Anti-allergic toothpaste containing bioactive glass with core-shell structure

Abstract

The invention provides anti-allergic toothpaste containing core-shell structure bioactive glass. The anti-allergic toothpaste comprises the following components in percentage by weight: 15-30% of a friction agent, 10-25% of a humectant, 0.5-2% of an adhesive, 0.1-1% of a sweetening agent, 0.1-0.5% of a preservative, 0.5-2% of essence, 1-20% of core-shell structure bioactive glass and the balance of glycerol. A shell of the core-shell structure bioactive glass is boron-containing boron-series bioactive glass, and an inner core of the core-shell structure bioactive glass is silicon-based bioactive glass. Boron-based bioactive glass and silicon-based bioactive glass with different properties are combined to form a core-shell structure, so that the problem that the activity and degradation resistance of the existing bioactive glass are difficult to balance when the existing bioactive glass is applied to anti-allergic toothpaste is solved, and the anti-allergic effect and storage stability of the toothpaste are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of oral care products, in particular to an anti-allergic toothpaste added with core-shell structure bioactive glass. BACKGROUND

[0002] Tooth sensitivity and gum bleeding are common oral problems, mainly manifested as short-term and sharp pain of teeth when subjected to cold, heat, acid, sweet, friction or biting hard objects, or gum bleeding during daily tooth brushing. The anti-allergic toothpastes on the market mostly relieve tooth hypersensitivity symptoms by sealing dentin tubules and reducing pulp nerve sensitivity, but have the problems of poor plugging effect, low toxicity and easy drug resistance. The use of bioactive glass as an anti-allergic ingredient can react with saliva proteins and minerals on the tooth surface, release calcium, phosphorus, silicon and other elements to stimulate bone regeneration, form a hydroxyapatite layer, and seal the dentin tubules, thereby achieving the effects of anti-allergy and hemostasis.

[0003] However, the existing bioactive glass has some problems in the application process. For example, although the high-activity boron-based bioactive glass can quickly react with saliva and the tooth surface, it degrades rapidly after being added into toothpaste during tooth brushing, although it releases calcium, phosphorus, silicon and other elements to stimulate bone regeneration and form a small amount of hydroxyapatite layer, the small amount of hydroxyapatite layer still cannot seal the dentin tubules, affecting the use effect of the toothpaste; and the degradation-resistant silicon-based bioactive glass has relatively low activity, although it can be attached to the dentin tubules, the generated hydroxyapatite is too slow and the adhesion is too low, resulting in unsatisfactory anti-allergic effect. Therefore, it is of great significance to develop a bioactive glass with high activity and good plugging effect for improving the performance of anti-allergic toothpaste. SUMMARY

[0004] The purpose of the present application is to provide an anti-allergic toothpaste containing core-shell structure bioactive glass, which combines boron-based bioactive glass and silicon-based bioactive glass with different properties to form a core-shell structure, solves the problem of difficulty in balancing activity and degradation resistance of existing bioactive glass in the application of anti-allergic toothpaste, and improves the anti-allergic effect and storage stability of the toothpaste.

[0005] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows: The anti-allergic toothpaste containing core-shell structure bioactive glass provided by the present application comprises the following components by weight percentage: friction agent 15-30%, humectant 10-25%, adhesive 0.5-2%, sweetener 0.1-1%, preservative 0.1-0.5%, essence 0.5-2%, core-shell structure bioactive glass 1-20%, and the balance is glycerol.

[0006] The shell of the core-shell structure bioactive glass is a boron-containing boron bioactive glass, and the inner core is a silicon-based bioactive glass. The shell thickness is 30 nm-1 µm, and the inner core particle size is 200 nm-800 µm. The chemical composition of the boron bioactive glass includes, in terms of mole percentage, SiO2 40-60%, Na2O 10-30%, CaO 10-30%, P2O5 5-15%, and B2O3 5-35%; and the chemical composition of the silicon-based bioactive glass includes, in terms of mole percentage, SiO2 40-80%, Na2O 5-30%, CaO 5-30%, and P2O5 2-15%.

[0007] The preparation method of the core-shell structure bioactive glass comprises the following steps: (1) First, the silicon-based bioactive glass inner core is prepared by a sol-gel method: tetraethyl orthosilicate, sodium nitrate, calcium nitrate, and triethyl phosphate are mixed according to the chemical composition ratio of the silicon-based bioactive glass, and an appropriate amount of ethanol and deionized water is added. After stirring uniformly, an acidic catalyst is added to adjust the pH value to be acidic. The sol is formed by stirring at room temperature for 2 h, and then the sol is transferred to a mold. The gel is formed by standing at a certain temperature for 24 h. Finally, the gel is calcined at high temperature to obtain the silicon-based bioactive glass inner core.

[0008] (2) Then, the boron bioactive glass precursor solution is prepared: boric acid, tetraethyl orthosilicate, sodium nitrate, calcium nitrate, and triethyl phosphate are mixed according to the chemical composition ratio of the boron bioactive glass, and an appropriate amount of ethanol and deionized water is added. After stirring uniformly, the boron bioactive glass precursor solution is obtained.

[0009] (3) Then, the boron bioactive glass shell is coated on the surface of the silicon-based bioactive glass inner core by an immersion-drawing method: the silicon-based bioactive glass inner core is immersed in the boron bioactive glass precursor solution for a period of time, and then it is drawn at a certain speed to uniformly attach a layer of precursor solution on the surface of the silicon-based bioactive glass inner core. The inner core with the attached precursor solution is dried at a certain temperature, and then calcined at high temperature to convert the precursor solution into the boron bioactive glass, forming the core-shell structure bioactive glass.

[0010] The advantages of the present application are: (1) Excellent anti-allergy performance: the shell of the core-shell structure bioactive glass added in the toothpaste of the application is a boron-based bioactive glass with high activity, which can quickly react with saliva proteins and minerals on the surface of the teeth to form an apatite layer on the surface of the teeth. After the outer layer of the boron-based bioactive glass in the core-shell structure degrades, the inner layer of the silicon-based bioactive glass is exposed. The silicon-based bioactive glass in the inner layer adheres to the hydroxyapatite layer and locks the dentin tubules, and long-term weak alkaline environment is created to effectively slow down the production of dental plaque.

[0011] (2) Long-term effect: it is generally believed that when bioactive glass is implanted into the body and contacts with body fluids and soft tissues, complex ion exchange occurs between the material and the tissues instantaneously. Alkaline reaction occurs on the surface of the glass, and Si-O-Si bonds are dissolved and broken. A hydroxyapatite layer is formed on the interface. Hydroxyapatite nucleates and crystallizes immediately to form a network of hydroxyapatite crystals. The structure of boron-based bioactive glass is unstable and can be quickly degraded when it contacts with oral fluids. The generated hydroxyapatite stimulated by the rapid degradation of boron-based bioactive glass is far from meeting the demand. Silicon-based bioactive glass has a relatively stable structure and a long release time, and it is difficult to achieve good results in a short period of time. In the core-shell structure, the silicon-based bioactive glass in the inner core has good degradation resistance. The boron-based bioactive glass in the shell quickly participates in the reaction during brushing, and the hydroxyapatite network stimulated by its degradation covers the silicon-based bioactive glass in the inner core. Then the silicon-based bioactive glass slowly acts and releases for a long time, providing the necessary nutrients for the periodontal tissues and prolonging the action time of the bioactive glass in the toothpaste.

[0012] (3) Synergistic effect: the design of the core-shell structure complements the performance of boron-based bioactive glass and silicon-based bioactive glass, greatly improves the anti-allergy effect of the toothpaste, and has good application prospects. BRIEF DESCRIPTION OF DRAWINGS

[0013] Figure 1 Degradation curve of boron-based bioactive glass, core-shell structure bioactive glass and silicon-based bioactive glass in simulated body fluid SBF solution; Figure 2 Scanning electron microscope image of the core-shell structure bioactive glass after synthesis; Figure 3 Before and after comparison of dentin tubules after using toothpaste containing core-shell structure bioactive glass for four weeks. DETAILED DESCRIPTION

[0014] The preparation method of the core-shell structure bioactive glass comprises the following steps: (1) First, the sol-gel method is used to prepare the silicon-based bioactive glass core (for example, in the molar ratio of SiO2: CaO: Na2O: P2O5= 60: 25: 12: 3): tetraethyl orthosilicate (52.8g), sodium nitrate (11.5g), calcium nitrate (29.6g), triethyl phosphate (6.1g) are mixed according to the chemical composition ratio of the silicon-based bioactive glass, 50ml of ethanol and 10ml of deionized water are added, and after stirring uniformly, 2ml of catalyst acetic acid is added to adjust the pH value to be acidic (about 3.0), stirring at room temperature at a speed of 300rpm for 2h to form a sol, then the sol is transferred to a mold, and placed in a constant temperature oven at 40℃ for 24h to form a gel, and then the gel is dried at 60℃ for 48h, and then the gel is calcined at 650℃ for 2h to obtain the silicon-based bioactive glass core; (2) Then, the boron-based bioactive glass precursor solution is prepared (for example, in the molar ratio of B2O3: SiO2: CaO: Na2O: P2O5= 30: 54: 10: 4: 2): boric acid (12.4g), tetraethyl orthosilicate (35.2g), sodium nitrate (2.9g), calcium nitrate (7.4g), triethyl phosphate (2.0g) are mixed according to the chemical composition ratio of the boron-based bioactive glass, 50ml of ethanol and 8ml of deionized water are added, and stirred uniformly at 500rpm for 3h at 40℃ to obtain the boron-based bioactive glass precursor solution; (3) Then, the silicon-based bioactive glass core is coated with a boron-based bioactive glass shell using the dip-coating method: the silicon-based bioactive glass core is immersed in the boron-based bioactive glass precursor solution for 60s, and is pulled out at a uniform speed of 0.2mm / s, so that a layer of precursor solution is uniformly attached to the surface of the silicon-based bioactive glass core, the inner core with the attached precursor solution is placed in a 40℃ / 2h, 80℃ / 4h step drying oven, and then calcined at 550℃ for 1h, so that the precursor solution is converted into boron-based bioactive glass, forming a core-shell structure bioactive glass.

[0015] In order to make the above features and advantages of the present application more obvious and easy to understand, the following examples are given for detailed description. The method of the present application is the conventional method in the art unless otherwise specified.

[0016] Example 1 An antiallergic toothpaste containing a core-shell structure bioactive glass, the weight percentage of each component is: abrasive (silicon dioxide) 20%, humectant (sorbitol) 15%, adhesive (sodium carboxymethyl cellulose) 1%, sweetener (aspartame) 0.5%, preservative (sodium benzoate) 0.3%, essence (peppermint essence) 1%, core-shell structure bioactive glass (inner core about 200nm, total particle size about 300nm) 7%, and the balance is glycerol.

[0017] The chemical composition of the boron-based bioactive glass in the core-shell structure bioactive glass is, in terms of mole percentage, SiO2 54%, Na2O 4%, CaO 10%, P2O5 2%, and B2O3 30%; and the chemical composition of the silicon-based bioactive glass is, in terms of mole percentage, SiO2 60%, Na2O 12%, CaO 25%, and P2O5 3%.

[0018] The core-shell structure bioactive glass is prepared according to the preparation method described above, and then the components are mixed in proportion, stirred uniformly, and subjected to grinding, degassing and other processes to obtain the anti-allergic toothpaste.

[0019] Example 2 An anti-allergic toothpaste containing a core-shell structure bioactive glass, the weight percentage of each component is: abrasive (calcium carbonate) 25%, humectant (sorbitol) 20%, binder (xanthan gum) 1.5%, sweetener (sucralose) 0.8%, preservative (potassium sorbate) 0.4%, essence (spearmint essence) 1.5%, core-shell structure bioactive glass (inner core of about 200 nm, total particle size of about 300 nm) 5%, and the balance is glycerol.

[0020] The chemical composition of the boron-based bioactive glass in the core-shell structure bioactive glass is, in terms of mole percentage, SiO2 45%, Na2O 18%, CaO 18%, P2O5 9%, and B2O3 10%; and the chemical composition of the silicon-based bioactive glass is, in terms of mole percentage, SiO2 45%, Na2O 24.5%, CaO 24.5%, and P2O5 6%.

[0021] The preparation method is the same as that in Example 1 to obtain the anti-allergic toothpaste.

[0022] Comparative Example 1 A general anti-allergic toothpaste, the weight percentage of each component is: abrasive (silicon dioxide) 20%, humectant (sorbitol) 15%, binder (sodium carboxymethyl cellulose) 1%, sweetener (aspartame) 0.5%, preservative (sodium benzoate) 0.3%, essence (peppermint essence) 1%, boron-based bioactive glass (chemical composition: SiO2 54%, Na2O 4%, CaO 10%, P2O5 2%, and B2O3 30%, particle size of about 300 nm) 7%, and the balance is glycerol.

[0023] The components are mixed in proportion, stirred uniformly, and subjected to grinding, degassing and other processes to obtain the general anti-allergic toothpaste.

[0024] Comparative Example 2 A general anti-allergic toothpaste, the weight percentage of each component is: abrasive (silicon dioxide) 20%, humectant (sorbitol) 15%, adhesive (sodium carboxymethyl cellulose) 1%, sweetener (aspartame) 0.5%, preservative (sodium benzoate) 0.3%, essence (peppermint essence) 1%, silicon-based bioactive glass (chemical composition in mole percentage: SiO2 60%, Na2O 12%, CaO 25%, P2O5 3%, particle size about 300 nm) 7%, the balance is glycerol.

[0025] Mix each component according to the proportion, stir uniformly, and prepare a general anti-allergic toothpaste through grinding, degassing and other processes.

[0026] Performance test 1. Anti-allergic effect test: Select 80 patients with tooth hypersensitivity, and randomly divide them into four groups, 20 people in each group. Use the toothpaste prepared by Example 1, Example 2, and the toothpaste prepared by Comparative Example 1 and Comparative Example 2, respectively, brush teeth twice a day, each time for not less than 3 minutes, and continuously use for 4 weeks. Before and after use, test the degree of tooth hypersensitivity by cold and hot stimulation method, and record the intensity and duration of the allergic reaction results (see table below). The results show that the patients using the toothpaste of Example 1 and Example 2 have significantly relieved tooth hypersensitivity symptoms, and the intensity and duration of allergic reactions have been significantly reduced; while the patients using the toothpaste of Comparative Example 1 and Comparative Example 2 have relatively weak relief of tooth hypersensitivity symptoms.

[0027] Note: (The clinical effective rate is defined as: VAS decreased by ≥50% or duration shortened by ≥60%) 2. Degradation experiment: Take 10g of boron-based bioactive glass, core-shell structure bioactive glass of Example 1, and silicon-based bioactive glass, respectively, and add them to SBF (simulated body fluid) solution. After a fixed interval, take them out and weigh them, and draw the degradation curve (as shown in Figure 1 ).

[0028] It is not difficult to find through testing that in a shaking environment, boron-based bioactive glass immersed in SBF solution degrades rapidly in the early stage, while silicon-based bioactive glass degrades relatively slowly. The core-shell structure bioactive glass combines the degradation rates of the two, can rapidly degrade in the early stage, and can continue to degrade and release in the later stage.

[0029] 3. Bioactive glass morphology detection and plugging effect test: After synthesizing the core-shell structure bioactive glass, observe it by scanning electron microscopy, as shown in Figure 2 , the successfully prepared core-shell structure bioactive glass is spherical.

[0030] The comparison photos of the front and back blocking of dentin tubules after using the toothpaste of Example 1 containing the bioactive glass with core-shell structure for 4 weeks are shown in Figure 8 (the left is before use and the right is after use, and it can be seen that the blocking effect is good and a large amount of hydroxyapatite layer has been attached). Figure 3

[0031] The above merely describes the preferred embodiments of the present application, and any equivalent changes and modifications made within the scope of the present application should be included in the scope of the present application.​

Claims

1. An anti-sensitivity toothpaste containing core-shell bioactive glass, characterized in that, It comprises the following components by weight percentage: abrasive 15-30%, humectant 10-25%, binder 0.5-2%, sweetener 0.1-1%, preservative 0.1-0.5%, fragrance 0.5-2%, core-shell bioactive glass 1-20%, and the balance being glycerin.

2. The anti-sensitivity toothpaste according to claim 1, characterized in that, The core-shell structured bioactive glass has an outer shell made of boron-containing boron-based bioactive glass and a core made of silicon-based bioactive glass.

3. The anti-sensitivity toothpaste according to claim 2, characterized in that, The core-shell structured bioactive glass has an outer shell thickness of 30nm-1µm and a core particle size of 200nm-800µm.

4. The anti-sensitivity toothpaste according to claim 2, characterized in that, The chemical composition of the boron-based bioactive glass, in molar percentage, includes: SiO2 40-60%, Na2O 4-30%, CaO 10-30%, P2O5 2-15%, and B2O3 5-35%.

5. The anti-sensitivity toothpaste according to claim 2, characterized in that, The chemical composition of the silicon-based bioactive glass, in molar percentage, includes: SiO2 40-80%, Na2O 5-30%, CaO 5-30%, and P2O5 2-15%.

6. The anti-sensitivity toothpaste according to claim 2, characterized in that, The preparation method of the core-shell structured bioactive glass includes the following steps: (1) First, the silicon-based bioactive glass core was prepared by sol-gel method: tetraethyl orthosilicate, sodium nitrate, calcium nitrate and triethyl phosphate were mixed according to the chemical composition ratio of silicon-based bioactive glass, and an appropriate amount of ethanol and deionized water were added. After stirring evenly, an acidic catalyst was added to adjust the pH value to acidic. The mixture was stirred at room temperature to form a sol. The sol was then transferred to a mold and aged at a certain temperature to form a gel. Finally, the gel was calcined at high temperature to obtain the silicon-based bioactive glass core. (2) Next, prepare a boron-based bioactive glass precursor solution: mix boric acid, tetraethyl orthosilicate, sodium nitrate, calcium nitrate and triethyl phosphate according to the chemical composition ratio of boron-based bioactive glass, add appropriate amounts of ethanol and deionized water, stir evenly to obtain a boron-based bioactive glass precursor solution. (3) Then, the silicon-based bioactive glass core is coated with a boron-based bioactive glass shell by the immersion-pulling method: The silicon-based bioactive glass core is immersed in the boron-based bioactive glass precursor solution and kept for a period of time. Then, it is pulled up at a certain speed to make the surface of the silicon-based bioactive glass core uniformly adhere to a layer of precursor solution. The core with the precursor solution is placed in a certain temperature to dry, and then calcined at high temperature to convert the precursor solution into boron-based bioactive glass, forming a core-shell structure bioactive glass.

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