Bioactive glass material, oral care composition, toothpaste and methods of making the same

Abstract

The present application relates to bioactive glass material, oral care composition, toothpaste and preparation method thereof. The bioactive glass material belongs to Na2O-CaO-SiO2-P2O5 system, which comprises SiO2 40-60%, P2O5 1-10%, CaO 18-30%, Na2O 10-30% by weight percentage. The X-ray diffraction pattern of the bioactive glass material contains diffraction peaks of the following 2θ angle values: 33.6±0.2°, 34.2±0.2°. The bioactive glass material provided by the present application has a special crystal structure, can dissolve calcium, phosphorus, silicon and other elements faster, generate silicon glass network and hydroxyapatite, can react with the tooth surface faster, realize the remineralization of dentin surface, and play a role in relieving or treating dentin sensitivity.

Description

Technical Field

[0001] This invention belongs to the technical field of oral care; more specifically, it relates to bioactive glass materials, oral care compositions, toothpaste, and methods for preparing the same. Background Technology

[0002] Dentin is an important component of teeth, containing dentinal tubules that radiate from the pulp end to the enamel-dentin interface. It is generally believed that when the openings of dentinal tubules on the dentin surface are exposed, stimulation by cold, heat, acid, sweetness, mechanical or chemical stimuli excites the nerve endings in the dental pulp, producing transient pain—the symptom of dentin hypersensitivity. Studies have shown that individuals with dentin hypersensitivity have a greater number of open dentinal tubules with a larger average diameter compared to those without dentin hypersensitivity. Therefore, dentin hypersensitivity can be alleviated or treated by sealing the dentinal tubules to reduce dentin permeability.

[0003] Based on their mechanism of action, sealing can be divided into physical sealing and chemical sealing. Chemical sealing materials, in particular, achieve their sealing effect by forming a chemical bond with the tooth. Currently, materials used for chemical sealing include bioactive glass and fluorides.

[0004] Among bioactive glasses, 45S5 bioglass is the most common. It is a Na2O-CaO-SiO2-P2O5 system formed by Na2O, CaO, SiO2 and P2O5. By adding P2O5 to the ordinary Na2O-CaO-SiO2 glass system, the material's elemental composition is closer to that of natural human bones. The addition of P2O5 increases the bioactivity of this material.

[0005] When this bioactive glass is exposed to water or body fluids, the bioactive glass, with silica as its main network component, forms a silica gel film during hydrolysis. This gel film not only adsorbs calcium and phosphorus ions but also, due to its narrow ion channels, prevents the desolvation of calcium and phosphorus ions, thus accelerating the repair of dentinal tubules. The calcium and phosphorus elements in the bioactive glass crystallize on the tooth surface into a mixed hydroxyapatite (commonly known as "hydroxyapatite"). The deposition of hydroxyapatite on the tooth surface creates a mineralization effect, sealing exposed dentinal tubules.

[0006] It is evident that silicon, calcium, and phosphorus elements in bioactive glass play a crucial role in sealing exposed dentinal tubules. The rate at which these elements dissolve determines whether the bioactive glass can react more quickly under the influence of water or body fluids, thereby sealing exposed dentinal tubules more effectively and alleviating or treating dentin hypersensitivity.

[0007] Solid substances exhibit different molecular lattice arrangements due to various factors such as molecular arrangement and intermolecular forces, resulting in crystal structures known as crystal forms. Generally, crystalline solids have lower dissolution rates than their amorphous counterparts. This is because the dissolution process of crystalline solids requires overcoming lattice energy, which limits their solubility and dissolution rate. Amorphous structures, lacking long-range order, do not require overcoming lattice energy. Therefore, amorphous structures typically exhibit higher apparent solubility and faster dissolution rates. Summary of the Invention

[0008] To address the aforementioned technical problems, the present invention aims to provide a bioactive glass material. This bioactive glass material possesses a unique crystalline structure, and in practical applications, compared to existing amorphous bioactive glasses, it can dissolve elements such as calcium, phosphorus, and silicon more quickly, generating a silica glass network and hydroxyapatite. This allows for faster reaction with the tooth surface, achieving remineralization of the dentin surface and alleviating or treating dentin hypersensitivity.

[0009] A second objective of this invention is to provide a method for preparing bioactive glass materials.

[0010] A third objective of this invention is to provide an application of a bioactive glass material in sealing dentinal tubules or in the preparation of oral care compositions.

[0011] A fourth object of the present invention is to provide an oral care composition.

[0012] The fifth object of the present invention is to provide a toothpaste.

[0013] The above-mentioned objectives of the present invention are achieved through the following technical solutions.

[0014] This invention claims protection for a bioactive glass material belonging to the Na2O-CaO-SiO2-P2O5 system, comprising, by weight percentage: SiO2 40-60%, P2O5 1-10%, CaO 18-30%, and Na2O 10-30%; the X-ray diffraction pattern of the bioactive glass material contains diffraction peaks at the following 2θ angle values: 33.6±0.2°, 34.2±0.2°.

[0015] In some embodiments, the X-ray diffraction pattern of the bioactive glass material contains diffraction peaks at the following 2θ angle values: 20.2±0.2°, 23.8±0.2°, 26.5±0.2°, 26.8±0.2°, 33.6±0.2°, 34.2±0.2°, and 48.6±0.2°.

[0016] In some embodiments, the X-ray diffraction pattern of the bioactive glass material includes diffraction peaks at the following 2θ angle values: 19.1±0.2°, 20.2±0.2°, 20.7±0.2°, 22.0±0.2°, 23.6±0.2°, 23.8±0.2°, 26.5±0.2°, 26.8±0.2°, 26.9±0.2°, 31.9±0.2°, 32.1±0.2°, 33.6±0.2°, 34.2±0.2°, and 48.6±0.2°.

[0017] In some embodiments, the bioactive glass material has the same properties as... Figure 1 , Figure 4 or Figure 5 Consistent X-ray diffraction patterns.

[0018] Furthermore, this invention claims protection for a method for preparing a bioactive glass material, comprising the following steps:

[0019] (1) The alkali metal silicate and inorganic acid are subjected to simultaneous acid-base titration, maintaining the solution pH at 2-6 and the reaction temperature at 40-95℃ during the titration process; or

[0020] Alkali metal silicates and inorganic acids are used for acid-base co-drop in a metal salt base solution. During the co-drop process, the pH of the solution is maintained at 2-6 and the reaction temperature is 40-95℃.

[0021] (2) After the reaction in step (1) is complete, add calcium oxide and stir; add phosphoric acid to react and stir; then add sodium-containing alkaline solution and stir; prepare bioactive glass material.

[0022] Furthermore, this invention claims protection for a method for preparing another bioactive glass material, comprising the following steps:

[0023] (1) Alkali metal silicates and phosphoric acid are reacted dropwise together, maintaining the pH of the solution at 3-10 and the reaction temperature at 40-95℃; or

[0024] Alkali metal silicates and phosphoric acid are used for acid-base co-drop in a metal salt base solution. During the co-drop process, the solution pH is maintained at 3-10 and the reaction temperature is 40-95℃.

[0025] (2) After the reaction in step (1) is complete, add calcium oxide and stir; then add sodium-containing alkaline solution and stir; prepare bioactive glass material.

[0026] Furthermore, this invention claims protection for a method for preparing another bioactive glass material, comprising the following steps:

[0027] S1. At 40-95℃, calcium hydroxide slurry and phosphoric acid are mixed and reacted. During the reaction, the pH is maintained at 7-9. After the reaction, the mixture is aged to obtain reaction solution A.

[0028] S2. Mix silica slurry and calcium oxide, stir; then add sodium-containing alkaline solution, stir, and obtain reaction solution B;

[0029] S3. Mix reaction solution A and reaction solution B, and dry them to obtain bioactive glass material.

[0030] Furthermore, the present invention claims protection for the use of bioactive glass materials in sealing dentinal tubules or in the preparation of oral care compositions.

[0031] Furthermore, the present invention claims protection for an oral care composition comprising, by weight percentage: 0.1-20% of the bioactive glass material and oral-acceptable excipients.

[0032] Furthermore, the present invention claims protection for a toothpaste comprising, by weight: 1-10 parts of the above-mentioned bioactive glass material, 20.5-26.5 parts of thickener, 45-60 parts of humectant, 11-20 parts of abrasive, 1-5 parts of foaming agent, 0-3 parts of colorant, 0-3 parts of flavoring agent, 0-0.5 parts of sweetener, and 0-0.5 parts of antibacterial agent.

[0033] Furthermore, the present invention claims protection for a toothpaste comprising, by weight: 1-10 parts of the above-mentioned bioactive glass material, 20.5-26.5 parts of thickener, 45-60 parts of humectant, 11-20 parts of abrasive, 1-5 parts of foaming agent, 0.1-3 parts of colorant, 0.1-3 parts of flavoring agent, 0.1-0.5 parts of sweetener, and 0.1-0.5 parts of antibacterial agent.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] (1) This invention provides a bioactive glass material with a specific crystal structure. In specific applications, it can dissolve elements such as calcium, phosphorus, and silicon more quickly to generate a silica glass network and hydroxyapatite, which can react with the tooth surface more quickly to achieve remineralization of the dentin surface and relieve or treat dentin hypersensitivity.

[0036] (2) The bioactive glass material provided by this invention has a pH between 8.0 and 10.0. Compared with bioglass with a pH greater than 10, it has a wider range of applicability, is less restricted by toothpaste formulations, and causes less irritation to the oral mucosa. The bioactive glass material provided by this invention has the advantages of good biocompatibility, non-toxicity, and low cost. Attached Figure Description

[0037] Figure 1 The X-ray diffraction pattern is shown for the bioactive glass material prepared in Example 1.

[0038] Figure 2 and Figure 3 This is a SEM image of the bioactive glass material prepared in Example 1.

[0039] Figure 4 The X-ray diffraction pattern is shown for the bioactive glass material prepared in Example 5.

[0040] Figure 5 The X-ray diffraction pattern is shown for the bioactive glass material prepared in Example 6.

[0041] Figure 6 The X-ray diffraction pattern is shown for the bioactive glass material in Comparative Example 1.

[0042] Figure 7 The X-ray diffraction pattern is shown for the bioactive glass material in Comparative Example 2.

[0043] Figure 8 , Figure 9 and Figure 10 The X-ray diffraction patterns are those of the products obtained by artificial saliva mineralization of the bioactive glass materials of Example 1, Comparative Example 1, and Comparative Example 2, respectively.

[0044] Figure 11 , Figure 12 and Figure 13 The figures show experimental results of mineralizing and sealing dentinal tubules with bioactive glass toothpaste prepared using the bioactive glass materials of Example 1, Comparative Example 1, and Comparative Example 2. Detailed Implementation

[0045] In the following description, certain specific details are set forth to provide a thorough understanding of the various embodiments of the invention. However, those skilled in the art will understand that the invention can be practiced without these details. The various embodiments described below are made with the understanding that this disclosure is intended to be illustrative of the claimed subject matter and not to limit the appended claims to the specific embodiments described. Headings used throughout this disclosure are merely for convenience and are not to be construed as limiting the claims in any way. Embodiments described under any heading may be combined with embodiments described under any other heading.

[0046] [Composition and Crystal Form]

[0047] Due to various factors such as the molecular arrangement, configuration, conformation, molecular forces, and eutectic substances, solid substances can have different molecular lattice arrangements, resulting in two or more different crystal structures. This phenomenon is called "polymorphism" or "isomorphism." Polymorphism is widespread in solids, and different crystal forms of the same substance may have different physicochemical properties, such as reaction rates, stability, solubility, dissolution rate, and bioavailability.

[0048] Crystal forms can be determined using a variety of techniques, such as X-ray diffraction (XRD), X-ray powder diffraction (XRPD), infrared absorption spectroscopy (IR), melting point method, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), nuclear magnetic resonance, Raman spectroscopy, calorimetry, scanning electron microscopy (SEM), quantitative analysis, solubility and dissolution rate, etc.

[0049] X-ray diffraction (XRD) can detect changes in crystal form, crystallinity, and crystal structure, and is a commonly used method for identifying crystal forms. It can distinguish between crystalline and amorphous substances. Different crystal forms exhibit differences in the number, position, intensity, and shape of diffraction peaks in their XRD patterns, thus serving as a fingerprint of the crystal for identification and differentiation. More specifically, the differences in crystal structure are primarily determined by the positions of the diffraction peaks in the XRD pattern. Therefore, in some embodiments, the distinguishing feature of the bioactive glass provided by this invention compared to existing bioactive glasses lies in the presence of certain characteristic peak positions characterized by 2θ angle values ​​and their XRD patterns, which are essentially as shown in the XRD patterns provided in the accompanying drawings. Based on the common understanding of those skilled in the art, the 2θ angle values ​​of the XRD pattern can have experimental errors; the 2θ angle values ​​of the XRD pattern may differ slightly between different instruments and different samples. Therefore, the 2θ angle values ​​provided by this invention should not be considered absolute. According to the instrument conditions used in the experiment of the present invention, the characteristic diffraction peak characterized by the 2θ angle value has an error tolerance of ±0.2°.

[0050] Furthermore, when referring to XRD patterns or XRPD patterns, "consistent with the pattern" does not mean that the pattern is completely identical to the pattern provided or described herein. Patterns falling within experimental errors or the aforementioned error tolerances should also be taken into account when considered by a person skilled in the art.

[0051] The bioactive glass material provided by this invention has a specific crystal form. Through research, the inventors were surprised to find that, compared with existing amorphous bioactive glass, the bioactive glass material with a specific crystal form provided by this invention can dissolve elements such as calcium, phosphorus, and silicon more quickly when mineralizing and sealing dentinal tubules under the action of water or body fluids, generating a silica glass network and hydroxyapatite. This allows it to react with the tooth surface more quickly, achieving remineralization of the dentin surface and relieving or treating dentin hypersensitivity.

[0052] Those skilled in the art can distinguish the bioactive glass material provided by this invention by the diffraction peaks containing the following 2θ angle values: 33.6±0.2°, 34.2±0.2°. More specifically, in some more detailed X-ray diffraction pattern data, the X-ray diffraction pattern of the bioactive glass material provided by this invention contains the following 2θ angle values: 20.2±0.2°, 23.8±0.2°, 26.5±0.2°, 26.8±0.2°, 33.6±0.2°, 34.2±0.2°, and 48.6±0.2°. More specifically, the diffraction peaks include the following 2θ angle values: 19.1±0.2°, 20.2±0.2°, 20.7±0.2°, 22.0±0.2°, 23.6±0.2°, 23.8±0.2°, 26.5±0.2°, 26.8±0.2°, 26.9±0.2°, 31.9±0.2°, 32.1±0.2°, 33.6±0.2°, 34.2±0.2°, and 48.6±0.2°. More specifically, the bioactive glass material provided by this invention has substantially the same properties as... Figure 1 , Figure 4 or Figure 5 Consistent X-ray diffraction patterns.

[0053] Furthermore, in some embodiments, the bioactive glass material provided by the present invention comprises, by weight percentage: 40-60% SiO2, 1-10% P2O5, 18-30% CaO, and 10-30% Na2O.

[0054] As a non-limiting example of the SiO2 content in bioactive glass materials, the weight percentage of SiO2 can be 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, etc., or any range formed by the above values, such as 42-50%, 52-58%, etc., and the present invention is not limited thereto.

[0055] As a non-limiting example of the P2O5 content in bioactive glass materials, the weight percentage of P2O5 can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, etc., or any range formed by the above values, such as 1-4%, 3-10%, etc., and the present invention is not limited thereto.

[0056] As a non-limiting example of the CaO content in bioactive glass materials, the weight percentage of CaO can be 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, etc., or any range formed by the above values, such as 20-25%, 23-29%, etc., and the present invention is not limited thereto.

[0057] As a non-limiting example of the Na2O content in bioactive glass materials, the weight percentage of Na2O can be 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, etc., or any range formed by the above values, such as 12-20%, 16-28%, etc., and the present invention is not limited thereto.

[0058] Illustrative, non-limiting examples of bioactive glass materials conforming to the present invention may have the following characteristics: In one or more embodiments, the bioactive glass material may have an apparent density of 0.5-1.2 g / mL; more specifically, the apparent density may be 0.5-0.7 g / mL. In one or more embodiments, the bioactive glass material may contain 0.3-2.0% water; more specifically, it may contain 0.3-1.0% water. In one or more embodiments, the D50 particle size of the bioactive glass material may be 3.5-4.0 μm; more specifically, the D50 particle size may be 3.5-3.9 μm. In one or more embodiments, the BET specific surface area of ​​the bioactive glass material may be 10-20 m². 2 / g. In one or more embodiments, the pore volume of the bioactive glass material can be 0.01-0.2 cm³. 3 / g; more specifically, the pore volume can be 0.1-0.2cm³. 3 / g. In one or more embodiments, the pore size of the bioactive glass material can be 10-40 nm; more specifically, the pore size can be 35-40 nm. In one or more embodiments, the oil absorption value of the bioactive glass material can be 20-100 g / 100 g; more specifically, the oil absorption value can be 70-85 g / 100 g. In one or more embodiments, the copper loss value of the bioactive glass material is 2-4 mg. In one or more embodiments, the Ganz whiteness of the bioactive glass material is >98; more specifically, the Ganz whiteness can be 98.5-99.9.

[0059] In one or more embodiments, the pH of the bioactive glass material can be 8.5-10. Compared to existing bioactive glass materials with pH values ​​generally exceeding 10, the pH control of the bioactive glass material at 8.5-10 has the advantage of a wider adaptability range and fewer formulation limitations when preparing oral compositions; in addition, the pH control at 8.5-10 also has the advantage of less irritation to the oral mucosa.

[0060] [Preparation Method]

[0061] The bioactive glass material with a specific crystal structure provided by this invention can be prepared by a variety of methods.

[0062] A non-limiting example conforming to the preparation method of the present invention may be obtained by the following first preparation method:

[0063] (1) The alkali metal silicate and inorganic acid are subjected to simultaneous acid-base titration, maintaining the solution pH at 2-6 and the reaction temperature at 40-95℃ during the titration process; or

[0064] Alkali metal silicates and inorganic acids are used for acid-base co-drop in a metal salt base solution. During the co-drop process, the pH of the solution is maintained at 2-6 and the reaction temperature is 40-95℃.

[0065] (2) After the reaction in step (1) is complete, add calcium oxide and stir; add phosphoric acid to react and stir; then add sodium-containing alkaline solution and stir; prepare bioactive glass material.

[0066] In the above method, as a non-limiting example, commercially available calcium oxide conventionally available in the art can be used instead. More specifically, sintered calcium oxide can also be obtained by sintering calcium salts (such as calcium carbonate). More specifically, in some embodiments, the calcium salts can be continuously calcined using a heat source (such as a muffle furnace) at a temperature not lower than 800°C, 850°C, 900°C, 950°C, 1000°C, 1100°C, or 1200°C. More specifically, the sintering temperature is 900-1200°C. More specifically, the sintering temperature is 1000-1100°C. The conversion rate of calcium oxide sintered using the above method can be ≥96%, more preferably ≥97%, more preferably ≥98%, and most preferably 100%. At this conversion rate, the sintered calcium oxide has higher activity. The conversion rate is calculated as follows: Conversion rate Y = Δm / 44%m, where Δm is the mass difference of calcium carbonate before and after combustion, and m is the mass of calcium carbonate. More specifically, the calcium salt can be calcium carbonate, calcium chloride, calcium bicarbonate, or a mixture thereof.

[0067] As a non-limiting example of an alkali metal silicate, the alkali metal silicate may be selected from sodium silicate, potassium silicate, or mixtures thereof. In some non-limiting examples, the modulus of the alkali metal silicate may be 1-3.8, and the concentration may be 1-2.9N. More specifically, the modulus of the alkali metal silicate may be 3-3.6, and the concentration may be 1.2-2.6N. More specifically, the modulus of the alkali metal silicate may be 3.1-3.5, and the concentration may be 1.2-2.2N. As a non-limiting example of an inorganic acid, the inorganic acid may be sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, or mixtures thereof. In some non-limiting examples, the concentration of the inorganic acid may be 2-12N. More specifically, the concentration of the inorganic acid may be 4-10N. As a non-limiting example of a metal salt substrate, it may be a metal salt substrate formed by a combination of the anion of the above-mentioned inorganic acid and the alkali metal of the alkali metal silicate, including but not limited to sodium sulfate. In some non-limiting examples, the sodium-containing alkali solution is primarily intended to provide sodium for bioactive glass, and may include substances such as sodium hydroxide.

[0068] In step (1) of the above method, as a non-limiting example of reaction time, the reaction time for simultaneous acid-base drop is not less than 0.5 h, not less than 1.0 h, and not less than 1.5 h. In some embodiments, the reaction time for simultaneous acid-base drop is 0.5-1.5 h.

[0069] In step (1) of the above method, as a non-limiting example of the reaction temperature, the reaction temperature can be 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, etc. More specifically, the reaction temperature can be 45-90℃. More specifically, the reaction temperature can be 60-90℃.

[0070] In step (2) of the above method, after adding calcium oxide, the stirring time should be no less than 10 minutes, no less than 15 minutes, no less than 20 minutes, no less than 30 minutes, etc., more specifically, the stirring time is 10-30 minutes. The stirring speed can be 100 rpm, 300 rpm, 500 rpm, 700 rpm, 900 rpm, 1000 rpm, etc., more specifically, the stirring speed is 100-1000 rpm. More specifically, the stirring speed is 400-800 rpm.

[0071] In step (2) of the above method, the concentration of added phosphoric acid can be 30-40%, and the reaction time is not less than 0.5 h, not less than 1.0 h, and not less than 1.5 h. More specifically, the reaction time is 0.5-1.5 h. More specifically, the reaction time is 0.5-1 h. After the reaction with added phosphoric acid is complete, continue stirring for a time not less than 10 min, not less than 15 min, not less than 20 min, not less than 30 min, etc. More specifically, the stirring time is 10-40 min. More specifically, the stirring time is 20-40 min. The stirring speed can be 100 rpm, 300 rpm, 500 rpm, 700 rpm, 900 rpm, 1000 rpm, etc. More specifically, the stirring speed is 100-1000 rpm. More specifically, the stirring speed is 400-800 rpm.

[0072] In step (2) of the above method, a sodium-containing alkaline solution is added, and the stirring time is not less than 10 minutes, not less than 15 minutes, not less than 20 minutes, not less than 30 minutes, etc. More specifically, the stirring time is 10-40 minutes. More specifically, the stirring time is 20-40 minutes. The stirring speed can be 100 rpm, 300 rpm, 500 rpm, 700 rpm, 900 rpm, 1000 rpm, etc. More specifically, the stirring speed is 100-1000 rpm. More specifically, the stirring speed is 400-800 rpm.

[0073] Furthermore, the present invention provides a method for preparing a second bioactive glass material, which includes the following steps:

[0074] (1) Alkali metal silicates and phosphoric acid are reacted dropwise together, maintaining the pH of the solution at 3-10 and the reaction temperature at 40-95℃; or

[0075] Alkali metal silicates and phosphoric acid are used for acid-base co-drop in a metal salt base solution. During the co-drop process, the solution pH is maintained at 3-10 and the reaction temperature is 40-95℃.

[0076] (2) After the reaction in step (1) is complete, add calcium oxide and stir; then add sodium-containing alkaline solution and stir; prepare bioactive glass material.

[0077] In step (1) of the above method, as a non-limiting example of pH, pH can be 4, 5, 6, 7, 8, 9, etc., or any range formed by the above values, such as 4-7, 8-10, etc., and the present invention is not limited thereto.

[0078] In step (1) of the above method, as a non-limiting example of the reaction temperature, the reaction temperature can be 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, etc. More specifically, the reaction temperature can be 45-90℃. More specifically, the reaction temperature can be 60-90℃.

[0079] In step (1) of the above method, as a non-limiting example of an alkali metal silicate, the modulus of the alkali metal silicate can be 1-3.8, and the concentration can be 1-2.9N. More specifically, the modulus of the alkali metal silicate can be 2-3.6, and the concentration can be 2-2.6N. More specifically, the modulus of the alkali metal silicate can be 3-3.5, and the concentration can be 2.1-2.4N. As a non-limiting example of an inorganic acid, the concentration of the inorganic acid can be 2-12N. More specifically, the concentration of the inorganic acid can be 4-8N. More specifically, the concentration of the inorganic acid can be 5-7N.

[0080] Other specific process parameters for the second type of bioactive glass material provided by the present invention can refer to the preparation method of the first type of bioactive glass material described above.

[0081] Furthermore, the present invention provides a third method for preparing a bioactive glass material, which includes the following steps:

[0082] S1. At 40-95℃, calcium hydroxide slurry and phosphoric acid are mixed and reacted. During the reaction, the pH is maintained at 7-9. After the reaction, the mixture is aged to obtain reaction solution A.

[0083] S2. Mix silica slurry and calcium oxide, stir; then add sodium-containing alkaline solution, stir, and obtain reaction solution B;

[0084] S3. Mix reaction solution A and reaction solution B, dry, and crush to obtain bioactive glass material.

[0085] As a non-limiting example of the reaction temperature in step S1, the reaction temperature can be 60-90°C; more specifically, it can be 80-90°C. As a non-limiting example of the calcium hydroxide slurry, the concentration of the calcium hydroxide slurry can be 0.5-1 mol / L; more specifically, it can be 0.6-0.8 mol / L. As a non-limiting example of phosphoric acid, the concentration of phosphoric acid can be 30-40%; more specifically, the concentration of phosphoric acid can be 35-40%.

[0086] In step S2, the sodium-containing alkaline solution is mainly used to provide sodium for the bioactive glass; it can be something like sodium hydroxide. In step S2, the stirring time is no less than 10 minutes, no less than 15 minutes, no less than 20 minutes, no less than 30 minutes, etc., more specifically, the stirring time is 10-40 minutes. More specifically, the stirring time is 20-40 minutes. The stirring speed can be 100 rpm, 300 rpm, 500 rpm, 700 rpm, 900 rpm, 1000 rpm, etc. More specifically, the stirring speed is 100-1000 rpm. More specifically, the stirring speed is 400-800 rpm. In step S2, after adding the sodium-containing alkaline solution, the stirring time is no less than 1 hour, no less than 2 hours, no less than 3 hours, no less than 4 hours, etc., more specifically, the stirring time is 1-4 hours.

[0087] [Oral Care Composition]

[0088] The bioactive glass material provided by this invention can be used in the preparation of oral care compositions for sealing dentinal tubules.

[0089] The oral care composition described in this invention can be any form known in the art suitable for oral care. As a non-limiting example of an oral care composition, it can be a toothpaste, gel, mouthwash, dental floss, dental cleaning agents such as pastes, powders, tablets, or liquid preparations used to clean the oral surface, teething gels, teething strips, oral sprays, tooth powder, foam, chewing gum, lip balm, sponge, mouthwash, chewing gum, or denture products, etc.

[0090] Oral acceptable excipients are those that, as components of oral care compositions, are suitable for the physiological environment of the oral cavity and do not cause excessive side effects on the oral cavity.

[0091] This invention provides an oral care composition comprising, by weight percentage: 0.1-20% of the aforementioned bioactive glass material and oral-acceptable excipients. The weight percentage of the bioactive glass material in the oral care composition can be 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 8%, 10%, 15%, 18%, etc., or any range formed by the above values, such as 1.5-3%, 2-5%, etc., and this invention is not limited thereto.

[0092] As a non-limiting example of an excipient, it may employ ingredients conventionally used in oral cavity formulations in the art, including but not limited to one or more of thickeners, sweeteners, antibacterial agents, abrasives, humectants, pigments or colorants, flavoring agents, and foaming agents.

[0093] Examples of thickeners include, but are not limited to: carbomer (such as carbomer 940), polyethylene glycol (such as PEG-400), hydroxyethyl cellulose, carboxymethyl cellulose and its salts (e.g., sodium carboxymethyl cellulose), carrageenan, carboxyvinyl polymers, xanthan gum, carrageenan, gelatin, amylopectin, sodium alginate, etc. In some embodiments, the thickener includes one or more of xanthan gum, carrageenan, or sodium carboxymethyl cellulose. Preferably, the thickener is selected from carbomer and / or polyethylene glycol.

[0094] Examples of sweeteners include, but are not limited to: sodium saccharin, flavored oils such as spearmint oil, peppermint oil, wintergreen oil, sassafras oil, clove oil, sage oil, eucalyptus oil, cinnamon oil, lemon oil, and orange peel oil, methyl salicylate, and eugenol. Preferably, the sweetener is selected from sodium saccharin.

[0095] Examples of antibacterial agents include, but are not limited to, methylparaben, zinc oxide, stannous chloride, tetrahydrocurcumin, hexadecylpyridine chloride, and triclosan. Preferably, the antibacterial agent is selected from methylparaben.

[0096] Examples of wetting agents include, but are not limited to, glycerin, sorbitol, xylitol, and propylene glycol. Preferably, the wetting agent is selected from glycerin.

[0097] Various other optional ingredients, well-known in practice, can be added to the toothpaste compositions of the present invention to improve the general aesthetic appearance. These ingredients include pigments, dyes, agents for forming stains, etc.

[0098] The flavoring agent used in the example may be a flavoring agent commonly used in the art, including but not limited to: wintergreen flavoring, peppermint flavoring, spearmint flavoring, sassafras flavoring and clove flavoring, etc.

[0099] Examples of foaming agents include, but are not limited to, sodium dodecyl sulfate, cocamidopropyl betaine, alkyl glycosides, alkyl sulfonates, alkylbenzene sulfonates, etc.

[0100] Examples of abrasives include, but are not limited to: silica, calcium carbonate, calcium bicarbonate, calcium pyrophosphate, etc.

[0101] Further, in some embodiments, the present invention provides a toothpaste, comprising, by weight: 1-10 parts of bioactive glass material, 20.5-26.5 parts of thickener, 45-60 parts of humectant, 11-20 parts of abrasive, 1-5 parts of foaming agent, 0-3 parts of colorant, 0-3 parts of flavoring agent, 0-0.5 parts of sweetener, and 0-0.5 parts of antibacterial agent. Further, by weight, the toothpaste comprises: 1-10 parts of bioactive glass material, 20.5-26.5 parts of thickener, 45-60 parts of humectant, 11-20 parts of abrasive, 1-5 parts of foaming agent, 0.1-3 parts of colorant, 0.1-3 parts of flavoring agent, 0.1-0.5 parts of sweetener, and 0.1-0.5 parts of antibacterial agent.

[0102] Raw material information and testing methods

[0103] Test method for apparent density: QB / T2346-2015.

[0104] Test method for copper loss: JSJ-C-ZG-36: (1) Take two copper pieces, clean them with distilled water, dry them with a blower, place them in a desiccator, and after 15 minutes, take out the copper pieces with tweezers. Weigh the weight W1 (unit: mg) of the two copper pieces before wear. After weighing, place the copper pieces in the trough of the hard particle tester.

[0105] (2) Accurately weigh 20g of bioactive glass material sample and uniformly disperse it in 120g of sorbitol solution. Transfer the obtained friction particle slurry to the material tank of the hard particle tester. Turn on the hard particle tester and continuously rub the copper sheet 10,000 times in the test slurry. After rubbing, remove the copper sheet with tweezers, rinse it with distilled water, dry it with a blower, and place it in a desiccator. After 15 minutes, remove the copper sheet with tweezers and weigh its worn weight W2 (unit: mg); (3) Copper wear value W = W1 - W2 (unit: mg). The deviation of parallel experimental results should not exceed 20%, and the average value is taken as the final result.

[0106] Test method for Ganz whiteness: QB / T2346-2015.

[0107] Moisture content test method: QB / T2346-2015.

[0108] Test method for particle size: GBT19087-2016.

[0109] Test methods for BET specific surface area, pore volume, and pore size: The specific surface area, pore volume, and pore size of amorphous silica particles were tested using a JW-BK112 static nitrogen adsorption instrument.

[0110] Oil absorption value test method: ASTM D281.

[0111] pH test method: QB / T2346-2015.

[0112] Bioactive glass 4516, Novamin 4516, 3M.

[0113] ZI-165: Silicon dioxide, Jin Sanjiang.

[0114] Core-shell type: Core-shell type silicon dioxide, Jin Sanjiang.

[0115] K12: Sodium dodecyl sulfate, Jiangsu Youyang Pharmaceutical Co., Ltd.

[0116] Example 1

[0117] (1) Sintering of calcium carbonate: Take a certain amount of analytical grade calcium carbonate; place it in a muffle furnace at 1000℃ for calcination; after cooling to room temperature, the conversion rate is 100% to obtain sintered calcium oxide. The formula for calculating the conversion rate is as follows: Y=△m / 44%m, where △m is the mass difference of calcium carbonate before and after calcination; m is the mass of calcium carbonate.

[0118] (2) The acid-base drop was carried out at a reaction temperature of 90℃, maintaining a pH of 2.5 during the drop process, and the reaction time was 1 h. The base used was sodium silicate with a modulus of 3.5 and a concentration of 1.2N. The corresponding mass of alkali metal silicate was added based on the fact that the silica generated by the alkali metal silicate accounted for 50% of the total mass of the bioactive glass material. The acid used was sulfuric acid with a concentration of 8N.

[0119] (3) After the reaction is complete, add the sintered calcium oxide from step (1). The amount of sintered calcium oxide added accounts for 22% of the total mass of the bioactive glass material. Stir at 600 rpm for 10 min until uniform. Then add dilute phosphoric acid. The reaction time is 0.6 h. The concentration of dilute phosphoric acid is 30%. The amount of dilute phosphoric acid added is based on the fact that the generated phosphorus pentoxide accounts for 5% of the total mass of the bioactive glass material. After the reaction is complete, continue stirring at 600 rpm for 30 min. Then add sodium hydroxide. The sodium introduced by sodium hydroxide is based on the generated sodium oxide. The sodium oxide accounts for 8.2% of the total mass of the bioactive glass material. Continue stirring at 600 rpm for 30 min and then discharge the material.

[0120] (4) Spray dry the liquid material discharged from step (3) with an inlet air temperature of 300°C and an outlet air temperature of 120°C; crush it to the required particle size to obtain the bioactive glass material.

[0121] The bioactive glass material prepared in this embodiment was analyzed and identified by X-ray diffraction (XRD) using a Bruker D8A A25 X-ray diffractometer with Cu-Kα radiation. It exhibited the following characteristic peaks expressed in terms of angle 2θ: 2θ = 19.1 ± 0.2°, 2θ = 20.2 ± 0.2°, 2θ = 23.8 ± 0.2°, 2θ = 26.5 ± 0.2°, 2θ = 26.9 ± 0.2°, 2θ = 31.9 ± 0.2°, 2θ = 32.1 ± 0.2°, 2θ = 33.6 ± 0.2°, 2θ = 34.2 ± 0.2°, and 2θ = 48.6 ± 0.2°. The X-ray diffraction pattern of the bioactive glass material prepared in this embodiment is shown below. Figure 1 As shown. The bioactive glass material prepared in Example 1 belongs to the Na2O-CaO-SiO2-P2O5 system, and by weight percentage, it includes: SiO2 50%, P2O5 5%, CaO 22%, and Na2O 23%.

[0122] SEM image of the bioactive glass material prepared in Example 1 is shown below. Figure 2 and Figure 3 As shown.

[0123] Example 2

[0124] (1) Sintering of calcium carbonate: Take a certain amount of analytical grade calcium carbonate; place it in a muffle furnace at 1000℃ for calcination; after cooling to room temperature, the conversion rate is 100% to obtain sintered calcium oxide. The formula for calculating the conversion rate is as follows: Y=△m / 44%m, where △m is the mass difference of calcium carbonate before and after calcination; m is the mass of calcium carbonate.

[0125] (2) Add 20% by volume (based on the reactor volume (5L)) of a metal salt base solution to the reaction vessel. The metal salt base solution is sodium sulfate. The sodium introduced by the sodium sulfate is calculated as sodium oxide generated. Sodium oxide accounts for 3% of the total mass of the bioactive glass material. The reaction temperature is 80℃, and acid and alkali are dropped simultaneously. The pH of the acid-alkali dropping process is maintained at 3.5, and the reaction time is 1h. The alkali used is sodium silicate with a modulus of 3.3 and a concentration of 1.5N. The corresponding mass of alkali metal silicate is added based on the fact that the silica generated by the alkali metal silicate accounts for 40% of the total mass of the bioactive glass material. The acid used is sulfuric acid with a concentration of 4N.

[0126] (3) After the reaction is complete, add the sintered calcium oxide from step (1); the amount of sintered calcium oxide added is 27% of the total mass of the bioactive glass material. Stir at 600 rpm for 15 min until uniform; then add dilute phosphoric acid. The reaction time is 0.5 h and the concentration of dilute phosphoric acid is 33%. The amount of dilute phosphoric acid added is based on the fact that the generated phosphorus pentoxide accounts for 5% of the total mass of the bioactive glass material. After the reaction is complete, continue stirring at 600 rpm for 30 min. Then add sodium hydroxide. The sodium introduced by sodium hydroxide is calculated as sodium oxide. Sodium oxide accounts for 12.5% ​​of the total mass of the bioactive glass material. Continue stirring at 600 rpm for 30 min and then discharge the material.

[0127] (4) Spray dry the liquid material discharged from step (3) with an inlet air temperature of 300°C and an outlet air temperature of 120°C; crush it to the required particle size to obtain the bioactive glass material.

[0128] The bioactive glass material prepared in this embodiment was analyzed and identified by X-ray diffraction (XRD) using a Bruker D8A A25 X-ray diffractometer with Cu-Kα radiation. It exhibited characteristic peaks consistent with those in Example 1, expressed in terms of angle 2θ. The X-ray diffraction pattern is basically as follows: Figure 1 As shown.

[0129] The bioactive glass material belongs to the Na2O-CaO-SiO2-P2O5 system. By weight percentage, the bioactive glass material includes: SiO2 40%, P2O5 5%, CaO 27%, and Na2O 28%.

[0130] Example 3

[0131] (1) Sintering of calcium carbonate: Take a certain amount of analytical grade calcium carbonate; place it in a muffle furnace at 1000℃ for calcination; after cooling to room temperature, the conversion rate is 100% to obtain sintered calcium oxide. The formula for calculating the conversion rate is as follows: Y=△m / 44%m, where △m is the mass difference of calcium carbonate before and after calcination; m is the mass of calcium carbonate.

[0132] (2) Add 25% by volume (based on the reactor volume (5L)) of a metal salt base solution to the reaction vessel. The metal salt base solution is sodium sulfate. The sodium introduced is based on the generated sodium oxide, which accounts for 1.3% of the total mass of the bioactive glass material. The reaction temperature is 70℃, and acid and alkali are added simultaneously. The pH of the acid-alkali simultaneous drop process is maintained at 4.5, and the reaction time is 1 hour. The alkali used is sodium silicate with a modulus of 3.2 and a concentration of 1.8N. Based on the silicon dioxide generated by alkali metal silicates accounting for 55% of the total mass of the bioactive glass material, the corresponding mass of alkali metal silicates is added. The acid used is sulfuric acid with a concentration of 6N.

[0133] (3) After the reaction is complete, add the sintered calcium oxide from step (1); the amount of sintered calcium oxide added is 22% of the total mass of the bioactive glass material, and stir at 600 rpm for 20 min until uniform; then add dilute phosphoric acid, the reaction time is 0.4 h, the concentration of dilute phosphoric acid is 35%, and the amount of dilute phosphoric acid added is based on the fact that the generated phosphorus pentoxide accounts for 3% of the total mass of the bioactive glass material; after the reaction is complete, continue stirring at 600 rpm for 30 min, then add sodium hydroxide, the sodium introduced by sodium hydroxide is based on the generated sodium oxide, the sodium oxide accounts for 1% of the total mass of the bioactive glass material, continue stirring at 600 rpm for 30 min, and then discharge the material.

[0134] (4) Spray dry the liquid material discharged from step (3) with an inlet air temperature of 300°C and an outlet air temperature of 120°C; crush it to the required particle size to obtain the bioactive glass material.

[0135] The bioactive glass material prepared in this embodiment was analyzed and identified by X-ray diffraction (XRD) using a Bruker D8A A25 X-ray diffractometer with Cu-Kα radiation. It exhibited characteristic peaks consistent with those in Example 1, expressed in terms of angle 2θ. The X-ray diffraction pattern is basically as follows: Figure 1 As shown.

[0136] The bioactive glass material belongs to the Na2O-CaO-SiO2-P2O5 system. By weight percentage, the bioactive glass material includes: SiO2 55%, P2O5 3%, CaO2 2%, and Na2O 20%.

[0137] Example 4

[0138] (1) Sintering of calcium carbonate: Take a certain amount of analytical grade calcium carbonate; place it in a muffle furnace at 1000℃ for calcination; after cooling to room temperature, the conversion rate is 100% to obtain sintered calcium oxide. The formula for calculating the conversion rate is as follows: Y=△m / 44%m, where △m is the mass difference of calcium carbonate before and after calcination; m is the mass of calcium carbonate.

[0139] (2) Add a metal salt base solution of 30% by volume (based on the reactor volume (5L)) to the reaction vessel. The metal salt base solution is sodium sulfate. The sodium introduced is based on the generated sodium oxide, which accounts for 4% of the total mass of the bioactive glass material. The reaction temperature is 60℃, and acid and alkali are dropped simultaneously. The pH of the acid-alkali dropping process is maintained at 5.5, and the reaction time is 1h. The alkali used is sodium silicate with a modulus of 3.1 and a concentration of 2.2N. Based on the fact that the silica generated by the alkali metal silicate accounts for 48% of the total mass of the bioactive glass material, the corresponding mass of alkali metal silicate is added. The acid used is sulfuric acid with a concentration of 10N.

[0140] (3) After the reaction is complete, add the sintered calcium oxide from step (1); the amount of sintered calcium oxide added is 23% of the total mass of the bioactive glass material. Stir at 600 rpm for 30 min until uniform; then add dilute phosphoric acid. The reaction time is 0.3 h and the concentration of dilute phosphoric acid is 40%. The amount of dilute phosphoric acid added is 6% of the total mass of the bioactive glass material. After the reaction is complete, continue stirring at 600 rpm for 30 min. Then add sodium hydroxide. The sodium introduced by sodium hydroxide is based on the sodium oxide produced. The sodium oxide accounts for 3% of the total mass of the bioactive glass material. Continue stirring at 600 rpm for 30 min and then discharge the material.

[0141] (4) Spray dry the liquid material discharged from step (3) with an inlet air temperature of 300°C and an outlet air temperature of 120°C; crush it to the required particle size to obtain the bioactive glass material.

[0142] The bioactive glass material prepared in this embodiment was analyzed and identified by X-ray diffraction (XRD) using a Bruker D8A A25 X-ray diffractometer with Cu-Kα radiation. It exhibited characteristic peaks consistent with those in Example 1, expressed in terms of angle 2θ. The X-ray diffraction pattern is basically as follows: Figure 1 As shown.

[0143] The bioactive glass material belongs to the Na2O-CaO-SiO2-P2O5 system. By weight percentage, the bioactive glass material comprises: SiO2 48%, P2O5 6%, CaO 23%, and Na2O 23%. The physicochemical properties of the bioactive glass materials prepared in Examples 1 to 4 are shown in Table 1 below.

[0144] Table 1

[0145]

[0146] Example 5

[0147] (1) Sintering of calcium carbonate: Take a certain amount of analytical grade calcium carbonate; place it in a muffle furnace at 1000℃ for calcination; after cooling to room temperature, the conversion rate is 100% to obtain sintered calcium oxide. The formula for calculating the conversion rate is as follows: Y=△m / 44%m, where △m is the mass difference of calcium carbonate before and after calcination; m is the mass of calcium carbonate.

[0148] (2) Add 20% by volume (based on the reactor volume (5L)) of a metal salt base solution to the reaction vessel. The metal salt base solution is sodium sulfate. The sodium introduced is based on the generated sodium oxide, which accounts for 5.7% of the total mass of the bioactive glass material. The reaction temperature is 80℃, and acid and alkali are dropped simultaneously. The pH is maintained at 8, and the reaction time is 1.2h. The alkali used is sodium silicate with a modulus of 3.5 and a concentration of 2.2N. Based on the assumption that the silica generated by the alkali metal silicate accounts for 45% of the total mass of the bioactive glass material, the corresponding mass of alkali metal silicate is added. The acid used is phosphoric acid with a concentration of 6N, and the generated phosphorus pentoxide accounts for 6% of the total mass of the bioactive glass material.

[0149] After the reaction is complete, add the sintered calcium oxide from step (1); the amount of sintered calcium oxide added is 24% of the total mass of the bioactive glass material. Stir at 600 rpm for 20 min until uniform; then add sodium hydroxide. The sodium introduced by sodium hydroxide is calculated as the generated sodium oxide. The sodium oxide accounts for 6% of the total mass of the bioactive glass material. Continue stirring at 600 rpm for 30 min and then discharge the material.

[0150] (3) The discharged liquid is spray-dried with an inlet air temperature of 300°C and an outlet air temperature of 120°C. The material is crushed to the required particle size to obtain the bioactive glass material.

[0151] The bioactive glass material prepared in this embodiment was analyzed and identified by X-ray diffraction (XRD) using a Bruker D8A A25 X-ray diffractometer with Cu-Kα radiation. It exhibited the following characteristic peaks expressed in terms of angle 2θ: 2θ = 20.7 ± 0.2°, 2θ = 22.0 ± 0.2°, 2θ = 23.6 ± 0.2°, 2θ = 23.8 ± 0.2°, 2θ = 26.8 ± 0.2°, 2θ = 33.6 ± 0.2°, 2θ = 34.2 ± 0.2°; 2θ = 48.6 ± 0.2°. The X-ray diffraction pattern of the bioactive glass material prepared in this embodiment is shown below. Figure 4 As shown.

[0152] The bioactive glass material belongs to the Na2O-CaO-SiO2-P2O5 system. By weight percentage, the bioactive glass material includes: SiO2 45%, P2O5 6%, CaO 24%, and Na2O 25%.

[0153] Example 6

[0154] (1) Preparation of reaction solution A: Calcium carbonate is calcined to obtain calcium oxide (refer to Example 1). The calcined calcium oxide is prepared into a calcium hydroxide slurry with a concentration of 0.8 mol / L. The calcium introduced is based on the calcium oxide generated, and the calcium oxide accounts for 6% of the total mass of the bioactive glass material. The temperature is raised to 85°C, and a dilute phosphoric acid solution is added dropwise to the calcium hydroxide slurry. Based on the phosphorus pentoxide generated accounting for 4% of the total mass of the bioactive glass material, the corresponding mass of dilute phosphoric acid is added. The concentration of the dilute phosphoric acid solution is 38%. The reaction is carried out until the pH of the reaction is 7-9, and the reaction time is 2 hours. After the reaction is completed, the mixture is aged and left to stand at room temperature for 2 hours for later use.

[0155] (2) Preparation of reaction solution B: Add 10% by volume (based on the volume of the reactor (5L)) of silica slurry to the reaction vessel. The silica introduced is based on the generated silica, and the silica accounts for 60% of the total mass of the bioactive glass material. Then add calcined calcium oxide, which accounts for 12% of the total mass of the bioactive glass material. Stir at 600 rpm for 30 min. Then add sodium hydroxide, which introduces sodium based on the generated sodium oxide, and the sodium oxide accounts for 18% of the total mass of the bioactive glass material. Stir at 600 rpm until homogeneous for 4 h.

[0156] (3) After mixing and stirring material A and material B evenly, dry them in an oven at 110°C until the moisture content is <3%, then crush them to obtain the bioactive glass material.

[0157] The bioactive glass material prepared in this embodiment was analyzed and identified by X-ray diffraction (XRD) using a Bruker D8A A25 X-ray diffractometer with Cu-Kα radiation. It exhibited the following characteristic peaks expressed in terms of angle 2θ: 2θ = 20.2 ± 0.2°, 2θ = 23.8 ± 0.2°, 2θ = 26.5 ± 0.2°, 2θ = 26.8 ± 0.2°, 2θ = 33.6 ± 0.2°, 2θ = 34.2 ± 0.2°, and 2θ = 48.6 ± 0.2°. The X-ray diffraction pattern of the bioactive glass material prepared in this embodiment is shown below. Figure 5 As shown.

[0158] The bioactive glass material belongs to the Na2O-CaO-SiO2-P2O5 system. By weight percentage, the bioactive glass material includes: SiO2 60%, P2O5 4%, CaO 18%, and Na2O 18%.

[0159] Comparative Example 1

[0160] This comparative example uses existing bioglass Novamin 4516, which, by mass percentage, comprises: 4.5 wt% Na2O, 24.5 wt% CaO, 6.0 wt% P2O, and 45 wt% SiO.

[0161] The bioglass Novamin 4516 was identified using X-ray diffraction (XRD) analysis with a Bruker D8A A25 X-ray diffractometer, employing Cu-Kα radiation. The X-ray diffraction pattern of the bioglass Novamin 4516 is shown below. Figure 6 As shown. By Figure 6 It can be seen that the X-ray diffraction pattern of the bioglass Novamin 4516 has no characteristic peaks, indicating that it has an amorphous structure.

[0162] Comparative Example 2

[0163] The bioactive glass material used in this comparative example was prepared in powder form according to the method described in Example 2 of patent application CN111017934A.

[0164] X-ray diffraction (XRD) analysis was performed using a Bruker D8A A25 X-ray diffractometer with Cu-Kα radiation. The X-ray diffraction pattern of the bioactive glass material in Comparative Example 2 is shown below. Figure 7 As shown. By Figure 7 It can be seen that the X-ray diffraction pattern of the bioactive glass material prepared in this comparative example has no characteristic peaks, indicating that it has an amorphous structure.

[0165] Test case

[0166] (1) Artificial saliva mineralization experiment

[0167] Example 1: Artificial saliva mineralization experiment was conducted on the bioactive glasses prepared in Comparative Examples 1 and 2. Experimental procedure: 0.60 g of sample was placed in a 100 mL beaker, and commercially available artificial saliva was added to the 100 mL mark. The beaker was stored at a constant temperature of 37 °C, and the artificial saliva was replaced every 24 hours. Experiments were conducted for 1 day, 3 days, and 7 days, and the experimental samples were numbered A, B, and C. Energy dispersive spectroscopy (EDS) analysis was performed to detect the change in the Ca / P molar ratio. Simultaneously, XRD analysis was performed on the reaction products.

[0168] If the Ca / P molar ratio gradually decreases with increasing artificial saliva mineralization time during the artificial saliva mineralization experiment, it indicates that the phosphorus in the saliva has undergone a chemical reaction with the calcium in the bioglass; if the Ca / P molar ratio gradually approaches 1.67, it is speculated that hydroxyapatite may have been formed.

[0169] Table 2

[0170] Artificial saliva mineralization time 1d 2d 3d Example 1 2.759 1.96 1.68 Comparative Example 1 2.964 2.124 1.81 Comparative Example 2 2.925 3.2 2.536

[0171] The results of the artificial saliva mineralization experiment are shown in Table 2 above. As can be seen from Table 2, the Ca / P molar ratio of the bioactive glass prepared in Example 1 of this invention gradually approaches 1.67 with the increase of artificial saliva mineralization time, suggesting that hydroxyapatite may have been formed. However, the Ca / P molar ratio of the bioactive glasses in Comparative Examples 2 and 3 still has a certain gap from 1.67 after artificial saliva mineralization.

[0172] The X-ray diffraction patterns of the products obtained by artificial saliva mineralization of the bioactive glass materials in Example 1, Comparative Example 1, and Comparative Example 2 are as follows: Figure 8 , Figure 9 and Figure 10 As shown. By Figure 8 It can be seen that the X-ray diffraction pattern of the bioactive glass material prepared in Example 1 after artificial saliva mineralization shows a characteristic peak of 2θ = 34.2358°, corresponding to the characteristic diffraction peak of hydroxyapatite, indicating that the bioactive glass material provided by the present invention generates hydroxyapatite after artificial saliva mineralization. Figure 9 and Figure 10 It can be seen that the products of bioactive glass mineralization in Comparative Examples 2 and 3 have no characteristic peaks, are amorphous products, and no hydroxyapatite crystals are produced.

[0173] (2) Experiment on mineralization and sealing of dentinal tubules with bio-glass toothpaste

[0174] By weight percentage, the bioglass toothpaste comprises: 0.95% carbomer 940, 21.25% PEG-400, 0.2% sodium saccharin, 0.2% methylparaben, 55% glycerin, 3% ZI-165, 11% core-shell type, 2% K12, 5% bioglass, 0.5% titanium dioxide, and 0.9% fragrance.

[0175] 1. Test method:

[0176] 1.1 Preparation of dentin samples: Freshly extracted bovine incisors were cut and polished to prepare 12 dentin blocks approximately 5mm × 5mm × 2mm in size. These blocks were etched with 40% orthophosphoric acid for 20 minutes, rinsed, and then etched with 5% sodium hypochlorite for 5 minutes. Finally, they were ultrasonically cleaned with deionized water for 20 minutes. The samples were observed under a polarized light microscope to ensure adequate exposure of the dentinal tubules.

[0177] 1.2 Grouping: Twelve dentin samples were randomly assigned to the blank control group, experimental group 1, experimental group 2, and experimental group 3, with three samples in each group.

[0178] 1.3 Preparation of toothpaste paste: Weigh a certain amount of toothpaste and artificial saliva according to the ratio of 1:1.6 (toothpaste: saliva). The toothpaste is weighed directly onto the toothbrush head. The toothbrush head is the most basic ORALB brush head.

[0179] 1.4 Partitioning: Half of the dentin sample (approximately 5mm × 2.5mm) was adhered with tape as the untreated area, and the other half (approximately 5mm × 2.5mm) was used as the experimental treatment area.

[0180] 1.5 Dentin Cycling Treatment: The blank control group was treated with deionized water. Experimental group 1 was treated with bio-glass toothpaste prepared using the bioactive glass material prepared in Example 1; Experimental group 2 was treated with bio-glass toothpaste prepared using the bioactive glass material prepared in Comparative Example 2; and Experimental group 3 was treated with bio-glass toothpaste prepared using the bioactive glass material prepared in Comparative Example 1. Students brushed their teeth with an electric toothbrush for 3 minutes, then rinsed thoroughly with deionized water, and then soaked in artificial saliva at 37°C. This process was repeated twice daily, brushing for 3 minutes, rinsing thoroughly with deionized water, and then soaking in artificial saliva. Dentin samples were collected one day after brushing and observed under a scanning electron microscope.

[0181] 4.6 Drying: The cyclically processed dentin samples were dried in a constant temperature oven at 25°C for 24 hours.

[0182] 4.7 Scanning electron microscope observation: After drying, the dentin was sprayed with gold, and then the condition before and after the sealing was observed under a scanning electron microscope.

[0183] The experimental diagrams of the mineralization and sealing of dentinal tubules using bioactive glass toothpaste prepared with the bioactive glass materials of Example 1, Comparative Example 1, and Comparative Example 2 are shown below. Figure 11 , Figure 12 and Figure 13 As shown. Figure 11 , Figure 12 and Figure 13 It can be seen that the bio-glass toothpaste prepared using the bioactive glass material prepared in Example 1 has a significantly better effect on mineralizing and sealing dentinal tubules than Comparative Example 1 and Comparative Example 2, and "bulges" were formed in Example 1; neither Comparative Example 1 nor Comparative Example 2 sealed the dentinal tubules well, and some pores of the dentinal tubules were still exposed. The sealing effect of Comparative Example 1 was significantly worse than that of Comparative Example 2.

[0184] (3) Experiment on the reaction rate of bio-glass toothpaste and tooth surface

[0185] Take 0.50g of the bioactive glass material from Example 1, Comparative Example 1, and Comparative Example 2 into a 50mL centrifuge tube, add deionized water to the 50mL mark, and store at a constant temperature of 37℃. Centrifuge at different time points and take the supernatant to detect the content of silicon, calcium, phosphorus, and sodium elements. Use inductively coupled plasma spectroscopy to analyze the concentration of silicon, calcium, phosphorus, and sodium elements in a 0.01% bioactive glass aqueous solution at different time points. The results of Example 1, Comparative Example 1, and Comparative Example 2 are shown in Tables 3, 4, and 5, respectively.

[0186] Table 3

[0187] time Silicon (ppm) Calcium (ppm) Phosphorus (ppm) Sodium (ppm) 1h 15.3 5.3 2.4 8.3 2h 18.1 7.6 2.0 10.1 4h 19.7 9.1 1.9 11.4 8h 20.5 10.9 1.5 14.8 12h 24.8 14.7 1.1 15.2 24h 25.7 15.5 0.6 16.8

[0188] Table 4

[0189]

[0190]

[0191] Table 5

[0192] time Silicon (ppm) Calcium (ppm) Phosphorus (ppm) 1h 13.4 4.2 1.4 2h 14.3 6.8 1.8 4h 16.5 9.3 1.9 8h 17.8 13.9 1.0 12h 19.5 17.4 0.8 24h 22.9 20.7 0.6

[0193] As shown in Tables 3, 4, and 5 above, the bioactive glass toothpaste formed from the bioactive glass material prepared in this invention exhibits the following leaching concentrations at 1 hour: silicon 15.3 ppm, calcium 5.3 ppm, phosphorus 2.4 ppm, and sodium 8.3 ppm. At 12 hours, the leaching concentrations are: silicon 24.8 ppm, calcium 15.5 ppm, phosphorus 0.6 ppm, and sodium 16.8 ppm.

[0194] In Comparative Example 1, the dissolved concentrations of silicon, calcium, phosphorus, and sodium in the bioactive glass material were 9.2 ppm, 3.1 ppm, 1.0 ppm, and 5.3 ppm after 1 hour. The dissolution rate of the bioactive glass material in Comparative Example 1 after 1 hour is significantly different from that of the bioactive glass material of this invention.

[0195] In Comparative Example 2, the dissolved concentrations of silicon, calcium, and phosphorus in the bioactive glass material were 13.4 ppm, 4.2 ppm, and 1.4 ppm after 1 hour. The dissolved rate of the bioactive glass material of this invention is also superior to that of the bioactive glass material in Comparative Example 2.

[0196] The above results demonstrate that, compared to existing bioactive glasses, the bioactive glass material provided by this invention exhibits superior dissolution rates of silicon, calcium, phosphorus, and sodium elements, enabling faster formation of a silica glass network in water or body fluids. Calcium and phosphorus elements are also released more quickly to the tooth surface, crystallizing into a mixed hydroxyapatite. This deposition on the tooth surface mineralizes and seals exposed dentinal tubules, facilitating faster reaction with the tooth surface and achieving remineralization of the dentin surface, thus alleviating or treating dentin hypersensitivity.

[0197] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A bioactive glass material, characterized in that, The bioactive glass material belongs to the Na2O-CaO-SiO2-P2O5 system and, by weight percentage, consists of the following components: SiO2 40-60%, P2O5 1-10%, CaO 18-30%, and Na2O 10-30%. The X-ray diffraction pattern of the bioactive glass material contains diffraction peaks at the following 2θ angles: 19.1±0.2°, 20.2±0.2°, 20.7±0.2°, 22.0±0.2°, 23.6±0.2°, 23.8±0.2°, 26.5±0.2°, 26.8±0.2°, 26.9±0.2°, 31.9±0.2°, 32.1±0.2°, 33.6±0.2°, 34.2±0.2°, and 48.6±0.2°. The preparation method of the bioactive glass material includes the following steps: (1) The alkali metal silicate and the inorganic acid are subjected to acid-base co-droplet reaction, maintaining the pH of the solution at 2-6 and the reaction temperature at 40-95℃ during the co-droplet reaction; or Alkali metal silicates and inorganic acids are used for acid-base co-drop in a metal salt base solution. During the co-drop process, the pH of the solution is maintained at 2-6 and the reaction temperature is 40-95℃. (2) After the reaction in step (1) is complete, add calcium oxide and stir; add phosphoric acid to react and stir; then add sodium-containing alkaline solution and stir; prepare bioactive glass material.

2. A bioactive glass material, characterized in that, The bioactive glass material belongs to the Na2O-CaO-SiO2-P2O5 system and, by weight percentage, consists of the following components: SiO2 40-60%, P2O5 1-10%, CaO 18-30%, and Na2O 10-30%. The X-ray diffraction pattern of the bioactive glass material contains diffraction peaks at the following 2θ angles: 19.1±0.2°, 20.2±0.2°, 20.7±0.2°, 22.0±0.2°, 23.6±0.2°, 23.8±0.2°, 26.5±0.2°, 26.8±0.2°, 26.9±0.2°, 31.9±0.2°, 32.1±0.2°, 33.6±0.2°, 34.2±0.2°, and 48.6±0.2°. The method for preparing the bioactive glass material includes the following steps: (1) Alkali metal silicates and phosphoric acid are reacted dropwise together, maintaining the solution pH at 3-10 and the reaction temperature at 40-95℃; or Alkali metal silicates and phosphoric acid are used for acid-base co-drop in a metal salt base solution. During the co-drop process, the solution pH is maintained at 3-10 and the reaction temperature is 40-95℃. (2) After the reaction in step (1) is complete, add calcium oxide and stir; then add sodium-containing alkaline solution and stir; prepare bioactive glass material.

3. A bioactive glass material, characterized in that, The bioactive glass material belongs to the Na2O-CaO-SiO2-P2O5 system and, by weight percentage, consists of the following components: SiO2 40-60%, P2O5 1-10%, CaO 18-30%, and Na2O 10-30%. The X-ray diffraction pattern of the bioactive glass material contains diffraction peaks at the following 2θ angles: 19.1±0.2°, 20.2±0.2°, 20.7±0.2°, 22.0±0.2°, 23.6±0.2°, 23.8±0.2°, 26.5±0.2°, 26.8±0.2°, 26.9±0.2°, 31.9±0.2°, 32.1±0.2°, 33.6±0.2°, 34.2±0.2°, and 48.6±0.2°. The method for preparing the bioactive glass material includes the following steps: S1. At 40-95℃, calcium hydroxide slurry and phosphoric acid are mixed and reacted. During the reaction, the pH is maintained at 7-9. After the reaction, the mixture is aged to obtain reaction solution A. S2. Mix the silica slurry and calcium oxide and stir; then add the sodium-containing alkaline solution and stir to obtain reaction solution B; S3. Mix reaction solution A and reaction solution B, and dry them to obtain bioactive glass material.

4. The bioactive glass material according to any one of claims 1-3, characterized in that, The bioactive glass material has an X-ray diffraction pattern consistent with Figure 1, Figure 4, or Figure 5.

5. The use of the bioactive glass material according to any one of claims 1-3 in sealing dentinal tubules or in the preparation of oral care compositions.

6. An oral care composition, characterized in that, By weight percentage, it comprises: 0.1-20% of the bioactive glass material of any one of claims 1-3 and oral-acceptable excipients.

7. A toothpaste, characterized in that, By weight, it comprises: 1-10 parts of the bioactive glass material according to any one of claims 1-3, 20.5-26.5 parts of thickener, 45-60 parts of wetting agent, 11-20 parts of abrasive, 1-5 parts of foaming agent, 0-3 parts of colorant, 0-3 parts of flavoring agent, 0-0.5 parts of sweetener, and 0-0.5 parts of antibacterial agent.

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