WO1996034593A1 - Dentifrice compositions - Google Patents

Dentifrice compositions Download PDF

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Publication number
WO1996034593A1
WO1996034593A1 PCT/US1996/005497 US9605497W WO9634593A1 WO 1996034593 A1 WO1996034593 A1 WO 1996034593A1 US 9605497 W US9605497 W US 9605497W WO 9634593 A1 WO9634593 A1 WO 9634593A1
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Prior art keywords
abrasive
particles
sodium
silica
ratio
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PCT/US1996/005497
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French (fr)
Inventor
David Earl Rice
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AT96911814T priority Critical patent/ATE197894T1/en
Priority to EP96911814A priority patent/EP0825847B1/en
Priority to JP8533336A priority patent/JPH11504919A/en
Priority to AU54879/96A priority patent/AU5487996A/en
Priority to CA002220026A priority patent/CA2220026C/en
Priority to DE69611165T priority patent/DE69611165T2/en
Priority to MX9708433A priority patent/MX9708433A/en
Priority to DK96911814T priority patent/DK0825847T3/en
Publication of WO1996034593A1 publication Critical patent/WO1996034593A1/en
Priority to GR20000402485T priority patent/GR3034792T3/en

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
    • C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/02—Amorphous compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/19—Oil-absorption capacity, e.g. DBP values
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/90—Other properties not specified above

Definitions

  • TECHNICAL FIELD This invention relates to dentifrice compositions such as toothpastes which provide improved oral cleaning.
  • Synthetically produced amorphous silicas play an important role as an ingredient in many of today's toothpaste formulations. In addition to their cleaning ability, they are also relatively safe, nontoxic, and compatible with other toothpaste ingredients, including glycerin, sorbitol (or xylitol), thickening agents, detergents coloring and fragrance materials and, optionally, fluoride containing compositions.
  • Synthetic precipitated silicas are prepared by admixing dilute alkali silicate solutions with strong aqueous mineral acids under conditions where aggregation to the sol and gel cannot occur, stirring and then filtering out the precipitated silica. The resulting precipitate is next washed, dried and comminuted to desired size.
  • Silica gels include silica hydrogels, hydrous gels, aerogels, and xerogels. Silica gels are also formed by reacting alkali silicate solutions with strong acids to form a hydrosol and aging the newly formed hydrosol to form the hydrogel. The hydrogel is then washed, dried and comminuted as described above.
  • Examples of precipitated silicas described in the art include U.S. Patent 4.122.161 to Wason, October 24, 1978, U.S. Patents 4.992.251 and 5.035.879 to Aldcroft et al., February 12, 1991 and July 30, 1991 respectively, U.S. Patent 5.098.695 to Newton et al., March 24, 1992, and U.S. Patent 5.279.815 to Wason et al., January 18, 1994.
  • silica gels have also been described in the art as demonstrated by U.S. Patent 4.303.641. December 1, 1981, to DeWolf, II et al., U.S. Patent 4.153.680. May 8, 1979, to Seybert, and U.S. Patent 3.538.230. November 3, 1970, to Pader et al..
  • silica compositions useful as dental cleaning abrasives there is still a need for additional compositions providing improved cleaning with minimal abrasion.
  • the present inventor has discovered amorphous silica abrasive compositions comprising precipitated and gel silicas providing improved dental cleaning with minimal abrasion.
  • amorphous silica abrasive compositions comprising: a.) a precipitated silica, comprising particles wherein said particles have: i.) a mean particle size of from about 5 to about 1 1 microns (s.d.
  • a gel silica comprising particles wherein said particles have: i.) a mean particle size of from about 5 to about 1 1 microns (s.d.
  • the pH of the present herein described compositions range from about 4 to about 9.5, with the preferred pH being from about 6.5 to about 9.0 and the most preferred pH being 7.0 to about 8.5, as measured in a 5% aqueous slurry.
  • safe and effective amount means a sufficient amount to reduce stain and/or plaque/gingivitis without harming the tissues and structures of the oral cavity.
  • orally-acceptable carrier means a suitable vehicle which can be used to apply the present compositions to the oral cavity in a safe and effective manner.
  • the amorphous silicas used to form the precipitated silica and gel silica combinations of the present invention can be characterized as either Low Structure or Medium Structure silicas in accordance with the definitions set forth in the J. Soc Cosmet. Chem. 29., 497-521 (August, 1978), and Pigment Handbook: Volume 1, Properties and Economics, Second Edition, Edited by Peter A. Lewis, John Wiley & Sons, Inc., 1988, p. 139-159 and are preferably characterized as synthetic hydrated amorphous silicas, also known as silicon dioxides or SiO2. Further, these silicas may be characterized as having a BET surface area in the range of 50 to 250 m2/g. and as containing less than about 10%, more preferably less than about 5%, alumina
  • the amorphous silica combinations of the present invention may be characterized as having a median average particle size ranging from about 5 microns to about 11 microns with at least 70% of the particle size distribution being less than 20 microns.
  • the average particle size (mean value and median or 50%) is measured using a Microtrac II apparatus, Leeds and Northrup. Specifically, a laser beam is projected through a transparent cell which contains a stream of moving particles suspended in a liquid. Light rays which strike the particles are scattered through angles which are inversely proportional to their sizes. The photodetector array measures the quantity of light at several predetermined angles. Electrical signals proportional to the measured light flux values are then processed by a microcomputer system to form a multi-channel histogram of the particle size distribution.
  • the amorphous precipitated and gel silicas used to form the combinatory compositions of the present invention are further characterized by means of their respective Einlehner hardness values, Radioactive Dentin Abrasion (RDA) values and oil absorption values.
  • Einlehner hardness values are measured using an Einlehner At- 1000 Abrader to measure the softness of the silicas in the following manner: A Fourdrinier wire screen is weighed and exposed to the action of a 10% aqueous silica suspension for a certain length of time. The amount of abrasion is then determined as milligrams weight lost of the Fourdrinier wire screen per 100,000 revolutions. Brass Einlehner (BE) and Polyester Einlehner (PE) results are expressed in milligrams. The RDA values are determined according to the method set forth by
  • the amorphous silica combinations are, preferably, characterized as having oil absorption values less than 200 cc/ 100 gm. Oil absorption values are measured using the ASTM rub-out method D281. Surface area is determined by the BET nitrogen adsorption method of Brunaur et al., J. Am. Chem. Soc, 60, 309 (1938). To measure brightness, fine powder materials that are pressed into a smooth surfaced pellet are evaluated using a Technidyne Brightimeter S-5/BC. This instrument has a dual beam optical system where the sample is illuminated at a angle of 45°, and the reflected light viewed at 0°. It conforms to TAPPI test methods T452 and T646, and ASTM Standard D985.
  • a series of filters direct to reflected light of desired wavelengths to a photocell where it is converted to an output voltage. This signal is amplified and then processed by an internal microcomputer for display and printout.
  • Precipitated silica suspensions are prepared in accordance with general methods described, for example, in prior U.S. Patents: 3,893,840. issued July 8, 1975, to Wason; 3.988.162. issued October 26, 1976, to Wason, 4.067.746. issued January 10, 1978, to Wason; and 4.340.583.
  • reaction parameters to form precipitated silicas having BE values in the range of from about 0.8 mg to about 2.5 mg and PE values in the range of about 5 mg to about 8 mg, an RDA ranging from about 25 to about 90, and an oil absorption of from about 95ml/100gm to about 135ml/100gm.
  • Reaction parameters which affect the characteristics of the resultant silica include: the rate at which the various reactants are added; the levels of concentration of the various reactants; the reaction pH; the reaction temperature or the rate at which electrolytes are added.
  • the formed suspension is subsequently filtered, followed by a washing and drying of the filtered precipitate.
  • the resulting precipitated silica is next milled to a particle size in which 70% of the particle size distribution is below 20 microns.
  • gel silicas are prepared in accordance with general methods described, for example, in prior U.S. Patents: 4.153.680. to Seybert, issued May 8, 1979; 4.303.641. to DeWolf II et al., issued December 1,1981 and 4.632.826. to Ploger et al., issued December 30, 1986, varying reaction parameters to form gel silicas having BE values in the range of from about 3 mg to about 15 mg and PE values in the range of 8 mg to about 20 mg, an RDA ranging from about 80 to about 200, and an oil absorption of from about 130ml/100gm to about 60ml 100gm.
  • the gel silica is milled to a particle size in which 70% of the particle size distribution is below 20 microns.
  • the precipitated and gel silicas are combined (e.g., by physical mixing) to form the amorphous silica compositions of the present invention.
  • the resultant amorphous silica composition can then be incorporated into suitable dentifrice compositions.
  • the dentifrice compositions of the present invention can contain a variety of optional dentifrice ingredients some of which are described below.
  • Optional ingredients include, for example, but are not limited to, adhesives, sudsing agents, flavoring agents, sweetening agents, additional antiplaque agents, abrasives, and coloring agents.
  • the Pellicle Cleaning Ratio (PCR) of the inventive silica composition which is a measurement of the cleaning characteristics of a dentifrice, ranges from 90 to 135 and preferably from 100 to 130 for the amorphous silica combination of the invention.
  • the Radioactive Dentin Abrasion (RDA) of the inventive silicas which is a measurement of the abrasiveness of the precipitated silica combination when incorporated into a dentifrice, ranges from 60 to 10, preferably from 80 to 90.
  • the PCR (Pellicle Cleaning Ratio) cleaning values are determined by a slightly modified version of the PCR test described in "In Vitro Removal of Stain With Dentifrice", G. K. Stookey, T.A. Burkhard and B.
  • the amorphous silica combinations of the present invention when incorporated into a dentifrice composition further provide an improved PCR/RDA ratio.
  • the PCR/RDA ratio is used to determine the relative ratio of cleaning and abrasion characteristics of a dentifrice formulation.
  • Commercially available dentifrice formulations generally have a PCR/RDA ratio in the range of 0.5 to below 1.0.
  • the amorphous silicas used in the compositions of the present invention provide PCR to RDA ratios to dentifrice formulations of greater than 1, usually in the range of 1.20 to 1.60, but more preferably in the range 1.25 to 1.50.
  • the abrasive, in the form of a precipitated silica and gel silica compositions of the present invention, when incorporated into the compositions described herein, is present at a level of from about 6% to about 70%, preferably from about 15% to about 35% when the dentifrice is a toothpaste. Higher levels, as high as 95%, may be used if the composition is a toothpowder.
  • the carrier for the components of the present compositions is optional and can be any dentifrice vehicle suitable for use in the oral cavity.
  • Such carriers include the usual components of toothpastes, tooth powders, prophylaxis pastes, lozenges, gums and the like and are more fully described hereinafter. Toothpastes are the preferred systems.
  • Surfactants One of the preferred optional agents of the present invention is a surfactant, preferably one selected from the group consisting of sarcosinate surfactants, isethionate surfactants and taurate surfactants. Preferred for use herein are alkali metal or ammonium salts of these surfactants.
  • This surfactant can be present in the compositions of the present invention from about 0.1% to about 2.5%, preferably from about 0.3% to about 2.5% and most preferably from about 0.5% to about 2.0% by weight of the total composition.
  • Suitable compatible surfactants can optionally be used along with the sarcosinate surfactant in the compositions of the present invention.
  • Suitable optional surfactants are described more fully in U.S. Patent 3.959.458. May 25, 1976 to Agricola et al. ; U.S. Patent 3.937.807. February 10, 1976 to Haefele; and U.S. Patent 4.051.234. September 27, 1988 to Gieske et al. These patents are incorporated herein by reference.
  • Preferred anionic surfactants useful herein include the water-soluble salts of al- kyl sulfates having from 10 to 18 carbon atoms in the alkyl radical and the water- soluble salts of sulfonated monoglycerides of fatty acids having from 10 to 18 carbon atoms.
  • Sodium lauryl sulfate and sodium coconut monoglyceride sulfonates are examples of anionic surfactants of this type. Mixtures of anionic surfactants can also be utilized.
  • Preferred cationic surfactants useful in the present invention can be broadly defined as derivatives of aliphatic quaternary ammonium compounds having one long alkyl chain containing from about 8 to 18 carbon atoms such as lauryl trimethylam- monium chloride; cetyl pyridinium chloride; cetyl trimethylammonium bromide; di-is- obutylphenoxyethyl-dimethylbenzylammonium chloride; coconut alkyltrimethylam- monium nitrite; cetyl pyridinium fluoride; etc.
  • Preferred compounds are the quater- nary ammonium fluorides described in U.S. Patent 3.535.421.
  • quaternary ammonium fluorides have detergent properties.
  • Certain cationic surfactants can also act as germicides in the compositions disclosed herein.
  • Cationic surfactants such as chlor- hexadine, although suitable for use in the current invention, are not preferred due to their capacity to stain the oral cavity's hard tissues. Persons skilled in the art are aware of this possibility and should incorporate cationic surfactants only with this limitation in mind.
  • Nonionic surfactants that can be used in the compositions of the present invention can be broadly defined as compounds produced by the condensa- tion of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound which may be aliphatic or alkylaromatic in nature.
  • suitable nonionic surfactants 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 diami ⁇ e, ethylene oxide condensates of aliphatic alcohols, long chain tertiary amine oxides, long chain tertiary phosphine oxides, long chain dialkyl sulfoxides and mixtures of such materials.
  • Preferred zwitterionic synthetic surfactants useful in the present invention can be broadly described as derivatives of aliphatic quaternary ammonium, phos- phomium, 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, sulfonate, sulfate, phosphate or phosphonate.
  • Typical alkyl dimethyl betaines include decyl betaine or 2-(N-decyl-N,N-dimethylammonio) acetate, coco betaine or 2-(N-coc-N, N- dimethyl ammonio) acetate, myristyl betaine, palmityl betaine, lauryl betaine, cetyl betaine, cetyl betaine, stearyl betaine, etc.
  • the amidobetaines are exemplified by cocoamidoethyl betaine, cocoamidopropyl betaine, lauramidopropyl betaine and the like.
  • the betaines of choice are preferably the cocoamidopropyl betaine and, more preferably, the lauramido propyl betaine.
  • Chelating agents Another preferred optional agent is a chelating agent selected from the group consisting of tartaric acid and pharmaceutically-acceptable salts thereof, citric acid and alkali metal citrates and mixtures thereof. Chelating agents are able to complex calcium found in the cell walls of the bacteria. Chelating agents can also disrupt plaque by removing calcium from the calcium bridges which help hold this biomass intact. However, it is possible to use a chelating agent which has an affinity for calcium that is too high. This results in tooth demineralization and is contrary to the objects and intentions of the present invention.
  • Sodium and potassium citrate are the preferred alkali metal citrates, with sodium citrate being the most preferred. Also preferred is a citric acid/alkali metal citrate combination.
  • Preferred herein are alkali metal salts of tartaric acid. Most preferred for use herein are disodium tartrate, dipotassium tartrate, sodium potassium tartrate, sodium hydrogen tartrate and potassium hydrogen tartrate.
  • the amounts of chelating agent suitable for use in the present invention are about 0.1% to about 2.5%, preferably from about 0.5% to about 2.5% and more preferably from about 1.0% to about 2.5%.
  • the tartaric acid salt chelating agent can be used alone or in combination with other optional chelating agents. Other optional chelating agents can be used. Preferably these chelating agents have a calcium binding constant of about 10 to 10 provide improved cleaning with reduced plaque and calculus formation.
  • the pyrophosphate salts used in the present compositions can be any of the alkali metal pyrophosphate salts. Specific salts include tetra alkali metal pyrophosphate, dialkali metal diacid pyrophosphate, trialkali metal monoacid pyrophosphate and mixtures thereof, wherein the alkali metals are preferably sodium or potassium.
  • the salts are useful in both their hy- drated and unhydrated forms.
  • An effective amount of pyrophosphate salt useful in the present composition is generally enough to provide at least 1.0% pyrophosphate ion, preferably from about 1.5% to about 6%, more preferably from about 3.5% to about 6% of such ions. It is to be appreciated that the level of pyrophosphate ions is that capable of being provided to the composition (i.e., the theoretical amount at an appropriate pH) and that pyrophosphate forms other than P O -4 (e.g., (HP O -3)) may be present when a final product pH is established.
  • chelating agents suitable for use in the present invention are the anionic polymeric polycarboxylates. Such materials are well known in the art, being employed in the form of their free acids or partially or preferably fully neutralized water soluble alkali metal (e.g. potassium and preferably sodium) or ammonium salts.
  • These copolymers are available for example as Gantrez AN 139 (M.W. 500,000), AN 1 19 (M.W. 250,000) and preferably S-97 Pharmaceutical Grade (M.W. 70,000), of GAF Chemicals Corporation.
  • operative polymeric polycarboxylates include those such as the 1: 1 copolymers of maleic anhydride with ethyl acrylate, hydroxyethyl methacrylate, N-vi- nyl-2-pyrollidone, or ethylene, the latter being available for example as Monsanto EMA No. 1103, M.W. 10,000 and EMA Grade 61, and 1 : 1 copolymers of acrylic acid with methyl or hydroxyethyl methacrylate, methyl or ethyl acrylate, isobutyl vinyl ether or N-vinyl-2-pyrrolidone.
  • Suitable flavor ⁇ ing 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 aspartame, acesulfame, saccharin, dextrose, levulose and sodium cyclamate. Flavoring and sweetening agents are generally used in dentifrices at levels of from about 0.005% to about 2% by weight.
  • a water-soluble fluoride compound present in dentifrices and other oral compositions in an amount sufficient to give a fluoride ion concentration in the composition at 25°C, and/or when it is used of from about 0.0025% to about 5.0% by weight, preferably from about 0.005% to about 2.0% by weight, to provide additional anticaries effectiveness.
  • fluoride ion- yielding materials can be employed as sources of soluble fluoride in the present compositions. Examples of suitable fluoride ion-yielding materials are found in U.S. Patent No. 3.535.421. October 20, 1970 to Briner et al. and U.S. Patent No. 3.678.154.
  • Representative fluoride ion sources include: stannous fluoride, sodium fluo ⁇ ride, potassium fluoride, sodium monofluorophosphate and many others. Stannous fluoride and sodium fluoride are particularly preferred, as well as mixtures thereof.
  • Water is also present in the toothpastes of this invention.
  • Water employed in the preparation of commercially suitable toothpastes should preferably be deionized and free of organic impurities.
  • Water generally comprises from about 10% to 50%, preferably from about 20% to 40%, by weight of the toothpaste compositions herein. These amounts of water include the free water which is added plus that which is introduced with other materials such as with sorbitol.
  • thickening agents are carboxyvinyl polymers, carrageenan, hydroxethyl cellulose and water soluble salts of cellulose ethers such as sodium carboxymethyl cellulose and sodium carboxymethyl hy ⁇ droxethyl cellulose.
  • Natural gums such as gum karaya, xanthan gun, gum arabic, and gum tragacanth can also be used.
  • Thickening agents in an amount from 0.5% to 5.0% by weight of the total composition can be used. It is also desirable to include some humectant material in a toothpaste to keep it from hardening. Suitable humectants include glycerin, sorbitol, and other edible polyhydric alcohols at a level of from about 15% to about 70%.
  • compositions of the present invention are other stannous salts such as stannous pyrophosphate and stannous gluconate and antimicrobials such as quaternary ammonium salts, such as cetyl pyridinium chloride and tetradecylethyl pyridinium chloride, bis-biquanide salts, copper bisglycinate, nonionic anti microbial salts and flavor oils.
  • antimicrobials such as quaternary ammonium salts, such as cetyl pyridinium chloride and tetradecylethyl pyridinium chloride, bis-biquanide salts, copper bisglycinate, nonionic anti microbial salts and flavor oils.
  • quaternary ammonium salts such as cetyl pyridinium chloride and tetradecylethyl pyridinium chloride, bis-biquanide salts, copper bisglycinate, nonionic anti microbial
  • biphasic dentifrice formulations such as those disclosed in U.S. Patents 5,213,790, issued May 23, 1993, 5, 145,666, issued
  • Example I A dentifrice composition of the present invention contains the following com ⁇ ponents as described below.
  • Component Wgt % Component Wgt %
  • the jacket temperature of a mixing tank is set to about 150°F (65°C) to about 160°F (71°C).
  • the humectants and water are added to the mixing tank and agitation is started.
  • the temperature reaches approximately 120°F (50°C) fluoride, sweetening agents, buffering agents, chelant, coloring agents and titanium dioxide are added.
  • Thickening agents are added to the abrasive and the resulting mixture is added to the mixing tank with high agitation.
  • the surfactant is added to the combination and mixing is continued.
  • the tank is cooled to 120°F (50°C) and the flavoring agents are added. Mixing is continued for approximately 5 minutes.
  • the resulting composition will have a pH of about 7.
  • Example II A dentifrice composition of the present invention contains the following com ⁇ ponents as described below.
  • APS Mean Value 8.3 microns
  • oil absorption 108cc/100g
  • BE 2.6
  • PE 9
  • PCR 118
  • RDA 80.
  • a gum composition of the present invention contains the following com ⁇ ponents as described below.

Abstract

Oral compositions, such as oral gels and toothpastes, containing a novel abrasive. An amorphous silica abrasive composition, comprising: a) a precipitated silica, comprising particles wherein said particles have: i) a mean particle size of from 5 to 11 microns (s.d. < 9); ii) an Einlehner hardness of from 0.8 to 2.5 for abrasive to brass screen and from 5 to 8 for abrasive to polyester screen; iii) an oil absorption of from 95 ml/100 gm to 135 ml/100 gm; and iv) a radioactive dentin abrasion of from 25 to 90; and b) a gel silica, comprising particles wherein said particles have: i) a mean particle size of from 5 to 11 microns (s.d. < 9); ii) an Einlehner hardness of from 3 to 15 for abrasive to brass screen and from 8 to 20 for abrasive to polyester screen; iii) an oil absorption of from 60 ml/100 gm to 130 ml/100 gm; and iv) a radioactive dentin abrasion of from 80 to 200 wherein at least 70 % of all of said particles have a diameter of below 25 microns and wherein the pellicle cleaning ratio is from 90 to 135, preferably from 110 to 135, and the radioactive dentin abrasion is from 60 to 100, preferably from 65 to 85, with a pellicle cleaning ratio/radioactive dentin abrasion ratio of from 1.20 to 1.60, preferably 1.25 to 1.50, and wherein the ratio of precipitated silica to gel silica is from 90:10 to 60:40, preferably 80:20 to 60:40, respectively.

Description

DENTIFRICE COMPOSITIONS
TECHNICAL FIELD This invention relates to dentifrice compositions such as toothpastes which provide improved oral cleaning.
BACKGROUND OF THE INVENTION
Synthetically produced amorphous silicas play an important role as an ingredient in many of today's toothpaste formulations. In addition to their cleaning ability, they are also relatively safe, nontoxic, and compatible with other toothpaste ingredients, including glycerin, sorbitol (or xylitol), thickening agents, detergents coloring and fragrance materials and, optionally, fluoride containing compositions.
Synthetic precipitated silicas are prepared by admixing dilute alkali silicate solutions with strong aqueous mineral acids under conditions where aggregation to the sol and gel cannot occur, stirring and then filtering out the precipitated silica. The resulting precipitate is next washed, dried and comminuted to desired size.
Silica gels include silica hydrogels, hydrous gels, aerogels, and xerogels. Silica gels are also formed by reacting alkali silicate solutions with strong acids to form a hydrosol and aging the newly formed hydrosol to form the hydrogel. The hydrogel is then washed, dried and comminuted as described above.
When preparing synthetic silicas, the objective is to obtain silicas which provide maximal cleaning with minimal damage to oral tissue. Dental researchers are continually concerned with identifying precipitated silicas meeting these objectives.
Examples of precipitated silicas described in the art include U.S. Patent 4.122.161 to Wason, October 24, 1978, U.S. Patents 4.992.251 and 5.035.879 to Aldcroft et al., February 12, 1991 and July 30, 1991 respectively, U.S. Patent 5.098.695 to Newton et al., March 24, 1992, and U.S. Patent 5.279.815 to Wason et al., January 18, 1994. Similarly, silica gels have also been described in the art as demonstrated by U.S. Patent 4.303.641. December 1, 1981, to DeWolf, II et al., U.S. Patent 4.153.680. May 8, 1979, to Seybert, and U.S. Patent 3.538.230. November 3, 1970, to Pader et al..
Moreover, various combinations of silicas have been described in the art. Silica combinations involving compositions of differing particle sizes and specific surface areas are disclosed in U.S. Patent 3.577.521 to Karlheinz Scheller et al., May 4, 1971 and U.S. Patent 4.618.488 to Maeya a et al., October 21, 1986, respectively. Similarly, U.S. Patents 5.1 10.574 to Reinhardt et al., May 5, 1992 discloses combining precipitated thickener and polishing silicas to form silica compositions having oil absorption values of at least 200. Further examples of silica combinations include U.S. Patent 5.124.143 to Muhlemann, June 23, 1992 and U.S. Patent 4.632.826 to Ploger et al., December 30, 1986.
While the prior art discloses a variety of silica compositions useful as dental cleaning abrasives, there is still a need for additional compositions providing improved cleaning with minimal abrasion. The present inventor has discovered amorphous silica abrasive compositions comprising precipitated and gel silicas providing improved dental cleaning with minimal abrasion.
Accordingly, it is the object of the present invention to provide a precipitated silica and gel silica compositions providing improved pellicle cleaning without a corresponding increase in dentin or enamel abrasion. Another object of the present invention is to provide an improved method for the prevention or removal tooth stains. A further object of the present invention is to provide an improved method for the prevention or removal of plaque. These and other objects will become readily apparent from the disclosure which follows.
SUMMARY OF THE INVENTION The present invention relates to amorphous silica abrasive compositions, comprising: a.) a precipitated silica, comprising particles wherein said particles have: i.) a mean particle size of from about 5 to about 1 1 microns (s.d. < 9); ii.) an Einlehner hardness of from about 0.8 to about 2.5 for abrasive to brass screen and from about 5 to about 8 for abrasive to polyester screen, iii.) an oil absorption of from about 95 ml/ 100 gm to about 135 ml/ 100 gm; and iv.) a radioactive dentin abrasion of from about 25 to about 90; and b.) a gel silica, comprising particles wherein said particles have: i.) a mean particle size of from about 5 to about 1 1 microns (s.d. < 9); ii.) an Einlehner hardness of from about 3 to about 15 for abrasive to brass screen and from about 8 to about 20 for abrasive to polyester screen; iii.) an oil absorption of from about 60 ml 100 gm to about 130 ml/100 gm; and iv) a radioactive dentin abrasion of from about 80 to about 200 wherein at least about 70% of all of said particles have a diameter of below about 25 microns and wherein the pellicle cleaning ratio is from about 90 to about 135 and the radioactive dentin abrasion is from about 60 to about 100 with a pellicle cleaning ratio/radioactive dentin abrasion ratio of from about 1.20 to about 1.60 and wherein the ratio of precipitated silica to gel silica is from about 90: 10 to about 60:40, respectively.
All levels and ratios are by weight of the total composition, unless otherwise indicated. Additionally, all measurements are made at 25°C unless otherwise specified.
The pH of the present herein described compositions range from about 4 to about 9.5, with the preferred pH being from about 6.5 to about 9.0 and the most preferred pH being 7.0 to about 8.5, as measured in a 5% aqueous slurry. DETAILED DESCRIPTION OF THE INVENTION By "safe and effective amount," as used herein, means a sufficient amount to reduce stain and/or plaque/gingivitis without harming the tissues and structures of the oral cavity.
By the term "orally-acceptable carrier," as used herein, means a suitable vehicle which can be used to apply the present compositions to the oral cavity in a safe and effective manner.
The essential as well as optional components of the compositions of the present invention are described in the following paragraphs. Abrasive
The amorphous silicas used to form the precipitated silica and gel silica combinations of the present invention can be characterized as either Low Structure or Medium Structure silicas in accordance with the definitions set forth in the J. Soc Cosmet. Chem. 29., 497-521 (August, 1978), and Pigment Handbook: Volume 1, Properties and Economics, Second Edition, Edited by Peter A. Lewis, John Wiley & Sons, Inc., 1988, p. 139-159 and are preferably characterized as synthetic hydrated amorphous silicas, also known as silicon dioxides or SiO2. Further, these silicas may be characterized as having a BET surface area in the range of 50 to 250 m2/g. and as containing less than about 10%, more preferably less than about 5%, alumina
The amorphous silica combinations of the present invention may be characterized as having a median average particle size ranging from about 5 microns to about 11 microns with at least 70% of the particle size distribution being less than 20 microns. The average particle size (mean value and median or 50%) is measured using a Microtrac II apparatus, Leeds and Northrup. Specifically, a laser beam is projected through a transparent cell which contains a stream of moving particles suspended in a liquid. Light rays which strike the particles are scattered through angles which are inversely proportional to their sizes. The photodetector array measures the quantity of light at several predetermined angles. Electrical signals proportional to the measured light flux values are then processed by a microcomputer system to form a multi-channel histogram of the particle size distribution. The amorphous precipitated and gel silicas used to form the combinatory compositions of the present invention are further characterized by means of their respective Einlehner hardness values, Radioactive Dentin Abrasion (RDA) values and oil absorption values.
Einlehner hardness values are measured using an Einlehner At- 1000 Abrader to measure the softness of the silicas in the following manner: A Fourdrinier wire screen is weighed and exposed to the action of a 10% aqueous silica suspension for a certain length of time. The amount of abrasion is then determined as milligrams weight lost of the Fourdrinier wire screen per 100,000 revolutions. Brass Einlehner (BE) and Polyester Einlehner (PE) results are expressed in milligrams. The RDA values are determined according to the method set forth by
Hefferren, Journal of Dental Research, July-August 1976, pp. 563-573, and described in the Wason U.S. Patents 4.340.583. 4.420.312 and 4.421.527. which publication and patents are incorporated herein by reference.
The amorphous silica combinations are, preferably, characterized as having oil absorption values less than 200 cc/ 100 gm. Oil absorption values are measured using the ASTM rub-out method D281. Surface area is determined by the BET nitrogen adsorption method of Brunaur et al., J. Am. Chem. Soc, 60, 309 (1938). To measure brightness, fine powder materials that are pressed into a smooth surfaced pellet are evaluated using a Technidyne Brightimeter S-5/BC. This instrument has a dual beam optical system where the sample is illuminated at a angle of 45°, and the reflected light viewed at 0°. It conforms to TAPPI test methods T452 and T646, and ASTM Standard D985. A series of filters direct to reflected light of desired wavelengths to a photocell where it is converted to an output voltage. This signal is amplified and then processed by an internal microcomputer for display and printout. Precipitated silica suspensions are prepared in accordance with general methods described, for example, in prior U.S. Patents: 3,893,840. issued July 8, 1975, to Wason; 3.988.162. issued October 26, 1976, to Wason, 4.067.746. issued January 10, 1978, to Wason; and 4.340.583. issued July 29, 1982, to Wason; all of which are herein incorporated by reference, varying reaction parameters to form precipitated silicas having BE values in the range of from about 0.8 mg to about 2.5 mg and PE values in the range of about 5 mg to about 8 mg, an RDA ranging from about 25 to about 90, and an oil absorption of from about 95ml/100gm to about 135ml/100gm. Reaction parameters which affect the characteristics of the resultant silica include: the rate at which the various reactants are added; the levels of concentration of the various reactants; the reaction pH; the reaction temperature or the rate at which electrolytes are added. The formed suspension is subsequently filtered, followed by a washing and drying of the filtered precipitate. The resulting precipitated silica is next milled to a particle size in which 70% of the particle size distribution is below 20 microns.
In a separate process, gel silicas are prepared in accordance with general methods described, for example, in prior U.S. Patents: 4.153.680. to Seybert, issued May 8, 1979; 4.303.641. to DeWolf II et al., issued December 1,1981 and 4.632.826. to Ploger et al., issued December 30, 1986, varying reaction parameters to form gel silicas having BE values in the range of from about 3 mg to about 15 mg and PE values in the range of 8 mg to about 20 mg, an RDA ranging from about 80 to about 200, and an oil absorption of from about 130ml/100gm to about 60ml 100gm. Once formed, the gel silica is milled to a particle size in which 70% of the particle size distribution is below 20 microns.
The precipitated and gel silicas, next, are combined (e.g., by physical mixing) to form the amorphous silica compositions of the present invention. The resultant amorphous silica composition can then be incorporated into suitable dentifrice compositions.
In addition to the above described essential components, the dentifrice compositions of the present invention can contain a variety of optional dentifrice ingredients some of which are described below. Optional ingredients include, for example, but are not limited to, adhesives, sudsing agents, flavoring agents, sweetening agents, additional antiplaque agents, abrasives, and coloring agents. These and other optional components are further described in U.S. Patent 5.004.597. April 2, 1991 to Majeti; U.S. Patent 4.885.155. December 5, 1989 to Parran, Jr. et al.; U.S. Patent 3.959.458. May 25, 1976 to Agricola et al. and U.S. Patent 3,937.807. February 10, 1976 to Haefele, all being incorporated herein by reference.
The Pellicle Cleaning Ratio (PCR) of the inventive silica composition, which is a measurement of the cleaning characteristics of a dentifrice, ranges from 90 to 135 and preferably from 100 to 130 for the amorphous silica combination of the invention. The Radioactive Dentin Abrasion (RDA) of the inventive silicas, which is a measurement of the abrasiveness of the precipitated silica combination when incorporated into a dentifrice, ranges from 60 to 10, preferably from 80 to 90. The PCR (Pellicle Cleaning Ratio) cleaning values are determined by a slightly modified version of the PCR test described in "In Vitro Removal of Stain With Dentifrice", G. K. Stookey, T.A. Burkhard and B. R. Schemerhorn, J. Dental Research, 61, 1236-9, 1982. Cleaning is assessed in vitro by use of the modified pellicle cleaning ratio test. This test is identical to that described by Stookey et al. with the following modifications: (1) a clear artificial pellicle film is applied to bovine chips prior to application of the stained film, (2) solution heating is used rather than radiative heating during film application, (3) the number of brush strokes is reduced to 200 strokes and (4) the slurry concentration is 1 part dentifrice to 3 parts water.
The amorphous silica combinations of the present invention, when incorporated into a dentifrice composition further provide an improved PCR/RDA ratio. The PCR/RDA ratio is used to determine the relative ratio of cleaning and abrasion characteristics of a dentifrice formulation. Commercially available dentifrice formulations generally have a PCR/RDA ratio in the range of 0.5 to below 1.0. The amorphous silicas used in the compositions of the present invention provide PCR to RDA ratios to dentifrice formulations of greater than 1, usually in the range of 1.20 to 1.60, but more preferably in the range 1.25 to 1.50.
The abrasive, in the form of a precipitated silica and gel silica compositions of the present invention, when incorporated into the compositions described herein, is present at a level of from about 6% to about 70%, preferably from about 15% to about 35% when the dentifrice is a toothpaste. Higher levels, as high as 95%, may be used if the composition is a toothpowder.
OPTIONAL COMPONENTS Pharmaceutically Acceptable Carrier
The carrier for the components of the present compositions is optional and can be any dentifrice vehicle suitable for use in the oral cavity. Such carriers include the usual components of toothpastes, tooth powders, prophylaxis pastes, lozenges, gums and the like and are more fully described hereinafter. Toothpastes are the preferred systems. Surfactants: One of the preferred optional agents of the present invention is a surfactant, preferably one selected from the group consisting of sarcosinate surfactants, isethionate surfactants and taurate surfactants. Preferred for use herein are alkali metal or ammonium salts of these surfactants. Most preferred herein are the sodium and potassium salts of the following: lauroyl sarcosinate, myristoyl sarcosinate, palmitoyl sarcosinate, stearoyl sarcosinate and oleoyl sarcosinate.
This surfactant can be present in the compositions of the present invention from about 0.1% to about 2.5%, preferably from about 0.3% to about 2.5% and most preferably from about 0.5% to about 2.0% by weight of the total composition.
Other suitable compatible surfactants can optionally be used along with the sarcosinate surfactant in the compositions of the present invention. Suitable optional surfactants are described more fully in U.S. Patent 3.959.458. May 25, 1976 to Agricola et al. ; U.S. Patent 3.937.807. February 10, 1976 to Haefele; and U.S. Patent 4.051.234. September 27, 1988 to Gieske et al. These patents are incorporated herein by reference.
Preferred anionic surfactants useful herein include the water-soluble salts of al- kyl sulfates having from 10 to 18 carbon atoms in the alkyl radical and the water- soluble salts of sulfonated monoglycerides of fatty acids having from 10 to 18 carbon atoms. Sodium lauryl sulfate and sodium coconut monoglyceride sulfonates are examples of anionic surfactants of this type. Mixtures of anionic surfactants can also be utilized.
Preferred cationic surfactants useful in the present invention can be broadly defined as derivatives of aliphatic quaternary ammonium compounds having one long alkyl chain containing from about 8 to 18 carbon atoms such as lauryl trimethylam- monium chloride; cetyl pyridinium chloride; cetyl trimethylammonium bromide; di-is- obutylphenoxyethyl-dimethylbenzylammonium chloride; coconut alkyltrimethylam- monium nitrite; cetyl pyridinium fluoride; etc. Preferred compounds are the quater- nary ammonium fluorides described in U.S. Patent 3.535.421. October 20, 1970, to Briner et al., herein incorporated by reference, where said quaternary ammonium fluorides have detergent properties. Certain cationic surfactants can also act as germicides in the compositions disclosed herein. Cationic surfactants such as chlor- hexadine, although suitable for use in the current invention, are not preferred due to their capacity to stain the oral cavity's hard tissues. Persons skilled in the art are aware of this possibility and should incorporate cationic surfactants only with this limitation in mind.
Preferred nonionic surfactants that can be used in the compositions of the present invention can be broadly defined as compounds produced by the condensa- tion of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound which may be aliphatic or alkylaromatic in nature. Examples of suitable nonionic surfactants 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 diamiπe, ethylene oxide condensates of aliphatic alcohols, long chain tertiary amine oxides, long chain tertiary phosphine oxides, long chain dialkyl sulfoxides and mixtures of such materials. Preferred zwitterionic synthetic surfactants useful in the present invention can be broadly described as derivatives of aliphatic quaternary ammonium, phos- phomium, 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, sulfonate, sulfate, phosphate or phosphonate.
Preferred betaine surfactants are disclosed in U.S. Patent 5,180,577 to Polefka et al., issued January 19, 1993. Typical alkyl dimethyl betaines include decyl betaine or 2-(N-decyl-N,N-dimethylammonio) acetate, coco betaine or 2-(N-coc-N, N- dimethyl ammonio) acetate, myristyl betaine, palmityl betaine, lauryl betaine, cetyl betaine, cetyl betaine, stearyl betaine, etc. The amidobetaines are exemplified by cocoamidoethyl betaine, cocoamidopropyl betaine, lauramidopropyl betaine and the like. The betaines of choice are preferably the cocoamidopropyl betaine and, more preferably, the lauramido propyl betaine. Chelating agents: Another preferred optional agent is a chelating agent selected from the group consisting of tartaric acid and pharmaceutically-acceptable salts thereof, citric acid and alkali metal citrates and mixtures thereof. Chelating agents are able to complex calcium found in the cell walls of the bacteria. Chelating agents can also disrupt plaque by removing calcium from the calcium bridges which help hold this biomass intact. However, it is possible to use a chelating agent which has an affinity for calcium that is too high. This results in tooth demineralization and is contrary to the objects and intentions of the present invention.
Sodium and potassium citrate are the preferred alkali metal citrates, with sodium citrate being the most preferred. Also preferred is a citric acid/alkali metal citrate combination. Preferred herein are alkali metal salts of tartaric acid. Most preferred for use herein are disodium tartrate, dipotassium tartrate, sodium potassium tartrate, sodium hydrogen tartrate and potassium hydrogen tartrate. The amounts of chelating agent suitable for use in the present invention are about 0.1% to about 2.5%, preferably from about 0.5% to about 2.5% and more preferably from about 1.0% to about 2.5%. The tartaric acid salt chelating agent can be used alone or in combination with other optional chelating agents. Other optional chelating agents can be used. Preferably these chelating agents have a calcium binding constant of about 10 to 10 provide improved cleaning with reduced plaque and calculus formation.
Another group of agents suitable for use as chelating agents in the present invention are the soluble pyrophosphates. The pyrophosphate salts used in the present compositions can be any of the alkali metal pyrophosphate salts. Specific salts include tetra alkali metal pyrophosphate, dialkali metal diacid pyrophosphate, trialkali metal monoacid pyrophosphate and mixtures thereof, wherein the alkali metals are preferably sodium or potassium. The salts are useful in both their hy- drated and unhydrated forms. An effective amount of pyrophosphate salt useful in the present composition is generally enough to provide at least 1.0% pyrophosphate ion, preferably from about 1.5% to about 6%, more preferably from about 3.5% to about 6% of such ions. It is to be appreciated that the level of pyrophosphate ions is that capable of being provided to the composition (i.e., the theoretical amount at an appropriate pH) and that pyrophosphate forms other than P O -4 (e.g., (HP O -3)) may be present when a final product pH is established.
The pyrophosphate salts are described in more detail in Kirk & Othmer, Ency¬ clopedia of Chemical Technology. Second Edition, Volume 15, Interscience Publish¬ ers (1968), incorporated herein by reference. Still another possible group of chelating agents suitable for use in the present invention are the anionic polymeric polycarboxylates. Such materials are well known in the art, being employed in the form of their free acids or partially or preferably fully neutralized water soluble alkali metal (e.g. potassium and preferably sodium) or ammonium salts. Preferred are 1 :4 to 4: 1 copolymers of maleic anhydride or acid with another polymerizable ethylenically unsaturated monomer, preferably methyl vinyl ether (methoxyethylene) having a molecular weight (M.W.) of about 30,000 to about 1,000,000. These copolymers are available for example as Gantrez AN 139 (M.W. 500,000), AN 1 19 (M.W. 250,000) and preferably S-97 Pharmaceutical Grade (M.W. 70,000), of GAF Chemicals Corporation. Other operative polymeric polycarboxylates include those such as the 1: 1 copolymers of maleic anhydride with ethyl acrylate, hydroxyethyl methacrylate, N-vi- nyl-2-pyrollidone, or ethylene, the latter being available for example as Monsanto EMA No. 1103, M.W. 10,000 and EMA Grade 61, and 1 : 1 copolymers of acrylic acid with methyl or hydroxyethyl methacrylate, methyl or ethyl acrylate, isobutyl vinyl ether or N-vinyl-2-pyrrolidone.
Additional operative polymeric polycarboxylates are disclosed in U.S. Patent 4.138.477. February 6, 1979 to Gaffar and U S. Patent 4.183.914. January 15, 1980 to Gaffar et al. both patents are incorporated herein by reference, and include co¬ polymers of maleic anhydride with styrene, isobutylene or ethyl vinyl ether, poly- acrylic, polyitaconic and polymaleic acids, and sulfoacrylic oligomers of M.W. as low as 1,000 available as Uniroyal ND-2. Flavoring agents can also be added to dentifrice compositions. Suitable flavor¬ ing 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 aspartame, acesulfame, saccharin, dextrose, levulose and sodium cyclamate. Flavoring and sweetening agents are generally used in dentifrices at levels of from about 0.005% to about 2% by weight.
It is common to have a water-soluble fluoride compound present in dentifrices and other oral compositions in an amount sufficient to give a fluoride ion concentration in the composition at 25°C, and/or when it is used of from about 0.0025% to about 5.0% by weight, preferably from about 0.005% to about 2.0% by weight, to provide additional anticaries effectiveness. A wide variety of fluoride ion- yielding materials can be employed as sources of soluble fluoride in the present compositions. Examples of suitable fluoride ion-yielding materials are found in U.S. Patent No. 3.535.421. October 20, 1970 to Briner et al. and U.S. Patent No. 3.678.154. July 18, 1972 to Widder et al., both being incorporated herein by refer- ence. Representative fluoride ion sources include: stannous fluoride, sodium fluo¬ ride, potassium fluoride, sodium monofluorophosphate and many others. Stannous fluoride and sodium fluoride are particularly preferred, as well as mixtures thereof.
Water is also present in the toothpastes of this invention. Water employed in the preparation of commercially suitable toothpastes should preferably be deionized and free of organic impurities. Water generally comprises from about 10% to 50%, preferably from about 20% to 40%, by weight of the toothpaste compositions herein. These amounts of water include the free water which is added plus that which is introduced with other materials such as with sorbitol.
In preparing toothpastes, it is necessary to add some thickening material to provide a desirable consistency. Preferred thickening agents are carboxyvinyl polymers, carrageenan, hydroxethyl cellulose and water soluble salts of cellulose ethers such as sodium carboxymethyl cellulose and sodium carboxymethyl hy¬ droxethyl cellulose. Natural gums such as gum karaya, xanthan gun, gum arabic, and gum tragacanth can also be used. Thickening agents in an amount from 0.5% to 5.0% by weight of the total composition can be used. It is also desirable to include some humectant material in a toothpaste to keep it from hardening. Suitable humectants include glycerin, sorbitol, and other edible polyhydric alcohols at a level of from about 15% to about 70%.
Also desirable for inclusion in the compositions of the present invention are other stannous salts such as stannous pyrophosphate and stannous gluconate and antimicrobials such as quaternary ammonium salts, such as cetyl pyridinium chloride and tetradecylethyl pyridinium chloride, bis-biquanide salts, copper bisglycinate, nonionic anti microbial salts and flavor oils. Such agents are disclosed in U.S. Patent No. 2,946,725, July 26, 1960, to Norris et al. and U.S. Patent No. 4,051,234, September 27, 1977 to Gieske et al., incorporated herein by reference. Other optional components include buffering agents, bicarbonates, peroxides, nitrate salts such as sodium and potassium nitrate. These agents, if present, are included at levels of from about 0.01% to about 30%.
Other useful carriers include biphasic dentifrice formulations such as those disclosed in U.S. Patents 5,213,790, issued May 23, 1993, 5, 145,666, issued
September 8, 1992, and 5,281,410 issued January 25, 1994 all to Lukacovic et al. and in U. S. Patents 4,849,213 and 4,528, 180 to Schaeffer the disclosures of which are incorporated by reference herein.
Suitable lozenge and chewing gum components are disclosed in U.S. Patent No. 4,083,955, April 11, 1978 to Grabenstetter et al., incorporated herein by refer¬ ence.
EXAMPLES The following examples further describe and demonstrate preferred em¬ bodiments within the scope of the present invention. The examples are given solely for illustration, and are not to be construed as limitation of this invention as many variations thereof are possible without departing from its spirit and scope.
Example I A dentifrice composition of the present invention contains the following com¬ ponents as described below. Component Wgt %
Sorbitol 70% soln 24.200
RO Water 24.757
Glycerin 7.000
Carboxymethyl Cellulose1 0.500 PEG 6 4.000
Sodium Fluoride 0.243
Sodium Saccharine 0.130 Monosodium Phosphate 0.415
Trisodium Phosphate 0.395
Sodium Tartrate 1.000
TiO2 0.500 Silica2 35.000
Sodium Lauroyl Sarcosinate (95% active) 1.060
Flavor 0.800
Supplied by Aqualon Company. 2The amorphous silica ingredient possesses the following characteristics: APS Mean Value = 8.3 microns; oil absorption = 108cc/100g; BE = 2.6; PE = 9; PCR = 1 18; RDA = 80.
The jacket temperature of a mixing tank is set to about 150°F (65°C) to about 160°F (71°C). The humectants and water are added to the mixing tank and agitation is started. When the temperature reaches approximately 120°F (50°C) fluoride, sweetening agents, buffering agents, chelant, coloring agents and titanium dioxide are added. Thickening agents are added to the abrasive and the resulting mixture is added to the mixing tank with high agitation. The surfactant is added to the combination and mixing is continued. The tank is cooled to 120°F (50°C) and the flavoring agents are added. Mixing is continued for approximately 5 minutes. The resulting composition will have a pH of about 7.
Example II A dentifrice composition of the present invention contains the following com¬ ponents as described below.
Component Wgt % Sorbitol 70% soln 29.810
RO Water 24.757
Glycerin 7.000
Carboxymethyl Cellulose1 0.750
PEG 6 4.000 Sodium Fluoride 0.243
Sodium Saccharine 0.130
Monosodium Phosphate 0.415
Trisodium Phosphate 0.395
TiO2 0.500 Silica2 30.000
Sodium Lauryl Sulfate 1.200
Flavor 0.800 Supplied by Aqualon Company. The amorphous silica ingredient possesses the following characteristics: APS Mean Value = 8.3 microns; oil absorption = 108cc/100g; BE = 2.6; PE = 9; PCR = 118; RDA = 80. Example III
A gum composition of the present invention contains the following com¬ ponents as described below.
Component Weight %
Gum Base 30.000 30 parts Estergum
45 parts Coumorone Resin 15 parts Dry Latex Silica1 10.00
Sugar 40.000 Corn Syrup 18.175
Sodium Lauroyl Sarcosinate 0.075
Sodium Tartrate 0.250
Flavor 1.500
!The amorphous silica ingredient possesses the following characteristics: APS Mean Value = 8.2 microns; oil absorption = 106 cc/lOOg; BE = 3.3; PE = 10.

Claims

WHAT IS CLAIMED IS:
1. An amorphous silica abrasive composition, comprising: a.) a precipitated silica, comprising particles wherein said particles have: i.) a mean particle size of from 5 to 11 microns (s.d. < 9); ii.) an Einlehner hardness of from 0.8 to 2.5 for abrasive to brass screen and from 5 to 8 for abrasive to polyester screen; iii.) an oil absorption of from 95 ml 100 gm to 135 ml/100 gm; and iv.) a radioactive dentin abrasion of from 25 to 90; and b.) a gel silica, comprising particles wherein said particles have: i.) a mean particle size of from 5 to 11 microns (s.d. < 9); ii.) an Einlehner hardness of from 3 to 15 for abrasive to brass screen and from 8 to 20 for abrasive to polyester screen; iii.) an oil absorption of from 60 ml/100 gm to 130 ml/100 gm; and iv) a radioactive dentin abrasion of from 80 to 200 wherein at least 70% of all of said particles have a diameter of below 25 microns and wherein the pellicle cleaning ratio is from 90 to 135, preferably from 110 to 135, and the radioactive dentin abrasion is from 60 to 100, preferably from 65 to 85, with a pellicle cleaning ratio/radioactive dentin abrasion ratio of from 1.20 to 1.60, preferably 1.25 to 1.50, and wherein the ratio of precipitated silica to gel silica is from 90: 10 to 60:40, preferably 80:20 to 60:40, respectively.
2. An amorphous silica abrasive composition according to Claim 1, wherein the pellicle cleaning ratio is from 90 to 135, preferably 1 10 to 135, the radioactive enamel abrasion is from 2.5 to 5, preferably 2.5 to 3.5, and wherein the pellicle cleaning ratio/radioactive enamel abrasion ratio of said amorphous silica abrasive composition is greater than 30, preferably from 35 to 44.
3. A dentifrice composition, comprising:
A). from 0.1% to 99% of an amorphous silica abrasive composition, comprising- a.) a precipitated silica, comprising particles wherein said particles have, i.) a mean particle size of from 5 to 1 1 microns (s.d < 9), ii.) an Einlehner hardness of from 0.8 to 2.5 for abrasive to brass screen and from 5 to 8 for abrasive to polyester screen; iii.) an oil absorption of from 95 ml/100 gm to 135 ml/100 gm; and iv.) a radioactive dentin abrasion of from 25 to 90; and b.) a gel silica, comprising particles wherein said particles have: i.) a mean particle size of from 5 to 11 microns (s.d. < 9); ii.) an Einlehner hardness of from 3 to 15 for abrasive to brass screen and from 8 to 20 for abrasive to polyester screen; iii.) an oil absorption of from 130 ml/ 100 gm to 60 ml/ 100 gm; and iv) a radioactive dentin abrasion of from 80 to 200 wherein at least 70% of said particles have a diameter of below 25 microns and wherein the pellicle cleaning ratio is from 90 to 135 and the radioactive dentin abrasion is from 60 to 100 with a pellicle cleaning ratio/radioactive dentin abrasion ratio of from 1.20 to 1.60 and wherein the ratio of precipitated silica to gel silica is from 90: 10 to 60:40, respectively; and B). from 0.1% to 99% of an orally-acceptable dentifrice carrier.
4. A dentifrice composition according to any one of the preceding Claims, wherein said composition further comprises a fluoride ion source wherein the fluoride ion source is selected from the group consisting of sodium fluoride, stannous fluoride, sodium monofluorophosphate, potassium fluoride and mixtures thereof.
5. A dentifrice composition according to any one of the preceding Claims, further comprising a surfactant selected from the group consisting of sarcosinate surfactants, isethionate surfactants and taurate surfactants.
6. A dentifrice composition according to any one of the preceding Claims, further comprising from 0.1% to 2.5% of a chelating agent selected from the group consisting of tartaric acid and pharmaceutically-acceptable salts thereof, citric acid and alkali metal citrates and mixtures thereof.
7. A dentifrice composition according to any one of the preceding Claims, wherein said composition has a pH above 7 and wherein the surfactant is selected from the group consisting of sodium lauroyl sarcosinate, sodium decyl sarcosinate, sodium myristyl sarcosinate, sodium stearyl sarcosinate, sodium palmitoyl sarcosinate, sodium oleoyl sarcosinate and mixtures thereof.
8. A dentifrice composition according to any one of the preceding Claims, further comprising from 15% to 70% of a humectant selected from among the group consisting of glycerin, sorbitol, Propylene glycol and mixtures thereof.
9. A dentifrice composition according to any one of the preceding Claims, wherein the surfactant is a combination of sodium lauroyl, sarcosinate and cocoamidopropyl betaine and the chelating agent is a combination of tartaric acid and sodium tartrate.
10. A dentifrice composition according to any one of the preceding Claims, in the form of a toothpaste, tooth powder, prophylaxis paste, lozenge, gum, or oral gel.
PCT/US1996/005497 1995-05-02 1996-04-19 Dentifrice compositions WO1996034593A1 (en)

Priority Applications (9)

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AT96911814T ATE197894T1 (en) 1995-05-02 1996-04-19 DENTAL CARE PRODUCTS
EP96911814A EP0825847B1 (en) 1995-05-02 1996-04-19 Dentifrice compositions
JP8533336A JPH11504919A (en) 1995-05-02 1996-04-19 Toothpaste composition
AU54879/96A AU5487996A (en) 1995-05-02 1996-04-19 Dentifrice compositions
CA002220026A CA2220026C (en) 1995-05-02 1996-04-19 Dentifrice compositions
DE69611165T DE69611165T2 (en) 1995-05-02 1996-04-19 DENTAL CARE
MX9708433A MX9708433A (en) 1995-05-02 1996-04-19 Dentifrice compositions.
DK96911814T DK0825847T3 (en) 1995-05-02 1996-04-19 Dental Cleaning Preparations
GR20000402485T GR3034792T3 (en) 1995-05-02 2000-11-08 Dentifrice compositions

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WO2000059460A1 (en) * 1999-04-07 2000-10-12 W.R. Grace & Co.-Conn. Additives for desensitizing and remineralizing dentifrice compositions
WO2011106289A3 (en) * 2010-02-24 2012-01-12 J.M. Huber Corporation Continuous silica production process and silica product prepared from same
US8609068B2 (en) 2010-02-24 2013-12-17 J.M. Huber Corporation Continuous silica production process and silica product prepared from same
AU2011221218B2 (en) * 2010-02-24 2014-01-16 Evonik Operations Gmbh Continuous silica production process and silica product prepared from same
US8945517B2 (en) 2010-02-24 2015-02-03 J. M. Huber Corporation Continuous silica production process and silica product prepared from same
AU2013205147B2 (en) * 2010-02-24 2016-03-24 Evonik Operations Gmbh Continuous Silica Production Process And Silica Product Prepared From Same
US9327988B2 (en) 2010-02-24 2016-05-03 J.M. Huber Corporation Continuous silica production process and silica product prepared from same
US9617162B2 (en) 2010-02-24 2017-04-11 J.M. Huber Corporation Continuous silica production process and silica product prepared from same
EP3210592A1 (en) * 2010-02-24 2017-08-30 J.M. Huber Corporation Silica and dentifrice composition comprising the same
EP3210592B1 (en) 2010-02-24 2019-08-21 Evonik Degussa GmbH Silica and dentifrice composition comprising the same
US9028605B2 (en) 2011-02-25 2015-05-12 J.M. Huber Corporation Coating compositions comprising spheroid silica or silicate

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US5658553A (en) 1997-08-19
EP0825847A1 (en) 1998-03-04
DE69611165T2 (en) 2001-07-19
PT825847E (en) 2001-04-30
DE69611165D1 (en) 2001-01-11
CA2220026A1 (en) 1996-11-07
JPH11504919A (en) 1999-05-11
CA2220026C (en) 2001-09-11
CO4750635A1 (en) 1999-03-31
PE3598A1 (en) 1998-03-27
ES2152520T3 (en) 2001-02-01
EP0825847B1 (en) 2000-12-06
ATE197894T1 (en) 2000-12-15
AU5487996A (en) 1996-11-21
DK0825847T3 (en) 2000-12-27
GR3034792T3 (en) 2001-02-28
MX9708433A (en) 1998-02-28

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