A multi-effect robust enamel-strengthening oral care composition and uses thereof

Abstract

The present application relates to the field of oral care preparations, and discloses a multi-effect strong enamel tooth enamel oral care composition and application thereof.The oral care composition comprises sodium polyglutamate, methyl vinyl ether-maleic anhydride copolymer, fluoride and a synergistic promoter; the synergistic promoter comprises cocamidopropyl betaine and / or alkyl glycoside; the mass ratio between the sodium polyglutamate and the methyl vinyl ether-maleic anhydride copolymer is 1:0.2-4.The oral care composition of the present application can not only improve the adsorption amount of fluoride on the tooth surface, improve the residence effect of fluoride in the oral cavity, but also promote the effective use of fluoride on the surface of the hard tissue of the tooth, improve the remineralization effect, and reduce the loss of calcium dissolution of the hard tissue of the tooth.

Description

Technical Field

[0001] This invention relates to the field of oral care preparations, and more particularly to an oral care composition for strengthening tooth enamel and its application. Background Technology

[0002] Dental caries is one of the most common oral health problems worldwide. Fluoride, as a recognized caries preventer and remineralizer, can repair early demineralization by promoting remineralization of the enamel surface and is widely used in toothpaste. However, considering the safety of fluoride, the fluoride content in toothpaste needs to be strictly controlled. How to improve the effectiveness of fluoride with limited fluoride content is an important research topic.

[0003] Methyl vinyl ether-maleic anhydride copolymer (PVM / MA copolymer) has good film-forming properties. By forming an adhesive barrier on the surfaces of teeth, gums, and oral soft tissues, it can increase the amount of fluoride adsorbed on the tooth surface and prolong the residence time of fluoride in the oral cavity, allowing it to exert its effects for a longer period. For example, patent CN118924661A discloses an anti-glycation composition and oral care product for improving fluoride utilization, as well as a method for preparing the same. This anti-glycation composition includes fluoride, blueberry fruit extract, and PVM / MA copolymer. However, while film-forming substances like PVM / MA copolymer can help fluoride remain on the tooth surface in a physically attached form, they are difficult to further participate in promoting mineralization reactions and cannot effectively improve the remineralization effect of fluoride on the hard tissues of teeth. Summary of the Invention

[0004] To address the technical problem that film-forming substances are insufficient to effectively enhance the remineralization effect of fluoride on tooth hard tissues, this invention provides a multi-effect oral care composition for strengthening tooth enamel. This oral care composition not only increases the amount of fluoride adsorbed on the tooth surface and improves the retention effect of fluoride in the oral cavity, but also promotes the effective utilization of fluoride on the surface of tooth hard tissues, reduces calcium dissolution and loss from tooth hard tissues, and enhances the remineralization effect.

[0005] The specific technical solution of this invention is as follows: In a first aspect, the present invention provides a multi-effect oral care composition for strengthening tooth enamel, comprising sodium polyglutamate, methyl vinyl ether-maleic anhydride copolymer, fluoride, and a synergistic promoter; wherein the synergistic promoter comprises cocamidopropyl betaine and / or alkyl glycoside; and wherein the mass ratio between the sodium polyglutamate and the methyl vinyl ether-maleic anhydride copolymer is 1:0.2~4.

[0006] In the composition formulation of this invention, in the presence of cocamidopropyl betaine (CAB) and / or alkyl glycoside (APG), sodium polyglutamate (PGA-Na) and methyl vinyl ether-maleic anhydride copolymer (PVM / MA copolymer) can synergistically promote the oral care effects of fluoride (increasing fluoride adsorption on the tooth surface, improving fluoride utilization, reducing calcium dissolution and loss from tooth hard tissues, and enhancing the remineralization effect of fluoride on tooth hard tissues). Specifically: PGA-Na can anchor and store calcium ions in tooth enamel by chelating calcium ions with its molecular carboxyl groups. In the acidic microenvironment of plaque, the carboxyl groups are protonated and calcium is released slowly, which, together with fluoride, promotes enamel remineralization. On this basis, PGA-Na is compounded with PVM / MA copolymer. The excellent film-forming and adhesion properties of PVM / MA copolymer on the tooth surface, combined with the calcium ion binding properties of PGA-Na, can synergistically increase the adsorption and retention of fluoride ions on the enamel surface and enhance the remineralization effect of tooth hard tissue.

[0007] However, the invention team discovered that the PGA-Na and PVM / MA copolymers did not actually produce a synergistic effect. The fluoride adsorption and remineralization effects on the enamel surface of the PGA-Na + PVM / MA copolymer + fluoride ternary compound system did not meet expectations. The presumed reasons are: both are anionic linear polymers, and electrostatic repulsion leads to uneven chain segment distribution; simultaneously, both have relatively long molecular chains, with some segments prone to excessive entanglement and others separating. These factors result in poor fluoride ion retention capacity of PGA-Na and PVM / MA copolymers, preventing the expected synergistic effect from being achieved.

[0008] When CAB or APG is present, the PGA-Na and PVM / MA copolymers can overcome the above problems and achieve effective synergy in promoting the oral care effects of fluoride. The reason is presumably that in systems containing CAB or APG, PGANa and PVM / MA copolymers can reduce excessive association between PGA-Na and PVM / MA copolymer molecules with the help of CAB or APG, optimizing the dispersion of polymer molecular chains. APG facilitates the full expansion of PGA-Na and PVM / MA copolymer molecules, while CAB helps prevent excessive entanglement and aggregation of PGA-Na and PVM / MA copolymer molecules, promoting the formation of a stable film on the enamel surface. Under the regulation of CAB or APG, PGANa and PVM / MA copolymers can achieve effective synergy. The composite film formed by the two on the enamel surface can effectively bind free fluoride ions and chelate calcium ions, promoting remineralization, reducing calcium dissolution and loss from tooth hard tissues, and synergistically enhancing the anti-cavity effect.

[0009] Optionally, the total mass of the sodium polyglutamate, methyl vinyl ether-maleic anhydride copolymer, and synergistic accelerator is 1 to 40 times the mass of fluorine in the fluoride.

[0010] Optionally, the synergistic promoter comprises cocamidopropyl betaine and alkyl glycoside in a mass ratio of 1:0.5~2.

[0011] CAB reduces electrostatic repulsion between PGA-Na and PVM / MA copolymer molecular chains through electrostatic association, while APG improves the dispersion and film stability of PGA-Na and PVM / MA copolymer molecules through hydrogen bonding and hydrophobic arrangement. When the two are compounded in a mass ratio of 1:0.5~2, they can synergistically regulate the aggregation state of PGA-Na and PVM / MA copolymer molecules, thereby enhancing the synergistic effect between PGA-Na and PVM / MA copolymers to a greater extent.

[0012] Optionally, the mass of the synergistic accelerator is 0.3 to 3.5 times the total mass of sodium polyglutamate and methyl vinyl ether-maleic anhydride copolymer.

[0013] By controlling the amount of synergistic accelerators (CAB and APG) relative to the PGA-Na and PVM / MA copolymers within the above-mentioned range, effective synergy between the PGA-Na and PVM / MA copolymers can be achieved using CAB and APG.

[0014] Optionally, the sodium polyglutamate has a weight-average molecular weight of 700-2000 kDa; the methyl vinyl ether-maleic anhydride copolymer has a weight-average molecular weight of 1000-3000 kDa; the fluoride includes one or more of sodium fluoride, sodium monofluorophosphate, stannous fluoride, and olafonium; and in the alkyl glycoside, the average degree of polymerization of the glycoside is 1.4-1.6, and the alkyl group has 12-14 carbon atoms.

[0015] Secondly, the present invention provides the use of the composition described above in oral care formulations.

[0016] Optionally, the oral care preparation is a preparation for promoting remineralization of tooth hard tissues and / or reducing calcium leaching and loss from tooth hard tissues.

[0017] Optionally, the composition is present in the oral care preparation at a concentration of 0.5 to 4 wt%.

[0018] Optionally, the oral care preparation may further contain one or more of the following: pH adjuster, thickener, abrasive, humectant, preservative, appearance modifier, and taste modifier; the oral care preparation may be toothpaste, dental mousse, or oral care gel.

[0019] Thirdly, the present invention provides the application of sodium polyglutamate, methyl vinyl ether-maleic anhydride copolymer and synergist in improving the remineralization effect of fluoride on dental hard tissues, wherein sodium polyglutamate, methyl vinyl ether-maleic anhydride copolymer and synergist are used in the composition described above.

[0020] Fourthly, the present invention provides an oral care preparation comprising the composition described above.

[0021] Optionally, the composition is present in the oral care preparation at a concentration of 0.5 to 4 wt%.

[0022] Optionally, the oral care preparation may further contain one or more of the following: pH adjuster, thickener, abrasive, humectant, preservative, appearance modifier, and taste modifier. Optionally, the oral care preparation is toothpaste, dental mousse, or oral care gel.

[0023] Optionally, the oral care preparation is a preparation for promoting remineralization of tooth hard tissues and / or reducing calcium leaching and loss from tooth hard tissues.

[0024] This invention discovers that when sodium polyglutamate, methyl vinyl ether-maleic anhydride copolymer, and synergistic accelerator are combined with fluoride, not only can the adsorption of fluoride ions on the tooth surface be increased and the residence time of fluoride in the oral cavity be prolonged, but also the effective utilization of fluoride ions on the hard tissue surface of the teeth be promoted, reducing the calcium dissolution and loss of hard tissue of the teeth, and effectively improving the remineralization effect.

[0025] Compared with the prior art, the present invention has the following advantages: (1) In the composition formulation of the present invention, in the presence of cocamidopropyl betaine and / or alkyl glycoside, methyl vinyl ether-maleic anhydride copolymer and sodium polyglutamate of a specific molecular weight can synergistically promote the oral care effect of fluoride, increase the amount of fluoride adsorbed on the tooth surface, improve the fluoride utilization rate, reduce the calcium dissolution and loss of hard tissues of the tooth, and enhance the remineralization effect.

[0026] (2) By controlling the ratio of fluorine, PGA-Na and PVM / MA copolymer within a specific range, and controlling the ratio of the total mass of PGA-Na and PVM / MA copolymer to the mass of the two synergistic promoters within a specific range, this invention can improve the effect of the two synergistic promoters, promote the synergistic effect of PGA-Na and PVM / MA copolymer, and thus further improve the oral care effect of fluoride. Detailed Implementation

[0027] The present invention will be further described below with reference to specific embodiments.

[0028] First, the present invention relates to a multi-effect oral care composition for strengthening tooth enamel, comprising sodium polyglutamate, methyl vinyl ether-maleic anhydride copolymer, fluoride, and a synergistic promoter; wherein the synergistic promoter comprises cocamidopropyl betaine and / or alkyl glycoside; and wherein the mass ratio of sodium polyglutamate to methyl vinyl ether-maleic anhydride copolymer is 1:0.2~4.

[0029] In some specific embodiments, the total mass of the sodium polyglutamate, methyl vinyl ether-maleic anhydride copolymer, and synergistic accelerator is 1 to 40 times the mass of fluorine in the fluoride.

[0030] In some specific embodiments, the synergistic promoter comprises cocamidopropyl betaine and alkyl glycoside in a mass ratio of 1:0.5~2.

[0031] In some specific embodiments, the mass of the synergistic promoter is 0.3 to 3.5 times the total mass of sodium polyglutamate and methyl vinyl ether-maleic anhydride copolymer.

[0032] In some specific embodiments, the weight-average molecular weight of the sodium polyglutamate is 700~2000 kDa.

[0033] In some specific embodiments, the weight-average molecular weight of the methyl vinyl ether-maleic anhydride copolymer is 1000~3000 kDa.

[0034] In some specific embodiments, the fluoride includes one or more of sodium fluoride, sodium monofluorophosphate, stannous fluoride, and olafluridine.

[0035] In some specific embodiments, the alkyl glycoside has an average degree of polymerization of 1.4 to 1.6 and the alkyl group has 12 to 14 carbon atoms.

[0036] Second, the present invention relates to the use of the composition in oral care formulations.

[0037] In some specific embodiments, the oral care preparation is a preparation for promoting remineralization of tooth hard tissue and / or reducing calcium dissolution and loss from tooth hard tissue.

[0038] In some specific embodiments, the composition is present in the oral care preparation at a concentration of 0.5 to 4 wt%.

[0039] In some specific embodiments, the oral care preparation further contains one or more of the following: pH adjuster, thickener, abrasive, humectant, preservative, appearance improver, and taste improver.

[0040] In some specific embodiments, the oral care preparation is toothpaste, dental mousse, or oral care gel.

[0041] Third, the present invention relates to the application of sodium polyglutamate, methyl vinyl ether-maleic anhydride copolymer and synergist in improving the remineralization effect of fluoride on dental hard tissues, wherein sodium polyglutamate, methyl vinyl ether-maleic anhydride copolymer and synergist are used in the composition.

[0042] Fourth, the present invention relates to an oral care preparation comprising the composition described above.

[0043] In some specific embodiments, the composition is present in the oral care preparation at a concentration of 0.5 to 4 wt%.

[0044] In some specific embodiments, the oral care preparation further contains one or more of the following: pH adjuster, thickener, abrasive, humectant, preservative, appearance modifier, and taste modifier; In some specific embodiments, the oral care preparation is toothpaste, dental mousse, or oral care gel.

[0045] In some specific embodiments, the oral care preparation is a preparation for promoting remineralization of tooth hard tissue and / or reducing calcium dissolution and loss from tooth hard tissue.

[0046] In this invention, there are no special restrictions on the preparation method of the oral care composition and oral care preparation, and conventional mixing methods in the art can be used for preparation.

[0047] The present invention will now be described with reference to specific embodiments and comparative examples. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention.

[0048] In the following examples and comparative examples, the meanings of the abbreviations are as follows: PGA-Na: Sodium polyglutamate; PVM / MA copolymer: Methyl vinyl ether-maleic anhydride copolymer; CAB: Cocamidopropyl betaine; APG: Alkyl glycoside.

[0049] The fluorine adsorption capacity test methods used in the following examples and comparative examples are as follows: (1) Select the crown portion of the extracted bovine tooth and cut it into tooth blocks with an enamel surface side length of 4-6 mm. Place the tooth block in the center of the mold and cast it into a rectangular bovine tooth resin block with epoxy resin, ensuring that the enamel surface faces outwards during casting. Use 240 grit, 800 grit, and 2000 grit sandpaper in sequence on a disc polisher to polish the enamel surface of the bovine tooth resin block until smooth. Place the bovine tooth resin block in a 1wt% citric acid solution for acid etching for 30 minutes. After rinsing and drying, apply nail polish to the remaining parts except for the enamel surface. Measure and record the enamel surface area, denoted as S0 (unit: cm).2 Each group contains 4 bovine tooth resin blocks. Calculate the total enamel area of ​​each group and record it as S (unit: cm). 2 When grouping, ensure that there is no significant difference in the total enamel area between groups.

[0050] (2) Prepare a toothpaste slurry with a concentration of 33wt% for the sample to be tested. Immerse the etched bovine tooth resin block in the toothpaste slurry and stir and soak at 37℃ for 2 hours. Rinse with running water for 10 seconds and air dry. Then etch with 3g of 2wt% citric acid solution for 3 minutes. Determine the fluoride ion concentration in the etching solution according to section 5.8 of GB / T 8372-2017 and record it as C (unit: mg / kg). Calculate the fluoride adsorption capacity F per unit area of ​​tooth enamel (unit: μg / cm²) according to F=C×3 / S. 2 Three parallel samples were set up for each sample.

[0051] The remineralization efficiency testing methods used in the following examples and comparative examples are as follows: (1) Select the crown portion of the extracted bovine tooth and cut it into tooth blocks with an enamel surface side length of 3-4 mm. Place the tooth block in the center of the mold and cast it into a rectangular bovine tooth resin block with epoxy resin, ensuring that the enamel surface faces outward during casting. Use 240 grit, 800 grit and 2000 grit sandpaper in sequence on a disc polisher to polish the enamel surface of the bovine tooth resin block until smooth. After rinsing, perform an initial hardness test on the enamel and record it as HV1. After the initial hardness test, place the bovine tooth resin block in a 1wt% citric acid solution for acid etching for 30 min. After rinsing and drying, perform a Vickers hardness test on the enamel again and record it as HV2. Group the bovine tooth resin blocks according to HV1 and HV2, with 3 parallel samples in each group to ensure that there is no significant difference in HV1 and HV2 between groups. All hardness test conditions are: Vickers indenter, load 200g, loading for 10 seconds.

[0052] (2) The test sample was prepared into a toothpaste slurry with a concentration of 33 wt%. The grouped bovine tooth resin blocks were soaked in the toothpaste slurry at 37°C with magnetic stirring for 2 hours. After soaking in the toothpaste slurry, the bovine tooth resin blocks were taken out, rinsed clean, and then soaked in simulated oral saliva for 48 hours. The composition of simulated oral saliva was as follows: 137.5 mM NaCl, 0.68 mM CaCl2·2H2O, 7.13 mM K2HPO4, 3 mM KCl, 4.2 mM NaHCO3, 0.5 mM Na2SO4, 1.5 mM MgCl2·6H2O, and the pH was adjusted to between 7.0 and 7.2 with HCl.

[0053] (3) After rinsing and drying the bovine tooth resin block, the hardness of the enamel is tested and recorded as HV3. The hardness recovery rate HFL is calculated according to HFL=(HV3-HV2) / (HV1-HV2)×100%. The higher the hardness recovery rate HFL, the better the remineralization effect.

[0054] The methods used in the following examples and comparative examples for determining the amount of calcium leaching and loss per unit area of ​​tooth enamel are as follows: (1) Select the crown portion of the extracted bovine tooth and cut it into tooth blocks with an enamel surface side length of 3-4 mm. Place the tooth block in the middle of the mold and cast it into a rectangular bovine tooth resin block with epoxy resin, ensuring that the enamel surface faces outwards during casting. Use 240 grit, 800 grit and 2000 grit sandpaper in sequence on a disc polisher to polish the enamel surface of the bovine tooth resin block until smooth. After rinsing, perform an initial hardness test on the enamel and record it as HV1. After the initial hardness test, select bovine tooth resin blocks with an initial hardness similar to HV1 to continue the experiment. Place the bovine tooth resin blocks in a 1wt% citric acid solution for acid etching for 30 min. After rinsing and drying, perform a Vickers hardness test on the enamel again and record it as HV2. Calculate the acid etching difference ∆H according to ∆H=HV1-HV2. Group the bovine tooth resin blocks according to ∆H, with 5 bovine tooth resin blocks in each group, and calculate the total enamel area of ​​each group, recorded as S (unit: cm). 2 To ensure no significant difference in ∆H and S between groups, all hardness test conditions were as follows: Vickers indenter, 200g load, 10 seconds.

[0055] (2) Prepare a toothpaste slurry with a concentration of 33wt% for the test sample. Soak the grouped bovine tooth resin blocks in the toothpaste slurry at 37℃ with magnetic stirring for 2 hours. After soaking in the toothpaste slurry, remove the bovine tooth resin blocks, wash and dry them. Stir each group of bovine tooth resin blocks with 15g of 111μmol / L lactic acid solution at 37℃ with magnetic stirring for 30 minutes.

[0056] (3) The calcium ion concentration C (mg / kg) in the lactic acid solution was determined using an inductively coupled plasma spectrometer, based on Q. Ca =(C×15) / S, calculate the amount of calcium removed per unit area Q. Ca (μg / cm) 2 Decalcification per unit area Q Ca The lower the value, the better the sample reduces calcium loss from the hard tissues of the teeth.

[0057] Examples A1-A6 and Comparative Example A1: The promoting effect of PGA-Na, PVM / MA copolymer and synergistic accelerator on fluorides The oral care formulations (toothpaste) of Examples A1-A6 and Comparative Example A1 are shown in Table 1. In Table 1: the amounts of each component are expressed as a weight percentage, i.e., in wt%; the weight-average molecular weight of PGA is 1500 kDa, and the weight-average molecular weight of the PVM / MA copolymer is 1100 kDa; the alkyl glycoside (APG) used is specifically APG 1214. Since the PVM / MA copolymer raw material itself has a low pH, which would cause the toothpaste pH to be too low, sodium hydroxide was added as a pH adjuster in Examples A1-A6 to make the pH of the prepared paste close to neutral.

[0058] Table 1 Oral care preparation formulation

[0059] Oral care preparations from Examples A1-A6 and Comparative Example A1 were used to test the fluoride adsorption, remineralization efficiency, and calcium leaching loss per unit area on the tooth surface. The results are shown in Table 2.

[0060] Table 2 Performance test results of oral care preparations

[0061] The test results for fluoride adsorption, remineralization efficiency, and calcium leaching loss per unit area showed that the fluoride adsorption and hardness recovery rate of Examples A1-A6 were higher than those of Comparative Example A1, while the calcium leaching loss was lower than that of Comparative Example A1, and the differences were significant (p<0.05). These results indicate that PGA-Na, PVM / MA copolymer, and CAB / APG can synergistically increase the adsorption of fluoride on the tooth surface, reduce calcium leaching loss from tooth hard tissue, and improve the remineralization effect.

[0062] Examples B1-B2 and Comparative Examples B1-B11: Synergistic effect between PGA-Na and PVM / MA copolymer The oral care formulations (toothpaste) of Examples B1-B2 and Comparative Examples B1-B11 are shown in Tables 3 and 4. In Tables 3 and 4: the amounts of each component are expressed as a weight percentage, i.e., wt%; the weight-average molecular weight of PGA-Na is 1500 kDa, and the weight-average molecular weight of the PVM / MA copolymer is 1100 kDa; the alkyl glycoside (APG) used is specifically APG 1214. Because the PVM / MA copolymer raw material itself has a low pH, which could cause the toothpaste pH to be too low, sodium hydroxide was added as a pH adjuster in the examples and comparative examples using PVM / MA copolymer to make the pH of the resulting paste close to neutral.

[0063] Table 3 Oral Care Preparation Formulations

[0064] Table 4 Oral Care Preparation Formulation

[0065] The oral care preparations of Examples B1-B2 and Comparative Examples B1-B11 were used to test the fluoride adsorption and remineralization efficiency on the tooth surface. The results are shown in Table 5.

[0066] Table 5 Performance test results of oral care preparations

[0067] The test results of fluoride adsorption and remineralization efficacy showed that the fluoride adsorption of Comparative Example B2 was higher than that of Comparative Example A1, but the hardness recovery rate was not improved compared with Comparative Example A1. Similar phenomena were also reflected between Comparative Example B6 and Comparative Example B10, as well as between Comparative Example B8 and Comparative Example B11. This indicates that, without the addition of PGA-Na, the PVM / MA copolymer can increase the amount of fluoride adsorbed on the tooth surface, but cannot improve the remineralization effect. This result suggests that fluoride is not effectively utilized and is merely physically attached to the tooth surface. Furthermore, the fluorine adsorption capacity of Comparative Example B1 was significantly lower than that of Comparative Example B2 (p<0.05), and there was no significant increase compared to Comparative Example B4 (p>0.05). The hardness recovery rate of Comparative Example B1 was significantly lower than that of Comparative Example B3 (p<0.05), and there was no significant increase compared to Comparative Example B5 (p>0.05), indicating that effective synergy cannot be achieved between PGA-Na and the PVM / MA copolymer in the absence of synergistic promoters CAB or APG. The fluorine adsorption capacity and hardness recovery rate of Example B1 were significantly higher than those of Comparative Example B6 and Comparative Example B2. In Example B7 (p<0.05), the fluoride adsorption capacity and hardness recovery rate of Example B2 were significantly higher than those of Comparative Examples B8 and B9 (p<0.05), indicating that in the presence of CAB or APG, the PGA-Na and PVM / MA copolymers can synergistically improve the fluoride adsorption capacity and remineralization effect on the tooth surface. The fluoride adsorption capacity and hardness recovery rate of Comparative Examples B10 and B11 did not show a significant improvement compared to Comparative Example A1 (p>0.05), indicating that CAB and APG themselves cannot improve the fluoride adsorption capacity or the fluoride-mediated remineralization effect.

[0068] The possible reasons for the above phenomenon are: (1) PVM / MA copolymer only increases the amount of fluoride retained and adsorbed on the tooth surface, but cannot mediate the orderly deposition of ionized calcium ions and phosphate ions. The retained fluoride cannot be fully utilized and cannot give full play to the effect of fluoride in promoting remineralization.

[0069] (2) When PGA-Na and PVM / MA copolymers form a composite film on the tooth surface, since both are anionic linear polymers, electrostatic repulsion will lead to uneven distribution of chain segments. At the same time, since both have long and flexible molecular chains, excessive chain entanglement and separation coexist, resulting in a loose composite film structure and high porosity. Multiple factors have led to the failure of PGA-Na and PVM / MA copolymers to produce a synergistic effect.

[0070] (3) CAB can promote the synergistic effect of PGA-Na and PVM / MA copolymer through multiple actions, increase the adsorption of fluoride on the tooth surface, and enhance the remineralization effect: The quaternary ammonium cationic group in CAB molecules can interact with the carboxyl groups of the two anionic polymers (PGA-Na and PVM / MA copolymer) through electrostatic interaction, which moderately weakens the electrostatic repulsion effect between the molecular chains of the two polymers; the small molecule CAB intersperses between the molecular chains of PGA-Na and PVM / MA copolymer, and promotes the orderly arrangement of the two polymer chains in the form of molecular bridges, forming a more regular and appropriately dense composite film system on the enamel; the alkyl hydrophobic chain of CAB molecules can enhance the adhesion stability of the composite film at the hydroxyapatite interface of the enamel and enrich the fluoride ions on the tooth surface for a long time; relying on the composite film, the enamel can be protected from the erosion of oral acidic substances, maintain the supersaturated environment of calcium and phosphorus ions on the enamel surface, and provide a stable ionic environment for remineralization.

[0071] (4) APG can promote the synergistic effect of PGA-Na and PVM / MA copolymers through multiple mechanisms: the hydrophilic glycoside groups in APG molecules can form intermolecular hydrogen bonds with the carboxyl groups of the two anionic polymers (PGA-Na and PVM / MA copolymers), reducing the surface energy of the system, improving the dispersibility of the two polymer molecules in the liquid phase, and alleviating the local aggregation phenomenon caused by electrostatic repulsion between them; the alkyl hydrophobic structure in APG molecules is distributed inside the aggregate structure of PGA-Na and PVM / MA copolymers, which can regulate the aggregation and arrangement of polymer molecules, improve the density and uniformity of the composite film, enhance the composite film's resistance to saliva erosion, and prolong the fluoride retention time on the tooth surface. The well-organized and appropriately dense composite film can form a physical barrier on the enamel surface, and the composite film can stabilize the supersaturated environment of calcium and phosphorus ions on the enamel surface, effectively exerting the remineralization effect of the system.

[0072] Examples C1-C4 and Comparative Examples C1-C2: The effect of the choice of synergistic enhancer on efficacy The oral care formulations (toothpaste) of Examples C1-C4 and Comparative Examples C1-C2 are shown in Table 6. In Table 6: the amounts of each component are expressed as a weight percentage, i.e., in wt%; the weight-average molecular weight of PGA-Na is 1500 kDa, and the weight-average molecular weight of the PVM / MA copolymer is 1100 kDa; the alkyl glycoside (APG) used is specifically APG 1214.

[0073] Table 6 Oral Care Preparation Formulations

[0074] The oral care preparations of Examples C1-C4 and Comparative Examples C1-C2 were used to test the fluoride adsorption and remineralization efficiency on the tooth surface. The results are shown in Table 7.

[0075] Table 7 Performance test results of oral care preparations

[0076] The test results for fluorine adsorption capacity and remineralization efficiency show that: (1) The fluorine adsorption capacity and hardness recovery rate of Examples C1-C4 were significantly higher than those of Comparative Example C1 (p<0.05), while the fluorine adsorption capacity of Comparative Example C2 was similar to that of Comparative Example C1, and the hardness recovery rate was significantly lower than that of Comparative Example C1 (p<0.05). The above results indicate that sodium dodecyl sulfate cannot effectively promote the synergistic effect between PGA-Na and PVM / MA copolymers. This may be because sodium dodecyl sulfate carries a negative charge after ionization, which cannot neutralize the carboxyl anions on the surface of PGA-Na and PVMMA copolymers. Instead, it exacerbates the electrostatic repulsion between the molecular chains of the two polymers, thus failing to effectively promote their synergistic effect.

[0077] (2) The fluorine adsorption amount and hardness recovery rate of Examples C3~C4 are higher than those of Examples C1~C2. It is speculated that this is because: CAB reduces the electrostatic repulsion between the molecular chains of PGA-Na and PVM / MA copolymer through electrostatic association, and APG improves the dispersion and film stability of PGA-Na and PVM / MA copolymer molecules through hydrogen bonding association and hydrophobic arrangement. The two types of additives synergistically regulate the aggregation state of PGA-Na and PVM / MA copolymer molecules by means of different intermolecular forces. The synergistic gain effect of the compound system on the polymer is better than that of CAB and APG used alone.

[0078] Examples D1-D3 and Comparative Examples D1-D2: Effect of the ratio of PGA-Na to PVM / MA copolymer on synergistic effect The oral care formulations (toothpaste) of Examples D1-D3 and Comparative Examples D1-D2 are shown in Table 8. In Table 8, the amounts of each component are expressed as a weight percentage, i.e., wt%; the weight-average molecular weight of PGA-Na is 1500 kDa, and the weight-average molecular weight of the PVM / MA copolymer is 1100 kDa. Since the PVM / MA copolymer raw material itself has a low pH, which could cause the toothpaste to have an excessively low pH, sodium hydroxide was added as a pH adjuster in the examples and comparative examples using PVM / MA copolymer to make the pH of the resulting paste close to neutral.

[0079] Table 8 Oral Care Preparation Formulations

[0080] The oral care preparations of Examples D1-D3 and Comparative Examples D1-D2 were used to test the fluoride adsorption and remineralization efficiency on the tooth surface. The results are shown in Table 9.

[0081] Table 9 Performance test results of oral care preparations

[0082] The test results of fluorine adsorption capacity and remineralization efficiency showed that the fluorine adsorption capacity and hardness recovery rate of Examples D1 to D3 were significantly higher than those of Comparative Examples D1 and D2 (p<0.05), and also higher than those of Comparative Examples B6 and B7 (p<0.05). This indicates that in the presence of a synergistic promoter, when the mass ratio between PGA-Na and PVM / MA copolymer is in the range of 1:0.2 to 4, the two components can produce a better synergistic effect.

[0083] Examples E1-E2 and Comparative Examples E1-E3: The effect of CAB dosage on its efficacy The oral care formulations (toothpaste) of Examples E1-E2 and Comparative Examples E1-E3 are shown in Table 10. In Table 10: the amount of each component is expressed as a weight percentage, i.e., in wt%; the weight average molecular weight of PGA-Na is 1500 kDa, and the weight average molecular weight of PVM / MA copolymer is 1100 kDa.

[0084] Table 10 Oral Care Preparation Formulations

[0085] The oral care preparations of Examples E1-E2 and Comparative Examples E1-E3 were used to test the fluoride adsorption and remineralization efficiency on the tooth surface. The results are shown in Table 11.

[0086] Table 11 Performance test results of oral care preparations

[0087] The test results for fluorine adsorption and remineralization efficiency showed that the fluorine adsorption and hardness recovery rate of Comparative Example E2 were not significantly improved compared with Comparative Example E1 (p>0.05). The fluorine adsorption and hardness recovery rates of Examples E1 and E2 were significantly higher than those of Comparative Example E1 (p<0.05). This indicates that when the amount of CAB relative to the PGA-Na and PVM / MA copolymer is too low, it cannot effectively promote the synergistic effect between PGA-Na and PVM / MA copolymer. However, when the mass of CAB is 0.3 to 3.5 times the total mass of PGA-Na and PVM / MA copolymer, effective synergy between PGA-Na and PVM / MA copolymer can be achieved. Although Comparative Example E3 also showed a significant improvement in fluorine adsorption and hardness recovery rate compared with Comparative Example E1, its paste stability was poor, resulting in leakage. Furthermore, the paste had a noticeable bitter and soapy taste, leading to a poor user experience.

[0088] Examples F1-F2 and Comparative Examples F1-F3: The effect of APG dosage on its efficacy The oral care formulations (toothpaste) of Examples F1-F2 and Comparative Examples F1-F3 are shown in Table 12. In Table 12: the amounts of each component are expressed as a percentage by weight, i.e., in wt%; the weight-average molecular weight of PGA-Na is 1500 kDa, and the weight-average molecular weight of the PVM / MA copolymer is 1100 kDa; the alkyl glycoside (APG) used is specifically APG 1214.

[0089] Table 12 Oral Care Preparation Formulations

[0090] The oral care preparations of Examples F1-F2 and Comparative Examples F1-F2 were used to test the fluoride adsorption and remineralization efficiency on the tooth surface. The results are shown in Table 13.

[0091] Table 13 Performance test results of oral care preparations

[0092] The test results for fluorine adsorption and remineralization efficiency showed that the fluorine adsorption and hardness recovery rate of Comparative Example F2 were not significantly improved compared with Comparative Example F1 (p>0.05). The fluorine adsorption and hardness recovery rates of Examples F1 and F2 were significantly higher than those of Comparative Example F1 (p<0.05). This indicates that when the amount of APG relative to the PGA-Na and PVM / MA copolymer is too low, it cannot effectively promote the synergistic effect between PGA-Na and PVM / MA copolymer. However, when the mass of APG is 0.3 to 3.5 times the total mass of PGA-Na and PVM / MA copolymer, effective synergy between PGA-Na and PVM / MA copolymer can be achieved. Although Comparative Example F3 also showed a significant improvement in fluorine adsorption and hardness recovery rate compared with Comparative Example F1, its paste stability was poor, and it was prone to seepage and stratification. It also tended to have a bitter taste and stickiness during use.

[0093] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, alterations, and equivalent transformations made to the above embodiments based on the technical essence of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A multi-functional oral care composition for strengthening tooth enamel, characterized in that, It includes sodium polyglutamate, methyl vinyl ether-maleic anhydride copolymer, fluoride, and synergistic accelerator; the synergistic accelerator includes cocamidopropyl betaine and / or alkyl glycoside; the mass ratio of sodium polyglutamate to methyl vinyl ether-maleic anhydride copolymer is 1:0.2~4.

2. The composition according to claim 1, characterized in that, The total mass of the sodium polyglutamate, methyl vinyl ether-maleic anhydride copolymer, and synergistic accelerator is 1 to 40 times the mass of fluorine in the fluoride.

3. The composition according to claim 1, characterized in that, The synergistic promoters include cocamidopropyl betaine and alkyl glycosides in a mass ratio of 1:0.5~2.

4. The composition according to claim 1 or 3, characterized in that, The mass of the synergistic accelerator is 0.3 to 3.5 times the total mass of sodium polyglutamate and methyl vinyl ether-maleic anhydride copolymer.

5. The composition according to claim 1, characterized in that, The sodium polyglutamate has a weight-average molecular weight of 700-2000 kDa; the methyl vinyl ether-maleic anhydride copolymer has a weight-average molecular weight of 1000-3000 kDa; the fluoride includes one or more of sodium fluoride, sodium monofluorophosphate, stannous fluoride, and olafonium; in the alkyl glycoside, the average degree of polymerization of the glycoside is 1.4-1.6, and the alkyl group has 12-14 carbon atoms.

6. The use of the composition according to any one of claims 1 to 5 in oral care preparations.

7. The application according to claim 6, characterized in that, The oral care preparation is a preparation used to promote remineralization of tooth hard tissues and / or reduce calcium dissolution and loss from tooth hard tissues.

8. The application according to claim 6, characterized in that, The composition is present in the oral care preparation at a concentration of 0.5-4 wt%.

9. The application according to claim 8, characterized in that, The oral care preparation also contains one or more of the following: pH adjuster, thickener, abrasive, humectant, preservative, appearance improver, and taste improver; the oral care preparation is toothpaste, dental mousse, or oral care gel.

10. The application of sodium polyglutamate, methyl vinyl ether-maleic anhydride copolymer, and synergistic accelerator in improving the remineralization effect of fluoride on dental hard tissues, characterized in that, Sodium polyglutamate, methyl vinyl ether-maleic anhydride copolymer, and synergistic accelerator are used in the composition according to any one of claims 1 to 5.

11. An oral care preparation, characterized in that, The composition comprises any one of claims 1 to 5.

Images