AU712266B2

AU712266B2 - Oral care ultramulsion based products

Info

Publication number: AU712266B2
Application number: AU59787/96A
Authority: AU
Inventors: Dale G. Brown; Ira D. Hill; Peter P. Walters
Original assignee: WhiteHill Oral Technologies Inc
Current assignee: WhiteHill Oral Technologies Inc
Priority date: 1995-06-05
Filing date: 1996-06-04
Publication date: 1999-11-04
Anticipated expiration: 2016-06-04
Also published as: BR9608343A; CN1190342A; EP0831762A4; AU5978796A; WO1996039116A1; EP0831762A1; MX9709735A; MXPA02005771A; CA2222407A1; JPH11506769A

Description

ORAL CARE ULTRAMULSION BASED PRODUCTS SUMMARY OF THE INVENTION The present invention is directed to oral care ULTRAMULSION based oral care products, including, toothpastes, treated flosses and dental stimulators, interdental coating substances, oral rinses, mouth/throat conditioning internal treatment products, and anti-gingivitis products. All of these products are improved when an ULTRAMULSION m dispersion containing silicone and a surfactant is used as taught herein. ULTRAMULSION is a trademark of WhiteHill Oral Technologies.

The ULTRAMULSION™ dispersions of the present invention combine certain characteristics of emulsions with certain features of microemulsions. Like conventional emulsions, they are two phase systems comprising a silicone dispersed in a continuous, surfactant phase, wherein the silicone is insoluble in the surfactant. Unlike conventional emulsions, but like microemulsions, these dispersions are stable. Unlike microemulsions, but like conventional emulsions, mechanical work is required to form ULTRAMULSION dispersions. Unlike microemulsions, but like conventional emulsions, these ULTRAMULSION dispersion are not formed spontaneously. Like conventional emulsions, the ULTRAMULSION™ dispersions do not contain a cosolvent commonly found in microemulsions. Of course, the ULTRAMULSION" dispersions of the present invention can be easily dispersed in various liquids such as water to obtain stable dispersions. These dispersions of ULTRAMULSION™ dispersions in water have excellent utility in various non-oral care products.

Thus the invention provides an oral care product selected from the group consisting of rinses, sprays, gels, creams, toothpastes, tooth powders, dental floss, interproximal simulators, mints and chewing gum, wherein said product contains an aqueousfree dispersion of a silicone in a surfactant wherein: the silicone is insoluble in said surfactant, has a viscosity up to about 50 million cs, and a particle size up to about 10 microns; the surfactant to silicone ratio in the dispersion is from between about 400:1 and about 1:1; and the surfactant has an orienting effect on 01/09/99, mp9556.speci,l lathe silicone; the dispersion forms stable dispersions in aqueous containing oral care products; and said oral care product exhibits enhanced substantivity to surfaces in the oral cavity while the dispersed silicone phase of said dispersion functions as a reservoir for various lipid soluble and lipid dispersible oral care active ingredients.

For the purposes of the present invention: a) "stable" is defined as follows; a dispersion of the ULTRAMULSION' dispersion in water when subjected to centrifuging in a 100 G environment for 5 minutes, less than about 10% by weight of the ULTRAMULSION™ dispersion separates from the continuous water phase and/or a substantial portion of the dispersed phase resists separation. This latter definition is particularly applicable *0 ye o °i 01/09/99, mp9556.speci,1

-L

WO 96/39116 PCT/US96/08714 -2to higher viscosity silicones.

b. "water-free" means that the ULTRAMULSIONT dispersion of silicone and surfactant is substantially free from water.

c. "solvent free" means that the ULTRAMULSIONT dispersion of silicone and surfactant is substantially free from co-solvents such as ethanol, isopropanol, and the like.

d. "oriented" means that the polar moieties of the "uncoiled" polydimethylsiloxane in the ULTRAMULSIONTM dispersion are generally aligned in one plane with the hydrophilic oil seeking moieties aligned in a second plane such as illustrated in Fig. 2.

e. "monolayer" means that the monomolecular film of the ULTRAMULSION T M dispersion of the present invention when dispersed in water is attracted to teeth and mouth surfaces by secondary bonding force to form a substantve coating thereon.

As described above, one preferred embodiment of the present invention relates to various oral care products containing stable dispersions of certain high viscosity silicones in certain surfactants; wherein: a. the dispersed silicones, which are insoluble in said surfactant, are oriented by the surfactant such that when dispersed in water they are particularly adept at forming oriented coatings on teeth and mouth surfaces with enhanced substantivity, and b. the particle size of the dispersed silicone is from between about 0.1 and about microns, with a particle size distribution such that from between about 80 and of the dispersed silicone is within this particle size range. In certain embodiments, between 80-95% of two dispersed silicones is less than 1 2 microns in particle size.

These stable dispersions are described as ULTRAMULSIONTM dispersions, which, together with their physical properties, when contained in oral care products, provide these oral care products with distinctive conditioning, moisturizing, protecting, etc.

properties where the non continuous silicone phase functions as a reservoir for various oral care treatment substances.

The present invention relates to various oral care rinses containing, stable, dispersions of certain high viscosity silicones in certain surfactants; wherein: a. the dispersed silicones, which are insoluble in said surfactant, are oriented by the surfactant such that when dispersed in water they are particularly adept at forming WO 96/39116 PCTIUS96/08714 -3oriented, coatings on surfaces of the mouth with enhanced substantivity, and b. the particle size of the dispersed silicone is from between about 0.1 and about microns, with a particle size distribution such that from between about 80 and of the dispersed silicone is within this particle size range. These stable dispersions are described as ULTRAMULSIONT dispersions, which, together with their physical properties, when contained in oral care rinses, provide these rinses with enhanced substantivity to mouth surfaces, where the non continuous silicone phase functions as a reservoir for various active ingredients contained therein, including but not limited to an essential mixture of thymol, eucalyptol, menthol and methyl salicylate.

The present invention relates to unique interdental delivery devices, other than dental floss, which are suitable for cleaning, massaging, and/or treating surfaces of teeth and gums including interproximal and subgingival areas; wherein these devices contain ULTRAMULSION T dispersions of high viscosity silicones dispersed in surfactants, these dispersions are released into the oral cavity from these devices during use wherein the dispersed silicone: a. is insoluble in the surfactant and oriented so as to form coatings in the oral cavity with enhanced substantivity, b. functions as a reservoir for various lipid soluble and/or liquid dispersible ingredients to be released onto oral cavity surfaces, and c. has a particle size from between about 0.1 and about 10 microns with from between about 80% and about 95% of the particles within this range.

The present invention relates to various oral care products containing stable, dispersions of certain high viscosity silicones in certain surfactants for use in treating mucus containing surfaces such as in the mouth, throat and stomach and intestine and the surface of the esophagus which contains no mucus.

a. the dispersed silicones, which are insoluble in said surfactant, are oriented by the surfactant such that when dispersed in water they are particularly adept at forming oriented coatings on mouth, throat and esophagus and stomach surfaces with enhanced substantivity, and b. the particle size of the dispersed silicone is from between about 0.1 and about microns, with a particle size distribution such that from substantially all of the dispersed silicone is within this particle size range. These stable dispersions are WO 96/39116 PCT/US96/08714 -4described as ULTRAMULSIONTM dispersions, which, together with their physical properties, when contained in mouth, throat, esophagus, stomach and intestine treatment properties, when contained in products, provide these products with substantive coating protection properties where the discontinuous silicone phase of said coating functions as a reservoir for various liquid suitable treatment substances, suitable for release onto the surface being treated.

The present invention relates to various toothpastes containing, stable, dispersions of certain high viscosity silicones in certain surfactants; wherein: a. the dispersed silicones, which contain triclosan, 2,4,4'-triclosan-2'hydroxy/epoxy/ether, are insoluble in said surfactant, are oriented by the surfactant such that when dispersed in water they are particularly adept at forming oriented, nonhelical coatings on surfaces of the mouth with enhanced substantivity, and b. the particle size of the dispersed silicone is from between about 0.1 and about microns, with a particle size distribution such that from between about 80 and of the dispersed silicone is within this particle size range. These stable dispersions are described as ULTRAMULSIONM dispersions, which, together with their physical properties, when contained in toothpastes, provide the toothpaste with enhanced with enhanced substantivity to mouth surfaces, where the non continuous silicone phase functions as a reservoir for the triclosan contained therein.

The present invention relates to various oral care products containing, stable, dispersions of certain high viscosity silicones in certain surfactants; wherein: a. the dispersed silicones, which are insoluble in said surfactant, are oriented by the surfactant such that when dispersed in water they are particularly adept at forming oriented, coatings on surfaces of the mouth with enhanced substantivity, and b. the particle size of the dispersed silicone is from between about 0.1 and about microns, with a particle size distribution such that from between about 80 and of the dispersed silicone is within this particle size range. These stable dispersions are described as ULTRAMULSIONS, which, together with their physical properties, when contained in oral care products, provide these oral care products with enhanced substantivity to mouth surfaces, where the non continuous silicone phase functions as a reservoir for various active ingredients contained therein.

WO 96/39116 PCT/US96/08714 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 illustrates the "coiled" molecular configuration proposed for polydimethylsiloxanes.

Fig. 2 illustrates the proposed molecular configuration of oriented polydimethylsiloxanes after ULTRAMULSIONTM dispersion processing; Fig. 3 illustrates schematically an ULTRAMULSIONM dispersion process of the present invention; and Figs. 4 and 5 illustrate that the ULTRAMULSIONT dispersions of the present invention produced via various high shear dispersing means having particle size distribution of 80+ under 10 microns.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring to the drawings, Fig. 1 illustrates the accepted "coiled" configuration advanced for polydimethylsiloxanes, wherein the methyl moieties are oriented outwardly while the oxygen moieties are oriented inwardly toward the axis of the coil or helix. This configuration does not readily promote, bonding between the oxygen moieties and compatible surfaces such as tooth enamel.

Fig. 2 illustrates the "uncoiled oriented" configuration proposed for polydimethylsiloxanes that have been dispersed in the stable, ULTRAMULSIONM dispersions of the present invention, wherein the oxygen moieties are generally oriented in one plane distinct from that of the methyl moieties. This proposed uncoiled oriented configuration appears to support the unique and unexpected stability, bonding and enhanced substantivity properties of the ULTRAMULSIONTM dispersions of the present invention, as evidenced by the various coating applications of these ULTRAMULSIONTM dispersions to teeth. See the Examples provided below.

Fig. 3 illustrates the ULTRAMULSIONTM dispersion process of the present invention wherein a nonionic surfactant and a polydimethyl-siloxane 1, substantially free from water and co-solvent, are mixed in vessel 2, provided with mixing means 3, heat source 4, and inert head space 5. The heated and mixed surfactant-poly- WO 96/39116 PCT/US96/08714 -6dimethylsiloxane 6, is then subjected to high shear dispersion at an elevated temperature in dispersing means 7, to produce the ULTRAMULSIONT r dispersion 8, of the present invention. The high shear dispersion device is typically selected from among devices manufactured by Ross, IKA Works, etc. Other energy sources such as flow-through ultrasonic cells may be used as well.

Fig. 4 is a chart describing the particle size distribution of an ULTRAMULSIONTM dispersion of the present invention containing from about 50 to by weight nonionic surfactant and from about 5 to 50% by weight polydimethylsiloxane (2.5 million cs) produced in a continuous process with an IKA Works dispersing means, (high shear dispersing) with an inlet temperature of 1400 C and an outlet temperature of 2100 C.

Fig. 5 is a chart describing the particle size distribution of an

ULTRAMULSION

T M dispersion of the present invention containing from about 50 to by weight nonionic surfactant and from about 5 to 50% by weight polydimethylsiloxane (2.5 million cs) produced in a batch process with a Ross M/E 100 LC dispersing means fitted with a 20 mesh screen, operated at a temperature from about 120° to 160 0

C.

For purposes of the present invention, the term silicone means a clear, colorless substance containing polydialkylsiloxane polymers with average kinematic viscosities ranging from about 100,000 centistokes (cs) to about 50 million cs, preferably from about 1 million .cs to about 25 million cs, more preferably from about 1.5 million cs to about 10 million cs, and most preferably from about 2 million to about 5 million cs. This definition intentionally includes the so-called "gum" silicones having viscosities of 30 to 50 million cs. Certain high viscosity polydimethylsiloxanes having viscosities from about 2.5 million cs to about 4 million cs are particularly preferred for the oral care products of the present invention. Other polydimethylsiloxanes suitable for the present invention include "substituted" water insoluble silicones and mixtures of polydiorganosiloxanes and substituted water insoluble silicones. Specifically, water soluble silicones are excluded from the

ULTRAMULSION

T M dispersions of the present invention. See also Tables 1 and 2 below.

The viscosity of some silicones can be measured by means of a glass capillary WO 96/39116 PCT/US96/0714 -7viscometer as set forth in Dow Coming Corporate Test Method CTM0004, July 1970.

The silicone may be either a high viscosity polyalkyl siloxane as described in detail below, a polyaryl siloxane, a polyalkylaryl siloxane or a polyether siloxane copolymer. Mixtures of these silicones may also be used and are preferred in certain embodiments of the present invention.

The polyalkylaryl siloxanes that may be used include, for example, polymethylphenylsiloxanes having viscosities above 1 million centistokes at Some of these siloxanes are available, for example, from the General Electric Company, from Dow Coming, and/or from Rhone-Poulenc.

The polyether siloxane copolymer that may be used is, for example, a polypropylene oxide modified dimethylpolysiloxane although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used.

References disclosing suitable silicone fluids include U.S. Patent No. 2,826,551 to Green; U.S. Patent No. 3,964,500 to Drakoff; U.S. Patent No. 4,364,837 to Padner and British Patent No. 849,433 to Woolston. See also, Silicon Compounds distributed by Petrarch Systems, Inc., 1984. This reference provides a very good listing of suitable silicone materials.

Silicone materials found especially useful in the present compositions to provide good dry combing are silicone gums. Silicone gums described by Petrarch and others including U.S. Patent No. 4,152,416, May 1, 1979 to Spitzer et al., and Noll, Walter, "Chemistry and Technology of Silicones," Academic Press, New York (1968). Also describing silicone gums are various General Electric Silicone Rubber Product Data Sheets. "Silicone gum" materials denote high molecular weight polydiorganosiloxanes having a viscosity up to about 50,000,000 cs. Specific examples include polydimethylsiloxane; polydimethylsiloxane; methylvinylsiloxane copolymer; polydimethylsiloxane; diphenylmethvinylsiloxane copolymer and mixtures thereof.

As noted above high viscosity polydimethylsiloxanes those above 100,000 cs are preferred in this invention. Particularly preferred are polydimethylsiloxanes having viscosities ranging from between about 2.5 million cs and about 50 million cs.

The safety of polydimethylsiloxanes for use in these various products is well documented. See Rowe et al., Journal of Industrial Hygiene, 30(6): 332-352 (1948).

WO 96/39116 PCT/US96/08714 -8- See also Calandra et al., ACS Polymer Preprints, 17: 1-4 (1976) and Kennedy et al., J. Toxicol. Environmental Health, 1: 909-920 (1976).

As noted above, the preferred polydimethylsiloxanes useful in the oral care compositions of the present invention are described as polymethylsiloxanes with the chemical composition

(CH

3 3 SiO[SiO(CH 3 2 ],Si(CH 3 3 wherein n is a whole number. These polydimethylsiloxanes have viscosities ranging up to about 50 million cs., and are generally described as having high molecular weight.

The particle size of the silicone in the ULTRAMULSIONTM dispersions of the present invention can range from between about 0.1 and about 10 microns. In a preferred embodiment of the present invention the particle size of polydimethylsiloxanes in the ULTRAMULSIONTM dispersion ranges from below 1 up to about microns. The particle size distribution of the polydimethylsiloxanes in the ULTRAMULSIONTM dispersions of the present invention generally range from between about 80% and about 95% of the particles under 10 microns. See especially Figs. 4 and 5. In a preferred embodiment of the present invention, from between about 80% and about 95% of the particles are under 5 microns. See also Table 2.

An essential component of the ULTRAMULSIONTM dispersion of the present invention is a surfactant. The surfactant, may be selected from any of a wide variety of synthetic anionic, amphoteric, zwitterionic and nonionic surfactants. The surfactants suitable for the purposes of the present invention must function as the continuous phase and contain the discontinuous silicone phase.

Synthetic anionic surfactants can be exemplified by the alkali metal salts of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from 8-22 carbon atoms and a sulfonic acid or sulfuric acid ester radical (NOTE: included in the term alkyl is the alkyl portion of higher acyl radicals).

Preferred are the sodium, ammonium, potassium or triethanolamine alkyl sulfates, especially those obtained by sulfating the higher alcohols carbon atoms), sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of 1 mole of a higher fatty alcohol tallow or coconut oil alcohols) and 1 to 12 moles of ethylene oxide WO 96/39116 PCT/US96/08714 -9ether sulfate with 1 to 10 units of ethylene oxide per molecule and in which the alkyl radicals contain from 8 to 12 carbon atoms, sodium alkyl glyceryl ether sulfonates; the reaction product of fatty acids having from 10 to 22 carbon atoms esterified with isethionic acid and neutralized with sodium hydroxide; water soluble salts of condensation products of fatty acids with sarcosine; and others known in the art.

Zwitterionic surfactants can be exemplified by those which 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, carboxyl, sulfonate, sulfate, phosphate, or phosphonate. A general formula for these compounds is: (R)x

R

2 -CH -R 4

Z

wherein R 2 contains an alkyl, alkenyl, or hydroxyl alkyl radical of from about 8 to 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety; Y is selected from the group consisting of nitrogen, phosphorous, and sulfur atoms; R 3 is an alkyl or monohydroxyalkyl group containing 1 to about 3 carbon atoms; x is 1 when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorous atom; R 4 is an alkylene or hydroxyalkylene of from I to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups. Examples include; 4-[N,N-di(2-hydroxyethyl)-Noctadecylammonio]-butane-1 -carboxylate; 5-(S-3-hydroxypropyl-Shexadecylsulfonio]-3-hydroxypentane- 1-sulfate; 3-[P,P-diethyl-P-3,6,9trioxatetradecocylphosphonio]-2-hydroxypropane-1 -phosphate; 3-[N,N-dipropyl-N-3dodecoxy-2-hydroxypropylammonio]-propane-1 -phosphate; 3-[N,N-dimethyl-Nhexadecylammonio-propane-1-sulfonate; 4-[N,N-di(2-hydroxyethyl)-N-(2hydroxydodecyl)ammonio]-butane- -carboxylate; 3-[S-ethyl-S-(3-dodecoxy-2hydroxypropyl)sulfonio]-propane-1 -phosphate; 3-[P,P-dimethyl-P-dodecylphosphonio]-propane-l-phosphonate; and 5-(N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxypentane- 1-sulfate.

WO 96/39116 PCTIUS96/08714 Other zwitterionics such as betaines are also useful in the present invention.

Examples of betaines useful herein include the higher alkyl betaines such as cocodimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha-carboxyethylene betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl)carboxy methyl betaine, stearyl carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl bis-(2hydroxypropyl)alpha-carboxyethyl betaine, etc. The sulfobetaines may be represented by cocodimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxy-ethyl)sulfopropyl betaine and the like; amido betaines and amidosulfo betaines, wherein the RCONH(CH 2 3 radical is attached to the nitrogen atom of the betaine are also useful in this invention. The amido betaines are preferred for use in some of the compositions of this invention. A particularly preferred composition utilizes an amido betaine, a quaternary compound, a silicone, a suspending agent and has a pH of from about 2 to about 4.

Examples of amphoteric surfactants which can be used in the ULTRAMULSIONTM dispersions of the present invention are those which can be broadly described as derivatives of aliphatic secondary and tertiary amine 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, carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples of compounds falling within this definition are sodium 3dodecylamino-propionate, sodium 3-dodecylamino-propane sulfonate, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teachings of U.S. Patent No. 2,658,072, N-higher alkyl aspartic acids such as those produced according to the teachings of U.S. Patent No. 2,438,091, and the products sold under the trade name "Miranol" and described in U.S. Patent No.

2,528,378.

Nonionic surfactants, which are preferably used in combination with an anionic, amphoteric or zwitterionic surfactant, 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.

Examples of preferred classes of nonionic surfactants are: WO 96/39116 PCTIUS96/08714 11 1. The polyethylene oxide condensates of alkyl phenols, the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 10 to 60 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived from polymerized propylene, disobutylene, octane, or nonane, for example.

2. Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine products which may be varied in composition depending upon the balance between the hydrophobic and hydrophilic elements which is desired. For example, compounds containing from about 40% to about 80% polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 15,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of 2,500 to 3,000 are satisfactory.

3. The condensation product of aliphatic alcohols having from 8 to 18 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, a coconut alcohol ethylene oxide condensate having from 10 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.

4. Long chain tertiary amine oxides corresponding to the following general formula:

R,

R

3 N O

R

2 wherein R, contains an alkyl, alkenyl or monohydroxy alkyl radical of from about 8 to about 18 carbon atoms from 0 to about 10 ethylene oxide moieties, and from 0 to 1 glyceryl moiety, and R2 and R, contains from 1 to about 3 carbon atoms and from 0 to about 1 hydroxy group, methyl, ethyl, propyl, hydroxy ethyl, or hydroxypropyl radicals. The arrow in the formula is a conventional representation of a semipolar bond. Example of amine oxides suitable for use in this invention include dimethyl-dodecylamine oxide, oleyldi(2-hydroxy-ethyl)amine oxide, WO 96/39116 PCTIUS96/08714 12dimethyloctylamine oxide, dimethyl-decylamine oxide, dimethyltetradecylamine oxide.

3,6,9-trioxaheptadecyl-diethylamine oxide, di(2-hydroxyethyl)-tetracylamine oxide, 2dodecoxyethyldimethylamine oxide, 3-dodecoxy-2-hydroxypropyldi-(3-hydroxypropyl)amine oxide, dimethylhexadecylamine oxide.

5. Long chain tertiary phosphine oxides corresponding to the following general formula:

R

P O

R"

wherein R contains an alkyl, alkenyl or monohydroxyalkyl radical ranging from 8 to 18 carbon atoms in chain length from 0 to about 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety and R' and R" are each alkyl or monohydroxyalkyl groups containing from I to 3 carbon atoms. The arrow in the formula is again the conventional representation of a semipolar bond. Examples of suitable phosphine oxides are: dodecyldimethylphosphine oxide, tetradecyl-dimethyl-phosphine oxide, tetradecyl-methylethylphosphine oxide. 3,6,9-trioxaocta-decyldimethylphosphine oxide, cetyldimethylphosphine oxide, 3-dodecoxy-2-hydroxypropyl-di(2-hydroxyl)phosphine oxide, stearyldimethylphosphine oxide, cetylethylpropylphosphine oxide, cetyldiethylphosphine oxide, dodecyl-diethylphosphine oxide, tetradecyldiethylphosphine oxide, dodecyldipropylphosphine oxide, dodecyldi(2hydroxyethyl)phosphine oxide, tetradecyl-methyl-2-hydroxydodecyldimethylphosphine oxide.

6. Long chain dialkyl sulfoxides containing one short chain alkyl or hydroxy alkyl radical of 1 to about 3 carbon atoms (usually methyl) and one long hydrophosphinic chain which contain alkyl, alkenyl, hydroxyalkyl, or keto alkyl radicals containing from about 8 to about 20 carbon atoms, from 0 to about ethylene oxide moieties and from 0 to 1 glyceryl moiety. Examples include octadecyl menthyl sulfoxide, 2-ketotridecyl methyl sulfoxide, 3,6,9,-trioxooctadecyl 2hydroxyethyl sulfoxide, dodecyl menthyl sulfoxide, oleyl 3-hydroxypropyl sulfoxide, tetradecyl menthyl sulfoxide, 3-methoxytridecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxy-butyl methyl sulfoxide.

Many additional nonsoap surfactants are described in McCUTCHEON'S, WO 96/39116 PCT/US96/08714 13- DETERGENTS AND EMULSIFIERS, 1979 ANNUAL, published by Allured Publishing Corporation. Particularly preferred nonionic surfactants are nonionic poloxamer surfactants of block copolymers of ethylene oxide and propylene oxide ranging from flowable liquids of varying viscosities, to paste, prills and cast solids with molecular weights from 1,100 to 150,000. Suitable nonionic surfactants are manufactured and marketed by BASF Corporation under the trademarks Pluronic.

Particularly preferred nonionic surfactants are Pluronic F-68, F-88, F-108 and Pluronic F-127. These are described in a BASF brochure entitled "Pluronic and Tetronic Block Copolymer Surfactant." These nonionic surfactants suitable for the present invention can be described by the following structure:

CH

3

I

OH-(CH

2

(CH

2 CHO), (CHCHO)x. H where x, y and x' are whole numbers. Surprisingly, the nonionic surfactants of choice for the ULTRAMULSIONTM dispersions of the present invention are reported in the referenced brochure to have marginal detergency, emulsification and wetting properties.

As noted above, the preferred nonionic poloxamer surfactants useful in the coating compositions of the present invention are described as polyoxyethylenepolyoxypropylene block copolymers such as Pluronic F-68, F-88, F-108 and F-127 (BASF) which have molecular weights of at least about 1000 such as those described in U.S. Patent Nos. 4,343,785, 4,465,663, 4,511,563 and 4,476,107.

Emulsions of various coating substances including polydimethylsiloxanes in various surfactants including nonionic surfactants are disclosed and claimed in U.S.

Patents 4,911,927, 4,942,034; 4,950,479; 5,009,881; 5,032,387; 5,057,306; 5,057,307; 5,057,308, 5,057,309; 5,057,310, 5,098,711, 5,165,913 and 5,284,648. There is however, no teaching or suggestion in these references that these high viscosity silicone emulsions are stable nor that the "coating" substances are oriented as they are in the ULTRAMULSIONTM dispersions of the present invention.

The ratio of surfactant to silicone in the ULTRAMULSIONTM dispersion coating compositions of the present invention can range from between about 400:1 and about WO 96/39116 PCT/US96/08714 14- 1:2. In a preferred embodiment of the invention the ratio of surfactant to silicone is from between about 25:1 and 1:2.

The ULTRAMULSIONT dispersions of the present invention may be prepared as follows; generally, if not a liquid, the surfactant is first heated to a temperature at which it becomes a liquid. The silicone is then dispersed in the heated surfactant with various high shear dispersing means.

In one preferred method, the heated surfactant is mechanically stirred along with the silicone, to form a pre-emulsion mixture in which the silicone is uniformly dispersed in the surfactant in droplets of a larger size than desired for the ULTRAMULSION dispersions but small enough to optimize the subsequent high shear dispersions. This mixture is subjected to high-shear dispersions with a means such as the IKA-WORKS DISPAX-Reactor with at least one superfine generator, alternatively, a Ross Model 100 LC fitted with a 20 mesh screen or a ultrasonicator such as MEDSONIC XL2010 fitted with 800-C Flow Cell 800-21CT 3/4 inch flanged horn can be used.

The discontinuous silicone phase of the ULTRAMULSIONT dispersion can also contain a wide range of lipid soluble and/or lipid dispersible oral care active ingredients ranging from antimicrobials to desensitizing/substances, to healants such as aloe to vitamins such as vitamin E, to flavorants, etc. These various ingredients in the silicone phase of the ULTRAMULSIONT dispersion perform in various oral care products as though they are contained in a "reservoir" as they continue to be available at the ULTRAMULSIONTM dispersion oral surface interface, as long as the ULTRAMULSIONTM dispersion coating remains substantive to mouth surfaces.

The various toothpastes of the present invention can be made by mixing the materials together and heating if necessary and following accepted manufacturing practices for these various products as described in detail below. In addition, other toothpastes are included in the present invention including whitening toothpastes, toothpastes for treating hyposensitivity, toothpastes for dry mouth sufferer, toothpastes for patients undergoing radiation therapy, etc.

The oral care products containing the ULTRAMULSIONT M dispersions of the present invention will contain a variety of essential components ranging from surfactants and abrasives for cleaning, to whiteners, to gelling aids to flavorants etc.

WO 96/39116 PCT/US96/08714 These are detailed in various Examples described below.

In addition to the foregoing, other oral care products are included in the present invention, such as chewing gums, prophylactic pastes and denture wearer products to treat stomatitis. While also in the latter the ULTRAMULSIONTM dispersion provides the base functioning as a carrier for specific active ingredients such as Candida yeast sp. antifungal agents such as stannous fluoride.

In addition the oral care products of this invention can contain a variety of nonessential optional components suitable for rendering such compositions more acceptable. Such conventional optional ingredients are well known to those skilled in the art, preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidiazolidinyl urea; cationic surfactants such as cetyl trimethylammonium chloride, lauryl trimethyl ammonium chloride, tricetyl methyl ammonium chloride, stearyldimethyl benzyl ammonium chloride, and di(partially hydrogenated tallow)dimethylammonium chloride; thickeners and viscosity modifiers such as diethanolamide of a long chain fatty acid PEG 3 lauramide), block polymers of ethylene oxide and propylene oxide such as Pluronic F88 offered by BASF Wyandotte, sodium chloride, sodium sulfate, polyvinyl alcohol, and ethyl alcohol; pH adjusting agents such as citric acid, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate, etc., perfumes; dyes; and, sequestering agents such as disodium ethylenediamine tetraacetate. Such agents generally are used individually at a level of from about 0.01% to about 10%, preferably from about 0.5% to about 5.0% by weight of the composition.

The discontinuous silicone phase of the ULTRAMULSIONTM dispersion based toothpastes can also contain a wide range of lipid soluble and/or lipid dispersible oral care ingredients ranging from antimicrobials to desensitizing/substances, to healants such as aloe to vitamins such as vitamin E, to flavorants, etc. These various ingredients in the silicone phase of the ULTRAMULSION T M dispersion based toothpastes of the present invention perform similar to the triclosan, as though they are contained in a "reservoir". These various lipid soluble substances in the silicone phase continue to be available at the ULTRAMULSIONT m dispersion oral surface interface as long as the ULTRAMULSION T dispersion coating remains substantive to mouth surfaces. Effects attributed to this "reservoir" are described by WO 96/39116 PCT/US96/0714 16- ROlla et al., supra.

The toothpastes containing the ULTRAMULSIONTM and triclosan dispersions of the present invention will contain a variety of essential components ranging from surfactants and abrasives for cleaning, to whiteners, to gelling aids to flavorants etc.

In addition the toothpaste products of the invention can contain a variety of nonessential optional components suitable for rendering such compositions more acceptable. Such conventional optional ingredients are well known to those skilled in the art, preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidiazolidinyl urea; cationic surfactants such as cetyl trimethylammonium chloride, lauryl trimethyl ammonium chloride, tricetyl methyl ammonium chloride, stearyldimethyl benzyl ammonium chloride, and di(partially hydrogenated tallow)dimethylammonium chloride; thickeners and viscosity modifiers such as diethanolamide of a long chain fatty acid PEG 3 lauramidc). block polymers of ethylene oxide and propylene oxide such as Pluronic F88 offered by BASF Wyandotte, sodium chloride, sodium sulfate, polyvinyl alcohol, and ethyl alcohol; pH adjusting agents such as citric acid, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate, etc., perfumes; dyes; and, sequestering agents such as disodium ethylenediamine tetraacetate. Such agents generally are used individually at a level of from about 0.01% to about 10%, preferably from about 0.5% to about 5.0% by weight of the composition.

When used for internal (mouth or ingested) treatment products, the discontinuous silicone phase of the ULTRAMULSION T M dispersion can also contain a wide range of lipid soluble and/or lipid dispersible ingredients suitable for treating various surface conditions on lips in the mouth, or the throat, stomach and esophagus. These various ingredients in the silicone phase of the ULTRAMULSIONTM dispersion perform their intended function in various treatment products etc. as though they are contained in a "reservoir" as they continue to be available at the ULTRAMULSIONTM dispersion containing surfaces to be treated interface as long as the ULTRAMULSIONTM dispersion coating remains substantive to said surface. These substantive treatment coatings are discussed in various examples below.

Such conventional optional ingredients are well known to those skilled in the art, preservatives such as benzyl alcohol, methyl paraben, propyl paraben and WO 96/39116 PCT/US96/08714 17imidazolidinyl urea; cationic surfactants such as cetyl trimethylammonium chloride, lauryl trimethyl ammonium chloride, tricetyl methyl ammonium chloride, stearyldimethyl benzyl ammonium chloride, and di(partially hydrogenated tallow)dimethylammonium chloride; thickeners and viscosity modifiers such as diethanolamide of a long chain fatty acid PEG 3 lauramide), block polymers of ethylene oxide and propylene oxide such as Pluronic F88 offered by BASF Wyandotte, sodium chloride, sodium sulfate, polyvinyl alcohol, and ethyl alcohol; pH adjusting agents such as citric acid, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate, etc., flavors; dyes; and, sequestering agents such as disodium ethylenediamine tetraacetate. Such agents generally are used individually at a level of from about 0.01% to about 10%, preferably from about 0.5% to about 5.0% by weight of the composition.

The treating surface conditions of lips and the esophagus as well as various mucus containing surfaces such as the mouth, throat, stomach and duodenum and intestines. These surfaces can be treated with various forms of the ULTRAMULSIONTM dispersions of the invention ranging from gels and lotions for the lips, to liquids, for the mouth to liquid and syrups for the throat to liquids for the esophagus to liquids tablets for the stomach, duodenum and intestines.

For internal the mouth, throat, etc.) treatment, the discontinuous silicone phase of the ULTRAMULSIONM dispersion can also contain a wide range of lipid soluble and/or lipid dispersible oral care active ingredients ranging from antimicrobials to desensitizing/substances, to healants such as aloe to vitamins such as vitamin E, to flavorants, etc. These various ingredients in the silicone phase of the

ULTRAMULSION

T M dispersion perform in various interdental delivery devices once they are released from the device as though they are contained in a "reservoir" as they continue to be available at the ULTRAMULSIONTM dispersion oral surface interface, as long as the ULTRAMULSION T dispersion coating remains substantive to mouth surfaces. Similar effects attributed to this reservoir effect are described by R6lla et al., supra.

The interdental delivery device of the present invention containing the ULTRAMULSIONTM dispersions will contain a variety of essential components ranging from surfactants for cleaning, to whiteners, to flavorants etc. These are WO 96/39116 PCT/US96/08714 18 detailed in various Examples described below.

The ULTRAMULSIONT M dispersions of the invention are particularly useful in compositions used by professionals to clean teeth. The inclusion of stannous fluoride in the discontinuous phase of the emulsion is particularly attractive as a means of treating interproximal caries. See Segueto et al., Journal of Dental Research, Vol. No. 1, pp. 90-96, 1961 and Peterson et al., Northwest Dentistry, 276-278, Sep./Oct.

1963. For oral care, the pH of the present compositions is preferably from 6 to 8.

The ULTRAMULSIONT dispersions of the invention are particularly useful in interdental devices whose use is under supervision of a professional. The inclusion of stannous fluoride in the discontinuous phase of the emulsion is particularly attractive as a means of treating interproximal caries. See Segueto et al., Journal of Dental Research, Vol. 10, No. 1, pp. 90-96, 1961 and Peterson et al., Northwest Dentistry, 276-278, Sep./Oct. 1963. The pH of the ULTRAMULSIONT M dispersions for use with interdental devices is preferably from about 6 to 8.

Oral care rinses containing the ULTRAMULSIONT M dispersions of the present invention may contain a variety of essential components ranging from other surfactants for cleaning, to other flavorants etc. In addition these oral care rinses may also contain a variety of nonessential optional components suitable for rendering such compositions more acceptable. Such conventional optional ingredients are well known to those skilled in the art, preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidiazolidinyl urea; cationic surfactants such as cetyl trimethylammonium chloride, lauryl trimethyl ammonium chloride, tricetyl methyl ammonium chloride, stearyldimethyl benzyl ammonium chloride, and di(partially hydrogenated tallow)- dimethylammonium chloride; thickeners and viscosity modifiers such as diethanolamide of a long chain fatty acid PEG 3 lauramide), block polymers of ethylene oxide and propylene oxide such as Pluronic F88 offered by BASF Wyandotte, sodium chloride, sodium sulfate, polyvinyl alcohol, and ethyl alcohol; pH adjusting agents such as citric acid, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate, etc., perfumes; dyes; and, sequestering agents such as disodium ethylenediamine tetraacetate. Such agents generally are used individually at a level of from about 0.01% to about 10%, preferably from about to about 5.0% by weight of the composition. The pH of the present WO 96/39116 PCT/US96/08714 19compositions for use with oral care rinse products is preferably from about 6 to 8.

Water is an essential component of most oral care products of the present invention which contain one or more of the various ULTRAMULSIONTM dispersions described above. The water in these products is generally present at a level of from about 20% to about 95%, preferably from between about 60% and about The following Tables provide a number of oral care examples utilizing the

ULTRAMULSION

T M dispersions of the present invention.

WO 96/39116 WO 9639116PCTIUS96/0871 4 20 TABLE 1 ORAL CARE ULTRAMULSION DISPERSIONS

W/W

1 23 4 56 7 8 9 Example No.

Components Dimethicone viscosity (cs) 100,000 600,000 2,500,000 4,000,000 30,000,000 50,000,000 Poloxamer-1 88 Poloxainer-238 Poloxanier-33 8 Poloxamer-407 10 11 IV 10 10- 10- 33 33 33 YUv YV Y'U YiV~ Y iV 67 TABLE 2 ORAL CARE ULTRAMIJLSION COMPOSiTONS

WIW

Example No.

Component Dimethicone viscosity (cs) 600,000 2,500,000 4,000,000 30,000,000 50,000,000 12 13 14 15 16 17 18 19 20 21 11.6 10.0 10.0 11.9 11.9 14.0 10.0 11.9 11.6 11.6 10.0 TABLE 2 (Continued) Example No. 12 13 14 15 16 17 18 19 20 21 Lipid Soluble Component Mixture Of: Thymol 0.063 0.063 1.0 2 Menthol 0.055 0.55 1.0 2 Eucalyptol 0.091 0.91 1.0 2 Methyl Salicylate 0.055 0.55 1.0 2 0.1 0.2 0.3 0.4 0.1 0.2 0.3 0.4 0.1 0.2 0.3 0.4 0.1 0.2 0.3 0.4 Surfactant Poloxanier-338 89.76 85.76 84.4 80.1 76.4 74.0 88.0 89.2 88.8 84.4 Example Product No. Composition 22 67/33 Poloxamer 338/100,000 cs. Dimethicone 23 90/10 Poloxamer 338/600,000 cs. Dimethicone 24 90/10 Poloxamer 407/2,500,000 cs. Dimethicone 90/10 Poloxanier 407/4,000,000 cs. Dimethicone TABLE 3 Particle Size Distribution(% 44 50 4 1 1 24 4 5 1 2 2 3 63 24 8 1.5 6 0.51 43.5 WO 96/39116 WO 9639116PCTIUS96/0871 4 24 TABLE 4 ORAL CARE

W/W

Example No. 26 27 28 29 30 31 32 33 34 Component Dimethicone viscosity (Cs) 600,000 2,500,000 10.0 4,000,000 30,000,000 50,000,000 Lipid Soluble Component Mixture Of- Thymol 24% Menthol -16% 1 Eucalyptol 36% Methyl Salicylate -24% Stannous Fluoride Triclosan Chorhexidine Metronidazole Benzocaine Surfactant Poloxamer 338 80.0 11.6 11.6 10.0 11.9 14.0 11.6 11.6 10.0 1.75 1.16 1.16 1.16 1.16 97.24 87.24 86.8 972 72 68 87.25 89.0 87.24 87.24 80.0 84.0 TABLE ULTRAMULSION TOOTHPASTE COMPOSITIONS

W/W

36 37 38 39 40 41 42 43 44 45 46 47 Example Component Dicalcium Phosphate Dihydrate 49.0 49.0 49.0 49.0 49.0 49.0 49.0 49.0 49.0 Sorbitol 70% Aq.

Water Glycerine SodiumCarboxyMe Cellulose Flavor 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 16.67 16.67 16.67 16.67 16.67 16.67 16.67 16.67 16.67 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 thyl 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 49.0 49.0 49.0 18.0 18.0 18.0 16.67 16.67 16.67 10.0 10.0 10.0 1.0 1.0 1.0 1.0 0.8 0.8 0.8 0.5 0.5 0.76 0.76 0.76 0.27 0.27 0.27 Sodium Lauryl Sulfate 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Titanium Dioxide 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Sodium MonoFluoro Phosphate 0.76 0.76 0.76 0.76 0.76 0.76 0.76 0.76 0.76 Sodium Saccharin 0.27 0.27 0.27 0.27 0.27 0.27 0.27 0.27 0.27 TABLE 5 (continued) ULTRAMULSION TOOTHPASTE COMPOSMONS

W/W

48 49 50 51 52 53 54 55 56 Example 57 58 59 Component IJLTRAMULSIONTm Example 1 Example 3 Example 6 Example 4 Example 7 Example 12 Example 14 Example 15 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Example 18 Example 21 2.0 TABLE 6 ULTRAMULSION DENTAL FLOSS COMPOSMONS

W/W

EXAMPLE Component 61 62 63 64 Dicalcium Phosphate Dihydrate 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 .Carrageenan Insoluble Saccharin 2.2 2.2 2.2 Flavor

EDTA

8.9 8.9 2.2 2.2 2.2 8.9 8.9 8.9 0.2 0.2 0.2 0.2 0.2 0.2 0.1 0.1 0.1 Propyl Gallate, 0.1 0.1

ULTRAMULSION

m Example 4 Example 5 Example 6

ULTRAMULSION

m Example 2 Example 3 Example I Example 10 60.6 60.6 60.6 60.6 60.6 60.0 60.6 Each composition was loaded on to 800 denier Nylon Dental floss at between 40 60 mg./yard.

WO 96/39116 PCT/US96/0871 4 28 TABLE 7 LJLTRAMULSION BREATH SPRAY COMPOSITIONS W/w Example Component Water Sorbitol 70% Aq.

Glycerin Xanthan Gum Sodium Saccharin Sodium Benzoate

EDTA

Flavor

ULTRAMULSION

Tm Example 3 Example 4 Example 5 Example 9 67 68 69 82.75 8.5 3.0 0.4 0.4 0.3 0.05 0.6 82.75 8.5 3.0 0.4 0.4 0.3 0.05 0.6 82.75 8.5 3.0 0.4 0.4 0.3 0.05 0.6 82.75 0.4 0.4 0.3 0.05 0.6 WO 96/39116 WO 9639116PCT/US96/08714 29 TABLE 8 ULTRAMULSION DRY-MOUTH SPRAY COMPOS]TIONS Pump Spray W/w Example 71 72 73 Component Water 93.86 93.86 93.86 Xanthan Gum 0.7 0.7 0.7 Sorbitol 70% Aq. 3.5 3.5 Potassium Chloride 0.1 0.1 0.1 Sodium Chloride 0.06 0.06 0.06 Calcium Chloride 0.02 0.02 0.02 Potassium Phosphate Dihydrate 0.04 0.04 0.04 Flavor 0.06 0.06 0.06 Propyl Gallate 0.1 0.1 0.1

ULTRAMULSION

Tm Example 2 1.5 Example 4 Example 6 WO 96/39116 PCTIUS96/08714 30 TABLE 9 ULTRAMULSION TEETHING GEL COMPOSITIONS WIw Example 74 Component Water 45.7 45.7 Sorbitol 70% Aq. 34.3 34.3 Glycerine 5.0 Potassium Sorbate 0.15 1 0.151 Sodium Saccharin 0.075 0.075 Citric Acid 0.1 0.1 Methyl. Paraben 0.15 0.15 Propylene Glycol 10.0 10.0 SodiumCarboxyMethyl Cellulose 2.52 2.52

ULTRAMIJLSION

Tm Example 4 Example 6 TABLE ULTRAMLJLSION ORAL CARE COMIPOSITONS

W/W

78 79 80 81 82 83 84 Example No. 76 77 Component Dimethicone viscosity (cs) 100,000 10 600,000 2,500,000 4,000,000 30,000,000 50,000,000 Triclosan 1 2 Poloxamer-188 Poloxarner-238 Poloxamer-338 89 88 Poloxamer-407 85 86 33 10 10 33 33 3 4 87 86 5 6 03 Ot 65 63 TABLE 11 ULTRAMULSION ORAL CARE COMPOSITIONS

W/W

87 88 89 90 91 92 93 94 95 0 96 Example No.

Component Dimethicone viscosity (cs) 600,000 2,500,000 4,000,000 30,000,000 50,000,000 Lipid Soluble Triclosan Surfactant Poloxainer-33 8 10.0 11.6 11.9 11.9 10.0 14.0 11.6 10 11.6 11.6 10.0 10 1.16 1.16 1.3 1.0 1.75 1.16 1.16 80.0 75.64 88.84 86.88718828.48.4834 87.15 88.25 87.24 88.84 83.4 84.0 WO 96/39116 WO 9639116PCTIUS96/0871 4 33 TABLE 12 Example No. 97 98 99 100 101 DDIETLIC ONE 2,500,000 cs. 10 10 4,000,000 Cs. LIEPID SOLUBLES/DISPERSABLE Dextromethophenyl 10 10 Hydrobromide Dextromethophenyl Hydrobromide Dextromethophenyl Hydrobromide Fragrance #17.92.3415 (1FF)

SURFACTANT

Poloxarner-33 8 1.0 2.0 1.0 1.5 89.0 88.0 89.0 88.5 89.0 WO 96/39116 PCT/US96/08714 -34- TABLE 13 ULTRAMULSION COMPOSITIONS FOR MOUTH AND LIPS

W/W

A. Lip Balm Examples: 102 103 Mineral Oil-USP 220 250 Petroleum Jelly-USP 50 Ozokerite box 13.0 Paraffin box 12.0 17.0

ULTRAMULSION

Example #3 Example #8 TABLE 14 B. Gel for Canker Sore Treatment 104 105 D.I. Water 56.1 46.6 Sorbitol 70% 32.0 32.0 Propylene Glycol Glycerin USP 6.0 Potassium Sorbate 0.14 0.14 Sodium Saccharin 0.06 0.06 Sodium CMC 2.50 2.50 Flavor 0.20 0.20 camphor 0.50 0.50

ULTRAMULSION:

Example #10 2.50 Example 7 WO 96/39116PCUS/074 PCT/US96/08714 35 TABLE EXAMPLES 106-108 Cough Drop or Sore Throat Compositions

W/W

Example 106 (Cough Drop): Glucose 26.5 Corn Syrup 40.0 Sugar 30.0 Flavor

ULTRAMULSION:

Example #8 Example 107 (Cough Corn Syrup Flavoring D.I. Water

IJLTRAMULSION:

Example #15 Syrup): 15.0 0.3 83.7 Example 108 (Sore D.I. Water Aq.

Glycerine Xanthan Gum Flavor

ULTRAMULSION:

Example #13 Throat Spray): 74.55 20.0 0.05 0.40 2.00 WO 96/39116 WO 9639116PCT/US96/08714 36 TABLE 16 EXAMPLES 109 110 Example 109 (Alcohol Free Rinse for Trench Mouth) D.I. Water 83.02 Sorbitol 70% aq. 10.0 Glycerine USP Sodium Saccharin 0.06 Sodium Butyrate 0.44 EDTA 0.05 Xanthan Gum 0.03

ULTRAMULSION:

Example #12 Example 110 (Dual Dispensed Mouthrinse Concentrate): Phase A Glycerine-Anhydrous 84.553 SlO-Zeodent 113 15.0 Stannous Fluoride 0.447 Phase B D.I. Water 70.0 Flavor 4.6 Color Blue #1 0.001

ULTRAMULSION:

Example #14 25.399 WO 96/39116 PCT/US96/08714 -37- TABLE 17 Example 111 (Antacid Tablets): Tablet: A. Mineral Oil 10.0 Flavor Sodium Polyphosphate Corn Starch 0.6 Sucrose 41.9 Talc Calcium Carbonate 39.0 B. ULTRAMULSION: Example #3 Phase A Alone 95.0 Compounding Procedure for Example 111: Phase A is dry blended together in a paddle mixer, Hobart, to form a socalled wet/dry granulation. Phase A is then heated to 65-70°C while mixing, and the

ULTRAMULSION

T M dispersion is added to the granulation. The ULTRAMULSIONTM dispersion melts and "plates out" on the surface of each granulation particle. The resulting granulated material is cooled to room temperature and is tableted using 1.3 grams and 40,000 lbs.

WO 96/39116 PCTIUS96/08714 -38- TABLE 18 Example 112 (Antacid Liquid): Phase A Calcium Carbonate 96.0

ULTRAMULSION:

Example #7 Phase B Phase A D.I. Water 85.4 Sucrose Flavor Xanthan Gum 0.1 Glycerine Compounding Procedure for Example 112: Phase A is prepared by heating calcium carbonate in an air stream to 65-70%; the

ULTRAMULSION

T

M dispersion is introduced at 65-70 0 C and melts in the hot air stream and "plates" each individual CaCO 3 particle. The material is cooled and prepared into a liquid antacid per Phase B.

Example 113 (Ulcer Treatment Tablet) Aluminum Hydroxide Powder 55.0 Mineral Oil 14.5 Sodium Polyphosphate 22.0 Talc

ULTRAMULSION:

Example #12 WO 96/39116 PCTIUS96/08714 -39- TABLE 19 INTERDENTAL DEVICE FORMULATIONS W/W) Example 114 115 116 117 118 Components: Sorbitol 70% Aq. 7.5 7.5 8.0 9.0 Sodium Saccharin 0.4 0.4 0.4 0.4 0.4 Flavor 5.0 5.0 5.4 5.1 4.8 D.I. Water 75.1 75.1 71.2 74.5 78.8

ULTRAMULSIONTM

Example 1 12 Example 3 12 Example 12 15 Example 14 11 Example 2 9 Procedure for Impregnating Interdental Stimulators 1. Material to be impregnated wooden sticks) with the ULTRAMULSIONTM dispersion (or formulation) is placed in suitable container capable of holding a vacuum, such as a desiccator, stainless steel covered reactor or similar device.

2. The liquid formulation is poured on top of the material and covered completely by the liquid. A perforated disk with ballast is placed on the material to keep from floating.

3. The container is then sealed, and vacuum applied for varying periods of time ranging from 1 min. to several hours with the preferred time being between 5-10 min.

4. Vacuum is maintained such that the liquid does not boil, but enough vacuum to remove entrapped air from the device.

WO 96/39116 PCT/US96/08714 TABLE 19 CONTINUED Example of laboratory preparation using wooden Interdental Stimulators (IDS) Collectively, 87.0 grams of wooden interdental stimulators (IDS) equals about 260 individual stimulators. This IDS batch was impregnated with the

ULTRAMULSION

T M dispersion formulation from Example 22 under vacuum, at mm of mercury for a period of 10 minutes. The resulting impregnated IDS batch was removed from the remaining solution and dried at 40 0 C in convection oven for hour. The IDS were dry and the final batch weight was 152.7 grams. This is a 56.9% increase in weight indicating the amount of dry formulation impregnated into the IDS.

WO 96/39116 PCT/US96/08714 -41 The present invention has been described in detail, including the preferred embodiments thereof. However, it will be appreciated that those skilled in the art, upon consideration of the present disclosure, may make modifications and/or improvements on this invention and still be within the scope and spirit of this invention as set forth in the following claims.

41a Where the terms "comprise", "comprises", "comprised" or "comprising" are used in this specification, they are to be interpreted as specifying the presence of the stated features, integers, steps or components referred to, but not to preclude the presence or addition of one or more other feature, integer, step, component or group thereof.

27/11/97GV9556.SPE,1

Claims

1. An oral care product selected from the group consisting of rinses, sprays, gels, creams, toothpastes, tooth powders, dental floss, interproximal simulators, mints and chewing gum, wherein said product contains an aqueous-free dispersion of a silicone in a surfactant wherein: a. the silicone is insoluble in said surfactant, has a viscosity up to about 50 million cs, and a particle size up to about 10 microns; b. the surfactant to silicone ratio in the dispersion is from between about 400:1 and about 1:1; and the surfactant has an orienting effect on the silicone; c. the dispersion forms stable dispersions in aqueous containing oral care products; and d. said oral care product exhibits enhanced substantivity to surfaces in the oral cavity while the dispersed silicone phase of said dispersion functions as a reservoir for various lipid soluble and lipid dispersible oral care active ingredients.

2. An oral care product according to claim 1, wherein the silicone contains an active ingredient selected from the group consisting of, anti-plaque, anti-tartar, anti-gingivitis and anti-periodontitis active ingredients.

3. An oral care product according to any one of claims 1 to 2 wherein the silicone contains triclosan.

4. An oral care product according to any one of claims 1 to 3, wherein the silicone contains the mixture of essential oils comprising: thymol, eucalyptol, menthol and methyl salicylate.

5. An oral care product according to any one of claims 1 to 4, wherein the silicone contains stannous fluoride. S.

6. An oral care product according to any one of claims 1 to wherein the silicone contains chlorhexidine.

7. An oral care product according to any one of claims 1 to 6, wherein the silicone contains metronidazole.

8. An oral care product according to any one of claims 1 to 7, RA4/T 01/09/99, mp9556.claims,42 -43- wherein the product is a gel treating periodontal pockets.

9. An oral care product according to claim 1, wherein the product is a toothpaste containing triclosan in said silicone.

An oral care product according to claim 1, wherein the product is a dental floss where the silicone contains one or more antimicrobials selected from the group consisting of stannous fluoride, triclosan, chlorhexidine and metronidazole.

11. An oral care product according to claim 1, wherein the product is a gel and the silicone contains benzocaine.

12. An oral care product according to claim 1, wherein said dispersion comprises a nonionic poloxamer surfactant and polydimethylsiloxane wherein: a. said polydimethylsiloxane has the chemical composition: (CH 3 3 SiO[SiO(CH 3 2 1nSi(CH 3 3 wherein n is a whole number; b. said surfactant has the chemical composition: CH 3 OH-(CH 2 CH 2 (CH 2 CHO), (CH 2 CH 2 H wherein x,y and x' are whole numbers; c. the viscosity of the polydimethylsiloxane ranges from between about 2.5 million and about 50 million cs; d. the particle size of most of the polydimethylsiloxane in the dispersion is from between about 0.1 and about 10 microns; e. from between about 80% and 95% of said polydimethylsiloxane particles in the dispersion are from between about 1 and about 10 microns; f. the nonionic surfactant is a polyoxyethylene-polyoxypropylene block copolymer having a molecular weight from between about 1,100 and about 150,000; g. the ratio of surfactant to polydimethylsiloxane is from between about 400:1 and about 1:2; and h. the dispersion, when dispersed in a water-based oral care product, 01109/99, mp9556.claims,43 -44- is stable.

13. An oral care product according to claim 12, wherein the ratio of said surfactant to said silicone is 2:1 and 100% of the silicone dispersion is less than 10 microns.

14. An oral care product according to claim 12, wherein the ratio of said surfactant to said silicone is 1:1 and the silicone particles in said dispersion are less than 10 microns.

An oral care product according to claim 12, wherein the ratio of said surfactant to said silicone is 9:1 and 90% of the silicone particles are from between about 1 and 3 microns.

16. An oral care product according to claim 12, wherein the ratio of surfactant to polydimethylsiloxane is 1:1 and at least 80% of the polydimethylsiloxane dispersed particles are between 1 and 9 microns.

17. An oral care product according to claim 12, wherein the ratio of surfactant to polydimethylsiloxane is 9:1 and about 90% of the polydimethylsiloxane dispersed particles are between 1 and 3 microns.

18. An oral care product according to claim 12, wherein the ratio or surfactant to polydimethylsiloxane is 2:1 and about 90% of the polydimethylsiloxane dispersed particles are between 1 and 3 microns.

19. An oral care product according to claim 12, wherein the ratio of surfactant to polydimethylsiloxane is 4:1 and about 90% of the polydimethylsiloxane dispersed particles are between 1 and 9 microns.

20. An oral care product according to claim 12, wherein the ratio of C. surfactant to polydimethylsiloxane is 9.5:0.5 and about 100% of the polydimethylsiloxane dispersed particles are between 1 and 9 microns.

21. An oral care product according to claim 12, wherein the polydimethylsiloxane has a viscosity of 2.5 million cs and the surfactant is a solid at S room temperature.

22. A method of manufacturing dispersions suitable for oral care *C I^ A 01/09/99, mp9556.claims,44 products as described in any of the preceding claims, comprising, heating said surfactant and silicone mixture in a heated, stirred vessel substantially free from water, followed by subjecting said mixture to high shear dispersion.

23. An oral care product according to claim 1 substantially as described in any one of the Examples. Dated this 2n d day of September, 1999 WHITEHILL ORAL TECHNOLOGIES, INC. By their Patent Atto e s: CALLINAN LAWRIE CV C C *o 01/09/99, mp9556.claims,45