GB2167956A - Astringent dentifrice - Google Patents

Astringent dentifrice Download PDF

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GB2167956A
GB2167956A GB8528462A GB8528462A GB2167956A GB 2167956 A GB2167956 A GB 2167956A GB 8528462 A GB8528462 A GB 8528462A GB 8528462 A GB8528462 A GB 8528462A GB 2167956 A GB2167956 A GB 2167956A
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Prior art keywords
zinc
dentifrice
sodium
ions
syloblanc
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GB2167956B (en )
GB8528462D0 (en )
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Kenneth Harvey
Harry Hayes
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Colgate-Palmolive Co
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Colgate-Palmolive Co
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q11/00Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/02Cosmetics or similar toilet preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/042Gels
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/19Cosmetics or similar toilet preparations characterised by the composition containing inorganic ingredients
    • A61K8/20Halogens; Compounds thereof
    • A61K8/21Fluorides; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/19Cosmetics or similar toilet preparations characterised by the composition containing inorganic ingredients
    • A61K8/25Silicon; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/19Cosmetics or similar toilet preparations characterised by the composition containing inorganic ingredients
    • A61K8/27Zinc; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/72Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • A61K8/731Cellulose; Quaternized cellulose derivatives
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41Particular ingredients further characterized by their size
    • A61K2800/412Microsized, i.e. having sizes between 0.1 and 100 microns
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54Polymers characterized by specific structures/properties
    • A61K2800/542Polymers characterized by specific structures/properties characterized by the charge
    • A61K2800/5424Polymers characterized by specific structures/properties characterized by the charge anionic

Abstract

The dentifrice contains a water-soluble zinc salt and a hydrous silica gel polishing agent compatible and substantially non-reactive with the zinc salt. The astringent dentifrice may additionally contain alkali metal monofluorophosphate, alkali metal carboxymethyl cellulose or combinations thereof, each of which is substantially non-reactive with the zinc salt and the hydrous silica gel.

Description

SPECIFICATION Astringent Dentifrice The present invention relates to a dentifrice containing a water-soluble zinc salt which provides an astringent effect on oral mucosa and periodontal tissue during toothbrushing, and optionally an alkali metal monofluorophosphate or a gelling agent, or both. Each of the components is compatible and substantially non-reactive with a hydrous silica gel polishing agent.

The astringent effectiveness of zinc ions provided by water-soluble zinc salts to promote and improve oral hygiene has long been known. Nevertheless, there have been limits on the practical use of zinc in dentifrice compositions since zinc ions can readily react with typical dentifrice components causing substantial loss of availability of zinc ions.

Likewise, the monofluorophosphate ion has long been known to promote oral hygiene and reduce caries formation by release of fluoride, but its effectiveness too has been reduced by incompatibility with some dentifrice components, such as water-soluble zinc compounds.

Nonionic gelling agents such as hydroxyethyl cellulose have been preferably used in dentifrices when a water-soluble zinc salt is employed. However, when alkali metal carboxymethyl cellulose has been employed in the presence of zinc ions, reaction occurs removing zinc ions, leading to possible gel breakdown and phase separation. In U.S. Patent 3,728,446, to Roberts et al, the in situ reaction between zinc ions and alkali metal carboxymethyl cellulose to form visible particles is described.

Furthermore, gel-type dentifrices providing zinc astringency have been limited due to the incompatibility of zinc ions with various siliceous polishing agents. Such siliceous polishing agents as silica xerogel having an average particle size between about 2 and 20 microns and generally a surface area of at least about 300 m2/gm, typically about 300-370 m2lgm, or about 600--800 m2/gm, which are described in U.S. Patent No.3,538,230 to Pader et al, undergo in situ reaction with zinc ion so that much of the theoretically available zinc is lost by physio-chemical means such as absorption.

Similar compatibility problems would occur when water-soluble zinc salt is present together with other dentifrice salt polishing agents, particularly calcium salts such as dicalcium phosphate or calcium carbonate. In fact it has been believed that it would be difficult to employ a water-soluble zinc salt and maintain a high level of availability-of zinc ions in such conventional dentifrices.

Compatibility is also a problem when an alkali metal monofluorophosphate is employed with such siliceous polishing agent in a dentifrice containing a water-soluble zinc salt.

It has therefore been difficult to prepare dentifrices containing a siliceous polishing agent and amounts of zinc ions with or without alkali metal monofluorophosphate or alkali metal carboxymethyl cellulose or both, which remain effective in providing the astringent properties of zinc and the anti-caries properties of fluoride. In particular, gel-type dentifrices providing both zinc astringency with or without a fluoride anti-caries effect have not been satisfactorily available due to the incompatibility of zinc ion with monofluorophosphate and with alkali metal carboxymethyl cellulose in the presence of various siliceous polishing agents.

In the present invention, use is made of a precipitated, amorphous silica gel which has been described in British Published PatentApplication No. 2038303 A to Feig etal and in U.S. Patent No. 4,528,181 granted 9 July 1985. In U.S. Patent No.4,528,181 a dentifrice containing the precipitated, amorphous silica gel is described in which a dual source of fluoride containing sodium fluoride and sodium monofluorophosphate and a source of calcium is stabilized by an alkali metal phytate to improve fluoride retention.

Such precipitated, amorphous silica gel material is available from Grace GmbH as product such as Syloblanc (Registered Trade Mark) 81, Syloblanc 81 C and Syloblanc 82. It is distinct from the types of Xerogel which have been sold by W. R. Grace and Co. under the trade mark Syloid and which are particularly described in U.S. Patent 3,538,230 to Pader et al. Indeed, although some products sold by Grace GmbH under the trade mark Syloblanc were formerly or are still available under the trade mark Syloid, none of Syloblane 81, Syioblane 81C or Syloblane 82 has ever been available under the trade mark Syloid.It is particularly noteworthy that the grades of the silica gel employed in the present invention are less abrasive as the surface area increases whereas the grades of silica xerogel which are described in U.S. Patent 3,538,230 are generally more abrasive as their surface area increases.

In view of the low compatibility of most polishing agents with zinc including those polishing agents of U.S. Patent No. 3,538,230. It was quite unexpected that a particular siliceous polishing material would not have such a problem and that further, in the presence of such polishing agent, the reaction between zinc ions and alkali metal carboxymethyl cellulose is substantially reduced. Furthermore, it was unexpected, that in the presence of these particular siliceous polishing materials and zinc ions, alkali metal monofluorophosphate remains stable and compatible to provide fluoride. Nevertheless, in accordance with the present invention, it has been found that retention of high levels of astringency from zinc ions is attained when such particular siliceous polishing material is employed, or monofluorophosphate is employed to give high levels of fluoride ions which are also retained.

It is an advantage of the present invention that an astringent dentifrice containing zinc ions is provided, which may effectively contain monofluorophosphate or an alkali metal carboxymethyl cellulose gelling agent or both.

It is a further advantage of the present invention that an astringent gel-type toothpaste containing zinc ions is provided, which may optionally contain monofluorophosphate or an alkali metal carboxymethyl cellulose gelling agent or both.

In accordance with certain of its aspects, the present invention relates to an astringent dentifrice comprising about 290% by weight of liquid vehicle comprising water in amount of at least about 3% by weight of the said dentifrice, about 0.05% by weight of a polishing agent comprising a synthetic precipitated, amorphous silica gel having an average particle size of 1 to 30 microns and a) a surface area of 1 to 600 m2/g, b) a pore volume of 0.05 to 0.5 cm3/g, c) a product of surface area (in m2/g by pore volume (in cam3/9) less than or equal to 240, d) a calculated pore diameter of 1.5 to 2.5 nm (10-9 metres), and e) a water content of less than 25% by weight, and up to about 5% of a water-soluble zinc salt which provides at least about 50 ppm of zinc ions to said dentifrice.Furthermore, the said dentifrice may contain an alkali metal carboxymethyl cellulose as the gelling agent and/or may contain an alkali metal monofluorophosphate in an amount to provide about 0.01-1% fluoride.

As indicated above, the synthetic precipitated silica is of the type described in British Published Patent Application 2038303 and U.S. Patent No.4,528,181. Specific grades of the silica material described therein are suitable for use in the practice of the present invention. Further, specific grades which are particularly preferred are described in an October 1980 trade publication of Grace GmbH of Norderstadt, Germany, as Syloblanc 81 and Syloblanc 82 and as having the following typical physical and chemical characteristics.

Syloblanc 81 Syloblanc 82 Average particle size (according to Coulter) microns 4 7 Wet screen residue (42 microns) % 0.02 0.02 pH (5% suspension in water) 3 6 Surface area (B.E.T.) m2lg 400 480 Loss on drying % 7 4 SiO2 content (on ignited substance) % 96 99 Refractive index 1.46 1.46 In a variation of Syloblanc 81 available as Syloblanc 81 C, the pH (5% suspension in water) is about 68.

Syloblanc 81 and 81 C, in particular, are highly effective in polishing dental surfaces. Syloblanc 82 is lower in polishing effect, but can be used by consumers desiring such reduced effect. Likewise, grades of the silica material may be proportioned in mixtures to produce appropriate polishing characteristics. It is noteworthy that the dentifrices are compatible in unlined aluminium dentifrice tubes even in the absence of phytate salt, which is necessary in the invention described in U.S. Patent No.4,528,181. The precipitated amorphous silica gel is employed in amount of about 1050% by weight, typically about 1C#40% in a gel dentifrice.

Aqueous slurries of the silica material (e.g. about 5 to 20% slurries) typically have a pH of about 2 to 9.

Since the dentifrice composition of the present invention preferably has a pH (measured in 10% aqueous slurry) of at least about 5.5, e.g. about 5.5--7.5, the pH of the dentifrice may be adjusted with an appropriate material such as sodium hydroxide.

The water-soluble zinc salt is present in the dentifrice in an amount of up to about 5% by weight, preferably from about 0.01 to 3% and most preferably from about 0.1 to 2%. Water-soluble zinc salts useful in the present invention are soluble in water to the extent of at least about 10% by weight, preferably at least 20%. There is provided at least about 50 ppm of zinc ions to the dentifrice, preferably at least about 750 ppm and most preferably at least about 1000 ppm of zinc ions. Suitable zinc salts include zinc sulphate, zinc chloride, zinc bromide, zinc iodide, zinc nitrate and zinc acetate. In the case of the 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 sulphate heptahydrate provides about 1000 ppm of zinc ions.In addition, zinc oxide, a sparingly soluble (below 0.0005%) zinc compound may also be added to prevent a lowering of the pH in the product. This acts as a buffer system and improves pH stability and compatibility in unlined aluminium tubes. It may be present in an amount of about 0.005%0.5% by weight The dentifrice comprises a liquid vehicle containing about 360% by weight of water, typically mixed with at least one humectant. The liquid phase comprises about 2090% by weight of the dentifrice and is generally about 2580% liquid, typically with about 350% by weight, preferably 310% of water in a substantially clear gel dentifrice or gel dentifrice which would be substantially clear except for the presence of an opacifying agent, such as titanium dioxide, and about 1150% of water in a hazy to opaque gel dentifrice with about 1090% by weight, preferably about 1 80%, of humectant. Typical humectants include glycerine, sorbitol (e.g. 70% solution), maltitol, polyethyleneglycol of molecular weight of about 40-600, propylene glycol and mixtures thereof.

The dentifrice also contains a gelling or binding agent such as a solid vehicle agent, although this may be in small amount, since the synthetic, precipitated silica can effect a thickening or gelling of the dentifrice into a creamy or pasty consistency. Alkali metal carboxymethyl cellulose is preferred in accordance with one aspect of the present invention, but other gelling or binding agents that may be present include hydroxyethyl cellulose, hydroxypropyl cellulose, xanthan, Irish moss, iota-carrageenan, gum tragacanth, polyvinyl pyrrolidone, starch and mixtures thereof. Such gelling agents may be used in an amount of about 0.05%5% by weight, typically about 0.052% and preferably about 0.11.5%. Particularly desirable is the use of sodium carboxymethyl cellulose.

Alkali metal monofluorophosphates, such as sodium, and potassium monofluorophosphates are compatible in the dentifrice. Sodium monofluorophosphate is especially preferred. In the past, when it has been attempted to formulate a dentifrice with liquid vehicle, gelling agent, polishing agent, zinc salt and sodium monofluorophosphate, substantial levels of zinc ions and fluoride ions have been lost by insolubilisation. Unexpectedly, when the polishing agent is the defined synthetic, precipitated, amorphous silica gel, high levels of fluoride ions and substantial retention of zinc ions are attained. Such high levels of fluoride retention are not attained when a simple fluoride such as sodium fluoride is employed.

Sodium monofluorophosphate, Na2PO3F, as commercially available, may vary considerably in purity. It may be used in any suitable purity provided that any impurities do not substantially adversely affect the desired properties. In general, the purity is desirably at least 80%, and preferably at least 90% by weight of sodium monofluorophosphate with the balance being primarily impurities or by products of manufacture such as sodium fluoride and water-soluble sodium phosphate salt. Expressed in another way, the sodium monofluorophosphate employed should have a total fluoride content of above 12%, preferably 12.7%, a content of not more than 1.5%, preferably not more than 1.2%, of free sodium fluoride, and a sodium monofluorophosphate content of at least 12%; preferably at least 12.1% all calculated as fluoride.Alkali metal monofluorophosphate is present in amount to provide fluoride in an amount of about 0.011% by weight, preferably about 0.1%. Thus, sodium monofluorophosphate can be present in amount of about 0.0767.6%, preferably 0.76%, which corresponds to about 100--10000 ppm of fluoride, preferably about 1000 ppm.

Any suitable surface active or detersive material may be included in the dentifrice compositions. Such compatible materials are desirable to provide additional detersive foaming and antibacterial properties depending upon the specific type of surface active material and are selected accordingly. These detergents are usually water-soluble compounds, and may be anionic, nonionic, amphoteric or cationic in structure. It is usually preferred to use water-soluble non-soap or synthetic organic detergents.Suitable detersive materials are known and include, for example, the water-soluble salts of higher fatty acid and monoglyceride monosulphate detergents (e.g. sodium coconut fatty acid monoglyceride monosulphate), higher alkyl sulphate (e.g. sodium lauryl sulphate), alkyl aryl sulphonate (e.g. sodium dodecyl benzene sulphonate, higher fatty acid esters of 1,2-dihydroxy propane sulphonate) and the like.

Further surface active agents include the substantially saturated higher aliphatic acyl amides of lower aliphatic amino carboxylic acid compounds, such as those having 12 to 16 carbons in the acyl radical. The amino acid portion is derived generally from the lower aliphatic saturated monoaminocarboxylic acid compounds. Suitable compounds are the fatty acid amides of glycine, sarcosine, alanine, 3-amino propanoic acid and valine having about 12 to 16 carbons in the acid group. It is preferred to use the N-lauroyl, myristoyl and palmitoyl sarcoside compounds, however, for optimum effects.

The amide compounds may be employed in the form of the free acid or preferably as the water-soluble salts thereof, such as the alkali metal, ammonium, amine and alkylolamine salts. Specific examples thereof are the sodium and potassium N-lauroyl, myristoyl and palmitoyl sarcosides, ammonium and ethanolamine N-lauroyl glycide and alanine. For convenience herein, reference to "amino carboxylic acid compound", "sarcoside" and the like refers to such compounds having afree carboxylic group or the water-soluble carboxylate salts.

Such materials are utilized in pure or substantially pure form. They should be as free as practicable from soap or similar higher fatty acid materials which tend to reduce the activity of these compounds. In usual 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 the said amide material.

Other particularly suitable surface-active materials include nonionic agents such as condensates of sorbitan monostearate with approximately 20 moles of ethylene oxide, condensates of ethylene oxide with propylene oxide, condensates of propylene glycol ("Pluronic" (Registered Trade Mark) materiais) and amphoteric agents such as long chain (alkyl) amide alkylene alkalated amine derivatives, which are available under the trademark "Miranol" C2M. Cationic surface active germicides and antibacterial compounds such as diisobutylphenoxyethoxyethyl dimethyl benzyl ammonium chloride, benzyl dimethyl stearyl ammonium chloride, tertiary amines having one fatty alkyl group (of from 12-18 carbon atoms) and two (poly) oxyethylene groups attached to the nitrogen (typically containing a total of from about 2 to 50 ethanoxy groups per molecule) and salts thereof with acids, and compounds of the structure <img class="EMIRef" id="027226830-00040001" />

wherein R represents a fatty alkyl group containing from about 12 to 18 carbon atoms, and x, y and z total 3 or higher, as well as salts thereof with mineral or organic acids, may also be used. It is preferred to use from about 0.05 to 5% by weight of the foregoing surface-active materials in the oral preparation of the present invention.

Various other materials may be incorporated in the dental creams of the present invention. Examples thereof are opacifiers, preservatives, stabilizers, silicones, chlorophyll compounds and ammoniated materials such as urea, diammonium phosphate and mixtures thereof. These adjuvants are incorporated in the compositions of the present invention in amounts which 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 antibacterial agents in the compositions of the present invention. Typical antibacterial agents (which may be used in amounts of about 0.01% to about 5%, preferably about 0.05 to about 1.0%, by weight of the dentifrice composition) include cetyl pyridinium chloride, and benzethonium chloride as well as.

Nt-4(chlorobenzyl)-N5-(2,4-dichlorobenzyl)biguanide, p-chlorophenyl biguanide, 4-chlorobenzhydryl biguanide; 4-chlorobenzhydrylguanylurea; N-3-lauroxypropyl-N5-p-chlorobenzyl biguanide, 1 ,6-di-p-chlorophenylbiguanidohexane; 1-(lauryldimethylammonium)-8-(p-chlorobenzyldimethylammonium)5,6-dichloro-2- guanidinobenzimidazole.

N'-p-chlorophenyl-N5-laurylbiguanide, 5-amino-1 ,3-bis(2-ethylhexyl)-5-methylhexahydropyrimidine, and their non toxic addition salts.

Any suitable flavouring orsweetening materials may be employed in formulating a flavour for the compositions of the present invention. Examples of suitable flavouring constituents include the flavouring oils, e.g. oils of spearmint, peppermint,wintergreen, sassafras, clove, sage, eucalyptus, marjoram, cinnamon, lemon and orange, as well as methyl salicylate. Suitable sweetening agents include sucrose, lactose, maltose, sorbitol, sodium cyclamate, sodium saccharine, dipeptides of U.S. Patent 3,939,261 and oxathiazin salts of U.S. Patent 3,932,606. Suitable flavour and sweetening agents may together comprise from about 0.01 to 5% or more of the composition.

The dentifrice is packaged in a container from which it can be readily extruded such as a pressure differential or mechanically operated dental cream dispenser or a lined or unlined aluminium tube or wax lined lead tube or plastic tube, which may be laminated with aluminium. The rheological properties are highly desirable when a mechanically operated dispensing container of the type described in British Patent Application 2,070,695A, published 9th September, 1981, is employed. This dispensing container comprises a dispensing mouthpiece, a tension member, a central rod, a piston and operating hand control.

A pressure differential dispensing container may be of the aerosol or vacuum type. Suitable pressure differential dispersers include those comprising a collapsible product-containing bag being disposed within a rigid container which contains a propellant fluid. In such dispensing containers, operation of the valve permits release of the product only, the propellant fluid being separated from the product by the fluid impermeable bag. Dispensers of this type are described in U.S. Patents 3,828,977 and 3,838,796. These are the so-called Sepro dispensers. So-called Exxel and Enviro Spray containers also utilize pressure.

Still another type dispenser is the barrier piston container described in U.S. 4,171,757. Such container includes a valve, a product-containing compartment and an essentially fluid-tight barrier piston which separates the propellant fluid from the contained product (the so-called Diamond container).

The dentifrice is typically prepared by forming a premix of the gelling agent with the liquid vehicle components, e.g. water and humectant, which may also contain additional ingredients such as the monofluorophosphate and/or sweetener, and blending therewith the synthetic precipitated silica gel and zinc salt. Additional employed ingredients may then be added.

The invention may be put into practice in various ways and a number of specific embodiments will be described to illustrate the invention with reference to the accompanying examples. All amounts are by weight unless otherwise indicated.

EXAMPLES 1Ato 1G The following opacified gel dentifrices having the compositions given in Table 1 ars prepared and placed in unlined aluminium tubes.

TABLE 1 Parts Example 1A 1B Ingredients Glycerine 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 0.480 0.480 Precipitated amorphous silica gel(1) 20.000 Silica xerogel(2) - 17.000 Silica aerogel(3) - 6.500 Sodium hydroxide (40%) 0.280 Sodium lauryl sulphate 1.760 1.760 Flavour 1.000 1.000 pH (20% slurry) 5.9 6.1 Notes on Table 1 (1) Syloblanc 81 available from Grace G.m.b.H.; (2) Syloid AL1 available from Grace G.m.b.H., formerly known as Syloid 63; (3) Syloid 244 thickener available from W. R. Grace & Co The theoretical amount of soluble zinc ions in each gel dentifrice is 1000 ppm or 0.100%.

The dentifrice of Example 1A does not require the presence of thickener material to provide desirable gel character. Its consistency is about equivalent to that of the dentifrice of Example 1 B.

Each dentifrice is aged at room temperature and at 43"C. Both retain generally equivalent desirable consistencies. The percentage amounts of available soluble zinc ions in each dentifrice on aging was determined and is given in Table 2 below: TABLE 2 % Zn+2-Room temperature 43"C 1 3 2 1 3 Example Initial Month Months Weeks Month Months 1A 0.084 0.080 0.050 0.091 0.070 0.050 1 B 0.054 0.042 0.005 0.049 0.048 0.005 The dentifrice of Example 1A containing Syloblanc 81 retains superior levels of soluble zinc ions compared to the otherwise generally equivalent dentifrice of Example 1 B containing Syloblanc AL1.

Similar superior levels of retention of soluble zinc ions are attained when the Syloblanc 81 of the dentifrice of Example 1A is replaced with Syloblanc 82 (Example 1 C) and with a 1:1 mixture of Syloblanc 81 and 82 (Example 1 D), in each case, with the levels of sodium hydroxide reduced or omitted, any omitted sodium hydroxide being replaced by an additional weight of sorbitol (70%).

Likewise, superior retention levels of soluble zinc ions are attained when Syloblanc 81 is replaced with Syloblanc 81 C (Example 1 E), with sodium hydroxide omitted and its amount added to sorbitol (70%) (i.e.

sodium hydroxide zero %, sorbitol 47.33%).

EXAMPLES 1Fand 1G 0.25 parts of zinc oxide are incorporated into each of the dentifrices of Examples 1 A and 1 B, in place of corresponding amounts of sorbitol, thereby stabilizing the pH during aging and improving the compatibility of the composition with unlined aluminium tubes for prolonged periods.

EXAMPLES 2Ato 2G The following opacified gel dentifrices having the compositions set out in Table 3 are prepared and placed in unlined aluminium tubes: TABLE 3 Parts Examples 2A 2B Ingredients Glycerine 25.000 25.000 Sorbitol (70%) 47.050 43.550 Sodium carboxymethyl cellulose 0.260 0.260 Sodium saccharin 0.170 0.170 Titanium dioxide 1.000 1.000 Water 3.000 3.000 Zinc sulphate heptahydrate 0.480 0.480 Precipitated amorphous silica gel(1) 20.000 Silica xerogel(2) 17.000 Silica aerogel(3) - 6.500 Sodium hydroxide (40%) 0.280 0.280 Sodium lauryl sulphate 1.760 1.760 Flavour 1.000 1.000 pH (20% slurry) 5.9 6.1 Notes on Table 3 (1), (2) and see notes (1), (2) and (3) on Table 1.

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

The dentifrice of Example 2A does not require the presence of thickener material to provide desirable gel character initially.

Each dentifrice is aged at room temperature and at 43"C. Both generally retain equivalent desirable consistencies. The percentage amounts of available soluble zinc ions in each dentifrice on aging was determined and is given in Table 4 below: TABLE 4 % Zn+2-Room Temperature 43"C 1 3 2 1 3 Example Initial Month Months Weeks Month Months 2A 0.080 0.079 0.050 0.082 0.069 0.050 2B 0.052 0.039 0.002 0.050 0.060 0.002 The dentifrice of Example 2A containing Syloblanc 81 retains gel character and superior levels of soluble zinc ions compared to the otherwise generally equivalent dentifrice of Example 2B containing Syloblanc 63.When the conventional 7 MXF grade of sodium carboxymethyl cellulose is employed there is phase separation and breakdown in the presence of Syloid 63 polishing agent which does not occur as much when Syloblanc 81 is employed.

It is noted that the two-week and one-month evaiuation levels of the dentifrice of Example 2B at 43 C reflect routine experimental variations.

Similar superior levels of retention of soluble zinc ions are attained when Syloblanc 81 of the dentifrice of Example 2A is replaced with Syloblanc 82 (Example 2C) and with a 1:1 mixture of Syloblanc 81 and 82 (Example 2D), in each, with levels of sodium hydroxide reduced, or omitted, any omitted sodium hydroxide being replaced by an additional weight of sorbitol (70%).

Likewise, superior retention levels of soluble zinc ions are attained when Syloblanc 81 is replaced with Syloblane 81C (Example 2E), with sodium hydroxide omitted and its amount added to sorbitol (70%) (i.e.

sodium hydroxide zero %, sorbitol 47.33%).

EXAMPLES 2F and 2G 0.25 parts of zinc oxide are incorporated into each of dentifrices of Examples 2A and 2B, in place of corresponding amounts of sorbitol, thereby stabilizing the pH during aging and improving compatibility with unlined aluminium tubes for prolonged periods.

EXAMPLES 3A to 31 The following opacified gel dentifrices having the compositions as set out in Table 5 below are prepared and placed in unlined aluminium tubes: TABLE 5 Parts Examples 3A 3B Ingredients Glycerine 25.000 25.000 Sorbitol (70%) 46.340 46.880 Sodium carboxymethyl cellulose 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(1) 20.000 20.000 Sodium hydroxide (40%) 0.300 0.300 Sodium lauryl sulphate 1.760 1.760 Flavour 1.000 1.000 pH (20% slurry) 6.0 5.9 Notes on Table 5 (1)~See note (1) on Table 1.

The theoretical amounts of soluble zinc ions and fluoride in each gel dentifrice is 1000 ppm or 0.100%, for each of the zinc ions and fluoride.

Each dentifrice is aged at room temperature and at 430C. The percentage amounts of available soluble zinc ions and of fluoride in each dentifrice on aging at room temperature was determined and is given in Table 6 below: TABLE 6 Example Initial One Month 3A 0.66 Zn(4) 0.066 Zn 0.096 F(5) 0.097 F 3B 0.070 Zn 0.051 Zn 0.100 F(6) 0.048 F Notes on Table 6 4)% Zn+2 5)% Monofluorophosphate as fluoride (6)~% Fluoride The dentifrice of Example 3A containing sodium monofiuorophosphate provides substantial retention of both zinc ions and fluoride compared to the dentifrice of Example 3B containing sodium fluoride.At 43 C, gas forms in the unlined aluminium tube containing the dentifrice of Example 3B, while the unlined aluminium tube containing the dentifrice of Example 3A remains stable.

Zinc ion and fluoride retention are low when the xerogel Syloid 63 (Examples 3C and 3D) available from W. R. Grace & Co. replaces Syloblanc 81.

Similar results to those determined with the dentifrice of Example 3A are attained when potassium monofluorophosphate replaces sodium monofluorophosphate.

Similar superior levels of retention of soluble zinc ions and fluoride are attained when Syloblanc 81 of dentifrice A is replaced with Syloblanc 82 (Example 3E) and with a 1:1 mixture of Syloblanc 81 and 82 (Example 3F), in each, with the levels of sodium hydroxide reduced or omitted, any omitted sodium hydroxide being replaced by an additional weight of sorbitol (70%).

Likewise, superior retention levels of soluble zinc ions and fluoride are attained when Syloblanc 81 is replaced with Syloblanc 81 C (Example 3G), with sodium hydroxide omitted and its amount added to sorbitol (70%) (i.e. sodium hydroxide zero %, sorbitol 46.64%).

EXAMPLES 3H and 31 0.25 parts of zinc oxide are incorporated into each of the dentifrices of Examples 3A and 3B, in place of corresponding amounts of sorbitol, thereby stabilizing the pH during aging and improving compatibility with unlined aluminium tubes for prolonged periods.

EXAMPLES 4Ato 4D The following stable visually clear gel dentifrices having the compositions set out in Table 7 below are prepared and placed in unlined aluminium tubes.

TABLE 7 Parts Example 4A 4B 4C 4D Ingredients Glycerine 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 81 C - 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 Flavour 1.000 1.000 1.000 1.000 Blue colour solution 0.200 0.200 0.200 0.200 EXAMPLES 5Ato 5D The following stable visually clear gel dentifrices having the compositions set out in Table 8 below are prepared and placed in unlined aluminium tubes.

TABLE 8 Parts Example 5A SB 5C 5D Ingredients Glycerine 25.000 25.000 25.000 25.000 Sorbitol (70%) 48.310 48.590 48.590 48.450 Sodium carboxymethyl cellulose 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 Syloblane 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 Flavour 1.000 1.000 1.000 1.000 Blue colour solution (1%) 0.200 0.200 0.200 0.200 Similarly stability is attained when potassium carboxymethyl cellulose replaces sodium carboxymethyl cellulose.

EXAMPLES 6Ato 6D The following stable visually clear gel dentifrices having the compositions set out in Table 9 below are prepared and placed in unlined aluminium tubes: TABLE 9 Parts Examples 6A 6B 6C 6D Ingredients Glycerine 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 81 C - 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 Flavour 1.000 1.000 1.000 1.000 Blue coloursolution (1%) 0.200 0.200 0.200 0.200 EXAMPLES 7Ato 7D The following hazy and opaque gel dentifrices having the compositions set out in Table 10 below are prepared and packaged to mechanically operated dispensing containers: TABLE 10 Parts Example 7A 7B 7C 7D Ingredients Glycerine 25.000 25.000 25.000 25.000 Sorbitol (70%) 24.970 24.870 24.870 24.870 lota carrageenan 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 - - 0.500 Zinc acetate dihydrate - - - 0.500 Syloblanc 81 C 21.000 21.000 21.000 21.000 Sodium iauryl sulphate 1.760 1.760 1.760 1.760 Flavour 1.000 1.000 1.000 1.000 EXAMPLES 8Ato 8D The following stable hazy and opaque gel dentifrices having the compositions set out in Table 11 below are prepared and placed in unlined aluminium tubes: TABLE 11 Parts Examples 8A 8B 8C 8D Ingredients Glycerine 25.000 25.000 25.000 25.000 Sorbitol (70%) 24.970 24.870 24.870 24.870 Sodium carboxymethyl cellulose 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 - - 0.500 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 Flavour 1.000 1.000 1.000 1.000 EXAMPLES 9Ato 9D The following stable hazy and opaque gel dentifrices having the compositions set out in Table 12 below are prepared and packaged in mechanically operated dispensing containers: TABLE 12 Parts Examples 9A 9B 9C 9D Ingredients Glycerine 25.000 25.000 25.000 25.000 Sorbitol (70%) 24.210 24.110 24.110 24.110 lota carrageenan 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 0.500 -- Zinc acetate dihydrate - - 0.500 Syloblane 81C 21.000 21.000 21.000 21.000 Sodium lauryl sulphate 1.760 1.760 1.760 1.760 Flavour 1.000 1.000 1.000 1.000 In all the examples sodium cyclamate may replace sodium saccharin.

Claims (18)

1. An astringent dentifrice comprising about 2090% by weight of liquid vehicle comprising water in amount of at least about 3% by weight of said dentifrice, about 0.55% by weight of a gelling agent and about 1 1050% by weight of a polishing agent comprising a synthetic precipitated, amorphous silica gel having an average particle size of 1 to 30 microns and a) a surface area of 1 to 600 m2lg, b) a pore volume of 0.05 to 0.5 cm3lg, c) a product of surface area (in m2/g)xpore volume (in cm3/g) less than or equal to 240, d) a calculated pore diameter of 1.5 to 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 of zinc ions to the said dentifrice.
2. An astringent dentifrice as claimed in Claim 1 in which the said gelling agent is an alkali metal carboxymethyl cellulose gelling agent.
3. An astringent dentifrice as claimed in Claim 1 or Claim 2 which further contains an alkali metal monofluorophosphate in an amount which provides about 0.011 % fluoride ions.
4. An astringent dentifrice as claimed in any one of Claims 1 to 3 in which the said zinc salt is present in an amount of 0.013% by weight.
5. An astringent dentifrice as claimed in any one of Claims 1 to 4 in which the said zinc salt is zinc sulphate, zinc bromide, zinc iodide, zinc nitrate or zinc acetate or a mixture thereof.
6. An astringent dentifrice as claimed in Claim 5 in which the said zinc salt is zinc sulphate heptahydrate.
7. An astringent dentifrice as claimed in any one of Claims 1 to 5 in which the said zinc salt is or includes zinc chloride.
8. An astringent dentifrice as claimed in any one of Claims 1 to 7 in which the said water in the said liquid vehicle comprises about 310% by weight of the said dentifrice.
9. An astringent dentifrice as claimed in any one of Claims 1 to 8 in which the said synthetic amorphous silica gel comprises about 1 10--40% by weight of the said dentifrice.
10. An astringent dentifrice as claimed in any one of Claims 1 to 7 in which the said water in the said liquid vehicle comprises about 1150% by weight of said dentifrice.
11. An astringent dentifrice as claimed in any one of Claims 1 to 10 in which the said synthetic amorphous silica gel is at least one of the synthetic amorphous silica gels having the further characteristics of: a b c Average particle size microns (according to Coulter) microns 4 7 4 Wet screen residue (42 microns) % 0.02 0.02 0.02 pH (5% suspension in water) 3 6 Surface area (B.E.T.) m21g 7 4 7 Loss in drying % 7 4 7 SiO2 content (on ignited substance) 96 99 96 Refractive index 1.46 1.46 1.46
12. An astringent gel dentifrice as claimed in.any one of Claims 1 to 11 in which the said gelling agent is sodium carboxymethyl cellulose.
13. An astringent dentifrice as claimed in any one of Claims 1 to 12 in which the said alkali metal monofluorophosphate is sodium monofluorophosphate.
14. An astringent dentifrice as claimed in Claim 3 and any one of Claims 4 to 13 when dependent on Claim 3 in which the said water-soluble zinc salt is present in an amount which provides about 1000 ppm of zinc ions and said alkali metal monofluorophosphate is present in an amount which provides about 1000 ppm of fluoride.
15. An astringent dentifrice as claimed in Claim 14 in which the said zinc salt is zinc sulphate heptahydrate and the said alkali metal monofluorophosphate is sodium monofluorophosphate.
16. An astringent dentifrice as claimed in any one of Claims 1 to 15 in which the said dentifrice also contains about 0.0050.5% by weight of zinc oxide.
17. An astringent dentifrice as claimed in Claim 1 substantially as specifically described herein with reference to any one of Examples lA, 1 C, ID, 1 E, F or 1 G, or 2A, 2C, 2D, 2E, 2F or 2G, 3A, 3B, 3E, 3F, 3G, 3H or 31, or 4A to 4D, 5A to 5D, 6A to 6D, 7A to 7D, 8A to 8D or 9A to 9D.
18. An astringent dentifrice as claimed in any one of Claims 1 to 17 in which the said dentifrice is packaged in an unlined aluminium tube.
GB8528462A 1984-12-11 1985-11-19 Astringent dentifrice Expired GB2167956B (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US06680424 US4562066A (en) 1984-12-11 1984-12-11 Astringent dentifrice containing monofluorophosphate
US06680425 US4562065A (en) 1984-12-11 1984-12-11 Astringent dentifrice
US06680426 US4562063A (en) 1984-12-11 1984-12-11 Astringent gel dentifrice

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GB8528462D0 GB8528462D0 (en) 1985-12-24
GB2167956A true true GB2167956A (en) 1986-06-11
GB2167956B GB2167956B (en) 1988-12-14

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CA (1) CA1260839A (en)
DE (1) DE3541160A1 (en)
DK (1) DK541985D0 (en)
ES (1) ES549124A0 (en)
FI (1) FI81718C (en)
FR (1) FR2574290B1 (en)
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NL (1) NL8503210A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5094842A (en) * 1989-10-06 1992-03-10 Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. Oral compositions
WO2012087288A2 (en) 2010-12-21 2012-06-28 Colgate-Palmolive Company Metal salt compositions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3538230A (en) * 1966-12-05 1970-11-03 Lever Brothers Ltd Oral compositions containing silica xerogels as cleaning and polishing agents
GB1296952A (en) * 1971-01-28 1972-11-22
US4022880A (en) * 1973-09-26 1977-05-10 Lever Brothers Company Anticalculus composition
GB2105991A (en) * 1981-09-17 1983-04-07 Johnson & Johnson Prod Inc Anticaries composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3538230A (en) * 1966-12-05 1970-11-03 Lever Brothers Ltd Oral compositions containing silica xerogels as cleaning and polishing agents
GB1296952A (en) * 1971-01-28 1972-11-22
US4022880A (en) * 1973-09-26 1977-05-10 Lever Brothers Company Anticalculus composition
GB2105991A (en) * 1981-09-17 1983-04-07 Johnson & Johnson Prod Inc Anticaries composition

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5094842A (en) * 1989-10-06 1992-03-10 Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. Oral compositions
WO2012087288A2 (en) 2010-12-21 2012-06-28 Colgate-Palmolive Company Metal salt compositions
WO2012087288A3 (en) * 2010-12-21 2012-12-27 Colgate-Palmolive Company Metal salt compositions
RU2560687C2 (en) * 2010-12-21 2015-08-20 Колгейт-Палмолив Компани Metal salt compositions
US9486396B2 (en) 2010-12-21 2016-11-08 Colgate-Palmolive Company Metal salt compositions

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BE903716A (en) 1986-05-26 grant
ES549124A0 (en) 1987-04-16 application
BE903716A1 (en) grant
ES8704724A1 (en) 1987-04-16 application
FI81718C (en) 1990-12-10 grant
ES549124D0 (en) grant
NL8503210A (en) 1986-07-01 application
CA1260839A (en) 1989-09-26 grant
FR2574290B1 (en) 1989-12-08 grant
DK541985D0 (en) 1985-11-22 grant
DK541985A (en) 1986-06-12 application
FI854602A (en) 1986-06-12 application
DE3541160A1 (en) 1986-06-12 application
FI81718B (en) 1990-08-31 application
FI854602D0 (en) grant
GB2167956B (en) 1988-12-14 grant
CA1260839A1 (en) grant
FI854602A0 (en) 1985-11-21 application
GB8528462D0 (en) 1985-12-24 grant
FR2574290A1 (en) 1986-06-13 application

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