EP3518865A1 - Reinigungszusammensetzung - Google Patents

Reinigungszusammensetzung

Info

Publication number
EP3518865A1
EP3518865A1 EP17769110.2A EP17769110A EP3518865A1 EP 3518865 A1 EP3518865 A1 EP 3518865A1 EP 17769110 A EP17769110 A EP 17769110A EP 3518865 A1 EP3518865 A1 EP 3518865A1
Authority
EP
European Patent Office
Prior art keywords
oil
composition
surface modifier
cleaning agent
abrasive 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Withdrawn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
EP17769110.2A
Other languages
English (en)
French (fr)
Inventor
Pierre Starck
Simeon Dobrev Stoyanov
Vesselin Nikolaev Paunov
Anupam A K DAS
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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 PLC, Unilever NV filed Critical Unilever PLC
Publication of EP3518865A1 publication Critical patent/EP3518865A1/de
Withdrawn legal-status Critical Current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
    • A61K8/25Silicon; Compounds thereof
    • 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
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • 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
    • 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
    • A61K8/361Carboxylic acids having more than seven carbon atoms in an unbroken chain; Salts or anhydrides 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
    • A61K8/96Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives 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 present invention relates to a cleaning composition, it further relates to a process to prepare said cleaning composition.
  • Abrasive cleaning compositions are prepared and used since a long time. They comprise an abrasive agent, like calcium carbonate, and surfactant.
  • the abrasive agent helps removing dirt from a surface and preferably polishing the surface.
  • the abrasive agent functions as a texture builder of the cleaning composition.
  • a significant amount of abrasive agent may be required, to provide a desired viscosity to the product.
  • the amount of abrasive agent is about 50 wt% in commercial toothpaste, in the form of calcium carbonate. There is a desire to reduce this amount, as the price of the product will be less, while maintaining the desired viscosity.
  • Abrasive cleaning compositions normally comprise surfactant.
  • Surfactants help in the cleaning process, and cause foaming during use of the composition, especially non- ionic and anionic surfactants. Foaming is experienced by the user that the cleaning composition is actually active. However, surfactants can be irritant to the skin of the user. Especially in case the abrasive cleaning composition is a toothpaste, surfactants can irritate the gum.
  • the use of surfactants, in particular in toothpaste, further has the disadvantage that integration of possible pigment microparticles is challenging, as surfactant prevents effective deposition on the surface, e.g. the tooth enamel surface.
  • a reduced use or even absence of surfactant in the cleaning composition is therefore desired, but not at the cost of foaming.
  • Oil-dissolvable surface modifier having a HLB value of less than 7,
  • oil-dissolvable surface modifier is chemically attracted to or bound to the abrasive cleaning agent
  • concentration of anionic surfactant in the composition is less than 1 .5 wt%.
  • the present invention relates to a process for preparing a composition according to the invention, the process comprising the step of providing a mixture comprising polar liquid, abrasive cleaning agent, oil, and oil-dissolvable surface modifier, wherein the oil-dissolvable surface modifier is chemically attracted to or bound to the abrasive cleaning agent.
  • the present invention relates to the use of a composition of the invention as a dentifrice.
  • Figure 1 shows photographs of (a) commercial toothpaste, (b) 25% (w/v) in-situ hydrophobised calcium carbonate particles in water containing 0.8% (v/v) guar gum, the same sample after the addition of 1 % (c) and 1.5% (d) (w/v) secondary phase (50:50 (v/v) oleic acid and peppermint oil).
  • the composition of the invention preferably comprises, more preferably is, an emulsion of an oil phase in a polar phase. It comprises abrasive cleaning agent.
  • the polar phase normally, and preferably comprises a polar liquid, normally and preferably water or glycerol.
  • the polar liquid employed in the present process can be pure liquid or a mixture of liquids.
  • the polar liquid may further contain one or more dissolved or dispersed components.
  • the composition preferably contains 40 to 90 wt.% of the total composition of polar liquid. More preferably, the composition contains 50 to 80 wt.% of the total composition of the polar liquid.
  • the polar liquid may contain 50 to 100 wt.% water. More preferably the polar liquid contains 70 to100 wt% water, even more preferably 90 to 100 wt.% of water, most preferably the polar liquid is water.
  • the water content of the composition preferably lies in the range of 50 to 85 wt.%, more preferably of 50 to 70 wt.%, based on the weight of the composition. In the case of glycerol the polar liquid contains 10 wt.% or less water.
  • the polar phase is preferably liquid, as understood.
  • the polar phase is normally, as understood by the skilled person, and preferably, immiscible with the oil phase. In this way, the polar phase is preferably the continuous phase.
  • the composition preferably is a water-continuous suspension.
  • the polar phase e.g. the polar liquid, preferably water, comprises the abrasive agent. Consequently, it is preferred that the oil-phase does not comprise abrasive agent. More than 95 wt% of the abrasive agent is preferably suspended in the polar phase, e.g. water.
  • the composition is preferably a water-based capillary suspension.
  • Capillary suspensions are known in the art.
  • it is a capillary suspension wherein a small amount of immiscible liquid is in a continuous phase.
  • the oil phase comprises the oil and a hydrophobic surface modifier with an HLB value of less than 7.
  • the capillary suspension comprises an oil phase, comprising oil and surface modifier with an HLB value of less than 7, preferably in a total amount of less than 4 wt% (based on the weight of the composition) and it comprises a continuous polar phase, preferably comprising water.
  • the secondary phase, the oil phase forms and/or stabilises a network with particles.
  • the particles are the abrasive agent.
  • the particles are hydrophilic. Therefore, preferably, the cleansing composition is a water-continuous capillary emulsion.
  • the composition comprises abrasive agent.
  • the abrasive agent is in the form of particles, which particles are preferably hydrophilic. They are preferably present in the polar liquid.
  • the particles can be abrasive agents as known in the art of abrasive cleaning compositions, preferably in the field of dentifrices.
  • the abrasive agent can for example comprise silica, alumina, calcium carbonate, calcium silicate, dicalcium phosphate, calcium pyrophosphate, hydroxyapatite, trimetaphosphate, insoluble hexametaphosphate, including agglomerated particulate abrasive agents.
  • the abrasive agent comprises silica (preferably amorphous hydrated silica), calcium carbonate or a mixture thereof, preferably calcium carbonate, as this provided optimal texture and rheology of the composition in the context of the invention.
  • a phosphate-type abrasive such as calcium secondary phosphate dehydrate, calcium secondary phosphate nonhydrate and calcium pyrophosphate
  • the particle size of the abrasive agent is preferably of between 0.05 to 30 micrometer, preferably of from 0.1 and 30 micrometer, more preferably of between 0.5 and 25 micrometers and most preferably of between 5 and 20 micrometers. Probably at least 80 wt%, more probably at least 90% of the abrasive agent has this particle size.
  • the amount of abrasive agent is preferably of between 10 and 60 wt%, more preferably of between 10 and 50 wt%, based on the total weight of the composition.
  • an even more preferred amount of abrasive agent is of between 20 and 30 wt%, more preferably of between 22 and 20 to 40 wt%, or even 20 to 30 wt%, calcium carbonate.
  • the relatively lower concentrations of abrasive agent, like calcium carbonate, are preferably in combination with relatively higher levels of secondary oil phase or relatively higher levels of a hydrophobizing agent. It may be preferred, that at lower concentrations the thickener (polymers, gums) in the aqueous phase (e.g. guar gum) is added for more texture but this may affect the foamability of the composition.
  • hydrophilic abrasive agent particles are used. When present in the composition, these agent particles become hydrophobised.
  • the composition comprises further hydrophobic particles, or pre- hydrophobized particles, for example to increase the foaming. It can be preferred however, that hydrophobic particles, or pre-hydrophobized particles are absent, as they are difficult to disperse in the polar phase during manufacturing of the composition of the invention.
  • composition of the invention comprises oil.
  • the function of the oil in the present invention is to form capillary bridges between the solid particles which may be abrasive.
  • the oil is liquid at 30 °C, preferably at 20 °C.
  • the oil is preferably a fragrance oil, and can be natural or a synthetic oil.
  • the oil is preferably selected from the group consisting of peppermint oil, spearmint oil, anis oil, eucalyptus oil, wintergreen oil, isopropyl myristate and mixtures thereof, especially in case the composition is an oral care composition.
  • the oil can preferably comprise isopropyl myristate, especially in combination with oleic acid present in or as being the surface modifier.
  • the amount of oil is preferably less than 2 wt%, preferably less than 1.5 wt% more preferably less than 1 wt% of the total composition, most preferably less than 0.8 wt%, based on the total weight of the composition. It is preferably more than 0.1 wt%, more preferably more than 0.2 wt%, even more preferably more than 0.3 wt% and even more preferably more than 0.7 wt%., based on the total weight of the composition. It can be preferred to range between 0.1 and 2 wt%, preferably between 0.2 and 1 .5 wt%, most preferably of between 0.2 and 1.0 wt%, based on the total weight of the composition.
  • Surface modifier preferably less than 2 wt%, preferably less than 1.5 wt% more preferably less than 1 wt% of the total composition, most preferably less than 0.8 wt%, based on the total weight of the composition. It is preferably more than 0.1 wt%, more
  • the composition comprises a surface modifier with an HLB value of below 7.
  • the surface modifier modifies the particle surface, and is preferably a solid-surface modifier.
  • the surface modifier is preferably oil-dissolvable.
  • the surface modifier is insoluble in the polar liquid, preferably water, and is preferably selected from the group consisting of hydrophobic polymers, surfactants, organic acids and mixtures thereof.
  • the surface modifier is chemically attracted to or bound to the abrasive cleaning agent, preferably via covalent or non-covalent interaction.
  • the interaction is preferably via electrostatic interaction, such as for example ionic interaction or hydrogen bonds; Van der Waals interaction, or via covalent bonds.
  • the oil-dissolvable surface modifier is chemically attracted to the abrasive cleaning agent via ionic interaction.
  • the surface modifier accesses the particle surface through the oil, typically in the form of oil drops, which form capillary bridges between the particles dispersed in the polar liquid.
  • the surface modifier is preferably an anionic compound, such as a fatty acid, preferably oleic acid, palmitic oleic or stearic acid, more preferably oleic acid.
  • the solid surface modifier preferably is chosen from the group consisting of long chain fatty acids (i.e. having a carbon chain of 14 or longer), preferably from the group consisting of oleic acid, palmitic acid, stearic acid, and most preferably, the solid surface modifier is oleic acid.
  • the surface modifier is preferably cationic, such as for example isopropylmeristate.
  • the surface modifier can be oil-soluble quaternary ammonium surfactants like octadecyl trimethyl ammonium bromide (ODTAB), etc.
  • OTAB oil-soluble quaternary ammonium surfactants
  • the particles can be pre-hydrophobised with this agent.
  • the oil-soluble quaternary ammonium surfactant can be delivered to the surface of the particles (e.g. calcium silicate) by using an ethanol solution, followed by drying the ethanol before adding the secondary oil phase. This proved suitable for negatively charged particles, like
  • the amount of solid surface modifier is preferably of less than 2 wt%, more preferably of less than 1.5 wt%, even more preferably less than 1 wt%, even more preferably less than 0.8 wt%, based on the total weight of the composition. It is preferably present in an amount of more than 0.1 wt%, more preferably of more than 0.2 wt%, even more preferably more than 0.3 wt%, even more preferably more than 0.7 wt%, based on the total weight of the composition. Preferred ranges are of between 0.1 to 2 wt% more preferably of from 0.5 to 1 .0 wt%, even more preferably 0.7 to 0.9 wt%, based on the total weight of the composition.
  • the amount of solid surface modifier is from 1 to 50 wt%, preferably of from 5 to 30 wt% based on the weight of the oil.
  • the secondary phase or oil-phase, comprising the combined amount of oil and solid surface modifier is preferably of between 1 and 4 wt%, more preferably of between 1 .5 and 3 wt%, more preferably of between 1 and 2.5 wt%, based on the total weight of the composition.
  • the skilled person understands that when a gum is present, relatively lower levels of secondary phase can be used. It can be preferred that a lower level of 0.8 wt% of the total composition is used.
  • the present invention allows to reduce the level of surfactant, in particular anionic surfactants, while maintaining foaming. As described, this can be beneficial to reduce irritation of the gum.
  • Surfactant e.g. anionic surfactant
  • the concentration of surfactant is preferably less than 1 .5 wt%, preferably less than 1 wt%, more preferably less than 0.5 wt%, even more preferably less than 0.1 wt%, based on the total weight of the composition.
  • the concentration of nonionic surfactant is less than 1 .5 wt%, preferably less than 1 wt%, more preferably less than 0.5 wt%, even more preferably less than 0.1 wt%, based on the total weight of the composition.
  • the concentration of anionic surfactant is less than 1 .5 wt%, preferably less than 1 wt%, more preferably less than 0.5 wt%, even more preferably less than 0.1 wt%, based on the total weight of the composition.
  • Solid surface modifier preferably oil-soluble quaternary ammonium surfactants like ODTAB, as described above, is preferably not counted for as 'surfactant' in the context of the invention.
  • Rheology modifier preferably oil-soluble quaternary ammonium surfactants like ODTAB, as described above, is preferably not counted for as 'surfactant' in the context of the invention.
  • the composition can comprise a rheology modifier, such as a gum.
  • abrasives are not counted as rheology modifier.
  • the concentration of rheology modifier, preferably a gum is preferably lower than 3 wt%, preferably lower than 1 wt%, more preferably lower than 0.1 wt%, based on the weight of the composition. It can be preferred, that gum is absent. Gum appears to have a negative effect on foam formation.
  • a rheology modifier such as a gum
  • a rheology modifier such as a gum
  • the cleaning composition is a dentifrice
  • a gum can reduce this effect.
  • gum is preferably present in an amount of between 0.1 and 1 wt%, more preferably of between 0.2 and 0.9 wt%, based on the weight of the composition.
  • gum is preferably guar gum or homo- and copolymers of acrylic acid crosslinked with a polyalkenyl polyether, sold as CarbopolTM, or a mixture thereof. Guar gum is preferred.
  • Xanthan gum is less desired, or more preferably absent, as it showed a negative effect on foam formation. If present, its concentration is preferably less than 0.1 wt% of the total composition.
  • the composition of the invention has a rheology in the form of a paste, preferably such as toothpaste.
  • a rheology in the form of a paste, preferably such as toothpaste.
  • the amount of abrasive agent can be significantly lower than in conventional cleaning compositions or dentifrices, respectively.
  • a rheology modifier such as a texturing agent, like a gum, becomes less needed or superfluous.
  • composition relates to both the concentration of abrasive agent and the stability of the network formed by the oil and the surface modifier with HLB value lower than 7. So, lower levels of abrasive agent require higher levels of oil and surface modifier, and for higher levels of abrasive agent lower oil and surface modifier are sufficient, to provide a texture as desired, e.g. similar to tooth paste. Miscellaneous
  • the composition is preferably an oral care composition, most preferably a dentifrice.
  • the pH of the composition is preferably of from 7.5 to 8.5 at 20°C.
  • the composition may include ingredients to enhance the performance in use, for example to the use as a dentifrice.
  • ingredients include colour, fragrance, enzymes, bleaching agents, fluoride, freeze-thaw stabilisers, bactericides,
  • the composition comprises a pigment.
  • a pigment is in particular advantageous in case the composition is a dentifrice.
  • the composition of the invention allows for the use of a low concentration of surfactant, or even the absence of surfactant, the composition of the invention provides for enhanced attachment of pigment to the surface to be cleaned, preferably to the teeth.
  • the composition preferably comprises a compound selected from the group consisting of Ti02, Mica, covarine blue (W6795) and mixtures thereof.
  • the amount of pigment is preferably from 0.01 to 0.3 wt%, preferably from 0.02 to 0.1 wt%, more preferably from 0.03 to 0.08 wt%. The amount does refer to the amount of actives, not to any carrier material in the pigment suspension.
  • the present invention relates to a process to prepare a composition of the invention.
  • the process preferably comprises the step of providing a mixture comprising polar liquid, abrasive cleaning agent, oil, and oil-dissolvable surface modifier, wherein the oil-dissolvable surface modifier is chemically attracted to or bound to the abrasive cleaning agent.
  • the process preferably comprises the steps of:
  • step a) Providing a mixture of abrasive cleaning agent and polar liquid, preferably water, b) Mixing oil and oil-dissolvable surface modifier having an HLB of less than 7 into the mixture resulting from step a).
  • a mixture is made of abrasive cleaning agent with polar liquid.
  • a texturiser preferably a gum is mixed with the polar liquid and abrasive material. The gum is preferably at a concentration of less than 3 % of the total composition.
  • Mixing is conveniently done by a mixing apparatus known in the art.
  • a step b) the mixture of polar liquid, abrasive cleaning agent and optionally texturizing agent such as gum, is combined with oil and surface modifier with an HLB of below 7. It can be preferred that first oil is combined with the mixture resulting from step a) and then the surface modifier with an HLB of below 7 is combined with the mixture comprising polar liquid, abrasive cleaning agent, optional texturizing agent such as gum, and oil. It may also be preferred, to add the oil and the surface modifier with an HLB of below 7 together to the mixture comprising polar liquid and abrasive cleaning agent, for example in the form of a pre-mix.
  • the invention further relates to a composition obtainable by, preferably obtained by, the process according to the invention.
  • the composition preferably comprises less than 1.5 wt% anionic surfactant, more preferably is free of anionic surfactant.
  • the present invention relates to the use of the composition of the invention as a dentifrice.
  • the Solvay Socal 31 calcium carbonate hydrophilic particles (Salin de Giraud, France) respectively was used for making these capillary suspensions.
  • the continuous phase used was Milli Q water.
  • the Guar gum FG60-70 was obtained from Multi-kern
  • the secondary phase used was pure oleic acid (10588810, Fisher Scientific, UK) and peppermint oil purified by triple distillation (W284823, Sigma Aldrich, UK).
  • the particles (25 w/v) are mixed into the bulk fluid (water containing guar gum) using a propeller stirrer at 500 rpm for 5 minutes.
  • the dispersion was then mixed with minute amounts of secondary phase oleic acid and peppermint oil (initially mixed at 50:50 ratio) using the same stirrer.
  • the foaming capability and stability was measured. 5 g of samples with 30 ml of water was hand shaken for 20 seconds in a 100 ml measuring cylinder. The foam height was then measured at various times in order to observe the foam stability. The produced foam was also observed under the microscope in order to observe its shape, size and structure.
  • Peppermint oil - 0.5 % w/v 0.75 % w/v
  • Composition 1 is a commercial toothpaste (Colgate) with a toothpaste rheological appearance (figure 1 , left upper panel).
  • Composition 2 does not contain a secondary phase, resulting in a very soft to liquid appearance. The low level of particles
  • composition 3 showed a texture similar to that of toothpaste, despite a relatively low level of particles.
  • Composition 4 showed that at an amount of 1 .5% secondary phase and a particle level of 25%, and a gum level of 0.8 % the texture becomes too hard. This indicates that the skilled person may vary the viscosity building components of particle concentration, secondary phase level and gum concentration to create a texture that fits his or her need. All compositions have a particle level lower than that of commercial toothpaste, and foam at a level that is acceptable for toothpaste purposes, despite the absence of anionic surfactant.
  • Oleic acid 0.02% w/v 0.1 % 0.2 w/v 0.04 w/v in-situ 30% w/w 10% w/v 20%w/v 20 %w/v hydrophobised

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Biotechnology (AREA)
  • Botany (AREA)
  • Microbiology (AREA)
  • Mycology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Cosmetics (AREA)
  • Detergent Compositions (AREA)
EP17769110.2A 2016-10-03 2017-09-26 Reinigungszusammensetzung Withdrawn EP3518865A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP16192017 2016-10-03
EP17170599 2017-05-11
PCT/EP2017/074414 WO2018065264A1 (en) 2016-10-03 2017-09-26 Cleaning composition

Publications (1)

Publication Number Publication Date
EP3518865A1 true EP3518865A1 (de) 2019-08-07

Family

ID=59914493

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17769110.2A Withdrawn EP3518865A1 (de) 2016-10-03 2017-09-26 Reinigungszusammensetzung

Country Status (4)

Country Link
EP (1) EP3518865A1 (de)
CN (1) CN109789059A (de)
BR (1) BR112019006214A2 (de)
WO (1) WO2018065264A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113631143B (zh) * 2019-03-28 2024-04-12 株式会社Lg生活健康 牙膏组合物

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040120902A1 (en) * 2001-04-24 2004-06-24 Wernett Patrick Clinton Fluoride compatible calcium carbonate

Also Published As

Publication number Publication date
WO2018065264A1 (en) 2018-04-12
CN109789059A (zh) 2019-05-21
BR112019006214A2 (pt) 2019-06-18

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