Bionic dental implant crown composite material and preparation method thereof

Abstract

The invention discloses a bionic dental implant crown composite material which is composed of nano-crystalline cellulose fibers and polyacrylic resin, the surface of the bionic dental implant crown composite material is provided with a ceramic coating with the thickness of 0.3-0.5 mm, the mass ratio of the nano-crystalline cellulose fibers to the polyacrylic resin is 1: (4-6), the ceramic coating is composed of micron-sized zirconium oxide particles and nano-sized titanium dioxide particles, and the nano-sized zirconium oxide particles and the nano-sized titanium dioxide particles are uniformly distributed on the surface of the ceramic coating. The mass ratio of titanium dioxide to zirconium oxide is 1: (9-19), the particle size difference of particles can form a micro-nano structure on the coating, and the mechanical property of the material is improved. The nano cellulose fiber and polyacrylic resin composite structure is a dentin-imitated structure, the ceramic coating is a tooth enamel-imitated structure, and the nano cellulose fiber with the length of 0.05-0.2 mm extends to the ceramic coating to form a connection interface, so that the effects of dispersing stress and improving the impact resistance and durability of the material can be achieved, and the implant tooth has excellent comprehensive performance.

Description

Technical Field

[0001] The invention relates to the field of medical dentistry, and in particular to a bionic dental implant crown composite material and a preparation method thereof. Background Art

[0002] Teeth are formed through biomineralization and are the hardest tissue in the human body. From the outside to the inside, human teeth are mainly composed of enamel, dentin, cementum and pulp. Enamel is the hard covering layer on the crown of the tooth, which serves as a protective shell for the tooth, while the relatively soft dentin is located below the enamel, acting as an energy absorption pad, which improves the fracture toughness of the tooth and enables the tooth to withstand hundreds of impacts of up to megapascals during daily chewing. At the same time, the interface between enamel and dentin can effectively prevent the cracks generated from the enamel from further expanding, preventing damage to the tooth. Tooth loss not only affects the patient's facial appearance, normal life, social interaction, work, etc., but also affects the function of the alveolar bone, reduces the metabolic capacity of the alveolar bone, and accelerates the absorption of alveolar bone. Currently, implant restoration is one of the effective repair and treatment methods for edentulousness, and has been widely used and developed in clinical practice. The crown material of dental implant restoration needs to have sufficient strength and hardness to withstand the various forces generated during chewing, ensuring that the implant is fixed in the alveolar bone for a long time. The development of crown restoration materials has gone through traditional nickel-chromium and cobalt-chromium alloys to composite materials such as resins, porcelain, and all-ceramic. The chemical composition and microscopic crystal structure of these materials are quite different from natural tooth enamel, and their appearance and performance are far inferior to natural tooth enamel. Therefore, crown restoration materials with good biocompatibility, similar structure, similar mechanical properties, and tight adhesion to natural tooth enamel are needed. With the technological innovation of materials science, modern crowns are not only required to meet the restoration needs in terms of function, but also need to achieve higher standards in aesthetics. By simulating the structure of natural teeth and using a layer-by-layer assembly method, bionic restoration materials with similar structures to natural teeth are synthesized, which meet the overall mechanical properties, biocompatibility, antibacterial properties, and other properties of dental implants. This provides an ideal strategy for implant restoration of missing teeth and has broad application prospects. Summary of the invention

[0003] Technical problem to be solved: The technical problem to be solved by the present invention is to provide a bionic dental implant crown composite material that simulates the enamel-dentin interface. Cellulose fibers are present at the interface between the resin and the ceramic coating to make the bond between the resin and the ceramic more stable and to disperse stress.

[0004] Technical solution: A bionic dental implant crown composite material composed of nanocellulose and resin with a ceramic coating on the surface. Preferably, the ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:9-19, and the thickness of the coating is 0.3-0.5 mm. Preferably, the method for preparing the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier to deionized water and stirring evenly to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse one end of the fibers in an aqueous acrylic emulsion, and dry the fibers to obtain a fiber mat; S3. Filling the fiber felt into the mold, adding an initiator and heating to polymerize the acrylic acid, cooling after the reaction is completed, and obtaining a polyacrylic acid resin-cellulose composite material; S4. Disperse zirconium oxide particles and titanium dioxide particles evenly in a photosensitive resin, coat the particles on the surface of a polyacrylic resin-cellulose composite material, and cure the composite material under light to obtain a bionic dental implant crown composite material. Preferably, the mass ratio of the aqueous acrylic acid, the emulsifier and the water in step S1 is 1:0.03-0.05:2-10. Preferably, the diameter of the nanocellulose fiber in step S2 is 80-110 nm, one end of the fiber has a length of 0.05-0.2 mm not immersed in the aqueous acrylic emulsion, and the mass ratio of cellulose to acrylic acid is 1:4-6. Preferably, in step S3, during the process of filling the fiber felt into the mold, the end not immersed in the aqueous acrylic emulsion faces upward. Preferably, the mass ratio of the initiator to the aqueous acrylic acid in step S3 is 2 to 4:100, and the heating temperature is 60 to 80° C. Preferably, the particle size of the zirconium oxide particles in step S4 is 10 to 20 μm, and the particle size of the titanium dioxide particles is 20 to 100 nm. Preferably, the ceramic particles in step S4 are coated on the upper surface and side surface of the polyacrylic resin-cellulose composite material. Beneficial effects: Compared with the prior art, the present invention has the following advantages and positive effects: 1. The present invention uses a composite structure of nanocellulose fibers and polyacrylic acid resin to imitate the hydroxyapatite crystals and collagen fiber structure of dentin. The resin with lower hardness can support the hard coating, absorb energy impact, and protect the internal soft tissue structure. Nanocellulose can improve the water resistance and thermal stability of the resin, and after being composited with polyacrylic acid resin, it can effectively improve the comprehensive mechanical properties of the resin, further protect the brittle hard coating, and improve the durability of the bionic implant crown. 2. The present invention prepares a zirconium oxide-carbon dioxide composite ceramic coating on the surface of a resin-cellulose composite material to imitate the tooth enamel layer. The ceramic has high hardness and is close to the mechanical properties of the tooth enamel layer. It can withstand adverse conditions such as vibration, repeated impact, and friction. Combined with the resin-cellulose composite material supported by the bottom, it has good impact resistance to ensure that the implant can be used for a long time. Zirconia has good mechanical properties and biocompatibility and is an ideal tooth restoration material. After being compounded with a small amount of titanium dioxide, the color is closer to natural teeth. Titanium dioxide has good self-cleaning properties, which can improve the antibacterial property of the coating and effectively reduce the incidence of oral diseases. In addition, micron-level zirconium oxide particles and nano-level titanium dioxide particles can form a micro-nano structured coating, which can enhance the adhesion and mechanical properties of the coating, while improving the hydrophobicity and antibacterial properties of the coating. 3. The present invention arranges the cellulose fibers in an orderly manner and retains part of the fiber length to extend into the ceramic coating to form an interface, imitating the enamel-dentin interface, connecting the hard ceramic coating with the relatively soft resin without stratification, which is highly similar to the real human tooth structure. The interface can effectively transfer and disperse the stress generated in the ceramic coating to the resin, maintain the integrity of the structure, and improve the impact resistance of the material. DETAILED DESCRIPTION In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. Specific preferred examples are as follows: Embodiment 1: A bionic dental implant crown composite material, composed of nanocellulose and resin, and having a ceramic coating on the surface; The ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:9, and the thickness of the coating is 0.3 mm; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier into deionized water and stirring evenly, the mass ratio of aqueous acrylic acid, emulsifier and water is 1:0.04:8 to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse one end of the nanocellulose fibers in an aqueous acrylic emulsion, and leave 0.05 to 0.2 mm of the other end not immersed in the aqueous acrylic emulsion, wherein the mass ratio of cellulose to acrylic acid is 1:4, and obtain a fiber felt after drying; S3. Fill the fiber felt into the mold, with the end not immersed in the aqueous acrylic emulsion facing upward, add an initiator dropwise and heat at 70°C to polymerize the acrylic acid, the mass ratio of the initiator to the aqueous acrylic acid being 3:100, and cool after the reaction to obtain a polyacrylic acid resin-cellulose composite material; S4. Dispersing zirconium oxide particles with a particle size of 10 to 20 μm and titanium dioxide particles with a particle size of 20 to 40 nm uniformly in a photosensitive resin, coating the particles on the upper and side surfaces of the polyacrylic resin-cellulose composite material, and curing the composite material under light to obtain a bionic dental implant crown composite material; The diameter of the nanocellulose fibers in step S2 is 110 nm. Embodiment 2: A bionic dental implant crown composite material, composed of nanocellulose and resin, and having a ceramic coating on the surface; The ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:14, and the thickness of the coating is 0.3 mm; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier into deionized water and stirring evenly, the mass ratio of aqueous acrylic acid, emulsifier and water is 1:0.04:8 to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse one end of the nanocellulose fibers in an aqueous acrylic emulsion, and leave 0.05 to 0.2 mm of the other end not immersed in the aqueous acrylic emulsion, wherein the mass ratio of cellulose to acrylic acid is 1:4, and obtain a fiber felt after drying; S3. Fill the fiber felt into the mold, with the end not immersed in the aqueous acrylic emulsion facing upward, add an initiator dropwise and heat at 70°C to polymerize the acrylic acid, the mass ratio of the initiator to the aqueous acrylic acid being 3:100, and cool after the reaction to obtain a polyacrylic acid resin-cellulose composite material; S4. Dispersing zirconium oxide particles with a particle size of 10 to 20 μm and titanium dioxide particles with a particle size of 20 to 40 nm uniformly in a photosensitive resin, coating the particles on the upper and side surfaces of the polyacrylic resin-cellulose composite material, and curing the composite material under light to obtain a bionic dental implant crown composite material; The diameter of the nanocellulose fibers in step S2 is 110 nm. Embodiment 3: A bionic dental implant crown composite material, composed of nanocellulose and resin, and having a ceramic coating on the surface; The ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:19, and the thickness of the coating is 0.3 mm; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier into deionized water and stirring evenly, the mass ratio of aqueous acrylic acid, emulsifier and water is 1:0.04:8 to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse one end of the nanocellulose fibers in an aqueous acrylic emulsion, and leave 0.05 to 0.2 mm of the other end not immersed in the aqueous acrylic emulsion, wherein the mass ratio of cellulose to acrylic acid is 1:4, and obtain a fiber felt after drying; S3. Fill the fiber felt into the mold, with the end not immersed in the aqueous acrylic emulsion facing upward, add an initiator dropwise and heat at 70°C to polymerize the acrylic acid, the mass ratio of the initiator to the aqueous acrylic acid being 3:100, and cool after the reaction to obtain a polyacrylic acid resin-cellulose composite material; S4. Dispersing zirconium oxide particles with a particle size of 10 to 20 μm and titanium dioxide particles with a particle size of 20 to 40 nm uniformly in a photosensitive resin, coating the particles on the upper and side surfaces of the polyacrylic resin-cellulose composite material, and curing the composite material under light to obtain a bionic dental implant crown composite material; The diameter of the nanocellulose fibers in step S2 is 110 nm. Embodiment 4: A bionic dental implant crown composite material, composed of nanocellulose and resin, and having a ceramic coating on the surface; The ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:19, and the thickness of the coating is 0.4 mm; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier into deionized water and stirring evenly, the mass ratio of aqueous acrylic acid, emulsifier and water is 1:0.04:8 to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse one end of the nanocellulose fibers in an aqueous acrylic emulsion, and leave 0.05 to 0.2 mm of the other end not immersed in the aqueous acrylic emulsion, wherein the mass ratio of cellulose to acrylic acid is 1:4, and obtain a fiber felt after drying; S3. Fill the fiber felt into the mold, with the end not immersed in the aqueous acrylic emulsion facing upward, add an initiator dropwise and heat at 70°C to polymerize the acrylic acid, the mass ratio of the initiator to the aqueous acrylic acid being 3:100, and cool after the reaction to obtain a polyacrylic acid resin-cellulose composite material; S4. Dispersing zirconium oxide particles with a particle size of 10 to 20 μm and titanium dioxide particles with a particle size of 20 to 40 nm uniformly in a photosensitive resin, coating the particles on the upper and side surfaces of the polyacrylic resin-cellulose composite material, and curing the composite material under light to obtain a bionic dental implant crown composite material; The diameter of the nanocellulose fibers in step S2 is 110 nm. Embodiment 5: A bionic dental implant crown composite material, composed of nanocellulose and resin, and having a ceramic coating on the surface; The ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:19, and the thickness of the coating is 0.5 mm; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier into deionized water and stirring evenly, the mass ratio of aqueous acrylic acid, emulsifier and water is 1:0.04:8 to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse one end of the nanocellulose fibers in an aqueous acrylic emulsion, and leave 0.05 to 0.2 mm of the other end not immersed in the aqueous acrylic emulsion, wherein the mass ratio of cellulose to acrylic acid is 1:4, and obtain a fiber felt after drying; S3. Fill the fiber felt into the mold, with the end not immersed in the aqueous acrylic emulsion facing upward, add an initiator dropwise and heat at 70°C to polymerize the acrylic acid, the mass ratio of the initiator to the aqueous acrylic acid being 3:100, and cool after the reaction to obtain a polyacrylic acid resin-cellulose composite material; S4. Dispersing zirconium oxide particles with a particle size of 10 to 20 μm and titanium dioxide particles with a particle size of 20 to 40 nm uniformly in a photosensitive resin, coating the particles on the upper and side surfaces of the polyacrylic resin-cellulose composite material, and curing the composite material under light to obtain a bionic dental implant crown composite material; The diameter of the nanocellulose fibers in step S2 is 110 nm. Embodiment 6: A bionic dental implant crown composite material, composed of nanocellulose and resin, and having a ceramic coating on the surface; The ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:9, and the thickness of the coating is 0.5 mm; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier into deionized water and stirring evenly, the mass ratio of aqueous acrylic acid, emulsifier and water is 1:0.04:8 to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse one end of the nanocellulose fibers in an aqueous acrylic emulsion, and leave 0.05 to 0.2 mm of the other end not immersed in the aqueous acrylic emulsion, wherein the mass ratio of cellulose to acrylic acid is 1:4, and obtain a fiber felt after drying; S3. Fill the fiber felt into the mold, with the end not immersed in the aqueous acrylic emulsion facing upward, add an initiator dropwise and heat at 70°C to polymerize the acrylic acid, the mass ratio of the initiator to the aqueous acrylic acid being 3:100, and cool after the reaction to obtain a polyacrylic acid resin-cellulose composite material; S4. Dispersing zirconium oxide particles with a particle size of 10 to 20 μm and titanium dioxide particles with a particle size of 20 to 40 nm uniformly in a photosensitive resin, coating the particles on the upper and side surfaces of the polyacrylic resin-cellulose composite material, and curing the composite material under light to obtain a bionic dental implant crown composite material; The diameter of the nanocellulose fibers in step S2 is 100 nm. Embodiment 7: A bionic dental implant crown composite material, composed of nanocellulose and resin, and having a ceramic coating on the surface; The ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:9, and the thickness of the coating is 0.5 mm; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier into deionized water and stirring evenly, the mass ratio of aqueous acrylic acid, emulsifier and water is 1:0.04:8 to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse one end of the nanocellulose fibers in an aqueous acrylic emulsion, and leave 0.05 to 0.2 mm of the other end not immersed in the aqueous acrylic emulsion, wherein the mass ratio of cellulose to acrylic acid is 1:4, and obtain a fiber felt after drying; S3. Fill the fiber felt into the mold, with the end not immersed in the aqueous acrylic emulsion facing upward, add an initiator dropwise and heat at 70°C to polymerize the acrylic acid, the mass ratio of the initiator to the aqueous acrylic acid being 3:100, and cool after the reaction to obtain a polyacrylic acid resin-cellulose composite material; S4. Dispersing zirconium oxide particles with a particle size of 10 to 20 μm and titanium dioxide particles with a particle size of 20 to 40 nm uniformly in a photosensitive resin, coating the particles on the upper and side surfaces of the polyacrylic resin-cellulose composite material, and curing the composite material under light to obtain a bionic dental implant crown composite material; The diameter of the nanocellulose fibers in step S2 is 90 nm. Embodiment 8: A bionic dental implant crown composite material, composed of nanocellulose and resin, and having a ceramic coating on the surface; The ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:9, and the thickness of the coating is 0.5 mm; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier into deionized water and stirring evenly, the mass ratio of aqueous acrylic acid, emulsifier and water is 1:0.04:8 to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse one end of the nanocellulose fibers in an aqueous acrylic emulsion, and leave 0.05 to 0.2 mm of the other end not immersed in the aqueous acrylic emulsion, wherein the mass ratio of cellulose to acrylic acid is 1:4, and obtain a fiber felt after drying; S3. Fill the fiber felt into the mold, with the end not immersed in the aqueous acrylic emulsion facing upward, add an initiator dropwise and heat at 70°C to polymerize the acrylic acid, the mass ratio of the initiator to the aqueous acrylic acid being 3:100, and cool after the reaction to obtain a polyacrylic acid resin-cellulose composite material; S4. Dispersing zirconium oxide particles with a particle size of 10 to 20 μm and titanium dioxide particles with a particle size of 20 to 40 nm uniformly in a photosensitive resin, coating the particles on the upper and side surfaces of the polyacrylic resin-cellulose composite material, and curing the composite material under light to obtain a bionic dental implant crown composite material; The diameter of the nanocellulose fibers in step S2 is 80 nm. Embodiment 9: A bionic dental implant crown composite material, composed of nanocellulose and resin, and having a ceramic coating on the surface; The ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:9, and the thickness of the coating is 0.5 mm; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier into deionized water and stirring evenly, the mass ratio of aqueous acrylic acid, emulsifier and water is 1:0.04:8 to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse one end of the nanocellulose fibers in an aqueous acrylic emulsion, and leave 0.05 to 0.2 mm of the other end not immersed in the aqueous acrylic emulsion, wherein the mass ratio of cellulose to acrylic acid is 1:5, and obtain a fiber felt after drying; S3. Fill the fiber felt into the mold, with the end not immersed in the aqueous acrylic emulsion facing upward, add an initiator dropwise and heat at 70°C to polymerize the acrylic acid, the mass ratio of the initiator to the aqueous acrylic acid being 3:100, and cool after the reaction to obtain a polyacrylic acid resin-cellulose composite material; S4. Dispersing zirconium oxide particles with a particle size of 10 to 20 μm and titanium dioxide particles with a particle size of 20 to 40 nm uniformly in a photosensitive resin, coating the particles on the upper and side surfaces of the polyacrylic resin-cellulose composite material, and curing the composite material under light to obtain a bionic dental implant crown composite material; The diameter of the nanocellulose fibers in step S2 is 80 nm. Embodiment 10: A bionic dental implant crown composite material, composed of nanocellulose and resin, and having a ceramic coating on the surface; The ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:9, and the thickness of the coating is 0.5 mm; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier into deionized water and stirring evenly, the mass ratio of aqueous acrylic acid, emulsifier and water is 1:0.04:8 to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse one end of the nanocellulose fibers in an aqueous acrylic emulsion, and leave 0.05 to 0.2 mm of the other end not immersed in the aqueous acrylic emulsion, wherein the mass ratio of cellulose to acrylic acid is 1:6, and obtain a fiber felt after drying; S3. Fill the fiber felt into the mold, with the end not immersed in the aqueous acrylic emulsion facing upward, add an initiator dropwise and heat at 70°C to polymerize the acrylic acid, the mass ratio of the initiator to the aqueous acrylic acid being 3:100, and cool after the reaction to obtain a polyacrylic acid resin-cellulose composite material; S4. Dispersing zirconium oxide particles with a particle size of 10 to 20 μm and titanium dioxide particles with a particle size of 20 to 40 nm uniformly in a photosensitive resin, coating the particles on the upper and side surfaces of the polyacrylic resin-cellulose composite material, and curing the composite material under light to obtain a bionic dental implant crown composite material; The diameter of the nanocellulose fibers in step S2 is 80 nm. Embodiment 11: A bionic dental implant crown composite material, composed of nanocellulose and resin, and having a ceramic coating on the surface; The ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:9, and the thickness of the coating is 0.5 mm; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier into deionized water and stirring evenly, the mass ratio of aqueous acrylic acid, emulsifier and water is 1:0.04:8 to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse one end of the nanocellulose fibers in an aqueous acrylic emulsion, and leave 0.05 to 0.2 mm of the other end not immersed in the aqueous acrylic emulsion, wherein the mass ratio of cellulose to acrylic acid is 1:6, and obtain a fiber felt after drying; S3. Fill the fiber felt into the mold, with the end not immersed in the aqueous acrylic emulsion facing upward, add an initiator dropwise and heat at 70°C to polymerize the acrylic acid, the mass ratio of the initiator to the aqueous acrylic acid being 3:100, and cool after the reaction to obtain a polyacrylic acid resin-cellulose composite material; S4. Dispersing zirconium oxide particles with a particle size of 10 to 20 μm and titanium dioxide particles with a particle size of 40 to 60 nm uniformly in a photosensitive resin, coating the particles on the upper and side surfaces of the polyacrylic resin-cellulose composite material, and curing the composite material under light to obtain a bionic dental implant crown composite material; The diameter of the nanocellulose fibers in step S2 is 80 nm. Embodiment 12: A bionic dental implant crown composite material, composed of nanocellulose and resin, and having a ceramic coating on the surface; The ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:9, and the thickness of the coating is 0.5 mm; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier into deionized water and stirring evenly, the mass ratio of aqueous acrylic acid, emulsifier and water is 1:0.04:8 to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse one end of the nanocellulose fibers in an aqueous acrylic emulsion, and leave 0.05 to 0.2 mm of the other end not immersed in the aqueous acrylic emulsion, wherein the mass ratio of cellulose to acrylic acid is 1:6, and obtain a fiber felt after drying; S3. Fill the fiber felt into the mold, with the end not immersed in the aqueous acrylic emulsion facing upward, add an initiator dropwise and heat at 70°C to polymerize the acrylic acid, the mass ratio of the initiator to the aqueous acrylic acid being 3:100, and cool after the reaction to obtain a polyacrylic acid resin-cellulose composite material; S4. Dispersing zirconium oxide particles with a particle size of 10 to 20 μm and titanium dioxide particles with a particle size of 60 to 80 nm uniformly in a photosensitive resin, coating the particles on the upper and side surfaces of the polyacrylic resin-cellulose composite material, and curing the composite material under light to obtain a bionic dental implant crown composite material; The diameter of the nanocellulose fibers in step S2 is 80 nm. Embodiment 13: A bionic dental implant crown composite material, composed of nanocellulose and resin, and having a ceramic coating on the surface; The ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:9, and the thickness of the coating is 0.5 mm; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier into deionized water and stirring evenly, the mass ratio of aqueous acrylic acid, emulsifier and water is 1:0.04:8 to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse one end of the nanocellulose fibers in an aqueous acrylic emulsion, and leave 0.05 to 0.2 mm of the other end not immersed in the aqueous acrylic emulsion, wherein the mass ratio of cellulose to acrylic acid is 1:6, and obtain a fiber felt after drying; S3. Fill the fiber felt into the mold, with the end not immersed in the aqueous acrylic emulsion facing upward, add an initiator dropwise and heat at 70°C to polymerize the acrylic acid, the mass ratio of the initiator to the aqueous acrylic acid being 3:100, and cool after the reaction to obtain a polyacrylic acid resin-cellulose composite material; S4. Dispersing zirconium oxide particles with a particle size of 10 to 20 μm and titanium dioxide particles with a particle size of 80 to 100 nm uniformly in a photosensitive resin, coating the particles on the upper and side surfaces of the polyacrylic resin-cellulose composite material, and curing the composite material under light to obtain a bionic dental implant crown composite material; The diameter of the nanocellulose fibers in step S2 is 80 nm. In order to further illustrate the technical effect of the present invention, the present invention also provides a comparative example, which is as follows: Comparative Example 1: A bionic dental implant crown composite material, composed of nanocellulose and resin, and having a ceramic coating on the surface; The ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:9, and the thickness of the coating is 0.3 mm; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier into deionized water and stirring evenly, the mass ratio of aqueous acrylic acid, emulsifier and water is 1:0.04:8 to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse them in an aqueous acrylic emulsion, and dry them to obtain a fiber felt; S3. Fill the fiber felt into the mold, add the initiator and heat at 70°C to polymerize the acrylic acid, the mass ratio of the initiator to the aqueous acrylic acid is 3:100, and cool after the reaction to obtain a polyacrylic acid resin-cellulose composite material; S4. Dispersing zirconium oxide particles with a particle size of 10 to 20 μm and titanium dioxide particles with a particle size of 20 to 40 nm uniformly in a photosensitive resin, coating the particles on the upper and side surfaces of the polyacrylic resin-cellulose composite material, and curing the composite material under light to obtain a bionic dental implant crown composite material; The diameter of the nanocellulose fibers in step S2 is 110 nm. Comparative Example 2: A bionic dental implant crown composite material, composed of nanocellulose and resin, and having a ceramic coating on the surface; The ceramic coating is composed of zirconium oxide and has a thickness of 0.3 mm; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier into deionized water and stirring evenly, the mass ratio of aqueous acrylic acid, emulsifier and water is 1:0.04:8 to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse one end in an aqueous acrylic emulsion, and leave 0.05 to 0.2 mm of the other end not immersed in the aqueous acrylic emulsion, and dry to obtain a fiber felt; S3. Fill the fiber felt into the mold, with the end not immersed in the aqueous acrylic emulsion facing upward, add an initiator dropwise and heat at 70°C to polymerize the acrylic acid, the mass ratio of the initiator to the aqueous acrylic acid being 3:100, and cool after the reaction to obtain a polyacrylic acid resin-cellulose composite material; S4. Dispersing zirconium oxide particles uniformly in a photosensitive resin, coating the resin on the upper and side surfaces of the polyacrylic acid resin-cellulose composite material, and curing the composite material under light to obtain a bionic dental implant crown composite material; The diameter of the nanocellulose fibers in step S2 is 110 nm. Comparative Example 3: A bionic dental implant crown composite material, consisting of nanocellulose and resin; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier into deionized water and stirring evenly, the mass ratio of aqueous acrylic acid, emulsifier and water is 1:0.04:8 to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse them in an aqueous acrylic emulsion, and dry them to obtain a fiber felt; S3. Fill the fiber felt into the mold, add the initiator and heat at 70°C to polymerize the acrylic acid, the mass ratio of the initiator to the aqueous acrylic acid is 3:100, and cool after the reaction to obtain a bionic dental implant crown composite material; The diameter of the nanocellulose fibers in step S2 is 110 nm. Comparative Example 4: A bionic dental implant crown composite material, composed of nanocellulose and resin, and having a ceramic coating on the surface; The ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:19, and the thickness of the coating is 0.5 mm; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier into deionized water and stirring evenly, the mass ratio of aqueous acrylic acid, emulsifier and water is 1:0.04:8 to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse one end in an aqueous acrylic emulsion, and leave 0.05 to 0.2 mm of the other end not immersed in the aqueous acrylic emulsion, and dry to obtain a fiber felt; S3. Fill the fiber felt into the mold, with the end not immersed in the aqueous acrylic emulsion facing upward, add an initiator dropwise and heat at 70°C to polymerize the acrylic acid, the mass ratio of the initiator to the aqueous acrylic acid being 3:100, and cool after the reaction to obtain a polyacrylic acid resin-cellulose composite material; S4. Dispersing zirconium oxide particles with a particle size of 10 to 20 μm and titanium dioxide particles with a particle size of 20 to 40 nm uniformly in a photosensitive resin, coating the particles on the upper and side surfaces of the polyacrylic resin-cellulose composite material, and curing the composite material under light to obtain a bionic dental implant crown composite material; The diameter of the nanocellulose fibers in step S2 is 150 nm. Comparative Example 5: A bionic dental implant crown composite material, composed of nanocellulose and resin, and having a ceramic coating on the surface; The ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:9, and the thickness of the coating is 0.5 mm; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier into deionized water and stirring evenly, the mass ratio of aqueous acrylic acid, emulsifier and water is 1:0.04:8 to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse one end of the nanocellulose fibers in an aqueous acrylic emulsion, and leave 0.05 to 0.2 mm of the other end not immersed in the aqueous acrylic emulsion, wherein the mass ratio of cellulose to acrylic acid is 1:8, and obtain a fiber felt after drying; S3. Fill the fiber felt into the mold, with the end not immersed in the aqueous acrylic emulsion facing upward, add an initiator dropwise and heat at 70°C to polymerize the acrylic acid, the mass ratio of the initiator to the aqueous acrylic acid being 3:100, and cool after the reaction to obtain a polyacrylic acid resin-cellulose composite material; S4. Dispersing zirconium oxide particles with a particle size of 10 to 20 μm and titanium dioxide particles with a particle size of 20 to 40 nm uniformly in a photosensitive resin, coating the particles on the upper and side surfaces of the polyacrylic resin-cellulose composite material, and curing the composite material under light to obtain a bionic dental implant crown composite material; The diameter of the nanocellulose fibers in step S2 is 80 nm. Comparative Example 6: A bionic dental implant crown composite material, consisting of a resin and a ceramic coating on the surface; The ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:9, and the thickness of the coating is 0.3 mm; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. The aqueous acrylic acid and the emulsifier are stirred evenly, the mass ratio of the aqueous acrylic acid and the emulsifier is 1:0.04, the initiator is added dropwise and heated at 70°C to polymerize the acrylic acid, the mass ratio of the initiator, the emulsifier and the aqueous acrylic acid is 3:4:100, and after the reaction is completed, the polyacrylic acid resin is obtained by cooling; S2. Zirconium oxide particles with a particle size of 10 to 20 μm and titanium dioxide particles with a particle size of 20 to 40 nm are uniformly dispersed in a photosensitive resin, coated on the upper surface and side surfaces of the polyacrylic resin, and cured under light to obtain a bionic dental implant crown composite material. Comparative Example 7: A bionic dental implant crown composite material, composed of nanocellulose and resin, and having a ceramic coating on the surface; The ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:9, and the thickness of the coating is 0.4 mm; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier into deionized water and stirring evenly, the mass ratio of aqueous acrylic acid, emulsifier and water is 1:0.04:8 to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse one end of the nanocellulose fibers in an aqueous acrylic emulsion, and leave 0.05 to 0.2 mm of the other end not immersed in the aqueous acrylic emulsion, wherein the mass ratio of cellulose to acrylic acid is 1:6, and obtain a fiber felt after drying; S3. Fill the fiber felt into the mold, with the end not immersed in the aqueous acrylic emulsion facing upward, add an initiator dropwise and heat at 70°C to polymerize the acrylic acid, the mass ratio of the initiator to the aqueous acrylic acid being 3:100, and cool after the reaction to obtain a polyacrylic acid resin-cellulose composite material; S4. uniformly dispersing ceramic particles in a binder, coating the binder on the upper and side surfaces of the polyacrylic acid resin-cellulose composite material, and curing the composite material to obtain a bionic dental implant crown composite material; The diameter of the nanocellulose fibers in step S2 is 80 nm. Comparative Example 8: A bionic dental implant crown composite material, composed of nanocellulose and resin, and having a ceramic coating on the surface; The ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:9, and the thickness of the coating is 0.5 mm; The preparation method of the bionic dental implant crown composite material comprises the following steps: S1. Adding aqueous acrylic acid and an emulsifier into deionized water and stirring evenly, the mass ratio of aqueous acrylic acid, emulsifier and water is 1:0.04:8 to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse one end of the nanocellulose fibers in an aqueous acrylic emulsion, and leave 0.05 to 0.2 mm of the other end not immersed in the aqueous acrylic emulsion, wherein the mass ratio of cellulose to acrylic acid is 1:6, and obtain a fiber felt after drying; S3. Fill the fiber felt into the mold, with the end not immersed in the aqueous acrylic emulsion facing upward, add an initiator dropwise and heat at 70°C to polymerize the acrylic acid, the mass ratio of the initiator to the aqueous acrylic acid being 3:100, and cool after the reaction to obtain a polyacrylic acid resin-cellulose composite material; S4. Uniformly dispersing zirconium oxide particles with a particle size of 10 to 20 μm and titanium dioxide particles with a particle size of 200 to 400 nm in a photosensitive resin, coating the particles on the upper and side surfaces of the polyacrylic resin-cellulose composite material, and curing the composite material under light to obtain a bionic dental implant crown composite material; The diameter of the nanocellulose fibers in step S2 is 80 nm. The bonding strength between the ceramic coating and the resin substrate was determined by a single pendulum impact scratch method. The samples of each embodiment and the comparative example were ground and polished, and placed horizontally on a sample table. The single pendulum was freely released from an initial swing angle of 120°, and the scratching head was hooked on the coating surface to produce an arc-shaped groove. The height of the sample table was adjusted by a lifting system to determine the nominal intrusion depth, and the actual depth of the groove was measured, and the ratio of the two was calculated; The impact resistance of each embodiment and comparative example was measured by a dynamic fatigue load test. The maximum load was set to 500N, 10% of the nominal peak value was used as the minimum load to generate a sine wave, the frequency was 15Hz, the stress ratio was 0.1, and the fatigue cycle was 5 million times to see whether the sample was damaged. The hardness of each embodiment and comparative example was tested using a microhardness tester; The samples of each embodiment and comparative example were sterilized by ultraviolet light irradiation, placed in a culture dish, inoculated with Escherichia coli culture solution, and cultured at 37° C. for 24 h. The colonies were counted and compared with the blank control sample to calculate the antibacterial rate. The test results are shown in Tables 1 to 6. Table 1 Effects of different coating components on the performance of dental implant crown materials Table 2 Effect of different coating thicknesses on the performance of dental implant crown materials Table 3 Effect of different fiber diameters on the performance of dental implant crown materials Table 4 Effect of cellulose to resin mass ratio on the performance of dental implant crown materials Table 5 Effects of different interface bonding modes between coating and substrate on the performance of dental implant crown materials Table 6 Effect of different coating component particle size ratios on the performance of dental implant crown materials In summary, the composite material prepared by the present invention has good impact resistance and fatigue resistance, and the composite ceramic coating has high hardness and high antibacterial properties, and is an excellent material suitable for bionic dental implant crowns.

Claims

1. A bionic dental implant crown composite material, characterized in that: The composite material consists of nano cellulose and resin, and has a ceramic coating on the surface.

2. The bionic dental implant crown composite material according to claim 1, characterized in that: The ceramic coating is composed of zirconium oxide and titanium dioxide, the mass ratio of titanium dioxide to zirconium oxide is 1:9-19, and the thickness of the coating is 0.3-0.5 mm.

3. The method for preparing the bionic dental implant crown composite material according to claim 1, characterized in that: The following steps are involved: S1. Adding aqueous acrylic acid and an emulsifier to deionized water and stirring evenly to obtain an aqueous acrylic emulsion; S2. Arrange the nanocellulose fibers neatly, immerse one end of the fibers in an aqueous acrylic emulsion, and dry the fibers to obtain a fiber mat; S3. Filling the fiber felt into the mold, adding an initiator and heating to polymerize the acrylic acid, cooling after the reaction is completed, and obtaining a polyacrylic acid resin-cellulose composite material; S4. Disperse zirconium oxide particles and titanium dioxide particles evenly in a photosensitive resin, coat the particles on the surface of a polyacrylic resin-cellulose composite material, and cure the composite material under light to obtain a bionic dental implant crown composite material.

4. The method for preparing the bionic dental implant crown composite material according to claim 3, characterized in that: The mass ratio of the aqueous acrylic acid, the emulsifier and the water in step S1 is 1:0.03-0.05:2-10.

5. The method for preparing the bionic dental implant crown composite material according to claim 3, characterized in that: The diameter of the nanocellulose fiber in step S2 is 80-110 nm, one end of the fiber has a length of 0.05-0.2 mm that is not immersed in the aqueous acrylic emulsion, and the mass ratio of cellulose to acrylic acid is 1:4-6.

6. The method for preparing the bionic dental implant crown composite material according to claim 3, characterized in that: In step S3, during the process of filling the fiber felt into the mold, the end that is not immersed in the aqueous acrylic emulsion faces upward.

7. The method for preparing the bionic dental implant crown composite material according to claim 3, characterized in that: In step S3, the mass ratio of the initiator to the aqueous acrylic acid is 2-4:100, and the heating temperature is 60-80°C.

8. The method for preparing the bionic dental implant crown composite material according to claim 3, characterized in that: In step S4, the particle size of the zirconium oxide particles is 10-20 μm, and the particle size of the titanium dioxide particles is 20-100 nm.

9. The method for preparing the bionic dental implant crown composite material according to claim 3, characterized in that: In step S4, the ceramic particles are coated on the upper surface and side surfaces of the polyacrylic acid resin-cellulose composite material.

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