HK1081121B - Oral compositions providing enhanced overall cleaning - Google Patents

Description

Oral compositions providing enhanced overall cleaning

Technical Field

Oral compositions and methods are disclosed that provide enhanced overall cleaning, whitening, stain removal and prevention of staining of natural teeth and dentures. In particular, these benefits are achieved by applying to the teeth a composition comprising a copolymer of Vinylpyrrolidone (VP) and Alkenyl Carboxylate (AC) monomers in an orally acceptable carrier.

Background

Plaque and calculus formation are the major causes of caries, gingivitis, periodontal disease and tooth loss. Plaque is a mixed matrix of bacteria, epithelial cells, leukocytes, macrophages, and other oral exudates. Bacteria comprise approximately three-quarters of the plaque matrix. Any given plaque sample may contain up to 400 different microorganisms. Such mixtures include aerobic and anaerobic bacteria, fungi and protozoa. Viruses have also been found in plaque samples.

This matrix of microorganisms and oral exudates continues to spread and bind with other plaque growths nearby. The bacteria synthesize levan and glucan from sucrose in the mouth, providing energy to the microorganisms. These glucans, fructans and microorganisms form an adhesive skeleton for the continued proliferation of plaque.

Calculus, sometimes referred to as tartar, is a deposit that forms on the tooth surfaces at the gingival margin. Calculus on the gums occurs mainly near the orifice of the salivary duct; for example, on the lingual surfaces of the lower anterior teeth and on the buccal surfaces of the upper first and second molars, and on the distal surfaces of the posterior molars. Mature calculus consists of an inorganic portion, which is primarily calcium phosphate arranged within a hydroxyapatite lattice structure, which resembles bone, enamel, and dentin. There is also an organic fraction consisting of desquamated epithelial cells, leukocytes, salivary sediment, food debris and various types of microorganisms. Progressive plaque adheres most readily to relatively irregular surfaces, such as those formed by calculus. As calculus develops, it becomes white or yellowish unless it is stained or discolored by some foreign substance. In addition to being unsightly and undesirable, mature calculus deposits are a common cause of gum inflammation.

The inability to delay or stop plaque and calculus growth is detrimental to oral hygiene. Plaque and calculus formation can lead to caries, gingival inflammation, periodontal disease and ultimately tooth loss. In addition, calculus and plaque, as well as behavioral and environmental factors, can lead to the formation of dental discoloration, which can seriously affect the aesthetic appearance of teeth. Behavioral and environmental factors contributing to the propensity for tooth staining include regular consumption of coffee, tea, cola or tobacco products, and also the use of oral products that promote discoloration, such as chlorhexidine.

The final degree of oral cleaning is provided by the dentist at the time of prophylaxis; daily oral care at home requires a product with multiple ingredients that work by different mechanisms to provide satisfactory cleaning and whitening. Thus, for daily use oral care products such as dentifrices and mouthwashes to provide overall cleaning, ingredients must be added to provide antiplaque and anticalculus benefits as well as stain removal, stain control, and tooth whitening benefits. These ingredients for removing and controlling discoloration and for whitening include bleaching agents, abrasives, or chemical chelators. Bleaching agents added to dentifrices are typically present at low concentrations due to stability and safety limitations unique to toothpastes. At these low concentrations, bleaching agents are typically oxidizing agents, which are generally ineffective in tooth whitening and tooth discoloration control. Dental abrasives provide important whitening benefits, particularly in the "brushed" area of the teeth, but unfortunately have limited utility in controlling aesthetically undesirable discolorations that develop along the proximal end of the gum line. Bleaching agents and abrasives do not functionally prevent the formation of discoloration. The use of abrasives can reduce the rate of discoloration formation by daily removal of newly formed discoloration, but this effect is a "treatment" of existing discoloration rather than a preventative chemical effect.

The use of chemical chelators has been proposed in the art to retard calculus formation and for the removal of formed calculus. Chemical methods of inhibiting dental calculus typically include sequestering calcium ions and/or inhibiting crystal growth by removing calcium to prevent calculus formation and/or to break mature calculus. Additionally, chemical chelators may substantially remove discoloration by binding to the tooth surface, thereby replacing the color bodies or chromogens. Retention of these chelating agents also prevents an increase in discoloration due to disruption of the bonding sites for the color bodies on the tooth surface.

Numerous agents having chelating properties have been disclosed in the art for controlling plaque, calculus and tooth discoloration. For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid and related compounds are disclosed in british patent 490,384 filed 2, 15, 1937; polyphosphonates are disclosed in U.S. patent 3,678,154 issued to Widder et al at 7/18 of 1972, U.S. patent 5,338,537 issued to White at 8/16 of 1994, jr., and U.S. patent 5,451,401 issued to Zerby et al at 9/19 of 1995; carbonyl diphosphonates are disclosed in U.S. patent 3,737,533 issued to Francis at 5.6.1973; mixtures of zinc polymers formed by the reaction or interaction of zinc compounds with anionic polymers containing carboxylic, sulfonic and/or phosphonic acid groups are disclosed in U.S. patent 4,138,477 to Gaffar on 2/6 1979; tartaric acid is disclosed in U.S. patent 5,849,271, published 12/15 in 1998 and 5,622,689, published 4/22 in 1997, both issued to Lukacovic; acid or salt forms of tartaric acid mono-succinic acid, tartaric acid di-succinic acid, and mixtures thereof are disclosed in U.S. patent 5,015,467 to Smitherman at 5,14, 1991; acrylic acid polymers or copolymers are disclosed in U.S. patent 4,847,070 to Pyrz et al at 11/7 in 1989 and U.S. patent 4,661,341 to Benedict et al at 28/4 in 1987; sodium alginate, disclosed in U.S. patent 4,775,525 to Pera at 10.4.1998; polyvinylpyrrolidone is disclosed in GB 741,315 published at 11/30.1955, WO 99/12517 published at 3/18.1999 and us patent 5,538,714 issued to Pink et al at 7/23.1996; copolymers of vinyl pyrrolidone and carboxylic acid esters are disclosed in U.S. patent 5,670,138 issued to Venema et al at 9/23 1997 and Japanese patent publication 2000-0633250 to Lion Corporation at 2/29 2000.

Also disclosed in the art are dentifrice mouthwashes comprising soluble pyrophosphate salts that can be used for a variety of purposes, including anticalculus agents. These publications include us patent 2,941,926 issued to Salzmann et al on 21/6/1960; U.S. patent 3,927,201 to Baines et al and U.S. patent 3,927,202 to Harvey et al, on 16.12.1975, respectively; U.S. patent 4,244,931, published on month 13 of 1981, and 4,247,526, published on month 27 of 1981, both to Jarvis et al; japanese patent application 4945-1974; U.S. patent 4,323,551, published on 6/4/1982, U.S. patent 4,515,772, published on 7/5/1986, and U.S. patent 4,885,155, published on 5/12/1989, all of which are issued to Parran et al; and us patent 4,822,599 to Mitra at 4/18/1989. Draus, Lesniewski and Miklos also disclose the in Vitro effectiveness of soluble Pyrophosphate salts against dental Calculus, see "Pyrophosphate and hexamethophosphate Effects in Vitro calcium Formation" arch. oral biol., volume 15, page 893-.

Dehydrated polyphosphates useful as linear molecules of tartar inhibitors are disclosed in GB patent application GB2,200,551 to Gaffar, Nabi, and Jannone, filed on 27.1.1988, published on 10.8.1988; and U.S. Pat. No. 4,627,977 to Gaffar et al, 12, 9, 1986. Among these salts are indeed Sodium Tripolyphosphate (STPP). Other references disclosing STPP include U.S. Pat. No. 4,923,684 issued on 5/8 of 1990 to Ibrahim et al and U.S. Pat. No. 5,096,701 issued on 3/17 of 1992 and U.S. Pat. No. 5,176,900 issued on 5/1 of 1993, both issued to White et al.

While products comprising chemical chelating agents and other plaque and calculus reducing agents are known, there is a continuing need to develop improved products, particularly products that provide enhanced overall cleaning, which simultaneously address calculus, plaque and discoloration issues.

The present inventors have discovered that administering oral compositions containing specific water-soluble or water-dispersible polymeric agents that bind color bodies such as polyphenols or catechols, provide enhanced cleaning, stain removal and whitening of teeth. In addition, the present polymeric agents provide overall cleaning and whitening benefits when mixed with polyphosphates, especially tripolyphosphates, and with abrasives, especially precipitated silicas, or with bleaching agents, which exceed the benefits provided by either component alone. Accordingly, the present invention provides oral compositions comprising specific water-soluble or water-dispersible polymeric agents that are capable of binding color bodies present in the oral cavity, and methods of applying the oral compositions to provide enhanced overall cleaning, color removal, prevention of color change, and whitening of teeth. Preferably, the present composition further comprises one or a mixture of other oral care agents selected from the group consisting of tripolyphosphates, abrasives and bleaching agents to provide even better cleaning performance due to the synergistic effect between the polymeric complexing agent and the other oral care agents.

Summary of The Invention

The present invention provides an oral composition for overall cleaning and whitening of natural teeth and dentures to prevent, reduce or remove discoloration deposited on the surface of the teeth, the composition comprising at least 0.1% by weight of a copolymer comprising one or a mixture of Vinylpyrrolidone (VP) monomers and one or a mixture of C2-C12 alkenyl C1-C19 Alkyl Carboxylate (AC) monomers, and an orally acceptable carrier. Preferably, the composition further comprises one or a mixture of other oral care agents selected from the group consisting of water soluble alkali metal or ammonium tripolyphosphate in an amount of at least about 0.5% by weight of the composition; an abrasive, preferably a precipitated silica abrasive, comprises at least about 6% by weight of a bleaching agent and comprises at least about 0.1% by weight. The present invention also relates to methods of cleaning, whitening and polishing natural teeth and dentures and preventing, reducing or removing deposited stains from the surface of teeth by applying the present compositions.

These and other features, aspects, and advantages of the present invention will become apparent to those skilled in the art from the following detailed description.

Detailed Description

While the specification concludes with claims particularly pointing out and distinctly claiming the invention, it is believed that the present invention will be better understood from the following description.

All citations are herein incorporated by reference in their relevant part and no admission is made that any reference is available as prior art to the present invention.

All percentages and ratios used herein are by weight of the particular oral composition, and not by weight of all oral formulations delivered, unless otherwise specified. All measurements were made at a temperature of 25 ℃ unless otherwise indicated.

Herein, "comprising" means that other steps and other ingredients which do not affect the end result can be added. The term includes "consisting of …" and "consisting essentially of …".

By "oral composition" is meant a product that, during ordinary use, is not swallowed for purposes of systemic administration of a particular therapeutic agent, but rather remains in the oral cavity for a time sufficient to contact substantially all of the dental surfaces and/or oral tissues for purposes of oral activity. The oral compositions of the present invention may be in various forms: toothpaste, dentifrice, tooth powder, topical oral gel, mouthwash, denture product, mouthspray, lozenge, oral tablet, or chewing gum.

The term "dentifrice" as used herein, unless otherwise indicated, refers to a paste, paste or liquid dosage form. The dentifrice composition may be a single phase composition or may be a combination of two or more dentifrice compositions. The dentifrice composition may be in any desired form, such as deep striped, light striped, multi-layered, gelled around a paste, or any combination thereof. Each dentifrice composition in a dentifrice comprising two or more different dentifrice compositions may be contained in physically separate dispenser compartments, dispensed side-by-side.

The term "dispenser" as used herein refers to any pump, tube or container suitable for dispensing toothpaste.

The term "tooth" as used herein refers to a natural tooth or an artificial tooth or denture.

As used herein, the term "orally acceptable carrier" refers to any safe and effective substance for use in the compositions of the present invention. These materials include sources of fluorine particles, additional anticalculus agents, buffering agents, abrasive polishing materials, peroxide sources, alkali metal bicarbonate salts, thickening agents, humectants, water, surfactants, titanium dioxide, flavor systems, sweeteners, xylitol, coloring agents, and mixtures thereof.

As used herein, the terms "tartar" and "calculus" are used interchangeably and refer to mineralized plaque deposits.

The present invention provides oral compositions having enhanced overall cleaning and whitening of teeth and stain removal, which compositions include as an essential component one or more water-soluble or water-dispersible polymeric agents capable of binding color bodies such as polyphenols. In particular, the water-soluble or water-dispersible polymeric agent is a copolymer prepared by copolymerizing one or a mixture of Vinylpyrrolidone (VP) monomers with one or a mixture of Alkenyl Carboxylate (AC) monomers, specifically C2-C12 alkenyl esters of saturated linear or branched C1-C19 alkyl carboxylic acids, as follows:

wherein R is¹、R²、R³、R⁴、R⁵H or saturated C1-C12 alkyl;

R⁶saturated C1-C19 alkyl;

R⁷═ C2-C12 monoalkenyl, and

the ratio of x/y ranges from about 30/70 to about 90/10.

Preferred ester monomers include vinyl, allyl and methallyl esters of straight or branched chain aliphatic carboxylic acids having from 2 to 20 carbon atoms, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl caproate, vinyl 2-ethylhexanoate, vinyl caprate, vinyl laurate and vinyl stearate, and the corresponding allyl and methallyl esters thereof. Preferred vinylpyrrolidone monomers are unsubstituted. Particularly preferred polymers include copolymers of vinylpyrrolidone and one or a mixture of vinyl acetate, vinyl propionate or vinyl butyrate. Preferred polymers have an average molecular weight in the range of from about 1,000 to about 1,000,000, preferably from 10,000 to 200,000, even more preferably from 30,000 to 100,000. The present copolymers are typically prepared by free radical solution or emulsion polymerization using solvents such as water, aliphatic alcohols having 1 to 4 carbon atoms, or alcohol/water mixtures, see, for example, U.S. Pat. Nos. 2,667,473, 4,520,179, 4,554,311, 5,319,041, 5,395,904, 6,107,397, and 6,103,820.

Preferably, the composition additionally comprises at least about 0.5% by weight of a water soluble tripolyphosphate salt, and/or at least about 6% by weight of an abrasive polishing agent such as silica, and/or at least about 0.1% of a bleaching agent.

The present inventors have found that the cleaning and whitening properties of the Vinylpyrrolidone (VP) polymer can be greatly enhanced by changing its water solubility and hydrophobicity. One method of increasing hydrophobicity is to copolymerize vinyl pyrrolidone with a number of hydrophobic alkenyl carboxylic acid esters. The resulting copolymer not only has polar pyrrolidone amide linkages and carboxylate groups, but also contains hydrophobic alkyl functionality to provide greater retention on the teeth, and excellent stain removal and prevention.

Without being bound by a particular mechanism of action, it is believed that the superior stain removal and prevention benefits of the present copolymers are due, at least in part, to their ability to form complexes with color bodies, such as polyphenolic compounds, and their ability to form coatings or films on tooth surfaces. Polyphenols, also known as catechins and tannins, are components of a variety of recipe products such as tea, coffee, wine, cola, and a variety of fruits and berries. It is known that consumption of these recipe products can cause deposition of discoloring substances on teeth. It is believed that the PVP/AC copolymer of the present invention forms a protective film on the tooth surface when the present composition is applied to the oral cavity, such as by brushing or rinsing. Thus, when color bodies are present in the oral cavity, they contact the PVP/AC film coating, but not the tooth surface, and form complexes with the PVP/AC copolymer. The PVP/AC/chromophore complex can then be removed from the tooth surface as the transient PVP/AC film is peeled off the surface, thereby preventing discoloration from forming on the tooth. In terms of discoloration removal, it is believed that the copolymer is capable of binding to other detergents in the product, such as abrasives, surfactants, and chelating agents. The action of these agents can cause existing discolorations on the teeth to be removed from the surface, the copolymers forming complexes with the released color bodies and preventing their redeposition on the teeth. In this regard, the copolymer acts synergistically with other cleaning ingredients. It also prevents the formation of new plaque on the teeth, and the copolymer inhibits plaque from absorbing staining components from digestive foods such as tea, beer, red wine, etc.

A suitable copolymer useful in the present invention is vinylpyrrolidone/vinyl acetate copolymer (PVP/VA) having a VP/VA weight ratio of 60/40 and an average molecular weight in the range of from about 1,000 to about 1,000,000 available from BASF corp. Preferred polymers are those having an average molecular weight in the range of 30,000 to 100,000. Copolymers having a VP/VA ratio of from 30/70 to 90/10 are also suitable. The copolymer is present in the present compositions in an amount of about 0.1% to about 20%, preferably about 0.5% to about 10% by weight.

Preferably, the present composition additionally comprises a water-soluble alkali metal tripolyphosphate or ammonium tripolyphosphate. The sodium form of this salt is preferred, although potassium salts or mixed sodium or potassium salts may also be used. This tripolyphosphate is supplied in either a hydrate or dehydrated form, available from Monsanto corp, or Sigma Chemical; both forms are also suitable for use in the present compositions. The tripolyphosphate is present in an amount of at least about 0.5% up to about 50% by weight. The practical limit of the amount of tripolyphosphate is primarily solubility. The preferred level of tripolyphosphate in the dentifrice formulation is from about 2% to about 20% by weight.

While the present copolymers are inherently useful as discoloration control agents, it has been surprisingly found that the combination of the copolymer with a tripolyphosphate provides a synergistic benefit in terms of removal and prevention of discoloration, which far exceeds the benefits of either agent alone.

The present compositions also preferably comprise at least about 6% of a polishing agent or abrasive, preferably a silica abrasive. The present inventors have found that the combination of the copolymer with an abrasive polishing agent provides significantly enhanced polishing of the enamel surface, as well as cleaning and discoloration removal. Polishing benefits include improved tooth appearance and good tooth feel characteristics.

The present compositions preferably further comprise a tooth whitening agent such as a bleaching agent, in particular a peroxide. It has been found that the copolymers of the invention can form complexes with inorganic compounds, especially hydrogen peroxide. Thus, the present copolymers provide a stabilizing benefit to the compositions of the present invention when a peroxide is present therein.

Accordingly, in one aspect of the present invention, there is provided a composition for whitening and cleaning teeth and dentures comprising a copolymer of Vinylpyrrolidone (VP) and an Alkenyl Carboxylate (AC). In another aspect, the present invention provides compositions comprising a combination of a VP/AC copolymer and a bleaching agent, wherein the bleaching agent is present in an amount of from about 0.1% to about 20.0%, more preferably from about 1% to about 15%. In another aspect of the present invention, there is provided a composition for cleaning, whitening, stain removal and preventing the formation of stains for teeth and dentures comprising a combination of a water-soluble alkali metal or ammonium salt of tripolyphosphate and a VP/AC copolymer. In yet another aspect, the present invention provides compositions that additionally have enhanced polishing benefits, the compositions comprising a VP/AC copolymer and an abrasive.

The oral composition of the present invention may be in various forms such as a dentifrice, toothpaste, tooth powder, topical oral gel, mouthwash, denture product, mouthspray, lozenge, oral tablet or chewing gum.

The pH of the present compositions is preferably from about 4.0 to about 10.0. The preferred pH of the composition is from about 6.0 to about 9.0.

In addition to the above components, the present compositions may include additional components, which are described below.

Orally acceptable carrier

The orally acceptable carrier comprises one or more compatible solid or liquid filling diluents or encapsulating substances suitable for topical oral administration. As used herein, "compatible" means that the components of the composition can be mixed in a manner without interaction that would significantly reduce the stability and/or efficacy of the composition.

The carrier or excipient of the present invention may include conventional and conventional components such as dentifrices (including non-abrasive gels and subgingival applied gels), mouthwashes, mouthsprays, chewing gums and lozenges (including breath mints), which are described in more detail below.

The choice of carrier to be used is essentially determined by the method by which the composition is introduced into the oral cavity. If a toothpaste (including tooth gels, etc.) is used, then a "toothpaste carrier" (e.g., abrasive substances, foaming agents, binders, humectants, flavoring and sweetening agents, etc.) may be selected, as disclosed, for example, in U.S. Pat. No. 3,988,433 to Benedict. If a mouthwash is used, then a "mouthwash carrier" (e.g., water, flavors and sweeteners, etc.) can be selected, as disclosed, for example, in U.S. Pat. No. 3,988,433 to Benedict. Similarly, if an oral spray is used, then a "mouth spray carrier" is selected, and if a lozenge is used, then a "lozenge carrier" is selected (e.g., a candy base), which is disclosed in, for example, Grabenstetter et al, U.S. patent nos. 4,083,955; if chewing gum is used, a "chewing gum carrier" (e.g., a gum base, flavoring agents, and sweeteners) is selected, as disclosed, for example, in U.S. Pat. No. 4,083,955 to Grabenstetter et al. If a sachet is used, a "sachet carrier" (e.g., sachet, flavor, and sweetener) is selected. If a subgingival gel is used (for delivering active agents to or around the periodontal pocket), then a "subgingival gel carrier" may be selected, as disclosed, for example, in U.S. Pat. No. 5,198,220, published 3/30 1993 and U.S. Pat. No. 5,242,910, published 9/7 1993, both issued to Damani. Suitable carriers for preparing the compositions of the present invention are known in the art. Their selection depends on secondary considerations such as taste, cost, shelf stability, etc.

The compositions of the present invention may be in the form of non-abrasive gels, including subgingival gels, which may be aqueous or anhydrous. Aqueous gels typically include a thickener (about 0.1% to about 20%), a humectant (about 10% to about 55%), a flavoring agent (about 0.04% to about 2%), a sweetener (about 0.1% to about 3%), a coloring agent (about 0.01% to about 0.5%), and the balance water. The composition may include an anticaries agent (about 0.05% to about 0.3% fluoride ion) and an anticalculus agent (about 0.1% to about 13%).

Preferred compositions of the present invention may also be in the form of dentifrices, such as toothpastes, tooth gels and tooth powders. The components of these toothpastes and tooth gels generally include one or more dental abrasives (about 6% to about 50%), surfactants (about 0.5% to about 10%), thickeners (about 0.1% to about 5%), humectants (about 10% to about 55%), flavoring agents (about 0.04% to about 2%), sweeteners (about 0.1% to about 3%), colorants (about 0.01% to about 0.5%), and water (about 2% to about 45%). These toothpastes or tooth gels may also include one or more anticaries agents (about 0.05% to about 0.3% fluoride ion) and anticalculus agents (about 0.1% to about 13%). Of course, the dentifrice includes substantially all of the non-liquid components.

Other preferred compositions of the invention are mouthwashes, including mouth sprays. The components of these mouthwashes and mouth sprays typically include one or more of water (about 45% to about 95%), ethanol (about 0% to about 25%), humectants (about 0% to about 50%), surfactants (about 0.01% to about 7%), flavors (about 0.04% to about 2%), sweeteners (about 0.1% to about 3%), and colorants (about 0.001% to about 0.5%). These mouthwashes and mouth sprays may also include one or more of an anticaries agent (about 0.05% to about 0.3% fluoride ion) and an anticalculus agent (about 0.1% to about 3%).

Other preferred compositions of the present invention are dental solutions, including irrigation fluids. The components of these dental solutions typically include one or more of water (about 90% to about 99%), preservatives (about 0.01% to about 0.5%), thickeners (0% to about 5%), flavoring agents (about 0.04% to about 2%), sweeteners (about 0.1% to about 3%), and surfactants (0% to about 5%).

Chewing gum compositions typically include one or more chewing gum bases (about 50% to about 99%), flavoring agents (about 0.4% to about 2%), and sweetening agents (about 0.01% to about 20%).

The term "lozenge" as used herein includes: breath freshening mints, lozenges (troches), pastilles (pastilles), microcapsules and fast dissolving solid forms, including freeze dried forms (cakes, wafers, films, tablets) and fast dissolving solid forms, including compressed tablets. The term "fast dissolving solid form" as used herein means that the solid dosage form dissolves in less than about 60 seconds, preferably less than about 15 seconds, more preferably less than about 5 seconds, after being placed in the oral cavity. The instant solid form is disclosed in U.S. patent application 08/253,890 to Brideau, filed on 3/6/1994; U.S. patent 4,642,903, U.S. patent 4,946,684, U.S. patent 4,305,502, U.S. patent 4,371,516, U.S. patent 5,188,825, U.S. patent 5,215,756, U.S. patent 5,298,261, U.S. patent 3,882,228, U.S. patent 4,687,662, U.S. patent 4,642,903.

The drag candy mass comprises a disk-shaped solid comprising a therapeutic agent within a flavored matrix. The substrate may be a hard candy, a glycerin gum, or a combination of candy and sufficient mucilage to impart a shape thereto. These dosage forms are described primarily in Remington: the Science and Practice of Pharmacy, 19 th edition, volume II, chapter 92, 1995. A drag candy bar composition (compressed tablet type) typically includes one or more fillers (compressed sugar), flavoring agents, and lubricants. Microcapsules of the type contemplated by the present invention are disclosed in U.S. patent No. 5,370,864 to Peterson et al, published 12/6, 1994.

In yet another aspect, the present invention includes a dental appliance impregnated with a composition of the present invention. The dental appliance includes a means for contacting the teeth and other tissues in the oral cavity, said means being impregnated with a composition comprising the present copolymer of vinylpyrrolidone and a saturated C2-C12 alkenyl ester of a C1-C19 alkyl carboxylic acid. The dental appliance may be impregnated fibers including dental floss or tape, dental flakes or tape, and polymer fibers.

The types of carriers or oral care excipients that may be included in the compositions of the present invention are discussed below, as well as specific non-limiting examples.

Abrasive agent

Dental abrasives useful in the topical oral carrier of the compositions of the present invention include a number of different materials. The material selected must be compatible with the relevant composition and not excessively abrasive to dentin. Suitable abrasives include, for example, silica including gels and precipitates, insoluble sodium polymetaphosphate, alumina hydrate, calcium carbonate, dicalcium orthophosphate dihydrate, calcium pyrophosphate, tricalcium phosphate, calcium polymetaphosphate and resinous abrasive materials such as particulate condensation products of urea and formaldehyde.

Another type of abrasive useful in the present compositions is a particulate thermoset polymeric resin, described in U.S. Pat. No. 3,070,510 to Cooley & Grabenstetter, 12.25.1962. Suitable resins include, for example, melamine, phenolics, ureas, melamine-formaldehydes, ureas-formaldehydes, melamine-ureas, cross-linked epoxies, and cross-linked polyesters.

Different types of silica dental abrasives are preferred due to their unique benefits of particularly high tooth cleaning and polishing performance without excessive abrasion of enamel or dentin. The silica abrasive polishing materials of the invention, as well as other abrasives, typically have an average particle size of about 0.1 to about 30 microns, preferably about 5 to about 15 microns. The abrasive can be precipitated silica or silica gel, such as silica xerogel, which is described in 1970 in U.S. Pat. No. 3/2 to Pader et al 3,538,230; and U.S. patent 3,862,307 to DiGiulio on 21/1/1975. Preferred are silica xerogels available under the trade name "Syloid" from w.r.grace&Company, Davison Chemical Division. Also preferred are precipitated silica materials such as those sold by the j.m. huber Corporation under the trade name "Zeodent", with a particular silica under the name Zeodent^®119、Zeodent^®118、Zeodent^®109 and Zeodent^®129. Such silica dental abrasives useful in the toothpastes of the present invention are described in more detail in U.S. Pat. Nos. 4,340,583 to Wason, 7/29 1982; and commonly assigned U.S. patent 5,603,920 published on 18/2/1997; us patent 5,589,160 published at 31.12.1996; U.S. Pat. Nos. 5,658,553, published 1997, 8, 19; us patent 5,651,958 published on 29/7/1997; and U.S. provisional patent application 60/300766 filed on 25/6/2001.

Mixtures of abrasives may be used, such as the different grades mentioned aboveZeodent^®A silica abrasive mixture. The total amount of abrasive in the dentifrice composition of the present invention preferably ranges from about 6% to about 70% by weight; toothpastes preferably comprise from about 10% to about 50% abrasive by weight of the composition. The solutions, mouth sprays, mouthwashes and non-abrasive gel compositions of the present invention are typically free of abrasives.

Surface active agent

The present compositions may also include surfactants, also commonly referred to as sudsing agents. Suitable surfactants are those that have moderate stability and foam throughout a wide pH range. The surfactant can be anionic, nonionic, amphoteric, zwitterionic, cationic, or a mixture thereof.

Anionic surfactants useful herein include water-soluble salts of alkyl sulfates having from 8 to 20 carbon atoms in the alkyl group (e.g., sodium alkyl sulfate) and also include water-soluble salts of sulfonated monoglycerides of fatty acids having from 8 to 20 carbon atoms. Examples of such anionic surfactants are sodium lauryl sulfate and sodium coconut monoglyceride sulfonate. Other suitable anionic surfactants are sarcosinates, such as sodium lauroyl sarcosinate, taurates, sodium lauryl sulfoacetate, sodium lauroyl isethionate, sodium laureth carboxylate and sodium dodecyl benzenesulfonate. Mixtures of anionic surfactants may also be used. A number of suitable anionic surfactants are disclosed in U.S. Pat. No. 3,959,458 issued to Agricola et al, 5/25 1976. The present compositions typically comprise anionic surfactants at levels of from about 0.025% to about 9%, preferably from about 0.05% to about 5%, most preferably from about 0.1% to about 1%.

Another preferred class of surfactants is selected from sarcosinate surfactants, isethionate surfactants and taurate surfactants. Preferred for use in the present invention are alkali metal or ammonium salts of these surfactants. Most preferred herein are the sodium or potassium salts of: lauroyl sarcosinate, myristoyl sarcosinate, palmitoyl sarcosinate, stearoyl sarcosinate, and oleoyl sarcosinate. The surfactant may be present in the compositions of the present invention at levels of from about 0.1% to about 2.5%, preferably from about 0.3% to about 2.5%, most preferably from about 0.5% to about 2.0% by weight of the total composition.

Preferred cationic surfactants for use in the present invention may be broadly defined as derivatives of aliphatic quaternary ammonium compounds (said compounds having one long chain alkyl chain containing from about 8 to 18 carbon atoms) such as lauryl trimethyl ammonium chloride; cetyl pyridinium chloride; cetyl trimethylammonium bromide; diisobutylphenoxyethyl dimethylbenzyl ammonium chloride; cocoyl alkyl trimethyl ammonium nitrite; fluorinated cetyl pyridinium, and the like. A preferred compound is quaternary ammonium fluoride, described in U.S. patent 3,535,421 to Briner et al, published 1970, 10, 20, wherein the quaternary ammonium fluoride has detergent properties. Certain cationic surfactants may also be used as bactericides in the compositions disclosed herein. Cationic surfactants such as chlorhexidine, although also suitable for use in the present invention, are not preferred because they can stain the hard tissues of the oral cavity. This possibility is known to the person skilled in the art and this limitation must be clear when incorporating cationic surfactants.

Preferred nonionic surfactants useful in the compositions of the present invention are broadly defined as compounds resulting from the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound which is aliphatic or alkyl aromatic in nature. Examples of suitable nonionic surfactants include addition polymers (polyethers) of polypropylene glycol and ethylene oxide, polyethylene oxide condensates of alkyl phenols, condensation products derived from the reaction products of ethylene oxide with propylene oxide and 1, 2-ethylenediamine, ethylene oxide condensates of aliphatic alcohols, long chain tertiary amine oxides, long chain tertiary phosphine oxides, long chain dialkyl sulfoxides, and mixtures of these materials.

Preferred zwitterionic synthetic surfactants for use in the present invention can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, 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. Pat. No. 5,180,577 to Po1efka et al, published 1/19 1993. Typical alkyldimethyl betaines include decyl betaine or 2- (N-decyl-N, N-dimethylamino) acetate, coco betaine or 2- (N-coco-N, N-dimethylamino) acetate, tetradecyl betaine, palmityl betaine, lauryl betaine, cetyl betaine, stearyl betaine, and the like. Examples of amido betaines are cocoamidoethyl betaine, cocoamidopropyl betaine, lauramidopropyl betaine, and the like. The betaine of choice is preferably cocamidopropyl betaine, more preferably laurylamidopropyl betaine.

Anticalculus agent

The present compositions may also include an anticalculus agent, preferably a source of pyrophosphate ions from pyrophosphates. Pyrophosphates that can be used in the present compositions include dialkali metal pyrophosphate salts, tetraalkali metal pyrophosphate salts, and mixtures thereof. Disodium dihydrogen pyrophosphate (Na)₂H₂P₂O₇) Tetrasodium pyrophosphate (Na)₄P₂O₇) And tetrapotassium pyrophosphate (K)₄P₂O₇) Are preferred materials. In the compositions of the invention, the pyrophosphate salt can be present in one of three ways: predominantly dissolved, predominantly undissolved, or a mixture of dissolved and undissolved pyrophosphate.

A composition comprising predominantly dissolved pyrophosphate refers to a composition wherein at least one pyrophosphate ion source is present in an amount sufficient to provide at least about 1.0% free pyrophosphate ions. The free pyrophosphate ion content may be from about 1% to about 15%, preferably from about 1.5% to about 10%, most preferably from about 2% to about 6%. Free pyrophosphate ions can exist in a variety of protonated states depending on the pH of the composition.

Compositions comprising predominantly undissolved pyrophosphate refer to compositions wherein the total pyrophosphate dissolved is present in an amount of no more than about 20%, preferably less than about 10%. Tetrasodium pyrophosphate salt is the preferred pyrophosphate salt in these compositions. Tetrasodium pyrophosphate may be in the anhydrous salt form, or the decahydrate form, or may be any other material that is stable in solid form in a dentifrice composition. The salt may be in the form of solid particles, which may be in crystalline and/or amorphous form, the particle size of the salt preferably being small enough to be aesthetically acceptable and readily soluble in use. The amount of pyrophosphate salt used in the preparation of these compositions is any amount effective in tartar control and is generally from about 1.5% to about 15%, preferably from about 2% to about 10%, most preferably from about 3% to about 8%, by weight of the dentifrice composition.

The composition may also include a mixture of dissolved and undissolved pyrophosphate salts. Any of the above-mentioned pyrophosphate salts can be used.

Pyrophosphate salts are described in more detail in Kirk-Othmer Encyclopedia of chemical technology, third edition, volume 17, Wiley-Interscience Press (1982).

Optional agents for use in place of or in combination with the pyrophosphate include those known such as synthetic anionic polymers including polyacrylates and copolymers of maleic anhydride or maleic acid with methyl ethyl ester (e.g., Gantrez); such materials are described, for example, in U.S. Pat. No. 4,627,977 to Gaffar et al, and, for example, polyaminopropylsulfonic Acid (AMPS), zinc citrate trihydrate, polyphosphates (e.g., tripolyphosphate; hexametaphosphate), diphosphates (e.g., EHDP, AHP), polypeptides (e.g., polyaspartic and polyglutamic acids), and mixtures thereof.

Examples of phosphate copolymers include diphosphate derived polymers, which are disclosed in U.S. Pat. No. 5,011,913 to Benedict et al. The preferred polymer is a bisphosphonate-modified polyacrylic acid. Other suitable phosphonate containing polymers are described in U.S. Pat. No. 5,980,776 to Zakikhani et al.

Polyphosphates may also be included in the present compositions. Polyphosphate generally refers to a material consisting of two or more phosphate groups arranged primarily in a linear configuration, although some cyclic derivatives may also be present. In addition to pyrophosphates and tripolyphosphates, which are strictly polyphosphates, it is also desirable that the polyphosphates have an average of about four or more phosphate groups, particularly, for example, tetrapolyphosphates and hexapolyphosphates. Polyphosphates larger than tetrapolyphosphates are generally amorphous glassy materials, for example linear "glassy" polyphosphates having the formula:

XO(XPO₃)_nX

wherein X is sodium or potassium and n has an average value of about 6 to about 125. Preferred polyphosphates are those prepared by FMCCcorporation and are available under the trade names Sodaphos (n.apprxeq.6), Hexaphos (n.apprxeq.13) and Glass H (n.apprxeq.21). These polyphosphates may be used alone or in combination.

Chelating agents

Other preferred optional agents are chelating agents such as tartaric acid and pharmaceutically acceptable salts thereof, citric acid and alkali metal citrates and mixtures thereof. Chelating agents complex calcium in the cell wall of bacteria. Chelating agents can also disrupt plaque by removing calcium from calcium bridges, which help keep the biomass intact. However, it is undesirable to use a chelating agent that has too high an affinity for calcium, as this can lead to tooth demineralization, which is contrary to the objects and intent of the present invention.

Sodium citrate and potassium citrate are the preferred alkali metal citrates, with sodium citrate being most preferred. Also preferred are citric acid/alkali metal citrate compositions. Preferred herein are alkali metal salts of tartaric acid. Most preferred for use in the present invention are disodium tartrate, dipotassium tartrate, sodium potassium tartrate, sodium hydrogen tartrate and potassium hydrogen tartrate. The amount of chelating agent suitable for use in the present invention is from about 0.1% to about 2.5%, preferably from about 0.5% to about 2.5%, most preferably from about 1.0% to about 2.5%. The tartrate chelating agent may be used alone or in combination with other optional chelating agents.

Other optional chelating agents may be used. Preferably, these chelating agents have a calcium binding constant of about 10¹To 10⁵To provide improved cleaning and to reduce plaque and calculus formation.

Other possible chelating agents also suitable for use in the present invention are anionic polymeric polycarboxylates. These materials are well known in the art and are used in the form of their free acids, or partially or preferably fully neutralized water soluble alkali metal (e.g., potassium, preferably sodium) or ammonium salts. Preferred are copolymers of 1: 4 to 4: 1 maleic anhydride or acid with another polymerizable ethylenically unsaturated monomer, preferably methyl vinyl ether (methoxyvinyl) having a molecular weight (M.W.) of about 30,000 to about 1,000,000. Examples of such copolymers are Gantrez AN139(M.W.500,000), AN 119(M.W.250,000), preferably S-97 pharmaceutical grade (M.W.70,000), available from GAF Chemicals Corporation.

Other useful polymeric polycarboxylates include 1: 1 copolymers of maleic anhydride with ethyl acrylate, hydroxyethyl methacrylate, N-vinyl-2-pyrrolidone or ethylene (the latter being commercially available, e.g., MonsantoEMA No.1103, molecular weight 10,000 and EMA rating of 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 effective polymeric polycarboxylates are disclosed in Gaffar, U.S. Pat. No. 4,138,477, published 2/6 1979, and Gaffar et al, U.S. Pat. No. 4,183,914, published 1/15 1980, which include copolymers of maleic anhydride with styrene, isobutylene or ethyl vinyl ether; polyacrylic acid, polyitaconic acid, and polymaleic acid; and sulfoacrylic oligomers, having molecular weights as low as 1,000, available from Uniroyal ND-2.

Fluoride source

Additional water-soluble fluoride compounds are typically present in dentifrices and other oral compositions in sufficient amounts to provide fluoride ion concentrations to the composition at 25℃ and/or to provide additional anticaries benefits when used at concentrations of from about 0.0025% to about 5.0%, preferably from about 0.005% to about 2.0%, by weight. Various fluoride ion generating species may be used as a source of soluble fluoride in the present compositions. Examples of suitable fluoride ion generating materials are found in U.S. Pat. No. 3,535,421 to Briner et al, published on 20/10 1970, and in U.S. Pat. No. 3,678,154 to Widder et al, published on 18/7 1972. Representative fluoride ion sources include: stannous fluoride, sodium fluoride, potassium fluoride, sodium monofluorophosphate and many others. Stannous fluoride and sodium fluoride, and mixtures thereof, are particularly preferred.

Tooth whitening actives

Tooth whitening actives may be included in the oral care compositions of the present invention. Suitable actives for whitening include peroxides, metal chlorites, perborates, percarbonates, peroxyacids, persulfates, and combinations thereof. Suitable peroxide compounds include hydrogen peroxide, carbamide peroxide, calcium peroxide, and mixtures thereof. Suitable metal chlorites include calcium chlorite, barium chlorite, magnesium chlorite, lithium chlorite, sodium chlorite, and potassium chlorite. A preferred chlorite is sodium chlorite. Additional whitening actives may be hypochlorite and chlorine dioxide. The preferred percarbonate is sodium percarbonate. Other suitable brighteners include potassium, ammonium, sodium and lithium persulfates, monohydrates and tetrahydrates of perborates, and sodium peroxypyrophosphate.

Thickening agent

In preparing toothpastes or gels, it is necessary to add thickening materials in order to provide a satisfactory consistency of the composition, a satisfactory release profile of the active substance, shelf stability and stability of the composition, etc. Preferred thickeners are carboxyvinyl polymers, carrageenan, hydroxyethyl cellulose, laponite and water soluble salts of cellulose ethers such as sodium carboxymethyl cellulose and sodium carboxymethyl hydroxyethyl cellulose. Natural gums such as karaya, xanthan, gum arabic and gum tragacanth can also be used. Colloidal magnesium aluminum silicate or finely divided silica can be used as part of the thickener to further improve structure.

A preferred class of thickening or gelling agents includes a class of homopolymers or carbomers of acrylic acid crosslinked with an alkyl ether of pentaerythritol or an alkyl ether of sucrose. Carbomer in Carbopol^®Series were obtained from b.f. goodrich. Particularly preferred carbopols include Carbopol 934, 940, 941, 956, and mixtures thereof.

Copolymers of lactide and glycolide monomers having a molecular weight of from about 1,000 to about 120,000 (number average) are useful for delivering actives to or around periodontal pockets as "subgingival gel carriers". These polymers are described in U.S. patent 5,198,220, published 3-30 1993 and U.S. patent 5,242,910, published 9-7 1993, both issued to Damani; and U.S. patent 4,443,430 to Mattei, published on 17.4.1984.

The thickening agent may be used in an amount of from about 0.1% to about 15%, preferably from about 2% to about 10%, more preferably from about 4% to about 8% by weight of the total toothpaste or gel composition. Higher concentrations are useful in chewing gums, lozenges (including fresh mints), sachets, non-abrasive gels and subgingival gels.

Wetting agent

Another optional component of the topical oral carrier of the compositions of the present invention is a humectant. Humectants are used to prevent hardening of toothpaste compositions upon exposure to air and to impart a moist feel to the composition to the oral cavity. Humectants can also be used to impart desirable sweetness to toothpaste compositions for a particular humectant. The humectant typically comprises from about 0% to about 70%, preferably from about 5% to about 25%, by weight of the composition of the present invention, based on pure humectant. Suitable humectants for use in the compositions of the invention include edible polyhydric alcohols such as glycerol, sorbitol, xylitol, butylene glycol, polyethylene glycol and propylene glycol, particularly sorbitol and glycerol.

Flavoring and sweetening agents

Flavoring agents may also be added to the composition. Suitable flavoring agents include wintergreen oil, peppermint oil, spearmint oil, clove bud oil, menthol, anethole, methyl salicylate, eucalyptol, cinnamon, 1-menthyl acetate, sage, eugenol, parsley oil, oxazolidinone (oxanone), alpha-ionone, origanum, lemon, orange, propenyl guaethol, cinnamon, vanillin, thymol, linalool, the cinnamic aldehyde glycerol acetal known as CGA, and mixtures thereof. Flavoring agents are typically used in the compositions at levels of from about 0.001% to about 5% by weight of the composition.

Sweeteners which may be used include sucrose, glucose, saccharin, dextrose, levulose, lactose, mannitol, sorbitol, fructose, maltose, xylitol, saccharin salts, thaumatin (thaumatin), aspartame, D-tryptophan, dihydrochalcones, acesulfame potassium (acesulfame), and cyclamate salts, especially sodium cyclamate and saccharin, and mixtures thereof. The compositions preferably comprise from about 0.1% to about 10%, preferably from about 0.1% to about 1%, by weight of the composition, of these agents.

In addition to flavoring and sweetening agents, coolants, salivating agents, warming agents and numbing agents may also be used as optional components of the compositions of the present invention. These agents are present at levels of from about 0.001% to about 10%, preferably from about 0.1% to about 1%, by weight of the composition.

The coolant may be any of a wide variety of substances. Among the materials included in the present invention are carboxyamide compounds, menthol, ketals, diols and mixtures thereof. Preferred coolants in the present composition are p-menthane carboxamide reagents, such as N-ethyl-p-menthane-3-carboxamide, having the trade name "WS-3"; n, 2, 3-trimethyl-2-isopropyl butanamide, trade name "WS-23"; and mixtures thereof. Another preferred coolant is selected from menthol, a scale manufactured by Takasago3-1-menthoxypropane-1, 2-diol which is TK-10, menthone glycerol acetal known as MGA produced by Haarmann and Reimer and Frescola produced by Haarmann and Reimer^®Menthyl lactate. The terms "menthol" and "menthyl" as used in the present invention include the dextro-and levorotatory isomers of these compounds, as well as racemic mixtures thereof. TK-10 is described in Amano et al, U.S. Pat. No. 4,459,425, published 10/7/1984. WS-3 and other reagents are described in U.S. Pat. No. 4,136,163 to Watson et al, published 1979, month 1, 23.

Preferred salivating agents of the invention include Jambu manufactured by Takasago^®. Preferred warming agents include capsicum and nicotinates such as benzyl nicotinate. Preferred numbing agents include benzocaine, lidocaine, clove bud oil, and ethanol.

Alkali metal bicarbonate

The present invention may include alkali metal bicarbonate salts. Alkali metal bicarbonate is water soluble and if it is unstable in aqueous systems, it tends to release carbon dioxide. Sodium bicarbonate, also known as baking soda, is a preferred alkali metal bicarbonate salt. The present compositions may comprise from about 0.5% to about 30%, preferably from about 0.5% to about 15%, most preferably from about 0.5% to about 5% of an alkali metal bicarbonate salt.

Hybrid carrier

The water used in preparing the commercial oral composition should preferably be low in ionic content and free of organic impurities. The water is present in an amount of from about 5% to about 70%, preferably from about 20% to about 50%, by weight of the aqueous composition of the present invention. These include added free water and water with other materials introduced (e.g. with sorbitol).

Titanium dioxide may also be added to the present compositions. Titanium dioxide is a white powder and provides opacity to the composition. Titanium dioxide typically comprises from about 0.25% to about 5% by weight of the dentifrice composition.

Preferably, a buffer is used to adjust the pH of the present composition. Buffering agents, as used herein, refer to agents that are capable of adjusting the pH of a composition to about pH 4.0 to about pH 10.0. Buffering agents include monosodium phosphate, trisodium phosphate, sodium hydroxide, sodium carbonate, sodium acid pyrophosphate, citric acid, and sodium citrate. The buffering agent may be applied at a level of from about 0.5% to about 10% by weight of the present composition.

Other optional agents that may be used in the present compositions include dimethicone copolyols selected from alkyl dimethicone copolyols and alkoxy dimethicone copolyols, such as C12-C20 alkyl dimethicone copolyols and mixtures thereof. Highly preferred is cetyl dimethicone copolyol marketed under the trade name Abil EM 90. Dimethicone copolyols are generally present at a level of from about 0.01% to about 25%, preferably from about 0.1% to about 5%, more preferably from about 0.5% to about 1.5% by weight. The dimethicone copolyol assists in providing positive tooth feel benefits.

Other useful carriers include dual phase dentifrice formulations such as those disclosed in the following references: U.S. patent 5,213,790 published on 5-23 of 1993, 5,145,666 published on 9-8 of 1992, and 5,281,410 published on 1-25 of 1994, all of which are Lukacovic et al; and U.S. Pat. Nos. 4,849,213 and 4,528,180 to Schaeffer.

Other active agents

Other agents, such as antimicrobial agents, may also be included in the present invention. Included among such agents are water insoluble non-cationic antimicrobial agents such as halogenated diphenyl ethers, phenolic compounds including phenol and its homologs, mono-and poly-alkyl and aromatic halophenols, resorcinol and its derivatives, bisphenol compounds and halogenated salicylanilides, benzoin esters and halogenated carbanilides. Water-soluble antimicrobials include quaternary ammonium salts and bis-diguanide (quanide) salts, among others. Triclosan monophosphate is an additional water soluble antimicrobial agent. The quaternary ammonium agents include those wherein one or two of the substituents on the quaternary nitrogen have a carbon chain length (typically alkyl group) of from about 8 to about 20, typically from about 10 to 18 carbon atoms, while the remaining substituents (typically alkyl or benzyl group) have a fewer number of carbon atoms, such as from about 1 to about 7 carbon atoms, typically methyl or ethyl. Examples of typical quaternary ammonium antibacterial agents are dodecyltrimethylammonium bromide, tetradecylpyridine chloride, domiphen bromide (dodecyldimethylamine bromide), N-tetradecyl-4-ethylpyridinium chloride, dodecyldimethyl (2-phenoxyethyl) ammonium bromide, benzyldimethylstearylammonium chloride, hexadecylpyridinium chloride, quaternized 5-amino-1, 3-bis (2-ethylhexyl) -5-methylhexahydropyrimidine, alkylbenzyldimethylammonium chloride, benzethonium chloride and methylbenzethonium chloride. Other compounds are bis [4- (R-amino) -1-pyridinium alkanes disclosed in Bailey's U.S. patent 4,206,215, published 6/3 1980. Other antimicrobial agents such as copper bisglycinate, copper glycinate, zinc citrate and zinc lactate may also be included. Also useful are enzymes including endoglycosidases, papain, glucanases, mutanases (mutanases), and mixtures thereof. These reagents are disclosed in U.S. Pat. No. 2,946,725 to Norris et al, 7/26 in 1960, and U.S. Pat. No. 4,051,234 to Gieske et al, 9/27 in 1977. Specific antimicrobial agents include chlorhexidine, triclosan monophosphate, and flavor oils such as thymol. Triclosan and such other agents are disclosed in U.S. patent 5,015,466 to Parran, Jr. et al, published 5/14 1991, and U.S. patent 4,894,220 to Nabi et al, published 1/16 1990. These agents providing antiplaque benefits can be present at a level of from about 0.01% to about 5.0% by weight of the dentifrice composition.

Application method

The present invention also relates to methods of cleaning and polishing teeth and reducing discoloration, plaque, gingivitis, and calculus production on enamel.

The method of use of the present invention comprises contacting the enamel surface and oral mucosa of a subject with an oral composition of the present invention. The method of use may be brushing with a dentifrice, rinsing with a dentifrice slurry or mouthwash, or chewing the gum product. Other methods include contacting a topical oral gel, mouth spray or other formulation with the teeth and oral mucosa of the subject. The subject may be any human or lower animal whose dental surfaces are contacted with the oral composition.

It will be appreciated that the present invention is not only directed to methods of delivering the present compositions to the oral cavity of humans, but also to methods of delivering these compositions to the oral cavity of other animals, such as domestic pets or other livestock, or caged animals.

For example, a method of use may include brushing the teeth of a dog with a dentifrice composition. Another example includes rinsing the mouth of the cat with the oral composition for a sufficient time to see a benefit. Pet care products such as chews and toys may be formulated to contain the present oral compositions. Compositions comprising the present copolymers are included in relatively soft, yet strong and durable materials such as rawhide, ropes made from natural or synthetic fibers, and polymeric articles made from nylon, polyester, or thermoplastic polyurethane. When the animal chews, licks or gnaws the product, the contained active ingredient is released into the saliva matrix in the animal's mouth, which corresponds to an effective brushing or rinsing.

Examples

The following examples further describe and illustrate embodiments within the scope of the present invention. These examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations or modifications thereof are possible without departing from the spirit and scope of the invention.

Example I evaluation of whitening Performance

The whitening performance of the oral solution of the present invention was compared to a treatment solution containing tripolyphosphate alone. The results show that the present copolymers have enhanced whitening properties when used in combination with tripolyphosphate, as can be seen by L^*、b^*And the change in E value.

Saliva-coated HAP powder was stained with tea water and rinsed with test solution for one minute. From L^*And b^*The change in value can be measured as a change in discoloration on the powder. These values were obtained using the International Commission on illumination (CIE) standard, denoted as L^*、a^*、b^*This is a numerical representation of the spacing of the color bars in three dimensions, where L^*Denotes lightness of y-axis, a denotes chromaticity of x-axis (red-green), b^*Denotes the chromaticity of the z-axis (yellow-blue). Δ E is the square root of the sum of the squares of the differences of the various representative values. Determination of L by means of light measurement^*And b^*Variations, which are important to the present test.

Treatment of	Variation of L	b change	Variation of E
				5% Tripolyphosphate (TPP)	7.36	-10.82	13.30
5％60/40PVP/VA	2.17	0.15	2.27
				5％TPP+5％60/40PVP/VA	15.15	-14.33	21.25

Example II efficacy of brushing with toothpaste formulations

Bovine slices stained with a color-changing mixture containing coffee, tea, iron and bacteria were brushed 200 times with the following slurry of toothpaste. Determining L using digital images^*Is changed. The results show that the present invention has enhanced whitening and discoloration removal compared to commercially available products.

Treatment of	L*Variations of (2)	Variation of E
			Fluoride toothpaste	1.88	1.91
Toothpaste for controlling dental calculus	9.31	9.71
			PVP/VA + TPP toothpaste	13.63	13.79

Example III polishing Effect of formulations comprising silica abrasives

The polishing effect of the formulation was determined based on the enamel polishing index, developed by the laboratory, described in commonly assignedUnited states provisional application 60/300766 filed on 25/6/2001. The percent reduction (%) in the roughness of bovine enamel surfaces was determined after brushing with the test dentifrice formulation slurry. The results show that formulations using the present copolymer and abrasive can reduce surface roughness to a lower level than formulations containing only abrasive.

Treatment of	Percent reduction of roughness%
		25% Zeodent 119 slurry	17.02
25% Zeodent 119+ PVP/VA slurry	23.99
		25% Zeodent 109 slurry	35.98
25% Zeodent 109+ PVP/VA slurry	40.10

Example IV dentifrice formulation

Dentifrice compositions of the present invention having varying levels of copolymer, tripolyphosphate, silica abrasive and bleaching agent are shown below. These compositions are prepared using conventional methods.

Components	Weight percentage of IVA (%)	IVB weight percent (%)	IVC weight percent (%)	IVD weight percent (%)	% by weight of IVE (%)	IVF weight percent (%)
							Sorbitol solution (70%)	24.0	30.0	24.0	24.0	26.0	30.0
silica-Zeodent 109	-	-	15.0	12.5	-	-
							silica-Zeodent 118	15.0	-	15.0	-	15.0	20.0
silica-Zeodent 119	15.0	-	-	12.5	15.0	-
							Tetrasodium pyrophosphate	-	-	-	-	5.0	-
Sodium tripolyphosphate	-	5.0	5.0	3.0	-	3.0
							60/40 PVP/VA	5.0	3.0	5.0	1.0	3.0	-
70/30 PVP/VA	-	-	-	-	-	2.0
							Thickened silica		6.0	1.0	1.0	-	1.0
Glycerol	8.0	12.0	8.0	8.0	6.0	10.0
							Polyethylene glycol 300, NF (PEG-6)	-	6.0	-	6.0	-	-

Alkyl sodium solution (27.9%)	5.0	5.0	5.0	5.0	5.0	5.0
							Sodium bicarbonate	1.5	1.5	-	-	1.5	1.5
Poloxamer 407, NF	1.5	1.25	1.25	1.25	-	1.5
							Flavouring agent	1.1	0.6	1.1	1.1	1.1	1.0
Titanium dioxide/carnauba wax particles	-	1.0	1.0	-	1.0	1.0
							Sodium carboxymethylcellulose	0.8	0.8		0.75	0.75	0.75
Xanthan gum	-	0.5	0.5	-	-	-
							Carbopol 956	-	0.4	0.4	-	-	-
Saccharin sodium salt	0.35	0.35	0.35	0.35	0.35	0.35
							Sodium carbonate	0.5	0.5	-	-	0.5	0.5
Sodium phosphate	-	0.5	0.5	-	-	-
							Trisodium phosphate	-	1.5	1.5	-	-	-
Sodium fluoride	0.243	0.243	0.243	0.243	0.243	0.243
							Colour(s)	-	0.05	0.05	0.05	0.05	0.05
Purified USP grade water	Proper amount of	Proper amount of	Proper amount of	Proper amount of	Proper amount of	Proper amount of

Components	IV G weight percent (%)	IV H weight percent (%)	IV J weight percent (%)	IV K weight percent (%)	IV M
							Part A weight percent (%)	Percentage by weight of part B (%)
					Sorbitol solution (70%)	-			-	-	-	48.0	-
Precipitated silica	30.0	25.0	30	20			26.0	-
					Sodium tripolyphosphate	5.0			-	-	-	3.5	-
60/40 PVP/VA	5.0	5.0	5.0	-			3.0	-
					70/30 PVP/VA	-			-	-	7.0	-	-
Thickened silica	1.0	1.0	1.0	1.0			-	-
					Alkyl sodium solution (27%)	-			-	-	-	5.0	-
Poloxomer 407，NF	1.25	1.25	1.25	1.25				-
					Flavouring agent	1.1			1.1	1.1	1.1	0.8	-
Titanium dioxide/carnauba wax particles	1.0	1.0	1.0	1.0			0.5	-

Sodium carboxymethylcellulose	-	-	-	-	0.6
							Xanthan gum	0.5	0.5	0.5	0.5	0.5	-
Carbopol 956	0.4	0.4	0.4	0.4		-
							Saccharin sodium salt	0.35	0.35	0.35	0.35	0.4	-
Sodium phosphate	0.5	0.5	0.5	0.5		-
							Trisodium phosphate	1.5	1.5	1.5	1.5	1.5	-
Sodium fluoride	0.243	0.243	0.243	0.243	0.243	-
							Carbamide peroxide	5.5	5.5	10.0	10.0	-	15.0
Carboxypolymethylene						5.0
							Glycerol	Proper amount of	Proper amount of	Proper amount of	Proper amount of	-	70.0
Purified USP grade water and micro component 1	-	-	-	-	Proper amount of	Proper amount of

E.g., NaOH, is used to adjust the pH.

Example V mouthwash

Weight percent of the ingredients (%)

24.000 g of water

Propylene glycol 53.459

Sodium tripolyphosphate 5.000

Sodium benzoate 0.320

Benzoic acid 0.021

Saccharin sodium 0.700

60/40 PVP/VA 5.000

Poloxamers 40710.000

Flavoring agent 1.500

Example V was prepared as follows: mixing water, poloxamer and propylene glycol. Flavor, benzoic acid, tripolyphosphate, and PVP/VA were then added. Finally, sodium benzoate and saccharin sodium are added and mixed until uniform.

Example VI dental gel

Example VI illustrates aqueous and anhydrous tooth gel compositions which can be prepared by mixing the liquid carrier, followed by the addition of saccharin, sodium tripolyphosphate, and PVP/VA, and mixing until homogeneous.

Components	VIA weight percent (%)	VIB weight percent (%)
			60/40 PVP/VA	5.0	5.0
Sodium tripolyphosphate	2.0	2.0
			Saccharin sodium salt	0.5	0.5
Carbamide peroxide	-	15.0
			Ethanol	32.5	-
Water (W)	60.0	-
			Glycerol	-	35.0
PEG	-	42.5

Example VII chewing Gum

The chewing gum composition of the present invention comprising coated chewing gum (VIIC) is shown below.

Components	VIIA	VIIB
			Xylitol, its preparation method and use	16.700	16.700
Gum bases (e.g., Prestige-PL, Cafosa)	28.000	28.000
			60/40 PVP/VA	5.000	3.000
Sodium tripolyphosphate	5.000	7.000
			Hydrogenated starch hydrolysate (85% solids)	8.000	8.000
Glycerol	7.000	7.000
			Mannitol	5.000	5.000
Flavouring agent	1.600	1.600
			Aspartame	0.200	0.200
Spray-dried menthol	0.150	0.150
			Sorbitol	Proper amount of	Proper amount of

Preparation guidance- -examples VIIA and VIIB

The gum base is heated to about 45 ℃ to soften it. The mixer cavity was maintained at about 45 ℃ throughout the mixing process. The gum base was added to the mixing chamber with a double sigma blade mixer and mixed for 5 minutes. Mannitol and spray dried menthol were added. Mix for 2 minutes. Add 50% sorbitol and mix for 2 minutes. Add glycerol and mix for 2 minutes. 50% xylitol was added and mixed for 2 minutes. The hydrogenated starch hydrolysate was added and mixed for 5 minutes. A second portion of 50% sorbitol was added and mixed for 3 minutes. A second 50% portion of xylitol, PVP/VA, sodium tripolyphosphate, and aspartame were added and mixed for 3 minutes. Flavor was added and mixed for 3 minutes.

VIIC component	Core weight ratio (%)	Coating weight ratio (%)	Total weight ratio (%)
					1 g/tablet	0.35 g/tablet	1.35 g/tablet
Sorbitol	49.35	-	36.56
				Gum matrix1	25.0	-	18.52
PVP/VA 60/40	5.0		3.70
				Sodium tripolyphosphate	5.0	-	3.70
Sodium fluoride	-	0.08	0.02
				Hydrogenated starch hydrolysates	5.0	-	3.70
Mannitol	2.0	-	1.48
				Glycerol	5.0	-	3.70
Titanium dioxide	-	2.0	0.52
				Flavouring agent	2.0	2.0	2.00
Additional spray-dried flavor	1.5	-	1.11
				Sucralose	0.05	0.03	0.05
Acesulfame potassium	0.10	0.10	0.10
				Sorbitol2	-	95.25	24.70
Polysorbate 60	-	0.30	0.08
				Insoluble edible glitter3(sapphire blue)	-	0.04	0.01
Wax4	-	0.20	0.05
				Total of	100.00	100.00	100.00

¹Including several ingredients including a preformed gum base, available from suppliers such as l.a. dreyfus, 3775 Park Avenue, Edison, new jersey, usa; cafosa Gum, Calabria267, 08029, Barcelona, Spain, etc.

²The sorbitol content refers to the absolute content after drying; the added sorbitol was a 70% aqueous solution.

³Watson Foods Company Incorporated, 301 Heffernan Drive, West Haven, Connecticut, USA.

⁴The content of wax is the absolute content after drying, and the wax is 28 percent ethanol solution; the waxes used comprise several components, as supplied by Kaul GmBH, elmshop, Germany.

Preparation guide

A core preparation: slowly heating to soften the gum base, adding mannitol, spray dried flavor, glycerin, 50% xylitol, hydrogenated starch hydrolysate, 50% sorbitol, and mixing thoroughly. A second 50% sorbitol portion was added and mixed for 2 minutes. A second 50% portion of xylitol, sodium tripolyphosphate, PVP/VA and aspartame, the remainder of the flavor, was added and further mixed. The entire chewing gum mass is divided into dispersible tablets of the desired shape and size using a roller and scoring device.

Coating solution: titanium dioxide and polysorbate 60% were added to a 70% aqueous solution of sorbitol and then mixed. Flavor is added, followed by sucralose and acesulfame-K, and further mixing.

Coating of the core preparation: the gum tablets were placed in a coating pan, the coating solution applied, and partially dried. The coating step is repeated until a coating of the desired thickness or weight is obtained. A clear 70% aqueous solution of sorbitol was applied to the surface of the product, the dry sprayed spots were applied in a wet state and then dried. A second coating of clear 70% sorbitol solution was applied followed by a wax coating to completely dry the product.

While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention, and it is intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (17)

1. An oral care composition comprising an orally acceptable carrier and at least 0.1% by weight of a water-soluble or water-dispersible copolymer of vinylpyrrolidone monomer units and C₂-C₁₂Alkenyl radical C₁-C₁₉Saturated alkyl carboxylate monomer units, which provide enhanced cleaning, whitening and stain removal of teeth.

2. The oral care composition of claim 1,characterized in that the copolymer is prepared by copolymerizing a vinylpyrrolidone monomer with C₁-C₁₉Saturated alkyl carboxylic acids C₂-C₁₂Alkenyl ester monomers, these two types of monomers are shown below:

wherein R is¹、R²、R³、R⁴、R⁵H or saturated C¹-C¹²An alkyl group;

R⁶saturated straight or branched chain C₁-C₁₉An alkyl group;

R⁷＝C₂-C₁₂alkenyl, and

the weight ratio of x/y ranges from 30/70 to 90/10.

3. The oral care composition of claim 2, wherein the copolymer is selected from a copolymer of vinyl pyrrolidone and one of vinyl acetate, vinyl propionate, or vinyl butyrate.

4. The oral care composition of claim 3, further comprising from 0.1% to 20.0% by weight of the composition of a dental bleaching agent.

5. An oral care composition, comprising:

(a) at least 0.1% by weight of a water-soluble or water-dispersible copolymer consisting of vinylpyrrolidone monomer units and C₂-C₁₂Alkenyl radical C₁-C₁₉The saturated alkyl carboxylic ester monomer unit,

(b) at least 0.5% by weight of a water-soluble tripolyphosphate, and

(c) an orally acceptable carrier, in a carrier vehicle,

the compositions provide enhanced cleaning, whitening and stain removal of teeth.

6. An oral care composition according to claim 5, wherein said water soluble or water dispersible copolymer is selected from copolymers of vinyl pyrrolidone and one of vinyl acetate, vinyl propionate, or vinyl butyrate, and wherein said tripolyphosphate is selected from alkali metal tripolyphosphate, ammonium tripolyphosphate, and mixtures thereof.

7. The oral care composition of claim 6, comprising from 0.5% to 10.0% of vinylpyrrolidone/vinyl acetate copolymer and from 2.0% to 20.0% of tripolyphosphate by weight of the composition.

8. The oral care composition of claim 7, further comprising from 0.1% to 20.0% by weight of the composition of a dental bleaching agent.

9. An oral care composition comprising

(a) At least 0.1% by weight of a water-soluble or water-dispersible copolymer obtained by copolymerizing vinylpyrrolidone monomer units with C₂-C₁₂Alkenyl radical C₁-C₁₉Saturated alkyl carboxylic ester monomer units are prepared,

(b) at least 6% by weight of an abrasive polishing agent, and

(c) an orally acceptable carrier, in a carrier vehicle,

the compositions provide enhanced cleaning, whitening, polishing and stain removal of teeth.

10. The oral care composition of claim 9, wherein the water-soluble or water-dispersible copolymer is selected from a copolymer of vinyl pyrrolidone and one of vinyl acetate, vinyl propionate, or vinyl butyrate, and wherein the polishing agent comprises one of a silica abrasive or a mixture thereof.

11. The oral care composition of claim 10, comprising from 0.5% to 10.0% of a vinylpyrrolidone/vinyl acetate copolymer and from 6% to 70% of a silica abrasive, by weight of the composition.

12. The oral care composition of claim 11, further comprising from 2.0% to 20.0% by weight of a tripolyphosphate salt selected from the group consisting of alkali metal tripolyphosphate, ammonium tripolyphosphate, and mixtures thereof.

13. The oral care composition of claim 12, further comprising from 0.1% to 20.0% by weight of the composition of a dental bleaching agent.

14. The oral care composition of claim 13, wherein the dental bleaching agent is selected from the group consisting of hydrogen peroxide, urea peroxide, calcium peroxide, sodium peroxide, and mixtures thereof.

15. A method for overall cleaning and whitening of teeth and removal and prevention of surface deposit staining from teeth, said method comprising contacting the teeth of a test subject with the oral composition of claim 1.

16. A method for overall cleaning and whitening of teeth and removal and prevention of surface deposit staining from teeth, said method comprising contacting the teeth of a test subject with an oral composition of claim 5.

17. A method for overall cleaning, whitening and polishing teeth and removing and preventing surface deposit staining from teeth, said method comprising contacting the teeth of a test subject with the oral composition of claim 9.