Dental restoration material with self-restoration capability and preparation method thereof
By adding self-repair microcapsules and modified mesoporous silica with a loaded catalyst as a dispersant to the dental restoration material, the problems of poor self-repair performance and insufficient mechanical performance in the prior art are solved, and efficient self-repair and mechanical performance improvement are achieved.
Patent Information
- Application Number
- CN202510188099.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-20
- Publication Date
- 2025-05-23
AI Technical Summary
In the prior art, the self-repairing performance of the dental restoration material with self-repairing ability is poor, and the mechanical properties need to be further improved.
The interface compatibility of the material and catalyst response efficiency are improved by adding self-repair microcapsules and modified mesoporous silica with a catalyst-loaded catalyst to the dental restoration material.
The self-repair efficiency and mechanical properties of dental restoration materials are significantly improved, including flexural strength, elastic modulus and Vickers hardness, and the self-repair efficiency is higher than 75%.
Smart Images
Figure BDA0005279153800000051 
Figure BDA0005279153800000081
Abstract
Description
Technical Field
[0001] The invention belongs to the field of tooth restoration materials, and in particular relates to a tooth restoration material with self-repairing ability and a preparation method thereof. Background Art
[0002] Resin-based dental restoration materials have the advantages of minimally invasive, beautiful, and excellent mechanical properties. They are currently commonly used composite materials in the field of dental restoration. In the complex oral environment, these dental restoration materials are prone to microcracks due to the influence of various factors. These microcracks may lead to clinical restoration failure. Traditional materials and methods are not sufficient to detect and repair these microcracks in situ. Therefore, microcapsule materials with self-repairing functions are introduced into the resin matrix material to give the material self-repairing functions. The microcapsule material consists of an external dense capsule wall covering an internal core material, and the corresponding repair monomer is encapsulated in a tiny container capsule. When microcracks are generated and puncture the microcapsule, the self-repairing monomer in the capsule flows to the crack surface through capillary action and contacts the catalyst pre-set in the resin matrix, triggering a polymerization reaction, completing the bonding of the crack surface, and thus achieving self-repairing. In addition, people also add antibacterial agents as core materials in microcapsules to achieve the dual effects of antibacterial and self-repairing of microcapsule materials, so as to reduce problems such as secondary caries after repair and extend the service life of the overall tooth restoration material. Therefore, in recent years, self-repairing tooth restoration materials based on microcapsules have developed rapidly.
[0003] However, to achieve good self-repairing performance, more microcapsules need to be added, which will damage the mechanical properties of the resin-based tooth restoration material itself and is not conducive to the practical application of the resin-based tooth restoration material. In response to such problems, the study found that when preparing tooth restoration materials, dispersants are added to enhance the interfacial compatibility between different components, thereby enhancing the overall mechanical properties of the restoration material, and catalysts are pre-placed in the resin base. The catalysts can interact with the self-repairing monomers released by the rupture of the microcapsules to exert self-repairing properties. However, the self-repairing properties of the existing self-repairing tooth restoration materials are relatively poor, and the mechanical properties still need to be further improved. Summary of the invention
[0004] The object of the present invention is to provide a self-repairing microcapsule and a preparation method thereof to solve the problems raised in the above background technology.
[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solutions: On the one hand, the present invention provides a tooth repair material with self-repairing ability, the raw materials for preparing the tooth repair material include the following components in mass: 50-80g of polyoxymethylene resin, 10-50g of inorganic filler, 5-20g of self-repairing microcapsules and 5-20g of dispersant, and the raw materials for preparing the dispersant include a catalyst and modified mesoporous silica.
[0006] As a further improvement, the catalyst is benzoyl peroxide and a calcium phosphate-based material, the calcium phosphate-based material comprises one or more of amorphous calcium phosphate nanoparticles and hydroxyapatite, and the mass ratio of the modified mesoporous silica, benzoyl peroxide and calcium phosphate-based material is (15-20):1:(4-10).
[0007] As a further improvement, the preparation method of the modified mesoporous silica comprises the following steps:
[0008] S3-1, adding an aqueous sodium hydroxide solution to an aqueous solution of hexadecyltrimethylammonium bromide, heating and stirring for 1-2 hours, then adding a mixed solution of ethyl orthosilicate and n-hexane, continuing the reaction for 2-4 hours, centrifuging, filtering, and drying to obtain an intermediate 1, and finally calcining the intermediate 1 at 500-600° C. for 4-6 hours to obtain mesoporous silica;
[0009] S3-2, ultrasonically dispersing the mesoporous silica obtained in step S3-1 in a mixture of KH560, deionized water and ethanol, reacting at 30-80° C. for 1-5 hours, centrifuging, filtering, washing and drying to obtain modified mesoporous silica.
[0010] As a further improvement, the raw materials for preparing the self-repairing microcapsules include acrylic acid ester derivatives, a reducing agent, a formaldehyde aqueous solution, an emulsifier, a core material and an auxiliary agent.
[0011] As a further improvement, the acrylate derivative comprises one or more of bisphenol A-dimethacrylate glycidyl ester and triethylene glycol dimethacrylate, the reducing agent is N,N-dihydroxyethyl-p-methylaniline, the mass percentage of the formaldehyde aqueous solution is 30-50%, the emulsifier comprises one or more of polyethylene maleic anhydride copolymer, fatty acid methyl ester sulfonate and polyoxyethylene ether, the core material comprises a quaternary ammonium salt antibacterial agent, and the quaternary ammonium salt antibacterial agent comprises one or more of dodecyltrimethylammonium chloride, dodecyldimethylbenzyl ammonium chloride and dodecyldimethylbenzyl ammonium bromide.
[0012] As a further improvement, the auxiliary agent comprises a cross-linking agent, a stabilizer and a pore-forming agent, the cross-linking agent comprises one or both of urea and melamine, the stabilizer is resorcinol, and the pore-forming agent comprises one or both of ammonium chloride and azodicarbonamide.
[0013] As a further improvement, the preparation method comprises the following steps: adding an acrylic acid ester derivative, a reducing agent, and distilled water into a round-bottom flask with a mechanical stirrer, stirring and reacting at a speed of 300-500 rpm / min for 20-30 minutes and standing to obtain a reaction solution 1; then fully mixing the emulsifier and the auxiliary agent, adjusting the pH to 3-5 to obtain a reaction solution 2; then adding the reaction solution 1 dropwise into the reaction solution 2, adding formaldehyde aqueous solution and core material at the same time, raising the water bath temperature to 40-60°C, reacting for 3-4 hours, and performing post-treatment to obtain microcapsules.
[0014] As a further improvement, the mass ratio of the formaldehyde aqueous solution to the core material is 1:(0.05-0.3).
[0015] As a further improvement, the inorganic filler comprises one or more of calcium sulfate whiskers, silicon dioxide and aluminum oxide.
[0016] In another aspect, the present invention provides a method for preparing a tooth restoration material having self-repairing ability, comprising the following steps:
[0017] S10-1, preparing a dispersant, first using ethanol as a solvent to prepare a catalyst solution with a concentration of 0.1-1 mg / mL, adding the modified mesoporous silica to the catalyst solution, and stirring ultrasonically for 5-10 hours to obtain a dispersant;
[0018] S10-2, fully mix the polyoxymethylene resin, inorganic filler, self-repairing microcapsule and dispersant, add them into a twin-screw extruder, extrude, granulate and dry to obtain a tooth repair material with self-repairing ability.
[0019] Compared with the prior art, the present invention has the following beneficial effects: the dispersant provided by the present invention is used to effectively adsorb and disperse polyoxymethylene resin, inorganic filler and self-repairing microcapsules by utilizing the large specific surface area and good biocompatibility of modified mesoporous silica, thereby improving the stability of the overall dispersion system and enhancing the mechanical properties of the tooth restoration material. At the same time, the catalyst is loaded in the modified mesoporous silica to improve the response efficiency of the catalyst and the self-repairing microcapsules, further improving the self-repairing efficiency of the tooth restoration material. DETAILED DESCRIPTION
[0020] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.
[0021] In the following examples, the compound monomers and related reagents used can be purchased from the market, among which polyoxymethylene resin was purchased from Suzhou Jiufu New Materials Co., Ltd. with the item number FG2025; PEG2000 was purchased from Shandong Fangda Chemical Technology Co., Ltd.; polyethylene maleic anhydride copolymer was purchased from Shanghai McLean Biochemical Technology Co., Ltd. with the item number P875047; calcium sulfate whiskers were purchased from Shijiazhuang Qiakexin Technology Co., Ltd. with the item number LSG001; bisphenol A epoxy acrylate was purchased from Shanghai Huicheng New Materials Technology Co., Ltd.; and dodecyltrimethylammonium chloride was purchased from Shanghai Gaoming Chemical Co., Ltd.
[0022] The following examples and comparative examples all comprise the following steps:
[0023] Preparation of modified mesoporous silica:
[0024] 3.5 mL of 1 mol / L sodium hydroxide solution was added to 240 mL of an aqueous solution containing 0.5 g of hexadecyltrimethylammonium bromide, and the mixture was heated to 80° C. and stirred for reaction for 1 h. Then, a mixed solution of 2.5 mL of ethyl orthosilicate and 2.5 mL of n-hexane was added, and the mixture was reacted for 4 h. The mixture was centrifuged, filtered, and dried to obtain an intermediate 1. Finally, the intermediate 1 was calcined at 600° C. for 4 h to obtain mesoporous silica.
[0025] 50 mg of the mesoporous silica prepared in the above step was ultrasonically dispersed in a mixed solution containing 3.8 mL of KH560, 5 mL of deionized water and 5 mL of ethanol, reacted at 70° C. for 2 h, and then centrifuged, filtered, washed and dried to obtain modified mesoporous silica.
[0026] Preparation of dispersion:
[0027] According to the components and contents shown in Table 1, the catalyst (benzoyl peroxide and calcium phosphate-based material) was weighed, and ethanol was used as a solvent to prepare a catalyst solution, wherein the mass volume ratio of the catalyst to ethanol was 1 mg:10 mL, and then the modified mesoporous silica was added to the catalyst solution, and ultrasonic stirring was performed for 6 h to obtain a dispersant.
[0028] The components and contents of the dispersants used in Examples 1-7 and Comparative Examples 1-2 are shown in Table 1.
[0029] Table 1
[0030]
[0031] Preparation of self-repairing microcapsules A:
[0032] Step 1, add 30mL triethylene glycol dimethacrylate, 3mL N,N-dihydroxyethyl-p-methylaniline and 50mL distilled water into a round-bottom flask with a mechanical stirrer, keep the speed at 400rpm / min, stir the reaction for 20min and then stand to obtain reaction solution 1; Step 2, after fully mixing 37.5g polyethylene maleic anhydride copolymer, 1.5g urea, 0.15g resorcinol, 0.15g ammonium chloride and 50mL distilled water, adjust the pH to 3.5 with glacial acetic acid to obtain reaction solution 2; Step 3, add reaction solution 1 dropwise to reaction solution 2, and at the same time add 5g of 40% formaldehyde aqueous solution and 0.5g of dodecyltrimethylammonium chloride, raise the water bath temperature to 55°C at a rate of 1°C / min, react for 4h, wash with distilled water and dry for 24h, and obtain self-repairing microcapsules A.
[0033] Preparation of self-repairing microcapsules B:
[0034] Step 1, bisphenol A epoxy acrylate, ethoxylated trimethylolpropane triacrylate, photoinitiator 184, and butyl titanate are mixed in a mass ratio of 100:25:3:35 to obtain an oil phase; Step 2, sodium dodecyl sulfate and water are configured into an aqueous phase in a mass ratio of 1:10; Step 3, the oil phase prepared in step 1 and the aqueous phase prepared in step 2 are mixed in a mass ratio of 0.4:1, and stirred into a uniform and stable O / W emulsion using a high-speed homogenizer; Step 4, 0.1 mol / L dilute hydrochloric acid, butyl titanate and the O / W emulsion prepared in step 3 are mixed in a mass ratio of 3:4:50, stirred at 50°C for 12 hours, filtered, washed, and vacuum dried to obtain self-healing microcapsules B.
[0035] The preparation method of the tooth restoration material with self-repairing ability of Examples 1-7 and Comparative Examples 1-2 comprises the following steps:
[0036] Weigh each component, fully mix the polyoxymethylene resin, inorganic filler, self-repairing microcapsule and dispersant and add them into a twin-screw extruder. The extrusion temperature is 170°C in zone one, 180°C in zone two, 200°C in zone three and 190°C in zone four. Extrusion granulation and drying are performed to obtain a tooth repair material with self-repairing ability.
[0037] Example 1 provides a tooth restoration material with self-repairing ability, including the following components by mass: 50g of polyoxymethylene resin, 25g of calcium sulfate whiskers, 15g of self-repairing microcapsules A and 10g of dispersant A.
[0038] Example 2 provides a tooth restoration material with self-repairing ability, including the following components by mass: 60g of polyoxymethylene resin, 20g of silica, 12g of self-repairing microcapsules A and 8g of dispersant B.
[0039] Example 3 provides a tooth restoration material with self-repairing ability, including the following components by mass: 80g of polyoxymethylene resin, 10g of aluminum oxide, 5g of self-repairing microcapsules A and 5g of dispersant C.
[0040] The raw materials and components of a tooth restoration material with self-repairing ability provided in Example 4 are basically the same as those in Example 1, except that 10 g of dispersant A is replaced with 25 g of dispersant A.
[0041] The raw materials and components of a tooth restoration material with self-repairing ability provided in Example 5 are basically the same as those in Example 1, except that 10 g of dispersant A is replaced by 2 g of dispersant A.
[0042] The raw materials and components of a tooth restoration material with self-repairing ability provided in Example 6 are basically the same as those in Example 1, except that 10 g of dispersant A is replaced by 10 g of dispersant D.
[0043] The raw materials and components of a tooth restoration material with self-repairing ability provided in Example 7 are basically the same as those in Example 1, except that 10 g of dispersant A is replaced by 10 g of dispersant E.
[0044] The raw materials and components of a tooth restoration material with self-repairing ability provided in Comparative Example 1 are basically the same as those in Example 1, except that 10 g of dispersant A is replaced by 10 g of dispersant F. The preparation method of dispersant F is as follows: 1 mg of benzoyl peroxide, 2 mg of amorphous calcium phosphate nanoparticles and 2 mg of hydroxyapatite are weighed, 50 mL of ethanol is added, and then 15 mg of PEG2000 is added to the catalyst solution, and ultrasonic stirring is performed for 6 hours to obtain dispersant F.
[0045] The raw materials and components of a tooth repair material with self-repairing ability provided in Comparative Example 2 are basically the same as those in Example 1, except that 15 g of self-repairing microcapsule A is replaced by 15 g of self-repairing microcapsule B.
[0046] The test method is as follows:
[0047] Bending performance test: the tooth restoration materials prepared in the above embodiments and comparative examples were prepared into test strips with a size of 2 mm × 2 mm × 25 mm, and the flexural strength of the samples was measured with reference to ISO 4049-2019; the tooth restoration materials prepared in the above embodiments and comparative examples were made into test strips of 80 mm × 10 mm × 4 mm, and the elastic modulus was tested according to the ISO178 method at a test speed of 2 mm / min.
[0048] Vickers hardness test: The tooth restoration materials prepared in the above embodiments and comparative examples were placed in a mold with a diameter of 6 mm and a height of 2 mm to prepare a cylindrical specimen. The surface hardness of the specimen was tested using a Vickers hardness tester with a loading force of 980 mN and continuous loading for 10 s. The digital hardness value was directly recorded. Each specimen was tested 3 times and the average value was taken.
[0049] Self-healing test: the tooth restoration materials prepared in the above examples and comparative examples were made into samples with a size of 100 mm × 10 mm × 2 mm, and scratches with a length of 5 mm × 1 mm × 1 mm were made on the samples. The samples were kept at 25°C for 12 hours, and the length of the scratches was observed under an electron microscope.
[0050]
[0051] L 0 is the initial scratch length, L 1 is the existing scratch length.
[0052] The test results are shown in Table 2. The details are as follows:
[0053] Table 2
[0054] Flexural strength / MPa Elastic modulus / GPa Vickers hardness / HV Self-repair rate / % Example 1 394 6.73 88 80 Example 2 375 6.33 86 72 Example 3 364 6.12 84 75 Example 4 314 4.51 82 70 Example 5 312 5.65 75 65 Example 6 355 6.35 85 61 Example 7 334 6.24 83 64 Comparative Example 1 286 4.14 67 50 Comparative Example 2 295 4.31 72 57
[0055] It can be seen from Examples 1-3 that the present invention provides a tooth restoration material with self-repairing ability, which adopts polyformaldehyde resin as a base material, adds inorganic fillers to enhance the mechanical properties, and adds self-repairing microcapsules to give the tooth restoration material a self-repairing property. The mesoporous silica loaded with a catalyst is added as a dispersant to effectively adsorb and disperse a variety of substances, improve the interface compatibility of the resin, filler and microcapsules, enhance the flexural strength and elastic modulus of the material, and also improve the response efficiency of the catalyst and the self-repairing microcapsules, further promoting the self-repairing efficiency of the tooth restoration material, which is higher than 75%, and has better flexural strength, elastic modulus and Vickers hardness.
[0056] By comparing Examples 4-7 with Example 1, it can be seen that the tooth restoration material with self-repairing ability provided by the present invention, when the content of the dispersant and the mass ratio of the modified mesoporous silica, benzoyl peroxide and the calcium phosphate-based material are all within an appropriate range, the flexural strength, elastic modulus and Vickers hardness of the tooth restoration material with self-repairing ability are better, and the self-repairing efficiency of this type of material is further enhanced.
[0057] From the comparison of Comparative Examples 1-2 and Example 1, it can be seen that the tooth repair material with self-repairing ability provided by the present invention adopts mesoporous silica loaded with a catalyst as a dispersant and the self-repairing microcapsules provided by the present invention, so that the various components of this type of material are evenly dispersed, while the response rate of the catalyst and the self-repairing microcapsules is improved, thereby improving the self-repairing rate of this type of tooth repair material.
[0058] In summary, the present invention provides a tooth restoration material with self-repairing ability, which adopts polyformaldehyde resin as a matrix, calcium sulfate whiskers as an inorganic filler, and self-repairing microcapsules as a functional body, and at the same time adds modified mesoporous silica loaded with a catalyst as a dispersant, thereby improving the interface compatibility between the various components of this type of restoration material, as well as the response efficiency of the catalyst and the self-repairing microcapsules, thereby enhancing the mechanical properties of the tooth restoration material while improving the self-repairing efficiency of the tooth restoration material.
[0059] The above implementation modes are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.
Claims
1. A tooth restoration material with self-repairing ability, characterized in that: The raw materials for preparing the tooth repair material include the following components by weight: 50-80g of polyoxymethylene resin, 10-50g of inorganic filler, 5-20g of self-repairing microcapsules and 5-20g of dispersant, wherein the raw materials for preparing the dispersant include a catalyst and modified mesoporous silica.
2. A tooth restoration material with self-repairing ability according to claim 1, characterized in that: The catalyst comprises benzoyl peroxide and a calcium phosphate-based material, wherein the calcium phosphate-based material comprises one or more of amorphous calcium phosphate nanoparticles and hydroxyapatite, and the mass ratio of the modified mesoporous silica, benzoyl peroxide and the calcium phosphate-based material is (15-20):1:(4-10).
3. A tooth restoration material with self-repairing ability according to claim 2, characterized in that: The preparation method of the modified mesoporous silica comprises the following steps: S3-1, adding an aqueous sodium hydroxide solution to an aqueous solution of hexadecyltrimethylammonium bromide, heating and stirring for 1-2 hours, then adding a mixed solution of ethyl orthosilicate and n-hexane, continuing the reaction for 2-4 hours, centrifuging, filtering, and drying to obtain an intermediate 1, and finally calcining the intermediate 1 at 500-600° C. for 4-6 hours to obtain mesoporous silica; S3-2, ultrasonically dispersing the mesoporous silica obtained in step S3-1 in a mixture of KH560, deionized water and ethanol, reacting at 30-80° C. for 1-5 hours, centrifuging, filtering, washing and drying to obtain modified mesoporous silica.
4. A tooth restoration material with self-repairing ability according to claim 1, characterized in that: The raw materials for preparing the self-repairing microcapsules include acrylic acid ester derivatives, reducing agents, formaldehyde aqueous solution, emulsifiers, core materials and auxiliary agents.
5. A tooth restoration material with self-repairing ability according to claim 4, characterized in that: The acrylic acid ester derivative comprises one or more of bisphenol A-dimethylacrylate glycidyl ester and triethylene glycol dimethacrylate, the reducing agent is N,N-dihydroxyethyl-p-methylaniline, the mass percentage of the formaldehyde aqueous solution is 30-50%, the emulsifier comprises one or more of polyethylene maleic anhydride copolymer, fatty acid methyl ester sulfonate and polyoxyethylene ether, the core material is a quaternary ammonium salt antibacterial agent, and the quaternary ammonium salt antibacterial agent comprises one or more of dodecyltrimethylammonium chloride, dodecyldimethylbenzyl ammonium chloride and dodecyldimethylbenzyl ammonium bromide.
6. A tooth restoration material with self-repairing ability according to claim 4, characterized in that: The auxiliary agent comprises a cross-linking agent, a stabilizer and a pore-forming agent, wherein the cross-linking agent comprises one or two of urea and melamine, the stabilizer is resorcinol, and the pore-forming agent comprises one or two of ammonium chloride and azodicarbonamide.
7. The tooth restoration material with self-repairing ability according to claim 4, characterized in that: The preparation method of the self-healing microcapsules comprises the following steps: adding an acrylic acid ester derivative, a reducing agent, and distilled water into a round-bottom flask with a mechanical stirrer, stirring at a speed of 300-500 rpm / min for reaction for 20-30 minutes, standing to obtain a reaction solution 1, and then fully mixing an emulsifier and an auxiliary agent, adjusting the pH to 3-5 to obtain a reaction solution 2, and then dropping the reaction solution 1 into the reaction solution 2, adding a formaldehyde aqueous solution and a core material at the same time, raising the water bath temperature to 40-60°C, reacting for 3-4 hours, and performing post-treatment to obtain microcapsules.
8. The tooth restoration material with self-repairing ability according to claim 1, characterized in that: The mass ratio of the formaldehyde aqueous solution to the core material is 1:(0.05-0.3).
9. The tooth restoration material with self-repairing ability according to claim 1, characterized in that: The inorganic filler comprises one or more of calcium sulfate whiskers, silicon dioxide and aluminum oxide.
10. A method for preparing a tooth restoration material with self-repairing ability according to any one of claims 1 to 9, characterized in that: The following steps are involved: S10-1, preparing a dispersant, first using ethanol as a solvent to prepare a catalyst solution with a concentration of 0.1-1 mg / mL, adding the modified mesoporous silica to the catalyst solution, and stirring ultrasonically for 5-10 hours to obtain a dispersant; S10-2, fully mix the polyoxymethylene resin, inorganic filler, self-repairing microcapsule and dispersant, add them into a twin-screw extruder, extrude, granulate and dry to obtain a tooth repair material with self-repairing ability.