US3337466A - Effervescent dental cleaner compositions - Google Patents

Effervescent dental cleaner compositions Download PDF

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US3337466A
US3337466A US463981A US46398165A US3337466A US 3337466 A US3337466 A US 3337466A US 463981 A US463981 A US 463981A US 46398165 A US46398165 A US 46398165A US 3337466 A US3337466 A US 3337466A
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sodium
water soluble
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Puetzer Bruno
Alexander V Finn
Mackles Leonard
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Revlon Inc
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Revlon Inc
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A61Q11/02Preparations for deodorising, bleaching or disinfecting dentures
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/20Halogens; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/22Peroxides; Oxygen; Ozone
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3942Inorganic per-compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/22Gas releasing
    • A61K2800/222Effervescent
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/51Chelating agents

Definitions

  • a composition comprising the combination of potassium monopersulfate and at least one other solid water soluble peroxygen compound other than potassium monopersulfate and an alkali in a quantity suflicient to give an aqueous solution of such composition a pH of at least 7, at which pH oxygen is generated by the composition in excess of its solubility in the solution so that the solution efiervesces strongly.
  • a water soluble halide which produces in the aqueous solution a halogen ion, the halogen ion being converted, by the oxygen released, from halogen ion to free halogen. Therefore, the present composition is ideally suited as a composition for the cleansing, sterilization and bleaching of dentures, pipe stems, cigarette holders, and for other uses as, for example, the cleansing and bleaching of the hair.
  • denture as used in the following description and in the appended claims includes artificial teeth, removable orthodontic bridges and denture plates of both upper and lower types. Dentures have a tendency to become stained by foods and by the nicotine and tars derived from smoking tobacco. Many dentures are of such irregular configuration that food particles tend to cling to the denture. Further, if dentures are not cleaned properly germs and slime may develop thereon giving rise to unpleasant odors.
  • the present process and com position provides means for cleansing, sterilizing, and bleaching and deodorizing dentures.
  • cleansing as used in the claims is intended to include all the actions of cleansing, sterilizing, bleaching, deodorizing and also the removal of residual food particles.
  • compositions of matter comprising a dry stable mixture of the aforesaid peroxygen compounds with other ingredients which provide a complete chemical system capable of self-inducing a series of reactions upon sinple addition of water.
  • potassium monopersulfate is activated in aqueous alkaline solutions by certain other peroxygen compounds and, in the same sense, these other peroxygen compounds are, so to speak, activated by potassium monopersulfate.
  • a two percent (2.0%) by weight water solution of potassium monopersulfate is acidic in nature and is relatively stable. Should the acid nature of the solution be slowly changed by the addition of base, it is noted that free oxygen becomes available in solution when the pH approaches a value of 7.0. The apparent rate at which oxygen becomes available increases as the pH of the solution increases above 7 and reaches a maximum value at a pH of about 9.
  • An alternate method involves preparing a mixture in the form of a powder or tablet comprising potassium monopersulfate and another solid peroxygen compound with an alkaline filler in such proportions that provide a neutral or alkaline, i.e., nonacid, solution of the ingredients upon admixture with water.
  • this latter method is preferred, specially in those applications in which presence of free oxygen in aqueous solution is essentially the sole requirement of the system, as for example, those situations where only aerobic conditions or antiseptic or light bleaching action is desired.
  • One embodiment of the invention concerns the utilizat tion of our free oxygen-producing system in oxidation reactions involving both organic and inorganic compounds.
  • a typical illustration is the case with which our system oxidizes halogen ion to free halogen.
  • Oxidation reactions of this type can be readily carried out in accordance with our teachings by the addition of a water soluble halide, to alkaline solutions of the aforementioned peroxygen compounds.
  • the water soluble halide is selected from the group consisting of water soluble metal halides and ammonium halides, such for example as the fluoride, chloride, bromide and iodide of the alkali metals and alkaline earth metals and of ammonium. It is characteristic of the water soluble halides that in aqueous solutions they will yield the halogen ion. Therefore, without limiting the invention, the following may be given as specific examples of water soluble halides useful in the present composition: sodium fluoride, sodium choride, potassium chloride, potassium iodide, ammonium chloride.
  • a more etfective use of this embodiment of the invention is accomplished by the preparation of a dry mixture of the critical components, which in the present instance includes the two peroxygen compounds, alkaline filler and the water soluble halide added to water.
  • the dry composition may be in the form of a free-flowing powder or granule or it may be sold in shaped form such, for example, as a tablet, pill, pellet, beads and the like.
  • other ingredients both reactive and nonreactive may be added such as detergents, chelating agents, wetting agents, perfumes or fragrances and others, as for example, bonding agents should the mixture be processed in shaped form such as a tablet, to more suitably adapt our invention to a specific use.
  • any of the Water soluble, solid peroxygen compounds other than potassium monopersulfate are the inorganic water soluble peroxides of metals constituting the elements of Groups I and II of the Periodic Table and the inorganic water soluble alkali metal salts of peroxy acids.
  • the exceptions to the above classes of peroxygen compounds which are useful in our invention include, among others, urea peroxide and the ammonium salts of peroxy acids.
  • peroxygen compounds as sodium perborate, potassium persulfate (the peroxydisulfuric acid salt), ammonium persulfate, sodium persulfate, sodium pyrophosphate peroxide, sodium carbonate peroxide, and urea peroxide, among others.
  • These peroxygen compounds are, as indicated above, water soluble and are usually available in finelydivided form. While the particle size of such peroxygen compounds is not significantly important insofar as our general teachings are concerned, we have found that as the particle size increases, the rate at which oxygen becomes available decreases and hence efiervescence continues over a longer period. The converse is of course also true, and selection of an appropriate particle size for the peroxygen compound becomes a function of the particular needs of the system.
  • water insoluble peroxygen compounds and impurities do not contribute oxygen to such systems and the kind of effervescence that results is not as desirable, or as effective, as that produced by the combination of water soluble solid peroxygen compounds and potassium monopersulfate.
  • the relative proportions of potassium monopersulfate and the other peroxygen compound which we can employ to provide an effervescent flow of oxygen in aqueous solutions is not narrowly critical and can vary over a wide range. We have obtained good results in terms of effervescence when potassium monopersulfate is present in our compositions in an amount of from about 0.1 part up to about 10 and more parts per part of the other peroxygen compound. Excellent effervescence of oxygen takes place when the potassium monopersulfate is present in amounts at least greater than the other peroxygen compound.
  • water soluble halide sodium chloride or other oxidizable compound when employed in the practice of the invention, we prefer it to be present, in terms of its oxidizable group of ion content, in stoichiometrically smaller amounts than the free oxygen made available by the system. By so doing, essentially complete oxidation will occur and the presence of excess free oxygen in the system is insured.
  • alkaline fillers in general, to be most useful as the component for providing the appropriate pH characteristics to the solution.
  • Such fillers are perhaps best characterized by their ability to disassociate in water.
  • a preferred class of alkaline fillers are those compounds usually referred to as mild alkaline detergents which function to provide both detergent capacity as well as the requisite alkalinity to the water solutions of our novel compositions.
  • mild alkaline detergents include, among others, trisodium phosphate, sodium carbonate (as well as sodium sesquicarbonate), tetrasodium pyrophosphate, sodium tripolyphosphate and sodium metasilicate.
  • a mixture of the mild alkaline detergents may be employed such as 110 to 101 parts of sodium tripolyphosphate and sodium sesquicarbonate.
  • the amount of such water soluble inorganic alkaline filler present in our compositions can vary over a wide range so long as it is sufficient to insure that the pH of an aqueous solution of the solid composition is greater than 7.0.
  • alkaline fillers in an amount of from about 0.8 part up to about 2 parts per part of the combined peroxygen compounds will provide suitable pH values, as for example values in the range of from 8 to 11.
  • dilute aqueous solutions containing the peroxygen compounds, the alkaline filler and water soluble halide in the proportions indicated are resistant to pH change by the addition of acid or base.
  • Oxone Tradenameamonopersullate compound available from E. I. du Pont de Nemours and Company, Inc., Wilmington, Del., as a. mixture containing approximately 50 mole percent potassium mono persullate, 25 mole percent potassium hydrogen sulfate and 25 mole percent potassium sulfate; available oxygen 4.5%).
  • chelating agent can also be added to our novel compositions. While in the above specific composition we employed nitrilotriacetic acid trisodium monohydrate, other chelating agents such as EDTA (ethylene diamine tetracetic acid tetra sodium salt) can be used with comparable results.
  • EDTA ethylene diamine tetracetic acid tetra sodium salt
  • a denture cleaner perhaps the most important single property sought in a denture cleaner is a high-degree of over-all cleansing action including the ability to physically remove particles and debris as well as adhesives from the denture and the capacity to remove slime resulting from deposition of mucin (a component of saliva).
  • mucin a component of saliva.
  • a denture cleanser should, of course, be capable of removing bacteria with high efiiciency.
  • composition A An over-all evaluation of the above denture cleanser was made by comparing its effectiveness in actual and simulated tests with commercially available products. The tests that were carried out as well as other evidence of improved cleansing action provided by our compositions are described in the following illustrative examples wherein the novel denture cleanser is referred to as Composition A.
  • the staining grease was thoroughly applied to several dentures and glass slides and the coated articles baked in an oven at an elevated temperature to harden or cure the grease.
  • About four (4) grams of Composition A were added to each of four (4) beakers of water (200 cc.) with the water temperature of each beaker diifering in units of 20 degrees (F.) of from a low of about 80 F. to a high of about 140 F.
  • Composition A Upon addition of Composition A to each of the beakers efiervescence occurred and four sets of the baked dentures and glass slides were immersed in the efiervescing mixture and allowed to stand for periods 'of for about five minutes up to about one-half hour.
  • the upper denture After allowing the upper denture to stand in its beaker for about twenty (20) minutes and the lower denture to stand in its beaker for forty (40) minutes, they were removed therefrom, rinsed with ml. of sterile water and then placed in 200 ml. of sterile fluid thioglycollate. The dentures were then incubated for seven (7) days at a temperature of 32 C. and subsequently examined. No evidence of growth was found in either denture, indicating the absence of viable bacteria.
  • the temperature of the water to which the novel compositions of our invention are added is not narrowly critical and can vary over a wide range.
  • the temperature of the water be in the range of from about 70 F. to about 180 F.
  • concentration of our novel compositions can vary over a wide range in accordance with the period of elfervescence desired.
  • composition A One indication of the efficiency of our compositions in producing oxygen is obtained by calculating the theoretical percent of available oxygen in the composition and comparing the value with that obtained by analytical measurement.
  • the theoretical amount of oxygen available in terms of percent by weight of the total composition is 2.35 percent.
  • the figure is based on the value of 4.5 percent available oxygen in potassium monopersulfate and percent of available oxygen in sodium perborate.
  • composition A composition A
  • composition B composition A
  • denture cleaner a specific composition
  • our novel compositions are most useful in providing continuous aerobic conditions, antiseptic activity, bleaching effects and detergent action.
  • Typical of such applications include textile bleaching, dye stripping, hygienic products and the like.
  • our most preferred compositions fell within the following range.
  • Halogen compounds 0.00 to 5.00 Chelating agents 0.10 to 5 .00 Surfactant 0.10 to 1.00
  • COMPOSITION B Compound: Parts Potassium monopersulfate 1 30.00 Sodium perborate 10.00 Sodium tri polyphosphate 15.00 Tri sodium phosphate 10.00 Sodium meta silicate penta hydrate 5.00 Sodium sulfate 10.00 Sodium carbonate 13.00
  • compositions B, C and D are employed to cleanse dentures, as for example by the procedure described in Example I, or to cleanse and bleach stained and colored surfaces as by the procedures set forth in Example VI, equivalent results are obtained.
  • compositions A, B, C and D in tablet form
  • a suitable binding agent such as sodium lauryl sulfate or a polyethylene glycol of a molecular weight of about 6000
  • results comparable to those obtained in Examples I through VII are obtained when the novel compositions are added to water in the form of a tablet.
  • a denture cleaner composition consisting of by weight from about 5 to 40 parts of a mixture consisting of about 50 mole percent potassium monopersulfate, about 25 mole percent potassium sulfate, and about 25 mole percent potassium hydrogen sulfate,
  • an inorganic water soluble peroxide of metal selected from the group consisting of Groups I and II of the Periodic Table, up to about 5 parts of a water soluble halide selected from the group consisting of the chloride, bromide and iodide of the alkali metals and alkaline earth metals and 'of ammonium; from about 15 to parts of a water soluble inorganic alkaline filler; from about 0.10 to 5 parts of a chelating agent selected from the group consisting of nitrilotriacetic acid trisodium monohydrate and ethylene diamine tetraacetic acid salt, and
  • a denture cleaner composition consisting of by Weight from about 5 to 40 parts of a mixture consisting of about 50 mole percent potassium monopcrsulfate, about 25 mole percent potassium sulfate, and about 25 mole percent potassium hydrogen sulfate,
  • a solid peroxygen compound selected from the group consisting of sodium perborate, potassium persulfate, ammonium persulfate, sodium persulfate, sodium pyrophosphate peroxide, sodium carbonate peroxide and urea peroxide;
  • a water soluble halide selected from the group consisting of the chloride, bromide and iodide of the alkali metals and alkaline earth metals and of ammonium;
  • a chelating agent selected from the group consisting of nitrilotriacetic acid trisodium monohydrate and ethylene diamine tetraacetic acid salt, and
  • a wetting agent selected from the group consisting of a water soluble alkyl aryl sulfonate and the sulfates of long chain alcohols, an aqueous solution of acid composition having a pH of at least 7, at which pH oxygen becomes available in said solution in excess of its solubility therein so that the solution eifervesces strongly, said eifervescence serving to stir said solution and to physically remove said particles from said dentures.
  • a denture cleaner composition consisting of by weight from about 5 to 40 parts of a mixture consisting of about 50 mole percent potassium monopersulfate, about 25 mole percent potassium sulfate, and about 25 mole percent potassiurn hydrogen sulfate,
  • a peroxygen compound other than potassium monopersulfate selected from the group consisting of inorganic water soluble peroxides of metals in Groups I and II of the Periodic Table and inorganic water soluble alkali metal salts of peroxy acids,
  • a water soluble halide selected from the group consisting of the chloride, bromide and iodide of the alkali metals and alkaline earth metals and of ammonium;
  • a chelating agent selected from the group consisting of nitrilotriacetic acid trisodium monohydrate and ethylene diamine tetraacetic acid salt, and
  • a Wetting agent selected from the group consisting of a water soluble alkyl aryl s'ulfonate and the sulfates of long chain alcohols,
  • an aqueous solution of said composition having a pH of at least 7, at which pH oxygen becomes available in said solution in excess of its solubility therein so that the solution effervesces strongly, said effervescence serving to stir said solution and to physically remove said particles from said dentures.
  • a denture cleaner consisting of the following ingredients in the respective amounts indicated by weight:
  • a denture cleaner consisting of the following ingredients in the respective amount-s indicated:
  • a denture cleaner consisting of the following ingredients in the respective amounts indicated- Ingredient: Parts by weight A mixture consisting of about 50 mole percent potassium monopersulfate, about mole percent potassium sulfate, and about 25 mole percent patossium hydrogen sulfate 30.00 Sodium perborate 10.00 Sodium tri polyphosphate 15.00 Tri sodium phosphate 10.00 Sodium meta silicate penta hydrate 5 .00 Sodium sulfate 10.00 Sodium carbonate 13.00 Sodium chloride 5.00 Nitrilo tri acetic acid tri sodium salt 1.50 Dodecyl benzene sodium sulfonate 0.25
  • a denture cleaner consisting of the following ingredients in the respective amounts indicated- Ingredient: Parts by weight A mixture consisting of about 50 mole percent potassium monopersulfate, about 25 mole in said solution in excess of its solubility therein so that the solution eifervesces strongly.
  • a denture cleaner consisting of the following ingredients in the respective amounts indicated- Ingredient: Parts by Weight A mixture consisting of about 5 0 mole percent potassium monopersulfate, about 25 mole percent potassium sulfate, and about 25 mole percent potassium hydrogen sulfate 24.75
  • an aqueous solution of said composition having a pH of at least 7, at which pH oxygen becomes available in said solution in excess of its solubility therein so that the solution eifervesces strongly.

Description

United States Patent Oil-ice 3,337,466 Patented Aug. 22, 1967 This invention relates in general to compositions of matter and processes for using the same to produce aerobic conditions, antiseptic activity, bleaching effects and detergent action and combinations Olf these activities. The invention relates in particular to compositions and processes for the cleansing, sterilizing and bleaching of dentures. This application is a continuation-in-part of our co-pending United States patent application, Ser. No. 185,246, filed April 5, 1962 now abandoned.
Therefore, it is a general object of the present invention to provide a composition and process for cleansing, sterilizing and bleaching in a simple and efiicacious manner.
It is a specific object of the present invention to provide a process and composition for cleansing, sterilizing and bleaching of dentures.
According to the present invention there is provided a composition comprising the combination of potassium monopersulfate and at least one other solid water soluble peroxygen compound other than potassium monopersulfate and an alkali in a quantity suflicient to give an aqueous solution of such composition a pH of at least 7, at which pH oxygen is generated by the composition in excess of its solubility in the solution so that the solution efiervesces strongly. In a preferred composition of the present invention there is present in addition a water soluble halide which produces in the aqueous solution a halogen ion, the halogen ion being converted, by the oxygen released, from halogen ion to free halogen. Therefore, the present composition is ideally suited as a composition for the cleansing, sterilization and bleaching of dentures, pipe stems, cigarette holders, and for other uses as, for example, the cleansing and bleaching of the hair.
The term denture as used in the following description and in the appended claims includes artificial teeth, removable orthodontic bridges and denture plates of both upper and lower types. Dentures have a tendency to become stained by foods and by the nicotine and tars derived from smoking tobacco. Many dentures are of such irregular configuration that food particles tend to cling to the denture. Further, if dentures are not cleaned properly germs and slime may develop thereon giving rise to unpleasant odors. The present process and com position provides means for cleansing, sterilizing, and bleaching and deodorizing dentures. The term cleansing as used in the claims is intended to include all the actions of cleansing, sterilizing, bleaching, deodorizing and also the removal of residual food particles.
We have discovered that certain combinations or mixtures of potassium monopersulfate with another peroxygen compound in aqueous alkaline solutions at a pH of 7 or above produce a highly effective effervescent flow of oxygen within the system. Based on this discovery, we have found that effervescence of oxygen in aqueous solutions makes possible the more elfective use of such systems in oxidation reactions and, in addition, provides considerable improvements in applications where peroxygen compounds are employed .for antiseptic, cleansing and bleaching activity, for example. Further findings in connection with our discovery have led to certain well defined novel compositions of matter comprising a dry stable mixture of the aforesaid peroxygen compounds with other ingredients which provide a complete chemical system capable of self-inducing a series of reactions upon sinple addition of water.
According to our invention, potassium monopersulfate is activated in aqueous alkaline solutions by certain other peroxygen compounds and, in the same sense, these other peroxygen compounds are, so to speak, activated by potassium monopersulfate. By way of illustration, a two percent (2.0%) by weight water solution of potassium monopersulfate is acidic in nature and is relatively stable. Should the acid nature of the solution be slowly changed by the addition of base, it is noted that free oxygen becomes available in solution when the pH approaches a value of 7.0. The apparent rate at which oxygen becomes available increases as the pH of the solution increases above 7 and reaches a maximum value at a pH of about 9. At no point, however, does it appear that the rate at which oxygen becomes available is considerably greater than the rate at which the oxygen so produced, becomes soluble in the system. In other words, the production of oxygen in such systems is not visually observable to any appreciative extent. On the other hand should another peroxygen compound as for example sodium perborate, be added to the water solution of potassium monoper sulfate when the pH of the solution is on the base side, the rate at which oxygen is produced is immediately increased to the extent that it far exceeds the rate at which it becomes soluble in water and, bubbling of oxygen commences, providi-ng a strongly elfervescent etfect in the system. The oxygen so produced in this system is contributed by both the potassium monopersulfate and sodium perborate.
We have determined that the method by which the peroxygen compounds are combined in aqueous alkaline solutions is not critically important. Moreover, these experiments have shown the physical form of the respective peroxygen compounds, prior to or immediately after their combination 'in solution does not materially alter the results achievable by our teachings. Thus, for example, We can prepare water solutions of the respective peroxygen compounds and subsequently combine them with sufiicient base to insure a pH of at least 7.0 for the over-all solution. We can also prepare an alkaline solution of potassium monopersulfate and simply add the other peroxygen compound in its natural state. With this procedure, it has been noted that when the peroxygen compound is added in solid form, effervescence continues until the peroxygen compound completely dissolves in solution. An alternate method involves preparing a mixture in the form of a powder or tablet comprising potassium monopersulfate and another solid peroxygen compound with an alkaline filler in such proportions that provide a neutral or alkaline, i.e., nonacid, solution of the ingredients upon admixture with water. For convenience of operation, this latter method is preferred, specially in those applications in which presence of free oxygen in aqueous solution is essentially the sole requirement of the system, as for example, those situations where only aerobic conditions or antiseptic or light bleaching action is desired.
One embodiment of the invention concerns the utiliza tion of our free oxygen-producing system in oxidation reactions involving both organic and inorganic compounds. A typical illustration is the case with which our system oxidizes halogen ion to free halogen. We can effectively and efficiently oxidize iodide ion to'iodine and chloride ion to chlorine and fluorine ion to fluorine and have found this capacity to be most useful where the action, or reaction, of free iodine, chlorine or fluorine is desired. Oxidation reactions of this type can be readily carried out in accordance with our teachings by the addition of a water soluble halide, to alkaline solutions of the aforementioned peroxygen compounds. The water soluble halide is selected from the group consisting of water soluble metal halides and ammonium halides, such for example as the fluoride, chloride, bromide and iodide of the alkali metals and alkaline earth metals and of ammonium. It is characteristic of the water soluble halides that in aqueous solutions they will yield the halogen ion. Therefore, without limiting the invention, the following may be given as specific examples of water soluble halides useful in the present composition: sodium fluoride, sodium choride, potassium chloride, potassium iodide, ammonium chloride. As far as we can determine, however, a more etfective use of this embodiment of the invention is accomplished by the preparation of a dry mixture of the critical components, which in the present instance includes the two peroxygen compounds, alkaline filler and the water soluble halide added to water. The dry composition may be in the form of a free-flowing powder or granule or it may be sold in shaped form such, for example, as a tablet, pill, pellet, beads and the like. To this base composition other ingredients both reactive and nonreactive may be added such as detergents, chelating agents, wetting agents, perfumes or fragrances and others, as for example, bonding agents should the mixture be processed in shaped form such as a tablet, to more suitably adapt our invention to a specific use.
In the practice of our invention, we can employ as the peroxygen compound referred to above, any of the Water soluble, solid peroxygen compounds other than potassium monopersulfate. With a few exceptions, these peroxygen compounds are the inorganic water soluble peroxides of metals constituting the elements of Groups I and II of the Periodic Table and the inorganic water soluble alkali metal salts of peroxy acids. The exceptions to the above classes of peroxygen compounds which are useful in our invention include, among others, urea peroxide and the ammonium salts of peroxy acids. We have employed with good results such solid peroxygen compounds as sodium perborate, potassium persulfate (the peroxydisulfuric acid salt), ammonium persulfate, sodium persulfate, sodium pyrophosphate peroxide, sodium carbonate peroxide, and urea peroxide, among others. These peroxygen compounds are, as indicated above, water soluble and are usually available in finelydivided form. While the particle size of such peroxygen compounds is not significantly important insofar as our general teachings are concerned, we have found that as the particle size increases, the rate at which oxygen becomes available decreases and hence efiervescence continues over a longer period. The converse is of course also true, and selection of an appropriate particle size for the peroxygen compound becomes a function of the particular needs of the system.
We have noted that water insoluble solids in the form of impurities, and even water insoluble solid peroxygen compounds such as magnesium peroxide, calcium peroxide or zinc peroxide, when added to, or present in, aqueous alkaline solutions of potassium monopersulfate cause some etfervescence in the system. However, studies of such systems have shown that the available oxygen so produced is, for all intents and purposes, totally attributable to the decomposition of potassium monopersulfate. In other words, water insoluble peroxygen compounds and impurities do not contribute oxygen to such systems and the kind of effervescence that results is not as desirable, or as effective, as that produced by the combination of water soluble solid peroxygen compounds and potassium monopersulfate.
The relative proportions of potassium monopersulfate and the other peroxygen compound which we can employ to provide an effervescent flow of oxygen in aqueous solutions is not narrowly critical and can vary over a wide range. We have obtained good results in terms of effervescence when potassium monopersulfate is present in our compositions in an amount of from about 0.1 part up to about 10 and more parts per part of the other peroxygen compound. Excellent effervescence of oxygen takes place when the potassium monopersulfate is present in amounts at least greater than the other peroxygen compound.
When the water soluble halide sodium chloride or other oxidizable compound is employed in the practice of the invention, we prefer it to be present, in terms of its oxidizable group of ion content, in stoichiometrically smaller amounts than the free oxygen made available by the system. By so doing, essentially complete oxidation will occur and the presence of excess free oxygen in the system is insured.
In accordance with the preferred'embodiment of our invention, i.e., wherein the reactive components are combined in a unitary dry solid composition capable of selfinducing a series of desired reactions upon simple addition to Water, we have found alkaline fillers, in general, to be most useful as the component for providing the appropriate pH characteristics to the solution. Such fillers are perhaps best characterized by their ability to disassociate in water. A preferred class of alkaline fillers are those compounds usually referred to as mild alkaline detergents which function to provide both detergent capacity as well as the requisite alkalinity to the water solutions of our novel compositions. Illustrative examples of such mild alkaline detergents, include, among others, trisodium phosphate, sodium carbonate (as well as sodium sesquicarbonate), tetrasodium pyrophosphate, sodium tripolyphosphate and sodium metasilicate. A mixture of the mild alkaline detergents may be employed such as 110 to 101 parts of sodium tripolyphosphate and sodium sesquicarbonate. The amount of such water soluble inorganic alkaline filler present in our compositions can vary over a wide range so long as it is sufficient to insure that the pH of an aqueous solution of the solid composition is greater than 7.0. In most instances we have found that the presence of alkaline fillers in an amount of from about 0.8 part up to about 2 parts per part of the combined peroxygen compounds will provide suitable pH values, as for example values in the range of from 8 to 11. Surprisingly, dilute aqueous solutions containing the peroxygen compounds, the alkaline filler and water soluble halide in the proportions indicated are resistant to pH change by the addition of acid or base.
The basic principles of the invention will be more fully described in a specific application towards the preparation and use of a unique denture cleaner, which, however is in no way to be considered as limiting the overall scope or utility of our discovery. In accordance with the foregoing principles and procedures the following composition was prepared by dry blending the compounds listed.
1 Parts of Oxone (Tradenameamonopersullate compound available from E. I. du Pont de Nemours and Company, Inc., Wilmington, Del., as a. mixture containing approximately 50 mole percent potassium mono persullate, 25 mole percent potassium hydrogen sulfate and 25 mole percent potassium sulfate; available oxygen 4.5%).
2 Added to mask odor of Oxone and to provide fragrance.
In the above composition, a small amount of an alkyl aryl sulfonate, a well known wetting agent was added to the like.
To assist in removing tartar from dentures, small amounts of chelating agent can also be added to our novel compositions. While in the above specific composition we employed nitrilotriacetic acid trisodium monohydrate, other chelating agents such as EDTA (ethylene diamine tetracetic acid tetra sodium salt) can be used with comparable results.
Perhaps the most important single property sought in a denture cleaner is a high-degree of over-all cleansing action including the ability to physically remove particles and debris as well as adhesives from the denture and the capacity to remove slime resulting from deposition of mucin (a component of saliva). Closely associated with the above property in terms of importance is the capacity to remove stains caused by such substances as coffee, tea, nicotine and the like without exerting harmful efiects on the plastics or metals generally employed in denture constructions such as phenolformaldehyde, acrylic and cellulose acetate resins and metals such as alloys of chromium and cobalt. Finally, a denture cleanser should, of course, be capable of removing bacteria with high efiiciency.
An over-all evaluation of the above denture cleanser was made by comparing its effectiveness in actual and simulated tests with commercially available products. The tests that were carried out as well as other evidence of improved cleansing action provided by our compositions are described in the following illustrative examples wherein the novel denture cleanser is referred to as Composition A.
EXAMPLE I Comparative evaluation of "Composition A in removing simulated food stains from dentures and simulated denture surfaces A grease composition known to cause severe staining of dentures was prepared from the following materials in the proportions indicated.
The staining grease was thoroughly applied to several dentures and glass slides and the coated articles baked in an oven at an elevated temperature to harden or cure the grease. About four (4) grams of Composition A were added to each of four (4) beakers of water (200 cc.) with the water temperature of each beaker diifering in units of 20 degrees (F.) of from a low of about 80 F. to a high of about 140 F. Upon addition of Composition A to each of the beakers efiervescence occurred and four sets of the baked dentures and glass slides were immersed in the efiervescing mixture and allowed to stand for periods 'of for about five minutes up to about one-half hour.
Upon removal from solution, the dentures and slides were examined and found to be extremely clean and free of all stain. The gas produced was analyzed and found to be essentially pure oxygen. Comparable evaluations carried out with two commercially available denture cleaners in accordance with the procedure described above showed both the dentures and slides to be noticeably less free of-stain.
6 EXAMPLE II Comparative evaluation of Composition A in removing adhesives from dentures and simulated denture surfaces A commercially available denture adhesive was applied to several sets of dentures and glass slides and the articles baked in an oven at an elevated temperature to harden the adhesive. Four (4), two percent (2.0%) solutions of Composition A were prepared as in Example I and four (4) sets of dentures and glass slides immersed therein. After allowing the dentures to stand immersed for periods of from about five (5) to thirty (30) minutes, they were removed from the respective solutions and examined. In all instances, the dentures and glass slides were found to be well cleansed and free of adhesive. Comparative tests carried out at the same water temperatures and concentrations with four (4) solutions of each of two (2) commercially available cleaners (the same as those employed in Example I) showed these cleansers to be far less effective in removing adhesive from the dentures and glass slides.
EXAMPLE HI Comparative evaluation of Composition A in removing cofiee and tea stains from dentures Several sets of dentures were immersed in hot concentrated solutions of black coffee and tea for varying periods and subsequently removed therefrom and dried. Two (2) sets of the four (4) two-percent (2.0%), solutions of Composition A were prepared as described in Example I and one series of the coffee-stained dentures was immersed in one set of the solutions while the tea-stained dentures were immersed in the remaining set of solutions. After allowing the dentures to stand in their respective solutions for periods of from five to thirty (5-30) minutes, they were removed and examined. In all instances, they were free of stain and exceptionally clean in appearance. Comparable evaluations carried out with coffeeand tea-stained dentures with the commercially available denture cleaners referred to in Example I by following a similar procedure, proved them far less effective in removing stains.
EXAMPLE IV Evaluation of the bactericidal properties of Composition A An upper and lower denture were sterilized by subjecting them to a steam environment (15 pounds) for a period of fifteen minutes and then planted into 200* ml. of a fluid thioglycollate medium, which had been contaminated with sputum. The dentures were incubated for a period of from sixteen to eighteen (16-18) hours at a temperature of 37 C. after which period they were removed from the contaminated medium and each denture placed into a separate beaker containing 200 ml. of warm water (120 F.) to which four (4) grams of Composition A had just been added. After allowing the upper denture to stand in its beaker for about twenty (20) minutes and the lower denture to stand in its beaker for forty (40) minutes, they were removed therefrom, rinsed with ml. of sterile water and then placed in 200 ml. of sterile fluid thioglycollate. The dentures were then incubated for seven (7) days at a temperature of 32 C. and subsequently examined. No evidence of growth was found in either denture, indicating the absence of viable bacteria.
EXAMPLE V Effect of temperature and concentration of Composition A with respect to efiervescent action .hand, the commercially available cleaners provided cloudy,
murky solutions and no elfervescence. Elfervescence is an important function of our novel compositions not only for the reason that it provides increased amounts of available oxygen in the system, but, in addition, because the mixing and stirring action within the solution, caused by effervescence, mechanically aids the bleaching and cleasing activity by providing what might best be described as a scrubbing function. Because of its importance, the following data are presented to more suitably illustrate etfervescence in our system, under varying conditions of temperature and concentration:
Duration of Eflervescence Available Oxygen Remainand Time Required for ing in Solution Alter Temperature 4 Grams of Composi- Complete Solubility is tion A to Completely Achieved (Calculated as Dissolve in 200 cc. of Percent by Weight of Water Composition A) 80 F 30 minutesiQ minutes 0. 24% 16 mi11utes;l:2 minutes 0.25% 9 minutesil minute 1. 0.33% 40 F s. 5 niinutosil minute 0. 39%
2 minutes 5 minutes 6 minutes 9 minutes 12 minutes 13 minutes 14 minutes As is apparent from the above, the temperature of the water to which the novel compositions of our invention are added is not narrowly critical and can vary over a wide range. For good results we prefer that the temperature of the water be in the range of from about 70 F. to about 180 F. In the same manner, it is apparent that the concentration of our novel compositions can vary over a wide range in accordance with the period of elfervescence desired.
One indication of the efficiency of our compositions in producing oxygen is obtained by calculating the theoretical percent of available oxygen in the composition and comparing the value with that obtained by analytical measurement. With respect to Composition A, the theoretical amount of oxygen available in terms of percent by weight of the total composition is 2.35 percent. The figure is based on the value of 4.5 percent available oxygen in potassium monopersulfate and percent of available oxygen in sodium perborate. Analytical determinations carried out on water solutions (2 percent concentration) of Composition A with sodium thiosulfate indicated the available oxygen to be in the range of from 2.15 to 2.30 percent by weight of the total composition, showing close agreement with the theoretical value.
Analytical determinations carried out on a water solution (1.5 percent) of Composition A for available chlorine indicated the solution contained 3.12 percent available chlorine, calculated as percent by weight of the composition.
While the basic principles of our invention are described above in detail with respect to a specific composition (Composition A) and to its application as a denture cleaner, the examples below illustrate the Wide variety of applications in which our novel compositions are most useful in providing continuous aerobic conditions, antiseptic activity, bleaching effects and detergent action. Typical of such applications include textile bleaching, dye stripping, hygienic products and the like. In these and other applications where such properties are most desirable, our most preferred compositions fell within the following range.
Alkaline fillers 15.00 to 85.00
Halogen compounds 0.00 to 5.00 Chelating agents 0.10 to 5 .00 Surfactant 0.10 to 1.00
1 Oxone as described for Composition A.
EXAMPLE VI Evaluation of bleaching and detergent properties of Composition A on various stained and colored surfaces (21) Aluminum.A one quart aluminum coifee percolator which had been utilized in the periodic preparation of coffee over a considerable period of time and which possessed the characteristic brown resinous coffee stain over its inner surface was filled to about one-half of its capacity with about 500 cc. of hot water (160 F.) and about 8 grams of Composition A was then added thereto. Eifervescence was noted by slight turbulence in the water. The percolator Was allowed to stand for a period of about fifteen (15) minutes at which point its contents were discarded and the percolator thoroughly rinsed with water. Upon examination it was found that the bottom half of the inner surface of the percolator (that portion which had been in contact with the water solution of Composition A) was free of the brown resinous coffee stain with the metallic luster of aluminum in evidence to the extent characteristic of an unused coffee percolator. By contrast the upper portion of the percolator (the portion not in contact with the water solution of Composition A) still retained the characteristic coffee stain over its inner surface.
(b) Human hair.-A lock of womans brown hair was placed in a beaker containing cc. of warm water (120 F.) and two (2) grams of Composition A added thereto. Elfervescence was noted in the water solution and the beaker allowed to stand for a period of fifteen to twenty (15-20) minutes, after which time the lock of hair was removed and thoroughly dried. Upon comparison with a lock of untreated hair taken from the same woman, it was noted that the treated lock of hair was uniformly lighter in color and was free of any noticeable deterioration of fiber structure.
(c) Wood.-A piece of hard dark-colored wood of unknown origin was immersed in a container containing about 100 cc. of warm water F.) and about ten (10) grams of Composition A added thereto. The container was allowed to stand for one (1) hour, after which time the piece of wood was removed, rinsed and dried. By comparison with an untreated piece of wood of the same nature and origin, it was noted that the treated piece appeared to be considerably cleaner and lighter in color.
((1) Melamine plastic-A melamine plastic cup which had been employed over a considerable period of time in serving coffee had become discolored (inner surface) with the characteristic coifee stain, that could not be removed by the use of commercially available detergents and scouring agents, was filled to about half its capacity with 100 cc. of warm water F.). Two (2) grams of Composition A were added to the cup and the resulting solution in the cup allowed to stand undisturbed for about ten (10) minutes, after which the solution was discarded and the cup thoroughly rinsed with water. It was noted that the inner surface of the cup which had been in contact with the solution of Composition A was extremely clean and completely free of all stain and discoloration while the upper portion of the inner surface of the cup not in contact with the solution of Composition A remained discolored.
9. EXAMPLE VII Preparation of compositions which provide antiseptic activity, bleaching efiects and detergent The following compositions were prepared by dry blending the compounds listed in the preparations set forth.
COMPOSITION B Compound: Parts Potassium monopersulfate 1 30.00 Sodium perborate 10.00 Sodium tri polyphosphate 15.00 Tri sodium phosphate 10.00 Sodium meta silicate penta hydrate 5.00 Sodium sulfate 10.00 Sodium carbonate 13.00
Sodium chloride 5.00 Nitrilo tri acetic acid tri sodium salt 1.50 Dodecyl benzene sodium sulfonate 0.25 Methyl salicylate 0.25
1 Oxone as described for Composition A.
COMPOSITION C Compound: Parts Potassium monopersulfate 1 40.50 Sodium pyrophosphate peroxide 14.50 Tetra sodium pyrophosphate 15.00 Sodium sesq-ui carbonate 15.00 Tri sodium phosphate 5.00 Sodium carbonate 5.25 Potassium chloride 3.00
Ethylenediamine tetra acetic acid tetra sodium salt 1.00 Sodium lauryl sulfate 0.50 Methyl salicylate 0.25
1 Oxon as described for Composition A.
COMPOSITION D Compound: Parts Potassium monopersulfate 1 24.75 Potassium persulfate 8.25 Sodium tri polyphosphate 20.00 g Sodium sesqui carbonate 21.00 Sodium carbonate 10.00 Sodium borate 13.00 Nitrilo tri acetic acid tri sodium salt 2.65 Dodecyl benzene sodium sulfonate 0.10 Methyl salicylate 0.25
1 Oxone as described for Composition A.
When Compositions B, C and D are employed to cleanse dentures, as for example by the procedure described in Example I, or to cleanse and bleach stained and colored surfaces as by the procedures set forth in Example VI, equivalent results are obtained.
EXAMPLE VIII Preparation and use of Compositions A, B, C and D in tablet form When compositions of the same constitution of Compositions A, B, C and D are dry blended to form powders and small amounts (one percent by weight) of a suitable binding agent such as sodium lauryl sulfate or a polyethylene glycol of a molecular weight of about 6000, added thereto, the compositions can be molded or pressed into tablet form. Results comparable to those obtained in Examples I through VII are obtained when the novel compositions are added to water in the form of a tablet.
Having thus described the subject matter of our invention what it is desired to secure by Letters Patent is:
1. A denture cleaner composition consisting of by weight from about 5 to 40 parts of a mixture consisting of about 50 mole percent potassium monopersulfate, about 25 mole percent potassium sulfate, and about 25 mole percent potassium hydrogen sulfate,
from about 40 to 5 parts of an inorganic water soluble peroxide of metal selected from the group consisting of Groups I and II of the Periodic Table, up to about 5 parts of a water soluble halide selected from the group consisting of the chloride, bromide and iodide of the alkali metals and alkaline earth metals and 'of ammonium; from about 15 to parts of a water soluble inorganic alkaline filler; from about 0.10 to 5 parts of a chelating agent selected from the group consisting of nitrilotriacetic acid trisodium monohydrate and ethylene diamine tetraacetic acid salt, and
from about 0.10 to 1.0 part of a wetting agent selected from the group consisting of a water soluble alkyl aryl sulfonate and the sulfates of long chain alcohols, an aqueous solution of said composition having a pH of at least 7, at which pH oxygen becomes available in said solution in excess of its solubility therein so that the solution effervesces strongly, said elfervescence serving to stir said solution and to physically remove said particles from said dentures. 2. A denture cleaner composition consisting of by Weight from about 5 to 40 parts of a mixture consisting of about 50 mole percent potassium monopcrsulfate, about 25 mole percent potassium sulfate, and about 25 mole percent potassium hydrogen sulfate,
from about 40 to 5 parts of a solid peroxygen compound selected from the group consisting of sodium perborate, potassium persulfate, ammonium persulfate, sodium persulfate, sodium pyrophosphate peroxide, sodium carbonate peroxide and urea peroxide;
up to about 5 parts of a water soluble halide selected from the group consisting of the chloride, bromide and iodide of the alkali metals and alkaline earth metals and of ammonium;
from about 15 to 85 parts of a water soluble inorganic alkaline filler;
from about 0.10 to 5 parts of a chelating agent selected from the group consisting of nitrilotriacetic acid trisodium monohydrate and ethylene diamine tetraacetic acid salt, and
from about 0.10 to 1.0 part of a wetting agent selected from the group consisting of a water soluble alkyl aryl sulfonate and the sulfates of long chain alcohols, an aqueous solution of acid composition having a pH of at least 7, at which pH oxygen becomes available in said solution in excess of its solubility therein so that the solution eifervesces strongly, said eifervescence serving to stir said solution and to physically remove said particles from said dentures.
3. A denture cleaner composition consisting of by weight from about 5 to 40 parts of a mixture consisting of about 50 mole percent potassium monopersulfate, about 25 mole percent potassium sulfate, and about 25 mole percent potassiurn hydrogen sulfate,
from about 40 to 5 parts of a peroxygen compound other than potassium monopersulfate selected from the group consisting of inorganic water soluble peroxides of metals in Groups I and II of the Periodic Table and inorganic water soluble alkali metal salts of peroxy acids,
up to about 5 parts of a water soluble halide selected from the group consisting of the chloride, bromide and iodide of the alkali metals and alkaline earth metals and of ammonium;
from about 15 to 85 parts of a water soluble inorganic alkaline filler;
from about 0.10 to 5 parts of a chelating agent selected from the group consisting of nitrilotriacetic acid trisodium monohydrate and ethylene diamine tetraacetic acid salt, and
from about 0.10 and 1.0 part of a Wetting agent selected from the group consisting of a water soluble alkyl aryl s'ulfonate and the sulfates of long chain alcohols,
an aqueous solution of said composition having a pH of at least 7, at which pH oxygen becomes available in said solution in excess of its solubility therein so that the solution effervesces strongly, said effervescence serving to stir said solution and to physically remove said particles from said dentures.
4. A denture cleaner consisting of the following ingredients in the respective amounts indicated by weight:
(a) from 5 to 40 parts of a mixture consisting of about 50 mole percent potassium monopersulfate, about 25 mole percent potassium sulfate and about 25 mole percent potassium hydrogen sulfate;
(b) from 40 to 5 parts sodium perborate;
() up to parts sodium chloride;
(d) from to 85 parts of an alkaline filler consisting of a mixture of 1-10 to 10-1 parts of sodium tripolyphosphate and sodium sesquicarbonate;
(e) from 0.10 to 5 parts of nitriloacetic acid-trisodium monohydrate; and
(f) from 0.10 to 10 parts of a water soluble alkyl aryl sulfonate; an aqueous solution of said composition having a pH of at least 7, at which pH oxygen becomes available in said solution in excess of its solubility therein so that the solution effervesces strongly.
5. A denture cleaner consisting of the following ingredients in the respective amount-s indicated:
an aqueous solution of said composition having a pH of at least 7, it which pH oxygen becomes available in said solution in excess of its solubility therein so that the solution eifervesces strongly. 6. A denture cleaner consisting of the following ingredients in the respective amounts indicated- Ingredient: Parts by weight A mixture consisting of about 50 mole percent potassium monopersulfate, about mole percent potassium sulfate, and about 25 mole percent patossium hydrogen sulfate 30.00 Sodium perborate 10.00 Sodium tri polyphosphate 15.00 Tri sodium phosphate 10.00 Sodium meta silicate penta hydrate 5 .00 Sodium sulfate 10.00 Sodium carbonate 13.00 Sodium chloride 5.00 Nitrilo tri acetic acid tri sodium salt 1.50 Dodecyl benzene sodium sulfonate 0.25
Methyl salicylate 0.25
an aqueous solution of said composition having a pH of at least 7, at which pH oxygen becomes available in said solution in excess of its solubility therein so that the solution effervesces strongly. 5 7. A denture cleaner consisting of the following ingredients in the respective amounts indicated- Ingredient: Parts by weight A mixture consisting of about 50 mole percent potassium monopersulfate, about 25 mole in said solution in excess of its solubility therein so that the solution eifervesces strongly. 8. A denture cleaner consisting of the following ingredients in the respective amounts indicated- Ingredient: Parts by Weight A mixture consisting of about 5 0 mole percent potassium monopersulfate, about 25 mole percent potassium sulfate, and about 25 mole percent potassium hydrogen sulfate 24.75
Potassium persulfate 8.2.5 Sodium tri polyphosphate 20.00 Sodium sesqui carbonate 21.00 Sodium carbonate 10.00
Sodium borate 13.00 Nitrilo tri acetic acid tri sodium salt 2.65 Dodecyl benzene sodium sulfonate 0.10 Methyl salicylate 0.25
an aqueous solution of said composition having a pH of at least 7, at which pH oxygen becomes available in said solution in excess of its solubility therein so that the solution eifervesces strongly.
LEON D. ROSDOL, Primary Examiner.
ALBERT T. MEYERS, Examiner.
M. WEINBLATT, Assistant Examiner.

Claims (1)

1. A DENTURE CLEANER COMPOSITION CONSISTING OF BY WEIGHT FROM ABOUT 5 TO 40 PARTS OF A MIXTURE CONSISTING OF ABOUT 50 MOLE PERCENT POTASSIUM MONOPERSULFATE, ABOUT 25 MOLE PERCENT POTASSIUM SULFATE, AND ABOUT 25 MOLE PERCENT POTASSIUM HYDROGEN SULFATE, FROM ABOUT 40 TO 5 PARTS OF AN INORGANIC WTER SOLUBLE PEROXIDE OF METAL SELECTED FROM THE GROUP CONSISTING OF GROUPS I AND II OF THE PERIODIC TABLE, UP TO ABOUT 5 PARTS OF A WATER SOLUBLE HALIDE SELECTED FROM THE GROUP CONSISTING OF THE CHLORIDE, BROMIDE AND IODIDE OF THE ALKALI METALS AND ALKALINE EARTH METALS AND OF AMMONIUM; FROM ABOUT 15 TO 85 PARTS OF A WATER SOLUBLE INORGANIC ALKALINE FILLER; FROM ABOUT 0.10 TO 5 PARTS OF A CHELATING AGENT SELECTED FROM THE GROUP CONSISTING OF NITRILOTRIACETIC ACID TRISODIUM MONOHYDRATE AND ETHYLENE DIAMINE TETRAACETIC ACID SALT, AND FROM ABOUT 0.10 TO 1.0 PART OF A WETTING AGENT SELECTED FROM THE GROUP CONSISTING OF A WATER SOLUBLE ALKYL ARYL SULFONATE AND THE SULFATES OF LONG CHAIN ALCOHOLS, AN AQUEOUS SOLUTION OF SAID COMPOSITION HAVING A PH OF AT LEAST 7, AT WHICH PH OXYGEN BECOMES AVAILABLE IN SAID SOLUTION IN EXCESS OF ITS SOLUBILITY THEREIN SO THAT THE SOLUTION EFFERVESCES STRONGLY, SAID EFFERVESCENCE SERVING TO STIR SAID SOLUTION AND TO PHYSICALLY REMOVE SAID PARTICLES FROM SAID DENTURES.
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Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3458446A (en) * 1966-05-18 1969-07-29 Colgate Palmolive Co Abrasive scouring cleanser
US3488288A (en) * 1968-03-04 1970-01-06 Peter Strong & Co Inc Denture cleansers
DE2357720A1 (en) * 1973-11-19 1975-05-28 Krisp Kg Kukirol Cleaning tablet for dentures - contg. quickly dissolving layer without oxygen-active substances and slower-dissolving oxidising layer
US3936385A (en) * 1973-08-09 1976-02-03 Colgate-Palmolive Company Denture cleanser
US4124522A (en) * 1977-03-02 1978-11-07 Barton Boyd O Method for cleaning mouthpiece of smoking article
US4217234A (en) * 1978-02-16 1980-08-12 Werner Krisp Denture cleansing tablet and method of manufacturing the same
US4247537A (en) * 1977-11-09 1981-01-27 Lunn Peter F R Bleaching systems comprising percarbonate, persulfate, and pyrogenic silica
US4256599A (en) * 1976-10-20 1981-03-17 Werner Krisp Denture cleansing tablet and process for making
US4405486A (en) * 1981-08-31 1983-09-20 Warner-Lambert Company Method for preparing granulated perborate salts containing a polymeric fluorocarbon
US4409118A (en) * 1981-04-03 1983-10-11 Warner-Lambert Company Tablet forming cleanser composition and method of preparation
US4490269A (en) * 1984-01-13 1984-12-25 Warner-Lambert Company Effervescent denture cleaning composition comprising monoperphthalate
US4499001A (en) * 1981-04-03 1985-02-12 Warner-Lambert Company Controlled fade effervescing cleanser
EP0253772A2 (en) * 1986-07-15 1988-01-20 Warner-Lambert Company Denture cleansing and/or washing compositions containing a bleach activator
USRE32771E (en) * 1983-04-22 1988-10-25 Warner-Lambert Company Denture cleaner having improved dissolution time and clarity and method of preparation
US4847089A (en) * 1986-07-16 1989-07-11 David N. Kramer Cleansing and distinfecting compositions, including bleaching agents, and sponges and other applicators incorporating the same
US6121213A (en) * 1998-07-28 2000-09-19 Block Drug Company, Inc. Stable peroxide denture paste
US6274122B1 (en) * 1999-01-07 2001-08-14 Mclaughlin Gerald Device and method using dry mixtures for whitening teeth
EP1160312A1 (en) * 2000-05-31 2001-12-05 Yasuo Sadoyama Detergent composition and process for producing composition thereof
US6361615B1 (en) * 1999-03-04 2002-03-26 Michael L. Callahan Cleaning compound additive and method
US20040009095A1 (en) * 1998-06-11 2004-01-15 Anthony Giletto Reactive decontamination formulation
US20040131561A1 (en) * 2001-03-14 2004-07-08 Mclaughlin Gerald Strips for treating teeth
US20050002975A1 (en) * 2003-06-06 2005-01-06 Densen Cao Structures and methods for delivering topical compositions
US20050089482A1 (en) * 2003-03-10 2005-04-28 Larsen Robert K. Bleaching toothpastes and methods for making and using them
US20060228307A1 (en) * 2005-04-08 2006-10-12 Cao Group, Inc. Structures and methods for delivering topical compositions
US20070190483A1 (en) * 2004-03-10 2007-08-16 Cao Group, Inc. Dental Bleaching Gels and Methods for Making and Using Them
US20070225194A1 (en) * 2004-08-20 2007-09-27 Cao Group, Inc. Household and Industrial Cleaners and Methods for Making and Using Them
US20080118445A1 (en) * 2004-08-20 2008-05-22 Cao Group, Inc. Dental Appliance Cleaners and Methods for Making and Using Them
US20090176683A1 (en) * 2008-01-04 2009-07-09 Bissell Homecare, Inc. Effervescent detergent dispenser kit and method
US20100140544A1 (en) * 2008-12-09 2010-06-10 Smith William L Solid-Layered Bleach Compositions
US20110027194A1 (en) * 2008-12-09 2011-02-03 The Clorox Company Hypochlorite denture compositions and methods of use
US20110052726A1 (en) * 2008-12-09 2011-03-03 The Clorox Company Solid-layered bleach compositions and methods of use
US20110059882A1 (en) * 2008-12-09 2011-03-10 The Clorox Company Solid-layered bleach compositions and methods of use
ITRC20130002A1 (en) * 2013-02-05 2013-05-07 Martelli Giancarlo NEW SYSTEM FOR THE PRODUCTION OF FREE REACTIVE RADICALS WITHOUT CATALYZERS, WITH REDUCING ACTIVITY, AND ITS USE FOR DISINFECTION AND / OR STERILIZATION OF MEDICAL DEVICES BY DIVING THEM IN ITS SOLUTION.
CN103153268A (en) * 2010-09-23 2013-06-12 露珍细胞再生株式会社 Oral composition for removing tooth stain
WO2016106075A1 (en) * 2014-12-24 2016-06-30 Colgate-Palmolive Company Novel products and methods
WO2017112672A1 (en) * 2015-12-23 2017-06-29 Colgate-Palmolive Company Storage-stable solid peroxymonosulfate composition

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2409718A (en) * 1941-11-13 1946-10-22 Foster D Snell Inc Composition for cleaning dentures
GB727419A (en) * 1952-04-21 1955-03-30 Stevensons Dyers Ltd Improvements in or relating to bleaching textile materials
AT197317B (en) * 1956-07-18 1958-04-25 Degussa Method of bleaching
GB871814A (en) * 1958-12-03 1961-07-05 Hedley Thomas & Co Ltd Improvements in and relating to a washing process and compositions therefor
US2996350A (en) * 1959-07-28 1961-08-15 Du Pont Controlling manganese ion impurities in permonosulfate bleaching

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2409718A (en) * 1941-11-13 1946-10-22 Foster D Snell Inc Composition for cleaning dentures
GB727419A (en) * 1952-04-21 1955-03-30 Stevensons Dyers Ltd Improvements in or relating to bleaching textile materials
AT197317B (en) * 1956-07-18 1958-04-25 Degussa Method of bleaching
GB871814A (en) * 1958-12-03 1961-07-05 Hedley Thomas & Co Ltd Improvements in and relating to a washing process and compositions therefor
US2996350A (en) * 1959-07-28 1961-08-15 Du Pont Controlling manganese ion impurities in permonosulfate bleaching

Cited By (61)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3458446A (en) * 1966-05-18 1969-07-29 Colgate Palmolive Co Abrasive scouring cleanser
US3488288A (en) * 1968-03-04 1970-01-06 Peter Strong & Co Inc Denture cleansers
US3936385A (en) * 1973-08-09 1976-02-03 Colgate-Palmolive Company Denture cleanser
DE2357720A1 (en) * 1973-11-19 1975-05-28 Krisp Kg Kukirol Cleaning tablet for dentures - contg. quickly dissolving layer without oxygen-active substances and slower-dissolving oxidising layer
US4256599A (en) * 1976-10-20 1981-03-17 Werner Krisp Denture cleansing tablet and process for making
US4124522A (en) * 1977-03-02 1978-11-07 Barton Boyd O Method for cleaning mouthpiece of smoking article
US4247537A (en) * 1977-11-09 1981-01-27 Lunn Peter F R Bleaching systems comprising percarbonate, persulfate, and pyrogenic silica
US4217234A (en) * 1978-02-16 1980-08-12 Werner Krisp Denture cleansing tablet and method of manufacturing the same
US4409118A (en) * 1981-04-03 1983-10-11 Warner-Lambert Company Tablet forming cleanser composition and method of preparation
US4499001A (en) * 1981-04-03 1985-02-12 Warner-Lambert Company Controlled fade effervescing cleanser
US4405486A (en) * 1981-08-31 1983-09-20 Warner-Lambert Company Method for preparing granulated perborate salts containing a polymeric fluorocarbon
USRE32771E (en) * 1983-04-22 1988-10-25 Warner-Lambert Company Denture cleaner having improved dissolution time and clarity and method of preparation
US4490269A (en) * 1984-01-13 1984-12-25 Warner-Lambert Company Effervescent denture cleaning composition comprising monoperphthalate
EP0253772A3 (en) * 1986-07-15 1989-07-19 Warner-Lambert Company Denture cleansing and/or washing compositions containing a bleach activator
EP0253772A2 (en) * 1986-07-15 1988-01-20 Warner-Lambert Company Denture cleansing and/or washing compositions containing a bleach activator
US4847089A (en) * 1986-07-16 1989-07-11 David N. Kramer Cleansing and distinfecting compositions, including bleaching agents, and sponges and other applicators incorporating the same
US20040009095A1 (en) * 1998-06-11 2004-01-15 Anthony Giletto Reactive decontamination formulation
US6121213A (en) * 1998-07-28 2000-09-19 Block Drug Company, Inc. Stable peroxide denture paste
US6274122B1 (en) * 1999-01-07 2001-08-14 Mclaughlin Gerald Device and method using dry mixtures for whitening teeth
US6638496B2 (en) 1999-01-07 2003-10-28 Mclaughlin Gerald Device and method using dry mixtures for whitening teeth
US6361615B1 (en) * 1999-03-04 2002-03-26 Michael L. Callahan Cleaning compound additive and method
EP1160312A1 (en) * 2000-05-31 2001-12-05 Yasuo Sadoyama Detergent composition and process for producing composition thereof
US20040131561A1 (en) * 2001-03-14 2004-07-08 Mclaughlin Gerald Strips for treating teeth
US20070077533A1 (en) * 2001-03-14 2007-04-05 Mclaughlin Gerald Strips for treating teeth
US20050089482A1 (en) * 2003-03-10 2005-04-28 Larsen Robert K. Bleaching toothpastes and methods for making and using them
US20050002975A1 (en) * 2003-06-06 2005-01-06 Densen Cao Structures and methods for delivering topical compositions
US20070190483A1 (en) * 2004-03-10 2007-08-16 Cao Group, Inc. Dental Bleaching Gels and Methods for Making and Using Them
US10285789B2 (en) * 2004-03-10 2019-05-14 Cao Group, Inc. Dental bleaching gels and methods for making and using them
US20070225194A1 (en) * 2004-08-20 2007-09-27 Cao Group, Inc. Household and Industrial Cleaners and Methods for Making and Using Them
US20080118445A1 (en) * 2004-08-20 2008-05-22 Cao Group, Inc. Dental Appliance Cleaners and Methods for Making and Using Them
US20060228307A1 (en) * 2005-04-08 2006-10-12 Cao Group, Inc. Structures and methods for delivering topical compositions
US20090176683A1 (en) * 2008-01-04 2009-07-09 Bissell Homecare, Inc. Effervescent detergent dispenser kit and method
US8486879B2 (en) 2008-12-09 2013-07-16 The Clorox Company Hypochlorite denture compositions and methods of use
US20110028368A1 (en) * 2008-12-09 2011-02-03 The Clorox Company Hypochlorite denture compositions and methods of use
US20110052726A1 (en) * 2008-12-09 2011-03-03 The Clorox Company Solid-layered bleach compositions and methods of use
US20110059882A1 (en) * 2008-12-09 2011-03-10 The Clorox Company Solid-layered bleach compositions and methods of use
US8287755B2 (en) 2008-12-09 2012-10-16 The Clorox Company Solid-layered bleach compositions
US8361942B2 (en) 2008-12-09 2013-01-29 The Clorox Company Hypochlorite denture compositions and methods of use
US8361945B2 (en) 2008-12-09 2013-01-29 The Clorox Company Solid-layered bleach compositions and methods of use
US8361944B2 (en) 2008-12-09 2013-01-29 The Clorox Company Solid-layered bleach compositions and methods of use
US8361943B2 (en) 2008-12-09 2013-01-29 The Clorox Company Hypochlorite denture compositions and methods of use
US20100140544A1 (en) * 2008-12-09 2010-06-10 Smith William L Solid-Layered Bleach Compositions
US20110027194A1 (en) * 2008-12-09 2011-02-03 The Clorox Company Hypochlorite denture compositions and methods of use
US8475678B2 (en) 2008-12-09 2013-07-02 The Clorox Company Method of using solid-layered bleach compositions
US8481471B2 (en) 2008-12-09 2013-07-09 The Clorox Company Method of using solid-layered bleach compositions
US20130189200A1 (en) * 2010-09-23 2013-07-25 Regenetiss, Inc. Oral Composition For Removing Tooth Stain
US9138387B2 (en) 2010-09-23 2015-09-22 Regenetiss, Inc. Oral composition for removing tooth stain
CN103153268B (en) * 2010-09-23 2015-10-14 露珍细胞再生株式会社 For removing the composition for oral cavity of tooth stain
CN103153268A (en) * 2010-09-23 2013-06-12 露珍细胞再生株式会社 Oral composition for removing tooth stain
ITRC20130002A1 (en) * 2013-02-05 2013-05-07 Martelli Giancarlo NEW SYSTEM FOR THE PRODUCTION OF FREE REACTIVE RADICALS WITHOUT CATALYZERS, WITH REDUCING ACTIVITY, AND ITS USE FOR DISINFECTION AND / OR STERILIZATION OF MEDICAL DEVICES BY DIVING THEM IN ITS SOLUTION.
WO2016106075A1 (en) * 2014-12-24 2016-06-30 Colgate-Palmolive Company Novel products and methods
AU2015369936B2 (en) * 2014-12-24 2018-11-01 Colgate-Palmolive Company Novel products and methods
RU2695614C2 (en) * 2014-12-24 2019-07-24 Колгейт-Палмолив Компани New products and methods
US20170181942A1 (en) * 2015-12-23 2017-06-29 Colgate-Palmolive Company Storage-stable solid peroxymonosulfate composition
CN108601957A (en) * 2015-12-23 2018-09-28 高露洁-棕榄公司 The solid permonosulphuric acid salt composite of stable storing
AU2016378548B2 (en) * 2015-12-23 2019-04-04 Colgate-Palmolive Company Storage-stable solid peroxymonosulfate composition
WO2017112672A1 (en) * 2015-12-23 2017-06-29 Colgate-Palmolive Company Storage-stable solid peroxymonosulfate composition
AU2016378548C1 (en) * 2015-12-23 2019-07-25 Colgate-Palmolive Company Storage-stable solid peroxymonosulfate composition
US10729626B2 (en) * 2015-12-23 2020-08-04 Colgate-Palmolive Company Storage-stable solid peroxymonosulfate composition
CN108601957B (en) * 2015-12-23 2021-12-10 高露洁-棕榄公司 Storage stable solid peroxymonosulfate compositions
US11229588B2 (en) 2015-12-23 2022-01-25 Colgate-Palmolive Company Storage-stable solid peroxymonosulfate composition

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