CN119053318A

CN119053318A - Oral care compositions

Info

Publication number: CN119053318A
Application number: CN202380032373.4A
Authority: CN
Inventors: D·T·利特尔伍德; R·G·赖利
Original assignee: Unilever IP Holdings BV
Current assignee: Unilever IP Holdings BV
Priority date: 2022-04-01
Filing date: 2023-03-22
Publication date: 2024-11-29
Also published as: EP4504142A1; WO2023186648A1

Abstract

The present invention relates to a non-aqueous oral care composition comprising i) more than 50wt% of an organic polyol having 3 or more hydroxyl groups in the molecule, ii) carrageenan, iii) an anionic surfactant comprising at least 50wt% of an alkyl sulfate salt based surfactant based on total anionic surfactant, iv) a mixture of calcium silicate and a phosphate source, which mixture when delivered to teeth results in situ generation of hydroxyapatite on said teeth.

Description

Oral care compositions

Technical Field

The present invention relates to non-aqueous oral care compositions.

Background

Oral care compositions such as dentifrices typically contain a dental acceptable abrasive, humectant, water, and a water soluble polymer that acts as a thickening agent and binder for the ingredients. Various other ingredients, such as flavors, sweeteners, preservatives, and fluoride are also used at low levels.

However, there are many materials that are physically or chemically incompatible with the aqueous environment present in typical toothpaste formulations.

Nonaqueous formulations have been proposed as a means of improving the stability of these materials. For example, WO96/03108 describes a non-aqueous dentifrice composition comprising a carboxyvinyl polymer, a humectant, polyethylene glycol and a dental acceptable abrasive.

EP 2585031 discloses a non-aqueous oral care composition having a liquid continuous phase comprising a thickener, a humectant, and one or more liquid polyethylene glycols having a melting point below 25 ℃, wherein the liquid continuous phase is constituted by crystals of one or more solid polyethylene glycols having a melting point of 25 ℃ or more.

However, there remains a need for non-aqueous compositions with good viscosity profile and flow characteristics (characteristics) as well as excellent storage characteristics.

It is therefore an object of the present invention to provide oral care compositions having good paste shape, belt height and storage stability.

Disclosure of Invention

A first aspect of the invention relates to a non-aqueous oral care composition comprising:

i) More than 50wt% of an organic polyol having 3 or more hydroxyl groups in the molecule;

ii) carrageenan;

iii) An anionic surfactant comprising at least 50wt% of an alkyl sulfate salt-based surfactant, based on total anionic surfactant;

iv) a mixture of calcium silicate and a phosphate source, which when delivered to the teeth results in situ generation of hydroxyapatite on the teeth.

Detailed Description

Unless in the examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and/or use may optionally be understood as modified by "about".

All amounts are by weight of the final composition unless otherwise indicated.

It should be noted that any particular upper value may be associated with any particular lower value when any numerical range is specified.

The disclosure of the invention as found herein should be considered to cover all embodiments as found in the claims that are multiple dependent on each other, irrespective of the fact that the claims may be found without multiple dependent or redundant.

Where features are disclosed with respect to a particular aspect of the invention (e.g., a composition of the invention), such disclosure should also be considered as applicable to any other aspect of the invention (e.g., a method of the invention) with appropriate modifications.

Any natural or naturally derived ingredient mentioned in the present application is from europe.

The compositions of the present invention are non-aqueous. "non-aqueous" generally means that no significant amounts of water are deliberately added to the composition. However, the term "non-aqueous" does not mean that a small amount of water cannot be present, for example as a result of its association with hygroscopic raw materials. Thus, for the purposes of the present invention, the term "non-aqueous" generally means that water is present in an amount of no more than 5 wt%, more preferably no more than 3 wt%, most preferably no more than 1 wt%, based on the total weight of the composition.

The composition according to the invention comprises carrageenan, preferably in a weight ratio of iota-carrageenan to kappa-carrageenan of from 1:2 to 2:1. The carrageenan present in the composition of the invention preferably consists of a total level of iota carrageenan of 33 to 66% by weight and kappa carrageenan of 33 to 66% by weight.

The total level of carrageenan is from 0.01 to 1wt%, more preferably from 0.05 to 0.5wt%, most preferably from 0.08 to 0.25wt% based on the total composition.

The composition of the present invention comprises polyethylene glycol or polypropylene glycol having a melting point below 42 ℃, more preferably below 25 ℃. In a preferred embodiment of the present invention, the melting point is greater than-20 ℃ and is in the range of-15 ℃ to 25 ℃, more preferably in the range of-5 ℃ to 8 ℃, most preferably in the range of 4 ℃ to 8 ℃.

Preferred liquid polyethylene glycols have an average value of n in the general formula H (OCH ₂CH₂)_n OH, as described above) in the range of about 4 to 12, more preferably in the range of about 6 to 8, most preferably about 8, their average molecular weight is suitably in the range of about 190 to 630 g/mole, more preferably about 285 to 420 g/mole, most preferably about 380 to 420 g/mole.

In the composition of the invention, the amount of polyethylene glycol in polyethylene glycol and/or polypropylene glycol iii (as defined above) is suitably in the range of from 0.1 to 10wt%, more preferably in the range of from 0.5 to 7wt%, most preferably in the range of from 1 to 5wt%, based on the total weight of the composition.

Preferred ratios of polyethylene glycol and/or polypropylene glycol iii) to carrageenan are from 1:200 to 1:4, preferably from 1:1 to 1:40.

The composition of the present invention contains an organic polyol (hereinafter referred to as "organic polyol") having 3 or more hydroxyl groups in the molecule. Examples of such materials include glycerol, sorbitol, xylitol, mannitol, lactitol, maltitol, erythritol and hydrogenated partially hydrolysed polysaccharide. The most preferred organic polyol is glycerol. Mixtures of any of the above materials may also be used.

The level of organic polyol will depend on the particular type selected but is generally in the range of about 20 to 90 wt% based on the total weight of the composition, with the amount of organic polyol suitably in the range of 35 to 85 wt%, more preferably 65 to 80 wt% based on the total weight of the composition. Desirably, the compositions of the present invention are glycerol-based (i.e., a higher proportion of glycerol to the weight of the composition as compared to any other compound) and contain 55 to 80 weight percent glycerol based on the total weight of the composition.

The composition of the invention comprises anionic surfactant, preferably at least 50wt% based on alkyl sulphate surfactant based on total anionic surfactant. Most preferably, the anionic surfactant is sodium lauryl sulfate.

Preferably, the level of anionic surfactant is from 0.1 to 5wt%, preferably from 0.5 to 3wt%, based on the total composition, more preferably sodium lauryl sulfate.

The additional surfactant, such as nonionic, cationic and zwitterionic or amphoteric surfactants, is preferably present at a level of less than 0.5wt% based on the total composition, preferably less than 0.1wt% based on the composition.

The compositions of the present invention are useful for cleaning, preferably, the surfaces of the oral cavity and are known as oral care compositions.

Thus, preferred product forms of the compositions of the present invention are those suitable for brushing and/or rinsing oral surfaces.

The composition of the present invention is most preferably in the form of a toothpaste. Such compositions are not intentionally swallowed for purposes of systemic administration of therapeutic agents, but rather are applied to the oral cavity for purposes of treatment of the oral cavity and then salivation. Typically, such compositions are used in conjunction with a cleaning implement, such as a toothbrush, typically by applying it to the bristles of the toothbrush and then brushing the accessible surfaces of the oral cavity.

Preferably, the dentifrice/toothpaste is in the form of an extrudable semi-solid such as a cream (stream), paste (paste) or gel (or mixtures thereof).

In addition to the ingredients specified above, the compositions (e.g., dentifrices/toothpastes) according to the present invention will typically contain additional ingredients to enhance performance and/or consumer acceptability.

The composition according to the invention, in particular toothpaste, preferably comprises particulate abrasive material such as silica, alumina, calcium carbonate, dicalcium phosphate, calcium pyrophosphate, hydroxyapatite, trimetaphosphate salts, insoluble hexametaphosphate salts and the like, including agglomerated particulate abrasive material, typically in an amount of 3 to 60% by weight based on the weight of the oral care composition.

Preferably, the composition, in particular a toothpaste, comprises a silica-based abrasive. The preferred abrasive silica for use in the present invention is silica having a low refractive index. It may be used as the sole abrasive silica or in combination with low levels of other abrasive silica types such as those according to EP 236070. The low refractive index silicas used as abrasives in the present invention are preferably silicas having an apparent refractive index (r.i.) in the range of 1.41 to 1.47, preferably in the range of 1.435 to 1.445, preferably having a weight average particle size of 5 to 15mm, a BET (nitrogen) surface area of 10 to 100mm ²/g, and an oil absorption of about 70 to 150cm ³/100 g, although abrasive silicas having lower apparent refractive indices may also be used. Typical examples of suitable low refractive index abrasive silicas (e.g., having an r.i. of 1.435 to 1.445) are Tixosil 63 and 73 from Rhone Poulenc, sident from Degussa, zeodent 113 from Zeofinn, zeodent 124 from Evonik, sorbosil AC 77 (having an r.i. of about 1.440) from PQ Corporation. The amount of these silicas in the composition is generally in the range from 5 to 60% by weight, generally from 5 to 20% by weight.

The composition, particularly if a toothpaste, preferably comprises an inorganic or natural or synthetic thickener or gelator in a proportion of about 0.10 to about 15% by weight, depending on the material selected. These proportions of thickening agent in the dentifrice composition of the present invention form an extrudable shape-retaining product which can be extruded from a tube onto a toothbrush and will not fall between the bristles of the toothbrush, but will substantially maintain its shape thereon. Suitable thickening or gelling agents that may be used in the practice of the present invention include inorganic thickening silica, such as amorphous silica available from Huber corporation under the trade name Zeodent 165, irish moss, iota carrageenan, tragacanth and polyvinylpyrrolidone.

The composition according to the invention preferably comprises a polymeric deposition aid. Preferably, the composition comprises an anhydride polymer, particularly preferably a copolymer of maleic anhydride and methyl vinyl ether, wherein the anhydride moiety (mole) may be in partially (partially) or fully hydrolyzed or alcoholyzed form. Preferred copolymers include Gantrez (R) polymers such as:

gantrez S-95, molecular weight 216,000;

gantrez S-96 having a molecular weight of 700,000;

gantrez S-97 having a molecular weight of 1,500,000, a free acid, and

Gantrez MS-955, molecular weight 1,060,000, calcium/sodium salt.

A particularly preferred copolymer of maleic acid and methyl vinyl ether has a molecular weight of 1,000,000 or greater, and a particularly preferred material is Gantrez S-97.

The composition according to the present invention may comprise a tooth whitening agent. The whitening agent preferably comprises green and/or blue pigments. Pigments are generally understood in the context of the present invention as being hues/materials which are insoluble in the relevant medium at the relevant temperature. This is in contrast to soluble dyes. In the context of the present invention, a "relevant medium" is human saliva, i.e. the liquid medium in which the composition is used in a liquid medium at the temperature of the oral cavity during brushing, i.e. at most 37 degrees celsius. As a reasonable approximation, the relevant medium may be considered water and the relevant temperature is 25 degrees celsius.

Preferably, the blue pigment is pigment blue 15, more preferably pigment blue 15:1, 15:2, 15:3, 15:4, 15:5 or 15:6, most preferably 15:1. Preferred pigments are blue pigments, phthalocyanine blue pigments, CI No. 74160, covarine blue (blue covarine).

The preferred green pigment is phthalocyanine green, preferably CI-74260.

Preferably, the total level of pigment in the composition is from 0.01wt% to 3wt%, more preferably from 0.02 to 2wt%.

If the composition is a toothpaste, it may be a biphasic paste in which the whitening pigment is present in one phase.

The composition according to the invention may comprise a water-soluble or water-slightly soluble source of metal salts. Preferred are zinc ions such as zinc chloride, zinc acetate, zinc gluconate, zinc sulfate, zinc fluoride, zinc citrate, zinc lactate, zinc oxide, zinc monoglyceride (zinc monoglycerolate), zinc tartrate, zinc pyrophosphate and zinc maleate, and also preferred are stannous ions such as stannous fluoride and stannous chloride.

The compositions according to the invention may comprise an oral care enzyme system, such as a hydrogen peroxide-producing enzyme system (e.g., oxidoreductase glucose oxidase), amyloglucosidase, glucanase and/or non-water soluble glucanase (mutanase) (optionally in the presence of zinc ion-providing compounds and/or 8-hydroxyquinoline derivatives), lactoperoxidase, lactoferrin, lysozyme and mixtures thereof;

the compositions of the present invention may comprise a fluoride source, such as sodium fluoride, stannous fluoride, sodium monofluorophosphate, zinc ammonium fluoride, tin ammonium fluoride, calcium fluoride, cobalt ammonium fluoride, and mixtures thereof.

The compositions of the present invention include agents for tooth remineralization. In the context of the present invention, the term "remineralisation" means the in situ generation of hydroxyapatite on the teeth.

Agents for tooth remineralization are calcium silicate and phosphate sources, which when delivered to teeth result in situ generation of hydroxyapatite on the teeth.

The amount of calcium silicate in the compositions of the present invention is typically in the range of 1 to 30%, preferably in the range of 5 to 20% by total weight of the oral care composition.

Illustrative examples of the types of phosphate sources that may be used in this context (hereinafter referred to as "remineralised phosphate sources") include, for example, monosodium phosphate, disodium phosphate, sodium pyrophosphate, tetrasodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, monopotassium phosphate, trisodium phosphate, tripotassium phosphate, and mixtures thereof. Preferably, the remineralised phosphate source is a mixture of trisodium phosphate and monosodium phosphate.

The amount of remineralised phosphate source (e.g. trisodium phosphate and monosodium phosphate) in the composition of the present invention is typically in the range of 2 to 15%, preferably in the range of 4 to 10% by total weight of remineralised phosphate source, based on the total weight of the oral care composition.

Mixtures of any of the above materials may also be used.

The composition according to the invention will additionally comprise ingredients common in the art, such as:

Antimicrobial agents such as chlorhexidine, sanguinarine extracts, metronidazole, quaternary ammonium compounds such as cetylpyridinium chloride, cetylpyridinium chloride clay complexes (cetylpyridium chloride clay complex), biguanides such as chlorhexidine digluconate, hexetidine, octonidine (octenidine), alexidine (alexidine), and halogenated bisphenol compounds such as 2,2' -methylenebis- (4-chloro-6-bromophenol);

Anti-inflammatory agents such as ibuprofen, flurbiprofen, aspirin, indomethacin, and the like;

Anticaries agents such as sodium fluoride and stannous fluoride, amine fluorides, sodium monofluorophosphate, sodium trimetaphosphate, and casein;

plaque buffers such as urea, calcium lactate, calcium glycerophosphate and strontium polyacrylates;

Vitamins such as vitamin a, vitamin C and vitamin E;

A plant extract;

Antioxidants derived from plants such as flavonoids, catechins, polyphenols and tannins and mixtures thereof;

desensitizing agents, such as potassium citrate, potassium chloride, potassium tartrate, potassium bicarbonate, potassium oxalate, potassium nitrate and strontium salts;

Anticalculus agents such as alkali metal pyrophosphates, hypophosphite-containing polymers, organic phosphonates (organic phosphonates) and phosphoryl citrates (phosphocitrates);

Biomolecules, such as bacteriocins, antibodies, enzymes, and the like;

flavoring agents such as peppermint oil and spearmint oil;

Proteinaceous materials such as collagen;

A preservative;

A light-shielding agent;

Hyaluronic acid;

amino acids such as arginine;

A colorant;

a pH regulator;

A sweetener;

pharmaceutically acceptable carriers, such as starch, sucrose, water or water/alcohol systems and the like;

humectants, such as glycerol, sorbitol, propylene glycol, xylitol, lactitol and the like;

binders and thickeners, e.g. sodium carboxymethyl cellulose, hydroxyethyl cellulose Xanthan gum, gum arabic, and the like, and synthetic polymers such as polyacrylates and carboxyvinyl polymers such as

May also comprise polymers that may enhance the delivery of active ingredients such as antimicrobial agents;

buffers and salts to buffer the pH and ionic strength of the oral care composition, and

Other optional ingredients that may be included are, for example, bleaching agents, e.g., peroxy compounds such as potassium peroxydiphosphate, effervescent systems such as sodium bicarbonate/citric acid systems, color-changing systems, and the like.

Embodiments of the present invention will now be illustrated by the following non-limiting examples:

Examples

TABLE 1

*1 Methylcocoyl sodium taurate

* Sodium 2 lauryl sulfate

*3 Alkyl polyglycol ether (stearyl alcohol +30 EO)

The viscosity was freshly measured from the batch and a band (rib) evaluation was performed at 24 hours.

The above examples demonstrate that the examples according to the invention have the most acceptable belt height and viscosity to the consumer after storage.

Claims

1. A non-aqueous oral care composition comprising:

i) greater than 50 wt% of an organic polyol having 3 or more hydroxyl groups in the molecule;

ii) carrageenan;

iii) an anionic surfactant comprising at least 50 wt% of an alkyl sulfate-based surfactant based on total anionic surfactant;

iv) a mixture of calcium silicate and a phosphate source which, when delivered to a tooth, results in the in situ production of hydroxyapatite on said tooth.

2. The non-aqueous oral care composition of claim 1, wherein the alkyl sulfate-based surfactant is sodium lauryl sulfate.

3. The non-aqueous oral care composition of claim 1 or claim 2, wherein the carrageenan consists essentially of iota-carrageenan to kappa-carrageenan in a weight ratio of 1:2 to 2:1.

4. A non-aqueous oral care composition according to any one of the preceding claims, wherein the organic polyol is glycerol.

5. A non-aqueous oral care composition according to any one of the preceding claims, further comprising polyethylene glycol and/or polypropylene glycol having a melting point below 42°C, preferably below 25°C.

6. The non-aqueous oral care composition of claim 5, wherein the polyethylene glycol has a melting point above -20°C.

7. A non-aqueous oral care composition according to any one of the preceding claims wherein the level of carrageenan is from 0.01 to 1 wt%, more preferably from 0.05 to 0.5 wt%, most preferably from 0.08 to 0.25 wt% of the total composition.

8. A non-aqueous oral care composition according to any preceding claim wherein the level of polyethylene glycol and/or polypropylene glycol is from 0.1 to 10 wt%, more preferably from 0.5 to 7 wt%, most preferably from 1 to 5 wt% of the total composition.

9. A non-aqueous oral care composition according to any one of the preceding claims, wherein the weight ratio of polyethylene glycol and/or polypropylene glycol iii) to carrageenan is from 1:200 to 1:4, preferably from 1:1 to 1:40.

10. A non-aqueous oral care composition according to any preceding claim in which the level of polyol is greater than 65 wt% of the total composition.

11. A non-aqueous oral care composition according to any preceding claim which is a toothpaste.

12. A non-aqueous oral care composition according to any preceding claim, further comprising an abrasive.

13. A non-aqueous oral care composition according to any preceding claim in which the level of abrasive is from 5 wt% to 60 wt% of the total composition.

14. A non-aqueous oral care composition according to any preceding claim wherein the level of anionic surfactant is from 0.1 to 5 wt%, preferably from 0.5 to 3 wt% of the total composition, the anionic surfactant preferably being sodium lauryl sulphate.