NZ202428A

NZ202428A - Dentifrice containing siliceous polishing agent and monofluorophosphate ion stabiliser

Info

Publication number: NZ202428A
Application number: NZ202428A
Authority: NZ
Inventors: K Harvey; S T Connors
Original assignee: Colgate Palmolive Co
Priority date: 1981-11-19
Filing date: 1982-11-08
Publication date: 1985-10-11
Also published as: GB2109683A; ES517458A0; BE895054A; FR2516382A1; BR8206655A; ES8401847A1; PH18522A; CH650670A5; FR2516382B1; NL8204516A; CA1193549A; ATA416782A; GB2109683B; IT8249524A0; SE8206565L; JPS58126807A; SE8206565D0; AU556739B2; IT1158028B; GR77040B

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £02428 2^2428 . ,, - 14-us * rr;cr!iy ubiCvo), 1? - 11 -&J2. Complete Specification Fi'sd: CUss: .AttiKlJilk.. Publication Date: - • - -B-1 ■ ACT- ' P.O. Journal, No: Patents l-onn No. 5 Number PATENTS ACT 1953 Dated COMPLETE SPECIFICATION STABLE DENTIFRICE CONTAINING ACIDIC SILICEOUS POLISHING AGENT I^We COLGATE-PALMOLIVE COMPANY a corporation organised under the laws of the State of Delaware, United States of America of 300 Park Avenue, New York, New York 10022, United States of America do hereby declare the invention for which //we pray that a Patent may be granted to kk/us, and the method by which it is to be performed, to be particularly described in and by the following statement: - 1 - (Followed by page la) 2024-2-8 1 a This invention relates to a staole dentifrice and in particular to a dentifrice which can be used in an unlined aluminium tube. According to tne present invention a stable dentifrice comprises an aqueous dentally acceptable oral vehicle, at least 27.5% and typically 30 to 60%, preferably '10 to 55'fc tor example about 45% by weight of the dentifrice comprising water and dispersed in the said oral vehicle from 10 to 40%, preferably 10 to 30% and especially 15 to 25% by weight of the dentifrice of an acidic siliceous e.g. alkali metal aluminosilicate polishing agent characterised as having a stirred slurry pH (as defined herein) in the range from 5 to less than 6.5 preferably 5 to 6.4 e.g. 5.1, 5.2, 5.3 or 5.4 to 6.3, 6.2, 6.1 or 6.0 especially 5.5 to 6.0 particularly 5.7 to 5.9, and a stablizing amount of ruono-fluoro-phosphate ion, the dentifrice having a stirred slurry ph in the range 5.5 to 8, preferably 6.5 to 7.5, and especially 6.7 to 7.3, optionally a'nontoxic amount of at least 0.2% by weight of the dentifrice of chloroform, and desirably, at least when chloroform is present, from 0.05 to 5% by weight of the dentifrice of a stablising anionic phosphate ester mixture, the said mixture comprising at least one monoester of the formula: 0 R(OC2H4)nOP OM OM !i and at least one diester of the formular 0 R (°C2H4 ) nO jL o (C2H4 0) nR OM JV.Z. PATEMTQvV'iJi 2$JULJ?§5 2. W24? wherein R is an alkyl group of 10 to 2 0 carbon atoms; n is a number from 1 to 6; and M is hydrogen, alkali metal or ammonium. The stabilizing anionic phosphate ester mixture reduces or prevents corrosion in the presence of chloroform and stabilises the dentifrice. It is an advantage of this invention that a stable dentifrice containing siliceous polishing agent is provided. The stability with which the present invention is concerned is the substantial absence of gas generating reactions between the components of the dentifrice anc the aluminium surface of an unlined aluminium, tube as shown by the absence of visually discernable distension of the closed toothpaste tube containing the dentifrice when the said tube has been held at 4 3°C for 168 days. The invention also extends to an unlined aluminium tube filled with a stable dentifrice in accordance with the present invention. . The stabilizing nmo-fluoropbosphate icn nay be provided by any appropriate compound thereof but a particularly convenient compound is sociuir. monofluorophosphate. This may be used in any amount having the necessary defined stabilizing effect on the particular embodiment of the dentifrice according to the invention but amounts providing at least 0.01% irono-fluorophosphate ion are prudently used and for greater certainty at least 0.05% or at least 0.075, or 0.09%, should be used. Sodium ncnofluorophosphate will provide such amounts of the monofltcrophosphate ion when present in amounts of 0.076, 0.38, 0.57, or 0.68% respectively. Use of 0.7 to 0.8% of sodium monofluorophosphate has been found particularly effective and thus a preferred proportion thereof is at least 0.7%. Higher amounts are not precluded but an upper limit of 7.6% will usually not be exceeded. 5. The polishing material employed in the present invention is an acidic siliceous material which may contain a small amount e.g. up to about 10% or somewhat more of alumina interbonded in the silica lattice. It can be further characterised as being synthetic and 10. amorphous and as having a refractive index between about.1.4 and 1.5. If desired, other polishing agents which as individual components do not contribute substantially to instability or corrosivity with an unlined aluminium 15. surface may also be present. Such additional polishing agents include dicalcium phosphate dihydrate and anhydrous dicalcium phosphate as well as tricalcium phosphate^calcium pyrophosphate and calcined alumina. When.an additional polishing agent is present, the 2C. amount of polishing material in the dentifrice may amount to up. to about 75% by weight preferably 30 to 55% of the dentifrice. When chloroform is present in the formulation it is employed in a non-toxic amount which is effective 25. to provide flavour to the dentifrice. However since chloroform in combination with the siliceous polishing agent results in instability and corrosion in the presence of an unlined aluminium surface an appropriate stabilizing amount of an anionic phosphate ester' 30. mixture is also incorporated in such chloroform containing formulations. The chloroform may be present in an amount as low as about 0.2% by weight of the dentifrice and as high as 8% by wei.ght or more. An amount of chloroform in the range of 0.5 to 3.5% by weight is preferred. It is noted that in view of the toxic properties of large amounts of chloroform some countries have or are establishing legal limits on the maximum amount of chloroform which can be used in products such as dentifrices, providing a safety margin by not approaching the toxic threshold too closely. However, even given such legal maxima, the effect of the stabilizing phosphate ester can be observed when non-tcxic amounts such as 8%, 5%, 3.5%, 0.5% or 0.2% by weight of chloroform are present. The anionic phosphate esters are mixtures of mono and di-esters of the formulas set forth above. Suitable esters are available from MoDo Kemi Aktiebolaget, formerly Berol Aktiebolaget, of Sweden under the name BEROL (BEROL is a trade mark) and may include an anionic triester moiety too, as well as some non-ionic portion. BEROL 729 has alkyl chain lengths of 16 to 18 carbon atoms and contains series of 4 ethylene oxide units. BEROL 729 is generally used in neutralised or partially neutralised form. Further anionic phosphate esters which may be used in acid or neutralised forms are BEROL 525 which contains alkyl groups of 10 to 18 carbon atoms and series of 5 ethylene oxide units and BEROL 513 which also contains alkyl groups of 16 to 18 carbon atoms. However, BEROL 525, is also preferred in neutralised or 5. 2D242& partially neutralised form. Further BEROL anionic phosphate esters are available as-BEROL 521, BEROL 724 and BEROL 733. The weight ratio of monoester to diester may vary, typically from about 1:10 to 10:1. When the acid forms of the anionic phosphate ester surface active agents are neutralised or partially neutralised, alkali metal, preferably sodium, or ammonium cations are present. Desirably the stirred slurry pH of the completed dentifrice is in the range from 6.5 to 8, preferably 6.5 to 7.5. The preferred anionic phosphate ester is BEROL 513, The anionic phosphate ester, when present, is used in an amount up to about 5% by weight effective to stabilize the dentifrice in an unlined aluminium tube. This amount can be as little as about 0.051 and would depend, at least in part on the amounts of chloroform and siliceous polishing agent present. For instance with about 3.5% chloroform, it would be desirable to employ about 1.5% of the anionic phosphate ester. A typical ester content would be in the range of 0.1 to 2% by weight, preferably 0.5 to 1.5%, of the dentifrice. Besides stabilizing the dentifrice the anionic phosphate ester also provides surface active properties. Such surface active properties are described in New Zealand Patent Specification 179672 and 179673. The dentifrice as'mentioned above contains a high proportion of a liquid vehicle which may comprise ULV585 202428, water, in amount of at least 27.5% by weight of the preparation. The liquid vehicle may-additionally or alternatively comprise humectants such as glycerine, but unlike conventional high liquid vehicle dentifrices 5. can dispense with such humectants as sorbitol solution or propylene glycol. A mixture of water and glycerine is particularly advantageous. The solid portion of the vehicle of the dentifrice is a gelling agent or binder such as hydroxyethyl cellulose or hydroxypropyl cellulose, Irish moss, gum 15. tragacanth, sodium carboxymethyl cellulose, polyvinyl pyrrolidone, xanthan, starch or water-soluble hyaro-philic colloidal carboxyvinyl polymers such as those sold as CARBOPOL 9 34 and 940 (CARJ30P0L is a trade mark). The dentifrices will include an organic surface 20. active agent which can be replaced by the anionic phosphate ester stabilizing agent if such is present, or retained. Such additional agent may be anionic, nonionic, cationic or ampholytic in nature, and it is preferred to employ as the surface active agent a 25. detersive material which imparts to the dentifrice detersive and foaming properties. Suitable types of such detergents are water-soluble salts of higher (i.e. having at least 12 carbon atoms) fatty acid monogly-ceride monosulphates, such as the sodium salt of the 30. monosulphated monoglyceride of hydrogenated coconut oil fatty acids, higher alkyl sulphates, such as sodium lauryl sulphate, alkyl aryl' sulphonates, such as sodium aodecyl benzene sulphonate, olefin sulphonates, such as a sodium olefin sulphonate in which the olefin 5. croup contains 12-21 carbon atoms, higher alkyl sulpho-acetates, higher fatty acid esters of 1,2-dihydroxy propane sulphonates, and the substantially saturated higher aliphatic acyl amides of lower (i.e. having not more than 4 carbon atoms) aliphatic amino carboxylic 10. acid compounds, such as those having 12 to 16 carbons in the fatty acid, alkyl or acyl radicals. Examples of the last mentioned amides are N-lauroyl sarcosine, and the sodium, potassium and ethanolamine salts of N-lauroyl, N-myristoyl or N-palmitoyl sarcosine, which 15. should be substantially free from soap or similar higher fatty acid material which tends to substantially reduce the effect of these compounds. The use of these sarcosine compounds in dentifrices is particularly advantageous since these materials exhibit a prolonged 20. and marked effect in the inhibition of acid formation in the oral cavity due to the carbohydrates breakdown in addition to exerting some reduction in the solubility of tooth enamel in acid solutions. Other particularly suitable surface-active 25. materials include nonionic agents such as condensates of sorbitan monostearate with approximately 60 moles of ethylene oxide, condensates of ethylene oxide with propylene glycol ("Pluronics"~PLURONIC is a Trade Mark) and amphoteric agents such as quaternised imidazole 30. derivatives, which are available under the trade mark 8. 2. MIRANOL such as KIRANOL C2M. Cationic surface active germicides and anti-bacterial compounds such as di- isobutylphenoxyethoxyethy1 dimethyl benzyl ammonium 5. 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 20 to 50 ethanoxy groups per molecule) and salts thereof with acids, and compounds of the structure 10. R—x\-ChT-CKr-CH0K 2 2 ^ 2 \ (CR-CH-O) K Z, 4. v wherein R is a fatty alkyl group typically containing from 12 to 18 carbon atoms, and x, y and z total 3 or 15. higher, as well as salts thereof with mineral or organic acids, may also be used. The total amount of surface active agent, including the anionic phosphate ester, if present, typically does not exceed about 5%. In certain fonts of this invention, in addition to the source of irmo-fluorophosphate ion, a fluoride-prcrvidinq compound is present in the oral preparation. These aatpounds may be slightly soluble in water or may be fully water-solt±>le. They are characterised by their ability to release fluoride icns in water and by substantial freedom frcm reaction with other ccnpounds of the oral preparation. Amcng these materials are organic amine fluorides such as oetylamine hydrofluoride and bis (hydroxyethyl) - aminopropyl-N-hydrojy-ethyl-octadecyl-amine dihydrofluoride or inorganic fluoride salts, such as suitable alkali metal, alkaline earth metal, and heavy metal salts, for example, sodium fluoride, potassium fluoride, 202^28 ammonium fluoride, a copper fluoride, such as cuprous fluoride, zinc fluoride, a tin fluoride such as stannous fluoride, or stannous chlorofluoride, sodium fluoro-silicate, ammonium fluorosilicate, sodiupi fluorozirco-5. nate, aluminium mono and di-fluorophosphate, and fluorinated sodium calcium pyrophosphate. Alkali metal and tin fluorides are preferred. A mixture of sodium fluoride and sodium monofluorphosphate is also highly desirable. 10. The amount of the fluorine-providing compound is dependent to some extent upon the type of compound, its solubility, ana the type of oral preparation, but it must be a non-toxic amount. It is considered that an amount of such compound which releases a maximum of 1% 15. ■ by weight of fluoride ion, based on the weight of the preparation, is satisfactory. Any suitable minimum amount of such compound may be used, but it is preferable to employ sufficient compound to release from 0.00.5% to 1%, most preferably about 0.1%, by weight of 20. fluoride ion. Typically, in the cases of alkali metal fluoride and stannous fluoride, this component is present in an amount up to 2% by weight, based on the weight of the preparation, and preferably in the range of from 0.05% to 1%. 25. Antibacterial agents may also be present, typically in an amount of 0.01-5% by weight. Typical antibacterial agents include - (4-chlorobenzyl) -- (2,4 - dichlorobenzyl) biguanide; p - chlorophenylbiguanide; 30. 4 - chlorobenzhydrylbiguanide; 4 - chlorobenzhydrylguanylurea; N - 3 - lauroxypropyl - - p - chlorobenzylbiguanide; 1,6 - di - p - chlorophenylbiguanidohexane; (chlorhexidine); 1,6 - bis (2 - ethylhexylbiguanido)hexane? 1 - (laurylaimethylammonium) - 8 - (p-chlorobenzyldi- methylammoniuro) octane dichloride; 5,6 - dichloro - 2 - guanidinobenzimidazole; N1 - p - chlorophenyl - N3 - laurylbiguanide; 5 - amino - 1,3 - bis (2 - ethylhexyl) - 5 - methylhexahydro pyrimidine; and their non-toxic acid addition salts. Various other materials may be incorporated in the oral preparations of this invention as adjuvants. Examples are colouring or whitening agents, preservatives, silicones, chlorophyll compounds, and ammoniated material such as urea, diammonium phosphate, and mixtures thereof. •These adjuvants, where present, are incorporated in the preparations in amounts which do not substantially adversely affect the properties and characteristics desired. Whitening agents such as titanium dioxide or zinc oxide, typically in amount of 0.2 to 1% by weight provide a particularly fine cosmetic appearance to the dentifrice. The dentifrice will usually contain, flavouring and/or sweetening material, in addition to any chloroform which may be employed. Examples of suitable flavouring constitutentfc are flavouring oils, e.g. oils of spearmint, peppermint, wintergreen, sassafras, \ 11. clove, sage, eucalyptus, marjoram, cinnamon, lemon and orange, and methylsalicylate. Suitable sweetening agents include sucrose, lactose, maltoses, sorbitol, sodium cyclamate, perillartine and saccharin. Suitably flavour and sweetening agents may together comprise from 0.01% to 5% or more of the preparation. The dentifrice is typically prepared by dispersing the polishing material (and when chloroform is to be present the phosphate ester) in the dental vehicle and other components, (except for the chloroform) and then subjecting the mixture to deaeration after which any chloroform which is to be incorporated may be introduced in a closed vacuum system. The dentifrice is then placed in an aluminium tube. Due to the compositions stability to aluminium, the inner surface of the aluminium tube need not be provided with a lining and thus the tubes can be unlined aluminium tubes. However the stability of the composition is of benefit even when lined tubes are to be used because in this case gassing of such tubes in which the lining may be defective or damaged in use so as to expose the aluminium surface is avoided. Also the invention permits the use of its chloroform containing embodiments in tubes which,although lined,use linings which can be penetrated by chloroform or its breakdown products. The invention may be put into practice in various ways and one specific embodiment will be 4. - 24 Zm described to illustrate the invention with reference to the accompanying Example All amounts and proportions given in this specification are by weight unless otherwise indicated. EXAMPLE The dentifrice formulation given in Table 1 below was prepared in conventional manner by mixing the ingredients together and allowing them to gel with the water for 15 minutes at 45 to 50°C after which the qelled blend was mixed to adequately disperse the powders. The Table qives the composition and initial properties of the dentifrice formulation. TSie pH measurement of solids as slurries may be liable to variation depending an hew the slurry is made up and we thus prefer to define the technique used for pE measurement herein. Hie pH values both for the sodium alumino silicate (SAS) and the dentifrice formulation were measured an KENT Model No. 7060 pH meter using an OBION ocntoination electrode calibrated at pH 9.2 + 0.1 at 20°C using British Drug Houses borate buffer and at pH 7.0 + 0.1 at 20°C using BDH phosphate buffer. A 20% aqueous slurry in distilled.water of the test material was then made up and stirred for 10 minutes using a magnetic stirrer prior to determination .of the pH at 20°C. A pH measured this way will be referred to herein as a stirred slurry pfi- 202428 13." The following points should be noted about the data in Table 1. Note 1 The sodium carboxymethyl cellulose is grade 7 MF. Note 2 The % soluble fluoride value given is the (average 2 of two readings) X 10 , i.e. a figure of 10 in Table 1 means an average fluoride content of 0.10. Note 3 The pH for the dentifrice was measured immediately after the dentifrice had been made up. The dentifrice formulations given in the Table is filled in conventional manner into unlined aluminium tubes. 14. 202428 TABLE 1 COMPONENT AMOUNT Glycerine Sodium Carboxymethyl Cellulose - (1) Titanium Dioxide Sodium Saccharin Sodium Mono-fluorophosphate %soluble fluoride (2) Water Sodium Aluminosilicate (SAS) SAS Type pH of SAS Sodium Lauryl Sulphate Water Flavour pH of dentifrice - (3) 25.00 1.00 0.40 0.18 0.76 10.7 42.16 24.00 Dentolex 644 5.8 1.50 4.00 1.00 6.6 </div>

Claims

<div class="application article clearfix printTableText" id="claims"> 202428 15. The dentifrice formulation of the Example aged well in the unlined aluminium tubes over a three month oversize particles being present in the Dentolex 644 SAS material used and it may be that this problem could be overcome by sieving of this SAS material. Dentolex 644 may be obtained from Zeofinn Oy, of Hainina, Finland and the manufacturers describe it as having the following characteristics: period at 43°C, and though it contained some hard lumps throughout this period and suffered some yellowing at the end, there was no gassing. This lumpiness is thought to be due to some Chemical Composition Sodium Silico Aluminate Primary Particle Diameter Moisture Loss 0.016 microns Not more than 7% on heating to 105^ for 2 hours. Density Bulk Density Oil Absorption Refractive Index 2.0 g/cm3 at 25°C 300 Kg/m3 as packed 170 ml oil/lOOg 1.47 at 20°c ,202428 16 WHAT WE CLAIM IS: 1. A stable dentifrice comprising an aqueous dentally acceptable oral vehicle, at least 27.5% by weight of the dentifrice comprising water and dispersed in the said oral vehicle from 10 to 40% by weight of the dentifrice of an acidic siliceous polishing agent having a stirred slurry pH (as herein defined) in the range from 5.0 to less than 6.5, and a stabilizing amount of monofluorophosphate ion, the dentifrice having a stirred slurry pH in the range from 5.5 to 8. comprising a non toxic amount of at least 0.2% by weight of the dentifrice of chloroform and from 0.05 to 5% by weight of the dentifrice of a stabilizing anionic phosphate ester mixture, the said mixture comprising at least one monoester of the formula: 2. A stable dentifrice as claimed in Claim 1 also 0 OM OM and at least' one diester of the formula: O OM 'ATF.xT O' 2 9 J iJ L1985 202-4X8 1-7. wherein E is an alkyl group of 10 to 20 carbon atoms? n is a number from 1 to 6; and M hydrogen, alkali ■metal or ammonium. 3. A dentifrice as claimed in Claim 2 in which the chloroform is present in an amount in the range from 0.5 to 3.5% by weight of the dentifrice. 4. A dentifrice as claimed in Claim 3, in which the chloroform is present in an amount of about 0.5% by weight of the dentifrice. 5; A dentifrice as claimed in any of Claims 2 to • 4, in which the R group in the anionic phosphate ester mixture contains 16 to 18 carbon atoms and the weight ratio of monoester to diester is from substantially 1:10 to 10:1. 6. A dentifrice as claimed in-any one of Claims 1 to 5 in which the dentifrice comprises at least 30% by weight of water. 7. A dentifrice as claimed in Claim 6 in which the dentifrice comprises 35 to 60% by weight of water. 8. A dentifrice as claimed in Claim 7 in which the dentifrice comprises 4 0 to 55% by weight of water. JUL1985 •lb. 202423 9. A dentifrice as claimed in any one of Claims 1 to 8 in which the siliceous polishing agent is an alkali metal aluminosilicate. 10. A dentifrice as claimed in any one of Claims 1 to 9 in which the siliceous polishing agent comprises 10 to 30% by weight of the dentifrice. 11. A dentifrice as claimed in Claim 10 in which the siliceous polishing agent comprises 15 to 251 by weight of the dentifrice. 12. A dentifrice as claimed in any one of Claims 1 to 11 in which the stirred slurry pH of the siliceous polishing agent is in the range 5.0 to 6.4. A dentifrice as claimed in Claim 12 in which the stirred slurry pH of the siliceous polishing agent is in the range 5.5 to 6.0. 14. a dentifrice as claimed in any one of Claims 1 to 13 comprising at least 0.01% of mono-fluorophosphate ion. 15. a dentifrice as claimed in Claim 14 comprising at least 0,05% of mono-fluorophosphate ion. 16. A dentifrice as claimed in Claim 15 •comprising at least 0.09% of mono-fluorophosphate. ion. 29 JULY'S 2.02.428 19. 17. A dentifrice comprising 35% to 50% by weight water, from 0% to 30% by weight glycerine,15 to 25% of an alkali metal aluminosilicate polishing agent having a stirred slurry pH in the range 5.0 to 6.4, at least 0.5% by weight of alkali metal monofluorophosphate, calcined alumina in an amount in the range 0% to 15% by weight and one or more organic surface active agents in an amount not in excess of 5% by weight, the dentifrice having a stirred slurry pH in the range of 5.5 to 8. 18. A packaged dentifrice comprising an unlined aluminium tube and contained therein a dentifrice as claimed in any of Claims 1 to 17 in contact with the aluminium surface of the unlined aluminium tube. 19. A stable dentifrice substantially as specifically described herein with reference to the Example. WEST-WALKER, McCABE r" 29oUU9O3 </div>