EP0675707A1 - Tin fluoride preparation for the care of the teeth - Google Patents
Tin fluoride preparation for the care of the teethInfo
- Publication number
- EP0675707A1 EP0675707A1 EP94914304A EP94914304A EP0675707A1 EP 0675707 A1 EP0675707 A1 EP 0675707A1 EP 94914304 A EP94914304 A EP 94914304A EP 94914304 A EP94914304 A EP 94914304A EP 0675707 A1 EP0675707 A1 EP 0675707A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tin
- fluoride
- preparation
- preparation according
- surfactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 title claims abstract description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 27
- DAOANAATJZWTSJ-UHFFFAOYSA-N N-Decanoylmorpholine Chemical compound CCCCCCCCCC(=O)N1CCOCC1 DAOANAATJZWTSJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 5
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical group [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 claims description 5
- 235000003599 food sweetener Nutrition 0.000 claims description 4
- 239000003765 sweetening agent Substances 0.000 claims description 4
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 3
- 229940081974 saccharin Drugs 0.000 claims description 3
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims description 3
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 claims description 2
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 claims description 2
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 claims description 2
- 239000001525 mentha piperita l. herb oil Substances 0.000 claims description 2
- 229940041616 menthol Drugs 0.000 claims description 2
- 235000019477 peppermint oil Nutrition 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 11
- 239000000551 dentifrice Substances 0.000 description 10
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 7
- 235000013772 propylene glycol Nutrition 0.000 description 6
- 229960004063 propylene glycol Drugs 0.000 description 6
- 210000004268 dentin Anatomy 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 208000002925 dental caries Diseases 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 210000003739 neck Anatomy 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QEORFEJQETYFCL-UHFFFAOYSA-N O(F)F.[Sn+4] Chemical compound O(F)F.[Sn+4] QEORFEJQETYFCL-UHFFFAOYSA-N 0.000 description 2
- WINXNKPZLFISPD-UHFFFAOYSA-M Saccharin sodium Chemical class [Na+].C1=CC=C2C(=O)[N-]S(=O)(=O)C2=C1 WINXNKPZLFISPD-UHFFFAOYSA-M 0.000 description 2
- DTMUJVXXDFWQOA-UHFFFAOYSA-N [Sn].FOF Chemical compound [Sn].FOF DTMUJVXXDFWQOA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002324 mouth wash Substances 0.000 description 2
- OJTDGPLHRSZIAV-UHFFFAOYSA-N propane-1,2-diol Chemical compound CC(O)CO.CC(O)CO OJTDGPLHRSZIAV-UHFFFAOYSA-N 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 tin (IV) ions Chemical class 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000000378 dietary effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229940051866 mouthwash Drugs 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000003578 releasing effect Effects 0.000 description 1
- 208000008655 root caries Diseases 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229960002799 stannous fluoride Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical compound [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/20—Halogens; Compounds thereof
- A61K8/21—Fluorides; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
Definitions
- the present invention relates to a tin fluoride preparation for dental care.
- tin forms two fluorides, namely SnF4 and SnF2. Furthermore, it is known that hard tooth substance can be protected against caries and other tooth decay phenomena by means of fluoride compounds which cause mineralization. For this purpose, dental care products are added with soluble fluoride compounds which form insoluble, protective calcium fluoride with the calcium compounds of the teeth and are incorporated into the hydroxylapatite.
- tin (II) fluoride is also suitable for protecting the dentin.
- Divalent tin ions have the property of forming double phosphates of the general formula (Sn, Ca) 3 (PO_ ⁇ ) 2 with the calcium phosphate of dentine, which effectively protect the dentine with the formation of a protective layer and make it less sensitive and insoluble. This effect cannot be achieved with tin (IV) ions.
- Tin (II) fluoride is a white, odorless, hygroscopic and crystalline powder which is water-soluble but practically insoluble in alcohol, chloroform and ether. Aqueous solutions decompose in a few hours because tin (II) fluoride is unstable in the air and forms tin oxyfluoride, SnOF2 due to the action of atmospheric oxygen. Merck Index, No. 8636.
- CH-A-645 * 268 Furthermore is in the field of dental care known that the fluoride-releasing effect of toothpastes containing stannous fluoride is steadily decreasing. The same has been observed with mouthwashes, so that effective dentifrices can only be obtained by dissolving or introducing the tin fluoride into them shortly before use, which is practically impossible and not recommended for normal "home care" use.
- the dentifrices described in US Pat. Nos. 4,396,599 and CH-A-645,268 contain tin (II) fluoride only as fluorine ion donors, including tin (IV) fluoride and tin oxyfluoride suitable is.
- the publication WO 90/10435 describes the addition of fluorostannates to tooth gel preparations.
- the divalent tin is complexly bound in these and is released too slowly to be sufficiently effective.
- the invention seeks to remedy this and to provide a tin (II) fluoride-containing agent in which the tin remains essentially and for long periods in the divalent form, i.e. in which the divalent form is time-stabilized, but for the reaction with the Dentine remains available.
- tin (II) fluoride dissolves in propylene glycol (1, 2-dihydroxypropane) in an amount sufficient to use the solution in dentifrices. It was further found that the dentifrices produced therewith are stable in storage for much longer periods, i. H. that the divalent tin is stabilized by the choice of the solvent by means of propylene glycol, but remains bioavailable.
- the invention is based on the assumption that the oxygen in the water causes the conversion of SnF2 into SnOF2 and on the measures for the consequent avoidance of water in the preparation, possibly apart from very small amounts .
- what- Another solvent had to be found in water or water-containing media, which dissolves SnF2 in sufficient quantity, which prevents or at least drastically delays the oxidative decomposition of SnF2 in compounds of tetravalent tin, which is still suitable for the production of gel-like preparations and is also physiologically harmless.
- propylene glycol (1, 2-propanediol) can meet these requirements.
- preparations according to the invention also act on the hydrophil dentin, as a result of which the effect of the preparation lasts much longer than that of known preparations.
- the stability of the divalent fluoride is increased when a surfactant is incorporated into the preparation according to the invention.
- Any physiologically acceptable surfactant can be used.
- a sodium dioctyl sulfosuccinate is preferably used.
- the "REWOPOL SBDO 70" product has proven particularly useful, in a proportion of 0.1 to about 5% by weight, preferably about 3% by weight, based on the finished preparation.
- sodium dioctyl sulfosuccinate like other analog dialkyl sulfosuccinates, which can replace sodium dioctyl sulfosuccinate, has a very desirable bactericidal action which gives an effect against plaque.
- the preparation according to the invention in which the tin is stabilized in its divalent stage, can be in the form of a liquid for use as a mouthwash or as a tooth gel. In the latter case, it contains about 1 to 2% by weight of a hydroxyalkyl cellulose, which is soluble in propylene glycol and forms a gel with it.
- a preparation according to the invention consists, for example, of 90 to 96% by weight of propylene glycol, which may also contain traces of water, 0.05 to 0.6% by weight of sweetener, 0.1 to 0.5% by weight of aroma substances (peppermint oil , Menthol), 0.1 to 5% by weight of surfactant as described above, and 0.4 to 0.6% by weight of SnF2.
- the tin fluoride can be in the form of a solution or as a combined solution and finely divided suspension.
- a gel-like preparation additionally contains 1 to 2% by weight of hydroxypropyl cellulose.
- the sweetener is the sodium salt of saccharin (benzoic acid sulfimide, sodium salt), which is commercially available, e.g. B. under the name crystallose, is particularly suitable since it has sufficient solubility in propylene glycol for the intended use.
- Na-saccharin has about 300 to 500 times the sweetness of cane sugar.
- the preparations according to the invention can be produced by mixing the constituents in a manner known per se.
- the preparations according to the invention can be kept for several months without loss of activity.
- the dentifrice according to the invention has the following special properties:
- tooth neck sensitivity is prevented and existing tooth neck sensitivity is weakened or completely eliminated.
- fluoride ions due to the presence of fluoride ions, the formation of dental caries and root caries is prevented.
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Cosmetics (AREA)
Abstract
The tin fluoride tooth-care preparation described and claimed contains tin (II) fluoride which is dissolved or suspended in propylene glycol. The preparation contains no water, and the tin (II) fluoride is stabilized against oxidation to the non-bioavailable quadrivalent state by a surfactant.
Description
ZINNFLÜORID-PRAEPÄRAT FÜER DIE ZAHNPFLEGE TIN FLUORIDE PREPARATION FOR DENTAL CARE
Die vorliegende Erfindung betrifft ein Zinnfluorid-Präparat für die Zahnpflege.The present invention relates to a tin fluoride preparation for dental care.
Es ist bekannt, dass Zinn zwei Fiuoride bildet, nämlich SnF4 und SnF2- Weiterhin ist bekannt, dass Zahnhartsubstanz mittels Fluoridverbindungen, die eine Mineralisierung be¬ wirken, vor Karies und anderen Zahnabbau-Erscheinungen geschützt werden kann. Zu diesem Zweck gibt man Zahnpflege¬ mitteln lösliche Fluoridverbindungen zu, welche mit den Calciumverbindungen der Zähne unlösliches, schützendes Cal- ciumfluorid bilden und in den Hydroxylapatit eingebaut wer¬ den.It is known that tin forms two fluorides, namely SnF4 and SnF2. Furthermore, it is known that hard tooth substance can be protected against caries and other tooth decay phenomena by means of fluoride compounds which cause mineralization. For this purpose, dental care products are added with soluble fluoride compounds which form insoluble, protective calcium fluoride with the calcium compounds of the teeth and are incorporated into the hydroxylapatite.
Beim Behandeln der Zähne mit Präparaten, die eine ausrei¬ chend wirksame Konzentration an SnF2 enthalten, ist Zinn(II)-fluorid zusätzlich zum Schutz des Dentins geeig¬ net. Zweiwertige Zinnionen haben die Eigenschaft, mit dem Calciumphosphat des Dentins Doppelphosphate der allgemeinen Formel (Sn,Ca)3(PO_})2 zu bilden, die das Dentin unter Bil¬ dung einer Schutzschicht wirksam schützen sowie es weniger empfindlich und unlöslich machen. Diese Wirkung lässt sich mit Zinn(IV)-Ionen nicht erzielen.When treating the teeth with preparations which contain a sufficiently effective concentration of SnF2, tin (II) fluoride is also suitable for protecting the dentin. Divalent tin ions have the property of forming double phosphates of the general formula (Sn, Ca) 3 (PO_ } ) 2 with the calcium phosphate of dentine, which effectively protect the dentine with the formation of a protective layer and make it less sensitive and insoluble. This effect cannot be achieved with tin (IV) ions.
Zinn(II)-fluorid ist ein weisses, geruchloses, hygroskopi¬ sches und kristallines Pulver, das wasserlöslich, aber praktisch unlöslich in Alkohol, Chloroform und Ether ist. Wässrige Lösungen zersetzen sich in wenigen Stunden, denn Zinn(II)-fluorid ist an der Luft instabil und bildet durch die Einwirkung des Luftsauerstoffes Zinnoxyfluorid, SnOF2, vgl. Merck-Index, Nr. 8636.Tin (II) fluoride is a white, odorless, hygroscopic and crystalline powder which is water-soluble but practically insoluble in alcohol, chloroform and ether. Aqueous solutions decompose in a few hours because tin (II) fluoride is unstable in the air and forms tin oxyfluoride, SnOF2 due to the action of atmospheric oxygen. Merck Index, No. 8636.
Es ist bereits bekannt, Zahnpflegemitteln Zinnfluoride zu- zugeben, z.B. aus den Veröffentlichungen US-A-4' 396' 599 undIt is already known to add tin fluoride to dentifrices, e.g. from publications US-A-4'396'599 and
CH-A-645*268. Weiterhin ist auf dem Gebiet der Zahnpflege
bekannt, dass die fluoridabgebende Wirkung von Zahnpasten, welche Zinn(II)-fluorid enthalten, laufend abnimmt. Das gleiche wurde bei Mundwässern beobachtet, so dass wirksame Zahnpflegemittel nur dadurch erhalten werden können, dass das Zinnfluorid erst kurz vor Gebrauch darin aufgelöst bzw. eingebracht werden muss, was bei der normalen "Homecare"- Anwendung praktisch unmöglich und nicht empfehlenswert ist. So enthalten die Zahnpflegemittel, die in den Dokumenten US-A-4'396'599 und CH-A-645'268 beschrieben sind, Zinn(II)- fluorid lediglich als Fluorionenspender, wozu auch Zinn(IV)-fluorid bzw. Zinnoxyfluorid geeignet ist.CH-A-645 * 268. Furthermore is in the field of dental care known that the fluoride-releasing effect of toothpastes containing stannous fluoride is steadily decreasing. The same has been observed with mouthwashes, so that effective dentifrices can only be obtained by dissolving or introducing the tin fluoride into them shortly before use, which is practically impossible and not recommended for normal "home care" use. The dentifrices described in US Pat. Nos. 4,396,599 and CH-A-645,268 contain tin (II) fluoride only as fluorine ion donors, including tin (IV) fluoride and tin oxyfluoride suitable is.
Die Veröffentlichung WO 90/10435 beschreibt die Zugabe von Fluorostannaten zu Zahngel-Präparaten. In diesen ist das zweiwertige Zinn komplex gebunden und wird zu langsam frei¬ gesetzt, um ausreichend wirksam zu sein.The publication WO 90/10435 describes the addition of fluorostannates to tooth gel preparations. The divalent tin is complexly bound in these and is released too slowly to be sufficiently effective.
Hier will die Erfindung Abhilfe schaffen und ein Zinn(II)- fluorid enthaltendes Mittel zur Verfügung stellen, in dem das Zinn im wesentlichen und über lange Zeiträume in der zweiwertigen Form verbleibt, worin also die zweiwertige Form zeitstabilisiert ist, jedoch für die Reaktion mit dem Dentin verfügbar bleibt.Here, the invention seeks to remedy this and to provide a tin (II) fluoride-containing agent in which the tin remains essentially and for long periods in the divalent form, i.e. in which the divalent form is time-stabilized, but for the reaction with the Dentine remains available.
Es ist bereits versucht worden, Zahnpflegemittel zu schaf¬ fen, in denen das zugesetzte Zinn(II)-fluorid längere Zeit in der zweiwertigen Form verbleibt. Dies kann durch Kom¬ plexbildung erreicht werden, vgl. die oben genannte WO 90/10435, was sich aber nicht bewährt hat, wie bereits erwähnt wurde. Auch die Auflösung des Zinn(II)-fluorids in wasserhaltigem Glycerin gemäss CH-A-645'268 führt nicht zu einer bezüglich zweiwertigem Zinn stabilen Zubereitung.Attempts have already been made to create dentifrices in which the tin (II) fluoride added remains in the divalent form for a relatively long time. This can be achieved by complex formation, cf. the above-mentioned WO 90/10435, but this has not proven itself, as has already been mentioned. The dissolution of the tin (II) fluoride in water-containing glycerol according to CH-A-645'268 does not lead to a preparation which is stable with regard to divalent tin.
Es wurde nun gefunden, dass die Oxydation von Zinn(II)- fluorid zu Zinn(IV)-oxyfluorid durch den Luftsauerstoff oder den in den Zahnpflegemitteln normalerweise, also auch
in wasserhaltigem Glycerin, enthaltenen Sauerstoff verhin¬ dert werden kann, wenn das Zahnpflegemittel wasserfrei ist. Es wird nämlich vermutet, dass die Oxydation nur in Gegen¬ wart von Wasser bzw. H+-Ionen vor sich gehen kann, d.h. über das Zinn(IV)-dihydroxydifluorid verläuft, das dann in Zinn(IV)-ox fluorid zerfällt. Es ist in der Praxis nicht möglich, wasserfreies Glycerin darzustellen bzw. es wasser¬ frei zu halten, da es sehr hygroskopisch ist.It has now been found that the oxidation of tin (II) fluoride to tin (IV) oxyfluoride by the atmospheric oxygen or in the dentifrices normally, so too oxygen contained in water-containing glycerol can be prevented if the dentifrice is anhydrous. It is assumed that the oxidation can only take place in the presence of water or H + ions, ie via the tin (IV) dihydroxydifluoride, which then breaks down into tin (IV) oxyfluoride. In practice, it is not possible to prepare anhydrous glycerol or to keep it water-free, since it is very hygroscopic.
Nun löst sich Zinn(II)-fluorid nicht in ausreichenden Men¬ gen in Glycerin; die Auswahl von Lösungsmitteln ist sehr beschränkt, da diese auch andere Bestandteile des Zahnpfle¬ gemittels auflösen müssen und die vielseitigsten Anforde¬ rungen an Unbedenklichkeit und Ungiftigkeit erfüllen müs- sen.Now tin (II) fluoride does not dissolve in glycerin in sufficient quantities; The choice of solvents is very limited, since they also have to dissolve other components of the dentifrice and have to meet the most varied requirements in terms of safety and non-toxicity.
Es wurde nun gefunden, dass sich Zinn(II)-fluorid in Propy- lenglycol (1 , 2-Dihydroxypropan) in einer Menge auflöst, die zur Verwendung der Lösung in Zahnpflegemitteln ausreicht. Es wurde weiter gefunden, dass die damit hergestellten Zahnpflegemittel über viel längere Zeiten lagerstabil sind, d. h. dass das zweiwertige Zinn durch die Wahl des Lösungs¬ mittels Propylenglycol stabilisiert wird, jedoch bioverfüg¬ bar bleibt.It has now been found that tin (II) fluoride dissolves in propylene glycol (1, 2-dihydroxypropane) in an amount sufficient to use the solution in dentifrices. It was further found that the dentifrices produced therewith are stable in storage for much longer periods, i. H. that the divalent tin is stabilized by the choice of the solvent by means of propylene glycol, but remains bioavailable.
Das im Patentanspruch 1 definierte und in den abhängigen Ansprüchen weiter spezifizierte Präparat erfüllt demnach die oben dargestellte Aufgabe. Weiterhin wurde ein beson¬ ders geeignetes Verfahren zu dessen Herstellung gefunden, das im unabhängigen Patentanspruch 7 beansprucht wird.The preparation defined in claim 1 and further specified in the dependent claims therefore fulfills the task presented above. Furthermore, a particularly suitable process for its production was found, which is claimed in independent claim 7.
Die Erfindung beruht, wie bereits erwähnt, auf der Vermu¬ tung, dass der im Wasser befindliche Sauerstoff die Umwand¬ lung von SnF2 in SnOF2 hervorruft, und auf den Massnahmen zur konsequenten Vermeidung von Wasser im Präparat, even¬ tuell von ganz geringen Mengen abgesehen. Anstelle von Was-
ser oder wasserhaltigen Medien musste ein anderes Lösungs¬ mittel gefunden werden, das SnF2 in ausreichender Menge löst, den oxydativen Zerfall des SnF2 in Verbindungen des vierwertigen Zinns verhindert oder zumindest drastisch ver- zögert, das weiterhin zur Herstellung von gelförmigen Prä¬ paraten geeignet ist und ausserdem physiologisch unbedenk¬ lich ist. Ausgedehnte Forschungen haben ergeben, dass Pro- pylenglycol (1 ,2-Propandiol) diese Anforderungen zu erfül¬ len vermag. Ueberraschenderweise wurde weiterhin gefunden, dass erfindungsgemasse Präparate ebenfalls auf das hydro¬ phil Dentin einwirken, wodurch die Wirkung des Präparates viel länger als diejenige bekannter Präparate anhält.As already mentioned, the invention is based on the assumption that the oxygen in the water causes the conversion of SnF2 into SnOF2 and on the measures for the consequent avoidance of water in the preparation, possibly apart from very small amounts . Instead of what- Another solvent had to be found in water or water-containing media, which dissolves SnF2 in sufficient quantity, which prevents or at least drastically delays the oxidative decomposition of SnF2 in compounds of tetravalent tin, which is still suitable for the production of gel-like preparations and is also physiologically harmless. Extensive research has shown that propylene glycol (1, 2-propanediol) can meet these requirements. Surprisingly, it was also found that preparations according to the invention also act on the hydrophil dentin, as a result of which the effect of the preparation lasts much longer than that of known preparations.
Lösungen von Zinn(II)-fluorid in Propylenglycol sind bisher nicht bekannt geworden. Es wurde gefunden, dass sich Zinn(II)—fluorid in Propylenglycol zu einer Konzentration im Bereich von etwa 1 Gew.-% löst, was für die Praxis aus¬ reicht.Solutions of tin (II) fluoride in propylene glycol have so far not been disclosed. It has been found that tin (II) fluoride dissolves in propylene glycol to a concentration in the range of about 1% by weight, which is sufficient in practice.
Es wurde weiterhin überraschend gefunden, dass die Stabili¬ tät des zweiwertigen Fluorids erhöht wird, wenn in das er¬ findungsgemasse Präparat ein Tensid eingearbeitet wird. Es kann ein beliebiges, physiologisch unbedenkliches Tensid verwendet werden. Bevorzugt wird ein Natriumdioctylsulfo- succinat eingesetzt. Besonders bewährt hat sich das Produkt "REWOPOL SBDO 70", und zwar in einem Mengenanteil von 0,1 bis etwa 5 Gew.-%, bevorzugt etwa 3 Gew.-%, bezogen auf das fertige Präparat. Darüber hinaus besitzt Natriumdioctylsul- fosuccinat wie auch andere, analoge Dialkylsulfosuccinate, welche das Natriumdioctylsulfosuccinat ersetzen können, ei¬ ne sehr erwünschte bakterizide Wirkung, die einen Effekt gegen Plaque ergibt.It was also surprisingly found that the stability of the divalent fluoride is increased when a surfactant is incorporated into the preparation according to the invention. Any physiologically acceptable surfactant can be used. A sodium dioctyl sulfosuccinate is preferably used. The "REWOPOL SBDO 70" product has proven particularly useful, in a proportion of 0.1 to about 5% by weight, preferably about 3% by weight, based on the finished preparation. In addition, sodium dioctyl sulfosuccinate, like other analog dialkyl sulfosuccinates, which can replace sodium dioctyl sulfosuccinate, has a very desirable bactericidal action which gives an effect against plaque.
Das erfindungsgemasse Präparat, in dem das Zinn in seiner zweiwertigen Stufe stabilisiert ist, kann als Flüssigkeit zur Anwendung als Mundspülmittel oder als Zahngel vorlie-
gen. Im letzteren Falle enthält es etwa 1 bis 2 Gew.—% ei¬ ner Hydroxyalkylcellulose, welche in Propylenglycol löslich und mit diesem gelbildend ist.The preparation according to the invention, in which the tin is stabilized in its divalent stage, can be in the form of a liquid for use as a mouthwash or as a tooth gel. In the latter case, it contains about 1 to 2% by weight of a hydroxyalkyl cellulose, which is soluble in propylene glycol and forms a gel with it.
Ein erfindungsgemässes Präparat besteht beispielsweise aus 90 bis 96 Gew.-% Propylenglycol, das auch Spuren von Wasser enthalten kann, 0,05 bis 0,6 Gew.-% Süssstoff, 0,1 bis 0,5 Gew.-% Aromastoffe (Pfefferminzöl, Menthol), 0,1 bis 5 Gew.—% Tensid wie oben beschrieben, und 0,4 bis 0,6 Gew.-% SnF2- Das Zinnfluorid kann in Form einer Lösung oder als kombinierte Lösung und feinteilige Suspension vorliegen.A preparation according to the invention consists, for example, of 90 to 96% by weight of propylene glycol, which may also contain traces of water, 0.05 to 0.6% by weight of sweetener, 0.1 to 0.5% by weight of aroma substances (peppermint oil , Menthol), 0.1 to 5% by weight of surfactant as described above, and 0.4 to 0.6% by weight of SnF2. The tin fluoride can be in the form of a solution or as a combined solution and finely divided suspension.
Ein gelförmiges Präparat enthält zusätzlich 1 bis 2 Gew.-% Hydroxypropylcellulose.A gel-like preparation additionally contains 1 to 2% by weight of hydroxypropyl cellulose.
Es hat sich gezeigt, dass als Süssstoff das Natriumsalz des Saccharins (Benzoesäuresulfimid, Natriumsalz), welches handelsüblich ist, z. B. unter der Bezeichnung Kristallose, besonders geeignet ist, da es eine für den Verwendungszweck ausreichende Löslichkeit in Propylenglycol besitzt. Na- Saccharin besitzt etwa die 300- bis 500-fache Süsskraft von Rohrzucker.It has been shown that the sweetener is the sodium salt of saccharin (benzoic acid sulfimide, sodium salt), which is commercially available, e.g. B. under the name crystallose, is particularly suitable since it has sufficient solubility in propylene glycol for the intended use. Na-saccharin has about 300 to 500 times the sweetness of cane sugar.
Die erfindungsgemässen Präparate können nach an sich bekannten Arbeitsweisen durch Vermischen der Bestandteile hergestellt werden.The preparations according to the invention can be produced by mixing the constituents in a manner known per se.
Die erfindungsgemässen Präparate sind über mehrere Monate ohne Aktivitätsverlust haltbar.The preparations according to the invention can be kept for several months without loss of activity.
Das erfindungsgemasse Zahnpflegemittel hat die folgenden besonderen Eigenschaften:The dentifrice according to the invention has the following special properties:
Grundsätzlich erhält die ganze Zahnoberfläche, besonders aber freiliegende Zahnhälse und Wurzeloberflächen, einen ausgeprägten Schutz gegen Erosion durch diätetische Säuren.
Das Entstehen von Zahnhals-Sensibilität wird verhindert und bestehende Zahnhals—Sensibilität abgeschwächt oder ganz be¬ seitigt. Ausserdem wird infolge der Anwesenheit von Fluo- ridionen dem Entstehen von Zahnhals- und Wurzelkaries vor- gebeugt.
Basically, the entire tooth surface, but especially exposed tooth necks and root surfaces, receives a pronounced protection against erosion through dietary acids. The development of tooth neck sensitivity is prevented and existing tooth neck sensitivity is weakened or completely eliminated. In addition, due to the presence of fluoride ions, the formation of dental caries and root caries is prevented.
Claims
1. Zinnfluorid-Präparat für die Zahnpflege, enthaltend Zinn(II)-fluorid, dadurch gekennzeichnet, dass das Präparat praktisch wasserfrei ist und das Zinn(II)-fluorid als Lö¬ sung oder als Lösung und Suspension in Propylenglycol vor¬ liegt, wodurch das Zinn in seiner zweiwertigen Form bioverfügbar stabilisiert ist.1. tin fluoride preparation for dental care, containing tin (II) fluoride, characterized in that the preparation is practically anhydrous and the tin (II) fluoride is present as a solution or as a solution and suspension in propylene glycol, whereby the tin is bioavailable stabilized in its divalent form.
2. Präparat nach Anspruch 1, dadurch gekennzeichnet, dass es weiterhin ein Tensid enthält.2. Preparation according to claim 1, characterized in that it further contains a surfactant.
3. Präparat nach Anspruch 2, dadurch gekennzeichnet, dass das Tensid Natriumdioctylsulfosuccinat ist.3. Preparation according to claim 2, characterized in that the surfactant is sodium dioctyl sulfosuccinate.
4. Präparat nach einem der vorstehenden Ansprüche, da¬ durch gekennzeichnet, dass es als Zahngel vorliegt und zu¬ sätzlich eine Hydroxyalkylcellulose, bevorzugt Hydroxypro- pylcellulose, enthält.4. Preparation according to one of the preceding claims, characterized in that it is present as a tooth gel and additionally contains a hydroxyalkyl cellulose, preferably hydroxypropyl cellulose.
5. Präparat nach einem der vorstehenden Ansprüche, da— druch gekennzeichnet, dass es zusätzlich Aromastoffe und Süssstoff enthält.5. Preparation according to one of the preceding claims, characterized in that it additionally contains flavorings and sweeteners.
6. Präparat nach Anspruch 4, gekennzeichnet durch folgen¬ de Zusammensetzung in Gew.-%:6. Preparation according to claim 4, characterized by the following composition in% by weight:
Propylenglycol (1 ,2-Dihydioxypropan) 90 - 96 Zinn(II)-fluorid 0 , 4 - 0 , 6 Tensid (Natriumdioctylsulfosuccinat) 0 , 1 — 5 Hydroxypropylcellulose 1 — 2 Süssstoff (Na—Saccharin) 0 , 05 - 0 , 6 Aromastoffe (Menthol, Pfefferminzöl) 0 , 1 — 0 , 5 ,Propylene glycol (1,2-dihydioxypropane) 90-96 tin (II) fluoride 0.4-0.6 surfactant (sodium dioctyl sulfosuccinate) 0.1-5 hydroxypropyl cellulose 1-2 sweetener (Na-saccharin) 0.05-0.6 Flavorings (menthol, peppermint oil) 0, 1 - 0, 5,
wobei das Präparat noch Farbstoffe und Wasser in Spurenmen¬ gen enthalten kann. the preparation can also contain dyes and water in trace amounts.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1609/93 | 1993-05-28 | ||
| CH160993 | 1993-05-28 | ||
| PCT/CH1994/000091 WO1994027565A1 (en) | 1993-05-28 | 1994-05-17 | Tin fluoride preparation for the care of the teeth |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0675707A1 true EP0675707A1 (en) | 1995-10-11 |
Family
ID=4214439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94914304A Withdrawn EP0675707A1 (en) | 1993-05-28 | 1994-05-17 | Tin fluoride preparation for the care of the teeth |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0675707A1 (en) |
| WO (1) | WO1994027565A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6592853B2 (en) * | 1999-03-10 | 2003-07-15 | Block Drug Company, Inc. | Dentin desensitizer containing stannous fluoride |
| EP1566166B1 (en) * | 2002-11-07 | 2013-02-13 | Nippon Zettoc Co., Ltd. | Base for oral composition and oral composition |
| RU2460512C2 (en) * | 2008-04-24 | 2012-09-10 | Габа Интернациональ Холдинг Аг | Oral care composition containing dissolved tin and fluoride |
| EP2111844A1 (en) * | 2008-04-24 | 2009-10-28 | Gaba International AG | Oral care composition comprising dissolved tin and fluoride |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5835965B2 (en) * | 1979-07-31 | 1983-08-05 | ライオン株式会社 | Oral composition |
| JPS5695112A (en) * | 1979-12-28 | 1981-08-01 | Lion Corp | Gel agent for oral cavity |
| US4396599A (en) * | 1981-09-17 | 1983-08-02 | Johnson & Johnson Products Inc. | Anticaries composition |
| US4568540A (en) * | 1984-04-18 | 1986-02-04 | Johnson & Johnson | Oral hygiene compositions |
| US4701319A (en) * | 1984-09-14 | 1987-10-20 | The Procter & Gamble Company | Toothpaste compositions |
| GB9110721D0 (en) * | 1991-05-17 | 1991-07-10 | Unilever Plc | Dentifrice compositions |
-
1994
- 1994-05-17 EP EP94914304A patent/EP0675707A1/en not_active Withdrawn
- 1994-05-17 WO PCT/CH1994/000091 patent/WO1994027565A1/en not_active Ceased
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9427565A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1994027565A1 (en) | 1994-12-08 |
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