High-performance wear-resistant reinforced dental composite repair material and preparation method thereof

Abstract

The invention relates to the technical field of composite materials for dental restoration, in particular to a high-performance wear-resistant reinforced dental composite restoration material and a preparation method thereof. The invention relates to a high-performance wear-resistant reinforced dental composite repair material, which is prepared from the following raw materials in parts by mass: 45 to 55 parts of resin, 30 to 35 parts of modified wear-resistant filler, 5 to 8 parts of modified glass fiber, 6 to 8 parts of hydroxy calcium phosphate, 0.5 to 0.8 part of antibacterial agent, 0.8 to 1.2 parts of coupling agent, 0.01 to 0.02 part of coloring agent and 0.1 to 0.2 part of antioxidant, comprising the following raw materials in parts by weight: 25-35 parts of epoxy resin, 60-75 parts of methacrylic acid compound and 1-1.5 parts of curing agent. The high-performance wear-resistant reinforced dental composite repair material has remarkable advantages in the aspects of mechanical property, antibacterial property, biocompatibility, application range and the like, and is expected to be widely applied to the field of dentistry.

Description

Technical Field

[0001] The present application relates to the technical field of composite materials for dental restoration, and in particular to a high-performance wear-resistant reinforced dental composite restoration material and a preparation method thereof. Background Art

[0002] Computer-aided design and computer-aided manufacturing (CAD / CAM) are currently becoming more and more popular in aesthetic dentistry and prosthodontics, and dental materials are being developed to support the emerging market for restorative dental materials. Ceramics and polymers are currently the two main restorative materials for aesthetic dentistry. Ceramic materials have excellent biocompatibility, good wear resistance, and good corrosion resistance, and have aesthetic properties similar to natural teeth. However, brittleness is the weakness of ceramic materials, and fracture failure may occur when the deformation rate is between 0.1% and 0.3%. When chewing repeatedly and non-axial loads are applied, tiny cracks inside the material will expand, causing fatigue damage to the ceramic material, and ultimately leading to the destruction and failure of the restoration. In addition, the elastic modulus and hardness of ceramic materials are much larger than those of natural teeth, which may cause excessive wear of the relative teeth in daily use. In addition, resin materials used in dentistry have high ductility, are simple to manufacture and use, and have good compatibility with teeth. However, factors such as curing shrinkage, low mechanical properties, and poor wear resistance of resin materials limit their further development and application. Although attempts have been made to improve resin restorations, and their mechanical properties have been improved to a certain extent, the direct use of dental composites is only suitable for small restorations. Therefore, there is a need to develop a new dental restorative material that combines the advantages of ceramic and resin materials and provides properties similar to those of natural teeth. Summary of the invention

[0003] The purpose of the present application is to provide a high-performance wear-resistant reinforced dental composite restorative material and a preparation method thereof in response to the deficiencies of the current technology. The high-performance wear-resistant reinforced dental composite restorative material of the present application has excellent mechanical properties, high hardness, good wear resistance, excellent antibacterial properties and biocompatibility, and can be used to prepare various dental restorative materials, such as temporary crowns, bridges, inlays, etc., and can also be used for 3D printing technology to prepare complex dental restorations to meet personalized and precise dental restoration needs.

[0004] In the first aspect, the present application provides a high-performance wear-resistant reinforced dental composite restorative material, which adopts the following technical solution: A high-performance wear-resistant enhanced dental composite restoration material comprises the following raw materials, calculated by weight: 45-55 parts of resin, 30-35 parts of modified wear-resistant filler, 5-8 parts of modified glass fiber, 6-8 parts of hydroxy calcium phosphate, 0.5-0.8 parts of antibacterial agent, 0.8-1.2 parts of coupling agent, 0.01-0.02 parts of colorant, and 0.1-0.2 parts of antioxidant. The resin comprises the following raw materials, calculated by weight: 25-35 parts of epoxy resin, 60-75 parts of methacrylic compound, and 1-1.5 parts of curing agent; the antibacterial agent is nano-silver cerium doped titanium dioxide.

[0005] By adopting the above technical scheme, resin: as a matrix material, it mainly provides adhesion and certain wear resistance. Among them, epoxy resin increases the strength and stability of the material, while methacrylic compounds form acrylic resin after curing, which further improves the biocompatibility of the material. Modified wear-resistant filler: this filler is specially treated to significantly enhance the mechanical properties and hardness of the composite material. It improves the bonding ability, dispersibility and compatibility with the resin matrix, so that the material exhibits better wear resistance when subjected to high loads. Modified glass fiber: through pretreatment and chemical modification, the modified glass fiber improves the bonding ability with the resin matrix, thereby enhancing the mechanical properties and wear resistance of the material. This makes the material less susceptible to damage when impacted or worn. Hydroxycalcium phosphate: this is a bioactive substance that can promote the regeneration and repair of tooth tissue and improve the biocompatibility of the material. Antibacterial agent (nano-silver cerium doped titanium dioxide): has excellent antibacterial properties, kills bacteria by releasing silver ions and other means, and effectively prevents bacterial growth. Its stable structure also ensures the long-term antibacterial effect of the material. Coupling agent: used to improve the interface bonding between different materials and improve the uniformity and stability of the overall material. Colorant: can give the material an appropriate color, making it closer to natural teeth and improving aesthetics. Antioxidant: protects the material from oxidative degradation and prolongs its service life. These components, through their respective characteristics and their synergistic effects, together constitute a high-performance dental restoration material, which is suitable for making temporary crowns, bridges, inlays, etc., and can even meet personalized and precise dental restoration needs through 3D printing technology.

[0006] Preferably, the epoxy resin is composed of bisphenol A epoxy resin, bisphenol E epoxy resin and bisphenol F epoxy resin in a mass ratio of 3:1:1-2.

[0007] Preferably, the methacrylic compound is composed of bisphenol A glycerol dimethacrylate and methacrylate in a mass ratio of 3:2-3; the curing agent is composed of methyltetrahydrophthalic anhydride and benzoyl peroxide in a mass ratio of 1:2.

[0008] Preferably, the preparation method of the nano silver cerium doped titanium dioxide comprises the following steps: S41. At room temperature, add 200 mL of tetra-n-butyl titanate to 380 mL of ethanol and stir for 25 min to form solution A. S42, adding 3.0 g of silver nitrate and 4.5 g of cerium nitrate to a solution consisting of 150 mL of ethanol, 35 mL of acetic acid and 120 mL of water to form solution B; S43. Add solution B dropwise into solution A, stir for 30 min, heat to 45°C, let stand for 16 h, then centrifuge, wash, dry at 80°C for 8 h, and finally calcine at 520°C for 3.5 h, cool, nano-grind, and sieve to obtain silver-cerium-doped titanium dioxide with an average particle size of 0.1 micron.

[0009] By adopting the above technical scheme, the prepared nano silver cerium doped titanium dioxide kills bacteria by releasing silver ions and other means, effectively preventing bacterial growth. This antibacterial property is particularly important for dental restorative materials, because there are a large number of bacteria in the oral environment, which can easily lead to infection and inflammation. Nano silver cerium doped titanium dioxide has a more stable structure, which is conducive to improving the long-term antibacterial properties of composite restorative materials. This means that during long-term use, the material can still maintain a good antibacterial effect. Nano silver cerium doped titanium dioxide has good biocompatibility and will not produce adverse reactions to the human body. This is crucial for dental restorative materials because they need to contact with human tissues and maintain long-term stability. In short, nano silver cerium doped titanium dioxide itself has excellent antibacterial ability, kills bacteria by releasing silver ions and other means, effectively preventing bacterial growth, and nano silver cerium doped titanium dioxide has a more stable structure, which is conducive to improving the long-term antibacterial properties of composite restorative materials.

[0010] Preferably, the preparation method of the modified wear-resistant filler is as follows: after uniformly mixing 6 parts of γ-glycidyloxypropyltrimethoxysilane, 200 parts of ethanol and 300 parts of water by mass, 100 parts of aluminum oxide, 150 parts of silicon oxide and 150 parts of calcium oxide-stabilized tetragonal zirconium oxide are added in sequence, stirred for 6 hours, heated to 75°C, refluxed for 60 minutes, the treated modified wear-resistant filler is filtered, dried, crushed, ground and sieved to obtain a modified wear-resistant filler with a particle size of 2-4 μm.

[0011] By adopting the above technical solution, the prepared modified wear-resistant filler can significantly improve the bonding ability, dispersibility and compatibility of the composite wear-resistant filler with the resin matrix by using γ-glycidyloxypropyltrimethoxysilane as a modifier. This modified filler can be more evenly distributed in the resin matrix, thereby improving the mechanical properties, wear resistance and hardness of the entire composite material. The modified wear-resistant filler not only enhances the wear resistance of the material, but also improves its overall mechanical properties, including hardness and strength. This is very important for dental restorative materials because these materials need to withstand chewing forces and other mechanical stresses.

[0012] Preferably, the method for preparing the modified glass fiber comprises the following steps: S61, dispersing the chopped glass fibers in an ethanol aqueous solution according to the mass fraction, then adding vinyl triethoxysilane thereto, adjusting the pH of the solution to 5-6, stirring for 2-3 hours, centrifuging, washing, and drying to obtain pretreated chopped glass fibers; S62. Disperse the pretreated chopped glass fibers in ethanol aqueous solution according to the mass fractions, add acrylamide, stir evenly, then add ammonium persulfate and dibenzoyl peroxide, heat to 60-70°C and reflux for reaction for 3-5 hours. After the reaction is completed, centrifuge, wash and dry the reaction product to obtain modified chopped glass fibers.

[0013] By adopting the above technical scheme, the prepared modified glass fiber can significantly improve the bonding ability, dispersibility and compatibility of the glass fiber with the resin matrix through the method of pretreatment and chemical modification. The modified glass fiber can be more evenly distributed in the resin matrix, thereby improving the mechanical properties of the entire composite material, including strength and toughness. The addition of modified glass fiber can also improve the wear resistance of the composite material, making it more suitable for dental restoration materials that need to withstand high wear environments. Modified glass fiber can improve the processing performance of the composite material, making it easier to shape and process into the desired shape and size, which is particularly important for the preparation of complex dental restorations.

[0014] Preferably, in step S61, the mass ratio of the chopped glass fibers to the vinyl triethoxysilane is 100:1-2; in step S62, the mass ratio of the pretreated chopped glass fibers, the acrylamide, the ammonium persulfate and the dibenzoyl peroxide is 10:(4-6):(0.3-0.4):(0.1-0.3).

[0015] Preferably, the coupling agent is composed of γ-glycidyloxypropyltrimethoxysilane and vinyltriethoxysilane in a mass ratio of 1:2.

[0016] By adopting the above technical scheme, the coupling agent is composed of γ-glycidyloxypropyl trimethoxysilane and vinyl triethoxysilane in a mass ratio of 1:2. It improves the mechanical properties and wear resistance of the composite material by enhancing the bonding force between the resin and the filler. γ-glycidyloxypropyl trimethoxysilane is an important silane coupling agent with a special functional epoxy functional group. It can improve the compatibility between the inorganic filler and the resin matrix in the composite material, and enhance the adhesion and wear resistance of the material. Vinyl triethoxysilane, as another important silane coupling agent, is mainly used to enhance the bonding ability between glass fiber and resin matrix. It can significantly improve the mechanical strength and durability of the composite material, while improving its processing performance. The synergistic effect of γ-glycidyloxypropyl trimethoxysilane and vinyl triethoxysilane in the material is significant, which enhances the bonding force between inorganic fillers, glass fibers, etc. and resin, and jointly improves the comprehensive performance of the composite material.

[0017] Preferably, the colorant is ferric oxide; and the antioxidant is 2,6-di-tert-butyl-p-cresol.

[0018] In a second aspect, the present application provides a method for preparing a high-performance wear-resistant reinforced dental composite restorative material, using the following technical solution: As a general technical concept, the present application also provides a method for preparing the above-mentioned high-performance wear-resistant reinforced dental composite restorative material, comprising the following steps: S101, according to the mass fractions, the epoxy resin and the methacrylic compound were mixed under ultrasound for 30 minutes, and then a curing agent was added, and high-speed shear dispersion was performed at a speed of 1000-1500 rpm for 1-1.2 hours to obtain a resin solution; S102, adding modified wear-resistant filler, modified glass fiber, calcium hydroxyphosphate, antibacterial agent, coupling agent, colorant and antioxidant to the resin solution according to their mass fractions, and performing high-speed shear dispersion at a speed of 1000 r / min for 30 minutes to obtain a composite material; S103, curing the composite material in a vacuum oven at a curing temperature of 95°C for 3 hours, and then raising the curing temperature to 130°C for 2.5 hours to obtain a high-performance wear-resistant reinforced dental composite restoration material.

[0019] In summary, the beneficial technical effects of this application are: 1. Excellent mechanical properties: The material has high hardness and good wear resistance, thanks to the modified wear-resistant fillers and modified glass fibers in its composition, which enhance the overall strength and durability of the material.

[0020] 2. Long-lasting antibacterial properties: The antibacterial agent used is nano-silver cerium doped titanium dioxide, which effectively kills bacteria by releasing silver ions and prevents bacterial growth, thereby providing long-term antibacterial protection.

[0021] 3. Good biocompatibility: The components in the material, especially the resin and calcium hydroxyphosphate, have good biocompatibility, which means that they do not cause adverse reactions in the human body and are suitable for dental restorations.

[0022] 4. Suitable for 3D printing technology: Due to its excellent physical and chemical properties, this material is very suitable for 3D printing technology and can be used to manufacture complex dental restorations to meet the needs of personalization and precision.

[0023] 5. Multifunctional application: This material can not only be used to make temporary crowns, bridges and inlays, but also can be applied to other types of dental restorations, and has broad application prospects. DETAILED DESCRIPTION

[0024] The following will be described in detail with reference to the embodiments of the present application, but those skilled in the art will understand that the following embodiments are only used to illustrate the present application and should not be considered to limit the scope of the present application. If the specific conditions are not specified in the examples, they are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used without indicating the manufacturer are all conventional products that can be purchased commercially. The bisphenol A epoxy resin brand: DER332 epoxy equivalent (g / eq): 172-176, viscosity (25°C): 40006000, purchased from Dow, USA. The bisphenol F epoxy resin brand: DER353 epoxy equivalent (g / eq): 190-200, viscosity (25°C): 5000-5260 purchased from Dow, USA. The bisphenol E epoxy resin brand: DM411-350 epoxy equivalent (g / eq): 181-192, viscosity (25°C): 50005150, purchased from Dow, USA.

[0025] In the following examples and preparation examples, 1 part means 100 g.

[0026] Preparation Example 1 Preparation of Nano-Silver-Cerium Doped Titanium Dioxide The preparation method of nano silver cerium doped titanium dioxide comprises the following steps: S41. At room temperature, add 200 mL of tetra-n-butyl titanate to 380 mL of ethanol and stir for 25 min to form solution A. S42, adding 3.0 g of silver nitrate and 4.5 g of cerium nitrate to a solution consisting of 150 mL of ethanol, 35 mL of acetic acid and 120 mL of water to form solution B; S43. Add solution B dropwise into solution A, stir for 30 min, heat to 45°C, let stand for 16 h, then centrifuge, wash, dry at 80°C for 8 h, and finally calcine at 520°C for 3.5 h, cool, nano-grind, and sieve to obtain silver-cerium-doped titanium dioxide with an average particle size of 0.1 micron.

[0027] Preparation Example 2 Preparation of modified wear-resistant filler The preparation method of the modified wear-resistant filler is as follows: after mixing 6 parts of γ-glycidyloxypropyltrimethoxysilane, 200 parts of ethanol and 300 parts of water, 100 parts of aluminum oxide with an average particle size of 2 μm, 150 parts of silicon oxide with an average particle size of 3 μm and 150 parts of calcium oxide-stabilized tetragonal zirconium oxide with an average particle size of 0.2 μm are added in sequence, stirred for 6 hours, heated to 75°C, refluxed for 60 minutes, the treated modified wear-resistant filler is filtered, dried, crushed, ground and sieved to obtain a modified wear-resistant filler with a particle size of 2-4 μm.

[0028] Preparation Example 3 The preparation method of modified glass fiber comprises the following steps: S61. Disperse 100 parts of chopped glass fibers (having a length of 4-6 mm and a diameter of 10-15 μm) in 200 parts of an ethanol aqueous solution by mass, add 1.5 parts of vinyltriethoxysilane thereto, adjust the pH of the solution to 5, stir for 2.3 h, centrifuge, wash, and dry to obtain pretreated chopped glass fibers; S62. Disperse 100 parts of pretreated chopped glass fibers in 200 parts of ethanol aqueous solution according to mass proportions, add 50 parts of acrylamide, stir evenly, then add 3.5 parts of ammonium persulfate and 2 parts of dibenzoyl peroxide, heat to 65°C and reflux for 4 hours. After the reaction is completed, centrifuge, wash and dry the reaction product to obtain modified chopped glass fibers.

[0029] Example 1 A high-performance wear-resistant enhanced dental composite restoration material, comprising the following raw materials by weight: 45 parts of resin, 30 parts of modified wear-resistant filler, 5 parts of modified glass fiber, 6 parts of hydroxy calcium phosphate, 0.5 parts of antibacterial agent, 0.8 parts of coupling agent, 0.01 parts of ferric oxide, 0.1 parts of 2,6-di-tert-butyl-p-cresol, wherein the resin, by weight, comprises the following raw materials: 25 parts of epoxy resin, 60 parts of methacrylic compound, 1 part of curing agent; the antibacterial agent is nano silver The invention discloses a cerium-doped titanium dioxide, wherein the epoxy resin comprises bisphenol A epoxy resin, bisphenol E epoxy resin and bisphenol F epoxy resin in a mass ratio of 3:1:1, the methacrylic compound comprises bisphenol A glycerol dimethacrylate and methacrylate in a mass ratio of 3:2, the coupling agent comprises γ-glycidyloxypropyltrimethoxysilane and vinyltriethoxysilane in a mass ratio of 1:2, and the curing agent comprises methyltetrahydrophthalic anhydride and benzoyl peroxide in a mass ratio of 1:2.

[0030] The method for preparing the above-mentioned high-performance wear-resistant reinforced dental composite restorative material comprises the following steps: S101, according to the mass fractions, the epoxy resin and the methacrylic compound were mixed under ultrasound for 30 minutes, and then a curing agent was added, and high-speed shear dispersion was performed at a speed of 1000 rpm for 1.2 hours to obtain a resin solution; S102, adding modified wear-resistant filler, modified glass fiber, calcium hydroxyphosphate, antibacterial agent, coupling agent, ferric oxide and 2,6-di-tert-butyl-p-cresol to the resin solution according to their mass fractions, and performing high-speed shear dispersion at a speed of 1000 r / min for 30 minutes to obtain a composite material; S103, curing the composite material in a vacuum oven at a curing temperature of 95°C for 3 hours, and then raising the curing temperature to 130°C for 2.5 hours to obtain a high-performance wear-resistant reinforced dental composite restoration material.

[0031] Example 2 A high-performance wear-resistant enhanced dental composite restoration material, comprising the following raw materials by weight: 55 parts of resin, 35 parts of modified wear-resistant filler, 8 parts of modified glass fiber, 8 parts of hydroxy calcium phosphate, 0.8 parts of antibacterial agent, 1.2 parts of coupling agent, 0.02 parts of ferric oxide, 0.2 parts of 2,6-di-tert-butyl-p-cresol, wherein the resin, by weight, comprises the following raw materials: 35 parts of epoxy resin, 75 parts of methacrylic acid compound, 1.5 parts of curing agent; the antibacterial agent is nano Silver cerium doped titanium dioxide, the epoxy resin consists of bisphenol A epoxy resin, bisphenol E epoxy resin and bisphenol F epoxy resin in a mass ratio of 3:1:2, the methacrylic compound consists of bisphenol A glycerol dimethacrylate and methacrylate in a mass ratio of 3:3, the coupling agent consists of γ-glycidyloxypropyltrimethoxysilane and vinyltriethoxysilane in a mass ratio of 1:2, and the curing agent consists of methyltetrahydrophthalic anhydride and benzoyl peroxide in a mass ratio of 1:2.

[0032] The method for preparing the above-mentioned high-performance wear-resistant reinforced dental composite restorative material comprises the following steps: S101, according to the mass fractions, the epoxy resin and the methacrylic acid compound were mixed under ultrasound for 30 minutes, and then a curing agent was added, and high-speed shear dispersion was performed at a speed of 1500 rpm for 1 hour to obtain a resin solution; S102, adding modified wear-resistant filler, modified glass fiber, calcium hydroxyphosphate, antibacterial agent, coupling agent, ferric oxide and 2,6-di-tert-butyl-p-cresol to the resin solution according to their mass fractions, and performing high-speed shear dispersion at a speed of 1000 r / min for 30 minutes to obtain a composite material; S103, curing the composite material in a vacuum oven at a curing temperature of 95°C for 3 hours, and then raising the curing temperature to 130°C for 2.5 hours to obtain a high-performance wear-resistant reinforced dental composite restoration material.

[0033] Example 3 A high-performance wear-resistant enhanced dental composite restoration material, comprising the following raw materials by weight: 50 parts of resin, 33 parts of modified wear-resistant filler, 7 parts of modified glass fiber, 7 parts of hydroxy calcium phosphate, 0.6 parts of antibacterial agent, 1 part of coupling agent, 0.05 parts of ferric oxide, 0.15 parts of 2,6-di-tert-butyl-p-cresol, wherein the resin, by weight, comprises the following raw materials: 30 parts of epoxy resin, 68 parts of methacrylic compound, 1.2 parts of curing agent; the antibacterial agent is nano silver cerium Titanium dioxide is doped, the epoxy resin is composed of bisphenol A epoxy resin, bisphenol E epoxy resin and bisphenol F epoxy resin in a mass ratio of 3:1:1.5, the methacrylic compound is composed of bisphenol A glycerol dimethacrylate and methacrylate in a mass ratio of 3:2.5, the coupling agent is composed of γ-glycidyloxypropyltrimethoxysilane and vinyltriethoxysilane in a mass ratio of 1:2, and the curing agent is composed of methyltetrahydrophthalic anhydride and benzoyl peroxide in a mass ratio of 1:2.

[0034] The method for preparing the above-mentioned high-performance wear-resistant reinforced dental composite restorative material comprises the following steps: S101, according to the mass fractions, the epoxy resin and the methacrylic compound were mixed under ultrasound for 30 minutes, and then a curing agent was added, and high-speed shear dispersion was performed at a speed of 1300 rpm for 1.1 hours to obtain a resin solution; S102, adding modified wear-resistant filler, modified glass fiber, calcium hydroxyphosphate, antibacterial agent, coupling agent, ferric oxide and 2,6-di-tert-butyl-p-cresol to the resin solution according to their mass fractions, and performing high-speed shear dispersion at a speed of 1000 r / min for 30 minutes to obtain a composite material; S103, curing the composite material in a vacuum oven at a curing temperature of 95°C for 3 hours, and then raising the curing temperature to 130°C for 2.5 hours to obtain a high-performance wear-resistant reinforced dental composite restoration material.

[0035] Comparative Example 1 The same as Example 3, except that an equal amount of chopped glass fibers (having a length of 4-6 mm and a diameter of 10-15 μm) are used instead of the modified glass fibers.

[0036] Comparative Example 2 The same as Example 3, except that an equal amount of mixed filler (alumina with an average particle size of 2 μm, silicon oxide with an average particle size of 3 μm and tetragonal zirconia stabilized by calcium oxide with an average particle size of 0.2 μm, mixed in a mass ratio of 1:1.5:1.5) is used instead of the modified wear-resistant filler.

[0037] Comparative Example 3 The same as Example 3, except that the coupling agent is γ-glycidyloxypropyltrimethoxysilane.

[0038] Comparative Example 4 The same as Example 3, except that the coupling agent is vinyltriethoxysilane.

[0039] Performance Testing The high performance wear-resistant reinforced dental composite restoration materials prepared in Example 1, Example 3 and Comparative Examples 1 to 4 were sampled respectively, and corresponding samples were made according to the test requirements, and the following tests were carried out. The test results are shown in Table 1.

[0040] Bending strength and elastic modulus: The bending strength and elastic modulus were tested using a universal testing machine (AGS, Shimadzu, Japan). A three-point bending test was used with a loading rate of 1 mm / min, the sample width × height × length was (2 ± 0.1) mm × (2 ± 0.1) mm × (25 ± 2) mm, and the span was 20 mm.

[0041] Hardness: The hardness was tested using a Vickers hardness tester (VH1150, Wilson, USA). The width × height × length of the sample was (6±0.1) mm × (3±0.1) mm × (25±2) mm.

[0042] Immediate antibacterial performance: Antibacterial testing was carried out according to JIS Z2801:2000 standard, antibacterial rate of Staphylococcus aureus ATTCC6538P; Long-term antibacterial rate: Cut the high-performance wear-resistant reinforced dental composite restoration material into 3cm×3cm samples. After disinfection with 70% ethanol solution, place the samples in simulated artificial saliva. The artificial saliva is replaced every 24 hours. Take the samples on the 28th day and conduct antibacterial testing according to JIS Z2801:2000 standard. The antibacterial rate of Staphylococcus aureus ATTCC6538P.

[0043] Table 1 Performance test Biocompatibility testing The more complete the curing of the composite repair material is, the less the residual polymer monomer is, the lower the water absorption value, solubility value and chemical solubility value of the material are, and the better the biocompatibility of the material is.

[0044] The high-performance wear-resistant reinforced dental composite restoration material prepared in Example 3 and the commercially available Tailor CAD / CAM fiber-reinforced resin product of Bioloren were tested. The test methods for water absorption and solubility values ​​were based on YY / T0710-2009 / ISO10477-2004 "Polymer-based crown and bridge materials in dentistry", and the test method for chemical solubility was based on ISO6872-2008 dental ceramic materials. The test results are shown in Table 2.

[0045] Table 2 Biocompatibility Analyzing the data in Table 1 and Table 2, we can see that: 1) The high-performance wear-resistant reinforced dental composite restoration materials prepared in Examples 1 to 3 have excellent mechanical properties, high hardness, good wear resistance, excellent antibacterial properties and biocompatibility, and can be used to prepare various dental restoration materials.

[0046] 2) The performance comparison analysis of the high-performance wear-resistant reinforced dental composite restoration material prepared in Example 3 and Comparative Example 1 shows that the prepared modified glass fiber can significantly improve the bonding ability, dispersibility and compatibility of the glass fiber and the resin matrix through pretreatment and chemical modification. The modified glass fiber can be more evenly distributed in the resin matrix, thereby improving the mechanical properties and hardness of the entire composite material.

[0047] 3) The performance comparison analysis of the high-performance wear-resistant reinforced dental composite restoration materials prepared in Example 3 and Comparative Example 2 shows that the modified wear-resistant filler prepared in the present application can significantly improve the bonding ability, dispersibility and compatibility of the composite wear-resistant filler with the resin matrix by using γ-glycidyl ether oxypropyl trimethoxysilane modification. The modified filler can be more evenly distributed in the resin matrix, thereby improving the mechanical properties, wear resistance and hardness of the entire composite material.

[0048] 4) The performance comparison analysis of the high-performance wear-resistant enhanced dental composite restoration material prepared in combination with Example 3 and Comparative Examples 3-4 shows that the coupling agent is composed of γ-glycidyloxypropyltrimethoxysilane and vinyltriethoxysilane in a mass ratio of 1:2, and the coupling agent can improve the interface compatibility between inorganic fillers (such as modified wear-resistant fillers, modified glass fibers and hydroxy calcium phosphate, etc.) and composite restoration materials. Through chemical bonding or physical adsorption, the coupling agent can promote the close bonding between the filler and the resin, reduce interface defects, and improve the overall performance of the composite material. The synergistic effect between γ-glycidyloxypropyltrimethoxysilane and vinyltriethoxysilane can maximize the mechanical properties, antibacterial properties and durability of the material while ensuring good interface compatibility.

[0049] The above embodiments are only used to explain the technical solutions of the present application rather than to limit them. Although the above embodiments provide a specific description of the present application, relevant technical personnel should understand that the specific implementation modes of the present invention can still be modified or replaced by equivalents, and any modifications and equivalent replacements that do not depart from the spirit and scope of the present application should be included in the scope of protection of the present application.

Claims

1. A high-performance wear-resistant reinforced dental composite restorative material, characterized in that: The preparation material comprises the following raw materials by weight: 45-55 parts of resin, 30-35 parts of modified wear-resistant filler, 5-8 parts of modified glass fiber, 6-8 parts of hydroxy calcium phosphate, 0.5-0.8 parts of antibacterial agent, 0.8-1.2 parts of coupling agent, 0.01-0.02 parts of colorant and 0.1-0.2 parts of antioxidant. The resin comprises the following raw materials by weight: 25-35 parts of epoxy resin, 60-75 parts of methacrylic compound and 1-1.5 parts of curing agent. The antibacterial agent is nano-silver cerium doped titanium dioxide.

2. A high-performance wear-resistant reinforced dental composite restorative material according to claim 1, characterized in that: The epoxy resin is composed of bisphenol A epoxy resin, bisphenol E epoxy resin and bisphenol F epoxy resin in a mass ratio of 3:1:1-2.

3. A high-performance wear-resistant reinforced dental composite restorative material according to claim 1, characterized in that: The methacrylic compound is composed of bisphenol A glycerol dimethacrylate and methacrylate in a mass ratio of 3:2-3; the curing agent is composed of methyltetrahydrophthalic anhydride and benzoyl peroxide in a mass ratio of 1:

2.

4. A high-performance wear-resistant reinforced dental composite restorative material according to claim 1, characterized in that: The preparation method of nano silver cerium doped titanium dioxide comprises the following steps: S41. At room temperature, add 200 mL of tetra-n-butyl titanate to 380 mL of ethanol and stir for 25 min to form solution A. S42, adding 3.0 g of silver nitrate and 4.5 g of cerium nitrate to a solution consisting of 150 mL of ethanol, 35 mL of acetic acid and 120 mL of water to form solution B; S43. Add solution B dropwise into solution A, stir for 30 min, heat to 45°C, let stand for 16 h, then centrifuge, wash, dry at 80°C for 8 h, and finally calcine at 520°C for 3.5 h, cool, nano-grind, and sieve to obtain silver-cerium-doped titanium dioxide with an average particle size of 0.1 micron.

5. A high-performance wear-resistant reinforced dental composite restorative material according to claim 1, characterized in that: The preparation method of the modified wear-resistant filler is as follows: after uniformly mixing 6 parts of γ-glycidyloxypropyltrimethoxysilane, 200 parts of ethanol and 300 parts of water by mass, 100 parts of aluminum oxide, 150 parts of silicon oxide and 150 parts of calcium oxide-stabilized tetragonal zirconium oxide are added in sequence, stirred for 6 hours, heated to 75° C., refluxed for 60 minutes, and the treated modified wear-resistant filler is filtered, dried, crushed, ground and sieved to obtain a modified wear-resistant filler with a particle size of 2-4 μm.

6. A high-performance wear-resistant reinforced dental composite restorative material according to claim 1, characterized in that: The preparation method of the modified glass fiber comprises the following steps: S61, dispersing the chopped glass fibers in an ethanol aqueous solution according to the mass fraction, then adding vinyl triethoxysilane thereto, adjusting the pH of the solution to 5-6, stirring for 2-3 hours, centrifuging, washing, and drying to obtain pretreated chopped glass fibers; S62. Disperse the pretreated chopped glass fibers in ethanol aqueous solution according to the mass fractions, add acrylamide, stir evenly, then add ammonium persulfate and dibenzoyl peroxide, heat to 60-70°C and reflux for reaction for 3-5 hours. After the reaction is completed, centrifuge, wash and dry the reaction product to obtain modified chopped glass fibers.

7. A high-performance wear-resistant reinforced dental composite restorative material according to claim 6, characterized in that: In step S61, the mass ratio of the chopped glass fiber to the vinyl triethoxysilane is 100:1-2; in step S62, the mass ratio of the pretreated chopped glass fiber, the acrylamide, the ammonium persulfate and the dibenzoyl peroxide is 10:(4-6):(0.3-0.4):(0.1-0.3).

8. The high-performance wear-resistant reinforced dental composite restorative material according to claim 1, characterized in that: The coupling agent is composed of γ-glycidyloxypropyltrimethoxysilane and vinyltriethoxysilane in a mass ratio of 1:

2.

9. A high-performance wear-resistant reinforced dental composite restorative material according to claim 1, characterized in that: The colorant is ferric oxide; the antioxidant is 2,6-di-tert-butyl-p-cresol.

10. A method for preparing a high-performance wear-resistant reinforced dental composite restorative material according to any one of claims 1 to 9, characterized in that: The following steps are involved: S101, according to the mass fractions, the epoxy resin and the methacrylic compound were mixed under ultrasound for 30 minutes, and then a curing agent was added, and high-speed shear dispersion was performed at a speed of 1000-1500 rpm for 1-1.2 hours to obtain a resin solution; S102, adding modified wear-resistant filler, modified glass fiber, calcium hydroxyphosphate, antibacterial agent, coupling agent, colorant and antioxidant to the resin solution according to their mass fractions, and performing high-speed shear dispersion at a speed of 1000 r / min for 30 minutes to obtain a composite material; S103, curing the composite material in a vacuum oven at a curing temperature of 95°C for 3 hours, and then raising the curing temperature to 130°C for 2.5 hours to obtain a high-performance wear-resistant reinforced dental composite restoration material.

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