NL8402234A - TOOTHPASTE. - Google Patents

Description

ft VO 6437 Toothpaste.

The invention relates to a plaque-resistant toothpaste, which contains a quaternary surfactant nitrogen compound and 1.5-2.0 wt.% Of a surfactant betaine, such as coconut amido-propylbetalne, lauramidopropy ibetalne, coconut betaine, etc., which promotes foaming and does not harm the anti-bacterial effect of the quateraary compound. Non-ionic surfactants do not provide sufficient foaming and anionic surfactants eliminate antibacterial activity. Carbowax 600 (polyethylene glycol) and / or sorbitol replace propylene glycol and glyce-10 roll as wetting agents to stabilize the betaine-containing toothpaste.

Carboxymethyl cellulose is preferably avoided because large organic molecules render the quaternary compound ineffective. Non-ionic gums, such as hydroxyethyl cellulose, are used as a gelling agent or thickener for the toothpaste. In particular, the toothpaste is free of anionic and non-ionic surfactants and that paste contains only a small amount of glycerol, i.e. 1-10 wt% and preferably 5-7 wt% as a fluoride stabilizer (when using a fluorine compound) in a single composition, the sole wetting agent containing polyethylene glycol.

It has been found that adding a surfactant betaine to a quaternary actives plaque-resistant toothpaste improves its foaming properties without removing the microbial quaternary activity. In addition, it has been found that wetting agents other than glycerol are required in the beta system to obtain cosmetic stability, in particular polyethylene glycol and / or sorbitol. Limiting the gelling agent / thickener to non-ionic gums, such as hydroxyethyl cellulose, is also a necessary measure.

30 The ability of quaternary ammonium compounds to prevent plaque build-up is well documented. However, these compounds have the problem of becoming inactive by conventional anionic surfactants, such as sodium lauryl sulfate, which are found in many toothpastes. Stable and clinically active toothpastes have already been obtained with quaternary ammonium compounds and non-ionic surfactants, but these materials have very poor foaming and therefore lead to inferior products. Toothpastes containing anti-plaque quaternary ammonium compounds and nonionic surfactant are described in U.S. Pat. Nos. 4,080,441; 4,110,429; 4,118,472; 4,118,473; 4,118,475; 4,118,476 and in British Patent 1,573,356.

U.S. Patent 4,161,518 discloses a dentifrice-inhibiting toothpaste containing 0.05-1% by weight of a quaternary ammonium organosiloxane as the active antibacterial agent in a suitable carrier, which includes known polishes, fluoride compounds, anionic surfactants substances, flavors and sweeteners, thickeners such as carboxymethylcellulose, wetting agents such as glycerol, sorbitol and other polyhydric alcohols.

US Patent 3,988,435 discloses pharmaceutical mixtures, including toothpastes, which contain a quaternary ammonium dihydrochalcon glucoside as a sweet-flavored antibacterial agent, in addition to abrasives, surfactants, including nonionic surfactants and "derivatives of fatty amines with a betainic structure", swelling agents, gelling agents or thickeners, such as hydroxyalkyl cellulose, especially hydroxyethyl cellulose, polyethylene glycols, polypropylene glycols, etc., wetting agents, such as sorbitol, mannitol, glycerol, propylene glycol, dyes and flavors.

The above patents simply list the usual additives useful in toothpastes. There is no mention of the betaine as the only surfactant in the production of a high foaming toothpaste. Also, there is no mention or suggestion of the need to limit the humectant to a polyethylene glycol and / or a sorbitol or to limit the thickener to nonionic gums, such as hydroxyethyl cellulose, to obtain a cosmetically stable toothpaste with a combination of a betaine and a quaternary substance.

United States Patent 4,363,795 and the corresponding international (published patent application WO 80/00057 8402234 f * -3-) disclose a dentifrice cleaning agent comprising a quaternary ammonium compound, an ampholytic surfactant containing an imidazoline or an may be betaine and an aminocarboxylic acid type sequestrant which has a synergistic effect with respect to the anti-bacterial properties of the treatment solution, all examples given relate to cleaning solutions There is no mention of pastes there or creams, or mention of wetting and thickening agents.

US Pat. No. 4,130,637 discloses a special group of beta compounds or a mixture of such betaine and the corresponding quaternary ammonium salt of a carboxylic acid in a ratio of 9 as stain-free, anti-microbial and anti-plaque agents in a toothpaste as a carrier which contains the above-mentioned conventional wetting agents and gelling agents, in addition to a nonionic surfactant. This patent does not describe the need to use a betaine as the only surfactant or to use hydroxyethyl cellulose as a nonionic gelling agent or to use polyethylene-20 glycol and / or sorbitol as a wetting agent to form a stable, highly foaming anti-plaque toothpaste. base of a quaternary substance.

US Pat. Nos. 4,117,107 and 4,117,108 also describe a special group of payment compounds and their salts as anti-plaque agents in a toothpaste, which contains conventional wetting agents and gelling agents in addition to anionic / nonionic surfactants. There is no mention of a quaternary ammonium compound as an antibacterial agent or of the exclusive use of a betaine as a surfactant. Nor is there any suggestion of a specific wetting agent and / or gelling agent nor the exclusion of anionic and nonionic surfactants in a quaternary beta system, although this is nevertheless necessary to obtain a stable, high foaming, plaque-resistant toothpaste.

However, none of the cited publications describe a »cosmetically stable, plaque-resistant toothpaste with improved foam stability and fluoride stability, which contains as essential ingredients a cationic, quaternary ammonium compound, which is active against plaque, a zwitterionic betaine surfactant substance, - a wetting agent, which is compatible with the cationic anti-plaque agent and is selected from polyethylene glycol and sorbitol and the nonionic gelling agent hydroxyethylcallulose, in an aqueous carrier containing a dental abrasive. Also, the literature does not mention sorbitol as a wetting agent, which improves long-term fluoride stability, nor the combination of small amounts of glycerol in a polyethylene glycol as wetting agent, to improve long-term fluoride stability.

It has now been found that toothpaste formulations containing anti-plaque quaternary ammonium compounds can be stabilized and exhibit better sdxum activity when using betaine type surfactants in place of the conventional anionic and nonionic surfactants. To improve the cosmetic stability of the product, polyethylene glycol and sorbitol should replace the usual glycerol. However, a small amount of glycerol can be used to chemically stabilize the fluoride-containing compounds when polyethylene glycol is the sole wetting agent. Non-ionic gums, such as hydroxyethyl cellulose, replace the anionic carboxymethyl cellulose as a gelling agent, the latter also being able to deactivate the quaternary ammonium compound.

Therefore, the main object of the invention is to provide a better foaming anti-plaque toothpaste based on active quaternary ammonium compounds by incorporating a zwitterionic betaine as surfactant foaming agent.

Another object of the invention is to provide a cosmetically stable foaming anti-plaque toothpaste containing polyethylene glycol and / or sorbitol as a wetting agent, which wetting agent is compatible with the betaine and quaternary actives.

Yet another object of the invention is to provide a stable antifoam anti-plaque toothpaste containing the nonionic gum hydroxyethyl cellulose as a gelling agent for the combination of 8402234

* V

-5- to stabilize the betaine and quaternary ammonium compound and prevent deactivation of the active quaternary ammonium compound by the anionic sites in the molecules of carboxymethyl cellulose.

A further object of the invention is to provide a cosmetically (physically) and chemically stable anti-plaque antifouling toothpaste containing a fluorine-providing compound and sorbitol or small amounts of glycerol (1-10% by weight) as a stabilizing agent for the fluorine-providing compound , without affecting the cosmetic stability of the toothpaste.

Other objects, advantages and features of the invention will be set forth in the description below, and in part will become apparent to those skilled in the art by studying the following or by experience in practicing the invention. The objects and advantages of the invention can be achieved by the means and combinations, which are particularly indicated in the claims below.

(To achieve these and other objectives, the inventive toothpaste includes as essential ingredients a plaque-resistant quaternary ammonium compound and a zwitterionic betaine surfactant and a wetting agent selected from polyethylene glycol and / or sorbitol, a nonionic gelling agent such as hydroxyethyl cellulose and preferably a fluorine-providing compound, in an aqueous carrier containing a dental abrasive.

In particular, the invention relates to a stable anti-plaque toothpaste with improved foaming properties and improved fluoride stability, comprising an effective amount of a microbe-resistant quaternary ammonium compound, about 1.5-2.0 wt% betaine, about 20-30 wt% wetting agent selected from the group consisting of polyethylene glycol, sorbitol and mixtures thereof, about 0.5-2 wt% hydroxyethyl cellulose and about 0.05-2 wt% of a fluorine-providing compound , in an aqueous carrier containing about 40-60% by weight water-insoluble dental abrasive. The sorbitol component, which stabilizes the system of betaine and quaternary ammonium compound, also improves long-term chemical fluoride stability of the toothpaste. When 8402234 2 i - * · -6- is only polyethylene glycol present as a wetting agent, a small amount of glycerol, for example 1%, can be used to improve the long term stability of the fluoride, without affecting the cosmetic stability of the toothpaste. harm.

Cationic, antibacterial materials are known per se.

"Quaternary Ammonium and Related Compounds" in the article on "Antiseptics and Disinfectants" in Kirk-Othmer Encyclopedia of Chemical Technology, 2nd edition. (Vol. 2, pp. 632-635), which is hereby incorporated by reference. Cationic materials with antibacterial activity (ie, germicidal activity) are used against bacteria and have already been used in oral anti-plaque preparations. formation caused by bacteria in the oral cavity.

Among the most common of these anti-plaque antibacterial quaternary ammonium compounds is benzethonium chloride, also known as Eyamine 1622 or diisobutylphenoxyethoxyethyl-dimethylbenzylammonium chloride, and cetylpyridinio chloride. In an oral formulation, this material is very effective in improving oral hygiene by reducing plaque and calculus formation, which is usually accompanied by a reduction in periodontal disease.

20. Other cationic antibacterial agents of this type are disclosed, for example, in U.S. Patent Nos. 2,984,639; 3,325,402; 3,431,208 and 3,703,583 and British Patent No. 1,319,396.

Other antibacterial and plaque-fighting quaternary ammonium compounds include those wherein 1 or 2 of the substituents and the quaternary nitrogen atom has a carbon chain (typically an alkyl group) of 8-20 and preferably 10-18 carbon atoms, while the other substituents have a smaller number have carbon atoms (typically alkyl groups or a benzyl group), such as 1-7 carbon atoms, typically methyl or ethyl groups. Typical quaternary ammonium compounds with antibacterial activity are dodecyl trimethyl ammonium bromide, benzyl dimethyl stearyl ammonium chloride, cetyl pyridinium chloride and quaternized 5-amino-1,3-bis- (2-ethylhexyl) -5-methylhexahydropyrimidine.

The toothpaste formulation according to the invention contains an effective amount of the plaque-resistant quaternary ammonium compound, preferably 0.01-2% by weight and most preferably 0.025-1% by weight, based on the preparation.

3402234 -7-

The ability of quaternary ammonium compounds to inhibit plaque formation is well known. However, they are deactivated by the anionic surfactants, such as sodium lauryl sulfate, which are commonly used in toothpaste formulations. Replacing these anionic surfactants with non-ionic surfactants avoids this deactivation, but does lead to products that foam poorly.

Processing of betaine surfactant with anti-plaque dentifrices based on quaternary ammonium compounds improves the foaming of these formulations unexpectedly without deactivating the antibacterial quaternary ammonium compounds.

The beta component of these toothpastes has the formula 1 of the formula sheet, wherein is an alkyl group with 10-20 carbon-15 atoms and most preferably 12-16 carbon atoms or the amino group of formula 2 of the formula sheet, wherein R is an alkyl group with 10- 20 carbon atoms and a an integer of 1-3, R2 and R1 each represent alkyl groups with 1-3 carbon atoms and most preferably with 1 carbon atom, an alkylene or hydroxyalkylene group with 1-4 carbon atoms and optionally a hydroxyl group. Typical alkyl dimethyl paynes include decyl betaine or 2-N-decyl-N, N-dimethylammonio) acetate, coconut betaine or 2- (N-coconut-N, -dimethylammonio) acetate, myristyl betalne, palmityl betalne, lauryl betaine, cetyl betalne, stearyl betaine. amidobetals similarly include coconut amidoethyl betalne, coconut amidopropyl betalne, lauramidopropyl betaine, and the like.

The betaines, which are zwitterionic materials, act as foaming agents in the toothpastes containing quaternary ammonium compounds. They work cationically over a wide pE region, but do not inactivate quaternary antimicrobial activity. This was demonstrated in in vitro experiments using woolen plugs simulating human skin and oral tissue as an absorbent material in the Red 80 Stain test, J. Soc. Cosmet. Chem. 31, 271-278 (Sept., Oct. 1980). Wool has the same type of absorption properties as oral tissue, due to the similar isoelectric and isoionic 35 points.

8402234 * -8-

With. this "Red 80 dye test" shows the following experiment, that a betaine surfactant does not deactivate the quaternary ammonium compounds. The "Red 80 test" was performed with a solution of coconut amidopropyl betaine alone, with benzethonium chloride ride alone and with a mixture of coconut amidopropyl betaine and benzethonium chloride The degree of staining on the wool plugs treated with bezethonium chloride alone or with the mixture of benzethonium chloride and betaine was practically the same and both were stained darker than the plug treated with coconut amidopropyl -10 betaine This indicates that benzethonium chloride is a stronger cationic compound than betaine, ie it has a greater attraction to the wool than the betaine, indicating that the betaine does not deactivate the benzethonium chloride. plugs which have been treated with a mixture of benzon thonium chloride and an anionic surfactant, sodium lauryl sulfate, no staining (no retention of red color), indicating complete deactivation of the benzethonium chloride by the anionic surfactant. The degree of coloring of the wool plugs treated with a mixture of benzethonium chloride and the nonionic surfactant polyoxyethylene (20 moles ethylene oxide) sorbitan diisostearate was practically equal to that of benzethonium chloride alone. This indicates that the benzethonium chloride is not deactivated by the nonionic surfactant. In addition to the fact that the betaines do not interfere with the activity of the quaternary ammonium compounds, laboratory foam tests have shown that formulations containing both the quaternary ammonium compounds and the betaine foam 2-3 times better than formulations with a nonionic surfactant and a quaternary ammonium compound. The foam index for mixtures of nonionic substance and quaternary ammonium compound is about 20, while the foam index for similar mixtures of a betaine and a quaternary ammonium compound is about 40-60. In the foam test used here, 1 g of the toothpaste to be tested is placed in 10 ml of water with a hardness of 175 ppm at 32 ° C in a 100 ml graduated cylinder, which is then shaken for 15 seconds, after which the height of the foam is read.

8402234 <r * -9-

The zwitterionic betaines are fully compatible with the anti-plaque quaternary antimicrobial ammonium compounds and provide a cleaning and foaming action to the toothpaste containing quaternary ammonium compounds without reducing its anti-microbial properties. The effective amount of betaine in the production of an improved foaming can be varied from about 1.5-2.0% by weight of active substance, based on the total formulation. Larger amounts of betaine have an adverse effect on the taste of the toothpaste.

Cosmetic stability problems occur with all toothpastes containing zwitterionic compounds, such as flavor shrinkage leakage. The flavoring agent separates and does not dissolve in the zwitterionic surfactant.

In order to obtain the cosmetic (physical) stability of the beta-15 system, a special group of humectants must be used which contains polyethylene glycol and / or sorbitol. Glycerol and propylene glycol alone do not provide sufficient cosmetic stability to the payment system. The humidification system comprises about 20-30 wt% and most preferably 20-25 wt% and it is selected from polyethylene-20 glycol and / or sorbitol.

Their other essential ingredient in the new toothpaste is a gelling agent, which consists of a non-ionic gum, in an amount of up to 5% by weight and most preferably 0.5-2% by weight. It has been found that large organic anionogen molecules, such as carboxymethyl cellulose, have the ability to destroy the quaternary antibacterial activity. Therefore, hydroxyethyl cellulose is used, which is a nonionic small organic molecule and leads to a stable gel in the system of betaine and quaternary ammonium compounds of the invention and it is the preferred gelling agent.

Other nonionic gelling agents can also be used, such as hydroxymethyl cellulose, and the like.

It has been found that only by using the specific combination of ingredients of betaine, polyethylene glycol and / or sorbitol as a wetting agent and a nonionic gelling agent can a stable plaque-resistant toothpaste be obtained with improved foaming properties based on quaternary antibacterial ammonium compounds.

8402234 J% -10-

The fluoride-providing compounds, which are preferably used as additional ingredients in the toothpaste according to the invention, are characterized by their ability to release fluoride ions in water and because they are practically free from reactions with other compounds in the toothpaste. Among these materials are inorganic fluoride salts such as soluble alkali metal salts, alkaline earth metal salts and heavy metal salts, for example sodium fluoride, potassium fluoride, ammonium fluoride, lead fluoride, a copper fluoride, such as cuprofluoride, zinc fluoride, one. tin fluoride, such as stannic or stannous chlorofluoride, barium fluoride, sodium fluorosilicate, ammonium fluorosilicate, sodium fluorosirconate, sodium monofluorophosphate, aluminum mono and difluorophosphate. fluorinated sodium calcium pyrophosphate. Alkali metal and tin fluorides, such as sodium and stannous fluorides, sodium monofluorophosphate and mixtures thereof are preferably used.

The amount of the fluorine-providing compound depends to some extent on the type of compound, its solubility and on the toothpaste, but it must be a non-toxic amount. In a solid oral preparation, such as a toothpaste or a dental cream, an amount of such a compound, which releases up to 1% by weight of the preparation, is considered satisfactory. Any suitable minimum amount of such a compound may be used, but preferably enough of this compound is used to release 0.005-1 wt%, and most preferably about 0.1 wt%, of fluoride ion. In the case of alkali metal fluoride and stannous fluoride, this amount is typically present in an amount of up to 2% by weight, based on the composition, and preferably in an amount of 0.05-1% by weight. In the case of sodium monofluorophosphate, the compound may be present in an amount up to 7.6% by weight, but most typically 0.76% by weight.

In addition, it has been found that the long-term chemical stability of the fluoride in a sorbitol-based wetting agent or in a mixed surfactant system containing polyethylene glycol and at least 5 wt% sorbitol is markedly improved, compared to a humectant based on polyethylene glycol alone, because then the stability of the fluoride is marginal, but still 8402234 -11- acceptable. However, in that case, the use of small amounts of glycerol, about 1-10 wt%, and most preferably 5-7 wt%, in a wetting agent based on polyethylene glycol, provides significantly improved long-term stability of the fluoride, without affecting -5 metallic stability of the toothpaste formulations is impaired.

The glycerol component there functions only as a chemical stabilizer for the fluoride component when polyethylene glycol is used as the sole wetting agent.

Based on a study at 49®C, it appears that after 3 weeks of aging, the presence of 5% glycerol improves fluoride stability by 25% without compromising cosmetic stability.

The reason why the presence of a small amount of glycerol improves fluoride stability is not clear. The fluoride stability after 12 weeks at 67 ° C further confirms the marked improvement using small amounts of glycerol in the toothpaste. Table A clearly shows this improved fluoride stability in a system with polyethylene glycol as a wetting agent.

TABLE A

Soluble Fluoride 20 Glycerol: Polyethylene- early 3 weeks 6 weeks 9 weeks 12 weeks

glycol value at 37 ° C at 37 ° C at 37 ° C at 37 ° C

0.-20 0.093 0.077 0.068 0.063 0.057 1:19 Or, 088 0.081 0.074 0.066 0.066 25 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 has further been found that an increase in the glycerol content leads to a decrease in pH, as shown in Table B.

30 TABLE B

Glycerol: polyethylene glycol pH

9 weeks at 49 ° C

0:20 9.8 1:19 "9.7 35 3:17. 9.4 5:15 9.4 10:10 8.9 8402 234 -12-

The toothpaste according to the invention, which may also be a dental cream, contains conventional in. water insoluble polishes or abrasives in an amount of 20-75 and preferably 40-60 wt. % of the total preparation. Suitable examples of such abrasives or polishes include sodium metaphosphate, potassium metaphosphate, tricalcium phosphate, calcium phosphate dihydrate, anhydrous dicalcium phosphate, calcium pyrophosphate, magnesium orthophosphate, trimagnesium phosphate, alumina, alumina, hydrated oxydate, hydrated The toothpaste according to the invention may also contain customary additional additives, such as dyes, whiteners, preservatives, flavors or fragrances, and ammonium-containing substances, such as monoammonium glycyrrizinate. These additional ingredients can each be added to the toothpaste in small amounts of up to 15% by weight and preferably not more than 1%, provided that they do not interfere with the foaming, anti-plaque and stability properties of the final product. toothpaste according to the invention is prepared according to conventional methods for the preparation of toothpastes and / or dental creams. In particular, a toothpaste can be prepared "by forming a gel with hydroxyethyl cellulose and water and adding thereto the powdered materials, including the fluoride compound and the wetting agent, under continuous mixing, followed by adding the polishing agent and mixing. finally the betaine and the flavoring, after which the finished mixture is filled into tubes.

In order to promote oral hygiene, the toothpaste according to the invention is regularly applied to the tooth enamel by brushing the teeth for 30-90 seconds at least once a day.

The invention is further illustrated by the following examples, which, however, do not limit the invention. The compositions mentioned in those examples are prepared in the usual manner and all amounts and ratios mentioned therein and mentioned in the claims are weight amounts and weight ratios unless otherwise stated.

35 8402 234 -13-

EXAMPLE I

Components. % hydroxyethyl cellulose 1.0

Carbowax 600 * 20.0 5 Na-saccharin 0.2 MPP2 0.76 C & B3 (35% A.I.) 3.5 dicalcium phosphate 49.0 BZC14 0.5 10 D.I. H2 O 24.04 flavor 1.0 polyethylene glycol, mol. Wt. 600 2 sodium monofluorophosphate 3 coconut amidopropylbetalne 15 ^ benzethonium chloride

The hydrous oxy thyce 1 lulose and the water are mixed for 10 minutes, after which a gel is obtained. The powdered materials MFP, BZCl and saccharin and the humectant carbowax are added to the gel and mixed for 10-20 minutes. Then the gelled mixture is added to the dicalcium phosphate and stirred at a speed of 8 in a Koss stirrer for 20 minutes. The betaine and flavor are added to the mixture and mixed in the same Ross stirrer at speed 6 for 5 minutes. The resulting dental cream, which is cosmetically attractive, is filled into tubes.

Aging tests conducted with this product in lined tubes at room temperature at 4 ° C and at 37 ° C for 9 weeks and in unlined tubes at 49 ° C for 9 weeks showed excellent cosmetic stability.

8402234 «-14-

PRE-SCHEDULED II

Components% hydroxyethyl cellulose 1.1

Carbowax 600 - 20.0 5 Na Saccharin 0.2 MFP 0.76 CAB (35% A.I.) 5.7 Dicalcium Phosphate 46.8 BZCl 0.5 10 H20 24.04 Flavor 1.0

This dental cream is prepared according to the procedure of Example I. The product has a pH of 6.7 and a foam height of 55, but it does not have a pleasant taste.

EXAMPLE III

Components% peppermint 1.0.

MAG1 0.1 BZC1 0.5 20 MFP 0.76

Na-saccharin 0.2 H2 O 23.44 PEG 6002 20.0 3

Natrosol 1.0 25 dicalcium phosphate 49.0 CAB (30% A.I.) 4.0 8402234 monoammonium glycyrrizinate 2 polyethylene glycol, mol. 600 ^ hydroxyethyl cellulose. This dental cream is prepared according to the procedure of Example I, but the pH is adjusted to 8.5 with dilute NaOH to promote hydration after the polyethylene glycol has been added to the previously gelled mixture.

• gr> -15-

The resulting cream has a good appearance, a foam height of 38-40 and shows excellent stability in aging tests for 12 weeks at 37 ° C and at 60 ° C in unlined tubes for 3 weeks.

EXAMPLE IV

Example XXI is repeated, but glycerol is used as the wetting agent instead of the polyethylene glycol. This product gives a foam height of 46, but shows traces of phase separation after 3 days at 60 ° C and wetness and phase separation at the neck of the tube at 49 ° C. This product is not cosmetically stable.

EXAMPLE V

Components% H 2 O 21.14

Natrosol 1.3 15 propylene glycol 20.0

Na-saccharin 0.2 BSC1 * 0.5 MAG 0.1 MFP 0.76 20 dicalcium phosphate 50.0 CAB (30% A.X.} 5.0 flavoring 1.0

This dental cream was prepared according to the procedure of Example I, except that the wetting agent, propylene glycol, is mixed with the previously prepared gel for only 10 minutes. The product obtained has good appearance and foaming; the foam height is 44.

However, the instability is evident in that phase separation and wetness occurs along the ribbon and leakage along the fold after 3 weeks at -13 ° C and at 4 ° C and turning pale yellow at 43 ° C and 49 ° C within 3 weeks.

30 EXAMPLE VX

Components% H20 19.68

Natrosol 1.1

Carbowax 600 20.0 35 Na-saccharin 0.2 8402234> A * -16-

Components% BZC1 0.5 MAG 0.1 MEP 0.76 5 dicalcium phosphate 50.0 CAB (30% A.I.) 6.66 flavor 1.0

This dental cream is prepared according to the procedure of Example I.

The product obtained is on the thick side, but exhibits good foaming and good stability.

EXAMPLE VXX

Components% H20 21.34 15 Natrosol 1.1

Carbowax 600 20.0

Na-saccharin 0.2 BZC1 0.5 MAG 0.1 20 MFP 0.76

Ca2P2071 50.0 CAB (30% A.I.) 5.0 flavoring 1.0 8402234 calcium pyrophosphate 25 This dental cream is prepared according to the procedure of example i.-

The cream obtained is thick and granular, which may be due to the coarseness of the calcium pyrophosphate used as a dental abrasive.

EXAMPLE VIII

Components% H20 17.68

Natrosol. 1.1

Carbowax 600 20.0 -17-

Components%

Na-saccharin 0.2 BZC1 0.5 MSG '0.1 5 MFP 0.76 dicalcium phosphate dihydrate 42.0 anhydrous dicalcium phosphate 10.0 CAB (30% A.I.) 6.66

Flavor "1.0

EXAMPLE IX

Gum components%

Carbowax 600 20.0

Natrosol 1.1

Na-saccharin 0.2 15 MAG 0.1 BZC1 0.5 H 2 O 17.68 MFP 0.76 hydrated A ^ O ^ 42.0 20 calcined A ^ O ^ 10.0 coconut amidopropyl betalne (30% AX «) 6.66 flavoring 1.0 pH 8.3

This product shows complete stability after aging for 9 weeks at room temperature, at 4 ° C, at 37 ° C and at 43 ° C.

EXAMPLES X and XI

Γ 1 - XX

Components%% PEG 600 20.0 20.0 30 Natrosol 1.1 1.3

Na-saccharin 0.3 0.3 hydrated A ^ Q ^ 42.0 42.0 calcined A ^ O ^ 10.0 10.0 CAB (30% Al} 5.0 5.0 35 MFP 0.76 0. 76 8402234> s * * -18- .. X.. XX.

Components%% flavor 1.0 1.0 H20 D.X. 19.27 18.64 BZC1 0.5 0.5 5 Red 40 (1% solution) 0.07 0.07

EXAMPLE XII

Components% sorbitol 70% "28.0

Natrosol 1.1 10 Na-saccharin 0.3 BZC1 0.5 MFP 0.76 hydrated Al. ^ 42.0 calcined Al2 ° 3 10/0 15 CAB (30% AI) 5.0 flavoring 1.0 S20 11, 34 start pH 7.4 after 3 weeks of pH 7.5 after 6 weeks of pH 7.6

This product shows complete stability at -13 ° C and at 4 ° C for 9 weeks, but a slightly wet cap at 42 ° C and at 49 ° C after 3-9 weeks.

In addition to good physical stability of this product, the active substance content (fluorine ions and benzethonium chloride) also remains stable, as can be seen from the practically unchanged pH.

EXAMPLE Kill

Components% H20 '21.14 30 Natrosol 1.3 Sorbitol 20.0

Na-saccharin 0.2 BZC1 0.5 MAG 0.1 35 MFP 0.76 8402 234 --V- -19-

Components% dicalcium phosphate dihydrate 50.0 CAB (30% A.I.) 5.0 flavoring 1.0 5 The resulting cream shows a foam height of 42 and no flavoring after 9 weeks at 49 ° C. This product is completely stable at -13 ° C and at 4 ° C for 9 weeks, but shows traces of a wet cap at 42 ° C and at 49 ° C after 3-9 weeks.

EXAMPLE XIV

10 Components%

Natrosol 1.1

Na-saccharin 0.3 BZC1 0.5 MFR 0.76 15 Carbowax 600 10.0 sorbitol (7Q% £ 10.0 H 2 O '19.34 hydrated Al 2 O ^ 10.0 calcined AljO 4 42.0 20 flavoring' 1.0 CAB (30% AI) 5.0

EXAMPLE XV

Components%

Natrosol 1.1 25 Na saccharin. * 0.3 MFP 0.76 BZ Cl 0.5

Carbowax 600 15.0 sorbitol (70%) 5.0 30 H 2 O 19.34 hydrated Al 2 ° 3 42.0 calcined Al 2 O. 10.0 flavor 1.0 CAB (30% A.I.) 5.0 35 This product, containing 5% sorbitol, exhibits a solubility fluoride availability of 84% at 37 ° C, compared to 8402234

- «* * V

-20- an availability of fluorine of 61% (acceptable level) for a system using only polyethylene as the wetting agent, as in Examples I-XI. This indicates that the presence of sorbitol in amounts as low as 5% (70% A.I.) provides better fluoride stability.

EXAMPLES XVI-XX

components Ex. XVI Ex. XVII Ex, XVIII Ex. XIX Ex. XX

__% ·%%,%% polyethylene glycol 15 ..17 19 10,. 20 10 (Carbowax 600) glycerol 5 3 1 10 0 hydroxyethyl cellulose 1.10 1.10 1.10 1.10 1.10

Na monofluorophosphate 0.76 0.76 0.76 0.76 0.76

Na-saccharin 0.30 0.30 0.30 0.30 0.30 IS benzethonium chloride 0.50 0.50 0.50 0.50 0.50 hydrated Al 2 O 4 2 42 42 42 42 42

calcined IQ IQ IQ IQ IQ

CAB (30% A.I.) 5 5 5 5 5 flavoring t 1 1 1. 1 20 water 19.34 19.34 19.34 19.34 19.34 11 content * 0.07 0.069 0.066 0.077 0.057 *

Chemical stability of the above composition after accelerated aging at 37 ° C for 12 weeks, determined as the percentage Pl content.

All of the above formulations are effective against plaque-related bacteria, while at the same time having improved foaming properties, improved cosmetic stability and chemical stability. The presence of a small amount of glycerol, which need only be 1%, improves the chemical stability of the fluoride in the polyethylene glycol as a wetting agent containing toothpaste to a value above the acceptable fluoride stability in the absence of glycerol (Example XX).

Variations can be made in the above formulations. For example, one can use other pays, such as 8402234m-21-lauraminopropylbe talne7 coconut betalne, and the like instead of the coconut amidopropylbetalne from the examples. Likewise, other polishes and abrasives can be used instead of those from the examples. Furthermore, other fluoride-containing compounds, such as sodium fluoride, potassium fluoride, etc., may be used in place of the sodium monofluorophosphate in the examples.

It will be understood that the above detailed description is given for illustrative purposes only and that variations can be made therein without departing from the spirit of the invention.

8402234

Claims (17)

1. Stable, plaque-resistant toothpaste with improved foaming properties and improved fluoride stability, which contains as essential components an effective amount of a plaque-resistant quaternary ammonium compound, at least 1.5% betaine as a surfactant, a humectant selected from the group consisting of polyethylene glycol, sorbitol and mixtures thereof, a nonionic gelling agent and preferably a fluoride-providing compound in an aqueous carrier containing a dental polishing agent. Toothpaste according to claim 1, characterized in that it contains 1.5-2 wt.% Betaine, based on the preparation. Toothpaste according to claim 2, characterized in that the non-ionic gelling agent is hydroxyethyl cellulose in an amount of 0.5-2% by weight. Toothpaste according to claim 3, characterized in that it contains 20-30 wt.% Polyethylene glycol with a molecular weight of 600. Toothpaste according to claim 3, characterized in that it contains 20-30% by weight of sorbitol. Toothpaste according to claim 1, characterized in that it contains 40-60% by weight of water-insoluble dental polish. Toothpaste according to claim 4, characterized in that the polishing agent is dicalcium phosphate. Toothpaste according to claim 3, characterized in that the anti-plaque agent is 0.01-5% by weight of benzethonium chloride. 9. Toothpaste according to claim 1, characterized in that the fluoride-providing compound constitutes 0.05-2% by weight of the toothpaste. Toothpaste according to claim 9, characterized in that the fluoride-providing compound is sodium monofluorophosphate. Toothpaste according to claim 9, characterized in that the wetting agent comprises 20-30% by weight of a mixture of polyethylene glycol and at least 5% sorbitol. Toothpaste according to claim 9, characterized in that it also contains 1-10% by weight of glycerol as a stabilizer for the fluoride and mixed with the polyethylene glycol as a wetting agent. Toothpaste according to claim 2, characterized in that it is betaine coconut amidopropyl betalne. 8402234 -23- Toothpaste according to claim 1, characterized in that it is free of nonionic and. anionic surfactants. Toothpaste according to claim 6, characterized in that the polishing agent consists of dicalcium phosphate. Toothpaste according to claim 6, characterized in that the polishing agent is aluminum oxide. Toothpaste according to claim 16, characterized in that the polishing agent is a mixture of hydrated alumina and calcined alumina. 8402234 R0 β1 “? + Β4" 000 “R ^ 2 Ο Η it t r„ C-N- (CHJ _ ^ a 8402234