WO1991009589A2 - Mouth and tooth care preparations - Google Patents

Abstract

The invention concerns mouth and tooth care preparations which provide improved protection against the formation of caries and which contain as their active ingredient a phosphoric acid ester of a cycloalkane carboxylic acid or of a salt of a cycloalkane carboxylic acid of the general formula (I) in which z is a whole number from 4 to 7, the individual R groups are, independently of each other, hydrogen or -(OCnH2n)m-OR2, n being a whole number from 2 to 5, m a number from 0 to 8 and R¿n? hydrogen or a -PO3M2 group, and M being hydrogen, an alkali metal or alkaline-earth metal ion, an ammonium ion or a mono-, di- or trihydroxyalkylammonium group with 2-4 carbon atoms in the hydroxyalkyl group, at least three of the R groups in the molecule being -(OCnH2n)m-OR?2¿ and at least one R2 group in the molecule being -PO¿3?M2, and/or a phosphoric acid ester of cycloalkene carboxylic acid or of a salt of a cycloalkene carboxylic acid derived from the group of compounds represented by formula (I) by the theoretical removal of a hydrogen atom from each of two neighbouring carbon atoms and to form a C=C double bond between these two carbon atoms. Preferred are phosphorylated, optionally ethoxylated, quinic acid and shikimic acid as their alkali metal salts.

Description

 "Oral and dental care products"

The invention relates to oral and dental care products with improved activity against tooth decay by virtue of a content of an active ingredient which reduces the solubility of hydroxylapatite and inhibits crystal growth and the phosphate ion exchange of hydroxylapatite.

Oral and dental care products are products that serve to clean and care for the teeth, the oral cavity and the throat. In addition to eliminating bad breath and dental plaque, your job is to prevent dental diseases such as tooth decay and periodontal disease and to prevent the formation of tartar.

It is known that water-soluble organic phosphates have a caries-prophylactic effect. For example, mono- and disodium glycerophosphate, fructose-6-phosphate, sorbitol-6-phosphate, glucose-1-phosphate and glucose-6-phosphate have been proposed as additives to oral and dental care products. Salts of phosphoric acid esters of lactose and sucrose have also been described as cariostatic components. Although these products have a certain action which reduces the solubility of the hydroxyapatite and inhibits crystal growth, the effects are not sufficient for effective protection against demineralization of the tooth enamel. Furthermore, DE-OS 34 39 094 phosphoric acid ester salts of ethoxylated polyols have been proposed as caries prophylactic agents. These show a significantly higher effect; however, there is still a need for substances with improved activity, particularly with a view to reducing the hydroxylapatite solubility.

It has now been found that phosphoric acid esters of certain cycloalkane and cycloalkenecarboxylic acids and their physiologically compatible water-soluble salts have an action which is considerably increased in comparison with known active ingredients with regard to reducing the solubility and inhibiting the crystal growth of hydroxyapatite and the phosphate ion exchange between hydroxyapatite and solution. These products are therefore suitable as caries-inhibiting active ingredients in oral and dental care products.

The invention therefore relates to oral and dental care products with improved activity against tooth decay, which as an active ingredient comprise a phosphoric acid ester of a cycloalkanecarboxylic acid or a salt of a cycloalkanecarboxylic acid of the general formula (I)

in which z is an integer from 4 to 7, the individual groups R independently of one another represent hydrogen or - (OC _n H _2n ) _m OR ² , where n is an integer from 2 to 5, m is a number from 0 to 8 and R ^{2 is} hydrogen or a group -PO ₃ M ₂ , and M stands for What serstoff, an alkali or alkaline earth metal ion, an ammonium group or a mono-, di- or trihydroxyalkylammonium group with 2-4 carbon atoms in the hydroxyalkyl group, at least three of the groups R being - (OC _n H _2n ) _m -OR ² and at least a group R ² = -PO ₃ M ₂ in the molecule, and / or a phosphoric acid ester of a cycloalkenecarboxylic acid or a salt of a cycloalkenecarboxylic acid, which formally arises from the compounds of the formula (I) by the elimination of one hydrogen atom on two adjacent carbon atoms and formation of one C = C double bond between these two carbon atoms.

New and therefore another object of the invention are the phosphoric acid esters of cycloalkanoic and cycloalkenecarboxylic acids according to formula (I) and their salts.

Phosphoric acid esters according to formula (I) are further understood to mean both the phosphoric acid esters of cycloalkane carboxylic acids according to formula (I) and the phosphoric acid esters of the cycloalkenecarboxylic acids mentioned and the salts of cycloalkane and cycloalkenecarboxylic acids mentioned.

These compounds can be prepared from known polyhydroxycycloalkanoic or alkenecarboxylic acids.

For example, alkylene oxides with 2 to 5 carbon atoms, i.e. ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide and pentene oxide, are added to the polyhydroxycycloalkane or -alkenecarboxylic acids using processes known from the literature, i.e. using basic catalysts such as NaOH, KOH, Na methylate , Ca acetate or acidic catalysts such as boron trifluoride, antimony pentachloride, triethyloxonium fluoroborate or SnCl ₄ . As is known to the person skilled in the art, no uniform products are obtained when n mol of alkylene oxide is added to a substrate which contains one or more OH groups. Rather, in the case of substrates with an OH group, mixtures of the starting compound and addition products with 1, 2, ... n, (n + 1), (n + 2) .... molecules of alkylene oxide are formed per molecule of substrate. Analogously, in the reaction of alkylene oxides with substrates which have several OH groups, mixtures are obtained which, in addition to the starting compound, contain products in which one, two, ... or all OH groups have reacted with one or more molecules of alkylene oxide .

The phosphorylation of the polyhydroxycycloalkane and alkenecarboxylic acids and their alkylene oxide addition products can be carried out, for example, by reaction with phosphorus pentoxide or polyphosphoric acid with a high content of phosphorus pentoxide, e.g. by the method described in U.S. Patent 4,311,662. By varying the amount of phosphorus pentoxide used, both predominantly monophosphoric esters and predominantly those compounds can be prepared in which the majority of the OH groups of the polyhydroxycycloalkane or alkenecarboxylic acids are phosphorylated. During the work-up, a brief hydrolytic treatment in the acidic pH range is advantageous, since P-O-P bonds that are still present are split. This has an advantageous effect on the storage stability of the formulated products. Detailed synthesis instructions can be found in the examples.

It has proven to be advantageous to use a molar ratio of 0.5 to 1.0 mol of P ₂ O ₅ per hydroxyl equivalent of the polyhydroxycycloalkane or -alkenecarboxylic acid or of the alkoxylate. Products are obtained whose hydroxyl groups are 40-100% in the Phos phosphoric ester group are transferred. Although products in which at least one of the free hydroxyl groups is esterified with phosphoric acid still have a good activity, a high degree of phosphating, that is to say preferably the esterification of all free hydroxyl groups of the polyhydroxycycloalkane or alkenecarboxylic acid or of the alkoxylate, has proven to be particularly advantageous. In addition to the organic phosphoric acid esters, the products contain inorganic phosphates as a by-product, predominantly orthophosphate, which is not detrimental to the cariostatic activity of the products and can therefore remain in the product. The degree of phosphorylation PG, i.e. the number of phosphorylated OH groups divided by the number of OH groups available for phosphorylation, can be determined from the analytical values for the content of inorganic phosphate and the total phosphate content as well as the amounts of substrate and phosphorylation agent used ( For example, phosphorus pentoxide) can be calculated

where the use ratio EV is defined as the ratio of the amount of substance P ₂ O _{5 used} to the number of gram equivalents of the substrate, based on the hydroxyl groups (hydroxyl equivalents).

After esterification, the phosphoric acid esters of polyhydroxycycloalkane or alkenecarboxylic acids can be neutralized with inorganic or organic bases and in this way converted into physiologically compatible, water-soluble salts.

Preferred phosphoric acid esters according to formula (I) are compounds in which z = 4 or 5, which are derived from cyclopentane, cyclopentene, cyclohexane or from cyclohexene. The cyclohexene and cyclohexane derivatives are particularly preferred. Very particularly preferred compounds are the derivatives of 1,3,4,5-tetrahydroxy-cyclohexane carboxylic acid (1) (quinic acid) and 3,4,5-trihydroxy cyclohexene (l) carboxylic acid (1) (shikimic acid). represents.

Preference is furthermore given to compounds of the formula (I) which contain at least one group - (OC _n H _2n ) _m -. Preferred alkyleneoxy groups (OC _n H _2n ) are the ethyleneoxy and the propyleneoxy group.

Compounds which are prepared by adding 1-4 mol of ethylene oxide or propylene oxide to the particular polyhydroxycycloalkane or -alkenecarboxylic acid are particularly preferred.

Preferred phosphoric acid esters according to formula (I) are the alkali metal salts, especially the sodium and potassium salts.

The oral and dental care products according to the invention containing phosphoric acid esters of the formula (I) can be prepared in the various designs customary for such products, for example as mouthwashes, toothpastes or tooth powder. The content of phosphoric acid esters according to formula (I) should be in the range from 0.05 to 5.0% by weight of the preparation. However, amounts of 0.1-2% by weight are usually sufficient in toothpastes, tooth powders and tooth gels to achieve a significant caries-inhibiting effect. In mouthwashes to be used undiluted, sufficient effects can be achieved with 0.05-1.0% by weight, in mouthwashes that are diluted before use with higher concentrations in accordance with the intended dilution ratio. Oral and dental care products can also be prepared in the form of chewing gum, mouth lozenges and dental treatment ointments. Such oral care products, which may be used several times a day and inevitably swallowed, may also contain the phosphoric acid esters of the formula (I). In these cases, however, the dosage should not exceed 1% by weight of the preparation.

In addition to the phosphoric acid esters, the oral and dental care compositions according to the invention can contain the carriers and additives customary for the particular preparation. In mouthwashes, a combination with the aqueous-alcoholic solutions of essential oils, emulsifiers, astringent and toning drug extracts, tartar-inhibiting and antibacterial additives and taste corrections is easily possible. Also surface-active substances, e.g. Anionic, nonionic, zwitterionic and ampholytic surfactants can be added in the usual amounts.

Toothpastes or toothpastes are generally understood to mean gel-like or pasty preparations made from water, thickeners, humectants, abrasive or cleaning bodies, surfactants, sweeteners, flavorings, deodorising active substances and active substances against mouth and tooth diseases. All of the usual cleaning materials, such as Chalk, dicalcium phosphate, insoluble sodium metaphosphate, aluminum silicates, calcium pyrophosphate, finely divided synthetic resins, silicas, aluminum oxide and aluminum oxide trihydrate can be used.

Particularly suitable cleaning bodies for the toothpastes according to the invention are, in particular, finely divided xerogel silicas, hydro gel silicas, precipitated silicas, aluminum oxide trihydrate and finely divided aluminum oxide or mixtures of these cleaning agents in amounts of 15-40% by weight of the toothpaste. Low molecular weight polyethylene glycols, glycerol, sorbitol or mixtures of these products in amounts of up to approx. 50% by weight are mainly suitable as humectants. Among the known thickening agents, the thickeners, finely divided silica gels and hydrocolloids, such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl guar, hydroxyethyl starch, polyvinyl pyrrolidone, high molecular weight polyethylene glycol, plant gums such as tragacanth, agar-agar, carrageenan, gum arabic, xantham gum, and carboxyvinyl polymers (for example Carbopol ^{(R )} Types).

Surface-active substances, preferably anionic high-foaming surfactants, such as, for example, linear sodium alkyl sulfates with 12-18 C atoms in the alkyl group, sodium salts of alkyl polyglycol ether sulfates with 12-16 C atoms in the linear alkyl group and 2-6 glycol ether groups in the molecule, of alkyl, (C _12-16 ) benzene sulfonate, linear alkane (C _12-18 ) sulfonates, sulfosuccinic acid monoalkyl (C _12-18 ) esters, sulfated fatty acid monoglycerides, sulfated fatty acid alkanolamides, sulfoacetic acid alkyl (C _12-18 ) esters, acyl sarcosides , Acyl taurides and acyl isethionates each containing 8-18 C atoms in the acyl group. Nonionic surfactants are also suitable, for example oxyethylates of fatty acid mono- and diglycerides, fatty acid-sorbitan esters and ethylene oxide-propylene oxide block polymers. In addition, alkyl glycosides of the general formula RO- (G) _x can also be used as nonionic surfactants, in which R is a primary straight-chain or aliphatic radical which has 10 to 22, preferably 12 to 18, C atoms and is methyl branched in the G position Is symbol that stands for a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x is between 1 and 10. Other common toothpaste additives are:

Preservatives and antimicrobial substances such as p-Hydroxybenzoic acid methyl, ethyl or propyl ester, sodium sorbate, sodium benzoate, bromochlorophene, phenylsalicylic acid ester, thymol etc.

Anti-calculus agents, e.g. Organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid, 1-phosphonopropane-1,2,3-tricarboxylic acid and others e.g. from US-PS 3,488,419, DE-OS 2224430 and DE-OS 2343 196 are known;

other caries-inhibiting substances such as Sodium fluoride, sodium monofluorophosphate, tin fluoride,

Sweeteners such as Saccharin sodium, sodium cyclamate, aspartame, glycyrrhizin, glycyrrhetinic acid, sucrose, lactose, maltose, fructose,

Flavors such as Peppermint oil, spearmint oil, eucalyptus oil, anise oil, fennel oil, caraway oil, menthyl acetate, cinnamaldehyde, anethole, vanillin, thymol and mixtures of these and other natural and synthetic flavors,

Pigments such as Titanium dioxide

Dyes

Buffer substances such as primary, secondary or tertiary alkali phosphates or citric acid / sodium citrate, wound healing and anti-inflammatory substances such as allantoin, urea, azulene, chamomile active ingredients and acetylsalicylic acid derivatives.

Due to the addition of phosphoric acid esters according to formula (I), the oral and dental care products according to the invention not only have a caries-inhibiting activity, but also successfully counteract the formation of tartar.

B e i s p i e l e

1. Manufacturing examples

1.1 General manufacturing regulations

a) Alkoxylation of the polyhydroxycycloalkane and alkenecarboxylic acids

The addition of the alkylene oxides to the polyhydroxycycloalkane and -alkenecarboxylic acids was carried out by a process known from the literature by reaction in a pressure vessel in the presence of catalytically active amounts of sodium methylate at a temperature of 100-150 ° C. The products were characterized by determining the hydroxyl number (OHZ).

b) phosphorylation

To 169 g (1 mol P ₂ O ₅ ) polyphosphoric acid (P ₂ O ₅ content 84% by weight) was added 1 hydroxyl equivalent of polyhydroxycycloalkane carboxylic acid, polyhydroxycycloalkenecarboxylic acid or the corresponding alkoxy- prepared according to a) with stirring at 70 ° C. lates slowly added. After the addition had ended, the temperature was slowly raised to 95-110 ° C. and the reaction mixture was left at this temperature for about 3-5 hours with stirring. The reaction mixture was then mixed with 250 ml of water and heated to boiling for 30 minutes. The brown-colored solution was then treated with 10 g of activated carbon, filtered, cooled and adjusted to pH = 7 by adding 50% sodium hydroxide solution.

The active substance content of the solutions was determined after the

Water content determined too

% Active ingredient = 100% -% phosphate _inorganic

1.2 Preparation of the sodium salt of phosphorylated quinic acid (reaction with EV = 1) (active ingredient 1)

36.3 g (0.189 mol) of quinic acid were added in small portions to 126.8 g of polyphosphoric acid (84% P ₂ O ₅ ) at a temperature of about 70 ° C. After a further reaction time of 4 hours at 100-110 ° C., the resin obtained was mixed with 250 ml of water and the solution was heated to boiling under reflux for a further 30 minutes. Then the pale yellow solution was adjusted from 22.1.1 g to a pH of 6.87 with 221.1 g of 50% sodium hydroxide solution, evaporated in a water jet vacuum and dried. A residue of 269 g remained with the following data:

Total phosphate content: 19.0%

Inorganic phosphate content: 14.4%

Degree of phosphorylation: 0.48

Water content: 16.5%

Active substance content: 27.8% 1.3 Preparation of the sodium salt of phosphorylated, ethoxylated (2 EO) quinic acid (reaction with EV = 1) (active ingredient 2)

38.4 g (0.2 mol) of quinic acid were reacted in an autoclave at approx. 5 bar and a temperature of 100 ° C. with 17.6 g (0.4 mol) of ethylene oxide in the presence of 1 g of boron trifluoride ethyl etherate. 33.5 g of a brown resin were obtained.

14.0 g (0.05 mol) of the ethoxylated quinic acid were added in small portions to 34.0 g of polyphosphoric acid (84% P ₂ O ₅ ) at a temperature of about 70 ° C. After a further reaction time of 4 hours at 100-110 ° C, the resin obtained was mixed with 250 ml of water, the dark brown solution was refluxed for 30 minutes and treated hot with activated carbon. The then light yellow solution was adjusted with 50% sodium hydroxide solution from a pH value of 0.7 to a pH value of 6.89 and distilled off in a water jet vacuum for 11 hours. A residue of 61 g of a light resin remained with the following data:

Total phosphate content: 20.2%

Inorganic phosphate content: 15.2%

Degree of phosphorylation: 0.50

Water content: 9.3%

Active substance content: 41.2%

1.4 Production of the sodium salt of phosphorylated, ethoxylated (4 E0) quinic acid (reaction with EV = 1) (active ingredient 3)

57.7 g (0.30 mol) of quinic acid were reacted in an autoclave at approx. 5 bar and a temperature of 105 ° C. with 52.9 g (1.2 mol) of ethylene oxide in the presence of 1 g of boron trifluoride ethyl etherate. 104.8 g of a brown resin were obtained. 36.8 g (0.1 mol) of the ethoxylated quinic acid were added in small portions to 67.1 g of polyphosphoric acid (84% P ₂ O ₅ ) at a temperature of about 70 ° C. After a further reaction time of 4 hours at 100-110 ° C, the resin obtained was mixed with 250 ml of water and the black solution was heated to reflux for a further 30 minutes. The solution was then adjusted from pH 0.48 to pH 6.86 with 120.0 g of 50% sodium hydroxide solution, evaporated in a water jet vacuum and dried. A residue of 68.0 g of light gray crystals remained with the following data:

Total phosphate content: 18.5%

Inorganic phosphate content: 12.2% degree of phosphorylation: 0.68

Water content: 6.7%

Active substance content: 46%

1.5 Preparation of the sodium salt of phosphorylated shikimic acid (reaction with EV = 1) (active ingredient 4)

8.7 g (0.05 mol) of shikimic acid were added to 25.4 g of polyphosphoric acid (84% P ₂ O ₅ ) at a temperature of about 70 ° C. in such portions that the respective temperature increase in the reaction to 80- 85 ° C was limited. After a further reaction time of 4 hours at 100-110 ° C., the brown, easily stirrable mixture obtained was taken up in 100 ml of water, the solution was refluxed for a further 30 minutes and then treated hot with activated carbon. The light yellow solution obtained was treated with 48.4 g of 50% sodium hydroxide solution from a pH of 0.63 to a pH of 6.97 adjusted, evaporated in a water jet vacuum and dried. A residue of 49.1 g of a gray solid remained with the following data:

Total phosphate content: 19.2%

Inorganic phosphate content: 14.2%

Degree of phosphorylation: 0.52

Water content: 5.4%

Active substance content: 35.0%

2. Determination of the effectiveness of the substances

The effectiveness of the substances according to the invention is determined with regard to a) the reduction in hydroxylapatite solubility (ALR), b) the inhibition of hydroxylapatite crystal growth (KWI) and c) the inhibition of the hydroxylapatite-phosphate ion exchange capacity (PIA).

2.1 Determination of the Reduction in Hydroxyapatite Solubility (ALR)

a) Blind test

0.5 g of hydroxylapatite powder (specific surface area 60 m ² / g, from Merck) was placed in a reaction vessel thermostatted at 37 ° C. with 300 ml of demineralized water. The pH of the suspension was kept at a constant pH = 5 by means of an automatic burette with which lactic acid solution can be added. The amount of 0.1 M lactic acid solution used for pH stabilization was obtained from a writer registered. The lactic acid consumption registered after 2 hours corresponded to the solubility of the untreated hydroxylapatite (Lu).

b) measurement

The measurement was carried out analogously to a). Before the addition of the hydroxyapatite powder, 30 mg of the active ingredient to be tested were dissolved. The consumption of lactic acid registered after 2 hours corresponded to the solubility of the treated apatite powder (Lb).

The reduction in hydroxylapatite solubility by the active ingredient is calculated

ALR [%] = (Lu-Lb) / Lu * 100%

The results of the measurements (ALR) are listed in Table I.

2.2 Determination of the Inhibition of the Crystal Growth of Hydroxyapatite (KWI)

a) Blind test

400 ml of a 0.0008 molar solution of KH ₂ PO ₄ and 45 ml of a 0.012 molar solution of CaCl ₂ were placed in a reaction vessel. This solution was adjusted to a pH of 7.4 by titration with a 0.05 molar solution of KOH. After obtaining a stable pH value for at least 30 minutes, 100 mg of hydroxyapatite powder (specific surface 60 m ² / g, Merck) added. The pH of the suspension was kept at a constant 7.4 by means of an automatic burette, with which 0.05 m KOH solution can be added. The amount of 0.05 m KOH solution consumed for pH statization was recorded by a writer. The consumption of KOH solution (Ku) registered after 2 hours corresponded to the formation of hydroxylapatite (growth of the crystals of the suspension). b) measurement

The measurement was carried out analogously to a). Before the pH was adjusted, 6 mg of the active ingredient to be tested were dissolved.

The consumption of 0.05 m KOH solution (Kb) registered after 2 hours corresponded to the formation of hydroxylapatite (growth of the crystals in the suspension) under the influence of the active ingredient.

The inhibition of crystal growth by the active ingredient is calculated

KWI [%] = (Ku-Kb) / Ku * 100%

The results of the measurements (KWI) are listed in Table I.

2.3 Determination of the Inhibition of the Phosphate Ion Exchange Ability of Hydroxyapatite (PIA).

a) Blind test

1 g of hydroxylapatite (specific surface area 60 m 2 / g, from Merck) was placed in a shaking vessel with 250 ml of a barbiturate buffer saturated with hydroxylapatite (pH = 7). The suspension was then shaken for 3 days at 20 ° C. to establish equilibrium. Then 1 ml of a Na ₂ HPO ₄ solution in barbiturate buffer with a ³² P activity of 10 μCi (1 mCi Na ₂ HPO ₄ (activity 200 Ci / mol) in 100 ml barbiturate buffer) was added. After 3 hours a sample was taken, filtered through a membrane filter and the residual activity A _{3n was} determined. The inhibition of the phosphate ion exchange ability of the untreated hydroxyapatite

PIA [%] = (A _3h / 10μCi) * 100%

was 20%.

b) pretreatment of the hydroxyapatite with active substances

400 mg of the active ingredient, dissolved in 10 ml of water, were shaken for 24 hours with 3 g of hydroxyapatite powder (specific surface area 60 m ² / g, from Merck) and 20 ml of a barbiturate buffer saturated with hydroxylapatite (pH = 7). Then the hydroxyapatite was filtered off through a membrane filter and dried at 50 ° C. for 2 hours. Measurement

1 g of the pretreated hydroxyapatite was examined in the same way as indicated under a). From the loss of activity of the solution of the pretreated hydroxyapatite, the inhibition of the phosphate ion exchange ability PIA was calculated as follows.

PIA [%] = (A ₃ h / 10μCi) * 100%

The results of the measurements (PIA) are shown in Table I.

3. Examples of use

3.1 toothpaste

Precipitated silica ¹⁾ 18% by weight

Thickening silica (pyrogenic) ²⁾ 0.8% by weight

Active ingredient 1 1.0% by weight

Sorbitol 17.5% by weight

Glycerin 17.5% by weight

Carboxymethyl cellulose ³⁾ 0.9% by weight

Sodium lauryl sulfate ⁴⁾ 2.0% by weight

Sodium fluoride 0.22% by weight

Saccharin sodium 0.2% by weight

Aromatic oils 1.0% by weight

Water, preservative ad 100 wt.%

3.2 mouthwash

Ethyl alcohol (96% by volume) 10% by weight

Polyoxyethylene sorbitan monolaurate ⁵ ) 0.4% by weight

Aroma oil 0.3% by weight

Sorbitol (70% aqueous solution) 8.0% by weight methyl p-hydroxybenzoate 0.16% by weight

Active ingredient 2 0.1% by weight

Saccharin sodium 0.1% by weight

Water, dyes to 100% by weight 1) Sident ^(R) 12DS, from Degussa

2) Aerosil ^(R) 200, from Degussa

3) Relatin ^(R) 100 S8, from Henkel KGaA

⁴⁾ Texapon K1296, from Henkel KGaA

⁵⁾ Tween ^(R) 20, Atlas Chemie

Claims

Claims 1. Oral and dental care products with improved activity against the formation of caries, characterized in that a phosphoric acid ester of a cycloalkane carboxylic acid or a salt of a cycloalkane carboxylic acid of the general formula (I)

in which z is an integer from 4 to 7, the individual groups R independently of one another are hydrogen or - (OC _n H _2n ) _m -OR ² , where n is an integer from 2 to 5, m is a number from 0 to 8 and R ^{2 is} hydrogen or a group -PO ₃ M ₂ , and M represents hydrogen, an alkali or alkaline earth metal ion, an ammonium group or a mono-, di- or trihydroxyalkylammonium group with 2-4 carbon atoms in the hydroxyalkyl group, at least three of the groups R stand for - (OC _n H _2n ) _m -OR ² and at least one group R ² = -PO ₃ M ₂ in the molecule, and / or a phosphoric acid ester of a cycloalkenecarboxylic acid or a salt of a cycloalkenecarboxylic acid, which consists of the compounds according to formula (I) is formed by the loss of one hydrogen atom on two adjacent carbon atoms and the formation of a C = C double bond between these two carbon atoms. 2. Oral and dental care composition according to claim 1, characterized in that the phosphoric acid ester of the general formula (I) according to claim 1 is a derivative of quinic acid or shikimic acid. 3. Oral and dental care product according to one of claims 1 or 2, characterized in that at least one group R represents a group - (OC _n H _2n ) _m -OR ² , where n is an integer from 2 to 3 and m is a Number from 1 to 4. 4. Oral and dental care product according to one of claims 1 to 3, characterized in that the phosphoric acid ester is contained in an amount of 0.05 to 5.0 wt .-% of the preparation in addition to the usual components of oral and dental care products. 5. Toothpaste in the form of a pasty preparation of water, humectants, thickeners, abrasive and cleaning agents, flavor and aroma additives, the abrasive and cleaning agents made entirely or predominantly of finely divided xerogel silicas, hydrogel silicas, precipitated silicas, aluminum oxide trihydrate and / or finely divided aluminum oxide exists, characterized in that a phosphoric acid ester of the type defined in claims 1-3 is contained as an active ingredient in an amount of 0.1-2.0% by weight of the total preparation. 6. mouthwash in the form of an aqueous or aqueous-alcoholic solution with customary flavor and aroma additives, characterized in that the active ingredient is a phosphoric acid ester of the type defined in claims 1-3 in an amount of 0.05-1% by weight diluted mouthwashes in a correspondingly higher concentration. 7. phosphoric acid esters of a cycloalkanecarboxylic acid or a salt of a cycloalkanecarboxylic acid of the general formula (I)

in which z is an integer from 4 to 7, the individual groups R independently of one another represent hydrogen or -O- (C _n H _2n O) _m -R ² , where n is an integer from 2 to 5, m is a number from 0 to 8 and R ^{2 is} hydrogen or a group -PO ₃ M ₂ , and M represents hydrogen, an alkali metal or alkaline earth metal ion, an ammonium group or a mono-, di- or trihydroxyalkylammonium group with 1-4 carbon atoms in the hydroxyalkyl group, and at least three of the groups R are -OH or -O- (C _n H _2n ) _m -R ² and at least one group R ² = -PO ₃ M ₂ in the molecule. 8. phosphoric acid ester of a cycloalkenecarboxylic acid or a salt of a cycloalkenecarboxylic acid which formally arises from the compounds of the formula (I) according to claim 7 by the elimination of one hydrogen atom on two adjacent carbon atoms and formation of a C = C double bond between these two carbon atoms.