Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
  • A61K8/20—Halogens; Compounds thereof
  • A61K8/21—Fluorides; Derivatives thereof
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
  • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
  • A61K8/365—Hydroxycarboxylic acids; Ketocarboxylic acids

Definitions

• the pH may be from 3.5 to 6.0 with the pH range of 4.0 to 5.5 being preferred. Higher pH values than 6 cause the stannous ions to react rapidly with other components of the paste and become non-available for reaction with dental enamel because of the insolubility of the reaction products. It is generally true that increas ing pH from about pH increases the rate, during storage of a toothpaste, at which stannous ions become non-available for reducing enamel solubility.
• stannous ions are supplied from the solid reservoir. How- 3,105,798 Patented Oct. 1, 1963 ever, some of the solid must dissolve before additional stannous ions are available to the enamel, and no more than 1000 ppm. of stannous ions are provided by the reservoir at a given time.
• stannous fluoride as the sole source of a high concentration of soluble stannous tin is not feasable.
• the stannous tin quickly becomes non-available for reaction with enamel as indicated above.
• the two moles of fluoride carried along with each mole of stannous tin may cause the dentifrice to have toxic effects.
• stannous chlorofluoride introduces one mole of fluoride per mole of stannous tin, but the concentration of fluoride at the stannous tin concentrations required for an eflective reservoir is still high. Also, the problem of maintaining the stannous tin in a water-soluble, available condition is not solved.
• Combinations of stannous salts which do not contain fluoride (e.g. stannous chloride) and fluoride salts which are not stannous salts (e.g. sodium fluoride) permit the adjustment of stannous tin to fluoride ratios, but do not solve the problem of maintaining the stannous tin in a watersoluble, available condition.
• An object of this invention is to provide a novel fluoridecontaining dentifrice in which the stannous ions are effectively maintained in an available condition for the reduction of the solubility of enamel.
• a further object is to provide a dentifrice containing a high level of stannous tin in a Water-soluble condition for the reduction of the acid-solubility of enamel.
• Another object is to provide a dentifrice containing a molar excess of stannous tin over fluoride, the stannous tin being maintained in a water-soluble, available condition.
• Another object is to provide a dentifrice in which the stannous ions are maintained in an available condition at pH values of from 5 to 7, and especially in the pH range of from 6 to 7.
• Another object is to provide a dentifrice in which the pH remains constant at the desired level.
• Another object is to provide a dentifrice in which good consumer properties are attained without sacrifice of the availability of stannous ions for the reduction of enamel solubility.
• Another object is to provide a dentifrice which is particularly effective in reducing the acid-solubility of enamel when it is applied in the presence of saliva.
• this invention comprises a dentifrice containing a water-soluble fluoride, a source of aldonate groups containing six carbon atoms, capable of forming water-soluble complexes with stannous ions, and from about 5000 to about 15,000 ppm. of stannous tin in the form of water-soluble salts.
• the molar ratio of aldonate groups to stannous tin is from about one to about three.
• the molar ratio of stannous tin to fluoride is greater than one.
• Stannous ions are maintained for long periods of time in the dentifrice in an unusually stable form available for the reduction of the acid-solubility of dental enamel. Furthermore, such availability of stannous ions is maintained at pH values of from about 5 to about 7, whereby a dentifrice more compatible with sudsing and flavor ingredients is provided.
• aldonate group is intended to mean a group of atoms characteristic of an aldonate ion, except that the aldonate group need not be ionic; that is, it may be present as an aldonic acid, as a salt of an aldonic acid or aldonate, as complexes of a metal cation with aldonate ions, etc.
• Aldonic acids can be regarded as derived from sugars and have the empirical formula OHzOH They are discussed by W. W. Pigman and R. M. Goepp in Carbohydrate Chemistry (Academic Press Inc., New York, 1948); chapters '1 and VII are especially pertinent.
• aldonic acids may vary from 3 to 7; but hereinafter the term aldonate group is intended to mean an aldonate group containing six carbon atoms. Like the sugars, they may belong to the D or the L-series according to the configuration of the asymmetric carbon atom farthest away from the COOi-I group in the chain.
• Aldonic acids quickly set up equilibria with lactones in aqueous solution. Hydroxyls in the gamma-position and in the delta-position can take part in the intermolecular elimination of a molecule of water required to form a lactone from an aldonic acid.
• An example of equilibria involving an aldonic acid containing six carbon atoms and gamma and delta lactones follows:
• Aldonic acids can form water-soluble complexes with metallic cations and this ability is presumed to be essential to the present invention.
• the complexing agent may be postulated to react with stannous ions to bind them tightly enough that their rate of becoming non-available to dental enamel by hydrolysis, oxidation, and precipitation is greatly reduced but not so tightly that they become non-available to dental enamel.
• complexers which bind the stannous tons more tightly than aldonates, and which do not serve to achieve the objects of this invention, are pyr phosphate, triphosphate, ethylenediaminetetraacetate, and phytate.
• complexers which apparently do not bind the stannous ions tightly enough are lactate and salicylate.
• the preferred aldonate group of this invention is the gluconate group.
• the term gluconate group is intended to mean a group of atoms characteristic of a gluconate ion, except that a gluconate group need not be ionic, that is, it may be present as a gluconic acid, as a water-soluble salt of a gluconic acid or a gluconate, as complexes of a metal cation with gluconate ions, etc.
• Gluconate groups may be supplied by any appropriate water-soluble compound. Examples of a preferred group of soluble compounds are stannous gluconate, sodium gluconate, potassium gluconate, gluconic acid, and glucono-lactone. In order to adjust the molar ratio of stannous tin to gluconate groups and the pH of the paste, it is often advantageous to use a mixture of more than one source of gluconate.
• Sources of aldonates which will be suitable for this invention are the 6-carbon aldonates of the L and D-series in the form of their water-soluble salts, in the form of aldonic acids, and in the form of aldono-lactones.
• the six-carbon aldonate groups suitable for use in this invention are the D and L forms of gluconate, mannonate,
• aldonate groups are of stannous ion leaves too much stannous tin uncomplexed, and the primary benefits of the aldonate are there by lost. More than about three moles of aldonate groups per mole of stannous tin is wasteful of material; and by the law of mass action, as applied to the complexation reaction involved, may reduce the concentration of tin available for reaction with enamel to an ineffective level.
• the ratio of aldonate groups to stannous tin can be adjusted, within the specified limits, to control the concentration of available tin.
• a desirable molar ratio of the preferred gluconate groups to stannous tin ions is in the range of from about twozone to threezone.
• Preferred Water-soluble stannous salts for providing a source of stannous tin in the dentifrice of this invention are stannous fluoride, stannous aldonates, stannous chloride, and stannous sulfate.
• Mixed stannous halides such as Sn ClF and SnClF are also suitable.
• the total stannous tin content of the dentifrice can not be supplied solely by those salts having a molar ratio of stannous ions to fluoride ions of one or less. They are ordinarily used with a non-fluoride stannous salt such as a stannous aldonate.
• the total stannous tin content must be from about 5000 to about 15,000 p.p.m., the preferred range being from about 6000 to about 10,500 p.p.m. stannous tin.
• Especially eifective dentifrices are obtained above a minimum total stannous tin content of 8000 p.p.m.
• the advantages of this invention are not substantially obtained below the lower limit; in the vicinity of the upper limit, treatment of enamel with increased concentration gives no further enamel solubility reduction. It is often preferred to add all or part of the stannous tin in the form frice is slurried with water, not all of the stannous tin is extracted into the water.
• fluoride salts are also intended to include complex water-soluble fluoride-containing salts such as fiuosilicates, i.e., Na SiF fluozirconates, i.e., CaZrF Na ZrF K ZrF fiuostannites, i.e., KSnF fluoborates, i.e., NaBF and fluotitanatcs. fluoride salts can also be used.
• fiuosilicates i.e., Na SiF fluozirconates, i.e., CaZrF Na ZrF K ZrF fiuostannites, i.e., KSnF fluoborates, i.e., NaBF and fluotitanatcs.
• fluoride salts can also be used.
• the quantity of the water-soluble fluoride compounds which is used for efficacious results in the fluorine-com Mixtures of taining dentifrices of this invention should be an amount equivalent to at least 25 parts of fluoride ions per million parts of dentifrice. Extremely large amounts of fluoride ions do not appreciably enhance the desirable properties of the dentifrice and may cause it to have toxic effects. Accordingly, the dentifrices of this invention in general do not contain a total of more than 4000 parts ionized and un-ionized fluorine per million parts of dentifrice, and preferably not more than about 1000 parts per million. The molar ratio of stannous tin to fluoride is greater than onezone.
• the pH of the dentifrice composition of this invention lies between about 5 and 7, the preferred range being from about 5.5 to 6.5. Above about pH 7 loss of stan: nous ions available for reaction with enamel can be too rapid; and, as has been mentioned before, certain flavoring substances, especially esters, deteriorate rapidly. Too low a pH, below about 5, in the dentifrice of this invention produces an astringent taste which is highly objectionable to most people. It also accelerates the hydrolysis of certain of the sudsing agents thereby producing an unpleasant fatty acid taste and reducing the amount of sudsing obtained in use. Furthermore, pH values below 5 tend to cause corrosion of metal tubes in which the paste is stored, and tend to hydrolyze other ingredients such as condensed phosphates if used as abrasives.
• Such hydrolysis can decrease the availability of stannous ions by providing anions with which they can form very stable complexes or with which they can precipitate as highly insoluble compounds.
• the pH values specified herein are for the supernatant from a slurry of one part dentifrice to three parts distilled water.
• the pH of the dentifrice may be adjusted with strong acids such as HCl but it is particularly advantageous to use an aldonic acid or aldono-lactone. There is the economy of using one of the essential ingredients to serve a dual purpose; and to many persons the flavor of the dentifrice is improved, especially in the pH range up to about 5.5.
• Dentifrices desirably should also contain abrasive rnaterials.
• the abrasives preferably should be relatively insoluble and relatively stable at the pH ranges herein specified. They desirably should not be too abrasive so as to scratch the surface of the teeth or unduly abrade the dentin, but they desirably should have just suflicient abrading power to clean the teeth.
• any dental abrasives can be used which have these properties, and are sufficiently compatible with stannous ions and fluoride ions.
• a preferred class of abrasives for use in fluoride containing dentifrices of this invention includes insoluble condensed phosphates.
• insoluble con densed phosphates include calcium pyrophosphate, insoluble highly polymerized calcium polyphosphate sometimes called calcium polymetaphosphate, and insoluble highly polymerized sodium polyphosphatesometimes called insoluble sodium polymetaphosphate.
• Mixtures of abrasives can be used.
• the total amount of abrasive materials in dentifrices of this invention can range from 0.5% to 95% by weight of the dentifrice.
• toothpastes contain from 20% to 60% by weight, and tooth powders contain from 60% to 95% by weight.
• Dentifrices conventionally contain sudsing agents, although these are not critical in the practice of the present invention. Any of the commonly used sudsing agents can be used if they are reasonably stable and form suds Within the pH range of the dentifrices of this invention.
• suitable sudsing agents include, but are not limited to, water-soluble alkyl and alkyl ether sulfates and sulfonates having alkyl groups of from about 8 to 18 carbon atoms, water-soluble salts of sulfonated monoglycerides of fatty acids having from 10 to 18 carbon "solution.
• Sudsing agents in an amount of from 0.5 to 5.0%, by weight of dentifrice, can be used in dentifrices of this invention.
• thickening agents are water-soluble salts of cellulose others such as sodium carboxym'ethyl cellulose and sodium carboxymethyl hydroxyethyl cellulose.
• Natural gums such as gum karaya, gum arabic, and gum tragacanth also can be used as thickeners, but may tend to cause undesirable odors or flavors in some formulations.
• Colloidal magnesium aluminum silicate or finely divided silica can be used as a part of the thickening agent for improvement in texture.
• Thickening agents in an amount of from 0.5% to 5.0% by weight of toothpaste, can be used to form a satisfactory toothpaste.
• Suitable hunrectants include glycerine, sorbitol, and other polyhydric alcohols.
• the humectants may comprise up to about 35% of the toothpaste composition.
• Dentifrices may additionally contain small amounts of fiavorings, such as oil of Wintergreen, oil of peppermint, oil of spearmint, oil of Sassafras, and oil of anise.
• small amounts of sweetening agents such as saccharin, dextrose, levulose, and sodium cyclamate are also conventionally added to dentifrices.
• a suitable food, drug and cosmetic-approved coloring agent may be added to the dentifrice.
• the ability of a dentifrice to reduce the solubility of enamel in acid after teeth are treated with that dentifrice can be measured in laboratory tests; and, of course, the stability of the dentifrice on storage, with respect to supplying available stannous and fluoride ions to produce this solubility reduction, can be measured as a function of the age of the dentifrice; The tests are performed as follows:
• the plastic and all but the enamel of the teeth is then covered with an inert wax.
• the radioactive teeth are then etched by a measured volume of 0.1 N solution of lactic acid-sodium lactate which has been adjusted with NaOH to a pH of 4.5 at room temperature.
• the solution is stirred at constant speed and is maintained at a constant temperature of 37 C. by a water bath and thermostat. After 15 minutes duplicate samples of the solution are taken.
• a fresh portion of solution is used for each etching of the teeth;
• the amount of phosphorus and calcium etched from the teeth can be calculated by measuring the increase in radioactivity of the etching
• the radioactivity of samples of the solution is not measured directly; but they are placed in planchets, neutralized with sodium carbonate, and evaporated to dryness before counting with an end window Geiger tube "i and automatic scaler. The counts are corrected for coincidence loss.
• An initial etching is performed until the rate of etching of the tooth enamel becomes constant.
• the teeth are then etched for minutes and the amount of enamel removed is calculated from the measured radioactivity of the samples.
• a slurry is made containing 1 part of dentifrice thoroughly dispersed in 3 parts of water.
• ESR enamel solubility reduction
• saliva ESR test results determined by its practice are called saliva ESR values.
• compositions are reported in weight percent.
• the stannous gluconate used in preparing the compositions of the examples was as supplied by Metal and Thermit Corporation. In reporting test results, a dash is intended to mean that no test was made after that time interval.
• Example I The following toothpaste compositions containing 9000 ppm. stannous tin were prepared. After the indicated time intervals, BER and pH values were determined.
• stannous tluorid e Sodium fluoride... Glycerine Sodium coconut monoglyceride sulfonate Sodiumlauryl sulfate-..
• Magnesium aluminum silicate Sodium carboxymethyl cellulose Water Molar ratio gluconate groups to stannous n. Molar ratio stannous tin to fluoride After 1 week After 12 months..-
• composition A where all of the stannous tin was furnished by stannous gluconate and fluoride was furnished by sodium fluoride, there was no decrease in stannous ions available for reduction of enamel solubility; the ESR value remained at a high level over an interval of a year of storage. The pH also did not change appreciably.
• composition B where both stannous gluconate and stannous fluoride were employed, the ESR values remained at a high level; and the pH was substantially constant. saliva ESR value determined on a sample of composition A after 13 months of storage was 45.
• Example II Example II
• the following toothpaste compositions containing 9000 ppm. of stannous tin in the form of water-soluble salts were prepared. After the intervals indicated, ESR, pH, and soluble stannous tin values were determined. Soluble stannous tin was determined by mixing one part toothpaste with three parts distilled water for 10 minutes. The solids were then separated by centrifugation for 20 minutes, at
• Results are reported as parts per million soluble stannous tin on the original paste basis.
• Example IV The following toothpaste compositions further illustrate the invention.
• the saliva ESR was 40 after- Sorbitol (30% water) n 20 .00 20.00 Sac harm 0.12 .12 Flavor 0.85 0.85 Color. 0 .47 0 .47 stannous glueonate (31.6% soln.) 5.00 8 .10 Calcium pyrophosphate 40 .00 40 .00 Stannous fluoride 0 A0 Sodium fluoride 0.19 Glycerin 10 .00 10 .00 Sodium coconut monoglyceride sulfonate 0.81 0.81 Sodium lauryl sulfate 0 .70 0 .70 Magnesium aluminum silicate 0 .40 0 .40 Sodium carboxymethyl cellulose 1 .10 1 .10 Water Balance Balance Molar ratio, stannous tin to fluoride 1.1 1 .1 Molar ratio gluconate groups to stannous t 1.1 2 .0 Total stannous tin, ppm 6720 6000 These compositions maintain stannous tin in .an available condition for the reduction
• Example V The following toothpaste composition containing 9000 p.p.m. stannous tin and adjusted to the desired pH with D-glucono-delta-lactone was prepared. ESR values were measured in saliva, and pH values were determined after the indicated time intervals.
• Example VI A toothpaste having the composition of Example I-A except that stannous galactonate is substituted for stannous gluconate exemplifies the invention.
• the composition maintains stannous tin in an available condition for reduction of enamel solubility, maintains a fairly constant pH of about 5.3 and is compatible with sudsing and flavor ingredients.
• a dentifrice composition having incorporated therein an enamel solubility reducing material consisting essentially of:
• a Water-soluble fluoride salt providing at least 25 parts of fluoride ions per million parts of dentifrice, the total amount of ionized and unionized fluorine not exceeding 4000 parts per million parts of dentifrice,
• stannous tin in the form of a Water-soluble salt providing a total content of stannous tin in solution of from about 5000 to about 15,000 parts per million parts of dentifrice, and
• a water-soluble source of six-carbon aldonate groups capable of forming water-soluble chemical complexes with stannous tin, the molar ratio of aldonate groups to stannous tin being in the range of from about onezone to about threezone, the molar ratio of stannous tin to fluoride ions being greater than onezone, said dentifrice having a pH of from about 5 to 7.
• the dentifrice composition of claim 1 wherein the source of aldonate groups is a sodium aldonate.
• the dentifrice composition of claim 1 wherein the aldonate is a member selected from the group consisting of g-luconate and galactonate groups and mixtures thereof.
• stannous tin salt is a member selected from the group consisting of stannous fluoride, stannous chloride, stannous sulfate, stannous aldonates containing six carbon atoms, and mixtures thereof and the source of at least part of the stannous tin and aldonate groups is a stannous aldonate containing six carbon atoms.
• a toothpaste having incorporated therein an enamel solubility reducing material consisting essentially of a quantity of a water-soluble fluoride salt and stannous gluconate sufficient to provide from about 6000 to about 10,500 parts of stannous tin and at least 25 parts of fluoride ions per million parts of toothpaste but not more than about 4000 parts total of ionized and un-ionized fluorine per million parts of toothpaste, and a molar ratio of gluconate to stannous tin in the range of from about onezone to about three:one and a molar ratio of stannous tin to fluoride greater than onezone, said toothpaste having a pH of from about 5.0 to 7.0.
• a toothpaste having incorporated therein an enamel solubility reducing material consisting essentially of a quantity of stannous fluoride and sodium gluconate suflicient to provide from about 6000 to about 10,500 parts of stannous tin and at least 25 parts of fluoride ions per million parts of toothpaste, but not more than about 4000 parts total of ionized and un-ionized fluorine, and a molar ratio of gluconate to stannous tin in the range from about one:one to about threezone and a molar ratio of stannous tin to fluoride greater than about onezone, said toothpaste having a pl-T in the range from about 5.0 to 7.0.

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Cited By (43)

Citations (10)

• 0
  • BE BE638714D patent/BE638714A/xx unknown
• 1958
  • 1958-05-29 US US738640A patent/US3105798A/en not_active Expired - Lifetime

Patent Citations (10)

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