DE3942643A1 - MOUTH CARE PRODUCTS - Google Patents

Abstract

An oral composition such as a dentifrice or mouth-wash, comprises an effective antiplaque amount of a substantially water-insoluble noncationic antibacterial agents, such as 2,4, 4'-trichloro-2'-hydroxy-diphenyl other (Triclosan) and an antibacterial-enhancing agent which enhances the delivery of said antibacterial agent to and retention thereof on, oral surfaces, such as a synthetic anionic polymeric polycarboxylate having a molecular weight of about 1,000 to about 1,000,000 and an orally acceptable vehicle effective to enable said antibacterial agent to dissolve in saliva in effective antiplaque amount.

Description

The invention relates to a bactericidal, zahnbelagver hindering with a content of essentially what seronoluble non-cationic bactericidal component for Prevention of dental plaque.

Dental plaque forms on the teeth as a soft deposit while tartar represents a hard calcified deposit. In contrast to the tartar, the plaque forms on each Area of the tooth surface and especially on the gingival Border Counties; he is barely recognizable and favors gin givitis.  

For this reason, it is desirable for oral care products antimicrobial agents or bactericidal components provide that reduce the plaque. For this were often cationic bactericides are proposed. According to US-PS 40 22 880 For example, a zinc ion-providing compound as anticalculus component with a bactericide ver mixed to prevent the growth of dental plaque bacteria. Numerous bactericides are used in combination with zinc compounds described including cationic compounds such as Guanidines and quaternary ammonium compounds, as well non-cationic compounds such as halogenated salicylanilides and halogenated hydroxydiphenyl ethers. A non-cationic bactericidal plaque preventing halogenated hydroxy diphenyl ether, namely triclosan, is also in combination with Zinc citrate trihydrate described in EU-PS 01 61 899. Further EU-PS 02 71 332 discloses a toothpaste containing Triclosan and propylene glycol as solubilizing agent.

Cationic bactericides such as chlorhexidine, benzethonium chloride and cetylpyridinium chloride are considered to be antibacterial plaque preventive measures have been thoroughly investigated; you are but generally in combination with anionic compo not effective. Non-cationic bactericides can but on the other hand with anionic components in a mouth be compatible with care products. But oral care products are usually mixtures of numerous components, with even neutral ones Ingredients such as humectants, the behavior of such Oral hygiene products.

In addition, even non-cationic bactericides have one only limited tooth decay when used with the commonly used other ingredients like tartar preventing polyphosphates, according to GB-PS 22 00 551 and EU-PS 02 51 591 are used. Previously unpublished work according to USSN 3 98 605 of 25 August 1989 showed that the tooth antifouling effectiveness can be significantly increased  can, if you have an antibacterial enhancer activator (AVA), which makes the provision of the bactericide increased for the oral areas and the retention of Bak terizids reinforced in these areas, being optimized Quantities and ratios of polyphosphate and AVA allows become.

The invention has the object of an oral care to propose medium for better prevention of dental plaque. To solve this problem, an oral hygiene product according to Main claim proposed, with particular embodiments mentioned in the subclaims.

The oral hygiene product according to the invention has the advantage that a substantially water-insoluble non-cationic bactericidal component and a reinforcing activator (AVA) are provided to prevent plaque formation, wherein the Composition contains an orally acceptable carrier, the it allows the bactericide to dissolve in a dental plaque dissolving amount in the saliva dissolves. Another advantage is that AVA is the provision and the reins small but effective plaque preventing amounts of bactericidal component on the tooth and mucous membranes allowing, in turn, as a further advantage a mouth care agent is created, which the occurrence of Gin prevents givitis.

Typical examples of water-insoluble, non-cationic antibacterial acting angentien or batericides, the ins special with regard to their tartar preventing effect speed and compatibility or safety are suitable the following connections:

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

Furthermore, halogenated salicylanilides such as 4 ', 5-dibromo, or 3,4 ', 5-trichloro, or 3,4', 5-tribromo, or 2,3,3 ', 5-tetra chloro or 3,3,3 ', 5-tetrachloro or 3,3,3', 5-tetrachloro salicylanilides and also 3,5-dibromo-3'- or 5-n-octanoyl-3'-, or 3,5-dibromo-4'- or 3,5-dibromo-3'-trifluoromethyl salicylanilide (fluorophene).

As benzoic acid esters are methyl, ethyl, propyl or butyl p-hydroxybenzoic acid ester suitable.

Halogenated carbanilides are 3,4,4'-trichlorocarbanilide, 3-trifluoromethyl-4-4'-dichlorocarbanilide and 3,3,4'-trichloro carbanilide in question.

As phenolic compounds, the following phenols and their homologues such as mono- and polyalkylphenols and aromatic Halophenols with e.g. F, Cl, Br, I and resorcinol and Use catechol and its derivatives and bisphenol compounds be.

Phenol compounds other than phenol are 2-methyl-, Methyl, 4-methyl, 4-ethyl, 2,4-dimethylethyl, 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 or 2-methoxy-4- (2-propenyl) -phenol (eugenol) or 2-isopropyl-5- Methyl-phenol (thymol) suitable.

As mono- and polyalkyl or aralkyl halophenols can be a be set: 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-amyl, 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-phenyl  ethyl-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-iso-propyl-3,5-dimethyl, 6-diethylmethyl-3-methyl, 6-iso-propyl-2-ethyl-3-methyl, 2 sec-amyl-3,5-dimethyl, 2-diethylmethyl-3,5-dimethyl-p-chloro phenol, or 6-sec-octyl-3-methyl-p-chlorophenol, and further p-bromophenol and its derivatives, such as methyl, ethyl, n-propyl, n-butyl, n-amyl, sec-amyl, n-hexyl and cyclo hexyl p-bromophenol and o-bromophenol including tert.- Amyl, n-hexyl or n-propyl-m, m-dimethyl-o-bromophenol ver 2-phenylphenol, 4-chloro-2-methylphenol, 4-chloro-3-methylphenol, 4-chloro-3,5-dimethylphenol, 2,4-di Chloro-3,5-dimethylpehnol, 3,4,5,6-tetrabromo-2-methylphenol, 5- Methyl 2-pentylphenol, 4-isopropyl-3-methylphenol, 5-chloro-2 hydroxydiphenyl.

Furthermore, resorcinol and its derivatives can 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 be used and 5-chloro or 4'-chloro or 5-bromo or 4 '' - bromine 2,4-dihydroxydiphenylmethane.

As bis-phenol compounds, bisphenol A and 2,2'- Methylene bis (4-chlorophenol), 2,2'-methylene bis (3,4,6-tri chlorophenol (hexachlorophene), 2,2'-methylene-bis- (4-chloro-6- bromophenol), bis (2-hydroxy-3,5-dichlorophenyl) sulfide, bis (2-hydroxy-3,5-dichlorophenyl) Hydroxy-5-chlorobenzyl) sulfide.

The non-cationic bactericidal component is in the mouth care agent in an effective plaque preventing amount present, generally in an amount of 0.01 to 5% by weight, preferably about 0.03 to 1% by weight and in particular in an amount of 0.25 to 0.5% by weight, or at best in in an amount of 0.25 to 0.35 wt.%, such as in in an amount of 0.3% by weight in a dentifrice or  preferably in an amount of 0.03 to 0.3 wt.% And ins particular in an amount of 0.03 to 0.1 wt.% in one Mouthwash or a liquid oral hygiene product. The Bactericide is essentially water-insoluble, i. that his Solubility in water at 25 ° C is below 1 wt.% And also may be lower than about 0.1% by weight.

The preferred halogenated diphenyl ether is triclosan. Preferred phenolic compounds are phenol, thymol, eugenol, Hexylresorcinol and 2,2'-methylenebis (4-chloro-6-bromophenol), however, triclosan is particularly preferred. Triclosan is as a bactericide in combination with a tartar-preventing Means which provides zinc ions, in said US-PS 40 22 880 and in combination with a copper compound in DE PS 35 32 860 described. Triclosan is in combination with a potassium ion-containing, the tooth insensitive ma ment funds described in EU PS 02 78 744. Further open bart EU-PS 01 61 898 the use of triclosan as tooth antifouling agent in a toothpaste that so for is that they are a lamellar liquid crystal surfactant phase contains with lamella spacings of less than 6.0 nm and which may preferably contain a zinc salt; also in Kom combination with zinc citrate trihydrate is triclosan according to EU-PS 01 61 899 discloses. The antibacterial reinforcing agent or the amplification activator AVA, which is the provision of the bactericide for the oral areas increased and the Reten tion of the bactericide in these areas is becoming Achieving this increase in amounts of about 0.005 to about 4 and preferably from 0.1 to about 3 and especially from 0.5 used to about 2.5 wt.%.

The AVA component may 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 be synthetic compound that is insoluble in water or pre is preferably water or saline soluble or swellable e.g. hydratable or swellable to form a hydrogel can be. The average weight molecular weight is in the range of 100 to around 1 000 000 and above preferably in a range of 1000 to about 1,000,000 and especially in a range of 2000 or 2500 to about 250,000 or 500,000.

The antibacterial enhancer activator AVA contains at least one residue which increases the availability of the bactericide; this radical is preferably an acid radical such as a sulfonic acid or phosphonic acid radical and in particular a phosphonic acid or carboxylic acid radical or a salt thereof, such as, for example, an alkali metal or ammonium salt. The reinforcing activator further contains at least one organic radical which increases the retention of the bactericide. Preferably, several such radicals are present. The retention-promoting radicals preferably have the general formula - (X) _n -R, where X is, for example, an O, N, S, SO, SO ₂ , P, PO or Si and R is a hydrophobic alkyl, alkenyl, Acyl, aryl, alkaryl, aralkyl or heterocyclic radical or Deriva te of these compounds having interten substituents, wherein n has the value of zero or 1 or more.

The mentioned intert-substituted derivatives are i.a. Sub substituents on the radical R, which are generally not hydro phil are and not with the desired mode of action of the AVA with a view to increasing the availability of the Bactericidal and the retention of the same to the oral preparation collide; such derivatives are halogen radicals such as Cl, Br, J and carbo groups. Examples of such retention increasing group are listed in the following table:  

The rest increasing the availability of the bactericide is one that has the antibacterial enhancement ak tivator AVA with the bactericide to the oral surfaces, such as Teeth and palate, adherent or substantive, adhesive, cohesive or otherwise attaches to the surfaces and thereby the Bactericide delivers. The rest, the retention of the Bak In general, promoting tericides in these areas is one hydrophobic residue; this binds the bactericide to the enhancer kung activator and thereby increases the retention of the bacteri  zids on the AVA and indirectly on the oral surfaces. In In some cases, the binding of the bactericide takes place physical involvement by the AVA, especially if it this is a crosslinked polymer, its structures more districts for such a holding provide. The presence of a high molecular weight, rather hydro phoben crosslinked residue in the cross-linked polymers increases the physical involvement of the bactericide on the or by the cross-linked AVA polymer.

Preferably, the AVA is an anionic polymer having a Chain or a chain skeleton, which is repetitive Having units each having at least one carbon atom and preferably at least one directly or indirectly attached monovalent, the provisioning Group and at least one directly or indirectly attached monovalent, retention-enhancing group, the geminal, vicinal or even less preferred atoms in other ways, preferably contains carbon atoms bound in the chain. The polymer can also be used in some cases providing increasing residues and / or retention increasing radicals and / or other divalent atoms or radicals as connecting parts in the polymer chain, namely instead of or in addition to the carbon atoms or as crosslinked groups.

Examples of the AVA disclosed herein that are not groups containing the provision of the bactericide and also do not contain those which contribute to the retention of Bak tericides can chemically do so in a known manner modified to contain AVA's containing both groups and preferably contain a plurality of these radicals. Both preferred polymeric AVA's it is desirable to increase substantivity and delivery of the bactericide to the oral surfaces, the repetitive units in the Polymer chain or in the backbone of the chain at least about  10% and preferably at least 50% and especially minde at least 80% to 95% or 100% by weight of the polymer of acid residues that increase the provision of services.

In a preferred embodiment of the invention the antibacterial enhancer activator AVA from a Polymers with repeating units, in which one or Several phosphonic acid residues are present, the Zur Increase this provision to one or more Carbon atoms are bonded in the polymeric chain. On Example of such an AVA is a Po ly (vinylphosphonic acid), which residues of the following formula includes:

however, this polymer does not contain a moiety containing the Retention increased. Remnants of this kind are however in a Po ly (1-phosphonopropene) and have units of the formula:

A preferred AVA containing phosphonic acid residues is one Compound containing poly (beta-styrenephosphonic acid) Units of the following formula:

contains, wherein Ph is a phenyl radical; the phosphonic acid residue, which increases the availability of the bactericide and which Phenyl residue, which improves retention, is vicinal Carbon atoms bound in the chain. It is also preferable a copolymer of beta-styrenephosphonic acid with vinyl  phosphonyl chloride, which has units of the formula III, alternating or in random distribution with units of formula I occur or a poly (alpha-styrene phosphonic acid) containing units of the following formula:

at which the supply and the retention increase Remains geminal bound to the chain.

These styrene phosphonic acid polymers and their copolymers with other inert ethylenically unsaturated monomers have general, a molecular weight in a range of about 2000 to 30,000 and preferably from about 2,500 to 10,000. Such inert monomers interfere with the desired function of copolymers used as AVA are not essential.

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

- [CH₂) ₁₄CHPO₃H₂] _Kn -

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

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

Other phosphonated polymers, such as poly (allyl phosphonoacetate), phosphonated polymethacrylates and the like chen and geminal diphosphonate according to EU Patent 03 21 233 can also be used as AVA, provided that they contain the above-mentioned organic radicals which are the Promote retention of the bactericide.

In one embodiment of the oral hygiene according to the invention tel have these an orally acceptable carrier, an effective the plaque preventing amount of a substantially what seronoluble non-cationic bactericide and an Tibacterial amplification activator with an average molecular weight of about 1000 to 1 000 000, the at least one provisioning function group and at least one organic retention containing increasing group, this AVA no or in we Substantially no water-soluble alkali or ammonium salt of a synthetic anionic linear polymeric polycarb oxylate having a molecular weight of about 1,000,000 to about 1 000 000.

Another preferred embodiment according to the invention be is that the AVA is a synthetic anionic polymer res carboxylate is. Although according to the invention synthetic anionic polymeric polycarboxylates having a molecular weight from about 1,000 to about 1,000,000, preferably about 30,000 to 500,000 not with the tartar-preventing poly are used as an inhibitor of alka phosphate phosphatase enzymes according to US Pat. No. 4,627,977 been to the tartar-preventing effect of linear to optimize molecular dehydrated polyphosphate salts. According to GB-PS 22 00 551 are polymeric polycarboxylates as optional ingredients in oral hygiene discloses the linear, molecularly dehydrated poly phosphate salts and substantially water-insoluble contain cationic bactericides. It was also in Zusam  associated with the present invention found that Such polycarboxylates are clearly effective to the Zurfü production and retention of non-ionic bactericides or plaque preventing agents to tooth surfaces increase if other ingredients, namely molecular dehydra Tiserte polyphosphates, with which the polymeric polycarb oxylates react, are absent; for example, if the component with which the polymeric polycarboxylates interact, in particular a non-cationic bactericide is.

Synthetic anionic polymeric polycarboxylates and their Complexes with various cationic germicides, zinc and Magnesium is an anticalculus in itself For example, from the US Pat'en 34 29 963, 41 52 420, 39 56 480, 41 38 477 and 41 83 914 known. The synthetic anionic polymeric polycarboxylates from this literature can, if they contain retention-promoting residues or are so modifi are adorned in the oral hygiene compositions according to the invention be set.

The synthetic anionic polymeric polycarboxylates which According to the invention are known and often as free acids and preferably as partial or complete dig neutralized water-soluble alkali metal salts or ammonium salt used. Preference is given to 1: 4 to 4: 1 copolymers of Maleic anhydride or maleic acid with others Bene ethylenically unsaturated monomers, preferably Me methyl vinyl ether / maleic anhydride having a molecular weight from about 30,000 to 1,000,000, especially 30,000 to about 500,000. These copolymers are used, for example, by the GAF Corporation named "Gantrez" e.g. as AN 139 with a molecular weight of 500,000 or as AN 119 with a molecular weight of 250,000 and especially as S 97 in pharmaceutical grade with a molecular weight of 70,000 distributed.  

Other polymeric polycarboxylates suitable as AVA and contain the retention of the bactericides promoting residues or are modified accordingly, are in US-PS 39 56 480 discloses how the 1: 1 copolymers of maleic anhydride with Ethyl acrylate, hydroxyethyl methacrylate, N-vinyl-2-pyrolidone or ethylene, the latter under the name "Monsanto EMA No. 1103 ", with a molecular weight of 10,000 and as "EMA Grade 61" is available, as well as 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.

Other effective polymeric polycarboxylates are those in the above US Pat. Nos. 4,138,477 and 4,183,914, which are incorporated herein by reference Retention-increasing residues contain or modifi are cited, namely copolymers of maleic anhydride with Styrene, isobutylene or ethyl vinyl ether, polacrylic acid, Polyitaconic acid and polymaleic acid and sulfoacrylic acid oligo mers with a molecular weight down to 1000, as "Uniroyal ND-2" are commercially available.

Generally suitable are polymerized olefinic or ethylenically unsaturated carboxylic acids with retention-promoting Residues containing an activated olefinic carbon Koh having a double bond in the polymerization easily reacts due to their presence in monomeric moles kül, either in the alpha-beta position with respect to the carboxyl group or as part of a terminal ethylene restes. Examples of such acids are acrylic, methacrylic Ethacrylic, alpha-chloroacrylic, crotonic, beta-acryloxypropionic, Sorbin, alpha-chlorosorbinic or cinnamic acid, beta Styrylacrylic acid, muconic acid, itaconic acid, citraconic acid, Mesaconic acid, glutaconic acid, aconitic acid, alpha-phenylacryl acid, 2-benzylacrylic acid, 2-cyclohexylacrylic acid, An gelic acid, umbellic acid, fumaric acid, maleic acid and their Anhydrides. Other olefinic monomers containing such  monomeric carboxylic acids are copolymerizable, are vinyl did, vinyl chloride or dimethyl maleate. Furthermore, copolymers which sufficient carboxylic acid salt residues for their water solubility contain.

Furthermore, the soge are suitable for the present invention termed carboxyvinyl polymers used as toothpaste components in the US-PS'en 39 80 767, 39 35 306, 39 19 409, 39 11 94 and 37 11 604 are described. These are in the trade example under the trademarks "Carbopol 934" and "940" and "941" from the B.F. Goodrich available. These products be consist essentially of a colloidal water-soluble Polymers of polyacrylic acid containing from about 0.75 to 2.0% by weight Polyallylsucrose or polyallylpentaerythritol as Vernet cross-linked, wherein the cross-linked structure and the cross-linked bonds increase the desired Retention by hydrophobicity or physical trapping of the Bactericidal effect and in a similar way. Suitable is also "polycarbophil" which is a polyacrylic acid, the is crosslinked with less than 0.2% Divinylglykol, wherein the lower proportion, molecular weight and / or hydro Phobia of this crosslinking agent, the retention of little or not raised at all. The 2,5-dimethyl-1,5-hexadiene is an example play for a very effective, retention-enhancing Crosslinking agent.

The synthetic anionic polymeric polycarboxylate is in essentially a hydrocarbon with preferably halogen and / or oxygen-containing substituents and bonds in, for example, ester, ether and OH groups and is described in the oral hygiene products in an amount of about 0.05 to 4, and preferably 0.05 to 3 and especially of 0.1 to 2 wt.% Used.

The antibacterial amplification activators AVA can natural anionic polymeric polycarboxylates which are the  Contain retention-promoting residues. carboxymethylcellulose and other binders such as gums and film-forming substances, not the ones mentioned above, increasing the delivery and / or retention-enhancing residues are termed AVA not suitable.

Examples of AVA having phosphinic acid residues and / or sulfonic acid residues for increasing the availability are, for example, polymers and copolymers containing units or groups derived by polymerization of vinyl or allyl phosphinic acid or sulfonic acids attached to the 1- or 2- or 3-carbon atom are substituted by an organic retention-enhancing group and contain, for example, the above-mentioned general formula - (X) _n -R. Mixtures of these monomers can be used and copolymers thereof with one or more inert polymerizable ethylenically unsaturated monomers of the type described above in conjunction with synthetic anionic polymeric polycarboxylates. In these and other polymeric AVA's, usually only one acidic addition-enhancing group is attached to any carbon atom or to another atom in the polymer backbone or branch thereof. Polysiloxanes which contain residues which contain the provision of the bactericide and the residues promoting it for the retention thereof or are modified accordingly can also be used as AVA. Also suitable as AVA are ionomers containing such groups. Such ionomers are described in Kirk Othmer, "Encyclopedia of Chemical Technology", 3rd Edition, Supplement Volume, pages 546 to 573. Other AVA's include polyesters, polyurethanes, and synthetic and natural polyamides, including proteins and proteinaceous materials such as collagen, poly (arginine), and other polymerized amino acids, as long as they contain residues containing the bactericide.

In one embodiment of the oral hygiene according to the invention The AVA has an average molecular weight of about 1,000 to about 1,000,000 and contains at least one functional residue that provided the bak terizids and an organic residue that increases retention improved, this compound no or substantially no water-soluble alkali or ammonium salts synthe tischer, anionic, linear, polymeric polycarboxylates with a molecular weight of about 1,000 to 1,000,000.

According to the invention, the oral hygiene product is a dental care product containing about 0.3% by weight of bactericide, such as Example, triclosan and about 1.5 to 2 wt.% Polycarboxylates as AVA.

It is believed that the AVA and in particular a polymeric AVA is generally an anionic film-forming material and adheres to the tooth surface and a kon forms continuous film on this surface and thereby prevents bacterial colonization on the tooth surface. It it is possible that the non-cationic bactericide is a Kom plex or another merger with the AVA forms and thus a film of this complex on the tooth surface he gives. The film-forming property of the AVA and the amplified Provision and the film-forming property of AVA and the increased retention of the bactericide on the tooth Surface due to AVA causes the tooth surfaces for bacterial accumulations are unsuitable, in the special, because the direct bacteriostatic effect of Bactericides inhibits the growth of bacteria. As a result, result combinations of three different effects evidence of increased availability of the bactericide and on the other a long retention time on the tooth surface and thirdly a prevention of Deposition of bacteria on the tooth surface, causing the Oral care according to the invention particularly good a tooth  prevents covering. An identical plaque-preventing effective The mucous membranes or the oral tissue on the palate area mediated.

According to the invention, the orally acceptable carrier causes itself the substantially water-insoluble non-cationic Bak in an effective plaque preventing amount in the Saliva dissolves.

The carrier is an aqueous phase with a Feuchthaltemit tel. In a dental gel containing usually 5 to 30% by weight of a SiO ₂ polish, water is usually present in an amount of at least about 3% by weight, and generally from about 3 to 35% by weight, and preferably, as a humectant Glycerol and / or sorbitol in amounts of 6.5 to 75 or 80 wt.% Of the dental gel used. The sorbitol quantities are generally based on the commercially available sorbitol in 70% strength aqueous solution.

Tooth gels containing 0.25 to 0.35% by weight of bactericide do not require any further additives for the carrier to make the bak to solubilize tericide, although solubilizer to be favoured. If the bactericide in amounts below 0.25 Weight%, e.g. 0.01 to 0.25 wt.% Is present, a solubilization be present to a sufficient Solubilisie saliva to prevent plaque. When the amount of the bactericide exceeds about 0.35% by weight, e.g. in a range of about 0.35 to 0.5 wt% or more or until present at 5%, a solubilizing agent should be present, otherwise an essential part of the bactericide will be insoluble remains.

If the oral hygiene product is a toothpaste delt, containing about 30 to 75 wt.% Of a polishing agent, so is the presence of such a solubilizing agent prefers.  

If the oral hygiene product as a mouthwash or as a liquid Oral care is present, so should the oral Carrier at least one surfactant, a flavoring oil or not contain toxic alcohol, all of these components being the Dissolve the bactericide support, in turn, the Presence of such a solubilizing agent is preferred becomes.

When in the oral hygiene compositions according to the invention a Solubili is present, it is generally in a Amount of 0.5 to 20 wt.% Used, where already 0.5 wt.% suffice if the amount of water-insoluble non-kat ionic bactericide is low and, for example, at about 0.3% by weight. At higher levels of bactericide, such as at least about 0.5% by weight and in particular in the presence of Polishing agents in an amount of about 5 to 30 wt.%, It is expedient if at least 5% by weight and usually up to 20% by weight or more solubilizing agents are present. It likes to toothpaste separations occur when more than 5% by weight of solu Bilisierungsmittel are present.

That for the solubilization of the bactericide in saliva provided agent may be in the water / humectant carrier be provided. Such solubilizers are wet such as polyols, namely propylene glycol, dipropylene glycol and hexylene glycol, "cellosolve" such as methyl cellosolve and ethyl cellosolve, vegetable oils and paraffins with at least 12 carbon atoms in the chain, such as olive oil, Castor oil, petrolatum and esters such as amyl acetate, ethyl acetate and benzyl benzoate. As propylene glycol is 1,2-propylene glycol and 1,3-propylene glycol used. Significant quantities Polyethylene glycol, in particular having a molecular weight of 600 or more, should be avoided because polyethylene glycol the bactericidal action of the non-cationic bactericide interferes. For example, polyethylene glycol (PEG) reduces 600 in Combination with triclosan in a weight ratio of 25  Share triclosan to 1 part PEG 600 the bactericidal effect of Triclosan by a factor of about 16 versus a pro which contains no polyethylene glycol.

The oral hygiene compositions according to the invention can be present as a dental gel and contain a polishing agent based on SiO ₂ , in particular crystalline silica having a particle size of up to about 5μ, an average particle size of about 1.1μ and a surface area of up to 50,000 cm ² / g , preferably as a silica gel or colloidal silica or complex, amorphous alkali aluminosilicates.

If optically clear or opaque gels are desired, then Polishing agents used a colloidal silica, as they are under the designation "SYLOID 72" or "SYLOID 74" or as Sold "SANTOCEL 100" as Alkalialuminosilikat complex becomes. The gel-like structure and the refractive indices, the near the refractive indices of the gelling agent and the are liquid components, are for such dental gels particularly suitable.

The polishing material is in the toothpastes according to the invention or tooth gels in an amount of about 5 to 30% by weight the.

In an oral hygiene product according to the invention in the form of a Toothpaste contains the carrier material with an aqueous phase a humectant, preferably glycerin and / or sor bit, wherein the proportion of water in a range of 15 to 35 or 40% by weight and the proportion of glycerol and / or sorbitol in a range of 20 to 25% by weight, and preferably 25 to 60 wt.% Is, the commercial sorbitol usually represents a 70% aqueous solution.

The oral hygiene products according to the invention can be present either as a toothpaste or, for example, in the presence of SiO ₂ -containing polishing agents as a tooth gel. The carrier component may contain polishing agents such as water-insoluble sodium metaphosphate, potassium metaphosphate, tricalcium phosphate, dehydrated or anhydrous dicalcium phosphate, calcium carbonate, aluminum silicate, hydrated alumina, silica, bentonite and mixtures thereof, as well as hard polishes such as calcined alumina and zirconium Silicate or particulate resins according to US-PS 30 70 510, such as melamine, phenol and urea-formaldehyde resins and cross-linked polyepoxides and polyesters, preferred polishing agents are insoluble sodium metaphosphate, dicalcium phosphate and hydra tized alumina.

Many "water-insoluble" polishes are anionic and may also contain small amounts of soluble ingredients. For example, as insoluble sodium metaphosphate can also Mandrell's salt and Kurrol's salt are used. These metaphosphates show low solubility in water and are generally considered to be insoluble metaphosphates records, but a small amount up to 4 wt.% Of sol containing phosphates such as sodium trimetaphosphate, which however, it can be washed out. The insoluble alkali metal Phosphates are mostly used as powders with a particle size not more than 1% larger than 37μ.

As a polishing material, for example, hydrated alumina which is non-ionic and 85% one Particle size below 20μ and has a gibbsite structure and is an alpha-aluminum trihydrate. The through average particle size of gibbsite is 6 to 9μ, where the sieve analysis can be as follows:  

μ % <30 94-99 <20 85-93 <10 56-67 <5 28-40

The polishing agent is generally in the toothpaste or in the Tooth gel in an amount of 30 to about 75 wt.% Available.

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 wt.%. Suitable thickening agents are synthetic colloidal, clay-like magnesium alkali silicate complexes, such as the La ponit types, where Laponite D is about 58.0% SiO ₂ , 25.4% MgO, 3.05% Na ₂ O, 0.98% Li ₂ O and water and 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, iota-carrageenan, gum-tragacanth, starch, polyvinylpyrrolidone, hydroxyethylpropylcellulose, hydroxybutylmethylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, sodium carboxymethylcellulose and especially in the presence of SiO ₂ polishers colloidal SiO ₂ , such as "SY - LOID 244 "or" SYLODENT 15 ".

Oral products in the form of mouthwash or liquid Dentifrices usually become a carrier / water used hol mixture, wherein the weight ratio of water to alcohol in the range of 1: 1 to about 20: 1, and preferably at 3: 1 to 10: 1 and especially 4: 1 to about 6: 1 lies. The total content of the water / alcohol mixture is usually in a range of 70 to about 99.9 wt.%. When Alcohol is ethanol or isopropanol. Humectants like Glycerin and sorbitol may be present in amounts of about 10 to 30% by weight.  to be available. Liquid oral care products usually contain about 50 to 85% by weight of water and may be about 0.5 to 20% by weight Alcohol and further about 10 to 40% by weight of a humectant such as glycerol and / or sorbitol. The alcohol and if necessary also the aroma oil support the dissolution of the water-insoluble non-cationic bactericide.

The non-cationic bactericide is essentially what repel- lant. According to the invention, however, with the help of Ver strengthening activator AVA such as e.g. with the in the mouthwash or present in the liquid oral care product polycarboxylate, the organic surfactant, the aroma oil or the non-toxic Alcohol allows dissolution of the bactericide with it this the mucous membranes, the palate area and the tooth surfaces reached. Surfactants and aroma oils support the dissolution of the Bactericide.

Organic surfactants are present in the oral care compositions according to the invention to achieve an increased prophylactic effect and to allow a thorough dispersion of the dental plaque preventing bactericides in the oral area and also to better form the oral hygiene according to the invention in kos metic sense. Surfactants used are anionic, nonionic or ampholytic surfactants which preferably have cleansing and foaming properties. Suitable anionic surfactants are water-soluble salts of higher fatty acid monoglyceride monosulfates, such as the sodium salt of monosulfated monoglycerides, hydrogenated coconut oil fatty acids, higher alkyl sulfates such as sodium lauryl sulfate, alkylaryl sulfonates such as sodium dodecylbenzenesulfonate, higher alkyl sulfoacetates, higher fatty acid esters of 1,2-dihydroxypropanesulfonate and substantially saturated higher aliphatic acylamides lower aliphatic aminocarboxylic acids having, for example, 12 to 16 carbon atoms in the fatty acid radical, alkyl or acyl radical. Examples of such compounds are N-lauroyl sarcosine as well as the sodium, potassium or ethanolamine salts of N-lauroyl, N-myristoyl, or N-palmitoyl sarcosine, which are substantially soap-free. Such sarcosinates are particularly advantageous in oral care, as they prevent the formation of acid in the oral cavity. Examples of water-soluble non-ionic surfactants are condensation products of ethylene oxide with various compounds having reactive hydrogen atoms with hydrophobic, long-chain compounds such as C ₁₂ - to C ₂₀ -Aliphaten, such as condensation products with hydrophilic Polyoxyethylenresten (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 in an amount of about 0.5 to 5% by weight, preferably in an amount of about 1 to 2.5 % By weight.

If the oral hygiene products are in liquid form, enthal In general, they are about 0.1 to 10 and preferably 0.5 to about 5% by weight of thickening or gelling agent.

In general, liquid oral care products do not contain Po liermittel. Nevertheless, e.g. according to US-PS 35 06 757 about 0.3 to 2.0% by weight of a polysaccharide having a molecular weight over 1 000 000 containing mannose, glucose, potassium gluconate and acetyl groups in an approximate ratio from 2: 1: 1: 1 as a suspending or thickening agent in one liquid oral care products are used, which then also about 10 to 20 wt.% Of a polishing material such as hydrated alumina, dicalcium phosphate dihydrate, Cal ciumpyrophosphate, insoluble sodium metaphosphate, what serous dicalcium phosphate, calcium carbonate, magnesium car carbonate, magnesium oxide, silicic acid and mixtures thereof th.  

It is believed that in the oral care of the invention the aqueous carrier in a mobile phase in Tensidmizellen solubilized, excluding the Gelling agent and any existing polish. The mobile dissolved phase of the oral care product is treated with saliva diluted, for example, the triclosan down suggests. For example, it was found that even at Absence of a particular solubilizing agent for Triclosan in an amount of 0.25 to 0.35 wt.% And at Presence of AVA as polycarboxylate sufficient triclosan is present in order to be effective in the area of connective tissue To allow plaque prevention. Similar effects give in to other water-insoluble, non-cationic Bactericides.

The oral care compositions of the invention may further include fluoride contain ion-supplying compounds that ver as caries ver hindering agent in an amount of 25 to 5000 ppm fluo are present. This low to complete what water-soluble compounds are, for example, inorganic Fluorides such as soluble alkali or alkaline earth fluorides, copper, Zinc or barium fluorides, as well as sodium fluorosilicate, Am monofluorosilicate, sodium fluorozirconate, ammonium fluorozirconate, sodium monofluorophosphate, aluminum mono- and difluorophosphate and sodium calcium pyrophosphate, wherein alkali fluorides and tin fluorides such as sodium fluoride and tin (II) fluo chloride and sodium monofluorophosphate and mixtures thereof be awarded.

The amount of fluorine-providing compounds depends on the type the compound in question, its solubility and others Parameters and is generally within a range of 0.0005 to 3.0% by weight, based on the total composition. For dentifrices, e.g. a tooth gel, should total 5000 ppm F-ions, based on the weight of Zahnpflegemit be present, being also 300 to 2000 ppm and above  preferably 800 to about 1500 ppm fluoride ions preferred who the.

Alkali fluorides are generally used in an amount of 2 % By weight, and preferably in a range of 0.05 to 1% by weight. used in toothpastes. Sodium monofluorophosphate is used in general in amounts of 0.1 to 3 and preferably in one Amount of 0.76 wt.% Used.

The oral hygiene products according to the invention can still further Additives such as whitening agent, Konser vierungsmittel, silicones, chlorophyll compounds and am moniakhaltige compounds, such as urea and / or diammonium phosphate. In addition, suitable flavoring or sweetening agents tel, and usually in an amount of 0.1 to 5% by weight or more. The aroma oils, like the surfactants, can Solvent power of the bactericide even in the absence of Ten increase siden.

The oral care compositions according to the invention can be used several times a day or in daily intervals. they have one pH of about 4.5 to 9 or 10 and generally of 5.5 to about 8, and preferably from 6 to 8, especially 6.5 to 7.6. Oral hygiene products with a pH below 5 no damages.

The oral care compositions of the invention may also be in a lozenge tablets, chewing gum or other preparations For example, by turning them into a warm, gummy Mass be stirred or by the gummy mass coated with a composition according to the invention, wherein these preparations nor the usual additives, plasticizers, Sü may contain agents or carbons.  

In the following the invention will become more apparent by way of examples are explained, with all quantities, if not stated otherwise, refer to the weight.

example 1

Two toothpastes of the following composition were prepared provides:

Toothpaste A gives triclosan to the teeth and mucous membranes essentially as good as the toothpaste B, which contains a solubilizing agent for triclosan. For this Toothpaste according to the invention is a particular solubilizer not required. A corresponding toothpaste,  in which the polycarboxylate (Gantrez) is missing, with respect to the Provision of triclosan much worse.

If you use triclosan with other batericides like phenol, thymol, Eugenol and 2,2'-methylene bis (4-chloro-6-bromophenol) replaced or the polycarboxylate (Gantrez) by other AVA-Ak replaced, such as by a 1: 1 Copolyme Res of maleic anhydride and ethyl acrylate, by sulfo acrylic oligomers, by carbopols, e.g. Carbopol No. 934, and Polymers of alpha- or beta-styrenephosphonic acid monomers and copolymers of these monomers with one or more ethyls unsaturated polymerizable monomers such as vinyl phosphonic acid, also gives improved results.

Example 2

The following liquid dentifrices A to D regarding their uptake and retention of triclosan with Saliva-coated hydroxyapatite (HA) discs after the examined further below. The Quantities relate to parts by weight.  

Triclosan uptake and retention were after adjustment of the pH to 6.5 with NaOH in each case with saliva be layered hydroxyapatite discs determined.

The above values show that the solution D contains Polyvinyl alcohol (without an AVA) a triclosan uptake of only 36.0 μ / g shows, what a recording of 31μ / g at the control Solution A without additives is similar. In contrast, results in the solution C with an addition of poly (alpha-styrene phosphonic acid) a take up of 0.86μ / g, so a double so large intake as in solutions A and D, while the Solution B with poly (beta-styrenephosphonic acid) one around the 5th times higher uptake compared to solutions A and D. shows, from which it can be deduced that a vicinal substitution of the rest providing the bactericide shows better results. The above results further show the surprisingly good retention values of triclosan on HA  Slices for a long time in solution B, the poly (beta styrenephosphonic acid) having molecular weights of about 3000 to about 10 000 contains.

Example 3

The effect of antibacterial enhancer activators (AVA) as synthetic, anionic, linear polycarb oxylates in terms of intake, storage and free administration of the water-insoluble, non-cationic bactericides of Tooth surfaces are coated with saliva in vitro Hydroxyapatite disks and with detached buccal epithelium Cells determined using the in vitro determination of release and corresponding to restraint on oral surfaces in vivo.

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

Parafilm stimulated saliva was frozen in an ice beaker by centrifuging at 15,000 g about 15 Clarified minutes at 4 ° C and then with stirring for one hour sterilized by UV irradiation.

Each sintered disc was placed in a polyethylene test tube water and after removal of the water with 2.0 ml Saliva. After an incubation period of about 12 Hours at 37 ° C with constant shaking in a water bath a saliva skin formed. Subsequently, over Remove saliva and slice with 1.0 ml Treated solution that is in the liquid phase  Solution of the dentifrice with the bactericide (triclosan) contained; it was again at 37 ° C under continuous Shaking in a water bath for 30 minutes incubated, whereupon the Schei be transferred to a new test tube and under gentle Shaking with 5.0 ml of water was added. The disc was then put in another tube and the washing process repeated twice. Subsequently, the disc was under Avoidance of entrainment of further liquid inventory divide into a new test tube and after addition of Shake vigorously with 1.0 ml of methanol and leave to room for 30 minutes leave the adsorbed triclosan through the Take in methanol. The methanol was then filtered off with suction and 5 Minutes in a Beckman # 11 microcentrifuge at 10,000 rpm centrifuged. Subsequently, the methanol became chromatogra phically examined for the bactericide, in all cases three samples were used.

To determine the retention of the bactericide on a with Saliva coated HA disc was this with slurry treated dentifrice as described above. The disc was after an incubation period of 30 minutes taken from the slurry at 37 ° C, twice with water washed and then incubated again with saliva through Centrifuging was clarified. After another incubation 37 ° C with constant shaking within different time distances, the HA disks were removed from the saliva, whereupon the amount of bactericidal (triclosan) released from the shit was retained and released to the saliva was determined by chromatography.

To assess the delivery or release of bactericide to the buccal epithelial cells, 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 picked up by gentle rubbing of a wood spatula on the mucous membrane and suspended in a buffer solution. As a buffer solution, a Resting Saliva Salts (Rss) buffer of 50 nM NaCl, 1.1 nM CaCl ₂ and 0.6 nM KH ₂ PO ₄ solution of pH 7.0 in an amount of 5 to 6 × 10 ⁵ cells / ml, using a hemocytometer to count the cell and stored until use in ice. A cell suspension of 0.5 ml, previously heated at 37 ° C in a water bath, was added with 0.5 ml of the antibacterial solution to be tested and incubated at 37 ° C in. 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 incubation for 30 minutes, the cells were harvested by centrifugation at 5000 rpm for 5 minutes, washed 3 times with the Rss buffer solution, and added with 1.5 ml of methanol, after which the bactericide was chromatographically analyzed after shaking vigorously.

There were two dentifrices of the following composition prepared, wherein the numbers are by weight Respectively.  

The uptake of triclosan in μ / g on the saliva-coated HA discs and in μ / g × 10 ⁵ epithelial cells is given in the following Table I for the oral hygiene product A without poly carboxylate and for the oral care product B with carboxylate.

Table I

These values clearly show that in dentifrice B contained polycarboxylate the supply and uptake of Triclosan in both HA discs and epithelial Cells increased.  

Similar results were obtained with dentifrices that 0.30 parts by weight triclosan.

Example 4

Further experiments with the saliva coated HA-Schei ben and epithelial cells with a modified Mundpflegemit tel B according to Example 3 with a content of 2.0% polycarb oxylate and 0.20% triclosan, 10.0% propylene glycol and 2.0% Sodium lauryl sulfate and an analogously formulated dental care medium B 'but containing 0.30% triclosan was used compared to a commercial oral care product C, which hydrated alumina as a polishing agent and

• a) 0.2% Triclosan
• b) no polycarboxylate
• c) no propylene glycol
• d) 0.5% zinc citrate
• e) 2.5% surfactant
• f) sodium monofluorophosphate

contained.

Further, a dentifrice C 'of the following composition was examined, which corresponded to the commercial Zahnpflegemit tel C, but still contained 0.30% triclosan.

Composition of the dentifrice C ' Wt.% Sorbitol (70%) 27.0 sodium 0.80 Sodium monofluorophosphate 0.85 zinc citrate 0.50 sodium 0.18 water 16.47 hydrated alumina polishing agent 50.0 ethanol 0.20 sodium lauryl sulfate 1.875 sodium dodecyl benzene sulfonate 0.625 triclosan 0.30 flavoring 1.20

Since the dentifrices C and C 'a total of 2.5 wt.% Tenside contain more surfactant for the dissolution of triclosan Available, as with the dentifrices B and B ', which only Contain 2.0% by weight. In the dentifrices B and B 'is however, propylene glycol in the siliceous polishing agent present, which in dentifrices C and C ', the contain hydrated alumina as a polishing agent, so that an optimal solution of triclosan takes place.

The benefit of dentifrices B and B ', the propylene glycol and polycarboxylate (Gantrez) is found opposite dentifrices C and C 'with respect to triclosan uptake saliva-coated HA discs and, in the case of epithelial Cells from the following Table II.  

Table II

Further experiments with the dentifrice B 'with 0.3% Triclo san and presence of polycarboxylate and propylene glycol in a 50% slurry of the dentifrice Determination of the retention of triclosan an with saliva layered HA discs also showed an excellent time Retention, as shown in the following Table III:

Time in minutes Retention of triclosan in μ / g on HA discs 0 70 30 60 60 70 120 65 180 57 240 59

The above values show that dentifrice contains at triclosan with polycarboxylate and propylene glycol a he Increased release of triclosan to the tooth surface and the Mucosa, as well as increased retention, resulting Plaque is better prevented and the bactericidal effect better.  

Example 5

For comparison, the following dentifrices were according to Formula A and B made:

The dentifrice according to formula A contains a carboxylate and 0.5 Triclosan as a plaque-preventing bactericide and no Solubilizing agent, while in the formula B propylene glycol is present as a solubilizing agent.

A dentifrice of formula A is with respect to the delivery of Triclosan to the epithelial cells much worse than in this relationship significantly more effective dentifrice  Formulation B, which clearly indicates the improved supply of tri closan proves.

Example 6

To determine how the dentifrice in question the Pretreatment of plaque was influenced by subjects according to the method of Addy, Wilis and Moran in J. Clin. Perio, 1983, Vol. 10, pp. 89-99, with a placebo Toothpaste (i) and a toothpaste according to the invention with 0.3 Wt% triclosan, 10% propylene glycol (instead of 3% propylene ethylene glycol 600) and 2% polycarboxylate (Gantrez S-97) and a humectant made from propylene glycol and sorbitol (ii) were used, the compositions of the dental care Medium as follows are:

With regard to plaque reduction, the experimental per persons who are treated with the dentifrice according to the invention (ii) were treated in comparison with the subjects who were treated with the Placebo composition (i) were treated, a significant Decrease of 20% noted.

Since lower amounts of propylene glycol are the same in toothpaste (ii) existing 0.3% Triclosan can dissolve, similar Likely results are expected when the amount of propylene glycol reduced to 0.5 parts by weight and the amount of sorbitol on 39.5 parts by weight is increased. Likewise, others can Solubilizing agents such as dipropylene glycol, hexylene glycol, Methyl cellosolve, ethyl cellosolve, olive oil, castor oil, petro latum, amyl acetate, ethyl acetate, glyceryl tristearate and benzyl benzoate instead of propylene glycol effective the supply of Increase triclosan to the mucous membranes. Furthermore, sim Liche results are expected when propylene glycol or other solubilizing agents in the 0.3% Triclosan enthal toothpaste (ii) should be omitted.

Example 7

There were the following two toothpastes according to the invention manufactured:  

The above compositions are also improved Results obtained when considering triclosan by others above replaced bactericides such as phenol, thymol, eugenol and 2,2'-methylene-bis (4-chloro-6-bromophenol) and / or by replaced the polycarboxylate (Gantrez) with other AVA, such as for example, by a 1: 1 copolymer of maleic acid hydride and ethyl acrylate, sulfoacrylic oligomers, carbopols, (e.g., 934), polymers of monomeric alpha or beta-styrene phosphonic acids and copolymers of these styrene phosphonic acid Monomers with other ethylenically unsaturated polymerisier ble monomers such as vinylphosphonic acid.  

Example 8

There were dentifrices of the following composition manufactured;

The toothpastes mentioned above showed an increased supply of Triclosan on the tooth surfaces and on the mucosa, and although in a much more effective way than corresponding tooth pastes where no polycarboxylate was present.  

example 9

The following toothpastes were made, with the Quantities are by weight:

The above toothpastes give triclosan to those with saliva coated HA discs more effective than corresponding Toothpastes that contain no polycarboxylate.

example 10

It became a plaque-preventing toothpaste from the following Ingredients prepared, the quantities are refer to the weight:  

glycerin 15.00 propylene glycol 2.00 sodium 1.50 water 24.93 Vinyl methyl ether / maleic anhydride copolymer (42% solution) 4.76 Sodium monofluorophosphate 0.76 sodium 0.30 insoluble sodium metaphosphate 47,00 Titanium dioxide 0.50 sodium lauryl sulfate 2.00 triclosan 0.30 flavorings 0.95

In the compositions according to the above example ver improved results also achieved when the triclosan by phenol or by 2,2'-methylene-bis- (4-chloro-6-bromo phenol) or replaced by eugenol and / or if that Polycarboxylate (Gantrez) by other AVA's such as Carbopol e.g. 934 or by styrene phosphonic acid polymers with a mole kulargewicht in a range of 3,000 to 10,000 replaced be such as by poly (beta-styrene phosphonic acid), by copolymers of vinylphosphonic acid with beta-styrenephosphonic acid and with poly (alpha-styrene phosphonic acid) or by sulfoacrylic acid oligomers or by a 1: 1 copolymer of maleic anhydride and with ethyl acrylates.

Example 11

Dentifrices have been prepared which are in their liquid Phase Triclosan contained and the following composition in % By weight:  

The concentration of the above components corresponds to one 1.33% toothpaste, with a 25% proportion of friction agent missing, for making a complete toothpaste is required. This liquid phase for a not full Constant toothpaste has been in terms of intake of Triclo san on saliva-coated HA discs, the results being recorded in the following Table IV are:

Table IV

The above results show a more than double increase in the uptake of triclosan with formulation B, which Polycarboxylate (Gantrez) contains, compared to the formulation A. without polycarboxylate.  

Example 12

It was the concentration and uptake of triclosan HA disks from the supernatant aqueous phase of a 1: 1 slurry of toothpaste and water, with a Dentifrices containing 0.5% triclosan and 2.5% Sodium lauryl sulfate, once with 25% hydrated silica and 1.5% polycarboxylate (Gantrez S-97) formulation A - and on the other hand a toothpaste with 50% alumina and 1.5% Polycarboxylate (Gantrez S-97) formulation B - used were. The results are in the following table V reproduced.

Table V

The supernatant liquid phases of the 1: 1 slurry of Toothpaste in water has been identified with regard to triclosan Concentration in the supernatant phase and in terms of Triclosan uptake on the saliva-coated HA slide ben determined. The results show that when using 50% alumina abrasive substantially added the triclosan a 1: 1 dilution increased from 1650 to 1905 and thereby allows an increased uptake of triclosan from 52 to 74 has been.  

Example 13

The following mouthwashes were produced, which are the Bil reduce the buildup of plaque by removing the receptacle and the Increase retention of triclosan in the oral range.

Example 14

The following liquid dentifrices were used for Ver Reduction of dental plaque by increasing the intake and retention tion of triclosan in the oral area, the Quantities are by weight.  

Likewise, good results are achieved when using the above Compositions the triclosan each by phenol or by 2,2'-methylene-bis- (4-chloro-6-bromophenol), by eugenol or replaced by thymol, or when the polycarboxylate (Gantrez) by other AVA's such as Carbopol e.g. 934 or through Styrene phosphonic acid polymers having a molecular weight in the Range from 3,000 to 10,000 are replaced, such as by poly-beta-styrenephosphonic acid, by copolymers of vinylphosphonic acid with beta-styrenephosphonic acid and by Poly (alpha-styrenephosphonic acid) or by Sulfoacryl-Oligo or by a 1: 1 copolymer of maleic anhydride with methyl acrylate.

Claims (38)

1. Oral hygiene products containing

• a) an effective plaque preventing amount of a substantially water-insoluble non-cationic bactericidal component,
• b) about 0.005 to 4% by weight of an antibacterial enhancer-activator (AVA) to increase the availability of the bis-acid for the oral areas and the retention of the bactericide in these areas and
• c) an orally acceptable carrier which dissolves the bactericidal component in an effective plaque preventing amount in saliva, wherein the oral care agent is substantially free of tartar preventing polyphosphate compounds.

2. Oral care product according to claim 1, characterized in that it is a dentifrice with a content of about 5 to 30 wt.% Of a SiO ₂ Poliermittels, wherein the bactericidal component in an amount of 0.25 to 0.35 wt.% and additionally at least one surfactant and a flavoring oil are present. 3. Oral care product according to claim 1, characterized in that it is a dentifrice with a content of about 5 to 30 wt.% Of a SiO ₂ Poliermittels, wherein the bactericidal component in an amount of 0.01 to 5 wt.% And further a solubilizing component is present in a sufficient amount to dissolve the bactericidal component in the saliva. 4. oral care product according to claim 3, characterized that the bactericidal component in an amount of about 0.05 to less than about 0.25% by weight. 5. oral hygiene product according to claim 3, characterized that the bactericidal component in an amount of about from about 0.35 up to about 5% by weight. 6. oral care product according to claim 5, characterized that the bactericidal component in an amount of more than about 0.35 to about 0.5 wt.% Is present. 7. oral hygiene product according to claim 1, characterized that it is a dentifrice with a content of 30 to 75 % By weight of a dental grade water-insoluble polish by means of is. 8. oral hygiene product according to claim 1, characterized that as a mouthwash or liquid dentifrice is present and that the orally acceptable carrier is an aqueous Carrier, wherein at least one surfactant, a flavoring oil or a non-toxic alcohol is present. 9. Oral care product according to claim 1 to 8, characterized marked records that it is about 0.05 to 5 wt% of a surfactant contains. 10. Oral care product according to claim 1 to 9, characterized records that it is an aroma oil in an amount of about 0.1 contains up to 5% by weight. 11. Oral care product according to claim 8, characterized in that that it is a mouthwash and that the aqueous carrier Contains ethanol, wherein the weight ratio of water to ethanol in a range of 1: 1 to about 20: 1.   12. oral care product according to claim 8, characterized that it is a liquid dentifrice, which is 0.3 to 2.0% by weight of a high molecular weight polysaccharide containing more than 1 000 000, which contains mannose, glucose, Potassium glucuronate and acetyl residues in an approximate Ratio of 2: 1: 1: 1 as suspending and thickening medium and about 10 to 20 wt.% Of a polish ent holds. 13. Oral care product according to claim 1 to 8, characterized records that the bactericidal component is selected from the group of halogenated diphenyl ethers, haloge ned salicylanilides, benzoic acid esters, halogenated Carbanilides and phenolic compounds. 14. Oral care product according to claim 13, characterized the bactericidal component is a halogenated diphenyl ether is. 15. Oral care product according to claim 14, characterized that the halogenated diphenyl ether is a 2,4,4'-trichloro-2 ' hydroxyphenyl ether. 16. Oral care product according to claim 1 and 3 to 6, characterized characterized in that the solubilizing agent in a Amount of 0.5 to 50% by weight is present and selected is from the group consisting of propylene glycol, dipro ethylene glycol, hexylene glycol, methyl cellosolve, ethyl cellosolve, vegetable oil and a paraffin with at least 12 carbon atoms, amyl acetate, ethyl acetate, glyceryl tristearate and benzyl benzoate. 17. oral hygiene product according to claim 16, characterized that the solubilizing agent is propylene glycol and in in an amount of about 0.5% by weight.   18. Oral care product according to claim 1 or 16, characterized signs that it is a dentifrice and a polisher contains agent selected from the group of Sodium metaphosphate, tricalcium phosphate, dihydrate or anhydrous dicalcium phosphate, calcium pyrophosphate, Magnesium orthophosphate, trimagnesium phosphate, calcium carbonate, aluminum silicate, hydrated aluminum oxide, Silica, bentonite and mixtures thereof. 19. Oral care product according to claim 18, characterized that the polishing agent dicalcium phosphate dihydrate or hydra tisiert alumina is. 20. Oral care product according to claim 1 to 8, characterized records that the antibacterial enhancer activator an average molecular weight of about 100 to about 1 000 000. 21. oral hygiene product according to claim 20, characterized that the antibacterial enhancer activator at least contains a functional residue that the Zur providing bactericidal and at least contains an organic radical whose retention elevated. 22. Oral care product according to claim 21, characterized that the rest increasing the availability of an acidic Rest is. 23. Oral care product according to claim 22, characterized that the restoring the availability of the remainder selected is selected from the group of carboxy-phosphonic, phosphine and Sulfonic acids and their salts and mixtures. 24. Oral care product according to claim 23, characterized in that the organic radical to increase the retention of the general formula O (X) -R corresponds, in the X the meaning O, N, S, SO, SO ₂ , P, PO or Si and R is a hydrophobic alkyl, alkylene, acyl, aryl, alkaryl, aralkyl or heterocyclic radical including the inertly substituted derivatives of these compounds and wherein n is 1 or zero. 25. Oral care product according to claim 20 to 24, characterized marked records that the antibacterial enhancer activator is an anionic polymer which is a plurality of Contains residues containing the provision of the Bak terizids and increase the retention of the bactericide increase. 26. Oral care product according to claim 25, characterized that the anionic polymer is a chain with it again each having at least one Contains carbon atom. 27. oral care product according to claim 26, characterized that each unit provides at least one of the supply containing bacteriocide-enhancing remnant that binds to the same che, vicinal or bound to other atoms in the chain is. 28. Oral care product according to claim 23, characterized that the increasing the availability of the bactericide Radical is a carboxyl radical or a salt thereof. 29. Oral care product according to claim 28, characterized the antibacterial reinforcing activator is a copoly meres of maleic acid or anhydride with another ethylenically unsaturated polymerizable monomers. 30. Oral care product according to claim 29, characterized the other monomer of the copolymer is a methyl  vinyl ethers in a molar ratio of 4: 1 to 1: 4 the maleic acid or its anhydride. 31 oral care product according to claim 30, characterized that the copolymer has a molecular weight of about 30,000 to 1 000 000 and in an amount of 0.1 to 2 Weight% is present. 32. Oral care product according to claim 31, characterized the copolymer has an average molecular weight of about 70,000. 33. Oral care product according to claim 23, characterized that the increasing the availability of the bactericide Residual is a phosphonic acid residue or a salt thereof. 34. Oral care product according to claim 33, characterized that the antibacterial enhancer activator is a Po ly (beta-styrenephosphonic acid) or a poly (alpha-styrene phosphonic acid) or a copolymer of one of these styrene Phosphonic acids with another ethylenically unsaturated Is monomers. 35. Oral care product according to claim 1, characterized that it is an orally acceptable carrier, effective plaque preventing amount of essentially what seronoluble non-cationic bactericidal component with an average molecular weight of about 1000 to 1 000 000 and at least one has the Zur Providing batericide functional enhancing Group and at least one organic retention Bactericidal group has increased, and these verbin No or substantially no water-soluble Alka Li or ammonium salt of a synthetic anionic linear polymeric polycarboxylic acid having a molecular weight of about 1000 to about 1 000 000 contains.   36. Oral care product according to claim 35, characterized that the bactericidal component in an amount of 0.25 to less than 0.5% by weight is present. 37. Oral care product according to claim 36, characterized that the bactericidal component in an amount of 0.25 to about 0.35 wt.% Is present. 38. Oral care product according to claim 36 or 37, characterized in that it contains a polishing agent based on SiO ₂ or a silicate.