Spray composition for oral hygiene, use of a spray composition for oral hygiene, method for minimizing or preventing tooth stains, and cosmetic use of a composition.

Abstract

A spray composition for oral hygiene, a method for minimizing or preventing tooth staining, and a cosmetic use of a composition. A spray composition for oral hygiene comprising: (a) a polymer with the structure: formula (i) wherein a is independently selected from 2 to 130 and b is from 15 to 67 and the molecular weight of the polymer is from 1,700 to 15,000 da; (b) hexametaphosphate; and (c) an orally acceptable base; wherein the weight ratio of the polymer to hexametaphosphate is from 1:5 to 5:1.

Description

[001] The present invention relates to an oral hygiene composition for minimizing tooth staining. Background of the Invention

[002] Long-lasting teeth whitening is of great interest to consumers. Foods and beverages such as tea, coffee, and wine can cause tooth stains by directly depositing chromogens on the tooth surface. The attraction of materials to the tooth surface plays a critical role in the deposition of extrinsic tooth stains. The chromogens in these beverages that are responsible for causing tooth stains are known as tannins and are composed of polyphenols such as catechins. These materials generate color due to the presence of conjugated double bonds.

[003] Traditional tooth whitening methods involve bleaching with peroxide from kit formats or abrasive stain removal from toothpaste formats. These particles are essentially insoluble particles that remove extrinsic stains from the tooth surface through abrasion when applied with a brush. The present invention relates to a novel oral hygiene composition that provides effective levels of stain protection and prolongs the effects of tooth whitening by preventing tooth discoloration. The invention discloses a stain-repellent coating with a synergistic mixture of a hydrophilic-hydrophobic block copolymer and a Ca2+ chelating agent (a phosphate salt) in a defined ratio. This helps to provide a stain-protective layer on the surface. Petition 870250028969, dated 10 / 04 / 2025, page 14 / 29 2 / 13 of the tooth may be damaged during food / drink consumption after whitening treatments.

[004] The block copolymers used in the present invention are generally known as Pluronics. These polymers are generally known for their use in oral hygiene. The phosphate salt used in the present invention is hexametaphosphate, which has also been used in oral hygiene.

[005] US patent 2014 / 377194 A (P&G) discloses an oral hygiene composition containing (a) a zinc citrate; and (b) a surfactant organophosphate compound and also refers to a method for preventing staining from depositing on the tooth surface or other oral surfaces.

[006] US patent 2003 / 124065 A (P&G) discloses an oral hygiene composition and methods for general cleaning, whitening and prevention, reduction or removal of surface stains on natural teeth and dental prostheses, the compositions comprising in an orally acceptable vehicle at least 0.1% by weight of a water-soluble or water-dispersible copolymer prepared by copolymerization of one or a mixture of vinyl pyrrolidone (VP) monomers with one or a mixture of C1-C19 alkyl carboxylic acid (AC) C2-C12 alkenyl ester monomers;Preferably, these compositions further comprise one or a mixture of other oral hygiene agents selected from a water-soluble alkali metal or ammonium tripolyphosphate in an amount of at least about 0.5% by weight of the composition, an abrasive, preferably a precipitated silica abrasive, in an amount of at least about 6% by weight of the composition, and a bleaching agent in an amount of at least about 0.1% by weight of the composition.

[007] It is therefore an objective of the present invention to provide a Petition 870250028969, dated 10 / 04 / 2025, page 15 / 29 3 / 13 oral hygiene composition that minimizes tooth discoloration. Brief Description of the Invention

[008] According to the first aspect of the present invention, an oral hygiene composition is provided comprising: (a) 0.1 to 2% by weight of the total polymer composition with the structure: where a is independently selected from 2 to 130 and b is from 15 to 67 and the molecular weight of the polymer is from 1700 to 15000 Da; (b) hexametaphosphate; and (c) an orally acceptable base; where the weight ratio of the polymer to hexametaphosphate is 1:5 to 5:1.

[009] According to another aspect of the present invention, a method is provided for minimizing or preventing tooth discoloration comprising the steps of applying the composition of the invention described above to a tooth.

[0010] Another aspect of the invention relates to the cosmetic use of a composition according to any of the previous claims to mitigate tooth discoloration. Detailed Description of the Invention

[0011] Except in examples, or where explicitly indicated otherwise, all numbers in this description indicating quantities of material or reaction conditions, physical properties of materials and / or use may optionally be understood as modified by the word “about”. Petition 870250028969, dated 10 / 04 / 2025, page 16 / 29 4 / 13

[0012] All quantities are by weight of the final composition, unless otherwise indicated.

[0013] Note that when specifying any range of values, any specific higher value can be associated with any specific lower value.

[0014] The disclosure of the invention as found herein should be considered as covering all embodiments found in the claims as being multiply dependent on each other, regardless of the fact that the claims may be found without dependence or multiple redundancy.

[0015] When a feature is disclosed in relation to a particular aspect of the invention (for example, a composition of the invention), such disclosure shall also be considered applicable to any other aspect of the invention (for example, a method of the invention) mutatis mutandis.

[0016] The present invention relates to an oral hygiene composition comprising a polymer with the structure of the compound of formula 1: Compound of formula 1

[0017] In the compound above, the molecular weight ratio of ethoxylate groups to propoxylate groups is in the range of 0.1 to 3.0, preferably in the range of 0.1 to 2.5. The molecular weight of the polymer is in the range of 1,700 to 15,000 Da, preferably in the range of 10,000 to 13,000 Da. The present invention preferably requires polymers containing EO and PO (propoxylate) moieties with the structure above. The ethoxylate (EO) moiety of the polymer should preferably be 10 to 80% of the total polymer, more preferably 10 to 60% of the total polymer. Commercially available polymers that are Petition 870250028969, dated 10 / 04 / 2025, page 17 / 29 5 / 13 polymers preferably used in the composition of the present invention include Pluronic L-61, Pluronic F88, Pluronic F77, Pluronic F108 or Pluronic 127, more preferably Pluronic 127. The polymer is preferably present at 0.1 to 2% by weight, more preferably 0.3 to 1.8% by weight.

[0018] The composition of the invention includes a phosphate compound that is hexametaphosphate. Sodium hexametaphosphate has the structure shown below: O0 o; II CL IIZOH PP CK ..-Ü CL ..--O ^PP^ 0' II Cl CL XL Ό ^-pρς ox|. l>0 00

[0019] Hexametaphosphate is preferably included at 0.1 to 4%, more preferably 0.1 to 2.0% by weight of the total composition.

[0020] According to the present invention, the weight ratio of polymer of formula 1 to hexametaphosphate is required to be 1:5 to 5:1, more preferably 1:4 to 4:1. In a preferred aspect, this ratio is 1:3 to 3:1. It is particularly preferred that the weight ratio of polymer of formula 1 to hexametaphosphate be greater than 1:1.

[0021] It is preferable that the total amount of polymer and hexametaphosphate in the composition of the invention be from 0.1 to 5% by weight of the total composition.

[0022] Without wishing to be limited by theory, the present inventors believe that it is the synergistic interaction of the two ingredients of which the polymer modifies the hydroxyapatite surface of the tooth to provide it with low interfacial energy, so as to repel surface stains, and the calcium binding affinity of the phosphate to the tooth surface that, in the specific weight proportions of the ingredients and the polymer structure, Petition 870250028969, dated 10 / 04 / 2025, page 18 / 29 6 / 13 specifically chosen within the chosen EO / PO ratio that provides the desired benefit of the present invention.

[0023] The compositions according to the invention are in the form of a product that is applied to the teeth as a spray.

[0024] The composition of the invention comprises an orally acceptable base. The orally acceptable base preferably comprises a humectant, water, volatile alcohol or combinations thereof. The orally acceptable base preferably constitutes 96 to 99.8% by weight of the composition. Preferably, the weight ratio of water to humectant is 1:2 to 2:1, more preferably 2:3 to 3:2.

[0025] A composition according to the invention will generally contain other ingredients to improve performance and / or consumer acceptability, in addition to the ingredients specified above.

[0026] The compositions according to the invention may comprise a polymeric deposition aid. Preferably, the composition comprises acid anhydride polymers, particularly preferred are maleic anhydride copolymers with methyl vinyl ether, wherein the anhydride moiety may be in a partially or fully hydrolyzed or alcoholized form. Preferred copolymers include Gantrez® polymers, such as: - Gantrez S-95: molecular weight 216,000; acid-free; - Gantrez S-96: molecular weight 700,000; acid-free; - Gantrez S-97: molecular weight 1,500,000; acid-free; and - Gantrez MS-955: molecular weight 1,060,000; calcium / sodium salt.

[0027] Particularly preferred maleic acid and methyl vinyl ether copolymers have a molecular weight of 1,000,000 or higher, and a particularly preferred material is Gantrez S-97.

[0028] The compositions according to the invention may Petition 870250028969, dated 10 / 04 / 2025, page 19 / 29 7 / 13 comprising a tooth whitening agent. The whitening agent preferably comprises a green and / or blue pigment. In the context of the present invention, a pigment is generally understood to be a shade / material that is insoluble in the relevant medium at the relevant temperature. This is in contrast to dyes which are soluble. In the context of this invention, the “relevant medium” is human saliva, the liquid medium in which the composition is used, at the temperature of the oral cavity during tooth brushing, i.e., up to 37 degrees C. As a reasonable approximation, the relevant medium can be considered to be water and the relevant temperature is 25 degrees C.

[0029] 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, more preferably 15:1. A preferred pigment is the blue pigment Phtalocyanine Blue Pigment, CI No. 74160, covarine blue.

[0030] The preferred green pigment is phthalocyanine green, preferably phthalocyanine green CI-74260.

[0031] Preferably, the total pigment level, in particular covarin blue in the total composition, is from 0.0005% by weight to 0.5% by weight, more preferably from 0.001% to 0.1% by weight, most preferably from 0.007% to 0.014% by weight.

[0032] The compositions according to the invention may comprise sources of water-soluble or sparingly water-soluble metallic salts. Zinc ions such as zinc chloride, zinc acetate, zinc gluconate, zinc sulfate, zinc fluoride, zinc citrate, zinc lactate, zinc oxide, zinc monoglycerate, zinc tartrate, zinc pyrophosphate and zinc maleate are preferred; stannous ions such as stannous fluoride and stannous chloride are also preferred.

[0033] The compositions according to the invention may Petition 870250028969, dated 10 / 04 / 2025, page 20 / 29 8 / 13 understand oral hygiene enzyme systems, such as hydrogen peroxide-producing enzyme systems (e.g., glucose oxidase oxidoreductase), amyloglucosidase, dextranase and / or mutanase (optionally in the presence of compounds that provide zinc ions and / or 8-hydroxyquinoline derivatives), lactoperoxidase, lactoferrin, lysozyme and mixtures thereof.

[0034] The compositions of the invention may comprise fluoride sources, such as sodium fluoride, tin fluoride, sodium monofluorophosphate, zinc-ammonium fluoride, tin-ammonium fluoride, calcium fluoride, cobalt-ammonium fluoride and mixtures thereof.

[0035] Preferably, the composition has a pH of 6 to 9 at 20 °C.

[0036] The composition according to the invention will comprise other ingredients that are common in the art, such as: - antimicrobial agents, for example, chlorhexidine, sanguinarine extract, metronidazole, quaternary ammonium compounds such as cetylpyridinium chloride; bis-guanides such as chlorhexidine digluconate, hexetidine, octenidine, alexidine; and halogenated bisphenol 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, amine fluorides, sodium monofluorophosphate, sodium trimetaphosphate and casein; - Plaque buffers such as urea, calcium lactate, calcium glycerophosphate and strontium polyacrylates; - Vitamins such as Vitamins A, C, and E; - plant extracts; - plant-derived antioxidants, such as compounds of Petition 870250028969, dated 10 / 04 / 2025, page 21 / 29 9 / 13 flavonoids, catechins, polyphenols and tannins and mixtures thereof; - Desensitizing agents, for example potassium citrate, potassium chloride, potassium tartrate, potassium bicarbonate, potassium oxalate, potassium nitrate and strontium salts; - anti-calculus agents, for example, alkali metal pyrophosphates, hypophosphite-containing polymers, organic phosphonates and phosphocitrates, etc.; - biomolecules, for example, bacteriocins, antibodies, enzymes, etc.; - aromas, for example, mint and peppermint oils; - protein materials such as collagen; - preservatives; - opacifying agents; - hyaluronic acid; - amino acids such as arginine; - coloring agents; - pH adjusting agents; - sweetening agents; - pharmaceutically acceptable vehicles, for example, starch, sucrose, water or water / alcohol systems, etc.; Surfactants, such as anionic, nonionic, cationic, and zwitterionic or amphoteric surfactants; - humectants such as glycerol, sorbitol, propylene glycol, 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®; Petition 870250028969, dated 10 / 04 / 2025, page 22 / 29 10 / 13 Polymeric compounds that can improve the delivery of active ingredients, such as antimicrobial agents, may also be included; - buffers and salts to buffer the pH and ionic strength of the oral hygiene composition; and Other optional ingredients that may be included are, for example, bleaching agents such as peroxy compounds, for example, potassium peroxydiphosphate, effervescent systems such as sodium bicarbonate / citric acid systems, color-changing systems, and so on.

[0037] The invention will now be illustrated by the following non-limiting examples.

[0038] Examples of the invention are represented by a number, comparative examples are illustrated by a letter. Examples Example 1 and Example A

[0039] Two sprayers were produced as in Table 1. Table 1 Ingredient Example 1 Example A Sorbitol 50.00 52.00 Sodium saccharin 0.27 0.27 Sodium hexametaphosphate 0.50 0 Pluronic F 127 1.50 0 Cremaphor 2.50 2.50 Flavor 0.50 0.50 Water 44.73 44.73 Total 100 100 Test method

[0040] The extracted teeth were cleaned with a silica-based toothpaste and placed in sterile human saliva for 2 hours to allow for the formation of a film. The initial tooth color was measured using a Petition 870250028969, dated 10 / 04 / 2025, pp. 23 / 29 11 / 13 colorimeter. The teeth were gently rubbed with a tissue to remove excess saliva, and each tooth received 2 spray applications of the anti-staining formulation (containing pluronic F127 and sodium hexametaphosphate) or the placebo formulation. The teeth were left for 30 seconds before being placed in a staining solution at 25 °C (1:1:1 black coffee solution, black tea solution, red wine) with gentle agitation (75 rpm). The teeth were removed at each time point, rinsed in 50 ml of water, the color was measured again, and then they were placed back in the stain. The total color change (ΔE) from baseline, and therefore the level of staining formation, was calculated following different time points using: ΔΕ = V[(L*q - L*t)2+ (a*o - a*t)2+ (b*0 - b*t)2]

[0041] Where L*o and L*t are values ​​of L* at the baseline and at time t, respectively; a*o and a*t are values ​​of a* at the baseline and at time t, respectively, and b*o and b*t are values ​​of b* at the baseline and at time t. Results

[0042] The mean values ​​of ΔE (se) for each treatment group (n = 15) after various time points in the staining solution are shown below in Table 2. The product differences were statistically significant (Student's t-test, p < 0.05) at each time point. TABLE 2 Formulation Average values ​​of ΔE (if) 1.5 hours 3 hours 4.5 hours Example 1 1.12 ± 0.12 1.38 ± 0.56 1.31 ± 0.15 Example A 1.97 ± 0.10 2.85 ± 0.90 3.25 ± 0.20

[0043] The data in Table 2 indicate that the oral hygiene compositions according to the invention (Example 1) provide much superior stain-removing efficacy (as evidenced by the low ΔE values) compared to the comparative Example (Example A). Petition 870250028969, dated 10 / 04 / 2025, pp. 24 / 29 12 / 13 Examples 2, 3 and 4 Table 3 Ingredient Example 2 Example 3 Example 4 Example A Sorbitol 50.00 50.00 50.00 52.00 Sodium saccharin 0.27 0.27 0.27 0.27 Sodium hexametaphosphate 0.50 0.50 0.50 0 Pluronic F 127 1.50 1.50 1.50 0 Covarin blue 0.005 0.01 0.015 0 Cremaphor 2.50 2.50 2.50 2.50 Flavor 0.50 0.50 0.50 0.50 Water 44.73 44.73 44.73 44.73 Total 100 100 100 100

[0044] The evaluation method for Examples A and 2-4 is the same as for Example 1, but with an exposure time of 10 s after spraying before an additional color measurement is taken (instantaneous whitening effect) and then immersion in the staining solution for 1.5 and 3 hours before the color measurements (anti-stain effect). The instantaneous whitening effect is described in terms of changes in the tooth whiteness index (WIO) from baseline and subsequent staining in terms of ΔE from baseline. The results are shown in Table 4. Table 4 Formulation Instant Whitening Effect Average ΔWIO (if) Spot Formation Average ΔE (if) 0.0 hour 1.5 hour 3.0 hours Example A 0.1 (0.4) A 6.0 (0.3)A 7.9 (0.3)A Example 2 4.8 (0.7) B 2.7 (0.5) B 2.9 (0.5) B Example 3 6.7 (0.9) B 2.4 (0.4) B 1.6 (0.3)C Example 4 12.3 (0.8)C 2.9 (0.3) B 3.5 (0.3) B

[0045] Values ​​with different letters within each time point indicate statistically significant differences between treatment groups (p < 0.05, ANOVA, Tukey-Kramer).

[0046] The data in Table 3 indicate that adding covarin blue at different levels to the spray formulation (Example 1) provides superior instant whitening benefits compared to the comparative formulation. Petition 870250028969, dated 10 / 04 / 2025, pages 25 / 29 13 / 13 (Example A), as is evident from the larger and more significant change in WIO values. Furthermore, the spray formulation containing covarin blue provides much superior anti-stain efficacy (as is evident from the significantly lower Δε values) compared to the comparison example (Example A).

Claims

1. SPRAY COMPOSITION FOR ORAL HYGIENE, characterized by comprising: (a) 0.1 to 2% by weight of the total composition of the polymer with the structure: wherein a is independently selected from 2 to 130 and b is from 15 to 67 and the molecular weight of the polymer is from 1,700 to 15,000 Da; (b) hexametaphosphate; and (c) an orally acceptable base; wherein the weight ratio of the polymer to hexametaphosphate is from 1:5 to 5:

1.

2. COMPOSITION, according to claim 1, characterized in that the weight ratio of polymer to hexametaphosphate is from 1:4 to 4:

1.

3. COMPOSITION, according to any one of claims 1 to 2, characterized in that the molecular weight of the polymer is from 10,000 to 13,000 Da.

4. COMPOSITION, according to any one of claims 1 to 3, characterized by comprising from 0.1 to 4% by weight of the total composition of hexametaphosphate.

5. COMPOSITION, according to any one of claims 1 to 4, characterized in that the total amount of polymer and hexametaphosphate is from 0.1 to 5% by weight of the total composition.

6. COMPOSITION, according to any of the claims 1 to 5, characterized by the composition further comprising a blue pigment, preferably covarin blue.

7. COMPOSITION, according to claim 6, characterized in that the level of blue pigment is from 0.001 to 0.1% by weight of the total composition, preferably from 0.007 to 0.014% by weight.

8. COMPOSITION, according to any one of claims 1 to 7, characterized by the orally acceptable base comprising a humectant, water, volatile alcohol or combinations thereof.

9. COMPOSITION, according to any one of claims 1 to 8, characterized by comprising from 96 to 99.8% of an orally acceptable basis.

10. COMPOSITION, according to any one of claims 8 to 9, characterized in that the humectant is a polyhydric alcohol, preferably sorbitol or glycerol.

11. COMPOSITION, according to any one of claims 8 to 10, characterized in the ratio by weight of water to humectant being from 1:2 to 2:

1.

12. COMPOSITION, according to any one of claims 1 to 11, characterized by having a pH at 20 °C of 6 to 9.

13. USE OF A SPRAY COMPOSITION FOR ORAL HYGIENE, as defined in any one of claims 1 to 12, characterized in that it is for manufacturing a product to treat stains on teeth.

14. METHOD FOR MINIMIZING OR PREVENTING STAINS ON TEETH, characterized by comprising the steps of applying the composition, as defined in any one of claims 1 to 12, onto a tooth surface.

15. COSMETIC USE OF A COMPOSITION, as defined in any one of claims 1 to 11, characterized by being for reducing stains on teeth.