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EP1345995A1 - Dioxyde de titane nanoparticulaire a surface modifiee et son utilisation dans des produits d'hygiene dentaire - Google Patents

Dioxyde de titane nanoparticulaire a surface modifiee et son utilisation dans des produits d'hygiene dentaire

Info

Publication number
EP1345995A1
EP1345995A1 EP01271822A EP01271822A EP1345995A1 EP 1345995 A1 EP1345995 A1 EP 1345995A1 EP 01271822 A EP01271822 A EP 01271822A EP 01271822 A EP01271822 A EP 01271822A EP 1345995 A1 EP1345995 A1 EP 1345995A1
Authority
EP
European Patent Office
Prior art keywords
titanium dioxide
teeth
dioxide according
surface modification
cleaning
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Withdrawn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
EP01271822A
Other languages
German (de)
English (en)
Inventor
Christian Kropf
Ulrike Brüninghaus
Michael Meinders
Peter Wülknitz
Hans Laska
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 EP1345995A1 publication Critical patent/EP1345995A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3684—Treatment with organo-silicon compounds
    • 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
    • A61K8/29—Titanium; Compounds thereof
    • 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
    • A61K8/55—Phosphorus compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3669—Treatment with low-molecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684

Definitions

  • the invention relates to nanoparticulate titanium dioxide with an average particle diameter in the range from 10 to 1000 nm, the particles being coated by a polar organic surface modification agent, preferably a phosphonic acid.
  • the particles have good adhesion to tooth surfaces and are suitable as tooth-whitening active ingredients in compositions for cleaning and / or caring for the teeth.
  • a disadvantage of the method mentioned under a) is that there is always the risk of undesired abrasion of the tooth surface itself, ie damage to the tooth substance.
  • both methods in addition, in the optimal case, only the color of the natural tooth surface can be achieved, which is always slightly yellowish and not bright enough for the taste of many people, ie not white enough.
  • these cleaning and / or ablative methods are therefore not suitable.
  • Titanium dioxide is usually used in dental cosmetics for the purpose of giving compositions for cleaning and / or caring for the teeth an aesthetic white appearance, ie as a white pigment for the compositions themselves.
  • the document CA 2,239,398 describes dental flosses which contain titanium dioxide particles with a size between 100 and 6000 nm as a means for cleaning and for whitening the interdental spaces.
  • the titanium dioxide particles should be transferred to the enamel and lighten it as a white pigment.
  • the titanium dioxide can serve as a mild abrasive for cleaning the tooth surface.
  • the titanium dioxide particles are embedded in the space between the hydroxyapatite crystals which form the tooth enamel and thus occupy spaces which can otherwise be occupied by undesired colored substances.
  • the titanium dioxide particles used cannot form a strong bond with the material of the tooth surface.
  • compositions for cleaning and / or caring for the teeth which can effectively and long-lighten the surface of teeth and which are convenient and simple to use.
  • nanoparticulate titanium dioxides with an average particle diameter in the range from 10 to 1000 nm and preferably in the range from 50 to 300 nm, in which the particles are encased by a polar organic surface modifier.
  • the size specifications are to be understood as diameters in the direction of the greatest linear expansion of the particles, and the mean is to be understood as the volume-weighted mean.
  • the finely divided particles particles are always obtained with a size that follows a distribution curve.
  • the method of dynamic light scattering known to the person skilled in the art can be used, in which a light beam is scattered by moving particles and the frequency shift of the scattered light is measured.
  • a device that works according to this measuring principle is, for example, the Ultrafine Particle Analyzer (UPA) 3,150 from Microtrac.
  • Coating the particles with a surface modifier is to be understood as partially or completely covering the surface of the titanium dioxide particles with molecules of this agent, the molecules of the surface modifier being connected to the titanium dioxide surface via covalent bonds or polar interactions.
  • the molecules of the surface modification agent must contain polar and / or reactive groups such as, for example, the carboxy, sulfo, phosphono, isocyanato, hydroxyl, amino, ammonium or epoxy group or alkoxysilane groups which match the surface of the Titanium dioxide particles can interact or react.
  • polar and / or reactive groups such as, for example, the carboxy, sulfo, phosphono, isocyanato, hydroxyl, amino, ammonium or epoxy group or alkoxysilane groups which match the surface of the Titanium dioxide particles can interact or react.
  • Suitable surface modification agents are, for example, substances which contain at least one functional group from the group formed by the carboxy, sulfo, phosphono, isocyanato, hydroxyl, amino, ammonium and epoxy group and their salts, and silanes of the type (ORV n SiR n , in which n is an integer between 1 and 3, R 'is an alkyl radical with 1 to 4 carbon atoms and R is an organic hydrocarbon radical having 1 to 18 carbon atoms, and the radical R additionally contains a carboxy, sulfo, phosphono, isocyanato, hydroxyl, amino, ammonium, ester or epoxy group.
  • Preferred surface modification agents for the purposes of the invention are substances which contain two or more functional groups in the molecule from the group of carboxy, phosphono and sulfo groups and silanes of the type (OR nSiRn, in which n is an integer between 1 and 3, R ' is an alkyl radical with 1 to 4 carbon atoms and R is an organic hydrocarbon radical with 1 to 18 carbon atoms, the radical R additionally containing a carboxy, sulfo or phosphono group.
  • Particularly preferred surface modification agents are mono-, di- and trisphosphonic acids, such as, for example, the commercial products Turpinal D2 (tris (phosphonomethyl) amine), Turpinal AHP (azacycloheptane-2,2-diphosphonic acid) and Turpinal SL (hydroxyethane-1,1-diphosphonic acid).
  • Turpinal D2 tris (phosphonomethyl) amine
  • Turpinal AHP azacycloheptane-2,2-diphosphonic acid
  • Turpinal SL hydroxyethane-1,1-diphosphonic acid
  • the surface-modified nanoparticulate titanium dioxides according to the invention can be prepared by first slurrying titanium dioxide in a solvent, preferably water. This slurry is combined, preferably in heat, with the surface modifier or a solution thereof in a second solvent that is miscible with the first. The mixture is then left to react, preferably again at elevated temperature, until the surface modification agent has been largely or completely absorbed by the titanium dioxide. The course of the reaction can be followed, for example, by measuring the decrease in the concentration of the free surface modification agent in the solvent.
  • a catalyst for example an acid, can optionally be added to accelerate this process.
  • Another object of the invention is accordingly a method for producing surface-modified titanium dioxide as described above, in which a dispersion of unmodified titanium dioxide is brought into contact with a solution of a surface-modifying agent.
  • the proportions between titanium dioxide and surface modifier can be varied within a wide range.
  • the absorption capacity of a titanium dioxide used in each case for a specific surface modification agent can be determined by simple routine tests.
  • the content of surface modification agent is between 1 and 50, particularly preferably between 2 and 30% by weight, based on the total weight of the surface-modified nanoparticles.
  • the titanium dioxides according to the invention are suitable as tooth-whitening components in compositions for cleaning and / or caring for the teeth.
  • compositions for cleaning and / or caring for the teeth can be in the form of solid preparations such as chewing gums or tablets, pastes such as toothpastes, liquid creams, gels or solutions such as mouthwashes. Even in liquid preparations, the titanium dioxides according to the invention are easily distributed, remain stably dispersed and do not tend to sedimentation.
  • the compositions for cleaning and / or caring for the teeth contain 0.01 to 10% by weight, but preferably 0.05 to 2% by weight, of a nanoparticulate titanium dioxide with an average particle diameter in the Range from 10 to 1000 nm, the particles being encased by a polar organic surface modifier.
  • compositions preferred according to the invention for cleaning and / or caring for the teeth are toothpastes, tooth gels, liquid toothpastes and mouthwashes.
  • a particularly preferred embodiment is toothpastes containing silica, polishing agents, humectants, binders and flavors, which contain 0.05 to 2% by weight of a nanoparticulate titanium dioxide according to the invention as described above.
  • compositions for cleaning and / or caring for the teeth can contain the usual components and auxiliaries of such compositions in the usual amounts.
  • auxiliaries of such compositions for toothpastes, these are e.g. B.
  • - Humectants such as B. glycerol, 1, 2-propylene glycol, sorbitol, xylitol and polyethylene glycols
  • Binder and consistency regulator e.g. B. natural and synthetic water-soluble polymers and water-soluble derivatives of natural products, for. B. cellulose ethers, layered silicates, finely divided silicas (airgel silicas, pyrogenic silicas)
  • - flavors e.g. B. peppermint oil, spearmint oil, eucalyptus oil, anise oil, fennel oil, caraway oil, menthyl acetate, cinnamaldehyde, anethole, vanillin, thymol and mixtures of these and other natural and synthetic flavors
  • sweeteners such as B. saccharin sodium, sodium cyclamate, aspartame, acesulfan K, stevioside, monellin, glycyrrhicin, dulcin, lactose, maltose or fructose - Preservatives and antimicrobial substances such as B. p-hydroxybenzoic acid ester, sodium sorbate, triclosan, hexachlorophen, phenylsalicylic acid ester, thymol
  • surfactants e.g. B. anionic, cationic, zwitterionic, ampholytic and nonionic surface-active substances, for example sodium lauryl sulfate
  • - Wound healing and anti-inflammatory agents e.g. B. allantoin, urea, azulene, panthenol, acetylsalicylic acid derivatives, plant extracts, vitamins, e.g. B. retinol or tocopherol
  • Caries-inhibiting fluorine compounds e.g. As sodium fluoride, tin fluoride, sodium monofluorophosphate or amine fluoride
  • Anti-tartar active ingredients e.g. B. organophosphonates, sodium pyrophosphate, sodium tripolyphosphate.
  • compositions according to the invention contain one or more remineralizing active ingredients.
  • Possible remineralizing agents include fluorides such as cetylamine hydrofluoride and calcium salts, such as. B. the nanoparticulate calcium salts described in the patent application DE 19858662.0 and the composite materials described in the patent application DE 19930335.5 composed of calcium salts and protein components.
  • a 10% by weight aqueous suspension of the surface-modified titanium dioxide is first prepared by dispersing with ultrasound or by means of a bead mill, and this is then stirred into the basic composition.
  • Another object of the invention is a method for teeth whitening, in which the teeth are brought into contact with a nanoparticulate titanium dioxide according to the invention as described above.
  • Example 1.1 Preparation of tris (phosphonomethyl) amine-modified titanium dioxide
  • TTO-S-3 titanium dioxide
  • Ishihara titanium dioxide
  • 18.7 g of turpinal D2 tris (phosphonomethyl) amine, 50% by weight of active substance in water
  • the reaction mixture was then stirred at 90 ° C. for a further 2 hours. After cooling to 20 ° C., the mixture was filtered off, the filter cake was washed several times with water and then freeze-dried. 56.1 g of white powder with a carbon content of 1.72% by weight were obtained.
  • Example 2 Preparation of an aqueous dispersion of surface-modified titanium dioxide (TTO-S-3, Ishihara) were added in portions to 500 g of water with vigorous stirring at 20 ° C. and slurried and heated to 90 ° C. with stirring. 8.26 g of turpinal AHP (azacycloheptane-2,2-diphosphonic acid) were dissolved in 100 ml of water, adjusted to a pH of 5-6 with dilute NaOH solution, and the clear solution formed was then added to the titanium dioxide within 1 hour. Dispersion added dropwise. The reaction mixture was then stirred at 90 ° C. for a further 3 hours. After cooling to 20 ° C., the mixture was filtered off, the filter cake was washed several times with water and then freeze-dried. 54.2 g of white powder with a carbon content of 3.15% by weight were obtained.
  • Example 2 Preparation of an aqueous dispersion of surface-modified titanium dioxide
  • Example 1.2 10 g of AHP-modified titanium dioxide from Example 1.2 were added in portions to 90 g of water with stirring and then dispersed for 5 minutes using ultrasound. The result was a translucent, stable suspension with an average particle size of 95 nm, measured by backscattering laser light with the UPA 3.150 device from Microtrac.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Organic Chemistry (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Inorganic Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Cosmetics (AREA)

Abstract

L'invention concerne du dioxyde de titane nanoparticulaire présentant un diamètre moyen de particules compris entre 10 et 1000 nm, les particules étant recouvertes d'un agent organique polaire modificateur de surface, de préférence un acide phosphonique. Ces particules présentent une bonne adhérence sur surfaces dentaires et peuvent être utilisées comme agents blanchissants dans des compositions de nettoyage et/ou d'hygiène dentaire.
EP01271822A 2000-12-22 2001-12-13 Dioxyde de titane nanoparticulaire a surface modifiee et son utilisation dans des produits d'hygiene dentaire Withdrawn EP1345995A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10064637 2000-12-22
DE2000164637 DE10064637A1 (de) 2000-12-22 2000-12-22 Nanopartikuläres oberflächenmodifiziertes Titanoxid und seine Verwendung in Zahnpflegemitteln
PCT/EP2001/014647 WO2002051945A1 (fr) 2000-12-22 2001-12-13 Dioxyde de titane nanoparticulaire a surface modifiee et son utilisation dans des produits d'hygiene dentaire

Publications (1)

Publication Number Publication Date
EP1345995A1 true EP1345995A1 (fr) 2003-09-24

Family

ID=7668712

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01271822A Withdrawn EP1345995A1 (fr) 2000-12-22 2001-12-13 Dioxyde de titane nanoparticulaire a surface modifiee et son utilisation dans des produits d'hygiene dentaire

Country Status (3)

Country Link
EP (1) EP1345995A1 (fr)
DE (1) DE10064637A1 (fr)
WO (1) WO2002051945A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10247359A1 (de) * 2002-10-10 2004-04-29 Basf Coatings Ag Nanopartikel, Verfahren zur Modifizierung ihrer Oberfläche, Dispersion der Nanopartikel, Verfahren zu ihrer Herstellung und ihre Verwendung
US7611588B2 (en) 2004-11-30 2009-11-03 Ecolab Inc. Methods and compositions for removing metal oxides
CN100392025C (zh) * 2005-05-30 2008-06-04 河南大学 原位制备改性氢氧化物、含羟基盐、氧化物纳米粉体的方法
CA2661611A1 (fr) * 2006-08-24 2008-02-28 Glaxo Group Limited Composition pour soins bucco-dentaires comprenant du dioxyde de titane nanoparticulaire
MX2009001983A (es) * 2006-08-25 2009-07-22 Sachtleben Chemie Gmbh Compuesto que contiene dioxido de titanio.
EP1935948B1 (fr) * 2006-12-20 2012-01-18 Centrum für Angewandte Nanotechnologie (CAN) GmbH Procédé de traitement de surface pour nanoparticules
DE102007042862A1 (de) * 2007-09-10 2009-03-12 Henkel Ag & Co. Kgaa Modifiziertes Titandioxid
EP2553026B1 (fr) 2010-03-26 2018-03-28 Merck Patent GmbH Particules d'oxyde métallique post-traitées avec des composés de phosphore organiques
EP2552382B1 (fr) 2010-03-31 2015-09-09 Colgate-Palmolive Company Composition de soins bucco-dentaires
EP3458026A4 (fr) * 2016-05-20 2020-04-22 University Of Ottawa Nanoparticules d'oxyde métallique revêtues de lignine et leur utilisation dans des compositions cosmétiques

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US5250289A (en) * 1987-07-24 1993-10-05 The Boots Company Plc Sunscreen compositions
GB8827968D0 (en) * 1988-11-30 1989-01-05 Boots Co Plc Sunscreen compositions
DE69217755T2 (de) * 1991-07-16 1997-09-04 Canon Kk Toner für die Entwicklung elektrostatischer Bilder
US5240697A (en) * 1991-10-17 1993-08-31 Colgate-Palmolive Company Desensitizing anti-tartar dentifrice
FR2724318B1 (fr) * 1994-09-13 1997-01-03 Oreal Composition cosmetique prevenant ou attenuant la photo-reactivite de manopigments de dioxyde de titane
JP3030380B2 (ja) * 1997-09-19 2000-04-10 卓郎 石橋 二酸化チタン光触媒による変色歯牙漂白法
DE19751857A1 (de) * 1997-11-22 1999-05-27 Kronos Titan Gmbh Phosphonatosiloxanbehandelte anorganische Partikel
DE19952383A1 (de) * 1999-10-30 2001-05-17 Henkel Kgaa Wasch- und Reinigungsmittel
DE19955816A1 (de) * 1999-11-19 2001-05-23 Cognis Deutschland Gmbh Verwendung

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Also Published As

Publication number Publication date
WO2002051945A1 (fr) 2002-07-04
DE10064637A1 (de) 2002-07-04

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