WO1998002135A1 - Compositions stabilisees contenant des ions stanneux pour soins buccaux - Google Patents

Compositions stabilisees contenant des ions stanneux pour soins buccaux Download PDF

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Publication number
WO1998002135A1
WO1998002135A1 PCT/US1997/010678 US9710678W WO9802135A1 WO 1998002135 A1 WO1998002135 A1 WO 1998002135A1 US 9710678 W US9710678 W US 9710678W WO 9802135 A1 WO9802135 A1 WO 9802135A1
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WO
WIPO (PCT)
Prior art keywords
stannous
oral care
fluoride
salt
aqueous composition
Prior art date
Application number
PCT/US1997/010678
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English (en)
Inventor
Robert E. Tricca
Pascal H. Destandau
Original Assignee
Gillette Canada Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Gillette Canada Inc. filed Critical Gillette Canada Inc.
Priority to AU34047/97A priority Critical patent/AU3404797A/en
Publication of WO1998002135A1 publication Critical patent/WO1998002135A1/fr

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Classifications

    • 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
    • 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
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof

Definitions

  • compositions for oral care with increased stannous ion stability are directed to compositions comprised of a soluble stannous salt and an insoluble stannous salt stabilized with an acyl sarcosinate salt, e.g. sodium, ammonium, potassium, triethanol amine (TEA) salts, or mixtures thereof.
  • acyl sarcosinate salt e.g. sodium, ammonium, potassium, triethanol amine (TEA) salts, or mixtures thereof.
  • Preferred compositions of the present invention also include a fluoride ion source, e.g. sodium fluoride, stannous fluoride or sodium monofluorophosphate.
  • the compositions of the invention are particularly useful in the form of aqueous toothpaste compositions.
  • Stannous fluoride has been used in oral care products since the early 1950's, and stannous fluoride has been reported to be an effective agent for treating various oral conditions and diseases including plaque, gingivitis, sensitivity, enamel decalcification, and periodontitis, among others.
  • Product stability is a notorious problem because stannous fluoride is unstable in water and forms stannous oxyfluoride and stannic compounds, both of which reduce or inhibit enamel fluoridation, that is, formation of stannous fluorophosphate and fluorapatite. This instability has required formulation of stannous-containing home treatment products as anhydrous gels.
  • stannous fluoride formulations have been reformulated as stannous ion-free compositions because of the instability of the stannous ion in water. Numerous stannous fluoride formulations with "stabilizing agents" have been proposed.
  • U.S. Patents Nos. 3,711,604; 3,919,409; 3,935,306 and 3,980,767 disclose toothpaste and dentifrice formulations including soluble fluoride compounds, including stannous fluoride.
  • the toothpaste formulations use a variety of standard ingredients and gelling agents including carboxyvinyl polymers sold under the trade name Carbopol and insoluble abrasives such as silica and silicates.
  • the stannous fluoride-containing embodiments disclosed in these patents lack the stability found in the compositions of this invention.
  • U.S. Patent No. 4,418,057 describes another approach.
  • Stannous fluoride is formulated as a non-aqueous gel mixture including anhydrous glycerin and hydroxyethyl cellulose gelling agent. Total exclusion of moisture from the gel is required to protect the stannous ion.
  • U.S. Patent No. 4,259,316 while noting the instability of stannous fluoride, proposes a composition containing phytic acid for inhibiting dental caries. Both dry dentifrices and aqueous gel and mouthwash formulations are described. If protected from moisture, the dentifrices would appear to retain the stannous ion in efficacious form.
  • the stannous ion would rapidly convert to the ineffective oxy- stannous or stannic forms upon exposure to moisture in solution or in the oral cavity. Apparently, excess amounts of stannous fluoride are added in an effort to offset the loss of stannous ion. However, this requires the exposure of the user to excessive levels of stannous ion.
  • EP application 88308337.0 (Publication No. 0 31 1 260 A3) published April 12, 1989 describes compositions containing stannous fluoride and, as a stannous reservoir to replace stannous ion lost through degradation, stannous gluconate. Mouthwashes are also described.
  • U.S. Patent No. 4,254,101 describes compositions containing a humectant, silica abrasive, a carboxyvinyl polymer, water and fluoride compounds as optional ingredients.
  • the only carboxyvinyl polymers disclosed are colloidally water-soluble polymers of acrylic acid crosslinked with polyallyl sucrose or polyallyl pentaerythritol.
  • a variety of fluoride compounds including sodium fluoride are described as suitable optional ingredients.
  • Stannous fluoride is included in the list of suitable fluoride compounds although no suggestion is made about its instability or that it could be used as an effective source of stannous ion. It is presented as equivalent to sodium fluoride as source of fluoride ion.
  • Phosphorus- containing anticalculus agents are also listed as optional ingredients. - j -
  • U.S. Patent No. 4,515,772 describes oral compositions including dentifrices and aqueous compositions including toothpastes and mouthwashes containing certain pyrophosphate salts as anticalculus formulations.
  • the prior art description lists a number of chelating agents proposed as anticalculus agents, including EDT (ethylenediaminetetraacetic acid), nitrilotriacetic acid, polyphosphonates and fluoride, and carbonyl diphosphonates.
  • EDT ethylenediaminetetraacetic acid
  • nitrilotriacetic acid polyphosphonates and fluoride
  • carbonyl diphosphonates carbonyl diphosphonates.
  • the patent lists as suitable abrasives silica, calcium pyrophosphate, ⁇ -phase pryophosphate, alumina and other materials.
  • fluoride ion sources are listed.
  • Stannous fluoride is included in the list although no suggestion is made about its instability or that it could be used as an effective source of stannous ion.
  • a variety of flavoring agents are disclosed. Included in a list of binders are gums and carboxyvinyl polymers.
  • U.S. Patent Nos. 4,960,586; 4,961 ,924; 4,970,065; 5,009,883; 5,009,884 and 5,017.363 to Suhonen relate generally to oral care compositions containing an alkyl vinyl ether and maleic anhydride or acid copolymer as a stabilizing agent for stannous fluoride.
  • the present invention provides a stannous ion-containing composition for oral care containing a soluble stannous salt, an insoluble stannous salt and an acyl sarcosinate salt in an amount sufficient to effectively stabilize the stannous ion concentration.
  • An embodiment of the invention resides in the stannous salt being in combination with an acyl sarcosinate sodium in an amount to effectively stabilize the stannous ion.
  • the composition for oral care is an aqueous dentifrice.
  • the present oral care compositions include two types of stannous salts which are stabilized with an acyl sarcosinate. Both water soluble and water insoluble stannous salts are utilized.
  • Suitable water soluble stannous salts include stannous fluoride, stannous chloride, stannous chloride fluoride, stannous acetate, sodium stannous fluoride, potassium stannous fluoride, stannous hexafluorozirconate, stannous sulfate, stannous tartrate, and mixtures thereof.
  • Suitable water insoluble stannous salts include stannous pyrophosphate, stannous metaphosphate, stannous oxide, stannous oxalate, stannous phosphate, and mixtures thereof.
  • the essential ingredients of the aqueous compositions of this invention are a soluble stannous salt, an insoluble stannous salt and a substituted acyl sarcosinate in an effective stabilizing amount.
  • the term "effectively stabilized” and “effectively stabilizing amount” is defined to mean that the stannous ion concentration, expressed as stannous fluoride, after 12 weeks storage under the conditions described in the examples below is equivalent to about 70 percent or more of the original concentration of stannous ion at the time of formulation.
  • the stannous ion stabilizing polymer are the sodium, ammonium, potassium or triethanol amine salts of acyl sarcosinate of the general formula:
  • acyl sarcosinate is a straight-chained, N-acyl sarcosinate.
  • a preferred stannous ion stabilizing polymer is sodium lauroyl sarcosinate [CAS Number 137-16-6] of the empirical formula C, ,- H o NO ⁇ -Na.
  • This material is available commercially under the following names: Crodasinic LS35 (Croda Chemicals Ltd.) Crodasinic LS40 (Croda Chemicals Ltd.) Glycine, N-Methyl-N-(l-Oxododecyl)-Sodium Salt Hamposyl L-3O (Hampshire)
  • Vanseal NALS-30 (R.T. Vanderbilt) Vanseal NALS-95 (R.T. Vanderbilt)
  • stannous ion stabilizing polymer is sodium cocoyl sarcosinate [CAS Number 61791-59-1] of the empirical formula:
  • I I o represents the fatty acids derived from coconut oil (chain length C 6 to C j g). This material is commercially available under the following names:
  • stannous ion stabilizing polymer is sodium myristoyl sarcosinate [CAS Number 30364-51-3] of the empirical formula:
  • stannous ion stabilizing polymers include: TEA Lauroyl Sarcosinate [CAS No. 68411-96-1], sold under Crodasinic LT40 (Croda Chemical Ltd.) and Hamposyl LT-40 (Hampshire); Ammonium Cocoyl Sarcosinate sold under Hamposyl AC-30 (Hampshire); Ammonium Lauroyl Sarcosinate [CAS No. 68003-46-3] sold under Hamposyl AL-30 (Hampshire); or a mixture of TEA Oleyl Sarcosinate & TEA Cocoyl Sarcosinate sold under the name Hamposyl TOC- 30 (Hampshire).
  • the acyl sarcosinate salt may be obtained commercially or, alternatively, the alkyl sarcosinate salt may be generated in-situ by neutralizing an acid sarcosine with bases such as Sodium and Potassium Hydroxide.
  • the composition is an aqueous toothpaste.
  • the composition may contain from about 0.1 to about 5 weight percent of the substituted acyl sarcosinate (preferably about 1.75%), from about 0.05 to about 1.1 weight percent soluble stannous salt (preferably about 0.45%)) and from about 0.1 to about 5 weight percent insoluble stannous salt (preferably about 1%).
  • compositions of the present invention also contain a fluorine-containing compound having a beneficial effect on the care and hygiene of the oral cavity, e.g., diminution of enamel solubility in acid and protection of the teeth against decay.
  • a fluorine-containing compound having a beneficial effect on the care and hygiene of the oral cavity, e.g., diminution of enamel solubility in acid and protection of the teeth against decay.
  • fluorine-containing compound having a beneficial effect on the care and hygiene of the oral cavity, e.g., diminution of enamel solubility in acid and protection of the teeth against decay.
  • examples thereof include sodium fluoride, stannous fluoride, potassium fluoride, potassium stannous fluoride (SnF 2 F), sodium hexafluoro- stannate, stannous chlorofluoride, sodium fluorozirconate and sodium mono- fluorophosphate.
  • compositions of this invention may also contain other conventional components such as anti-foaming agents, gelling agents, flavoring agents (e.g., natural or synthetic flavor oils), anticariogenic agents, soluble fluoride compounds, coloring or whitening agents, antibacterial agents, preservatives and chlorophyll compounds.
  • Additional ammoniated materials which do not interfere with the stability of the stannous ion by reacting therewith or with the substituted acyl sarcosinate may also be used, e.g., the materials described in U.S. Patents 4,418,057; 4,254,101 and 4,627,977.
  • humectants include sorbitol, glycerin, or other polyhydric alcohols.
  • the compositions which are toothpastes may contain one or more compatible abrasive agents.
  • the dentifrice compositions contain from about 3% to 30%, preferably from about 5% to about 20% by weight of a silica abrasive polishing material.
  • the silica abrasive polishing material used generally has an average particle size ranging between about 0.1 to about 30 microns, preferably about 5 to about 15 microns.
  • the abrasive can be precipitated silica or silica gels such as the silica xerogels described in Pader et al; U.S.
  • Patent No. 3,538,230 Preferred are the silica xerogels marketed under the trade names "Syloid” and “Sylodent” by the W.R. Grace & Company, Davidson Chemical Division.
  • the types of silica dental abrasives useful in the toothpastes of the present invention are described in more detail in DiGiulio, U.S. Patent No. 3,862,307.
  • the toothpaste compositions of the invention may have a pH within the range of from 2.5 to 6 and preferably from 4 to 5.
  • compositions which are non-abrasive home treatment gels may also contain conventional aqueous gelling agents.
  • Gelling agents may be Irish moss, gum tragacanth, starch, polyvinylpyrolidone, hydroxyethyl propylcellulose, hydroxy- butyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, sodium carboxymethyl cellulose, xantham gum, carrageenan, fumed silicas, hydroxypropylcellulose and the like.
  • Sorbitol, sodium saccharin, PVM/MA copolymer (solution), and stannous fluoride were added to mixing vessel.
  • the vessel was sealed under vacuum and Carbomer dispersed in water was drawn in with mixing. Part of the sodium hydroxide solution was added followed by the glycerin and PEG-8.
  • Zinc citrate was premixed with remaining amount of calcium pyrophosphate, xantham gum and stannous pyrophosphate and added to main vessel while mixing.
  • the remaining amount of sodium hydroxide solution was added followed by the sodium lauroyl sarcosinate and the flavor.
  • Glycerin 10.42 10.42 10.42
  • Stability data illustrating effect of surfactant and pH on available stannous over time.
  • concentration of stannous ion is expressed in ppm.
  • the pH reported are the stabilized pH. For all samples the pH dropped by approximately 0.5 unit within forty eight hours of preparation and stabilized at that level. We attribute the increase in stannous ion during the first week of preparation to the pH shift.
  • Sorbitol, water, sodium saccharin titanium dioxide, and stannous fluoride were added to mixing vessel.
  • the gum slurry was added to the main mixing vessel and mixed till homogenous.
  • Syloid 244 was added and mixed.
  • the stannous pyrophosphate was blended with the Sylodent 750 and added to the batch.
  • the surfactant and the flavor were added and mixed in.
  • the product was then deaerated by mixing under vacuum.
  • Flavor 1.0 1.0
  • Syloid 244 10.0 10.0 10.0 10.00 10.0 10.0 10.00
  • Sylodent 750 8.0 8.0 8.0 8.0 8.0 8.0 Glycerin 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0
  • Titanium Dioxide 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
  • Example XII show that the effect of the surfactant on the available stannous level remain the same with high level of insoluble stannous salt.
  • EXAMPLE XIV A full production sized pilot batch was prepared to evaluate the influence of processing on the long term stability of available stannous in the product.
  • a quantity of premix sufficient to prepare three 2,500 kg batches of toothpaste was prepared in an open vessel. Sufficient amount of premix was then drawn into a vacuum vessel to complete the manufacturing process.
  • the premix was prepared by loading sorbitol into mixing vessel, adding water, stannous fluoride, sodium saccharin, and titanium dioxide and mixing till homogenous.
  • a side vessel equipped with a Cowles disperser blade the glycerin was added, the disperser blade was started and the xantham gum and the carrageenan were added.
  • the PEG-8 was added.
  • the gum slurry was then added to the main mixing vessel and mixed till homogenous. This premix can be held for up lo 24 hours without affecting the available stannous level in the finished product.
  • the toothpaste was prepared according to the formula:
  • the toothpaste was prepared by loading the premix in a vacuum vessel, adding the sodium hydroxide solution and the monoammonium glycyrrhizinate. The tank was sealed under vacuum and the stannous pyrophosphate, Sylodent 750 and Syloid 244 drawn into the tank and mixed. The sodium lauroyl sarcosinate was added and mixed under vacuum. The flavor was then added and mixed. At zero time the available stannous concentration was 3160 ppm, after 50 weeks at room temperature the available stannous concentration was 3120 ppm.
  • the formula in this example is similar to formula IX listed above.

Abstract

La présente invention concerne une composition contenant des ions stanneux pour soins buccaux, comprenant un sel stanneux soluble, un sel stanneux non soluble et un sel d'acylsarcosinate en une quantité suffisante pour stabiliser efficacement la concentration d'ions stanneux. Dans un des modes de réalisation, le sel stanneux est combiné avec un sodium d'acylsarcosinate, en une quantité pouvant efficacement stabiliser les ions stanneux. De préférence, la composition pour soins buccaux se présente sous la forme d'un dentifrice aqueux.
PCT/US1997/010678 1996-07-15 1997-06-19 Compositions stabilisees contenant des ions stanneux pour soins buccaux WO1998002135A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU34047/97A AU3404797A (en) 1996-07-15 1997-06-19 Stabilized stannous-containing compositions for oral care

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US68072996A 1996-07-15 1996-07-15
US08/680,729 1996-07-15

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007061328A1 (fr) * 2005-11-25 2007-05-31 'wds' Company Composition de soins et de prevention pour la cavite buccale
EP2374446A1 (fr) * 2010-04-07 2011-10-12 GABA International Holding AG Compositions de soins oraux comprenant des ions nitrate et étain(II)
US10555883B2 (en) 2015-07-01 2020-02-11 Colgate-Palmolive Company Oral care compositions and methods of use
US10588840B2 (en) 2016-06-24 2020-03-17 Colgate-Palmolive Company Oral care compositions and methods of use
WO2020131401A1 (fr) * 2018-12-20 2020-06-25 Colgate-Palmolive Company Dentifrice contenant du bicarbonate de sodium et du fluorure stanneux
CN111989083A (zh) * 2018-03-29 2020-11-24 宝洁公司 用于促进牙龈健康的口腔护理组合物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3029191A (en) * 1958-04-28 1962-04-10 Colgate Palmolive Co Dental preparations consisting essentially of a fluoride compound and a sarcoside compound to reduce the fluoride toxicity
US4335102A (en) * 1979-09-20 1982-06-15 Lion Corporation Oral composition for caries prophylaxis
WO1995007682A1 (fr) * 1993-09-16 1995-03-23 Unilever N.V. Compositions orales contenant des composes stanneux

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3029191A (en) * 1958-04-28 1962-04-10 Colgate Palmolive Co Dental preparations consisting essentially of a fluoride compound and a sarcoside compound to reduce the fluoride toxicity
US4335102A (en) * 1979-09-20 1982-06-15 Lion Corporation Oral composition for caries prophylaxis
WO1995007682A1 (fr) * 1993-09-16 1995-03-23 Unilever N.V. Compositions orales contenant des composes stanneux

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007061328A1 (fr) * 2005-11-25 2007-05-31 'wds' Company Composition de soins et de prevention pour la cavite buccale
EA011125B1 (ru) * 2005-11-25 2008-12-30 Общество С Ограниченной Ответственностью "Вдс" Лечебно-профилактический состав для ухода за полостью рта
KR101234172B1 (ko) 2005-11-25 2013-02-19 "더블유디에스"컴퍼니 구강 치료 및 예방 조성물
EP2374446A1 (fr) * 2010-04-07 2011-10-12 GABA International Holding AG Compositions de soins oraux comprenant des ions nitrate et étain(II)
WO2011124659A1 (fr) * 2010-04-07 2011-10-13 Gaba International Holding Ag Composition de soin buccal comprenant des ions stanneux et nitrate
US8926950B2 (en) 2010-04-07 2015-01-06 Gaba International Holding Ag Oral care composition comprising stannous and nitrate ions
US10555883B2 (en) 2015-07-01 2020-02-11 Colgate-Palmolive Company Oral care compositions and methods of use
US10588840B2 (en) 2016-06-24 2020-03-17 Colgate-Palmolive Company Oral care compositions and methods of use
US10617620B2 (en) 2016-06-24 2020-04-14 Colgate-Palmolive Company Oral care compositions and methods of use
US11207254B2 (en) 2016-06-24 2021-12-28 Colgate-Palmolive Company Oral care compositions and methods of use
US11234915B2 (en) 2016-06-24 2022-02-01 Colgate-Palmolive Company Oral care compositions and methods of use
CN111989083A (zh) * 2018-03-29 2020-11-24 宝洁公司 用于促进牙龈健康的口腔护理组合物
CN111989083B (zh) * 2018-03-29 2024-02-13 宝洁公司 用于促进牙龈健康的口腔护理组合物
WO2020131401A1 (fr) * 2018-12-20 2020-06-25 Colgate-Palmolive Company Dentifrice contenant du bicarbonate de sodium et du fluorure stanneux

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