice compositions |
| US6350436B1 (en) * | 1996-11-21 | 2002-02-26 | The Procter & Gamble Company | Method of reducing staining of stannous in dentifrice compositions |
| US6190644B1 (en) * | 1996-11-21 | 2001-02-20 | The Procter & Gamble Company | Dentifrice compositions containing polyphosphate and monofluorophosphate |
| US5977043A (en) * | 1997-04-17 | 1999-11-02 | Howie; Jane B. | Cleaning compound and method of use |
| US10376451B2 (en) | 1999-11-12 | 2019-08-13 | The Procter & Gamble Company | Method of protecting teeth against erosion |
| US10702460B2 (en) | 1999-11-12 | 2020-07-07 | The Procter & Gamble Company | Method of protecting teeth against erosion |
| US10369090B2 (en) | 1999-11-12 | 2019-08-06 | The Procter & Gamble Company | Method of protecting teeth against erosion |
| US6713049B1 (en) | 1999-11-12 | 2004-03-30 | The Procter & Gamble Company | Oral compositions providing optimal surface conditioning |
| US6521216B1 (en) | 1999-11-12 | 2003-02-18 | The Procter & Gamble Company | Dual phase stannous oral compositions |
| US20070025928A1 (en) * | 1999-11-12 | 2007-02-01 | The Procter & Gamble Company | Stannous oral care compositions |
| US6555094B1 (en) | 1999-11-12 | 2003-04-29 | The Procter & Gamble Company | Stannous oral compositions |
| US10258549B2 (en) | 1999-11-12 | 2019-04-16 | The Procter & Gamble Company | Method of protecting teeth against erosion |
| US10470985B2 (en) | 1999-11-12 | 2019-11-12 | The Procter & Gamble Company | Method of protecting teeth against erosion |
| US10258550B2 (en) | 1999-11-12 | 2019-04-16 | The Procter & Gamble Company | Method of protecting teeth against erosion |
| US20060115434A1 (en) * | 2000-03-10 | 2006-06-01 | Cadbury Adams Usa Llc. | Chewing gum and confectionery compositions with encapsulated stain removing agent compositions, and methods of making and using the same |
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