WO1990005113A1 - Compositions abrasives de dioxyde de silicium precipite presentant un haut degre de compatibilite avec les agents fluores anti-plaque et therapeutiques, pour des applications aux produits dentifrices, produits dentifrices les contenant, et procede de fabrication de ces compositions - Google Patents

Compositions abrasives de dioxyde de silicium precipite presentant un haut degre de compatibilite avec les agents fluores anti-plaque et therapeutiques, pour des applications aux produits dentifrices, produits dentifrices les contenant, et procede de fabrication de ces compositions Download PDF

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Publication number
WO1990005113A1
WO1990005113A1 PCT/US1989/004866 US8904866W WO9005113A1 WO 1990005113 A1 WO1990005113 A1 WO 1990005113A1 US 8904866 W US8904866 W US 8904866W WO 9005113 A1 WO9005113 A1 WO 9005113A1
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WIPO (PCT)
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composition
fluoride
alkaline earth
silicon dioxide
weight
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PCT/US1989/004866
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English (en)
Inventor
William C. Fultz
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J.M. Huber Corporation
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Publication of WO1990005113A1 publication Critical patent/WO1990005113A1/fr

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    • 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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • 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

Definitions

  • Such toothpaste compositions exhibit both high fluoride and high chlorhexidine compatibility, as well as high cleaning performance. Further, the present invention relates to dentifrices exhibiting high fluoride compatibility and high chlorhexidine compatibility with minimal loss of the same at ambient temperatures over an extended period of time. 2 .
  • Fluoride ion sources tend to interact with toothpaste impurities as well as with such toothpaste components as abrasives, buffers, etc. Such interaction diminishes the ability of the fluoride source to provide "soluble fluoride" upon use.
  • the propensity of the toothpaste compositions to maintain their levels of soluble fluoride after storage is expressed hereinafter as "toothpaste fluoride compatibility".
  • the toothpaste fluoride compatibility of a particular toothpaste composition is that percentage of the theoretical maximum amount of fluoride source that is actually measured as soluble fluoride after storage for a specified time and at a specified temperature (e.g. one week at 120°F) ..
  • the propensity of a dentifrice component such as an abrasive to interact with the fluoride source to diminish the measured "soluble fluoride” level from the theoretical maximum amount of fluoride source, is expressed as "abrasive fluoride compatibility".
  • anti-plaque, anti-microbials such as chlorhexidine digluconate, the acetates and glycerides of chlorhexidine, tetradecyl-4-ethyl- pyridinium chloride, and octenidine dihydrochloride.
  • Use of these active ingredients in dentifrice applications has been plagued by poor compatibility of the active ingredient with the abrasive system.
  • Abrasive systems based on aluminas have been found to be compatible, but silica abrasive systems, even those having good fluoride compatibility, have a tendency to show only marginal, and often poor, compatibility with chlorhexidine digluconate and related anti-plaque, anti-microbials.
  • a toothpaste component which can pose special difficulties in formulating fluoride toothpastes is thus a silica abrasive component, particularly a precipitated silica abrasive.
  • Precipitated silica abrasives are desirable for use in toothpastes since they have very desirably low dentin abrasion values.
  • Certain prior art precipitated silica abrasives are generally compatible with soluble fluoride sources but have low abrasivity, and therefore, do not provide an effective cleaning performance.
  • U.S. Patents No. 4,340,583, 4,420,312 and 4,421,527 to Wason disclosed a precipitated silicon dioxide abrasive for toothpaste compositions containing soluble fluoride salts and phosphates salts.
  • the patent discloses that the reaction with an alkaline earth metal ion minimizes the abrasive's interaction with the fluoride ion source yielding a toothpaste having fluoride compatibility values of about 90%.
  • the entire content, including the prior art cited therein, of the above patent is incorporated herein by reference.
  • U.S. Patent 3,864,470 discloses a toothpaste composition and a synthetic hydrated precipitated silica for use in the composition.
  • the toothpaste may also contain other materials including an. antibacterial agent such as l,6-di-(p-chlorophenyl biguanido) hexane and its salts.
  • U.S. Patent 3,862,307 discloses dentifrices which contain amorphous silica abrasives. This patent discloses that these silica abrasives have good compatibility with cationic therapeutic agents when the silica is pretreated with hydrofluoric acid.
  • the cationic therapeutic agent is primarily stannous ion, indium ion or calcium ion.
  • U.S. Patent 4,051,234 discloses toothpaste compositions which contain a particulate substantive bis-biguanide compound which inhibits the formation of plaque.
  • the abrasive to be used in the toothpaste with this anti-plaque agent comprises those with a high degree of compatibility with the bis-biguanides including silica xerogels and hydrofluoric acid treated amorphous silica abrasives, such as those of U.S. Patent 3,862,307.
  • U.S. Patent 4,157,387 discloses a dentifrice abrasive which 'has been coated with a cationic water soluble polymer so that the abrasive is made less absorptive to therapeutic cationic agents and therapeutic compositions containing the abrasive.
  • the abrasive includes silica abrasives.
  • the antibacterial agents include bis-biguanide compounds.
  • U.S. Patent 4,198,392 discloses toothpaste compositions which contain bis-biguanide compounds which inhibit the formation of plaque and caries.
  • the abrasive polishing agents which can be used in this composition include silica xerogels, as well as the hydrofluoric acid treated amorphous silica abrasives of 3,862,307.
  • U.S. Patent 4,272,509 teaches the use of a silicon dioxide abrasive in a dentifrice composition. The patent indicates that such abrasives can be used with anti-plaque agents.
  • U.S. Patent 4,474,824 teaches dentifrice compositions which contain hydrous silica gels which can be used in combination with germicides, antibiotics and astringents.
  • the silicas are produced by acidulation of sodium silicate and that after washing and drying, the silica has an SOpole content of .28%.
  • U.S. Patent 4,421,527 teaches a silicon dioxide abrasive which has high fluoride compatibility. To achieve this, the silicon dioxide has been treated with alkaline earth metal ion subsequent to acidulation of the alkali metal silicate.
  • the dentifrices may also contain anti-plaque agents such as chlorohexidine.
  • U.S. Patent 4,140,757 discloses a toothpaste composition which may include a silica thickener, as well as antibacterial agents.
  • U.S. Patent 4,515,772 discloses an oral composition containing pyrophosphate salt which provides an anti- calculus benefit alone with silica abrasives, a fluoride ion source, and bis-biguanide anti-plaque agents.
  • U.S. Patent 3,804,946 discloses a crystalline silica polishing agent used with cationic prophylactic agents such as l,6-di-(p-chlorophen ⁇ l-biguanido) hexane.
  • U.S. patent 4,080,441 discloses an oral composition including chlorohexidine and an anti-stain additive with crystalline silica, silica gel and alumino silicate polishing materials.
  • U.S. Patent 4,118,472 discloses an oral composition containing an anti-plaque agent such as chlorohexidine, a quaternary aminoalkaline phosphonic compound with crystalline silica, silica gel and aluminosilicate polishing agents.
  • U.S. Patent 4,575,456 discloses a phytate salt free gel dentifrice included a precipitated amorphous silica gel polishing agent and an antibacterial agent.
  • U.S. Patent 4,584,189 discloses a dentifrice containing cationic bactericidal agent, an abrasive and a modified hydroxyethyl cellulose thickener.
  • Japanese Patent 60-75422 discloses a dentifrice containing chlorohexidine and a silica polishing agent.
  • European Patent 0,181,161 discloses a fluoride-free oral hygiene product containing a cationic bis-biguanide antiseptic, such as chlorohexidine, and zinc.
  • European Patent 0,151,203 discloses an anti-plaque, two-phase cleansing tablet containing silicone dioxide and an anti-plaque agent.
  • European Patent 0,177,303 discloses a cationic bacterical agent and a cationic bactericidal agent and a dental abrasive and thickner. 1 0
  • silica abrasives which provide high fluoride compatibility and high anti-plaque, anti-microbiai compatibility retaining relatively high levels of such agents even after periods of storage.
  • a novel abrasive material for toothpaste compositions which comprises in its broadest embodiment, a precipitated silicon dioxide which is prepared from fresh water alkali metal silicate by acidulation.
  • Such precipitated abrasives contain about 10 - 300 parts per million of alkaline earth metal ion, and are characterized by an RDA value of at least 40, an oil absorption value of about 70 - 100 ccs/100 gram, a pack density of between about 0.24 and 0.055 grams per milliliter, a loss on ignition value of between about 4 to 6% and a BET surface area of about 10 to 300 m 2 /g with an average particle size of about 2 to 15 microns; a sulfate ion level below about 0.25% and a pH in the range of 4.0 - 7.5.
  • a method for the preparation of the novel abrasives of this invention which in general comprises formation of a low structure precipitated silicon dioxide by the acidulation of certain fresh 1 1
  • the present invention further relates to fluoride- 5 containing and anti-plaque, anti-microbial toothpaste compositions which exhibit minimal loss of active ingredients upon storage at normal temperatures and which provide excellent cleaning performance.
  • toothpaste compositions comprise the amorphous, 10 precipitated silica abrasives of the present invention, a source of fluoride ions, an anti-plaque, anti ⁇ microbial agent, a binding agent, a humectant and water.
  • Such toothpaste compositions provide a pH of from about 5.0 to 7.5, preferably 5.5 to 6.0, when slurried with 15 water in a 3:1 water/composition weight ratio.
  • the amorphous, precipitated silica abrasives of the present invention comprise from about 6% to 35% by weight of the toothpaste compositions.
  • the fluoride ion source comprises from about 0.01% 20 to 3.0% by weight of the toothpaste compositions and can be any water-soluble material which yields fluoride ions in aqueous solution.
  • the binder comprises from about 0.2% to 2% of the toothpaste compositions. 25 1 2
  • the humectant comprises from about 5% to 55% by weight of the toothpaste composition.
  • the water in the toothpastes herein comprises from about 15% to 80% by weight of composition. It is an object of the present invention to increase the compatibility of a preferred silica abrasive, both anti-plaque and anti-microbials, such as chlorhexidine digluconate, chlorhexidine acetate, chlor ⁇ hexidine glyceride, tetradecyl-4-ethyl-pyridinium chloride, or octenidine dihydrochloride and mixtures thereof, while maintaining good fluoride compatibility.
  • a preferred silica abrasive such as chlorhexidine digluconate, chlorhexidine acetate, chlor ⁇ hexidine glyceride, tetradecyl-4-ethyl-pyridinium chloride, or octenidine dihydrochloride and mixtures thereof, while maintaining good fluoride compatibility.
  • the present invention relates to novel, precipitated silicon dioxide dentifrice abrasives, methods for- their preparation, and their incorporation into toothpastes to provide resulting compositions having excellent toothpaste and anti-plaque, anti ⁇ microbial compatibility values and excellent abrasivity values.
  • the toothpaste compositions herein further essentially comprise a water-soluble fluoride ion source, an anti-plaque, anti-microbial agent, a preferred abrasive, a binding agent, and certain amounts 1 5
  • pH of the silica abrasive pH of the resulting toothpaste, and pH of the reaction mixture at various points are referred to.
  • the pH of the novel silica abrasive is in the range of 4.0 to 7.5.
  • the silica abrasive is incorporated into a toothpaste, the toothpaste formu- lation will have a pH of 5.0 to 7.5, and preferably 5.5 to 6.0.
  • the pH of the reaction mixture is reduced to the range of 4.6 to 5.0.
  • the pH should be in the range of 6.0 to 7.5.
  • sodium sulfate is determined using a LECO model SC-132 sulfur analyzer.
  • the sample is mixed with vanadium pentoxide (combustion accelerator) and ignited in the instrument's combustion tube at 2500°F in an oxygen atmosphere.
  • Sulfur dioxide thus formed is then measured by a solid state infrared detector. Accuracy for most samples is ⁇ 1% of the sulfur content or ⁇ 4% of the sodium sulfate content.
  • the present invention relates to low structure precipitated silicon dioxide materials which are suitable for use as dental abrasives.
  • Such abrasives have ultimately associated therewith about 10 - 300 parts per million, preferably 10 - 100 parts per million, of alkaline earth metal, preferably calcium, based on the amount of recoverable dry material.
  • This dental abrasive material is characterized further by having a greater than 80 percent, preferably 90 percent, fluoride compatibility, and anti-plaque, anti-microbiai compatibility in the range of at least 80 percent, preferably 90%, an RDA of at least 40, preferably from about 70 to 120, a loss on ignition (hereinafter "LOI") in the range of 4 - 6%, a pack density in the range of about 0.24 to 0.55 grams per milliliter, an oil absorption in the range of about 70 - 105 cc/100 grams, a sulfate ion level of less than 0.25%, a pH in the range of 4.0 to 7.5, and a BET sur ace area in the range of about 10 - 300 m /g or higher, with an average particle size in the range of 2 - 15 microns.
  • LOI loss on ignition
  • the dental abrasives herein provide compatability of at least 80 percent, preferably 90 percent, fluoride and high anti-plaque, anti-microbial compatibility of at least 80 percent, preferably 90 percent, and excellent cleaning performance.
  • the dental abrasive materials of the present invention are precipitated silicon dioxides which are prepared by the general methods described, for example, in prior U.S. Patents 3,893,840, 3,988,162, 4,067,746, 4,340,583, 4,420,312 and 4,421,527 to Wason. Each of these patents is incorporated herein by reference. According to this invention, silica abrasives produced by such methods are subsequently treated with alkaline earth metal ions, washed free of sulfate, and the pH adjusted in the manner described herein.
  • the process for preparation of the silicon dioxides comprises the acidulation of an aqueous alkali metal silicate solution with a mineral acid to effect precipitation of silicon dioxide.
  • the acid addition is continued to an acid pH and the resulting precipitated silicon dioxide is then removed such as by filtration, and washed to remove any by-product or residual materials, such as alkali metal sulfate, to provide a wet cake.
  • the wet cake is washed with deionized or tap water sufficiently to reduce the sulfate (ion) level to 0.25% or less.
  • the resulting wet cake is then reslurried in its own water or with additional water and thereafter is treated with the required amount of alkaline earth metal ions in the form of a soluble salt 1 6
  • the reslurried wet cake may be acidulated with an acid such as, for example, hydrochloric acid to adjust the pH to the range of 6.0 - 7.5 to provide the abrasive material of the present invention.
  • an acid such as, for example, hydrochloric acid to adjust the pH to the range of 6.0 - 7.5 to provide the abrasive material of the present invention.
  • the silicon dioxide abrasives of the present invention are akaline earth metal-treated precipitated silicon dioxides which are prepared from fresh water silicate solutions. Such a process does not make use of any electrolyte, such as sodium sulfate, in preparation of the untreated precipitated silicon dioxide. Further, in the products of the present invention, it has been found that the presence of alkaline earth metal ions, intimately associated with the resulting silicon dioxide, must be present within a particular narrow range to provide the fluoride compatibility necessary for use in the present invention. Thus, the abrasive products of the present invention have fluoride compatibility values of at least 80 percent, preferably go percent, and anti-plaque compatibility values of at least 80 percent, preferably 90 percent.
  • the precipitated silicon dioxide abrasives are preferably prepared by charging an aqueous solution of an alkali metal silicate solution, preferably a sodium silicate solution having an. Si0 2 to Na 2 0 mole ratio of about 2.0 to 3.3 to a reactor for acidulation.
  • the aqueous sodium silicate solution is a fresh water • 7
  • aqueous sodium silicate solution having a sodium silicate concentration range of about 10-17 weight percent, and more preferably 12.5 to 15.5 weight percent, and a sodium silicate composition of Na 2 0-2.6 Si0 2 for best results.
  • the aqueous sodium silicate solution is then raised to a temperature of about 50° to 95°C, and with continuous agitation, the solution is acidulated by the addition of an aqueous solution of a mineral acid having a concentration of about 10 - 20 weight percent at a substantially constant pH in the range of about 8.5 to 10.5.
  • the mineral acid preferably dilute sulfuric acid, provides best results, but as is known in the art (See U.S.
  • Patents 3,988,162, 3,893,840 and 4,067,746) other acidulation agents, such as nitric acid, phosphoric acid, hydrochloric acid, carbonic acid and the like, can also be employed.
  • acidulation agents such as nitric acid, phosphoric acid, hydrochloric acid, carbonic acid and the like.
  • the metal silicate is initially charged to the reactor. The remaining portion is then added with the sulfuric acid. The time period over which the alkali metal
  • silicate and sulfuric acid are added to the alkali metal silicate in the reactor can be predetermined and is generally based on the volume of the reactor and the difficulties in control of the temperature and agitation.
  • the acidulation agent is continually added until the pH of the reaction slurry falls below about 6.0 and preferably to within the range of about 4.6 - 5.0.
  • the resulting slurry is the precipitated silicon dioxide contained in the process
  • the slurry is then heated for a digestion period at a temperature of 10° to 30°C above the reaction temperature and the reaction pH again adjusted as necessary to maintain the 0 pH below 6.0.
  • the resulting slurry is then filtered and washed with additional water to remove any reaction by-product, such as sodium sulfate, which may be contained in the silicon dioxide product.
  • the product is washed to reduce the sulfate ion level to 5 below 0.25% and most preferably to below 0.20%.
  • the wet cake moisture of the resulting filter cake is in the range of about 60 - 66% and is a low structure material.
  • the material is then subjected to treatment with alkaline earth metal ions, as described in Wason U.S. Patent 4,421,527, to produce the new abrasive products which are further processed as described herein to produce the products of the present invention.
  • the wet washed filter cake is then reslurried in its own water or with the addition of fresh water at ambient temperature with agitation.
  • this slurry is then treated with sufficient alkaline earth metal ions, preferably calcium ions, in the form of a salt or compound sufficiently soluble to provide an amount of alkaline earth metal ions corresponding to about 10 to 300 parts per million, or .001 to .03 weight percent (based on the weight of the dry recoverable silicon dioxide) , of alkaline earth metal ions intimately associated with the silicon dioxide.
  • alkaline earth metal ions preferably calcium ions
  • the alkaline earth metal ion added at this point is preferably calcium ion because of its ready availability, low cost, and ease of incorporation into the silicon dioxide.
  • the calcium ions can be incorporated into the silicon dioxide at this stage in any sufficiently water soluble form (i.e., soluble in water to the extent of at least .07 g/100 cc H 2 0 at 20°C) such as with solutions of calcium nitrate, calcium oxide, calcium hydroxide, or calcium chloride. Lime or calcium hydroxide is preferred. Also, solutions of organic salts, such as calcium acetate, calcium formate, and the like, can also be used. The corresponding strontium and magnesium salts of the alkaline earth class can also be used. Food grade salts or compounds should be used.
  • the pH be reduced by acidulation to less than 5.5 so that upon drying the preferred finished product will be in the pH range of 4.0 to 7.5 and more preferably between 6.0 and 6.5.
  • the cake slurry is then agitated vigorously for 10 - 20 minutes, preferably 15 minutes, to provide the effective level of alkaline earth metal for treatment onto the surface of the silicon dioxide abrasive.
  • the resulting product is then dried.
  • the abrasive may be washed at this point to remove some or all of the sulfate.
  • drying is conducted in a spray dryer at an inlet temperature of 483°C and outlet temperature of 122°C as known in the art, and subsequently milled to the desired degree of fineness.
  • the toothpaste compositions of the present invention further comprise certain amounts of a water-soluble fluoride ion source, an anti-plaque, anti-microbial agent, a binding agent, a humectant and water.
  • the toothpaste will have a pH in the range of 5.0 to 7.5, preferably 5.5 to 6.0.
  • Each of these additional toothpaste components as well as optional toothpaste components are described in detail as follows: A. Abrasive
  • the instant precipitated silica abrasives are particularly suitable for incorporation into fluoride-containing therapeutic toothpaste compositions.
  • Therapeutic toothpastes employing such abrasives provide satisfactory tooth cleaning performance and also possess excellent abrasive fluoride and anti-plaque, anti-microbial compatibility characteristics.
  • the instant therapeutic toothpaste compositions further contain from about 0.01% to 3%, preferably from about 0.1% to 1.0%, by weight of a water-soluble, fluorine-containing maerial which yields fluoride ions in aqueous solutions.
  • fluoride ions combine with dental enamel and thereby reduce enamel solubility in acid.
  • Application of fluoride ions to dental enamel serves to protect teeth against decay.
  • fluoride ion-yielding materials can be employed as sources of soluble fluoride in the instant compositions.
  • suitable fluoride ion-yielding material are found in U.S. Patent 3,535,421 and U.S. Patent 3,678,154; both patents being incorporated herein by reference.
  • Preferred fluoride ion sources for use herein include sodium fluoride (NaF) , stannous fluoride (SnF 2 ), potassium fluoride (KF) , potassium stannous fluoride (SnF 2 - F) , indium fluoride (InF 3 ), zinc fluoride (ZnF 2 ), ammonium fluoride (NH ⁇ F), and stannous chlorofluoride (SnClF) .
  • sodium fluoride and stannous fluoride are particularly preferred as well as mixtures thereof. 2 3
  • the instant toothpaste compositions provide from about 50 ppm to 500 ppm, more preferably from about 100 to 400 ppm, of fluoride ions in the aqueous solutions which contact dental surfaces when the toothpastes of the present invention are used in the mouth.
  • such solutions are simulated by preparing 3:1 water/toothpaste slurries (by weight) of the toothpaste compositions herein and by subsequently centrifuging such slurries to obtain an aqueous supernatant.
  • the fluoride ion concentration in such a supernatant is taken as a measure of the "soluble fluoride" provided by any given fluoride toothpaste composition.
  • Binder A binder is essentially employed to present separation of the liquid and solid phases in the toothpaste compositions herein.
  • Such binder materials are well known in the toothpaste art.
  • the most conventionally used binders are the seaweed colloids, such as Carrageenan (Irish moss or Vicarin") and derivatives of cellulose, such as sodium carboxymethyl cellulose and hydroxyethyl cellulose.
  • Another type of binder which is suitable for use herein is gums, such as 1) vegetable gums, e.g., guar gums and 2) fermentation products, e.g., xanthan gum.
  • the binder component generally comprises from about 0.1% to 5%, preferably 24
  • the toothpastes herein can optionally contain a relatively small amount of a preservative.
  • preservatives typically employed are the esters of parahydroxyl benzoates.
  • Toothpaste binders are more fully described in U.S. Patent 2,839,448 and U.S. Patent 3,862,307. These patents are incorporated herein by reference. D. Humectant
  • humectant Another essential component of the toothpaste compositions herein is a humectant.
  • Suitable humectant materials are also well known in the toothpaste art.
  • the humectant serves to retain moisture and thereby to keep the toothpaste compositions from hardening upon exposure to air.
  • Certain humectants can also impart desirable sweetness or flavor to toothpaste compo ⁇ sitions.
  • the humectant generally comprises from about 5% to 55%, preferably from about 20% to 36%, by weight of the toothpaste compositions herein.
  • Suitable humectants for use in this invention include edible polyhydric alcohols such as glycerin, sorbitol, xylitol and propylene glycol. Sorbitol is frequently employed as a 70% aqueous solution known as 25
  • Sorbo ® Mixtures of glycerins and sorbitol are especially preferred as the humectant component of the toothpaste compositions herein.
  • Water Water is another essential element of the toothpastes of this invention. Water employed in the preparation of commercially suitable toothpastes should be deionized and free of organic impurities. Water comprises from about 15% to 80%, preferably from about 15% to 40%, by weight of the toothpaste compositions herein.
  • Phosphorus-containing, anticalculus agents and/or bis-biguanide, anti-pla ue agents can also optionally be added to the toothpastes of this invention.
  • Phosphorus- containing, anticalculus agents such as disodium ethane-l-hydroxy-1,1-diphosphonate and related materials are described more fully in U.S. Patent 3,488,419, incorporated herein by reference.
  • Bis-biguanide anti- plaque agents such as chlorohexidine (l,6-bis[N 5 -p- chlorophenyl-M x -biguanido]hexane) , the soluble and insoluble salts thereof and related materials such as chlorhexidine 1,2-bis(N s -p-trifluoromethylphenyl-N* • - biguanido) ethane are described more fully in U.S. Patent 3,934,002, U.S. Patent 3,937,807, Procter & Gamble Belgian Patent 843,244, published December 22, 2 6
  • the preferred anti-plaque, anti-microbial agents of the present invention are chlorhexidine digluconate, chlorhexidine acetate, chlorhexidine glyceride, tetradecyl-4-eth ⁇ l-pyridinium chloride, octenidine dihydrochloride, and mixtures thereof.
  • Chlorhexadine digluconate is especially preferred and is used by way of example throughout this application.
  • the optional anticalculus and/or anti-plaque, anti-microbial agents generally comprise from about 0.01% to 2.5% by weight of the toothpaste compositions herein.
  • the toothpastes of this invention can contain a variety of optional conventional toothpaste ingredients.
  • optional ingredients include (1) sudsing agents, (2) pellicle film penetration agents, (3) flavoring and sweetening agents, (4) pigments and coloring agents, and (5) stain reducing agents.
  • a preferred optional ingredient is a sudsing agent.
  • Suitable sudsing agents are those which are reasonably stable and form suds throughout a wide pH range, i.e., non-soap anionic, nonionic, cationic, zwitterionic and amphoteric organic synthetic detergents. Sudsing agents of these types are described more fully in U.S. Patent 3,959,458 and in U.S. Patent 3,937,807. Both of these patents are incorporated herein by reference.
  • Anionic sudsing agents useful herein include the N-alkylolysarcosinates.
  • nonionic sudsing agents which can be used in the toothpastes of the present invention can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound which may be aliphatic or alkyl-aromatic in nature.
  • suitable nonionic sudsing agents include the Pluronics, polyethylene oxide condensates of alkyl phenols, products derived from the condensation of ethylene oxide with the reaction product of propylene oxide and ethylene diamine, ethylene oxide condensates of aliphatic alcohols, long chain tertiary a ine oxides, long chain tertiary phosphine oxides, long chain dialkyl sulfoxides and mixtures of such materials.
  • the zwitterionic synthetic sudsing agents useful in the toothpastes of the present invention can be broadly described as derivatives of aliphatic quaternary ammonium phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxy or phosphonate.
  • the cationic sudsing agents useful in the toothpastes of the present invention can be broadly defined as quaternary ammonium compounds having one long alkyl chain containing from about 8 to about 18 carbon atoms such as lauryl trimethylammonium chloride, cetyl pyridinium chloride, cetyl trimethylammonium bromide, di-isobutyl-phenoxyethoxyethyl-dimethyobenzylammonium chloride, coconutalkyltrimethylammonium nitrite, cetyl pyridinium fluoride, etc.
  • quaternary ammonium fluorides described in U.S. Patent 3,535,421, incorporated by reference hereinbefore where said quaternary ammonium fluorides have detergent properties.
  • the cationic sudsing agents can also act as germicides in certain of the toothpastes herein.
  • amphoteric sudsing agents useful in the present invention can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxylate, or phosphonate.
  • the sudsing agent can be present in the toothpaste compositions of this invention in an amount from 0.1% to 6% by weight of the total composition.
  • Pellicle Penetration Agents Pellicle film penetration agents can also optionally be added to the fluoride containing toothpastes of the present invention. Such optional ingredients may further enhance the fluoride pellicle penetration benefits.
  • Such agents include, for example, hydroxy acids and salts thereof, such as citric acid, trisodium citrate, malic acid and tartaric acid. If present, such additional pellicle penetration agents comprise from about 0.2 to 5.0% by weight of the toothpaste composition.
  • Flavoring agents can also be added to the instant compositions. Suitable flavoring agents include oil of wintergreen, oil of peppermint, oil of spearmint, oil of sassafras and oil of clove. Sweetening agents which can be used include saccharin, dextrose, levulose, aspartame, D- ryptophan, acetosulpham, dihydrochalcones and sodium cyclamate. Flavoring agents are generally used in toothpastes at levels of from about 0.01% to 2% by weight and sweetening agents at levels of from about 0.05% to about 3% by weight. (4) Pigments and Coloring Agents, Misc.
  • a variety of other optional components well known in the art may be added to the toothpaste compositions herein to improve the usual aesthetics. These include pigments, dyes, speckles and the like. When present, these optional components generally comprise from about 0.001 to about 2% by weight of the toothpastes herein.
  • COMPOSITION PREPARATION Toothpaste compositions of the present invention are prepared simply by mixing together in any order and by an conventional means the essential and optional components herein. Once prepared, the compositions herein provide a pH of from about 5.0 to 7.5, when said compositions are slurried with water in a 3:1 weight ratio of water to composition. Fluoride toothpastes providing pH values within the 5.0 to 7.5 range provide especially effective dental enamel antisolubility benefits compared to toothpastes with pH values outside this range. Flavoring of toothpastes within this pH range is also comparatively easy.
  • Toothpaste compositions of the present invention are used in conventional manner.
  • the toothpaste compositions or slurries thereof are brushed onto dental surfaces and subsequently rinsed away.
  • pastes or slurries generally contact dental surfaces for at least about 30 seconds. More preferably, such pastes or slurries contact dental surfaces for at least about 60 seconds.
  • reaction slurry was heated to about 93°C 3 for twenty minutes and the reaction pH was adjusted again to between 4.8 - 5.0.
  • the resulting silica slurry was filtered and washed to remove the reaction by-product sodium sulfate down to a sulfate ion level of less than 0.25%.
  • the washed filter cake was then reslurried without water addition at ambient temperature with agitation.
  • the slurry was treated with 102 grams of Codex grade (U.S. purity food grade) hydrated lime (calcium hydroxide) to provide 25 ppm of calcium ion treatment based on the total weight of dry recoverable solid product in the slurry form.
  • Codex grade U.S. purity food grade
  • hydrated lime calcium hydroxide
  • the cake slurry was agitated vigorously for 15 minutes to provide the effective level of calcium ion treatment onto the surface of the silicon dioxide abrasive.
  • the slurry is then acidulated with 20% hydrochloric acid to a pH of less than 5.5.
  • the resulting product is then spray dried, milled and characterized for abrasive and physical properties.
  • the pH of the resulting product is from 6.0 to 7.5.
  • a dentifrice silica abrasive was prepared by initially adding 1420 liters of sodium silicate solution (4.09 percent Na 2 0, 10.31 percent
  • the washed filter cake was then reslurried without water addition at ambient temperature with agitation. While under agitation, the slurry was treated with 510 grams of Codex grade (U.S. purity food grade) hydrated lime (calcium hydroxide) to provide 125 ppm of calcium ion treatment based on the total weight of the dry recoverable silicon dioxide abrasive present in the slurry form. After treatment with the calcium ion, the cake slurry was agitated vigorously for 15 minutes to provide the effective level of calcium ion treatment onto the surface of the silicon dioxide abrasive.
  • Codex grade U.S. purity food grade
  • hydrated lime calcium hydroxide
  • the resulting product was then spray dried, milled and then characterized.
  • the pH of the resulting product is from 6.0 to 7.5.
  • a toothpaste is formulated utilizing the precipitated silica abrasive of Example 1 which has the following composition:
  • the above toothpaste composition is prepared by admixing the components thereof in the normal manner of toothpaste preparation.
  • the water component may be added first to a suitable container to which thereafter is added with moderate agitation, the anti-plaque agent, the flavor, the humectant and, thereafter, the remaining components.
  • a 3:1 weight slurry of the above freshly prepared composition with water (3:1 is water to composition) produces a pH of about 7.1.
  • Such a toothpaste composition provides beneficial fluoride treatment for dental tissue brushed therewith due to the high toothpaste fluoride compatibility.
  • the toothpaste also provides good cleaning and an EDA of 75. When stored for prolonged periods of time at 80°F, such a toothpaste exhibits minimal loss of soluble fluoride.
  • Toothpastes providing substantially similar fluoride treatment benefits, toothpaste fluoride and anti-plaque and cleaning performance are realized when the precipitated silica abrasive component prepared as in Example 1 is replaced with an equivalent amount of abrasive prepared by Example 2.
  • a toothpaste providing substantially similar fluoride treatment and anti-plaque benefits is realized when the chlorhexidine digluconate in Example 3 composition is replaced by about 1.0% by weight of chlorhexidine acetate, chlorhexidine glyceride, tetradecyl-4-ethyl-pyridium chloride, octenidiene hydrochloride, or mixture thereof.
  • the precipitated silica abrasives herein can be used to prepare especially desirable therapeutic toothpaste compositions containing anti-plaque, anti-microbial agents. Such compositions provide both high abrasive compatibility and yet have good tooth cleaning performance. The following tests and evaluation serve to demonstrate the excellent compatibility provided by the precipitated silica dental abrasives herein in the toothpaste composition of the present invention.
  • Precipitated silica dental abrasives can be screened for their relative compatibility with fluoride materials by means of a 24 hr. abrasive slurry test. Such a test can be used to generate data which can predict the availability of soluble fluoride in certain types of fluoride toothpastes after storage over approximately a four-week period at 80°F.
  • the 24 hour abrasive slurry test is used to generate fluoride compatibility values which are defined as that percentage of theoretical maximum available fluoride, which is actuallly measured after 24 hours as soluble fluoride by the following test method.
  • this method (Orion Specific Ion Electrode Method) a standard sodium fluoride stock solution containing 1624 ppm of fluoride is prepared by dissolving 2.80 grams of sodium fluoride, 21.5 grams of NaH j PO,, and 83.4 grams of Na,HPOhorizon-2H 2 0 in 672.5 grams of deionized distilled water and stored in a polyethylene bottle. Thirty (30) grams of this solution is then weighed out.
  • the EDTA/THAM solution is a 0.2 molar in EDTA (ethylene diaminetetraacetic acid, disodium salt) and 0.2 molar in THAM (2-Amino-2-hydroxymethyl-l, 2-propanediol) and adjusted to pH 8.0 with sodium hydroxide.
  • a magnetic stirring bar is added and gentle stirring is initiated.
  • the fluoride ion concentration is determined by direct potentiometry with the Orion fluoride electrode (Model 95-09). Emf is converted to parts per million (ppm) fluoride in the supernatant by means of a logarithmic equation.
  • the fluoride compatibility value is then calculated by expressing the measured ppm soluble fluoride as a percentage of the theoretically available soluble fluoride.
  • Preferred toothpastes herein containing precipitated silica abrasives and pellicle film penetration agents are evaluated for abrasive fluoride compatibility.
  • the toothpastes which are prepared for evaluation have the composition of the toothpaste of the Example 3 and differ only in the variation of the abrasive component.
  • a soluble fluoride determination method is used, which is similar to the method described above, for the determination of abrasive 40
  • the toothpaste compositions are stored for a specified length of time in a laminate tube. Thereafter, 15.0 grams of the composition is placed in a 100 ml. beaker and then 45.0 grams of distilled water is added. The mixture then is stirred to form a slurry in which the toothpaste is uniformly dispersed. The slurry is subsequently centrifuged for 20 minutes at 15,000 rpm or until the supernatant is clear. The supernatant is then treated as in the abrasive fluoride compatibility determination method described above. Soluble fluoride concentration is similarly measured and an abrasive fluoride compatibility value for each toothpaste is similarly calculated. The toothpaste fluoride compatibility values of the respective toothpastes evaluated are show below. The abrasives evaluated are those prepared as described in Examples 1 and 2.
  • toothpaste fluoride compatibility values for toothpastes stored for longer periods, or at more severe temperatures are generally lower than those exemplified above.
  • Toothpaste Fluoride Compatibility High Temperature/Prolonged Storage
  • the dental cleaning ability of the silica abrasives herein can be estimated by means of Radioactive Dentin Abrasion (PDA) testing.
  • RDA values can be used to estimate the relative cleaning performance of various abrasives for any given type of dentifrice abrasive.
  • an RDA value (measured by the method provided below) of at least 40, preferably between 70 and 120, is needed to insure that the abrasive has sufficient abrasivity to be an effective dentifrice cleaner.
  • Prior art precipitated silica abrasives, which do exhibit high toothpaste fluoride compatibility, generally are poor cleaners for oral hygiene purposes as evidenced by low RDA values.
  • the alkaline earth treated abrasives provide both effective tooth cleaning and high fluoride compatibility.
  • Several commercial precipitated silica abrasives which demonstrate relatively high toothpaste fluoride compatibility as measured herein are selected for evaluation for RDA values. Testing is conducted within a standard toothpaste matrix having the composition of the toothpaste of Example 3, which di fers only in the variation of the abrasive component.
  • Teeth are then scraped clean with a scalpel.
  • the crown and root tip of each tooth are removed using an abrasive disc so as to prepare a dentin sample 14 mm long and at least 2 mm wide at the narrower end. Cut pieces of root (dentin chips) , or, alternatively, an additional tooth, are also prepared to be later used in determining a correction factor for self-absorption of radiation.
  • Step A are exposed to a neutron flux of 2 x 10 12 neutrons/cm 2 for three hours.
  • Toothbrushes used throughout the test are 50-Tuft, medium, flat, "Pepsodent” toothbrushes. 44
  • the freshly mounted, irradiated roots are brushed with a reference slurry (lOg calcium pyrophosphate + 50 ml of a 0.5% CMC-10% glycerine solution) for 6,000 brush strokes.
  • a reference slurry laOg calcium pyrophosphate + 50 ml of a 0.5% CMC-10% glycerine solution
  • the dentin samples are then conditioned with the reference slurry (same slurry as in Step D) for 1,500 brush strokes at the beginning, during and end of each test run.
  • the test run consists of brushing dentin samples for 1,500 brush strokes with a slurry of test product (25g dentifrice + 40 ml deionized of distilled water) .
  • the correction factors are prepared by dissolving the dentin chips or, alternatively, an additional tooth, from Step B in 5 ml. cone. HCI brought to a volume of 250 ml. with distilled water. One ml. of this solution is added to test pastes and reference slurries which are prepared similarly to those in STep E, and then neutralized with 0.1 N NaOH.
  • the radioactivity of the slurry samples (1.0 ml.) is determined with an Intertechnique SL-30 liquid scintillation counter. Alternate counting procedure: 3 ml. aliquots of each slurry are transferred to stainless steel, flat-bottom 1 inch x 5/16 inch planchets and counted using Nuclear Chicago Geiger Counting System.
  • the radioactive dentin abrasion value (RDA) for a particular paste will be the ratio of the average corrected counts for that paste to the average count for the reference multiplied by 100.
  • the reference abrasive is given an arbitrary dentin abrasion value of 100 units.
  • Neosyl 2 25+2 78% 10.
  • the Table V data demonstrate the commercial pre ⁇ cipitated silica abrasives may well demonstrate high abrasive fluoride compatibility but are not suffi- ciently abrasive so as to be useful as dentifrice abrasives.
  • the instant novel pre ⁇ cipitated silica abrasives provide outstanding abrasive fluoride compatibility yet simultaneously provide excellent RDA abrasivity values, which values can be used as an indicator of relative dental cleaning performance.
  • a sample of abrasive is slurried in a solution of chlorhexidine digluconate, and the chlorhexidine remaining in the supernatant is compared with that in a
  • UV-visible spectrophotometer UV-visible spectrophotometer.
  • amorphous silicon dioxide abrasive compositions are produced having fluoride and chlorhexidine digluconate compatabilities in excess of of at least about 80%.
  • Table VI the sulfate ion content, pH of the abrasive sample as well as other criteria are set forth.
  • samples of the amorphous silicon dioxide abrasive composition, which had been calcium treated are evaluated at various places in the treatment procedure to determine the critical treatments necessary to provide the amorphous silicon dioxide abrasive which has the desirable fluoride compatability and anti-plaque compatibility levels.
  • the samples are provided as slurries.
  • Sample Al is a sample of the amorphous silicon dioxide abrasive composition as produced by the teachings of U.S. Patent 4,421,527.
  • Sample A3 is the same sample but wherein the pH has been adjusted by the addition of hydrochloric acid but without washing with deionized water.
  • Sample A4 is the same sample wherein the sample has been washed to lower sulfate content and pH has been adjusted by the addition of hydrochloric acid. Sample A4 represents the product of the invention.
  • Sample Bl, B2, B3 and B4 are different samples from the same batch subjected to the same treatments as
  • Sample C is subjected to different treatments to further precisely determine the criteria necessary to produce an abrasive within the scope of the present invention.
  • the sample is received as a slurry and in Sample Cl, the slurry is simply dried and evaluated.
  • the slurry is filtered to remove additional liquid and then dried without washing.
  • the slurry is filtered and washed with deionized water.
  • the pH of the slurry is adjusted by the addition of hydrochloric acid and then dried.
  • Sample C5 the pH of the slurry is adjusted by addition of hydrochloric acid, and the sample is then filtered but not dried or washed.
  • the pH is adjusted by addition of hydrochloric acid, the sample is filtered and then washed.
  • Sample C6 is the sample within the scope of the invention.
  • Sample D is subjected to still additional treatments.
  • deionized water is added to the slurry and it is then filtered without pH adjustment.
  • Sample D2 deionized water is added to the slurry, it is filtered and then washed which removes additional sulfate.
  • Sample D3 deionized water is added to the slurry, the pH is adjusted to 5.2 by the addition of hydrochloric acid, and the slurry is filtered but not washed.
  • sample D4 deionized water is added to the slurry, but the pH is adjusted to a lower value by the addition of more hydrochloric acid and the slurry is then filtered.
  • the sodium sulfate content was measured by the LECO method as described herein.
  • SA means surface area
  • OA oil absorption
  • F/C means fluoride compatibility
  • A/C means anti-plaque compatibility and specifically compatibility with chlorhexidine digluconate, all of these measurements being described herein.
  • toothpaste formulations are prepared in order to compare a silica abrasive from U.S. Patent No. 4,421,527 with a silica abrasive of this invention.
  • Table VII a silica abrasive prepared according to U.S. Patent 4,421,527 (recognized to have high fluoride compatibility), is compared for anti-plaque compatibility (with chlorhexidine digluconate) with a similar silica abrasive which has controlled pH, and sulfate ion levels.
  • the silica abrasive of the invention is sample No. B4 from Table VI which has a sulfate ion level of 0.07% and a pH of 4.3.
  • Table VII is as follows:
  • soluble chlorhexidine represents the concentration in the mouth during brushing. It is measured by slurrying the dentifrice with 3 parts of water, centrifuging to obtain a clear supernatant, and measuring all the chlorhexidine in the supernatant. The chlorhexidine is measured by reacting the supernatant with alkaline hypobro ite to produce a colored solution. The intensity of the color is determined by a spectrophotomer and compared to standard solutions prepared in a similar manner. The percentage of chlorhexidine retained or percent compatibility is the percent of the theoretical level of chlorhexidine in the supernatant (i.e., 100% retention or 100% compatibility means all of the chlorhexidine dissolves in the water slurry) .

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Abstract

Nouvelles compositions abrasives au dioxyde de silicium précipité qui peuvent être incorporées à des compositions de pâtes dentifrices thérapeutiques contenant des fluorures solubles ainsi que des agents anti-plaque et antiseptiques. Les abrasifs comprennent des dioxydes de silicium précipités que l'on a fait réagir avec environ 10 à 300 ppm d'un ion de métal alcalino terreux, en particulier le calcium. Ces abrasifs contiennent moins de 0.25% d'ions sulfate et possèdent un pH contrôlé de 4,0 à 7,5. Procédés de préparation des nouveaux abrasifs au dioxyde de silicium et formulations de pâtes dentifrices contenant de tels abrasifs.
PCT/US1989/004866 1988-11-09 1989-11-02 Compositions abrasives de dioxyde de silicium precipite presentant un haut degre de compatibilite avec les agents fluores anti-plaque et therapeutiques, pour des applications aux produits dentifrices, produits dentifrices les contenant, et procede de fabrication de ces compositions WO1990005113A1 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996009809A1 (fr) * 1994-09-26 1996-04-04 The Procter & Gamble Company Compositions pour dentifrices
WO1996034593A1 (fr) * 1995-05-02 1996-11-07 The Procter & Gamble Company Compositions dentifrices
WO1996034594A1 (fr) * 1995-05-02 1996-11-07 The Procter & Gamble Company Compositions dentifrices
WO1996034592A1 (fr) * 1995-05-02 1996-11-07 The Procter & Gamble Company Compositions dentifrices
WO1999043291A1 (fr) * 1998-02-27 1999-09-02 Colgate-Palmolive Company Abrasif dentaire ameliore
US6143281A (en) * 1987-03-31 2000-11-07 Smithkline Beecham P.L.C. Dentifrice compositions
US11285088B2 (en) * 2017-08-29 2022-03-29 Evonik Operations Gmbh Spherical silica particle size for RDA control
WO2024033276A1 (fr) * 2022-08-08 2024-02-15 Amyris Bio Products Portugal Unipessoal Lda Sphères de silice non nano amorphes

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9124538D0 (en) * 1991-11-19 1992-01-08 Unilever Plc Liquid dentifrices

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4312845A (en) * 1979-09-10 1982-01-26 J. M. Huber Corporation Method of producing amorphous silica of controlled oil absorption
US4421527A (en) * 1977-12-20 1983-12-20 J. M. Huber Corporation High fluoride compatibility dentifrice abrasives and compositions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4421527A (en) * 1977-12-20 1983-12-20 J. M. Huber Corporation High fluoride compatibility dentifrice abrasives and compositions
US4312845A (en) * 1979-09-10 1982-01-26 J. M. Huber Corporation Method of producing amorphous silica of controlled oil absorption

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6143281A (en) * 1987-03-31 2000-11-07 Smithkline Beecham P.L.C. Dentifrice compositions
WO1996009809A1 (fr) * 1994-09-26 1996-04-04 The Procter & Gamble Company Compositions pour dentifrices
AU699813B2 (en) * 1994-09-26 1998-12-17 Procter & Gamble Company, The Dentifrice compositions
CN1107494C (zh) * 1994-09-26 2003-05-07 普罗克特和甘保尔公司 洁牙剂组合物
WO1996034593A1 (fr) * 1995-05-02 1996-11-07 The Procter & Gamble Company Compositions dentifrices
WO1996034594A1 (fr) * 1995-05-02 1996-11-07 The Procter & Gamble Company Compositions dentifrices
WO1996034592A1 (fr) * 1995-05-02 1996-11-07 The Procter & Gamble Company Compositions dentifrices
WO1999043291A1 (fr) * 1998-02-27 1999-09-02 Colgate-Palmolive Company Abrasif dentaire ameliore
US11285088B2 (en) * 2017-08-29 2022-03-29 Evonik Operations Gmbh Spherical silica particle size for RDA control
WO2024033276A1 (fr) * 2022-08-08 2024-02-15 Amyris Bio Products Portugal Unipessoal Lda Sphères de silice non nano amorphes

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