FI81718C - ADSTRINGERANDE TANDPASTA. - Google Patents

Description

1 81718

This invention relates to a toothpaste containing a water-soluble zinc salt which has a constricting effect on the oral mucosa and gingival tissues during brushing of teeth, and optionally an alkali metal monofluorophosphate or gelling agent or both. Each of the components is compatible and substantially unreactive with the crystalline silica gel polish.

The reducing effect of zinc ions produced by water-soluble zinc salts, which promotes and improves oral hygiene, has long been known. However, there have been limitations to the use of zinc in the toothpaste mixture because zinc ions can easily react with typical toothpaste components, causing a significant loss of zinc ion availability.

Similarly, monofluorophosphate ion has long been known to promote oral hygiene and reduce the formation of holes by releasing fluoride, but its effectiveness has also been reduced by incompatibility with certain toothpaste components, such as water-soluble sulfur compounds.

Nonionic gelling agents such as hydroxyethylcellulose have been used primarily in toothpastes when a water-soluble zinc salt is used. However, when alkali metal carboxymethylcellulose is used in the presence of zinc ions, a reaction takes place which removes zinc ions, leading to possible gel breakage and phase separation. U.S. Patent 3,728,446 describes an in situ reaction between zinc ions and alkali metal carboxymethylcellulose to form. visible particles are formed.

In addition, gel-type toothpastes that provide zinc shrinkage have been limited due to the incompatibility of zinc ions ** with various silicon-containing polishes. Such silicon-containing polishes, such as 2,81718 silica xerogels, have an average particle size of between about 2-20 microns and a surface area of at least about 300 m 2 / g, typically about 300-370 m 2 / g or about 600-800 m 2 / g, and described in U.S. Patent No. 3,538,230, an in situ reaction with a zinc ion occurs so that much of the theoretically available zinc is lost in a physicochemical manner such as by absorption.

Similar compatibility problems would occur when a water-soluble zinc salt is present in combination with toothpaste salt polishes, especially calcium salts such as dicalcium phosphate or calcium carbonate. In fact, it has been speculated that it would be difficult to use a water-soluble zinc salt and maintain a high level of zinc ion availability in such conventional toothpastes.

Compatibility is also a problem when alkali metal monofluorophosphate is used with such a silicon-containing polish in a toothpaste containing a water-soluble zinc salt.

• This has made it difficult to produce toothpastes containing a silicon-containing polish and certain amounts of zinc ions with or without alkali metal monofluorophosphate or alkali metal carboxymethylcellulose, or both, which toothpaste would remain effective in providing zinc-reducing properties and fluoride holes. In particular, gel-type toothpastes which provide zinc contraction with or without the hole-inhibiting effect of fluoride have not been satisfactorily obtained due to the incompatibility of zinc ions with monofluorophosphate and alkali metal carboxymethylcellulose in the presence of various silicon-containing polishes.

The present invention utilizes the precipitated amorphous silica gel described in published GB Patent Application No. 2,038,303 A and U.S. Patent No. 4,528,181. U.S. Patent No. 4,528,181 discloses toothpaste; containing 3,81718 of a precipitated amorphous silica gel in which a dual source of fluoride containing sodium fluoride and sodium monofluorophosphate and a source of calcium are stabilized with an alkali metal pyrite to improve fluoride stability.

Such precipitated, amorphous silica gel material is available from Grace G.m.b.H. as products such as Syloblanc 81, Syloblanc 81 C, and Syloblanc 82. They are clearly different from the types of xerogels that W.R. Grace et Co. has been sold under the tradename Syloid and is specifically described in U.S. Patent No. 3,538,230. Indeed, although some of the products described by Grace G.m.b.H. sells under the trade name Syloblanc, was previously and is equally available under the trade name Syloid, none of the products Syloblanc 81, Syloblanc 81C or Syloblanc 82 have ever been available under the trade name Syloid. Of particular note is that the silica gel grades used in this invention are less abrasive as the surface area increases, while the silica xerogel grades described in U.S. Patent No. 3,538,230 are generally more abrasive as their surface area increases.

* -. Given the poor compatibility of most polishes with zinc, including the polishes of U.S. Patent No. 3,538,230, it was quite unexpected that a particular silicon-containing polish would not have such a problem and, in addition, in the presence of such a polish, the reaction "*" between zinc ions and alkali metal carboxymethylcellulose is substantially reduced, moreover, it was unexpected that in the presence of such a particular silicon-containing polishing material and zinc ions, alkali metal monofluorophosphate remains stable and compatible with The persistence of high levels of shrinkage is achieved by the use of such a specified silicon-containing polish, whether or not alkali · *: metal carboxymethylcellulose is used or monofluoro- •: phosphate fluoride is used. to obtain large amounts of ions, which are also preserved.

4,81718 It is an advantage of the present invention to provide a zinc ion-containing astringent toothpaste which may effectively contain monofluorophosphate or an alkali metal carboxymethylcellulose gelling agent or both.

A further advantage of the present invention is to provide a zinc ion-containing astringent gel-type toothpaste which may optionally contain a monofluorophosphate or an alkali metal carboxymethylcellulose gelling agent or both.

Other advantages of the invention will become apparent upon consideration of the following specification.

According to certain aspects of the present invention, it relates to a contractile toothpaste comprising about 20 to 90% by weight of a liquid carrier containing at least about 3% by weight of water of said toothpaste, about 0.05 to 5% by weight of a gelling agent. and about 10-50% by weight of a polishing agent comprising a synthetic precipitated amorphous silica gel having an average particle size of 1-30 microns and 2: a) a surface area of 1-600 m / g,: ob) a pore volume of 0.05- 0.5 cm / g, c) input surface area (m / g) times volume (cm / g) less than or equal to 240, d) calculated pore volume 1.5-2.5 nm, and e) water content is less than 25% by weight; and up to about 5% of a water-soluble zinc salt that provides at least about 50 ppm of zinc ions to said toothpaste. In addition, said toothpaste may contain alkali metal carboxymethylcellulose as a gelling agent and / or may contain alkali metal monofluorophosphate in an amount to provide about 0.01-1% fluoride.

As mentioned above, synthetic precipitated silica is of the type described in published GB Patent Application: 2,038,303 A and U.S. Patent No. 4,528,181. The special grades of silica material described therein are suitable for use in the practice of this invention. Still special qualities,

II

5,81718, which are particularly preferred, are described in Grace G.m.b.H., Norderstadt, Federal Republic of Germany, October 1980, under the names Syloblanc 81 and Syloblanc 82, which have the following typical physical and chemical properties.

Syloblanc 81 Syloblanc 82

Medium particle size (according to Coulter) 4 μm Wet sieve residue (42 μm)% 0.02 0.02 pH (5% aqueous suspension) 3 6

Area (B.E.T.) m2 / g 400 480

Loss on drying% 7 4

SiO 2 content (of combusted material)% 96 99

Refractive index 1.46 1.46

In a variant of Syloblanc 81, available as Syloblanc 81C, the pH (50% aqueous suspension) is about 6-8.

Syloblanc 81 and especially 81C are very effective in polishing tooth surfaces. Syloblanc 82 has a lower polishing power, but can be used by consumers who ···. want such a weaker effect. Likewise, grades of silica material can be added to the blends to provide proper polishing properties. It is noteworthy that toothpastes are compatible with unlined aluminum toothpaste tubes even without the pyrite salt required in the invention described in U.S. Patent No. 4,528,181. The precipitated amorphous silica gel is used in an amount of about 10-50% by weight, typically about 10-40 * of the gel toothpaste.

Aqueous slurries of silica materials (e.g., about 5-20% slurries) typically have a pH of about 2-9. Since the pH of the toothpaste mixture of the present invention is preferably (measured from a 10% aqueous slurry) at least about 5.5, e.g., about 5.5-7.5, the pH of the toothpaste can be adjusted with a suitable material such as sodium hydroxide, etc. .

Water-soluble zinc salt is present in toothpaste up to approx.

6,81718 in an amount of 5% by weight, preferably more than 0.01-3% and most preferably about 0.1-2%. The water-soluble zinc salts of this invention are at least about 10% by weight, and preferably at least 20% by weight, soluble in water. At least about 50 ppm zinc ions, preferably at least about 50 ppm, are provided in the toothpaste.

750 ppm and most preferably at least about 1000 ppm zinc ions. Suitable zinc salts include zinc sulfate, zinc chloride, zinc bromide, zinc iodide, zinc nitrate and zinc acetate. In the case of zinc chloride, 0.01% by weight provides about 50 ppm of zinc ions and 0.2% by weight provides about 1000 ppm of zinc ions. 0.48% by weight of zinc sulfate heptahydrate provides about 1000 ppm of zinc ions. In addition, zinc oxide, a sparingly soluble (less than 0.0005%) zinc compound, can also be added to prevent the pH from falling in the product. This acts as a buffer system and improves pH stability and compatibility in unlined aluminum tubes. It may be present in an amount of about 0.005 to 0.5% by weight.

Toothpaste contains a liquid carrier with approx.

3-60% by weight of water, typically mixed with at least one wetting agent. The liquid phase constitutes about 20-90% by weight ·; toothpaste and generally contains about 25-80% liquid, typically about 3-50% by weight, preferably about 3-10% water in a substantially clear gel toothpaste or gel toothpaste that would be substantially clear in the absence of a opacifying agent such as titanium dioxide, and about 11-50% water in a opaque to cloudy gel toothpaste together with about 10-90% by weight, preferably about 15-80% wetting agent. Typical wetting agents include glycerin, sorbitol (e.g.

70% solution), maltitol, polyethylene glycol having a molecular weight of about 400-600, propylene glycol and mixtures thereof.

:: Toothpaste also contains a gelling or binding agent as a solid carrier, although this may be a small amount, as synthetic, precipitated silica can cause the toothpaste to thicken or gel to a cream or paste consistency. Alkali metal carboxymethylcellulose is preferred in accordance with one aspect of this invention, but other gelling or

II

7,81718 binders that may be present include hydroxyethylcellulose, hydroxypropylcellulose, xanthan, Irish moss, iota-carrageenan, gum tragacanth, polyvinylpyrrolidone, starch, and mixtures thereof. Such gelling agents may be used in an amount of about 0.05-5% by weight, typically about 0.05-2% and preferably about 0.1-1.5%. The use of sodium carboxymethylcellulose is particularly preferred.

An alkali metal such as sodium monofluorophosphate and potassium monofluorophosphate are compatible with toothpaste. Sodium monofluorophosphate is particularly preferred. In the past, when attempts have been made to mix toothpaste using a liquid carrier, gelling agent, polish, zinc salt and sodium monofluorophosphate, significant amounts of zinc ions and fluoride ions have been lost due to insolubility. Surprisingly, when a synthetic, precipitated, amorphous silica gel is defined as a polishing agent, large amounts of fluorine ions and a considerable amount of zinc ion retention are bound. Such high levels of fluoride ion retention are not achieved when a simple fluoride such as sodium fluoride is used.

The purity of commercially available sodium fluorophosphate Na2PO.jF can vary considerably. It can be used in any suitable purity, provided that any impurities do not substantially adversely affect the desired properties. In general, it is desirable to have a purity of at least 80% and preferably at least 90% by weight of sodium monofluorophosphate with the remainder being mainly impurities or by-products of the preparation such as sodium fluoride and water-soluble sodium phosphate salt. In other words, the total fluoride content of the sodium monofluorophosphate used should be more than 12%, preferably 12.7%, the free sodium fluoride content not more than 1.5% and preferably not more than 1.2%; and a sodium monofluorophosphate content of at least 12% and preferably at least 12.1% all calculated as fluoride. The alkali metal monofluorophosphate is present in an amount to provide about 0.01 to 1% by weight of fluoride, preferably about 0.1%. Thus' ·; sodium monophosphate may be present in an amount of about 0.076-7.6%, 8,81718, preferably 0.76%, corresponding to about 100-10,000 ppm fluoride, preferably about 1000 ppm.

Any surfactant or detergent material can be included in the tap paste compositions. It is desirable that such compatible materials provide additional detergent foaming and antibacterial properties depending on the particular type of surfactant material and are selected accordingly. These detergents are usually water-soluble compounds and can be anionic, non-ionic, amphoteric or cationic in structure. It is usually preferred to use water-soluble non-soap-based or synthetic organic detergents. Suitable detergent materials are known and include, for example, water-soluble salts of a higher fatty acid and a monoglyceride monosulphate detergent (e.g. sodium coconut fatty acid monoglyceride monosulphate), higher alkyl sulphate disodium sulphonate sulfone (e.g. sodium lauryl sulphate).

Other surfactants include substantially saturated higher aliphatic acylamides of lower aliphatic aminocarboxylic acid compounds, such as those having 12 to 16 carbons in the acyl radical. The amino acid moiety is generally derived from lower aliphatic, saturated monoaminocarboxylic acid compounds. Suitable compounds include fatty acid amides of glycine, sarcosine, alanine, 3-aminopropanoic acid and valine having about 12-16 carbons in the aryl group. However, in order to achieve optimal effects, it is preferable to use N-lauroyl, myristoyl and palmitoyl sarcoside compounds.

The amide compounds can be used in the form of the free acid or, preferably, as water-soluble salts thereof, such as alkali metal, ammonium, amine and alkylolamine salts. Specific examples of these include sodium and potassium N-lauroyl, myristoyl and palmitoyl sarcosides, ammonium and ethanolamine N-lauroyl glycidide and alanine. For the sake of simplicity, this

II

9,81718, the term "aminocarboxylic acid compound", "sarcoside", etc., refers to compounds having a free carboxyl group or water-soluble carboxylate salts.

Such materials are used in pure or substantially pure form. They should be as free as possible from soap or a similar higher fatty acid material that tends to reduce the activity of these compounds. In ordinary practice, the amount of such higher fatty acid material is less than 15% by weight of the amide and insufficient to adversely affect it, and preferably less than about 10% of said amide material.

Other particularly suitable surfactants include nonionic agents such as condensates of sorbitan monostearate with approximately 20 moles of ethylene oxide, condensates of ethylene oxide with propylene oxide, propylene glycol ("Pluronic" materials) and amphoteric agents such as long chain amide (such as long chain). condensates of alkaline amine derivatives available under the trade name ·. ; Miranol C2M. Cationic surfactant and bactericidal compounds such as diisobutylphenoxyethoxyethyldimethylbenzylammonium chloride, benzyldimethylstearylammonium chloride, tertiary amines of all types containing one fatty alkyl group (12-18 carbon atoms) and two (poly) atoms about 2-50 ethaneoxy groups per molecule) and their salts with acids, and compounds having the structure (ch2ch2o) xh (ch2ch2o) zh RN-CH2CH2CH2N / ^ /

;; (Cn2cH2o) yH

!! wherein R represents a fatty alkyl group having about 12 to 18 carbon atoms and x, y and z are a total of 3 or more, and their salts with mineral or organic acids can also be used. It is preferred to use about 0.05-5% by weight of the above surfactants in the oral preparation of this invention.

10 81718

Various other materials can be incorporated into the toothpastes of this invention. Examples are opacifiers, preservatives, stabilizers, silicones, chlorophyll compounds and ammonia-containing materials such as urea, diammonium phosphate and mixtures thereof. These excipients are added to these mixtures in amounts that do not substantially adversely affect the desired properties and characteristics and are suitably selected and used in conventional amounts.

For some purposes, it may be desirable to include bactericidal agents in the compositions of this invention. Typical bactericidal agents that can be used are approx.

0.01-5%, and preferably about 0.05-1.0% by weight of the toothpaste mixture, are cetylpyridinium chloride, benzethonium chloride and: N, N- (chlorobenzyl) -N- (2, 4-dichlorobenzyl) biguanide; p-kloorifenyylibiguanidi; 4-klooribentshydryylibiguanidi; 4-chlorobenzhydryl guanyl urea; N-B-lauroksipropyyli-N? -P-klooribentsyylibiguanidi; 1,6-di-p-chlorophenylbiguanidohexane; 1- (lauryldimethylammonium) -8- (p-chlorobenzyldimethylammonium) -5,6-dichloro-2-guanidobenzimidazole; 15 N-p-chlorophenyl-N-lauryl biguanide; 5-Amino-1,3-bis- (2-ethylhexyl) -5-methylhexahydropyrimidine, and non-toxic addition salts thereof.

Any suitable spices or sweeteners may be used to blend the spice into the compositions of this invention. Examples of suitable spice ingredients are spice oils, e.g. mint, peppermint, winter, sassafras, cloves, sage, eucalyptus, marjoram, cinnamon, lemon and orange oils, and methyl salicylate. Suitable sweeteners include sucrose, lactose, malfose, sirbitol, sodium cyclamate, sodium saccharin, the dipeptides of U.S. Patent 3,939,261, and the oxathiazine salts of U.S. Patent 3,932,606. Suitable spices and sweeteners may together form about 0.01-5% or more of the mixture.

Il 11 81718

The toothpaste is packaged in a container from which it can be easily extruded, such as a differential pressure or mechanically operated toothpaste dispenser or a lined or unlined aluminum tube or a wax lined lead tube or plastic tube which may be laminated with aluminum. Rheological properties are highly desirable when using a mechanically operated manifold of the type described in published GB patent application 2,070,695 A. This manifold includes a manifold, drive member, center rod, piston and manual drive adjustment.

The differential pressure distribution tank can be of the aerosol or vacuum type. Suitable differential pressure dispensers are those that include a collapsible product-containing bag housed in a rigid container containing washing liquid. In such distribution tanks, opening the valve allows the mere release of the product as the liquid-impermeable bag separates the propellant from the product. Dispensers of this type are described in U.S. Patents 3,828,977 and 3,838,796. These are so-called Sepro dispensers.

* ·] The so-called Exxel and Enviro Spray tanks also use pressure.

Yet another type of dispensing device is a closure piston container described in U.S. Patent 4,171,757.

Toothpaste is typically prepared by premixing a gelling agent with liquid carrier components, e.g. water and a wetting agent, which may also contain additives such as monofluorophosphate and / or a sweetener, and mixing it with a synthetic, precipitated silica gel and zinc salt. Other ingredients used may then be added.

Although the invention has been described with reference to typical examples, it will be apparent to one skilled in the art that various modifications may be made therein which fall within its scope. All amounts are by weight unless otherwise indicated.

Example 1

The following clouded gel toothpastes are prepared and placed in unlined aluminum tubes.

Some of

A B

Glycerin 25,000 25,000

Sorbitol (70%) 47,050 43,830

Xanthan 0.260 0.260

Sodium saccharin 0.170 0.170

Titanium dioxide 1,000 1,000

Water 3,000 3,000

Zinc sulphate heptahydrate

Precipitated amorphous silica gel * 20,000

Silica mixer gel ** - 17,000

Silica Aerogel *** - 6,500

Sodium hydroxide (40%) 0.280 - Sodium lauryl sulphate 1.760 1.760

Spice 1,000 1,000 pH (20% slurry) 5.9 6.1 * Syloblanc 81, available from Grace G.m.b.H .; ** Syloid ALI, available from Grace G.m.b.H., formerly Syloid 63; *** Syloid 244 thickener, available from W.R. Grace & Co.

The theoretical amount of soluble zinc ions in each gel toothpaste is 1000 ppm or 0.100%.

Toothpaste A does not require the presence of a thickener material to provide the desired gel character. Its consistency is approximately the same as that of toothpaste B.

Both toothpastes are aged at room temperature and 43 ° C. Both usually retain the corresponding desired ones

II

13 81718 consistencies. The percentages of zinc ions of the available particles in each toothpaste are determined to be as follows:% Zn + ^ at room temperature _4 at 3 ° C_

At the beginning 1 month 3 months 2 Weeks. 1 month 3 months

Toothpaste A 0.084 0.080 0.050 0.091 0.070 0.050

Toothpaste B 0.054 0.042 0.005 0.049 0.048 0.005

Toothpaste A containing Syloblanc 81 retains excellent levels of soluble zinc ions compared to the otherwise generally similar toothpaste B containing Syloblanc AL1.

Similar excellent levels of soluble zinc ion retention are achieved when Syloblanc 81 of toothpaste A is replaced with Syloblanc 82 and a 1: 1 mixture of Syloblanc 81 and 82 in each, reducing or eliminating the amounts of sodium hydroxide and adding 70% sorbol. ).

Also, excellent soluble zinc ions are achieved. . shelf levels when Syloblanc 81 is replaced by Syloblanc 81 C, omitting sodium hydroxide and adding it to sorbitol (70%).

0.25 parts of zinc oxide is added to each toothpaste A. *; and B in place of the corresponding amounts of sorbitol, whereby the pH stabilizes during aging and the compatibility with unlined aluminum tubes is improved for a long time.

Example 2

The following opaque gel toothpastes are made and placed in unlined aluminum tubes:

Some of

A B

Glycerin 25,000 25,000

Sorbitol (70%) 47,050 43,550; Sodium carboxymethylcellulose

Sodium saccharin 0.170 0.170

Titanium dioxide 1,000 1,000

Water 3,000 3,000 14,81718

Part A B ·

Zinc sulphate heptahydrate

Precipitated amorphous silica gel * 20,000 Silica mixer gel ** - 17,000

Silica Aerogel *** - 6,500

Sodium hydroxide (40%) 0.280 0.280

Sodium lauryl sulphate

Spice 1,000 1,000 pH (20% slurry) 5.9 6.1 *? **; *** - see Example 1.

The theoretical amount of soluble zinc ions in each gel toothpaste is 1000 ppm or 0.100%.

Toothpaste A does not require the presence of a thickening material to initially achieve the desired gel character.

Both toothpastes are aged at room temperature and 43 ° C. Both generally maintain the corresponding desired • consistencies. The percentage of soluble zinc ions available in each toothpaste is determined to be as follows: + 2% Zn at room temperature _43 ° C_

At the beginning 1 month 3 months 2 Weeks. 1 month 3 months

Toothpaste A 0.080 0.079 0.050 0.082 0.069 0.050

Toothpaste B 0.052 0.039 0.002 0.050 0.060 0.002

Toothpaste A, which contains Syloblanc 81, retains its gel character and excellent levels of soluble zinc ions compared to the otherwise generally similar toothpaste B, which contains Syloid 63. When the conventional 7 MXF grade of sodium carboxymethylcellulose is used, phase separation and breakage occurs in the presence of Syloid 63 polish, which does not occur as much when using Syloblanc 81.

It is noted that the two-week and one-month result levels of toothpaste B at 43 ° C reflect variations in routine testing.

is 81718

Similar excellent retention levels of soluble zinc ions are achieved when Syloblanc 81 toothpaste A is replaced with Syloblanc 82 and a 1: 1 mixture of Syloblanc 81 and 82 in each, reducing or eliminating the amounts of sodium hydroxide and adding 70 %) -

Likewise, excellent levels of solubility of soluble zinc ions are achieved when Syloblanc 81 is replaced by Syloblanc 81C, omitting sodium hydroxide and adding it to sorbitol (70%).

0.25 parts of zinc oxide is added to each toothpaste A and B in place of the corresponding amounts of sorbitol, whereby the pH stabilizes during aging and the compatibility with uncoated aluminum tubes is improved for a long time.

Example 3

Prepare the following opaque gel toothpastes and place them in unlined aluminum tubes:

Some of

A B

... * Glycerin 25,000 25,000

Sorbitol (70%) 46,340 46,880 ·: · Sodium carboxymethylcellulose 0.190 0.190

Sodium saccharin 0.170 0.170

Titanium dioxide 1,000 1,000

Water 3,000 3,000

Zinc sulphate heptahydrate 0.480 0, '480

Sodium monofluorophosphate 0.760

Sodium fluoride - 0.220

Precipitated amorphous silica gel * 20,000 20,000

Sodium hydroxide (40%) 0.300 0.300

Sodium lauryl sulphate

Spices 1,000 1,000; pH (20% pour) 6.0 5.9: * Ks. Example 1.

ie 81718

The theoretical amounts of soluble zinc ions and fluoride in each gel toothpaste are 1000 ppm or 0.100% separately for zinc ions and fluoride.

Both toothpastes are aged at room temperature and 43 ° C. The percentages of soluble zinc ions and fluoride available in each toothpaste are determined to be as follows at room temperature:% Zn + ^; % monofluorophosphate as fluoride (toothpaste A); % fluoride (toothpaste B) __

Room temperature At the beginning 1 month

Toothpaste A 0.66 Zn 0.066 Zn

0.096 F 0.097 F

Toothpaste B 0.070 Zn 0.051 Zn

0.100 F 0.048 F

Toothpaste A, which contains sodium monofluorophosphate, provides substantial retention of both zinc ions and fluoride compared to toothpaste B, which contains sodium fluoride. 4 At 3 ° C, gas is formed in an unlined aluminum tube containing toothpaste B, while an unlined aluminum tube containing toothpaste A remains stable.

The retention of zinc ions and fluoride is poor when the Ksero gel Syloid 63 available from W.R. Grace & Co., replaces Syloblanc 81.

Results similar to those determined with toothpaste A are obtained when calcium monofluorophosphate replaces sodium monofluorophosphate.

Similar excellent levels of solubility in soluble zinc ions and fluoride are achieved when Syloblanc 81 toothpaste A is replaced with Syloblanc 82 and a 1: 1 mixture of Syloblanc 81 and 82 in each, reducing or eliminating the amounts of sodium hydroxide and adding sorb to them. (70%).

Il 17 81718

Likewise, excellent levels of solubility of soluble zinc ions and fluoride are achieved when Syloblanc 81 is replaced by Sylo-Blanc 81C, omitting sodium hydroxide and adding it to sorbitol (70%).

0.25 parts of zinc oxide is added to each toothpaste A and B in place of the corresponding amounts of sorbitol, whereby the pH is stabilized during aging and the compatibility with uncoated aluminum tubes is improved for a long time.

Example 4

The following stable, visually clear gel toothpastes are made and placed in unlined aluminum tubes:

Some of

A B C D

Glycerin 25,000 25,000 25,000 25,000

Sorbitol (70%) 48.310 48.590 48.590 48.450

Xanthan 0.260 0.260 0.260 0.260

Sodium saccharin 0.170 0.170 0.170 0.170

Water 3,000 3,000 3,000 3,000

Zinc chloride 0.020 0.020 0.020 0.020

Syloblanc 81 20,000 - - 10,000

Syloblanc 81C - 20,000

Syloblanc 82 - 20,000 10,000

Sodium hydroxide (40%) 0.280 - 0.140

Sodium lauryl sulphate 1,760 1,760 1,760 1,760

Spices 1,000 1,000 1,000 1,000

Blue color solution (1%) 0.200 0.200 0.2Q0 0.200

Example 5

The following stable, visually clear gel toothpastes are prepared and placed in uncoated aluminum tubes: 18 81718

Some of

A B C 'D

Glycerin 25,000 25,000 25,000 25,000

Sorbitol (70%) 48.310 48.590 48.590 48.450

Sodium carboxymethylcellulose 0.260 0.260 0.260 0.260

Sodium saccharin 0.170 0.170 0.170 0.170

Water 3,000 3,000 3,000 3,000

Zinc chloride 0.020 0.020 0.020 0.020

Syloblanc 81 20,000 - - 10,000

Syloblanc 81C - 20,000

Syloblanc 82 - - 20,000 10,000

Sodium hydroxide (40%) 0.280 - 0.140

Sodium lauryl sulphate 1,760 1,760 1,760 1,760

Spices 1,000 1,000 1,000 1,000

Blue color solution (1%)

Similar stability is achieved when potassium carboxymethylcellulose replaces sodium carboxymethylcellulose.

Example 6

The following stable, visually clear gel-toothpastes are prepared and placed in unlined aluminum tubes:

Some of

A B C D

Glycerin 25,000 25,000 25,000 25,000

Sorbitol (70%) 47,550 47,830 47,830 47,690

Xanthan 0.260 0.260 0.260 0.260

Sodium saccharin 0.170 0.170 0.170 '0.170

Water 3,000 3,000 3,000 3,000

Sodium monofluorophosphate 0.760 0.760 0.760 0.760

Zinc chloride 0.020 0.020 0.020 0.020

Syloblanc 81 20,000 - - 10,000

Syloblanc 81C - 20,000

Syloblanc 82 - - 20,000 10,000

Sodium hydroxide (40%) 0.280 - 0.140

Sodium lauryl sulphate 1,760 1,760 1,760 1,760

Spices 1,000 1,000 1,000 1,000

Blue color solution (1%) 0.200 0.200 0.200 0.200 19 81718

Example 7

The following matte and opaque gel tooth pastes are prepared and packaged in mechanically operated dispensing containers.

Part A B C _D_

Glycerin 25,000 25,000 25,000 25,000

Sorbitol (70%) 24,970 24,870 24,870 24,870

Iotacarragen 0.700 0.700 0.700 0.700

Sodium saccharin 0.170 0.170 0.170 0.170

Water 25,000 25,000 25,000 25,000

Zinc bromide dihydrate 0.400 -

Zinc iodide - 0.500

Zinc nitrate hexahydrate

Zinc acetate dihydrate - 0.500

Syloblanc 81C 21,000 21,000 21,000 21,000

Sodium lauryl sulphate 1,760 1,760 1,760 1,760

Spices 1,000 1,000 1,000 1,000

In the examples, sodium cyclamate may replace sodium saccharin. Example 8 '· The following stable opaque and opaque ... * gel tooth s pastes are prepared and placed in unlined aluminum tubes.

Some of

A B C D

IV Glycerin 25,000 25,000 25,000 25,000

Sorbitol (70%) 24,970 24,870 24,870 24,870

Sodium carboxymethylcellulose 0.700 0.700 0.700 0.700

Sodium saccharin 0.170 0.170 0.170 0.170

Water 25,000 25,000 25,000 25,000; Zinc bromide dihydrate 0,400 - - - - - Zinc iodide - 0,500

Zinc nitrate hexahydrate

Zinc acetate dihydrate

Syloblanc 81C 21,000 21,000 21,000 21,000. : Sodium laurilsulfate 1,760 1,760 1,760 1,760

Spices 1,000 1,000 1,000 1,000 20 81 71 8

In the examples, sodium cyclamate may replace sodium saccharin. Example 9

The following stable, opaque and opaque gel toothpastes are prepared and packed in mechanically operated dispensing containers:

Some of

A B C D

Glycerin 25,000 25,000 25,000 25,000

Sorbitol (70%) 24,210 24,110 24,110 24,110

Iotacarragen 0.700 0.700 0.700 0.700

Sodium saccharin 0.170 0.170 0.170 0.170

Water 25,000 25,000 25,000 25,000

Sodium monofluorophosphate 0.760 0.760 0.760 0.760

Zinc bromide dihydrate 0.400 -

Zinc iodide - 0.500

Zinc nitrate hexahydrate - - 0,500 S. zinc acetate dihydrate - 0,500

Syloblanc 81C 21,000 21,000 21,000 21,000

Sodium lauryl sulphate 1,760 1,760 1,760 1,760

Spices 1,000 1,000 1,000 1,000

In the examples, sodium cyclamate may replace sodium saccharin.

It will be apparent to those skilled in the art that further modifications may be made to the examples illustrating the invention.

Il

Claims (16)

An astringent toothpaste, characterized in that it comprises about 20-90% by weight of liquid vehicle comprising water in an amount of at least about 3% by weight of said toothpaste, about 0.5-5% by weight of a gelling agent and about 10-50% by weight of a polish, comprising a synthetic precipitated amorphous silica gel having an average particle size of 1-30 microns and a) a surface area of 1-600 m 2 / g, b) a pore volume of 0.05 C) a product of surface area (in m2 / g) x pore volume (in cm3 / g) less than or equal to 240; d) a calculated pore diameter of 1.5-2.5 nm and e. ) a water content of less than 25% by weight, and with up to about 5% of a water-soluble zinc salt, which provides at least about 50 ppm zinc ions to said toothpaste. An astringent toothpaste according to claim 1, characterized in that the gelling agent is an alkali metal carboxymethyl cellulose gelling agent. An astringent toothpaste according to claim 1 or 2, characterized in that it additionally contains an alkali metal monofluorophosphate in an amount which provides about 0.01-1% fluoride ions. An astringent toothpaste according to any one of claims 1-3, characterized in that said zinc salt is present in an amount of 0.01-3% by weight. 5. An astringent toothpaste according to any one of claims 1-3, characterized in that said zinc salt is selected from the group consisting of zinc sulphate, zinc chloride, zinc bromide, zinc iodide, zinc nitrate and zinc acetate. II 25 81 71 8 An astringent toothpaste according to claim 5, characterized in that said zinc salt is zinc sulphate heptahydrate. An astringent toothpaste according to claim 5, characterized in that said zinc salt is zinc chloride. An astringent toothpaste according to claim 1, characterized in that the water in said liquid vehicle constitutes about 3-10% by weight of said toothpaste and said synthetic amorphous silica gel constitutes about 10-40% by weight of said toothpaste. 9. An astringent toothpaste according to claim 1, characterized in that the water in said liquid vehicle constitutes about 11-50% by weight of said toothpaste. An astringent toothpaste according to claim 1, characterized in that said synthetic amorphous silica gel is at least one of the synthetic amorphous silica gels having the following additional characteristics: --- abc Average particle size (according to Coulter) pm 4 7 4 Liquid screen residue (42 pm) % 0.02 0.02 0.02 pH (5% suspension in water) 3 6 6-8 Surface area (BET) m 2 / g 747 Drying loss% 7 4 7 SiO2 ~ Contains (on ignited substance) 96 99 96 Refractive index 1.46 1.46 1.46 26 81 71 8 An astringent gel-shaped toothpaste according to any one of claims 2, 4 or 5, characterized in that said gelling agent is sodium carboxymethyl cellulose. An astringent toothpaste according to any of claims 3, 4 or 5, characterized in that said alkali metal monofluorophosphate is sodium monofluorophosphate. An astringent toothpaste according to claim 4, characterized in that said water-soluble zinc salt is present in an amount providing about 1000 ppm zinc ions and said alkali metal monofluorophosphate is present in an amount providing about 1000 ppm fluoride. A toothpaste extract according to claim 13, characterized in that said zinc salt is zinc sulfate heptahydrate and said alkali metal monofluorophosphate is sodium monofluorophosphate. 15. An astringent toothpaste according to any one of claims 1, 2 or 3, characterized in that said toothpaste is packaged in an unlined aluminum tube. An astringent toothpaste according to any one of claims 1, 2 or 3, characterized in that said toothpaste also contains about 0.005-0.5% by weight of zinc oxide. Il