CH660686A5 - RESISTANT ANTIPLAQUE DENTAL CARE WITH FOAM AND FLUORIDE STABILITY. - Google Patents

Description

The invention particularly relates to an anti-plaque or anti-plaque dentifrice containing a quaternary compound as an active ingredient and 1.5 to 2% by weight of a betaine surfactant such as e.g. Contains cocoamidopropylbetaine, lauramido-propylbetaine, cocobetaine etc., which increases foaming and does not inactivate the antibacterial activity of the quaternary compound. Nonionic surfactants do not produce a satisfactory foam, anionic surfactants inactivate the antibacterial activity of the quaternary compound. Carbowax 600 (polyethylene glycol) and / or sorbitol replace propylene glycol and glycerin as a humectant or moisture stabilizer to ensure the stability of the betaine-containing mixture. The use of carboxymethyl cellulose is preferably avoided, since large organic molecules deactivate the quaternary compound. Nonionic gums such as B. hydroxyethyl cellulose are used for the toothpaste as a gelling agent or thickener. In particular, this mixture is free from anionic and nonionic surfactants and contains only a small amount, 1-10 and preferably 5-7% by weight, of glycerol as a fluoride stabilizer (if a fluoride is used) in a mixture containing only polyethylene glycol as a moisture stabilizer.

It has been found that the addition of a betaine surfactant to an antiplaque dentifrice based on quaternary active ingredients improves the foaming behavior of the same without deactivating the antimicrobial activity of the quaternary compound. In addition, it has been found that humectants other than glycerin are required in the betaine system in order to achieve cosmetic resistance, especially polyethylene glycol and / or sorbitol. The setting of the gelling / thickening agent on nonionic gums such as hydroxyethyl cellulose is also a necessary measure.

The ability of quaternary ammonium compounds to prevent the formation of dental plaque or plaque is well documented. However, these compounds are problematic when formulated in a dentifrice in that they are deactivated by conventional anionic surfactants such as sodium lauryl sulfate. Stable, clinically effective dentifrices have been made with quaternary ammonium compounds and nonionic surfactants, but these formulations are very poor foaming agents and result in mediocre products. Mixtures which contain quaternary ammonium compounds as antiplaque substances and nonionic surfactants are described in US Pat. No. 4,080,441.4,110,429.4,118,472.4,118,473.4,118,475 and 4,118,476 and in British Pat. No. 1,573,356 .

US Pat. No. 4,161,518 proposes a dental care product for preventing plaque formation, which contains 0.05-1% by weight of a quaternary ammonium organosiloxane as an active antibacterial substance in a suitable carrier, which contains suitable polishing agents, fluorides, anionic surfactants, flavoring agents. and sweeteners, thickeners such as carboxymethyl cellulose, humectants such as glycerin, sorbitol and other polyhydric alcohols.

US Pat. No. 3,988,435 proposes pharmaceutical mixtures including a dentifrice which contains a quaternary ammonium dihydrochalconglucoside as an antibacterial substance with a sweet taste, and abrasives, surfactants including nonionic surfactants and "derivatives of fatty amines with betaine structure", swelling, gelling or thickening agents such as hydroxyalkyl -lulose, especially hydroxyethyl cellulose, polyethylene glycols, polypropylene glycols etc., contains humectants such as sorbitol, mannitol, glycerin, propylene glycol, colorants and flavorings.

All of the above-mentioned patents simply list the usual additives that can be used for dentifrices. The use of betaine as an exclusive surfactant (exclusive manufacturer) for the production of high foaming dentifrices is not suggested.

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Also, the need to base the humectant on polyethylene glycol and / or sorbitol and the thickener on nonionic gums such as hydroxyethyl cellulose in order to obtain a cosmetically stable dentifrice in a betaine and quaternary compound system is neither previously described nor suggested.

U.S. Patent 4,363,795 and the corresponding PCT application, publication number WO 80/00057, describe a tooth surface cleaning agent which is a quaternary ammonium compound, an ampholytic surfactant, which may be an imidazoline or a betaine, and an aminocarboxylic acid type sequestering agent , which has a synergistic effect on the antibacterial properties of the treatment solution. All examples describe cleaning solutions. Dentifrices in the form of toothpastes are not mentioned, nor is the use of humectants or thickeners.

US Pat. No. 4,130,637 proposes a special group of betaine compounds or a mixture of such a betaine with its corresponding quaternary ammonium carboxylic acid salt in a ratio of 9: 1 as non-staining antimicrobial antiplaque substances in a dentifrice carrier which has the usual humectants given above - Contains gelling agents and a nonionic surfactant.

This patent specification does not specify the need to use only a betaine surfactant, the nonionic hydroxyethyl cellulose as a special gelling agent and the special moisture stabilizers polyethylene glycol and / or sorbitol, in order to obtain a stable, highly foaming, anti-plaque or anti-abrasive dentifrice containing a quaternary compound.

In US Pat. Nos. 4,117,107 and 4,117,108, a special group of betaine compounds and their salts are proposed as anti-plaque substances in a dentifrice carrier which contains the usual humectants and gelling agents as well as anionic / nonionic surfactants. An antibacterial quaternary ammonium compound and betaine as the exclusive surfactant are not specified. Also not specified is the specificity of the humectant and gelling agent and the exclusion of anionic / nonionic surfactants in a system of quaternary compound and betaine, which is necessary to ensure a stable,

obtain high foaming anti-plaque dentifrice.

None of the prior art references cited above describes a cosmetically resistant anti-plaque dentifrice with improved foam and fluoride resistance, which as essential components contains a cationic quaternary ammonium antiplaque compound, a zwitterionic betaine surfactant, a moisturizing agent from the group Sorb Polyethylene, which is compatible with the cationic antiplaque compound and the nonionic gelling agent contains hydroxyethyl cellulose in an aqueous carrier containing a dental abrasive. There is also no indication in the prior art that sorbitol as a humectant improves the long-term fluoride resistance, nor that the combination of small amounts of glycerol in a polyethylene glycol humectant improves the long-term fluoride resistance.

It has now been found that toothpastes which contain quaternary ammonium compounds as antiplaque substances can be stabilized and foam better if the conventional anionic and nonionic surfactants are replaced by surfactants of the betaine type. For better cosmetic resistance of the product, humectants such as polyethylene glycol and sorbitol have to replace the usual glycerin. However, a small amount of

Glycerin can be used to chemically stabilize the fluoride-containing compound in a humectant consisting exclusively of polyethylene glycol. Nonionic gums such as hydroxyethyl cellulose replace the anionic carboxymethyl cellulose, which potentially also deactivates the quaternary compound as a gelling agent.

The object of the invention is therefore to make a better foaming anti-plaque or anti-dental coating based on quaternary compounds available as active ingredients by incorporating a zwitterionic betaine surfactant as a foaming agent; to also propose a cosmetically stable, foaming anti-dental coating, the polyethylene glycol and / or sorbitol as a moisture stabilizer, which is compatible with the betaine and the quaternary active ingredients; and that the nonionic gum, hydroxyethyl cellulose, as a gel former to stabilize the betaine quaternary system and to prevent the deactivation of the quaternary active ingredient by the anionic sites in carboxymethyl cellulose molecules. contains.

Finally, the object of the invention is a cosmetically (physically) and chemically resistant foaming antiplaque dentifrice which contains a fluoride supplier and sorbitol or minimal amounts of glycerol (1-10% by weight) as stabilizing substances for the fluoride supplier, without the cosmetic stability of the dentifrice to affect.

Further objects, advantages and features of the invention are evident from the following description.

In order to achieve the object of the invention, a new, stable, foaming anti-plaque dentifrice is proposed which, as essential components, contains an effective amount of a quaternary ammonium antiplaque compound. at least 1.5% by weight, based on the dentifrice, of a zwitterionic betaine surfactant, a humectant from the group consisting of polyethylene glycol, sorbitol and mixtures thereof, a nonionic gelling agent such as hydroxyethyl cellulose, and preferably a fluoride supplier. in an aqueous carrier containing a dental abrasive.

In particular, the invention relates to a stable tiplaque dental care formulation with improved foaming and fluoride resistance, which contains an antimicrobially effective amount of a quaternary ammonium compound, about 1.5-2% by weight betaine, about 20-30% by weight humectant from the group consisting of polyethylene glycol, sorbitol and mixtures thereof, containing about 0.5-2% hydroxyethyl cellulose and about 0.05-2% by weight of a fluoride supplier in an aqueous carrier having about 40-60% water-insoluble dental abrasive. The sorbitol component that stabilizes the betaine quaternary system or the betaine and quaternary compound system also improves the long-term chemical fluoride stability of the dentifrice. In polyethylene glycol as the only humectant, a small amount of glycerin, about 1%, can be used to improve long-term fluoride resistance without adversely affecting the cosmetic resistance of the dentifrice.

Cationic antibacterial substances are well known in the prior art. For example, reference is made to the section “Quaternary Ammonium and Related Compounds” in the article on “Antiseptics and Disinfectants” in Encyclopedia of Chemical Technology by Kirk-Orthmer, 2nd edition (Volume 2, pages 632-635), to which reference is made here becomes. Cationic materials that have antibacterial activity (these are Germici-de) are used against bacteria and have been used in oral care products to prevent bacteria from getting into

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counteract plaque formation caused by the oral cavity.

Examples of the most common of these quaternary ammonium compounds used as antibacterial tip lacquers are benzethonium chloride, also known as Hyami-ne 1622 or diisobutylphenoxyethoxyethyldimethylbenzylammonium chloride, and cetylpyridinium chloride. In an oral care product, this material is highly effective in improving oral hygiene by reducing the formation of dental plaque and tartar, which is generally accompanied by a reduction in periodontal diseases. Other cationic antibacterial substances of this type are those mentioned, for example, in US Pat. Nos. 2,984,639, 3,325,402, 3,431,208 and 3,703,583, and GB 1,319,396.

Other antibacterial anti-fouling quaternary ammonium compounds include those in which one or two of the substituents on the quaternary nitrogen have a carbon chain length (mostly alkyl group) of 8 to 20, mostly 10 to 18 carbon atoms, while the remaining substituents have a lower number of carbon atoms (mostly alkyl - or benzyl groups) have, for example 1 to 7 carbon atoms, with methyl or ethyl groups being typical. Typical antibacterial quaternary ammonium compounds are dodecyltrimethylammonium bromide, benzyldimethylstearylammonium chloride, cetylpyridinium chloride and quaternized 5-amino-1,3-bis (2-ethylhe-xyl) -5-methyl-hexahydropyrimidine.

The dentifrice formulation of the invention contains an effective amount of the anti-fouling quaternary ammonium compound, preferably about 0.01-5% and more preferably 0.025-1% by weight of the mixture.

The ability of quaternary ammonium compounds to prevent plaque formation is well known. However, they are due to the anionic surfactants commonly used in dentifrices such as. B. Deactivated sodium lauryl sulfate. Replacing the anionic surfactants with nonionic surfactants eliminates the deactivation problem, but results in products with weak foam.

The incorporation of betaine surfactants in anti-plaque formulations based on quaternary active ingredients surprisingly improves the foaming behavior of these formulations without deactivating the quaternary antibacterial substances.

The betaine component of the dentifrice according to the invention preferably has the formula

R, -N + -R.-COO 1 i * + ■

wherein R) is an alkyl group with 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms or the amido radical

0 h

• i f

R-C-N- (CH9)

^ a means where R is an alkyl group of about 10 to 20 carbon atoms and a is an integer from 1 to 3; R2 and Rj each represent alkyl groups having 1 to 3 carbon atoms and preferably one carbon atom; R4 represents an alkylene or hydroxyalkylene group with 1 to 4 carbon atoms and optionally a hydroxyl group. Typical alkyl dimethyl betaines include decyl betaine or 2- (N-decyl-N, N-dimethylammonio) acetate, cocobetaine or 2- (N-coco-N, N-dimethylammonio) acetate, myristyl betaine, palmityl betaine, lauryl betaine, cetyl betaine, stearyl betaine, etc. The Amidobetaines similarly include coco-amidoethylbetaine, cocoamidopropylbetaine, lauramido propylbetaine and the like.

The betaines, which are zwitterionic substances, act as foaming agents in the dentifrices containing the quaternary compound. They have a cationic effect over a wide pH range, but do not deactivate the antimicrobial activity of the quaternary compound. This is demonstrated by in vitro tests using wool samples that simulate human skin and oral tissue as an absorbent material in the Red 80 Color Test, J. Soc. Cosmet, Chem. 31, 271-278 (September, October 1980). Wool has the same type of absorptive properties as oral tissue due to the similar isoelectric and isoionic points.

Using the red 80 color test, the following experiment shows that the betaine surfactant does not deactivate the quaternary compound. The red 80 color test was performed using a solution of cocoamidopropyl betaine alone, benzethonium chloride alone, and a mixture of cocoamidopropyl betaine and benzethonium chloride. The degree of staining of the wool samples treated with benzethonium chloride alone and the mixture of benzethonium chloride and betaine was almost the same, and both were colored darker than the sample treated with cocoamidopropyl betaine. This indicates that benzethonium chloride is a "stronger" cationic compound than betaine, i.e. it is more attractive to wool than betaine, which means that betaine does not deactivate benzoethonium chloride.

However, the samples treated with a mixture of benzethonium chloride and the anionic surfactant, sodium lauryl sulfate, show no coloring (retention of red color), which indicates a complete deactivation of the benzethonium chloride by the anionic surfactant.

The degree of coloration of the wool samples treated with a mixture of benzethonium chloride and the nonionic surfactant, polyoxyethylene (20 moles of ethylene oxide) sorbitan diisostearate, was substantially the same as that of benzethonium chloride alone. This indicates that the non-ionic surfactant does not deactivate the benzethonium chloride.

In addition to the betaines not affecting the activity of the quaternary compound, laboratory foam tests have shown that formulations containing both the quaternary compound and betaine foam two to three times better than the non-ionic / quaternary formulations. The foam index for nonionic / quaternary mixtures is about 20, whereas the foam index for betaine / quaternary mixtures is about 40-60. The foam test used here consists in placing 1 g of the test dentifrice in 10 ml water with 175 ppm at 32.2 C (90 ° F) in a 100 ml measuring cylinder, shaking for 15 minutes and reading the foam height.

The zwitterionic betaines are completely compatible with the antimicrobial quaternary antiplaque compounds and impart cleaning and improved foam properties to the dentifrice containing the quaternary compound without impairing the antimicrobial properties thereof. The amount of betaine effective to produce the improved foam or foaming can range from about 1.5-2% by weight of the active ingredient

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Overall formulation vary. Larger amounts of betaine worsen the taste of the dentifrice.

Problems of cosmetic stability arise with all dentifrices containing zwitterionic surfactants such as e.g. B. to loss (crimp leakage) of flavorings during pressing. The flavor disappears and is not solubilized in the zwitterionic surfactant.

In order to achieve cosmetic (physical) stability of the betaine system, a special group of humectants or moisture stabilizers comprising polyethylene glycol, sorbitol or mixtures thereof must therefore be used. Glycerin and propylene glycol alone result in unsatisfactory cosmetic stability in the betaine system. The humectant system typically makes up about 20-30%, preferably 20-25%, and is selected from the group consisting of polyethylene glycol, sorbitol and mixtures thereof.

Another essential component in the dentifrice according to the invention is a gelling agent, which is a non-ionic gum and is usually used in an amount of up to 5% by weight, preferably about 0.5-2%. It has been found that large organic anionic molecules such as carboxymethyl cellulose are able to deactivate the antibacterial activity of the quaternary substance. Therefore, hydroxyethyl cellulose, which is a nonionic small organic molecule, gives a stable mucilaginous gel in the betaine quaternary system of the invention and is the preferred gelling agent. Other nonionic gelling agents such as B. hydroxymethyl cellulose and the like can be used.

It was found that only by using the special combination of the components betaine, polyethylene glycol and / or sorbitol as a humectant and non-ionic gelling agent can a stable anti-plaque dentifrice with improved foam based on the antibacterial quaternary compounds be obtained.

The fluoride-providing compounds, which are preferably additional components of the dentifrices according to the invention, are distinguished by their ability to release fluoride ions in water and by the fact that they essentially do not react with the other compounds of the dentifrice. Examples of these substances are inorganic fluoride salts such as soluble alkali metal, alkaline earth metal and heavy metal salts, e.g. Sodium fluoride, potassium fluoride, ammonium fluoride, lead fluoride, a copper fluoride such as copper (II) fluoride, zinc fluoride, a tin fluoride such as tin (IV) fluoride, stannous fluoride, or tin (II) chlorofluoride, stannochlorofluoride, barium fluoride, sodium fluorosilicate, ammonium , Sodium monofluorophosphate, aluminum mono- and di-fluorophosphate, and fluorinated (fluorinated) sodium calcium pyrophosphate. Alkali metal and tin fluorides, such as. B. sodium and tin-II fluorides, sodium monofluorophosphate and Mi-5 mixtures thereof are preferred.

The amount of fluoride providing compound depends to some extent on the type of compound, its solubility and the dentifrice, but must be a non-toxic amount. In a solid preparation for oral care such as a toothpaste or toothpaste, an amount of such a compound which releases a maximum of 1% by weight, based on the preparation, is considered to be satisfactory. Any suitable minimum amount of such a compound can be used. However, it is preferred to use a sufficient amount of this compound to release 0.005% to 1% and preferably about 0.1% fluoride ions. In the case of the alkali metal fluorides and stannofluorides, this compound is present in an amount up to 2% by weight based on the weight of the preparation, and preferably in the range of 0.05% to 1%. In the case of sodium monofluorophosphate, the compound can be present in an amount of up to 7.6% by weight, usually 0.76%.

In addition, it was found that the long-term chemical fluoride stability in a humectant based on sorbitol or a mixed surfactant system that contains polyethylene glycol and at least 5% sorbitol is significantly improved compared to a humectant based on polyethylene, in which its fluoride stability is close to the 3o lowest Limit, but is acceptable. However, the use of small amounts of glycerin, about 1-10 and preferably 5-7% by weight, in a polyethylene glycol-based humectant improved the long-term fluoride stability without impairing the cosmetic stability of the dental care formulation according to the invention. The glycerin component acts and is only used as a chemical stabilizer for the fluoride component if polyethylene glycol is present as the sole humectant.

Based on the results of the aging study after 40 3 weeks at 49 ° C (120 ° F), 5% glycerin improves the fluoride stability 25% without impairing the cosmetic resistance. The mechanistic reason why the presence of a small amount of glycerol improves the fluoride resistance is not clear. The fluoride resistance values after 12 weeks at 38 C (100 F) further confirm the significant improvement through the use of small amounts of glycerin in the dentifrice. Table I clearly shows this improved fluoride stability in a system with polyethylene glycol as a humectant.

Table I

Soluble fluoride

Glycerin:

At first

3 weeks

6 weeks

9 weeks

12 weeks

Polyethylene glycol

at at at at

100 °

100

100

100

0:20

0.093

0.077

0.068

0.063

0.057

1:19

0.088

0.081

0.074

0.066

0.066

3:17

0.093

0.082

0.074

0.069

0.067

5:15

0.093

0.081

0.077

0.071

0.070

10:10

0.094

0.086

0.083

0.080

0.077

It was also found that increasing the glycerin content leads to a decrease in pH as shown in Table II.

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Table II

Glycerin: polyethylene glycol pH

9 weeks at 120 "

0:20 9.8

1:19 9.7

3:17 9.4

5:15 9.4

10:10 8.9

The dentifrice of the invention, which is preferably in the form of a toothpaste or toothpaste, contains conventional water-insoluble polishing agents or dental abrasives, in particular in amounts of about 20 to 75 and preferably about 40 to 60% by weight of the total formulation. Suitable examples of dental abrasives or polishing agents are sodium metaphosphate, potassium metaphosphate, tricalcium phosphate, dihydrated calcium phosphate, anhydrous dicalcium phosphate, calcium pyrophosphate, magnesium orthophosphate, trimagnesium phosphate, calcium carbonate, aluminum oxide, hydrated aluminum oxide, aluminum silicate, silicon dioxide, zirconium silicate, zirconium silicate and zirconium silicate, zirconium silicate, zirconium silicate and zirconium silicate.

The dentifrice of the invention may also contain common additional ingredients such as e.g. coloring or whitening substances, protective substances, flavorings or sweeteners and ammonia-containing materials (ammoniated materials) such as monoammonium glycyrrhizinate. These additional components can each be added to the dentifrice in small amounts of up to 5% by weight and preferably up to 1% by weight, provided that they do not impair the foam, antiplaque and stability behavior of the finished product.

The dentifrice of the invention is usually made by methods known per se for making toothpaste and / or toothpastes. In particular, a toothpaste can be produced by forming a gel with hydroxyethyl cellulose and water, to which the powdery materials including the fluoride compound and humectant and then the polishing agent and then the betaine and the flavoring agent are added while mixing, and that the finished mixture is added Tubes being filled.

The dentifrice of the invention can be applied regularly to the enamel by brushing the teeth at least once a day for 30 to 90 seconds to promote oral hygiene.

The following examples illustrate the invention, all amounts and ratios by weight unless otherwise specified.

example 1

Components%

Hydroxyethyl cellulose 1.0

Carbowax 6001 20.0

Sodium saccharin 0.2

MFP2 0.76

CAB3 (35% active ingredient A.B.) 3.5

Dicalcium phosphate 49.0

BZC14 0.5

D.I.H20 24.04

Flavor 1.0

1 polyethylene glycol. Molecular weight 600

2 sodium monofluorophosphate

3 cocoamidopropyl betaine

4 benzethonium chloride

The hydroxyethyl cellulose and water are premixed for 10 minutes to form a gel. The powdered materials MFP, BZC1 and saccharin and the Carbowax humectant are added to the gel and mixed for 10 to 20 minutes. The gelled mixture is added to dicalcium phosphate and mixed in a Ross agitator at speed 8 for 20 minutes. The betaine and flavor are added to the mixture and stirred for 5 minutes at speed 6 in the Ross stirrer. The toothpaste obtained, which is cosmetically attractive, is filled into tubes.

Aging tests performed with this product in coated tubes at room temperature, 4 'C (40 F) and 38 C (100 ° F) for 9 weeks, and in uncoated tubes at 49 ° C (120 ° F) for 9 weeks show excellent results cosmetic resistance.

Example 2

Components

%

Hydroxyethyl cellulose

1.1

Carbowax 600

20.0

Sodium saccharin

0.2

MFP

0.76

CAB (35% A.B.)

5.7

Dicalcium phosphate

46.8

BZC1

0.5

h2o

24.04

Flavoring

1.0

This toothpaste was made according to the procedure of Example 1. The product had a pH of 6.7 and a foam height of 55, but did not taste good.

Example 3

Components%

Highly sweet peppermint 1.0

MAG1 0.1

BZC1 0.5

MFP 0.76

Sodium saccharin 0.2

H20 23.44

PEG 6002 20.0

Natrosol3 1.0

Dicalcium phosphate 49.0

CAB (30% active ingredients (A.B.)) 4.0

1 monoammonium glycyrrhizinate

2 polyethylene glycol, molecular weight 600

3 hydroxyethyl cellulose

This toothpaste was prepared according to the procedure of Example 1, except that after the addition of the polyethylene glycol to the gelled premix, the pH was adjusted to 8.5 with hydrated NaOH for hydration purposes.

The cream obtained looks good, has a foam height of 38-40 and shows excellent resistance to aging tests over a period of 12 weeks

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at 38 C (100 F) as well as at 60 C (140 F) for 3 weeks in uncoated or unlined tubes.

Example 4

Example 3 was repeated except that glycerin was used as the humectant instead of polyethylene glycol. This product gave a foam height of 46, but showed signs of separation (trace separation) after 3 days at 60 ° C (140 ° F) and moisture and separation at the tube neck at 49 ° C (120 ° F) over 3 weeks. This product is not cosmetically stable.

Example 5

Components%

H20 21.14 Natrosol 1.3

Propylene glycol 20.0 sodium saccharin 0.2 BZC1 0.5 MAG 0.1 MFP 0.76

Dicalcium phosphate 50.0 CAB (30% A.B.) 5.0 flavoring 1.0

This toothpaste was made according to the procedure of Example 1, except that the propylene glycol colourant was mixed with the premix gel for only 10 minutes. The product obtained looked good and foamed well with a foaming height of 44. Its instability was clearly demonstrated by separation, moisture along the strand or ribbon (tape) and leakage at the closure (clip leakage) within 3 weeks at -13 ° (8 ° F) and 4 ° C (40 ° F) and slight yellowing at 43 ° C (110 ° F) and 49 ° C (120 ° F) within 3 weeks.

Example 6

Components

%

h2o

19.68

Natrosol

1.1

Carbowax 600

20.0

Sodium saccharin

0.2

BZC1

0.5

LIKE

0.1

MFP

0.76

Dicalcium phosphate

50.0

CAB (30% A.B.)

6.66

Flavoring

1.0

This toothpaste was made according to the procedure of Example 1.

The product obtained was somewhat thick, but foamed well and was stable.

Example 7

Components%

H20 21.34

Natrosol 1.1

Carbowax 600 20.0

Sodium saccharin 0.2

BZC1 0.5

MAG 0.1

MFP 0.76

Ca2P, (V 50.0 CAB (30% A.B.) 5.0 flavoring 1.0

1 calcium pyrophosphate

This toothpaste was made according to the procedure of Example 1.

The cream obtained was thick and granular, possibly due to the coarseness of the calcium pyrophosphate used as an abrasive.

Example 8

Components

%

h20

17.68

Natrosol

1.1

Carbowax 600

20.0

Sodium saccharin

0.2

BZC1

0.5

LIKE

0.1

MFP

0.76

Dicalci umphosphate dihydrate

42.0

Anhydrous dicalcium phosphate

10.0

CAB (30% A.B.)

6.66

Flavoring

1.0

Example 9

Components

%

Carbowax 600

20.0

Natrosol

1.1

N atri umsaccharin

0.2

LIKE

0.1

BZC1

0.5

h20

17.68

MFP

0.76

Hydrated alumina

42.0

Calcined alumina

10.0

Cocoamidoprophylbetaine (30% A.B.)

6.66

Flavoring

1.0

pH 8.3

This product was completely stable after 9 weeks of aging at room temperature, 4 C (40 F), 38 C (100 F) and 49 C (120 F).

Examples 10 and 11

Components

Example 10

Example 11

%

%

PEG 600

20.0

20.0

Natrosol

1.1

1.3

Sodium saccharin

0.3

0.3

Hydrated alumina

42.0

42.0

Calcined alumina

10.0

10.0

CAB (30% A.B.)

5.0

5.0

MFP

0.76

0.76

Flavoring

1.0

1.0

H20 D.I.

19.27

18.64

BZC1

0.5

0.5

Red 40 (1% solution)

0.07

0.07

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Examples 12

Components

%

Sorbitol 70%

28.0

Natrosol

1.1

Sodium saccharin

0.3

BZC1

0.5

MFP

0.76

Alumina

42.0

Calcined alumina

10.0

CAB (30% A.B.)

5.0

Flavoring

1.0

H20

11.34

Initially pH 7.4 15

pH after 3 weeks 7.5 pH after 6 weeks 7.6

This product was completely stable after a period of 9 weeks 20 at - 13 "C (8 ° F) and 4 ° C (40 ° F), but after 3 to 9 weeks the cap was slightly damp at 43 ° C (110 F ) and 49 ° C (120 ° F). In addition to the good physical resistance of this product, the content of active ingredients (ionic fluoride and benzoethonium chloride) also remained constant, as evidenced by the essentially constant pH.

Example 13

r -in

Components%

H20 21.14 Natrosol 1.3

Sorbitol 20.0 sodium saccharin 0.2 BZC1 0.5 MAG 0.1 MFP 0.76

Dicalcium phosphate dihydrate 50.0 CAB (30% A.B.) 5.0 flavoring 1.0

The cream obtained had a foam height of 42 and 45 and no aroma separation after 9 weeks at 49 ° C (120 F). This product was completely stable at

-13 C (8 F) and 4 C (40 F) over a 9 week period, but showed traces of a wet lid at 43 C (110 F) and 49 C (120 ° F) after 3 to 9 weeks.

Examples 14

Components

%

Natrosol

1.1

Sodium saccharin

0.3

BZC1

0.5

MFP

0.76

Carbowax 600

10.0

Sorbitol (70%)

10.0

H20 deionized

19.34

Hydrated alumina

10.0

Calcined alumina

42.0

Flavoring

1.0

CAB (30% A.B.)

5.0

Example 15

Components

%

Natrosol

1.1

Sodium saccharin

0.3

MFP

0.76

BZC1

0.5

Carbowax 600

15.0

Sorbitol (70%)

5.0

h2o

19.34

Hydrated alumina

42.00

Calcined alumina

10.0

Flavoring

1.0

CAB (30% A.B.)

5.0

This product, which contained 5% sorbitol, enabled 84% recovery of soluble fluoride after 12 weeks at 38 ° C (100 ° F) compared to 61% recovery of fluoride (acceptable level) with only polyethylene glycol as the humectant under the same conditions, e.g. B. Examples 1 to 11. This means that the presence of sorbitol in amounts of only 5% (70% active ingredient) ensures superior fluoride resistance.

Examples 16-20

Components

%

%

%

%

%

Ex. 16

Ex. 17

Ex. 18

Ex. 19

Ex. 20

Polyethylene glycol (Carbowax 600)

15

17th

19th

10th

20th

Glycerin

5

3rd

1

10th

0

Hydroxyethyl cellulose

1.10

1.10

1.10

1.10

1.10

Sodium monofluorophosphate

0.76

0.76

0.76

0.76

0.76

Sodium saccharin

0.30

0.30

0.30

0.30

0.30

Benzethonium chloride

0.50

0.50

0.50

0.50

0.50

Hydrated alumina

42

42

42

42

42

Calcined alumina

10th

10th

10th

10th

10th

CAB (30% A.B.)

5

5

5

5

5

Flavoring

1

1

1

1

1

water

19.34

19.34

19.34

19.34

19.34

For salary *

0.07

0.067

0.066

0.077

0.057

* The chemical stability of the above formulations after accelerated aging for 12 weeks at 38 C (100 F), which was determined by the percentage of the Fl "content.

All of the above formulations are effective against bacterial plaque and at the same time have improved foaming properties, cosmetic and chemical resistance. The presence of a small amount of glycerin, e.g. of only 1% by weight increases the chemical resistance of the fluoride in the dentifrice containing polyethylene glycol as a moisture stabilizer over the acceptable fluoride resistance in the absence of glycerol (Example 20).

The above formulations can be ab660 686

be changed. For example, other betaines such as Lauramidopropyl betaine, cocobetaine and the like can be used in place of the cocoamidopropyl betaine in the examples. Likewise, other abrasives can be used instead of the abrasives specifically mentioned in the examples. Other fluoride-containing compounds such as sodium fluoride, potassium fluoride etc. can also be used instead of the sodium monofluorophosphate specifically mentioned in the examples.

9

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

Claims (16)

660 686 PATENT CLAIMS 1. Resistant antiplaque dentifrice with foaming and fluoride stability, characterized in that it contains an effective amount of a quaternary ammonium compound as an antiplaque compound, at least 1.5% by weight betaine surfactant, based on the dentifrice, a humectant from the group Polyethylene glycol, sorbitol and mixtures thereof, and a nonionic gelling agent in an aqueous carrier containing a dental abrasive. 2. Dental care product according to claim 1, characterized in that the betaine content is 1.5 to 2% by weight of the dental care product. 3. Dentifrice according to claim 2, characterized in that the nonionic gelling agent is hydroxyethyl cellulose, and is contained in amounts of 0.5-2% by weight, based on the dentifrice. 4. Dental care product according to claim 3, characterized in that it contains 20-30% by weight, based on the dental care product, of polyethylene glycol with an MW of 600. 5. Dentifrice according to claim 3, characterized in that it contains 20-30% by weight, based on the dentifrice, of sorbitol. 6. Dental care product according to claim 1, characterized in that it contains 40-60% by weight, based on the dental care product, of a water-insoluble dental abrasive. 7. Dental care product according to claim 1, characterized in that the dental abrasive is dicalcium phosphate. 8. Dentifrice according to claim 3, characterized in that the anti-plaque compound is benzethonium chloride, and is contained in an amount of 0.01-5% by weight, based on the dentifrice. 9. Dentifrice according to claim 1, characterized in that it additionally contains a fluoride supplier, which preferably constitutes 0.05-2% by weight of the dentifrice. 10. Dental care product according to claim 9, characterized in that the fluoride supplier is sodium monfluorophosphate. 11. Dentifrice according to claim 9, characterized in that the humectant consists of a mixture of 20-30% by weight of polyethylene glycol and at least 5% by weight of sorbitol, the percentages by weight relating to the dentifrice. 12. Dentifrice according to claim 9, characterized in that it additionally contains 1 - 10% by weight, based on the dentifrice, glycerol as a fluoride stabilizer and polyethylene glycol as a humectant. 13. Dental care product according to claim 2, characterized in that the betaine is cocoamidopropyl betaine. 14. Dentifrice according to claim 1, characterized in that it is free of nonionic and anionic surfactants. 15. Dental care product according to claim 1, characterized in that the dental abrasive is aluminum oxide. 16. Dental care product according to claim 15, characterized in that the dental abrasive is a mixture of hydrated aluminum oxide and calcined aluminum oxide.