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(11) EP 3 222 326 A1

(12) EUROPEAN PATENT APPLICATION

(43) Date of publication: (51) Int Cl.: 27.09.2017 Bulletin 2017/39 A61Q 11/00 (2006.01) A61K 8/19 (2006.01) A61K 8/24 (2006.01) (21) Application number: 17161926.5

(22) Date of filing: 20.03.2017

(84) Designated Contracting States: (72) Inventors: AL AT BE BG CH CY CZ DE DK EE ES FI FR GB • BUGNI, Claudia GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Bebington, Wirral, Merseyside CH63 3JW (GB) PL PT RO RS SE SI SK SM TR • JOINER, Andrew Designated Extension States: Bebington, Wirral, Merseyside CH63 3JW (GB) BA ME • LIMER, Adam, John Designated Validation States: Bebington, Wirral, Merseyside CH63 3JW (GB) MA MD (74) Representative: Tansley, Sally Elizabeth (30) Priority: 23.03.2016 EP 16161806 Unilever PLC Unilever Patent Group (71) Applicants: Colworth House • Unilever PLC Sharnbrook London, Greater London EC4Y 0DY (GB) Bedford Designated Contracting States: Bedfordshire MK44 1LQ (GB) CY GB IE MT • Unilever N.V. 3013 AL Rotterdam (NL) Designated Contracting States: AL AT BE BG CH CZ DE DK EE ES FI FR GR HR HU IS IT LI LT LU LV MC MK NL NO PL PT RO RS SE SI SK SM TR

(54) TOOTHPASTE COMPOSITION

(57) The present invention relates to a source having a water solubility less than 0.1 moles per litre at room temperature in combination with a source for use in preventing calculus. EP 3 222 326 A1

Printed by Jouve, 75001 PARIS (FR) 1 EP 3 222 326 A1 2

Description [0009] The calcium source suitable for use in this in- vention is limited only to the extent that the same may [0001] The present invention relates to materials that be used in an oral cavity. In a preferred embodiment, the prevent the formation of calculus and their inclusion into calcium source employed is insoluble or slightly soluble toothpaste compositions. 5 in water, but most preferably, insoluble in water. [0002] Dental calculus is a deposit which forms on the [0010] Illustrative examples of the types of calcium surfaces of the teeth at the gingival margin. As the cal- source that may be used in this invention include, for culus develops, it becomes visibly white or yellowish in example, (i.e., added), calcium glu- colour unless stained or discoloured by some extraneous conate, calcium oxide, , calcium carbon- agent. This is undesirable from an aesthetic standpoint. 10 ate, calcium hydroxide, calcium sulfate, calcium car- [0003] WO9822080 (Procter and Gamble) discloses boxymethyl cellulose, calcium alginate, calcium salts of toothpastes that are said to have anti-tartar activity. The citric acid, calcium silicate, mixtures thereof or the like. composition comprise polyphosphates. In a preferred embodiment, the calcium source is calcium [0004] The present invention discloses compositions silicate. In a more preferred embodiment, the calcium 15 with improved anti-calculus activity. silicate used is (CaSiO 3) whereby the same is made com- mercially available under the name Microcal ET by Ineos Description of the Invention Silicas, Ltd. [0011] In yet another preferred embodiment, the calci- [0005] The present invention relates to a calcium um source is insoluble calcium silicate, present as the 20 source having a solubility less than 0.1 moles per litre at composite material calcium oxide-silica (CaO-SiO2) as room temperature in combination with a phosphate described in commonly-owned application Publication source for use in preventing calculus. No. 2008/015117. [0012] When a calcium silicate composite material is Detailed Description of the Invention employed, the ratio of calcium to silicon (Ca:Si) may be 25 from 1:10 to 3:1. The Ca:Si ratio is preferably from 1:5 [0006] The present invention relates to a toothpaste to 2:1, and more preferably, from 1:3 to 2:1, and most composition for use in preventing calculus, the compo- preferably, from about 1:2 to 2:1. The calcium silicate sition comprising a water insoluble and/or slightly soluble may comprise mono-calcium silicate, bi-calcium silicate, calcium source and a phosphate source. or tri-calcium silicate whereby ratios of calcium to silicon [0007] Compositionsfor use in theinvention comprises 30 (Ca:Si) should be understood to be atom ratios. a water insoluble and/or slightly soluble calcium source [0013] The calcium source employed in this invention and a phosphate source. may be in a crystalline or amorphous state, and prefer- [0008] Soluble and insoluble calcium source, as used ably, the same is in an amorphous state. In an often pre- herein, refers to the solubility of the calcium source in ferred embodiment, the calcium source is in a mesopo- water. Soluble means a source that dissolves in water to 35 rous state, i.e. the source is a material having pores with give a solution with a concentration of at least 0.1 moles diameters from 1 nm to 50 microns. Mesoporous calcium per litre at room temperature. Insoluble means a source silicate (MCS) is often preferred. that dissolves in water to give a solution with a concen- [0014] The MCS which may be used in this invention tration of less than 0.001 moles per litre at room temper- can be made by combining a calcium , a silica pre- ature. Slightly soluble, therefore, is defined to mean a 40 cursor like silicate and a structure-directing agent to yield source that dissolves in water to give a solution with a a solid suitable for calcinating. A more detailed descrip- concentration of greater than 0.001 moles per litre at tion of the process that may be conducted to make the room temperature and less than 0.1 moles per litre at MCS suitable for use in this invention is described in the room temperature. Substantially free of, as used herein, aforementioned commonly-owned application, Publica- means less than 1.5%, and preferably, less than 1.0%, 45 tion No. WO 2008/015117. and most preferably, from 0.0 to 0.75% by weight, based [0015] The amount of calcium source in the composi- on total weight of the oral care composition, including all tion of this invention is typically from 0.1 to 50%, and ranges subsumed therein. Single-phase composition preferably, from 1 to 30%, and most preferably, from 5 means a one phase composition having both calcium to 20% by weight of the oral care composition based on and phosphate sources therein and prior to dispensing 50 total weight of the oral care composition and including all or unpackaging and use. Anhydrous, as used herein, ranges subsumed therein. means substantially free of water. Generated calcium [0016] The phosphate source that may be used in this and phosphate comprising compound means a com- invention is limited only to the extent that the same may pound with calcium and phosphate like calcium phos- be used in a composition suitable for use in an oral cavity. phate and hydroxyapatite that is formed within the55 Illustrative examples of the types of phosphate source monophase product from distinct compounds comprising suitable for use in this invention include monosodium calcium and phosphate. Toothpaste compositions re- phosphate, dihydrogen phosphate, disodium hy- lates to pastes and gel compositions, preferably pastes. drogen phosphate, sodium pyrophosphate, tetrasodium

2 3 EP 3 222 326 A1 4 pyrophosphate, sodium tripolyphosphate, sodium hex- flavors, e.g., peppermint and spearmint oils; ametaphosphate, dihydrogenphosphate, , tripotassium phosphate, mixtures proteinaceous materials such as collagen; thereof or the like. The phosphate source is preferably one which is water soluble. 5 preservatives; [0017] Typically, the phosphate source makes up from 0.5 to 15%, and preferably, from 2 to 12%, and most opacifying agents; preferably, from 4 to 9% by weight of the oral care com- position, based on total weight of the oral care composi- coloring agents like FD&C blue, yellow and/or red tion and including all ranges subsumed therein. In a pre- 10 dyes/colorants; ferred embodiment, the phosphate source used is one which results in an oral care composition having a pH pH-adjusting agents; from 5.5 to 8, preferably from 6 to 7.5, and most prefer- ably, about neutral. In a most preferred embodiment, the sweetening agents; phosphate source used is trisodium phosphate and15 monosodium dihydrogen phosphate at a trisodium phos- surfactants, such as anionic, nonionic, cationic phate to monosodium dihydrogen phosphate weight ratio and zwitterionic or amphoteric surfactants (e.g., so- of 1:4 to 4:1, preferably 1:3 to 3:1, and most preferably, dium lauryl sulfate, sodium dodecylbenzene sul- from 1:2 to 2:1, including all ratios subsumed therein. fonate); [0018] The oral care compositions described herein 20 may comprise ingredients which are common in the art, particulate abrasive materials such as abrasive such as: silicas, aluminas, calcium carbonates, zirconium sil- icate, polymethylmethacrylate, dicalciumphos- antimicrobial agents, e.g. Triclosan, chlorhexi- phates, calcium pyrophosphates, hydroxyapatites, dine, -, - and stannous salts such as zinc 25 trimetaphosphates, insoluble hexametaphosphates citrate, zinc sulphate, zinc glycinate, sodium zinc ci- as well as agglomerated particulate abrasive mate- trate and stannous pyrophosphate, sanguinarine ex- rials; tract, metronidazole, quaternary ammonium com- pounds, such as cetylpyridinium chloride; bis-gua- fluoride sources like , stannous nides, such as chlorhexidine digluconate, hexeti- 30 fluoride, sodium monofluorophosphate, zinc ammo- dine, octenidine, alexidine; and halogenated bisphe- nium fluoride, tin ammonium fluoride, calcium fluo- nolic compounds such as 2,2’ methylenebis-(4-chlo- ride, cobalt ammonium fluoride or mixtures thereof; ro-6-bromophenol); polymeric compounds which can enhance the de- anti-inflammatory agents such as ibuprofen, flur- 35 livery of active ingredients such as antimicrobial biprofen, aspirin, indomethacin, etc.; agents can also be included. Examples of such pol- ymers are copolymers of polyvinylmethylether with anti-caries agents such as sodium trimetaphos- maleic anhydride and other similar delivery enhanc- phate and casein; ing polymers, e.g., those described in DE- 40 A03,942,643; plaque buffers such as urea, calcium lactate, cal- cium glycerophosphate and strontium polyacrylates; buffers and salts to buffer the pH and ionic strength of the oral care compositions; and vitamins such as Vitamins A, C and E; 45 other optional ingredients that may be included plant extracts; are, e.g., bleaching agents such as peroxy com- pound, e.g., potassium peroxydiphosphate, effer- desensitising agents, e.g. , po- vescing systems such as sodium bicarbonate/citric tassium chloride, potassium tartrate, potassium bi- acid systems, colour change systems, and the like. carbonate, potassium oxalate, and potassium ni- 50 trate; [0019] Such ingredients common in the art typically and collectively make-up less than 20% by weight of the anti-calculus agents, e.g. alkali-metal pyrophos- oral care composition, and preferably, from 0.0 to 15% phates, hypophosphite-containing polymers, organ- by weight, and most preferably, from about 0.01 to about ic phosphonates and phosphocitrates, etc.; 55 12% by weight of the oral care composition, including all ranges subsumed therein. biomolecules, e.g. bacteriocins, antibodies, en- [0020] Thickener may also be used in this invention zymes, etc. and is limited only to the extent that the same may be

3 5 EP 3 222 326 A1 6 added to a composition suitable for use in an oral cavity. following non-limiting Examples: Illustrative examples of the types of thickeners that may be used in this invention include, sodium carboxymethyl Examples cellulose, hydroxyl ethyl cellulose, methyl cellulose, ethyl cellulose, gum tragacanth, gum Arabic, gum karaya, so- 5 [0029] Oral care compositions (monophase) were pre- dium alginate, carrageenan, guar, xanthan gum, Irish pared by mixing (in weight percent) the following ingre- moss, starch, modified starch, silica based thickeners dients under moderate shear until a homogeneous com- including silica aerogels, aluminum silicate position was obtained. (i.e., Veegum) Carbomers (cross-linked acrylates) and mixtures thereof. 10 Ingredient % [0021] Typically, sodium carboxymethyl cellulose and/or Carbomers are preferred. When a Carbomer is Glycerin (99.5%) To 100 employed, those having a molecular weight of at least Calcium silicate 15.0 700,000 are desired, and preferably, those having a mo- PEG 400 10,5 lecular weight of at least 1,200,000, and most preferably, 15 those having a molecular weight of at least about Hydrated Silica 6,0 2,500,000 are desired. Mixtures of Carbomers may also Trisodium Phosphate anhydrous 3.8 be used herein. [0022] In an especially preferred embodiment, the Car- Monosodium Phosphate Anhydrous 3.2 ® bomer is Carbopol 980. It has been described as a high 20 Sodium Lauryl sulfate 2.0 molecular weight and cross-linked polyacrylic acid and identified via CAS number 9063-87-0. The same is avail- PEG 3000S 2.0 able commercially from Lubrizol Advanced Materials, Sodium Monofluorophosphate 1.1 Inc. Optamint 405213® 1.1 [0023] Thickener typically makes up from 0.01 to about 25 10%, and preferably, from 0.1 to 8%, and most preferably, TiO2 0.5 from 1.5 to 6% by weight of the oral care composition, Hydrated Silicon Dioxide 0.5 based on total weight of the oral care composition and including all ranges subsumed therein. Sodium saccharin 0.3 30 [0024] Suitable carrier humectants are preferably used Polyacrylic acid cross linked 0.1 in the oral care composition of the present invention and they include, for example, glycerin, sorbitol, propylene glycol, dipropylene glycol, diglycerol, triacetin, [0030] The composition of 1 was further mixed at a 1:1 oil, polyethylene glycol (preferably, PEG-400), alkane di- ratio with a serum having the following formula: ols like butane diol and hexanediol, ethanol, pentylene 35 glycol, or a mixture thereof. The carrier humectants Ingredients % should, in any case, be substantially free of water, and Glycerin (99.5%) 53.8 preferably, anhydrous. The same, for example, can be used in solid form, whereby glycerin is the preferred car- Calcium silicate 6.4 rier humectant. 40 PEG 400 5.3 [0025] The carrier humectant is used to take the bal- ance of the compositions up to 100%, and the same may Trisodium Phosphate anhydrous 1.9 be present in the range of from 10 to 90% by weight of Monosodium Phosphate Anhydrous 1.6 the oral care composition. Preferably, the carrier humect- ant makes up from 25 to 80%, and most preferably, from 45 Sodium Lauryl sulfate (PAS) 1.0 45 to 70% by weight of the oral care composition, based PEG 3000S 1.0 on total weight of the oral care composition and including all ranges subsumed therein. Sodium Monofluorophosphate 0.6 [0026] Preferably the composition is a single phase Sodium Fluoride 98% 0.2 composition. 50 Water and minors To 100 [0027] The compositions of this invention are prepared by conventional methods of making oral care formula- tions.Such methodsinclude mixing the ingredients under [0031] The product mix above was tested against a moderate shear and atmospheric pressure. The compo- standard fluoride toothpaste comprising dicalcium Phos- sitions are used in the oral cavity, and preferably, are of 55 phate Dihydrate, Aqua, Glycerin, Sorbitol, PEG-12, So- the form that may be brushed onto teeth with a tooth- dium Lauryl Sulfate, Aroma, Cellulose Gum, Sodium brush. Monofluorophosphate, Tetrasodium Pyrophosphate, [0028] The invention will now be demonstrated by the

4 7 EP 3 222 326 A1 8

Sodium Saccharin, Calcium Glycerophosphate, Sodium the composition further comprises a thickener se- Fluoride, Limonene lected form the groups consisting of carboxymethyl [0032] The products were tested using 218 panellists cellulose, Carbomer or mixtures thereof. over a 6 week period. Products were assessed using a Volpe-manhold score summed across 6 specific sites. 5 11. Use according to any one of claims 2 to 10 in which [0033] Results showed that the subjects using the the composition further comprises a carrier humect- product of the invention had significantly less calculus ant selected from the group consisting of glycerin, than those using the conventional toothpaste. sorbitol, propylene glycol, dipropylene glycol, diglyc- erol, triacetin, mineral oil, polyethylene glycol (pref- 10 erably, PEG-400), alkane diols like butane diol and Claims hexanediol, ethanol, pentylene glycol or mixtures thereof. 1. A calcium source having a solubility less than 0.1 moles per litre at room temperature in combination 12. Use according to any one of claims 2 to 1 1 in which with a phosphate source for use in preventing cal- 15 the composition has a pH from 5.5 to 8. culus.

2. Use according to claim 1 in which the a water insol- uble and/or slightly soluble calcium source and a phosphate source is formulated in a toothpaste com- 20 position.

3. Use according to claim 2 in which the composition is substantially free of water. 25 4. Use according to any preceding claim in which the phosphate source of the composition is water-solu- ble.

5. Use according to any preceding claim in which the 30 calcium source of the composition comprises calci- um gluconate, calcium oxide, calcium lactate, calci- um carbonate, calcium hydroxide, calcium sulphate, calcium carboxymethyl cellulose, calcium alginate, calcium salts of citric acid, calcium silicate or a mix- 35 ture thereof.

6. Use according to any of the preceding claims in which the calcium source is calcium silicate. 40 7. Use according to claim 6 in which the calcium silicate is one having a of Ca:Si ratio of 1:10 to 3:1.

8. Use according to any of the preceding claims where- in the phosphate source of the composition is mono- 45 sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium pyrophos- phate, tetrasodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, po- tassium dihydrogenphosphate, trisodium phos-50 phate, tripotassium phosphate or a mixture thereof.

9. Use according to claim 8 wherein the phosphate source is trisodium phosphate, disodium hydrogen phosphate, monosodium dihydrogen phosphate or 55 a mixture thereof.

10. Use according to any one of claims 2 to 9 in which

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REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• WO 9822080 A [0003] • DE 3942643 A0 [0018] • WO 2008015117 A [0011] [0014]

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