WO2006050777A1 - Toothpaste composition - Google Patents

Toothpaste composition Download PDF

Info

Publication number
WO2006050777A1
WO2006050777A1 PCT/EP2005/010876 EP2005010876W WO2006050777A1 WO 2006050777 A1 WO2006050777 A1 WO 2006050777A1 EP 2005010876 W EP2005010876 W EP 2005010876W WO 2006050777 A1 WO2006050777 A1 WO 2006050777A1
Authority
WO
WIPO (PCT)
Prior art keywords
toothpaste
phase
citrate
zinc
agents
Prior art date
Application number
PCT/EP2005/010876
Other languages
French (fr)
Inventor
Philip Christopher Waterfield
Original Assignee
Unilever N.V.
Unilever Plc
Hindustan Lever Limited
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 Unilever N.V., Unilever Plc, Hindustan Lever Limited filed Critical Unilever N.V.
Publication of WO2006050777A1 publication Critical patent/WO2006050777A1/en

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
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36Carboxylic acids; Salts or anhydrides thereof
    • A61K8/365Hydroxycarboxylic acids; Ketocarboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0216Solid or semisolid forms
    • A61K8/0233Distinct layers, e.g. core/shell sticks
    • A61K8/0237Striped compositions
    • 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
    • A61K8/21Fluorides; Derivatives 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
    • A61K8/27Zinc; 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
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/88Two- or multipart kits

Definitions

  • the present invention relates to an oral care composition comprising bioactive zinc salts and chalk.
  • EP-Al-O 740 932 discloses a visually-clear gel type dentifrice comprising a zinc salt which is more water soluble than zinc citrate, an amino acid which can bind zinc and a low refractive index type abrasive silica.
  • US 5 470 561 discloses an anti -plaque mouthwash comprising a zinc salt and triclosan .
  • the composition may also comprise glycine and has a pH of between 4 and 8 , preferably between 5 and 7 , the preferred pH being 6 .
  • GBA-2 052 978 discloses a toothpaste comprising zinc salts with glycine and a pH of from 4.5 to 8.0.
  • US 5 632 972 discloses a method for minimising damage to gingival and periodontal tissue by delivering a first component comprising zinc and a second component comprising a bicarbonate.
  • the present invention provides a toothpaste comprising a first phase and a second phase stored in contact with one another, the first phase comprising calcium carbonate as abrasive and an alkali-metal citrate salt, the second phase comprising a zinc salt .
  • the invention provides a toothpaste which does not form water insoluble zinc species, e.g. zinc hydroxide, upon storage in a closed container such as a toothpaste tube and hence no gassing on the resulting formation of carbon dioxide. This is because the excess citrate in the first phase associates with any water-soluble zinc species which passes from the second phase to the first phase and prevents it from dissociating and reacting with calcium ions in the chalk.
  • water insoluble zinc species e.g. zinc hydroxide
  • the zinc salt is sparingly soluble in water. This reduces the amount of water-soluble zinc species available for migration into the chalk phase.
  • the most preferred zinc salt is zinc citrate.
  • the molar ratio between the zinc ions and the total citrate is from 1:1 to 1:2, there being at least as much, and preferably more, citrate as zinc.
  • the molar ratio between the zinc and the total citrate from 1:1.3 to 1:1.7.
  • zinc citrate is present at from 0.01 to 5% by weight of the toothpaste composition, preferably from 0.5 to 3.0% by weight of the composition.
  • This ratio between the zinc and the citrate salt provides, in this type of formulation, an optimal balance between making enough zinc ions bioavailable, and capable of interacting with bacteria, without forming a deleterious amount of water-insoluble zinc species such as zinc hydroxide.
  • the excess citrate is incorporated into the composition as an alkali metal citric acid salt such as potassium citrate or sodium citrate.
  • the toothpaste composition also comprises water. Preferably, it comprises from 5 to 50% by weight and most preferably from 15 to 35% by weight of the total composition water.
  • the abrasive system employed in the first phase is calcium carbonate based. This does not prevent the use of non- calcium carbonate abrasives in addition, such as silicas, perlite, tungsten carbide and silicon carbide. Further, any of these further abrasives may be employed in either phase.
  • the second phase comprises abrasive silica.
  • the first phase preferably comprises from 10 to 70% by weight of the first phase calcium carbonate, more preferably from 20% and most preferably from 35 to 60% by weight of the first phase calcium carbonate.
  • the second phase preferably comprises from 2 to 20% by weight of the second phase abrasive silica, more preferably from 5 to 12%.
  • Preferred calcium carbonates include fine ground natural chalk since it has a surprising stability with regard to its interactivity with zinc salts.
  • fine ground natural chalk FGNC
  • FGNC fine ground natural chalk
  • suitable examples of such are disclosed in US 2003/0072721 Al (Riley) the contents of which with regards to the definition, types and grades of FGNC are incorporated herein by reference.
  • FGNC is meant chalk which is obtained by milling limestone or marble deposits.
  • the FGNC comprises particulate matter of weight-based median particle size ranging from 1 to 15 ⁇ m and BET surface area ranging from 0.5 to 3 m 2 /g.
  • the toothpaste composition according to the invention also preferably comprises a fluoride ion source such as an alkali metal salt of monofluorophosphate, preferably sodium monofluorophosphate.
  • a fluoride ion source such as an alkali metal salt of monofluorophosphate, preferably sodium monofluorophosphate.
  • Such fluoride ion source will be present at such an amount to provide free fluoride ion at from 100 to 2000 ppm, preferably from 900 to 1500 ppm.
  • the toothpaste according to the invention comprises an agent selected from the group consisting of anti-caries agents, anti-tartar agents, anti-malodour agents, whitening teeth agents, anti-gingivitis agents and mixtures thereof.
  • the first phase comprises from 35 to 45% by weight of the first phase calcium carbonate, from 2 to 4% by weight of the first phase alkali- metal citrate while the second phase comprises from 6 to 10% of the second phase abrasive silica and from 1.5 to 2.5% by weight of the second phase zinc citrate trihydrate.
  • the toothpaste according to the invention comprise further ingredients which are common in the art, such as:
  • antimicrobial agents e.g. chlorhexidine, sanguinarine extract, metronidazole, quaternary ammonium compounds, such as cetylpyridinium chloride; bis-guanides, such as chlorhexidine digluconate, hexetidine, octenidine, alexidine; and halogenated bisphenolic compounds, such as 2,2 ' methylenebis- (4-chloro-6-bromophenol) ;
  • anti-inflammatory agents such as ibuprofen, flurbiprofen, aspirin, indomethacin etc.;
  • anti-caries agents such as sodium- and stannous fluoride, aminefluorides, sodium monofluorophosphate, sodium trimeta phosphate and casein;
  • plaque buffers such as urea, calcium lactate, calcium glycerophosphate and strontium polyacrylates
  • vitamins such as Vitamins A, C and E;
  • desensitising agents e.g. potassium citrate, potassium chloride, potassium tartrate, potassium bicarbonate, potassium oxalate, potassium nitrate and strontium salts;
  • anti-calculus agents e.g. alkali-metal pyrophosphates, hypophosphite-containing polymers, organic phosphonates and phosphocitrates etc. ; biomolecules, e.g. bacteriocins, antibodies, enzymes, etc.;
  • flavours e.g. peppermint and spearmint oils
  • proteinaceous materials such as collagen
  • pharmaceutically acceptable carriers e.g. starch, sucrose, water or water/alcohol systems etc.;
  • surfactants such as anionic, nonionic, cationic and zwitterionic or amphoteric surfactants
  • particulate abrasive materials such as silicas, aluminas, calcium carbonates, dicalciumphosphates, calcium pyrophosphates, hydroxyapatites, trimetaphosphates, insoluble hexametaphosphates and so on, including agglomerated particulate abrasive materials, usually in amounts between 3 and 60% by weight of the oral care composition.
  • Preferred abrasives are chalk and silica, more preferably fine ground natural chalk.
  • Humectants such as glycerol, sorbitol, propyleneglycol, xylitol, lactitol etc.;
  • binders and thickeners such as sodium carboxymethyl- cellulose, hydroxyethyl cellulose (Natrosol ® ) , xanthan gum, gum arabic etc. as well as synthetic polymers such as polyacrylates and carboxyvinyl polymers such as Carbopol ® ; polymeric compounds which can enhance the delivery of active ingredients such as antimicrobial agents can also be included;
  • bleaching agents such as peroxy compounds e.g. potassium ' peroxydiphosphate, effervescing systems such as sodium bicarbonate/citric acid systems, colour change systems, and so on.
  • Liposomes may also be used to improve delivery or stability of active ingredients.
  • the buffering agent is sodium hydroxide.
  • the two phases are preferably extruded into a toothpaste tube using devices known in the art, for example as described in WO 99/01342 (SKB) . They may be extruded such that they are dispensed side-by-side or such that one forms a stripe within the other.
  • first and second phases are coaxially arranged in and dispensed from a toothpaste tube, the second phase substantially surrounding the first phase.
  • the following example is a toothpaste made by standard processes .
  • the two pastes are coextruded into a toothpaste tube using known processes.

Abstract

Toothpaste comprising a first phase and a second phase which are stored in contact with one another, the first phase comprising calcium carbonate as abrasive and an alkali-metal citrate salt, the second phase comprising water and a zinc salt.

Description

TOOTHPASTE COMPOSITION
The present invention relates to an oral care composition comprising bioactive zinc salts and chalk.
EP-Al-O 740 932 (Unilever) discloses a visually-clear gel type dentifrice comprising a zinc salt which is more water soluble than zinc citrate, an amino acid which can bind zinc and a low refractive index type abrasive silica.
US 5 470 561 (Klugkist ) discloses an anti -plaque mouthwash comprising a zinc salt and triclosan . The composition may also comprise glycine and has a pH of between 4 and 8 , preferably between 5 and 7 , the preferred pH being 6 .
GBA-2 052 978 (Unilever) discloses a toothpaste comprising zinc salts with glycine and a pH of from 4.5 to 8.0.
US 5 632 972 (Williams) discloses a method for minimising damage to gingival and periodontal tissue by delivering a first component comprising zinc and a second component comprising a bicarbonate.
The present invention provides a toothpaste comprising a first phase and a second phase stored in contact with one another, the first phase comprising calcium carbonate as abrasive and an alkali-metal citrate salt, the second phase comprising a zinc salt .
The invention provides a toothpaste which does not form water insoluble zinc species, e.g. zinc hydroxide, upon storage in a closed container such as a toothpaste tube and hence no gassing on the resulting formation of carbon dioxide. This is because the excess citrate in the first phase associates with any water-soluble zinc species which passes from the second phase to the first phase and prevents it from dissociating and reacting with calcium ions in the chalk.
Preferably, the zinc salt is sparingly soluble in water. This reduces the amount of water-soluble zinc species available for migration into the chalk phase. The most preferred zinc salt is zinc citrate.
Preferably, the molar ratio between the zinc ions and the total citrate is from 1:1 to 1:2, there being at least as much, and preferably more, citrate as zinc. Preferably, the molar ratio between the zinc and the total citrate from 1:1.3 to 1:1.7.
Preferably, zinc citrate is present at from 0.01 to 5% by weight of the toothpaste composition, preferably from 0.5 to 3.0% by weight of the composition. This ratio between the zinc and the citrate salt provides, in this type of formulation, an optimal balance between making enough zinc ions bioavailable, and capable of interacting with bacteria, without forming a deleterious amount of water-insoluble zinc species such as zinc hydroxide.
Preferably, the excess citrate is incorporated into the composition as an alkali metal citric acid salt such as potassium citrate or sodium citrate. The toothpaste composition also comprises water. Preferably, it comprises from 5 to 50% by weight and most preferably from 15 to 35% by weight of the total composition water.
The abrasive system employed in the first phase is calcium carbonate based. This does not prevent the use of non- calcium carbonate abrasives in addition, such as silicas, perlite, tungsten carbide and silicon carbide. Further, any of these further abrasives may be employed in either phase. Preferably, the second phase comprises abrasive silica.
The first phase preferably comprises from 10 to 70% by weight of the first phase calcium carbonate, more preferably from 20% and most preferably from 35 to 60% by weight of the first phase calcium carbonate.
The second phase preferably comprises from 2 to 20% by weight of the second phase abrasive silica, more preferably from 5 to 12%.
Preferred calcium carbonates include fine ground natural chalk since it has a surprising stability with regard to its interactivity with zinc salts. The term fine ground natural chalk (FGNC) is a known term in the art and suitable examples of such are disclosed in US 2003/0072721 Al (Riley) the contents of which with regards to the definition, types and grades of FGNC are incorporated herein by reference. Nevertheless, by FGNC is meant chalk which is obtained by milling limestone or marble deposits. Preferably, the FGNC comprises particulate matter of weight-based median particle size ranging from 1 to 15 μm and BET surface area ranging from 0.5 to 3 m2/g.
The toothpaste composition according to the invention also preferably comprises a fluoride ion source such as an alkali metal salt of monofluorophosphate, preferably sodium monofluorophosphate. Such fluoride ion source will be present at such an amount to provide free fluoride ion at from 100 to 2000 ppm, preferably from 900 to 1500 ppm.
Preferably, the toothpaste according to the invention comprises an agent selected from the group consisting of anti-caries agents, anti-tartar agents, anti-malodour agents, whitening teeth agents, anti-gingivitis agents and mixtures thereof.
In a most preferred embodiment the first phase comprises from 35 to 45% by weight of the first phase calcium carbonate, from 2 to 4% by weight of the first phase alkali- metal citrate while the second phase comprises from 6 to 10% of the second phase abrasive silica and from 1.5 to 2.5% by weight of the second phase zinc citrate trihydrate.
The toothpaste according to the invention comprise further ingredients which are common in the art, such as:
antimicrobial agents, e.g. chlorhexidine, sanguinarine extract, metronidazole, quaternary ammonium compounds, such as cetylpyridinium chloride; bis-guanides, such as chlorhexidine digluconate, hexetidine, octenidine, alexidine; and halogenated bisphenolic compounds, such as 2,2 ' methylenebis- (4-chloro-6-bromophenol) ;
anti-inflammatory agents such as ibuprofen, flurbiprofen, aspirin, indomethacin etc.;
anti-caries agents such as sodium- and stannous fluoride, aminefluorides, sodium monofluorophosphate, sodium trimeta phosphate and casein;
plaque buffers such as urea, calcium lactate, calcium glycerophosphate and strontium polyacrylates;
vitamins such as Vitamins A, C and E;
plant extracts;
desensitising agents, e.g. potassium citrate, potassium chloride, potassium tartrate, potassium bicarbonate, potassium oxalate, potassium nitrate and strontium salts;
anti-calculus agents, e.g. alkali-metal pyrophosphates, hypophosphite-containing polymers, organic phosphonates and phosphocitrates etc. ; biomolecules, e.g. bacteriocins, antibodies, enzymes, etc.;
flavours, e.g. peppermint and spearmint oils;
proteinaceous materials such as collagen;
preservatives; opacifying agents;
colouring agents;
pH-adjusting agents;
sweetening agents;
pharmaceutically acceptable carriers, e.g. starch, sucrose, water or water/alcohol systems etc.;
surfactants, such as anionic, nonionic, cationic and zwitterionic or amphoteric surfactants;
particulate abrasive materials such as silicas, aluminas, calcium carbonates, dicalciumphosphates, calcium pyrophosphates, hydroxyapatites, trimetaphosphates, insoluble hexametaphosphates and so on, including agglomerated particulate abrasive materials, usually in amounts between 3 and 60% by weight of the oral care composition. Preferred abrasives are chalk and silica, more preferably fine ground natural chalk.
Humectants such as glycerol, sorbitol, propyleneglycol, xylitol, lactitol etc.;
binders and thickeners such as sodium carboxymethyl- cellulose, hydroxyethyl cellulose (Natrosol®) , xanthan gum, gum arabic etc. as well as synthetic polymers such as polyacrylates and carboxyvinyl polymers such as Carbopol®; polymeric compounds which can enhance the delivery of active ingredients such as antimicrobial agents can also be included;
buffers and salts to buffer the pH and ionic strength of the oral care composition; and
other optional ingredients that may be included are e.g. bleaching agents such as peroxy compounds e.g. potassium ' peroxydiphosphate, effervescing systems such as sodium bicarbonate/citric acid systems, colour change systems, and so on.
Liposomes may also be used to improve delivery or stability of active ingredients.
Preferably, the buffering agent is sodium hydroxide.
The two phases are preferably extruded into a toothpaste tube using devices known in the art, for example as described in WO 99/01342 (SKB) . They may be extruded such that they are dispensed side-by-side or such that one forms a stripe within the other.
In another preferred embodiment the first and second phases are coaxially arranged in and dispensed from a toothpaste tube, the second phase substantially surrounding the first phase.
Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material ought to be understood as modified by the word 'about' .
The term 'comprising' is meant not to be limiting to any subsequently stated elements but rather to encompass non- specified elements of major or minor functional importance. In other words the listed steps, elements or options need not be exhaustive. Whenever the words 'including' or 'having' are used, these terms are meant to be equivalent to 'comprising' as defined above.
Embodiments according to the invention shall now be discussed with reference to the following non-limiting examples.
EXAMPLE 1
The following example is a toothpaste made by standard processes . The two pastes are coextruded into a toothpaste tube using known processes.
Figure imgf000010_0001

Claims

1. Toothpaste comprising a first phase and a second phase which are stored in contact with one another, the first phase comprising calcium carbonate as abrasive and an alkali-metal citrate salt, the second phase comprising water and a zinc salt.
2. Toothpaste composition according to claim 1 wherein the molar ratio between the zinc ions and total citrate is from 1:1 to 1:2.
3. Toothpaste composition according to claim 1 wherein the molar ratio between the zinc ions and total citrate is from 1:1.3 to 1:1.7.
4. Toothpaste composition according to any preceding claim wherein the alkali-metal citrate salt is potassium citrate.
5. Toothpaste composition according to any of claims 1 to 3 wherein the alkali-metal citrate salt is sodium citrate.
6. Toothpaste composition according to any preceding claim wherein the calcium carbonate is fine ground natural chalk.
7. Toothpaste composition according to any preceding claim wherein the composition comprises a fluoride ion source.
8. Toothpaste composition according to any preceding claim wherein the zinc salt is sparingly-soluble in water.
9. Toothpaste according to any preceding claim wherein the zinc salt is zinc citrate.
10. Toothpaste according to any preceding claim wherein the zinc salt is present at from 0.01 to 5% by weight of the composition.
11. Toothpaste according to any preceding claim comprising an agent selected from the group consisting of anti- caries agents, anti-tartar agents, anti-malodour agents, whitening teeth agents, anti-gingivitis agents and mixtures thereof .
12. Toothpaste according to any preceding claim, wherein the first and second phases are coaxially arranged in and dispensed from a toothpaste tube, the second phase substantially surrounding the first phase.
PCT/EP2005/010876 2004-11-15 2005-10-04 Toothpaste composition WO2006050777A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP04257064 2004-11-15
EP04257064.8 2004-11-15

Publications (1)

Publication Number Publication Date
WO2006050777A1 true WO2006050777A1 (en) 2006-05-18

Family

ID=34930800

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2005/010876 WO2006050777A1 (en) 2004-11-15 2005-10-04 Toothpaste composition

Country Status (1)

Country Link
WO (1) WO2006050777A1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007122146A1 (en) * 2006-04-26 2007-11-01 Unilever Plc Toothpaste
WO2014147630A1 (en) * 2013-03-19 2014-09-25 Colgate-Palmolive Company Two-phase dentifrices
JP2016503036A (en) * 2012-12-24 2016-02-01 コルゲート・パーモリブ・カンパニーColgate−Palmolive Company Oral care composition
WO2016077688A3 (en) * 2014-11-14 2016-07-14 Colgate-Palmolive Company Oral care composition containing zinc salts and calcium carbonate
CN106994103A (en) * 2016-01-26 2017-08-01 白育纶 Mouthwash constituent
CN107007482A (en) * 2017-03-13 2017-08-04 广州薇美姿实业有限公司 A kind of oral care implement for removing implication and preparation method thereof
WO2017167535A1 (en) * 2016-03-31 2017-10-05 Unilever N.V. Toothpaste composition

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0740932A1 (en) * 1995-05-03 1996-11-06 Unilever N.V. Clear gel-type dentifrices
US5616313A (en) * 1994-06-30 1997-04-01 Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. Method for treating gingival and periodontal tissues
US5948390A (en) * 1997-08-25 1999-09-07 Pfizer Inc. Stable zinc/citrate/CPC oral rinse formulations

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5616313A (en) * 1994-06-30 1997-04-01 Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. Method for treating gingival and periodontal tissues
EP0740932A1 (en) * 1995-05-03 1996-11-06 Unilever N.V. Clear gel-type dentifrices
US5948390A (en) * 1997-08-25 1999-09-07 Pfizer Inc. Stable zinc/citrate/CPC oral rinse formulations

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007122146A1 (en) * 2006-04-26 2007-11-01 Unilever Plc Toothpaste
US10064794B2 (en) 2012-12-24 2018-09-04 Colgate-Palmolive Company Oral care composition
EP2934693A4 (en) * 2012-12-24 2016-09-14 Colgate Palmolive Co Oral care composition
JP2016503036A (en) * 2012-12-24 2016-02-01 コルゲート・パーモリブ・カンパニーColgate−Palmolive Company Oral care composition
US20160000667A1 (en) * 2013-03-19 2016-01-07 Colgate-Palmolive Company Two-Phase Dentifrices
CN105120830A (en) * 2013-03-19 2015-12-02 高露洁-棕榄公司 Two-phase dentifrices
AU2013382938B2 (en) * 2013-03-19 2015-11-05 Colgate-Palmolive Company Two-phase dentifrices
WO2014147630A1 (en) * 2013-03-19 2014-09-25 Colgate-Palmolive Company Two-phase dentifrices
WO2016077688A3 (en) * 2014-11-14 2016-07-14 Colgate-Palmolive Company Oral care composition containing zinc salts and calcium carbonate
CN107072896A (en) * 2014-11-14 2017-08-18 高露洁-棕榄公司 Oral care composition containing zinc salt and calcium carbonate
US10251823B2 (en) 2014-11-14 2019-04-09 Colgate-Palmolive Company Oral care composition containing zinc salts and calcium carbonate
RU2714131C2 (en) * 2014-11-14 2020-02-12 Колгейт-Палмолив Компани Oral care composition containing zinc salts and calcium carbonate
US10646422B2 (en) 2014-11-14 2020-05-12 Colgate-Palmolive Company Oral care composition containing zinc salts and calcium carbonate
CN107072896B (en) * 2014-11-14 2021-04-20 高露洁-棕榄公司 Oral care compositions containing zinc salt and calcium carbonate
CN106994103A (en) * 2016-01-26 2017-08-01 白育纶 Mouthwash constituent
WO2017167535A1 (en) * 2016-03-31 2017-10-05 Unilever N.V. Toothpaste composition
CN107007482A (en) * 2017-03-13 2017-08-04 广州薇美姿实业有限公司 A kind of oral care implement for removing implication and preparation method thereof

Similar Documents

Publication Publication Date Title
EP1773279B1 (en) Toothpaste comprising calcium carbonate and zinc citrate
EP1843741B1 (en) Opaque toothpaste composition
EP0740932B1 (en) Clear gel-type dentifrices
US6106811A (en) Oral care composition
WO2008006725A1 (en) Toothpaste composition
EP1107725B1 (en) Toothpaste comprising fine and coarse calcium carbonate
EP2349187B1 (en) Oral care composition
WO2006050777A1 (en) Toothpaste composition
WO2006012977A1 (en) Composition
EP1183006B1 (en) Oral composition containing perlite
EP1263401B1 (en) Oral composition comprising 2'-hydroxypropiophenone
US6602491B2 (en) Composition containing alkylhydroxybenzoates
US20030068283A1 (en) Composition
US6436372B2 (en) Oral composition with abrasive mixture of chalk and carbide
EP1408920A1 (en) Oral composition comprising peroxyamidophthalamide derivatives
US20030068282A1 (en) Composition
US20070065375A1 (en) Oral composition comprising micron-sized lanthanide metal oxide

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV LY MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DPEN Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 05800269

Country of ref document: EP

Kind code of ref document: A1