CH680111A5 - - Google Patents

Description

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description

The invention relates to an antibacterial dental plaque-preventing and tartar-preventing oral care product which a) an orally acceptable carrier,

b) an effective tartar-preventing amount of 0.1 to 3% by weight of at least one linear, molecularly dehydrated polyphosphate salt as tartar-preventing agent,

c) an effective plaque-preventing amount of an essentially water-insoluble, non-cationic antibacterial agent; and d) up to 4% by weight of an antibacterial reinforcement activator which increases the availability of bactericide and increases its retention on the oral surfaces , wherein the weight ratio of antibacterial reinforcement activator to polyphosphate ions is in a range from 1: 1 to 3.5: 1, preferably 1: 6: 1 to 2.7: 1.

Compositions to be used orally containing various polyphosphate compounds are known from US Pat. Nos. 4,627,977, 4,515,772 and 4,323,551. According to this, a linear polyphosphate salt without water of crystallization is used together with a fluoride supplier and a synthetic linear polymeric carboxylate to prevent tartar formation. In EU-A 89 200 710.5 the tartar-preventing effect is improved with a smaller amount of linear polyphosphate salt free of water of crystallization in combination with a fluoride supplier and an increased amount of synthetic linear polymeric carboxylate. According to US Pat. No. 4,323,551, a water-soluble dialkalipyrophosphate is used alone or in a mixture with tetraalkali pyrophosphate. Oral care products with a tartar-preventing effect are desirable since the tartar has a negative effect on the periodontal conditions, so that tartar reduction serves for oral hygiene.

Dental plaque creates the initial conditions for the formation of tartar, but in contrast to the latter, it forms on every area of the tooth surfaces and especially at the gingival border areas. In addition to the fact that dental plaque is hardly recognizable, it favors the occurrence of gingivitis.

Accordingly, it is desirable to add antimicrobial or microbicidal substances that reduce plaque to oral compositions containing tartar preventive agents. Accordingly, U.S. Patent 4,022,550 discloses a zinc ion providing compound as a tartar preventing agent in admixture with an antibacterial agent which retards the growth of plaque bacteria. Numerous bactericidal agents have been described for these zinc compounds, including cationic compounds such as guanidines and quaternary ammonium compounds and also non-cationic compounds such as halogenated salicylaniiides and halogenated hydroxydiphenyl ethers.

Cationic bactericides such as chlorhexidine, benzethonium chloride and cetylpyridinium chloride are well described as antibacterial anti-plaque agents. Although used together with anti-tartar zinc compounds, they are not effective when used with anionic compounds such as an anti-tartar polyphosphate. This ineffectiveness is quite surprising since polyphosphates are chelating agents and the chewing effect has hitherto been used to increase the effectiveness of cationic bactericides according to “Disinfection, Sterilization and Préservation”, 2nd edition, Black, 1977, page 915 and “Inhibition and Destruction of the Microbial Cell” by Hugo, 1971, page 215. Indeed, U.S. Patent 4,323,551 discloses quaternary ammonium compounds in a pyrophosphate mouthwash against plaque; U.S. Patent 4,515,772 also shows the use of bisqueu-antifouling in an oral composition containing anti-tartar pyrophosphate.

In view of the surprising incompatibility of cationic bactericides with the anti-tartar polyphosphates, it was surprising that other bactericides could be effective.

An advantage of the present invention resides in the fact that certain bactericides are effective in tartar-preventing oral compositions which contain a linear crystal-free polyphosphate salt, a fluoride ion supplier and the above-mentioned antibacterial enhancement activator to prevent plaque formation.

Another advantage of the invention is that a composition is proposed which effectively reduces the formation of tartar and optimizes the reduction of plaque.

The object of the invention is to propose an oral care product which has a tooth-plaque and tartar-preventing effect and effectively prevents the occurrence of gingivitis.

To solve this problem, an oral care product is proposed as defined in claim 1. Preferred embodiments are explained in more detail in the dependent claims.

According to one aspect of the invention, an oral composition is proposed which, in an orally acceptable carrier, has an effective tartar-preventing amount of about 0.1 to 3% by weight of at least one linear molecular dehydrated, i.e. crystal water-free polyphosphate salt as a tartar-preventing agent and an effective one Amount of an essentially water-insoluble non-cationic antibacterial agent and up to 4% by weight

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% of an antibacterial enhancement activator which increases the release and retention of the bactericide on the oral surfaces, preferably the weight ratio of antibacterial enhancement activator to polyphosphate ions in a range from 1.7: 1 to 2, 3: 1 and best in a range from 1.9: 1 to 2: 1. For example, when using 2% tetranatrium pyrophosphate, which provides about 1.3% pyrophosphate ions, and 2.5% of an antibacterial enhancement activator, the most preferred weight ratio of about 1.9: 1 is achieved.

Typical examples of water-insoluble agents that are particularly suitable with regard to their tartar-preventing activity and compatibility or safety are the following compounds:

Halogenated diphenyl ethers such as 2 ', 4,4'-trichloro-2-hydroxydiphenyl ether (triclosan) and 2,2'-dihydroxy-5,5'-dibromodiphenyl ether.

Halogenated salicylanilides such as 4 ', 5-dibromo- or 3.4', 5-trichloro- or 3.4 ', 5-tribromo- or 2,3,3', 5-tetrachloro-, or 3,3,3 ', 5-tetrachloro- or 3,3,3', 5-tetrachlorosalicylanilides as well as 3,5-dibromo-3'- or 5-n-octanoyl-3'- or 3 , 5-dibromo-4'- or 3,5-dibromo-3'-trifluoromethylsalicylanilide (fluorophene).

Methyl, ethyl, propyl or butyl-p-hydroxybenzoic acid esters are suitable as benzoic acid esters.

Suitable halogenated carbanilides are 3,4,4'-trichlorocarbanilide, 3-trifluoromethyl-4-4'-dichlorocarbanide and 3,3,4'-trichlorocarbanilide.

As phenolic compounds, the following phenols and their homologues such as mono- and poly-alkylphenols and aromatic haiogenphenols with e.g. F, Cl, Br, I and resorcinol and catechol and their derivatives and bis-phenol compounds can be used.

In addition to phenol, the phenol compounds which are 2-methyl, 3-methyl, 4-methyl, 4-ethyl, 2,4-dimethyl, 2,5-dimethyl, 3,4-dimethyl, 2 , 6-Dimethyl-, 4-n-propyl-, 4-n-butyl-, 4-n-amyl-, 4-tert-amyl-, 4-n-hexyl- or 4-n-heptyl-phenol resp 2-methoxy-4- (2-propenyl) phenol (eugenol) or 2-isopropyl-5-methylphenol (thymol) are suitable.

The following can be used as mono- and polyalkyl or aralkyl halophenols: methyl, ethyl, n-propyl, n-butyl, n-amyl, sec.-amyl, n-hexyl, cyclohexyl, n-heptyl or n-octyl-p-chlorophenol; furthermore o-chlorophenol or methyl, ethyl, n-propyl, n-butyl, n-amyi, tert-amyl, n-hexyl or n-heptyl-o-chlorophenol.

Furthermore, p-chlorophenol and o-benzyl, o-benzyl-m-methyl, o-benzyl-m, m-dimethyl, o-phenylethyl, o-phenylethyl-m-methyl, 3-methyl, 3,5-dimethyl, 6-ethyl-3-methyl, 6-n-propyl-3-methyl, 6-iso-propyl-3-methyl, 2-ethyl-3,5-dimethyl , 6-sec-butyl-3-methyl-, 2-isopropyl-3,5-dimethyl, 6-diethylmethyl-3-methyl-, 6-isopropyl-2-ethyl-3-methyl -, 2-sec.-Amyi-3,5-dimethyl-, 2-diethyl-methyl-3,5-dimethyl-p-chlorophenol, or 6-sec.-octyl-3-methyl-p-chlorophenol and also p -Bromphe-nol and its derivatives such as methyl, ethyl, n-propyl, n-butyl, n-amyl, sec.-amyl, n-hexyl and cyclohexyl-p-bromophenol and o-bromophenol including tert-amyl, n-hexyl or n-propyl-m, m-dimethyl-o-bromophenol can be used, furthermore 2-phenylphenol, 4-chloro-2-methylphenoi, 4-chloro-3-methylphenol, 4- Chloro-3,5-dimethylphenol, 2,4-dichloro-3,5-dimethylpehnol, 3,4,5,6-tetrabromo-2-methylphenol, 5-methyl-2-pentylphenol, 4-isopropyl-3- methylphenol, 5-chloro-2-hydroxydiphenylmethane.

Resorcinol and its derivatives can also be used, such as methyl, ethyl, n-propyl, n-butyl, n-amyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, Phenyl-, benzyl-, phenylethyl-, phenylpropyl- or p-chlorobenzylresorcinol can be used as well as 5-chloro-, or 4'-chloro-, or 5-bromo- or 4 "-bromo-2,4-dihydroxydiphenylmethane.

Bisphenol A and 2,2'-methylene-bis- (4-chlorophenol), 2,2'-methylene-bis- (3,4,6-trichlorophenol [hexachlorophene], 2,2 ' -Methylene bis (4-chloro-6-bromophenol), bis (2-hydroxy-3,5-dichlorophenyl) sulfide, bis (2-hydroxy-5-chlorobenzyl) sulfide can be used.

The non-cationic bactericidal component is present in the oral care product in an effective anti-plaque amount, generally in an amount of 0.01 to 5% by weight, preferably about 0.03 to 1% by weight and especially in an amount of 0.25 to 0.5% by weight or at best in an amount of 0.25 to 0.35% by weight such as, for example, in an amount of 0.3% by weight in a dentifrice or preferably in an amount of 0.03 to 0.3% by weight and in particular in an amount of 0.03 to 0.1% by weight in a mouthwash or a liquid oral care product. The bactericide is essentially water-insoluble, i.e. its solubility in water at 25 ° C is less than 1% by weight and can also be less than about 0.1% by weight. If ionizable residues are present, the pH is adjusted to determine the solubility to a value at which no ionization takes place.

The preferred halogenated diphenyl ether is triclosan. Preferred phenol compounds are phenol, thymol, eugenol, hexylresorcinol and 2,2'-methylene-bis (4-chloro-6-bromophenol), but triclosan is particularly preferred. Triclosan is described as a bactericide in combination with a tartar-preventing agent which provides zinc ions in the mentioned US Pat. No. 4,022,880 and in combination with a copper compound in DE-PS 3,532,860. Triclosan is described in combination with a tooth ion-insensitive agent containing potassium ions in EU-PS 0 278 744. Furthermore, EU-PS 0 161 898 discloses the use of triclosan as an anti-plaque agent in one

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Toothpaste formulated to contain a lamellar liquid crystal surfactant phase with lamellar spacing of less than 6.0 nm and which may preferably contain a zinc salt; also in combination with zinc citrate trihydrate, triclosan according to EU-PS 0 161 899 is disclosed.

The linear crystal water-free or molecularly dewatered polyphosphates, which are used as tartar-preventing agents, are generally known and are used as completely or partially neutralized water-soluble alkali salts such as potassium or sodium salts and also as ammonium salts, including mixtures thereof. Typical examples are sodium hexametaphosphate, sodium tripolyphosphate such as sodium dihydrogen, trisodium monohydrogen and tetrasodium pyrophosphates and their corresponding potassium salts. Linear polyphosphates of the formula (NaP03) n, in which n has a value from 2 to 125, are added to the oral care compositions according to the invention in amounts of 0.1 to 3 and usually from 1 to 2.5 and in particular from 1.5 to 2% by weight. -% used. If the value of n in the above formula is at least 3, the polyphosphates are glassy.

Particularly suitable tartar preventive agents are tetraalkali pyrophosphates, such as tetrasodium or tetrapotassium pyrophosphate. Accordingly, the oral care product may contain polyphosphates as an anti-tartar which have substantially no tetrasodium pyrophosphate or are substantially free of a combination of tetrapotassium pyrophosphate and tetrasodium pyrophosphate in which the ratio of potassium to sodium pyrophosphate is 3: 1 or higher than 3: 1. A tartar-preventing agent which contains about 2% by weight, based on the oral care agent, of tetrasodium pyrophosphate is particularly effective.

The antibacterial reinforcement activator AVA, which increases the availability of the bactericide for the oral areas and increases the retention of the bactericide in these areas, is used to achieve this increase in amounts of up to 4% by weight and preferably of 0.005 or 0.1 to 3 and in particular from 0.5 to 2.5 wt .-% used.

The AVA component can be a simple compound, preferably a polymerizable monomer, preferably a polymer in the general sense, such as an oligomer, homopolymer, copolymer of two or more monomers, ionomer, block copolymer, graft copolymer, cross-linked polymers and copolymers . The AVA component can be a natural or synthetic compound that is water-insoluble or preferably water or saliva soluble or swellable e.g. can be hydrated or swellable to form a hydrogel. The average weight molecular weight is usually in the range of 100 to 1,000,000, preferably in the range of 1,000 to 1,000,000, and particularly in the range of 2,000 or 2,500 to 250,000 or 500,000.

The antibacterial enhancement activator AVA contains at least one residue which increases the availability of the bactericide; this residue is preferably an acid residue such as a sulfonic acid or phosphinic acid residue and in particular a phosphonic acid or carboxylic acid residue or a salt thereof, such as an alkali or ammonium salt. The enhancement activator also contains at least one organic residue that increases the retention of the bactericide. There are preferably several such residues. The residues promoting the retention preferably have the general formula (X) n-R, where X e.g. is an O, N, S, SO, SO2, P, PO or Si and R is a hydrophobic alkyl, alkenyl, acyl, aryl, alkaryl, aralkyl or heterocyclic radical or derivatives of these compounds with inert substituents , where n is zero or 1 or more.

The inter-substituted derivatives mentioned are, inter alia, Substituents on the radical R which are generally not hydrophilic and do not conflict with the desired mode of action of the AVA with a view to increasing the availability of the bactericide and its retention in the oral regions; Such derivatives are halogen radicals such as Cl, Br, J and carbo groups. Examples of such retention enhancing groups are listed in the following table:

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n X

- <X) nR

0

Methyl, ethyl, propyl, butyl, isobutyl, t-butyl, cyclohexyl, allyl, benzyl, phenyl, chlorine

phenyl, xylyl, pyridyl, furanyl, acetyl, benzoyl, butyryl, terephthaloyl,

1 0

Ethoxy, benzyloxy, thioacetoxy, phenoxy, carbethoxy, carbbenzyloxy,

N

Ethylamino, diethylamino, propylamido, benzylamino, benzoylamido, phenylacetamido,

S

Thiobutyl, thioisobutyl, thioallyl, thiobenzyl, thiophenyl, thiopropionyl, phenylthioace-

tyl, thiobenzoyl,

SO

Butylsulfoxy, allylsulfoxy, benzylsulfoxy, phenylsulfoxy,

SOa

Butylsulfonyi, allylsulfonyl, benzylsulfonyl, phenylsulfonyl,

P

Dieihylphosphinyl, ethylvinylphosphinyl, ethylallylphosphinyl, ethylbenzylphosphinyl,

Ethylphenylphosphinyl,

PO

Diethylphosphinoxy, ethylvinylphosphinoxy, methylallylphosphinoxy, methylbenzyl

phosphinoxy, methylphenylphosphinoxy,

Si

Trimethylsilyl, Dimethylbutylsiiyl, Dimethylbenzylsilyl, Dimethylvinylsilyi, Dimethylallylsilyl.

The residue which increases the availability of the bactericide is one which adheres the antibacterial reinforcement activator AVA with the bactericide to the oral surfaces, such as teeth and palate, or attaches them substantively, adhesively, cohesively or in some other way to the surfaces and thereby the bactericide delivers. The residue which promotes the retention of the bactericide in these areas is generally a hydrophobic residue; this binds the bactericide to the enhancement activator and thereby increases the retention of the bactericide on the AVA and indirectly on the oral surfaces. In some cases, the bactericide is bound by physical incorporation by the AVA, especially if the AVA is a cross-linked polymer, the structures of which provide more districts for such retention. The presence of a high molecular weight, rather hydrophobic cross-linked residue in the cross-linked polymers increases the physical integration of the bactericide on or through the cross-linked AVA polymer.

Preferably, the AVA is an anionic polymer with a chain or skeleton, which has repeating units, each having at least one carbon atom and preferably at least one directly or indirectly attached monovalent, increasing the availability and at least one directly or indirectly attached monovalent, the Retention-increasing group, which geminai, vicinal or less preferably contains atoms, preferably carbon atoms bound in the chain. The polymer may also, in some cases, contain the availability increasing residues and / or the retention increasing residues and / or other divalent atoms or residues as connecting parts in the polymer chain, instead of or in addition to the carbon atoms or as cross-linked groups.

Examples of the AVA disclosed here which do not contain groups which serve to provide the bactericide and also do not contain those which serve to retain the bactericide can be chemically modified in a manner known per se to contain AVAs which contain both groups and preferably contain a plurality of these residues. In the preferred polymeric AVAs, it is desirable that in order to increase the substantivity and delivery of the bactericide to the oral surfaces, the repeating units in the polymer chain or in the backbone of the chain should be at least about 10%, and preferably at least 50%, and especially at least 80% to 95% or 100% by weight of the polymer have acidic residues which increase the availability.

In a preferred embodiment of the invention, the antibacterial reinforcement activator AVA consists of a polymer with repeating units, in which one or more phosphonic acid residues are present, which increase the availability, which are bound to one or more carbon atoms in the polymer chain . An example of such an AVA is a poly (vinylphosphonic acid) which contains residues of the following formula:

I - [CH2 - ÇH] -

PO3H2,

however, this polymer does not contain a residue that increases retention. However, residues of this type are contained in a poly (l-phosphonopropene) and have units of the formula:

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II - [CH - CH] -

Ìh3 po3h2.

A preferred AVA containing phosphonic acid residues is a compound containing poly (beta-styrene-phosphonic acid) units of the following formula:

III - [CH - CH] -

ih p03h2,

contains, wherein Ph is a phenyl radical; the phosphonic acid residue, which increases the availability of the bactericide, and the phenyl residue, which improves the retention, are attached to vicinal carbon atoms in the chain. Also preferred is a copolymer of beta-styrenephosphonic acid with vinylphosphonyl chloride which has units of the formula III which occur alternately or in a random distribution with units of the formula I or a poly (alpha-styrene-phosphonic acid) which units of the following Formula contains:

IV - [CH2 - C] -

éîT ^ PO3H2,

in which the availability and retention increasing residues are geminai bound to the chain.

These styrene-phosphonic acid polymers and their copolymers with other inert ethylenically unsaturated monomers generally have a molecular weight in a range from about 2000 to 30,000 and preferably from about 2500 to 10,000. Such inert monomers do not substantially impair the desired function of the copolymers used as AVA .

Other polymers containing phosphonic acid are, for example, phosphonated ethylenes having units of the following formula:

V- [CH2) i4CHP03H2] n-

in which, for example, n can be an integer or can have a value to give the polymer a molecular weight of 3000. Sodium polybutene-4,4-diphosphonates with the residues of the following formula are also suitable:

VI - [CH2 - cp] -

CH2 - CH <(P03Na2) 2

and poly (allyl-bis-phosphonethylamine) with units of the following formula:

VII - [CH2 - CH] -

CH2 - N <(P03H2) 2.

Other phosphonated polymers such as poly (allylphosphonoacetate), phosphonated poly-methacrylates and the like and geminal diphosphonate polymers according to EU-PS 0 321 233 can also be used as AVA, provided that they contain the above-mentioned organic residues, which the retention of the bactericide promote.

In one embodiment of the oral care products according to the invention, they have an orally tolerable carrier, an effective plaque-preventing amount of a substantially water-insoluble non-cationic antibacterial agent and an antibacterial reinforcement activator with an average molecular weight of 1000 to 1,000,000, which is at least one available enhancing functional group and at least one organic retention enhancing group, said AVA containing no or substantially no water-soluble alkali or ammonium salt of a synthetic anionic linear polymeric polycarboxylate having a molecular weight of 1,000,000 to 1,000,000; they also contain a polyphosphate tartar prevention agent! such as a mixture of potassium and sodium salts with a K: Na ratio of up to 3: 1, e.g. from 0.37 to 1.04: 1.

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Another preferred embodiment according to the invention is that the AVA is a synthetic anionic polymeric carboxylate; that also inhibits alkaline phosphatase enzymes.

Synthetic anionic polymeric polycarboxylates and their complexes with various cationic germicides, zinc and magnesium are known per se as tartar-preventing agents, for example from US Pat. Nos. 3,429,963, 4,152,420, 3,956,480, 4,138,477 and 4,183,914. The synthetic anionic polymeric polycarboxylates from this literature, if they contain retention-promoting residues or are modified in this way, can be used in the oral care products according to the invention.

The synthetic anionic polymeric polycarboxylates which are used according to the invention are known and are often used as free acids and preferably as partially or completely neutralized water-soluble alkali metal salts or ammonium salts. 1: 4 to 4: 1 copolymers of maleic anhydride or maleic acid with other polymerizable ethylenically unsaturated monomers, preferably methyl vinyl ether / maleic anhydride with a molecular weight of about 30,000 to 1,000,000, in particular 30,000 to about 500,000, are preferred. These copolymers are for example from the GAF Corporation under the name "Gantrez" for example sold as AN 139 with a molecular weight of 500,000 or as AN 119 with a molecular weight of 250,000 and in particular as S 97 in pharmaceutical purity with a molecular weight of 70,000.

Other polymeric polycarboxylates which are suitable as AVA and contain the residues which promote the retention of the bactericides or are modified accordingly are disclosed in US Pat. No. 3,956,480, such as the 1: 1 copolymers of maleic anhydride with ethyl acrylate, hydroxyethyl methacrylate, N-vinyl 2-pyrolide or ethylene, the latter being available under the name "Monsanto EMA No. 1103", with a molecular weight of 10,000 and as "EMA Grade 61", and 1: 1 copolymers of acrylic acid with methyl or hydroxyethyl methacrylate, Methyl or ethyl acrylate, isobutyl or isobutyl vinyl ether or N-vinyl-2-pyrolidone.

Further effective polymeric polycarboxylates are disclosed in the above-mentioned US Pat. Nos. 4,138,477 and 4183914, which contain retention-increasing radicals or are modified accordingly, namely copolymers of maleic anhydride with styrene, isobutylene or ethyl vinyl ethers, polyacrylic acid, polyitaconic acid and polymaleic acid and sulfoacrylic acid Oligomers with a molecular weight down to 1000, which are commercially available as "Uniroyal ND-2".

Generally suitable are polymerized olefinic or ethylenically unsaturated carboxylic acids with retention-promoting residues which have an activated olefinic carbon-carbon double bond which reacts easily during the polymerization due to their presence in the monomeric molecule, either in the alpha-beta position the carboxyl group or as part of a terminal ethylene radical. Examples of such acids are acrylic, methacrylic-ethacrylic, alpha-chloroacrylic, crotonic, beta-acryloxypropionic, sorbic, alpha-chlorosorbic or cinnamic acid, beta-styrylacrylic acid, muconic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid , Alpha-phenyl acrylic acid, 2-benzyl acrylic acid, 2-cyclohexyl acrylic acid, angelic acid, umbellic acid, fumaric acid, malic acid and their anhydrides. Other olefinic monomers which can be copolymerized with such monomeric cabonic acids are vinyl acetate, vinyl chloride or dimethyl maleate. Furthermore, copolymers which contain sufficient carboxylic acid salt residues for their water solubility.

Also suitable for the present invention are the so-called carboxyvinyl polymers which are described as toothpaste components in US Pat. Nos. 3,980,767, 3,935,306, 3,919,409, 391,194 and 3,711,604. These are commercially available from B.F. under the trademark “Carbopol 934” or “-940” and “-941”. Goodrich available. These products consist essentially of a colloidal water-soluble polymer of polyacrylic acid, which is crosslinked with about 0.75 to 2.0% by weight of polyallyl sucrose or polyallylpentaerythritol as the crosslinking agent, the crosslinked structure and the crosslinked bonds providing the desired increase in retention by hydrophobicity or physical trapping of the bactericide and acts in a similar way. Also suitable is “polycarbophil”, which is a polyacrylic acid that is crosslinked with less than 0.2% divinylglycol, the lower proportion, the molecular weight and / or the hydrophobicity of this crosslinking agent increasing the retention little or not at all. The 2,5-dimethyl-1,5-hexadiene is an example of a very effective crosslinking agent that increases retention.

The synthetic anionic polymeric polycarboxylate is essentially a hydrocarbon with preferably halogen and / or oxygen-containing substituents and bonds in, for example, ester, ether and OH groups and is used in the present oral care products in an amount of up to 4 and preferably at least 0.05 Wt .-% used.

The antibacterial reinforcement activators AVA can be natural anionic polymeric polycarboxylates which contain residues which promote retention. Carboxymethyl cellulose and other binders such as gums and film-forming substances which do not contain the above-mentioned, enhancement and / or retention-enhancing residues are unsuitable as AVA.

Examples of AVA with phosphinic acid residues and / or suifonic acid residues to increase the availability are, for example, polymers and copolymers which contain units or groups which come from the polymerization of vinyl or allylphosphinic acid or sulfonic acids which are derived from the 1 or 2 or 3 carbon atoms an organic residue which increases the retention

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and contain, for example, the general formula - (X) -n-R mentioned above. Mixtures of these monomers can be used and copolymers of these with one or more inert polymerizable ethylenically unsaturated monomers of the type described above in connection with synthetic, anionic polymeric polycarboxylates. In these and other polymeric AVAs, usually only one acidic, enhancing group is attached to any carbon atom or other atom in the polymer backbone or to a branch thereof. Polysiloxanes which contain residues which contain or are appropriately modified for the provision of the bactericide and the residues promoting the retention thereof can also be used as AVA. Also suitable as AVA are ionomers which contain such groups. Such ionomers are described in Kirk Othmer, "Encyclopedia of Chemical Technology", 3rd edition, Supplement Volume, on pages 546 to 573. Further AVAs are polyesters, polyurethanes and synthetic and natural polyamides including the proteins and protein-containing materials such as collagen, poly (arginine) and other polymerized amino acids, provided that they contain residues containing the bactericide.

When the oral care product is prepared by initially dissolving the polyphosphate and the bactericide in a humectant and a surfactant and then adding AVA, in particular polycarboxylate, the solution gradually becomes clear and can be referred to as a microemulsion. If the amount of polycarboxylate increases so that the total composition contains at least 2.2% by weight of carboxylate, the solution becomes cloudy and can be called a macroemulsion in which the plaque-preventing effect of the bactericide appears to be the best.

A desired weight ratio of the substantially water-insoluble non-cationic bactericide to the tartar-preventing polyphosphate is above about 0.72: 1 to slightly less than about 4: 1 and, for example, in a range from 1: 1 to 3.5: 1 and especially in one Range from 1.6: 1 to about 2.7: 1.

In order to optimize the tartar-preventing effectiveness of the oral care product, inhibitors against the enzymatic hydrolysis of the polyphosphates are preferably present. Such components are fluoride ion suppliers when they provide 25 to 5000 ppm fluoride ions and up to 3 weight percent or more synthetic anionic polymeric carboxylates having a molecular weight from about 1000 to about 1,000,000, preferably from about 30,000 to about 500,000.

The fluoride ion supplier or the fluorine providing compound are known as acid phosphatase inhibitors and pyrophosphatase enzymes as anti-caries components. These compounds can be slightly or completely water-soluble; they are able to release fluoride ions in water and do not interfere with the other ingredients of the oral care products. These include inorganic fluorides such as soluble alkali metal or alkaline earth metal salts such as sodium fluoride, potassium fluoride, ammonium fluoride, calcium fluoride, copper fluorides, such as copper (I) fluoride, zinc fluoride, barium fluoride, sodium fluorosilicate, ammonium fluorosilicate, sodium or Ammoniumfluorzirkonat, sodium monofluorophosphate, aluminum mono and difluorophosphate and fluorinated Natriumcalciumpyrophosphate. Alkali and tin fluorides such as sodium and tin (II) fluorides and / or sodium monofluorophosphate are preferred.

The amount of the fluorine-providing compounds depends to a certain extent on the compound used, its solubility and the type of oral care product; generally 0.005 to about 3% by weight is provided. In the case of a dentifrice such as a tooth gel, toothpaste, tooth powder or tooth tablet, these compounds are present in such quantities that they provide up to about 5000 ppm of fluorine ions. These compounds can be used in any minimum amount, but they should preferably be present in an amount such that they provide at least about 300 to 2000 ppm and preferably 800 to 1500 ppm fluorine ions.

The alkali fluorides are usually present in the oral care product in amounts of up to 2% by weight and preferably in amounts of 0.05 to 1% by weight, while sodium monofluorophosphate is present in amounts of 0.1 to 3 and mostly in amounts of approximately 0.76% is present.

For other oral care products such as mouthwash, lozenges and chewing gum, the fluorine supplier is usually present in such an amount that it provides up to about 500 ppm and preferably 25 to 300 ppm of fluoride and is generally in an amount of 0.005 to 1.0 wt .-% available.

In certain preferred oral care products according to the invention, they should be present in liquid form as mouthwash. In the case of such preparations, a water / alcohol mixture is usually used as the carrier, which preferably also contains a humectant. Generally, the weight ratio of water to alcohol is in a range from about 1: 1 to about 20: 1, and preferably in a range from 3: 1 to 10: 1, and particularly in a range from 4: 1 to about 6: 1. The total amount of water / alcohol mixture in these preparations is in a range from 70 to 99% by weight. Ethanol is usually used as the alcohol, but isopropanol is also used.

The pH of such liquid preparations is generally in the range from 4.5 to about 9 and preferably in the range from 5.5 to 8. The compositions according to the invention can also be used at a pH below 5, without the tooth enamel to decalcify or otherwise disturb. The pH can be adjusted by acids such as citric acid or benzoic acid or by bases such as sodium hydroxide or buffered with sodium citrate, benzoate, carbonate or bicarbonate or disodium hydrogen phosphate or sodium dihydrogen phosphate.

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In other preferred embodiments of the oral care products according to the invention, they are essentially solid or pasty and are present as tooth powder, as a tooth tablet or as a toothpaste or as a tooth gel. The carrier of such solid or pasty composition contains a polishing material, such as water-insoluble Natriumetaphosphat, potassium metaphosphate, tricalcium phosphate, dihydrated calcium phosphate, anhydrous calcium phosphate, calcium pyrophosphate, magnesium orthophosphate, trimagnesium phosphate, Cacliumcarbonat, hydrated alumina, calcined alumina, aluminum silicate, zirconium silicate, silica and / or Bentonite. Other suitable polishing agents including particulate thermosetting resins are described in US Pat. No. 3,070,510 including melamine, phenol and urea formaldehyde as well as cross-linked polyepoxides and polyesters. A preferred polishing agent is crystalline silica with a particle size of up to about 5 μm and an average particle size of up to about 1.1 μm and a surface area of about 50,000 cm 2 / g, furthermore silica gels and colloidal silica and complex amorphous alkali aluminosilicates

If optically clear gels are required, a colloidal silica is used as the polishing agent, such as those sold under the name «SYLOID 72» or «SYLOID 74» or as «SANTOCEL 100». Alkali aluminosilicate complexes are particularly suitable for such tooth gels because their refractive indices are close to the refractive indices of the gelling agent and the liquid components.

Many “water-insoluble” polishing agents are anionic and can also contain small amounts of soluble components. For example, Mandrell's salt and Kurrol's salt can also be used as insoluble sodium metaphosphate.

These metaphosphates show a low solubility in water and are generally referred to as insoluble metaphosphates, which however contain a small amount of up to 4% by weight of soluble phosphates such as sodium trimetaphosphate, which can, however, be washed out. The insoluble alkali metaphosphates are mostly used as powders with a particle size of which no more than 1% is larger than 37 n.

The polishing agent is generally present in the solid or pasty compositions in weight concentrations of about 10 to 99% by weight, and preferably in an amount of 10 to 75% by weight in toothpaste and about 70 to 99% by weight in tooth powders . Toothpastes containing a silicon dioxide-based polishing agent generally contain this in amounts of 10 to 30% by weight. Other polishing agents are usually present in amounts of 30 to 75% by weight.

In the case of a toothpaste, the liquid carrier composed of water and a humectant can usually be present in amounts of 10 to about 80% by weight, based on the total composition. Suitable humectants or carriers are glycerin, propylene glycol, sorbitol and polypropylene glycol. Mixtures of water, glycerin and sorbitol are also advantageous. For clear gels, where the refractive index is essential, about 2.5 to 30% by weight of water, 0 to about 70% by weight of glycerol and about 20 to 80% by weight of sorbitol are preferably used.

Toothpastes and tooth gels usually contain a natural or synthetic thickening or gelling agent in amounts of 0.1 to about 10 and preferably 0.5 to about 5% by weight. Suitable thickeners are synthetic colloidal, clay-like magnesium alkali silicate complexes, such as, for example, hectorite or the laponite types, where Laponite D is about 58.0% SÌO2, 25.4% MgO, 3.05% NaaO, 0.98% U2O and water and Contains trace metals, has a specific gravity of 2.53 and a bulk density at 8% moisture of about 1.0.

Other suitable thickening or gelling agents are Irish moss, lota-carrageenan, gum-tragacanth, starch, polyvinylpyrrolidone, hydroxyethylpropylcellulose, hydroxybutylmethylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, sodium carboxymethylcellulose and in particular colloidal SÌO224, such as “.

For some oral care products according to the invention and in particular if more than 0.35% by weight of a water-insoluble bactericidal agent and a silica polishing agent are used in amounts of less than about 30% by weight, it may be expedient to provide an additive which contains the bactericide solves. Such solubilizing agents are moisturizing polyols such as propylene glycol, dipropylene glycol and hexylene glycol, cellosolves such as methyl cellosolve and ethyl cellosolve, vegetable oils and paraffins which have at least 12 carbon atoms in a straight chain, such as olive oil, castor oil, petrolatum and esters such as amyl acetate, ethyl acetate and ethyl acetate.

As is customary, the present oral care products are provided in appropriately labeled containers such as mouthwash bottles or in toothpaste tubes or pump dispensers.

Organic surfactants can be present in the oral care products according to the invention in order to achieve an increased prophylactic effect and to enable thorough dispersion of the dental plaque-preventing bactericide in the oral area and to further improve the cosmetic form of the oral care product according to the invention. Anionic, nonionic or ampholytic surfactants are usually used as surfactants, which preferably have cleaning and foaming properties. Suitable anionic surfactants are water-soluble salts of higher Fettsäuremo-noglyceridmonosulfate, such as the sodium salt of the monosulfated monoglycerides hydrogenated coconut nut oil fat, higher alkyl sulfates such as sodium lauryl sulfate, alkyl aryl sulfonates Natriumdodecylben-zolsulfonat as, higher alkyl sulfoacetates, higher fatty acid ester of 1,2-dihydroxy propane sulfonate, and substantially saturated higher aliphatic acylamides of lower aliphatic aminocarboxylic acids,

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which have, for example, 12 to 16 carbon atoms in the fatty acid residue, alkyl or acyl residue. Examples of such compounds are N-lauroyl sarcosine and the sodium, potassium or ethanolamine salts of N-lauroyl, N-myristoyl, or N-palmitoyl sarcosine, which are essentially soap-free. Sarcosinates of this type are particularly advantageous in oral care products because they prevent acid formation in the oral cavity. Examples of water-soluble non-ionic surfactants are condensation products of ethylene oxide with various compounds with reactive hydrogen atoms with hydrophobic, long-chain compounds, such as, for example, C12 to C2o aliphatics, such as condensation products with hydrophilic polyoxyethylene radicals (ethoxamers) or condensation products of poly (ethylene oxides) with fatty acids , Fatty alcohols or fatty amides and polyhydric alcohols such as sorbitan monostearate and polypropylene oxides.

The surfactants are generally present in an amount of about 0.5 to 5% by weight, preferably in an amount of about 1 to 2.5% by weight. These can also serve as a solubilizing agent for the bactericide, thereby reducing the proportion of solubilizing humectant.

The oral care compositions according to the invention can also contain further additives, such as whitening agents, preservatives, silicones, chlorophyll compounds and ammonia-containing compounds, such as ureas and / or diammonium phosphate. Suitable flavorings or sweeteners may also be present, such as peppermint etc. or sucrose etc., mostly in an amount of 0.1 to 5% by weight or more.

Like surfactants, the aromatic oils can increase the dissolving power of the bactericide even in the absence of surfactants.

The oral care products according to the invention can be used several times a day or even at daily intervals. They have a pH of about 4.5 to 9 or 10 and generally from 5.5 to about 8 and preferably from 6 to 8, in particular from 6.5 to 7.6. Oral care products with a pH below 5 do not cause any damage.

The oral care products according to the invention can also be incorporated into lozenges, chewing gum or other preparations, for example by stirring them into a warm, rubber-like mass or by coating the rubber-like mass with a composition according to the invention, these preparations still containing the usual additives, plasticizers, sweeteners or may contain carbons.

In the following, the invention will be explained in more detail with the aid of examples, with all quantity data, unless stated otherwise, based on the weight.

In the following examples, the triclosan or the 2,4,4'-trichloro-2 -'-hydroxydiphenyl ether is referred to as "TCHE"; Sodium lauryl sulfate is referred to as "SLS", the copolymer of maleic anhydride and methyl vinyl ether, which is sold by GAF Corporation under the name "Gantrez S-97" -Wz, is referred to as "Gantrez".

example 1

The adsorption of the tartar-preventing and plaque-preventing components on the tooth areas and their release is determined by the adsorption of bactericide on saliva-coated hydroxylapatite disks in the presence of tetrasodium pyrophosphate and different amounts of polycarboxylate. Toothpastes A and B of the following composition were used (in% by weight):

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Components a

B

Glycerin lota-carrageenan

Sorbitol (70% solution)

Propylene glycol

Gantrez (13.02% solution)

Titanium dioxide

Water, desalinated

NaF

Sodium saccharin pyrophosphate sodium hydroxide (50%)

10,000

0.750

30,000

0.500

19,000

0.500

9.957

0.243

0.300

2,000

1,000

10,000

0.750

30,000

0.500

15,500

0.500

13.457

0.243

0.300

2,000

1,000

20,000

2,500

0.950

0.300

2,000

Silicic acid polishing agent ("Zeodent 113" tool) 20,000 Silicic acid thickener ("Sylodent 15" tool) 2,500

Aroma oil

TCHE

SLS

0.950 0.300 2,000

Gantrez is present in an active amount of 2.5 parts by weight in toothpaste A and 2 parts by weight in toothpaste B.

To determine the release of the bactericide on HA slices coated with saliva, an HA obtained from Monsanto Co. was washed thoroughly with distilled water, taken up after vacuum filtration and dried at about 37 ° C. overnight. The dried HA was ground to a powder in a mortar. 150.0 mg HA were pressed in tablet form or 6 minutes in a laboratory press with about 5000 kg to 13 mm discs and sintered at 800 ° C for 4 hours.

Saliva stimulated with Parafilm was clarified in an ice-cooled beaker by centrifugation at 15,000 g for about 15 minutes at 4 ° C. and then sterilized with UV radiation for one hour with stirring.

Each sintered disc was soaked in a polyethylene test tube, and 2.0 ml of saliva was added after the water was removed. After an incubation period of about 12 hours at 37 ° C with constant shaking in a water bath, a saliva membrane formed. Excess saliva was then removed and the discs were treated with 1.0 ml of a solution which contained the liquid dentifrice solution containing the bactericide (triclosan); it was again incubated at 37 ° C. with continuous shaking in a water bath for 30 minutes, whereupon the disc was transferred to a new test tube and 5.0 ml of water was added with gentle shaking. The disc was then placed in another tube and the washing process repeated twice. The disc was then placed in a new test tube while avoiding entrainment of further liquid components and, after adding 1.0 ml of methanol, shaken vigorously and left at room temperature for 30 minutes in order to absorb the adsorbed triclosan by the methanol. The methanol was then aspirated and centrifuged for 5 minutes in a Beckman No. 11 microcentrifuge at 10,000 rpm. The methanol was then chromatographically examined for the bactericide, three samples being used in all cases.

To determine the retention of the bactericide on a saliva-coated HA disc, this was treated with slurries of the dentifrice as described above. After an incubation period of 30 minutes at 37 ° C., the disc was removed from the slurry, washed twice with water and then incubated again with saliva, which had been clarified by centrifugation. After a further incubation at 37 ° C. with constant shaking within different time intervals, the HA disks were removed from the saliva, and the amount of bactericide (triclosan) which had been retained by the disk and which had been delivered to the saliva was chromatographed was determined.

To estimate the delivery or delivery of bactericide to the buccal epithelial cells, the delivery was determined to assess the effect of PVM / MA in delivering the bactericide (triclosan) to the mucosa from a dentifrice. The epithelial cells were taken up by gently rubbing a wooden spatula against the mucous membrane and suspended in a buffer solution. An Rss buffer (Resting Saliva Saits) consisting of 50 nM NaCl, 1.1 nM CaCl2 and 0.6 nM KH2P04 solution with a pH value of 7.0 in a quantity of 5 to 6 x 105 cells / ml was added using a hemocytometer to count the cell and stored in ice until use. Egg-

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A 0.5 ml cell suspension, which had previously been heated in a water bath at 37 ° C., was mixed with 0.5 ml of the antibacterial solution to be examined and incubated at 37 ° C. This mixture was diluted at least 10 times to reduce the surfactant concentration and to avoid destruction of the cell membranes by the surfactant. After 30 minutes of incubation, the cells were harvested by centrifugation at 5000 rpm for 5 minutes, washed 3 times with the Rss buffer solution and mixed with 1.5 ml of methanol, after which the bactericide was analyzed by chromatography after vigorous shaking.

The values obtained are given in Table I below, namely the supply of TCHE to the saliva-coated HA disks, in n / g.

Table I

Zanhpasta

Feed in fi / g

A

130

B

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The above values show that with an increased amount of Gantrez in toothpaste A, there is a significant increase in the supply of TCHE in tooth minerals coated with saliva.

Example 2

A toothpaste of the following composition was produced, which is extremely effective for both tartar and plaque prevention.

Components

Parts by weight

Sorbitol (70% ïg)

22.00

lrish moss

1.00

Sodium hydroxide (50%)

1.00

Gantrez (13.02% solution)

19.00

Water, desalinated

2.69

Sodium monofluorophosphate

0.76

Sodium saccharin

0.30

Tetrapotassium pyrophosphate

2.00

hydrated aluminum oxide

48.00

Aroma oil

0.95

TCHE

0.30

Sodium lauryl sulfate

2.00

Example 3

A mouthwash with the following composition was produced:

Ingredients parts by weight

Tetrasodium pyrophosphate 2.00 (Gantrez S-97) 2.50 glycerin 10.00 sodium fluoride 0.05 sodium lauryl sulfate 0.20 TCHE 0.06 aroma oil 0.40 water per 100.00

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Example 4

A lollipop was made with the following composition:

Ingredients weight percent

Sugar 75-80 corn syrup 1-20 aromatic oil 0.1-1 tetrasodium pyrophosphate 2.0 Gantrez S-97 2.5 NaF 0.01-0.05 TCHE 0.01-0.1 magnesium stearate as lubricant 1-5 water 0. 01-0.2

Example 5

A chewing gum composition was made as follows:

Ingredients parts by weight

Gum base 25.00 sorbitol (70%) 17.00 TCHE 0.50 to 0.10 tetrasodium pyrophosphate 2.00 Gantrez S-97 2.50

If this composition is modified, the Gantrez S-97 can also be omitted. Example 6

Chewing gum of the following composition was produced:

Components

Parts by weight

Gum base

30.00

TCHE

0.50

Gantrez

2.00

NaF

0.05

Glycerin

0.50

crystalline sorbitol

53.00

Tetrasodium pyrophosphate

2.00

Aroma oil and water

100

The good results with compositions according to the preceding examples are also achieved if the TCHE is replaced by phenol or by 2,2'-methylene-bis- (4-chloro-6-bromophenol) or by eugenol or by thymol and furthermore when Gantrez is replaced by other antibacterial enhancement activators such as Carbopol (e.g. Carbopol 934) or by styrene-phosphonic acid polymers with a molecular weight in the range of about 3000 to 10,000, such as for example by poly (beta-styrene-phosphonic acid), copolymers of Vinylphosphonic acid with beta-styrenephosphonic acid and poly (alphastyrenephosphonic acid) or sulfoacrylic acid oligomers or by a 1: 1 copolymer of maleic anhydride with ethylene acrylate.

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Good results are also achieved when the tetrasodium pyrophosphate is replaced by a mixture of tetrasodium pyrophosphate and tetrapotassium pyrophosphate, the weight ratios of potassium to sodium being either in a range of 0.37: 1 or in a range of 1.04: 1 or in a range of 3: 1 and also in a range of 3.5: 1.

Claims (31)

Claims 1. oral care products containing a) an orally acceptable carrier, b) an effective tartar-preventing amount of 0.1 to 3% by weight of at least one linear, molecularly dehydrated polyphosphate salt as tartar-preventing agent, c) an effective plaque-preventing amount of an essentially water-insoluble, non-cationic antibacterial agent; and d) up to 4% by weight of an antibacterial reinforcement activator which increases the availability of bactericide and the retention thereof on the oral surfaces, whereby the weight ratio of antibacterial reinforcement activator to polyphosphate ions is in a range from 1: 1 to 3.5: 1. 2. Oral care product according to claim 1, characterized in that the weight ratio of antibacterial reinforcement activator to polyphosphate ions is in a range from 1.6: 1 to 2.7: 1. 3. Oral care product according to claim 1 or 2, characterized in that the bactericide is selected from the group consisting of halogenated diphenyl ethers, halogenated salicylanilides, benzoic acid esters, halogenated carbanilides and phenolic compounds. 4. Oral care product according to claim 1 or 2, characterized in that the bactericide is a halogenated diphenyl ether. 5. Oral care product according to claim 4, characterized in that the halogenated diphenyl ether is a 2,4,4'-trichloro-2'-hydroxyphenyl ether. 6. Oral care product according to claim 1 or 2, characterized in that the bactericide is a phenolic compound. 7. Oral care product according to claim 6, characterized in that the phenol compound is selected from the group consisting of phenol, thymol, eugenol and 2,2'-methylene-bis- (4-chloro-6-bromophenol). 8. Oral care composition according to claim 3, characterized in that the bactericide is present in an amount of 0.01 to 5 wt .-%. 9. Oral care composition according to claim 8, characterized in that the amount of the bactericide is 0.25 to 0.5 wt .-%. 10. Oral care product according to claim 1 or 2, characterized in that the linear, molecularly dehydrated polyphosphate salt is an alkali metal pyrophosphate and is present in an amount of 1 to 2.5% by weight. 11. Oral care product according to claim 10, characterized in that the alkali pyrophosphate is a tetrasodium pyrophosphate. 12. Oral care product according to claim 11, characterized in that the weight ratio of antibacterial reinforcement activator polyphosphate ions is in a range from 1.7: 1 to 2.3: 1. 13. Oral care product according to claim 12, characterized in that it is present as toothpaste and has a carrier made of water, humectant and a gelling agent and contains a water-insoluble polishing agent. 14. Oral care product according to one of claims 1 to 12, characterized in that it is in the form of a mouthwash and in that the orally acceptable carrier contains water and a non-toxic alcohol. 15. Oral care product according to one of claims 1 to 14, characterized in that the antibacterial reinforcement activator has an average molecular weight of 1000 to 1,000,000. 16. Oral care product according to claim 15, characterized in that the antibacterial reinforcement activator contains at least one functional residue which increases the availability of the bactericide and contains at least one organic residue which increases its retention. 17. Oral care product according to claim 16, characterized in that the rest increasing the availability is an acidic residue. 18. Oral care product according to claim 17, characterized in that the rest increasing the availability is selected from the group of carboxylic, phosphonic, phosphinic and sulfonic acids and their salts and mixtures. 19. Oral care product according to claim 18, characterized in that the organic radical to increase the retention corresponds to the general formula - (X) nR, in which X has the meaning of O, N, S, SO, SO2, P, PO or Si and R is a hydrophobic alkyl, alkenyl, acyl, aryl, alkaryl, aralkyl or a heterocyclic radical including the inertly substituted derivatives of these compounds and where n has a value of 1 or zero. 20. Oral care product according to claim 19, characterized in that the antibacterial reinforcement 14 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 CH 680111 A5 tion activator is an anionic polymer which contains a plurality of residues which increase the availability of the bactericide and which increase the retention of the bactericide. 21. Oral care composition according to claim 20, characterized in that the anionic polymer has a chain with repeating units, each of which contains at least one carbon atom. 22. Oral care product according to claim 21, characterized in that each unit contains at least one residue which increases the availability of the bactericide and which is bound to the same, vicinal or to other atoms in the chain. 23. Oral care composition according to claim 18, characterized in that the rest increasing the availability of the bactericide is a carboxyl residue or a salt thereof. 24. Oral care composition according to claim 23, characterized in that the antibacterial reinforcement activator is a copolymer of maleic acid or anhydride with another ethylenically unsaturated polymerizable monomer. 25. Oral care product according to claim 24, characterized in that the other monomer of the copolymer is a methyl vinyl ether in a molar ratio of 4: 1 to 1: 4 to the maleic acid or its anhydride. 26. Oral care composition according to claim 25, characterized in that the copolymer has a molecular weight of 30,000 to 1,000,000 and is present in an amount of 0.1 to 2% by weight. 27. Oral care composition according to claim 26, characterized in that the copolymer has an average molecular weight of about 70,000. 28. Oral care composition according to claim 18, characterized in that the rest increasing the availability of the bactericide is a phosphonic acid residue or a salt thereof. 29. Oral care product according to claim 18, characterized in that the antibacterial reinforcement activator is a poly (beta-styrene-phosphonic acid) or a poly (alpha-styrene-phosphonic acid) or a copolymer of one of these styrene-phosphonic acids with another ethylenically unsaturated monomer. 30. Oral care product according to claim 29, characterized in that the antibacterial reinforcement activator has a molecular weight of 1000 to 30,000. 31. Oral care product according to one of claims 1 to 30, characterized in that it contains a fluoride ion supplier. 15