FI58066B - FLUORHALTIGT TANDVAORMEDEL - Google Patents

Description

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Patent and registration authorities' AmBIcm uthgd oeh utUkrHtm publkmd 29-08.80 (32) (33) (31) Requested «ttioHcwt — Bagkrd priority l6.11.73

United Kingdom-Storbritannien (GB) 53330/73 Tot aesthet et etty-Styrkt (71) Beecham Group Limited, Beecham House, Great West Road, Brentford,

Middlesex, Engianti-England (GB) (72) Geoffrey Charles Forward, Redhill, Surrey, Susan Ann Duke, Croydon,

The present invention relates to fluorine-containing dentifrices having an anti-tooth decay effect.

In the last few years, several proposals have been made to include a wide variety of fluoride compounds in oral care compositions, such as dentifrices, to give them an anti-tooth effect. This effect is believed to be due to the ability of the fluorine compound to reduce the solubility of tooth enamel in weakly acidic media, which often occurs in the mouth as a result of the action of bacteria on food. The solubility-reducing effect of tooth enamel is believed to be the result of hydroxyapatite, i. a mineral that forms the bulk of tooth enamel, and the interaction between fluoride to form fluoroapatite. This is because the lowering solubility increases as the fluoride content of hydroxyapatite increases. However, the receipt of fluoride is apparently not the only criterion, because although more fluoride is transferred to the dental hydroxyapatite mineral when sodium fluoride is used instead of sodium monofluorophosphate, sodium monofluorophosphate (at the same level of fluoride addition) results in a greater decrease in tooth enamel solubility.

2 58066

Although sodium fluoride was the first fluoride added to dentifrices, it has achieved relatively little use because it has long been believed that calcium-containing polishes, especially calcium carbonate, often used in dentifrices are incompatible with ionic fluorides such as sodium fluoride. Thus, it was long ago reported that the anti-decay effect of sodium fluoride was inhibited in the presence of calcium carbonate, no doubt because it was believed that these substances would react primarily with each other to form insoluble and inactive calcium fluoride. For this reason, the use of sodium fluoride as an anti-tooth decay agent in oral care compositions has also not gained popularity in recent years, and sodium monofluorophosphate has often been used instead.

It has now surprisingly been found that inactivation of sodium fluoride by calcium carbonate is not absolute but occurs only up to the sodium fluoride threshold. Equally surprisingly, it has now been found that an improved anti-tooth effect is obtained in oral care compositions containing a calcium carbonate polish if these contain a mixture of ion fluoride and ion monofluorophosphate. It has been found that this improved effect is significant when 40-80%> preferably 40-55% of the fluoride content of the mixture is added as ion fluoride and 20-60%, preferably 45-60% is added as ion monofluorophosphate.

The present invention is therefore directed to a fluorine-containing dental care composition comprising a calcium carbonate polish and an ionic monofluorophosphate, and the invention is characterized in that the therapeutic agent further comprises ionic fluoride, wherein the ion fluoride provides 40-80% and the monofluorophosphate 20-60% of the mixture. entirely of fluorine.

Ion fluoride is capable of generating fluoride ions in aqueous solution. Preferably, an alkali metal fluoride such as sodium, potassium or lithium fluoride is used, with the use of sodium fluoride being particularly preferred. Other suitable fluorides include ammonium, tin and zinc fluorides.

The ion monofluorophosphate is also preferably an alkali metal monofluorophosphate. Sodium monofluorophosphate, NaHPO 2 F, is particularly preferred, but the corresponding potassium and / or lithium salts may also be used. The term "monofluorophosphate" as used herein also means monofluoropolyphosphates, such as those of the formulas Na 2 P 2 O 2 F; 3,58066 K „p309F; Na3KP3OgF; (NH 1,) jNaPjOgF and LijjPjOgF.

The total amount of fluoride and monofluorophosphate used depends to some extent on the type of dental care mixture, but its amount must be effective although not toxic. Fluoride and monofluorophosphate are usually present in the oral care composition in an amount sufficient to provide 0.025-0.2% of total fluorine based on the weight of the oral care composition. The preferred total fluoride level is 0.05-0.12% by weight of the mixture. Fluoride and fluorophosphate also preferably make up 40-55% and 45-60% of the total fluorine content, respectively.

The oral care composition of the invention also contains a tooth polish which is or contains calcium carbonate in abrasive form. Such calcium carbonate may be one of the geological forms called aragonite and calcite or a mixture of the two. Preferred forms are synthetically precipitated chalks, in particular water treatment chalk precipitated from hard water with lime. Other calcium carbonates include ground limestone and ground marble or quarried powdered products. The calcium carbonate should preferably have a median diameter of less than 40 microns.

Other tooth polishes may also be present in admixture with calcium carbonate.

For example, water-insoluble sodium or potassium metaphosphates, hydrated or anhydrous dicalcium phosphate, calcium pyrophosphate, zirconium silicate, or mixtures thereof may be used. Particularly useful polishes include various forms of silica, especially the silica mixer gels described in U.S. Patent No. 5,538,230, although these xerogels may have an average particle size diameter of up to 50 microns. The polishing agent or agents may be used in a total amount of 10 to 99% by weight of the mixture according to the invention. These compositions are preferably toothpastes with 20-75% tooth polish, although they may be in the form of powders containing 70-99% polish. If desired, the compositions according to the invention can be prepared as fibrous or striped dental compositions, in particular with an opaque core or stripes (containing a calcium carbonate polish) inside or on a transparent gel. The gel may contain one or more fluorine-containing ingredients, and in these cases the mixture is taken as a whole in determining the proportions of the ingredients as described above.

The oral care compositions of the invention usually also contain surfactants, gelling agents and other additives such as flavors and colorants.

The surfactant is usually a water-soluble non-soap or synthetic organic detergent. Suitable surfactants include the use of higher alkyl fatty acid monoglyceride monosulfates (e.g., sodium-hydrogenated coconut fatty acid monoglyceride monosulfate)> higher alkyl sulfates (e.g., sodium lauryl sulfate), alkyl aliphatic (about sodium lauryl sulfate), alkyl alkyl sulfonate (e.g., sodium aryl sulfonate), e.g. Saturated higher aliphatic acylamides of lower aliphatic aminocarboxylic acids having 12 to 16 carbon atoms in the acyl radical and having an amino acid moiety derived from low aliphatic saturated monoaminocarboxylic acids having 3 to 6 carbon atoms, glycine, such as glycine can also be used. -aminopropanoic acid and valine fatty acid amides, in particular N-lauroyl, myristoyl and palmitoyl sarcosinate compounds. Conventional nonionic cleaning agents may also be added if desired.

Surfactants are usually present in an amount of 0.05-10%, preferably 0.5-5% by weight of the mixture.

Tooth powders and toothpastes are prepared in a conventional manner. The ingredients can thus be mixed in the dry state or as slurries or solutions.

Liquids in toothpaste are usually water, glycerol, sorbitol or propylene glycol, as well as suitable mixtures thereof. It is usually preferred to use a mixture of water and glycerol, preferably in combination with sorbitol. The total amount of liquid is usually 20-75 wt / l. the preparation. Gelling agents such as natural or synthetic gums or gums such as Irish moss, gum tragacanth, sodium carboxymethylcellulose, polyvinylpyrrolidone or starch are also preferably used in toothpastes. Irish moss and sodium carboxymethylcellulose are preferred gelling agents. The concentration is usually up to 10% and preferably 0.5-5% by weight. the preparation.

5 58066

The pH of the aqueous slurry of toothpaste or tooth powder is substantially neutral, such as about 6-8. If desired, a small amount of acid, such as citric acid or a basic substance, may be added.

Other substances may be added, such as soluble saccharin, spice oils (e.g. peppermint.1 grains, winter peppermint oils), chloroform, colorants or bleaches (e.g. titanium dioxide), preservatives (e.g. sodium benzoate), emulsifiers (e.g. e.g. citric acid), silicones, alcohols, menthol, chlorophyll compounds (e.g. sodium copper chlorophyllin) and antibacterial agents (e.g. chlorhexidine).

The compositions of the invention may also be in the form of other oral care compositions, the essential fluorine and calcium carbonate ingredients may be added, for example, to suspension-type mouthwashes or mixtures which are chewed by the user, e.g. chewing gum, tablets, lozenges and tablets. These mixtures contain conventional bases together with suitable flavors and sweeteners and can be formed in a conventional manner.

The mixtures according to the invention are described in more detail below by means of examples:

Contents Example 12 3 4 (% by weight)

Glycerol 25.0 12.5 25.0 12.5

Sorbitol ($ 70 solution) - 12.5 - 12.5

Sodium carboxymethylcellulose

Sodium fluoride 0.17 0.17 0.17 0.17

Sodium monofluorophosphate 0.17 0.17 0.17 0.17

Sodium laurilsulfate

Sodium saccharin 0.2 0.2 0.2 0.2

Calcium carbonate 45.0 45.0 45.0 45.0

Calcium silicate 0.20 0.20 0.20 0.20

Flavor 1.00 1.00 5.0 5.0

Water increase increase increase increase 100% 100% 100% 100%

The efficacy of the invention is illustrated by the following examples, which have been performed on the rate of degradation of hydroxyapatite. This is a suitable model because it is responsible for the mineral mixture of tooth enamel and decomposes under the influence of dilute acids formed from orally decomposing food.

The sheets were made of hydroxyapatite by mixing it with 10% polyethylene to improve the bonding properties, after which the individual sheets were formed by pressing with 5000 kg for 90 sec. and then heating at 110 ° C. Separate plates were treated with dental care slurry for a water test (water dental care = 3: 1) for one minute. The dental composition was stored for 2 weeks after its preparation and was the general composition of Example 3, but in which the ratio of sodium fluoride to sodium monofluorophosphate was varied while maintaining the total fluorine concentration in the dental agent at a constant level of 1000 ppm (0.1 wt% of the total composition).

The treated hydroxyapatite sheets were each placed under rotating propel in acetic acid buffer solution at pH 4.65 and 37 ° C for one hour. The percentage decrease in solubility compared to treatment with identical fluoride-free dental agent11a was determined in each case. The results are shown in Table I below.

Table I

NaF content F - concentration F content Reduction of solubility% w / w of total NaF (ppm) NaHPO 2 F reduction from fluorine (%) 0 - 1000 16.7 3.1 100 900 21.4 6.7 200 800 26.2 22.6 500 500 32.0 30.4 600 400 32.0 46.5 750 250 31.0 100 1000 - 23.8

The results show that when 40-80% of the total fluorine content is obtained with alkali metal fluoride, the solubility-reducing effect on hydroxyapatite is improved as compared with the fact that all the fluorine is derived from either alkali metal fluoride or alkali metal monofluorophosphate. This effect is very pronounced when 50.70% of the total fluorine content is obtained with alkali metal fluoride.

In order to show that the inhibition of the anti-spreading effect caused by the initial reaction of chalk and ion fluoride can be avoided by adding small amounts of sodium fluoride to sodium monofluorophosphate, the experiments below were performed as described above using the fluoride / monofluoride mixture of Example 3. The results obtained using an aqueous slurry of the mixture (1: 3) 2 minutes after preparation (column B) have been compared with those resulting from the action of the aqueous solution of the corresponding fluoride / monofluorophosphate content (column A).

Table II

NaF concentration of Na-monofluoro- Total- Solution A Slurry B

phosphate concentrate fluoride percentage percentage concentration alkaline decrease decrease 5.0x10 ~ 2 5x10-2 36.0 29.5 Ι, ΙχΙΟ-3 5, 1x10-2 5.2x10-2 54.1 46, 5 Ι, ΟχΙΟ-2 4, lxl0 ~ 2 5, lxl0-2 50.9 47.1 l, 6xl0 ~ 2 3.5xl0-2 5, lxl0-2 52.6 53.6

The above results show that by maintaining the total fluoride level at 5.1 x 10 M or 1000 ppm in toothpaste, but by increasing the proportion of sodium fluoride in the sodium fluoride / sodium monofluorophosphate mixture, the initial reaction of fluoride with chalk can be avoided. This is evident from the convergence of the activities of columns A and B, which shows that as the proportion of fluoride in the mixture increases, the inactivation of fluoride by lime (present only in the slurry) decreases.

Claims (3)

8 58066 1. Fluorocarbon compounds in the form of calcium carbonate polymers and ionic monofluorophosphates, in turn, at the same time, in the form of ionic fluorides, colors of ionic fluoride and 20% of the total fluorine composition of the composition %. A fluorine-containing dentifrice comprising a calcium carbonate polish and an ionic monofluorophosphate, further comprising ionic fluoride, wherein the ion fluoride provides 40-80% and the monofluorophosphate 20-60% of the total fluorine of the mixture. 2. Tandvärdsmedel enligt patentkravet 1, känneteck-n a tärav, att den ioniska fluoridens andel compositional total fluorine up to 40-55% and monofluorophosphates up to 45-60%. Dental care product according to Claim 1, characterized in that the proportion of ion fluoride is 40 to 65% and that of monofluorophosphate is 45 to 60% of the total fluorine in the mixture. Dental care product according to Claim 1 or 2, characterized in that the total fluorine content is 0.025 to 0.2% by weight of the mixture. Dental care product according to Claim 3, characterized in that the total fluorine content is 0.05 to 0.12% by weight of the mixture. Dental care product according to one of the preceding claims, characterized in that the calcium carbonate polishing agent is present in the opaque core or in stripes which are enclosed in a transparent gel containing at least one of the fluorine-containing ingredients or which are at least partially on the gel surface. 3. Tandvärdsmedel enligt patentkravet 1 eller 2, k il n n e -