EP1128799A2 - Fluorchemische zahnpasta die fluorkompatibel kalziumartig schleifkörper enthält - Google Patents

Fluorchemische zahnpasta die fluorkompatibel kalziumartig schleifkörper enthält

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Publication number
EP1128799A2
EP1128799A2 EP99954081A EP99954081A EP1128799A2 EP 1128799 A2 EP1128799 A2 EP 1128799A2 EP 99954081 A EP99954081 A EP 99954081A EP 99954081 A EP99954081 A EP 99954081A EP 1128799 A2 EP1128799 A2 EP 1128799A2
Authority
EP
European Patent Office
Prior art keywords
toothpaste composition
calcium
composition according
abrasive particles
particles
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Withdrawn
Application number
EP99954081A
Other languages
English (en)
French (fr)
Inventor
Adrien Dromard
Sylvie Lavault
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
Original Assignee
Rhodia Chimie SAS
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 Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP1128799A2 publication Critical patent/EP1128799A2/de
Withdrawn legal-status Critical Current

Links

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
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/11—Encapsulated compositions
    • 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
    • A61K8/19—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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns

Definitions

  • the field of the present invention is that of toothpaste compositions and more precisely of the formulation thereof using different active ingredients in the cleaning and bleaching of teeth as well as in the fight against canes. particularly in the context of the invention to abrasive agents and fluorinated agents.
  • the present ⁇ n ⁇ ent ⁇ on relates to toothpaste compositions comprising at least one abrasive agent formed by abrasive particles constituted by a solid material based on calcium and at least one fluorinated agent, the compatibility between the abrasive agent and the fluorinated agent being significantly improved
  • a subject of the invention is also the use, as an ingredient, in particular as an abrasive agent, in toothpaste compositions, of abrasive particles comprising a core of abrasive calcium material coated with a hydrophobic bark of compatibilization with fluorine.
  • toothpastes comprise one or more abrasive materials intended to intervene in the mechanical cleaning of the teeth
  • abrasive materials are powders of insoluble particles having a hardness and a defined form
  • Calcium materials such as calcium carbonate and dicalcium phosphate are thus commonly used in toothpaste compositions as abrasive agents participating in the mechanical removal of dental plaque when brushing teeth.
  • Calcium carbonate (CC) of natural origin (chalk) or synthetic origin (calcium carbonate precipitates -CCP -) is one of the oldest dental abrasives, Apart from these calcium abrasives, silica is also widely used in toothpaste as an abrasive or even as a thickener
  • fluorine as long as it is in the form of fluoride, has the virtue of chemically binding, in the form of fluoride, with the enamel (or hydroxyapatite Ca ⁇ (P0), OH) to transform it en fluoroapatite
  • This fluorinated email is thus much more resistant to the attack of dental plaque, which intervenes, in particular, by solubihsation in acid medium II in result better prevention of canes
  • the fluoride-providing products are generally sodium monofluorophosphate (MFP) and sodium fluoride (NaF).
  • fluorides pose the problem of their compatibility with calcium-based abrasives (calcium carbonate for example), which, due to their surface properties and their ability to trap fluorides in the form of insoluble complexes, deprives the toothpaste of its fluorinated ingredient in active form, resulting in a loss of therapeutic effectiveness vis-à-vis cavities.
  • calcium-based abrasives calcium carbonate for example
  • the applicant has set itself the essential objective of developing a powdered calcium abrasive for toothpaste having increased compatibility with respect to fluorine and more precisely compatibility> to 90%, in the case where the fluorinated agent is sodium fluoride (NaF) or sodium monofluorophosphate (MFP).
  • the fluorinated agent is sodium fluoride (NaF) or sodium monofluorophosphate (MFP).
  • Another essential objective of the invention is to provide a toothpaste composition comprising abrasive particles based on solid calcium materials, such as CaCO 3 or dicalcium phosphate, having a high compatibility with fluorine without this being to the detriment of the abrasive power.
  • Another essential objective of the invention is to provide a toothpaste composition comprising abrasive particles of calcium nature compatible with fluorine and which are economical and simple to obtain.
  • Another essential objective of the invention is to propose a use of the abovementioned particles in fluorinated toothpaste formulations in which the action of fluorine is not hampered by the abrasive.
  • the plaintiff has managed to achieve, in a completely surprising and unexpected manner, all of the objectives set out above, among others, by proposing to prevent contact between, on the one hand, the Ca 2+ ions of the crystalline particles of calcium material and, on the other hand, the fluoride ions likely to be present in the toothpaste compositions, by carrying out a coating (surface treatment) of said particles using a hydrophobic product, preferably a hydrophobic organic product.
  • the invention relates, firstly, to a toothpaste composition
  • abrasive particles comprising a solid calcium-based material and at least one fluorinated agent
  • the abrasive particles are formed by a core based on calcium material coated with a shell comprising at least one hydrophobic product comprising at least one fatty chain, preferably of C 8 -C 24 .
  • the hydrophobic product is chosen from the group comprising: - fatty acids and salts of fatty acid and counter anion (s), on the one hand, belonging to the group comprising ions derived from alkali metals, alkali metals - earthy with the exclusion of calcium, the ammonium ion and their mixtures and, on the other hand, having less affinity for the carboxylic anion than calcium; - fatty alcohols;
  • fatty esters preferably: natural triglycerides and more preferably still those contained in coconut, soybean, flaxseed, palm, sunflower or cotton seed oil; D esters of glycerol and fatty acids;
  • esters of glycerol and fatty acids 0 mono and diacetylated glycerol esters of fatty acids; hemisynthetic glycerides; Q sucroglycerides; Q fatty acid sucroesters; - and their mixtures; the subgroup comprising fatty acids and their salts being very particularly preferred.
  • fatty acids and more particularly their salts have the additional notable advantage of their capacity to trap Ca 2 * ions and to prevent their diffusion in an aqueous medium. This effect is added to the barrier effect mentioned above.
  • the calcium-based solid material of the abrasive particles is calcium carbonate and / or dicalcium phosphate, knowing that the calcium carbonate is more preferably retained.
  • the compatibility of the abrasive particles with respect to fluorine is understood as the ratio expressed in% of C / Co C representing the concentration of fluorine ions in a liquid medium comprising the abrasive particles of calcium nature and a fluorinated agent (MFP or NAF) after a time t of contacting and Co the initial concentration at time to of fluorine ions of the liquid medium considered.
  • Compatibility makes it possible to evaluate the trapping of fluorides by the calcium abrasion material.
  • the shell of the CC particles is based on sodium, potassium or lithium stearate, sodium stearate being very particularly preferred.
  • the hydrophobic shell is therefore formed by an organic product and more especially by a carboxylic acid salt with a long apolar hydrocarbon chain.
  • carboxylic acids can comprise one or more carboxylic functions. As evidenced by the preferred choice of sodium stearate, monocarboxylic acids are preferred.
  • fatty acids the alkali metal salts of which are capable of being used in the context of the invention, mention may be made of long chain saturated fatty acids and preferably those whose chain length is between about 9 and 21 carbon atoms, such as capric acid, lauric acid, tridecylic acid, myristic acid, palmitic acid or behenic acid. It is possible that said acids are in salified form, preferably in sodium form. It should be noted that there may be mixtures of fatty acids among which there are unsaturated acids, for example oleic acid but in a minor amount.
  • the cation of the coating acid salt has less affinity for the carboxylic flag than calcium, so that the particles of CC, CCP or dicalcium phosphate attract to them. the largest number of long hydrocarbon chain carboxylic anions, which thus form an effective hydrophobic barrier between fluorine on the one hand and calcium on the other hand.
  • the toothpaste composition according to the invention is quantitatively characterized in that the coating rate Te of the particles defined mass of the bark by the ratio of; ; ; : -: - x 100, and gives ci- total core + shell core of the particles after in% dry weight: 0.1 ⁇ Te ⁇ 30 preferably 0.5 ⁇ Te ⁇ 40 and more preferably still 1 ⁇ Te ⁇ 15
  • the coating rate Te is preferably adapted to the specific surface of the particles of calcium material to be coated, preferably CaCO 4.
  • the greater this specific surface the more the coating rate must be increased accordingly to ensure uniformity of the coating.
  • the specific surface of the particles must not exceed a certain limit, beyond which their size will be too small for them to still have abrasive properties. The whole problem is therefore to find a compromise between the coating rate Te, the specific surface and the size of the particles of solid calcium material, preferably CC or CCP.
  • the abrasive particles of the toothpaste composition are obtained from particles of calcium material, preferably CC or CCP, the BET specific surface area of which is of the order of 1 to 40 m 2 / g, preferably of the order of 2 to 15 m 2 / g.
  • the BET specific surface is determined according to the BRUNAUER-EMET-TELLER method described in "The journal of the American Chemical Society", Vol. 60, page 309, February 1938 and corresponding to standard NFT 45007 (November 1987).
  • this calcium carbonate may be precipitated carbonate (CCP) of aragonite or calcite type, or alternatively a powdery natural carbonate CC obtained by grinding.
  • CCP precipitated carbonate
  • This CCP or this CC can have different crystalline forms (for example scalenohedral rhombic or aragonite).
  • STURGE CCP CALOFORT U, CALOPAKE F STURCAL, F, H or L
  • SCHAEFER CCP LIGHT PPC or DENSE PCC
  • natural CCs from OMYA DURCAL 2 or SETACARB OG.
  • the abrasive particles of calcium materials CCP or CC for example, preferably have a median diameter of the order of 0.5 ⁇ m to 20 ⁇ m.
  • the particle size of the coated abrasive particles given by the D 50 in ⁇ m, is between 0.5 and 30, preferably between 1 and 20.
  • the coated abrasive particles do not have a detrimental effect on their abrasiveness; on the contrary, the coated abrasive particles have an RDA abrasiveness of the order of 20 to 250, preferably of the order of 30 to 200.
  • the RDA abrasiveness (“Radioactive Dentine Abrasion") is measured according to the method described by JJ HEFFERREN in "Journal of Dental Research", Vol. 55 (4), page 563, 1976.
  • the coated abrasive particles in accordance with the invention are particularly compatible with respect to the monofluorophosphoric acid MPF and with respect to sodium fluoride NaF.
  • the fluorinated agent included in the toothpaste composition of the invention is preferably a salt of the monofluorophosphoric acid MFP and / or an alkali metal fluoride.
  • the fluorinated agent is a sodium, potassium, lithium, calcium, aluminum or ammonium salt of monofluorophosphoric acid or sodium fluoride.
  • the inventors had the merit of highlighting that it is quite interesting, with regard to the compatibility of the calcium particles coated with a hydrophobic product (eg Na stearate) with respect to fluorine, that the toothpaste composition also comprises at least one surfactant
  • abrasive particles comprising a core of calcium material, preferably calcium carbonate and a shell of hydrophobic product comprising at least one fatty chain, preferably of C 8 -C 24 , particularly of a fatty acid salt and more particularly of Na stearate,
  • a fluorinated compound in an amount corresponding to a concentration of the order of 0.005 to 3%, preferably of the order of 0.1 to 1% by weight of fluorine.
  • the toothpaste composition may also contain:
  • - anionic, non-anionic, amphoteric or zwitterionic surfactants at a rate of about 0.1 to 10%, preferably about 1 to 5% by weight, - water at a rate of about 5 to 50 %, preferably about 10 to 40% by weight,
  • - humectants at a rate of approximately 10 to 85%, preferably from 10 to 70% by weight, - thickening agents at a rate of 0.1 to 15% by weight,
  • polishing abrasives therapeutic agents, bactericides, antimicrobials, anti-plaque, flavoring agents, sweeteners, colors, preservatives.
  • surfactants include: alkyl sulfates, C 8 -C] 8 may optionally contain up to 10 oxyethylene and oxypropylene or (particularly sodium lauryl sulfate) - alkyl sulfoacetates, C 8 -C 18 (including sodium lauryl sulfate)
  • C 8 -C 18 alkyl sarcosinates, C 8 -C, 8 (in particular sodium lauryl sarcosinate) - alkyl phosphates, C 8 -C 18 which may optionally contain up to
  • non-ionic surfactants such as fatty sorbitan esters optionally polyethoxylated, ethoxylated fatty acids, polyethylene glycol esters
  • amphoteric surfactants such as betaines, sulfobetaines.
  • the humectants which can be used in this composition are for example: glycerol, sorbitol, polytethylene glycols, lactitol, xylitol, etc.
  • the thickener may be silica-based agent such as Tixosil 43 sold by Rhodia ® or many polymers used alone or in combination as xanthan gum, guar gum, cellulose derivatives (carboxymethylcellulose, hydroxyethylcellulose , hydroxypropylcellulose, hydroxypropylmethylcellulose ....), crosslinked polyacrylates such as CARBOPOL ® distributed by GOODRICH, alginates or carrageenans, VISCARIN ® .
  • functional ingredients which can be envisaged for the toothpaste composition of the invention, mention may be made of:
  • polishing abrasives such as silica, magnesium carbonate, calcium phosphates, titanium, zinc or tin oxides, talc, kaolin ...
  • the toothpaste composition can comprise:
  • the toothpaste composition according to the invention can be in different forms, for example paste, gel, cream, prepared using conventional methods.
  • the present invention also relates to the use as an ingredient, in particular as an abrasive agent, in toothpaste compositions, of abrasive particles formed by a core based on solid calcium material, preferably calcium carbonate, and coated with a bark comprising at least one hydrophobic product comprising at least one fatty chain, preferably of C 8 -C 24 .
  • hydrophobic product is chosen from the group comprising:
  • fatty esters preferably: natural triglycerides and more preferably still those contained in coconut, soybean, flaxseed, palm, sunflower or cotton seed oil;
  • These particles can be prepared by implementing a process comprising the following essential steps: - bringing into contact in a liquid, preferably aqueous, medium a hydrophobic product comprising at least one chain, advantageously of C 8 -C 2 , of preferably a carboxylic acid salt - and more especially a sodium stearate - with particles of calcium material - preferably calcium carbonate;
  • a first embodiment of this process essentially consists of: to prepare a solution / suspension of hydrophobic product, preferably of carboxylic acid salt, and more preferably still of sodium stearate,
  • the coating by bringing the calcium material, preferably calcium carbonate, into contact with the hydrophobic product, preferably the carboxylic acid salt, and more preferably still the sodium stearate, is carried out for several hours at a temperature which can be of the order of 85 ° C.
  • Spray drying can be carried out conventionally using pressurized air heated to a temperature between 100 and 150 ° C.
  • Steam drying can succeed or replace atomization, takes place in an oven at a temperature of 100 ⁇ 20 ° C, preferably under vacuum.
  • NaOH sodium hydroxide, stearic acid and water are brought into contact.
  • This mixture is stirred and heated to a temperature of the order of 90 ° ⁇ 10 ° C, so as to obtain a solution titrating 10% by weight of sodium stearate.
  • An aqueous slurry of CCP at 20% w / v heated to 45 ° C. is then incorporated into this solution.
  • reaction medium is kept under stirring until the coating of the CCP particles is obtained with the alkyl chains of the stearate which form hydrophobic tails all around the said particles.
  • the coated abrasive particles are used in an amount of 5 to 40%, preferably approximately 5 to 40%, preferably approximately 5 to 35% by weight, relative to the mass of the composition. toothpaste. It is important to emphasize that the abrasive particles based on calcium material, preferably CaCO 3 , coated by a hydrophobic barrier based on a hydrophobic product having at least one fatty chain - advantageously in C 8 -C 24 - preferably based on carboxylic acid salt, and more preferably still based on Na stearate, allow NaF compatibilities of the order of 98% to be achieved, in a simple and economical manner, in particular starting from crystalline particles of CaCO 3 of aragonite type, for a coating rate of 10%.
  • step a) To the solution obtained in step a) and maintained under magnetic stirring, 300 g of calcium carbonate are added.
  • This dispersion is heated to a temperature of 85 ° C, with magnetic stirring for 5 hours 30 minutes.
  • the final result is 292.1 g of carbonate treated with 2% sodium stearate.
  • step a) To the solution obtained in step a) and maintained under magnetic stirring, 40 g of calcium carbonate are added.
  • This dispersion is heated to a temperature of around 75 ° C, with magnetic stirring for 7 hours.
  • the treated CaCO 3 is filtered, dried for 18 hours in an oven at 100 ° C. under industrial vacuum ( ⁇ 300 mm of Hg)
  • This environment includes:
  • SLS sodium lauryl sulfate
  • the coating of the CCP particles in tests 7 and 8 was carried out according to variant B (point 1.2.2- above) - filtration / drying.
  • composition% by weight carboxymethylcellulose 0.8 sorbitol 18 sodium monoflurorophosphate (MFP) 0.8 or or sodium fluoride (NaF) 0.24 sodium sacchannate (sweetener) 0.2 sodium benzoate (preservative) 0.3 abrasive tested 40
  • Tixosil 43 (thickening silica) 5 sodium lauryl sulfate (30% aqueous solution>) 4 flavor 0.8 deionized water qs 100 are suspended in 90 g of water for 5 minutes at room temperature. The suspension is then centrifuged and the supernatant filtered.
  • the assay by isonometne of the total fluorine soluble in the supernatant requires in the case of MFP beforehand a hydrolysis treatment in an acid medium, which releases the fluorine ions present in the form of a complex in the MFP.
  • the hydrolysis is carried out by bringing 25 ml of supernatant into contact with 5 ml of 5N sulfunque acid and 20 ml of deionized water, and placing in the oven at 60 ° C. for at least 5 hours.
  • the fluorine concentration of the supernatant tested is measured after hydrolysis, as well as before hydrolysis.
  • Table 3 gives the results obtained with respect to NaF (tests 9 and 10).
  • Table 4 gives the results obtained with respect to MFP (tests 1 1 to 12).
  • the measurement conditions of the C accounting vis-à-vis NaF are those of Example 2 with a water / sorbitol solution (50/150) at 625 ppm of fluorine. Table 5 above gives the results obtained for tests 13 (control) and 14. Compatibility C in% relative to NaF (CCP coated with Geleol sucroester 7).

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Cosmetics (AREA)
EP99954081A 1998-11-09 1999-11-08 Fluorchemische zahnpasta die fluorkompatibel kalziumartig schleifkörper enthält Withdrawn EP1128799A2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9814231A FR2785534A1 (fr) 1998-11-09 1998-11-09 Composition dentifrice fluoree comprenant des particules abrasives de materiau calcique compatibles avec le fluor
FR9814231 1998-11-09
PCT/FR1999/002725 WO2000027338A2 (fr) 1998-11-09 1999-11-08 Composition dentrifice fluoree comprenant des particules abrasives de materiau calcique compatibles avec le fluor

Publications (1)

Publication Number Publication Date
EP1128799A2 true EP1128799A2 (de) 2001-09-05

Family

ID=9532659

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99954081A Withdrawn EP1128799A2 (de) 1998-11-09 1999-11-08 Fluorchemische zahnpasta die fluorkompatibel kalziumartig schleifkörper enthält

Country Status (8)

Country Link
US (1) US20020001569A1 (de)
EP (1) EP1128799A2 (de)
CN (1) CN1325296A (de)
AU (1) AU1052900A (de)
BR (1) BR9915154A (de)
FR (1) FR2785534A1 (de)
ID (1) ID29200A (de)
WO (1) WO2000027338A2 (de)

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CN106232088B (zh) 2014-05-15 2019-09-20 宝洁公司 具有改善的清新感的口腔护理组合物
EP3154503B1 (de) 2014-05-15 2018-08-15 The Procter and Gamble Company Zahnpastazusammensetzungen mit optimierten konservierungsmitteln
ES2686645T3 (es) 2014-05-15 2018-10-18 The Procter & Gamble Company Composiciones para el cuidado bucal que contienen polietilenglicol para la estabilidad física
ES2686269T3 (es) 2014-05-15 2018-10-17 The Procter & Gamble Company Composiciones para el cuidado bucal que contienen polietilenglicol para la estabilidad física
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Also Published As

Publication number Publication date
US20020001569A1 (en) 2002-01-03
BR9915154A (pt) 2001-08-07
ID29200A (id) 2001-08-09
WO2000027338A3 (fr) 2000-10-05
CN1325296A (zh) 2001-12-05
FR2785534A1 (fr) 2000-05-12
AU1052900A (en) 2000-05-29
WO2000027338A2 (fr) 2000-05-18

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