EP1601337A1

EP1601337A1 - Oral and dental care agent

Info

Publication number: EP1601337A1
Application number: EP04719419A
Authority: EP
Inventors: Peter Wülknitz; Hans Laska
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2003-03-12
Filing date: 2004-03-11
Publication date: 2005-12-07
Also published as: CA2518267A1; DE10311171A1; US20060088482A1; JP2006519809A; WO2004080434A1

Abstract

The invention relates to oral and dental care agents, containing: an active ingredient combination (A) of at least one cationic component with an anti-bacterial action, (B) at least one active ingredient with an anti-tartar action, selected from the group of azacycloalkane diphosphonic acids or their physiologically compatible salts and (C) at least one binding agent, selected from xanthan gum, carboxymethylcellulose or a mixture of said two components. The oral and dental care anti-bacterial agents do not cause the discoloration associated with chlorohexidine and reduce or prevent discoloration to human teeth. This is unique for oral and dental care agents based on chlorohexidine. The inventive oral and dental care agents also have a tartar prevention and plaque reducing action.

Description

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The invention relates to oral and dental care products which, on the basis of a special combination of active ingredients, can contribute to the reduction and inhibition of discoloration on human teeth and to the inhibition of tartar and plaque.

Modern oral and dental care products are primarily used to clean and remove food residues, discoloration and firmly adhering dental plaque from the tooth surface. In particular, plaque is the basis for the formation of tartar, which in turn leads to the development and progression of gingivitis, bleeding (gingivitis) and caries.

Accordingly, in order to keep the teeth and gums healthy, the bacterial coating must be removed quantitatively by appropriate dental care. Ideally, a mouth and dental care product should even completely inhibit the formation of plaque and tartar through special additives.

Attempts have been made in the past to solve the above problems. It is known from the literature, for example, that certain antibacterial substances as an additive in toothpastes and mouthwashes can counter inflammation of the gums. In this context, chlorhexidine has long been known as a very effective antibacterial agent. The effect of chlorhexidine is based on its high retention rate in the oral cavity, which is associated with a certain depot effect or a long-term effect.

However, the problem with long-term use of chlorhexidine has so far been the formation of discoloration in the oral cavity, which is caused by chlorhexidine-related deposits primarily from polyphenols of various luxury foods such as tea, coffee or red wine. These discolorations particularly affect the toughness are unaesthetic and are generally not accepted by consumers. Therefore, long-term use is usually not practiced despite the high effectiveness of chlorhexidine in oral and dental care products.

In EP 304 627 B1 the synergistic combination of chlorhexidine and an alkyl polyglycoside tried to counteract the problem of discoloration. Due to the synergistic increase in the effectiveness of the two components, the chlorhexidine content could be reduced to such an extent that the problem of discoloration could be significantly reduced. However, this did not lead to a move towards more effective removal or inhibition of plaque.

An attempt to reduce tartar and plaque was made in EP 480 811 A1 by combining a cationic, antibacterial agent with an anti-numbering agent (preferably an azacycloalkane diphosphonic acid salt). However, the problem of discoloration could not be countered with regular use of the agents due to the high concentrations of chlorhexidine.

There is therefore still a need for oral and dental care products which are able to inhibit and / or prevent the formation of plaque and tartar without the disadvantages of the prior art, such as discoloration, having to be accepted.

Completely surprisingly, a mouth and dental care product has now been found which not only has a discolouration-reducing and -preventing effect due to a special combination of active ingredients, but also a high tartar-inhibiting effect and an anti-plaque effect.

The invention therefore relates to oral and dental care compositions containing an active ingredient combination

(A) at least one cationic, antibacterial component, (B) at least one anti-tartar active ingredient selected from the group of azacycloalkane diphosphonic acids or their physiologically tolerable salts, and

(C) at least one binder selected from xanthan gum, carboxymethyl cellulose or a mixture of these two components.

According to the invention, bisbiguanide derivatives are understood as cationic, antibacterial components. The compounds chlorhexidine and alexidine are particularly preferred. These two compounds are preferably used in the oral and dental care products in the form of their water-soluble, physiologically tolerable salts. Such salts are, for example, the acetates, gluconates, hydrochlorides, hydrobromides, citrates, bisulfites, fluorides, sorbates, salicylates, maleate, tartrates, fumarates, ethylenediaminotetraacetates, iminodiacetates, cinnamates, thiocyanates, arginates, benzoates and glutaride deschlorates.

Other useful in this invention antibacterial biguanide compounds are for example obtained from the polyhexamethylene type Vantocil ^® IB (ICI) which is known from DE-A-1964196 known 1, 6-bis (4- chlorbenzylbiguanido) hexane (fluorhexidine), and further known antibacterial biguanide compounds from documents US-A-2,684,924, US-A-2,990,425, US-A-3,468,898, US-A-4,022,834, US-A-4,053,636 and US-A-4, 198,392.

According to the invention, it is very particularly preferred to use chlorhexidine digluconate as an antibacterial component in the oral and dental care products.

The antibacterial component (A) is used in the oral and dental care compositions according to the invention in amounts of 0.001 to 3% by weight, based on the total weight of the composition. A preferred amount of the antibacterial component is from 0.01 to 1% by weight and in particular from 0.01 to 0.2% by weight, based on the total weight of the agent. According to the invention, compounds of the formula are used as anti-tartar active ingredient (B)

where n stands for integers between 3 and 5, R stands for hydrogen or a CrC r alkyl group and X stands for hydrogen, ammonium, substituted ammonium salts such as mono-, di- or triethanolammonium salts or alkali ions such as sodium or potassium ions, with a maximum of 3 groups X simultaneously represent hydrogen.

The 2,2-diphosphono-1-azacycloalkanes are excellent sequestering agents for polyvalent metal ions, especially for 2- and 3-valent metal ions. They are particularly suitable as complexing agents for alkaline earth metal ions.

According to the invention, it is very particularly preferred to use aza-cycloheptane-2,2-diphosphonic acid as an anti-tartar active ingredient or a physiologically acceptable salt, for example the sodium salt of azacycloheptane-2,2-diphosphonic acid, in the oral and dental care products.

The anti-tartar active ingredient (B) is used in the oral and dental care compositions according to the invention in amounts ranging from 0.001 to 5% by weight, based on the total weight of the composition. An amount of component (B) is preferably used in a quantity range of 0.01 to 3% by weight, in particular 0.05 to 2% by weight.

The third, mandatory component (C) of the active ingredient combination according to the invention is the binder.

Binders that can be used in the context of the invention are xanthan gum and carboxymethyl cellulose. They are usually used in amounts of min at least 0.01% by weight and in particular in amounts of 0.05 to 2% by weight, based on the total weight of the agent.

According to the invention, it may be preferred to add further binders or thickeners to the oral and dental care products, which have a consistency-regulating effect and furthermore prevent the separation of the liquid and solid components.

The amounts used in the compositions according to the invention are 0.1-5% by weight, preferably 0.1-3% by weight and in particular 0.5-2% by weight.

According to the invention, natural and / or synthetic water-soluble polymers such as alginates, carrageenans, agar-agar, guar gum, arabic gum, succinoglycan gum, guar flour, locust bean gum, tragacanth, karaya gum, pectins, hydroxyethyl cellulose or methylhydroxypropyl cellulose, hydrophobically modified Cellulose, starch and starch ether.

Water-soluble carboxyvinyl polymers (eg Carbopol ^® types), polyvinyl alcohol, polyvinylpyrrolidone and higher molecular weight polyethylene glycols (in particular those with molecular weights of 10 ^{2 to} 10 ⁶ D) are also suitable as binders or thickeners. Layered silicates and finely divided silicas (aerosilica and pyrogenic silicas) can also fulfill this function.

Water-insoluble, non-derivatized celluloses, which are offered, for example, by J. Rettenmaier & Sons under the names Arbocel ^® and Vitacel ^® , are particularly suitable as further binding or thickening agents. For the purposes of the invention, water-insoluble is understood to mean a solubility of less than 1% by weight in water at 20 ° C., ie less than 1% by weight of the cellulose is dissolved in 100 g of a saturated solution at 20 ° C.

Arbocel ^® CGP 5000, a highly viscous paste made of powder cellulose with thixotropic properties, is a particularly effective thickener that has strong consistency properties even at low concentrations, against ionic see components is inert and can be easily combined with other thickeners.

According to a preferred embodiment of the invention, the oral and dental care compositions further contain surface-active surfactants or surfactant mixtures to improve the cleaning effect and the foaming. They promote the rapid, complete dissolution and distribution of oral and dental care products in the oral cavity and at the same time support the mechanical removal of dental plaque, especially in areas that are difficult to access with a toothbrush. In addition, they promote the incorporation of water-insoluble substances, such as aromatic oils, stabilize the polishing agent dispersion and support the anti-caries effect of fluorides.

In principle, anionic surfactants, zwitterionic and ampholytic surfactants, nonionic surfactants, cationic surfactants or mixtures of these compounds can be used as surfactants in toothpaste formulations. According to the invention, toothpastes preferably contain at least one surfactant from the group of anionic surfactants, while mouthwashes preferably contain at least one surfactant from the group of nonionic surfactants.

In the compositions according to the invention, the surfactant or the surfactant mixture is usually present in an amount of 0.1-10% by weight, preferably 0.3-7% by weight and in particular 1-5% by weight, based on the total weight of the Composition used.

Anionic surfactants

Suitable surfactants with good foaming action are anionic surfactants, which also have a certain enzyme-inhibiting effect on the bacterial metabolism of the plaque.

These include, for example, alkali or ammonium salts, in particular sodium salts, of C ₈ -C ₈ -alkane carboxylic acids, of alkyl polyglycol ether sulfates with 12-16 C atoms in the linear alkyl group and 2-6 glycol ether groups in the mole cool, of linear alkane (Cι ₂ -Cι ₈ ) sulfonates, sulfosuccinic acid monoalkyl (Cι ₂ - Ci ₈ ) esters, sulfated fatty acid monoglyceride, sulfated fatty acid alkanolamides, sulfoacetic acid alkyl (Ci ₂ -Ci ₆ ) esters, acyl sarcosines, Acyl taurides and acyl isethionates each with 8 - 18 carbon atoms in the acyl group.

It is preferred to use at least one anionic surfactant, in particular a sodium laurylalkyl sulfate with 12-18 C atoms in the alkyl group. Such a surfactant is sodium lauryl sulfate which is commercially available for example under the name Texapon.RTM ^® K1296 commercially.

Zwitterionic and ampholytic surfactants

It can be preferred according to the invention to use zwitterionic and / or ampholytic surfactants, preferably in combination with anionic surfactants. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the trimethylammonium glycinate, cocoalkyldimethylam onium glycinate, N-acylamino-propyl-N, N-dimethylammoniumglycinate, for example the cocoacylaminopropyldimethyl and ammoniumglycine 2-alkyl-3-carboxylmethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylethylethylcarboxymethylglycinate. The fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine is particularly preferred. Such products are commercially available, for example, under the names Tego-Betain ^® BL 215 and ZF 50 and Genagen ^® CAB.

Ampholytic surfactants are surface-active compounds which, in addition to a Cs-C-jβ-alkyl or acyl group, contain at least one free amino group and at least one -COOH or -S0 ₃ H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkyl aminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamido propylglycine, N-alkyl taurine, N-alkylisarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid, each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholic surfactants are N-coconut alkyl aminopropionate, coconut amino amino ethyl propinate and C ₁₂ -C ₁₈ acyl sarcosine. In addition to the ampholytic emulsifiers, quaternary emulsifiers are also suitable, those of the ester quat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.

Nonionic surfactants

Non-ionic surfactants are particularly suitable according to the invention for supporting the cleaning action. Those nonionic surfactants which are selected from at least one of the following groups are particularly preferred:

- Adducts of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group;

- C ₁₂ -C 18 fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol;

- Glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids with 6 to 22 carbon atoms and their ethylene oxide addition products;

- Alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogues;

- Adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;

- Polyol and especially polyglycerol esters, such as. B. polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate.

Mixtures of compounds from several of these classes of substances are also suitable; - Adducts of 2 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;

- Partial esters based on linear, branched, unsaturated or saturated Ce Gaa fatty acids, ricinoleic acid as well as 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (eg sorbitol), sucrose, alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g. cellulose);

- Mono-, di- and trialkyl phosphates as well as mono-, di- and / or tri-PEG-alkyl phosphates and their salts;

- wool wax alcohols;

- Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

- Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 1165574 and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol and

- polyalkylene glycols.

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters with fatty acids or with castor oil are known, commercially available products and are preferred according to the invention. These are homolog mixtures whose average degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. Ci ₂ -C ₈ fatty acid mono- and - diesters of addition products of ethylene oxide with glycerol are known from DE-PS 2024051 as refatting agents for cosmetic preparations.

C ₈ -C ₈ alkyl mono- and oligoglycosides, their preparation and their use are from the prior art, for example from US-A-3,839,318, DE-A-20 36472, EP-A-77 167 or WO-A-93 / 10132 known. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. With regard to the glycoside residue, it applies that both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol is, as well as oligomeric glycosides with a degree of oligomerization up to preferably about 8 suitable. The degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products. An alkyl (oligo) glycoside is preferably an alkyl (oligo) glycoside of the formula RO (C ₆ H ₀ O) χ-H, in which R represents an alkyl group having 12 to 14 carbon atoms and x is one Averages from 1 to 4.

A particularly preferred surfactant which is used in the oral and dental care products according to the invention is the alkyl glycoside sold by the company Cognis under the trade name Plantacare 1200 UP (Ci ₂ -i ₆ -fatty alcohol-1,4-glucoside).

The oral and dental care compositions of the invention further contain humectants to protect against drying out and to regulate the consistency and low-temperature stability of the products. However, they can also be used to impart suspensions and to influence taste or gloss.

Toxicologically acceptable polyols, such as, for example, sorbitol, xylitol, glycerol, mannitol, 1, 2-propylene glycol or mixtures thereof, are usually used as humectants, but polyethylene glycols with molecular weights of 200-2000, in particular from 200 to 1500, can also be used as humectant components in Serve toothpastes.

The combination of several humectant components is preferred, the combination of glycerol and / or sorbitol containing 1,2-propylene glycol or polyethylene glycol being particularly preferred.

The combination of xylitol with one or both of the humectants glycerol and sorbitol should also be mentioned as a preferred combination, the anticariogenic property of xylitol also being mentioned in addition to the property as a humectant. In the event that the oral and dental care compositions of the invention are packaged as mouthwashes, they can furthermore contain ethanol in amounts of 0 to 10% by weight, preferably in amounts of 1 to 5% by weight, based on the total weight of the composition , contain.

Depending on the product type, the humectant or the mixture of humectants is contained in the total composition in an amount of 10-85% by weight, preferably 20-70% by weight and in particular 30-50% by weight.

In a further preferred embodiment, the composition according to the invention additionally contains oil / fat and / or wax components. In particular in combination with surfactants, these give the compositions according to the invention gloss and smoothness. According to the invention, natural, chemically modified and synthetic waxes, fats and oils can be used alone or in any combination.

The oil / fat and wax components are used in an amount of 0.1 to 10% by weight, based on the total compositions, preferably 0.5 to 5% by weight and in particular 0.8 to 3% by weight.

Oils / fats

For the purposes of the invention, mono-, di- and triglycerides with liquid to solid consistency as well as hydrocarbons and silicone oils are understood, which can be of natural or synthetic origin. According to the invention, it is preferred to select the oil components from the group of triglycerides and / or paraffin oils. These can be of plant, animal or synthetic origin.

Mono-, di- and triglycerides are the mono-, di- and triesters of fatty acids with glycerol, ie acylglycerols, where the glycerol can be esterified with the same or with different fatty acids or fatty acid derivatives (eg lecithin). The fatty acids are preferably C ₆ -C ₃ o-fatty acids which may be saturated or unsaturated and branched or unbranched. These include a. the products of the esterification of glycerol with naturally occurring fatty acids such as, for example, caproic acid, oenanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonodecanoic acid, arenachic acid Lignoceric acid, cerotinic acid, melissic acid, 2-ethyl-hexanoic acid, isotridecanoic acid, isostearic acid, palmitoleic acid, oleic acid, elaidic acid, petroselinic acid, elaeostearic acid, erucic acid, linoleic acid, linolenic acid, arachidonic acid, clupanodonic acid and gadoleic acid, blends, docosahex , B. in the pressure splitting of natural fats and oils or the dimerization of unsaturated fatty acids. The use of natural fats and oils such as e.g. B. beef tallow, peanut oil, turnip oil, cottonseed oil, soybean oil, sunflower oil, palm oil, palm kernel oil, linseed oil, almond oil, castor oil, corn oil, olive oil, rapeseed oil, sesame oil, cocoa butter and coconut oil and the like. The hydrogenated or hardened oils, e.g. B. hydrogenated soybean oil, castor oil and peanut oil can be used.

According to the invention be used are also thin and thick silicone oils or natural and synthetic hydrocarbons such as, for example, available thin to thick liquid paraffin oils, isohexadecane, isoeicosane or polydecene, for example, under the designation Emery ^® 3004, 3006, 3010, Ethylflo ^® or Nexbase ^® 2004G.

The use of so-called inverse fats (e.g. esters of vicinal tricarboxylic acids with C ₆ -C ₃₀ fatty alcohols) or glyceryl trialkyl ether is also conceivable here.

waxes

Waxing is understood to mean naturally or artificially obtained substances with the following properties: they have a solid to brittle hard consistency, coarse to fine crystalline, translucent to opaque, but not glassy, and melt without decomposition above 35 ° C. They are low viscosity and not stringy a little above the melting point and show a strongly temperature-dependent consistency and solubility. From a chemical point of view, the most common representatives from the wax group are esters of fatty acids and higher fatty alcohols, which are of animal and vegetable origin. Natural vegetable waxes, such as, for example, B. jojoba oil, candelilla wax, camauba wax, Japanese wax, esparto grass wax, cork wax, guarma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, sunflower wax, fruit waxes such as orange waxes, lemon waxes, grapefruit wax, laurel wax (= bayberry wax) and animal waxes, for example, bax waxes , Shellac wax, walrus, wool wax and pretzel fat. It can also be advantageous to use hydrogenated or hardened waxes.

The natural waxes that can be used according to the invention also include the mineral waxes, such as, for. B. ceresin and ozokerite or the petrochemical waxes such as paraffin waxes (z. B. Vaseline) and micro waxes. As a wax component are also chemically modified waxes, such as. B. Montanester waxes, Sasol waxes and hydrogenated jojoba waxes can be used. The synthetic waxes which can be used according to the invention also include, for example, wax-like polyalkylene waxes and silicone waxes.

Synthetic waxes can also be used according to the invention, in particular the esters of Cβ-Cao fatty acids with C ₆ -C ₃ o -fatty alcohols, which can be of natural or synthetic origin. Both the fatty acid component and the fatty alcohol component can be straight-chain or branched and saturated or mono- or polyunsaturated.

The wax component is preferably selected from the group of vegetable or animal and / or paraffin waxes or any mixture of these waxes.

The use of beeswax and jojoba oil is particularly preferred. In a further preferred embodiment of the oral and dental care products, these can also contain additional active substances such as anti-caries substances, remineralising substances, flavorings or other antimicrobial substances and / or tartar inhibitors, or any combination of these substances.

Anti-caries agents

To combat and prevent caries, fluorine compounds are particularly suitable, preferably from the group of fluorides or monofluorophosphates in an amount of 0.1-0.5% by weight of fluorine. Suitable fluorine compounds are e.g. As sodium fluoride, potassium fluoride, tin fluoride, disodium monofluorophosphate (Na ₂ P0 ₃ F), dipotassium monofluorophosphate or the fluoride of an organic amino compound. Organic amine fluorides for the purposes of the invention are, for example, ammonium fluoride, cetylamine hydrofluoride and bis (hydroxyethyl) aminopropyl-N-hydroxyethyloctadecylamine dihydrofluoride.

In a particularly preferred embodiment of the invention, sodium fluoride, ammonium fluoride or an organic amine fluoride is added to the oral and dental care product.

Antimicrobial agents

As antimicrobial components are, for. B. phenols, resorcinols, bisphenols, salicylanilides and amides and their halogenated derivatives, halogenated carabanilides and p-hydroxybenzoic acid esters.

Among the antimicrobial components, those which inhibit the growth of PIaque bacteria are particularly suitable. For example, halogenated diphenyl ethers such as 2,4-dichloro-2'-hydroxydiphenyl ether, 4,4'-dichloro-2'-hydroxydiphenyl ether, 2,4,4'-tribromo-2'-hydroxydiphenyl ether, 2,4,4 '-Trichlor-2'-hydroxy-diphenyl ether (triclosan) suitable as antimicrobial agents. In addition to bromine Chlorophen, phenylsalicylic acid esters and 5-amino-1, 3-bis (2-ethylhexyl) hexa- hydro-5-methylpyrimidine (hexetidine) also have zinc and copper ions antimicrobial, whereby synergistic effects occur especially in combination with hexetidine and triclosan , Quaternary ammonium compounds such as cetylpyridinium chloride, benzalkonium chloride, domiphen bromide and dequalinium chloride can also be used. Octapinol, octenidines and sanguinarine have also proven to be antimicrobial. The antimicrobial active ingredients are preferably used in amounts of 0.01-1% by weight in the agents according to the invention. Irgacare ^® MP is particularly preferred in an amount from 0.01 to 0.3 wt .-% is used.

Tartar inhibitors

Tartar is mineral deposits that are very similar to natural tooth enamel. In order to inhibit tartar formation, substances are added to the tooth cleaning agents according to the invention which specifically intervene in the crystal nucleation and prevent existing germs from continuing to grow. These are, for example, condensed phosphates, which are preferably selected from the group of tripolyphosphates, pyrophophates, trimetaphosphates or mixtures thereof. They are used in the form of their alkali or ammonium salts, preferably in the form of their sodium or potassium salts. Aqueous solutions of these phosphates typically have an alkaline reaction, so that the pH of the dentifrices according to the invention is adjusted to values of 7.5-9, if necessary by adding acid. As acids z. B. citric acid, phosphoric acid or acidic salts, e.g. B. NaH ₂ P0 ₄ can be used. The desired pH of the dentifrice can also be achieved by adding acidic salts of the condensed phosphates, e.g. B. K ₂ H ₂ P ₂ O ₇ can be set.

Mixtures of different condensed phosphates and / or hydrated salts of the condensed phosphates can also be used according to the invention. Tartar inhibitors are usually used in amounts of 0.1-5% by weight, preferably 0.1- 3% by weight and in particular 0.1-2% by weight are used in the agents according to the invention.

Other suitable tartar inhibitors are organophosphonates such as 1-hydroxyethane-1, 1-diphosphonate (Na salt) and zinc citrate.

Remineralsierunqswirkstoffe

The agents according to the invention preferably also contain substances which promote re-mineralization of the tooth enamel and are able to close dental lesions. These are usually contained in a total amount of 0.1-10% by weight, preferably 0.1-5% by weight and in particular 0.1-3% by weight. These include e.g. B. fluorides, phosphate salts of calcium such. As calcium glycerol phosphates, calcium hydrogen phosphate, hydroxyapatite, fluoroapatite, F-doped hydroxyapatite, dicaicium phosphate dihydrate and calcium fluoride. But also magnesium salts such as. B. magnesium sulfate, magnesium fluoride or magnesium monofluorophosphate have a remineralizing effect.

flavorings

The agents according to the invention preferably contain flavorings, to which e.g. B. sweeteners and / or aromatic oils. Examples of suitable sweeteners are saccharinates (in particular sodium saccharinate), cyclamates (in particular sodium cyclamate) and sucrose, lactose, maltose or fructose. Aromatic oils that can be used are all natural and synthetic aromas that are common for oral and dental care products. Natural flavors can be used both in the form of the essential oils (mixture) isolated from the drugs and in the form of the individual components isolated from them. At least one aromatic oil from the group of peppermint oil, spearmint oil, anise oil, star anise oil, caraway oil, eucalyptus oil, fennel oil, cinnamon oil, clove oil, geranium oil, sage oil, allspice oil, thyme oil, marjoram oil, basil oil, citrus oil, Gaultheria oil or one or more synthetically isolated or should be preferred produced components of these oils be included. The most important components of the oils mentioned are e.g. B. menthol, carvone, anethole, cineol, eugenol, cinnamaldehyde, caryophyllene, geraniol, citronellol, linalool, salvos, thymol, terpinene, terpinol, methylchavicol and methyl salicylate. Other suitable flavors are e.g. B. menthyl acetate, vanillin, jonone, linalyl acetate, rhodinol and piperiton.

In the event that the oral and dental care products according to the invention are packaged as toothpastes, tooth gels or liquid transparent dentifrices, they contain at least one cleaning body as a further component.

The cleaning bodies are used for the mechanical removal of the uncalcified dental plaque and should ideally lead to the gloss of the tooth surface (polishing effect) with at the same time minimal abrasion (abrasion effect) and damage to the tooth enamel and dentin. The abrasion behavior of the plaster is essentially determined by their hardness, particle size distribution and surface structure. When selecting suitable cleaning bodies, those which have a minimal abrasion effect with high cleaning performance are therefore particularly preferred.

Nowadays, mainly cleaning materials are used which have small grain sizes and are largely free of sharp corners and edges.

Water-soluble inorganic substances are usually used as cleaning bodies or polishing agents. The use of very finely divided polishing agents with an average grain size of 1 - 200 μm, preferably 1 - 50 μm and in particular 1 - 10 μm is particularly advantageous.

In principle, the polishing agents according to the invention can be selected from silicas, aluminum hydroxide, aluminum oxide, silicates, organic polymers or mixtures thereof. Furthermore, so-called metaphosphates and calcium-containing polishing components can also be present in the agents according to the invention in amounts of up to 5% by weight. It can be preferred according to the invention to use silicas as polishing agents in toothpastes or liquid tooth cleaning agents. A distinction is basically made between silica polishing agents between gel silicas, hydrogel silicas and precipitated silicas. Precipitated and gel silicic acids are particularly preferred according to the invention because they can be varied widely in their production and are particularly well tolerated with fluoride active ingredients. They are also particularly suitable for the production of gel or liquid toothpastes.

Gel silicic acids are generated by the reaction of sodium silicate solutions with strong, aqueous mineral acids with the formation of a hydrosol, aging to the hydrogel, washing and subsequent drying. If drying is carried out under gentle conditions to water contents of 15 to 35% by weight, so-called hydrogel silicas are obtained, as are also described, for example, in US Pat. No. 4,153,680. By drying these hydrogel silicas to water contents below 15% by weight there is an irreversible shrinkage of the previously loose structure to the dense structure of the so-called xerogel. Such xerogel silicas are known, for example, from US Pat. No. 3,538,230.

A second, preferably suitable group of silicic acid polishing agents are the precipitated silicas. These are obtained by precipitating silica from dilute alkali silicate solutions by adding strong acids under conditions in which aggregation to the sol and gel cannot occur. Suitable processes for the preparation of precipitated silicas are described, for example, in DE-OS 25 22 586 and in DE-OS 31 14 493. A precipitated silica prepared according to DE-OS 31 14 493 with a BET surface area of 15-110 m ² / g and a particle size of 0.5 to 20 μm is particularly suitable according to the invention, with at least 80% by weight of the primary particles below 5 µm should be, and a viscosity in 30% glycerol water (1: 1) dispersion of 30 - 60 Pa s (20 ° C) in an amount of 10 - 20 wt .-% of the toothpaste. Precipitated silicas of this type which are preferably suitable also have rounded ones Corners and edges and are available under the trade name Sident ^® 12 DS from Degussa.

Other precipitated silicas of this type are Sident ^® 8 from Degussa and Sorbosil ^® AC 39 from Crosfield Chemicals. These silicas are characterized by a lower thickening effect and a somewhat higher average particle size of 8 - 14 μm with a specific surface area of 40 - 75 m ² / g (according to BET) and are particularly suitable for liquid toothpastes. These should have a viscosity (25 ° C, shear rate D = 10 s ^"1 ) of 10 - 100 Pa s.

Furthermore, the silicas of the type Zeodent ^® Huber-Corp., Tixosil® Rhodia and other Sorbosil® types can be used in the agents. Zeodent ^® 113, Tixosil ^® 123 and 73 and Sorbosil ^® AC33 are particularly preferred.

Toothpastes that have a significantly higher viscosity of more than 100 Pa s (25 ° C, D = 10 s ^"1 ), on the other hand, require a sufficiently high proportion of silicas with a particle size of less than 5 μm, preferably at least 3% by weight. % of a silica with a particle size of 1 to 3 μm. Toothpastes are therefore preferably added in addition to the precipitated silicas mentioned, more finely divided, so-called thickening silicas with a BET surface area of 150-250 m ² / g. As examples of commercial products that Sipemat ^® 22 LS or Sipernat ^® 320 DS from Degussa must be mentioned in particular.

A weakly calcined alumina with a content of at least 10% by weight of so-called gamma-alumina modifications other than alpha-alumina is preferably suitable as the alumina polishing agent.

Suitable weakly calcined clays are produced by calcination from aluminum hydroxide. Aluminum hydroxide passes through calcination into the α-Al ₂ 0 _{3 which is} thermodynamically stable at temperatures above 1200 ° C. The thermodynamically unstable, occurring at temperatures between 400 and 1000 ° C len A θ ₃ modifications are called gamma forms (cf. Ulimann, Encyclopedia of Industrial Chemistry, 4th edition (1974), volume 7, page 298). By choosing the temperature and the duration of the calcination, the degree of calcination, ie the conversion into the thermodynamically stable α-A ^ Oa, can be set to any desired level. Weak calcination gives an alumina with a γ-A Os content which is lower, the higher the calcination temperature and the longer the caicination time. Weakly calcined clays differ from pure 01-Al ₂ O _{3 in} that the agglomerates have a lower hardness, a larger specific surface area and larger pore volumes.

The dentin abrasion (RDA) of the weakly calcined alumina to be used according to the invention with a proportion of 10-50% by weight γ-Al ₂ O ₃ is only 30-60% of the dentin abrasion of a strongly calcined, pure CC-Al 2 O ₃ (measured in a standard toothpaste with 20% by weight alumina as the only polishing agent).

In contrast to α-Al ₂ θ ₃ can be the γ-A θ ₃ with an aqueous-ammoniacal solution of Alizarin S (1, 2-dihydroxy-9,10-anthraquinone-4-sulfonic acid) stain red. The degree of dyeability can be chosen as a measure of the degree of calcination or of the proportion of δ-A ^ Os in a calcined clay:

Approximately 1 g of Al ₂ O ₃ , 10 ml of a solution of 2 g / l Alzarin S in water and 3 drops of an aqueous 10% by weight solution of NH3 are placed in a test tube and boiled briefly. The Al ₂ 0 ₃ is then filtered off, washed, dried and assessed under a microscope or evaluated colorimetrically.

Suitable, weakly calcined clays with a content of 10-50% by weight of γ-Al ₂ O ₃ can be colored slightly to deep pink using this process.

Aluminum oxide polishing agents of various degrees of calcination, fineness and bulk density are commercially available, for example the "polishing clay" from Giulini-Chemie or ALCOA. A preferred suitable quality “polishing clay P10 finest” has an agglomerate size of less than 20 μm, an average primary crystal size of 0.5-1.5 μm and a bulk density of 500-600 g / l.

The use of silicates as polishing agent components can also be preferred according to the invention. They are used as cleaning bodies, particularly in modern practice. Examples of silicates which can be used according to the invention are aluminum silicates and zirconium silicates. In particular, the sodium aluminum silicate of the empirical formula Nai2 (Alθ2) i2 (Siθ2) i2 x 7H2O can be suitable as a polishing agent, such as the synthetic zeolite A.

Examples of water-insoluble metaphosphates according to the invention are, in particular, sodium metaphosphate, calcium phosphate such as, for example, tricalcium phosphate, calcium hydrogen phosphate, calcium hydrogen phosphate dihydrate and calcium pyrophosphate.

In addition, according to the invention, magnesium carbonate, magnesium hydrogen phosphate, trimagnesium phosphate or sodium hydrogen carbonate can be used as the polishing agent, in particular as a mixture with other polishing agents.

The oral and dental care products according to the invention can preferably contain a number of further components. These include a .:

Vitamins, e.g. B. retinol, biotin, tocopherol, ascorbic acid and their derivatives (e.g. esters, salts);

• pigments, e.g. B. titanium dioxide or zinc oxide; o Colored pigment particles, for example colored silica particles such as those e.g. B. are commercially available under the sales name Sorbosil ^® BFG 51, BFG 52 and BFG 53 or Sorbosil ^® 2352. Mixtures of differently colored pigment particles can also be used. Such, e.g. B. strong orange, red or blue colored silica particles can in Quantities of 0.1-1.0% by weight can be contained in the agents according to the invention; o bleach; o dyes; o pH adjusting agents and buffer substances, e.g. B. sodium citrate, sodium bicarbonate or potassium and sodium phosphates, o sodium benzoate;

• wound healing and anti-inflammatory substances such. B. allantoin, urea, panthenol, azulene or chamomile extract, acetylsalicylic acid derivatives, rhodanide; hydrogen peroxide;

• Zinc and manganese sulfate.

With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schrader, basics and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989 or W. Umbach, Cosmetics: Development, manufacture and application of cosmetic products, 2nd edition, Thieme Verlag, Stuttgart 1995.

Oral and dental care in the sense of the invention is to be understood as a daily cosmetic, non-therapeutic treatment. The teeth are cleaned and stains and food residues are removed, which makes their cosmetic appearance more beautiful and attractive.

A second subject of the invention is therefore a non-therapeutic method for reducing and preventing discoloration on human teeth, in which a mouth and dentifrice containing a combination of active ingredients

(A) at least one cationic, antibacterial component,

(B) at least one anti-tartar active ingredient selected from the group of azacycloalkane diphosphonic acids or their physiologically tolerable salts, and (C) at least one binder, selected from xanthan gum, carboxymethyl cellulose or a mixture of these two components, is used for daily oral and dental care.

A third subject of the invention is therefore a non-therapeutic method for the inhibition of tartar and plaque, in which a mouth and tooth care product containing a combination of active ingredients

(A) at least one cationic, antibacterial component,

(B) at least one anti-tartar active ingredient selected from the group of azacycloalkane diphosphonic acids or their physiologically tolerable salts, and

(C) at least one binder, selected from xanthan gum, carboxymethyl cellulose or a mixture of these two components, is used for daily oral and dental care.

A fourth object of the invention is the non-therapeutic use of a combination of active ingredients

(A) at least one cationic, antibacterial component,

(C) at least one binder selected from xanthan gum, carboxymethyl cellulose or a mixture of these two components for reducing and preventing discoloration on human teeth.

A fifth object of the invention is the non-therapeutic use of a combination of active ingredients

(A) at least one cationic, antibacterial component,

(C) at least one binder selected from xanthan gum, carboxymethyl cellulose or a mixture of these two components, for the inhibition of tartar and plaque.

The following examples are intended to describe the subject of the invention in more detail:

Examples:

1.) Wniieninc effect or reduction of discoloration of teeth

The proof of effectiveness of the discoloration reduction or the whitening effect was carried out in vitro on bovine teeth using a special staining and measuring method.

reagents:

Bag tea, East Frisian blend

Materials and equipment:

Gray wax (Kerr)

sample carrier

Dyeing wheel made of plastic (22 cm diameter)

Plastic tub for dye wheel (18 x 5 x 3.5)

Equipment with motor for moving a maximum of 5 wheels

Colorimetric measuring device, Micro-Color, Dr. Long

Test Description:

The cattle front teeth are cut in such a way that the flatest possible slabs of the labial sides with 7x7 mm surface are obtained. These slabs are attached to the center of the sample holder with the wax so that only the enamel surface is exposed. The enamel surface is evenly treated with 600 grit sandpaper to remove unevenness and contamination.

The colorimetric measuring device from Dr. Long used.

The sample is illuminated with light of the standard illuminant D65 (corresponds to daylight). The entire slab surface is measured in each case. Blinding prevents stray light from entering during the measurement. To assess the discoloration of the sample or the discoloration-inhibiting effect, the brightness value L * defined in accordance with DIN 6174 is used as the test barometer.

4 slabs of each group are placed in the plastic beaker with the melting side up and then either with 40 g mouthwash or the centrifugate one

Pour 10 g of toothpaste into 40 g of distilled water.

Treatment with the active ingredient solution is carried out twice a day in the morning and in the evening.

After 5 min. Exposure time at RT, the slabs are distilled under flowing

Rinse water well, then attach it to the dye wheel and run it at 2 rpm

Dye bath moves, which is freshly applied twice a day by brewing

3 g bag tea in 300 ml water. Then let it steep for 10 minutes.

Before each bath change, the slabs are rinsed with distilled water and, after the procedure has been completed, additionally wiped dry with cellulose in order to remove loose deposits.

This treatment regimen was carried out for 10 days.

After the last tea coloring on the 10th day, the brightness value L * of the samples was measured and the difference to the initial values was determined and mean values were formed.

2.) Tartar and Pia iue-inhibiting effect

The effectiveness of the tartar and PIaque-inhibiting effect was determined by determining the crystal growth of hydroxyapatite.

By adding hydroxyapatite to a supersaturated Ca phosphate solution, the crystallization is triggered according to the following equation:

5Ca ²⁺ + 3HP0 ₄ ^{2 "} + H ₂ 0 -» Ca ²⁺ ₅ (PO ₄ ³ -) ₃ OH + 4H ⁺

The rate of crystal growth, which can be influenced by active substances, is determined by titration with an alkali.

Equipment:

thermostat

Magnetic stirrers and chopsticks

Auto burette 25 ml (ABU 80 radiometer) pH meter (82 radiometer) pH electrode (N61 Schott)

Titrator (TTT80 radiometer)

Servograph (Rec 80 Radiometer)

Centrifuge, centrifuge glasses

Beakers: 800 ml double-walled

200 ml pipette: 10 ml

Measuring cylinder: 500 ml burette: 50 ml

General description:

400 ml of 0.0008 molar KH ₂ PO solution and 45 ml of 0.012 molar CaCl2 solution are placed in a reaction vessel thermostatted to 37 ° C. Then titrate to pH = 7.4 with 0.05 molar KOH. If the pH is 15 min. is stable there 100 mg of apatite are added and the mixture is titrated for 2 hours with stirring at pH 7.4. The amount of KOH used is recorded over time using a servograph.

Preparation of the preparations:

Toothpaste slurry consisting of 20 g toothpaste and 80 g deionized water is 15 min. stirred well and then centrifuged. 10 ml of this clear solution are added to the Ca phosphate solution and adjusted to pH = 7.4 before adding 100 mg of apatite.

When testing mouthwash, 10 g of mouthwash are added to the Ca phosphate solution.

Amplifier / cΛsatJSwe / τi / np ;:

The curve without toothpaste is evaluated as a zero curve with 0% inhibition. The consumption of KOH of the zero curve is read after 2 hours and compared with the consumption of the toothpaste solution.

% I =% inhibition

ON = consumption of the zero curve

AZ = consumption of the toothpaste solution

The following test mixtures were prepared (unless stated otherwise, all quantities are based on% by weight):

Table 1

Result:

Only sample D, i.e. the formula with the combination of three AHP, xanthan gum

(Keltrol F) and chlorhexidine digluconate shows a whitening effect.

Table 2

Result:

The formula stability is only from a concentration of 0.1% Keltrol (xanthan

Gum) guaranteed, with lower Keltrol content precipitations result.

Table 3

Result:

In this composition, too, only the addition of the polymer component carboxymethyl cellulose results in a discoloration-inhibiting effect.

The following raw materials and commercial products were used in the examples:

1 distributed by Degussa as a 20% solution

2 INCI name: Lauryl Glucoside; AS: 50 - 53%, distributed by the Cognis company

3 INCI name: Xanthan Gum, sold by CP Kelco

4 INCI name: Disodium Azacycloheptane Diphosphonate, sold by Albright & Wilson

5 INCI name: PEG-60 Hydrogenated Castor Oil, sold by Goldschmidt

Claims

Eβntans

1. Oral and dental care products containing an active ingredient combination

(A) at least one cationic, antibacterial component,

2. Oral and dental care product according to claim 1, characterized in that component (B) is azacycloheptane-2,2-diphosphonic acid or a physiologically acceptable salt of this compound.

3. Oral and dental care product according to one of claims 1 or 2, characterized in that the antibacterial component (A) is selected from the cationically derivatized bisbiguanides.

4. Mouth, and dentifrice according to one of claims 1 to 3, characterized in that the antibacterial component (A) is a physiologically tolerable salt of chlorhexidine or alexidine.

5. Oral and dental care product according to claim 4, characterized in that the antibacterial component (A) is chlorhexidine digluconate.

6. Oral and dental care agent according to one of claims 1 to 5, characterized in that the antibacterial component (A) with 0.001 to 3 wt .-%, based on the total weight of the agent, is included.

7. Oral and dental care agent according to one of claims 1 to 6, characterized in that the anti-tartar active ingredient (B) with 0.001 to 5 wt .-%, based on the total weight of the agent, is used.

8. Oral and dental care agent according to one of claims 1 to 7, characterized in that the binder (C) or the mixture of binders is used with at least 0.01% by weight based on the total weight of the agent.

9. Oral and dental care agent according to one of claims 1 to 8, characterized in that at least one surfactant from the group of nonionic surfactants is further contained in the agents.

10. Oral and dental care product according to claim 9, characterized in that the nonionic surfactant is selected from the group of alkyl polyglycosides.

11. Oral and dental care product according to one of claims 1 to 10, characterized in that further contains at least one fluoride source.

12. Oral and dental care product according to claim 11, characterized in that the fluoride source is sodium fluoride, ammonium fluoride or an organic amine fluoride.

13. Non-therapeutic method for reducing and preventing discoloration on human teeth, characterized in that an oral and dental care product containing an active ingredient combination

(A) at least one cationic, antibacterial component,

(C) at least one binder selected from xanthan gum, carboxymethyl cellulose or a mixture of these two components is used for daily oral and dental care.

14. Non-therapeutic method for the inhibition of tartar and plaque, characterized in that an oral and dental care product containing an active ingredient combination

(A) at least one cationic, antibacterial component,

15. Non-therapeutic use of a combination of active ingredients

(A) at least one cationic, antibacterial component,

16. Non-therapeutic use of a combination of active ingredients

(A) at least one cationic, antibacterial component,

(C) at least one binder, selected from xanthan gum, carboxymethyl cellulose or a mixture of these two components, in oral and dental care products for the inhibition of tartar and plaque.