Oral compositions providing enhanced overall cleaning

The subject of the invention is an oral care composition providing a cleaning, whitening, stain removal effect.

The composition prevents discoloration of natural teeth and dentures. In particular, these advantages are achieved by applying to the teeth a composition comprising, in an orally acceptable carrier, a copolymer consisting of vinylpyrrolidone (WP) and alkenyl carboxylate (AK) monomers.

The formation of plaque and calculus is a major source of tooth decay, gingivitis, periodontal disease, and tooth loss. Dental plaque is a deposit that is a mixture of bacteria, epithelial cells, leukocytes, macrophages, and other oral exudates. Bacteria make up approximately three-quarters of the plaque. Each plaque sample can contain as many as 400 different types of microorganisms. This mixture includes both aerobic and anaerobic bacteria, fungi and protozoa. Viruses were also found in the plaque samples.

This buildup of organisms and oral exudates continues to expand and merge with other adjacent plaques.

Bacteria synthesize levans and glycans from sucrose found in the oral cavity, providing energy for microbes. Glycans, levans and microbes form an adhesive backbone for the continued spread of plaque.

Tartar is a deposit that forms on the surface of the teeth at the edge of the gum. Supragingival calculus appears mainly in areas close to the salivary canal openings, e.g. on the lingual surfaces of the lower anterior teeth and on the buccal surfaces of the first and second upper molars, and on the distal surfaces of the posterior molars. A fully developed stone consists of an inorganic part, predominantly calcium phosphate, with a hydroxyapatite crystal lattice structure similar to bone, enamel and dentin. An organic portion is also present, consisting of exfoliated epithelial cells, leukocytes, salivary sediment, food debris, and various types of microorganisms. Developing plaque can most readily adhere to relatively irregular surfaces such as tartar. As a fully developed stone develops, it becomes distinctly white or yellowish, unless it becomes stained or discolored by some external factor. Being unsightly and aesthetically undesirable, fully developed tartar deposits are a constant source of gum irritation.

Failure to delay or stop the spread of plaque and tartar is detrimental to oral health. The formation of plaque and tartar can lead to tooth decay, gingivitis, periodontal disease, and eventually tooth loss. In addition, calculus and plaque, together with environmental factors, lead to the formation of discoloration on the teeth, significantly affecting the aesthetic appearance of the teeth. Environmental factors that influence tooth discoloration include regular drinking of coffee, tea, cola, or the use of tobacco products, and the use of discoloration-promoting oral products such as chlorhexidine.

The highest level of cleaning action for the oral cavity is the level provided by dentists during prophylaxis; daily oral care at home requires products with a variety of ingredients that work according to different mechanisms to ensure satisfactory cleansing and whitening. So for everyday oral care products such as dentifrices and rinses that provide an overall cleaning performance, ingredients must be added to provide beneficial effects against plaque and tartar, as well as to remove stains, combat stains and whiten teeth. . Bleaching agents, abrasives, and chelating agents are such discoloration and anti-whitening ingredients. Bleaching agents added to dentifrices are typically present in low concentrations with toothpaste limitations in terms of shelf life and safety. At these low concentrations, typically oxidizing bleaching agents are generally ineffective at whitening teeth and combating discoloration. Dental abrasives provide significant whitening benefits, especially in the "brushed areas of the teeth," but unfortunately have a limited effect in combating aesthetically undesirable discoloration that forms along the gumline and between adjacent teeth. Bleaching agents and abrasives do not functionally prevent formation

Discoloration. The use of abrasives can reduce the rate of discoloration by removing new stains on a daily basis, but the treatment is "healing for existing stains and not a chemical preventive measure."

The use of chelating agents has been suggested in the literature to slow down the formation of scale and its removal after formation. A chemical approach to inhibiting scale formation generally involves chelating calcium ions and / or inhibiting crystal growth, which prevents scale formation and / or breaks down the scale formed by removing calcium. Additionally, chelating agents can in principle remove discoloration by binding to the surface of the teeth, thereby replacing color substances or chromagens. Retention of these chelating agents can also prevent the build-up of these discolorations by disrupting the binding sites of the colored substances on the tooth surface.

A number of chelating agents used to combat plaque, calculus and discoloration have been disclosed in the literature. For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid and related compounds are disclosed in British Patent 490384, issued February 15, 1937; polyphosphonates in U.S. Patents 3,678,154 filed Jul 18, 1972 (Widder et al.), U.S. Patents 5,338,537 filed August 16, 1994 (White Jr.), and U.S. 5,451,401 filed September 19, 1995. (Zerby et al.); carbonyldiphosphonates in US Patent No. 3,737,533 issued June 5, 1973 (Francis); a zinc-polymer combination formed by the reaction or interaction of a zinc compound with an anionic polymer containing carboxyl, sulfonic and / or phosphono groups, in US Pat. No. 4,138,477, issued Feb. 6, 1979 (Gaffar); tartaric acid in patents US 5,849,271 issued December 15, 1998 (Lukacovic) and US 5,622,689 issued April 22, 1997. (Lukacovic); tartrate monosuccinate acid or salt, tartrate disuccinate, and mixtures thereof in US Patent 5,015,467 issued May 14, 1991 (Smitherman); acrylic acid polymer or copolymer in US Pat. Nos. 4,847,070 issued Jul. 11, 1989 (Pyrz et al.) and US Patent 4,661,341 issued Apr. 28, 1987 (Benedict et al.); sodium alginate in U.S. Patent 4,775,525, issued October 4, 1988. (Pera); polyvinylpyrrolidone in British Patent 741,315 issued November 30, 1955, in Patent Application Publication WO 99/12517 issued March 18, 1999, and in US Patent 5,538,714 issued July 23, 1996 (Pink et al.); and copolymers of vinylpyrrolidone with carboxylates in US Patent No. 5,670,138 issued on September 23, 1997 (Venema et al.) and JP 2000-0633250 issued on February 29, 2000 (Lion Corporation).

Dentifrices and mouthwashes containing soluble pyrophosphates are also disclosed, the use of pyrophosphates being recommended for a variety of purposes, including as an anticalculus agent. They are disclosed, inter alia, in U.S. Patent Nos. 2,941,926 issued January 21, 1960 (Salzmann et al.); US 3,927,201 filed on December 16, 1975 (Baines et al.) And US 3,927,202 filed on December 16, 1975 (Harvey et al.); US 4244931 of January 13, 1981 and US 4247526 of January 27, 1981. (Jarvis et al.); Japanese Patent Application No. 4945-1974; in U.S. Patent Nos. 4,323,551 issued April 6, 1982, US 4,515,772 issued May 7, 1986, and US 4,885,155 issued December 5, 1989 (Parran et al.); and 4,822,599 as of April 18, 1989 (Mitra). Also Draus, Lesniewski and Miklos revealed the in vitro efficacy of soluble pyrophosphates against tartar in the publication "Pyrophosphate and Hexametaphosphate Effects in Vitro Calculus Formation, Arch. Oral Biol., Vol. 15, pages 893-896, (1970).

Linear molecularly dehydrated polyphosphates for use as tartar inhibitors are disclosed in British Patent 2,200,551 (Gaffar, Nabi and Jannone) issued January 27, 1988, published August 10, 1988; and in U.S. Patent 4,627,977 issued December 9, 1986 (Gaffar et al.). Among these salts is sodium tripolyphosphate (STPP). Other publications describing STPP are US 4,923,684 issued May 8, 1990 (Ibrahim et al.) And US 5,096,701 issued March 17, 1992. and US 5,176,900 issued January 5, 1993 (White et al.).

While products containing chelating agents and other plaque and tartar reducing agents are known, there is a continuing need for improved products, particularly products that provide enhanced overall cleaning performance by simultaneously attacking the problems of tartar, plaque and discoloration.

In the prior art, there is no understanding of the stain removal capacity of the copolymers of the compositions of the invention, and of the synergistic interaction between the copolymer and another oral care agent selected from polyphosphates with a chain length of at least 3. Thus, it is not disclosed that it would be obvious the compositions of the present invention and their use to effectively remove stain and prevent stain.

PL 210 477 B1

EP 979649 relates to the use of copolymers with a K value of 50-200 containing 15-50 wt. % N-vinylpyrrolidone and 85-50 wt. vinyl acetate as an ingredient in the preparation of solid oral forms such as tablets, pills, capsules and powders.

EP 172671 relates to coating a dental floss with a non-wax coating such as a polyvinylpyrrolidone coating. Polyvinylpyrrolidone copolymers are not disclosed.

US 6,221,341 discloses tooth whitening using glycerin triacetate. Compositions may include polyvinylpyrrolidone-vinyl acetate copolymer. However, the disclosure also indicates that the samples containing the copolymer showed significantly poorer whitening properties. Therefore, this disclosure points one skilled in the art to a different route than that leading to the solution of the present invention.

The use of an oral care composition containing individual water-soluble or water-dispersible polymeric binders for color substances, such as polyphenols or catechols, has been found to provide enhanced cleaning performance, stain removal and tooth whitening. In addition, polymeric agents in combination with polyphosphates, especially tripolyphosphates, with abrasives, especially precipitated silica, or with bleaching agents, provide an overall cleaning and whitening effect that goes beyond the action of either of the components alone. The present invention thus provides oral compositions containing specific water-soluble or water-dispersible polymeric agents to bind colored substances present in the oral cavity. These compositions are administered to the oral cavity to provide enhanced cleaning performance, stain removal, stain prevention, and tooth whitening. Preferably the compositions further contain one or a mixture of other oral care agents selected from the group consisting of tripolyphosphates, abrasive and whitening agent to provide even better cleaning performance due to synergy between the polymeric complexing agent and other oral care agents.

The present invention relates to an oral care composition providing cleaning, whitening and removal of tooth discoloration containing an orally acceptable aqueous vehicle containing 5 - 70% water and 0.5 - 50% by weight of one oral care agent or mixture selected from from the group consisting of tripolyphosphates and tooth whitening agents, wherein the composition comprises 0.1-20% by weight of a water-soluble or water-dispersible copolymer. as a stain removing and anti-stain agent, consisting of one unit or mixture of vinylpyrrolidone monomer units (WP) and one or mixture of C1-C19- (saturated) alkylcarboxylate C2-C12-alkenyl (AK) monomer units.

Preferably the composition according to the invention comprises a copolymer made by copolymerizing one monomer or mixture of vinylpyrrolidone monomers (WP) with one monomer or mixture of C2-C12-alkenyl ester monomers of saturated C1-C19-alkyl carboxylic acids (AK) as shown below:

<td>f— 45 - RR C = CH</td><td> +</td><td>ABOUT "6 1/7</td>

<td>^R M.</td><td></td><td>RC-OR</td>

<td>R- R¹</td><td>X</td><td></td>

where r¹, R², R³, R⁴, R⁵ = H or saturated C1-C12-alkyl,

R⁶ = straight chain or branched saturated C1-C19-alkyl,

R⁷ = C2-C12-alkenyl, and the ratio x / y ranges from 30/70 to 90/10.

Preferably the composition according to the invention comprises a copolymer selected from copolymers of vinylpyrrolidone with one monomer or a mixture of monomers selected from vinyl acetate, vinyl propionate and vinyl butyrate.

Preferably, the inventive composition comprises 0.1-20.0% of a tooth whitening agent. Preferably the composition according to the invention comprises

PL 210 477 B1 (a) 0.1 - 20% by weight of a water-soluble or water-dispersible copolymer consisting of one unit or mixture of vinylpyrrolidone (WP) monomer units and one unit or mixture of C1-C19- (saturated) monomer units C2-C12-alkenyl alkyl carboxylates (AK), (b) 0.5-50% by weight of water-soluble tripolyphosphate, and (c) an orally acceptable aqueous carrier containing 5-70% water.

Preferably the composition according to the invention comprises a water-soluble or water-dispersible copolymer selected from copolymers of vinylpyrrolidone with one monomer or mixture of monomers selected from vinyl acetate, vinyl propionate and vinyl butyrate, and a tripolyphosphate selected from the group consisting of alkali metal tripolyphosphates, ammonium tripolyphosphate and mixtures thereof .

Preferably the composition according to the invention comprises 0.5-10.0% of a copolymer of vinylpyrrolidone and vinyl acetate and 2.0-20.0% of tripolyphosphate.

Preferably, the inventive composition further comprises at least 6 wt.% Polishing abrasive.

Preferably the composition according to the invention comprises a water-soluble or water-dispersible copolymer selected from copolymers of vinylpyrrolidone with one or a mixture of monomers selected from vinyl acetate, vinyl propionate and vinyl butyrate, and a polishing agent consisting of one or a mixture of silica abrasives.

Preferably the composition according to the invention comprises 0.5-10.0% vinylpyrrolidone / vinyl acetate copolymer and 6-70% by weight silica abrasive, based on the weight of the composition.

Preferably the composition according to the invention comprises 2.0-20.0% by weight of a tripolyphosphate selected from the group consisting of alkali metal tripolyphosphates, ammonium tripolyphosphate and mixtures thereof.

Preferably, the composition according to the invention comprises 0.1-20.0% of a whitening agent selected from the group consisting of hydrogen peroxide, urea peroxide, calcium peroxide, sodium percarbonate, and mixtures of these compounds.

These and other features, forms and advantages of the invention will become apparent to those skilled in the art from reading the detailed description provided below.

All percentages and ratios provided herein are based on the weight of the particular oral care composition and not the total formulation that is provided, unless otherwise stated. All measurements were made at 25 ° C unless otherwise noted.

The term "comprising" as used herein means that other steps and other ingredients may be added which do not affect the end result. The term also includes the terms "consisting of and" consisting essentially of.

"An oral care composition is a product that, in the normal course of use, is not intended to be swallowed for systemic administration of a particular therapeutic agent, but rather is kept in the oral cavity for a time sufficient to contact all tooth surfaces and / or oral tissues. orally to act in the oral cavity. The oral care composition may be in the form of toothpaste, dentifrice, tooth powder, topical oral gel, mouthwash, dental prosthesis product, mouth spray, lozenges, tablets. for use in the mouth or chewing gum.

The term "dentifrice" as used herein shall mean paste, gel or liquid preparations unless otherwise stated. The dentifrice composition can be a single phase composition or can be a combination of two or more dentifrice compositions. The dentifrice composition may take any desired form, such as deeply striated, surface striated, multi-layered, with a gel surrounding the paste, or a combination thereof. Each dentifrice composition in a dentifrice consisting of two or more separate dentifrice compositions may be contained in physically separate dispenser containers from which they are dispensed in parallel.

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

The term "teeth as used herein refers to both natural teeth and artificial teeth or dentures.

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The term "orally acceptable carrier" as used herein means any safe and effective material used in the compositions of the present invention. Such materials include fluoride ion sources, additional tartar control agents, buffers, polishing abrasives, peroxide sources, alkali metal bicarbonates, thickeners, humectants, water, surfactants, titanium dioxide, flavors, sweeteners, xylitol, coloring agents, and mixtures of these substances.

The terms "calculus and" tartar, when used interchangeably, refer to mineralized plaque deposits.

The oral care compositions of the present invention that provide enhanced overall cleaning performance and whitening and stain removal from teeth contain as an essential ingredient one or more water-soluble or water-dispersible polymeric agents capable of binding color substances such as polyphenols. In particular, the water-soluble or water-dispersible polymeric agents are copolymers made by copolymerization of one or a mixture of vinylpyrrolidone (WP) monomers with one monomer or mixture of alkenyl carboxylate (AK) monomers, namely C2-C12-alkenyl esters of saturated, linear or branched C1 acids. -C19alkylcarboxylic acids as shown below:

<td>f— 45 - RR C = CH</td><td> +</td><td> 0 „ 6 1/ 7</td>

<td>^R M.</td><td></td><td>RC-OR</td>

<td>R- R¹</td><td>X</td><td></td>

where r¹, R², R³, R⁴, R⁵ = H or saturated C1-C12-alkyl,

R⁶ = saturated C1-C19-alkyl,

R⁷ = C2-C12-monoalkenyl, and the ratio x / y ranges from 30/70 to 90/10.

Preferred ester monomers are vinyl, allyl and methallyl esters of linear or branched aliphatic carboxylic acids having 2-20 carbon atoms, such as acetate, propionate, butyrate, valerate, hexanoate, 2-ethylhexanoate, decanoate, vinyl laurate and stearate, and the corresponding allyl esters and metallylic. Preferably the vinylpyrrolidone monomer is unsubstituted. Particularly preferred polymers are copolymers of vinylpyrrolidone with one or a mixture of vinyl acetate, vinyl propionate or vinyl butyrate. Preferred polymers have an average molecular weight of 1,000-1,000,000, preferably 10,000-200,000, especially 30,000-100,000. These copolymers are generally prepared by free radical solvent polymerization or emulsion polymerization using solvents such as water, aliphatic alcohols containing 1-4 carbon atoms, or mixtures of alcohol and water, as described e.g. in U.S. Patents 2,667,473, 4,520,179, 4,554,311, 5319041, 5395904, 6107397, and 6103820.

Preferably the compositions further comprise at least 0.5 wt. water-soluble tripolyphosphate and / or at least 6 wt. a polishing abrasive such as silica and / or at least 0.1% whitening agent.

It has been found that the cleaning and whitening properties of vinylpyrrolidone (WP) polymers can be greatly enhanced by altering their water solubility and hydrophobicity. One way to increase hydrophobicity is by copolymerizing vinylpyrrolidones with a series of hydrophobic alkenyl carboxylates. The resulting copolymers not only contain polar pyrrolidone amide bonds and carboxylate ester groups, but also contain hydrophobic alkyl functional groups for longer retention on the teeth and improved stain removal and stain prevention.

Without wishing to be limited to a particular mechanism of action, it is believed that the copolymers used in the compositions of the invention provide improved stain removal and stain prevention due, at least in part, to their ability to complex with color substances such as polyphenolic compounds and their ability to form coatings or layers on

The surface of the teeth. Polyphenols, also known as catechols and tannins, are found in various food products such as tea, coffee, wine, cola, and various fruits and berries. It is known that consumption of these nutritional products causes the deposition of colored materials on the teeth. PWP / AK copolymers are believed to form a protective layer on the tooth surface when the compositions of the invention are used in the oral cavity, e.g. in brushing or rinsing. Thus, when the colored substances are in the oral cavity, they contact the PWP / AK layer, not the tooth surface, and form a complex with the PWP / AK copolymer. The PWP / AK / colored substance complex is then removed from the tooth surface when the transition PWP / AK layer peels off, which prevents the formation of discoloration on the teeth. In terms of stain removal, the copolymer is believed to work in conjunction with other cleaners in the product, such as abrasives, surfactants, and chelating agents. The action of these agents causes the already existing discoloration on the teeth to move away from the surface, and the copolymer forms a complex with the released color substances and prevents them from re-depositing on the teeth. In this respect, the effect of the copolymer is synergistic with the other cleaning ingredients. The formation of fresh plaque can also be prevented in this way, and the copolymer also inhibits the absorption by the plaque of colored ingredients from the food you eat, such as tea, beer, red wine, etc.

A suitable copolymer used in the invention is a vinylpyrrolidone-vinyl acetate (PWP / WA) copolymer with a WP / WA weight ratio of 60/40 and an average molecular weight of 1,000 - 1,000,000, available from BASF Corp. and ISP. Preferred polymers are polymers with an average molecular weight of 30,000-100,000. Suitable copolymers are also copolymers with a WP / WA ratio of 30/70 to 90/10. The content of the copolymer in the composition according to the invention is 0.1% - 20% by weight, preferably 0.5% - 10% by weight.

Preferably, the composition according to the invention further comprises a water-soluble alkali metal or ammonium tripolyphosphate. The sodium salt is preferred, although the potassium salt or a mixture of the sodium and potassium salts can also be used. Tripolyphosphates are supplied hydrate or dehydrated from Monsanto Corp. or Sigma Chemical. Both forms of salt are suitable for use in the composition. The amount of tripolyphosphate is at least 0.5 wt.%. up to 50%. The practical limitation of the amount of tripolyphosphate is mainly its solubility. The preferred amount of tripolyphosphate is 2-20 wt% of the dentifrice formulation.

Although the copolymer component of the composition of the present invention is an active anti-stain agent, it has been surprisingly found that the combination of the copolymer with tripolyphosphate leads to a synergistic effect in stain removal and prevention, far superior to either acting alone.

The compositions of the invention preferably also contain at least 6% of a polishing agent or abrasive, preferably silica. The combination of a copolymer with a polishing abrasive has been found to provide a significantly enhanced polishing effect on tooth enamel surfaces, in addition to cleaning and stain removal. The benefits of polishing include an improved tooth appearance and a positive tooth clean feel.

The compositions according to the invention preferably further contain a tooth whitening agent, in particular a peroxide. It has been found that the copolymers contained in these compositions form complexes with inorganic compounds, in particular with hydrogen peroxide. Thus, these copolymers have a stabilizing effect on the peroxide component when present in the compositions.

Accordingly, in one embodiment, the invention relates to a composition for whitening and cleaning teeth and dentures, comprising a vinylpyrrolidone (WP) copolymer with an alkenyl carboxylate (AK). In another embodiment, the invention relates to a composition comprising a WP / AK copolymer blend and 0.1% - 20.0%, more preferably 1% - 15%, of a whitening agent. In a further aspect, the invention relates to a composition for cleaning, whitening, stain removal and prevention of stain formation on teeth and dentures, comprising a mixture of a water-soluble alkali metal or ammonium tripolyphosphate and WP / AK copolymer. In yet another aspect, the invention relates to a composition further providing an enhanced polishing action comprising a WP / AK copolymer and an abrasive.

The oral care compositions of the present invention may be in the form of a dentifrice, toothpaste, tooth powder, topical oral gel, mouthwash, dental prosthesis product, mouth spray, lozenges. , tablets for use in the mouth or chewing gum.

PL 210 477 B1

The optimum pH of the compositions according to the invention is 4.0-10.0. Preferably the pH of the composition is 6.0-9.0.

In addition to the ingredients described above, the compositions of the invention may contain additional ingredients as described below.

An orally acceptable carrier

The orally acceptable carrier includes one or more compatible solid or liquid fillers as diluents or encapsulating substances suitable for topical administration in the oral cavity. The term "compatible" as used herein means that the components of the composition are compatible with each other without interacting significantly reducing the stability and / or effectiveness of the composition.

The carriers or excipients may include the usual and conventional dentifrice ingredients (including non-abrasive gels and subgingival gels), mouthwashes, mouth sprays, chewing gums, and lozenges (including mint freshening lozenges). breath), which is described in more detail later in the description.

The choice of carrier to be used is generally determined by the method of insertion into the oral cavity. If toothpaste (including tooth gels, etc.) is to be used, then the "toothpaste carrier" is selected (e.g., abrasives, foaming agents, binders, humectants, flavors and sweeteners. etc.) as disclosed e.g. in US Patent 3,988,433 (Benedict). If a mouthwash is to be used, then the "mouthwash carrier (eg, water, flavors and sweeteners, etc.) is selected as disclosed in eg US Patent 3,988,433 (Benedict). Likewise, if a mouth spray is to be used then a "mouth spray carrier is selected, or if a lozenge carrier is to be used then a" lozenge carrier (e.g., candy base) is selected, candy bases are disclosed e.g. in U.S. Patent 4,083,955 (Grabenstetter et al.). If a chewing gum is to be used, then the "chewing gum carrier (eg, gum base, flavorings and sweeteners) is selected as disclosed in eg US Patent 4,083,955 (Grabenstetter et al.). If a sachet is to be used, then "a sachet carrier (e.g., sachet pouches, flavors and sweeteners) is selected. If a subgingival gel is to be used (for delivering the active ingredients into or around the periodontal pockets), then the "subgingival gel carrier" is selected as disclosed e.g. in US 5,198,220 and 5,242,910, March 30, 1993 and September 7, 1993, respectively. r. (Damani). Carriers suitable for the preparation of the compositions according to the invention are known. Their selection depends on secondary considerations such as taste, cost and shelf life etc.

The compositions of the invention may be in the form of non-abrasive aqueous or non-aqueous gels, including subgingival gels. Aqueous gels generally contain a thickening agent (0.1% - 20%), a humectant (10% - 55%), a flavor (0.04% - 2%), a sweetener (0.1% - 3%), colorant (0.01% - 0.5%) and balance water. The compositions may include an anti-caries agent (0.05% - 0.3% as fluoride ion) and an anti-tartar agent (0.1% - 13%).

The preferred compositions of the invention may also be in the form of dentifrices such as toothpastes, tooth gels and tooth powders. The ingredients of such toothpastes and tooth gels are generally one or more ingredients including tooth abrasive (6% - 50%), surfactant (0.5% - 10%), thickening agent (0.1% 5%), humectant (10% - 55%), flavor (0.04% - 2%), sweetener (0.1% - 3%), coloring agent (0.01% - 0 , 5%) and water (2% - 45%). Such toothpastes and gels may also contain one or more anticaries agents (0.05% - 0.3% as fluoride ion) and anticalculus agents (0.1% - 13%). Of course, tooth powders basically contain only non-liquid ingredients.

Other preferred compositions of the invention are mouthwashes, including mouth sprays. The ingredients of such mouthwashes and mouth sprays are typically water (45% - 95%), ethanol (0% - 25%), humectant (0% - 50%), surfactant (0.01% - 7%), flavor (0.04% - 2%), sweetener (0.1% - 3%) and color (0.001% - 0.5%). Such mouthwashes and mouth sprays may also contain one or more anti-caries agents (0.05% - 0.3%, in the form of fluoride ions) and anti-calculus agents (0.1% - 3%).

Other preferred compositions of the invention are dental solutions, including irrigation fluids. The ingredients of such dental solutions are generally water (90% - 99%), serving agent (0.01% - 0.5%), thickening agent (0% - 5%), flavoring (0 , 04% 2%), sweetener (0.1% - 3%) and surfactant (0% - 5%).

Chewing gum compositions typically include a gum base (50% - 99%), a flavor (0.04% - 2%), and a sweetener (0.01% - 20%).

The term "lozenge as used herein includes: breath freshening mint lozenges, lozenges, microcapsules and fast dissolving solids, including lyophilized forms (lumps, wafers, thin films, tablets) and fast dissolving solids including compressed tablets. The term "fast dissolving solids" as used herein means that the solid dosage form is dissolved in less than 60 seconds, preferably less than 15 seconds, especially less than 5 seconds, after the solid dosage form is placed in the mouth. Fast dissolving solid drug forms are disclosed in US Patent Application 08/253890, filed June 3, 1994. (Brideau); in US patents 4,642,903, 4,946,684, 4305,502, 4,371,516, 5,188,825, 5,215,756, 5,298,261; 3,882,228, 4,687,662, and 4,642,903.

Lozenges include disc-shaped solids containing a therapeutic agent in a flavor base. The base may be a hard candy, glycerinated gelatin, or a mixture of sugar with a sufficient amount of sticky solution to give the desired form. These dosage forms are generally described in Remington: The Science and Practice of Pharmacy, 19th Edition, Vol. II, Chapter 92, 1995. Lozenges (compressed tablet type) compositions typically contain one or more fillers (compressible sugar), flavorings and lubricants. Microcapsules of this type are disclosed in U.S. Patent 5,370,864 (Peterson et al.) Issued December 6, 1994.

A dental appliance can also be impregnated with the composition according to the invention. The dental appliance is an appliance intended to come into contact with teeth or other tissues in the oral cavity, the appliance being impregnated with a composition comprising the inventive copolymer of vinylpyrrolidone with C2-C12 alkenyl esters of saturated C1-C19 alkyl carboxylic acids. The dental appliance may be in the form of fiber impregnated with the composition, including dental floss or tapes, chips, or polymer strands and fibers.

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

Abrasive materials

The dental abrasives in the topical oral carriers of the compositions of the present invention include a wide variety of materials. The material selected must be compatible with the composition of the invention and not excessively abrasion of the dentin. Suitable abrasives are e.g. silicas, including silica gels and precipitated silica; insoluble sodium polymetaphosphate, hydrated alumina, calcium carbonate, dicalcium orthophosphate dihydrate, calcium pyrophosphate, tricalcium phosphate, calcium polymetaphosphate, and resin abrasives such as ground urea formaldehyde condensation products.

Another class of abrasives used in the compositions of the present invention are comminuted thermosetting resins, such as disclosed in US Patent No. 3,070,510 issued on December 25, 1962 (Cooley and Grabenstetter). Suitable resins are, for example, melamines, phenoplasts, urea resins, melamine-urea resins, melamine-formaldehyde resins, urea-formaldehyde resins, melamine-urea-formaldehyde resins, cross-linked epoxies and cross-linked polyesters.

Various silica dental abrasives are preferred because of their unique advantages in cleaning and polishing dental surfaces without unnecessarily abrading tooth enamel or dentin. Generally, the average particle size of the silica abrasive polishes, as well as other abrasives, is in the range 0.1-30 µm, preferably 5-15 µm. The abrasive may be precipitated silica or silica gels such as the silica xerogels described in US Pat. Nos. 3,538,230 issued March 2, 1970 (Pader et al.) And US Patent 3,862,307 issued Jan 21, 1975 (DiGiulio). Preferred are silica xerogels distributed under the trade name "Syloid by WR Grace &amp; Company, Davison Chemical Division." Precipitated silica materials such as those distributed by JM are also preferred Huber Corporation under the trade name Zeodent®, especially the silicas designated Zeodent® 119, Zeodent® 118, Zeodent® 109 and Zeodent® 129. The types of silica abrasives in useful toothpastes of the invention are described in more detail in US Patent 4,340,583 of 29 Jul 1982 (Wason) and U.S. Patent Nos. 5,603,920 issued Feb. 18, 1997; US 5589160 filed on December 31

PL 210 477 B1

1996 r; 5,658,553 filed August 19, 1997; US 5651958 filed July 29, 1997 and provisional patent application US 60/300766 filed June 25, 2001.

Mixtures of abrasives may also be used, such as the various grades of the Zeodent® silica abrasives described above. The total amount of abrasive in the toothpaste compositions of the invention is 6 - 70 wt.%. The toothpastes preferably contain 10-50% abrasive, by weight of the composition. The inventive solutions, mouth sprays, mouthwashes, and non-abrasive gel compositions are typically non-abrasive.

Surfactants

The compositions according to the invention may also contain surfactants, commonly also referred to as foaming agents. Suitable surfactants are those that are reasonably stable and foam over a wide pH range. The surfactant can be anionic, non-ionic, amphoteric, zwitterionic, cationic or mixtures thereof.

Anionic surfactants useful in the invention include water-soluble salts of alkyl sulfates having 8-20 carbon atoms in the alkyl group (e.g., sodium alkyl sulfate) and water-soluble salts of sulfonated monoglycerides of fatty acids containing 8-20 carbon atoms. Sodium lauryl sulfate and sodium sulfonated coconut monoglyceride are examples of anionic surfactants of this type. 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 can also be used. Many suitable anionic surfactants are disclosed in U.S. Patent 3,959,458 to Agricola et al. Issued May 25, 1976. The composition according to the invention usually comprises an anionic surfactant in an amount of 0.025% - 9%, preferably 0.05% - 5%, especially 0.1% - 1%.

Another preferred surfactant is a compound selected from the group consisting of sarcosinate surfactants, isethionate surfactants and taurate surfactants. Most preferred are the sodium and potassium salts of the following anionic groups: lauroyl sarcosinate, myristoyl sarcosinate, palmitoyl sarcosinate and oleoyl sarcosinate. The surfactant may be present in the composition according to the invention in an amount of 0.1% - 2.5%, preferably 0.3% - 2.5%, especially 0.5% - 2.0% by weight, based on the weight of the product. entire composition.

Preferred cationic surfactants useful in the compositions of the invention can be broadly defined as derivatives of quaternary aliphatic ammonium compounds having a long alkyl chain of 8-18 carbon atoms, such as lauryltrimethylammonium chloride; cetylpyridinium chloride; cetyltrimethylammonium bromide; diisobutylphenoxyethyldimethylbenzylammonium chloride; cocoalkyltrimethylammonium nitrite; cetylpyridinium fluoride; e.t.c. Preferred compounds are the quaternary ammonium fluorides described in US Pat. No. 3,535,421 issued October 20, 1970 (Briner et al.), Which demonstrated the detergent properties of quaternary ammonium fluorides. Certain cationic surfactants may act as germicides in the compositions of the invention. Cationic surfactants such as chlorhexidine, while suitable for use in the present invention, are not preferred because they stain hard oral tissues. Those skilled in the art are aware of this possibility and should incorporate cationic surfactants with this limitation in mind.

Preferred nonionic surfactants that can be used in the compositions of the invention can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with hydrophobic organic aliphatic or alkyl aromatic compounds. Examples of suitable nonionic surfactants are Pluronics, polyethylene oxide condensation products with alkylphenols, products derived from the condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine, condensation products of ethylene oxide with aliphatic alcohols, long-chain tertiary amine oxides, tertiary phosphine oxides long chain dialkyl sulfoxides, and mixtures of such substances.

Preferred zwitterionic surfactants that can be used in the compositions of the invention can be broadly described as derivatives of quaternary aliphatic ammonium, phosphonium and sulfonium compounds in which the aliphatic groups may be straight or branched and in which one of the aliphatic substituents contains 8-18 atoms

The latter contains an anionic water-solubilizing group, e.g., a carboxyl, sulfonate, sulfate, phosphate or phosphonate group.

Preferred betaine surfactants are disclosed in U.S. Patent 5,180,577 (Polefka et al.), Issued January 19, 1993. Typical alkyldimethylbetaines are decylbetaine or 2- (N-decyl-N, N-dimethylammonium) acetate, coconut betaine or 2- acetate. (N-coco-N, N-dimethylammonium), myristylbetaine, palmitylbetaine, laurylbetaine, cetylbetaine, stearylbetaine, etc. Examples of amidobetaines are cocamide ethyl betaine, cocamidopropyl betaine, lauramidopropyl betaine and the like. The preferred betaines are cocamidopropyl betaine, more preferably lauramidopropyl betaine.

Anti-tartar remedy

The compositions of the invention may also contain an anti-calculus agent, preferably a source of pyrophosphate ions. The pyrophosphate salts useful in the compositions of the present invention are alkali metal diion pyrophosphates, alkali metal tetra ion pyrophosphates, and mixtures thereof. Preferred compounds are disodium dihydrogen pyrophosphate (Na2H2P2O7), tetrasodium pyrophosphate (Na4P2O7) and tetrapotassium pyrophosphate (K4P2O7) in anhydrous and hydrated form. In the compositions according to the invention, the pyrophosphates can be present in one of three forms: predominantly dissolved, predominantly undissolved, or as a mixture of dissolved and undissolved pyrophosphates.

Typically, compositions containing pyrophosphates are dissolved compositions in which at least one source of pyrophosphate ions is sufficient to provide at least 1.0% of free pyrophosphate ions. The amount of free pyrophosphate ions may be 1% - 15%, preferably 1.5% - 10%, especially 2% - 6%. Free pyrophosphate ions can be present in varying degrees of protonation depending on the pH of the composition.

Compositions containing predominantly undissolved pyrophosphates are compositions containing in a dissolved state not more than 20% of the total amount of pyrophosphates, preferably less than 10%. In these compositions, tetrasodium pyrophosphate is the preferred pyrophosphate. The tetrasodium pyrophosphate may be in the form of the anhydrous or decahydrate salt or any other form stable in a solid dentifrice composition. The salt is in the form of a particulate solid which may be crystalline and / or amorphous, with a particle size preferably small enough to be aesthetically acceptable and readily dissolve upon use. The amount of pyrophosphates useful in the preparation of these compositions is any amount effective to counteract limescale, generally in the range 1.5% - 15%, preferably 2% - 10%, especially 3% - 8% by weight, based on the weight of the composition to teeth cleaning.

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

Pyrophosphate salts are described in more detail in Kirk &amp; Othmer, Encyclopedia of Chemical Technology, Third Edition, Volume 17, Wiley-Interscience Publishers (1982).

Agents which may optionally be used in place of or in combination with pyrophosphate salts are known materials such as synthetic anionic polymers, including polyacrylates and copolymers of maleic acid anhydride or maleic acid and methyl vinyl ether (e.g., Gantrez), as described herein. e.g. in US Patent 4,627,977 (Gaffar et al); as well as e.g. polyaminopropanesulfonic acid (AMPS), zinc citrate trihydrate, polyphosphates (e.g. tripolyphosphates; hexametaphosphates), diphosphonates (e.g., EHDP; AHP), polypeptides (such as polyaspartic and polyglutamic acid), and mixtures thereof.

Examples of phosphonate copolymers are the diphosphonate modified polymers disclosed in US Patent 5,011,913 (Benedict et al.). A preferred polymer is diphosphonate modified poly (acrylic acid). Other suitable phosphonate-containing polymers are described in US Patent 5,980,776 (Zakikhani et al.).

The compositions of the invention may also contain polyphosphates. Polyphosphates generally consist of two or more phosphate groups arranged primarily in a linear configuration, although some cyclic derivatives may be present. Although pyrophosphates and tripolyphosphates are technically polyphosphates, compounds with an average of four or more phosphate groups, i.e. inter alia tetrapolyphosphates and hexametaphosphates. Polyphosphates higher than tetrapolyphosphates typically occur as glassy amorphous materials. Linear "glassy polyphosphates can be represented by the formula:

XO (XPO3) nX

Where X is sodium or potassium and n is on average 6-125. Preferred polyphosphates are made by FMC Corporation, commercially known as Sodaphos (n = 6), Hexaphos (n = 13) and Glass H (n = 21). The polyphosphates can be used singly or as mixtures.

Chelating agents

Another preferred optional agent is a chelating agent, such as tartaric acid and its pharmaceutically acceptable salts, citric acid and alkali metal citrates, and mixtures thereof. Chelating agents are capable of complexing calcium ions found in the bacterial cell walls. Chelating agents can also disrupt plaque by removing calcium from calcium bridges that help keep this biomass intact. However, it is undesirable to use a chelating agent with too high affinity for calcium ions as this may result in tooth demineralisation, which is contrary to the aims and intentions underlying the present invention.

The preferred alkali metal citrates are sodium and potassium citrates, with sodium citrate being the most preferred salt. A mixture of citric acid and alkali metal citrate is also preferred. The salts of tartaric acid with alkali metal ions are preferred. Most preferred are disodium tartrate, dipotassium tartrate, sodium potassium tartrate, sodium bitartrate and potassium bitartrate. The amounts of chelating agent suitable for use in the invention are 0.1% - 2.5%, preferably 0.5% - 2.5%, especially 1.0% - 2.5%. The tartaric acid salt chelating agent may be used alone or in combination with other optional chelating agents.

Optionally, other chelating agents can be used. The calcium ion binding constant of these chelating agents is preferably 10¹ - 10⁵resulting in improved cleaning with reduced tendency to build up plaque and calculus.

Yet another possible group of chelating agents suitable for use in the present invention are the anionic polymeric polycarboxylates. Such materials are well known and are used in their acid form, or in the form of partially or preferably fully neutralized water-soluble alkali metal (e.g. potassium and preferably sodium) or ammonium salts. Preferred are 1: 4 to 4: 1 copolymers of maleic anhydride or maleic acid with another polymerizable ethylenically unsaturated monomer, preferably methyl vinyl ether (methoxyethylene) with a molecular weight (MW) of 30,000 - 1,000,000. These copolymers are available e.g. as Gantrez AN 139 (MW 500,000), AN 119 (MW 250,000) and preferably pharmaceutical grade S-97 (MW 70,000), available from GAF Chemicals Corporation.

Other effective polymeric polycarboxylates are 1: 1 copolymers of maleic anhydride with ethyl acrylate, hydroxyethyl methacrylate, N-vinyl-2-pyrrolidone or ethylene, the latter being available e.g. as Monsanto EMA No. 1103, MW 10000 and EMA grade 61, and 1: 1 copolymers of acrylic acid with methyl or hydroxyethyl methacrylate, methyl or hydroxyethyl acrylate, isobutyl vinyl ether or N-vinyl-2-pyrrolidone.

Additional effective polymeric polycarboxylates are disclosed in US Pat. Nos. 4,138,477, issued Feb. 6, 1979 (Gaffar) and US Pat. acrylic, itaconic and maleic polyacids; and sulfoacrylate oligomers with a MW of 1000, available as Uniroyal ND-2.

Fluoride ion sources

To provide additional anti-caries efficacy, dentifrices and other oral compositions commonly additionally include water-soluble fluoride in an amount sufficient to provide a concentration of fluoride ion in the composition at 25 ° C and / or within 0 ° C when used. 0.0025% - 5% by weight, preferably 0.005% - 2.0% by weight. A wide variety of fluoride ion generating materials can be used as a source of soluble fluoride in the compositions of the present invention. Examples of suitable fluoride ion generating materials can be found in US Pat. Nos. 3,535,421 issued Oct. 20, 1970 (Briner et al.) And US Pat. Representative sources of fluoride ions are tin (II) fluoride, sodium fluoride, potassium fluoride, sodium monofluorophosphate and many other compounds. Tin (II) fluoride and sodium fluoride, as well as mixtures thereof, are particularly preferred.

Active teeth whitening substances

Teeth whitening actives can be incorporated into oral care compositions. Active substances suitable for bleaching are selected from the group consisting of peroxides, metal chlorites, perborates, percarbonates, peroxy acids, peroxodisulfates and mixtures thereof. Suitable peroxide compounds are hydrogen peroxide, urea peroxide, calcium peroxide, and mixtures of these compounds. Suitable metal chlorites

These are calcium chlorite, barium chlorite, magnesium chlorite, lithium chlorite, sodium chlorite and potassium chlorite. The preferred chlorite is sodium chlorite. Additional active whitening substances may be hypochlorites and chlorine dioxide. The preferred percarbonate is sodium percarbonate. Other suitable bleaching agents are potassium, ammonium, sodium and lithium peroxodisulfate and perborate mono- and tetrahydrates and sodium pyrophosphate peroxyhydrate.

Thickening agents

In the preparation of toothpastes or gels, it is necessary to add some thickening material to provide the desired consistency of the composition, the desired release characteristics of the active ingredients during use of the composition, to ensure storage stability and overall 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 gum, xanthan gum, gum arabic and gum tragacanth can also be used. Colloidal magnesium aluminum silicate and fine silica can be used as part of the thickening agent to further improve texture.

A preferred class of thickeners or gelling agents are acrylic acid homopolymers cross-linked with pentaerythritol alkyl ether or sucrose alkyl ether or carbomers. Carbomers are commercially available from BF Goodrich as products of the Carbopol® series. Particularly preferred Carbopols are Carbopol 934, 940, 941, 956 and mixtures thereof.

Copolymers of lactide and glycolide monomers having a molecular weight of 1,000 - 120,000 (number average) are useful for delivering the active ingredients into or around the periodontal pockets as a "subgingival gel carrier." These polymers are described in US Patents 5,198,220 and 5,242,910, issued March 30, 1993 and September 7, 1993 (Damani), respectively, and US Pat. No. 4,443,430, issued April 17, 1984 (Mattei).

Thickening agents may be used in an amount of 0.1% - 15%, preferably 2% - 10%, especially 4% - 8% by weight, based on the total weight of the toothpaste or gel. Higher concentrations can be used for chewing gums, lozenges (including breath freshening mint lozenges), sachets, non-abrasive gels and subgingival gels.

Humectants

Another optional component of the carriers of the compositions for topical administration in the oral cavity is a humectant. The humectant serves to prevent the toothpaste from hardening upon exposure to air, helps the mouth feel of the composition moist, and certain wetting agents can also impart a desired sweetish flavor to the toothpaste. The humectant is generally 0% - 70%, preferably 5% - 25% by weight. composition. Suitable humectants for use in the compositions of the invention are edible polyhydric alcohols such as glycerin, sorbitol, xylitol, butylene glycol, polyethylene glycol and propylene glycol, especially sorbitol and glycerin.

Flavoring agents and sweetening agents

Flavoring agents can also be added to the composition. Suitable flavors are wintergreen oil, peppermint oil, spearmint oil, clove bud oil, menthol, anethole, methyl salicylate, eucalyptol, cassia (cinnamon) oil, 1-menthyl acetate, sage oil, eugenol, oil parsley, oxanone, α-irisone, marjoram oil, lemon oil, orange oil, propenylguaethole, cinnamon oil, vanillin, thymol, linalool, cinnamaldehyde glycerol acetal known as CGA and mixtures of these compounds. Flavoring agents are used in the composition generally in an amount in the range of 0.001% - 5% by weight, based on the weight of the composition.

Sweetening agents which may be used are sucrose, glucose, saccharin, dextrose, levulose, lactose, mannitol, sorbitol, fructose, maltose, xylitol, saccharin salts, thaumatin, aspartame, D-tryptophan, dihydrochalkones, acesulfame and cyclamate salts, especially cyclamate salts. sodium and sodium saccharin, and mixtures of these compounds. The composition preferably comprises 0.1% -10% of these agents, preferably 0.1% -1% by weight, based on the weight of the composition.

In addition to flavoring agents and sweetening agents, cooling agents, salivatives, warming agents, and numbing agents may be used in the compositions of the present invention. These agents are present in the composition at a level of 0.001% - 10% of these agents, preferably 0.1% - 1% by weight, based on the weight of the composition.

PL 210 477 B1

The coolant is selected from a variety of available materials. Among these materials are carboxamides, menthol, ketals, diols, and mixtures thereof. Preferred cooling agents in the compositions of the invention are p-menthane carboxamide agents such as N-ethyl-p-menthane-3-carboxamide, commercially known as "WS-3, N-2,3-trimethyl-2-isopropyl-butanamide," known as "WS-23, and mixtures of these compounds. Additional preferred cooling agents are selected from the group consisting of menthol, 3-1-menthoxypropane-1,2-diol known as TK-10 manufactured by Takasago, menthone glycerol acetal known as MGA manufactured by Haarmann and Reimer, and menthyl lactate , known as Frescolat® manufactured by Haarmann and Reimer. The terms menthol and menthyl as used herein include the right-handed and left-handed isomers of these compounds and their racemic mixtures. TK-10 is described in U.S. Patent No. 4,459,425 (Amano et al.), July 10, 1984. WS-3 and other agents are described in U.S. Patent No. 4,136,163 (Watson et al.) Issued January 23, 1979. Jambu® manufactured by Takasago. Preferred warming agents are capsaicin and nicotinate esters such as benzyl nicotinate. Preferred numbing agents are anesthesin, lidocaine, clove bud oil and ethanol.

Alkali metal bicarbonates

An alkali metal bicarbonate may be present in the composition according to the invention. The alkali metal bicarbonates are water-soluble and, if not stabilized, tend to release carbon dioxide in an aqueous system. Sodium bicarbonate, also known as baking soda, is the preferred alkali metal bicarbonate. The composition according to the invention may contain alkali metal bicarbonate in an amount of 0.5% - 30%, preferably 0.5% - 15%, especially 0.5% - 5%.

A variety of media

The water used in the preparation of commercially available oral compositions should preferably be low in ion content and free of organic impurities. In oral compositions, water generally constitutes 5% - 70%, preferably 20% - 50% by weight, based on the weight of the composition. This amount of water includes free water added plus water introduced with other materials such as sorbitol.

Titanium dioxide may also be added to the compositions of the invention. Titanium dioxide is a white powder that renders the compositions opaque. Overall, titanium dioxide constitutes 0.25% - 5% by weight. dentifrice compositions.

The pH of the composition may advantageously be adjusted with buffering agents. The term buffering agents refers to agents that can be used to adjust the pH of a composition in the range of 4.0-10.0. Buffering agents are monosodium phosphate, trisodium phosphate, sodium hydroxide, sodium carbonate, sodium pyrophosphate, citric acid, and sodium citrate. The buffering agents are used in an amount in the range of 0.5% -10% by weight, based on the weight of the composition of the invention.

Other agents that may optionally be used in the compositions of the invention are dimethicone copolyols selected from the group of alkyl and alkoxydimethicone copolyols such as C12-C20 alkyldimethicone copolyols and mixtures thereof. The content of dimethicone copolyol is 0.01% - 25%, preferably 0.1% - 5%, especially 0.5% - 1.5% by weight. Dimethicone copolyols help to achieve a pleasant mouthfeel.

Other suitable carriers are biphasic dentifrices such as those disclosed in US 5,213,790 filed May 23, 1993, US 5,145,666 filed September 8, 1992, and US 5,281,410 filed January 25, 1994 (Lukacovic et al.) And US Pat. 4,849,213 and 4,528,180 (Schaeffer).

Other active agents

The compositions of the invention may also contain other agents such as antimicrobials. Among such agents are water-insoluble non-cationic antimicrobials such as halogenated diphenyl ethers, phenolic compounds including phenol and its homologues, mono and polyalkylated and aromatically substituted halogen phenols, resorcinol and its derivatives, bisphenolic and halogenated salicylanilides and esterified benzoic acid esters carbanilides. Water-soluble antimicrobial agents include, but are not limited to, quaternary ammonium salts and bis-biguanide salts. Triclosan monophosphate is an additional water-soluble antimicrobial agent. Quaternary ammonium salt agents include those in which one or two of the substituents on the quaternary nitrogen atom are a carbon chain (typically an alkyl group) of 8-20, typically 10-18 carbon atoms, while the remaining substituents (typically alkyl or benzyl) have fewer carbon atoms, e.g. 1-7 carbon atoms, and are usually methyl or ethyl groups. Examples of typical quaternary ammonium antimicrobials are dodecyltrimethylammonium bromide, tetradePL 210 477 B1 cyclopyridinium chloride, domiphene bromide, N-tetradecyl-4-ethylpyridinium chloride, dodecyldimethyl chloride, benzyl dimethyl chloride (2-phenoxy-dimethyl) chloride. quaternary 5-amino-1,3-bis (2-ethylhexyl) -5-methyl-hexahydropyrimidine, benzalkonium chloride, benzethonium chloride and methylbenzethonium chloride. Other compounds are bis [4- (R-amino) -1-pyridinium] alkanes as disclosed in US Patent 4,206,215, issued June 3, 1980 (Bailey). Other antimicrobial agents such as copper bisglycinate, copper glycinate, zinc citrate, and zinc lactate may also be included in the composition. Enzymes are also useful, including endoglycosidase, papain, dextranase, mutanase, and mixtures of these enzymes. Such agents are disclosed in US 2,946,725 issued on Jul 26, 1960 (Norris et al) and US 4,051,234 issued on September 27, 1977 (Gieske et al). Particular antimicrobial agents are chlorhexidine, triclosan, triclosan monophosphate, and perfume oils such as thymol. Triclosan and other agents of this type are disclosed in US 5,015,466 issued May 14, 1991 (Parran Jr. et al.) And US 4,894,220 issued January 16, 1990 (Nabi et al). These anti-plaque agents may be present in an amount of 0.01% - 5% by weight. dentifrice compositions.

The compositions of the invention can be used in methods of cleaning and polishing teeth and reducing the incidence of discoloration, plaque, gingivitis and calculus on tooth enamel.

The use of the compositions of the invention consists in treating the enamel surfaces of the teeth and the oral mucosa of a subject. Application of these compositions may include brushing with dentifrice, rinsing with a dentifrice suspension or mouthwash, or chewing a gum product. In addition, the teeth and oral mucosa may be treated with an oral topical gel, oral spray, or other form. The subject treated in this manner may be any person or animal whose tooth surfaces are in contact with the oral care composition.

It should be understood that the compositions of the invention can be used not only for the care of the oral cavity of humans, but also for the oral care of other living creatures, e.g. domestic or other tame animals or captive animals.

For example, the application may consist of brushing the dog's teeth with one of the dentifrice compositions. Another example is the rinsing of a cat's mouth with an oral composition for a period of time sufficient to obtain favorable results. Pet care products such as chews and toys can be formulated to contain the compositions of the invention. The composition containing the described copolymer is incorporated into a relatively soft but strong and tough material such as raw leather, ropes made of natural or synthetic fibers, and polymeric items made of nylon, polyester or thermoplastic polyurethane. The moment an animal chews, licks or bites the product, the active agents contained therein are released into the animal's mouth and saliva, which is comparable to effective brushing or rinsing.

The following examples further describe and demonstrate the embodiments falling within the scope of the invention. These examples are provided for the purpose of illustrating the invention only, as many changes are possible without departing from the spirit and scope of the invention.

Example I. Evaluation of the whitening effect

The whitening effect of the solutions according to the invention used in the oral cavity was compared to a solution containing only tripolyphosphate. The results show an enhanced whitening effect when the copolymer is used in combination with tripolyphosphate as measured by changes in L *, b * and E * values.

HAP powder coated with saliva was stained with tea and rinsed for one minute with the test solutions. The change in powder discoloration was determined from the changes in L * and b * values. These values ​​are derived from the International Commission of Illumination (CIE) standard and are expressed as L *, a *, b *, a numerical expression for the three-dimensional color space where L * is the y-axis brightness and * is the color saturation (red-green) on the x-axis, ab * means the color saturation (blue-yellow) on the z-axis. Delta E is the square root of the sum of the squared differences for each expression. The changes in L * and b * important for this test were determined photometrically.

<td>The type of agent working</td><td>Change of L.</td><td>Change b</td><td>Change E.</td>

<td>5% Tripolyphosphate (TPP)</td><td> 7,36</td><td> -10,82</td><td> 13,30</td>

<td>5% 60/40 PWP / WA</td><td> 2,17</td><td> 0,15</td><td> 2,27</td>

<td>5% TPP + 5% 60/40 PWP / WA</td><td> 15,15</td><td> -14,33</td><td> 21,25</td>

PL 210 477 B1

Example II. Effect of brushing with toothpaste preparations

Fragments of bovine teeth, stained with a mixture containing coffee, tea, iron compound and bacteria, were brushed with a suspension of the following toothpastes while performing 200 brush strokes. The L * change was determined using digital imaging. The results show enhanced whitening and stain removal with the compositions of the invention compared to commercial products.

<td>The type of agent working</td><td>L change *</td><td>Change E.</td>

<td>Fluoride toothpaste</td><td> 1,88</td><td> 1,91</td>

<td>Anti-limescale toothpaste</td><td> 9,31</td><td> 9,71</td>

<td>PWP / WA + TPP toothpaste</td><td> 13,63</td><td> 13,79</td>

Example III. Polishing effect of preparations containing silica abrasive The polishing effect of the preparations was determined according to the enamel polishing index developed in our laboratories and described in provisional application US 60/300766, dated June 25, 2001. Reduction of bovine enamel surface expressed as a percentage was measured after brushing with suspensions of the tested preparations for cleaning teeth. The results show that a greater reduction in surface roughness was achieved with the formulations of the invention containing the copolymer and an abrasive, compared to formulations containing only an abrasive.

<td>The type of agent working</td><td>Roughness reduction (%)</td>

<td>25% Zeodent 119 suspension</td><td> 17,02</td>

<td>Suspension 25% Zeodent 119 + PWP / WA</td><td> 23,99</td>

<td>25% Zeodent 109 suspension</td><td> 35,98</td>

<td>25% Zeodent 109 + PWP / WA suspension</td><td> 40,10</td>

Example IV. Preparations for cleaning teeth

The dentifrice compositions of the present invention having various contents of copolymer, tripolyphosphate, silica abrasive and whitening agent are provided below. These compositions were prepared using conventional methods.

<td>Ingredient</td><td>IVA wt.%</td><td>IVB wt.%</td><td>IVC wt.%</td><td>IVD wt.%</td><td>IVE wt.%</td><td>IVF wt.%</td>

<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td>

<td>Sorbitol solution (70%)</td><td> 24,0</td><td> 30,0</td><td> 24,0</td><td> 24,0</td><td> 26,0</td><td> 30,0</td>

<td>Krzemionka - Zeodent 109</td><td> -</td><td> -</td><td> 15,0</td><td> 12,5</td><td> -</td><td> -</td>

<td>Krzemionka - Zeodent 118</td><td> 15,0</td><td> -</td><td> 15,0</td><td> -</td><td> 15,0</td><td> 20,0</td>

<td>Krzemionka - Zeodent 119</td><td> 15,0</td><td> -</td><td> -</td><td> 12,5</td><td> 15,0</td><td> -</td>

<td>Tetrasodium pyrophosphate</td><td> -</td><td> -</td><td> -</td><td> -</td><td> 5,0</td><td> -</td>

<td>Sodium tripolyphosphate</td><td> -</td><td> 5,0</td><td> 5,0</td><td> 3,0</td><td> -</td><td> 3,0</td>

<td>60/40 PWP / WA</td><td> 5,0</td><td> 3,0</td><td> 5,0</td><td> 1,0</td><td> 3,0</td><td> -</td>

<td>70/30 PWP / WA</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> 2,0</td>

<td>Thickening silica</td><td> -</td><td> 6,0</td><td> 1,0</td><td> 1,0</td><td> -</td><td> 1,0</td>

<td>Glycerine</td><td> 8,0</td><td> 12,0</td><td> 8,0</td><td> 8,0</td><td> 6,0</td><td> 10,0</td>

<td>Polyethylene glycol 300, NF (PEG-6)</td><td> -</td><td> 6,0</td><td> -</td><td> 6,0</td><td> -</td><td> -</td>

<td>Alkyl sodium solution (27.9%)</td><td> 5,0</td><td> 5,0</td><td> 5,0</td><td> 5,0</td><td> 5,0</td><td> 5,0</td>

<td>Sodium bicarbonate</td><td> 1,5</td><td> 1,5</td><td> -</td><td> -</td><td> 1,5</td><td> 1,5</td>

<td>Poloxamer 407, NF</td><td> 1,5</td><td> 1,25</td><td> 1,25</td><td> 1,25</td><td> -</td><td> 1,5</td>

PL 210 477 B1 cont. table

<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td>

<td>Flavor</td><td> 1,1</td><td> 0,6</td><td> 1,1</td><td> 1,1</td><td> 1,1</td><td> 1,0</td>

<td>Titanium dioxide / Carnauba wax nuggets</td><td> -</td><td> 1,0</td><td> 1,0</td><td> -</td><td> 1,0</td><td> 1,0</td>

<td>Sodium carboxymethylcellulose</td><td> 0,8</td><td> 0,8</td><td> -</td><td> 0,75</td><td> 0,75</td><td> 0,75</td>

<td>Xanthan gum</td><td> -</td><td> 0,5</td><td> 0,5</td><td> -</td><td> -</td><td> -</td>

<td>Carbopol 956</td><td> -</td><td> 0,4</td><td> 0,4</td><td> -</td><td> -</td><td> -</td>

<td>Saccharin sodium</td><td> 0,35</td><td> 0,35</td><td> 0,35</td><td> 0,35</td><td> 0,35</td><td> 0,35</td>

<td>Sodium carbonate</td><td> 0,5</td><td> 0,5</td><td> -</td><td> -</td><td> 0,5</td><td> 0,5</td>

<td>Sodium phosphate</td><td> -</td><td> 0,5</td><td> 0,5</td><td> -</td><td> -</td><td> -</td>

<td>Trisodium phosphate</td><td> -</td><td> 1,5</td><td> 1,5</td><td> -</td><td> -</td><td> -</td>

<td>Sodium Fluoride</td><td> 0,243</td><td> 0,243</td><td> 0,243</td><td> 0,243</td><td> 0,243</td><td> 0,243</td>

<td>Coloring agent</td><td> -</td><td> 0,05</td><td> 0,05</td><td> 0,05</td><td> 0,05</td><td> 0,05</td>

<td>Water, purified according to USP</td><td>how much need</td><td>how much need</td><td>how much need</td><td>how much need</td><td>how much need</td><td>how much need</td>

<td rowspan="2">Ingredient</td><td rowspan="2">IVG wt.%</td><td rowspan="2">IVH wt.%</td><td rowspan="2">IVJ wt.%</td><td rowspan="2">IVK wt.%</td><td colspan="2">IVM</td>

<td>Part A wt.</td><td>Part B wt.</td>

<td>Sorbitol solution (70%)</td><td> -</td><td> -</td><td> -</td><td> -</td><td> 48,0</td><td> -</td>

<td>Precipitated silica</td><td> 30,0</td><td> 25,0</td><td> 30</td><td> 20</td><td> 26,0</td><td> -</td>

<td>Sodium tripolyphosphate</td><td> 5,0</td><td> -</td><td> -</td><td> -</td><td> 3,5</td><td> -</td>

<td>60/40 PWP / WA</td><td> 5,0</td><td> 5,0</td><td> 5,0</td><td> -</td><td> 3,0</td><td> -</td>

<td>70/30 PWP / WA</td><td> -</td><td> -</td><td> -</td><td> 7,0</td><td> -</td><td> -</td>

<td>Thickening silica</td><td> 1,0</td><td> 1,0</td><td> 1,0</td><td> 1,0</td><td> -</td><td> -</td>

<td>Alkyl sodium solution (27%)</td><td> -</td><td> -</td><td> -</td><td> -</td><td> 5,0</td><td> -</td>

<td>Poloxamer 407, NF</td><td> 1,25</td><td> 1,25</td><td> 1,25</td><td> 1,25</td><td> -</td><td> -</td>

<td>Flavor</td><td> 1,1</td><td> 1,1</td><td> 1,1</td><td> 1,1</td><td> 0,8</td><td> -</td>

<td>Titanium dioxide / Carnauba wax nuggets</td><td> 1,0</td><td> 1,0</td><td> 1,0</td><td> 1,0</td><td> 0,5</td><td> -</td>

<td>Sodium carboxymethylcellulose</td><td> -</td><td> -</td><td> -</td><td> -</td><td> 0,6</td><td> -</td>

<td>Xanthan gum</td><td> 0,5</td><td> 0,5</td><td> 0,5</td><td> 0,5</td><td> 0,5</td><td> -</td>

<td>Carbopol 956</td><td> 0,4</td><td> 0,4</td><td> 0,4</td><td> 0,4</td><td> -</td><td> -</td>

<td>Saccharin sodium</td><td> 0,35</td><td> 0,35</td><td> 0,35</td><td> 0,35</td><td> 0,4</td><td> -</td>

<td>Sodium phosphate</td><td> 0,5</td><td> 0,5</td><td> 0,5</td><td> 0,5</td><td> -</td><td> -</td>

<td>Trisodium phosphate</td><td> 1,5</td><td> 1,5</td><td> 1,5</td><td> 1,5</td><td> 1,5</td><td> -</td>

<td>Sodium Fluoride</td><td> 0,243</td><td> 0,243</td><td> 0,243</td><td> 0,243</td><td> 0,243</td><td> -</td>

<td>Urea peroxide</td><td> 5,5</td><td> 5,5</td><td> 10,0</td><td> 10,0</td><td> -</td><td> 15,0</td>

<td>Carboxypolymethylene</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> 5,0</td>

<td>Glycerine</td><td>how much need</td><td>how much need</td><td>how much need</td><td>how much need</td><td> -</td><td> 70,0</td>

<td>Water, purified under USP, and small amounts of minor substances¹</td><td> -</td><td> -</td><td> -</td><td> -</td><td>as much as needed</td><td>as much as needed</td>

¹Eg NaOH to adjust the pH

PL 210 477 B1

Example 5 Mouthwash

Ingredient% by weight

Water 24,000

Propylene glycol 53,459

Sodium tripolyphosphate 5,000

Sodium benzoate 0.320

Benzoic acid, 0.021

Saccharin sodium 0.700

60/40 PWP / WA 5,000

Poloxamer 407 10,000

Flavoring 1,500

The mouthwash was prepared as follows: water, poloxamer and propylene glycol were mixed. The flavor, benzoic acid, tripolyphosphate and PWP / WA were then added. Finally, sodium benzoate and sodium saccharin were added, and then the mixture was stirred until homogeneous.

Example VI. Tooth gel

Example VI illustrates aqueous and non-aqueous tooth gel compositions made by mixing liquid carriers followed by adding saccharin, sodium tripolyphosphate and PWP / WA and mixing the mixture until uniform.

<td>Ingredient</td><td>VIA wt.%</td><td>VIB wt.%</td>

<td>60/40 PWP / WA</td><td> 5,0</td><td> 5,0</td>

<td>Sodium tripolyphosphate</td><td> 2,0</td><td> 2,0</td>

<td>Saccharin sodium</td><td> 0,5</td><td> 0,5</td>

<td>Urea peroxide</td><td> -</td><td> 15,0</td>

<td>Ethanol</td><td> 32,5</td><td> -</td>

<td>Water</td><td> 60,0</td><td> -</td>

<td>Glycerine</td><td> -</td><td> 35,0</td>

<td>PEG</td><td> -</td><td> 42,5</td>

Example VII. Chewing gum

The chewing gum compositions including the coated chewing gum (VIIC) of the present invention are provided below.

<td>Ingredient</td><td>VIIA</td><td>VIIB</td>

<td>Xylitol</td><td> 16,700</td><td> 16,700</td>

<td>Rubber base (e.g. Prestige-PL, Cafosa)</td><td> 28,000</td><td> 28,000</td>

<td>60/40 PWP / WA</td><td> 5,000</td><td> 3,000</td>

<td>Sodium tripolyphosphate</td><td> 5,000</td><td> 7,000</td>

<td>Hydrogenated starch hydrolyzate (85% solids)</td><td> 8,000</td><td> 8,000</td>

<td>Glycerine</td><td> 7,000</td><td> 7,000</td>

<td>Mannitol</td><td> 5,000</td><td> 5,000</td>

<td>Flavor</td><td> 1,600</td><td> 1,600</td>

<td>Aspartame</td><td> 0,200</td><td> 0,200</td>

<td>Spray-dried menthol</td><td> 0,150</td><td> 0,150</td>

<td>Sorbit</td><td>as much as needed</td><td>as much as needed</td>

PL 210 477 B1

Examples VIIA and VIIB. Manufacturing procedure

To soften, heat the gum base to ~ 45 ° C. Maintain a temperature of ~ 45 ° C inside the mixer tank throughout the mixing process. Place gum base in double sigma paddle agitator tank and mix for 5 minutes. Add mannitol and spray-dried menthol. Mix for 2 minutes. Add 50% sorbitol and mix for 2 minutes. Add glycerin and mix for 2 minutes. Add 50% xylitol and mix for 2 minutes. Add hydrogenated starch hydrolyzate and mix for 5 minutes. Add second 50% sorbitol and mix for 3 minutes. Add second 50% xylitol, PWP / WA, sodium tripolyphosphate, aspartame and mix for 3 minutes. Add flavor and mix for 3 minutes.

<td>Component VIIC</td><td>Core wt.%</td><td>Coating wt.%</td><td>Total wt.%</td>

<td></td><td>1 g / pc</td><td>0.35 g / pc</td><td>1.35 g / pc</td>

<td>Sorbit</td><td> 49,35</td><td> -</td><td> 36,56</td>

<td>Rubber substrate¹</td><td> 25,0</td><td> -</td><td> 18,52</td>

<td>PWP / WA 60/40</td><td> 5,0</td><td> -</td><td> 3,70</td>

<td>Sodium tripolyphosphate</td><td> 5,0</td><td> -</td><td> 3,70</td>

<td>Sodium Fluoride</td><td> -</td><td> 0,08</td><td> 0,02</td>

<td>Hydrogenated starch hydrolyzate</td><td> 5,0</td><td> -</td><td> 3,70</td>

<td>Mannitol</td><td> 2,0</td><td> -</td><td> 1,48</td>

<td>Glycerine</td><td> 5,0</td><td> -</td><td> 3,70</td>

<td>Titanium dioxide</td><td> -</td><td> 2,0</td><td> 0,52</td>

<td>Flavor</td><td> 2,0</td><td> 2,0</td><td> 2,00</td>

<td>Additional flavor, spray dried</td><td> 1,5</td><td> -</td><td> 1,11</td>

<td>Sucralose</td><td> 0,05</td><td> 0,03</td><td> 0,05</td>

<td>Acesulfame potassium</td><td> 0,10</td><td> 0,10</td><td> 0,10</td>

<td>Sorbit²</td><td> -</td><td> 95,25</td><td> 24,70</td>

<td>Polysorbate 60</td><td> -</td><td> 0,30</td><td> 0,08</td>

<td>Insoluble edible reflective pigment³(Brilliant Blue)</td><td> -</td><td> 0,04</td><td> 0,01</td>

<td>Wax⁴</td><td> -</td><td> 0,20</td><td> 0,05</td>

<td>Sum</td><td> 100,00</td><td> 100,00</td><td> 100,00</td>

¹ Contains several ingredients, including base substrates supplied by suppliers such as LA Dreyfus Company, 3775 Park Avenue, Edison, N. Jersey, USA; Cafosa Gum, Calabria 267, 08029, Barcelona, ​​Spain, etc.

² The sorbitol content refers to the absolute content after drying; sorbitol is added as a 70% aqueous solution³ Watson Foods Company Incorporated, 301 Heffernan Drive, West Haven, Connecticut, USA ⁴ The wax content refers to the absolute content after drying; wax is added as a 28% ethanol solution. The wax used contains several components, such as in the wax supplied by Kaul GmBH, Elmshorn, Germany.

Manufacturing procedure

Core Preparation: Soften the gum base by gentle heating and add mannitol, spray dried flavor, glycerin, 50% xylitol, hydrogenated starch hydrolyzate, 50% sorbitol and mix thoroughly. Add second 50% sorbitol and mix for 2 minutes. Add second 50% xylitol, sodium tripolyphosphate, PWP / WA, and aspartame, the remainder of the flavor and continue to mix the mixture. Shape the resulting gum mass into discrete pieces of gum of the desired shape and size using roll and cut equipment.

Coating solution: To 70% aqueous sorbitol solution, add titanium dioxide and polysorbate 60 and mix the resulting mixture. Add flavor, then sucralose and acesulfame potassium and mix the mixture further.

PL 210 477 B1

Coating the core preparation: Place the rubber pieces in the coating pan, apply the coating solution and dry partially. Repeat the coating process until the desired coating thickness or mass is achieved. Apply a transparent 70% water solution of sorbitol and dry spray the spots on the wet surface of the product, then dry the surface. Apply a second coat of clear 70% aqueous sorbitol solution followed by a coat of wax and dry the product completely.

While specific embodiments of the invention have been illustrated and described, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The appended claims cover all such changes and modifications falling within the scope of the invention.