EP2731678A2 - Agents de soins et d'hygiène bucco-dentaires désensibilisants - Google Patents

Agents de soins et d'hygiène bucco-dentaires désensibilisants

Info

Publication number
EP2731678A2
EP2731678A2 EP12727148.4A EP12727148A EP2731678A2 EP 2731678 A2 EP2731678 A2 EP 2731678A2 EP 12727148 A EP12727148 A EP 12727148A EP 2731678 A2 EP2731678 A2 EP 2731678A2
Authority
EP
European Patent Office
Prior art keywords
weight
dental care
mouth
cleaning
agent according
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.)
Ceased
Application number
EP12727148.4A
Other languages
German (de)
English (en)
Inventor
Christel Adomat
Nicole Duschek
Kristin Miehlich
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2731678A2 publication Critical patent/EP2731678A2/fr
Ceased legal-status Critical Current

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/24Phosphorous; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/20Halogens; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses

Definitions

  • the invention relates to oral and dental care compositions with a combination of active ingredients for reducing the sensitivity of the teeth against mechanical and thermal stimuli, which simultaneously
  • Dentifrices are available in various forms on the market and are primarily used to clean the tooth surface and to prevent tooth and gum disease. They usually contain a combination of polishes, humectants, surfactants, binders, flavorings and fluoride-containing and antimicrobial agents. In addition to toothpowder, which play a minor role because of their increased abrasiveness, dentifrices are mainly offered in paste, cream and translucent or transparent gel form. Liquid or liquid toothpastes and mouthwashes have also become increasingly important in recent years.
  • the polishing agents must, in order to develop their cleaning and polishing action, have a certain abrasiveness against the tooth surface.
  • the abrasives used must not cause unnecessary removal of the enamel, and should also not harm the underlying, softer dentin if possible, since in persons with pain-sensitive teeth, the cause often lies in a thin enamel layer or exposed tooth necks. With extreme sensitivity of the teeth too high abrasiveness can increase the problem of unpleasant feelings to the point of pain. There is therefore a need to further develop the field of toothpastes for sensitive teeth.
  • the object of the present invention was to provide preparations for oral and dental care and cleaning that desensitize the teeth and, despite good cleaning performance, are less abrasive than conventional toothpastes.
  • the invention therefore oral and Zahntician- and -curismittel containing - based on their weight - a) 0.1 to 10 wt .-% potassium chloride;
  • Oral and dental care products as well as mouth and tooth cleaning agents in the sense of the invention are mouthwashes and toothpowder, oral and toothpastes, liquid mouthwashes and toothpastes, oral and dental rinses, and oral and dental gels.
  • suitable are toothpastes and liquid dentifrices.
  • the oral and dental care and cleaning agents e.g. in the form of toothpastes, liquid toothpastes, toothpowder, mouthwashes or possibly also as gum, e.g. B. as chewing gum, present.
  • they are present as more or less flowable or plastic toothpastes, as they are used for cleaning the teeth using a toothbrush.
  • Another particularly preferred embodiment of the present invention are mouthwashes and mouthwashes used to rinse the oral cavity.
  • compositions according to the invention contain, based on their weight, from 0.1 to 10% by weight of potassium chloride.
  • wt .-% preferably 0.5 to 7.0 wt .-%, particularly preferably 1, 0 to 6.0 wt .-%, more preferably 2.0 to 5.0 wt .-% and in particular 3.5 to 4.0 wt .-% potassium chloride.
  • compositions of the invention contain, based on their weight 0.1 to 10.0 wt .-% of calcium hydrogen phosphate dihydrate, CaHP0 4 '2H 2 0. dihydrate as "brushite” or as dicalcium phosphate, depending on the reference, this compound is .
  • CaHP0 4 '2H 2 0 obtained by the CAS No: 7789-77-7 will be described.
  • agents according to the invention contain further cleaning bodies (abrasives).
  • Cleaning bodies are amorphous, predominantly inorganic, largely water-insoluble, smallest-particle powders which have no sharp edges. In dental and oral care products, they promote the cleaning of the teeth and at the same time polish the tooth surface (polishing agent).
  • polishing agent are in principle all known for toothpastes friction body, in particular those that do not contain calcium ions.
  • suitable polishing agent components are therefore silicic acids, aluminum hydroxide, aluminum oxide, sodium aluminum silicates, organic polymers or mixtures of such friction bodies.
  • Suitable silicic acids are, for example, gel silicic acids, hydrogel silicic acids and precipitated silicas.
  • Gel silicas are prepared by reacting sodium silicate solutions with strong, aqueous mineral acids to form a hydrosol, aging to the hydrogel, washing and drying. If the drying takes place under mild conditions to water contents of 15 to 35 wt .-%, the so-called hydrogel silicas are obtained. Drying to water contents below 15% by weight results in an irreversible shrinkage of the previously loose structure of the hydrogel to the dense structure of the so-called xerogel.
  • a second, preferably suitable group of silica polishing agents are the precipitated silicas. These are obtained by precipitation of silica from dilute alkali silicate solutions by addition of strong acids under conditions in which aggregation to the sol and gel can not occur.
  • Suitable methods for preferably suitable is a precipitated silica having a BET surface area of 15 to 10 m 2 / g, a particle size of 0.5 to 20 ⁇ m, where at least 80% by weight of the primary particles are below 5 ⁇ m, and one Viscosity in 30% glycerol-water (1: 1) dispersion of 30 - 60 Pa.s (20 ° C) in an amount of 10 - 20 wt .-% of the toothpaste.
  • Particularly suitable precipitated silicas of this type have rounded corners and edges and are commercially available under the trade name ® Sident 12 DS (DEGUSSA).
  • Such toothpastes are therefore preferably used in addition to the mentioned precipitated silicas, finely divided, so-called thickened silicas having a BET surface area of 150-250 m 2 / g, for example the commercial products Sipernat 22 LS or Sipernat ® 320 DS.
  • polishing agent component it is also possible, for example, for aluminum oxide to be present in the form of slightly calcined clay containing - and - aluminum oxide in an amount of about 1 to 5% by weight.
  • a suitable alumina is available under the trade designation "Polianton earth P10 finest" (Giulini Chemie).
  • As a polishing agent are all further known for toothpastes friction body such.
  • zeolite A organic polymers such. As polymethacrylate or mixtures of these and the aforementioned friction body.
  • oral and dental care and cleaning compositions according to the invention are particularly preferred which additionally comprise cleaning bodies from the group of silicas, preferably in amounts of from 1 to 30% by weight, preferably from 2.5 to 25% by weight and in particular from 5 to 22 % By weight, based in each case on the total agent.
  • Mouth and dental care and cleaning compositions according to the invention are preferred in which the weight ratio of the cleaning bodies from the group of silicic acids to calcium hydrogen phosphate dihydrate is 10: 1 to 1: 1, preferably 8: 1 to 2: 1, more preferably 6: 1 to 3: 1 and in particular 5: 1 to 4: 1.
  • Mouth and dental care and cleaning agents according to the invention may contain further ingredients. It has been shown that certain magnesium salts can increase the synergistic effect of the combination of potassium chloride and calcium hydrogen phosphate dihydrate, CaHP0 4 "2H 2 0 further. Accordingly, oral and dental care and cleaning compositions according to the invention are particularly preferred, the 0.25 to 7.5 wt .-%, preferably 0.5 to 6.0 wt .-%, particularly preferably 1, 0 to 5.0 wt. -%, more preferably 1, 5 to 3.0 wt .-% and in particular 1, 75 to 2.5 wt .-% magnesium sulfate heptahydrate.
  • Surface-active substances can also be used in the agents according to the invention. They are used, for example, in toothpastes to support the cleaning action and, if desired, also for the development of foam during tooth brushing or mouth rinsing and for stabilizing the polishing body dispersion in the vehicle and are usually used in mouthwashes and toothpastes in an amount of 0.1-5% by weight. % used.
  • Suitable surfactants are, for. B. linear sodium alkyl sulfates having 12-18 C atoms in the alkyl group. These substances additionally have an enzyme-inhibiting effect on the bacterial metabolism of the dental plaque.
  • alkali metal salts preferably sodium salts of Alkylpolyglycolethersulfat with 12-16 C atoms in the linear alkyl group and 2-6 glycol ether groups in the molecule, of linear alkane (CI2 d 8) sulfonate, of Sulfobernsteinklamonoalkyl (C 2 -C 8) esters, of sulfated fatty acid monoglycerides, sulfated fatty acid alkanolamides, sulfoacetic acid alkyl (Ci 2 -C 6 ) esters, acylsarcosines, acyl taurides and acyl isothionates each having 8-18 C atoms in the acyl group.
  • alkali metal salts preferably sodium salts of Alkylpolyglycolethersulfat with 12-16 C atoms in the linear alkyl group and 2-6 glycol ether groups in the molecule
  • zwitterionic, ampholytic and nonionic surfactants are suitable, for.
  • mouth and dental care and cleansing preparations according to the invention which - based on their weight - less than 5 wt .-%, preferably less than 4 wt .-%, more preferably less than 3 wt .-% and in particular less than 2 wt .-% surfactant (s), according to the invention particularly preferred.
  • Mouth and dental care and cleaning agent according to the invention characterized in that they contain less than 2 wt .-%, preferably less than 1 wt .-%, more preferably less than 0.5 wt .-% and in particular less than 0, 1 wt. % anionic surfactant (s), preferred agents being free of anionic surfactants.
  • amphoteric surfactants are to be used, preferably within the abovementioned maximum limits, the use of amphoteric surfactants is preferred.
  • Mouth and dental care and cleaning compositions according to the invention contain 0, 1 to 5 wt .-%, preferably 0.25 to 4 wt .-%, particularly preferably 0.5 to 3.0 wt .-%, more preferably 0.75 to 2.0 wt .-% and in particular 1, 0 to 1, 5 wt .-% amphoteric surfactant (s).
  • compositions according to the invention contain from 0.1 to 5% by weight, preferably from 0.2 to 4% by weight, more preferably from 0.25 to 3% by weight, more preferably 0, 3 to 2 wt .-% and in particular 0.4 to 0.8 wt .-% cocoamidopropyl betaine.
  • the oral and dental care and cleaning agents according to the invention may contain further ingredients. Preference is given to the use of so-called humectants, the at Toothpastes prevent drying out. In so-called liquid tooth creams with flowable rheology, these serve as a matrix and are used in higher amounts. In mouthwashes and mouthwashes, these alcohols serve as consistency regulators and additional sweeteners.
  • oral and dental care and cleaning compositions according to the invention are preferred which - based on their weight - 0.5 to 60 wt .-%, preferably 0.75 to 55 wt .-%, particularly preferably 1 to 50 wt .-% and in particular 2 to 40 wt .-% of at least one polyhydric alcohol from the group sorbitol and / or glycerol and / or 1, 2-Propylenglycol .-% or mixtures thereof.
  • sorbitol is preferred.
  • mixtures of two of the three or all three may be preferred.
  • a mixture of glycerol, sorbitol and 1,2-propylene glycol in a weight ratio of 1: (0.5-1) :( 0, 1-0.5) has proved particularly advantageous.
  • suitable further polyhydric alcohols are those having at least 2 OH groups, preferably mannitol, xylitol, polyethylene glycol, polypropylene glycol and mixtures thereof.
  • suitable further polyhydric alcohols those having at least 2 OH groups, preferably mannitol, xylitol, polyethylene glycol, polypropylene glycol and mixtures thereof.
  • these compounds those having 2 to 12 OH groups, and especially those having 2, 3, 4, 5, 6 or 10 OH groups are preferred.
  • the (n, n + 1) or (n, n + 2) diols with non-terminal OH groups can also be used.
  • polyhydroxy compounds having 2 OH groups are also the polyethylene and polypropylene glycols.
  • polyhydric alcohols may, for. B. xylitol, propylene glycols, polyethylene glycols, especially those having average molecular weights of 200-800 are used.
  • sorbitol particularly preferred is the use of sorbitol, so that agents which contain no other polyhydric alcohols other than sorbitol, are particularly preferred.
  • oral and dental care and cleaning agents may more preferably contain anti-caries agents.
  • anti-caries agents may be selected, for example, from organic or inorganic fluorides, for.
  • zinc fluoride, stannous fluoride are preferred.
  • An amount of 0.01-0.2% by weight of fluorine should preferably be present in the form of the compounds mentioned.
  • Oral and dental care and cleaning compositions according to the invention which additionally contain anti-caries agents, preferably fluorine compound (s), in particular sodium fluoride, potassium fluoride, Sodium monofluorophosphate, zinc fluoride, stannous fluoride and sodium fluorosilicate, preferably in amounts of from 0.01 to 5% by weight, preferably in amounts of from 0.01 to 5% by weight, preferably from 0.02 to 2.5% by weight and in particular from 0 , 04 to 1, 1 wt.%, In each case based on the total agent, are preferred according to the invention.
  • fluorine compound s
  • sodium fluoride potassium fluoride
  • Sodium monofluorophosphate zinc fluoride
  • stannous fluoride and sodium fluorosilicate preferably in amounts of from 0.01 to 5% by weight, preferably in amounts of from 0.01 to 5% by weight, preferably from 0.02 to 2.5% by weight and in particular from 0 , 04 to 1, 1 wt.%,
  • anti-caries agents
  • compositions according to the invention can also additionally other wound-healing and anti-inflammatory substances, eg. B. agents for gingivitis included.
  • B. agents for gingivitis included Such substances may, for. B. be selected from allantoin, azulen, chamomile extracts, tocopherol, panthenol, bisabolol, sage extracts.
  • Oral and dental care and cleaning agents may e.g. also contain substances that are effective against plaque and / or tartar.
  • Anti-calculus substances may be, for example, chelating agents such.
  • Ethylenediaminetetraacetic acid and its sodium salts, pyrophosphate salts such as
  • water-soluble dialkali or tetraalkali metal pyrophosphate salts e.g. B. Na 4 P 2 0 7 , K 4 P 2 0 7 , Na 2 K 2 P 2 0 7 , Na 2 H 2 P 2 0 7 and K 2 H 2 P 2 0 7 or polyphosphate salts, the z. B. from water-soluble Alkalimethalltripolyphosphaten as sodium tripolyphosphate and potassium tripolyphosphate can be selected.
  • Oral and dental care and cleaning agents which are preferred according to the invention are characterized in that they additionally contain phosphate (s), preferably alkali metal phosphate (s) and in particular sodium tripolyphosphate, preferably in amounts of from 1 to 10% by weight, more preferably from 2 to 8% by weight .-% and in particular from 3 to 7 wt .-%, each based on the total agent included.
  • phosphate preferably alkali metal phosphate (s) and in particular sodium tripolyphosphate, preferably in amounts of from 1 to 10% by weight, more preferably from 2 to 8% by weight .-% and in particular from 3 to 7 wt .-%, each based on the total agent included.
  • a consistency regulator serve z.
  • natural and / or synthetic water-soluble polymers such as alginates, carrageenan, tragacanth, starch and starch ethers, cellulose ethers such. Carboxymethylcellulose (Na salt), hydroxyethylcellulose, methylhydroxypropylcellulose, guar, acacia, agar, xanthan gum, succinoglycan gum, locust bean gum, pectins, water-soluble carboxyvinyl polymers (e.g., Carbopo D types), polyvinyl alcohol, polyvinylpyrrolidone, Polyethylene glycols, in particular those having molecular weights of 1 500-1 000 000.
  • z. B phyllosilicates
  • montmorillonite clays colloidal thickened silicas such.
  • airgel silicas fumed silicas or finely ground precipitated silicas.
  • viscosity-stabilizing additives from the group of cationic, zwitterionic or ampholytic nitrogenous surfactants, hydroxypropyl-substituted hydrocolloids or polyethylene glycol / polypropylene glycol copolymers having an average molecular weight of 1000 to 5000 or a combination of the compounds mentioned in the toothpastes.
  • the dentifrices according to the invention may contain further adjuvants and additives known per se.
  • Additive which has been known for a long time as a toothpaste component, is particularly effective in the dentifrices of the invention: calcium glycerophosphate, the calcium salt of glycerol-1-phosphoric acid or glycerol-2-phosphoric acid or glycerol-1-phosphoric acid enantiomeric glycerol-3 phosphoric acid - or a mixture of these acids.
  • the compound has a remineralizing effect in dentifrices as it provides both calcium and phosphate ions.
  • the dentifrices according to the invention calcium glycerophosphate is preferably used in amounts of 0.01 to 1 wt .-%. Overall, the dentifrices according to the invention may contain customary auxiliaries and additives in amounts of up to 10% by weight.
  • the dentifrices according to the invention may e.g. be improved by the addition of aromatic oils and sweeteners in their organoleptic properties.
  • aroma oils all the natural and synthetic flavors customary for oral and dental care products can be used. Natural flavors can be contained both in the form of natural essential oils isolated from drugs and the individual components isolated therefrom.
  • Suitable flavors are e.g. Whistle oil, spearmint oil, eucalyptus oil, aniseed oil, fennel oil, caraway oil, menthyl acetate, cinnamaldehyde, anethole, vanillin, thymol and mixtures of these components.
  • Suitable sweeteners are e.g. Saccharin sodium, sodium cyclamate, sucrose, lactose, meltose, fructose.
  • Surfactants preferably anionic, zwitterionic, amphoteric, nonionic surfactants or a combination of several different surfactants
  • Solvents and solubilizers e.g. lower monohydric or polyhydric alcohols or ethers, e.g. Ethanol, 1, 2-propylene glycol, diethylene glycol or Butyldi- glycol
  • Titanium dioxide e.g. Titanium dioxide
  • Buffer substances e.g. primary, secondary or tertiary alkali phosphates or citric acid / Na citrate
  • wound healing or anti-inflammatory agents e.g. Allantoin, urea, azulene, chamomile agents, acetylsalicylic acid derivatives or rhodanide
  • vitamins such as e.g. Ascorbic acid, biotin, tocopherol or rutin
  • compositions according to the invention can be formulated as toothpastes or toothpastes.
  • Another object of the present invention is a method for the prevention and treatment of sensitive teeth, wherein a preparation of the invention are applied to a toothbrush and brushed with his teeth.
  • compositions according to the invention can also be formulated as mouthwashes or mouthwashes.
  • Another object of the present invention is a method for the prevention and treatment of sensitive teeth, wherein a preparation according to the invention in the form of a mouthwash solution introduced into the oral cavity and there for a period of at least 10 seconds, preferably at least 20 seconds and in particular at least 45 seconds is left.
  • the RDA value was determined for the inventive composition E and the comparative formulation V.
  • the RDA value of the composition E according to the invention was 20 units lower than that of the comparative formulation V.
  • the composition E is thus significantly less abrasive than the composition V.

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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)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Cosmetics (AREA)

Abstract

L'invention concerne des agents de soins et d'hygiène bucco-dentaires contenant par rapport à leur poids, 0,1 à 10 % en poids de chlorure de potassium et 0,1 à 10 % en poids de dihydrate de calciumhydrogénophosphate, CaHPO4•2H2O. Les agents selon l'invention présentent un effet désensibilisant amélioré sur des dents hypersensibles et augmentent considérablement l'abrasivité.
EP12727148.4A 2011-07-15 2012-06-12 Agents de soins et d'hygiène bucco-dentaires désensibilisants Ceased EP2731678A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201110079257 DE102011079257A1 (de) 2011-07-15 2011-07-15 Desensibilisierende Mund- und Zahnpflege- und -reinigungsmittel
PCT/EP2012/061102 WO2013010724A2 (fr) 2011-07-15 2012-06-12 Agents de soins et d'hygiène bucco-dentaires désensibilisants

Publications (1)

Publication Number Publication Date
EP2731678A2 true EP2731678A2 (fr) 2014-05-21

Family

ID=46262109

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12727148.4A Ceased EP2731678A2 (fr) 2011-07-15 2012-06-12 Agents de soins et d'hygiène bucco-dentaires désensibilisants

Country Status (3)

Country Link
EP (1) EP2731678A2 (fr)
DE (1) DE102011079257A1 (fr)
WO (1) WO2013010724A2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013209898A1 (de) * 2013-05-28 2014-12-04 Henkel Ag & Co. Kgaa Mund- und Zahnpflege- und -reinigungsmittel für sensitive Zähne

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3122483A (en) 1960-07-21 1964-02-25 Block Drug Co Strontium ion toothpaste
DE1467902C3 (de) * 1965-12-17 1974-11-21 Farbwerke Hoechst Ag, Vormals Meister Lucius & Bruening, 6000 Frankfurt Mundpflegemittel
DE2419384C2 (de) 1974-04-23 1984-05-17 Hodosh, Milton, 02906 Providence, R.I. Verwendung von Kalium-, Natrium- und Lithiumnitrat in einem Mittel zur Desensibilisierung von überempfindlichen Zähnen
JPS54140740A (en) * 1978-04-23 1979-11-01 Matsura Kouji Tooth paste
US4631185A (en) * 1984-03-13 1986-12-23 The Trustees Of Columbia University In The City Of New York Method of desensitizing hypersensitive dentin employing compositions containing potassium salts
SU1715352A1 (ru) * 1985-06-18 1992-02-28 Алма-Атинский Государственный медицинский институт Состав дл лечени кариеса зубов
DE3705845A1 (de) * 1987-02-24 1988-09-01 Hoechst Ag Zahnpasten sowie putzkoerper fuer zahnpasten auf basis dicalciumphosphat-dihydrat und ein verfahren zur herstellung solcher putzkoerper
DE19730651A1 (de) * 1997-07-17 1999-01-21 Henkel Kgaa Mund- und Zahnpflegemittel für empfindliche Zähne
MXPA05008191A (es) * 2003-02-05 2006-02-17 Fmc Corp Composiciones de pasta dental con capacidad de abrasion reducida.
TWI469795B (zh) * 2009-04-01 2015-01-21 Colgate Palmolive Co 防止過敏和促進再礦化之雙作用牙劑組成物

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2013010724A2 *

Also Published As

Publication number Publication date
DE102011079257A1 (de) 2013-01-17
WO2013010724A3 (fr) 2013-05-02
WO2013010724A2 (fr) 2013-01-24

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